JP2019116523A - Polymer compound, composition containing the same, resin composition containing them, and molding of the same - Google Patents

Abstract

To provide a polymer compound which can continuously impart an excellent antistatic effect to a synthetic resin, a composition containing the same, a resin composition containing them, and a molding of the same.SOLUTION: A polymer compound is obtained by reaction of polyester (a) obtained by reaction of diol and a dicarboxylic acid, a compound (b) having hydroxyl groups on both terminals having one or more ethyleneoxy groups, and epoxy modified silicone oil (D) having two or more epoxy groups.SELECTED DRAWING: None

Description

  The present invention relates to a polymer compound, a composition containing the same, a resin composition containing the same, and a molded article thereof, and in particular, continuously imparting an excellent antistatic effect to a synthetic resin. The present invention relates to a polymer compound that can be used, a composition containing the same, a resin composition containing them, and a molded article thereof.

  Not only are synthetic resins such as thermoplastic resins light in weight and easy to process, but they also have excellent properties such as being able to design the base material according to the application, so they can not be indispensable at the present age It is an important material. In addition, thermoplastic resins are frequently used for components of electric products, etc. because they have excellent electrical insulation properties. However, since the thermoplastic resin has too high insulation, there is a problem that it is easily charged by friction or the like.

  The charged thermoplastic resin attracts surrounding dust and dirt, causing a problem of damaging the appearance of the resin molded product. Further, among electronic products, for example, in precision equipment such as a computer, the circuit may not be able to operate normally due to charging. In addition, there is also a problem with lightning. When a resin generates an electric shock to the human body, it not only makes the person feel uncomfortable, but it may also cause an explosion accident in the presence of combustible gas and dust.

  In order to solve such a problem, conventionally, a process for preventing charging of a synthetic resin has been performed. The most common antistatic treatment method is to add an antistatic agent to the synthetic resin. Such antistatic agents include a coating type that is applied to the surface of a resin molded product and a kneading type that is added when processing and molding a resin, but the coating type has poor sustainability. In addition to that, there is a problem that the contact with the surface is contaminated because a large amount of organic matter is applied to the surface.

  From this point of view, conventionally, kneading-type antistatic agents have been mainly studied. For example, Patent Documents 1 and 2 propose polyetheresteramides for imparting antistatic properties to polyolefin resins. . Further, Patent Document 3 proposes a block polymer having a structure in which a block of polyolefin and a block of hydrophilic polymer are repeatedly and alternately bonded. Further, Patent Document 4 proposes a polymeric antistatic agent having a block of polyester.

Japanese Patent Application Laid-Open No. 58-118838 Unexamined-Japanese-Patent No. 3-290464 JP 2001-278985 A JP, 2016-23254, A

  However, these conventional antistatic agents are not always sufficient in antistatic performance, and further improvement is desired at present.

  Therefore, an object of the present invention is to provide a polymer compound capable of continuously imparting an excellent antistatic effect to a synthetic resin, a composition containing the same, a resin composition containing these, and a molded article thereof To provide.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polymer compound having a predetermined structure can impart excellent antistatic performance to a synthetic resin. It has been found that the above problems can be solved, and the present invention has been completed.

  That is, the polymer compound of the present invention comprises a polyester (a) obtained by reacting a diol and a dicarboxylic acid, a compound (b) having a hydroxyl group at both ends having one or more ethyleneoxy groups, and an epoxy group. It is characterized in that it is obtained by reacting two or more epoxy-modified silicone oils (D) with one another.

  The polymer compound of the present invention comprises a polyester block (A) composed of the polyester (a) and a polyether block (B) composed of the compound (b), and the polyester (a) Through an ester bond or an ether bond formed by the reaction of the hydroxyl group or carboxyl group at the end of), the hydroxyl group at the end of compound (b), and the epoxy group of the epoxy-modified silicone oil (D) It is preferable to have a structure formed by bonding. In addition, in the polymer compound of the present invention, the polyester block (A) and the polyether block (B) have carboxyl groups at both ends, which are alternately and repeatedly bonded via an ester bond. It is preferable to have a structure in which the block polymer (C) and the epoxy-modified silicone oil (D) are bonded via an ester bond. Furthermore, in the polymer compound of the present invention, the polyester (a) preferably has a structure having a carboxyl group at both ends. Furthermore, in the polymer compound of the present invention, the compound (b) is preferably polyethylene glycol.

  Further, the composition of the present invention is characterized in that the polymer compound of the present invention is further blended with one or more selected from the group of an alkali metal salt and an ionic liquid. .

  Furthermore, the resin composition of the present invention is characterized in that the polymer compound of the present invention or the composition of the present invention is blended with a synthetic resin.

  Furthermore, the molded article of the present invention is characterized by comprising the resin composition of the present invention.

  According to the present invention, a polymer compound capable of continuously imparting an excellent antistatic effect to a synthetic resin, a composition containing the same, a resin composition containing the same, and a molded article thereof are provided. can do. Since the resin composition of the present invention is excellent in antistatic property and its durability, the molded article of the present invention has the advantage of being less likely to cause deterioration of the commercial value due to contamination of the surface by static electricity and adhesion of dust. ing.

Hereinafter, embodiments of the present invention will be described in detail. The polymer compound of the present invention (hereinafter also referred to as “polymer compound (E)”) is a polyester (a) obtained by the reaction of a diol and a dicarboxylic acid, and at both ends having one or more ethyleneoxy groups. It is obtained by the reaction of a compound (b) having a hydroxyl group and an epoxy-modified silicone oil (D) having two or more epoxy groups. Here, the ethyleneoxy group is a group represented by the following general formula (1).

  The polymer compound (E) of the present invention comprises a polyester block (A) composed of a polyester (a) and a polyether block (B) composed of a compound (b), the polyester Formed by the reaction of a hydroxyl group or carboxyl group at the end of (a), a hydroxyl group at the end of compound (b), and an epoxy group of epoxy-modified silicone oil (D) having two or more epoxy groups, It is preferable to have a structure formed by bonding via an ester bond or an ether bond. In particular, a block polymer (C) having a carboxyl group at both ends, in which a polyester block (A) and a polyether block (B) are repeatedly and alternately bonded via an ester bond, and an epoxy group It is preferable to have a structure in which an epoxy-modified silicone oil (D) having one or more particles is bonded via an ester bond. The polyester (a) can be obtained by subjecting a diol and a dicarboxylic acid to an esterification reaction.

  First, diol which is a component of polyester (a) will be described. Examples of the diol used in the polymer compound (E) of the present invention include aliphatic diols and aromatic group-containing diols. The diol may be a mixture of two or more.

  As aliphatic diols, for example, 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2-butanediol, 1,3-butanediol , 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl- 1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5- Pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediyl , 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 1, 2-, 1,3- or 1,4-cyclohexanediol, cyclododecanediol, dimer diol, hydrogenated dimer diol, diethylene glycol, dipropylene glycol, triethylene glycol and the like. Among these aliphatic diols, 1,4-cyclohexanedimethanol and hydrogenated bisphenol A are preferable from the viewpoint of the antistatic property and the durability, and 1,4-cyclohexanedimethanol is more preferable. In addition, since it is preferable that aliphatic diol has hydrophobicity from the point of antistatic property and its persistence, use of the polyethyleneglycol which has hydrophilicity is unpreferable.

  As the aromatic group-containing diol, for example, bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, 1,4-benzenedimethanol, ethylene oxide adduct of bisphenol A, Examples thereof include propylene oxide adducts of bisphenol A, 1,4-bis (2-hydroxyethoxy) benzene, resorcin, polyhydroxyethyl adducts of mononuclear dihydric phenol compounds such as pyrocatechol, and the like. Among the diols having these aromatic groups, ethylene oxide adduct of bisphenol A and 1,4-bis (β-hydroxyethoxy) benzene are preferable. The aromatic diol is preferably hydrophobic from the viewpoint of antistaticity and its durability.

