JP2020164711A - Antistatic agent, antistatic agent composition containing the same, antistatic resin composition containing these, and molded body thereof - Google Patents

Abstract

To provide an antistatic agent that can continuously impart an excellent antistatic effect to synthetic resin and, also, has an excellent storage stability and productivity, and to provide an antistatic agent composition containing the same, an antistatic resin composition containing these, and a molded body thereof.SOLUTION: An antistatic agent, containing one or more of a polymer compound (E) obtained by the reaction of a polyester (a) obtained by reacting a diol (a1) and a dicarboxylic acid (a2), a compound (b) having one or more ethyleneoxy groups and having hydroxyl groups at both ends, and a polyvalent alcohol compound (D) having three or more hydroxyl groups, and in which the diol (a1) is at least one of 1,4-butanediol or ethylene glycol, and the dicarboxylic acid (a2) is succinic acid or a mixture of dicarboxylic acid containing succinic acid.SELECTED DRAWING: None

Description

The present invention relates to an antistatic agent, an antistatic agent composition containing the same, an antistatic resin composition containing these (hereinafter, also simply referred to as “resin composition”), and a molded product thereof. On the other hand, an antistatic agent which can continuously impart an excellent antistatic effect and is also excellent in storage stability and productivity, an antistatic agent composition containing the same, an antistatic resin composition containing these, and an antistatic resin composition containing these. Regarding the molded body.

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.

Since the charged thermoplastic resin attracts dust and dirt around it, there arises a problem that the appearance of the resin molded product is spoiled. 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.

In order to solve such a problem, a treatment for preventing charging of the synthetic resin has been conventionally performed. The most common antistatic treatment method is to add an antistatic agent to the synthetic resin. Such antistatic agents include a coating type that is applied to the surface of a resin molded 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. Further, the conventional polymer-type antistatic agent has a problem in its storage stability such as stickiness and blocking during long-term storage and storage in a high temperature state.

In particular, polymer-type antistatic agents are often used by cutting the polymer obtained by polymerization into pellets, and when these pellets are stored for a long period of time or at a high temperature, they may become sticky or block. There was a problem with its storage stability. In addition, when cutting into pellets, the pellets may be irregular and have an irregular shape, some of the pellets may not be cut and several pellets may remain connected, or the pellet surface may be jagged. There is also a problem that cutting defects such as burrs and cracks occur, which greatly reduces productivity.

Therefore, an object of the present invention is an antistatic agent capable of continuously imparting an excellent antistatic effect to a synthetic resin and further excellent in storage stability and productivity (cutting property), and charging including the antistatic agent. It is an object of the present invention to provide an inhibitor composition, an antistatic resin composition containing these, and a molded product thereof.

As a result of diligent studies to solve the above problems, the present inventors have excellent storage stability and productivity (cutting property) in the polymer compound having a predetermined structure, which is superior to the synthetic resin. It has been found that the above-mentioned problems can be solved by using the antistatic performance, and the present invention has been completed.

That is, the antistatic agent of the present invention is a polyester (a) obtained by reacting a diol (a1) with a dicarboxylic acid (a2), and a compound (b) having one or more ethyleneoxy groups and having hydroxyl groups at both ends. An antistatic agent containing at least one of a polymer compound (E) obtained by reacting with a polyhydric alcohol compound (D) having three or more hydroxyl groups.
The diol (a1) is at least one of 1,4-butanediol or ethylene glycol, and the dicarboxylic acid (a2) is succinic acid or a mixture of dicarboxylic acids containing succinic acid. Is.

In the antistatic agent of the present invention, the polymer compound (E) includes a polyester block (A) composed of the polyester (a), a polyether block (B) composed of the compound (b), and the like. The ester bond or carboxyl group formed by the reaction of the hydroxyl group or carboxyl group at the end of the polyester (a), the hydroxyl group at the end of the compound (b), and the hydroxyl group of the polyhydric alcohol compound (D). A compound having a structure formed by bonding via an ether bond is preferable, and the polymer compound (E) has a polyester block (A) and a polyether block (B) repeatedly alternately via an ester bond. It is more preferable that the block polymer (C) having a carboxyl group at both ends formed by bonding and the polyvalent alcohol compound (D) have a structure in which they are bonded via an ester bond. Further, in the antistatic agent of the present invention, the polyester (a) preferably has a structure having carboxyl groups at both ends. Furthermore, 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 crystallization temperature of the polymer compound (E) is preferably in the range of 20 to 70 ° C. Further, in the antistatic agent of the present invention, the number average molecular weight of the polyester (a) is preferably 1,000 to 10,000 in terms of polystyrene. Furthermore, in the antistatic agent of the present invention, the number average molecular weight of the block polymer (C) is preferably 5,000 to 50,000 in terms of polystyrene.

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, the synthetic resin is preferably one or more 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.

According to the present invention, an antistatic agent capable of continuously imparting an excellent antistatic effect to a synthetic resin and further excellent in storage stability and productivity (cutting property), and an antistatic agent containing the same. A composition, an antistatic resin composition containing these, and a molded product thereof can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
The antistatic agent of the present invention comprises a polyester (a) obtained by reacting a diol (a1) with a dicarboxylic acid (a2), a compound (b) having one or more ethyleneoxy groups and having hydroxyl groups at both ends. It contains one or more of the polymer compound (E) obtained by reacting with the polyhydric alcohol compound (D) having three or more hydroxyl groups. Here, the ethyleneoxy group is a group represented by the following general formula (1).

In the antistatic agent of the present invention, the diol (a1) is at least one of 1,4-butanediol or ethylene glycol. Compared with other diols, these are excellent in antistatic property, their durability, storage stability, and productivity (cutting property).

In the antistatic agent of the present invention, the dicarboxylic acid (a2) is succinic acid or a mixture of succinic acid-containing dicarboxylic acids. Compared with other dicarboxylic acids, succinic acid is excellent in antistatic property, its durability, storage stability, and productivity (cutting property).

Examples of dicarboxylic acids that can be used as a mixture with succinic acid include aliphatic dicarboxylic acids and aromatic dicarboxylic acids, which may be used alone or in combination of two or more.

The aliphatic dicarboxylic acid preferably includes an aliphatic dicarboxylic acid having 2 to 20 carbon atoms, and examples thereof include oxalic acid, malonic acid, glutaric acid, methylsuccinic acid, dimethylmalonic acid, 3-methylglutaric acid and ethylsuccinic acid. , Isopropylalonic acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid (1,10-decandicarboxylic acid), tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecane Diacid, Eikosandioic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 , 4-Cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid, 1,1-cyclohexanedioacetic acid, dimeric acid, maleic acid, fumaric acid and the like.

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.

The dicarboxylic acid used in the mixture with succinic acid is preferably an aliphatic dicarboxylic acid, more preferably adipic acid and sebacic acid, from the viewpoints of antistatic property, its durability, storage stability and productivity (cutting property). Adipic acid is most preferred.

The dicarboxylic acid (a2) has a molar ratio of succinic acid to another dicarboxylic acid (for example, adipic acid) in terms of antistatic property, its durability, storage stability, and productivity (cutting property). , 100: 0 to 50:50 is preferable. 100: 0 to 70:30 is more preferable, 100: 0 to 80:20 is even more preferable, and 100: 0 to 90:10 is particularly preferable.

