WO2020203618A1

WO2020203618A1 - Antistatic agent, antistatic agent composition containing same, antistatic resin composition containing same, molded body and film thereof

Info

Publication number: WO2020203618A1
Application number: PCT/JP2020/013573
Authority: WO
Inventors: 景佑清水; 直樹圓城; 和清野村
Original assignee: 株式会社Adeka
Priority date: 2019-03-29
Filing date: 2020-03-26
Publication date: 2020-10-08
Also published as: TW202104526A

Abstract

Provided are: an antistatic agent which can sustainably impart a superior antistatic effect to a synthetic resin; an antistatic agent composition containing the same; an antistatic resin composition containing the same; and a molded body and a film thereof.　This antistatic agent contains at least one polymer compound (E) having a structure made by bonding, via an ester bond or an ether bond, a polyester block (A) composed of a polyester (a) obtained by reacting a diol (a1) and a dicarboxylic acid (a2), a polyester block (B) composed of a compound (b) having hydroxyl groups at both ends and having one or more ethyleneoxy groups, and an epoxy compound (D) having two or more epoxy groups, wherein the number average molecular weight calculated by an acid number measuring method is 1,600-10,000, and the number average molecular weight calculated by a hydroxyl value measuring method is 1,000-6,000.

Description

Antistatic agent, antistatic agent composition containing the same, antistatic resin composition containing these, molded article and film thereof.

The present invention relates to an antistatic agent, an antistatic agent composition containing the antistatic agent, an antistatic resin composition containing these (hereinafter, also simply referred to as “resin composition”), a molded product thereof, and a film thereof. The present invention relates to an antistatic agent capable of continuously imparting an excellent antistatic effect to a resin, an antistatic agent composition containing the same, an antistatic resin composition containing these, a molded product and a film thereof.

Synthetic resins such as thermoplastic resins are indispensable in modern times because they are not only lightweight and easy to process, but also have excellent properties such as the ability to design a base material according to the application. It is an important material. Further, since the thermoplastic resin has a property of being excellent in electrical insulation, it is frequently used for components of electric products and the like. However, since the thermoplastic resin has too high an insulating property, there is a problem that it is easily charged by friction or the like.

The charged thermoplastic resin attracts dust and dirt around it, which causes a problem of spoiling the appearance of the resin molded product. Further, among electronic products, for example, precision instruments such as computers may not be able to operate normally due to charging. In addition, there are problems with electric shock. When an electric shock is generated from the resin to the human body, it not only causes discomfort to the human body, but also may induce an explosion accident in the presence of flammable gas or dust. Furthermore, even in synthetic resin films used for packaging materials for electrical and electronic equipment and electrical and electronic parts, the generation of static electricity due to charging causes electric shocks and fine dust, which causes damage to the parts and equipment, which is large. It becomes a problem.

In order to solve such a problem, the synthetic resin has been conventionally treated to prevent charging. The most common antistatic treatment method is to add an antistatic agent to the synthetic resin. Such antistatic agents include a coating type that is applied to the surface of a resin molded body and a kneading type that is added when the resin is processed and molded, but the coating type is inferior in sustainability. In addition, since a large amount of organic matter is applied to the surface, there is a problem that those touching the surface are contaminated.

From this point of view, conventional polymer-type antistatic agents that are mainly used by kneading them into synthetic resins have been studied. For example, in Patent Documents 1 and 2, a polyether is used to impart antistatic properties to a polyolefin resin. Esteramides have been proposed. Further, Patent Document 3 proposes a block polymer having a structure in which a block of polyolefin and a block of hydrophilic polymer are repeatedly and alternately bonded. Further, Patent Document 4 proposes a polymer-type antistatic agent having a polyester block.

Japanese Unexamined Patent Publication No. 58-118838 JP-A-3-290464 Japanese Unexamined Patent Publication No. 2001-278985 Japanese Unexamined Patent Publication No. 2016-23254

However, these conventional antistatic agents are not always sufficient in antistatic performance, and further improvement is desired at present. In particular, when it is used for a film made of synthetic resin, there is a problem that sufficient antistatic property cannot be exhibited, and its durability is not sufficient. Further, since sufficient performance cannot be obtained unless a large amount is added to the resin, there is a problem that if the compatibility with the synthetic resin is poor, the transparency of the film is adversely affected.

Therefore, an object of the present invention is an antistatic agent capable of continuously imparting an excellent antistatic effect to a synthetic resin, an antistatic agent composition containing the antistatic agent, and an antistatic resin composition containing these. , The molded article and the film. In particular, it is an object of the present invention to provide a film having excellent antistatic properties, less likely to generate static electricity, less likely to cause a decrease in commercial value due to surface contamination due to static electricity and adhesion of dust, and further excellent in transparency.

As a result of diligent studies to solve the above problems, the present inventors have been able to impart excellent antistatic performance to the synthetic resin by the polymer compound having a predetermined structure, and further to the synthetic resin. It has been found that the transparency of the synthetic resin is not adversely affected because of its excellent compatibility. Based on such findings, the present inventors have further diligently studied and found that the above problems can be solved by using the present invention, and have completed the present invention.

That is, the antistatic agent of the present invention has a polyester block (A) composed of a polyester (a) obtained by reacting a diol (a1) and a dicarboxylic acid (a2), and one or more ethyleneoxy groups. A block (B) of a polyester composed of a compound (b) having a hydroxyl group at both ends and an epoxy compound (D) having two or more epoxy groups are bonded via an ester bond or an ether bond. An epoxy agent containing one or more of the polymer compound (E) having a structure.
The number average molecular weight of the polyester (a) calculated by the acid value measurement method is 1,600 to 10,000, and the number average molecular weight of the compound (b) calculated by the hydroxyl value measurement method is 1. It is characterized in that it is 000 to 6,000.

In the antistatic agent of the present invention, the polymer compound (E) has the block (A) and the block (B), and has a hydroxyl group or a carboxyl group at the end of the polyester (a), and the above. Bonded via an ester bond or an ether bond formed by the reaction of the hydroxyl group at the end of compound (b) and the epoxy group of the epoxy compound (D) or the hydroxyl group formed by reacting the epoxy group. It is preferable that the polymer compound (E) has a structure in which the block (A) and the block (B) are repeatedly and alternately bonded via an ester bond to both ends. It is more preferable that the block polymer (C) having a group and the epoxy compound (D) have a structure in which they are bonded via an ester bond. Further, in the antistatic agent of the present invention, the block polymer (C) preferably has a number average molecular weight calculated by an acid value measurement method of 8,000 to 50,000. Furthermore, in the antistatic agent of the present invention, the polyester (a) preferably has a structure having carboxyl groups at both ends. Further, in the antistatic agent of the present invention, the compound (b) is preferably polyethylene glycol. Further, in the antistatic agent of the present invention, the ratio of the block (B) to the total mass of the block (A) and the block (B) is in the range of 20 to 50% by mass. preferable.

The antistatic agent composition of the present invention is characterized in that the antistatic agent of the present invention is further blended with one or more selected from the group consisting of alkali metal salts and ionic liquids. Is.

The antistatic resin composition of the present invention is characterized in that the antistatic agent of the present invention is blended with a synthetic resin. Further, the other antistatic resin composition of the present invention is characterized in that the antistatic agent composition of the present invention is blended with the synthetic resin.

In the antistatic resin composition of the present invention, it is preferable that the synthetic resin is at least one selected from the group consisting of polyolefin resins, polystyrene resins and copolymers thereof.

The molded product of the present invention is characterized by comprising the antistatic resin composition of the present invention.

The molded product of the present invention is preferably a film, and preferably, the Haze value at a thickness of 50 μm is 0% or more and 40.0% or less.

According to the present invention, an antistatic agent capable of continuously imparting an excellent antistatic effect to a synthetic resin, an antistatic agent composition containing the antistatic agent, an antistatic resin composition containing these, and the like thereof. Molds and films can be provided. The film of the present invention has excellent antistatic properties, is less likely to generate static electricity, is less likely to cause surface contamination due to static electricity, and is less likely to lose its commercial value due to adhesion of dust, and is also excellent in transparency.

Hereinafter, embodiments of the present invention will be described in detail.
The antistatic agent of the present invention has a polyester block (A) composed of a polyester (a) obtained by reacting a diol (a1) and a dicarboxylic acid (a2), and both ends having one or more ethyleneoxy groups. A structure in which a polyester block (B) composed of a compound (b) having a hydroxyl group and an epoxy compound (D) having two or more epoxy groups are bonded via an ester bond or an ether bond. It contains one or more of the polymer compounds (E) having. Here, the ethyleneoxy group is a group represented by the following general formula (1).

In the antistatic agent of the present invention, the number average molecular weight calculated by the acid value measurement method of the polyester (a) is 1,600 to 10,000, and the antistatic property, its durability, and the transparency of the film are considered. Therefore, it is preferably 2,000 to 8,000, and more preferably 3,000 to 8,000. The method for calculating the number average molecular weight of the antistatic agent of the present invention by the acid value measurement method is as follows.

<Calculation method of number average molecular weight by acid value measurement method>
The acid value was measured by the following acid value measuring method, and the number average molecular weight (hereinafter, also referred to as “Mn”) was determined by the following formula.
Mn = 112220 / acid value <method for measuring acid value>
First, 0.2 g of a sample is weighed in a 100 mL Erlenmeyer flask, and 40 mL of a xylene / ethanol solution is added to dissolve the sample. Titrate with 0.1N-KOH aqueous solution and calculate by the following formula.
Acid value [mgKOH / g] = 56.11 × f × T / S
f: factor of 0.1N-KOH aqueous solution
T: Quantitative test titration [mL]
S: Sample amount [g]

If one end or both ends of the polyester (a) are hydroxyl groups, treat the hydroxyl groups with maleic anhydride to form a carboxyl group, measure the acid value in the same manner, calculate the number average molecular weight, and then use it for treatment. It may be calculated by making a correction excluding the maleic anhydride.

In the antistatic agent of the present invention, the number average molecular weight of the compound (b) having one or more ethyleneoxy groups and having hydroxyl groups at both ends is 1,000 to 6,000 calculated by the hydroxyl value measurement method. From the viewpoint of antistatic property, its durability, and the transparency of the film, it is preferably 1,500 to 5,000, and more preferably 1,800 to 4,000. The method for calculating the number average molecular weight of the antistatic agent of the present invention by the hydroxyl value measurement method is as follows.

<Calculation method of number average molecular weight by hydroxyl value measurement method>
The hydroxyl value was measured by the following method for measuring the hydroxyl value, and the number average molecular weight (hereinafter, also referred to as “Mn”) was determined by the following formula.
Number average molecular weight = (56110 × 2) / hydroxyl value <method for measuring hydroxyl value>
・ Reagent A (acetylating agent)
(1) Triethyl phosphate 1560 mL
(2) Acetic anhydride 193 mL
(3) Perchloric acid (60%) 16g
These reagents are mixed in the order of (1) → (2) → (3).
・ Reagent B
Pyridine and pure water are mixed in a volume ratio of 3: 1.
・ Reagent C
Add 2-3 drops of phenolphthalein solution to 500 mL of isopropyl alcohol and neutralize with 1N-KOH aqueous solution.

