JP2000192016A - Antistatic agent and antistatic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin with an antistatic effect and its durability, as well as excellent weather resistance. SOLUTION: An antistatic agent containing cerium oxide and polyetherester is blended with a thermoplastic resin such as ABS and PMMA.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic agent which is extremely excellent in antistatic effect, durability of antistatic effect, transparency and weather resistance, and an antistatic resin composition containing the same.

[0002]

2. Description of the Related Art Thermoplastic resins are generally lightweight and have excellent moldability, and are also excellent in heat resistance, mechanical properties and electrical properties, and are also excellent in aesthetics. It is used in large quantities for various applications such as automotive parts and packaging materials. However, thermoplastic resin is inferior in antistatic properties, so dust easily adheres to products using it due to static electricity, which impairs aesthetic appearance, or electric products, electrical equipment and automobile drive equipment malfunction due to charged static electricity Has the drawback of rubbing. In order to improve these drawbacks, it is customary to add various antistatic agents, particularly a permanent antistatic agent having a high sustaining effect, to the thermoplastic resin. As such a permanent antistatic agent, for example, JP-A-9-59601 discloses a polyether obtained by reacting a poly (alkylene oxide) glycol, a monoglycol and a sulfonated metal salt of phthalic acid or an ester thereof. Ester antistatic agents are described.

[0003]

However, when the polyetherester-based antistatic agent described in JP-A-9-59601 is used, there is a drawback when the antistatic effect is reduced by light irradiation or the like. . The problem to be solved by the present invention is to impart excellent weather resistance to the thermoplastic resin, together with the antistatic effect and its durability,
For a transparent thermoplastic resin, an antistatic agent that does not impair transparency, as well as having excellent antistatic properties and weather resistance, and impairing transparency when using a transparent thermoplastic resin The present invention provides an antistatic resin composition free of any problem.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by adding cerium oxide to a polyetherester-based antistatic agent, transparency is not impaired and weather resistance is improved. The inventors have found that the present invention is excellent and can exhibit an antistatic effect continuously, and have completed the present invention.

That is, the present invention provides an antistatic agent comprising a cerium compound (A) and a polyetherester (B) as essential components, and the antistatic agent and a thermoplastic resin as essential components. The present invention relates to an antistatic resin composition characterized by the above.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The cerium compound (A) compounded as an essential component in the antistatic agent of the present invention is an inorganic compound containing a cerium atom as a constituent element, and is not particularly limited. , Hydrides such as CeH ₃ , Ce
Cerium oxide such as O ₂ , Ce ₂ O ₃ , Ce (OH) ₃ , Ce
(OH) _{4 and} other cerium hydroxides, Ce ₂ S _{3 and} other cerium sulfides, CeF ₃ , CeF ₄ , CeCl ₃ , CeBr ₃ , Ce
Cerium halides such as I ₃ , Ce (SO ₄ ) ₂ , Ce
₂ (SO ₄₎ cerium sulfate ₃ etc., Ce (NO ₃₎ cerium nitrate ₃ etc., Ce ₂ (CO _{3) 3} cerium carbonate such as, (C ₅
H ₅ NH) ₂ CeCl _6, such as _{Ce (NO 3) · 2NH 4} NO 3 , etc. of the complex or double salt and the like. Among these, cerium oxide is preferred because the effect of improving weather resistance is particularly remarkable.

[0007] When cerium oxide is used as the cerium compound (A), the particles are composite particles of cerium oxide and another inorganic compound and whose surface is coated with amorphous silica (hereinafter referred to as "particles"). (Abbreviated as “particle (A ′)”) is preferred from the viewpoint of dispersibility in polyetherester (B) and moldability, and the effects of the present invention can be further improved.

Here, the inorganic compound to be complexed with cerium oxide is not particularly limited, but silica or talc is preferable from the viewpoint of transparency and color tone of the molded article.

Here, the shape of the particles (A ′) is not particularly limited, but the average particle diameter is 0.05 to 5.0 μm.
m is preferable. Those having a thickness of 0.05 μm or more are easy to produce, have an excellent production cost, and have good dispersibility in the polyetherester (B). On the other hand, 5.0 μ
If m or less, the ultraviolet absorbing effect is improved, the effect of imparting weather resistance is remarkable, and the color tone of the molded product is also excellent.

The ratio of cerium oxide to silica (excluding amorphous silica covering the surface) or talc in the particles (A ′) is not particularly limited, but is 10:90 to 80 by weight. : 20 is preferable from the viewpoint of not blocking the ultraviolet ray blocking effect and the brightness of the polyetherester.

The amount of the amorphous silica coating the surface of the particles is preferably from 5 to 70% by weight of the particles from the viewpoint of the effect of blocking ultraviolet rays and the mechanical strength of the particles.

The mixing ratio of the cerium compound (A) and the polyetherester (B) in the antistatic agent of the present invention is not particularly limited, but when used as the particles (A '), the particles (A') When the content of the particles (A ′) is in the range of 0.01 to 30% by weight based on the total weight of both of the polyetheresters (B), from the viewpoint of excellent antistatic properties, transparency, weather resistance, and the like. preferable.

The polyether ester (B) used as the antistatic agent of the present invention is not particularly limited, but has a polyether structure site and a polyester structure site in the molecular structure. .

The polyether structural site is not particularly limited, but may be a polyethylene oxide structural unit, poly-
1,2-propylene oxide structural unit, poly-1,3-
Propylene oxide structural unit, polytetramethylene oxide structural unit, poly-hexamethylene oxide structural unit, poly-hexafluoroethylene oxide structural unit,
Polyether structural units such as poly-hexafluoropropylene oxide structural units, ethylene oxide and propylene oxide block or random copolymer structural units, and ethylene oxide and tetrahydrofuran block or random copolymer structural units, or terminal hydroxyl groups of bisphenols And a poly (alkylene oxide) glycol-added structural unit of a bisphenol to which the above-mentioned polyether structural unit is bonded.

