WO2021065727A1

WO2021065727A1 - Antistatic agent, antistatic agent composition containing same, antistatic resin composition containing said antistatic agent or said antistatic agent composition, and molded body of said antistatic resin composition

Info

Publication number: WO2021065727A1
Application number: PCT/JP2020/036310
Authority: WO
Inventors: 美帆永井; 直樹圓城; 和清野村
Original assignee: 株式会社Adeka
Priority date: 2019-09-30
Filing date: 2020-09-25
Publication date: 2021-04-08
Also published as: TW202118849A

Abstract

The present invention provides: an antistatic agent which is capable of continuously imparting a synthetic resin with an excellent antistatic effect, while having excellent storage stability and excellent productivity (cutting properties); an antistatic agent composition which contains this antistatic agent; an antistatic resin composition which contains this antistatic agent or this antistatic agent composition; and a molded body of this antistatic resin composition.　The present invention contains one or more polymer compounds (C), each of which has a polyester segment (A) and a polyether segment (B), while having a structure where the segments (A) and (B) are bonded to each other via an ester bond, wherein: the segment (A) is composed of a polyester that is obtained from (a1) at least one of 1,4-butanediol and ethylene glycol, (a2) adipic acid and terephthalic acid, and (a3) a polyhydric alcohol compound that has three or more hydroxyl groups; the ratio of the terephthalic acid in component (a2) is 40% by mole or more but less than 100% by mole relative to the total number of moles of the adipic acid and the terephthalic acid; and the segment (B) is composed of (b) a polyethylene glycol.

Description

An antistatic agent, an antistatic agent composition containing the antistatic agent, an antistatic resin composition containing the antistatic agent, and a molded product thereof.

The present invention relates to an antistatic agent, an antistatic agent composition containing the antistatic agent, an antistatic resin composition containing the antistatic agent, and a molded product thereof. An antistatic agent that can be continuously applied and has excellent storage stability and productivity (cutting property), an antistatic agent composition containing the antistatic agent, an antistatic resin composition containing these, and molding thereof. Regarding the 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.

The charged thermoplastic resin attracts dust and dirt around it, which causes a problem of spoiling the appearance of the resin molded product. Further, among electronic products, for example, precision instruments such as computers may not be able to operate normally due to charging. In addition, there are problems with electric shock. When an electric shock is generated from the resin to the human body, it not only causes discomfort to the human body, but may also induce an explosion accident in the presence of flammable gas or dust.

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

Japanese Unexamined Patent Publication No. 58-118838 Japanese Unexamined Patent Publication No. 3-290464 Japanese Unexamined Patent Publication No. 6-57153

However, these conventional antistatic agents are not always sufficient in antistatic performance, and further improvement is desired at present. In addition, conventional polymer-type antistatic agents have problems in 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 in a high temperature state, they become sticky or block. There was a problem with its storage stability. In addition, when cutting into pellets, the pellets may be uneven and have an irregular shape, some of the pellets may not be completely 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 to contain an antistatic agent which can continuously impart an excellent antistatic effect to a synthetic resin and is also excellent in storage stability and productivity (cutting property). It is an object of the present invention to provide an antistatic agent 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 continuously imparting antistatic performance, and by using this, the present invention has been completed.

That is, the antistatic agent of the present invention has a polyester segment (A) and a polyether segment (B).
The polyester segment (A) is
(A1) At least one of 1,4-butanediol or ethylene glycol,
(A2) Adipic acid and terephthalic acid, and
(A3) A polyester obtained from a polyhydric alcohol compound having three or more hydroxyl groups.
(A2) The ratio of terephthalic acid to adipic acid and terephthalic acid is 40 mol% or more and less than 100 mol% with respect to the total number of moles of adipic acid and terephthalic acid.
The polyether segment (B) is (b) polyethylene glycol,
It is characterized by containing one or more kinds of polymer compounds (C) having a structure in which a polyester segment (A) and a polyether segment (B) are bonded via an ester bond.

In the antistatic agent of the present invention, the proportion of the polyhydric alcohol compound having three or more hydroxyl groups (a3) in the polymer compound (C) is equal to at least one of (a1) 1,4-butanediol or ethylene glycol. , (A3) is preferably 0.05 to 5 mol% with respect to the total number of moles of the polyhydric alcohol compound having 3 or more hydroxyl groups. Further, in the antistatic agent of the present invention, the mass ratio (A) / (B) of the polyester segment (A) and the polyether segment (B) of the polymer compound (C) is 0.1 to 1. It is preferably 4.0. Further, in the antistatic agent of the present invention, it is preferable that the polymer compound (C) has a melting point in the range of 100 ° C. or higher and 200 ° C. or lower.

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 of alkali metal salts and ionic liquids. is there.

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

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

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

The molded product of the present invention is characterized by being obtained from the antistatic resin composition of the present invention.

According to the present invention, an antistatic agent which can continuously impart an excellent antistatic effect to a synthetic resin and is also excellent in storage stability and productivity (cutting property), and an antistatic agent containing the same. An agent 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.
First, the antistatic agent of the present invention will be described. The antistatic agent of the present invention contains one or more of the polymer compound (C), and the polymer compound (C) has a polyester segment (A) and a polyether segment (B). ..

The polyester segment (A) is obtained from (a1) at least one of 1,4-butanediol or ethylene glycol, (a2) adipic acid and terephthalic acid, and (a3) a polyhydric alcohol compound having three or more hydroxyl groups. Is polyester. Then, (a2) the ratio of terephthalic acid in adipic acid and terephthalic acid is 40 mol% or more and less than 100 mol% with respect to the total number of moles of adipic acid and terephthalic acid. Further, the polyether segment (B) is (b) polyethylene glycol, and has a structure in which the polyester segment (A) and the polyether segment (B) are bonded via an ester bond.

In the antistatic agent of the present invention, the monomer (a1) constituting the polyester of the polyester segment (A) is at least one of 1,4-butanediol or ethylene glycol, and may be only 1,4-butanediol. , Ethylene glycol alone, or a mixture of 1,4-butanediol and ethylene glycol. In (a1), 1,4-butanediol or a mixture of 1,4-butanediol and ethylene glycol is preferable from the viewpoint of antistatic property, its durability, storage stability, and productivity (cutting property). , 4-Butanediol is most preferred. When (a1) is a mixture of 1,4-butanediol and ethylene glycol, the ratio of 1,4-butanediol is preferably 50 mol% or more, more preferably 70 mol% or more, based on the total number of moles of both. Preferably, 80 mol% or more is more preferable, and 90 mol% or more is particularly preferable.

In the antistatic agent of the present invention, the monomer (a2) constituting the polyester of the polyester segment (A) is adipic acid and terephthalic acid. In (a2), the ratio of terephthalic acid is in the range of 40 mol% or more and less than 100 mol% with respect to the total number of moles of adipic acid and terephthalic acid, and antistatic property, its durability, and storage stability. From the viewpoint of productivity (cutting property), 45 mol% or more and 95 mol% or less are preferable, 50 mol% or more and 90 mol% or less are more preferable, and 60 mol% or more and 90 mol% or less are further preferable.

The adipic acid and terephthalic acid of (a2) may be derivatives thereof as long as they can react with a hydroxyl group to form an ester bond, and the derivatives include, for example, an acid anhydride and an ester (for example, a methyl ester). , Etc.), alkali metal salts (for example, sodium salts), acid halides (for example, acid chloride), and alkyl esters such as methyl esters are preferable from the viewpoint of easiness of reaction.

In the polymer compound (C) according to the antistatic agent of the present invention, a dicarboxylic acid other than the adipic acid and terephthalic acid of (a2) may be used as long as the effect of the present invention is not impaired. Examples of the dicarboxylic acid other than adipic acid and terephthalic acid include sebacic acid and isophthalic acid. However, the use of orthophthalic acid and its derivatives (for example, phthalic anhydride and orthophthalic acid ester) is not preferable from the viewpoint of antistatic property and its durability, storage stability and productivity (cutting property).

In the antistatic agent of the present invention, the monomer (a3) constituting the polyester of the polyester segment (A) is a polyhydric alcohol compound having three or more hydroxyl groups. The polyhydric alcohol compound (a3) having 3 or more hydroxyl groups is not particularly limited as long as it has 3 or more hydroxyl groups, and is, for example, glycerin, 1,2,3-butantriol, 1,2,4-. Butantriol, 2-methyl-1,2,3-propanetriol, 1,2,3-pentantriol, 1,2,4-pentantriol, 1,3,5-pentantriol, 2,3,4-pentane Triol, 2-methyl-2,3,4-butanetriol, trimethylolethane, 2,3,4-hexanetriol, 2-ethyl-1,2,3-butanetriol, trimethylpropane, 4-propyl-3 , 4,5-Heptanetriol, 2,4-dimethyl-2,3,4-pentantriol, triethanolamine, triisopropanolamine, 1,3,5-tris (2-hydroxyethyl) isocyanurate, etc. Alcohol; pentaerythritol, 1,2,3,4-pentantetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentantetrol, 1,3,4,5-hexane Tetrol, diglycerin, ditrimethylol propane, sorbitan, N, N, N', N'-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N', N'-tetrakis (2-hydroxyethyl) ethylenediamine, etc. 4 valent alcohols; pentavalent alcohols such as adonitol, arabitol, xylitol, triglycerin; hexavalent alcohols such as dipentaerythritol, sorbitol, mannitol, iditol, inositol, darcitol, talose, allose; Be done. 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 also be used. In the antistatic agent of the present invention, the polyhydric alcohol compound (a3) having three or more hydroxyl groups may be used alone or in combination of two or more.