  Next, the dicarboxylic acid which is a component of polyester (a) is demonstrated. In the polymer compound (E) of the present invention, the dicarboxylic acid which is a component of the polyester (a) is a combination of both an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid from the viewpoint of the antistatic property and its persistence. Is preferred.

  The aliphatic dicarboxylic acid used in the polymer compound (E) of the present invention may be a derivative of aliphatic dicarboxylic acid (eg, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.). The aliphatic dicarboxylic acid and its derivative may be a mixture of two or more.

  The aliphatic dicarboxylic acid preferably includes aliphatic dicarboxylic acids having 2 to 20 carbon atoms, and examples thereof include 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, dicarboxylic acids having 4 to 16 carbon atoms are preferable, and dicarboxylic acids having 6 to 12 carbon atoms are more preferable, from the viewpoint of antistatic properties and their durability.

  The aromatic dicarboxylic acid may also be a derivative of aromatic dicarboxylic acid (for example, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.). The aromatic dicarboxylic acid and its derivative may be a mixture of two or more.

  The aromatic dicarboxylic acid preferably includes an aromatic dicarboxylic acid having 8 to 20 carbon atoms, and examples thereof include 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-sulfoisophthalic acid and 3-sulfoisophthalic acid Potassium and the like can be mentioned. Among these aromatic dicarboxylic acids, terephthalic acid, isophthalic acid and phthalic acid (including phthalic anhydride) are preferable, and phthalic acid (including phthalic anhydride) is more preferable, from the viewpoint of the antistatic property and the durability.

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

ここで、ｍは５〜２５０の数を表す。ｍは、帯電防止性とその持続性の点から、２０〜２００が好ましく、４０〜１８０がより好ましい。 As the compound (b) having one or more ethyleneoxy groups represented by the general formula (1) and having a hydroxyl group at both ends, a compound having hydrophilicity is preferable, and ethyleneoxy represented by the general formula (1) Polyethers having a group are more preferable, polyethylene glycol is even more preferable, and polyethylene glycol represented by the following general formula (2) is particularly preferable, from the viewpoint of the antistatic property and the durability.

Here, m represents a number of 5 to 250. m is preferably 20 to 200, and more preferably 40 to 180, from the viewpoint of the antistatic property and its durability.

  As the compound (b), in addition to polyethylene glycol obtained by addition reaction of ethylene oxide, ethylene oxide and other alkylene oxides such as propylene oxide, 1,2-, 1,4-, 2,3-, Or polyethers in which one or more species such as 1,3-butylene oxide are subjected to an addition reaction, and the polyethers may be random or block.

  Examples of the compound (b) further include a compound having a structure in which ethylene oxide is added to an active hydrogen atom-containing compound, ethylene oxide and other alkylene oxides such as propylene oxide, 1,2-, 1,4-, The compound of the structure which one or more sorts, such as 2,3- or 1,3- butylene oxide, added is mentioned. 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, an aromatic glycol having 8 to 26 carbon atoms, and the like can be used.

  As aliphatic glycol, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol 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 can be mentioned.

  As an alicyclic glycol, for example, 1-hydroxymethyl-1-cyclobutanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1-methyl-3,4-cyclohexanediol 2-hydroxymethylcyclohexanol, 4-hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol, 1,1'-dihydroxy-1,1'-dicyclohexyl and the like.

  Examples of aromatic glycols include dihydroxymethylbenzene, 1,4-bis (β-hydroxyethoxy) benzene, 2-phenyl-1,3-propanediol, 2-phenyl-1,4-butanediol, 2-benzyl There may be mentioned 1,3-propanediol, triphenyl ethylene glycol, tetraphenyl ethylene glycol, benzopinacol and the like.

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

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

  As secondary diamines, aliphatic secondary diamines having 4 to 18 carbon atoms, heterocyclic secondary diamines having 4 to 13 carbon atoms, alicyclic secondary diamines having 6 to 14 carbon atoms, the number of carbon atoms 8 to 14 aromatic secondary diamines and secondary alkanol diamines having 3 to 22 carbon atoms can be used.

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

  As a heterocyclic secondary diamine, a piperazine, 1-amino piperidine etc. are mentioned, for example.

  As the alicyclic secondary diamine, for example, N, N'-dimethyl-1,2-cyclobutanediamine, N, N'-diethyl-1,2-cyclobutanediamine, N, N'-dibutyl-1,2- Cyclobutanediamine, N, N'-dimethyl-1,4-cyclohexanediamine, N, N'-diethyl-1,4-cyclohexanediamine, N, N'-dibutyl-1,4-cyclohexanediamine, N, N'- Dimethyl-1,3-cyclohexanediamine, N, N'-diethyl-1,3-cyclohexanediamine, N, N'-dibutyl-1,3-cyclohexanediamine and the like can be mentioned.

  As an aromatic secondary diamine, for example, N, N'-dimethyl-phenylenediamine, N, N'-dimethyl-xylylenediamine, N, N'-dimethyl-diphenylmethanediamine, N, N'-dimethyl-diphenylether diamine And N, N'-dimethyl-benzidine and N, N'-dimethyl-1,4-naphthalenediamine.

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

  As a dicarboxylic acid, C2-C20 dicarboxylic acid can be used, For example, aliphatic dicarboxylic acid, aromatic dicarboxylic acid, alicyclic dicarboxylic acid etc. are used.

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

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

  As an alicyclic dicarboxylic acid, for example, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid Examples include acids, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid, and dicyclohexyl-4,4'-dicarboxylic acid.

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

  Next, the epoxy-modified silicone oil (D) having two or more epoxy groups constituting the polymer compound (E) will be described.

  First, silicone oil will be described. As an example of silicone oil, the side chain of polysiloxane, dimethyl silicone oil whose end is all methyl group, side chain of polysiloxane, methyl end whose end is methyl group and part of the side chain is phenyl group Examples thereof include silicone oil, methylhydrogensilicone oil in which the side chain of polysiloxane and the terminal end are methyl groups and part of the side chain is hydrogen, and copolymers of these. An epoxy-modified silicone oil is one in which an epoxy group is introduced to part of these side chains and / or ends. The component (D) related to the polymer compound (E) of the present invention is an epoxy-modified silicone oil having two or more epoxy groups and two or more epoxy groups introduced. The epoxy group may be a cycloaliphatic epoxy group. The position of the epoxy group may be any one of both ends, one end, and a side chain of silicone oil as long as it is two or more, but from the viewpoint of antistaticity and durability, those having both ends are preferable.

  The epoxy-modified silicone oil (D) having two or more epoxy groups is preferably one having an epoxy group at both ends of the compound from the viewpoint of the antistatic property and its persistence.

  The epoxy-modified silicone oil (D) having two or more epoxy groups may be commercially available, and as a specific example thereof, those having an epoxy group at both ends, X-22-163 (Shin-Etsu Chemical Co., Ltd.) KF Co., Ltd., KF-105 (Shin-Etsu Chemical Co., Ltd.), X-22-163A (Shin-Etsu Chemical Co., Ltd.), X-22-163 B (Shin-Etsu Chemical Co., Ltd.), X -22-163C (Shin-Etsu Chemical Co., Ltd. product), BY16-855 (Toray-Dow Corning Co., Ltd. product), etc., and those having an alicyclic epoxy group at both ends, X-22-169 AS (Shin-Etsu Chemical Co., Ltd. product), X-22-169B (Shin-Etsu Chemical Co., Ltd. product), etc., and X-22-9002 (Shin-Etsu Chemical Co., Ltd.) as having an epoxy group at both ends and a side chain. Industrial Co., Ltd.) That. Among these, X-22-163 (Shin-Etsu Chemical Co., Ltd. product), KF-105 (Shin-Etsu Chemical Co., Ltd. product), having epoxy groups at both ends from the viewpoint of antistatic property and its durability. X-22-163A (Shin-Etsu Chemical Co., Ltd.), X-22-163 B (Shin-Etsu Chemical Co., Ltd.), X-22-163 C (Shin-Etsu Chemical Co., Ltd.), BY16-855 (Toray Dow Corning Co., Ltd.) is preferred.

