TW202122553A - Antistatic agent, antistatic agent composition containing same, antistatic resin composition containing said agent and said composition, and article molded therefrom - Google Patents

Abstract

The present invention pertains to: an antistatic agent that is capable of sustainably imparting superior antistatic effects to synthetic resins, and also has superior storage stability and productivity (cutting properties); an antistatic agent composition containing the same; an antistatic resin composition containing said agent and said composition; and an article molded therefrom. The present invention contains at least one types of polymer compound (C) having a structure that comprises a polyester segment (A) and a polyether segment (B), (A) being a polyester obtained from (a1) 1,4-butanediol and/or ethylene glycol, (a2) adipic acid and terephthalic acid, and (a3) a polycarboxylate compound, the proportion of terephthalic acid in (a2) being at least 40 mol% and less than 100 mol% with respect to the total mole of adipic acid and terephthalic acid; (B) being (b) polyethylene glycol; and (A) and (B) being bonded via an ester bond.

Description

Antistatic agent, antistatic agent composition containing the same, antistatic resin composition containing the same, and its molded body

The present invention relates to an antistatic agent, an antistatic agent composition containing the same, an antistatic resin composition containing the same, and a molded body thereof, and in detail, it relates to the ability to impart excellent antistatic effects to synthetic resins with durability. , And further store antistatic agents with excellent stability and productivity (cutting properties), antistatic agent compositions containing them, antistatic resin compositions containing them, and molded bodies thereof.

Synthetic resins such as thermoplastic resins are not only lightweight and easy to process, but also can be used to design substrates and other excellent characteristics, so they are important materials that modern times cannot lack. In addition, since thermoplastic resins have excellent electrical insulation properties, they are frequently used in components of electrical products. However, since the thermoplastic resin is also too high in insulation, there is a problem that it is easily charged due to friction or the like.

Since the charged thermoplastic resin attracts surrounding dust or dust, there is a problem of impairing the appearance of the resin molded product. In addition, among electronic products, for example, precision machines such as computers may fail to operate normally due to electrification. Furthermore, there are also problems caused by electric shock. When the resin generates electric shock to the human body, it not only makes people feel unpleasant, but also may cause an explosion accident when there is flammable gas or dust.

In order to solve such problems, from the past, synthetic resins have been treated to prevent electrification. The most common method of antistatic treatment is to add antistatic agent to synthetic resin. For such antistatic agents, although there are coating types that are coated on the surface of resin moldings, and kneading types that are added during processing and molding of the resin, not only the coating type is continuously degraded, but also due to the surface A large amount of organic matter is coated, so there is a problem of contaminating those in contact with the surface.

From this point of view, it has been previously studied to knead polymer type antistatic agents used in synthetic resins as the main ones. For example, in Patent Documents 1 and 2, in order to impart antistatic properties to polyolefin resins, polyether esters have been proposed. Amide. In addition, in Patent Document 3, in order to impart antistatic properties to thermoplastic resins, polyether esters have been proposed. Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Laid-Open No. 58-118838 Patent Document 2: Japanese Patent Laid-Open No. 3-290464 Patent Document 3: Japanese Patent Application Laid-Open No. 6-57153

The problem to be solved by the invention

However, the antistatic performance of these antistatic agents in the past cannot be said to be sufficient, but it is still the status quo that further improvements are expected. In addition, conventional polymer antistatic agents have problems with their storage stability due to sticking or blocking during long-term storage or storage at high temperatures.

In particular, high-molecular antistatic agents are used more often by cutting the polymer obtained by polymerization into particles. When these particles are stored for a long time or in a high-temperature state, there is a problem such as sticking or blocking. There is a problem with its preservation stability. In addition, when cutting into granules, the granules are uneven and become indefinite shapes, or a part of the granules cannot be cut, and they are directly connected to several granules, or the surface of the granules is in a jagged state, or observation Poor cutting, such as burrs or cracks, also has the problem of greatly reducing productivity.

Therefore, the object of the present invention is to provide an antistatic agent that can impart excellent antistatic effects to synthetic resins with durability, and furthermore has excellent storage stability and productivity (cutting properties), an antistatic agent composition containing it, and an antistatic agent composition containing it. These antistatic resin compositions and their molded bodies. Means to solve the problem

As a result of diligent research to solve the above-mentioned problems, the inventors found that a polymer compound with a specified structure has excellent storage stability and productivity (cutting properties), and can impart excellent antistatic properties to synthetic resins. Performance, and use of this, can eliminate the above-mentioned problems, and finally complete the present invention.

That is, the antistatic agent of the present invention is characterized by having a polyester segment (A) and a polyether segment (B), and the polyester segment (A) is composed of: (a1) At least one of 1,4-butanediol or ethylene glycol, (a2) Adipic acid and terephthalic acid and (a3) Polyester obtained from polycarboxylic acid compound, The ratio of terephthalic acid in (a2) adipic acid and terephthalic acid relative to The total moles of adipic acid and terephthalic acid are more than 40 mole% and less than 100 mole%, The polyether segment (B) is (b) polyethylene glycol, And it contains one or more polymer compounds (C) having a structure in which the polyester segment (A) and the polyether segment (B) are bonded through an ester bond.

In the antistatic agent of the present invention, the ratio of the (a3) polycarboxylic acid compound of the polymer compound (C) to the ratio of (a2) adipic acid and terephthalic acid and (a3) polycarboxylic acid compound is preferred. The total number of moles is 0.05 to 5 mole%. In addition, in the antistatic agent of the present invention, the mass ratio (A)/(B) of the polyester segment (A) of the polymer compound (C) to the polyether segment (B) is preferably 0.1 to 4.0. Furthermore, 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 more and 200°C or less.

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.

The antistatic resin composition of the present invention is characterized by blending synthetic resin with the antistatic agent of the present invention.

The other antistatic resin composition of the present invention is characterized by blending the antistatic agent composition of the present invention with synthetic resin.

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

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

According to the present invention, it is possible to provide an antistatic agent that can impart excellent antistatic effects to synthetic resins with durability, and furthermore has excellent storage stability and productivity (cutting properties), an antistatic agent composition containing it, and an antistatic agent composition containing the same. The antistatic resin composition and its molded body.

