TW201920383A - Composition, resin composition including same, and molded body thereof - Google Patents

Abstract

Provided are a composition, a resin composition including the same, and a molded body thereof that can sustainably impart a superior antistatic effect to a synthetic resin, and can impart a superior workability to the same. A composition including: an (X) component that comprises a polymer compound (E); and a (Y) component that comprises a salt of an alkali metal, wherein the polymer compound (E) is obtained by reacting a polyester (a) that is obtained by reacting a diol and an aliphatic dicarboxylic acid or similar, a compound (b) that has one or more ethyleneoxy groups and has a hydroxyl group at both ends, and an epoxy compound (D) that has two or more epoxy groups, the polymer compound (E) is bonded via an ester bond or similar comprising a hydroxyl group or similar at an end of a block (A) that comprises the polyester (a), a hydroxyl group at an end of a block (B) that comprises the compound (b), and an epoxy group of the epoxy compound (D), and the included molar quantity of the (Y) component is within a range of 2.3-5.4% of the number of moles of the ethyleneoxy group within the block (B).

Description

Composition, resin composition containing the same, and formed body thereof

The present invention relates to a composition, a resin composition containing the same, and a molded article thereof, and in particular, it relates to a composition that imparts excellent antistatic effects to synthetic resins and provides excellent processability. 2. A resin composition containing the same, and a formed body thereof.

Thermoplastic resins are not only lightweight and easy to process, but also have excellent characteristics that can be used to design substrates according to their applications. Therefore, they are essential materials for modern times. In addition, thermoplastic resins have so-called excellent electrical insulation properties, and are therefore frequently used in components and the like of electrical products. However, the thermoplastic resin has a problem of being easily charged due to friction because the insulating property is too high.

The charged thermoplastic resin attracts surrounding dust and dust, which causes a problem that damages the appearance of the resin molded product. In addition, in electronic products, there is a case where a precision device such as a computer is unable to operate normally due to electrification. Furthermore, there are problems caused by electric shock. If electric shock is generated by the resin to the human body, it will not only give people an uncomfortable feeling, but also may cause an explosion accident in a place with flammable gas and dust.

In order to eliminate such a problem, conventionally, synthetic resin has been subjected to a treatment for preventing electrification. The most common antistatic treatment method is a method of adding an antistatic agent to a synthetic resin. Among such antistatic agents, although there are a coating type coated on the surface of a resin molded body and a kneaded type added during processing and molding of a resin, the coating type is continuously deteriorated, and Because the surface is coated with a large amount of organic matter, there is a problem that the contact with the surface is contaminated.

From this point of view, conventionally, kneading-type antistatic agents have been mainly discussed. For example, in Patent Documents 1 and 2, polyetheresteramide is proposed in order to impart antistatic properties to polyolefin resins. Further, Patent Document 3 proposes a block polymer having a structure in which a block of a polyolefin and a block of a hydrophilic polymer are repeatedly and alternately bonded. Furthermore, Patent Document 4 proposes a polymer-type antistatic agent having a polyester block.
Prior art literature patent literature

Patent Document 1: Japanese Patent Application Laid-Open No. 58-118838 Patent Document 2: Japanese Patent Application Laid-Open No. 3-290464 Patent Literature 3: Japanese Patent Application Laid-Open No. 2001-278985 Patent Literature 4: Japanese Patent Application Laid-Open No. 2016-23254

Problems to be solved by the invention

However, these conventional antistatic agents are not necessarily sufficient in antistatic performance. In addition, in the processing and molding of synthetic resins using such antistatic agents, burrs, silver streaks, and the like may occur, which poses a problem in processability, and further improvements are currently required.

Therefore, an object of the present invention is to provide a composition that can impart excellent antistatic effects to synthetic resins and can provide excellent processability, a resin composition containing the same, and a molded article thereof.

Solutions to problems

As a result of intensive research to solve the above problems, the inventors discovered that the above problems can be solved by using a polymer compound having a specific structure and a salt of an alkali metal, and the present invention has been completed.

That is, the composition of the present invention is characterized in that it contains a component (X) composed of a polymer compound (E) and a component (Y) composed of a salt of an alkali metal,
The polymer compound (E) is a polyester (a) obtained by reacting a diol with an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and a compound (b) having hydroxyl groups at both ends of one or more ethyloxy groups. ) A polymer compound obtained by reacting with an epoxy compound (D) having two or more epoxy groups,
A block (A) of a polyester composed of the polyester (a) and a block (B) of a polyether composed of the compound (b); A structure in which a hydroxyl group or a carboxyl group at the terminal, an ester bond or an ether bond formed by the reaction of the hydroxyl group at the terminal of the compound (b) with the epoxy group of the epoxy compound (D),
The molar content of the component (Y) is within a range of 2.3 to 5.4% of the number of ethoxylated mols in the block (B) of the polyether in the polymer compound (E) of the component (X). .

In the composition of the present invention, the polymer compound (E) of the component (X) has the polyester block (A) and the polyether block (B) repeatedly and interactively bonded through an ester bond. The block polymer (C) having a carboxyl group at both ends is preferably a structure in which the block polymer (C) is bonded to the epoxy compound (D) through an ester bond. Moreover, in the composition of the present invention, the polyester (a) constituting the block (A) of the polyester of the polymer compound (E) of the polymer compound (E) as the component (X) preferably has a structure having carboxyl groups at both ends. Furthermore, in the composition of the present invention, the compound (b) of the block (B) constituting the polyether block (B) of the polymer compound (E) as the component (X) is preferably polyethylene glycol. Furthermore, in the composition of the present invention, the number average molecular weight of the compound (b) constituting the block (B) of the polyether block (B) of the polymer compound (E) as the component (X) is preferably 400 to 10,000. In the composition of the present invention, the number average molecular weight of the block polymer (C) in the polymer compound (E) of the component (X) is preferably 5,000 to 30,000.

The resin composition of the present invention is obtained by blending a thermoplastic resin with the composition of the present invention.

In the resin composition of the present invention, the thermoplastic resin is preferably one or more selected from the group consisting of a polyolefin resin, a polystyrene resin, and a copolymer thereof.

The molded article of the present invention is characterized by being formed from the resin composition of the present invention.

Invention effect

According to the present invention, it is possible to provide a composition capable of imparting an excellent antistatic effect to a synthetic resin, and at the same time, an excellent processability, a resin composition containing the same, and a formed body thereof. Therefore, the resin composition of the present invention is excellent in antistatic properties, durability, and processability. In addition, the formed article of the present invention is made of a thermoplastic resin which is unlikely to cause surface contamination due to static electricity or decline in product value due to dust adhesion, and is a formed article having no poor processability.

Hereinafter, embodiments of the present invention will be described in detail. The composition of the present invention is a composition containing a component (X) composed of a polymer compound (E) and a component (Y) composed of a salt of an alkali metal. First, the (X) component of this invention is demonstrated.

The component (X) of the present invention is made of a polymer compound (E). The polymer compound (E) of the present invention is a polyester (a) obtained by reacting a diol with an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and one having hydroxyl groups at both ends of the polyester (a). A polymer compound obtained by reacting a compound (b) with an epoxy compound (D) having two or more epoxy groups. The polymer compound (E) of the present invention has a block (A) of a polyester composed of polyester (a) and a block (B) of a polyether composed of compound (b). Moreover, it has an ester bond or an ether formed by the reaction of a hydroxyl group or a carboxyl group at the terminal of the polyester (a), a hydroxyl group of a terminal of the compound (b), and an epoxy group of the epoxy compound (D). Bonded structure. Here, the term "ethoxy" refers to a group represented by the following general formula (1).

The block (A) of the polyester of the polymer compound (E) is composed of a polyester (a) obtained by reacting a diol with an aliphatic carboxylic acid and an aromatic dicarboxylic acid. The polyester (a) is obtained by esterifying a diol with an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid.

First, the diol which is a component of polyester (a) is demonstrated. Examples of the diol used in the present invention include an aliphatic diol and an aromatic group-containing diol. The diol may be a mixture of two or more kinds.

Examples of the aliphatic diol include 1,2-ethylene glycol (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 propylene glycol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3 -Pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, 1,4-cyclohexanedimethanol, water-added bisphenol A, 1,2-, 1,3- or 1,4-cyclohexanediol, cyclododecanediol Alcohols, dimer diols, water-added dimer diols, diethylene glycol, dipropylene glycol, triethylene glycol, and the like. Among these aliphatic diols, 1,4-cyclohexanedimethanol and water-added bisphenol A are preferred from the viewpoints of antistatic properties, durability, and processability. 1,4-cyclohexane Alkylenedimethanol is more preferred. In addition, aliphatic diols are preferred because of their antistatic properties, their persistence, and processability, because those with hydrophobic properties are better.

Examples of the aromatic group-containing diol include bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, 1,4-benzenedimethanol, and bisphenol A. Ethylene oxide adduct, propylene oxide adduct of bisphenol A, mononuclear dihydric phenol such as 1,4-bis (2-hydroxyethoxy) benzene, resorcinol, catechol, etc. Polyhydroxyethyl adducts of compounds 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 preferred. Aromatic diols are preferred from the standpoint of antistatic properties, durability, and processability.