  Two or more of these epoxy-modified silicone oils (D) may be used.

  The epoxy equivalent of the epoxy-modified silicone oil (D) is preferably 70 to 2000, more preferably 100 to 1000, and particularly preferably 150 to 600, from the viewpoints of antistatic properties and durability.

  The polymer compound (E) comprises a polyester (a) obtained by reacting a diol and a dicarboxylic acid, a compound (b) having hydroxyl groups at both ends having one or more ethyleneoxy groups, and two epoxy groups. It is obtained by the reaction of the above-described epoxy-modified silicone oil (D), and is a block of polyester (A) composed of polyester (a) and a block of polyether composed of compound (b) B) an epoxy group of an epoxy-modified silicone oil (D) having a hydroxyl group or carboxyl group at the end of the polyester (a), a hydroxyl group at the end of the compound (b), and two or more epoxy groups And those having a structure formed by the reaction of and via an ester bond or an ether bond are preferable.

  Further, the polymer compound (E) is a block of a polyester (A) composed of a polyester (a) and a block of a polyether (B) composed of a compound (b) from the viewpoint of antistaticity and its durability. Block polymer (C) having a carboxyl group at both ends formed by repeating and alternately bonding via an ester bond, an epoxy-modified silicone oil (D), a carboxyl group of the block polymer (C), and an epoxy-modified resin What has a structure formed by bonding with the epoxy group of silicone oil (D) via the ester bond is preferable.

  The polyester (a) constituting the block of the polyester (A) according to the polymer compound (E) of the present invention may be a diol and a dicarboxylic acid as long as it is composed of a diol and a dicarboxylic acid. Preferably, it has a structure in which the residue excluding the hydroxyl group of the diol and the residue excluding the carboxyl group of the dicarboxylic acid are linked via an ester bond. The polyester (a) constituting the block of the polyester (A) according to the polymer compound (E) according to the present invention is more preferably a diol, an aliphatic dicarboxylic acid and an aromatic dicarbon from the viewpoint of antistaticity and its durability. And a residue from which a hydroxyl group of a diol is removed and a residue from which a carboxyl group of an aliphatic dicarboxylic acid is removed, through an ester bond. And a residue in which the hydroxyl group of the diol is removed and a residue in which the carboxyl group of the aromatic dicarboxylic acid is removed are bonded via an ester bond.

  The polyester (a) is preferably of a structure having a carboxyl group at both ends from the viewpoint of the antistatic property and its durability. Furthermore, the polymerization degree of the polyester (a) is preferably in the range of 2 to 50 from the viewpoint of the antistatic property and its durability.

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

  The aliphatic dicarboxylic acid may be a derivative of aliphatic dicarboxylic acid (for example, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.), and when the derivative is used to obtain polyester (a), Finally, both ends may be treated to form carboxyl groups, and in the state as such, the reaction may be advanced to obtain a block polymer (C) having a structure having carboxyl groups at both ends. In addition, aliphatic dicarboxylic acid and its derivative (s) may be 2 or more types of mixtures.

  The aromatic dicarboxylic acid may be a derivative of aromatic dicarboxylic acid (for example, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.), and if derivative is used to obtain polyester, the final Both ends may be treated to form a carboxyl group, and in the state as it is, the reaction may proceed to the next reaction for obtaining a block polymer (C) having a structure having a carboxyl group at both ends. Also, the aromatic dicarboxylic acid and its derivative may be a mixture of two or more.

  Ratio of the residue except the carboxyl group of aliphatic dicarboxylic acid in the polyester (a) and the residue other than the carboxyl group of aromatic dicarboxylic acid when using aliphatic dicarboxylic acid and aromatic dicarboxylic acid 90:10 to 99.9: 0.1 is preferable in terms of antistatic property and durability, and a molar ratio of 93: 7 to 99.9: 0.1 is more preferable.

  The polyester (a) having a carboxyl group at both ends is, for example, the dicarboxylic acid or the derivative thereof (preferably, the aliphatic dicarboxylic acid or the derivative thereof, and the aromatic dicarboxylic acid or the derivative thereof), and the diol It can be obtained by polycondensation reaction.

  The reaction ratio of the dicarboxylic acid or derivative thereof (preferably aliphatic dicarboxylic acid or derivative thereof and aromatic dicarboxylic acid or derivative thereof) with the diol is such that the dicarboxylic acid or derivative thereof is such that both terminals are carboxyl groups It is preferable to use an excess (preferably an aliphatic dicarboxylic acid or a derivative thereof and an aromatic dicarboxylic acid or a derivative thereof), and it is preferable to use it in a molar ratio of 1 molar excess to a diol.

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

  Also, depending on the compounding ratio and reaction conditions, a polyester composed of only diol and aliphatic dicarboxylic acid, or a polyester composed only of diol and aromatic dicarboxylic acid may be produced. They may be mixed in a), and they may be reacted with compound (b) to obtain block polymer (C).

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

  In addition, dicarboxylic acids, preferably aliphatic dicarboxylic acids and aromatic dicarboxylic acids, and derivatives thereof such as carboxylic acid esters, carboxylic acid metal salts, carboxylic acid halides, etc., instead of dicarboxylic acids, are used together with diols After that, both ends may be treated to form a dicarboxylic acid, or in the state as it is, the reaction may proceed to the next reaction for obtaining a block polymer (C) having a structure having a carboxyl group at both ends.

  A suitable polyester (a) comprising a diol and a dicarboxylic acid, preferably an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid and having carboxyl groups at both ends forms an ester bond by reacting with the compound (b), Those forming the structure of the block polymer (C) are preferred, and the carboxyl groups at both ends may be protected, modified, or in the form of a precursor. Moreover, in order to suppress the oxidation of a product at the time of reaction, an antioxidant such as a phenolic antioxidant may be added to the reaction system.

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

A block polymer (C) having a structure having a carboxyl group at both ends according to the polymer compound (E) of the present invention comprises a block (A) composed of the above polyester (a) and the above compound (b) And (B), which has a structure in which these blocks are repeatedly and alternately bonded via an ester bond formed by a carboxyl group and a hydroxyl group. If an example of this block polymer (C) is given, what has a structure represented by following General formula (3) will be mentioned, for example.

  In the above general formula (3), (A) represents a block composed of a polyester (a) having a carboxyl group at the both ends, and (B) represents a compound (b) having a hydroxyl group at the both ends Represents a constructed block, and t is the number of repeating units, preferably from 1 to 10 in terms of antistaticity and durability. t is more preferably a number of 1 to 7, and most preferably a number of 1 to 5.

  When an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid are used for the polyester (a), a part of the block composed of the polyester (a) in the block polymer (C) is composed only of a diol and an aliphatic dicarboxylic acid It may be replaced by a block consisting of the above-mentioned polyester, or a block consisting of a polyester consisting only of a diol and an aromatic dicarboxylic acid.

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

  When the reaction ratio of the polyester (a) to the compound (b) is adjusted such that the polyester (a) is X + 1 mol with respect to X mol of the compound (b), carboxyl groups at both ends are obtained. Preferably, the block polymer (C) having

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

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

  When aliphatic dicarboxylic acid and aromatic dicarboxylic acid are used for polyester (a), polyester (a) may be a polyester composed of only diol and aliphatic dicarboxylic acid, or only diol and aromatic dicarboxylic acid The polyesters may be mixed, and they may be reacted as they are with the compound (b) to obtain the block polymer (C). The block polymer (C) is composed of a polyester composed only of a diol and an aliphatic dicarboxylic acid, in addition to a block (A) composed of a polyester (a) and a block (B) composed of a compound (b) Or a block composed of a polyester composed only of a diol and an aromatic dicarboxylic acid may be included in the structure.