Hereinafter, the 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 already contains at least one type of polymer compound (C), and the polymer compound (C) has a polyester segment (A) and a polyether segment (B).

The polyester segment (A) is a poly (a1) at least one of 1,4-butanediol or ethylene glycol, (a2) adipic acid and terephthalic acid, and (a3) a polycarboxylic acid compound. ester. In addition, the ratio of terephthalic acid in (a2) adipic acid and terephthalic acid relative to the total moles of adipic acid and terephthalic acid is 40 mole% or more and less than 100 moles %. In addition, the polyether segment (B) is (b) polyethylene glycol, and the polyester segment (A) and the polyether segment (B) have a structure bonded through 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- Butylene glycol may be only ethylene glycol, or a mixture of 1,4-butanediol and ethylene glycol. (a1) From the viewpoints of antistatic property and its durability, storage stability, and productivity (cutting property), 1,4-butanediol or a mixture of 1,4-butanediol and ethylene glycol is preferred , The best is 1,4-butanediol. (a1) When it is a mixture of 1,4-butanediol and ethylene glycol, the ratio of 1,4-butanediol relative to the total number of moles of the two is preferably 50 mole% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more.

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. (a2) The ratio of terephthalic acid to the total moles of adipic acid and terephthalic acid is within the range of 40 mole% or more and less than 100 mole%. From the antistatic property and its durability , In terms of storage stability and productivity (cutting properties), it is preferably 45 mol% or more and 95 mol% or less, more preferably 50 mol% or more and 90 mol% or less, and still more preferably 60 mol% Ear% above 90 mol%.

(a2) If the adipic acid and terephthalic acid can react with the hydroxyl group to form an ester bond, they can be derivatives thereof. Examples of derivatives include acid anhydrides and esters (e.g., alkyl groups such as methyl esters). Ester), alkali metal salt (for example, sodium salt), and acid halide (for example, acid chloride) are preferably alkyl esters such as methyl ester from the viewpoint of ease of reaction.

In the polymer compound (C) related to the antistatic agent of the present invention, it does not matter if the adipic acid and dicarboxylic acids other than terephthalic acid of (a2) can be used in a range that does not impair the effects of the present invention. Examples of dicarboxylic acids other than adipic acid and terephthalic acid include sebacic acid and isophthalic acid. However, the use of phthalic acid and its derivatives (such as phthalic anhydride, phthalic acid esters), from the point of view of antistatic properties and durability, storage stability, and productivity (cutting properties), good.

In the antistatic agent of the present invention, the monomer (a3) constituting the polyester of the polyester segment (A) is a polycarboxylic acid compound (a3). As a polycarboxylic acid compound (a3), the carboxylic acid which has 3 or more carboxyl groups, and the carboxylic acid which has 2 or more carboxyl groups and 1 or more hydroxyl groups are mentioned. From the viewpoints of antistatic properties, durability, storage stability, and productivity (cutting properties), a carboxylic acid having 3 or more carboxyl groups is preferred. The polycarboxylic acid compound (a3) may be a mixture of these.

Examples of carboxylic acids having 3 or more carboxyl groups include aconitic acid, 1,2,3-propane tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, 3-butene-1,2 ,3-Tricarboxylic acid, trimellitic acid, pyromellitic acid, mellitic acid, cyclohexanetricarboxylic acid, naphthalene-1,2,5-tricarboxylic acid, naphthalene-2,6,7-tricarboxylic acid Acid, 1,3,5-pentanetricarboxylic acid, Mesylic acid, 3,3',4-diphenyltricarboxylic acid, benzophenone-3,3',4-tricarboxylic acid Acid, diphenylene-3,3',4-tricarboxylic acid, diphenylether-3,3',4-tricarboxylic acid, diphenyl-2,2',3,3'-tetracarboxylic acid Acid, benzophenone-2,2',3,3'-tetracarboxylic acid, diphenylsulfonium-2,2',3,3'-tetracarboxylic acid, diphenyl-2,2',3 ,3'-tetracarboxylic acid, benzophenone-2,2',3,3'-tetracarboxylic acid, diphenyl sulfonium-2,2',3,3'-tetracarboxylic acid, diphenyl ether -2,2',3,3'-tetracarboxylic acid, etc., and further, acid-modified polyethylene wax or polyacrylic acid having 3 or more carboxyl groups may also be used.

Carboxylic acids having 3 or more carboxyl groups may be derivatives thereof. Examples of derivatives include acid anhydrides, esters (such as alkyl esters such as methyl esters), alkali metal salts (such as sodium salts), and acid halides (such as Acid chloride). The carboxylic acid and its derivatives having 3 or more carboxyl groups may be a mixture of 2 or more kinds.

Examples of carboxylic acids having two or more carboxyl groups and one or more hydroxyl groups include tartaric acid, malic acid, citric acid, isocitrate, citramalic acid, and tartronic acid.

Carboxylic acids having two or more carboxyl groups and one or more hydroxyl groups may be derivatives thereof, such as acid anhydrides, esters (such as alkyl esters such as methyl esters), alkali metal salts (such as sodium salts), and acid halides (E.g. acid chloride). The carboxylic acid and derivatives thereof having two or more carboxyl groups and one or more hydroxyl groups may be a mixture of two or more kinds.

In the antistatic agent of the present invention, two or more polycarboxylic acid compounds (a3) can be used.

In the antistatic agent of the present invention, the polycarboxylic acid compound (a3) is preferably pyromellitic anhydride and butane-1 from the viewpoints of antistatic properties, durability, storage stability, and productivity (cutting properties). , 2,3,4-tetracarboxylic dianhydride, trimellitic anhydride.

The ratio of the polymer compound (C) to the (a3) polycarboxylic acid compound is compared with (a2) adipic acid and The total molar number of terephthalic acid and (a3) polycarboxylic acid compound is 0.05-5 mol%, preferably 0.1-3.0 mol%, more preferably 0.3-2.0 mol%.

In the antistatic agent of the present invention, (b) polyethylene glycol 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 ranging from 4 to 250. m is preferably 20-200, more preferably 40-180 from the point of view of antistatic property and 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, from the point of view of antistatic property and its durability, storage stability, and productivity (cutting property) , Preferably 400-10,000, more preferably 900-8,000, still more preferably 2,000-8,000. The method of measuring the hydroxyl value and the method of calculating the number average molecular weight of the hydroxyl value are described below.