First, weigh 2 g of a sample into a 200 mL Erlenmeyer flask, add 10 mL of triethyl phosphate, and heat to dissolve. Add 15 mL of Reagent A, plug and shake vigorously. Add 20 mL of Reagent B, plug and shake vigorously. Add 50 mL of Reagent C. Titrate with 1N-KOH aqueous solution and calculate by the following formula.
Hydroxy group value [mgKOH / g] = 56.11 × f × (TB) / S
f: Factor of 1N-KOH aqueous solution
B: Empty test titration [mL]
T: Quantitative test titration [mL]
S: Sample amount [g]

The polymer compound (E) has both a polyester block (A) composed of the polyester (a) and one or more ethyleneoxy groups from the viewpoint of antistatic property, its durability, and the transparency of the film. A block (B) of a polyether composed of a compound (b) having a hydroxyl group at the terminal, a hydroxyl group or a carboxyl group having a hydroxyl group at the end of the polyester (a), and a hydroxyl group having a hydroxyl group at the end of the compound (b). , A structure formed by the reaction of the epoxy group of the epoxy compound (D) having two or more epoxy groups or the hydroxyl group formed by the reaction of the epoxy group, and the structure formed by bonding via an ester bond or an ether bond. It is preferable to have. Here, the hydroxyl group formed by the reaction of the epoxy group is a hydroxyl group formed by the ring-opening reaction of the epoxy group of the epoxy compound (D) with the hydroxyl group or the carboxyl group.

In the polymer compound (E), the polyester block (A) and the polyether block (B) are repeatedly alternated via an ester bond in terms of antistatic property, its durability, and film transparency. It is preferable that the block polymer (C) having a carboxyl group at both ends and the epoxy compound (D) having two or more epoxy groups are bonded to each other via an ester bond. The ester bond here is an ester bond formed by the reaction of the carboxyl group of the block polymer (C) and the epoxy group of the epoxy compound (D), and further, an ester bond formed by the reaction of forming the ester bond. Examples thereof include an ester bond formed by reacting a hydroxyl group formed by opening a ring with a carboxyl group. In the antistatic agent of the present invention, the antistatic agent may be bonded via any of these ester bonds, and the binding via the ester bond between the two is the antistatic property, its durability, and the transparency of the film. More preferable from the point of view.

Examples of the diol (a1) used in the polymer compound (E) include an aliphatic diol and an aromatic group-containing diol. The diol may be a mixture of two or more kinds.

Examples of the aliphatic diol include 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2-butanediol, and 1,3-butanediol. , 2-Methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl- 1,3-Propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptan), 3-methyl-1,5- Pentandiol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9 -Nonandiol, 1,10-decanediol, 1,12-octadecanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 1,2-, 1,3- or 1,4-cyclohexanediol, cyclododecane Examples thereof include diols, dimer diols, hydrogenated dimer diols, diethylene glycols, dipropylene glycols and triethylene glycols.

Among these aliphatic diols, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,12-dodecanediol, and hydrogenated bisphenol A are used in terms of antistatic properties, their durability, and film transparency. Preferably, 1,4-cyclohexanedimethanol, 1,6-hexanediol and 1,12-dodecanediol are more preferable, and 1,4-cyclohexanedimethanol is even more preferable. Since the aliphatic diol is preferably hydrophobic from the viewpoint of antistatic property, its durability, and transparency of the film, it is not preferable to use polyethylene glycol having hydrophilicity.

Examples of the aromatic group-containing diol include bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, 1,4-benzenedimethanol, and an ethylene oxide adduct of bisphenol A. Examples thereof include a propylene oxide adduct of bisphenol A, a polyhydroxyethyl adduct of a mononuclear divalent phenol compound such as 1,4-bis (2-hydroxyethoxy) benzene, resorcin, and pyrocatechol.

Among these diols having an aromatic group, ethylene oxide adduct of bisphenol A and 1,4-bis (β-hydroxyethoxy) benzene are preferable. The aromatic diol preferably has hydrophobicity from the viewpoint of antistatic property, its durability, and transparency of the film.

Among these, 1,4-cyclohexanedimethanol, 1,6-hexanediol, and 1,12-dodecanediol are preferable as the diol (a1) from the viewpoints of antistatic property, its durability, and film transparency.

In the antistatic agent of the present invention, examples of the dicarboxylic acid (a2) used in the polymer compound (E) include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. The dicarboxylic acid may be a mixture of two or more kinds.

In the antistatic agent of the present invention, the dicarboxylic acid (a2) used in the polymer compound (E) is a derivative of the dicarboxylic acid (for example, an acid anhydride, an ester such as an alkyl ester, an alkali metal salt, an acid halide, etc.). It may be. Examples of the derivative include carboxylic acid anhydride, carboxylic acid ester (for example, carboxylic acid alkyl ester such as carboxylic acid methyl ester), carboxylic acid alkali metal salt (for example, carboxylic acid sodium salt), and carboxylic acid halide (for example, carboxylic acid). Chloride) and the like.

The aliphatic dicarboxylic acid preferably includes an aliphatic dicarboxylic acid having 2 to 20 carbon atoms, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, methylsuccinic acid, dimethylmalonic acid and 3-methylglutaric acid. , Ethylsuccinic acid, isopropylmalonic acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid (1,10-decandicarboxylic acid), tridecanedioic acid, tetradecanedioic acid, hexadecanedi Acid, octadecanedioic acid, eikosandioic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid Examples thereof include acids, 1,4-cyclohexanedioacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid, 1,1-cyclohexanediacetic acid, dimeric acid, maleic acid, and fumaric acid. Among these aliphatic dicarboxylic acids, a dicarboxylic acid having 4 to 16 carbon atoms is preferable, and a dicarboxylic acid having 6 to 12 carbon atoms is more preferable, from the viewpoint of antistatic property, its durability, and transparency of the film.

The aromatic dicarboxylic acid preferably includes an aromatic dicarboxylic acid having 8 to 20 carbon atoms, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid and β-phenylglutal. Acid, α-Phenyladiponic acid, β-phenyladipic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate and 3-sulfoisophthalic acid Examples include potassium. Among these aromatic dicarboxylic acids, terephthalic acid, isophthalic acid, and phthalic acid (including phthalic anhydride) are preferable, and phthalic acid (including phthalic anhydride) is preferable from the viewpoint of antistatic property, its durability, and film transparency. ) Is more preferable. In the antistatic agent of the present invention, as the dicarboxylic acid (a2), adipic acid, sebacic acid, and terephthalic acid are preferable from the viewpoints of antistatic property, its durability, and transparency of the film.

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

As the compound (b) having one or more ethyleneoxy groups represented by the general formula (1) and having hydroxyl groups at both ends, a hydrophilic compound is preferable, and the ethyleneoxy group represented by the general formula (1) is used. The possessed polyether is more preferable, polyethylene glycol is even more preferable from the viewpoint of antistatic property and its durability, and the transparency of the film, and polyethylene glycol represented by the following general formula (2) is particularly preferable.

Here, m represents a number from 4 to 250. m is preferably 20 to 200, more preferably 40 to 180, from the viewpoint of antistatic property, its durability, and transparency of the film.

Examples of the compound (b) include ethylene oxide and other alkylene oxides such as propylene oxide, 1,2-, 1,4-, 2,3-, in addition to polyethylene glycol obtained by addition reaction of ethylene oxide. Alternatively, a polyether obtained by addition reaction with one or more kinds of 1,3-butylene oxide and the like can be mentioned, and this polyether may be either random or blocked.

To further give an example of the compound (b), a compound having a structure in which ethylene oxide is added to an active hydrogen atom-containing compound, ethylene oxide and other alkylene oxides, for example, propylene oxide, 1,2-, 1,4-, Examples thereof include compounds having a structure in which one or more kinds such as 2,3- or 1,3-butylene oxide are added. These may be either random addition or block addition.

Examples of the active hydrogen atom-containing compound include glycols, dihydric phenols, primary monoamines, secondary diamines and dicarboxylic acids.

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

Examples of the aliphatic glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,3-. Hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecane Examples thereof include diols, 1,20-eicosane diols, diethylene glycols, triethylene glycols and thiodiethylene glycols.

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

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

As the divalent phenol, phenol having 6 to 30 carbon atoms can be used, for example, catechol, resorcinol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, dihydroxydiphenyl thioether, binaphthol and alkyl (carbon atoms) thereof. Numbers 1 to 10) or halogen-substituted products can be mentioned.

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

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

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

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

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

Examples of the aromatic secondary diamine include N, N'-dimethyl-phenylenediamine, N, N'-dimethyl-xylylenediamine, N, N'-dimethyl-diphenylmethanediamine, and N, N'-dimethyl-diphenyletherdiamine. , N, N'-dimethyl-benzidine and N, N'-dimethyl-1,4-naphthalenediamine and the like.

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

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

Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, methylsuccinic acid, dimethylmalonic acid, β-methylglutaric acid, ethylsuccinic acid, isopropylmalonic acid, adipic acid, pimelic acid, and suberic acid. Examples include azelaic acid, suberic acid, undecandic acid, dodecandic acid, tridecandic acid, tetradecandic acid, hexadecandic acid, octadecandic acid and icosandic acid.

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

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

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

Next, the epoxy compound (D) having two or more epoxy groups constituting the polymer compound (E) will be described.
The epoxy compound (D) used in the antistatic agent of the present invention is not particularly limited as long as it has two or more epoxy groups, and is, for example, mononuclear polynuclear such as hydroquinone, resorcin, pyrocatechol, fluoroluxinol, etc. Polyglycidyl ether compound of valence phenol compound; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), etilidenbisphenol, isopropyridene bisphenol (bisphenol A), isopropyridenebis (orthocresol), tetrabromobisphenol A , 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2, Of polynuclear polyvalent phenolic compounds such as 2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcin novolac, terpenphenol Polyglycyl ether compounds; ethylene glycol, propylene glycol, butylene glycol, hexanediol, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A -Polyglycidyl ethers of polyhydric alcohols such as ethylene oxide adducts and dicyclopentadiene dimethanol; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid , Trimmeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylene tetrahydrophthalic acid and other aliphatic, aromatic or alicyclic poly Homopolymers or copolymers of glycidyl esters of basic acids and glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, diglycidyl orthotoluidine, etc. Epoxy compounds with glycidylamino groups; vinylcyclohe Xendiepoxide, dicyclopentadiene diepoxyside, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3, Epoxy compounds of cyclic olefin compounds such as 4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymers, heterocyclic compounds such as triglycidyl isocyanurate. , Epoxy soybean oil and the like. In addition, these epoxy compounds are internally crosslinked with a prepolymer of terminal isocyanate, or polyvalent active hydrogen compounds (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.) are used to increase the molecular weight. It may be the one that has been used. Two or more kinds of such epoxy compounds (D) may be used.

The epoxy compound (D) contains bisphenol F diglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hexanediol diglycidyl from the viewpoints of antistatic property, its durability, and film transparency. Ether is preferred.

The epoxy equivalent of the epoxy compound (D) is preferably 70 to 2000, more preferably 100 to 1000, and particularly preferably 150 to 600, from the viewpoint of antistatic property, its durability, and transparency of the film.

The polyester (a) constituting the polyester block (A) according to the polymer compound (E) may be composed of a diol (a1) and a dicarboxylic acid (a2), and has antistatic properties and its durability, and a film. From the viewpoint of transparency, preferably, the residue of the diol (a1) excluding the hydroxyl group and the residue of the dicarboxylic acid (a2) excluding the carboxyl group have a structure in which they are bonded via an ester bond.

Further, the polyester (a) preferably has a structure having carboxyl groups at both ends from the viewpoint of antistatic property, its durability, and transparency of the film. Further, the degree of polymerization of the polyester (a) is preferably in the range of 2 to 50 from the viewpoint of antistatic property, its durability, and transparency of the film.