In the antistatic agent of the present invention, the polyhydric alcohol compound (a3) having three or more hydroxyl groups contains pentaerythritol and di, from the viewpoints of antistatic property, its durability, storage stability, and productivity (cutting property). Pentaerythritol, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane are preferable, and glycerin is the most preferable.

The proportion of the polyhydric alcohol compound having three or more hydroxyl groups (a3) in the polymer compound (C) is (a1) from the viewpoint of antistatic property, its durability, storage stability, and productivity (cutting property). It is preferably 0.05 to 5 mol% with respect to the total number of moles of at least one of 1,4-butanediol or ethylene glycol and the polyhydric alcohol compound having 3 or more hydroxyl groups (a3). It is more preferably 1 to 3.0 mol%, and even more preferably 0.3 to 2.0 mol%.

In the antistatic agent of the present invention, the polyethylene glycol (b) of the polyether segment (B) is preferably polyethylene glycol represented by the following general formula (1).

In the general formula (1), m represents a number from 4 to 250. m is preferably 20 to 200, more preferably 40 to 180, from the viewpoint of antistatic property, its durability, and storage stability.

In the antistatic agent of the present invention, (b) the number average molecular weight of polyethylene glycol is calculated from the measured value of the hydroxyl value, and from the viewpoint of antistatic property and its sustainability, storage stability, and productivity (cutting property). It is preferably 400 to 10,000, more preferably 900 to 8,000, and even 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 xylene, 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: Blank test titration [mL]
T: Quantitative test titration [mL]
S: Sample amount [g]

The number average molecular weight of the polyester segment (A) in the polymer compound (C) is preferably 1,000 in terms of polystyrene conversion from the viewpoint of antistatic property, its durability, storage stability, and productivity (cutting property). It is ~ 10,000, more preferably 1,500 to 8,000, and even more preferably 2,500 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 (C) may take a long time and the economic efficiency may be inferior. The molecular compound (C) may be colored by a long-term reaction.

The gel permeation chromatography (GPC) method is preferable as the method for measuring the number average molecular weight in terms of polystyrene, 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 chromatography (GPC) method. The measurement conditions for Mn are as follows.
Equipment: GPC equipment manufactured by JASCO Corporation Solvent: Chloroform reference material: Polystyrene detector: UV detector Column stationary phase: Showa Denko Corporation Shodex LF-804
Column temperature: 40 ° C
Sample concentration: 1 mg / 1 mL
Flow rate: 0.5 mL / min.
Injection volume: 30 μL

The number average molecular weight of the polyester segment (A) is determined by measuring the polystyrene-equivalent number average molecular weight of polyester (A'), polyester (A "), etc., which are intermediates obtained in the manufacturing process of the polymer compound (C). It may be calculated from them. As a method for measuring the number average molecular weight in terms of polystyrene, the gel permeation chromatography (GPC) method is preferable, and the measuring method is shown above.

The degree of polymerization of the polyester segment (A) in the polymer compound (C) is preferably 4 to 50, preferably 6 to 50, from the viewpoints of antistatic property, its durability, storage stability, and productivity (cutting property). 40 is more preferable.

The polymer compound (C) according to the antistatic agent of the present invention has at least one of (a1) 1,4-butanediol or ethylene glycol, (a2) adipic acid and terephthalic acid, and (a3) three or more hydroxyl groups. It can be obtained by subjecting a polyhydric alcohol compound and (b) polyethylene glycol to an esterification reaction. The esterification reaction may be any one that forms an ester bond by the reaction, and includes a transesterification reaction. Each component may be a derivative thereof, and examples of the derivative of adipic acid and terephthalic acid in (a2) include acid anhydrides, esters such as alkyl esters, alkali metal salts, and acid halides such as acid chloride. In particular, from the viewpoint of ease of reaction, the use of terephthalic acid methyl ester is preferable for terephthalic acid.

For the esterification reaction (including the transesterification reaction), a catalyst that promotes the esterification reaction (including the transesterification reaction) may be used, and as the catalyst, dibutyltin oxide, tetraalkyl titanate, zirconium acetate, acetic acid Conventionally known substances such as zinc can be used. The esterification reaction or transesterification reaction may be carried out under reduced pressure.

Further, in order to suppress the oxidation of the product during the reaction, an antioxidant such as a phenolic antioxidant may be added to the reaction system.

As a preferable production method for obtaining the polymer compound (C), first, polyester (A') is synthesized from at least one of (a1) 1,4-butanediol or ethylene glycol, and (a2) adipic acid and terephthalic acid. After that, a method of subjecting the polyester (A'), (a3) a polyhydric alcohol compound having three or more hydroxyl groups, and (b) polyethylene glycol to an esterification reaction (including a transesterification reaction) is preferable. In the reaction, after the synthesis reaction of the polyester (A') is completed, the polyhydric alcohol compound having three or more hydroxyl groups (a3) and the polyethylene glycol (b) are used in the reaction system without isolating the polyester (A'). In addition, the reaction may be carried out as it is. The polyhydric alcohol compound (a3) having three or more hydroxyl groups and (b) polyethylene glycol may be added to the reaction system at the same time, or (b) polyethylene glycol is added first, and then (a3) hydroxyl groups are added to 3. Polyhydric alcohol compounds having more than one may be added, and vice versa.

Polyester (A') has hydroxyl groups at both ends from the viewpoint of ease of subsequent reaction for obtaining the polymer compound (C) and suppression of coloration during the synthesis reaction of the obtained polymer compound (C). Is preferable.

In the synthetic reaction of polyester (A'), the reaction ratio of at least one of (a1) 1,4-butanediol or ethylene glycol to (a2) adipic acid and terephthalic acid was such that (a1) was out of the system during the reaction. Considering distillation, it is preferable to use (a1) in excess so that both ends become hydroxyl groups, and (a1) is added in excess of 1 mol with respect to (a2) in terms of molar ratio. It is preferable to use 1.2 times the value obtained. The polyester (A') having hydroxyl groups at both ends obtained here, (a3) a polyhydric alcohol compound having three or more hydroxyl groups, and (b) polyethylene glycol are preferably subjected to a transesterification reaction to form a polymer compound. (C) can be obtained. In this transesterification reaction, 1,4-butanediol or ethylene glycol bonded to both ends of the polyester (A') is transesterified, and they can be easily removed from the reaction system, so that the reaction is easy. Proceeding, preferably the polymer compound (C) can be obtained. Further, the obtained polymer compound (C) is preferable because it is not colored during the synthesis reaction. This transesterification reaction is preferably carried out under reduced pressure because the reaction easily proceeds.

The number average molecular weight of polyester (A') is preferably 1,200 to 10,200 in terms of polystyrene in terms of antistatic property, its durability, storage stability, and productivity (cutting property). It is preferably 1,700 to 8,200, more preferably 2,000 to 7,700, more preferably 2,000 to 4,500, and even more preferably 2,000 to 4,000. is there. If the number average molecular weight is less than 1,200, the storage stability may be inferior, and if it exceeds 10,200, the reaction for obtaining the polymer compound (C) may take a long time and the economic efficiency may be inferior. The molecular compound (C) 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 chromatography (GPC) method is preferable, and the measuring method is as described above.

In addition, as a production method for obtaining the polymer compound (C), first, at least one of (a1) 1,4-butanediol or ethylene glycol, (a2) adipic acid and terephthalic acid, and (a3) hydroxyl group are added to three. Another method is to synthesize a polyester (A ") from a polyhydric alcohol compound having one or more compounds, and then cause the polyester (A") and (b) polyethylene glycol to undergo an esterification reaction (including a transesterification reaction). In the reaction, after the synthesis reaction of the polyester (A ″) is completed, (b) polyethylene glycol may be added to the reaction system and the reaction may be carried out as it is without isolating the polyester (A ″).

The number average molecular weight of the polyester (A ") is preferably 1,100 to 10,100 in terms of polystyrene, from the viewpoint of antistatic property and its durability, storage stability, and productivity (cutting property). It is preferably 1,600 to 8,100, more preferably 2,100 to 7,600. If the number average molecular weight is less than 1,100, the storage stability may be inferior, and if it exceeds 10,100. The reaction for obtaining the polymer compound (C) may take a long time and may be inferior in economic efficiency, or the obtained polymer compound (C) may be colored by a long-term reaction.

The gel permeation chromatography (GPC) method is preferable as the method for measuring the number average molecular weight in terms of polystyrene, and the measuring method is as described above.

The number average molecular weight of the polyether segment (B) may be calculated from the number average molecular weight of (b) polyethylene glycol. The number average molecular weight of the polyether segment (B) is preferably 380 to 9,980, more preferably 880 to 7, from the viewpoint of antistatic property, its durability, storage stability, and productivity (cutting property). , 980, more preferably 1,980 to 7,980.

In the polymer compound (C), the mass ratio (A) of the polyester segment (A) and the polyether segment (B) is considered from the viewpoint of antistatic property, its durability, storage stability, and productivity (cutting property). / (B) is preferably 0.1 to 4.0, more preferably 0.2 to 3.0, and even more preferably 0.3 to 2.5.