In the antistatic agent of the present invention, the polymer compound (E) is a polyester block composed of the polyester (a) in terms of antistatic property, its durability, storage stability, and productivity (cutting property). A hydroxyl group or a carboxyl group having (A) and a block (B) of a polyether composed of the compound (b) at the end of the polyester (a), and a hydroxyl group having a hydroxyl group at the end of the compound (b). It is preferable to have a structure formed by the reaction of the hydroxyl groups of the polyhydric alcohol compound (D) having three or more hydroxyl groups, which are bonded via an ester bond or an ether bond, preferably an ester bond.

Further, in the antistatic agent of the present invention, the polymer compound (E) is different from the polyester block (A) in terms of antistatic property, its durability, storage stability, and productivity (cutting property). , A block polymer (C) having a carboxyl group at both ends formed by repeatedly and alternately bonding a polyester block (B) via an ester bond, and a polyhydric alcohol compound (D) having three or more hydroxyl groups. And are preferably bonded via an ester bond.

In the antistatic agent of the present invention, the polyester (a) contains at least one of 1,4-butanediol or ethylene glycol as the diol component (a1), and succinic acid or succinic acid as the dicarboxylic acid component (a2). Any mixture of dicarboxylic acids to be subjected to an esterification reaction (including a transesterification reaction) may be used. The esterification reaction referred to in the antistatic agent of the present invention may be a reaction that forms an ester bond by the reaction. The diol component (a1) may be only 1,4-butanediol, may be ethylene glycol alone, or may be both 1,4-butanediol and ethylene glycol. The diol component (a1) is preferably 1,4-butanediol from the viewpoint of antistatic property and its durability, storage stability and productivity (cutting property), and when 1,4-butanediol and ethylene glycol are used in combination. The higher the proportion of 1,4-butanediol, the more preferable it is from the viewpoint of antistatic property and its durability, storage stability and productivity (cutting property).

In the antistatic agent of the present invention, the diol component (a1) is composed of 1,4-butanediol and ethylene glycol in terms of antistatic property and its durability, storage stability and productivity (cutting property). The ratio is a molar ratio, preferably 100: 0 to 50:50, more preferably 100: 0 to 70:30, and even more preferably 100: 0 to 80:20.

In the antistatic agent of the present invention, succinic acid, which is a dicarboxylic acid component (a2), may be a derivative of succinic acid, and the derivatives include, for example, succinic acid anhydride and succinic acid ester (for example, succinic acid). Examples thereof include succinic acid alkyl esters such as methyl esters), succinic acid alkali metal salts (eg, sodium succinate salts), and succinic acid halides (eg, succinic acid chloride). Further, the dicarboxylic acid used as a mixture with succinic acid may also be a derivative of the dicarboxylic acid. 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). Acid chloride) and the like. The number of dicarboxylic acids used as a mixture with succinic acid may be two or more.

Next, the compound (b) and the block (B) of the preferred polymer compound (E) in the polyether 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, storage stability, and productivity (cutting property), and polyethylene glycol represented by the following general formula (2) is particularly preferable. preferable.

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

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 such as 1,3-butylene oxide can be mentioned, and this polyether may be random or block.

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. Examples thereof include -1,3-propanediol, triphenylethylene glycol, tetraphenylethylene glycol and benzopinacol.

As the divalent phenol, phenol having 6 to 30 carbon atoms can be used, and for example, catechol, resorcinol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, dihydroxydiphenyl thioether, binaphthol and alkyls thereof (carbon atoms) can be used. 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. An aromatic secondary diamine of 8 to 14 and a secondary alkanol diamine 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'-dibutylhexamethylenediamine, 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 sveric acid. Included are azelaic acid, sebacic 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 polyhydric alcohol compound (D) having three or more hydroxyl groups constituting the polymer compound (E) will be described. The polyhydric alcohol compound (D) used in the antistatic agent of the present invention is not particularly limited as long as it has three or more hydroxyl groups.

Examples of the polyhydric alcohol compound (D) include glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 2-methyl-1,2,3-propanetriol, 1,2,3. -Pentantriol, 1,2,4-pentantriol, 1,3,5-pentantriol, 2,3,4-pentantriol, 2-methyl-2,3,4-butanetriol, trimethylolethane, 2, 3,4-Hexanetriol, 2-ethyl-1,2,3-butanetriol, trimethylpropane, 4-propyl-3,4,5-heptantriol, 2,4-dimethyl-2,3,4-pentane Triol alcohols such as triol, triethanolamine, triisopropanolamine, 1,3,5-tris (2-hydroxyethyl) isocyanurate; pentaerythritol, 1,2,3,4-pentantetrol, 2,3 4,5-Hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin, ditrimethylolpropane, sorbitan, N, N, N', N' -Tetrax (2-hydroxypropyl) ethylenediamine, N, N, N', N'-tetravalent alcohols such as tetrakis (2-hydroxyethyl) ethylenediamine; pentahydric alcohols such as adonitol, arabitol, xylitol, triolcerin; dipenta Hexiolytic alcohols such as erythritol, sorbitol, mannitol, iditor, inositol, darsitol, tarose, allose; further include tripentaerythritol. The molecular weight of the polyhydric alcohol compound is not particularly limited, and high molecular weight polyhydric alcohols such as polypentaerythritol and polyvinyl alcohol can be used, and synthetic polyhydric alcohols such as polyester polyol can also be used. In the antistatic agent of the present invention, two or more kinds of polyhydric alcohol compounds (D) may be used in combination.

Since the phenol compound is not included in the alcohol compound, the phenol compound having a phenolic hydroxyl group is not included in the polyhydric alcohol compound (D) in the antistatic agent of the present invention.

In the antistatic agent of the present invention, the polymer compound (E) is a polyester (a) obtained by reacting a diol (a1) with a dicarboxylic acid (a2), and both ends having one or more ethyleneoxy groups. It is obtained by reacting a compound (b) having a hydroxyl group and a polyhydric alcohol compound (D) having three or more hydroxyl groups, and is obtained by reacting with a polyester block (A) composed of the ester (a). , A block (B) of polyether composed of compound (b), a hydroxyl group or carboxyl group having a hydroxyl group at the end of polyester (a), a hydroxyl group having a hydroxyl group at the end of compound (b), and 3 hydroxyl groups. Those having a structure formed by a reaction with the hydroxyl group of the polyhydric alcohol compound (D) having one or more compounds and having a structure formed by bonding via an ester bond or an ether bond, preferably an ester bond, have antistatic properties and their persistence. It is preferable from the viewpoint of property, storage stability, and productivity (cutting property).

In the antistatic agent of the present invention, the polymer compound (E) is a polyester composed of the polyester (a) in terms of antistatic property, its durability, storage stability, and productivity (cutting property). A block polymer (C) having a carboxyl group at both ends, which is formed by repeatedly and alternately bonding a block (A) of a polyester composed of the block (A) and the compound (b) via an ester bond, and a polyvalent block polymer (C). It is preferable that the alcohol compound (D) has a structure formed by bonding via an ester bond formed by the carboxyl group of the block polymer (C) and the hydroxyl group of the polyhydric alcohol compound (D).