＜Calculation method of number average molecular weight derived from hydroxyl valence＞ The hydroxyl value is measured by the following hydroxyl value measurement method, and the number average molecular weight (hereinafter, also referred to as "Mn") is determined by the following formula. Number average molecular weight = (56110×2)/hydroxyl value

＜Measurement method of hydroxyl value＞ ・Reagent A (acetylation agent) (1) Triethyl phosphate 1560mL (2) Acetic anhydride 193mL (3) Perchloric acid (60%) 16g Mix the above reagents in the order of (1)→(2)→(3). ・Reagent B Mix pyridine and pure water at a volume ratio of 3:1. ・Reagent C Add 2 to 3 drops of phenolphthalein solution to 500 mL of isopropyl alcohol, and make it neutral in 1N-KOH aqueous solution.

First, measure 2 g of a sample in a 200 mL Erlenmeyer flask, and add 10 mL of xylene to dissolve it by heating. Add 15mL of reagent A, cover with stopper and shake vigorously. Add reagent B20mL, cover with stopper and shake vigorously. Add reagent C50mL. Titrate with 1N-KOH aqueous solution and calculate with the following formula. Hydroxyl value [mgKOH/g]=56.11×f×(T-B)/S f: the factor of 1N-KOH aqueous solution B: Empty test titration [mL] T: Titration of this test [mL] S: sample size [g]

The number average molecular weight of the polyester segment (A) of the polymer compound (C) is calculated in terms of polystyrene, and it is preferable from the point of view of antistatic property, durability, storage stability, and productivity (cutting property) It is 1,000 to 10,000, more preferably 1,500 to 8,000, and still more preferably 2,500 to 7,500. When the number average molecular weight is less than 1,000, the storage stability may deteriorate, and when it exceeds 10,000, the reaction to obtain the polymer compound (C) may take time and economic efficiency may be deteriorated, or the obtained polymer compound (C) may be deteriorated. There is a risk of coloring due to long-term reaction.

The method of measuring the number average molecular weight in terms of polystyrene is preferably the gel permeation chromatography (GPC) method, and the measuring method is shown below.

＜Measuring method of number average molecular weight converted from polystyrene＞ The number average molecular weight (hereinafter, also referred to as "Mn") is measured by the gel permeation chromatography (GPC) method. The measurement conditions of Mn are as follows. Device: GPC device manufactured by Japan Spectroscopy Co., Ltd. Solvent: chloroform Reference material: Polystyrene Detector: UV detector Column stationary phase: Shodex LF-804 manufactured by Showa Denko Co., Ltd. Column temperature: 40℃ Sample concentration: 1mg/1mL Flow rate: 0.5mL/min. Injection volume: 30μL

The number average molecular weight of the polyester segment (A) is measured in the polystyrene conversion of intermediates obtained in the production step of the polymer compound (C), ie polyester (A'), polyester (A"), etc. The molecular weight can be calculated from these. The method of measuring the number average molecular weight in terms of polystyrene is preferably the gel permeation chromatography (GPC) method, and the measuring method is shown above.

In addition, the degree of polymerization of the polyester segment (A) of the polymer compound (C) is preferably 4-50 from the standpoints of antistatic properties, durability, storage stability, and productivity (cutting properties). , More preferably 6-40.

The polymer compound (C) of the antistatic agent of the present invention can be obtained by using (a1) at least one of 1,4-butanediol or ethylene glycol, (a2) adipic acid and terephthalic acid, (a3) Polycarboxylic acid compound and (b) polyethylene glycol are obtained by esterification reaction. The esterification reaction may be one that forms an ester bond by a reaction, and it also includes a transesterification reaction. The individual components may be derivatives thereof, for example, as derivatives of adipic acid and terephthalic acid of (a2), examples include acid anhydrides, alkyl esters and other esters, alkali metal salts, acid chlorides and other acid halides Especially from the viewpoint of ease of reaction, terephthalic acid is preferably the use of methyl terephthalate.

In the esterification reaction (including the transesterification reaction), a catalyst that promotes the esterification reaction (also including the transesterification reaction) can be used. As a catalyst, dibutyltin oxide, tetraalkyl titanate, zirconium acetate, It is known in the past such as zinc acetate. The esterification reaction or the transesterification reaction can be carried out under reduced pressure.

In addition, in order to suppress 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), it is preferable to first start with (a1) at least one of 1,4-butanediol or ethylene glycol, and (a2) adipic acid and terephthalic acid. A method of synthesizing polyester (A') with formic acid, and then subjecting the polyester (A'), (a3) polycarboxylic acid compound and (b) polyethylene glycol to esterification reaction (including transesterification reaction). During the reaction, after the completion of the synthesis reaction of polyester (A'), not only separate polyester (A'), but add (a3) polycarboxylic acid compound and (b) polyethylene glycol to the reaction system directly Carry out the reaction. (a3) Polycarboxylic acid compound and (b) polyethylene glycol can be added to the reaction system at the same time, or (b) polyethylene glycol can be added first, and then (a3) polycarboxylic acid compound can be added, or vice versa.

Polyester (A') is better than the ease of reaction after obtaining the polymer compound (C) from the viewpoint of the prevention of coloration during the synthesis reaction of the obtained polymer compound (C). Preferably, both ends are hydroxyl groups.

In the synthesis reaction of polyester (A'), the reaction ratio of (a1) at least one of 1,4-butanediol or ethylene glycol, and (a2) adipic acid and terephthalic acid is preferably considered During the reaction, (a1) is distilled out of the system, and both ends become hydroxyl groups. Use (a1) in excess. Compare (a1) to (a2) by molar ratio, and the value becomes 1 molar excess. Preferably it is used 1.2 times. The obtained polyester (A') with hydroxyl at both ends, (a3) polycarboxylic acid compound and (b) polyethylene glycol are subjected to esterification reaction or transesterification reaction, preferably to obtain a polymer Compound (C). In this transesterification reaction, the 1,4-butanediol or ethylene glycol bonded to the two ends of the polyester (A') can be easily removed out of the reaction system due to the transesterification, so the reaction can proceed easily , Preferably, the polymer compound (C) can be obtained. In addition, the obtained polymer compound (C) is preferably not colored during the synthesis reaction. This esterification reaction or transesterification reaction is carried out under reduced pressure, and it is preferred because the reaction proceeds easily.

