JP5090112B2 - Antistatic agent and resin composition containing the same - Google Patents

Description

  The present invention relates to a block polymer type antistatic agent for polyolefin. More specifically, the present invention relates to an antistatic agent that exhibits an antistatic effect by being kneaded and used in polyolefin.

  Antistatic agents that are kneaded into polyolefin and have an antistatic effect are roughly classified into low molecular types and high molecular types. Among these, the low molecular type has a problem in the stability of the effect and may not be preferable.

  On the other hand, as a polymer-type antistatic agent for polyolefin, the block polymer described in Patent Document 1 is known, but the required amount is large, and the influence on the resin physical properties is not preferable. It was.

The copolymer used in the present invention corresponds to the vicinal substituted functional group-containing polymer described in Patent Document 2. Patent Document 2 discloses the usefulness as an antistatic agent, but the amount added as an antistatic agent is not sufficiently low.
JP 2001-278985 A JP 2006-131870 A

  An object of the present invention is to provide a polymer-type antistatic agent that exhibits an antistatic effect when added in a small amount to polyolefin.

 The present invention includes the following inventions.

(I) The following general formula (1)

(In the formula, A is a group having a number average molecular weight of 400 to 1500 obtained by polymerization of an olefin having 2 to 20 carbon atoms, R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 18 carbon atoms and at least one of them. One is a hydrogen atom, and X ¹ and X ² are the same or different and each represents a group represented by the following general formula (2) or general formula (4) having a number average molecular weight of 50 to 1800. An antistatic agent comprising a terminal branched copolymer having a number average molecular weight of 2300 or less.
General formula (2):

(In the formula, E represents an oxygen atom or a sulfur atom, X ³ represents a polyalkylene glycol group,
Or the following general formula (3)

(In the formula, R ³ represents an m + 1 valent hydrocarbon group, G is the same or different, and is represented by -OX ⁴ , -NX ⁵ X ⁶ (X ^{4 to} X ⁶ represent a polyalkylene glycol group). Represents a group, and m represents the number of bonds of G and represents an integer of 1 to 10))
Or general formula (4)

(Wherein X ⁷ and X ⁸ are the same or different and each represents a polyalkylene glycol group or a group represented by the above general formula (3)).

( Ii ) In the terminal branched copolymer represented by the general formula (1), either X ¹ or X ² is represented by the following general formula (5).

(Wherein X ⁹ and X ¹⁰ are the same or different and each represents a polyalkylene glycol group, and Q ¹ and Q ² are the same or different and each represents a divalent alkylene group). Antistatic agent.

( Iii ) In the terminal branched copolymer represented by the general formula (1), both X ¹ and X ² are represented by the general formula (6).

The antistatic agent according to (i), which is a group represented by the formula (wherein X11 represents a polyalkylene glycol group).

(Iv) (i) ~ ( iii) and the antistatic agent according to any one of (i) ~ than terminally branched copolymer contained in the antistatic agent according to any one of (iii) A thermoplastic resin composition.

(V) the resin composition according to the antistatic agent 0.1 to 20% by weight and containing said heat 80 to 99.9% by weight thermoplastic resin (iv).

(Vi) of al alkali metal or alkaline earth metal salt, a surfactant, and contain at least one selected from the compatibilizer and the group consisting of polymeric antistatic agents other than the antistatic agents of the The resin composition according to (iv) or (v) .

According to the present invention, an antistatic agent that imparts an antistatic effect by adding a small amount to a polyolefin and an antistatic resin composition containing the same are provided.

  The present invention will be described below.

(In the formula, A is a group having a number average molecular weight of 400 to 1500 obtained by polymerization of an olefin having 2 to 20 carbon atoms, R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 18 carbon atoms and at least one of them. One is a hydrogen atom, and X ¹ and X ² are the same or different and each represents a group represented by the general formula (2) or the general formula (4) having a number average molecular weight of 50 to 1800.

  Examples of the olefin having 2 to 20 carbon atoms constituting A in the general formula (1) include α-olefins such as ethylene, propylene, 1-butene, and 1-hexene. As the polymer, these olefins may be used alone. It may be a polymer, a copolymer, or one copolymerized with another polymerizable unsaturated compound within a range that does not impair the characteristics. Among these olefins, ethylene, propylene, and 1-butene are particularly preferable.

  The number average molecular weight (Mn) of the group represented by A measured by gel permeation chromatography (hereinafter abbreviated as GPC) is 400-1500, preferably 500-1300. Here, the number average molecular weight (Mn) is a value in terms of polystyrene.

  The ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC of the group represented by A in the general formula (1), that is, the molecular weight distribution (Mw / Mn) is not particularly limited. Although there are 1.0 to several tens of materials, 4.0 or less, particularly 3.0 or less are preferable in terms of uniformity of physical properties.

The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the group represented by A by GPC can be measured under the following conditions using GPC-150 manufactured by Millipore, for example.
Separation column: TSK GNH HT (column size: diameter 7.5 mm, length: 300 mm)
Column temperature: 140 ° C
Mobile phase: Orthodichlorobenzene (Wako Pure Chemical Industries, Ltd.)
Antioxidant: Butylhydroxytoluene (manufactured by Takeda Pharmaceutical Company Limited) 0.025% by weight
Movement speed: 1.0 ml / min Sample concentration: 0.1% by weight
Sample injection volume: 500 microliters Detector: differential refractometer.

  The molecular weight of the group represented by A can be measured by measuring the molecular weight of a polyolefin having an unsaturated group at one end, which will be described later, and subtracting the molecular weight corresponding to the terminal.

R ¹ and R ² are hydrogen or a hydrocarbon group having 1 to 18 carbon atoms bonded to the double bond of the olefin constituting A, preferably hydrogen, methyl group, ethyl group, propyl group Etc.

In the general formula ^(1), X 1, ^{X 2} are the same or different, to display the group represented by the general formula of 50 to 1800 number average molecular weight, respectively (2) or general formula (4).

The number average molecular weight of the terminal branched copolymer represented by the general formula (1) is 2300 or less, preferably 550 to 2300, more preferably 800 to 2300, more preferably 800 to 2200, more preferably 800 to. 2100, more preferably 800-2000. The number average molecular weight is represented by the sum of the group represented by A, the number average molecular weights of X ¹ and X ² and the molecular weights of R1, R2 and C2H.