The polyester (a) having a carboxyl group at both ends can be obtained by subjecting a diol (a1) and a dicarboxylic acid (a2) to an esterification reaction.

The dicarboxylic acid (a2) may be a derivative thereof (for example, an acid anhydride, an ester such as an alkyl ester, an alkali metal salt, an acid halide, etc.), and when the polyester (a) is obtained by using the derivative. Finally, both ends may be treated to form a carboxyl group, and the reaction may proceed as it is to obtain the next block polymer (C) having a structure having a carboxyl group at both ends.

As for the reaction ratio of the dicarboxylic acid (a2) and the diol (a1), it is preferable to use an excess of the dicarboxylic acid (a2) so that both ends become carboxyl groups, and the molar ratio of the dicarboxylic acid (a1) is adjusted to the diol (a1). On the other hand, it is preferable to use an excess of 1 mol.

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

When derivatives such as esters, alkali metal salts, and acid halides are used instead of dicarboxylic acids, both ends may be treated as dicarboxylic acids after the reaction between them and diols, and the dicarboxylic acids may be used as they are. The next reaction may proceed to obtain a block polymer (C) having a structure having a carboxyl group at both ends.

A suitable polyester (a) composed of a diol (a1) and a dicarboxylic acid (a2) and having a carboxyl group at both ends forms an ester bond by reacting with the compound (b) to form a structure of the block polymer (C). The carboxyl groups at both ends may be protected, modified, or in the form of a precursor. Further, an antioxidant such as a phenolic antioxidant may be added to the reaction system in order to suppress the oxidation of the product during the reaction.

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

The block polymer (C) having a structure having a carboxyl group at both ends of the polymer compound (E) is a block (A) composed of polyester (a) and a block (B) composed of compound (b). These blocks have a structure in which they are repeatedly and alternately bonded via an ester bond formed by a carboxyl group and a hydroxyl group. As an example of such a block polymer (C), for example, one having a structure represented by the following general formula (3) can be mentioned.

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

The block polymer (C) having a structure having a carboxyl group at both ends is obtained by subjecting a polyester (a) having a carboxyl group at both ends and a compound (b) having a hydroxyl group at both ends to undergo a polycondensation reaction. However, the polyester (a) and the compound (b) have a structure equivalent to that having a structure in which the polyester (a) and the compound (b) are repeatedly and alternately bonded via an ester bond formed by a carboxyl group and a hydroxyl group. If so, it is not always necessary to synthesize the polyester (a) and the compound (b).

The reaction ratio of the polyester (a) to the compound (b) is a block polymer having carboxyl groups at both ends if the reaction ratio of the compound (b) is adjusted to be X + 1 mol with respect to X mol. (C) can be preferably obtained.

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

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

The polymer compound (E) preferably has a block polymer (C) having a structure having carboxyl groups at both ends and two or more epoxy groups from the viewpoints of antistatic property, its durability, and transparency of the film. It has a structure in which the epoxy compound (D) having the above is bonded via an ester bond. The ester bond is formed by an ester bond formed by the reaction of the carboxyl group at the end of the block polymer (C) and the epoxy group of the epoxy compound (D), and further by this reaction (reaction between the carboxyl group and the epoxy group). Any of the ester bonds formed by the reaction of the hydroxyl group and the carboxyl group may be used, and the presence of both ester bonds is preferable from the viewpoint of antistatic property and its durability, storage stability, and transparency of the film. ..

Further, the polymer compound (E) may further contain an ester bond formed by the carboxyl group of the polyester (a) and the epoxy group of the epoxy compound (D).

Further, the polymer compound (E) may contain an ester bond formed by the carboxyl group of the polyester (a) and the hydroxyl group formed by the reaction of the epoxy group of the epoxy compound.

Furthermore, the polymer compound (E) may further contain an ether bond formed by the hydroxyl group of the polyester (a) or the hydroxyl group of the compound (b) and the epoxy group of the epoxy compound (D). ..

In order to obtain a preferable polymer compound (E), the block polymer (C) and the epoxy compound (D) may be reacted. That is, the carboxyl group of the block polymer (C) may be reacted with the epoxy group of the epoxy compound (D). More preferably, the hydroxyl group formed from the reacted epoxy group may be reacted with the carboxyl group. The number of epoxy groups in the epoxy compound (D) is preferably 0.5 to 5 equivalents, more preferably 0.5 to 1.5 equivalents, of the number of carboxyl groups in the block polymer (C) to be reacted. Further, the above reaction may be carried out in various solvents or in a molten state.

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

In the reaction, after the synthesis reaction of the block polymer (C) is completed, the epoxy compound (D) may be added to the reaction system and reacted as it is without isolating the block polymer (C). In that case, the carboxyl group of the unreacted polyester (a) used excessively when synthesizing the block polymer (C) reacts with a part of the epoxy groups of the epoxy compound (D) to form an ester bond. You may.

In the antistatic agent of the present invention, the preferred polymer compound (E) is a block polymer (C) having a structure having a carboxyl group at both ends and an epoxy compound (D) having two or more epoxy groups, respectively. If it has a structure equivalent to that having a structure bonded via an ester bond formed by a carboxyl group and an epoxy group of the above, it is not always necessary to synthesize from the block polymer (C) and the epoxy compound (D). There is no. The ester bond formed by the carboxyl group and the epoxy group referred to here also includes an ester bond formed by the carboxyl group and the hydroxyl group formed from the epoxy group by reacting with the carboxyl group.

In the antistatic agent of the present invention, the number average molecular weight of the block polymer (C) having a structure having a carboxyl group at both ends calculated by the acid value measurement method is antistatic property and its durability, and the transparency of the film. From the viewpoint of sex, it is preferably 8,000 to 50,000, and more preferably 9,000 to 40,000.

In the antistatic agent of the present invention, the method for calculating the number average molecular weight of the block polymer (C) by the acid value measurement method may be the same as the above-mentioned <Method for calculating the number average molecular weight by the acid value measurement method>.

In the antistatic agent of the present invention, the polymer compound (E) is a compound obtained by obtaining a polyester (a) from a diol (a1) and a dicarboxylic acid (a2) without isolating the polyester (a). It may react with (b) and / or the epoxy compound (D).

In the antistatic agent of the present invention, the polymer compound (E) is the sum of the polyester block (A) and the polyether block (B) in terms of antistatic property, its durability, and film transparency. On the other hand, the proportion of the block (B) of the polyether is preferably in the range of 20 to 50% by mass, more preferably 24 to 45% by mass, and even more preferably 24 to 40% by mass. The mass of the block (A) and the block (B) may be calculated from the mass of the polyester (a) and the compound (b).

In the antistatic agent of the present invention, it is preferable to use the polymer compound (E) in the form of pellets from the viewpoint of handleability. To make pellets, after the polymerization reaction, the polymer may be extruded from an extruder and cut into pellets. A machine such as a pelletizer may be used for cutting.

Next, the antistatic agent composition of the present invention will be described.
The antistatic agent composition of the present invention is obtained by further blending the antistatic agent of the present invention with one or more selected from the group of alkali metal salts and ionic liquids. The antistatic agent of the present invention further contains one or more selected from the group of alkali metal salts and ionic liquids to obtain an antistatic agent composition having excellent antistatic performance and durability thereof. preferable.

Hereinafter, the alkali metal salt will be described first.
Examples of alkali metal salts include salts of organic acids or inorganic acids, and examples of alkali metals include lithium, sodium, potassium, cesium, rubidium and the like. Examples of organic acids include aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid; oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid, etc. An aliphatic dicarboxylic acid having 1 to 12 carbon atoms; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethane. Examples thereof include sulfonic acids having 1 to 20 carbon atoms such as sulfonic acids. Examples of inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, perchloric acid and the like. Among them, salts of lithium, sodium, and potassium are preferable, and sodium is more preferable, from the viewpoints of friction band voltage, surface resistivity, and safety to living organisms and the environment. Further, from the viewpoint of antistatic property and its durability, a salt of acetic acid, a salt of perchloric acid, a salt of p-toluenesulfonic acid and a salt of dodecylbenzenesulfonic acid are preferable, and a salt of dodecylbenzenesulfonic acid is more preferable. Two or more kinds of alkali metal salts may be used.

Specific examples of alkali metal salts include, for example, lithium acetate, sodium acetate, potassium acetate, lithium chloride, sodium chloride, potassium chloride, lithium phosphate, sodium phosphate, potassium phosphate, lithium sulfate, sodium sulfate, and perchlorine. Lithium acid, sodium perchlorate, potassium perchlorate, lithium p-toluenesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, dodecylbenzenesulfonic acid Examples include potassium. Of these, lithium p-toluenesulfonate, sodium p-toluenesulfonate, lithium dodecylbenzenesulfonate, and dodecylbenzenesulfone are preferable from the viewpoints of antistatic property, their sustainability, and safety to living organisms and the environment. Sodium acid and the like, most preferably sodium dodecylbenzenesulfonate.

The alkali metal salt may be blended with the antistatic agent of the present invention, or may be blended with the synthetic resin together with the antistatic agent of the present invention. The amount of the alkali metal salt to be blended is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the antistatic agent of the present invention from the viewpoint of antistatic property, its durability, and transparency of the film. 1 to 15 parts by mass is more preferable, and 3.0 to 12 parts by mass is most preferable.

Next, the ionic liquid will be described.
Examples of ionic liquids have a melting point of 100 ° C. or lower, at least one of the cations or anions constituting the ionic liquid is an organic ion, and has an initial conductivity of 1 to 200 mS / cm, preferably 10 to 10 to. A room temperature molten salt having a temperature of 200 mS / cm, for example, the room temperature molten salt described in International Publication No. 95/15572.

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

(1) Imidazolinium cations Examples thereof include those having 5 to 15 carbon atoms, for example, 1,2,3,4-tetramethylimidazolinium, 1,3-dimethylimidazolinium;

(2) Imidazole cation Examples thereof include those having 5 to 15 carbon atoms, for example, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium;

(3) Tetrahydropyrimidinium cation Examples thereof include those having 6 to 15 carbon atoms, for example, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetra. Methyl-1,4,5,6-tetrahydropyrimidinium;

(4) Dihydropyrimidinium cation Examples thereof include those having 6 to 20 carbon atoms, for example, 1,3-dimethyl-1,4-dihydropyrimidinium, 1,3-dimethyl-1,6-dihydropyrimidi. Nium, 8-methyl-1,8-diazabicyclo [5,4,0] -7,9-undecagenium, 8-methyl-1,8-diazabicyclo [5,4,0] -7,10-un Decagenium.

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

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

Examples of guanidinium cations include the following.

(1) Guanidinium cation having an imidazolinium skeleton Examples thereof include those having 8 to 15 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethylimidazolinium and 2-diethylamino-1,3. , 4-trimethylimidazolinium;

(2) Guanidinium cation having an imidazolium skeleton Examples thereof include those having 8 to 15 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethylimidazolium and 2-diethylamino-1,3,4. -Trimethylimidazolium;

(3) Guanidinium cation having a tetrahydropyrimidinium skeleton Examples thereof include those having 10 to 20 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydro. Pyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium;

(4) Guanidinium cation having a dihydropyrimidinium skeleton Examples thereof include those having 10 to 20 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethyl-1,4-dihydropyrimidinium. 2-Dimethylamino-1,3,4-trimethyl-1,6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4-dihydropyrimidinium, 2-diethylamino-1 , 3-Dimethyl-4-ethyl-1,6-dihydropyrimidinium.