The number average molecular weight of the polyester (A') is calculated as polystyrene, and from the viewpoints of antistatic properties, durability, storage stability, and productivity (cutting properties), it is preferably 1,200-10,200, more preferably 1,700 ～8,200, still more preferably 2,000～7,700, still more preferably 2,000～4,500, still more preferably 2,000～4,000. When the number average molecular weight is less than 1,200, the storage stability may be deteriorated. When it exceeds 10,200, the reaction to obtain the polymer compound (C) may take time and economic efficiency may be deteriorated, or the obtained polymer compound (C) may be deteriorated. There is a risk of coloring due to long-term reaction. Furthermore, the method of measuring the number average molecular weight in terms of polystyrene is preferably the gel permeation chromatography (GPC) method, 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, and (a2) adipic acid and terephthalic acid can also be cited. And (a3) a method of synthesizing a polyester (A") with a polycarboxylic acid compound, and then subjecting the polyester (A") and (b) polyethylene glycol to an esterification reaction (including transesterification reaction). During the reaction, after the completion of the synthesis reaction of the polyester (A"), not only the polyester (A") is isolated, but (b) polyethylene glycol can be added to the reaction system for direct reaction.

The number average molecular weight of polyester (A") is calculated as polystyrene. From the viewpoints of antistatic properties and durability, storage stability, and productivity (cutting properties), it is preferably 1,100-10,100, more preferably 1,600 ~8,100, more preferably 2,100~7,600. When the number average molecular weight is less than 1,100, the storage stability may deteriorate, and when it exceeds 10,100, the reaction to obtain the polymer compound (C) may take time and economic efficiency may be deteriorated. Or the resulting polymer compound (C) may be colored due to long-term reaction.

The method of measuring the number average molecular weight in terms of polystyrene is preferably the gel permeation chromatography (GPC) method, 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 from 380 to 9,980, more preferably from 880 to 7,980 from the viewpoints of antistatic property and its durability, storage stability, and productivity (cutting property). Preferably, it is 1,980 to 7,980.

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

Regarding the polymer compound (C) of the antistatic agent of the present invention, it is preferable that the melting point is 100°C or higher than 200 in terms of antistatic property and durability, especially in terms of storage stability and productivity (cutting property). Within the range of degrees C or less, it is more preferably 110 degrees C or more and 195 degrees C or less, and still more preferably 120 degrees C or more and 190 degrees C or less. If the melting point is less than 100°C, storage stability and productivity (cutting properties) may deteriorate, and if it exceeds 200°C, it must be processed at a high temperature, which may limit the processing temperature range.

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

The polymer compound (C) related to the antistatic agent of the present invention is used in the form of particles, which is preferable from the viewpoint of operability. In order to become a pellet, what is necessary is just to extrude the polymer from an extruder after the polymerization reaction, and cut it into pellets. Machines such as granulators can 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 is further blended with one or more selected from the group consisting of alkali metal salts and ionic liquids to become an antistatic agent composition with excellent antistatic performance and durability. good.

Hereinafter, the alkali metal salt will be described first. Examples of alkali metal salts include organic acid or inorganic acid salts, and examples of alkali metals include lithium, sodium, potassium, cesium, rubidium, and the like. Examples of organic acids include aliphatic monocarboxylic acids with 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, and maleic acid , Adipic acid and other aliphatic dicarboxylic acids with 1-12 carbon atoms; benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid and other aromatic carboxylic acids; methanesulfonic acid, p-Toluenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid and other sulfonic acids with 1 to 20 carbon atoms. 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, from the viewpoint of triboelectric charge voltage, surface resistivity, and safety to living organisms or the environment, salts of lithium, sodium, and potassium are preferred, and sodium is more preferred. Also, from the viewpoint of antistatic properties and durability, acetic acid salt, perchloric acid salt, p-toluenesulfonic acid salt, dodecylbenzenesulfonic acid salt are more preferable, and twelve benzenesulfonic acid salt is more preferable. Salt of alkyl benzene sulfonic acid. There may be two or more kinds of alkali metal salts.

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, dodecylbenzenesulfonate Sodium, potassium dodecylbenzene sulfonate, etc. Among these, from the viewpoint of antistatic property and durability, and safety to organisms or the environment, lithium p-toluenesulfonate, sodium p-toluenesulfonate, and lithium dodecylbenzenesulfonate are preferred. , Sodium dodecylbenzene sulfonate, etc., the best is sodium dodecylbenzene sulfonate.

The alkali metal salt may be blended with the polymer compound (C) related to the antistatic agent of the present invention, or it may be blended with the polymer compound (C) in a synthetic resin for use. In addition, it can be added to the reaction vessel for blending during the production of the polymer compound (C). The blending amount of the alkali metal salt is preferably 0.01-30 parts by mass, and more preferably 0.1, relative to 100 parts by mass of the polymer compound (C) from the viewpoint of antistatic properties and durability and storage stability. ~20 parts by mass, most preferably 3.0-15 parts by mass.

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

Examples of cations constituting the ionic liquid include cations selected from the group consisting of amidinium, pyridinium, pyrazolium, and Guanidinium cations.

Among them, as the amidonium cation, the following can be cited.

(1) Imidazolium cation Examples include those with 5 to 15 carbon atoms, such as 1,2,3,4-tetramethylimidazolium and 1,3-dimethylimidazolium; (2) Imidazolium cation Examples include those with 5 to 15 carbon atoms, such as 1,3-dimethylimidazolium and 1-ethyl-3-methylimidazolium; (3) Tetrahydropyrimidinium cation Examples include those with 6 to 15 carbon atoms, such as 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetramethyl-1,4,5, 6-tetrahydropyrimidinium; (4) Dihydropyrimidinium cation Examples include those with 6 to 20 carbon atoms, such as 1,3-dimethyl-1,4-dihydropyrimidinium, 1,3-dimethyl-1,6-dihydropyrimidinium, 8-methyl- 1,8-diazabicyclo[5,4,0]-7,9-undecanedienium (undecadienium), 8-methyl-1,8-diazabicyclo[5,4, 0]-7,10-Undecanedienium.