Next, the dicarboxylic acid which is a component of polyester (a) is demonstrated. The aliphatic dicarboxylic acid used in the present invention may be a derivative of an aliphatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.). The aliphatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

Examples of the aliphatic dicarboxylic acid include 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. Among these aliphatic dicarboxylic acids, dicarboxylic acids having 4 to 16 carbon atoms are preferred, and dicarboxylic acids having 6 to 12 carbon atoms are more preferred from the viewpoints of antistatic properties, durability, and processability. good.

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

Examples of the aromatic dicarboxylic acid include an aromatic dicarboxylic acid having 8 to 20 carbon atoms, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, phthalic acid, Phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-di Carboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate and potassium 3-sulfoisophthalate. Among these aromatic dicarboxylic acids, from the viewpoints of antistatic properties, durability, and processability, terephthalic acid, isophthalic acid, and phthalic acid (including phthalic anhydride) are preferred, and phthalic acid (including phthalic anhydride) ) Better.

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

As the compound (b) having one or more ethoxy groups represented by the above-mentioned general formula (1) and having hydroxyl groups at both ends, a compound having hydrophilicity is preferred, and the above-mentioned general formula (1) Polyethylene ethers of the shown ethoxy groups are more preferred. From the standpoint of antistatic properties, durability, and processability, polyethylene glycol is even more preferred. Polyethylene represented by the following general formula (2) Diol is particularly good.

In the general formula (2), m represents a number of 5 to 250. From the point of antistatic property and its durability and processability, 20 ~ 200 is preferable, and 40 ~ 180 is more preferable.

As the compound (b), in addition to polyethylene glycol obtained by an addition reaction of ethylene oxide, examples of the compound include ethylene oxide and one or more other alkylene oxides (for example, propylene oxide, propylene oxide, 1,2-, 1,4-, 2,3-, 1,3-butene oxide, etc.) polyether formed by addition reaction, this polyether can be random or block.

Further examples of the compound (b) include compounds having a structure in which ethylene oxide is added to a compound containing an active hydrogen atom, or ethylene oxide and one or more other alkylene oxides are added. (E.g., propylene oxide, 1,2-, 1,4-, 2,3-, or 1,3-butylene oxide). These may be random additions or block additions.

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

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

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

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

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

As the divalent phenol, a phenol having 6 to 30 carbon atoms can be used, and examples thereof include catechol, resorcinol, 1,4-dihydroxybenzene, hydroquinone, bisphenol A, bisphenol F, and bis Phenol S, dihydroxydiphenyl ether, dihydroxydiphenyl sulfide, binaphthol, and alkyl groups (1 to 10 carbon atoms) or halogen substituents and the like.

Examples of the primary monoamine include aliphatic primary monoamines having 1 to 20 carbon atoms, and examples thereof include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, s-butylamine, Isobutylamine, n-pentylamine, 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, and an alicyclic secondary 2 to 6 carbon atom can be used. Diamines, aromatic secondary diamines having 8 to 14 carbon atoms, and secondary alkanol diamines having 3 to 22 carbon atoms.

Examples of the aliphatic secondary diamine include N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine, N, N'-dibutylethylenediamine, N, N'-dimethylpropanediamine, N, N'-diethylpropanediamine, N, N'-dibutylpropanediamine, N, N'-dimethylbutanediamine, N, N ' -Diethylbutanediamine, N, N'-dibutylbutanediamine, N, N'-dimethylhexanediamine, N, N'-diethylhexanediamine, N, N'-di Butylhexanediamine, N, N'-dimethyldecanediamine, N, N'-diethyldecanediamine, N, N'-dibutyldecanediamine, and the like.

Examples of the heterocyclic secondary diamine include piperidine , 1-aminopiperidine and the like.

Examples of the alicyclic secondary diamine include N, N'-dimethyl-1,2-cyclobutanediamine and 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.

Examples of the aromatic secondary diamine include N, N'-dimethyl-phenylenediamine, N, N'-dimethyl-stemyl diamine, and N, N'-dimethyl-diamine. Phenylmethanediamine, N, N'-dimethyl-diphenyl ether diamine, N, N'-dimethyl-benzidine and N, N'-dimethyl-1,4-naphthalene diamine Wait.

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

As the dicarboxylic acid, a dicarboxylic acid having 2 to 20 carbon atoms can be used, and examples thereof include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids.

Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, methylsuccinic acid, dimethylmalonic acid, β-methylglutaric acid, ethylsuccinic acid, and isoisocyanate. Propylmalonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, Hexadecanedioic acid, octadecanedioic acid, and eicosenedioic acid.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, phthalic acid, phenylsuccinic acid, β-phenylglutaric acid, and α-phenylhexanoic acid. Diacid, β-phenyladipate, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate, and 3 -Potassium sulfoisophthalate and the like.

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

These active hydrogen atom-containing compounds may be used singly or as a mixture of two or more kinds.

Next, the epoxy compound (D) which has two or more epoxy groups which comprises the polymer compound (E) is demonstrated.

The epoxy compound (D) used in the present invention is not particularly limited as long as it has two or more epoxy groups, and examples thereof include hydroquinone, resorcinol, catechol, and resorcinol. Poly-epoxypropyl ether compound of mononuclear polyphenol compound; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (o-cresol), ethylene bisphenol, iso-methylene Propyl bisphenol (bisphenol A), isopropylidene bis (o-cresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4 -Hydroxycumylbenzene), 1,1,3-ginseng (4-hydroxyphenyl) butane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, thiobisphenol, Sulfobisphenol, oxybisphenol, phenol novolac, o-cresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinol novolac, terpene phenol, etc. Poly-epoxypropyl ether compounds of polynuclear polyphenol compounds; ethylene glycol, propylene glycol, butanediol, hexanediol, polyethylene glycol, polyethylene glycol, thiodiglycol, glycerol, trimethylolpropane, pentaerythritol , Sorbitol, bisphenol A-ethylene oxide adduct, dicyclopentane Polyglycidyl ethers of polyalcohols such as dimethyl alcohol; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid , Dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylenetetramethylene A homopolymer or copolymer of epoxypropyl esters and epoxypropylmethacrylates of aliphatic, aromatic or alicyclic polybasic acids such as hydrophthalic acid; N, N-diepoxypropylaniline Epoxy compounds with glycidylamine groups, such as bis (4- (N-methyl-N-glycidylamino) phenyl) methane, diglycidyl o-toluidine, etc .; vinylcyclohexene bicyclic Oxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexyl Epoxides of cyclic olefin compounds such as methyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized poly Epoxidized conjugated diene polymers such as butadiene, epoxidized styrene-butadiene copolymers, etc. Oxopropyl heterocyclic compound isopropyl ester of cyanuric acid, epoxidized soybean oil. In addition, these epoxy compounds may be those crosslinked internally by a prepolymer of a terminal isocyanate, or a plurality of active hydrogen compounds (polyphenols, polyamines, carbonyl-containing compounds, polyphosphates, etc.) ) Those who have been quantified by the polymer. This epoxy compound (D) may use 2 or more types.

When the epoxy compound (D) as a constituent of the polymer compound (E) is a diglycidyl ether of polyethylene glycol, in the present invention, the diglycidyl ether of polyethylene glycol is used. The number of moles of the ethylenyloxy group present in the polymer is calculated as the number of moles of the ethylenoxy group in the polyether block (B), and the total of the two is determined as the polymer compound (E). Molar number of ethylenoxy group in the polyether block (B).

The epoxy equivalent of the epoxy compound (D) is preferably 70 to 2,000 in terms of antistatic properties, durability, and processability.

The polymer compound (E) is formed by a reaction of a hydroxyl group or a carboxyl group at the terminal of the polyester (a), a hydroxyl group of the terminal of the compound (b), and an epoxy group of the epoxy compound (D). An ester bond or an ether bond, and a polyester block (A), a polyether block (B), and an epoxy-reacted epoxy compound (D) are bonded through an ester bond or an ether bond.

Further, the polymer compound (E) has a polyester block (A) composed of a polyester (a) and a compound (b) in terms of antistatic properties, durability, and processability. The block polymer (C) of the polyether composed of a block polymer (C) having carboxyl groups at both ends is repeatedly and alternately bonded through an ester bond, and an epoxy compound (D) is passed through the block polymer ( The structure in which the carboxyl group of C) and the ester bond formed by the epoxy group of the epoxy compound (D) are bonded is preferable.

As long as the polyester (a) constituting the block (A) of the polyester of the present invention is made of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, the antistatic property and the durability From the viewpoint of processability, it is preferable to have a structure in which a residue having a hydroxyl group of a diol removed and a residue having a carboxyl group of an aliphatic dicarboxylic acid removed through an ester bond, and a structure having a hydroxyl group of a diol. The structure of the removed residue and the removed residue of the carboxyl group of the aromatic dicarboxylic acid is bonded through an ester bond.

The polyester (a) is more preferably a structure having carboxyl groups at both ends in terms of antistatic properties, durability, and processability. Further, the degree of polymerization of the polyester (a) is more preferably in the range of 2 to 50 from the viewpoints of antistatic properties, durability, and processability.