In the antistatic agent of the present invention, 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). From the viewpoint of antistatic property, its durability, storage stability, and productivity (cutting property), preferably, the residue excluding the hydroxyl group of the diol (a1) and the residue excluding the carboxyl group of the dicarboxylic acid (a2). The group has a structure in which it is bonded via an ester bond.

Further, in the antistatic agent of the present invention, the polyester (a) has a structure having carboxyl groups at both ends from the viewpoint of antistatic property and its durability, storage stability and productivity (cutting property). preferable. Further, the degree of polymerization of the polyester (a) is preferably in the range of 2 to 50 from the viewpoint of antistatic property and its durability, storage stability and productivity (cutting property).

The polyester (a) having a carboxyl group at both ends causes a diol (a1) (at least one of 1,4-butanediol or ethylene glycol) to undergo an esterification reaction with a dicarboxylic acid (a2) (for example, succinic acid). Can be obtained by

The dicarboxylic acid (a2) (for example, succinic acid) 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 a polyester (a) using the derivative may be used. ), It is sufficient to finally treat both ends to form a carboxyl group, and in the same state, to obtain the next block polymer (C) having a structure having a carboxyl group at both ends. You may proceed to the reaction.

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.

For the esterification reaction, a catalyst that promotes the esterification reaction may be used, and as the catalyst, 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 a 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.

In the antistatic agent of the present invention, 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. It forms a bond to form the structure of the block polymer (C), and the hydroxyl groups at both ends may be protected, modified, or in the form of a precursor.

In the antistatic agent of the present invention, the block polymer (C) having a structure having carboxyl groups at both ends according to the polymer compound (E) is a block (A) composed of the polyester (a) and a compound ( It is preferable to have a block (B) composed of b), and to have a structure in which these blocks 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 a polyester (a) having a carboxyl group at both ends, and (B) is composed of a compound (b) having a hydroxyl group 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 storage stability. 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 carboxyl group at both ends can be 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, if 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, It is not always necessary to synthesize from 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 the X mol of the polyester (a). (C) can be preferably obtained.

In the reaction, after the synthetic 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.

In the antistatic agent of the present invention, the polymer compound (E) preferably has a structure having carboxyl groups at both ends from the viewpoint of antistatic property, its durability, storage stability, and productivity (cutting property). The block polymer (C) having the above-mentioned substance and the polyhydric alcohol compound (D) having three or more hydroxyl groups are bonded to each other via an ester bond. This ester bond is an ester bond formed by the reaction of the carboxyl group at the end of the block polymer (C) with the hydroxyl group of the polyhydric alcohol compound (D), which is antistatic property, its durability, and storage stability. , Preferred from the viewpoint of productivity (cutting property).

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

In order to obtain a preferable polymer compound (E), the block polymer (C) may be reacted with the polyhydric alcohol compound (D). That is, the carboxyl group of the block polymer (C) may be reacted with the hydroxyl group of the polyhydric alcohol compound (D). The number of hydroxyl groups of the polyhydric alcohol compound (D) to be reacted is preferably 0.5 to 5.0 equivalents, more preferably 0.5 to 2.0 equivalents of the number of carboxyl groups of the block polymer (C) to be reacted. preferable. Further, the above reaction may be carried out in various solvents or in a molten state.

The polyhydric alcohol compound (D) having three or more hydroxyl 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. Is more preferable.

In the reaction, after the synthesis reaction of the block polymer (C) is completed, the polyhydric alcohol 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 some hydroxyl groups of the polyhydric alcohol compound (D) to form an ester bond. It may be formed.

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 a polyhydric alcohol compound (D) having three or more hydroxyl groups. As long as it has a structure equivalent to that having a structure bonded via an ester bond formed by each carboxyl group and a hydroxyl group, it is not necessarily synthesized from the block polymer (C) and the polyhydric alcohol compound (D). do not have to.

In the antistatic agent of the present invention, the number average molecular weight of the compound (b) constituting the block (B) composed of the compound (b) having hydroxyl groups at both ends in the polymer compound (E) is the hydroxyl value. From the viewpoint of antistatic property, its durability, storage stability, and productivity (cutting property), it is preferably 400 to 10,000, more preferably 1,000 to 8,000. Yes, more preferably 2,000 to 8,000. The method for measuring the hydroxyl value and the method for calculating the number average molecular weight from the hydroxyl value are described below.

<Calculation method of number average molecular weight from hydroxyl value>
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.

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]

Further, in the antistatic agent of the present invention, the number average molecular weight of the polyester (a) constituting the block (A) composed of the polyester (a) in the polymer compound (E) is antistatic in terms of polystyrene. From the viewpoint of properties, durability, storage stability, and productivity (cutting property), it is preferably 1,000 to 10,000, more preferably 1,500 to 8,000, and even more preferably 2,. It is 500 to 7,500. If the number average molecular weight is less than 1,000, the storage stability may be inferior, and if it exceeds 10,000, the reaction for obtaining the polymer compound (E) may take a long time and the economic efficiency may be inferior. The molecular compound may be colored by a long-term reaction.

As a method for measuring the number average molecular weight in terms of polystyrene, a gel permeation chromatograph (GPC) method is preferable, and the measuring method is shown below.

<Measurement method of number average molecular weight by polystyrene conversion>
The number average molecular weight (hereinafter, also referred to as “Mn”) was measured by a gel permeation chromatograph method. The measurement conditions for Mn are as follows.
Equipment: GPC equipment manufactured by JASCO Corporation Solvent: Chloroform standard substance: Polystyrene detector: Differential refractometer (RI detector)
Column stationary phase: Showa Denko Corporation Shodex LF-804
Column temperature: 40 ° C
Sample concentration: 1 mg / 1 mL
Flow rate: 0.8 mL / min.
Injection volume: 100 μL

Further, in the antistatic agent of the present invention, the number average molecular weight of the block polymer (C) having a structure having carboxyl groups at both ends in the polymer compound (E) is antistatic property and its duration in terms of polystyrene. From the viewpoint of property, storage stability, and productivity (cutting property), it is preferably 5,000 to 50,000, more preferably 10,000 to 45,000, and further preferably 15,000 to 40, It is 000. If the number average molecular weight is less than 5,000, the storage stability may be inferior, and if it exceeds 50,000, the reaction for obtaining the polymer compound (E) may take a long time and the economic efficiency may be inferior. The molecular compound may be colored by a long-term reaction. As a method for measuring the number average molecular weight in terms of polystyrene, a gel permeation chromatograph (GPC) method is preferable, and the measuring method is as described above.

Further, 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 be reacted with (b) and / or the polyhydric alcohol compound (D).