In the terminal branched copolymer represented by the general formula (1), X ¹ and X ² are the same or different, and the general formula (2)

(In the formula, E represents an oxygen atom or a sulfur atom, X ³ represents a polyalkylene glycol group,
Or the following general formula (3)

(In the formula, R ³ represents an m + 1 valent hydrocarbon group, G is the same or different, and is represented by -OX ⁴ , -NX ⁵ X ⁶ (X ^{4 to} X ⁶ represent a polyalkylene glycol group). Represents a group, and m represents the number of bonds of G and represents an integer of 1 to 10))
Or general formula (4)

(Wherein X ⁷ and X ⁸ are the same or different and represent a polyalkylene glycol group or a group represented by the above general formula (3)).

In the general formula (3), the group represented by R ³ is an m + 1 valent hydrocarbon group having 1 to 20 carbon atoms, and m is 1 to 10, preferably 1 to 6, and preferably 1 to 2. Is particularly preferred.

As a preferable example of the terminal branched copolymer represented by the general formula (1), either one of X ¹ and X ^{2 in} the general formula (1) is a group represented by the general formula (4). A certain terminal branched copolymer is mentioned. More preferable examples include a terminal branched copolymer in which ^one of X ¹ and X ² is represented by the general formula (4) and the other is a group represented by the general formula (2).

As another preferable example of the terminal branched copolymer represented by the general formula (1), ^one of X ¹ and X ^{2 in} the general formula (1) is a group represented by the general formula (2). Yes, more preferably, a terminal branched copolymer in which both X ¹ and X ² are groups represented by the general formula (2) can be mentioned.

As a more preferable structure of X ¹ and X ² represented by the general formula (4), the general formula (5)

Wherein X ⁹ and X ¹⁰ are the same or different and represent a polyalkylene glycol group, and Q ¹ and Q ² are the same or different and each represents a divalent hydrocarbon group. .

In the general formula (5), the divalent hydrocarbon group represented by Q ¹ and Q ² is a hydrocarbon group having 2 to 20 carbon atoms and may or may not have a substituent. Ethylene group, methylethylene group, ethylethylene group, dimethylethylene group, phenylethylene group, chloromethylethylene group, bromomethylethylene group, methoxymethylethylene group, aryloxymethylethylene group, propylene group, trimethylene group, tetramethylene group, Examples include a hexamethylene group and a cyclohexylene group. A preferable alkylene group is a hydrocarbon-based alkylene group, particularly preferably an ethylene group or a methylethylene group, and still more preferably an ethylene group. Q ¹ and Q ² may be one kind of alkylene group, or two or more kinds of alkylene groups may be mixed.

As a more preferable structure of X ¹ and X ² represented by the general formula (2), the general formula (6)

(Wherein X ¹¹ represents a polyalkylene glycol group).

The polyalkylene glycol group represented by X ^{3 to} X ¹¹ is a group obtained by addition polymerization of alkylene oxide. Examples of the alkylene oxide constituting the polyalkylene glycol group represented by X ^{3 to} X ¹¹ include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl A glycidyl ether etc. are mentioned. Of these, propylene oxide, ethylene oxide, butylene oxide, and styrene oxide are preferable. More preferred are propylene oxide and ethylene oxide, and particularly preferred is ethylene oxide. The polyalkylene glycol group represented by X ^{3 to} X ¹¹ may be a group obtained by homopolymerization of these alkylene oxides or a group obtained by copolymerization of two or more kinds. Examples of preferred polyalkylene glycol groups are polyethylene glycol groups, polypropylene glycol groups, or groups obtained by copolymerization of polyethylene oxide and polypropylene oxide, and particularly preferred groups are polyethylene glycol groups.

  The polymer of the present invention can be produced by the following method.

  First, as a polymer corresponding to the structure of A represented by the general formula (1) in the target polymer, the general formula (7)

(In the formula, A is a group having a number average molecular weight of 400 to 1500 obtained by polymerization of an olefin having 2 to 20 carbon atoms, R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least either of them. One of them represents a hydrogen atom.), And a polyolefin having a double bond at one end is produced.

This polyolefin can be produced by the following method.
(1) A transition metal compound having a salicylaldoimine ligand as shown in JP-A Nos. 2000-239312, 2001-27331, 2003-73412, etc. is used as a polymerization catalyst. Polymerization method.
(2) A polymerization method using a titanium catalyst comprising a titanium compound and an organoaluminum compound.
(3) A polymerization method using a vanadium catalyst comprising a vanadium compound and an organoaluminum compound.
(4) A polymerization method using a Ziegler-type catalyst comprising a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane).

  Among the above methods (1) to (4), particularly according to the method (1), the polyolefin can be produced with high yield. In the method (1), a polyolefin having a double bond at one end is produced by polymerizing or copolymerizing the olefin described above in the presence of the transition metal compound having the salicylaldoimine ligand. Can do.

The polymerization of the olefin by the method (1) can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Detailed conditions and the like are already known, and the above-mentioned patent documents can be referred to.

  The molecular weight of the polyolefin obtained by the method (1) can be adjusted by allowing hydrogen to be present in the polymerization system, changing the polymerization temperature, or changing the type of catalyst used.

  Next, the polyolefin is epoxidized, that is, the double bond at the terminal of the polyolefin is oxidized to obtain a polymer containing an epoxy group at the terminal represented by the general formula (8).

(In the formula, A, R ¹ and R ² are as described above.)

Although the epoxidation method is not particularly limited, the following methods can be exemplified.
(1) Oxidation with peracids such as performic acid, peracetic acid, perbenzoic acid (2) Oxidation with titanosilicate and hydrogen peroxide (3) Oxidation with rhenium oxide catalyst such as methyltrioxorhenium and hydrogen peroxide ( 4) Oxidation with a porphyrin complex catalyst such as manganese porphyrin or iron porphyrin and hydrogen peroxide or hypochlorite (5) Salen complex such as manganese Salen and oxidation with hydrogen peroxide or hypochlorite (6) Manganese- Oxidation with a TACN complex such as a triazacyclononane (TACN) complex and hydrogen peroxide (7) Oxidation with hydrogen peroxide in the presence of a group VI transition metal catalyst such as a tungsten compound and a phase transfer catalyst The above (1) to (7) Among these methods, the methods (1) and (7) are particularly preferable in terms of the active surface.