The content of the polyether structural unit in the polyether ester (B) is preferably such that the polyether structural site is contained in a ratio of 40 to 85% by weight based on the raw material weight. Here, the raw material weight ratio is a ratio of the weight of poly (alkylene oxide) glycol as a constituent raw material of the polyether structure site to the weight of the polyether ester (B). Here, when the content is 40% by weight or more, the antistatic effect of the polyether ester is remarkably good. On the other hand, when the content is 85% by weight or less, the obtained polyether ester has good mechanical properties and heat resistance.

The ester structure site in the polyetherester is a structure portion derived from the carboxyl group-containing compound as a raw material and the raw material carboxylic acid forming the ester bond. Although not limited, the ratio of the weight of the carboxylic acid as a constituent material of the polyester structural portion to the weight of the polyetherester (B) is 1 to 60.
It is preferable that the ratio be a percentage by weight.

That is, when the amount is 1% by weight or more, the mechanical properties and heat resistance of the molded article become good, and when it is 60% by weight or less, the obtained polyetherester (B) has a good antistatic effect. In particular, the range of 10 to 60% by weight is preferable from the viewpoint of excellent balance between them.

The polyetherester (B) preferably has a sulfonate group in the molecular structure, since the antistatic effect becomes more remarkable. here,
The sulfonate group is, for example, one represented by the following general formula 1.

[0019]

## STR1 ## where M is an alkali metal or an alkaline earth metal, particularly preferably Na, K, Li, Mg, Ca or the like.

The content of the sulfonic acid salt is not particularly limited, but the sulfonic acid salt group present in the polyether ester is converted to the weight of the raw material monomer. (B) It is preferable from the viewpoint of the effect of improving the antistatic property that the ratio is 0.1 to 10% by weight based on the weight.

Such a polyetherester (B) is
Although not particularly limited, a polycondensate of a poly (alkylene oxide) glycol component (b1), a polyvalent carboxylic acid component (b2) and a dihydroxy compound component (b3) is preferable. Therefore, in this case, the ester structure site is a polyether structure site derived from the poly (alkylene oxide) glycol component (b1), and the ester structure site is the polyvalent carboxylic acid component (b2)
And an ester structure site.

The molecular weight of such polyetherester polycondensate (B) is not particularly limited, but from the viewpoints of dispersibility as an antistatic agent, antistatic effect, and transparency, the number average molecular weight. 1,000-1,000,000
0, particularly preferably 10,000 to 500,000.

The production method of such polyetherester polycondensate is not particularly limited. Examples of the method include: (b1) a poly (alkylene oxide) glycol component, and (b2) a polyvalent carboxylic acid component. (B3) a method of reacting a dihydroxy compound component as an essential component.

Further, as described above, when a metal sulfonate is introduced into the molecular structure of the polyetherester (B) in order to improve the antistatic effect, the method is as follows: (b1) Poly (alkylene oxide) glycol component (B2) a polyvalent carboxylic acid component; (b3) a dihydroxy compound component; and (b4) a method of reacting a sulfonated metal phthalate or an alkyl ester thereof as an essential component.

Here, the poly (alkylene oxide) glycol component (b1) is not particularly limited, but may be a poly (alkylene oxide) glycol or a poly (alkylene oxide) glycol adduct of bisphenols. It is preferable from the viewpoint of antistatic effect and mechanical strength.

Examples of the poly (alkylene oxide) glycol include poly (ethylene oxide) glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, and poly (tetramethylene oxide) glycol. Hexamethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran. These may be used alone or in combination of two or more.

The bisphenols in the poly (alkylene oxide) glycol adduct of bisphenols are not particularly limited. For example, bisphenol A, bisphenol S, fluorinated bisphenol A, chlorinated bisphenol A, brominated bisphenol A, 4,4-bis (hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) methane, bis (4
Examples thereof include -hydroxyphenyl) ether and bis (4-hydroxyphenyl) amine, and among them, a compound having a bisphenol A skeleton is preferable.

Among these poly (alkylene oxide) glycols, those having 2 to 4 carbon atoms in the alkylene oxide structural unit constituting the glycol are particularly preferred because of their excellent antistatic effect. Ethylene oxide, propylene oxide, 1,2
-It is preferable to have butylene oxide, tetramethylene oxide or the like as an alkylene oxide structural unit.

The alkylene oxide structural unit may be composed of a single component, or may be composed of a plurality of different components as in the above-mentioned exemplified compounds. It is preferable to contain ethylene oxide as a constituent component from the viewpoint of being excellent. Specifically, those having an ethylene oxide chain content (ratio of the molecular weight of the ethylene oxide group portion to the molecular weight of the poly (alkylene oxide) glycol) of 10% by weight or more are preferable from the viewpoint of the antistatic effect, and in particular, poly (ethylene oxide) Glycols are preferred.

The poly (alkylene oxide) glycol adduct of bisphenols has a number average molecular weight of 400 to 20 particularly from the viewpoint of antistatic effect and mechanical properties.
000 is preferred. That is, the number average molecular weight is 40
By setting it to 0 or more, the antistatic effect is more remarkably improved, and when the number average molecular weight is 200,000 or less, the obtained polyetherester has good mechanical properties. The number average molecular weight is particularly preferably in the range of 500 to 9,000 from the viewpoint of excellent balance between these.

The amount of the poly (alkylene oxide) glycol component (b1) is not particularly limited, but may be a value corresponding to the content of the polyether structural unit.
That is, the content is preferably in the range of 40 to 85% by weight based on all the raw material components.

The polyvalent carboxylic acid component (b2) used in the present invention is not particularly limited, but may be divalent, trivalent or tetravalent or higher carboxylic acid and carboxylic acid anhydride or a polycarboxylic acid anhydride or polycarboxylic acid anhydride. It shows one kind of a monovalent carboxylic acid ester alone or a mixture of two or more kinds thereof, and the polyvalent carboxylic acid preferably has 4 to 20 carbon atoms.