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

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

As the guanidinium cation, the following can be mentioned.

(1) Guanidinium cation with imidazolium skeleton Examples include those with 8 to 15 carbon atoms, such as 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium ； (2) Guanidinium cation with imidazolium skeleton Examples include those with 8 to 15 carbon atoms, such as 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium ； (3) Guanidinium cation with tetrahydropyrimidinium skeleton Examples include those with 10 to 20 carbon atoms, such as 2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino- 1,3-Dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium; (4) Guanidinium cation with dihydropyrimidinium skeleton Examples include those with 10 to 20 carbon atoms, such as 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-diethyl Amino-1,3-dimethyl-4-ethyl-1,6-dihydropyrimidinium.

These cations may be used singly, or two or more of them may be used in combination. Among these, from the viewpoint of triboelectric charge voltage and surface resistivity, amidinium cations are preferred, imidazolium cations are more preferred, and 1-ethyl-3-methylimidazolium cations are particularly preferred.

In the ionic liquid, as the organic acid or inorganic acid constituting the anion, the following can be cited. Examples of organic acids include carboxylic acids, sulfuric acid esters, sulfonic acids, and phosphoric acid esters; examples of inorganic acids include superacids such as fluoroboric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid, and Hexafluoroarsenic acid), phosphoric acid and boric acid. The above-mentioned organic acid and inorganic acid may be used singly, or two or more of them may be used in combination.

Among the above-mentioned organic acids and inorganic acids, from the viewpoint of the antistatic property of the ionic liquid and its sustainability, it is preferable that the Hammett acidity function (-H0) of the anion constituting the ionic liquid is 12-100 to form a super acid. Conjugation group, acid of anion other than the conjugate group of super acid, and mixtures of these.

Examples of the anions other than the conjugated group of the super acid include halogen (e.g. fluorine, chlorine and bromide) ions, alkyl (1-12 carbon atoms) benzenesulfonic acid (e.g. p-toluenesulfonic acid and dodecyl Benzenesulfonic acid) ion and poly(n=1-25)fluoroalkanesulfonic acid (for example, undecafluoropentanesulfonic acid) ion.

Moreover, as a super strong acid, what is derived from a protic acid and a combination of a protic acid and a Lewis acid, and these mixtures are mentioned. As the protic acid used as a super acid, for example, bis(trifluoromethylsulfonyl)imidic acid, bis(pentafluoroethylsulfonyl)imidic acid, ginseng (trifluoromethylsulfonyl)imidic acid, Group) methane, perchloric acid, fluorosulfonic acid, alkane (1-30 carbon atoms) sulfonic acid (such as methanesulfonic acid, dodecanesulfonic acid, etc.), poly(n=1-30) fluoroalkane (carbon atom Number 1-30) Sulfonic acid (e.g. trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and trifluorohexanesulfonic acid), Fluoroboric acid and tetrafluoroboric acid. Among these, from the viewpoint of ease of synthesis, fluoroboric acid, trifluoromethanesulfonic acid, bis(trifluoromethanesulfonyl)imidic acid, and bis(pentafluoroethylsulfonyl) are preferred. Imidic acid.

Examples of proton acids used in combination with Lewis acids include hydrogen halides (such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and pentafluorocarbon. Ethane sulfonic acid, nonafluorobutane sulfonic acid, undecafluoropentane sulfonic acid, tridecafluorohexane sulfonic acid and mixtures thereof. Among these, from the viewpoint of the initial conductivity of the ionic liquid, hydrogen fluoride is preferred.

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

Although the combination of proton acid and Lewis acid is arbitrary, examples of super acids including these combinations include tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, and tantalum hexafluoride. Sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chlorinated trifluoroboric acid, hexafluoroarsenic acid and mixtures of these.

Among these anions, from the viewpoint of the antistatic property of ionic liquids, the conjugated group of super acid (super acid containing protic acid and super acid containing the combination of protic acid and Lewis acid are preferred ), and more preferably the conjugated group of super acid containing protic acid and super acid containing protic acid, boron trifluoride and/or phosphorus pentafluoride.

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

The ionic liquid may be blended with the polymer compound (C) related to the antistatic agent of the present invention, or it may be blended with the polymer compound (C) in a synthetic resin for use. In addition, during the production of the polymer compound (C), it can be added to the reaction vessel for blending. The blending amount of the ionic liquid is preferably from 0.01 to 20 parts by mass, more preferably from 0.1 to 100 parts by mass, relative to 100 parts by mass of the polymer compound (C), from the viewpoints of antistatic properties, durability, and storage stability. 15 parts by mass, most preferably 1-12 parts by mass.

Furthermore, in the antistatic agent composition of the present invention, an alkali metal salt and an ionic liquid can be used in combination.

In order to obtain the antistatic agent composition of the present invention, the polymer compound (C) and one or more selected from the group of alkali metal salts and ionic liquids may be further mixed with other optional components if necessary. Various mixers can be used for mixing. It can be heated during mixing. Examples of usable mixers include tumbler mixers, Henschel mixers, ribbon mixers, V-type mixers, W-type mixers, super mixers, and Norta mixers. In addition, in the synthesis reaction of the polymer compound (C), one or more selected from the group consisting of alkali metal salts and ionic liquids can be added to the reaction system.

In addition, the antistatic agent of the present invention can be used as an antistatic agent composition having antistatic properties by blending a salt of a group 2 element within a range that does not impair the effects of the present invention. Examples of the salts of the group 2 elements include salts of organic acids or inorganic acids, and examples of the group 2 elements include beryllium, magnesium, calcium, strontium, and barium. Examples of organic acids include aliphatic monocarboxylic acids with 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, and maleic acid , Adipic acid and other aliphatic dicarboxylic acids with 1-12 carbon atoms; benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid and other aromatic carboxylic acids; methanesulfonic acid, p-Toluenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid and other sulfonic acids with 1 to 20 carbon atoms. 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 it may be blended with the polymer compound (C) in a synthetic resin for use. The blending amount of the salt of the group 2 element is preferably 0.01-20 parts by mass, more preferably 0.1-15 parts by mass, and most preferably 3.0-12 parts by mass relative to 100 parts by mass of the polymer compound (C).