The aliphatic dicarboxylic acid may be a derivative of an aliphatic dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.). When the derivative is used to obtain the polyester (a), it is finally In this case, it is sufficient to treat both ends to be carboxyl groups, or the subsequent reaction to obtain a block polymer (C) having a structure having carboxyl groups at both ends may be performed directly in the original state. The aliphatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

Aromatic dicarboxylic acids can be derivatives of aromatic dicarboxylic acids (for example, acid anhydrides, alkyl esters, alkali metal salts, acid halides, etc.). When derivatives are used to obtain polyesters, two The terminal may be a carboxyl group, or the subsequent reaction to obtain a block polymer (C) having a structure having a carboxyl group at both ends may be performed directly in its original state. The aromatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

The ratio of the residue of the carboxyl group of the aliphatic dicarboxylic acid in the polyester (a) to the residue of the carboxyl group of the aromatic dicarboxylic acid is removed from the point of antistatic property and its persistence and processability. Seeing that it is more preferably 90: 10 ~ 99.9: 0.1 in terms of mole ratio, more preferably 93: 7 ~ 99.9: 0.1.

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

The reaction ratio of the aliphatic dicarboxylic acid or its derivative and the aromatic dicarboxylic acid or its derivative to the diol is to use the aliphatic dicarboxylic acid or its derivative and the aromatic dicarboxylic acid in an excessive amount in order to make both ends become carboxyl groups. A carboxylic acid or a derivative thereof is preferable, and it is more preferable to use an excess of 1 mol relative to a diol in terms of a molar ratio.

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

In addition, depending on the blending ratio or reaction conditions, there may be cases where a polyester composed only of a diol and an aliphatic dicarboxylic acid or a polyester composed only of a diol and an aromatic dicarboxylic acid is produced. In the present invention, these may be mixed in the polyester (a), or these may be directly reacted with the compound (b) to obtain a block polymer (C).

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

In addition, when aliphatic dicarboxylic acids and aromatic dicarboxylic acids are used in place of dicarboxylic acids, such as carboxylic acid esters, carboxylic acid metal salts, carboxylic acid halides, and the like, after the reaction with the diol, Treatment of both ends into a dicarboxylic acid can also be performed directly in the original state to obtain the next reaction to obtain a block polymer (C) having a structure having a carboxyl group at both ends.

A more suitable polyester (a) composed of a diol, 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) to form a block polymer. The structure of (C) is preferred, and the carboxyl groups at both ends may be protected or modified, and may also be in the form of a precursor. In addition, in order to suppress oxidation of the product during the reaction, an antioxidant such as a phenolic antioxidant may be added to the reaction system.

The compound (b) having one or more ethoxy groups and having hydroxyl groups at both ends is a structure formed by reacting with the polyester (a) through an ester bond or an ether bond. The structure forming the block polymer (C) is preferred, and the hydroxyl groups at both ends may be protected or modified, and may also be in the form of a precursor.

The block polymer (C) having a structure having carboxyl groups at both ends of the present invention has a block (A) composed of the polyester (a) and a block (B) composed of the compound (b). And has a structure in which these blocks are repeatedly and alternately bonded through an ester bond formed by a carboxyl group and a hydroxyl group. As an example of the block polymer (C), for example, those having a structure represented by the following general formula (3) can be cited.

In the general formula (3), (A) represents a block composed of the polyester (a) having a carboxyl group at both ends, and (B) represents a block composed of the compound (b) having a hydroxyl group at both ends. , T is the number of repetitions of the repeating unit, and is preferably a number from 1 to 10 in terms of the antistatic property, its durability, and processability. t is more preferably a number from 1 to 7, and most preferably is a number from 1 to 5.

In the block polymer (C), a part of the block composed of the polyester (a) may be replaced with a block composed of a polyester composed only of a diol and an aliphatic dicarboxylic acid. Or a block made of a polyester composed of only a diol and an aromatic dicarboxylic acid.

The block polymer (C) having a structure having carboxyl groups at both ends can be obtained by performing a polycondensation reaction between the polyester (a) having a carboxyl group at both ends and the compound (b) having a hydroxyl group at both ends. However, as long as it has an equivalent structure with a structure having the polyester (a) and the compound (b) repeatedly and alternately bonded through an ester bond formed by a carboxyl group and a hydroxyl group, the above-mentioned structure is not necessarily required. The polyester (a) is synthesized with the compound (b).

The reaction ratio between the polyester (a) and the compound (b) can be better obtained by adjusting the polyester (a) to X + 1 mole relative to the compound (b) of X mole. A block polymer (C) having a carboxyl group.

During the reaction, after the synthesis reaction of the polyester (a) is completed, the compound (b) may be added to the reaction system without leaving the polyester (a) alone, and the reaction may be directly performed.

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

The polyester (a) may be a polyester composed of only a diol and an aliphatic dicarboxylic acid, or a polyester composed of only a diol and an aromatic dicarboxylic acid. It reacts directly with the compound (b) to obtain a block polymer (C).

The block polymer (C), in addition to the block (A) composed of the polyester (a) and the block (B) composed of the compound (b), may also contain diols only in the structure. A block composed of a polyester composed of an aliphatic dicarboxylic acid or a block composed of a polyester composed only of a diol and an aromatic dicarboxylic acid.

The polymer compound (E) of the present invention is preferably a block polymer (C) having a structure having a carboxyl group at both ends and an epoxy compound (D) having two or more epoxy groups. The structure in which the carboxyl group at the terminal of the segment polymer (C) is bonded to the ester bond formed by the epoxy group of the epoxy compound (D). The polymer compound (E) may further contain an ester bond formed by a carboxyl group of the polyester (a) and an epoxy group of the epoxy compound (D). The polymer compound (E) may further contain an ether bond formed between the hydroxyl group of the polyester (a) or the hydroxyl group of the compound (b) and the epoxy group of the epoxy compound (D).

In order to obtain the polymer compound (E), the carboxyl group of the block polymer (C) can be reacted with the epoxy group of the epoxy compound (D). The number of epoxy groups of the epoxy compound is preferably 0.5 to 5 equivalents and 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 performed in various solvents, or may be performed in a molten state.

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

During the reaction, after the synthesis reaction of the block polymer (C) is completed, the epoxy compound (D) may be added to the reaction system without isolating the block polymer (C), and the reaction may be performed directly. In this case, the carboxyl group of the unreacted polyester (a) used excessively in the synthesis of the block polymer (C) may react with a part of the epoxy group of the epoxy compound (D) to form an ester bond.

The preferred polymer compound (E) of the present invention is a block polymer (C) having a structure having a carboxyl group at both ends and an epoxy compound (D) having two or more epoxy groups. Constructors formed by the ester bond formed by the respective carboxyl group and epoxy group having the same structure need not necessarily be synthesized from the block polymer (C) and the epoxy compound (D).

In the present invention, among the polymer compound (E), the number average molecular weight of the block (A) composed of the polyester (a) is preferable from the viewpoints of antistatic properties, durability, and processability. In terms of polystyrene, it is 800 to 8,000, more preferably 1,000 to 6,000, and even more preferably 2,000 to 4,000.

In the present invention, among the polymer compound (E), the number average molecular weight of the block (B) composed of the compound (b) having hydroxyl groups at both ends is calculated from the measured value of the hydroxyl value, and the antistatic property is In terms of its sustainability and processability, it is preferably 400 to 10,000, more preferably 1,000 to 8,000, and even more preferably 2,000 to 8,000.

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

Furthermore, after the polymer compound (E) of the present invention is obtained from a diol, an aliphatic dicarboxylic acid, and an aromatic dicarboxylic acid, the polyester (a) is not separated from the polyester (a), and the The compound (b) and / or the epoxy compound (D) are reacted.

Next, the component (Y) of the composition of the present invention will be described. The component (Y) of the present invention is a salt of an alkali metal. Examples of the alkali metal salt include organic or inorganic acid salts, and examples of the alkali metal include lithium, sodium, potassium, cesium, rubidium, 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, and maleic acid. , Adipic acid and other aliphatic dicarboxylic acids with 1 to 12 carbon atoms; benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid and other aromatic carboxylic acids; methanesulfonic acid, p-toluene Sulfonic acids such as sulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, etc. having 1 to 20 carbon atoms. Examples of the inorganic acid include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, and perchloric acid. Among them, sodium is preferred from the viewpoints of antistatic properties, durability, and processability. Moreover, from the viewpoint of antistatic property, durability, and processability, a salt of dodecylbenzenesulfonic acid is preferable.

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, and sodium hydroxide. Lithium chlorate, sodium perchlorate, potassium perchlorate, lithium p-toluenesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate , Potassium dodecylbenzenesulfonate, and so on. Among these, sodium dodecylbenzenesulfonate is preferred from the viewpoints of antistatic properties, durability, and processability.

In the composition of the present invention, the molar content of the component (Y) is the ethylene oxide represented by the general formula (1) in the block (B) of the polyether in the polymer compound (E) of the (X) component. Within the range of 2.3 to 5.4% of the molar number of the alkoxy group, it is preferably in the range of 2.7 to 5.0%, and more preferably 3.1 to 4.6%, in terms of antistatic properties, durability, and processability. Within range.

The mole number of the ethylenoxy group represented by the general formula (1) in the polyether block (B) in the polymer compound (E) of the component (X) corresponds to the general number of the ethoxy groups present in the compound (b). Total molar number of ethoxy groups of formula (1).

When the component (Y) is in this range, the composition of the present invention is excellent in antistatic properties, durability, and processability. Although it is uncertain, it is believed that the general formula (1) ) And the compatibility of alkali metals with synthetic resins is moderately adjusted, so the antistatic property and the durability are excellent, and the processability is excellent.