The polyvalent carboxylic acid is a divalent or higher carboxylic acid or a carboxylic anhydride thereof. Examples of the divalent carboxylic acid and its anhydride include, but are not limited to, terephthalic acid, isophthalic acid, phthalic acid, and the like. Naphthalene-2,
6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, indene-4,7-dicarboxylic acid, naphthalene-2,5-dicarboxylic acid, naphthalene-
2,6-dicarboxylic acid, azulene-2,5-dicarboxylic acid, heptalen-1,7-dicarboxylic acid, biphenylene-1,5-dicarboxylic acid, as-indacene-2,6-dicarboxylic acid, s-indacene-1 , 7-dicarboxylic acid, acenaphthylene-3,8-dicarboxylic acid, fluorene-
1,8-dicarboxylic acid, phenalene-4,8-dicarboxylic acid, phenanthrene-1,6-dicarboxylic acid, anthracene-1,8-dicarboxylic acid, fluoranthene-6
7-dicarboxylic acid, acephenanthrylene-3,8-dicarboxylic acid, aceanthrylene-3,7-dicarboxylic acid, triphenylene-2,10-dicarboxylic acid, pyrene-1,6-dicarboxylic acid, chrysene 1,7 -Dicarboxylic acid, naphthacene-1,5-dicarboxylic acid, preyandene 2,5-dicarboxylic acid, picene-2,8-dicarboxylic acid, perylene-2,8-dicarboxylic acid, pentaphen-
Aromatic dicarboxylic acids such as 5,11-dicarboxylic acid, pentacene 2,6-dicarboxylic acid, their alkyl nucleus-substituted carboxylic acids, and their halogen nucleus-substituted carboxylic acids, 1,4-cyclohexanedicarboxylic acid, 1,2 -Cyclohexanedicarboxylic acid and dicyclohexyl-
Alicyclic dicarboxylic acids such as 4,4'-dicarboxylic acid, pentalene-1,6-dicarboxylic acid, and their alkyl nucleus-substituted carboxylic acids, succinic acid, oxalic acid, adipic acid, sebacic acid, maleic acid, and fumaric acid Acid, itaconic acid,
Acyclic aliphatic dicarboxylic acids such as dodecane dicarboxylic acid,
Maleic anhydride, phthalic anhydride, and anhydrides of each of the above dicarboxylic acids, and the like,

The trivalent carboxylic acids include 1,2,4-trimellitic acid, 1,2,5-naphthalene tricarboxylic acid, 2,6,7-naphthalene tricarboxylic acid, 3,3
', 4-diphenyltricarboxylic acid, benzophenone 3,3', 4-tricarboxylic acid, diphenylether-
3,3 ', 4-tricarboxylic acid, indene-3,4,7
-Tricarboxylic acid, naphthalene-2,5,7-tricarboxylic acid, naphthalene-2,4,6-tricarboxylic acid, azulene-2,5,7-tricarboxylic acid, heptalene-
1,3,7-tricarboxylic acid, biphenylene-1,3,3
5-tricarboxylic acid, as-indacene-2,4,6-tricarboxylic acid, s-indacene-1,3,7-tricarboxylic acid, acenaphthylene-3,6,8-tricarboxylic acid,
Fluorene-1,5,8-tricarboxylic acid, phenalene-2,4,8-tricarboxylic acid, phenanthrene-1,
6,8-tricarboxylic acid, anthracene-1,5,8-
Tricarboxylic acid, fluoranthene-4,6,7-tricarboxylic acid, acephenanthrylene-3,6,8-tricarboxylic acid, aceanthrylene-3,5,7-tricarboxylic acid, triphenylene-2,6,10-tricarboxylic acid Acid, pyrene-1,3,6-tricarboxylic acid, chrysene 1,4,7-tricarboxylic acid, naphthacene-1,3,5
-Tricarboxylic acid, preyandene 2,5,8-tricarboxylic acid, picene-2,5,8-tricarboxylic acid, perylene-2,4,8-tricarboxylic acid, pentaphen-
5,11,14-tricarboxylic acid, pentacene 2,6
14-tricarboxylic acid, and aromatic tricarboxylic acids such as substituted alkyl nuclei and substituted halogen nuclei thereof, ethylene 1,1,2-tricarboxylic acid, propylene-1,
Aliphatic tricarboxylic acids such as 2,3-tricarboxylic acid and pentalene-1,4,6-tricarboxylic acid, and anhydrides of the above tricarboxylic acids;

Examples of the tetravalent carboxylic acid include pyromellitic acid, diphenyl-2,2 ', 3,3'-tetracarboxylic acid, benzophenone-2,2', 3,3'-tetracarboxylic acid, diphenylsulfone-2 , 2 ', 3,3'-tetracarboxylic acid, diphenyl ether-2,2', 3
3'-tetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, indene-2,3,4,7-tetracarboxylic acid, naphthalene-2,3,5,7-tetracarboxylic acid, naphthalene- 2,4,6,7-tetracarboxylic acid, azulene-2,3,5,7-tetracarboxylic acid, heptalene-1,3,4,7-tetracarboxylic acid, biphenylene-1,3,5,7- Tetracarboxylic acid, as-indacene-2,4,6,7-tetracarboxylic acid, s-indacene-1,2,3,7-tetracarboxylic acid, acenaphthylene-3,4,6,8-tetracarboxylic acid, Fluorene-1,2,5,8-tetracarboxylic acid, phenalene-
2,3,4,8-tetracarboxylic acid, phenanthrene-
1,2,6,8-tetracarboxylic acid, anthracene-
1,5,6,8-tetracarboxylic acid, fluoranthene-
4,5,6,7-tetracarboxylic acid, acephenanthrylene-2,3,6,8-tetracarboxylic acid, acetantetralen-3,4,5,7-tetracarboxylic acid, tetraphenylene-2 , 3,6,10-tetracarboxylic acid,
Pyrene-1,3,6,7-tetracarboxylic acid, chrysene 1,4,7,8-tetracarboxylic acid, naphthacene-1,
2,5,7-tetracarboxylic acid, preyandene 2,
5,8,9-tetracarboxylic acid, picene-2,5,7,
8-tetracarboxylic acid, perylene-2,4,5,8-tetracarboxylic acid, pentaphen-5,11,12,14
-Aromatic tetracarboxylic acids such as tetracarboxylic acid, pentacene 2,3,6,14-tetracarboxylic acid, ethylene-1,1,2,2-tetracarboxylic acid, propylene-
1,1,3,3-tetracarboxylic acid, pentalene-1,
Examples thereof include aliphatic tetracarboxylic acids such as 2,4,6-tetracarboxylic acid, and tetracarboxylic monoanhydrides and tetracarboxylic dianhydrides of the above compounds. These can be used alone or in combination of two or more.