  For example, VIKOLOX ™ (registered trademark, manufactured by Arkema) can be used as the low molecular weight terminal epoxy group-containing polymer having a Mw of about 400 to 600.

  By reacting the terminal epoxy group-containing polymer represented by the general formula (8) obtained by the above-described method with various reaction reagents, the α-, β-positions of the polymer terminal as represented by the general formula (9) are obtained. A polymer (polymer (I)) into which various substituents Y1 and Y2 are introduced can be obtained.

(Wherein, A, R1, R2 are as defined above ^.Y 1, ^{Y 2} are the same or different hydroxyl, amino or the following general formula, (10a) ~ represents a (10c))

(In the formula, E represents an oxygen atom or a sulfur atom, R ³ represents an m + 1 valent hydrocarbon group, T represents the same or different hydroxyl group and amino group, m represents the number of bonds of T, Represents an integer of 10)

For example, by hydrolyzing the terminal epoxy group-containing polymer represented by the general formula (8), a polymer in which both Y ¹ and Y ² are hydroxyl groups in the general formula (9) is obtained, and ammonia is reacted. By doing so, a polymer in which ^one of Y ¹ and Y ² is an amino group and the other is a hydroxyl group is obtained.

In addition, by reacting the terminal epoxy group-containing polymer with the reaction reagent A represented by the general formula (11a), ^one of Y ¹ and Y ² in the general formula (9) is a group represented by the general formula (10a). A polymer having a hydroxyl group on the other side is obtained.

(In the formula, E, R3, T and m are as described above.)

Further, by reacting the terminal epoxy group-containing polymer with the reaction reagent B represented by the general formulas (11b) and (11c), ^one of Y ¹ and Y ² in the general formula (9) is represented by the general formula (10b) or A polymer having the group shown in (10c) and the other hydroxyl group is obtained.

(Wherein R ³ , T and m are as described above.)

  Examples of the reaction reagent A represented by the general formula (11a) include glycerin, pentaerythritol, butanetriol, dipentaerythritol, polypentaerythritol, dihydroxybenzene, and trihydroxybenzene.

  Examples of the reaction reagent B represented by the general formulas (11b) and (11c) include ethanolamine, diethanolamine, aminophenol, hexamethyleneimine, ethylenediamine, diaminopropane, diaminobutane, diethylenetriamine, N- (aminoethyl) propanediamine, and imino. Bispropylamine, spermidine, spermine, triethylenetetramine, polyethyleneimine and the like can be mentioned.

  Addition reactions of epoxy compounds with alcohols and amines are well known and can be easily performed by ordinary methods.

  The terminal branched copolymer represented by the general formula (1) can be produced by addition polymerization of alkylene oxide using the polymer (I) represented by the general formula (9) as a raw material. Examples of the alkylene oxide include propylene oxide, ethylene oxide, butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, and allyl glycidyl ether. Two or more of these may be used in combination. Of these, propylene oxide, ethylene oxide, butylene oxide, and styrene oxide are preferable. More preferred are propylene oxide and ethylene oxide.

  For the catalyst, polymerization conditions, etc., known ring-opening polymerization methods of alkylene oxides can be used. For example, Takayuki Otsu, “Chemistry of Revised Polymer Synthesis”, Kagaku Dojin, January 1971, p. . 172-180 discloses an example in which a polyol is obtained by polymerizing various monomers. Catalysts used for ring-opening polymerization include Lewis acids such as AlCl3, SbCl5, BF3, and FeCl3 for cationic polymerization, alkali metal hydroxides or alkoxides for anionic polymerization, and amines, as disclosed in the above documents. Alkali earth metal oxides, carbonates, alkoxides or alkoxides such as Al, Zn, Fe, etc. can be used for phosphazene catalysts and coordination anionic polymerization. Here, as the phosphazene catalyst, for example, an anion of a compound disclosed in JP-A-10-77289, specifically, a commercially available tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride is alkalinized. The thing made into the alkoxy anion using the metal alkoxide etc. can be utilized.

  When a reaction solvent is used, the polymer (I) can be inert to the alkylene oxide, alicyclic hydrocarbons such as n-hexane and cyclohexane, and aromatic hydrocarbons such as toluene and xylene. And ethers such as dioxane, and halogenated hydrocarbons such as dichlorobenzene.

  Except for the phosphazene catalyst, the catalyst is used in an amount of preferably 0.05 to 5 mol, more preferably 0.1 to 3 mol, relative to 1 mol of the starting polymer (I). The amount of the phosphazene catalyst used is preferably 1 × 10 −4 to 5 × 10 −1 mol, more preferably 5 × 10 −5 mol per mol of the polymer (I) from the viewpoint of polymerization rate, economy and the like. 4 to 1 × 10 −1 mol.

  The reaction temperature is usually 25 to 180 ° C., preferably 50 to 150 ° C., and the reaction time varies depending on the reaction conditions such as the amount of catalyst used, reaction temperature, reactivity of olefins, etc., but is usually several minutes to 50 hours. .

The number average molecular weight of the terminal branched copolymer of the compound represented by the general formula (1) is represented by the general formula (9).
Can be calculated from the number average molecular weight of the polymer (I) represented by the formula (1), the weight of the polymer (I) used for the polymerization, and the weight of the alkylene oxide to be polymerized.

  The terminal branched copolymer of the present invention (also referred to as a polymer), a resin composition containing the polymer, a resin composition containing the polymer and another thermoplastic resin other than the polymer are excellent. It has an antistatic action and is useful as an antistatic agent.

  The amount of the end-branched copolymer blended with other thermoplastic resins can be changed depending on the required performance, but in order to have sufficient antistatic properties and mechanical strength, the end-branched copolymer is Based on the total weight of the polymer and thermoplastic resin, 0.1 to 20 wt%, preferably 0.1 to 10 wt%, more preferably 0.2 to 5.0 wt%, still more preferably 0.2. ~ 2.5 wt%.

  In blending, a resin composition (master batch) containing a terminal branched copolymer in a high concentration may be formed in advance. At that time, the concentration of the terminal branched copolymer in the resin composition is desirably about 10 to 80% by weight based on the total weight of the terminal branched copolymer and the other thermoplastic resin.