In the antistatic agent of the present invention, the polymer compound (E) has a crystallization temperature of 20 ° C. or higher and 70 ° C. or lower from the viewpoint of antistatic property and its durability, particularly storage stability and productivity (cutting property). It is preferably within the range of 30 ° C. or higher and 70 ° C. or lower, 40 ° C. or higher and 70 ° C. or lower, even more preferably 50 ° C. or higher and 70 ° C. or lower, and 55 ° C. or higher and 70 ° C. or lower. Preferably, 60 ° C. or higher and 70 ° C. or lower is even more preferable. If the crystallization temperature is less than 20 ° C., storage stability and productivity (cutting property) may deteriorate, and if it exceeds 70 ° C., productivity (cutting property) may deteriorate. The crystallization temperature is measured by the following crystallization temperature measuring method.

<Crystallization temperature measurement method>
The crystallization temperature is measured using a differential scanning calorimetry device (DSC).
Weigh 3 ± 1 mg of the sample into an aluminum pan, raise the temperature from room temperature (25 ° C.) to 130 ° C. at a rate of 10 ° C./min, hold for 5 minutes, and cool to 0 ° C. at a rate of 10 ° C./min. In the obtained chart, the temperature at which the peak heat absorption was reached was defined as the crystallization temperature.

In the antistatic agent of the present invention, the polymer compound (E) is preferably used 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 consisting of alkali metal salts and ionic liquids. The antistatic agent of the present invention further comprises one or more selected from the group consisting of alkali metal salts and ionic liquids, whereby an antistatic agent composition having excellent antistatic performance and durability thereof. It is 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 are 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. Among these, lithium p-toluenesulfonate, sodium p-toluenesulfonate, lithium dodecylbenzenesulfonate, and dodecylbenzenesulfone are preferable from the viewpoints of antistatic property and 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 antistatic agent of the present invention and used with a synthetic resin. The blending amount of the alkali metal salt 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 storage stability. ~ 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 the initial conductivity is 1 to 200 ms / cm, preferably 10 to 10. 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 cations 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 the guanidinium cation 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.

Examples of the organic acid or the inorganic acid constituting the anion in the ionic liquid 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 anion constituting the ionic liquid has a Hamette acidity function (-H0) of 12 to 100, which is super Acids that form anions other than the conjugated bases of strong acids and the conjugated bases of superacids, and mixtures thereof.

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 acid and Lewis acid, 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 halide (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.

Lewis acids include, for example, 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 composed 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, an ionic liquid having an amidinium cation is preferable from the viewpoint of antistatic property, and an ionic liquid having a 1-ethyl-3-methylimidazolium cation is more preferable, and a particularly preferable ionic liquid. Is 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium dodecylbenzene sulfonate.

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 with respect to 100 parts by mass of the antistatic agent of the present invention from the viewpoint of antistatic property, its durability, and storage stability, and is 0.1 to 0.1 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, one or more selected from the group of alkali metal salts and ionic liquids, and other optional components as required. 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 effects of the present invention are 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 blending 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 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 polyether ester amide can be used, and as a known polyether ester amide, for example, Japanese Patent Application Laid-Open No. 7-10989 Examples thereof include polyether ester amides comprising 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, 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 in a synthetic resin. The blending amount of the compatibilizer is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, based on 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 components listed above, as long as the effects of the present invention are not impaired. .. These other components may be directly blended with the antistatic agent composition, or the antistatic agent of the present invention or the antistatic agent composition of the present invention may be blended with a synthetic resin such as a thermoplastic resin to prevent static electricity. When used as a resin composition having properties, it may be blended with a synthetic resin.

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, polyapple 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 polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, fibrous resin, polyimide tree Examples thereof include thermoplastic resins such as fats, polysulfones, polyphenylene ethers, polyetherketones, polyetheretherketones, and liquid crystal polymers, and blends thereof.

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

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, more preferably 0.5 to 50 μm.

As a method of blending the antistatic agent of the present invention into a synthetic resin, the antistatic agent of the present invention is kneaded with a block polymer (C) and a polyvalent alcohol compound (D) having three or more hydroxyl groups at the same time as the synthetic resin. The agents may be synthesized and blended, and at that time, one or more selected from the group of alkali metal salts and ionic liquids may be kneaded at the same time, and the present invention may be used during molding such as injection molding. The antistatic agent and the synthetic resin may be mixed to obtain a molded product, and at that time, one or more selected from the group of alkali metal salts and ionic liquids may be further blended. Further, a masterbatch of the antioxidant of the present invention and the synthetic resin may be manufactured in advance, and this masterbatch may be blended, at which time, it is selected from the group of alkali metal salts and ionic liquids. One or more 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-6-3rd Butylphenol), 2,2'-Methylenebis (4-Ethyl-6-3rd Butylphenol), 4,4'-Butylidenebis (6-3rd 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) -2,4,6 -Trimethylbenzene, 2-third butyl-4-methyl-6- (2-acryloyloxy-3-third butyl-5-methylbenzyl) phenol, stearyl (3,5-ditrithibyl-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-3-3rd 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-Third Butyl-4-Hydroxy-5-Methylphenyl) Propionyloxy} Ethyl] -2,4,8,10-tetraoxaspiro [5,5] unde Can, triethylene glycol bis [(3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate] and the like can be mentioned. 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 the phosphorus-based antioxidant 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-ditrimeric butyl-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-tertiary 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 phosphite of 2,4,6-tritrith butylphenol. 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-ditertiary 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-ditertiary butylphenyl) -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 light stabilizer 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-piperidyl methacrylate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4- Diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], 1,2,3 4-Butanecarboxylic 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-pi) Peridylamino) 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) -Piperidil) 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-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-tetraoxa Spiro [5.5] undecane, bis (1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6-tetramethyl-4-piperidylhexadeca Examples thereof include hindered amine compounds such as Noate, 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, phosphate flame retardants, inorganic phosphorus flame retardants, (poly) phosphate flame retardants, halogen flame retardants, silicon flame retardants, antioxidants such as antimon trioxide, and other inorganic flame retardants. Fuel retardants, other organic flame retardants, 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 phosphoric acid ester flame retardant include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate) and the like.

Examples of the (poly) phosphate-based flame retardant 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 blended in the resin composition of the present invention may be added directly to the synthetic resin, or may be blended in the antistatic agent of the present invention or the antistatic agent composition and then added to the synthetic resin. Good.

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 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 copier, 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 recorders, mini discs, CD players, speakers, AV equipment such as liquid crystal displays, connectors, relays, capacitors, switches, printed boards, coil bobbins, semiconductor encapsulation materials, LED encapsulation materials, electric wires, cables, transformers, deflection yokes. , Electric / electronic parts such as distribution boards and watches and communication equipment, interior / 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, 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. can be used for various purposes.

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 weight of compound (b) is calculated by the following <method for calculating the number average molecular weight from hydroxyl groups>, and the number average molecular weights other than compound (b) are calculated by the following <polystyrene conversion. It was calculated by the method for measuring the number average molecular weight>.

<Calculation method of number average molecular weight from hydroxyl value>
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.