The polymer compound (C) according to the antistatic agent of the present invention has a melting point within the range of 100 ° C. or higher and 200 ° C. or lower from the viewpoint of antistatic property and its durability, particularly storage stability and productivity (cutting property). It is preferably 110 ° C. or higher and 195 ° C. or lower, more preferably 120 ° C. or higher and 190 ° C. or lower. If the melting point is less than 100 ° C, storage stability and productivity (cutting property) may deteriorate, and if it exceeds 200 ° C, processing must be performed at a high temperature, limiting the temperature range in which processing is possible. There is a risk of being done.

The melting point in the present invention is measured by the following melting point measuring method.
<Melting point measurement method>
The melting point is measured using a differential scanning calorimetry device (DSC).
The sample is weighed in an aluminum pan at 3 ± 1 mg, heated from 50 ° C to 250 ° C at 10 ° C / min, cooled from 250 ° C to -20 ° C at 10 ° C / min, and then lowered to 250 ° C at 10 ° C / min. Let the peak top of the melting peak at the time of the second temperature rise be the melting point.

The polymer compound (C) according to the antistatic agent of the present invention 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 of alkali metal salts and ionic liquids. The antistatic agent of the present invention further contains 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.

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

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

The alkali metal salt may be blended with the polymer compound (C) according to the antistatic agent of the present invention, or may be blended with the polymer compound (C) and used in a synthetic resin. Further, it may be added to the reaction vessel at the time of producing the polymer compound (C) and blended. The blending amount of the alkali metal salt is preferably 0.01 to 30 parts by mass, preferably 0.1 to 100 parts by mass, based on 100 parts by mass of the polymer compound (C) from the viewpoint of antistatic property, its durability, and storage stability. Up to 20 parts by mass is more preferable, and 3.0 to 15 parts by mass is most preferable.

Next, the ionic liquid will be described.
Examples of ionic liquids have a melting point of 100 ° C. or lower, at least one of the cations or anions constituting the ionic liquid is an organic ion, and has an initial conductivity of 1 to 200 ms / cm, preferably 10 to 10. A room temperature molten salt at 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.

Of these, the following are examples of amidinium cations.

(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 guanidinium cations include the following.

(1) Guanidinium cation having an imidazolinium skeleton Examples thereof include those having 8 to 15 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethylimidazolinium and 2-diethylamino-1,3. , 4-trimethylimidazolinium;
(2) Guanidinium cation having an imidazolium skeleton Examples thereof include those having 8 to 15 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethylimidazolium and 2-diethylamino-1,3,4. -Trimethylimidazolium;
(3) Guanidinium cation having a tetrahydropyrimidinium skeleton Examples thereof include those having 10 to 20 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydro. Pyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium;
(4) Guanidinium cation having a dihydropyrimidinium skeleton Examples thereof include those having 10 to 20 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethyl-1,4-dihydropyrimidinium. 2-Dimethylamino-1,3,4-trimethyl-1,6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4-dihydropyrimidinium, 2-diethylamino-1 , 3-Dimethyl-4-ethyl-1,6-dihydropyrimidinium.

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

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

Among the above organic acids and inorganic acids, the ionic liquid is preferably from the viewpoint of antistatic property and its durability, and the Hammett acidity function (−H0) of the anion constituting the ionic liquid is 12 to 100. Acids that form anions other than superacid conjugate bases, superacid conjugate bases, and mixtures thereof.

Examples of anions other than the conjugated 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.

Further, examples of the super strong acid include those derived from a protonic acid and a combination of a protonic acid and a Lewis acid, and a mixture 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.

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

The combination of the protonic acid and the Lewis acid is arbitrary, but examples of the super strong acid composed of these combinations include tetrafluoroboric acid, hexafluorophosphate, tantalum hexafluoride, antimonic acid 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, from the viewpoint of antistatic property of the ionic liquid, 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 more preferable. Is a conjugate base of a superacid consisting of a protonic acid and a superacid consisting of a boron trifluoride and / or a phosphorus pentafluoride.

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

The ionic liquid may be blended with the polymer compound (C) according to the antistatic agent of the present invention, or may be blended with the polymer compound (C) and used in a synthetic resin. Further, it may be added to the reaction vessel at the time of producing the polymer compound (C) and blended. The blending amount of the ionic liquid is preferably 0.01 to 20 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the polymer compound (C) from the viewpoint of antistatic property, its durability, and storage stability. 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 polymer compound (C), one or more selected from the group of alkali metal salts and ionic liquids, and other optional components as necessary. And 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, nouter mixers and the like. Further, one or more selected from the group consisting of alkali metal salts and ionic liquids may be added to the reaction system during the synthesis reaction of the polymer compound (C).

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

The salt of the Group 2 element may be blended with the polymer compound (C), or may be blended with the polymer compound (C) and used with a synthetic resin. The amount of the salt of the Group 2 element is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and 3.0 to 12 parts by mass with respect to 100 parts by mass of the polymer compound (C). Parts by mass are most preferred.

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; and fatty acid esters of polyethylene oxide and glycerin. , Pentaerythlit fatty acid ester, sorbit or sorbitan fatty acid ester, polyhydric alcohol alkyl ether, polyhydric alcohol type nonionic surfactant such as aliphatic amide of alkanolamine and the like. Examples of the anionic surfactant include carboxylates such as alkali metal salts of higher fatty acids; sulfate esters such as higher alcohol sulfates and higher alkyl ether sulfates, alkylbenzene sulfonates and alkyl sulfonates. Sulfates such as paraffin sulfonates; phosphate salts such as higher alcohol phosphates and the like can be mentioned. Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of the amphoteric tenside include amino acid amphoteric tenside agents such as higher alkylaminopropionate, betaine amphoteric tenside agents 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 these 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 polymer compound (C) or may be blended with the polymer compound (C) into a synthetic resin for use. 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 polymer compound (C). ..

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

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

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 the compatibilizer, the compatibility between the polymer compound (C) and other components or synthetic resin 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.

The compatibilizer may be blended with the polymer compound (C) according to the antistatic agent of the present invention, or may be blended with the polymer compound (C) 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 with respect to 100 parts by mass of the polymer compound (C).

The antistatic agent composition of the present invention may contain other components as arbitrary components in addition to the polymer compound (C) 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 of the present invention, or the polymer compound (C) or the antistatic agent composition of the present invention may be blended with a synthetic resin such as a thermoplastic resin. , When used as a resin composition having antistatic properties, it may be blended with a synthetic resin.

Next, the antistatic resin composition of the present invention will be described.
The antistatic resin composition of the present invention is obtained by blending the antistatic agent of the present invention with a synthetic resin. The polymer compound (C) and the antistatic agent composition according to the antistatic agent of the present invention are blended with a synthetic resin, particularly preferably a thermoplastic resin, and used as an antistatic resin composition having antistatic properties. it can. 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, etc., a polyolefin resin which is a homopolymer or copolymer of an olefin monomer; polystyrene, Polymers of styrene and / or α-methylstyrene and other monomers (eg, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) (eg, AS resin, ABS (with acrylonitrile butadiene styrene, etc.) Polymer) resin, ACS resin, SBS resin, MBS resin, heat-resistant ABS resin, etc.) and other polystyrene-based resins that are homopolymers or copolymers of styrene monomers; polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, Chlorinated polypropylene, polyvinylidene fluoride, rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymer , Halogen-containing resins such as vinyl chloride-acrylic acid ester copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-cyclohexylmaleimide copolymers; petroleum resins, kumaron resins, polyvinyl acetate, acrylic resins, polymethyl Methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyalkylene terephthalate such as polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polyalkylene naphthalate such as polybutylene naphthalate, and poly Linear polyesters such as tetramethylene terephthalate; degradable fats such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polyapple acid, polyglycolic acid, polydioxane, poly (2-oxetanone) Group polyesters; polymers such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, polycarbonate, polycarbonate / ABS resin, branched Examples thereof include thermoplastic resins such as polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, fibrous resin, polyimide resin, polysulfone, polyphenylene ether, polyetherketone, polyetheretherketone, and liquid crystal polymer, 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 antistatic 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, one or more selected from the group of polyolefin-based resins or polystyrene-based resins is preferable from the viewpoint of antistatic properties.

The mass ratio of the synthetic resin to the polymer compound (C) according to the antistatic agent of the present invention or the antistatic agent composition of the present invention in the antistatic resin composition of the present invention is 99/1 to 40. The range of / 60 is preferable.

The method for blending the polymer compound (C) according to the antistatic agent of the present invention into the synthetic resin, particularly preferably the thermoplastic resin, is not particularly limited, and any commonly used method can be used, for example. It may be mixed and kneaded by roll kneading, bumper kneading, extrusion machine, kneader or the like. At that time, one or more selected from the group consisting of alkali metal salts and ionic liquids may be mixed and kneaded at the same time. Further, the polymer compound (C) 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 for 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, those obtained by chemically modifying the surface of these carriers, and solid ones among the flame retardants 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.

Further, to give a method of blending the polymer compound (C) according to the antistatic agent of the present invention, the polymer compound (C) and a synthetic resin, particularly preferably a thermoplastic resin, are mixed at the time of molding such as injection molding. It may be blended by a method for obtaining 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, and further, with the polymer compound (C) in advance. A masterbatch with a synthetic resin may be produced and this masterbatch may be blended, and at that time, one or more selected from the group of alkali metal salts and ionic liquids may be blended.