  Examples of other thermoplastic resins in the resin composition include polyolefin resins such as polyethylene and polypropylene, polystyrene resins such as polystyrene and acrylonitrile / butadiene / styrene copolymers (ABS resins), polymethyl methacrylate, and polyacrylic acid. Acrylic resins such as butyl, rubbery (co) polymers such as polybutadiene and polyisoprene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyacetal resins, polycarbonate resins, thermoplastic polyurethane resins, fluorine resins, etc. Or a mixture of two or more thereof.

  The resin composition includes a group consisting of an alkali metal or alkaline earth metal salt, a surfactant, and another polymer antistatic agent (a polymer antistatic agent other than the antistatic agent by the polymer of the present invention). At least 1 sort (s) chosen from may be contained. According to these components, the antistatic property of the resin composition can be further improved.

  Examples of the alkali metal or alkaline earth metal salt include monocarboxylic acid or dicarboxylic acid having 1 to 20 carbon atoms (for example, formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.), and sulfonic acid having 1 to 20 carbon atoms (for example, Methanesulfonic acid, p-toluenesulfonic acid, etc.), alkali metals, alkaline earth metals and salts of organic acids such as thiocyanic acid, hydrohalic acids (eg hydrochloric acid, hydrobromic acid, etc.), hydrobromic acid, peroxy Preferred examples include salts of inorganic acids such as chloric acid, sulfuric acid and phosphoric acid. Among these, halides such as lithium chloride, sodium chloride and potassium chloride, acetates such as potassium acetate, and perchlorates such as potassium perchlorate are preferable.

  The content of the alkali metal or alkaline earth metal salt in the resin composition is usually 0.001 to 3% by weight, preferably 0.01 to 2% by weight, based on the total amount of the polymer or resin.

As the surfactant, nonionic, anionic, cationic or amphoteric surfactants can be used. Nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; polyethylene oxide, fatty acid esters of glycerin Polyanhydric alcohol type nonionic surfactants such as fatty acid ester of pentaerythritol, fatty acid ester of sorbit or sorbitan, alkyl ether of polyhydric alcohol, aliphatic amide of alkanolamine, etc. Is, for example, carboxylates such as alkali metal salts of higher fatty acids; sulfate esters such as higher alcohol sulfates, higher alkyl ether sulfates, alkylbenzes Sulfonates such as sulfonates, alkyl sulfonates, and paraffin sulfonates; and phosphate ester salts such as higher alcohol phosphates. Examples of cationic surfactants include alkyltrimethylammonium salts. And quaternary ammonium salts. Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaines and higher alkyldihydroxyethylbetaines, which can be used alone or Two or more types can be used in combination.
Among the surfactants, anionic surfactants are preferable, and sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates are particularly preferable.

  Content of surfactant in the said resin composition is 0.001 to 5 weight% normally with respect to a polymer or resin whole quantity, Preferably it is 0.01 to 3 weight%.

  As the other polymer antistatic agent, for example, a polymer type antistatic agent such as a known polyether ester amide can be used, and as a known polyether ester amide, for example, JP-A-7-10989 And polyether ester amides comprising a polyoxyalkylene adduct of bisphenol A described in 1. above.

  As the other polymer antistatic agent, a block polymer having a repeating structure in which the unit of bonding between the polyolefin block and the hydrophilic polymer block is 2 to 50 can be used, and examples thereof include a block polymer described in US6552131. .

  The content of the other polymer antistatic agent in the resin composition is usually 0 to 40% by weight, preferably 5 to 20% by weight, based on the total amount of the polymer or resin.

  Moreover, a compatibilizing agent may be contained in the resin composition. According to the compatibilizing agent, the compatibility between the polymer of the present invention and another thermoplastic resin can be improved. Examples of the compatibilizer include a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and a polyoxyalkylene group, such as And a polymer described in JP-A-258850, a modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, or a block polymer having a polyolefin portion and an aromatic vinyl polymer portion.

  The content of the compatibilizer in the resin composition is usually 0.1 to 15% by weight, preferably 1 to 10% by weight, based on the total amount of the polymer and the other thermoplastic resin.

Other resin additives can be arbitrarily added to the resin composition as long as the effects of the polymer of the present invention are not impaired depending on the application. Examples of such additives for resin include pigments, dyes, fillers, glass fibers, carbon fibers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, and antibacterial agents.
The antistatic agent comprising the terminally branched copolymer of the present invention is an additive of the resin composition, an alkali metal or alkaline earth metal salt, a surfactant, and other polymer charging agents. It may contain at least one selected from the group consisting of an inhibitor (polymer antistatic agent other than the antistatic agent by the polymer of the present invention), a compatibilizing agent, and other additives for resins.

  A molded body formed by molding the resin composition has excellent antistatic properties and good paintability and printability. Examples of the molding method of the resin composition include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.). Depending on the method, it can be formed by any method.

  Examples of the method for coating the molded body include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, immersion coating, roller coating, and brush coating. Examples of the paint that can be used include paints generally used for plastic coating such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint. Although a coating film thickness can be suitably selected according to the objective, it is 10-50 micrometers (dry film thickness) normally.

The method for printing on the molded body may be any printing method that is generally used for plastic printing, such as gravure printing, flexographic printing, screen printing, offset printing, and the like. Is mentioned. As the ink in these printings, those usually used for plastic printing can be used.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

The number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) were measured by GPC using the method described in the text. For the melting point (Tm), the peak top temperature obtained by measurement using DSC was employed.
1H-NMR was measured at 120 ° C. after completely dissolving the polymer in deuterated-1,1,2,2-tetrachloroethane serving as a lock solvent and a solvent in a measurement sample tube. The chemical shift was determined by setting the peak of deuterated-1,1,2,2-tetrachloroethane to 5.92 ppm and determining the chemical shift value of other peaks.

  As a base polymer of the antistatic resin composition, LLDPE (Linear Low Density Polyethylene) used Evolue SP2320, a prime polymer product.

  For kneading with a lab plast mill, a lab plast mill having a cell capacity of 60 ml was used. As for the kneading temperature, the external mold temperature was 180 ° C., the kneading time was 10 minutes, and the screw rotation speed was 100 rpm.

  The surface resistivity was measured according to JIS-K6911 after adjusting the state to 23 ± 2 ° C. and 50 ± 5% RH.