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]

<Measurement method of number average molecular weight by polystyrene conversion>
The number average molecular weight was measured by gel permeation chromatography. The measurement conditions for Mn are as follows.
Equipment: GPC equipment manufactured by Nippon Kogaku Co., Ltd. Solvent: Chlororeference material: Polystyrene detector: Differential refraction meter (RI detector)
Column stationary phase: Showa Denko Corporation Shodex LF-804
Column temperature: 40 ° C
Sample concentration: 1 mg / 1 mL
Flow rate: 0.8 mL / min.
Injection volume: 100 μL

[Manufacturing Example 1]
In a separable flask, in the presence of 0.2 g of an antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) , 1,4-Butanediol (122 g (1.35 mol)) and 168 g (1.42 mol) of succinic acid were polymerized at normal pressure for 3 hours while gradually increasing the temperature from 140 ° C. to 190 ° C. to obtain polyester (1.4-butanediol). a) -1 was obtained. The number average molecular weight of the obtained polyester (a) -1 was 3,000.

Next, 250 g of the obtained polyester (a) -1 and 160 g of polyethylene glycol having a number average molecular weight of 3,300 and the number of repeating units of ethyleneoxy groups = 75 as compound (b) -1 having hydroxyl groups at both ends. , 0.2 g of antioxidant (Adecastab AO-60) and 0.4 g of zirconium octylate were charged and polymerized at 200 ° C. for 3 hours under reduced pressure to form a block polymer having a structure having carboxyl groups at both ends. C) -1 was obtained in an amount of 400 g. The number average molecular weight Mn of the block polymer (C) -1 having a structure having a carboxyl group at both ends was 16500.

To 400 g of the obtained block polymer (C) -1 having a structure having a carboxyl group at both ends, 1 g of pentaerythritol was charged as a polyhydric alcohol compound (D) -1 having three or more hydroxyl groups, and at 220 ° C. After polymerizing under reduced pressure for 5 hours, it is extruded at 220 ° C. using Laboplastomil μ (manufactured by Toyo Seiki Seisakusho Co., Ltd.) and cut into 5 mm square pellets to obtain the high antistatic agent of the present invention. 400 g of pellets of the molecular compound (E) -1 were obtained. The crystallization temperature of the obtained pellets was measured by the following <Crystallization temperature measuring method>. The results are shown in Table 1.

In addition, 15 g of the obtained pellets (about 2000 pellets) were sampled, and visually good-shaped (5 mm square) pellets and other defective-shaped pellets were confirmed, and the entire defective-shaped pellets were confirmed. The ratio (mass%) to the amount was calculated, and <productivity (cutting property)> was evaluated. Poor shapes of pellets include those in which a part of the pellets cannot be cut and several pellets are connected, those in which the pellet surface is jagged, and those in which burrs and cracks are observed in the pellets. It can be said that the smaller the proportion of defectively shaped pellets, the better the cutting performance and the higher the productivity.

In addition, the obtained pellets were evaluated for storage stability by the following <method for testing storage stability of antistatic agent>. The results are shown in Table 1.

<Crystallization temperature measurement method>
The crystallization temperature is measured using a differential scanning calorimetry device (Diamond DSC manufactured by Perkin). The sample is finely cut into pellets, weighed 3 ± 1 mg in an aluminum pan, heated from room temperature (25 ° C.) to 130 ° C. at a rate of 10 ° C./min, held for 5 minutes, and then at a rate of 10 ° C./min. In the chart obtained by cooling to 0 ° C., the temperature at which the endothermic peak was reached was defined as the crystallization temperature.

<Preservation stability test method for antistatic agents>
5 g of pellets was placed in a glass sample bottle having a capacity of 130 mL, and the mixture was allowed to stand in an oven at 80 ° C. for 1 hour. After 1 hour, the sample bottle was taken out, the lid was closed, the sample bottle was gently turned upside down, and the blocking property was evaluated from the falling state of the antistatic agent pellets.

〇: All antistatic agent pellets fell without adhering to the bottom of the bottle. It is evaluated as having excellent storage stability.
Δ: A part of the antistatic agent pellet remains attached to the bottom of the bottle. Evaluate that the storage stability is a little poor.
X: All of the antistatic agent pellets remain attached to the bottom of the bottle. Evaluate as poor storage stability.

[Manufacturing Example 2]
To 400 g of the block polymer (C) -1 obtained in the same manner as in Production Example 1, 1 g of trimethylolpropane as the polyhydric alcohol compound (D) -2 having 3 or more hydroxyl groups was charged, and the temperature was 220 ° C. for 5 hours. After polymerization under reduced pressure, 400 g of pellets of the polymer compound (E) -2, which is the antistatic agent of the present invention, was obtained in the same manner as in Production Example 1.

The crystallization temperature of the obtained pellet of the polymer compound (E) -2 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Manufacturing Example 3]
To 400 g of the block polymer (C) -1 obtained in the same manner as in Production Example 1, 3 g of dipentaerythritol was charged as the polyhydric alcohol compound (D) -3 having 3 or more hydroxyl groups, and the temperature was 220 ° C. for 5 hours. After polymerization under reduced pressure, 400 g of pellets of the polymer compound (E) -3, which is the antistatic agent of the present invention, was obtained in the same manner as in Production Example 1. The crystallization temperature of the obtained pellet of the polymer compound (E) -3 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Manufacturing Example 4]
To 400 g of the block polymer (C) -1 obtained in the same manner as in Production Example 1, 1 g of glycerin as a polyhydric alcohol compound (D) -4 having three or more hydroxyl groups was charged, and the pressure was reduced at 220 ° C. for 5 hours. After polymerization underneath, 400 g of pellets of the polymer compound (E) -4, which is the antistatic agent of the present invention, was obtained in the same manner as in Production Example 1. The crystallization temperature of the obtained pellets of the polymer compound (E) -4 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Manufacturing Example 5]
To 400 g of the block polymer (C) -1 obtained in the same manner as in Production Example 1, 2 g of diglycerin as a polyhydric alcohol compound (D) -5 having three or more hydroxyl groups was charged, and the mixture was charged at 220 ° C. for 5 hours. After polymerization under reduced pressure, 400 g of pellets of the polymer compound (E) -5, which is the antistatic agent of the present invention, was obtained in the same manner as in Production Example 1. The crystallization temperature of the obtained pellets of the polymer compound (E) -5 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Manufacturing Example 6]
To 400 g of the block polymer (C) -1 obtained in the same manner as in Production Example 1, 2 g of ditrimethylolpropane as the polyhydric alcohol compound (D) -6 having 3 or more hydroxyl groups was charged, and the mixture was charged at 220 ° C. for 5 hours. After polymerization under reduced pressure, 400 g of pellets of the polymer compound (E) -6, which is the antistatic agent of the present invention, was obtained in the same manner as in Production Example 1. The crystallization temperature of the obtained pellets of the polymer compound (E) -6 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Manufacturing Example 7]
In a separable flask, in the presence of 0.2 g of an antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) , 1,4-Butanediol 58 g (0.65 mol) and 91 g (0.77 mol) of succinic acid were polymerized at normal pressure for 3 hours while gradually raising the temperature from 140 ° C. to 190 ° C. to polyester ( a) -2 was obtained. The number average molecular weight of the obtained polyester (a) -2 was 1,000.