The antistatic resin composition of the present invention may contain various additives such as a phenolic antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, an ultraviolet absorber, and a hindered amine-based light stabilizer, if necessary. Further can be added, which can stabilize the antistatic resin composition of the present invention.

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 (C). In particular, an antioxidant is preferable because it can prevent oxidative deterioration of the polymer compound (C) during production by blending it at the time of producing the polymer compound (C).

Examples of the phenolic antioxidant include 2,6-ditertiary butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and distearyl (3,5-ditertiary butyl-4-4). Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-dithiary butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tertiary butyl-m-cresol) , 2,2'-Methylenebis (4-methyl-6-tertiary butylphenol), 2,2'-methylenebis (4-ethyl-6-third butylphenol), 4,4'-butylidenebis (6-tertiary butyl-) m-cresol), 2,2'-etylidenebis (4,6-di-tertiary butylphenol), 2,2'-etylidenebis (4-second butyl-6-third butylphenol), 1,1,3- Tris (2-methyl-4-hydroxy-5-third butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-third 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-ditriary butyl-4-hydroxyphenyl) ) Propionate, tetrakis [3- (3,5-ditriary butyl-4-hydroxyphenyl) methyl propionate] methane, thiodiethylene glycol bis [(3,5-ditritiary butyl-4-hydroxyphenyl) propionate], 1,6-Hexamethylenebis [(3,5-ditertiary butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-hydroxy-3-third butylphenyl) butyric acid] glycol Estel, bis [2-tertiary butyl-4-methyl-6- (2-hydroxy-3-third butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-di) Tertiary Butyl-4-Hydroxyphenyl) Propionyloxyethyl] Isocyanurate, 3,9-Bis [1,1-Dimethyl-2-{(3-Triary Butyl-4-Hydroxy-5-Methylphenyl) Propionyloxy} Ethyl] -2,4,8,10-tetraoxaspiro [5,5] ung Decane, 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 phosphorus-based antioxidants include trisnonylphenyl phosphite and tris [2-tertiary butyl-4- (3-third butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phos. Fight, tridecylphosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-dith) Tributylphenyl) pentaerythritol diphosphite, bis (2,6-ditertiary 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-ethylhexyl phosphite , 2,2'-Methylenebis (4,6-3rd Butylphenyl) -Octadecylphosphite, 2,2'-Echilidenebis (4,6-di3rd Butylphenyl) Fluorophosphite, Tris (2-[( 2,4,8,10-Tetraxyl butyldibenzo [d, f] [1,3,2] dioxaphosfepin-6-yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol And 2,4,6-triterone butylphenol phosphite and the like. The amount of these phosphorus-based antioxidants added is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin.

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

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-Hydroxybenzophenones such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-ditertiary butylphenyl) -5-chlorobenzo Triazol, 2- (2'-hydroxy-3'-tertiary butyl-5'-methylphenyl) -5-chlorobenzotriazol, 2- (2'-hydroxy-5'-tertiary octyl) Phenyl) benzotriazol, 2- (2'-hydroxy-3', 5'-dicumylphenyl) benzotriazol, 2,2'-methylenebis (4-third octyl-6- (benzotriazolyl) phenol ), 2- (2'-Hydroxyphenyl) benzotriazoles such as 2- (2'-hydroxy-3'-tertiary butyl-5'-carboxyphenyl) benzotriazole; phenylsalicylate, resorcinol monobenzoate, 2,4 -Di-tertiary butylphenyl-3,5-di-tertiary butyl-4-hydroxybenzoate, 2,4-di-tertiary amylphenyl-3,5-di-tertiary butyl-4-hydroxybenzoate, hexadecyl-3,5 -Benzoates such as di-ternary 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-tetramethyl-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-Butancarboxylic acid / 2,2-bis (hydroxymethyl) -1,3-propanediol / 3-hydroxy-2,2-dimethylpropanal / 1,2,2,6,6-pentamethyl-4- Piperidinyl ester polycondensate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) = decandioate / methyl = 1,2,2,6,6-pentamethyl-4-piperidyl = sebacato mixture , 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1, 6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-) Piperidineamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4- Dichloro-6-3 octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-) 4-Piperidyl) amino) -s-triazine-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N-) (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2 , 4-Bistyl (N-Butyl-N- (2,2,6,6-Tetramethyl-4-piperidyl) Amino) -s-Triazine-6-ylamino] Undecane, 1,6,11-Tris [2, 4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6-ylamino] undecane, 3,9-bis [1,1-bis] Dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3 , 9-bis [1,1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) butylcarbonyloxy} ethyl] -2,4,8,10-tetra Oxaspiro [5.5] undecane, bis (1-undecyloxy-2,2,6,6-tetramethylpiperidine-4-yl) carbonate, 2,2,6,6-tetramethyl-4-piperidylhexa Examples thereof include hindered amine compounds such as decanoate and 2,2,6,6-tetramethyl-4-piperidyl octadecanoate. The amount of these hindered amine-based light stabilizers added is preferably 0.001 to 30 parts by mass, 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 antistatic resin composition of the present invention, as other additives, if necessary, an aromatic carboxylic acid metal salt, an alicyclic alkyl carboxylic acid metal salt, as long as the effects of the present invention are not impaired. Crystal nucleating agents such as aluminum p-tertiary butyl benzoate, aromatic phosphate metal salts, dibenzylidene sorbitols, metal soaps, hydrotalcites, triazine ring-containing compounds, metal hydroxides, phosphoric acid ester flame retardants. , Condensed Phosphate Flame Retardant, Inorganic Phosphate Flame Retardant, (Poly) Phosphate Flame Retardant, Halogen Flame Retardant, Silicon Flame Retardant, Antimonium Oxide such as Antimon Trioxide, Other Inorganic Flame Retardant Agents, other organic flame retardant aids, neutralizers, anti-aging agents, fillers, pigments, lubricants, processing aids, plasticizers, reinforcements, 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 Kagaku Kogyo Co., Ltd.) and the like.

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

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

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

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

Examples of the anti-aging agent include naphthylamine-based, diphenylamine-based, p-phenyldiamine-based, quinoline-based, hydroquinone derivatives, monophenol-based, thiobisphenol-based, hindered phenol-based, and phosphite ester-based agents.

Examples of the crystal nucleating agent include an inorganic crystal nucleating agent and an organic crystal nucleating agent, and specific examples of the inorganic crystal nucleating agent include kaolinite, synthetic mica, clay, zeolite, silica, graphite, carbon black, and oxidation. Metal salts such as magnesium, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, aluminum oxide, neodium oxide and phenylphosphonate can be mentioned. These inorganic crystal nucleating agents may be modified with an organic substance in order to enhance the dispersibility in the composition.

Specific examples of the organic crystal nucleating agent include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, calcium oxalate. , Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosate, calcium octacosate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, stearic acid Organic carboxylates such as barium, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, etc. Salt, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearic acid amide, ethylenebislauric acid amide, partimate amide, hydroxystearic acid amide, erucic acid amide, tristrimethic acid (t-butylamide) ) Etc., benzylidene sorbitol and its derivatives, phosphorus compound metal salts such as sodium-2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate, and 2,2-methylbis (4). , 6-di-t-butylphenyl) sodium and the like.

The neutralizing agent is added to neutralize the residual catalyst in the synthetic resin, and is, for example, a fatty acid metal salt such as calcium stearate, lithium stearate, sodium stearate, or ethylene bis (stearoamide). Examples thereof include fatty acid amide compounds such as ethylene bis (12-hydroxystearoamide) and stearic acid amide.

Examples of the lubricant include pure hydrocarbon-based lubricants such as liquid paraffin, natural paraffin, microwax, synthetic paraffin, low molecular weight polyethylene, and polyethylene wax; halogenated hydrocarbon-based lubricants; fatty acid-based lubricants such as higher fatty acids and oxyfatty acids; Fatty acid amide-based lubricants such as fatty acid amide and bis fatty acid amide; ester-based lubricants such as lower alcohol ester of fatty acid, polyhydric alcohol ester of fatty acid such as glyceride, polyglycol ester of fatty acid, and fatty alcohol ester of fatty acid (ester wax); Examples thereof include metal soaps, fatty alcohols, polyhydric alcohols, polyglycols, polyglycerols, partial esters of fatty acids and polyhydric alcohols, fatty acids and polyglycols, partial ester-based lubricants of polyglycerols, silicone oils, mineral oils and the like.

Examples of the processing aid include acrylic processing aids, and as the acrylic processing aid, one type of (meth) acrylic acid ester may be polymerized or two or more types may be copolymerized. Examples of polymerized or copolymerized (meth) acrylic acid esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, isobutyl. Examples thereof include (meth) acrylic acid esters such as acrylate, t-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate and tridecyl methacrylate. In addition to the above, (meth) acrylic acid and (meth) acrylic acid ester containing a hydroxy group can also be mentioned.

Examples of the plasticizer include polyester-based plasticizers, glycerin-based plasticizers, polyvalent carboxylic acid ester-based plasticizers, polyalkylene glycol-based plasticizers, ether ester-based plasticizers, epoxy-based plasticizers, and the like.