Among them, terephthalic acid, isophthalic acid, adipic acid, 2,2
6-Naphthalenedicarboxylic acid is preferred, and terephthalic acid and 2,6-naphthalenedicarboxylic acid are particularly preferred. Further, it is preferable to use a trivalent or higher polycarboxylic acid in combination, since the molecular weight of the target polyether ester can be easily increased.

The polyvalent carboxylic acid ester is a compound in which a part or all of the polyvalent carboxylic acid such as the monoester, diester and tri- or tetraester of the above-mentioned polycarboxylic acid is esterified. Can also be used.

As described above, the amount of the polyvalent carboxylic acid component (b2) used is preferably a value corresponding to the content of the ester structure site, that is, a range of 1 to 60% by weight based on all the raw material components.

Next, in the present invention, the combined use of the alkylene glycol (b3) significantly improves the antistatic effect and the mechanical strength. Examples of such an alkylene glycol (b3) include ethylene glycol, propylene glycol, 1,4-butanediol,
1,3-butanediol, 1,2-butylene glycol, trimethylene glycol, neopentyl glycol, diethylene glycol, 2-methyl-1,3-propylene glycol, triethylene glycol, octamethylene glycol, 1,4-cyclohexanedimethanol And alkylene glycols such as 1,4-cyclohexanediol, 1,6-hexaneglycol, and 3-methyl-1,5-pentanediol. These may be used alone or in combination of two or more. Among these, glycols having 2 to 8 carbon atoms are preferable because of excellent mechanical strength, and ethylene glycol is particularly preferable.

In the method, an antistatic effect is obtained by using a sulfonated phthalic acid salt or an alkyl ester thereof (b4) in addition to the above-mentioned (b1) to (b3) as a carboxylic acid component forming an ester. It can be dramatically improved.

The structure of the sulfonated phthalic acid salt or its alkyl ester (b4) is not particularly limited, but a metal sulfonated phthalate, a sulfonated phosphonium phthalate, a sulfonated ammonium phthalate, Or a compound in which a part or the whole of a sulfonated phthalate such as a monoester and a diester thereof is esterified, specifically, sodium sulfoterephthalate, potassium sulfoterephthalate, sulfoterephthalate, and the like. Magnesium terephthalate, calcium sulfoterephthalate, zinc sulfoterephthalate, phosphonium sulfoterephthalate, ammonium sulfoterephthalate, ammonium sulfoterephthalate, sodium sulfoisophthalate, potassium sulfoisophthalate, sulfoyi Magnesium phthalate, calcium sulfoisophthalate, zinc sulfoisophthalate, phosphonium sulfoisophthalate, ammonium sulfoisophthalate, monomethyl sodium sulfoterephthalate, monomethyl potassium sulfoterephthalate, monomethylmagnesium sulfoterephthalate, Monomethyl calcium sulfoterephthalate, monomethyl zinc sulfoterephthalate, monomethyl phosphonium sulfoterephthalate, monomethyl ammonium sulfoterephthalate, dimethyl sodium sulfoterephthalate, dimethyl potassium sulfoterephthalate, dimethylmagnesium sulfoterephthalate, sulfo Dimethyl calcium terephthalate, dimethyl zinc sulfoterephthalate, dimethyl sulfoterephthalate Honiumu salt,
Sulfoterephthalic acid dimethyl ammonium salt, sulfoisophthalic acid monomethyl sodium salt, sulfoisophthalic acid monomethyl potassium salt, sulfoisophthalic acid monomethyl magnesium salt, sulfoisophthalic acid monomethyl calcium salt, sulfoisophthalic acid monomethyl zinc salt, sulfoisophthalic acid monomethylphosphonium salt, sulfo Monomethyl ammonium isophthalate, dimethyl sodium sulfoisophthalate, dimethyl potassium sulfoisophthalate, dimethylmagnesium sulfoisophthalate, dimethyl calcium sulfoisophthalate, dimethyl zinc sulfoisophthalate, dimethylphosphonium sulfoisophthalate, sulfoisophthalate Acid dimethyl ammonium salt and the like.

Of these, alkali metal salts such as sodium salt, potassium salt, magnesium salt, and calcium salt, and alkaline earth metal salts are preferable, and these sulfonated phthalates are partially or partially. Compounds which are all esterified are preferred. In particular, lower alkyl esters having 6 or less carbon atoms, such as methyl esters and ethyl esters, are preferred. These may be used alone or in combination of two or more.

The amount of the sulfonated phthalate or its alkyl ester (b4) is not particularly limited, but may be a value corresponding to the content of the sulfonate group, that is, each raw material constituting the polyetherester. Is preferably used at a ratio of 0.1 to 10% by weight in the charging ratio. When the content is 0.1% by weight or more, the antistatic effect of the polyetherester is remarkably improved. On the other hand, when the content is 10% by weight or less, the mechanical properties of the obtained polyetherester and the durability of the antistatic effect are improved.

The specific method of reacting such raw material components is not particularly limited. For example, in the method,
The poly (alkylene oxide) glycol (b1), the polyvalent carboxylic acid component (b2) and the alkylene glycol (b3) are subjected to a first step under normal pressure at 100 to 200 ° C.
In the second step, the reaction is carried out at a temperature of 200 to 300 ° C., and the reaction is carried out under reduced pressure to obtain the desired polyether ester. Further, in the method, the polyvalent carboxylic acid component (b2), the sulfonated phthalate or its alkyl ester (b4), and the alkylene glycol (b3) are reacted at 100 to 200 ° C. under normal pressure to determine the amount. Since it was confirmed that the ester had been formed as a target, poly (alkylene oxide) glycol (b1) was further added, and as a second step, the temperature was raised to 200 to 300 ° C., and the reaction was carried out under reduced pressure to obtain the desired poly (alkylene oxide) glycol. A method for obtaining an ether ester may be mentioned.