Next, 130 g of the obtained polyester (a) -2, 277 g of polyethylene glycol having a number average molecular weight of 3,300 and the number of repeating units of ethyleneoxy groups = 75 as the compound (b) -1 having hydroxyl groups at both ends. , 0.2 g of antioxidant (Adecastab AO-60) and 0.4 g of zirconium octylate, polymerized at 200 ° C. for 3 hours under reduced pressure, and a block polymer having a structure having carboxyl groups at both ends ( C) -2 was obtained in an amount of 400 g. The number average molecular weight Mn of the block polymer (C) -2 having a structure having a carboxyl group at both ends was 9,600.

To 400 g of the obtained block polymer (C) -2 having a structure having a carboxyl group at both ends, 2 g of pentaerythritol was charged as a polyhydric alcohol compound (D) -1 having three or more hydroxyl groups, and at 220 ° C. After polymerization under reduced pressure for 5 hours, 400 g of pellets of the polymer compound (E) -7, which is the antioxidant of the present invention, was obtained in the same manner as in Production Example 1. The crystallization temperature of the obtained pellets of the polymer compound (E) -7 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Manufacturing Example 8]
In a separable flask, in the presence of 0.2 g of an antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) , Ethylene glycol 100 g (1.61 mol) and succinic acid 199 g (1.69 mol) were polymerized at normal pressure for 3 hours while gradually increasing the temperature from 140 ° C. to 190 ° C. to obtain polyester (a) -3. Got The number average molecular weight of the obtained polyester (a) -3 was 3,000.

Next, 250 g of the obtained polyester (a) -3, 160 g of polyethylene glycol having a number average molecular weight of 3,300 and the number of repeating units of ethyleneoxy groups = 75 as compound (b) -1 having hydroxyl groups at both ends. , 0.2 g of antioxidant (Adecastab AO-60) and 0.4 g of zirconium octylate were charged and polymerized at 200 ° C. for 3 hours under reduced pressure to form a block polymer having a structure having carboxyl groups at both ends. C) -3 was obtained in an amount of 400 g. The number average molecular weight Mn of the block polymer (C) -3 having a structure having a carboxyl group at both ends was 16,500.

1 g of pentaerythritol was charged as a polyhydric alcohol compound (D) -1 having 3 or more hydroxyl groups into 400 g of the obtained block polymer (C) -3 having a structure having carboxyl groups at both ends, and at 220 ° C. After polymerization under reduced pressure for 5 hours, 400 g of pellets of the polymer compound (E) -8, which is the antioxidant of the present invention, was obtained in the same manner as in Production Example 1. The crystallization temperature of the obtained pellets of the polymer compound (E) -8 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Manufacturing Example 9]
In a separable flask, in the presence of 0.2 g of an antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) , 1,4-Butanediol 101 g (1.12 mol), ethylene glycol 17 g (0.28 mol), and succinic acid 173 g (1.47 mol) while gradually raising the temperature from 140 ° C. to 190 ° C. Polymerization at normal pressure for 3 hours gave polyester (a) -4. The number average molecular weight of the obtained polyester (a) -4 was 3,000.

Next, 243 g of the obtained polyester (a) -4, 161 g of polyethylene glycol having a number average molecular weight of 3,300 and the number of repeating units of ethyleneoxy groups = 75 as compound (b) -1 having hydroxyl groups at both ends. , 0.2 g of antioxidant (Adecastab AO-60) and 0.4 g of zirconium octylate were charged and polymerized at 200 ° C. for 3 hours under reduced pressure to form a block polymer having a structure having carboxyl groups at both ends. C) 400 g of -4 was obtained. The number average molecular weight Mn of the block polymer (C) -4 having a structure having a carboxyl group at both ends was 16500.

1 g of pentaerythritol was charged as a polyhydric alcohol compound (D) -1 having 3 or more hydroxyl groups into 400 g of the obtained block polymer (C) -4 having a structure having carboxyl groups at both ends, and at 220 ° C. After polymerization under reduced pressure for 5 hours, 400 g of pellets of the polymer compound (E) -9, which is the antistatic agent of the present invention, was obtained in the same manner as in Production Example 1. The crystallization temperature of the obtained pellets of the polymer compound (E) -9 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Manufacturing Example 10]
In a separable flask, in the presence of 0.2 g of an antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) , 120 g (1.33 mol) of 1,4-butanediol, 149 g (1.26 mol) of succinic acid, and 21 g (0.14 mol) of adipic acid while gradually raising the temperature from 140 ° C. to 190 ° C. It was polymerized at normal pressure for 3 hours to obtain polyester (a) -5. The number average molecular weight of the obtained polyester (a) -5 was 3,000.

Next, 248 g of the obtained polyester (a) -5, 157 g of polyethylene glycol having a number average molecular weight of 3,300 and the number of repeating units of ethyleneoxy groups = 75 as compound (b) -1 having hydroxyl groups at both ends. , 0.2 g of antioxidant (Adecastab AO-60) and 0.4 g of zirconium octylate were charged and polymerized at 200 ° C. for 3 hours under reduced pressure to form a block polymer having a structure having carboxyl groups at both ends. C) 400 g of -5 was obtained. The number average molecular weight Mn of the block polymer (C) -5 having a structure having a carboxyl group at both ends was 16500.

To 400 g of the obtained block polymer (C) -5 having a structure having a carboxyl group at both ends, 1 g of pentaerythritol was charged as a polyhydric alcohol compound (D) -1 having three or more hydroxyl groups, and at 220 ° C. After polymerization under reduced pressure for 5 hours, 400 g of pellets of the polymer compound (E) -10, which is the antistatic agent of the present invention, was obtained in the same manner as in Production Example 1. The crystallization temperature of the obtained pellets of the polymer compound (E) -10 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Manufacturing Example 11]
In a separable flask, in the presence of 0.2 g of an antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) , 1,4-Butanediol 118 g (1.31 mol), succinic acid 130 g (1.10 mol), and adipic acid 40 g (0.28 mol) while gradually raising the temperature from 140 ° C. to 190 ° C. Polyester (a) -6 was obtained by polymerization at normal pressure for 3 hours. The number average molecular weight of the obtained polyester (a) -6 was 3,000.

Next, 246 g of the obtained polyester (a) -6, 155 g of polyethylene glycol having a number average molecular weight of 3,300 and the number of repeating units of ethyleneoxy groups = 75 as compound (b) -1 having hydroxyl groups at both ends. , 0.2 g of antioxidant (Adecastab AO-60) and 0.4 g of zirconium octylate were charged and polymerized at 200 ° C. for 3 hours under reduced pressure to form a block polymer having a structure having carboxyl groups at both ends. C) -6 was obtained in an amount of 400 g. The number average molecular weight Mn of the block polymer (C) -6 having a structure having a carboxyl group at both ends was 16500.

To 400 g of the obtained block polymer (C) -6 having a structure having a carboxyl group at both ends, 1 g of pentaerythritol was charged as a polyhydric alcohol compound (D) -1 having three or more hydroxyl groups, and at 220 ° C. After polymerization under reduced pressure for 5 hours, 400 g of pellets of the polymer compound (E) -11, which is the antioxidant of the present invention, was obtained in the same manner as in Production Example 1. The crystallization temperature of the obtained pellets of the polymer compound (E) -11 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Manufacturing Example 12]
In a separable flask, in the presence of 0.2 g of an antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) , 1,4-Butanediol 116 g (1.28 mol), 144 g (1.22 mol) of succinic acid, and 27 g (0.14 mol) of sebacic acid while gradually raising the temperature from 140 ° C. to 190 ° C. It was polymerized at normal pressure for 3 hours to obtain polyester (a) -7. The number average molecular weight of the obtained polyester (a) -7 was 3,000.