These cations may be used alone or in combination of two or more. Of these, from the viewpoint of friction zone voltage and surface resistivity, an amidinium cation is preferable, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is particularly preferable.

In the ionic liquid, examples of the organic acid or the inorganic acid constituting the anion include the following. Organic acids include, for example, carboxylic acids, sulfuric acid esters, sulfonic acids and phosphoric acids; inorganic acids include, for example, super-strong acids (eg, borofluoric acid, boron tetrafluoroacid, perchloric acid, phosphorus hexafluoride). Acids, antimonic acid hexafluoride and arsenic hexafluoride), phosphoric acid and boric acid. The organic acid and the inorganic acid may be used alone or in combination of two or more.

Of the organic acids and inorganic acids, the ionic liquid is preferable from the viewpoint of antistatic property and its durability, and the transparency of the film, because the Hamettet acidity function (-H0) of the anion constituting the ionic liquid is 12 to 12 to A conjugate base of a superacid, an acid forming an anion other than the conjugate base of a superacid, and a mixture thereof, which is 100.

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

Examples of superacids include protonic acids and those derived from a combination of protonic acids and Lewis acids, and mixtures thereof. Examples of the protonic acid as a super strong acid include bis (trifluoromethylsulfonyl) imide acid, bis (pentafluoroethylsulfonyl) imide acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, and alkane ( 1 to 30 carbon atoms) sulfonic acid (eg, methane sulfonic acid, dodecane sulfonic acid, etc.), poly (n = 1 to 30) fluoroalkane (1 to 30 carbon atoms) sulfonic acid (eg, trifluoromethane sulfonic acid, etc.) Pentafluoroethane sulfonic acid, heptafluoropropane sulfonic acid, nonafluorobutane sulfonic acid, undecafluoropentane sulfonic acid and tridecafluorohexane sulfonic acid), borofluoric acid and boron tetrafluorofluoric acid. Of these, borofluoric acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) imide acid and bis (pentafluoroethylsulfonyl) imide acid are preferable from the viewpoint of ease of synthesis.

Protonic acids used in combination with Lewis acid include, for example, hydrogen halides (eg, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethane. Included are sulfonic acids, pentafluoroethane sulfonic acids, nonafluorobutane sulfonic acids, undecafluoropentane sulfonic acids, tridecafluorohexane sulfonic acids and mixtures thereof. Of these, hydrogen fluoride is preferable from the viewpoint of the initial conductivity of the ionic liquid.

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

The combination of the protonic acid and the Lewis acid is arbitrary, but examples of the super strong acid consisting of these combinations include tetrafluoroboric acid, hexafluorophosphate, tantalic hexafluoride, antimonic hexafluoride, and hexafluoride. Examples thereof include tantalum sulphonic acid, boron tetrafluoride acid, phosphoric acid hexafluoride, boron trifluoride chloride, arsenic hexafluoride and mixtures thereof.

Among these anions, a conjugated base of a super strong acid (a super strong acid composed of a protonic acid and a super strong acid composed of a combination of a protonic acid and a Lewis acid) is preferable from the viewpoint of antistatic property of an ionic liquid, and further preferable. Is a conjugate base of a superacid consisting of a protonic acid and a superacid consisting of a boron trifluoride and / or a phosphorus pentafluoride.

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

The ionic liquid may be blended with the antistatic agent of the present invention, or may be blended with the synthetic resin together with the antistatic agent of the present invention. The blending amount of the ionic liquid is preferably 0.01 to 20 parts by mass, preferably 0.1 to 100 parts by mass, based on 100 parts by mass of the antistatic agent of the present invention, from the viewpoint of antistatic property, its durability, and transparency of the film. To 15 parts by mass is more preferable, and 1 to 12 parts by mass is most preferable.

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

Further, the antistatic agent of the present invention may be used as an antistatic agent composition having antistatic properties by blending a salt of a Group 2 element as long as the effect of the present invention is not impaired. Examples of the salt of the group 2 element include salts of organic acids or inorganic acids, and examples of the group 2 element include beryllium, magnesium, calcium, strontium, barium and the like. Examples of organic acids include aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid; oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid, etc. An aliphatic dicarboxylic acid having 1 to 12 carbon atoms; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethane. Examples thereof include sulfonic acids having 1 to 20 carbon atoms such as sulfonic acids. Examples of inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, perchloric acid and the like.

The salt of the Group 2 element may be blended with the antistatic agent of the present invention, or may be blended with the synthetic resin together with the antistatic agent of the present invention. The amount of the salt of the Group 2 element is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and 3.0 to 12 parts by mass with respect to 100 parts by mass of the antistatic agent of the present invention. Most preferably by mass.

Further, the antistatic agent of the present invention may be used as an antistatic agent composition having antistatic properties by blending a surfactant as long as the effects of the present invention are not impaired. As the surfactant, a nonionic, anionic, cationic or amphoteric surfactant can be used. Examples of the nonionic surfactant include polyethylene glycol-type nonionic surfactants such as higher alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, and polypropylene glycol ethylene oxide adduct; fatty acid ester of polyethylene oxide and glycerin. , Pentaerislit fatty acid ester, sorbit or sorbitan fatty acid ester, polyhydric alcohol alkyl ether, polyhydric alcohol type nonionic surfactant such as alkanolamine aliphatic amide, etc., and examples thereof include anionic surfactants. For example, carboxylates such as alkali metal salts of higher fatty acids; sulfate esters such as higher alcohol sulfates and higher alkyl ether sulfates, alkylbenzene sulfonates, alkyl sulfonates, paraffin sulfonates and the like. Sulfates; Phosphates such as higher alcohol phosphates and the like can be mentioned, and examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of the amphoteric surfactant include amino acid-type amphoteric surfactants such as higher alkylaminopropionate, betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethyl betaine, and these may be used alone or. Two or more types can be used in combination. In the antistatic agent composition of the present invention, among the above-mentioned surfactants, anionic surfactants are preferable, and sulfonates such as alkylbenzene sulfonates, alkyl sulfonates and paraffin sulfonates are particularly preferable.

The surfactant may be blended with the antistatic agent of the present invention, or may be blended with the synthetic resin together with the antistatic agent of the present invention. The blending amount of the surfactant is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and most preferably 1 to 10 parts by mass with respect to 100 parts by mass of the antistatic agent of the present invention. ..

Further, the antistatic agent of the present invention may be used as an antistatic agent composition having antistatic properties by blending a polymer type antistatic agent as long as the effects of the present invention are not impaired. As the polymer antistatic agent, for example, a known polymer type antistatic agent such as a polyether ester amide can be used, and as a known polyether ester amide, for example, JP-A-7-10989 can be used. Examples thereof include the polyether ester amide composed of the polyoxyalkylene adduct of bisphenol A described above. Further, a block polymer having a repeating structure in which the bonding unit between the polyolefin block and the hydrophilic polymer block is 2 to 50 can be used, and examples thereof include the block polymer described in US Pat. No. 6,552,131.

The polymer-type antistatic agent may be blended with the antistatic agent of the present invention, or may be blended with a synthetic resin together with the antistatic agent of the present invention. The blending amount of the polymer-type antistatic agent is preferably 0 to 50 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the antistatic agent of the present invention.

Furthermore, the antistatic agent of the present invention may be blended with a compatibilizer as long as the effects of the present invention are not impaired to prepare an antistatic agent composition having antistatic properties. By blending a compatibilizer, the compatibility between the antistatic agent of the present invention and other components or synthetic resins can be improved. Examples of such a 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. Examples thereof include the polymer described in Japanese Patent Application Laid-Open No. 3-258850, the modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, and the block polymer having a polyolefin moiety and an aromatic vinyl polymer moiety. Be done. More preferable compatibilizers include acid anhydride-modified polyolefins such as maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, itaconic anhydride-modified polyethylene, and itaconic anhydride-modified polypropylene.

The compatibilizer may be blended with the antistatic agent of the present invention, or may be blended with the antistatic agent of the present invention and used. The blending amount of the compatibilizer is preferably 0.1 to 15 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the antistatic agent of the present invention.

The antistatic agent composition of the present invention may contain other components as arbitrary components in addition to the antistatic agent of the present invention and the above components as long as the effects of the present invention are not impaired. These other components may be directly blended in the composition, or the antistatic agent of the present invention or the antistatic agent composition of the present invention may be blended in a synthetic resin such as a thermoplastic resin to have antistatic properties. When used as a resin composition, it may be blended with a synthetic resin.

The antistatic agent and antistatic agent composition of the present invention can be blended with a synthetic resin, particularly preferably a thermoplastic resin, and used as an antistatic resin composition having antistatic properties.

Next, the antistatic resin composition of the present invention will be described.
The resin composition of the present invention is obtained by blending the antistatic agent of the present invention and the antistatic agent composition of the present invention with a synthetic resin. As the synthetic resin, a thermoplastic resin is preferable.

Examples of thermoplastic resins include polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, crosslinked polyethylene, ultrahigh-molecular-weight polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, and the like. Α-olefin polymer or ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene copolymer and other polyolefin-based resins and their copolymers; polyvinyl chloride, polyvinylidene chloride, chlorine Polyethylene chloride, chlorinated polypropylene, polyvinylidene chloride, rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary Halogen-containing resins such as copolymers, vinyl chloride-acrylic acid ester copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-cyclohexylmaleimide copolymers; petroleum resin, kumaron resin, polystyrene, polyvinyl acetate, etc. Copolymers of acrylic resins, styrene and / or α-methylstyrene with other monomers (eg, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) (eg, AS resin, ABS (acrylonitrile, etc.) (Butadiene-styrene copolymer) resin, ACS resin, SBS resin, MBS resin, heat-resistant ABS resin, etc.); Polymethylmethacrylate, polyvinyl alcohol, polyvinylformal, polyvinylbutyral; polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, etc. Aromatic polyesters such as polyalkylene naphthalate such as polyalkylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and linear polyesters such as polytetramethylene terephthalate; polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate , Polylactic acid, polyappleic acid, polyglycolic acid, polydioxane, poly (2-oxetanone) and other degradable aliphatic polyesters; polyamides such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, polycarbonate, polycarbonate / ABS resin , Branched polymer, polyacetal, polyphenylene sulfide, polyurethane, fibrous resin, polyimide Examples thereof include thermoplastic resins such as resins, polysulfones, polyphenylene ethers, polyetherketones, polyetheretherketones, and liquid crystal polymers, and blends thereof.

Further, in the resin composition of the present invention, the thermoplastic resin includes isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, olefin elastomer, and styrene elastomer. It may be an elastomer such as a polyester-based elastomer, a nitrile-based elastomer, a nylon-based elastomer, a vinyl chloride-based elastomer, a polyamide-based elastomer, or a polyurethane-based elastomer. In the resin composition of the present invention, these thermoplastic resins may be used alone or in combination of two or more. Moreover, the thermoplastic resin may be alloyed.

These thermoplastic resins have molecular weight, degree of polymerization, density, softening point, ratio of insoluble matter in solvent, degree of stereoregularity, presence or absence of catalyst residue, type and compounding ratio of monomer as raw material, type of polymerization catalyst. It can be used regardless of (for example, Ziegler catalyst, metallocene catalyst, etc.). Among these thermoplastic resins, at least one selected from the group consisting of polyolefin-based resins, polystyrene-based resins and copolymers thereof is preferable from the viewpoint of antistatic properties.

The mass ratio of the synthetic resin to the antistatic agent of the present invention or the antistatic agent composition of the present invention in the resin composition of the present invention is preferably in the range of 99/1 to 40/60.