In order to obtain the composition of the present invention, the (X) component and the (Y) component, which are essential components, and any other optional components as necessary, may be mixed, and various mixers may be used for the mixing. Heating can also be performed during mixing. Examples of usable mixers include drum mixers, Henschel mixers, ribbon mixers, V-type mixers, W-type mixers, super mixers, and conical spiral mixers (Nauta Mixer) and so on. In the synthesis reaction of the polymer compound (E) of the component (X), the reaction system may be added with the component (Y).

In the composition of the present invention, other components may be blended as an optional component in addition to the above (X) component and (Y) component, as long as the effect of the present invention is not impaired. Other components may be directly blended into the composition. When the composition of the present invention is blended into a synthetic resin such as a thermoplastic resin and used as a resin composition, it may also be blended into a synthetic resin.

Hereinafter, components other than (X) component and (Y) component which can be mix | blended with the composition of this invention are demonstrated. The composition of the present invention may further contain a salt of a Group 2 element within a range that does not impair the effects of the present invention.

Examples of the salt of the Group 2 element include salts of organic or inorganic acids, and examples of the Group 2 element include beryllium, magnesium, calcium, strontium, and barium. 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, and maleic acid. , Adipic acid and other aliphatic dicarboxylic acids with 1 to 12 carbon atoms; benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid and other aromatic carboxylic acids; methanesulfonic acid, p-toluene Sulfonic acids such as sulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, etc. having 1 to 20 carbon atoms. Examples of the inorganic acid include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, and perchloric acid.

Further, a surfactant may be blended in the composition of the present invention within a range that does not impair the effects of the present invention. However, when the surfactant of an alkali metal salt is blended, since (Y) component is contained, attention should be paid to its blending. As the surfactant, a nonionic, anionic, cationic or amphoteric surfactant can be used. Examples of nonionic surfactants include higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, and the like. Polyethylene glycol nonionic surfactant; polyethylene oxide, fatty acid esters of glycerol, fatty acid esters of neopentyl tetraol, fatty acid esters of sorbitol or sorbitan, polyalkanols Polyol-type nonionic surfactants such as alkyl ethers, aliphatic amidines of alkanolamines, and the like. Examples of the anionic surfactant include carboxylates such as alkali metal salts of higher fatty acids; higher alcohol sulfates Salts, sulfate salts of higher alkyl ether sulfate salts, sulfonates of alkylbenzene sulfonates, alkyl sulfonates, paraffin sulfonates, etc .; phosphate salts of higher alcohol phosphates, etc., Examples of the cationic surfactant include a fourth-order ammonium salt such as an alkyltrimethylammonium salt and the like. Examples of the amphoteric surfactant include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, betaine-type surfactants such as higher alkyldimethylbetaine, and higher alkyldihydroxyethylbetaines. Amphoteric surfactants and the like can be used alone or in combination of two or more kinds. In the present invention, among the above-mentioned surfactants, anionic surfactants are preferred, and sulfonates such as alkylbenzenesulfonate, alkylsulfonate, and paraffinsulfonate are preferred.

The surfactant may be blended in the composition of the present invention, or may be blended with the composition in a synthetic resin such as a thermoplastic resin and used. The blending amount 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 relative to 100 parts by mass of the composition of the present invention.

Furthermore, a polymer-type antistatic agent may be blended in the composition of the present invention as long as the effect of the present invention is not impaired. As the polymer antistatic agent, for example, a known polymer-type antistatic agent such as polyetheresteramide may be used. As the known polyetheresteramine, for example, it is described in Japanese Patent Application Laid-Open No. 7-10989. A polyetheresteramide made from the polyoxyalkylene adduct of bisphenol A. In addition, a block polymer having a repeating structure of 2 to 50 in a unit of bonding between a polyolefin block and a hydrophilic polymer block may be used, and examples thereof include block polymers described in US Pat. No. 6,552,131.

The polymer-type antistatic agent may be blended in the composition of the present invention, or may be blended with the composition in a synthetic resin such as a thermoplastic resin and used. The blending amount of the polymer-type antistatic agent is preferably 0 to 50 parts by mass, and more preferably 5 to 20 parts by mass relative to 100 parts by mass of the composition of the present invention.

Furthermore, the composition of the present invention may be blended with an ionic liquid as long as the effect of the present invention is not impaired. Examples of the ionic liquid include 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 1 to 200 ms / cm, preferably 10 to A normal temperature molten salt of 200 ms / cm is, for example, the normal temperature molten salt described in International Publication No. 95/15572.

Examples of the cation constituting the ionic liquid include cations selected from the group consisting of sulfonium, pyridinium, pyrazolium, and guanidinium cations. Among these, as the sulfonium cation, the following may be mentioned.

(1) Examples of imidazolinium cations include those having 5 to 15 carbon atoms, such as 1,2,3,4-tetramethylimidazolinium and 1,3-dimethylimidazolinium;

(2) Examples of the imidazolium cation include those having 5 to 15 carbon atoms, such as 1,3-dimethylimidazolium and 1-ethyl-3-methylimidazolium;

(3) Examples of the tetrahydropyrimidinium cation include 6 to 15 carbon atoms, for example, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetrahydropyrimidinium Methyl-1,4,5,6-tetrahydropyrimidinium;

(4) Examples of the dihydropyrimidinium cation include 6 to 20 carbon atoms, for example, 1,3-dimethyl-1,4-dihydropyrimidinium, 1,3-dimethyl-1,6-di Hydropyrimidinium, 8-methyl-1,8-diazinebicyclo [5,4,0] -7,9-undecadienium, 8-methyl-1,8-diazinebicyclo [5,4 , 0] -7,10-undecadienium.

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

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

Examples of the guanidinium cation include the following.

(1) Examples of guanidinium cations having an imidazolinium skeleton include those having 8 to 15 carbon atoms, such as 2-dimethylamino-1,3,4-trimethylimidazolinium and 2-diethylamino -1,3,4-trimethylimidazolinium;

(2) Examples of guanidinium cations having an imidazolium skeleton include 8 to 15 carbon atoms, such as 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1 3,4-trimethylimidazolium;

(3) Examples of guanidinium cations having a tetrahydropyrimidinium skeleton include those having 10 to 20 carbon atoms, such as 2-dimethylamino-1,3,4-trimethyl-1,4,5,6- Tetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium;

(4) Examples of guanidinium cations having a dihydropyrimidinium skeleton include those having 10 to 20 carbon atoms, such as 2-dimethylamino-1,3,4-trimethyl-1,4-dihydropyrimidinium , 2-dimethylamino-1,3,4-trimethyl-1,6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4 -Dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,6-dihydropyrimidinium.

These cations may be used singly or in combination of two or more kinds. Any of them may be used. Among these, from the viewpoint of antistatic properties, a sulfonium cation is preferred, an imidazolium cation is more preferred, and a 1-ethyl-3-methylimidazolium cation is particularly preferred.

Examples of the organic acid or inorganic acid constituting the anion in the ionic liquid include the following. Examples of the organic acid include carboxylic acids, sulfates, sulfonic acids, and phosphates; and examples of the inorganic acid include superacids (for example, borofluoric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluoro Antimony acid and arsenic hexafluoride), phosphoric acid and boric acid. The organic acid and inorganic acid may be used singly or in combination of two or more kinds. Any of them may be used.

Among the above organic and inorganic acids, from the viewpoint of the antistatic property of the ionic liquid, it is preferred that the Hammett acidity function (-H ₀ ) forming the anion constituting the ionic liquid is 12 to 100, and the super acid is Anionic acids other than conjugate bases of super strong acids, conjugate bases of superacids, and mixtures thereof.

Examples of the anions other than the conjugate base of a super acid include halogen (for example, fluorine, chlorine, and bromine) ions, alkyl (1 to 12 carbon atoms) benzenesulfonic acids (for example, p-toluenesulfonic acid and dodecane) Phenylbenzenesulfonic acid) ion and poly (n = 1-25) fluoroalkanesulfonic acid (such as undecylfluoropentanesulfonic acid) ion.

Examples of the super acid include those derived from proton acids and combinations of proton acids and Lewis acids, and mixtures thereof. Examples of the protonic acid that is a super acid include bis (trifluoromethylsulfonyl) sulfonium imidic acid, bis (pentafluoroethylsulfonyl) sulfonyl imine, and ginseng (trifluoromethylsulfonate) (Fluorenyl) methane, perchloric acid, fluorosulfonic acid, alkane (carbon number 1-30) sulfonic acid (e.g. methanesulfonic acid, dodecanesulfonic acid, etc.), poly (n = 1-30) fluoroalkane (carbon 1 to 30 atoms) sulfonic acids (e.g. trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecylfluoropentanesulfonic acid, and tridecylfluorohexanesulfonic acid) , Borofluoric acid and tetrafluoroborate. Among these, from the viewpoint of the ease of synthesis, borofluoric acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) fluorenimide, and bis (pentafluoroethylsulfonium) are preferred. Group) hydrazone.

Examples of the proton acid used in combination with the Lewis acid include hydrogen halide (for example, hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and Fluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecylfluoropentanesulfonic acid, tridecylfluorohexanesulfonic acid and mixtures thereof. Among these, hydrogen fluoride is preferable from the viewpoint of the initial conductivity of the ionic liquid.

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

Although the combination of a protonic acid and a Lewis acid is arbitrary, examples of superacids formed by the combination thereof include tetrafluoroboric acid, hexafluorophosphoric acid, tantalum hexafluoride acid, antimony hexafluoride acid, and hexafluoride. Tantalum fluoride sulfonic acid, boron tetrafluoride acid, phosphoric acid hexafluoride, boron chloride trifluoride acid, arsenic acid hexafluoride and mixtures thereof.