In addition, the antistatic agent of the present invention can be blended with a surfactant in a range that does not impair the effects of the present invention, and used as an antistatic agent composition having antistatic properties. As the surfactant, nonionic, anionic, cationic or amphoteric surfactants can be used.

Examples of nonionic surfactants include higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, etc. Ionic surfactants; polyoxyethylene, fatty acid esters of glycerin, fatty acid esters of pentaerythrite, fatty acid esters of sorbitol or sorbitol, alkyl ethers of polyhydric alcohols, aliphatics of alkanolamines Polyol type nonionic surfactants such as amides. Examples of anionic surfactants include carboxylates such as alkali metal salts of higher fatty acids; sulfates such as higher alcohol sulfates, higher alkyl ether sulfates, alkylbenzene sulfonates, and alkyl benzene sulfonates. Sulfonates such as sulfonate and paraffin sulfonate; Phosphate ester salts such as higher alcohol phosphate ester salts, etc. Examples of cationic surfactants include fourth-grade ammonium salts such as alkyltrimethylammonium salts and the like. Examples of amphoteric surfactants include amino acid type amphoteric surfactants such as higher alkyl amino propionates, higher alkyl dimethyl betaine, higher alkyl dihydroxy ethyl betaine and other betaine type Amphoteric surfactants, etc., can be used alone or in combination of two or more kinds. In the antistatic agent composition of the present invention, among these surfactants, anionic surfactants are preferred, and sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates are particularly preferred. Acid salt.

The surfactant may be blended with the polymer compound (C), or may be blended with the polymer compound (C) in a synthetic resin for use. The blending amount of the surfactant is preferably 0.01-20 parts by mass, more preferably 0.1-15 parts by mass, and most preferably 1-10 parts by mass relative to 100 parts by mass of the polymer compound (C).

Furthermore, the antistatic agent of the present invention may be blended with a polymer type antistatic agent in a range that does not impair the effects of the present invention, and used as an antistatic agent composition having antistatic properties. As the polymer antistatic agent, for example, a known polymer type antistatic agent such as polyether ester amide can be used. As a known polyether ester amide, for example, those described in Japanese Patent Application Laid-Open No. 7-10989 can be mentioned. Polyether ester amide made of polyoxyalkylene adduct of bisphenol A. In addition, as the bonding unit between the polyolefin block and the hydrophilic polymer block, a block polymer having a repeating structure of 2 to 50 can be used. For example, a block polymer described in U.S. Patent No. 6,552,131 can be cited.

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

Furthermore, the antistatic agent of the present invention can be blended with a compatibilizing agent as an antistatic agent composition having antistatic properties in a range that does not impair the effects of the present invention. By blending a compatibilizer, the compatibility of the polymer compound (C) with other components or with synthetic resin can be improved. Examples of the compatibilizer include modification with at least one functional group (polar group) selected from the group consisting of carboxyl group, epoxy group, amino group, hydroxyl group (Hydroxyl) and polyoxyalkylene group. Vinyl polymers, such as those described in Japanese Patent Application Laid-Open No. 3-258850, or modified vinyl polymers having sulfonyl groups described in Japanese Patent Application Laid-Open No. 6-345927, or have a polyolefin moiety Block polymers with aromatic vinyl polymers, etc.

The compatibilizer may be blended with the polymer compound (C) of the present invention, or it may be blended with the polymer compound (C) in a synthetic resin for use. The blending amount of the compatibility agent is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass relative to 100 parts by mass of the polymer compound (C).

In the antistatic agent composition of the present invention, in a range that does not impair the effects of the present invention, in addition to the polymer compound (C) and the components listed so far, other components may be blended as optional components. These other ingredients can be directly blended into the antistatic agent composition of the present invention, and the polymer compound (C) or the antistatic agent composition of the present invention can be blended with synthetic resins such as thermoplastic resins as having antistatic properties. When the resin composition is used, it can also be blended with synthetic resin.

Next, the antistatic resin composition of the present invention will be described. The antistatic resin composition of the present invention is formed by blending synthetic resin with the antistatic agent of the present invention. The polymer compound (C) and the antistatic agent composition related to the antistatic agent of the present invention can be blended with a synthetic resin, particularly preferably blended with a thermoplastic resin, and used as an antistatic resin composition having antistatic properties. Examples of thermoplastic resins include polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, cross-linked polyethylene, ultra-high molecular weight polyethylene, polybutene-1, poly-3-methyl Alpha-olefin polymers such as pentene and poly-4-methylpentene, or olefin monomers such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene copolymer, etc. Compounds or copolymers are polyolefin resins; polystyrene, styrene and/or α-methylstyrene and other monomers (such as maleic anhydride, phenylmaleimide, methyl methacrylate, butylene Diene, acrylonitrile, etc.) copolymers (such as AS resin, ABS (acrylonitrile butadiene styrene copolymer) resin, ACS resin, SBS resin, MBS resin, heat-resistant ABS resin, etc.) Single polymer or copolymer, namely polystyrene resin; polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer Vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate Halogen-containing resins such as copolymers, vinyl chloride-cyclohexylmaleimide copolymers, etc.; petroleum resins, coumarone resins, polyvinyl acetate, acrylic resins, polymethmethacrylic acid Polyester, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; polyethylene terephthalate, polybutylene terephthalate, polycyclohexane methyl terephthalate, etc. Polyalkylene terephthalate (Polyalkylene terephthalate), polyethylene naphthalate, polyethylene naphthalate and other aromatic polyesters and polytetramethylene terephthalate Straight-chain polyesters such as esters; polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxin Decomposable aliphatic polyester such as alkane, poly(2-oxetanone), etc.; Polyphenylene oxide (Polyphenylene oxide), polycaprolactam and polyhexamethylene hexamethylene hexamethylene diamide (Adipamide), etc. Polyamide, polycarbonate, polycarbonate/ABS resin, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, cellulose resin, polyimide resin, polyimide , Polyphenylene ether, polyether ketone, polyether ether ketone, liquid crystal polymer and other thermoplastic resins and their mixtures. In addition, the thermoplastic resin may be isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, olefin elastomer, Elastomers such as styrene-based elastomers, polyester-based elastomers, nitrile-based elastomers, nylon-based elastomers, vinyl chloride-based elastomers, polyamide-based elastomers, and polyurethane-based elastomers. In the antistatic resin composition of the present invention, these thermoplastic resins may be used alone or in combination of two or more kinds. In addition, the thermoplastic resin can be alloyed.