As the catalyst used in the production method of the above method, a very large number of compounds are effective. Particularly, in the first step, an alkali metal or alkaline earth metal acetate is used, and in the second step, zinc or manganese is used. , Cobalt, antimony, germanium, titanium, tin, and zirconium compounds. Particularly, a tetraalkyl titanate or tin oxalate is preferably used as a catalyst effective for all of the transesterification reaction and the polycondensation reaction. The catalyst is usually used in an amount of 0.005 to 1.0% by weight based on the total amount of the raw materials of the polyetherester.
It is preferable to use them.

In any of the above methods for producing the polyetherester, the weathering agent particles (A) can be added during the production of the polyetherester or at any time after the production.

In any of the above methods for producing a polyetherester, an antioxidant can be added during the production of the polyetherester or at any time after the production. In particular, it is effective to add an antioxidant that does not inhibit the polycondensation reaction in order to prevent the polyester elastomer from being oxidized and deteriorated at the time of entering the second stage polycondensation step.

Examples of these antioxidants include aliphatic and aromatic esters of phosphoric acid and phosphorous acid or phenolic derivatives, particularly so-called hindered phenols having a highly sterically hindered group. It is also preferable to use several kinds of stabilizers such as antioxidants and ultraviolet absorbers.

The method for preparing the antistatic agent of the present invention from the cerium compound (A) and the polyetherester (B) described in detail above is not particularly limited. It can be obtained by adding the cerium compound (A) during the production or kneading and dispersing the cerium compound (A) after the production of the polyetherester (B).

The antistatic resin composition of the present invention is an antistatic resin composition comprising the above-described antistatic agent of the present invention and a thermoplastic resin as essential components.

The content of the antistatic agent in the whole antistatic resin composition of the present invention is not particularly limited, but is preferably, for example, 1 to 30% by weight. That is, when the content is 1% by weight or more, the antistatic property of the antistatic resin composition and the durability thereof are good, and 30% by weight.
The following cases are preferable because the mechanical properties of the resin composition are improved. From the point that these are excellent in balance,
Preferably it is 5% by weight.

The thermoplastic resin used in the present invention includes:
There is no particular limitation, for example, polystyrene resin, polymethylstyrene resin, rubber-modified polystyrene resin (HIPS resin), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), Acrylonitrile-acryl rubber-styrene copolymer (AAS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), alloy of ABS resin and polycarbonate, alloy of ABS resin and polyester resin, AB
Styrene-based resins such as alloys of S-resin and polyamide-based resin, and alloys of polystyrene and polyphenylene oxide;
Polycarbonate resins such as polycarbonate resins, alloys of polycarbonate resins and polyester resins, and alloys of polycarbonate resins and polyamide resins; polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyhexamethylene terephthalate, polyethylene naphthalene dicarboxylate, poly Polyester resins such as butylene naphthalene dicarboxylate and polyhexamethylene naphthalene dicarboxylate; polyolefin resins such as polyethylene, polypropylene, and polybutene; polyamide resins such as nylon 6 and nylon 66; polyphenylene oxide resins; and acrylic resins. .

Among these, transparent thermoplastic resins, ie, polystyrene resin, polymethylstyrene resin, acrylonitrile-styrene copolymer (AS), are excellent in compatibility with antistatic agents and have a remarkable effect of improving transparency. Resins), styrene resins such as polystyrene and polyphenylene oxide alloys; polycarbonate resins such as polycarbonate resins, alloys of polycarbonate resins and polyester resins, and alloys of polycarbonate resins and polyamide resins; polyethylene terephthalate (PE
T), polyester resins such as polybutylene terephthalate (PBT), polyhexamethylene terephthalate, polyethylene naphthalenedicarboxylate, polybutylene naphthalenedicarboxylate, and polyhexamethylene naphthalenedicarboxylate; polyolefin resins such as polyethylene, polypropylene, and polybutene Preferred are resins; polyamide resins such as nylon 6 and nylon 66; polyphenylene oxide resins. Further, a styrene-based resin, a polyester-based resin, and a polycarbonate-based resin are preferable in that the effect of improving the antistatic effect becomes remarkable.

Of course, even a non-transparent thermoplastic resin can be preferably used because it exhibits the effect of exhibiting excellent durability of the antistatic effect of the molded product. Examples of such a non-transparent thermoplastic resin include a rubber-modified polystyrene resin (HIPS resin) and an acrylonitrile-butadiene-styrene copolymer (ABS).
Resin), acrylonitrile-acryl rubber-styrene copolymer (AAS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), AB
Alloys of S resin and polycarbonate, alloys of ABS resin and polyester resin, alloys of ABS resin and polyamide resin, and the like can be given.

Although the antistatic resin composition of the present invention has a sufficient antistatic property, a known ionic antistatic agent may be mixed at any time depending on the application. Representative examples of these known ionic antistatic agents include:

[0056]

Embedded image R-SO ₃ M An organic sulfonic acid metal salt represented by the general formula 2 is exemplified.

Here, the metal organic sulfonic acid salt represented by the general formula 2 is a metal organic sulfonic acid salt wherein R is an alkyl group or an alkylaryl or aryl group and M is an alkali metal or an alkaline earth metal. Any one may be used as long as R has 8 carbon atoms.
About 30 alkyl groups or alkylaryl groups, M
Is preferably selected from Na, K, Li, Mg, Ca and the like.

Specific examples of such organic metal sulfonic acid salts include sodium octyl sulfonate, sodium nonyl sulfonate, sodium decyl sulfonate, sodium dodecyl sulfonate, sodium octadecyl sulfonate, sodium decyl benzene sulfonate, dodecyl benzene Sodium sulfonate, sodium stearylbenzenesulfonate, sodium octylbenzenesulfonate, sodium octylnaphthalenesulfonate, sodium dodecylnaphthalenesulfonate, potassium dodecylsulfonate, potassium dodecylbenzenesulfonate, potassium dodecylnaphthalenesulfonate, lithium dodecylsulfonate, Lithium dodecylbenzenesulfonate, magnesium dodecylsulfonate, calcium dodecylsulfonate And the like.