Among the above-mentioned anions, from the viewpoint of the antistatic property of the ionic liquid, a conjugate base of a super acid (a super acid made of a proton acid and a super acid made of a combination of a proton acid and a Lewis acid) are preferred. Strong acid), more preferably a super acid made from a proton acid and a conjugate base made from a proton acid, boron trifluoride and / or phosphorus pentafluoride.

Among the ionic liquids, from the viewpoint of antistatic properties, preferred are ionic liquids having a sulfonium cation, and more preferred are ionic liquids having a 1-ethyl-3-methylimidazolium cation, Particularly preferred is 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) fluorenimine.

The ionic liquid may be blended in the composition of the present invention, or may be blended with the composition in a synthetic resin such as a thermoplastic resin and used. The blending amount of the ionic liquid is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the composition of the present invention, more preferably 0.1 to 15 parts by mass, and most preferably 1 to 10 parts by mass.

Furthermore, the composition of the present invention may be mixed with a solubilizing agent within a range that does not impair the effects of the present invention. By blending a compatibilizing agent, the compatibility of the components of the composition with other components or synthetic resins such as thermoplastic resins can be improved. Examples of the compatibility agent include modified vinyl polymers having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amine group, a hydroxyl group, and a polyoxyalkylene group. For example, the polymer described in Japanese Patent Application Laid-Open No. 3-258850, or the modified vinyl polymer having a sulfofluorene group described in Japanese Patent Application Laid-Open No. 6-345927, or having a polyolefin portion and aromatic Block polymer of vinyl polymer part and the like.

The compatibilizing agent may be blended in the composition of the present invention, or may be blended with the composition of the present invention in a synthetic resin such as a thermoplastic resin and used. The blending amount of the compatibilizing agent is preferably 0.1 to 15 parts by mass and more preferably 1 to 10 parts by mass relative to 100 parts by mass of the composition of the present invention.

The composition of the present invention may be blended with a synthetic resin, and particularly preferably blended with a thermoplastic resin as a resin composition. Examples of the thermoplastic resin include polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, cross-linked polyethylene, ultra-high molecular weight polyethylene, polybutene-1, and poly-3. -Α-olefin polymers such as methylpentene and poly-4-methylpentene, or polyolefin resins such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-propylene copolymer, and These copolymers; polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene copolymers Polymer, vinyl chloride-dichloroethylene copolymer, vinyl chloride-dichloroethylene-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-ring Hexyl maleimide copolymers and other halogen-containing resins; petroleum resins, coumarone resins, polystyrene, polyvinyl acetate, acrylic resins, styrene and / or α-methylstyrene and other monomers (such as , Maleic anhydride, phenylmaleimide, methyl methacrylate, butane Ene, acrylonitrile, etc.) copolymers (for example, 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, etc. Aromatic polyesters such as alkyl terephthalate, polyethylene naphthalate, polybutylene naphthalate, etc., and polytetramethylene terephthalic acid Linear polyesters such as esters; polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, Decomposable aliphatic polyesters such as poly (2-oxetanone); polyamines such as polyphenylene ether, polycaprolactam and polyhexamethylene adipamide, polycarbonate, Polycarbonate / ABS resin, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, cellulose resin, polyimide resin, polyfluorene, polyphenylene ether, poly ether , The thermoplastic resin is a polyether ether ketone, liquid crystal polymer, and blends of these. In addition, the thermoplastic resin may be isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluorine rubber, silicone rubber, and olefin-based elasticity. Elastomers such as elastomers, styrene-based elastomers, polyester-based elastomers, nitrile-based elastomers, nylon-based elastomers, vinyl chloride-based elastomers, polyamide-based elastomers, and polyurethane-based elastomers. In 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 can be used regardless of molecular weight, degree of polymerization, density, softening point, ratio of insoluble content to solvents, degree of stereoregularity, presence or absence of catalyst residues, type and blending ratio of monomers as raw materials, The type of the polymerization catalyst (for example, Ziegler catalyst, metallocene catalyst, etc.) is used. Among these thermoplastic resins, from the viewpoint of antistatic properties, durability, and processability, they are selected from the group consisting of polyolefin resins, polystyrene resins, and copolymers thereof. One or more is preferable.

In the resin composition of the present invention, the mass ratio of the thermoplastic resin to the composition of the present invention is preferably in the range of 99/1 to 40/60.

The method for blending the thermoplastic resin of the composition of the present invention is not particularly limited, and any method generally used can be used, for example, it can be mixed by roller kneading, bumper kneading, extruder, kneader, etc., Knead to blend. In addition, although the composition of the present invention can be directly added to a thermoplastic resin, if necessary, it can be impregnated in a carrier and then added. For impregnation in the carrier, it can be directly heated and mixed. If necessary, it can also be diluted with an organic solvent and then impregnated in the carrier, and then the solvent is removed. Examples of such a carrier include those known as fillers or fillers for synthetic resins, or solid flame retardants and light stabilizers that can be used at room temperature, such as calcium silicate powder, silicon dioxide powder, talc powder, Alumina powder, titanium oxide powder, or those on which the surface of the support is chemically modified are those described below as solids among flame retardants or antioxidants. Among these carriers, it is preferable to chemically modify the surface of the carrier, and it is more preferable to chemically modify the surface of the silicon dioxide powder. These carriers are preferably those having an average particle diameter of 0.1 to 100 μm, and more preferably 0.5 to 50 μm.

Furthermore, as a method for blending the resin component with the composition of the present invention, a polymer compound of the component (X) can be synthesized while kneading the block polymer (C) and the epoxy compound (D) to the resin component ( E) Blending, at this time, the alkali metal salt of the component (Y) may be kneaded at the same time, and the polymer compound of the (X) component and the base of the (Y) component are mixed at the time of molding such as injection molding. The metal salt and the resin component may be blended in a method of obtaining a molded article. Further, a master batch of the component (X) and / or (Y) and a synthetic resin may be prepared in advance, and the master batch may be blended.

Furthermore, the polymer compound (E) of the component (X) and the salt of the alkali metal of the component (Y) can be mixed in advance and blended into a synthetic resin, or an alkali metal salt can be added to the synthesis reaction for synthesis. The resulting polymer compound (E) is blended into a synthetic resin.

To the resin composition of the present invention, various additives such as a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, an ultraviolet absorber, and a hindered amine-based light stabilizer can be further added as needed. The resin composition of the invention is stabilized.

Various additives such as antioxidants can also be incorporated into the composition of the present invention before being incorporated into the synthetic resin. Furthermore, it is also possible to carry out blending at the time of producing the polymer compound (E). In particular, the antioxidant is preferably blended during the production of the polymer compound (E) to prevent the polymer compound (E) from being oxidatively deteriorated during production, and is therefore preferred.

Examples of the phenol-based 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) ammonium propionate] , 4,4'-thiobis (6-third-butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-third-butylphenol), 2,2 '-Methylenebis (4-ethyl-6-third-butylphenol), 4,4'-butylenebis (6-third-butyl-m-cresol), 2,2'-ethylene Bis (4,6-di-tert-butylphenol), 2,2'-ethylenebis (4-second-butyl-6-tert-butylphenol), 1,1,3-gins (2 -Methyl-4-hydroxy-5-third butylphenyl) butane, 1,3,5-ginseng (2,6-dimethyl-3-hydroxy-4-third butylbenzyl) iso Cyanurate, 1,3,5-ginseng (3,5-di-tert-butyl-4-hydroxybenzyl) isotricyanate, 1,3,5-ginseng (3,5-di Tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-propenyloxy-3-tert-butyl) Methyl-5-methylbenzyl) phenol, octadecyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, [3- (3,5-di-tert-butyl) 4-Hydroxyphenyl) methyl propionate ] Methane, thiodiethylene glycol bis [(3,5-di-third-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di- Tributyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-hydroxy-3-third butylphenyl) butanoic acid] glycol ester, bis [2-thirdbutyl 4-methyl-6- (2-hydroxy-3-tertiarybutyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-gins [(3,5-di Tert-butyl-4-hydroxyphenyl) propanyloxyethyl] isotricyanate, 3,9-bis [1,1-dimethyl-2-{(3-thirdbutyl- 4-hydroxy-5-methylphenyl) propanyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol bis [(3- Tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like. The addition amount of these phenol-based antioxidants is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the thermoplastic resin.

Examples of the phosphorus-based antioxidant include ginsyl nonylphenylphosphite, and ginseng [2-thirdbutyl-4- (3-thirdbutyl-4-hydroxy-5-methylphenylsulfide). ) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, bis (decyl) monophenyl phosphite, bis (tridecyl) Pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl) 4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) Pentaerythritol diphosphite, tetrakis (tridecyl) isopropylidene diphosphite, tetrakis (tridecyl) -4,4'-n-butylenebis (2-thirdbutyl- 5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-ginseng (2-methyl-4-hydroxy-5-third butylphenyl) butane triphosphite (2,4-Di-tert-butylphenyl) phenylene diphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2 '-Methylenebis (4,6-third butylphenyl) -2-ethyl Hexyl phosphite, 2,2'-methylenebis (4,6-third butylphenyl) -octadecyl phosphite, 2,2'-ethylenebis (4,6-di Tert-butylphenyl) fluorophosphite, ginseng (2-[(2,4,8,10-tert-butyldibenzo [d, f] [1,3,2] dioxaphos Hetero-6-yl) oxy] ethyl) amine, 2-ethyl-2-butylpropanediol, and phosphites of 2,4,6-tri-tert-butylphenol and the like. The addition amount of these phosphorus-based antioxidants is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the thermoplastic resin system.