These thermoplastic resins can be used regardless of molecular weight, degree of polymerization, density, softening point, ratio of insoluble content to solvent, degree of stereoregularity, presence or absence of catalyst residue, type of raw material monomer or blending ratio, polymerization The type of catalyst (for example, Ziegler catalyst, Metallocene catalyst, etc.) is used. Among these thermoplastic resins, from the viewpoint of antistatic properties, one or more selected from the group of polyolefin-based resins and polystyrene-based resins are preferred.

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

Regarding the synthetic resin of the polymer compound (C) of the antistatic agent of the present invention, it is particularly preferred that the blending method of the thermoplastic resin is not particularly limited, and any method generally used can be used, for example, by roll kneading , Bumper kneading, extruder, kneader, etc. can be mixed and kneaded to blend. At this time, it is possible to further simultaneously mix and knead at least one selected from the group consisting of alkali metal salts and ionic liquids. In addition, the polymer compound (C) can be directly added to the synthetic resin, but if necessary, it can be added after being impregnated in a carrier. In order to impregnate the carrier, it can be directly heated and mixed. If necessary, it can be diluted with an organic solvent, then impregnated in the carrier, and then the solvent is removed. As such a carrier, those known as fillers or fillers for synthetic resins, or flame retardants or light stabilizers that are solid at room temperature can be used. Examples include calcium silicate powder, silicon dioxide powder, talc powder, and oxide Aluminum powder, titanium oxide powder, or those that chemically modify the surface of these carriers, or those that are solid among the flame retardants or antioxidants listed below. Among these carriers, one that chemically modifies the surface of the carrier is preferred, and one that chemically modifies the surface of silica powder is more preferred. These carriers preferably have an average particle diameter of 0.1-100 μm, more preferably 0.5-50 μm.

Furthermore, when enumerating the method of blending the polymer compound (C) related to the antistatic agent of the present invention, it can be used for injection molding and other molding by mixing the polymer compound (C) with synthetic resin, and it is particularly preferably a thermoplastic resin. In the method of blending the molded product, at this time, one or more selected from the group of alkali metal salts and ionic liquids can be further blended, and furthermore, the precursor of the polymer compound (C) and the synthetic resin can be produced in advance. Masterbatch is blended with this masterbatch, and at this time, one or more selected from the group of alkali metal salts and ionic liquids can be blended.

In the antistatic resin composition of the present invention, if necessary, various additives such as phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, ultraviolet absorbers, hindered amine light stabilizers, etc. can be further added, thereby , Can stabilize the antistatic resin composition of the present invention.

Various additives such as these antioxidants can be blended into the antistatic agent composition of the present invention before being blended into the synthetic resin. Furthermore, it can be blended during the production of the polymer compound (C). In particular, the antioxidant is preferably blended during the production of the polymer compound (C) to prevent the oxidative degradation of the polymer compound (C) during the production.

Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di Tert-butyl-4-hydroxybenzyl) phosphate, 1,6-hexamethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'- Thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4 -Ethyl-6-tert-butylphenol), 4,4'-butylene bis(6-tert-butyl-m-cresol), 2,2'-ethylene bis(4,6-di-tert-butyl) Phenol), 2,2'-ethylene bis(4-sec-butyl-6-tert-butylphenol), 1,1,3-ginseng(2-methyl-4-hydroxy-5-tert-butyl Phenyl) butane, 1,3,5-gin (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-gin (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-ginseng (3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-tri Methylbenzene, 2-tert-butyl-4-methyl-6-(2-propenyloxy-3-tert-butyl-5-methylbenzyl)phenol, stearyl(3,5-di-tert Butyl-4-hydroxyphenyl) propionate, 4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl) methyl propionate] methane, thiodiethylene glycol bis[(3 ,5-Di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], Bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butanoic acid]glycol ester, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert Butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-ginseng[(3,5-di-tert-butyl-4-hydroxyphenyl)propionoxyethyl ]Isocyanurate, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl)propionoxy}ethyl] -2,4,8,10-Tetraoxaspiro[5,5]undecane, triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] Wait. The addition amount of these phenolic antioxidants is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the synthetic resin.

Examples of phosphorus antioxidants include ginsenoside phenyl phosphite, ginseng [2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5- Methylphenyl) phosphite, tridecyl phosphite, octyl diphenyl phosphite, di(decyl) monophenyl phosphite, di(tridecyl) pentaerythritol diphosphite , Bis(nonylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) ) Pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, tetra( Tridecyl) isopropylidene diphenol diphosphite, tetra(tridecyl)-4,4'-n-butylene bis(2-tert-butyl-5-methylphenol) diphosphite Esters, hexa(tridecyl)-1,1,3-gins(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetradecyl(2,4-di-tert-butyl) Biphenylene Diphosphonite, 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, 2,2'-methylenebis(4, 6-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylene bis(4,6-tert-butylphenyl)-octadecyl phosphite, 2,2 '-Ethylene bis(4,6-di-tert-butylphenyl) fluorophosphite, ginseng (2-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][ 1,3,2]dioxaphosphepin-6-yl)oxy)ethyl)amine, 2-ethyl-2-butylpropanediol and 2,4,6-tri-tert-butyl Phosphite esters of base phenols, etc. The addition amount of these phosphorus-based antioxidants is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the synthetic resin.

Examples of thioether antioxidants include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate. , And pentaerythritol tetra (β-alkylthiopropionic acid) esters. The addition amount of these thioether antioxidants is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the synthetic resin.