Of these, sodium dodecylbenzenesulfonate and sodium dodecylsulfonate are preferably used.

A known ionic antistatic agent represented by the formula (2) is not always necessary for the antistatic resin composition of the present invention. It is preferable because the antistatic performance is remarkably improved from the function. When the amount of addition is 5% by weight or less based on the whole antistatic resin composition of the present invention, the antistatic effect can be improved without deteriorating the appearance or physical properties of a molded article of the resin composition. From the viewpoint, it is preferably in the range of 0.1 to 3% by weight.

Further, in the present invention, other known antistatic agents may be used in combination.

The thermoplastic resin composition of the present invention may further contain known additives.

Examples of the known additives include 2,6-di-tert-butyl-4-methylphenol and 2- (1-methylcyclohexyl) -4,6-dimethylphenol as antioxidants. -Methylenebis- (4-ethyl-6-t-methylphenol), 4,4'-thiobis- (6-t-butyl-3-methylphenol), dilaurylthiodipropionate, tris (di-nonylphenyl) Phosphite and the like;
-T-butylphenyl salicylate, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole, etc., and paraffin wax and stearic acid as lubricants. , Hydrogenated oil, stearoamide, methylene bis-stearamide, ethylene bis-stearamide, n
-Butyl stearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride and the like. Flame retardants such as antimony oxide, aluminum hydroxide, zinc borate, tricresyl phosphate, tris (dichloropropyl) phosphate, chlorination Paraffin, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A, etc .; titanium oxide, carbon black, etc. as coloring agents; calcium carbonate, clay, silica, glass fibers, glass spheres, carbon fibers as fillers And the like.

Further, other thermoplastic resins such as polyamide, polybutylene terephthalate, polyphenylene oxide, polyoxymethylene and chlorinated polyethylene can be mixed as required.

The thermoplastic resin composition of the present invention may further contain a known compatibilizer. Examples of the known compatibilizer include styrene-ethylene-butadiene block copolymer, polyethylene-polymethyl methacrylate block copolymer, polyethylene-polystyrene graft copolymer, polyethylene-polymethyl methacrylate as a non-reactive compatibilizer. Graft copolymers, polypropylene-acrylonitrile graft copolymers and the like, and as the reactive compatibilizer, maleic anhydride graft polypropylene, styrene-maleic anhydride copolymer, ethylene-glycidyl methacrylate copolymer, ethylene- Styrene graft copolymer on glycidyl methacrylate copolymer, methyl methacrylate graft copolymer on ethylene-glycidyl methacrylate copolymer, polypropylene-β-hydroxyethyl methacrylate Graft copolymers, polypropylene - glycidyl methacrylate graft copolymers, and the like.

The method for preparing the resin composition of the present invention is not particularly limited. For example, the antistatic agent, the thermoplastic resin, and, if necessary, the metal salt of sulfonic acid and other additives may be used. It can be easily produced by blending a predetermined amount of the components and premixing with a mixer such as a Henschel mixer or a tumbler mixer, and then melt-mixing with an extruder, a kneader, a hot roll, a Banbury mixer or the like.

[0067]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the following examples,% and parts indicate% by weight and parts by weight, respectively.

Example 1 A flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade) was charged with 700 parts of a poly (ethylene oxide) glycol adduct having a number average molecular weight of 2000, dimethyl naphthalene-2,6-dicarboxylate. 375 parts, 5
-29 parts of dimethyl sodium sulfoisophthalate, 295 parts of ethylene glycol, and 2.0 parts of calcium acetate as a catalyst were charged, and stirring was continued at 180 ° C for 2 hours under a nitrogen flow while removing methanol. Then, the reaction was allowed to proceed at 210 ° C. for 2 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 1330 Pa. Add 2 parts of Serigard S-3018-02 to this,
1.5 parts of tetrabutyl titanate was added as a catalyst,
The temperature was raised to 30 ° C. Next, the mixture was reacted under a reduced pressure of 13 Pa for 3 hours, taken out into a strand under nitrogen pressure, and pelletized to obtain a pellet-like polyetherester. Hereinafter, this is referred to as antistatic agent A.

The melt viscosity of the antistatic agent A was measured by using a rheometer RDS-II (manufactured by RHEOMETRIC INC.
240 ° C. under a nitrogen atmosphere,
When measured at 100 rpm, the measured value was 17
It was 8 Pa · s.

Example 2 A flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade) was charged with 620 parts of a poly (ethylene oxide) glycol adduct having a number average molecular weight of 2000, 377 parts of dimethyl terephthalate, and 5-sulfo. 34 parts of dimethyl potassium isophthalate, ethylene glycol 480
Parts and 2.0 parts of calcium acetate as a catalyst,
Stirring was continued at 180 ° C. for 2 hours while removing methanol while flowing nitrogen. Then, while removing distillate such as excess ethylene glycol under a reduced pressure of 1330 Pa,
The reaction was allowed to proceed at 210 ° C. for 2 hours. Further, 3 parts of Serigard M-3018-03 and 2 parts of tetrabutyl titanate as a catalyst were added, and the temperature was raised to 230 ° C. Next, the mixture was reacted under a reduced pressure of 13 Pa for 2 hours, then taken out into a strand under nitrogen pressure, and pelletized to obtain a pellet-like polyetherester. Hereinafter, this is referred to as antistatic agent B. For the antistatic agent B, the melt viscosity measured in the same manner as in Example 1 was 158 Pa ·
s.