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

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 5 , 2-hydroxybenzophenones such as 5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2'-hydroxy-5'-methylphenyl) Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tertiary butyl -5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-third octylphenyl) benzotriazole, 2- (2'-hydroxy- 3 ', 5'-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-third octyl-6- (benzotriazolyl) phenol), 2- (2'-hydroxy-3'-third butyl-5'-carboxyphenyl) benzotriazole and other 2- (2'-hydroxyphenyl) benzotriazoles; phenyl salicylate, m Hydroquinone monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-pentylphenyl -3,5-Di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, and other benzoates; 2- Ethyl-2'-ethoxypyridoxanilide, 2-ethoxy-4'-dodecylpyridoxine Substituted grass anilines such as amines; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl ) Cyanoacrylates such as acrylates; 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-di-tert-butylphenyl) -s-tri , 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-tri , 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,4-di-tert-butylphenyl) -s-tri Triaryl class. The addition amount of these ultraviolet absorbers is preferably 0.001 to 30 parts by mass, and more preferably 0.05 to 10 parts by mass relative to 100 parts by mass of the thermoplastic resin.

Examples of the hindered amine-based light stabilizer include, for example, 2,2,6,6-tetramethyl-4-piperidinyl stearate, and 1,2,2,6,6-pentamethyl-4. -Piperidinyl stearate, 2,2,6,6-tetramethyl-4-piperidinylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidinyl) ) Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis (1-octyloxy-2,2,6,6-tetra (Methyl-4-piperidinyl) sebacate, (2,2,6,6-tetramethyl-4-piperidinyl) -1,2,3,4-butane tetracarboxylic acid ester, (1,2,2,6,6-pentamethyl-4-piperidinyl) -1,2,3,4-butane tetracarboxylate, bis (2,2,6,6-tetramethyl) Yl-4-piperidinyl), bis (tridecyl) -1,2,3,4-butane tetracarboxylic acid ester, bis (1,2,2,6,6-pentamethyl-4- Piperidinyl) ・ Di (tridecyl) -1,2,3,4-butane tetracarboxylic acid ester, bis (1,2,2,4,4-pentamethyl-4-piperidinyl) 2-butyl-2- (3,5-di-third-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl 4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidinylamino) hexane / 2,4- Dichloro-6-morpholinyl-s-tri Polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidinylamino) hexane / 2,4-dichloro-6-third octylamino-s- three Polycondensate, 1,5,8,12-([2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidinyl) amino)- s-three -6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-cyclo [2,4-bis (N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidinyl) amino) -s-tri -6-yl] -1,5,8-12-tetraazadodecane, 1,6,11-ginseng [2,4-bis (N-butyl-N- (2,2,6,6 -Tetramethyl-4-piperidinyl) amino) -s-tri -6-yl] aminoundecane, 1,6,11-ginseng [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperazine) (Pyridyl) amino) -s-tri -6-yl] hindered amine compounds such as aminoundecane. The amount of these hindered amine-based light stabilizers is preferably 0.001 to 30 parts by mass, and more preferably 0.05 to 10 parts by mass relative to 100 parts by mass of the thermoplastic resin.

In addition, when a polyolefin resin is used as the thermoplastic resin, it is preferable to add a known neutralizing agent in order to further neutralize the residue catalyst in the polyolefin resin, as long as the effect of the present invention is not impaired. . Examples of the neutralizing agent include fatty acid metal salts such as calcium stearate, lithium stearate, and sodium stearate, or ethylidenebis (stearylamine) and ethylidenebis (12-hydroxyl). Fatty acid ammonium compounds such as stearylamine), ammonium stearate, etc., and these neutralizing agents may also be used in combination. However, when an alkali metal salt neutralizer is blended, since it is contained in the (Y) component, attention must be paid to its blending.

In the resin composition of the present invention, as other additives, if necessary, the aromatic carboxylic acid metal salt, alicyclic alkyl carboxylic acid metal salt, and p-tert-butyl group may be further added within a range that does not impair the effect of the invention. Aluminum benzoate, aromatic phosphate metal salt, dibenzylidene sorbitol, nucleating agent, metal soap, hydrotalcite, Ring compounds, metal hydroxides, phosphate-based flame retardants, condensed phosphate-based flame retardants, phosphate-based flame retardants, inorganic phosphorus-based flame retardants, (poly) phosphate-based flame retardants, halogen-based barriers Fuel, silicon flame retardant, antimony oxide such as antimony trioxide, other inorganic flame retardant additives, other organic flame retardant additives, fillers, pigments, lubricants, foaming agents, etc. However, when the above-mentioned other additives of the alkali metal salt are blended, since the (Y) component is contained, the blending thereof requires attention.

As above containing three Examples of the cyclic compound include melamine, diamine, benzomelamine, acetoguanamine, phthalocyanine diguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanide, norbornene diguanide Amine, methylene diguanamine, ethylene dimelamine, trimethylene di melamine, tetramethylene di melamine, hexamethylene di melamine, 1,3-hexyl di melamine, and the like.

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

Examples of the phosphoric acid ester-based flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, chloroethyl phosphate, and dichloride. Propyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, octyl diphenyl phosphate, xylyl diphenyl phosphate, Phenyl isopropyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, gin- ( t-butylphenyl) phosphate, cumylphenyl diphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, gins- (isopropylphenyl) phosphate, and the like.

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

Examples of the (poly) phosphate-based flame retardant include ammonium polyphosphate, melamine polyphosphate, and piperazine polyphosphate , Melamine pyrophosphate, piperidine pyrophosphate Equal to ammonium or amine salts of (poly) phosphoric acid.

Examples of other inorganic flame retardant additives include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, and montmorillonite, and surface-treated products thereof. For example, TIPAQUE R-680 ( Titanium oxide: manufactured by Ishihara Industry Co., Ltd., KYOWAMAG150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), ALCAMIZER4 (zinc modified hydrotalcite: Kyowa Chemical Industry Co., Ltd.) and other commercial products. In addition, examples of other organic flame retardant aids include pentaerythritol.

In addition, as for the resin composition of the present invention, additives that are used in general synthetic resins such as a cross-linking agent and Aerosols, anti-bleeding agents, surface treatment agents, plasticizers, lubricants, flame retardants, fluorescent agents, antifungal agents, fungicides, foaming agents, metal deactivators, release agents, pigments, processing aid Agents, antioxidants, light stabilizers, etc.

The additives incorporated in the resin composition of the present invention may be directly added to the thermoplastic resin, or may be added to the thermoplastic resin after being incorporated in the composition of the present invention.

By molding the resin composition of the present invention, a molded body can be obtained. The molding method is not particularly limited, and examples thereof include extrusion processing, calendar processing, injection molding, rollers, compression molding, blow molding, and rotational molding, and resin plates, sheets, films, bottles, fibers, and irregular shapes can be produced. Products of various shapes. The formed article obtained from the resin composition of the present invention is one having excellent antistatic performance and durability. In addition, the resin composition of the present invention is excellent in processability, and there is no risk of processing defects such as silver streaks. Therefore, a molded product without processing defects can be obtained.

The resin composition of the present invention and a molded article using the same can be used in electrical, electronic, and telecommunications, agriculture, forestry and fisheries, mining, construction, food, fiber, clothing, medical, coal, petroleum, rubber, leather, automobiles, precision equipment , Wood, building materials, civil engineering, furniture, printing, musical instruments, etc.

More specifically, the resin composition and its molded article of the present invention can be used in printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, photocopiers, facsimiles, ECR (electronics) Type cash register), calculators, electronic notebooks, cards, holders, stationery, etc., OA equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting appliances, game machines, irons, warming tables and other household appliances, TV, VTR AV cameras, cameras, radios, tape recorders, mini discs, CD players, speakers, LCD monitors, connectors, relays, condensers, switches, printed circuit boards, bobbins, semiconductor packaging materials, LED packaging materials, Electrical and electronic parts and communications equipment such as wires, cables, transformers, deflection yokes, distributors, clocks, automotive interior and exterior materials, plate-making films, adhesive films, bottles, food containers, food packaging films, pharmaceuticals, etc. Medical packaging film, product packaging film, agricultural film, agricultural sheet, greenhouse film, etc.

Furthermore, the resin composition and its formed body of the present invention can be used in seats (fillers, fabrics, etc.), belts, ceiling mounting, convertible tops, armrests, door trims, rear packaging trays, carpets, cushions, and sun visors. , Wheel covers, mattress covers, airbags, insulation materials, rings, rings, wire covering materials, electrical insulation materials, coatings, coating materials, upper surface materials, floor boards, corner walls, carpets, wallpapers, wall materials, Exterior materials, interior materials, roofing materials, nail plates, wall materials, pillar materials, cladding materials, frameworks and trims, windows and door shapes, shingle plates, sidings, platforms, terraces, soundproof panels, Thermal insulation boards, window materials, etc. for automobiles, vehicles, ships, aircrafts, buildings, residential and construction materials and civil materials, clothing, curtains, sheets, nonwovens, plywood, plywood, fleece blankets, entrance mats, sheets, buckets , Hoses, containers, glasses, bags, boxes, goggles, skis, rackets, tents, musical instruments and other daily necessities, sporting goods, and other applications.