Further, when the antistatic agent of the present invention or the antistatic agent composition of the present invention is used for the polyolefin resin to form a film, it is preferable because it is excellent in antistatic property, its durability, and transparency of the film. Examples of the polyolefin resin include polypropylene, high-density polyethylene, low-density polyethylene, straight-chain low-density polyethylene, crosslinked polyethylene, ultra-high molecular weight polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene and the like. Examples thereof include polyolefin resins such as α-olefin polymer or ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-propylene copolymer, and copolymers thereof. These films are suitable for packaging materials for electric / electronic parts, electric / electronic products, precision parts, precision machinery, precision products, and the like.

The amount of the antistatic agent of the present invention to be blended with the synthetic resin is preferably 0.9 to 90 parts by mass with respect to 100 parts by mass of the synthetic resin from the viewpoint of antistatic property, its durability, and transparency of the film. .8 to 55 parts by mass is more preferable, and 4.5 to 45 parts by mass is even more preferable.

Further, the amount of the antistatic agent composition of the present invention blended with respect to the synthetic resin is such that the antistatic agent composition is added to 100 parts by mass of the synthetic resin from the viewpoint of antistatic property, its durability, and transparency of the film. It is preferably 1.0 to 100 parts by mass, more preferably 2.0 to 60 parts by mass, and even more preferably 5.0 to 50 parts by mass.

The method of blending the antistatic agent of the present invention into the synthetic resin is not particularly limited, and any commonly used method can be used, for example, mixing by roll kneading, bumper kneading, extruder, kneader or the like. , Knead and mix. Further, the antistatic agent of the present invention may be added to the synthetic resin as it is, or may be added after impregnating the carrier, if necessary. In order to impregnate the carrier, the mixture may be heated and mixed as it is, or if necessary, the carrier may be impregnated after diluting with an organic solvent, and then the solvent may be removed. As such a carrier, those known as fillers and fillers of synthetic resins, flame retardants and light stabilizers that are solid at room temperature can be used, and for example, calcium silicate powder, silica powder, talc powder, and alumina powder can be used. , Titanium oxide powder, chemically modified surface of these carriers, solid ones among the flame retardant agents and antioxidants listed below. Among these carriers, those in which the surface of the carrier is chemically modified are preferable, and those in which the surface of the silica powder is chemically modified are more preferable. These carriers preferably have an average particle size of 0.1 to 100 μm, and more preferably 0.5 to 50 μm.

As a method of blending the antistatic agent of the present invention into the synthetic resin, the antistatic agent of the present invention is kneaded with the block polymer (C) and the epoxy compound (D) having two or more epoxy groups at the same time as the synthetic resin. The polymer compound (E) as an agent may be synthesized and blended, and at that time, one or more selected from the group of an alkali metal salt and an ionic liquid may be kneaded at the same time, or may be injected. The antistatic agent of the present invention and a synthetic resin may be mixed at the time of molding such as molding to obtain a molded product, and at that time, the epoxy is further selected from the group of alkali metal salts and ionic liquids. Seeds or more may be blended, and a master batch of the antioxidant of the present invention and the synthetic resin may be manufactured in advance, and this master batch may be blended. At that time, alkali metal salts and ions may be blended. One or more selected from the group of sex liquids may be blended.

Various additives such as phenol-based antioxidants, phosphorus-based antioxidants, thioether-based antioxidants, ultraviolet absorbers, and hindered amine-based light stabilizers are further added to the resin composition of the present invention, if necessary. This allows the resin composition of the present invention to be stabilized.

Various additives such as these antioxidants may be added to the antistatic agent composition of the present invention before being added to the synthetic resin. Further, it may be blended at the time of producing the polymer compound (E) which is the antistatic agent of the present invention. In particular, the antioxidant is preferable because it can prevent oxidative deterioration of the polymer compound (E) during production by blending it at the time of producing the polymer compound (E).

Examples of the phenolic antioxidant include 2,6-ditertiary butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and distearyl (3,5-ditertiary butyl-4-4). Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-dithiary butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tertiary butyl-m-cresol) , 2,2'-Methylenebis (4-methyl-6-tertiary butylphenol), 2,2'-methylenebis (4-ethyl-6-third butylphenol), 4,4'-butylidenebis (6-tertiary butyl-) m-cresol), 2,2'-ethylidenebis (4,6-di-tertiary butylphenol), 2,2'-etiridenbis (4-second butyl-6-third butylphenol), 1,1,3- Tris (2-methyl-4-hydroxy-5-3 butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-3 butylbenzyl) isocyanurate, 1,3 , 5-Tris (3,5-di-tertiary butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-Tris (3,5-di-tertiary butyl-4-hydroxybenzyl) -2,4,5 -Trimethylbenzene, 2-third butyl-4-methyl-6- (2-acryloyloxy-3-third butyl-5-methylbenzyl) phenol, stearyl (3,5-ditriary butyl-4-hydroxyphenyl) ) Propionate, tetrakis [3- (3,5-ditriary butyl-4-hydroxyphenyl) methyl propionate] methane, thiodiethylene glycol bis [(3,5-ditritiary butyl-4-hydroxyphenyl) propionate], 1,6-Hexamethylenebis [(3,5-ditertiary butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-hydroxy-3-third butylphenyl) butyric acid] glycol Estel, bis [2-tertiary butyl-4-methyl-6- (2-hydroxy-3-third butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-di) Tertiary Butyl-4-Hydroxyphenyl) Propionyloxyethyl] Isocyanurate, 3,9-Bis [1,1-Dimethyl-2-{(3-Triary Butyl-4-Hydroxy-5-Methylphenyl) Propionyloxy} Ethyl] -2,4,8,10-tetraoxaspiro [5,5] un Examples thereof include decane and triethylene glycol bis [(3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate]. The amount of these phenolic antioxidants added is preferably 0.001 to 10 parts by mass and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin.

Examples of phosphorus-based antioxidants include trisnonylphenyl phosphite and tris [2-tertiary butyl-4- (3-third butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phos. Fight, tridecylphosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-dith) Tributylphenyl) pentaerythritol diphosphite, bis (2,6-ditetrabutyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritrith butylphenyl) pentaerythritol diphos Fight, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropyridene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-third butyl-) 5-Methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-3 butylphenyl) butanetriphosphite, tetrakis (2,4-ditertiary butylphenyl) ) Biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-teriary butylphenyl) -2-ethylhexylphosphite , 2,2'-Methylenebis (4,6-3rd Butylphenyl) -Octadecylphosphite, 2,2'-Echilidenebis (4,6-di3rd Butylphenyl) Fluorophosphite, Tris (2-[( 2,4,8,10-Tetraxyl butyldibenzo [d, f] [1,3,2] dioxaphosfepin-6-yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol And 2,4,6-tritrith butylphenol phosphite and the like. The amount of these phosphorus-based antioxidants added is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin.

Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra (β-alkylthiopropionic acid) ester. Kind. The amount of these thioether-based antioxidants added is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-Hydroxybenzophenones such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-ditertiary butylphenyl) -5-chlorobenzo Triazol, 2- (2'-hydroxy-3'-tertiary butyl-5'-methylphenyl) -5-chlorobenzotriazol, 2- (2'-hydroxy-5'-tertiary octyl) Phenyl) benzotriazol, 2- (2'-hydroxy-3', 5'-dicumylphenyl) benzotriazol, 2,2'-methylenebis (4-third octyl-6- (benzotriazolyl) phenol ), 2- (2'-Hydroxyphenyl) benzotriazoles such as 2- (2'-hydroxy-3'-tertiary butyl-5'-carboxyphenyl) benzotriazole; phenylsalicylate, resorcinol monobenzoate, 2,4 -Di-tertiary butylphenyl-3,5-di-tertiary butyl-4-hydroxybenzoate, 2,4-di-tertiary amylphenyl-3,5-di-tertiary butyl-4-hydroxybenzoate, hexadecyl-3.5 -Benzoates such as di-tertiary butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano- Cyanoacrylates such as β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6- Bis (2,4-ditertiary butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy) Examples thereof include triaryltriazines such as -5-methylphenyl) -4,6-bis (2,4-ditetrabutylphenyl) -s-triazine. The amount of these ultraviolet absorbers added is preferably 0.001 to 30 parts by mass, and more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the synthetic resin.

Examples of the hindered amine-based photostabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6. , 6-Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane Tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, bis (2,2,6,6-tetramethyl-4) -Piperidil) bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) bis (tridecyl) -1,2, 3,4-Butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditertiary butyl-4-hydroxybenzyl) malonate , 1,2,2,6,6-pentamethyl-4-piperidylmethacrylate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4- Diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], 1,2,3 4-Butancarboxylic acid / 2,2-bis (hydroxymethyl) -1,3-propanediol / 3-hydroxy-2,2-dimethylpropanal / 1,2,2,6,6-pentamethyl-4-pipe Ridinyl ester polycondensate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) = decandioate / methyl = 1,2,2,6,6-pentamethyl-4-piperidyl = sebacato mixture, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6 -Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4- Piperidineamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4- Dichloro-6-3 octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-) 4-Piperidyl) amino) -s-triazine-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N-) (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2 , 4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6-ylamino] undecane, 1,6,11-tris [2, 4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6-ylamino] undecane, 3,9-bis [1,1-bis] Dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3 , 9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetra Oxaspiro [5.5] undecane, bis (1-undecyloxy-2,2,6,6-tetramethylpiperidine-4-yl) carbonate, 2,2,6,6-tetramethyl-4-piperidylhexa Examples thereof include hindered amine compounds such as decanoate and 2,2,6,6-tetramethyl-4-piperidyl octadecanoate. The amount of these hindered amine-based light stabilizers added is preferably 0.001 to 30 parts by mass, and more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the synthetic resin.

When a polyolefin resin is used as the synthetic resin, a known neutralizing agent is added as necessary to further neutralize the residual catalyst in the polyolefin resin as long as the effects of the present invention are not impaired. It is preferable to do so. Examples of the neutralizing agent include fatty acid metal salts such as calcium stearate, lithium stearate, and sodium stearate, or fatty acid amides such as ethylene bis (stearoamide), ethylene bis (12-hydroxystearoamide), and stearic acid amide. Compounds are mentioned, and these neutralizing agents may be mixed and used.

In the resin composition of the present invention, as other additives, if necessary, an aromatic carboxylic acid metal salt, an alicyclic alkyl carboxylic acid metal salt, p-th, as long as the effects of the present invention are not impaired. Tributylaluminum benzoate, aromatic phosphate metal salts, nucleating agents such as dibenzylidene sorbitols, metal soaps, hydrotalcites, triazine ring-containing compounds, metal hydroxides, phosphoric acid ester flame retardants, condensed phosphorus Acid ester flame retardants, inorganic phosphorus flame retardants, (poly) phosphate flame retardants, halogen flame retardants, silicon flame retardants, antioxidants such as antimon trioxide, other inorganic flame retardants, etc. Organic flame retardant aids, fillers, pigments, lubricants, foaming agents and the like may be added.

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

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

Examples of the phosphoric acid ester flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, and triki. Sirenyl phosphate, octyldiphenyl phosphate, xylenyldiphenyl phosphate, trisisopropylphenyl phosphate, 2-ethylhexyldiphenyl phosphate, t-butylphenyldiphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t-butylphenyl) ) Phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate and the like.