(Synthesis Example 1)
According to Synthesis Example 2 of JP-A-2006-131870, a terminal epoxy group-containing ethylene polymer (E-1) having Mw = 2058, Mn = 1118, Mw / Mn = 1.84 (GPC) was synthesized and used as a raw material. Using.

1H-NMR: δ (C2D2Cl4) 0.88 (t, 3H, J = 6.92 Hz), 1.18-1.66 (m), 2.38 (dd, 1H, J = 2.64, 5.28 Hz), 2.66 (dd, 1H, J = 4.29 , 5.28 Hz) 2.80-2.87 (m, 1H)
Melting point (Tm) 121 ℃

  A 1000 mL flask was charged with 84 g of terminal epoxy group-containing ethylene polymer (E-1) (75 mmol as Mn 1118), 39.4 g (375 mmol) of diethanolamine, and 150 g of toluene, and stirred at 150 ° C. for 4 hours. Thereafter, acetone was added while cooling to precipitate the reaction product, and the solid was collected by filtration. The obtained solid was stirred and washed once with an aqueous acetone solution and further three times with acetone, and then the solid was collected by filtration. Thereafter, the polymer (I-1) (Mn = 1223, A: a group formed by polymerization of ethylene (Mn = 1075) in the general formula (9) (Mn = 1075), R1 = R2 = by drying under reduced pressure at room temperature. A hydrogen atom, one of Y1 and Y2 was a hydroxyl group, and the other was a bis (2-hydroxyethyl) amino group).

1H-NMR: δ (C2D2Cl4) 0.88 (t, 3H, J = 6.6 Hz), 0.95-1.92 (m), 2.38-2.85 (m, 6H), 3.54-3.71 (m, 5H)
Melting point (Tm) 121 ℃

  Charge a polymer (I-1) 20.0g and toluene 100g to a 500mL flask equipped with a nitrogen inlet tube, thermometer, condenser, and stirrer, and heat it in an oil bath at 125 ° C while stirring. Dissolved in. After cooling to 90 ° C., 323 mg of 85% KOH previously dissolved in 5.0 g of water was added to the flask and mixed for 2 hours under reflux conditions. Thereafter, water and toluene were distilled off while gradually raising the temperature in the flask to 120 ° C. Further, while supplying a slight amount of nitrogen to the flask, the pressure in the flask was reduced, and the internal temperature was raised to 150 ° C. and maintained for 4 hours to further distill off water and toluene in the flask. After cooling to room temperature, the solidified solid in the flask was crushed and taken out.

A stainless steel 1.5 L pressure reactor equipped with a heating device, a stirring device, a thermometer, a pressure gauge, and a safety valve was charged with 18.0 g of the obtained solid and 200 g of dehydrated toluene, and the gas phase was replaced with nitrogen. Then, it heated up to 130 degreeC, stirring. After 30 minutes, 9.0 g of ethylene oxide was added, and the mixture was further maintained at 130 ° C. for 5 hours, and then cooled to room temperature to obtain a reaction product. The solvent is removed from the obtained reaction product by drying, and a terminal branched copolymer (T-1) (Mn = 1835, in formula (1), A: group formed by polymerization of ethylene (Mn = 1975) R1 = R2 = hydrogen atom, ^one of X ¹ and X ² is a group represented by the general formula (6) (X ¹¹ = polyethylene glycol group), and the other is a group represented by the general formula (5) (Q ¹ = Q ² = ethylene group, X ⁹ = X ¹⁰ = polyethylene glycol group)).

1H-NMR: δ (C2D2Cl4) 0.88 (3H, t, J = 6.8 Hz), 1.06-1.50 (m), 2.80-3.20 (m), 3.33-3.72 (m)
Melting point (Tm) 116 ° C

(Synthesis Example 2)
A terminal branched copolymer (T-2) (Mn = 2446) was obtained in the same manner as in Synthesis Example 1 except that the amount of ethylene oxide used was changed to 18.0 g.

(Synthesis Example 3)
According to Synthesis Example 8 of JP-A-2006-131870, a terminal epoxy group-containing ethylene-propylene copolymer (E-2) having Mw = 1576, Mn = 843, and Mw / Mn = 1.87 (GPC) is obtained. Synthesized and used as raw material.

1H-NMR: δ (C2D2Cl4) 0.80-0.88 (m), 0.9-1.6 (m), 2.37-2.40 (1H, dd, J = 2.97, 5.28 Hz), 2.50 (m), 2.66 (1H, dd, J = 3.96, 5.28 Hz) 2.80-2.86 (1H, m), 2.95 (m)
Mw = 1576 Mw / Mn = 1.87 (GPC)
Melting point (Tm) 107 ℃

In Synthesis Example 1, the same procedure except that 63.2 g of a terminal epoxy group-containing ethylene-propylene copolymer (E-2) (75 mmol as Mn = 843) is used instead of the terminal epoxy group-containing polymer (E-1). Polymer (I-2) (Mn = 948, in general formula (9), A: group formed by copolymerization of ethylene and propylene (Mn = 800), R ¹ , R ² : one is a hydrogen atom And the other was a hydrogen atom or a methyl group, ^one of Y ¹ and Y ² was a hydroxyl group, and the other was a bis (2-hydroxyethyl) amino group.

1H-NMR: δ (C2D2Cl4) 0.80-0.90 (m), 0.90-1.56 (m), 2.46 (dd, 1H, J = 9.2, 13.5 Hz), 2.61 (dd, 1H, J = 3.3, 13.5 Hz), 2.61-2.84 (m, 4H), 3.58-3.68 (m, 5H)
Melting point (Tm) 106 ℃

In the same manner as in Synthesis Example 1, except that (I-2) is used instead of the polymer (I-1) and the amount of 85% KOH used is 418 mg, a terminal branched copolymer (T-3) is used. (Mn = 1422, in formula (1), A: a group formed by copolymerization of ethylene and propylene (Mn = 800), R ¹ , R ² : one is a hydrogen atom and the other is a hydrogen atom or a methyl group, X ¹ or X ² is a group represented by the general formula (6) (X ¹¹ = polyethylene glycol group), and the other is a group represented by the general formula (5) (Q ¹ = Q ² = ethylene group, X ⁹ = X ¹⁰ = polyethylene glycol group)).