Examples of the reinforcing material include glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wallastenite, sepiolite, asbestos, and slag fiber. Inorganic fibrous reinforcing materials such as zonolite, elestadite, gypsum fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate. Organic fibrous reinforcements such as fiber, kenaf, ramie, cotton, jute, hemp, sisal, flax, linen, silk, Manila hemp, sugar cane, wood pulp, paper scraps, waste paper and wool, glass flakes, non-swelling mica, graphite, Metal foil, ceramic beads, clay, mica, cericite, zeolite, bentonite, dolomite, kaolin, fine powder silicic acid, pebbles, potassium titanate, silas balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, Examples thereof include plate-like or granular reinforcing materials such as titanium oxide, aluminum silicate, silicon oxide, gypsum, novacurite, dosonite and white clay. These reinforcing materials may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, and may be coated or focused with a coupling agent such as aminosilane or epoxysilane. It may have been processed.

In the antistatic resin composition of the present invention, as other additives, as long as the effects of the present invention are not impaired, if necessary, additives usually used for synthetic resins, such as a cross-linking agent and a fungicide, are used. Antifogging agents, antistatic agents, surface treatment agents, fluorescent agents, fungicides, fungicides, metal deactivators, mold release agents and the like can be blended within a range that does not impair the effects of the present invention.

The additive contained in the antistatic resin composition of the present invention may be added directly to the synthetic resin, or may be added to the polymer compound (C) or the antistatic agent composition which is the antistatic agent of the present invention. Then, it may be added to the synthetic resin.

Next, the molded product of the present invention will be described.
The molded product of the present invention is obtained from the antistatic resin composition of the present invention. By molding the antistatic 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 antistatic resin composition of the present invention is excellent in antistatic performance and its durability.

The antistatic 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. It can be used in a wide range of industrial fields such as equipment, wood, 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, household appliances such as kotatsu, TVs, VTRs, video cameras, radio cassette recorders. , 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. , Distribution boards, electrical and electronic parts such as watches and communication equipment, interior and exterior materials for automobiles, plate making films, adhesive films, bottles, food containers, food packaging films, pharmaceutical / pharmaceutical wrap films, product packaging films , Agricultural film, agricultural sheet, greenhouse film, etc.

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

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

The polymer compound (C), which is the antistatic agent of the present invention, was produced according to the following production example. Further, in the following production example, the number average molecular weight of the compound (b) is calculated by the following <method for calculating the number average molecular weight from the hydroxyl value>, and the number average molecular weights other than the compound (b) are calculated by the following <polystyrene conversion]. It was calculated by the method for measuring the number average molecular weight according to>.

<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 <hydroxyl value measurement method>
・ 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 dissolve by heating. 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: Blank test titration [mL]
T: Quantitative test titration [mL]
S: Sample amount [g]

[Manufacturing Example 1]
In a separable flask, 87 g (0.96 mol) of 1,4-butanediol as (a1), 33 g (0.22 mol) of adipic acid and 102 g (0.52 mol) of dimethyl terephthalate as (a2). , Antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) 0.24 g, tetraisopropyl titanate 0 .27 g was charged and polymerized at normal pressure for 6 hours while gradually increasing the temperature from 25 ° C. to 195 ° C. to obtain polyester (A')-1 having hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-1 was 3300.

Next, 160 g of the obtained polyester (A')-1 was used, 0.92 g (0.01 mol) of glycerin as the polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups, and the number average molecular weight of polyethylene glycol. 3300, 98 g of polyethylene glycol (b) -1 having 75 repeating units of ethyleneoxy groups, 0.2 g of antioxidant (Adecastab AO-60), 1.2 g of tetraisopropyl titanate were charged, and 10 at 220 ° C. After polymerizing by performing an ester exchange reaction under reduced pressure for a long time, it is extruded at 230 ° C. using Laboplastomill μ (manufactured by Toyo Seiki Seisakusho Co., Ltd.) and cut into 5 mm square pellets to prevent antistatic of the present invention. 200 g of pellets of the polymer compound (C) -1 (antistatic agent (C) -1) as an agent were obtained. The melting point of the obtained pellet was measured by the following <melting point measuring method>.

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 whole of the good-shaped pellets was confirmed. The ratio (mass%) to the amount was calculated, and <productivity (cutting property)> was evaluated. The defective shape of the pellets includes those in which a part of the pellets cannot be cut and several pellets are connected, those in which the pellet surface is in a jagged state, 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.

<Melting point measurement method>
The melting point was measured using a differential scanning calorimetry device (Diamond DSC manufactured by Perkin). That is, the pellet of the sample is cut into small pieces, 3 ± 1 mg is weighed in an aluminum pan, the temperature is raised from 50 ° C. to 250 ° C. at 10 ° C./min, the temperature is lowered from 250 ° C. to -20 ° C. at 10 ° C./min, and then. The melting point is defined as the peak top of the melting peak at the time of the second temperature rise when the temperature is raised to 250 ° C. at 10 ° C./min.

<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 100 ° C. for 3 hours. After 3 hours, 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]
In a separable flask, 88 g (0.98 mol) of 1,4-butanediol as (a1), 62 g (0.42 mol) of adipic acid as (a2) and 67 g (0.35 mol) of dimethyl terephthalate as (a2). , Antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) 0.24 g, tetraisopropyl titanate 0 .27 g was charged and polymerized at normal pressure for 6 hours while gradually increasing the temperature from 25 ° C. to 195 ° C. to obtain polyester (A')-2 having hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-2 was 3100.

Next, 160 g of the obtained polyester (A')-2, 0.92 g (0.01 mol) of glycerin as a polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups, and a number average molecular weight as polyethylene glycol. 3300, 98 g of polyethylene glycol (b) -1 having 75 repeating units of ethyleneoxy groups, 0.2 g of antioxidant (Adecastab AO-60), 1.2 g of tetraisopropyl titanate were charged, and 16 at 220 ° C. After polymerizing by performing an ester exchange reaction under reduced pressure for a long time, pellets of the polymer compound (C) -2 (antistatic agent (C) -2), which is the antistatic agent of the present invention, are carried out in the same manner as in Production Example 1. 200 g was obtained. The melting point of the obtained pellet of the polymer compound (C) -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. The results are shown in Table 1.

[Manufacturing Example 3]
In a separable flask, 88 g (0.98 mol) of 1,4-butanediol as (a1), 56 g (0.38 mol) of adipic acid as (a2) and 74 g (0.38 mol) of dimethyl terephthalate as (a2). , Antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) 0.24 g, tetraisopropyl titanate 0 .27 g was charged and polymerized at normal pressure for 5 hours while gradually increasing the temperature from 25 ° C. to 195 ° C. to obtain polyester (A')-3 having hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-3 was 2900.

Next, 160 g of the obtained polyester (A')-3, 0.92 g (0.01 mol) of glycerin as a polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups, and a number average molecular weight as polyethylene glycol. 3300, 98 g of polyethylene glycol (b) -1 having 75 repeating units of ethyleneoxy groups, 0.2 g of antioxidant (Adecastab AO-60), 1.2 g of tetraisopropyl titanate were charged, and 15 at 220 ° C. After polymerizing by performing an ester exchange reaction under reduced pressure for a long time, pellets of the polymer compound (C) -3 (antistatic agent (C) -3), which is the antistatic agent of the present invention, are carried out in the same manner as in Production Example 1. 200 g was obtained. The melting point of the obtained pellet of the polymer compound (C) -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. The results are shown in Table 1.

[Manufacturing Example 4]
88 g (0.97 mol) of 1,4-butanediol as (a1), 50 g (0.34 mol) of adipic acid and 81 g (0.42 mol) of dimethyl terephthalate as (a2) in a separable flask. , Antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) 0.24 g, tetraisopropyl titanate 0 .27 g was charged and polymerized at normal pressure for 7 hours while gradually increasing the temperature from 25 ° C. to 195 ° C. to obtain polyester (A')-4 having hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-4 was 3000.

Next, 160 g of the obtained polyester (A') -4, 0.92 g (0.01 mol) of glycerin as a polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups, and a number average molecular weight as polyethylene glycol. 3300, 98 g of polyethylene glycol (b) -1 having 75 repeating units of ethyleneoxy groups, 0.2 g of antioxidant (Adecastab AO-60), 1.2 g of tetraisopropyl titanate were charged, and 12 at 220 ° C. After polymerizing by performing an ester exchange reaction under reduced pressure for a long time, pellets of the polymer compound (C) -4 (antistatic agent (C) -4), which is the antistatic agent of the present invention, are carried out in the same manner as in Production Example 1. 200 g was obtained. The melting point of the obtained pellet of the polymer compound (C) -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. The results are shown in Table 1.

[Manufacturing Example 5]
In a separable flask, 87 g (0.96 mol) of 1,4-butanediol as (a1), 44 g (0.30 mol) of adipic acid as (a2), and 88 g (0.45 mol) of dimethyl terephthalate as (a2). , Antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) 0.24 g, tetraisopropyl titanate 0 .27 g was charged and polymerized at normal pressure for 11 hours while gradually increasing the temperature from 25 ° C. to 195 ° C. to obtain polyester (A') -5 having hydroxyl groups at both ends. The obtained polyester (A')-5 had a number average molecular weight of 3100.