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

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

Examples of other inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talcite, and montmorillonite, and surface-treated products thereof. For example, TIPAQUE R-680 ( Titanium oxide: Ishihara Sangyo Co., Ltd., Kyowa Mag 150 (magnesium oxide: Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite: Kyowa Chemical Industry Co., Ltd.), Alchemizer 4 (zinc-modified hydro) Hydrotalcite: Various commercially available products such as Kyowa Chemical Industry Co., Ltd. can be used. Further, as another organic flame retardant, for example, pentaerythritol can be mentioned.

In addition, the resin composition of the present invention includes additives usually used for synthetic resins, such as a cross-linking agent, an antifogging agent, and a plate-out inhibitor, as needed, as long as the effects of the present invention are not impaired. Surface treatment agents, plasticizers, lubricants, flame retardants, fluorescent agents, fungicides, bactericides, foaming agents, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, etc. It can be blended within a range that does not impair the effects of the present invention.

The additive to be blended in the resin composition of the present invention may be added directly to the synthetic resin, and after being blended in the polymer compound (E) which is the antistatic agent of the present invention or the antistatic agent composition, It may be added to the synthetic resin.

By molding the resin composition of the present invention, a resin molded product having antistatic properties can be obtained. The molding method is not particularly limited, and examples thereof include extrusion processing, calendar processing, injection molding, roll, compression molding, blow molding, rotary molding, and the like, and include resin plates, sheets, films, bottles, fibers, and deformed products. It is possible to manufacture molded products having various shapes such as.

The molded product obtained by the resin composition of the present invention is excellent in antistatic performance and its durability. The molded product obtained from the resin composition of the present invention is a molded product that does not easily generate static electricity and does not easily cause surface contamination due to static electricity or deterioration of commercial value due to adhesion of dust.

Among the molded products obtained by the resin composition of the present invention, the film is particularly preferable because it is excellent in antistatic property, its durability, and the transparency of the film. These films are less likely to generate static electricity, are less likely to cause surface contamination due to static electricity, and are less likely to lose their commercial value due to adhesion of dust, and are also excellent in transparency. Therefore, it is suitable for packaging materials for electric / electronic parts, electric / electronic products, precision parts, precision equipment, and the like.

The film obtained by the resin composition of the present invention has excellent transparency. As the transparency of the film, the Haze value (cloudiness) at a thickness of 50 μm is preferably 0% or more and 40.0% or less, and more preferably 0% or more and 35.0% or less. The Haze value can be measured in accordance with JIS K7136.

The resin composition of the present invention and a molded product using the same can be used for electricity / electronics / communication, agriculture, forestry and fisheries, mining, construction, food, textiles, clothing, medical care, coal, petroleum, rubber, leather, automobiles, precision equipment, and wood. Can be used in a wide range of industrial fields such as building materials, civil engineering, furniture, printing, and musical instruments.

More specifically, the resin composition of the present invention and a molded product thereof include a printer, a personal computer, a word processor, a keyboard, a PDA (small information terminal), a telephone, a copying machine, a facsimile, an ECR (electronic money registration machine), and the like. Office work such as calculators, electronic notebooks, cards, holders, stationery, OA equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, home appliances such as kotatsu, TVs, VTRs, video cameras, radio cassettes , Tape recorder, mini disc, CD player, speaker, AV equipment such as liquid crystal display, connector, relay, condenser, switch, printed board, coil bobbin, semiconductor encapsulation material, LED encapsulation material, electric wire, cable, transformer, deflection yoke , Distribution boards, electrical and electronic parts such as watches and communication equipment, interior and exterior materials for automobiles, plate making films, adhesive films, bottles, food containers, food packaging films, pharmaceutical / pharmaceutical wrap films, product packaging films , Agricultural film, agricultural sheet, greenhouse film, packaging film for electrical and electronic parts, etc.

Further, the resin composition of the present invention and a molded product thereof are used for seats (filling, outer material, etc.), belts, ceiling coverings, compatible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, foil covers, mattress covers. , Airbags, Insulations, Hanging Hands, Hanging Bands, Wire Coatings, Electrical Insulations, Paints, Coatings, Upholstery, Flooring, Corner Walls, Carpets, Wallpapers, Wall Covers, Exteriors, Interior Materials , Roofing materials, deck materials, wall materials, pillar materials, floor boards, wall materials, skeletons and plywood, window and door shapes, moss boards, siding, terraces, balconies, soundproof boards, heat insulating boards, window materials, etc. Automobiles, vehicles, ships, aircraft, buildings, housing and building materials and civil engineering materials, clothing, curtains, sheets, non-woven fabrics, plywood, synthetic fiber boards, rugs, entrance mats, sheets, buckets, hoses, containers, glasses, bags, cases , Goggles, ski boards, rackets, tents, daily necessities such as musical instruments, sporting goods, etc.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

The polymer compound (E) was produced according to the following production example. Further, in the following production example, the number average molecular weights of the polyester (a) and the block polymer (C) are calculated by the following <method for calculating the number average molecular weight by the acid value measurement method>, and the number average molecular weight of the compound (b). Was calculated by the following <method for calculating the number average molecular weight by the hydroxyl value measurement method>.

<Calculation method of number average molecular weight by acid value measurement method>
The acid value was measured by the following acid value measuring method, and the number average molecular weight (hereinafter, also referred to as “Mn”) was determined by the following formula.
Mn = 112220 / acid value

<Measurement method of acid value>
First, 0.2 g of a sample is weighed in a 100 mL Erlenmeyer flask, and 40 mL of a xylene / ethanol solution is added to dissolve the sample. Titrate with 0.1N-KOH aqueous solution and calculate by the following formula.
Acid value [mgKOH / g] = 56.11 × f × T / S
f: factor of 0.1N-KOH aqueous solution
T: Quantitative test titration [mL]
S: Sample amount [g]

<Calculation method of number average molecular weight by hydroxyl value measurement method>
The hydroxyl value was measured by the following method for measuring the hydroxyl value, and the number average molecular weight (hereinafter, also referred to as “Mn”) was determined by the following formula.
Number average molecular weight = (56110 × 2) / hydroxyl value

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

[Manufacturing Example 1]
In a separable flask, 87.3 g (0.61 mol) of 1,4-cyclohexanedimethanol, 127.9 g (0.63 mol) of sebacic acid, and an antioxidant (tetrakis [3- (3,5-di)). Tertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 (manufactured by ADEKA Corporation) was charged in 0.2 g, and polymerized at normal pressure for 3 hours while gradually raising the temperature from 140 ° C to 190 ° C. To obtain polyester (a) -1. The obtained polyester (a) -1 had an acid value of 16 and a number average molecular weight of 7,000.

Next, 193.4 g of the obtained polyester (a) -1 was used as compound (b) -1 having hydroxyl groups at both ends, the number average molecular weight was 3,300 (hydroxyl value 34), and the number of repeating units of ethyleneoxy groups. 68.1 g of polyethylene glycol of = 75, 0.2 g of antioxidant (Adecastab AO-60), 0.4 g of zirconium octylate were charged, and polymerized at 200 ° C. for 3 hours under reduced pressure to carboxyl to both ends. 238.3 g of block polymer (C) -1 having a structure having a group was obtained. The acid value of the block polymer (C) -1 having a structure having a carboxyl group at both ends was 2.9, and the number average molecular weight was 38,000.

Bisphenol F diglycidyl ether (epoxy equivalent) was obtained as an epoxy compound (D) -1 having two or more epoxy groups in 220.0 g of the obtained block polymer (C) -1 having a structure having carboxyl groups at both ends. 170 g / eq) 0.87 g was charged and polymerized at 220 ° C. for 5 hours under reduced pressure to obtain 205.5 g of the polymer compound (E) -1. The ratio of the block (B) of the polyether to the total of the block (A) of the polyester and the block (B) of the polyether of the obtained polymer compound (E) -1 was 26% by mass.

[Manufacturing Example 2]
In a separable flask, 97.4 g (0.68 mol) of 1,4-cyclohexanedimethanol, 147.5 g (0.73 mol) of sebacic acid, and an antioxidant (tetrakis [3- (3,5-di)). Tertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 (manufactured by ADEKA Corporation) was charged in 0.2 g, and polymerized at normal pressure for 3 hours while gradually raising the temperature from 140 ° C to 190 ° C. Obtained polyester (a) -2. The obtained polyester (a) -2 had an acid value of 28 and a number average molecular weight of 4,000.

Next, 220.6 g of the obtained polyester (a) -2 was used as compound (b) -2 having hydroxyl groups at both ends, the number average molecular weight was 3,100 (hydroxyl value 36), and the number of repeating units of ethyleneoxy groups. 85.3 g of polyethylene glycol of = 70, 0.2 g of antioxidant (Adecastab AO-60), 0.4 g of zirconium octylate were charged, and polymerized at 200 ° C. for 3 hours under reduced pressure to carboxyl to both ends. 278.3 g of block polymer (C) -2 having a structure having a group was obtained. The acid value of the block polymer (C) -2 having a structure having a carboxyl group at both ends was 10, and the number average molecular weight was 10,000.

Dicyclopentadiene dimethanol diglycidyl ether as an epoxy compound (D) -2 having two or more epoxy groups in 260.0 g of the obtained block polymer (C) -2 having a structure having carboxyl groups at both ends. 3.47 g (epoxy equivalent 170 g / eq) was charged and polymerized at 220 ° C. for 5 hours under reduced pressure to obtain 248.6 g of polymer compound (E) -2. The ratio of the block (B) of the polyether to the total of the block (A) of the polyester and the block (B) of the polyether of the obtained polymer compound (E) -2 was 28% by mass.

[Manufacturing Example 3]
In a separable flask, 55.5 g (0.38 mol) of 1,4-cyclohexanedimethanol, 59.2 g (0.41 mol) of adipic acid, and an antioxidant (tetrakis [3- (3,5-di)). Tertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 (manufactured by ADEKA Corporation) was charged in 0.2 g, and polymerized at normal pressure for 3 hours while gradually raising the temperature from 140 ° C to 190 ° C. To obtain polyester (a) -3. The obtained polyester (a) -3 had an acid value of 22 and a number average molecular weight of 5,000.

Next, 100.8 g of the obtained polyester (a) -3 was used as compound (b) -1 having hydroxyl groups at both ends, the number average molecular weight was 3,300 (hydroxyl value 34), and the number of repeating units of ethyleneoxy groups. = 75 g of polyethylene glycol, 0.2 g of antioxidant (Adecastab AO-60), 0.4 g of zirconium octylate were charged, polymerized at 200 ° C. for 3 hours under reduced pressure, and carboxyl at both ends. 118.2 g of block polymer (C) -3 having a structure having a group was obtained. The acid value of the block polymer (C) -3 having a structure having a carboxyl group at both ends was 3.8, and the number average molecular weight was 29,500.

Bisphenol F diglycidyl ether (epoxy equivalent) as the epoxy compound (D) -1 having two or more epoxy groups in 100.0 g of the obtained block polymer (C) -3 having a structure having carboxyl groups at both ends. 170 g / eq) 0.63 g was charged and polymerized at 220 ° C. for 5 hours under reduced pressure to obtain 93.2 g of the polymer compound (E) -3. The ratio of the block (B) of the polyether to the total of the block (A) of the polyester and the block (B) of the polyether of the obtained polymer compound (E) -3 was 33% by mass.

[Manufacturing Example 4]
In a separable flask, 56.7 g (0.48 mol) of 1,6-hexanediol, 105.1 g (0.52 mol) of sebacic acid, and an antioxidant (tetrakis [3- (3,5-dith)). Tributyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 (manufactured by ADEKA Corporation) was charged in 0.2 g, and polymerized at normal pressure for 3 hours while gradually increasing the temperature from 140 ° C to 190 ° C. , Polyester (a) -4 was obtained. The obtained polyester (a) -4 had an acid value of 31 and a number average molecular weight of 3,600.