  The polymer compound (E) according to the present invention is preferably a block polymer (C) having a structure having a carboxyl group at both ends, and an epoxy-modified silicone oil (D) having two or more epoxy groups, It has a structure formed by bonding via an ester bond formed by the terminal carboxyl group of the block polymer (C) and the epoxy group of the epoxy-modified silicone oil (D). The polymer compound (E) may further contain an ester bond formed by the carboxyl group of the polyester (a) and the epoxy group of the epoxy-modified silicone oil (D). The polymer compound (E) further includes an ether bond formed by the hydroxyl group of the polyester (a) or the hydroxyl group of the compound (b) and the epoxy group of the epoxy-modified silicone oil (D). It may be.

  In order to obtain the polymer compound (E), the carboxyl group of the block polymer (C) and the epoxy group of the epoxy-modified silicone oil (D) may be reacted. The number of epoxy groups of the epoxy-modified silicone oil (D) is preferably 0.5 to 5 equivalents, more preferably 0.5 to 1.5 equivalents of the number of carboxyl groups of the block polymer (C) to be reacted. The above reaction may be carried out in various solvents or in a molten state.

  The epoxy-modified silicone oil (D) having two or more epoxy groups to be reacted is preferably 0.1 to 2.0 equivalents of the number of carboxyl groups of the block polymer (C) to be reacted, 0.2 to 1.5 The equivalent is more preferred.

  In the reaction, after completion of the synthesis reaction of the block polymer (C), the epoxy-modified silicone oil (D) may be added to the reaction system without isolation of the block polymer (C), and the reaction may be carried out as it is. In that case, the carboxyl group of the unreacted polyester (a) used in excess when synthesizing the block polymer (C) and the epoxy group of a part of the epoxy-modified silicone oil (D) react to form an ester bond. May be formed.

  The preferred polymer compound (E) of the present invention comprises a block polymer (C) having a structure having carboxyl groups at both ends and an epoxy-modified silicone oil (D) having two or more epoxy groups, with each carboxyl group and As long as it has a structure equivalent to one having a structure bonded via an ester bond formed by an epoxy group, it is necessarily required to be synthesized from the block polymer (C) and the epoxy-modified silicone oil (D). There is no.

  In the present invention, the number average molecular weight of the block composed of the compound (b) having a hydroxyl group at both ends in the polymer compound (E) is calculated from the measured value of the hydroxyl value, and the antistatic property and its persistence From the point of view, it is preferably 400 to 10,000, more preferably 1,000 to 8,000, and still more preferably 2,000 to 8,000.

  Further, in the present invention, the number average molecular weight of the block composed of the polyester (a) in the polymer compound (E) is preferably 800 to 8,000 in terms of polystyrene in terms of antistatic property and its durability. More preferably, it is 1,000-6,000, More preferably, it is 2,000-4,000.

  Furthermore, in the polymer compound (E), the number average molecular weight of the block composed of the block polymer (C) having a structure having a carboxyl group at both ends is preferably 5,000 to 30,000 in terms of polystyrene More preferably, it is 7,000 to 20,000, and more preferably 9,000 to 17,000.

  In addition, the polymer compound (E) of the present invention can be obtained from a diol, a dicarboxylic acid (preferably an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid) after obtaining the polyester (a), and then without isolating the polyester (a), It may be reacted with a compound (b) and / or an epoxy modified silicone oil (D).

  Next, the composition of the present invention will be described. The composition of the present invention comprises, in addition to the polymer compound of the present invention, one or more selected from the group of alkali metal salts and ionic liquids. The polymer compound (E) of the present invention can be further blended with at least one selected from the group of an alkali metal salt and an ionic liquid to obtain a composition having excellent antistatic performance and its durability. preferable.

  Hereinafter, salts of alkali metals will be described first. Examples of the alkali metal salt include salts of organic acids or inorganic acids, and examples of the alkali metal include lithium, sodium, potassium, cesium, rubidium and the like. Examples of organic acids include aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid and lactic acid; oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid and the like Aliphatic dicarboxylic acids having 1 to 12 carbon atoms; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethane Examples 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, sulfuric acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, perchloric acid and the like. Among them, salts of lithium, sodium and potassium are preferable, and sodium is more preferable, from the viewpoint of friction voltage and surface resistivity, and safety to the living body and the environment. Further, from the viewpoint of the antistatic property and its durability, salts of acetic acid, salts of perchloric acid, salts of p-toluenesulfonic acid and salts of dodecylbenzenesulfonic acid are preferable, and salts of dodecylbenzenesulfonic acid are more preferable. Two or more alkali metal salts may be used.

  Specific examples of the alkali metal salt include, for example, lithium acetate, sodium acetate, potassium acetate, lithium chloride, sodium chloride, potassium chloride, lithium phosphate, sodium phosphate, potassium phosphate, lithium sulfate, sodium sulfate, perchlorine Lithium acid, sodium perchlorate, potassium perchlorate, lithium p-toluenesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, dodecylbenzenesulfonic acid Potassium and the like can be mentioned. Among these, lithium p-toluenesulfonate, sodium p-toluenesulfonate, lithium dodecylbenzenesulfonate, and dodecylbenzene sulfone are preferred from the viewpoint of antistatic properties and their durability, and safety to the living body and the environment. Sodium acid and the like, most preferred is sodium dodecyl benzene sulfonate.

  The alkali metal salt may be blended with the polymer compound (E) of the present invention, or may be blended with the polymer compound (E) in a synthetic resin. The compounding amount of the alkali metal salt is preferably 0.01 to 20 parts by mass, and 0.1 to 15 parts by mass with respect to 100 parts by mass of the polymer compound (E) from the viewpoint of the antistatic property and its persistence. The part is more preferable, and 3.0 to 12 parts by mass is the most preferable.

  Next, the ionic liquid will be described. As an example of the ionic liquid, it has a melting point below room temperature, and at least one of the cations or anions constituting the ionic liquid is an organic ion, and the initial conductivity is 1 to 200 ms / cm, preferably 10 to 200 ms. It is a room temperature molten salt which is / cm, for example, the room temperature molten salt described in WO 95/15572.

  As a cation which comprises an ionic liquid, the cation chosen from the group which consists of amidinium, pyridinium, pyrazolium, and guanidinium cation is mentioned. Among these, as the amidinium cation, the following may be mentioned.

(1) Imidazolinium cation A C5-C15 thing is mentioned, For example, 1,2,3,4- tetramethyl imidazolinium, a 1, 3- dimethyl imidazolinium;
(2) Imidazolium cation A C5-C15 thing is mentioned, For example, a 1, 3- dimethyl imidazolium, 1-ethyl- 3-methyl imidazolium;
(3) Tetrahydropyrimidinium cation: those having 6 to 15 carbon atoms, and examples thereof include 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium and 1,2,3,4-tetra Methyl-1,4,5,6-tetrahydropyrimidinium;
(4) Dihydropyrimidinium cation: those having 6 to 20 carbon atoms, and examples thereof include 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.

  As a pyridinium cation, a C6-C20 thing is mentioned, For example, 3-methyl- 1-propyl pyridinium and 1-butyl- 3, 4- dimethyl pyridinium are mentioned.

  As a pyrazolium cation, a C5-C15 thing is mentioned, For example, a 1, 2- dimethyl pyrazolium and 1-n- butyl -2- methyl pyrazolium are mentioned. The following are mentioned as guanidinium cation.