Example 3 A flask equipped with a temperature controller, a nitrogen inlet tube and a stirrer (double helical blade) was charged with 590 parts of an adduct of bisphenol A / poly (ethylene oxide) glycol having a number average molecular weight of 3500, and naphthalene-2,6- 503 parts of dimethyl dicarboxylate, 85 parts of dimethyl 5-sulfoisophthalate sodium salt, 878 parts of ethylene glycol and 2.8 parts of calcium acetate as a catalyst were charged, and stirred at 180 ° C. for 2 hours under a nitrogen flow while removing methanol. Continued. Then, the reaction was allowed to proceed at 210 ° C. for 2 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 1330 Pa. In addition, Serigard SC-6
832 as a catalyst and tetrabutyl titanate as catalyst.
8 parts were added and the temperature was raised to 245 ° C. Then, 13Pa
After reacting under reduced pressure for 2 hours, the mixture was taken out into a strand under nitrogen pressure and pelletized to obtain a pellet-like polyetherester. Hereinafter, this is referred to as antistatic agent C. About this antistatic agent C, Example 1
The melt viscosity measured in the same manner as in Example 1 was 201 Pa · s.

Example 4 A flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade) was charged with 620 parts of a poly (ethylene oxide) glycol adduct having a number average molecular weight of 2000, dimethyl naphthalene-2,6-dicarboxylate. 394 copies, 5
-30 parts of dimethyl potassium sulfoisophthalate, 621 parts of ethylene glycol and 3.1 parts of calcium acetate as a catalyst were charged, and stirring was continued for 2 hours at 180 ° C under a nitrogen flow while removing methanol. Then 6
The reaction was allowed to proceed at 210 ° C. for 2.8 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 50 Pa. In addition, 3 parts of Serigard T-3018-02,
1.7 parts of tetrabutyl titanate was added as a catalyst,
The temperature was raised to 30 ° C. Next, the mixture was reacted under a reduced pressure of 13 Pa for 3 hours, taken out into a strand under nitrogen pressure, and pelletized to obtain a pellet-like polyetherester. Hereinafter, this is referred to as antistatic agent D.
For this antistatic agent D, the melt viscosity measured in the same manner as in Example 1 was 198 Pa · s.

Example 5 A flask equipped with a temperature controller, a nitrogen inlet tube and a stirrer (double helical blade) was charged with 600 parts of an adduct of bisphenol A / poly (ethylene oxide) glycol having a number average molecular weight of 4500, and naphthalene-2,6- 480 parts of dimethyl dicarboxylate, 34 parts of dimethyl potassium 5-sulfoterephthalate, 580 parts of ethylene glycol, and 3 parts of calcium acetate as a catalyst are charged, and the mixture is charged with 180 parts of nitrogen.
Stirring was continued at 2 ° C. for 2 hours while removing methanol. Then, the reaction was allowed to proceed at 210 ° C. for 2 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 900 Pa. Further, Serigard S-3018-0
2 and 1.8 parts of tetrabutyl titanate as a catalyst were added, and the temperature was raised to 245 ° C. Next, the mixture was reacted under a reduced pressure of 13 Pa for 2 hours, then taken out into a strand under nitrogen pressure, and pelletized to obtain a pellet-like polyether. Hereinafter, this is referred to as an antistatic agent E. For this antistatic agent E, the melt viscosity measured in the same manner as in Example 1 was 291 Pa · s.

Example 6 In a flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade), 630 parts of a poly (ethylene oxide) glycol adduct having a number average molecular weight of 600, dimethyl naphthalene-2,6-dicarboxylate were added. 419 parts, 5-
35.5 parts of dimethyl potassium sulfoisophthalate, 540 parts of ethylene glycol and 1.3 parts of calcium acetate as a catalyst were charged, and stirring was continued while removing methanol at 180 ° C. for 2 hours under a flow of nitrogen. Then, the reaction was allowed to proceed at 210 ° C. for 2 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 1300 Pa. Further, 4 parts of Serigard T-3018-2 and 1.9 parts of tetrabutyl titanate as a catalyst were added to give 25 parts.
The temperature was raised to 0 ° C. Then, after reacting under a reduced pressure of 13 Pa for 2.8 hours, it was taken out into a strand under nitrogen pressure,
The pelletized polyetherester was obtained by pelletizing. Hereinafter, this is referred to as antistatic agent F. For this antistatic agent F, the melt viscosity measured in the same manner as in Example 1 was 104 Pa · s.

Example 7 A flask equipped with a temperature controller, a nitrogen inlet tube and a stirrer (double helical blade) was charged with 580 parts of a poly (ethylene oxide) glycol adduct having a number average molecular weight of 3000, dimethyl naphthalene-2,6-dicarboxylate. 430 parts, ethylene glycol 510 parts and 1.8 parts of calcium acetate as a catalyst were charged, and stirring was continued while removing methanol at 180 ° C. for 2 hours under a flow of nitrogen. Then, the reaction was allowed to proceed at 210 ° C. for 2 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 1330 Pa. In addition, 3.1 parts of Serigard SC-6832,
As a catalyst, 1.9 parts of tetrabutyl titanate was added, and 2
The temperature was raised to 40 ° C. Then 3.9 under reduced pressure of 13 Pa.
After reacting for an hour, the resultant was taken out into a strand under nitrogen pressure and pelletized to obtain a pellet-like polyetherester. Hereinafter, this is referred to as antistatic agent G. For this antistatic agent G, the melt viscosity measured in the same manner as in Example 1 was 227 Pa · s.

Comparative Example 1 In a flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade), 614 parts of poly (ethylene oxide) glycol having a number average molecular weight of 1010, 361 parts of dimethyl terephthalate, 5-sulfoisophthalic acid 69 parts of dimethyl sodium salt, 390 parts of ethylene glycol and 2.7 parts of calcium acetate as a catalyst were charged, and stirring was continued while removing methanol at 180 ° C. for 2 hours under a flow of nitrogen. Then, while removing distillate such as excess ethylene glycol under a reduced pressure of 1330 Pa, 21
The reaction was allowed to proceed at 0 ° C. for 2 hours. Further, 1.5 parts of tetrabutyl titanate was added as a catalyst, and the temperature was raised to 250 ° C. Then, the mixture was reacted under a reduced pressure of 35 Pa for 2 hours, and taken out to a cooling pan. After cooling, cutting was performed to obtain a pellet-like polyetherester. Hereinafter, this is referred to as antistatic agent H.

The melt viscosity of the antistatic agent H was measured with a rheometer RDS-II (manufactured by RHEOMETRIC INC.
(Hereinafter referred to as RDS) using a nitrogen atmosphere at 250 ° C.
When measured at 100 rpm, the measured value was 84
Pa · s.