Next, 160 g of the obtained polyester (A') -5, 0.92 g (0.01 mol) of glycerin as a polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups, and a number average as polyethylene glycol. 98 g of polyethylene glycol (b) -1 having a molecular weight of 3300 and the number of repeating units of ethyleneoxy groups = 75, 0.2 g of an antioxidant (Adecastab AO-60), and 1.2 g of tetraisopropyl titanate were charged at 220 ° C. After the ester exchange reaction was carried out under reduced pressure for 8 hours to polymerize, the polymer compound (C) -5 (antistatic agent (C) -5), which is the antistatic agent of the present invention, was prepared in the same manner as in Production Example 1. 200 g of pellets were obtained. The melting point of the obtained pellet of the polymer compound (C) -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. The results are shown in Table 1.

[Manufacturing Example 6]
In a separable flask, 86 g (0.95 mol) of 1,4-butanediol as (a1), 22 g (0.15 mol) of adipic acid as (a2) and 115 g (0.59 mol) of dimethyl terephthalate as (a2). , Antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) 0.24 g, tetraisopropyl titanate 0 .27 g was charged and polymerized at normal pressure for 9 hours while gradually increasing the temperature from 25 ° C. to 195 ° C. to obtain polyester (A')-6 having hydroxyl groups at both ends. The obtained polyester (A')-6 had a number average molecular weight of 3000.

Next, 160 g of the obtained polyester (A')-6, 0.92 g (0.01 mol) of glycerin as a polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups, and a number average as polyethylene glycol. 98 g of polyethylene glycol (b) -1 having a molecular weight of 3300 and the number of repeating units of ethyleneoxy groups = 75, 0.2 g of an antioxidant (Adecastab AO-60), and 1.2 g of tetraisopropyl titanate were charged at 220 ° C. After the ester exchange reaction was carried out under reduced pressure for 9 hours to polymerize, the polymer compound (C) -6 (antistatic agent (C) -6), which is the antistatic agent of the present invention, was prepared in the same manner as in Production Example 1. 200 g of pellets were obtained. The melting point of the obtained pellet of the polymer compound (C) -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. The results are shown in Table 1.

[Manufacturing Example 7]
In a separable flask, 85 g (0.94 mol) of 1,4-butanediol as (a1), 11 g (0.073 mol) of adipic acid as (a2) and 128 g (0.66 mol) of dimethyl terephthalate as (a2). , Antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) 0.24 g, tetraisopropyl titanate 0 .27 g was charged and polymerized at normal pressure for 8 hours while gradually increasing the temperature from 25 ° C. to 195 ° C. to obtain polyester (A') -7 having hydroxyl groups at both ends. The obtained polyester (A')-7 had a number average molecular weight of 3000.

Next, 160 g of the obtained polyester (A') -7, 0.92 g (0.01 mol) of glycerin as a polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups, and a number average as polyethylene glycol. 98 g of polyethylene glycol (b) -1 having a molecular weight of 3300 and the number of repeating units of ethyleneoxy groups = 75, 0.2 g of an antioxidant (Adecastab AO-60), and 1.2 g of tetraisopropyl titanate were charged at 220 ° C. After the ester exchange reaction was carried out under reduced pressure for 9 hours to polymerize, the polymer compound (C) -7 (antistatic agent (C) -7), which is the antistatic agent of the present invention, was prepared in the same manner as in Production Example 1. 200 g of pellets were obtained. The melting point of the obtained pellet of the polymer compound (C) -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. The results are shown in Table 1.

[Manufacturing Example 8]
In a separable flask, 69 g (1.11 mol) of ethylene glycol as (a1), 38 g (0.26 mol) of adipic acid and 118 g (0.61 mol) of dimethyl terephthalate as (a2), an antioxidant. (Tetrax [3- (3,5-ditertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) was charged in 0.24 g, and tetraisopropyl titanate was charged in 0.27 g. Polymerization was carried out at normal pressure for 4 hours while gradually raising the temperature from 25 ° C. to 195 ° C. to obtain polyester (A') -8 having hydroxyl groups at both ends. The obtained polyester (A')-8 had a number average molecular weight of 3000.

Next, 160 g of the obtained polyester (A') -8, 0.92 g (0.01 mol) of glycerin as a polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups, and a number average as polyethylene glycol. 100 g of polyethylene glycol (b) -1 having a molecular weight of 3300 and the number of repeating units of ethyleneoxy groups = 75, 0.2 g of an antioxidant (Adecastab AO-60), and 1.3 g of tetraisopropyl titanate were charged at 220 ° C. After the ester exchange reaction was carried out under reduced pressure for 10 hours to polymerize, the polymer compound (C) -8 (antistatic agent (C) -8), which is the antistatic agent of the present invention, was prepared in the same manner as in Production Example 1. 200 g of pellets were obtained. The melting point of the obtained pellet of the polymer compound (C) -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. The results are shown in Table 1.

[Manufacturing Example 9]
In a separable flask, 46 g (0.51 mol) of 1,4-butanediol as (a1) and 32 g (0.51 mol) of ethylene glycol, and 35 g (0.24 mol) of adipic acid as (a2). 109 g (0.56 mol) of dimethyl terephthalate, antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation ) And 0.27 g of tetraisopropyl titanate were charged and polymerized at normal pressure for 5 hours while gradually increasing the temperature from 25 ° C. to 195 ° C. to obtain polyester (A') -9 having hydroxyl groups at both ends. It was. The obtained polyester (A')-9 had a number average molecular weight of 3300.

Next, 160 g of the obtained polyester (A') -9, 0.92 g (0.01 mol) of glycerin as a polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups, and a number average as polyethylene glycol. 99 g of polyethylene glycol (b) -1 having a molecular weight of 3300 and the number of repeating units of ethyleneoxy groups = 75, 0.2 g of an antioxidant (Adecastab AO-60), and 1.3 g of tetraisopropyl titanate were charged at 220 ° C. After the ester exchange reaction was carried out under reduced pressure for 9 hours to polymerize, the polymer compound (C) -9 (antistatic agent (C) -9), which is the antistatic agent of the present invention, was prepared in the same manner as in Production Example 1. 200 g of pellets were obtained. The melting point of the obtained pellet of the polymer compound (C) -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. The results are shown in Table 1.

[Manufacturing Example 10]
In a separable flask, 71 g (0.79 mol) of 1,4-butanediol as (a1) and 12 g (0.20 mol) of ethylene glycol, and 34 g (0.23 mol) of adipic acid as (a2). 105 g (0.54 mol) of dimethyl terephthalate, antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation ) And 0.27 g of tetraisopropyl titanate were charged and polymerized at normal pressure for 6 hours while gradually increasing the temperature from 25 ° C. to 195 ° C. to obtain polyester (A') -10 having hydroxyl groups at both ends. It was. The obtained polyester (A')-10 had a number average molecular weight of 3300.

Next, 160 g of the obtained polyester (A') -10, 0.92 g (0.01 mol) of glycerin as a polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups, and a number average as polyethylene glycol. 98 g of polyethylene glycol (b) -1 having a molecular weight of 3300 and the number of repeating units of ethyleneoxy groups = 75, 0.2 g of an antioxidant (Adecastab AO-60), and 1.3 g of tetraisopropyl titanate were charged at 220 ° C. After the ester exchange reaction was carried out under reduced pressure for 11 hours to polymerize, the polymer compound (C) -10 (antistatic agent (C) -10), which is the antistatic agent of the present invention, was prepared in the same manner as in Production Example 1. 200 g of pellets were obtained. The melting point of the obtained pellet of the polymer compound (C) -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. The results are shown in Table 1.

[Manufacturing Example 11]
To 160 g of polyester (A')-1 obtained in the same manner as in Production Example 1, 1.0 g (0.0074 mol) of pentaerythritol as a polyhydric alcohol compound (a3) -2 having 3 or more hydroxyl groups was added. As polyethylene glycol, 98 g of polyethylene glycol (b) -1 having a number average molecular weight of 3300 and the number of repeating units of ethyleneoxy groups = 75, 0.2 g of an antioxidant (Adecastab AO-60), and tetraisopropyl titanate were used. After charging 2 g and carrying out an ester exchange reaction at 220 ° C. for 14 hours under reduced pressure to polymerize, the polymer compound (C) -11 (antistatic agent (antistatic agent)) which is the antistatic agent of the present invention is carried out in the same manner as in Production Example 1. 200 g of pellets of C) -11) was obtained. The melting point of the obtained pellet of the polymer compound (C) -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. The results are shown in Table 1.

[Manufacturing Example 12]
To 160 g of polyester (A')-1 obtained in the same manner as in Production Example 1, 1.34 g (0.01 mol) of trimethylolpropane as a polyhydric alcohol compound (a3) -3 having three or more hydroxyl groups. As polyethylene glycol, 98 g of polyethylene glycol (b) -1 having a number average molecular weight of 3300 and 75 repeating units of ethyleneoxy groups, 0.2 g of an antioxidant (Adecastab AO-60), and 1 tetraisopropyl titanate. After charging 2 g and carrying out an ester exchange reaction at 220 ° C. for 10 hours under reduced pressure to polymerize, pellets (charged) of the polymer compound (C) -12, which is the antistatic agent of the present invention, are carried out in the same manner as in Production Example 1. 200 g of the inhibitor (C) -12) was obtained. The melting point of the obtained pellet of the polymer compound (C) -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. The results are shown in Table 1.