(1) Guanidinium cation having an imidazolinium skeleton: those having 8 to 15 carbon atoms, and examples thereof include 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3. , 4-trimethylimidazolinium;
(2) Guanidinium cation having an imidazolium skeleton: those having 8 to 15 carbon atoms, and examples thereof include 2-dimethylamino-1,3,4-trimethylimidazolium and 2-diethylamino-1,3,4. -Trimethylimidazolium;
(3) Guanidinium cation having a tetrahydropyrimidinium skeleton Examples thereof include those having 10 to 20 carbon atoms, and examples thereof include 2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydrofuran Pyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium;
(4) Guanidinium cation having a dihydropyrimidinium skeleton: those having 10 to 20 carbon atoms, and examples thereof include 2-dimethylamino-1,3,4-trimethyl-1,4-dihydropyrimidinium, 2-Dimethylamino-1,3,4-trimethyl-1,6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4-dihydropyrimidinium, 2-diethylamino-1 , 3-Dimethyl-4-ethyl-1,6-dihydropyrimidinium.

  The cations may be used alone or in combination of two or more. Among these, in terms of friction voltage and surface resistivity, it is preferably an amidinium cation, more preferably an imidazolium cation, and particularly preferably a 1-ethyl-3-methylimidazolium cation.

  Examples of the organic acid or inorganic acid constituting the anion in the ionic liquid include the following. As an organic acid, for example, carboxylic acid, sulfuric acid ester, sulfonic acid and phosphoric acid ester; As an inorganic acid, for example, borofluoric acid, tetraboronic acid, perchloric acid, hexafluorophosphoric acid, hexafluorinated acid Super acids such as antimonic acid and hexafluoroarsenic acid, phosphoric acid and boric acid can be mentioned. The organic acid and the inorganic acid may be used alone or in combination of two or more.

  Among the above organic acids and inorganic acids, the ionic liquid preferably has a Hammett acidity function (-H0) of 12 to 100 for the anion constituting the ionic liquid from the viewpoint of the antistatic property and the durability. Conjugated bases of superacids, acids forming anions other than those of superacids and mixtures thereof.

  As anions other than the conjugate base of super strong acid, for example, halogen (for example, fluorine, chlorine and bromine) ion, alkyl (C1 to C12) benzenesulfonic acid (for example, p-toluenesulfonic acid and dodecylbenzenesulfonic acid) And ions of poly (n = 1 to 25) fluoroalkanesulfonic acid (e.g. undecafluoropentanesulfonic acid).

  Also, super acids include those derived from protic acids and combinations of protic acids and Lewis acids, and mixtures thereof. Examples of protonic acids as super strong acids include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkanes (for example, Carbon number of 1 to 30) sulfonic acid (for example, methanesulfonic acid, dodecanesulfonic acid, etc.), poly (n = 1 to 30) fluoroalkane (for carbon number of 1 to 30) sulfonic acid (for example, trifluoromethanesulfonic acid, Pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), borofluoric acid and tetrafluoroboronic acid can be mentioned. Among these, borofluoric acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) imidic acid and bis (pentafluoroethylsulfonyl) imidic acid are preferable from the viewpoint of easiness of synthesis.

  Protic acids used in combination with Lewis acids include, for example, hydrogen halide (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 can be mentioned. Among these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of the ionic liquid.

  As the Lewis acid, for example, boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride and mixtures thereof can be mentioned. 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 as a superstrong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, hexafluorinated acid And tantalum sulfonic acid, boron tetrafluoride, phosphoric acid hexafluoride, boron trichloride chloroborate, arsenic hexafluoride hexafluoride, and mixtures thereof.

  Among the above-mentioned anions, preferred are super-acid conjugate bases (super-strong acids consisting of protic acids and super-strong acids consisting of a combination of protic acids and Lewis acids) from the viewpoint of the antistatic properties of ionic liquids, more preferred Is a conjugate base of a super strong acid consisting of a protic acid and a super strong acid consisting of a protic acid and a boron trifluoride and / or a phosphorus pentafluoride.

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

  The ionic liquid may be blended with the polymer compound (E) of the present invention, or may be blended with the polymer compound (E) in a synthetic resin. The compounding amount of the ionic liquid is preferably 0.01 to 20 parts by mass, and 0.1 to 15 parts by mass with respect to 100 parts by mass of the polymer compound (E) from the viewpoint of the antistatic property and the durability. Is more preferable, and 1 to 12 parts by mass is the most preferable.

  In the composition of the present invention, an alkali metal salt and an ionic liquid may be used in combination.

  In order to obtain the composition of the present invention, the polymer compound (E), and one or more selected from the group of salts of alkali metals and ionic liquids, and optionally other optional components may be mixed. Various mixing machines can be used for mixing. It may be heated at the time of mixing. Examples of mixers that can be used include tumbler mixers, Henschel mixers, ribbon blenders, V-type mixers, W-type mixers, super mixers, Nauta mixers, and the like. Further, during the synthesis reaction of the polymer compound (E), one or more selected from the group of an alkali metal salt and an ionic liquid may be added to the reaction system.

  In addition, the polymer compound (E) of the present invention may be used as a composition having antistatic properties by blending a salt of a Group 2 element within the range not impairing the effects of the present invention. Salts of group 2 elements include salts of organic acids or inorganic acids, and examples of group 2 elements include beryllium, magnesium, calcium, strontium, barium and the like. Examples of organic acids include aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid and lactic acid; oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid and the like Aliphatic dicarboxylic acids having 1 to 12 carbon atoms; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethane Examples 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, sulfuric acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, perchloric acid and the like.

  The salt of the group 2 element may be blended in the polymer compound (E), or may be blended in the synthetic resin together with the polymer compound (E). 0.01-20 mass parts is preferable with respect to 100 mass parts of a high molecular compound (E), and, as for the compounding quantity of the salt of a group 2 element, 0.1-15 mass parts is more preferable, and 3.0- 12 parts by weight is most preferred.

  Further, the polymer compound (E) of the present invention may be used as a composition having an antistatic property by blending a surfactant within a range not to impair the effects of the present invention. As the surfactant, nonionic, anionic, cationic or amphoteric surfactants can be used. Polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts as nonionic surfactants; fatty acid esters of polyethylene oxide, glycerin And polyvalent alcohol type nonionic surfactants such as fatty acid esters of pentaerythritol, fatty acid esters of sorbite or sorbitan, alkyl ethers of polyhydric alcohols, aliphatic amides of alkanolamines, etc., and as anionic surfactants For example, carboxylates such as alkali metal salts of higher fatty acids; sulfates such as higher alcohol sulfates, higher alkyl ether sulfates, alkyl benzenes Sulfonic acid salts such as fluoro acid salts, alkyl sulfonic acid salts and paraffin sulfonic acid salts; phosphoric acid ester salts such as higher alcohol phosphoric acid ester salts and the like, and as cationic surfactants, alkyl trimethyl ammonium salts etc. Examples include quaternary ammonium salts and the like. Amphoteric surfactants include amino acid type amphoteric surfactants such as higher alkyl amino propionates, and betaine type amphoteric surfactants such as higher alkyl dimethyl betaines and higher alkyl dihydroxyethyl betaines, etc. These may be used alone or in combination. Two or more can be used in combination. In the present invention, among the above surfactants, anionic surfactants are preferred, and in particular, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates and paraffin sulfonates are preferred.

  The surfactant may be blended in the polymer compound (E) or may be blended in the synthetic resin together with the polymer compound (E). The content of the surfactant is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and most preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymer compound (E). preferable.