1H-NMR: δ (C2D2Cl4) 0.83-0.92 (m), 1.08-1.50 (m), 2.70-3.00 (m), 3.55
-3.69 (m)
Melting point (Tm) 105 ° C

(Synthesis Example 4)
In Synthesis Example 1, (I-2) was used instead of the polymer (I-1), the amount used of 85% KOH was changed to 418 mg, and the amount of ethylene oxide used was changed to 18.0 g. A branched copolymer (T-4) (Mn = 1896) was obtained.

1H-NMR: δ (C2D2Cl4) 0.83-0.92 (m), 1.08-1.50 (m), 2.70-3.00 (m), 3.55-3.69 (m)
Melting point (Tm) 102 ° C

(Synthesis Example 5)
In Synthesis Example 1, (I-2) was used instead of the polymer (I-1), the amount used of 85% KOH was changed to 418 mg, and the amount of ethylene oxide used was changed to 36.0 g. A branched copolymer (T-5) (Mn = 2844) was obtained.

(Synthesis Example 6)
According to Example 20 of JP-A No. 2006-131870, polymer (I-3) (Mn = 1136, in general formula (9), A: group formed by polymerization of ethylene (Mn = 1075), R ¹ = R ² = Hydrogen atom, Y ¹ and Y ² are both hydroxyl groups) were synthesized and used as raw materials.

1H-NMR δ (C2D2Cl4) 0.89 (3H, t, J = 6.92 Hz), 1.05-1.84 (m), 3.41 (2H, dd, J = 5.94, 9.89 Hz), 3.57-3.63 (1H, m)

In Synthesis Example 1, a terminal branched copolymer (T-) was prepared in the same manner except that (I-3) was used instead of the polymer (I-1) and the amount of 85% KOH was 308.1 mg. 6) (Mn = 1704, in formula (1), A: group formed by polymerization of ethylene (Mn = 1075), R1, R2: both are hydrogen atoms, both X1 and X2 are in formula (6) The group shown (X11 = polyethylene glycol group) was obtained.

1H-NMR δ (C2D2Cl4) 0.88 (3H, t, J = 6.6 Hz), 1.04-1.47 (m), 3.32-3.69 (m)
Melting point (Tm) 119 ℃

(Synthesis Example 7)
A terminal branched copolymer (T-7) (Mn = 2038) was obtained in the same manner as in Synthesis Example 1 except that the amount of ethylene oxide used was changed to 12.0 g.

(Synthesis Example 8)
A terminal branched copolymer (T-8) (Mn = 2181) was obtained in the same manner as in Synthesis Example 1 except that the amount of ethylene oxide used was changed to 14.1 g.

(Synthesis Example 9)
In the same manner as in Synthesis Example 3, a terminal epoxy group-containing ethylene-propylene copolymer (E-2) was synthesized and used as a raw material.

A 1000 mL flask was charged with 75.0 g of a terminal epoxy group-containing ethylene-propylene copolymer (E-2) (89 mmol as Mn = 843) and 270 g of toluene, dissolved by heating under reflux of toluene, and then 30 g of formic acid ( 1 mol) was slowly added and stirred for 8 hours, and 100 g of warm water was added to separate the aqueous layer. Thereafter, 75 g (KOH 66.8 mmol) of 5% KOH / n-BuOH was slowly added at 90 ° C., stirred at 115 ° C. for 2 hours, cooled to 80 ° C., acetonitrile was added to precipitate the reaction product, The solid was collected by filtration. The obtained solid was stirred and washed once with an aqueous methanol solution and three times with methanol, and then the solid was collected by filtration and dried at 60 ° C. under reduced pressure to obtain polymer (I-4) (Mn = 861, general In formula (9), A: a group formed by copolymerization of ethylene and propylene (Mn = 800), R ¹ , R ² : one is a hydrogen atom and the other is a hydrogen atom or a methyl group, both Y ¹ and Y ² Was a hydroxyl group).

1H-NMR: δ (C2D2Cl4) 0.80-0.90 (m), 0.90-1.62 (m), 3.40 (dd, 1H, J = 6.9, 10.2 Hz), 3.50-3.68 (m, 2H)
Melting point (Tm) 108 ℃

In Synthesis Example 1, a terminal branched copolymer (T-) was prepared in the same manner except that (I-4) was used instead of the polymer (I-1) and the amount of 85% KOH was 406.5 mg. 9) (Mn = 1292, in formula (1), A: group formed by copolymerization of ethylene and propylene (Mn = 800), R ¹ , R ² : one is a hydrogen atom and the other is a hydrogen atom or a methyl group , X ¹ and X ² are both groups represented by the general formula (6) (X ¹¹ is a polyethylene glycol group).

1H-NMR: δ (C2D2Cl4) 0.84-0.91 (m), 1.01-1.61 (m), 3.30-3.74 (m)
Melting point (Tm) 102 ° C

[Example 1]
40.5 g of LLDPE, 4.5 g of terminal branched copolymer (T-1), and 90 mg of potassium acetate are mixed and kneaded at 180 ° C. for 10 minutes using a lab plast mill, and a master batch (MT-1) is prepared. Obtained. Further, 40.5 g of LLDPE and 4.5 g of master batch (MT-1) were kneaded at 180 ° C. for 10 minutes using a lab plast mill, and a resin composition in which 1 wt% of (T-1) was added to LLDPE. Obtained. 7.0 g of the obtained resin composition was preheated in a vacuum state at 170 ° C. for 3 minutes using a vacuum press apparatus, and then pressed at 170 ° C. for 2 minutes to obtain a circular sheet sample having a thickness of 500 μm. When the surface specific resistance value of the obtained circular sheet sample was measured, it was 5.8 × 10 ¹² Ω.

[Comparative Example 1]
To 40.5 g of LLDPE, 4.5 g of a terminal branched copolymer (T-2) and 135 mg of potassium acetate are mixed and kneaded at 180 ° C. for 10 minutes using a lab plast mill. ) Further, 40.5 g of LLDPE and 4.5 g of master batch (MT-2) were kneaded at 180 ° C. for 10 minutes using a lab plast mill to obtain a resin composition in which 1 wt% of (T-2) was added to LLDPE. It was. 7.0 g of the obtained resin composition was preheated in a vacuum state at 170 ° C. for 3 minutes using a vacuum press apparatus, and then vacuum pressed at 170 ° C. for 2 minutes to obtain a circular sheet sample having a thickness of 500 μm. When the surface specific resistance value of the obtained circular sheet sample was measured, it was 1.7 × 10 ¹⁵ Ω.