Next, 144.5 g of the obtained polyester (a) -4 was used as compound (b) -2 having hydroxyl groups at both ends, the number average molecular weight was 3,100 (hydroxyl value 36), and the number of repeating units of ethyleneoxy groups. 88.0 g of polyethylene glycol of = 75, 0.2 g of antioxidant (Adecastab AO-60), 0.4 g of zirconium octylate were charged, and polymerized at 200 ° C. for 3 hours under reduced pressure to carboxyl to both ends. 202.3 g of block polymer (C) -4 having a structure having a group was obtained. The acid value of the block polymer (C) -4 having a structure having a carboxyl group at both ends was 6.5, and the number average molecular weight was 17,400.

Bisphenol F diglycidyl ether (epoxy equivalent) as the epoxy compound (D) -1 having two or more epoxy groups in 150.0 g of the obtained block polymer (C) -4 having a structure having carboxyl groups at both ends. 170 g / eq) 1.68 g was charged and polymerized at 220 ° C. for 5 hours under reduced pressure to obtain 128.2 g of the polymer compound (E) -4. The ratio of the block (B) of the polyether to the total of the block (A) of the polyester and the block (B) of the polyether of the obtained polymer compound (E) -4 was 38% by mass.

[Manufacturing Example 5]
160.5 g of polyester (a) -4 (acid value 31, number average molecular weight is 3,600) obtained in the same manner as in Production Example 4 is numerically averaged as compound (b) -3 having hydroxyl groups at both ends. 53.3 g of polyethylene glycol having a molecular weight of 2,000 (hydroxyl value 56) and 45 repeating units of ethyleneoxy groups, 0.2 g of antioxidant (Adecastab AO-60), and 0.4 g of zirconium octylate were charged. , Polymerized at 200 ° C. for 3 hours under reduced pressure to obtain 179.3 g of block polymer (C) -5 having a structure having a carboxyl group at both ends. The block polymer (C) -5 having a structure having a carboxyl group at both ends had an acid value of 7.0 and a number average molecular weight of 16,000.

Hydrogenated bisphenol A diglycidyl ether (as an epoxy compound (D) -3 having two or more epoxy groups in 150.0 g of the obtained block polymer (C) -5 having a structure having carboxyl groups at both ends. 2.1 g of epoxy equivalent (215 g / eq) was charged and polymerized at 220 ° C. for 5 hours under reduced pressure to obtain 139.8 g of the polymer compound (E) -5. The ratio of the block (B) of the polyether to the total of the block (A) of the polyester and the block (B) of the polyether of the obtained polymer compound (E) -5 was 25% by mass.

[Manufacturing Example 6]
In a separable flask, 97.8 g (0.48 mol) of 1,12-dodecanediol, 84.9 g (0.51 mol) of terephthalic acid, and an antioxidant (tetrakis [3- (3,5-di)). Tributyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 (manufactured by ADEKA Corporation) was charged in 0.2 g, and polymerized at normal pressure for 3 hours while gradually increasing the temperature from 140 ° C to 190 ° C. , Polyester (a) -5 was obtained. The obtained polyester (a) -5 had an acid value of 18 and a number average molecular weight of 6,000.

Next, 165.3 g of the obtained polyester (a) -5 was used as compound (b) -1 having hydroxyl groups at both ends, the number average molecular weight was 3,300 (hydroxyl value 34), and the number of repeating units of ethyleneoxy groups. 68.1 g of polyethylene glycol of = 75, 0.2 g of antioxidant (Adecastab AO-60), 0.4 g of zirconium octylate were charged, and polymerized at 200 ° C. for 3 hours under reduced pressure to carboxyl to both ends. 199.6 g of block polymer (C) -6 having a structure having a group was obtained. The block polymer (C) -6 having a structure having a carboxyl group at both ends had an acid value of 3.3 and a number average molecular weight of 34,000.

Hydrogenated bisphenol A diglycidyl ether (as an epoxy compound (D) -3 having two or more epoxy groups in 160.0 g of the obtained block polymer (C) -6 having a structure having carboxyl groups at both ends. 1.1 g of epoxy equivalent (215 g / eq) was charged and polymerized at 220 ° C. for 5 hours under reduced pressure to obtain 143.8 g of the polymer compound (E) -6. The ratio of the block (B) of the polyether to the total of the block (A) of the polyester and the block (B) of the polyether of the obtained polymer compound (E) -6 was 29% by mass.

[Manufacturing Example 7]
In a separable flask, 91.2 g (0.63 mol) of 1,4-cyclohexanedimethanol, 96.5 g (0.66 mol) of adipic acid, and an antioxidant (tetrakis [3- (3,5-di)). Tertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 (manufactured by ADEKA Corporation) was charged in 0.2 g, and polymerized at normal pressure for 3 hours while gradually raising the temperature from 140 ° C to 190 ° C. To obtain polyester (a) -6. The obtained polyester (a) -6 had an acid value of 18 and a number average molecular weight of 6,000.

Next, 164.9 g of the obtained polyester (a) -6 was used as compound (b) -3 having hydroxyl groups at both ends, the number average molecular weight was 2,000 (hydroxyl value 56), and the number of repeating units of ethyleneoxy groups. 36.7 g of polyethylene glycol of = 45, 0.2 g of antioxidant (Adecastab AO-60), 0.4 g of zirconium octylate were charged, polymerized at 200 ° C. for 3 hours under reduced pressure, and carboxyl at both ends. 191.9 g of block polymer (C) -7 having a structure having a group was obtained. The block polymer (C) -7 having a structure having a carboxyl group at both ends had an acid value of 5.2 and a number average molecular weight of 22,000.

Bisphenol F diglycidyl ether (epoxy equivalent) as the epoxy compound (D) -1 having two or more epoxy groups in 100.0 g of the obtained block polymer (C) -7 having a structure having carboxyl groups at both ends. 170 g / eq) 0.55 g was charged and polymerized at 220 ° C. for 5 hours under reduced pressure to obtain 87.5 g of the polymer compound (E) -7. The ratio of the block (B) of the polyether to the total of the block (A) of the polyester and the block (B) of the polyether of the obtained polymer compound (E) -7 was 18% by mass.

[Manufacturing Example 8]
In a separable flask, 30.3 g (0.26 mol) of 1,6-hexanediol, 59.9 g (0.30 mol) of sebacic acid, and an antioxidant (tetrakis [3- (3,5-dith)) Butyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 (manufactured by ADEKA Corporation) was charged in 0.2 g, and polymerized at normal pressure for 3 hours while gradually increasing the temperature from 140 ° C to 190 ° C. Polyester (a) -7 was obtained. The obtained polyester (a) -7 had an acid value of 55 and a number average molecular weight of 2,000.

Next, 80.9 g of the obtained polyester (a) -7 was used as compound (b) -1 having hydroxyl groups at both ends, the number average molecular weight was 3,300 (hydroxyl value 34), and the number of repeating units of ethyleneoxy groups. 99.0 g of polyethylene glycol = 75, 0.2 g of antioxidant (Adecastab AO-60), 0.4 g of zirconium octylate were charged, polymerized at 200 ° C. for 3 hours under reduced pressure, and carboxyl at both ends. 165.2 g of block polymer (C) -8 having a structure having a group was obtained. The block polymer (C) -8 having a structure having a carboxyl group at both ends had an acid value of 5.8 and a number average molecular weight of 19,200.

Bisphenol F diglycidyl ether (epoxy equivalent) as the epoxy compound (D) -1 having two or more epoxy groups in 100.0 g of the obtained block polymer (C) -8 having a structure having carboxyl groups at both ends. 170 g / eq) 0.70 g was charged and polymerized at 220 ° C. for 5 hours under reduced pressure to obtain 89.0 g of the polymer compound (E) -8. The ratio of the block (B) of the polyether to the total of the block (A) of the polyester and the block (B) of the polyether of the obtained polymer compound (E) -8 was 55% by mass.

[Manufacturing Example 9]
In a separable flask, 201.6 g (0.84 mol) of hydrogenated bisphenol A, 130.9 g (0.90 mol) of adipic acid, and an antioxidant (tetrakis [3- (3,5-ditriary butyl)] -4-Hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 (manufactured by ADEKA Corporation), charged 0.4 g, gradually increasing the temperature from 140 ° C to 200 ° C for 3 hours at normal pressure and 3 under reduced pressure. Time polymerization was carried out to obtain polyester (a) -8. The obtained polyester (a) -8 had an acid value of 22 and a number average molecular weight of 5,000.

Next, 201.8 g of the obtained polyester (a) -8 was used as compound (b) -1 having hydroxyl groups at both ends, the number average molecular weight was 3,300 (hydroxyl value 34), and the number of repeating units of ethyleneoxy groups. 99.0 g of polyethylene glycol = 75, 0.3 g of antioxidant (Adecastab AO-60), 0.4 g of zirconium octylate were charged, and polymerized at 200 ° C. for 3 hours under reduced pressure to carboxyl to both ends. 184.2 g of block polymer (C) -9 having a structure having a group was obtained. The block polymer (C) -9 having a structure having a carboxyl group at both ends had an acid value of 5.2 and a number average molecular weight of 21,700.

Bisphenol F diglycidyl ether (epoxy equivalent) as the epoxy compound (D) -1 having two or more epoxy groups in 100.0 g of the obtained block polymer (C) -9 having a structure having carboxyl groups at both ends. 170 g / eq) 0.52 g was charged and polymerized at 220 ° C. for 6 hours under reduced pressure to obtain 88.1 g of the polymer compound (E) -9. The ratio of the block (B) of the polyether to the total of the block (A) of the polyester and the block (B) of the polyether of the obtained polymer compound (E) -9 was 30% by mass.

[Manufacturing Example 10]
In a separable flask, 165.9 g (0.69 mol) of hydrogenated bisphenol A, 86.5 g (0.59 mol) of adipic acid, 24.6 g (0.15 mol) of terephthalic acid, and an antioxidant (antioxidant (0.15 mol). Add 0.3 g of tetrakis [3- (3,5-ditertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) and gradually raise from 140 ° C to 200 ° C. Polyester (a) -9 was obtained by polymerization under normal pressure for 3 hours and under reduced pressure for 3 hours while warming. The obtained polyester (a) -9 had an acid value of 22 and a number average molecular weight of 5,000.

Next, 201.7 g of the obtained polyester (a) -9 was used as compound (b) -1 having hydroxyl groups at both ends, the number average molecular weight was 3,300 (hydroxyl value 34), and the number of repeating units of ethyleneoxy groups. 66.0 g of polyethylene glycol = 75, 0.3 g of antioxidant (Adecastab AO-60), 0.3 g of zirconium octylate were charged, polymerized at 200 ° C. for 3 hours under reduced pressure, and carboxyl at both ends. 213.2 g of block polymer (C) -10 having a structure having a group was obtained. The block polymer (C) -10 having a structure having a carboxyl group at both ends had an acid value of 8.5 and a number average molecular weight of 13,300.

Hydrogenated bisphenol A diglycidyl ether (as an epoxy compound (D) -3 having two or more epoxy groups in 100.0 g of the obtained block polymer (C) -10 having a structure having carboxyl groups at both ends. Epoxy equivalent 215 g / eq) 0.81 g was charged and polymerized at 220 ° C. for 6 hours under reduced pressure to obtain 84.0 g of the polymer compound (E) -10. The ratio of the block (B) of the polyether to the total of the block (A) of the polyester and the block (B) of the polyether of the obtained polymer compound (E) -10 was 25% by mass.