  Furthermore, the polymer compound (E) of the present invention may be used as a composition having an antistatic property by compounding a polymer type antistatic agent, as long as the effects of the present invention are not impaired. As the polymeric antistatic agent, for example, known polymeric antistatic agents such as polyether ester amide can be used, and as the known polyether ester amide, for example, JP-A 7-10989 Mention may be made of polyether ester amides which consist of polyoxyalkylene adducts of bisphenol A as described. In addition, block polymers in which the bonding units of the polyolefin block and the hydrophilic polymer block have a repeating structure of 2 to 50 can be used, and for example, block polymers described in US Pat. No. 6,552,131 can be mentioned.

  The polymer type antistatic agent may be blended with the polymer compound (E) of the present invention, or may be blended with a polymer compound (E) and used in a synthetic resin. 0 to 50 parts by mass is preferable, and 5 to 20 parts by mass is more preferable with respect to 100 parts by mass of the polymer compound (E).

  Furthermore, the polymer compound (E) of the present invention may be blended with a compatibilizing agent as long as the effects of the present invention are not impaired, to give a composition having antistatic properties. By blending the compatibilizer, the compatibility of the polymer compound (E) with other components and the thermoplastic resin can be improved. As such a compatibilizer, modified vinyl polymers 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, for example, Examples thereof include polymers described in JP-A-3-258850, modified vinyl polymers having a sulfonyl group described in JP-A-6-345927, and block polymers having a polyolefin portion and an aromatic vinyl polymer portion. Be

  The compatibilizer may be blended with the polymer compound (E) of the present invention, or may be blended with the polymer compound (E) in a synthetic resin. 0.1-15 mass parts is preferable with respect to 100 mass parts of a high molecular compound (E), and, as for the compounding quantity of a compatibilizer, 1-10 mass parts is more preferable.

  In the composition of the present invention, other components may be blended as optional components in addition to the polymer compound (E) and the components listed above, as long as the effects of the present invention are not impaired. These other components may be directly blended into the composition, or a resin composition having antistatic properties by blending the polymer compound (E) or the composition of the present invention into a synthetic resin such as a thermoplastic resin. When used as, it may be blended with a synthetic resin.

  Next, the resin composition of the present invention will be described. The resin composition of the present invention is obtained by blending the polymer compound (E) of the present invention or the composition of the present invention with a synthetic resin. The polymer compound (E) and the composition of the present invention can be blended into a synthetic resin, particularly preferably a thermoplastic resin, and used as a resin composition having antistatic properties. Examples of the thermoplastic resin include polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, crosslinked polyethylene, ultrahigh molecular weight polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene and the like Polyolefin resins such as α-olefin polymers or ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-propylene copolymers and copolymers thereof; polyvinyl chloride, polyvinylidene chloride, chlorine Polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary Copolymer, vinyl chloride-acrylic Halogen-containing resins such as acid ester copolymer, vinyl chloride-maleate ester copolymer, vinyl chloride-cyclohexyl maleimide copolymer; petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, styrene and / or α -A copolymer of methyl styrene and another monomer (eg, maleic anhydride, phenyl maleimide, methyl methacrylate, butadiene, acrylonitrile etc.) (eg AS resin, ABS (acrylonitrile butadiene styrene copolymer) resin, ACS resin, SBS resin, MBS resin, heat-resistant ABS resin, etc.); polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate Aromatic polyesters such as polyalkylene terephthalates such as phthalates, polyethylene naphthalates, polyalkylene naphthalates such as polybutylene naphthalates, and linear polyesters such as polytetramethylene terephthalates; polyhydroxybutyrates, polycaprolactones, polybutylene succinates, Degradable aliphatic polyesters such as polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, poly (2-oxetanone); Polyamides such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, polycarbonates, polycarbonates / ABS resin, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, fibrous resin, polyimide resin Can polysulfone, polyphenylene ether, polyether ketone, polyether ether ketone, include thermoplastic resins and blends thereof such as a liquid crystal polymer. Further, the thermoplastic resin may be isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, olefin elastomer, styrene elastomer, polyester elastomer, nitrile elastomer, nylon It may be an elastomer such as a system elastomer, a vinyl chloride elastomer, a polyamide elastomer, or a polyurethane elastomer. In the resin composition of the present invention, these thermoplastic resins may be used alone or in combination of two or more. The thermoplastic resin may be alloyed.

  These thermoplastic resins have a molecular weight, polymerization degree, density, softening point, ratio of insoluble matter to solvent, degree of stereoregularity, presence or absence of catalyst residue, kind and blending ratio of raw material monomers, kind of polymerization catalyst For example, it can be used regardless of Ziegler catalyst, metallocene catalyst, etc. Among these thermoplastic resins, at least one selected from the group consisting of polyolefin resins, polystyrene resins and copolymers thereof is preferable from the viewpoint of antistatic properties.

  The mass ratio of the synthetic resin to the polymer compound (E) or the composition in the resin composition of the present invention is preferably in the range of 99/1 to 40/60.

  The method for blending the polymer compound (E) into the synthetic resin is not particularly limited, and any commonly used method can be used. For example, mixing by roll kneading, bumper kneading, extruder, kneader, etc. , And may be blended. Further, the polymer compound (E) may be added to the synthetic resin as it is, but may be added after being impregnated in the carrier, if necessary. In order to impregnate the carrier, it may be heated and mixed as it is, or, if necessary, it may be diluted with an organic solvent and then impregnated into the carrier, and then the solvent may be removed. As such a carrier, a filler known as a filler of a synthetic resin or a filler, or a flame retardant or a light stabilizer which is solid at normal temperature can be used. For example, calcium silicate powder, silica powder, talc powder, alumina powder Examples thereof include titanium oxide powder, those obtained by chemically modifying the surface of these carriers, and solid substances among the flame retardants and antioxidants listed below. 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. The carrier preferably has an average particle diameter of 0.1 to 100 μm, and more preferably 0.5 to 50 μm.

  As a method of blending the polymer compound (E) into the synthetic resin, the polymer compound (C) and the epoxy-modified silicone oil (D) having two or more epoxy groups are simultaneously kneaded with the synthetic resin while the polymer compound ( E) may be synthesized and compounded, and at the same time, one or more selected from the group of an alkali metal salt and an ionic liquid may be simultaneously kneaded, or a polymer at the time of molding such as injection molding The compound (E) and the synthetic resin may be mixed to obtain a molded article, and at this time, even if one or more selected from the group of an alkali metal salt and an ionic liquid are further compounded. Well, furthermore, a masterbatch of the polymer compound (E) and the synthetic resin may be prepared beforehand, and this masterbatch may be blended, and at that time, the salt and ionic property of the alkali metal One or more selected from the group of the body may be blended.

  To the resin composition of the present invention, various additives such as phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, ultraviolet light absorbers, hindered amine light stabilizers and the like are further added as necessary. Thus, the resin composition of the present invention can be stabilized.

  Various additives such as these antioxidants may be blended into the composition of the present invention before blending into the synthetic resin. Furthermore, you may mix | blend at the time of manufacture of a high molecular compound (E). In particular, the antioxidant is preferable at the time of the production of the polymer compound (E) because it can prevent the oxidative degradation of the polymer compound (E) during the production.

  Examples of the above-mentioned phenolic antioxidants include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4) -Hydroxybenzyl) phosphonate, 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide], 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) -M-cresol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 2,2′-ethylidenebis (4-sec-butyl-6-tert-butyl) Nole), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-third) 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 [methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycol Bis [(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) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methyl] Benzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-, {(3-tert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] ウAnd triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like. It is preferable that it is 0.001-10 mass parts with respect to 100 mass parts of synthetic resins, and, as for the addition amount of these phenolic antioxidants, it is more preferable that it is 0.05-5 mass parts.