[Example 2]
To 40.5 g of LLDPE, 4.5 g of a terminal branched copolymer (T-3) and 90 mg of potassium acetate are mixed and kneaded at 180 ° C. for 10 minutes using a lab plast mill. ) Further, 40.5 g of LLDPE and 4.5 g of master batch (MT-3) were kneaded at 180 ° C. for 10 minutes using a lab plast mill to obtain a resin composition in which 1 wt% of (T-3) was added to LLDPE. It was. 7.0 g of the obtained resin composition was preheated in a vacuum state at 170 ° C. for 3 minutes using a vacuum press apparatus, and then pressed at 170 ° C. for 2 minutes to obtain a circular sheet sample having a thickness of 500 μm. When the surface specific resistance value of the obtained circular sheet sample was measured, it was 9.2 × 10 ¹¹ Ω.

[Example 3]
To 40.5 g of LLDPE, 4.5 g of a terminal branched copolymer (T-4) and 135 mg of potassium acetate are mixed and kneaded at 180 ° C. for 10 minutes using a lab plast mill. ) Further, 40.5 g of LLDPE and 4.5 g of master batch (MT-4) were kneaded at 180 ° C. for 10 minutes using a lab plast mill to obtain a resin composition in which 1 wt% of (T-4) was added to LLDPE. It was. 7.0 g of the obtained resin composition was preheated in a vacuum state at 170 ° C. for 3 minutes using a vacuum press apparatus and then pressed at 170 ° C. for 2 minutes to obtain a circular sheet sample having a thickness of 500 μm. When the surface resistivity of the obtained circular sheet sample was measured, it was 8.3 × 10 ¹² Ω.

[Example 4]
Resin in which 2.25 g of (MT-4) obtained in Example 3 and 42.75 g of LLDPE were kneaded at 180 ° C. for 10 minutes using a Laboplast mill, and 0.5 wt% of (T-4) was added to LLDPE. A composition was obtained. 7.0 g of the obtained resin composition was preheated in a vacuum state at 170 ° C. for 3 minutes using a vacuum press apparatus, and then pressed at 170 ° C. for 2 minutes to obtain a circular sheet sample having a thickness of 500 μm. When the surface specific resistance value of the obtained circular sheet sample was measured, it was 3.5 × 10 ¹² Ω.

[Comparative Example 2]
To 40.5 g of LLDPE, 4.5 g of a terminal branched copolymer (T-5) and 180 mg of potassium acetate are mixed, and kneaded at 180 ° C. for 10 minutes using a lab plast mill. ) Furthermore, 40.5 g of LLDPE and 4.5 g of master batch (MT-5) were kneaded at 180 ° C. for 10 minutes using a lab plast mill to obtain a resin composition in which 1 wt% of (T-5) was added to LLDPE. It was. 7.0 g of the obtained resin composition was preheated in a vacuum state at 170 ° C. for 3 minutes using a vacuum press apparatus and then pressed at 170 ° C. for 2 minutes to obtain a circular sheet sample having a thickness of 500 μm. When the surface specific resistance value of the obtained circular sheet sample was measured, it was 1.1 × 10 ¹⁶ Ω.

[Comparative Example 3]
Resin in which 2.25 g of (MT-5) obtained in Comparative Example 2 and 42.75 g of LLDPE were kneaded at 180 ° C. for 10 minutes using a lab plast mill, and 0.5 wt% of (T-5) was added to LLDPE. A composition was obtained. 7.0 g of the obtained resin composition was preheated in a vacuum state at 170 ° C. for 3 minutes using a vacuum press apparatus and then pressed at 170 ° C. for 2 minutes to obtain a circular sheet sample having a thickness of 500 μm. When the surface specific resistance value of the obtained circular sheet sample was measured, it was 6.3 × 10 ¹⁵ Ω.

[Example 5]
To 40.5 g of LLDPE, 4.5 g of a terminal branched copolymer (T-6) and 90 mg of potassium acetate are mixed, kneaded at 180 ° C. for 10 minutes using a lab plast mill, and master batch (MT-6). ) Further, 40.5 g of LLDPE and 4.5 g of master batch (MT-6) were kneaded at 180 ° C. for 10 minutes using a lab plast mill to obtain a resin composition in which 1 wt% of (T-6) was added to LLDPE. It was. 7.0 g of the obtained resin composition was preheated in a vacuum state at 170 ° C. for 3 minutes using a vacuum press apparatus, and then pressed at 170 ° C. for 2 minutes to obtain a circular sheet sample having a thickness of 500 μm. The surface resistivity of the obtained circular sheet sample was measured and found to be 6.1 × 10 ¹¹ Ω.

[Example 6]
Resin in which 2.25 g of (MT-6) obtained in Example 5 and 42.75 g of LLDPE were kneaded at 180 ° C. for 10 minutes using a Laboplast mill, and 0.5 wt% of (T-6) was added to LLDPE. A composition was obtained. 7.0 g of the obtained resin composition was preheated in a vacuum state at 170 ° C. for 3 minutes using a vacuum press apparatus, and then pressed at 170 ° C. for 2 minutes to obtain a circular sheet sample having a thickness of 500 μm. When the surface specific resistance value of the obtained circular sheet sample was measured, it was 2.6 × 10 ¹² Ω.

[Example 7]
1.125 g of (MT-6) obtained in Example 5 and 43.875 g of LLDPE were kneaded at 180 ° C. for 10 minutes using a lab plast mill, and 0.25 wt% of (T-6) was added to LLDPE. A composition was obtained. 7.0 g of the obtained resin composition was preheated in a vacuum state at 170 ° C. for 3 minutes using a vacuum press apparatus and then pressed at 170 ° C. for 2 minutes to obtain a circular sheet sample having a thickness of 500 μm. When the surface specific resistance value of the obtained circular sheet sample was measured, it was 1.0 × 10 ¹³ Ω.