Examples

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these.

The polymer compound (E) of the component (X) used in the present invention is produced according to the following production examples. In the following production examples, the number average molecular weight of the compound (b) was measured using the following <molecular weight measuring method 1>, and the number average molecular weight other than the compound (b) was measured using 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 formula.
Number average molecular weight = (56110 × 2) / hydroxyl value

＜ Hydroxy valency measurement method ＞
・ Reagent A (acetylating agent)
(1) 1560mL of triethyl phosphate
(2) 193mL acetic anhydride
(3) Perchloric acid (60%) 16g
The above reagents are mixed in the order of (1) → (2) → (3).
・ Reagent B
Pyridine and pure water were mixed at a volume ratio of 3: 1.
・ Reagent C
Add 2-3 drops of phenolphthalein solution to 500mL of isopropanol, and make it neutral with 1N-KOH aqueous solution.

First, 2 g of the sample was measured in a 200 mL Erlenmeyer flask, 10 mL of xylene was added, and the mixture was heated and dissolved. Add 15 mL of reagent A, stopper the bottle and shake vigorously. Add 20 mL of reagent B, stopper the bottle and shake vigorously. 50 mL of reagent C was added. Titrate with 1N-KOH aqueous solution and calculate with the following formula.

Hydroxyl value [mgKOH / g] = 56.11 × f × (TB) / S
f: factor of 1N-KOH aqueous solution
B: Empty test titer [mL]
T: titer in this test [mL]
S: sample size [g]

<Molecular weight measurement method 2>
The number average molecular weight (hereinafter, also referred to as "Mn") is measured by a gel permeation chromatography (GPC) method. The measurement conditions of Mn are as follows.

Device: manufactured by JASCO Corporation, GPC device Solvent: tetrahydrofuran Reference material: polystyrene detector: differential refractometer (RI detector)
Column stationary phase: Showa Denko, Ltd., Shodex KF-804L
Column temperature: 40 ℃
Sample concentration: 1mg / 1mL
Flow: 0.8mL / min.
Injection volume: 100 μL

[Manufacturing example 1]
In a separable flask, 109 g (0.76 mol) of 1,4-cyclohexanedimethanol, 117 g (0.81 mol) of adipic acid, 0.1 g (0.0008 mol) of phthalic anhydride, and an antioxidant (4 [3 -(3,5-Di-tert-butyl-4-hydroxyphenyl) propanyloxymethyl] methane, ADEKA Stub AO-60 (manufactured by ADEKA) 0.5 g, slowly heated from 160 ° C to 210 ° C and At the same time, it was polymerized under normal pressure for 4 hours, and then polymerized under reduced pressure at 210 ° C for 3 hours to obtain polyester (a) -1.

Next, 200 g of the obtained polyester (a) -1, 100 g of polyethylene glycol having a number average molecular weight of 3,100 as the compound (b) -1 having hydroxyl groups at both ends, and repeating units of ethyloxy groups = 70 were charged. (0.032 moles, moles of ethoxylate is 2.3 moles), 0.5 g of antioxidant (ADEKA Stub AO-60), 0.8 g of zirconium octoate, polymerization was performed at 210 ° C for 7 hours under reduced pressure To obtain a block polymer (C) having a structure having carboxyl groups at both ends
-1 299g. This block polymer (C) has a structure having carboxyl groups at both ends
The acid value of -1 was 11, and the number average molecular weight Mn was 16,000 in terms of polystyrene.

299 g of the obtained block polymer (C) -1 having a structure having carboxyl groups at both ends was charged with bisphenol F diglycidyl ether (epoxy equivalent 170 g / eq) 3.2 g, polymerized under reduced pressure at 240 ° C for 3 hours to obtain 304 g of the polymer compound (E) -1 as the component (X) of the present invention. In (304) g of (E) -1, in the block (B) of the polyether, there were 2.3 moles of the ethylenyloxy group derived from the compound (b) -1.

[Manufacturing example 2]
The same procedure as in Production Example 1 was performed to obtain 300 g of polyester (a) -1. 300 g of the obtained polyester (a) -1, 200 g (0.064) of polyethylene glycol having a number average molecular weight of 3,100 as the compound (b) -1 having hydroxyl groups at both ends and a repeating number of ethyloxy groups of 70 were charged. Moore, Molar number of ethoxyl is 4.5 Moore), 0.5g of antioxidant (ADEKA Stub AO-60), 0.8g of zirconium octoate, and polymerization at 210 ° C for 7 hours under reduced pressure to obtain 498 g of a block polymer (C) -2 having a structure having carboxyl groups at both ends. The block polymer (C) -2 having a structure having carboxyl groups at both ends had an acid value of 10 and a number average molecular weight Mn of 16,000 in terms of polystyrene.

Into the obtained 498 g of the block polymer (C) -2 having a structure having carboxyl groups at both ends, bisphenol F diglycidyl ether (epoxy equivalent 170 g / eq) 4.7 g, polymerized under reduced pressure at 240 ° C for 3 hours to obtain 507 g of the polymer compound (E) -2 as the component (X) of the present invention. (E) -2 In 507 g, in the block (B) of the polyether, the -CH ₂ -CH ₂ -O- group derived from the compound (b) -1 had 4.5 moles.

[Manufacturing example 3]
107 g of polyester (a) -1 was obtained in the same manner as in Production Example 1. 107 g of the obtained polyester (a) -1, compound (b) -2 having hydroxyl groups at both ends, a number average molecular weight of 7,500, and a repeating unit number of ethoxyl groups = 170, 100 g of polyethylene glycol (0.013) Moore, the molar number of ethoxy groups is 2.3 Moore), 0.5 g of antioxidant (ADEKA Stub AO-60), 0.8 g of zirconium octoate, and polymerize under reduced pressure at 210 ° C for 7 hours to obtain 207 g of a block polymer (C) -3 having a structure having carboxyl groups at both ends. The block polymer (C) -3 having a structure having carboxyl groups at both ends had an acid value of 11 and a number average molecular weight Mn of 16,000 in terms of polystyrene.

207 g of the obtained block polymer (C) -3 having a structure having carboxyl groups at both ends was charged with bisphenol F diglycidyl ether (epoxy equivalent 170 g / eq) 1.7 g, polymerized under reduced pressure at 240 ° C. for 3 hours to obtain 210 g of polymer compound (E) -3 as component (X) of the present invention. In 210 g of (E) -3, 2.3 mol of the ethylenoxy group derived from the compound (b) -2 in the block (B) of the polyether was present.

[Example 1]
The polymer compound (E) -1 obtained in Production Example 1 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a composition-1. Due to the presence of 2.3 moles of the ethoxyl group in (E) -1, 0.052 moles of sodium dodecylbenzenesulfonate containing a Na mole number of 2.3% relative to the mole number was used.

Next, 20 parts by mass of the obtained composition-1 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a resin composition-1. The obtained resin composition-1 was pelletized under conditions of 230 ° C. and 6 kg / time by using a (shaft) Ikegai biaxial extruder (with PCM30, 60 mesh attached). The obtained pellets were molded using a horizontal injection molding machine (NEX80: manufactured by Nissei Resin Industry Co., Ltd.) under processing conditions of a resin temperature of 230 ° C and a mold temperature of 40 ° C to obtain test pieces (100mm × 100mm × 3mm) . Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 1.

[Example 2]
The polymer compound (E) -1 obtained in Production Example 1 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a composition-2. Due to the presence of 2.3 moles of the ethoxyl group in (E) -1, 0.057 moles of sodium dodecylbenzenesulfonate containing a Na mole number of 2.5% relative to the mole number was used.

Next, 20 parts by mass of the obtained composition-2 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a resin composition-2. The obtained resin composition-2 was performed in the same manner as in Example 1 to obtain a test piece (100 mm × 100 mm × 3 mm). Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 1.

[Example 3]
The polymer compound (E) -1 obtained in Production Example 1 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a composition-3. Due to the presence of 2.3 moles of the ethoxyl group in (E) -1, 0.061 moles of sodium dodecylbenzenesulfonate having a Na mole number of 2.7% relative to the mole number was used.

Next, 20 parts by mass of the obtained composition-3 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a resin composition-3. The obtained resin composition-3 was performed in the same manner as in Example 1 to obtain a test piece (100 mm × 100 mm × 3 mm). Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 1.

[Example 4]
The polymer compound (E) -1 obtained in Production Example 1 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a composition-4. Due to the presence of 2.3 moles of the ethoxyl group in (E) -1, 0.070 moles of sodium dodecylbenzenesulfonate having a Na mole number of 3.1% relative to the mole number was used.

Next, 20 parts by mass of the obtained composition-4 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a resin composition-4. The obtained resin composition-4 was performed in the same manner as in Example 1 to obtain a test piece (100 mm × 100 mm × 3 mm). Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 1.

[Example 5]
The polymer compound (E) -2 obtained in Production Example 2 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a composition-5. Since 4.5 mol of the ethoxy group exists in (E) -2, 0.15 mol of sodium dodecylbenzenesulfonate containing Na mol number of 3.2% relative to the mol number was used.

Next, 20 parts by mass of the obtained composition-5 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a resin composition-5. The obtained resin composition-5 was performed in the same manner as in Example 1 to obtain a test piece (100 mm × 100 mm × 3 mm). Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 1.