[Manufacturing Example 11]
In a separable flask, 90.7 g (0.45 mol) of 1,12-dodecanediol, 11.7 g (0.11 mol) of 2,2-dimethyl-1,3-propanediol, and 99. of terephthalic acid. 7 g (0.60 mol), antioxidant (tetrakis [3- (3,5-ditrital butyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) was added to 0. 3 g was charged and polymerized at normal pressure for 3 hours while gradually raising the temperature from 140 ° C. to 200 ° C. to obtain polyester (a) -10. The obtained polyester (a) -10 had an acid value of 25 and a number average molecular weight of 4,500.

Next, 136.4 g of the obtained polyester (a) -10 was used as compound (b) -1 having hydroxyl groups at both ends, the number average molecular weight was 3,300 (hydroxyl value 34), and the number of repeating units of ethyleneoxy groups. 74.3 g of polyethylene glycol of = 75, 0.2 g of antioxidant (Adecastab AO-60), 0.3 g of zirconium octylate were charged, polymerized at 200 ° C. for 3 hours under reduced pressure, and carboxyl at both ends. 185.3 g of block polymer (C) -11 having a structure having a group was obtained. The block polymer (C) -11 having a structure having a carboxyl group at both ends had an acid value of 4.0 and a number average molecular weight of 28,000.

Hydrogenated bisphenol A diglycidyl ether (as an epoxy compound (D) -3 having two or more epoxy groups in 100.0 g of the obtained block polymer (C) -11 having a structure having carboxyl groups at both ends. Epoxy equivalent 215 g / eq) 0.53 g was charged and polymerized at 220 ° C. for 6 hours under reduced pressure to obtain 82.1 g of the polymer compound (E) -11. The ratio of the block (B) of the polyether to the total of the block (A) of the polyester and the block (B) of the polyether of the obtained polymer compound (E) -11 was 30% by mass.

[Comparative Manufacturing Example 1]
In a separable flask, 50.6 g (0.35 mol) of 1,4-cyclohexanedimethanol, 89.2 g (0.44 mol) of sebacic acid, and an antioxidant (tetrakis [3- (3,5-di)). Tertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 (manufactured by ADEKA Corporation) was charged in 0.2 g, and polymerized at normal pressure for 3 hours while gradually raising the temperature from 140 ° C to 190 ° C. To obtain polyester (a) -11. The obtained polyester (a) -11 had an acid value of 80 and a number average molecular weight of 1,400.

Next, 127.2 g of the obtained polyester (a) -11 was used as compound (b) -2 having hydroxyl groups at both ends, the number average molecular weight was 3,100 (hydroxyl value 36), and the number of repeating units of ethyleneoxy groups. 186.0 g of polyethylene glycol = 70, 0.2 g of antioxidant (Adecastab AO-60), 0.4 g of zirconium octylate were charged, polymerized at 200 ° C. for 3 hours under reduced pressure, and carboxyl at both ends. 311.0 g of block polymer (C) -12 having a structure having a group was obtained. The block polymer (C) -12 having a structure having a carboxyl group at both ends had an acid value of 16 and a number average molecular weight of 10,000.

Bisphenol F diglycidyl ether (epoxy equivalent) as the epoxy compound (D) -1 having two or more epoxy groups in 200.0 g of the obtained block polymer (C) -12 having a structure having carboxyl groups at both ends. 170 g / eq) 3.8 g was charged and polymerized at 220 ° C. for 5 hours under reduced pressure to give 181.7 g of Comparative Antistatic Agent-1. The ratio of the polyether block (B) to the total of the polyester block (A) and the polyether block (B) of the obtained comparative antistatic agent-1 was 60% by mass.

[Comparative Manufacturing Example 2]
202.1 g of polyester (a) -4 (acid value 31, number average molecular weight is 3,600) obtained in the same manner as in Production Example 4 is numerically averaged as compound (b) -4 having hydroxyl groups at both ends. 26.7 g of polyethylene glycol having a molecular weight of 800 (hydroxyl value 140) and 18 repeating units of ethyleneoxy groups, 0.2 g of antioxidant (Adecastab AO-60), 0.4 g of zirconium octylate, 200 Polymerization at ° C. for 3 hours under reduced pressure gave 214.3 g of block polymer (C) -13 having a structure having carboxyl groups at both ends. The acid value of the block polymer (C) -13 having a structure having a carboxyl group at both ends was 8.5, and the number average molecular weight was 13,500.

Bisphenol F diglycidyl ether (epoxy equivalent) as the epoxy compound (D) -1 having two or more epoxy groups in 200.0 g of the obtained block polymer (C) -13 having a structure having carboxyl groups at both ends. 170 g / eq) 2.1 g was charged and polymerized at 220 ° C. for 5 hours under reduced pressure to give 178.2 g of Comparative Antistatic Agent-2. The ratio of the polyether block (B) to the total of the polyester block (A) and the polyether block (B) of the obtained comparative antistatic agent-2 was 12% by mass.

[Comparative Manufacturing Example 3]
In a separable flask, 72.2 g (0.36 mol) of 1,12-dodecanediol, 61.0 g (0.37 mol) of terephthalic acid, and an antioxidant (tetrakis [3- (3,5-di)). Tributyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 (manufactured by ADEKA Corporation) was charged in 0.2 g, and polymerized at normal pressure for 3 hours while gradually increasing the temperature from 140 ° C to 190 ° C. , Polyester (a) -12 was obtained. The obtained polyester (a) -12 had an acid value of 9 and a number average molecular weight of 12,000.

Next, 120.3 g of the obtained polyester (a) -12 was used as compound (b) -5 having hydroxyl groups at both ends, the number average molecular weight was 7,900 (hydroxyl value 14), and the number of repeating units of ethyleneoxy groups. = 180 polyethylene glycol (39.5 g), antioxidant (Adecastab AO-60) (0.2 g), zirconium octylate (0.4 g), polymerized at 200 ° C. for 3 hours under reduced pressure, and carboxyl at both ends. 135.0 g of block polymer (C) -14 having a structure having a group was obtained. The block polymer (C) -14 having a structure having a carboxyl group at both ends had an acid value of 3.5 and a number average molecular weight of 32,000.

Bisphenol F diglycidyl ether (epoxy equivalent) as the epoxy compound (D) -1 having two or more epoxy groups in 120.0 g of the obtained block polymer (C) -14 having a structure having carboxyl groups at both ends. 170 g / eq) 0.63 g was charged and polymerized at 220 ° C. for 5 hours under reduced pressure to obtain 98.3 g of Comparative Antistatic Agent-3. The ratio of the polyether block (B) to the total of the polyester block (A) and the polyether block (B) of the obtained comparative antistatic agent-3 was 25% by mass.

[Examples 1 to 25, Comparative Examples 1 to 9]
Using each resin composition blended based on the blending amounts (parts by mass) shown in Tables 1 to 7 below, a test film was obtained according to the test film preparation method shown below. Using the obtained test film, the surface resistivity (SR value) was measured according to the following measurement method, and the antistatic property and its durability were evaluated. Further, the Haze value was measured according to the following measurement method. The results are shown in the table.

<Method for producing linear low-density polyethylene resin composition test film>
Each resin composition is melt-extruded at 180 ° C. using an extrusion molding machine equipped with a T-type die manufactured by Toyo Seiki Seisakusho Co., Ltd., and rapidly cooled with a cooling roll at 40 ° C. to obtain a test film (100 cm × 5 cm ×). 50 μm) was obtained.

<Surface resistivity (SR value) measurement method>
Immediately after the molding process, the obtained test film is stored under the conditions of a temperature of 25 ° C. and a humidity of 50% RH, and after 1 day and 30 days of the molding process, under the same atmosphere, Mitsubishi Chemical Analytech Co., Ltd. The surface resistivity (Ω / □) was measured under the conditions of an applied voltage of 100 V and an applied time of 1 minute using a high rester-UX high rester (MCP-HT800) resistor meter manufactured by Nittoseiko Analytical Co., Ltd. The measurement was performed on 5 test films at 5 points per film, and the average value was calculated.

When the surface resistivity (Ω / □) is> 1 × 10 ¹⁶ Ω / □, it cannot be measured and is set to Over Range (OR).

<Measurement method of Haze value>
Measured according to ISO14782.

* 1: NaDBS: Sodium dodecylbenzenesulfonate * 2: IBTFS: 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide * 3: LLDPE: C6-LLDPE (linear low density polyethylene, melt flow rate) = 2.0)
* 4: (B) / [(A) + (B)]: Ratio of block (B) to the total of block (A) and block (B)

From the results shown in Tables 1 to 7, it is clear that according to the present invention, an antistatic agent having an excellent antistatic effect and its durability and excellent transparency of the film can be obtained.

Claims

A polyester block (A) composed of a polyester (a) obtained by reacting a diol (a1) and a dicarboxylic acid (a2), and a compound (b) having one or more ethyleneoxy groups and having hydroxyl groups at both ends. A polymer compound (E) having a structure in which a block (B) of a polyester composed of the above and an epoxy compound (D) having two or more epoxy groups are bonded via an ester bond or an ether bond. An epoxy agent containing at least one type.
The number average molecular weight of the polyester (a) calculated by the acid value measurement method is 1,600 to 10,000, and the number average molecular weight of the compound (b) calculated by the hydroxyl value measurement method is 1. An antistatic agent characterized by being 000 to 6,000.
The polymer compound (E) has the block (A) and the block (B), and has a hydroxyl group or a carboxyl group at the end of the polyester (a) and a hydroxyl group at the end of the compound (b). 1. A structure having a structure formed by a reaction between an epoxy group of the epoxy compound (D) and a hydroxyl group formed by the reaction of the epoxy group, and a hydroxyl group formed by the reaction of the epoxy compound (D) with an ester bond or an ether bond. The antistatic agent described.
The polymer compound (E) is a block polymer (C) having a carboxyl group at both ends, in which the block (A) and the block (B) are repeatedly and alternately bonded via an ester bond. The antistatic agent according to claim 1 or 2, which has a structure in which the epoxy compound (D) is bonded to the epoxy compound (D) via an ester bond.
The antistatic agent according to claim 3, wherein the number average molecular weight of the block polymer (C) calculated by the acid value measurement method is 8,000 to 50,000.
The antistatic agent according to any one of claims 1 to 4, wherein the polyester (a) has a structure having carboxyl groups at both ends.
The antistatic agent according to any one of claims 1 to 5, wherein the compound (b) is polyethylene glycol.
The charge according to any one of claims 1 to 6, wherein the ratio of the block (B) to the total mass of the block (A) and the block (B) is in the range of 20 to 50% by mass. Inhibitor.
The antistatic agent according to any one of claims 1 to 7, further comprising one or more selected from the group consisting of alkali metal salts and ionic liquids. Inhibitor composition.
An antistatic resin composition comprising a synthetic resin mixed with the antistatic agent according to any one of claims 1 to 7.
An antistatic resin composition characterized in that the antistatic agent composition according to claim 8 is blended with a synthetic resin.
The antistatic resin composition according to claim 9 or 10, wherein the synthetic resin is at least one selected from the group consisting of polyolefin resins, polystyrene resins and copolymers thereof.
A molded product obtained from the antistatic resin composition according to any one of claims 9 to 11.
The molded product according to claim 12, which is a film.
The molded product according to claim 13, wherein the Haze value at a thickness of 50 μm is 0% or more and 40.0% or less.