[Example 8]
To 40.5 g of LLDPE, 4.5 g of a terminal branched copolymer (T-7) and 108 mg of potassium acetate were mixed, kneaded at 180 ° C. for 10 minutes using a lab plast mill, and master batch (MT-7). )
Furthermore, 40.5 g of LLDPE and 4.5 g of master batch (MT-7) were kneaded at 180 ° C. for 10 minutes using a lab plast mill to obtain a resin composition in which 1 wt% of (T-7) was added to LLDPE. It was.
7.0 g of the obtained resin composition was preheated in a vacuum state at 170 ° C. for 3 minutes using a vacuum press apparatus, and then pressed at 170 ° C. for 2 minutes to obtain a circular sheet sample having a thickness of 500 μm. When the surface specific resistance value of the obtained circular sheet sample was measured, it was 1.5 × 10 ¹¹ Ω.

[Example 9]
Resin in which 2.25 g of (MT-7) obtained in Example 8 and 42.75 g of LLDPE were kneaded at 180 ° C. for 10 minutes using a Laboplast mill, and 0.5 wt% of (T-7) was added to LLDPE. A composition was obtained. 7.0 g of the obtained resin composition was preheated in a vacuum state at 170 ° C. for 3 minutes using a vacuum press apparatus and then pressed at 170 ° C. for 2 minutes to obtain a circular sheet sample having a thickness of 500 μm. When the surface specific resistance value of the obtained circular sheet sample was measured, it was 3.2 × 10 ¹¹ Ω.

[Example 10]
To 40.5 g of LLDPE, 4.5 g of a terminal branched copolymer (T-8) and 118 mg of potassium acetate are mixed, kneaded at 180 ° C. for 10 minutes using a lab plast mill, and a master batch (MT-8). )
Further, 40.5 g of LLDPE and 4.5 g of master batch (MT-8) were kneaded at 180 ° C. for 10 minutes using a lab plast mill to obtain a resin composition in which 1 wt% of (T-8) was added to LLDPE. It was. 7.0 g of the obtained resin composition was preheated in a vacuum state at 170 ° C. for 3 minutes using a vacuum press apparatus, and then pressed at 170 ° C. for 2 minutes to obtain a circular sheet sample having a thickness of 500 μm. When the surface specific resistance value of the obtained circular sheet sample was measured, it was 3.1 × 10 ¹¹ Ω.

[Example 11]
Resin in which 2.25 g of (MT-8) obtained in Example 10 and 42.75 g of LLDPE were kneaded at 180 ° C. for 10 minutes using a Laboplast mill, and 0.5 wt% of (T-8) was added to LLDPE. A composition was obtained. 7.0 g of the obtained resin composition was preheated in a vacuum state at 170 ° C. for 3 minutes using a vacuum press apparatus and then pressed at 170 ° C. for 2 minutes to obtain a circular sheet sample having a thickness of 500 μm. The surface resistivity of the obtained circular sheet sample was measured and found to be 7.2 × 10 ¹¹ Ω.

[Example 12]
To 40.5 g of LLDPE, 4.5 g of a terminal branched copolymer (T-9) and 90 mg of potassium acetate are mixed, kneaded at 180 ° C. for 10 minutes using a lab plast mill, and master batch (MT-9). ) Furthermore, 40.5 g of LLDPE and 4.5 g of master batch (MT-9) were kneaded at 180 ° C. for 10 minutes using a lab plast mill to obtain a resin composition in which 1 wt% of (T-9) was added to LLDPE. It was. 7.0 g of the obtained resin composition was preheated in a vacuum state at 170 ° C. for 3 minutes using a vacuum press apparatus, and then pressed at 170 ° C. for 2 minutes to obtain a circular sheet sample having a thickness of 500 μm. When the surface specific resistance value of the obtained circular sheet sample was measured, it was 1.3 × 10 ¹² Ω.

  The antistatic agent comprising the terminally branched copolymer of the present invention is useful as an antistatic agent that imparts sufficient antistatic ability to a polyolefin with a lower additive amount than before. The antistatic polyolefin has improved processability and handleability, and is advantageous during production and use. Further, when used as a molded product, dust adhesion due to static electricity can be suppressed.

Claims (6)

The following general formula (1)

(In the formula, A is a group having a number average molecular weight of 400 to 1500 obtained by polymerization of an olefin having 2 to 20 carbon atoms, R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 18 carbon atoms and at least one of them. one is a hydrogen atom, ^{X 1} and ^{X 2} are, unlike the same or different, represents a group represented by the following formula having a number average molecular weight, respectively from 50 to 1,800 (2) or general formula (4).)
An antistatic agent comprising a terminal branched copolymer having a number average molecular weight of 2300 or less.
General formula (2):

(In the formula, E represents an oxygen atom or a sulfur atom, and X ³ represents a polyalkylene glycol group or a group represented by the following general formula (3).)

(In the formula, R ³ represents an m + 1 valent hydrocarbon group, G is the same or different, and is represented by —OX ⁴ , —NX ⁵ X ⁶ (X ^{4 to} X ⁶ represent a polyalkylene glycol group). And m is the number of bonds of G and represents an integer of 1 to 10.)
General formula (4):

(In the formula, X ⁷ and X ⁸ are the same or different and represent a polyalkylene glycol group or a group represented by the general formula (3).) In the terminal branched copolymer represented by the general formula (1), either X ¹ or X ² is represented by the following general formula (5).

(In the formula, X ⁹ and X ¹⁰ are the same or different and each represents a polyalkylene glycol group, and Q ¹ and Q ² are the same or different and each represents a divalent alkylene group . )
The antistatic agent according to claim 1. In the terminal branched copolymer represented by the general formula (1), at least one of X ¹ and X ² is represented by the general formula (6).

(In the formula, X ¹¹ represents a polyalkylene glycol group . )
The antistatic agent according to claim 1. And a claim from 1 to 3 of any thermoplastic resin other than the terminally branched copolymer contained in the antistatic agent according to any one of the antistatic agent according to claim 1-3, wherein one Section Resin composition. The resin composition of claim 4 comprising said antistatic agent 0.1 to 20% by weight and said thermoplastic resin 80 to 99.9 wt%. Alkali metal or alkaline earth metal salt of al, surfactants, comprising at least one selected from the group consisting of polymeric antistatic agents other than the compatibilizing agent and before Symbol band antistatic agent according Item 6. The resin composition according to Item 4 or 5 .