  Examples of the above-mentioned phosphorus antioxidant include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] Phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di) Tert-Butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol di- Phosphite, bis (2,4-dicumylphenyl) pen Erythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1 1,1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-di-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6- Di-tert-butylphenyl) -octadecyl phosphite, 2,2'-ethylidene bis 4,6-di-tert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyl dibenzo [d, f] [1,3,2] dioxaphosphepin Examples include -6-yl) oxy] ethyl) amine, phosphites of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol, and the like. It is preferable that it is 0.001-10 mass parts with respect to 100 mass parts of synthetic resins, and, as for the addition amount of these phosphorus antioxidants, it is more preferable that it is 0.05-5 mass parts.

  Examples of the above-mentioned thioether-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra (β-alkylthiopropionic acid). Esters are mentioned. It is preferable that it is 0.001-10 mass parts with respect to 100 mass parts of synthetic resins, and, as for the addition amount of these thioether type antioxidants, it is more preferable that it is 0.05-5 mass parts.

  Examples of the UV absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone). And the like; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chloro; Benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-third) Octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole, 2 ,, 2- (2) -methylenebis (4-tert-octyl-6- (benzotriazolyl) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl) benzotriazole, etc. '-Hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl- Benzoates such as 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy- Substituted oxanilides such as 4'-dodecyl oxanilide; ethyl-.alpha.-cyano-.beta.,. Beta.-diphenylacrylate And 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 triaryl triazines such as (4) -4,6-bis (2,4-di-tert-butylphenyl) -s-triazine. It is preferable that it is 0.001-30 mass parts with respect to 100 mass parts of synthetic resins, and, as for the addition amount of these ultraviolet absorbers, it is more preferable that it is 0.05-10 mass parts.

  Examples of the above-mentioned hindered amine light stabilizers include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,3, 6,6-Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-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- Butane tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, bis (2,2 6,6-Tetramethyl-4-piperidyl) bis (tridecyl) -1,2,3,4-butane tetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) bis (Tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert) Butyl-4-hydroxybenzyl) malonate, 1,2,2,6,6-tetramethyl-4-piperidyl methacrylate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3 5-Triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino }, 1, , 3,4-butanecarboxylic acid / 2,2-bis (hydroxymethyl) -1,3-propanediol / 3-hydroxy-2,2-dimethylpropanal / 1,2,2,6,6-pentamethyl- 4-piperidinyl ester polycondensate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) = decanedioate / methyl = 1,2,2,6,6-pentamethyl-4-piperidyl = Sebacato mixture, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4 -Piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4 -Dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl) -4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N) -(1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [ 2,4-bis (N-butyl-N- (2,2,6) 6-Tetramethyl-4-piperidyl) amino-s-triazin-6-ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6, 6) 6-pentamethyl-4-piperidyl) amino-s-triazin-6-ylamino] undecane, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-) Piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2,7) 2,6,6-Pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, bis (1-undeci Oxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6-tetramethyl-4-piperidyl hexadecanoate, 2,2,6,6-tetramethyl- Hindered amine compounds such as 4-piperidyl octadecanoate can be mentioned. It is preferable that it is 0.001-30 mass parts with respect to 100 mass parts of synthetic resins, and, as for the addition amount of these hindered amine type light stabilizers, it is more preferable that it is 0.05-10 mass parts.

  Moreover, when using polyolefin resin as a thermoplastic resin, in order to neutralize the residual catalyst in polyolefin resin further as needed in the range which does not impair the effect of the present invention, It is preferable to add. Examples of the neutralizing agent include fatty acid metal salts such as calcium stearate, lithium stearate and sodium stearate, or fatty acid amides such as ethylene bis (stearoamide), ethylene bis (12-hydroxy stearoamide) and stearic acid amide. The compound is mentioned and these neutralizing agents may be mixed and used.

  The resin composition of the present invention may further contain, as other additives, metal salts of aromatic carboxylic acids, metal salts of alicyclic alkyl carboxylic acids, and p-numbers, as needed, within the range not to impair the effects of the present invention. Nucleating agents such as aluminum tributylbenzoate, metal salts of aromatic phosphates, dibenzylidene sorbitols, metal soaps, hydrotalcites, triazine ring-containing compounds, metal hydroxides, phosphoric acid ester flame retardants, condensed phosphorus Acid ester flame retardants, phosphate flame retardants, inorganic phosphorus flame retardants, (poly) phosphate flame retardants, halogen flame retardants, silicon flame retardants, antimony oxides such as antimony trioxide, other inorganic flame retardants Fuel aids, other organic fire retardant aids, fillers, pigments, lubricants, foaming agents, etc. may be added.

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

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

  Examples of the phosphate ester flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, tris dichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, Trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, tris isopropyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butyl phenyl diphenyl phosphate, bis- (t-butyl phenyl) phenyl phosphate, tris- (t-butyl phosphate) Phenyl) phosphate, isopropylphenyl diphenyl phosphate, bis- (a) Propyl phenyl) diphenyl phosphate, tris - (isopropylphenyl) phosphate, and the like.

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

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

  Other inorganic flame retardant aids include, for example, inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, montmorillonite, and surface-treated products thereof. For example, TIPAQUE R-680 ( Titanium oxide: manufactured by Ishihara Sangyo Co., Ltd., Kyowa Mag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), Alkamizer 4 (zinc modified hydro) Talsite: Various commercial products such as Kyowa Chemical Industry Co., Ltd. can be used. Moreover, as another organic type flame retardant auxiliary agent, pentaerythritol is mentioned, for example.

  In addition, the resin composition of the present invention may, if necessary, be an additive generally used for a synthetic resin, as long as the effects of the present invention are not impaired, such as a crosslinking agent, an antifogging agent, an antiplateout agent, Surface treatment agents, plasticizers, lubricants, flame retardants, fluorescent agents, fungicides, bactericides, foaming agents, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, etc. It can mix | blend in the range which does not impair the effect of this invention.

  The additive to be added to the resin composition of the present invention may be added directly to the thermoplastic resin, or added to the thermoplastic resin after being added to the polymer compound (E) or the composition of the present invention It is also good.

  Next, the molded article of the present invention will be described. The molded article of the present invention comprises the resin composition of the present invention. By molding the resin composition of the present invention, a resin molded product having antistatic properties can be obtained. The molding method is not particularly limited, and extrusion, calendering, injection molding, rolling, compression molding, blow molding, rotational molding, etc. may be mentioned, resin plate, sheet, film, bottle, fiber, profiled article Molded articles of various shapes such as can be manufactured.

  The molded object obtained by the resin composition of this invention is excellent in antistatic performance and its sustainability.

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

  More specifically, the resin composition of the present invention and the molded article thereof can be used in printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic cash registers), Calculators, electronic organizers, cards, holders, stationery, office work, office automation equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, household appliances such as irons, TVs, VTRs, video cameras, radio cassette players , Tape recorder, mini disc, CD player, speaker, AV equipment such as liquid crystal display, connector, relay, capacitor, switch, printed circuit board, coil bobbin, semiconductor sealing material, LED sealing material, electric wire, cable, transformer, deflection yoke , Electric and electronic parts such as distribution boards and watches, communication devices, interior and exterior materials for automobiles, for plate making Irumu, adhesive film, bottles, food containers, food packaging films, pharmaceutical and pharmaceutical wrap film, product packaging film, agricultural film, agricultural sheeting, used in applications such as greenhouse films.

  Furthermore, the resin composition of the present invention and the molded article thereof can be used for seating (filling, outer covering, etc.), belts, ceilings, compatible tops, arm rests, door trims, rear package trays, carpets, mats, sun visors, foil covers, mattress covers , Air bag, insulation material, hanging hand, hanging band, electric wire coating material, electric insulation material, paint, coating material, covering material, flooring material, floor material, corner wall, carpet, wallpaper, wall covering material, exterior material, interior material , Roofing materials, decking materials, wall materials, pillars, floorboards, materials for fences, frameworks and moldings, windows and door profiles, shingles, crosses, terraces, balconies, soundproofing boards, insulation boards, window materials, etc. Materials and civil engineering materials for automobiles, vehicles, ships, aircraft, buildings, houses and buildings, clothing, curtains, sheets, non-woven fabrics, plywood, synthetic fiber boards, carpets, entrance mats, 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 in more detail using examples, but the present invention is not limited thereto.