[Manufacturing Example 13]
To 160 g of polyester (A')-1 obtained in the same manner as in Production Example 1, 1.9 g (0.0074 mol) of ditrimethylolpropane as a polyhydric alcohol compound (a3) -4 having three or more hydroxyl groups was added. As polyethylene glycol, 98 g of polyethylene glycol (b) -1 having a number average molecular weight of 3300 and the number of repeating units of ethyleneoxy groups = 75, 0.2 g of an antioxidant (Adecastab AO-60), and 1 tetraisopropyl titanate. After charging 2 g and carrying out an ester exchange reaction at 220 ° C. for 10 hours under reduced pressure to polymerize, the polymer compound (C) -13 (antistatic agent) which is the antistatic agent of the present invention is the same as in Production Example 1. 200 g of pellets of (C) -13) were obtained. The melting point of the obtained pellet of the polymer compound (C) -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. The results are shown in Table 1.

[Manufacturing Example 14]
As a polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups in 160 g of polyester (A') -1 obtained in the same manner as in Production Example 1, 0.92 g (0.01 mol) of glycerin was added. As polyethylene glycol, 30 g of polyethylene glycol (b) -2 having a number average molecular weight of 1000 and 22 repeating units of ethyleneoxy groups, 0.2 g of an antioxidant (Adecastab AO-60), and tetraisopropyl titanate were used. After charging 2 g and carrying out an ester exchange reaction at 220 ° C. for 12 hours under reduced pressure to polymerize, the polymer compound (C) -14 (antistatic agent (antistatic agent)) which is the antistatic agent of the present invention is carried out in the same manner as in Production Example 1. 200 g of pellets of C) -14) were obtained. The melting point of the obtained pellet of the polymer compound (C) -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. The results are shown in Table 1.

[Manufacturing Example 15]
To 160 g of polyester (A') -1 obtained in the same manner as in Production Example 1, 0.92 g (0.01 mol) of glycerin as a polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups, polyethylene. As glycol, 178 g of polyethylene glycol (b) -3 having a number average molecular weight of 6000 and the number of repeating units of ethyleneoxy groups = 136 g, 0.2 g of an antioxidant (Adecastab AO-60), and 1.2 g of tetraisopropyl titanate. After charging, the ester exchange reaction was carried out at 220 ° C. for 14 hours under reduced pressure to polymerize, and then the polymer compound (C) -15 (antistatic agent (C)), which is the antistatic agent of the present invention, was prepared in the same manner as in Production Example 1. ) -15) pellets were obtained in an amount of 200 g. The melting point of the obtained pellet of the polymer compound (C) -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. The results are shown in Table 1.

[Manufacturing Example 16]
170 g (1.9 mol) of 1,4-butanediol as (a1), 56 g (0.38 mol) of adipic acid and 173 g (0.89 mol) of dimethyl terephthalate as (a2) in a separable flask. , Antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) 0.84 g, tetraisopropyl titanate 0 .95 g was charged and polymerized at normal pressure for 3 hours while gradually increasing the temperature from 25 ° C. to 195 ° C. to obtain polyester (A')-11 having hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-11 was 1000.

Next, 100 g of the obtained polyester (A')-11, 1.9 g (0.02 mol) of glycerin as a polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups, and a number average molecular weight as polyethylene glycol. 3300, 201 g of polyethylene glycol (b) -1 having 75 repeating units of ethyleneoxy groups, 0.2 g of antioxidant (Adecastab AO-60), 1.5 g of tetraisopropyl titanate were charged, and 15 at 220 ° C. After polymerizing by performing an ester exchange reaction under reduced pressure for a long time, pellets of the polymer compound (C) -16 (antistatic agent (C) -16), which is the antistatic agent of the present invention, are carried out in the same manner as in Production Example 1. Was obtained in an amount of 250 g. The melting point of the obtained pellet of the polymer compound (C) -16 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. The results are shown in Table 1.

[Manufacturing Example 17]
In a separable flask, 124 g (1.4 mol) of 1,4-butanediol as (a1), 48 g (0.33 mol) of adipic acid as (a2), and 150 g (0.77 mol) of dimethyl terephthalate. , Antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) 0.29 g, tetraisopropyl titanate 0 .33 g was charged and polymerized at normal pressure for 10 hours while gradually increasing the temperature from 25 ° C. to 195 ° C. to obtain polyester (A') -12 having hydroxyl groups at both ends. The obtained polyester (A')-12 had a number average molecular weight of 6000.

Next, 200 g of the obtained polyester (A')-12, 0.63 g (0.0068 mol) of glycerin as a polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups, and a number average as polyethylene glycol. 68 g of polyethylene glycol (b) -1 having a molecular weight of 3300 and the number of repeating units of ethyleneoxy groups = 75, 0.2 g of an antioxidant (Adecastab AO-60), and 1.3 g of tetraisopropyl titanate were charged at 220 ° C. After polymerizing by performing an ester exchange reaction under reduced pressure for 14 hours, pellets of the polymer compound (C) -17, which is the antistatic agent of the present invention, (antistatic agent (C) -17) were carried out in the same manner as in Production Example 1. ) Was obtained in an amount of 230 g. The melting point of the obtained pellet of the polymer compound (C) -17 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. The results are shown in Table 1.

[Manufacturing Example 18]
In a separable flask, 107 g (1.2 mol) of 1,4-butanediol as (a1), 39 g (0.27 mol) of adipic acid and 121 g (0.62 mol) of dimethyl terephthalate as (a2) , Antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) 0.39 g, tetraisopropyl titanate 0 .44 g was charged and polymerized at normal pressure for 4 hours while gradually increasing the temperature from 25 ° C. to 195 ° C. to obtain polyester (A') -13 having hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A') -13 was 2000.

Next, 130 g of the obtained polyester (A') -13, 0.92 g (0.01 mol) of glycerin as a polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups, and a number average as polyethylene glycol. 148 g of polyethylene glycol (b) -1 having a molecular weight of 3300 and the number of repeating units of ethyleneoxy groups = 75, 0.2 g of an antioxidant (Adecastab AO-60), and 1.4 g of tetraisopropyl titanate were charged at 220 ° C. After the ester exchange reaction was carried out under reduced pressure for 13 hours to polymerize, pellets of the polymer compound (C) -18, which is the antistatic agent of the present invention, (antistatic agent (C) -18) were carried out in the same manner as in Production Example 1. ) Was obtained. The melting point of the obtained pellet of the polymer compound (C) -18 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. The results are shown in Table 1.

[Manufacturing Example 19]
In a separable flask, 129 g (1.4 mol) of 1,4-butanediol as (a1), 50 g (0.34 mol) of adipic acid as (a2) and 156 g (0.80 mol) of dimethyl terephthalate. , Antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) 0.29 g, tetraisopropyl titanate 0 .33 g was charged and polymerized at normal pressure for 9 hours while gradually increasing the temperature from 25 ° C. to 195 ° C. to obtain polyester (A') -14 having hydroxyl groups at both ends. The obtained polyester (A')-14 had a number average molecular weight of 5000.

Next, 200 g of the obtained polyester (A')-14, 1.1 g (0.012 mol) of glycerin as a polyhydric alcohol compound (a3) -1 having three or more hydroxyl groups, and a number average molecular weight as polyethylene glycol. 3300, 61 g of polyethylene glycol (b) -1 having 75 repeating units of ethyleneoxy groups, 0.2 g of antioxidant (Adecastab AO-60), 1.2 g of tetraisopropyl titanate were charged, and 8 at 220 ° C. After polymerizing by performing an ester exchange reaction under reduced pressure for a long time, pellets of the polymer compound (C) -19 (antistatic agent (C) -19), which is the antistatic agent of the present invention, are carried out in the same manner as in Production Example 1. 220 g was obtained. The melting point of the obtained pellet of the polymer compound (C) -19 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. The results are shown in Table 1.

[Manufacturing Example 20]
160 g of the obtained polyester (A') -1 was used as polyethylene glycol, 98 g of polyethylene glycol (b) -1 having a number average molecular weight of 3300 and the number of repeating units of ethyleneoxy groups = 75, and an antioxidant (Adecastab AO-). 0.2 g of 60) and 0.24 g of tetraisopropyl titanate were charged, and a transesterification reaction was carried out at 195 ° C. for 7.5 hours under reduced pressure to carry out polymerization to obtain a block polymer.

Next, as a polyhydric alcohol compound (a3) -1 having 100 g of the obtained block polymer and three or more hydroxyl groups, 0.34 g (0.0037 mol) of glycerin and 1.2 g of tetraisopropyl titanate were charged, and the temperature was 220 ° C. After the transesterification reaction was carried out under reduced pressure for 3 hours to polymerize, the polymer compound (C) -20 (antistatic agent (C) -20), which is the antistatic agent of the present invention, was obtained in the same manner as in Production Example 1. 80 g of pellets was obtained. The melting point of the obtained pellet of the polymer compound (C) -20 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. The results are shown in Table 1.

[Comparative Manufacturing Example 1]
In a separable flask, 184 g (2.0 mol) of 1,4-butanediol (corresponding to (a1)), 235 g (1.6 mol) of adipic acid, and an antioxidant (tetrakis [3- (3,5 mol)). -Ditertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 (manufactured by ADEKA Corporation) was charged in 0.48 g, and the temperature was gradually raised from 25 ° C to 195 ° C for 3 hours at normal pressure. The polymerization gave a comparative polyester-1 having hydroxyl groups at both ends. The number average molecular weight of the obtained comparative polyester-1 was 3300.