[Example 6]
The polymer compound (E) -1 obtained in Production Example 1 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a composition-6. Due to the presence of 2.3 moles of the ethoxyl group in (E) -1, 0.077 moles of sodium dodecylbenzenesulfonate having a Na mole number of 3.4% relative to the mole number was used.

Next, 20 parts by mass of the obtained composition-6 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a resin composition-6. The obtained resin composition-6 was performed in the same manner as in Example 1 to obtain a test piece (100 mm × 100 mm × 3 mm). Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 1.

[Example 7]
The polymer compound (E) -1 obtained in Production Example 1 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a composition-7. Due to the presence of 2.3 moles of the ethoxyl group in (E) -1, 0.086 moles of sodium dodecylbenzenesulfonate containing a Na mole number of 3.8% relative to the mole number was used.

Next, 20 parts by mass of the obtained composition-7 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a resin composition-7. The obtained resin composition-7 was performed in the same manner as in Example 1 to obtain a test piece (100 mm × 100 mm × 3 mm). Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 2.

[Example 8]
The polymer compound (E) -3 obtained in Production Example 3 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a composition-8. Due to the presence of 2.3 moles of the ethoxy group in (E) -3, 0.086 moles of sodium dodecylbenzenesulfonate containing a Na mole number of 3.8% relative to the mole number was used.

Next, 20 parts by mass of the obtained composition-8 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a resin composition-8. The obtained resin composition-8 was performed in the same manner as in Example 1 to obtain a test piece (100 mm × 100 mm × 3 mm). Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 2.

[Example 9]
The polymer compound (E) -1 obtained in Production Example 1 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a composition-9. Due to the presence of 2.3 moles of the ethoxyl group in (E) -1, 0.095 moles of sodium dodecylbenzenesulfonate having a Na mole number of 4.2% relative to the mole number was used.

Next, 20 parts by mass of the obtained composition-9 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a resin composition-9. The obtained resin composition-9 was performed in the same manner as in Example 1 to obtain a test piece (100 mm × 100 mm × 3 mm). Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 2.

[Example 10]
The polymer compound (E) -1 obtained in Production Example 1 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a composition-10. Due to the presence of 2.3 moles of the ethoxyl group in (E) -1, 0.10 moles of sodium dodecylbenzenesulfonate having a Na mole number of 4.6% relative to the mole number was used.

Next, 20 parts by mass of the obtained composition-10 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a resin composition-10. The obtained resin composition-10 was performed in the same manner as in Example 1 to obtain a test piece (100 mm × 100 mm × 3 mm). Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 2.

[Example 11]
The polymer compound (E) -1 obtained in Production Example 1 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a composition -11. Due to the presence of 2.3 moles of the ethoxyl group in (E) -1, 0.11 mole of sodium dodecylbenzenesulfonate having a Na mole number of 5.0% relative to the mole number was used.

Next, 20 parts by mass of the obtained composition-11 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a resin composition-11. The obtained resin composition-11 was performed in the same manner as in Example 1 to obtain a test piece (100 mm × 100 mm × 3 mm). Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 2.

[Example 12]
The polymer compound (E) -1 obtained in Production Example 1 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a composition-12. Due to the presence of 2.3 moles of the ethoxy group in (E) -1, 0.12 moles of sodium dodecylbenzenesulfonate having a Na mole number of 5.4% relative to the mole number was used.

Next, 20 parts by mass of the obtained composition-12 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a resin composition-12. The obtained resin composition-12 was performed in the same manner as in Example 1 to obtain a test piece (100 mm × 100 mm × 3 mm). Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 2.

[Comparative Example 1]
The polymer compound (E) -1 obtained in Production Example 1 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a comparative composition-1. Due to the presence of 2.3 moles of the ethylenoxy group in (E) -1, 0.043 moles of sodium dodecylbenzenesulfonate having a Na mole number of 1.9% relative to the mole number was used.

Next, 20 parts by mass of the obtained comparative composition-1 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a comparative resin composition-1. The obtained comparative resin composition-1 was performed in the same manner as in Example 1 to obtain a test piece (100 mm × 100 mm × 3 mm). Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 3.

[Comparative Example 2]
The polymer compound (E) -1 obtained in Production Example 1 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a comparative composition-2. Due to the presence of 2.3 moles of the ethoxy group in (E) -1, 0.048 moles of sodium dodecylbenzenesulfonate having a Na mole number of 2.1% relative to the mole number was used.

Next, 20 parts by mass of the obtained comparative composition-2 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a comparative resin composition-2. The obtained comparative resin composition-2 was performed in the same manner as in Example 1 to obtain a test piece (100 mm × 100 mm × 3 mm). Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 3.

[Comparative Example 3]
The polymer compound (E) -1 obtained in Production Example 1 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a comparative composition-3. Due to the presence of 2.3 moles of the ethoxy group in (E) -1, 0.13 moles of sodium dodecylbenzenesulfonate having a Na mole number of 5.7% relative to the mole number was used.

Next, 20 parts by mass of the obtained comparative composition-3 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a comparative resin composition-3. The obtained comparative resin composition-3 was performed in the same manner as in Example 1 to obtain a test piece (100 mm × 100 mm × 3 mm). Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 3.

[Comparative Example 4]
The polymer compound (E) -1 obtained in Production Example 1 as the component (X) and sodium dodecylbenzenesulfonate (molecular weight 348.5) as the component (Y) were mixed to prepare a comparative composition-4. Due to the presence of 2.3 moles of the ethoxy group in (E) -1, 0.14 moles of sodium dodecylbenzenesulfonate having a Na mole number of 6.1% relative to the mole number was used.

Next, 20 parts by mass of the obtained comparative composition-4 was blended with 80 parts by mass of homopolypropylene (melt flow rate = 8) to obtain a comparative resin composition-4. The obtained comparative resin composition-4 was performed in the same manner as in Example 1 to obtain a test piece (100 mm × 100 mm × 3 mm). Using the obtained test piece, the processability and surface resistivity were evaluated by the following evaluation methods. The results are shown in Table 3.

＜ Processability evaluation method ＞
The surface of the obtained test piece was visually observed, and the area of the surface where silver streaks occurred was confirmed. The evaluation is to divide the surface of one test piece into 10 equal parts and evaluate the presence or absence of silver streaks with a 10% portion, and calculate the average value of 5 test pieces. 0% where silver streaks do not occur at all is the most excellent in workability, and 100% in all surfaces is the worst.

<Method for measuring surface resistivity (SR value)>
The obtained test piece was stored under the conditions of a temperature of 25 ° C. and a humidity of 50% RH immediately after the forming process, and was stored on the 1st and 30th days of the forming process. The R8340 resistance meter measures the surface resistivity (Ω / □) under the conditions of an applied voltage of 100V and an applied time of 1 minute. For the measurement system, five test pieces were used, and five points were performed per one piece to determine the average value.

It is clear from the results shown in the above Tables 1 to 3 that according to the present invention, it is possible to obtain a composition having excellent antistatic effect and durability, and further excellent processability.

Claims (9)

A composition comprising a component (X) composed of a polymer compound (E) and a component (Y) composed of a salt of an alkali metal, wherein The polymer compound (E) is a polymer compound obtained by reacting the polyester (a) and the compound (b) with an epoxy compound (D). The polyester (a) is a diol, an aliphatic dicarboxylic acid, and an aromatic compound. The polyester obtained by the reaction of a group dicarboxylic acid, the compound (b) is a compound having one or more ethoxy groups at both ends, and the epoxy compound (D) is a compound having two or more epoxy groups. Epoxy compound, The polymer compound has a block (A) of a polyester composed of the polyester (a) and a block (B) of a polyether composed of the compound (b), and has a transmission through the polyester The hydroxyl group or carboxyl group at the terminal of (a) and the ester or ether bond formed by the reaction of the hydroxyl group at the terminal of the compound (b) with the epoxy group of the epoxy compound (D) structure, The molar content of the component (Y) is within a range of 2.3 to 5.4% of the number of ethoxylated mols in the block (B) of the polyether in the polymer compound (E) of the component (X). . For example, the composition of claim 1, wherein the polymer compound (E) of the component (X) has a structure in which a block polymer (C) and the epoxy compound (D) are bonded through an ester bond, and the block The polymer (C) is a block polymer having a carboxyl group at both ends of the block (A) of the aforementioned polyester and the block (B) of the aforementioned polyether repeatedly and interactively bonded through an ester bond. For example, the composition of claim 1 or 2, wherein the polyester (a) constituting the block (A) of the polyester of the polymer compound (E) of the polymer compound (E) as described above has a structure having carboxyl groups at both ends. The composition according to claim 1 or 2, wherein the compound (b) of the block (B) constituting the polyether (B) of the polymer compound (E) as the component (X) is a polyethylene glycol. The composition according to claim 1 or 2, wherein the number average molecular weight of the compound (b) of the block (B) of the polyether block (B) of the polymer compound (E) of the component (X) is 400 to 10,000. The composition according to claim 2, wherein the number average molecular weight of the block polymer (C) in the polymer compound (E) of the component (X) is 5,000 to 30,000. A resin composition is characterized in that a thermoplastic resin is blended with the composition according to any one of claims 1 to 6. The resin composition according to claim 7, wherein the thermoplastic resin is one or more selected from the group consisting of a polyolefin resin, a polystyrene resin, and a copolymer thereof. A molded article characterized by being formed from a resin composition according to claim 7 or 8.