  Polymer compound (E) was produced according to the following production example. Moreover, in the following production example, the number average molecular weight of the compound (b) was measured by the following <molecular weight measuring method 1>, and the number average molecular weights other than the compound (b) were measured by the following <molecular weight measuring method 2> .

<Molecular weight measurement method 1>
The hydroxyl value was measured by the following hydroxyl value measurement method, and the number average molecular weight (hereinafter also referred to as "Mn") was determined by the following equation.
Number average molecular weight = (56110 x 2) / hydroxyl value

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

First, 2 g of a sample is weighed into a 200 mL Erlenmeyer flask, and 10 mL of xylene is added and dissolved by heating. Add 15 mL of Reagent A, stopper and shake vigorously. Add 20 mL of Reagent B, stopper and shake vigorously. Add 50 mL of reagent C. Titrate with 1 N KOH aqueous solution, and calculate by the following formula.
Hydroxyl value [mg KOH / g] = 56. 11 x f x (T-B) / S
f: factor of 1 N KOH aqueous solution
B: Blank test titer [mL]
T: main test titer [mL]
S: Sample amount [g]

<Molecular weight measurement method 2>
The number average molecular weight (hereinafter also referred to as “Mn”) was measured by gel permeation chromatography (GPC). The measurement conditions of Mn are as follows.
Device: JASCO Ltd. product, GPC device Solvent: Tetrahydrofuran standard substance: Polystyrene detector: Differential refractometer (RI detector)
Column stationary phase: Shodex KF-804L, manufactured by Showa Denko KK
Column temperature: 40 ° C
Sample concentration: 1 mg / 1 mL
Flow rate: 0.8 mL / min.
Injection volume: 100 μL

Production Example 1
In a separable flask, 33 g of 1,4-cyclohexanedimethanol, 36 g of adipic acid, 0.04 g of phthalic anhydride, and an antioxidant (tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl)] 0.2g of propionyl oxymethyl] methane, Adekastab AO-60 (manufactured by ADEKA), charged, gradually raising temperature from 160 ° C to 210 ° C for 4 hours at normal pressure, then at 210 ° C for 3 hours under reduced pressure It polymerized and obtained polyester (a).

  Next, 61 g of the obtained polyester (a), 31 g of polyethylene glycol having a number average molecular weight of 3100 and the number of repeating units of ethyleneoxy group = 31 g as a compound (b) having hydroxyl groups at both ends, 0.2 g of AO-60) and 0.4 g of zirconium octylate were charged and polymerized under reduced pressure at 210 ° C. for 7 hours to obtain 100 g of a block polymer (C) having a structure having a carboxyl group at both ends . The acid value of the block polymer (C) having a structure having a carboxyl group at both ends is 11, and the number average molecular weight Mn is 16,000 in terms of polystyrene.

  In 100 g of the block polymer (C) having a structure having a carboxyl group at both ends obtained, as an epoxy-modified silicone oil (D) having two or more epoxy groups, an epoxy-modified silicone oil having an epoxy group at both ends A certain amount of X-22-163 (Shin-Etsu Chemical Co., Ltd. product (epoxy equivalent 200 g / eq) 1.2 g) was charged and polymerized under reduced pressure at 240 ° C. for 3 hours to obtain 101 g of a polymer compound (E) .

Comparative Production Example 1
In 100 g of the block polymer (C) obtained in the same manner as in Production Example 1, 1.0 g of bisphenol F diglycidyl ether (epoxy equivalent 170 g / eq) was charged, and polymerized under reduced pressure at 240 ° C. for 3 hours. 102 g of Comparative Polymer Compound 1 was obtained.

[Examples 1 to 4, Comparative Examples 1 to 3]
Using the resin composition of each example blended based on the compounding amount (parts by mass) described in Table 1 below, test pieces were obtained according to the test piece preparation conditions shown below. The surface resistivity (SR value) was measured according to the following using the obtained test piece, and the antistatic property and its durability were evaluated. Similarly, the resin composition of the comparative example was prepared by the compounding amount (parts by mass) shown in Table 2 below, and evaluated.

<Conditions for producing homopolypropylene resin composition test pieces>
The resin composition blended based on the compounding amount shown in the following Tables 1 and 2 is manufactured under conditions of 230 ° C. and 6 kg / hour using a twin screw extruder (containing PCM 30, 60 mesh) manufactured by Ikegai Co., Ltd. Granulated to obtain pellets. The obtained pellets are molded using a horizontal injection molding machine (NEX 80: manufactured by Nissei Resin Industry Co., Ltd.) under processing conditions of a resin temperature of 230 ° C. and a mold temperature of 40 ° C., test pieces (100 mm × 100 mm × 3 mm) I got

<Method of measuring surface resistivity (SR value)>
Immediately after molding, the obtained test piece was heated at a temperature of 25 ° C. and a humidity of 50%. H. After storage for 1 day and 30 days of molding processing under the same conditions, using an R8340 resistance meter manufactured by Advantest, under the conditions of an applied voltage of 100 V and an application time of 1 minute, surface resistivity ( Ω / □ was measured. The measurement was carried out at five points per five test pieces, and the average value was determined. The results obtained are shown in Tables 1 and 2.

＊１：ＮａＤＢＳはドデシルベンゼンスルホン酸ナトリウムを表す。
＊２：ｈＰＰはホモポリプロピレン（メルトフローレート＝８）を表す。

* 1: NaDBS represents sodium dodecylbenzene sulfonate.
* 2: hPP represents homopolypropylene (melt flow rate = 8).

From the results shown in Tables 1 and 2, it was confirmed that according to the present invention, a polymer compound having an excellent antistatic effect and its durability can be obtained.

Claims (10)

  Polyester (a) obtained by the reaction of a diol and a dicarboxylic acid, a compound (b) having a hydroxyl group at both ends having one or more ethyleneoxy groups, and an epoxy-modified silicone oil (D) having two or more epoxy groups And a polymer compound (E) characterized by being obtained by the reaction of   It has a block (A) of polyester composed of the polyester (a) and a block (B) of polyether composed of the compound (b), and has a hydroxyl group or a carboxyl group at the end of the polyester (a) A structure formed by the reaction of a hydroxyl group at the end of the compound (b) and the epoxy group of the epoxy-modified silicone oil (D), which is formed by an ester bond or an ether bond. The high molecular compound (E) as described in 1).   A block polymer (C) having a carboxyl group at both ends formed by repeating alternately alternating the polyester block (A) and the polyether block (B) via an ester bond, and the epoxy-modified silicone The polymer compound (E) according to claim 2, having a structure in which the oil (D) is bonded via an ester bond.   The polymer compound (E) according to any one of claims 1 to 3, wherein the polyester (a) has a carboxyl group at both ends.   The polymer compound (E) according to any one of claims 1 to 4, wherein the compound (b) is polyethylene glycol.   A polymer compound (E) according to any one of claims 1 to 5, further comprising one or more selected from the group of an alkali metal salt and an ionic liquid. Composition.   A resin composition comprising the polymer compound (E) according to any one of claims 1 to 5 blended with a synthetic resin.   A resin composition comprising the composition according to claim 6 blended with a synthetic resin.   The resin composition according to claim 7 or 8, wherein the synthetic resin is one or more selected from the group consisting of polyolefin resins, polystyrene resins and copolymers thereof. A molded article comprising the resin composition according to any one of claims 7 to 9.