Next, 160 g of the obtained comparative polyester-1 was used, 0.92 g (0.01 mol) of glycerin (corresponding to (a3)), polyethylene glycol, a number average molecular weight of 3300, and the number of repeating units of ethyleneoxy groups = 97 g of 75 polyethylene glycol (corresponding to (b)), 0.2 g of antioxidant (Adecastab AO-60), 1.2 g of tetraisopropyl titanate were charged, and the transesterification reaction was carried out at 220 ° C. for 10 hours under reduced pressure. After polymerization, 200 g of pellets of the comparative polymer compound (C') -1 (comparative antistatic agent (C') -1) were obtained in the same manner as in Production Example 1. The melting point of the obtained pellet of the comparative polymer compound (C')-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. The results are shown in Table 1.

[Comparative Manufacturing Example 2]
In a separable flask, 118 g (1.3 mol) of 1,4-butanediol (corresponding to (a1)), 198 g (1.0 mol) of dimethyl terephthalate, and an antioxidant (tetrakis [3- (3, 3,)). 5-Ditertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 (manufactured by ADEKA Corporation) 0.34 g, tetraisopropyl titanate 0.38 g, gradually from 25 ° C to 195 ° C Polymerization was carried out at normal pressure for 4 hours while raising the temperature to obtain comparative polyester-2 having hydroxyl groups at both ends. The number average molecular weight of the obtained comparative polyester-2 was 3000.

Next, 160 g of the obtained comparative polyester-2, 0.92 g (0.01 mol) of glycerin (corresponding to (a3)), polyethylene glycol, a number average molecular weight of 3300, and the number of repeating units of ethyleneoxy groups = 75. 98 g of polyethylene glycol (corresponding to (b)), 0.2 g of antioxidant (Adecastab AO-60), and 1.2 g of tetraisopropyl titanate were charged, and a transesterification reaction was carried out at 220 ° C. for 10 hours under reduced pressure. After the polymerization, 240 g of pellets of the comparative polymer compound (C')-2 (comparative antistatic agent (C')-2) were obtained in the same manner as in Production Example 1. The melting point of the obtained pellet of the comparative polymer compound (C')-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. The results are shown in Table 1.

[Comparative Manufacturing Example 3]
In a separable flask, 161 g (1.8 mol) of 1,4-butanediol (corresponding to (a1)), 84 g (0.42 mol) of sebacic acid and 189 g (0.97 mol) of dimethyl terephthalate, Antioxidant (tetrakis [3- (3,5-ditetrabutyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) 0.48 g, tetraisopropyl titanate 0. 55 g was charged and polymerized at normal pressure for 7 hours while gradually increasing the temperature from 25 ° C. to 195 ° C. to obtain Comparative Polyester-3 having hydroxyl groups at both ends. The number average molecular weight of the obtained comparative polyester-3 was 3300.

Next, 160 g of the obtained comparative polyester-3, 0.92 g (0.01 mol) of glycerin (corresponding to (a3)), polyethylene glycol, a number average molecular weight of 3300, and the number of repeating units of ethyleneoxy groups = 99 g of 75 polyethylene glycol (corresponding to (b)), 0.2 g of antioxidant (Adecastab AO-60), 1.3 g of tetraisopropyl titanate were charged, and the transesterification reaction was carried out at 220 ° C. for 10 hours under reduced pressure. After polymerization, 200 g of pellets of the comparative polymer compound (C')-3 (comparative antistatic agent (C') -3) were obtained in the same manner as in Production Example 1. The melting point of the obtained pellet of the comparative polymer compound (C')-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. The results are shown in Table 1.

[Comparative Manufacturing Example 4]
In a separable flask, 173 g (1.9 mol) of 1,4-butanediol (corresponding to (a1)), 66 g (0.45 mol) of adipic acid, 204 g (1.1 mol) of dimethyl orthophthalate, Antioxidant (tetrakis [3- (3,5-ditritiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane, ADEKA STAB AO-60 manufactured by ADEKA Corporation) 0.48 g, tetraisopropyl titanate 0. 55 g was charged and polymerized at normal pressure for 9 hours while gradually raising the temperature from 25 ° C. to 195 ° C. to obtain a comparative polyester-4 having hydroxyl groups at both ends. The number average molecular weight of the obtained comparative polyester-4 was 3000.

Next, 160 g of the obtained comparative polyester-4, 0.92 g (0.01 mol) of glycerin (corresponding to (a3)), polyethylene glycol, a number average molecular weight of 3300, and the number of repeating units of ethyleneoxy groups = 75. 98 g of polyethylene glycol (corresponding to (b)), 0.2 g of antioxidant (Adecastab AO-60), and 1.2 g of tetraisopropyl titanate were charged, and a transesterification reaction was carried out at 220 ° C. for 15 hours under reduced pressure. After the polymerization, 200 g of pellets of the comparative polymer compound (C') -4 (comparative antistatic agent (C') -4) were obtained in the same manner as in Production Example 1. The melting point of the obtained pellet of the comparative polymer compound (C') -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. The results are shown in Table 1.

In Table 1, the values in parentheses after the antistatic agents (C) -1 to (C) -20 are the total moles of adipic acid and terephthalic acid of the constituent monomer (a2) of the polymer compound (C). The ratio (mol%) of terephthalic acid (including derivatives such as dimethyl terephthalate) to the number is shown. Similarly, for the comparative antistatic agents (C') -1 to 3, the ratio (mol%) of terephthalic acid (including derivatives such as dimethyl terephthalate) in the total carboxylic acid used is shown. For the comparative antistatic agent (C')-4, not terephthalic acid, but orthophthalic acid (including derivatives such as dimethyl orthophthalate) and orthophthalic acid (including derivatives such as dimethyl orthophthalate) with respect to the total number of moles of adipic acid. The ratio (mol%) of is shown.

[Examples 1 to 53, Comparative Examples 1 to 20]
Using each resin composition blended based on the blending amounts (parts by mass) shown in Tables 2 to 11 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 2-11.

<Conditions for preparing block polypropylene resin composition test piece>
The block polypropylene resin composition blended based on the blending amounts shown in Tables 2 to 11 below was subjected to the conditions of 230 ° C. and 6 kg / hour using a twin-screw extruder manufactured by Ikegai Co., Ltd. (containing PCM30 and 60 mesh). Granulated with, and pellets were obtained. 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

<Conditions for preparing test piece of ABS resin composition>
The ABS resin composition blended based on the blending amounts shown in Tables 2 to 11 below was used in a twin-screw extruder manufactured by Ikegai Co., Ltd. (containing PCM30, 60 mesh) at 230 ° C. and 6 kg / hour. Granulation was performed 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 50 ° 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. The surface resistivity (Ω / □) was measured under the conditions of an applied voltage of 500 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: NaDBS represents sodium dodecylbenzenesulfonate.
* 2: C2mimDBS represents 1-ethyl-3-methylimidazolium dodecylbenzene sulfonate.
* 3: bPP represents an impact copolymer (melt flow rate = 14).
* 4: ABS represents an acrylonitrile-butadiene-styrene copolymer synthetic resin (melt flow rate = 27).

From the results shown in Tables 1 to 11, according to the present invention, it is possible to obtain an antistatic agent having an excellent antistatic effect and its durability, and having excellent storage stability and productivity (cutting property). it is obvious.

Claims

It has a polyester segment (A) and a polyether segment (B).
The polyester segment (A) is
(A1) At least one of 1,4-butanediol or ethylene glycol,
(A2) Adipic acid and terephthalic acid, and
(A3) A polyester obtained from a polyhydric alcohol compound having three or more hydroxyl groups.
(A2) The ratio of terephthalic acid to adipic acid and terephthalic acid is 40 mol% or more and less than 100 mol% with respect to the total number of moles of adipic acid and terephthalic acid.
The polyether segment (B) is (b) polyethylene glycol,
An antistatic agent comprising one or more of a polymer compound (C) having a structure in which a polyester segment (A) and a polyether segment (B) are bonded via an ester bond.
The proportion of the polyhydric alcohol compound having 3 or more hydroxyl groups (a3) in the polymer compound (C) is at least one of (a1) 1,4-butanediol or ethylene glycol and 3 or more hydroxyl groups (a3). The antistatic agent according to claim 1, which is 0.05 to 5 mol% with respect to the total number of moles of the polyhydric alcohol compound.
The first or second claim, wherein the mass ratio (A) / (B) of the polyester segment (A) and the polyether segment (B) of the polymer compound (C) is 0.1 to 4.0. Antistatic agent.
The antistatic agent according to any one of claims 1 to 3, wherein the polymer compound (C) has a melting point in the range of 100 ° C. or higher and 200 ° C. or lower.
The antistatic agent according to any one of claims 1 to 4, further comprising one or more selected from the group consisting of alkali metal salts and ionic liquids. Inhibitor composition.
An antistatic resin composition characterized in that the antistatic agent according to any one of claims 1 to 4 is blended with the synthetic resin.
An antistatic resin composition characterized in that the antistatic agent composition according to claim 5 is blended with a synthetic resin.
The antistatic resin composition according to claim 6 or 7, wherein the synthetic resin is at least one selected from the group consisting of polyolefin-based resins or polystyrene-based resins.
A molded product obtained from the antistatic resin composition according to any one of claims 6 to 8.