Next, 251 g of the obtained polyester (a) -7, 154 g of polyethylene glycol having a number average molecular weight of 3,300 and the number of repeating units of ethyleneoxy groups = 75 as compound (b) -1 having hydroxyl groups at both ends. , 0.2 g of antioxidant (Adecastab AO-60) and 0.4 g of zirconium octylate were charged and polymerized at 200 ° C. for 3 hours under reduced pressure to form a block polymer having a structure having carboxyl groups at both ends. C) -7 was obtained in an amount of 400 g. The number average molecular weight Mn of the block polymer (C) -7 having a structure having a carboxyl group at both ends was 16500.

To 400 g of the obtained block polymer (C) -7 having a structure having a carboxyl group at both ends, 1 g of pentaerythritol was charged as a polyhydric alcohol compound (D) -1 having three or more hydroxyl groups, and at 220 ° C. After polymerization under reduced pressure for 5 hours, 400 g of pellets of the polymer compound (E) -12, which is the antioxidant of the present invention, was obtained in the same manner as in Production Example 1. The crystallization temperature of the obtained pellet of the polymer compound (E) -12 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Manufacturing Example 13]
In a separable flask, in the presence of 0.2 g of an antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) , 1,4-Butanediol 110 g (1.22 mol), succinic acid 122 g (1.04 mol), and sebacic acid 52 g (0.26 mol) while gradually raising the temperature from 140 ° C. to 190 ° C. It was polymerized at normal pressure for 3 hours to obtain polyester (a) -8. The number average molecular weight of the obtained polyester (a) -8 was 3,000.

Next, 259 g of the obtained polyester (a) -8, 152 g of polyethylene glycol having a number average molecular weight of 3,300 and the number of repeating units of ethyleneoxy groups = 75 as compound (b) -1 having hydroxyl groups at both ends. , 0.2 g of antioxidant (Adecastab AO-60) and 0.4 g of zirconium octylate were charged and polymerized at 200 ° C. for 3 hours under reduced pressure to form a block polymer having a structure having carboxyl groups at both ends. C) -8 was obtained in an amount of 400 g. The number average molecular weight Mn of the block polymer (C) -8 having a structure having a carboxyl group at both ends was 16500.

To 400 g of the obtained block polymer (C) -8 having a structure having a carboxyl group at both ends, 1 g of pentaerythritol was charged as a polyhydric alcohol compound (D) -1 having three or more hydroxyl groups, and at 220 ° C. After polymerization under reduced pressure for 5 hours, 400 g of pellets of the polymer compound (E) -13, which is the antioxidant of the present invention, was obtained in the same manner as in Production Example 1. The crystallization temperature of the obtained pellets of the polymer compound (E) -13 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Manufacturing Example 14]
In a separable flask, in the presence of 0.2 g of an antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) , 1,4-Butanediol 105 g (1.17 mol), succinic acid 103 g (0.87 mol), and sebacic acid 75 g (0.37 mol) while gradually raising the temperature from 140 ° C. to 190 ° C. Polyester (a) -9 was obtained by polymerization at normal pressure for 3 hours. The number average molecular weight of the obtained polyester (a) -9 was 3,000.

Next, 250 g of the obtained polyester (a) -9, 161 g of polyethylene glycol having a number average molecular weight of 3,300 and the number of repeating units of ethyleneoxy groups = 75 as compound (b) -1 having hydroxyl groups at both ends. , 0.2 g of antioxidant (Adecastab AO-60) and 0.4 g of zirconium octylate were charged and polymerized at 200 ° C. for 3 hours under reduced pressure to form a block polymer having a structure having carboxyl groups at both ends. C) -9 was obtained in an amount of 400 g. The number average molecular weight Mn of the block polymer (C) -9 having a structure having a carboxyl group at both ends was 16500.

To 400 g of the obtained block polymer (C) -9 having a structure having a carboxyl group at both ends, 1 g of pentaerythritol was charged as a polyhydric alcohol compound (D) -1 having three or more hydroxyl groups, and at 220 ° C. After polymerization under reduced pressure for 5 hours, 400 g of pellets of the polymer compound (E) -14, which is the antioxidant of the present invention, was obtained in the same manner as in Production Example 1. The crystallization temperature of the obtained pellets of the polymer compound (E) -14 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Manufacturing Example 15]
In a separable flask, in the presence of 0.2 g of an antioxidant (tetrakis [3- (3,5-ditrital butyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) , 1,4-Butanediol 115 g (1.27 mol), succinic acid 143 g (1.21 mol), and 2,6-naphthalenedicarboxylic acid 29 g (0.13 mol), gradually from 140 ° C. to 190 ° C. Polyester (a) -10 was obtained by polymerizing at normal pressure for 3 hours while raising the temperature. The number average molecular weight of the obtained polyester (a) -10 was 3,000.

Next, 256 g of the obtained polyester (a) -10, 170 g of polyethylene glycol having a number average molecular weight of 3,300 and the number of repeating units of ethyleneoxy groups = 75 as compound (b) -1 having hydroxyl groups at both ends. , 0.2 g of antioxidant (Adecastab AO-60) and 0.4 g of zirconium octylate were charged and polymerized at 200 ° C. for 3 hours under reduced pressure to form a block polymer having a structure having carboxyl groups at both ends. C) 400 g of -10 was obtained. The number average molecular weight Mn of the block polymer (C) -10 having a structure having a carboxyl group at both ends was 16500.

To 400 g of the obtained block polymer (C) -10 having a structure having a carboxyl group at both ends, 1 g of pentaerythritol was charged as a polyhydric alcohol compound (D) -1 having three or more hydroxyl groups, and at 220 ° C. After polymerization under reduced pressure for 5 hours, 400 g of pellets of the polymer compound (E) -15, which is the antioxidant of the present invention, was obtained in the same manner as in Production Example 1.

The crystallization temperature of the obtained pellets of the polymer compound (E) -15 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Comparative Manufacturing Example 1]
0.2 g of antioxidant (tetrakis [3- (3,5-ditritiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) is present in a separable flask. Below, 142 g (0.98 mol) of 1,4-cyclohexanedimethanol and 112 g (0.95 mol) of succinic acid were polymerized at normal pressure for 3 hours while gradually raising the temperature from 140 ° C. to 190 ° C. Comparative polyester-1 was obtained. The number average molecular weight of the obtained comparative polyester-1 was 3,000.

Next, 250 g of the obtained comparative polyester-1 was used as compound (b) -1 having hydroxyl groups at both ends, and 160 g of polyethylene glycol having a number average molecular weight of 3,300 and the number of repeating units of ethyleneoxy groups = 75 was oxidized. 0.2 g of an inhibitor (Adecastab AO-60) and 0.4 g of zirconium octylate were charged, polymerized at 200 ° C. for 3 hours under reduced pressure, and a comparative block polymer-1 having a structure having carboxyl groups at both ends. Was obtained in an amount of 400 g. The number average molecular weight Mn of the comparative block polymer-1 having a structure having a carboxyl group at both ends was 16500.