Comparative Example 2 A flask equipped with a temperature controller, a nitrogen inlet tube and a stirrer (double helical blade) was charged with 615 parts of poly (ethylene oxide) glycol having a number average molecular weight of 572, 419 parts of dimethyl terephthalate, and dimethyl potassium sulfoisophthalate. 35 parts of salt, 432 parts of ethylene glycol and 0.8 part of calcium acetate as a catalyst were charged.
Stirring was continued at 80 ° C. for 2 hours while removing methanol. Then, the reaction was allowed to proceed at 210 ° C. for 2 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 1330 Pa. Further, 1.9 parts of tetrabutyl titanate was added as a catalyst, and the temperature was raised to 250 ° C.
Then, the mixture was reacted for 5 hours under a reduced pressure of 13 Pa, and was taken out to a cooling pan. After cooling, by cutting
A pellet-like polyetherester was obtained. Hereinafter, this is referred to as antistatic agent I. For this antistatic agent I, the melt viscosity measured in the same manner as in Example 1 was 17 Pa · s.

Examples 8 to 23 and Comparative Examples 3 to 12 The components were mixed at the ratios shown in Tables 1 to 7 below.
Using a 25 mm twin screw extruder manufactured by Toyo Seiki Seisaku-sho, Ltd.
The PC system was kneaded at 270 ° C, the ABS at 230 ° C, and the PMMA and PS systems at 220 ° C. The obtained pellets were prepared using a 1 oz. Injection molding machine manufactured by Yamashiro Seiki Co., Ltd.
S type cylinder temperature at 250 ° C, ABS type 230
Each test piece was prepared at 220 ° C. for the PMMA system and 265 ° C. for the PC system at 200 ° C., and the following evaluations were made. The evaluation results are shown in Tables 1 to 7.

(1) Drop Weight Impact Test In accordance with ASTM D-3763, an instrumented drop weight impact tester Dynatup (GRC manufactured by General Research Corporation)
730-I) using a flat plate of 80 × 80 × 3 mm as a test plate. (2) Antistatic performance test After adjusting the condition of a 80 × 80 × 3 mm flat plate at 23 ° C. and 50% relative humidity for 24 hours, use a SM-8210 super-insulation meter (manufactured by Toa Denpa Kogyo Co., Ltd.) The resistance was measured.
The unit of the measured value is Ω / □. (3) Transparency test According to JIS K7105, the total light transmittance (%) was measured using a haze meter (Model ND-1001DP manufactured by Nippon Denshoku Industries Co., Ltd.) with a 30 × 30 × 3 mm flat plate as a test plate. ) Was measured. (4) Weather resistance test Sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.)
Model: WEL-SUN-DCH-8) 80 × 80 × 3
A 300 mm thick flat plate was put therein, and after elapse of 300 hours at 63 ° C., the surface resistivity was measured by the same method as in the antistatic property test (2).

In the table, PC is “S-3000” manufactured by Mitsubishi Engineering-Plastics Co., Ltd., and PS is “Dick Styrene GR-” manufactured by Dainippon Ink & Chemicals, Inc.
3500 ”, PMMA is“ Acrypet MD ”manufactured by Mitsubishi Rayon Co., Ltd., ABS is“ ABS170 ”manufactured by Technopolymer Co., Ltd., and SMAA is styrene / methacrylic acid (= 85/15). Polymer and DB
S represents sodium dodecylbenzenesulfonate manufactured by Takemoto Yushi Co., Ltd.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

[Table 4]

[0086]

[Table 5]

[0087]

[Table 6]

[0088]

[Table 7]

[0089]

The antistatic agent of the present invention can provide a thermoplastic resin with an antistatic effect and its durability, as well as excellent weather resistance. Further, an antistatic effect and its durability can be imparted to a transparent thermoplastic resin without impairing the transparency. In addition, the antistatic resin composition of the present invention has both excellent antistatic properties and weather resistance, and does not impair transparency when a transparent thermoplastic resin is used, and further has a mechanical strength. It is also useful for housing materials for electric appliances, parts for electric appliances, automobile parts, packaging materials, furniture, etc. because of its excellent weather resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 67/02 C08L 67/02 69/00 69/00 101/00 101/00

Claims (13)

[Claims] 1. An antistatic agent comprising a cerium compound (A) and a polyetherester (B) as essential components. 2. The antistatic agent according to claim 1, wherein the cerium compound (A) is cerium oxide. 3. The method according to claim 1, wherein the cerium compound (A) is a composite particle of cerium oxide and another inorganic compound, and is used as the particle (A) whose surface is coated with amorphous silica. 2. The antistatic agent according to 2. 4. The antistatic agent according to claim 1, wherein the other inorganic compound is silica or talc. 5. The polyetherester (B) according to any one of claims 1 to 4, wherein the content of the polyether structure site is in a range of 40 to 85% by weight in terms of a raw material weight ratio. Antistatic agent. 6. The polyetherester (B) according to claim 5, which is a polycondensate of a poly (alkylene oxide) glycol component (b1), a polyvalent carboxylic acid component (b2) and an alkylene glycol component (b3). Antistatic agent. 7. The antistatic agent according to claim 6, wherein the poly (alkylene oxide) glycol component (b1) has a number average molecular weight of 300 to 50,000. 8. The polyetherester (B) contains a sulfonate group in its molecular structure.
7. The antistatic agent according to any one of 7. 9. The antistatic agent according to claim 1, wherein the polyetherester (B) has a number average molecular weight of 1,000 to 1,000,000. 10. An antistatic resin composition comprising the antistatic agent according to any one of claims 1 to 9 and a thermoplastic resin as essential components. 11. The antistatic resin composition according to claim 10, wherein the content of the antistatic agent is 1 to 30% by weight. 12. The antistatic resin composition according to claim 10, wherein the thermoplastic resin is a transparent thermoplastic resin. 13. The antistatic resin composition according to claim 10, wherein the thermoplastic resin is a polycarbonate resin, a polyester resin, an acrylic resin or a styrene resin.