To 400 g of the obtained comparative block polymer-1 having a structure having a carboxyl group at both ends, 1 g of pentaerythritol as a polyhydric alcohol compound (D) -1 having 3 or more hydroxyl groups was charged, and the mixture was charged at 220 ° C. for 5 hours. After polymerization under reduced pressure, 400 g of pellets of Comparative Antistatic Agent-1 were obtained in the same manner as in Production Example 1. The crystallization temperature of the obtained pellet of the comparative antistatic agent-1 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Comparative Manufacturing Example 2]
In a separable flask, in the presence of 0.2 g of an antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) , 1,4-Butanediol (104 g (1.15 mol)) and 179 g (1.22 mol) of adipic acid were polymerized at normal pressure for 3 hours while gradually increasing the temperature from 140 ° C. to 190 ° C. for comparison. Polyester-2 was obtained. The number average molecular weight of the obtained comparative polyester-2 was 3,000.

Next, 250 g of the obtained comparative polyester-2, 160 g of polyethylene glycol having a number average molecular weight of 3,300 and the number of repeating units of ethyleneoxy groups = 75 as compound (b) -1 having hydroxyl groups at both ends was oxidized. 0.2 g of inhibitor (Adecastab AO-60) and 0.4 g of zirconium octylate are charged and polymerized at 200 ° C. for 3 hours under reduced pressure. Comparative block polymer-2 having a structure having carboxyl groups at both ends. Was obtained in an amount of 400 g. The number average molecular weight Mn of the comparative block polymer-2 having a structure having a carboxyl group at both ends was 16500.

To 400 g of the obtained comparative block polymer-2 having a structure having a carboxyl group at both ends, 1 g of pentaerythritol was charged as a polyhydric alcohol compound (D) -1 having 3 or more hydroxyl groups, and the mixture was charged at 220 ° C. for 5 hours. After polymerization under reduced pressure, 400 g of pellets of Comparative Antistatic Agent-2 were obtained in the same manner as in Production Example 1. The crystallization temperature of the obtained pellet of the comparative antistatic agent-2 was measured in the same manner as in Production Example 1. Furthermore, the productivity (cutting property) and the storage stability of the antistatic agent were evaluated.

[Examples 1-33, Comparative Examples 1-5]
Using the resin compositions of Examples and Comparative Examples blended based on the blending amounts (parts by mass) shown in Tables 1 to 6 below, test pieces were obtained according to the test piece preparation conditions shown below. Using the obtained test piece, the surface resistivity (SR value) was measured according to the following, and the antistatic property and its durability were evaluated. The results are shown in Tables 1-6.

<Conditions for preparing test piece of homopolypropylene resin composition>
The resin composition blended based on the blending amounts shown in Tables 1 to 6 below is produced using a twin-screw extruder manufactured by Ikekai Co., Ltd. (containing PCM30, 60 mesh) at 230 ° C. and 6 kg / hour. Granulated to obtain pellets. The obtained pellets are molded using a horizontal injection molding machine (NEX80: manufactured by Nissei Resin Industry Co., Ltd.) under processing conditions of a resin temperature of 230 ° C. and a mold temperature of 40 ° C., and a test piece (100 mm × 100 mm × 3 mm). Got

<Surface resistivity (SR value) measurement method>
Immediately after the molding process, the obtained test piece was 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, the R8340 resistor meter manufactured by Advantest Co., Ltd. was stored in the same atmosphere. The surface resistivity (Ω / □) was measured under the conditions of an applied voltage of 100 V and an applied time of 1 minute. The measurement was performed on 5 test pieces at 5 points per piece, and the average value was calculated.

＊１：ドデシルベンゼンスルホン酸ナトリウム
＊２：１−エチル−３−メチルイミダゾリウムドデシルベンゼンスルホナート
＊３：ホモポリプロピレン（メルトフローレート（ＩＳＯ１１３３ ２３０℃×２．１６ｋｇ）＝８ｇ／１０ｍｉｎ））

* 1: Sodium dodecylbenzene sulfonate * 2: 1-ethyl-3-methylimidazolium Dodecylbenzene sulfonate * 3: Homopolypropylene (melt flow rate (ISO1133 230 ° C. x 2.16 kg) = 8 g / 10 min))

From the results shown in Tables 1 to 6, it is clear that according to the present invention, an antistatic agent having an excellent antistatic effect and its durability and excellent storage stability and productivity (cutting property) can be obtained. Is.

Claims (13)

Polyester (a) obtained by reacting diol (a1) and dicarboxylic acid (a2), compound (b) having one or more ethyleneoxy groups and having hydroxyl groups at both ends, and polyvalent having three or more hydroxyl groups. An antistatic agent containing one or more of a polymer compound (E) obtained by reacting with an alcohol compound (D).
The charge is characterized in that the diol (a1) is at least one of 1,4-butanediol or ethylene glycol, and the dicarboxylic acid (a2) is succinic acid or a mixture of dicarboxylic acids containing succinic acid. Inhibitor. The polymer compound (E) has a block (A) of polyester composed of polyester (a) and a block (B) of polyether composed of compound (b), and is composed of the polyester (a). It is bonded via an ester bond or an ether bond formed by the reaction of the hydroxyl group or carboxyl group at the terminal, the hydroxyl group at the end of compound (b), and the hydroxyl group of the polyhydric alcohol compound (D). The antistatic agent according to claim 1, which has a structure. A block polymer (C) having a carboxyl group at both ends, wherein the polymer compound (E) is formed by repeatedly and alternately bonding a polyester block (A) and a polyether block (B) via an ester bond. The antistatic agent according to claim 2, which has a structure in which the polyhydric alcohol compound (D) is bonded to the polyhydric alcohol compound (D) via an ester bond. The antistatic agent according to any one of claims 1 to 3, wherein the polyester (a) has a structure having carboxyl groups at both ends. The antistatic agent according to any one of claims 1 to 4, wherein the compound (b) is polyethylene glycol. The antistatic agent according to any one of claims 1 to 5, wherein the crystallization temperature of the polymer compound (E) is in the range of 20 to 70 ° C. The antistatic agent according to any one of claims 1 to 6, wherein the polyester (a) has a number average molecular weight of 1,000 to 10,000 in terms of polystyrene. The antistatic agent according to any one of claims 3 to 7, wherein the block polymer (C) has a number average molecular weight of 5,000 to 50,000 in terms of polystyrene. The antistatic agent according to any one of claims 1 to 8, 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 blended with the antistatic agent according to any one of claims 1 to 8. An antistatic resin composition, which comprises blending the antistatic agent composition according to claim 9 with a synthetic resin. The antistatic resin composition according to claim 10 or 11, wherein the synthetic resin is at least one selected from the group consisting of a polyolefin resin, a polystyrene resin, and a copolymer thereof. A molded product comprising the antistatic resin composition according to any one of claims 10 to 12.