Examples of ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 5,5 '-Methylenebis(2-hydroxy-4-methoxybenzophenone) and other 2-hydroxybenzophenones; 2-(2'-hydroxy-5'-methylphenyl)benzo Triazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5' -Methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5' -Dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol), 2-(2'-hydroxy- 3'-tert-butyl-5'-carboxyphenyl) benzotriazole and other 2-(2'-hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzyl Ester, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3,5-di-tert-butyl Benzoic acid esters such as -4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxy oxalate Aniline (Oxanilide), 2-ethoxy-4'-dodecyl oxanilide (Oxanilide) and other substituted oxanilides; ethyl-α-cyano-β, β-diphenyl acrylate, Cyanoacrylates such as methyl-2-cyano-3-methyl-3-(p-methoxyphenyl) acrylate; 2-(2-hydroxy-4-octyloxyphenyl)- 4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine Triazine, 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, etc. Azines. The addition amount of these ultraviolet absorbers is preferably 0.001 to 30 parts by mass, and more preferably 0.05 to 10 parts by mass relative to 100 parts by mass of the synthetic resin.

Examples of hindered amine-based light stabilizers include 2,2,6,6-tetramethyl-4-piperidinyl stearate, 1,2,2,6,6-pentamethyl-4-piper Pyridinyl stearate, 2,2,6,6-tetramethyl-4-piperidinyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidinyl)decanoate Diester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl -4-piperidinyl) sebacate, Si(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane carboxylate (carboxylate) , Si (1,2,2,6,6-pentamethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylic acid ester, bis(2,2,6,6-tetra Methyl-4-piperidinyl)･bis(tridecyl)-1,2,3,4-butane tetracarboxylic acid ester, bis(1,2,2,6,6-pentamethyl-4 -Piperidinyl)･bis(tridecyl)-1,2,3,4-butane tetracarboxylic acid ester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) )-2-Butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1,2,2,6,6-tetramethyl-4-piperidylmethyl Acrylate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6 ,6-Tetramethyl-4-piperidinyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidinyl)imino}], 1,2 ,3,4-Butanecarboxylic acid/2,2-bis(hydroxymethyl)-1,3-propanediol/3-hydroxy-2,2-dimethylpropanal/1,2,2,6 ,6-Pentamethyl-4-piperidinyl ester condensation polymer, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)=Decanedioic acid/methyl= 1,2,2,6,6-Pentamethyl-4-piperidinyl=sebacate mixture, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 1- (2-Hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl 4-piperidinylamino)hexane/dibromoethane polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane/2 ,4-Dichloro-6-morpholinyl-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane/2, 4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-four[2,4-bis(N-butyl-N-(2,2,6, 6-Tetramethyl-4-piperidinyl)amino)-s-triazin-6-yl)-1,5,8,12-tetraazadodecane, 1,5,8,12-si [2,4-Bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-s-triazin-6-yl]-1 , 5,8,12-tetraazadodecane, 1,6,11-gins[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piper (Pyridinyl)amino)-s-triazine-6-ylamino)undecane, 1,6,11-gin[2,4-bis(N-butyl-N-(1,2,2, 6,6-Pentamethyl-4-piperidinyl)amino)-s-triazine-6-ylamino]undecane, 3,9-bis[1,1-dimethyl-2-{ Ref. (2,2,6,6-Tetramethyl-4-piperidinyloxycarbonyl)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5] eleven Alkyl, 3,9-bis[1,1-dimethyl-2-{reference(1,2,2,6,6-pentamethyl-4-piperidinyloxycarbonyl)butylcarbonyloxy} Ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, bis(1-undecyloxy-2,2,6,6-tetramethylpiperidine-4- Base) carbonate, 2,2,6,6-tetramethyl-4-piperidinyl hexadecanoate, 2,2,6,6-tetramethyl-4-piperidinyl octadecanoate And other hindered amine compounds. The addition amount of these hindered amine-based light stabilizers is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass relative to 100 parts by mass of the synthetic resin.

In addition, when a polyolefin-based resin is used as a synthetic resin, it is preferably within a range that does not impair the effects of the present invention. If necessary, in order to further neutralize the residual catalyst in the polyolefin resin, a known neutralizing agent is added. As the neutralizing agent, for example, fatty acid metal salts such as calcium stearate, lithium stearate, sodium stearate, etc., or ethylene bis (stearyl amine), ethylene bis (12-hydroxystearyl amine), Fatty acid amide compounds such as stearic acid amide, and these neutralizers can be used in combination.

In the antistatic resin composition of the present invention, as other additives, if necessary in a range that does not impair the effects of the present invention, aromatic carboxylic acid metal salts, alicyclic alkyl carboxylic acid metal salts, and p- Aluminium tert-butyl benzoate, metal salts of aromatic phosphates, Dibenzylidene sorbitol and other crystallization nucleating agents, metal soaps, hydrotalcite, compounds containing triazine rings, metal hydroxides, Oxidation of phosphate flame retardants, condensed phosphate flame retardants, inorganic phosphorus flame retardants, (poly)phosphate flame retardants, halogen flame retardants, silicon flame retardants, antimony trioxide, etc. Antimony, other inorganic flame-retardant auxiliary agents, other organic flame-retardant auxiliary agents, neutralizers, anti-aging agents, fillers, pigments, lubricants, processing aids, plasticizers, reinforcing materials, foaming agents, etc.

Examples of compounds containing a triazine ring include melamine, Ammeline, benzoguanamine, acetguanamine, Phthalo diguanamine, melamine cyanurate, and pyrophosphoric acid. Melamine, butylene biguanamine, norbornene biguanamine, methylene biguanamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3- Xylylene dimelamine and so on.

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

Examples of phosphate-based flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxy ethyl phosphate, ginseng chloroethyl phosphate, and ginseng dichloropropyl. Phosphate, Triphenyl Phosphate, Tricresyl Phosphate, Cresyl Diphenyl Phosphate, Trixylyl Phosphate, Octyl Diphenyl Phosphate, Xylyl Diphenyl Phosphate, Ginseng Propyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butyl phenyl diphenyl phosphate, bis-(t-butylphenyl) phenyl phosphate, ginseng-(t- Butyl phenyl) phosphate, isopropyl phenyl diphenyl phosphate, bis-(isopropyl phenyl) diphenyl phosphate, ginseng-(isopropyl phenyl) phosphate and the like.

Examples of condensed phosphate flame retardants include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (xylyl phosphate), bisphenol A bisphenol (Diphenyl phosphate) and so on.

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

As other inorganic flame retardant auxiliary agents, for example, inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, montmorillonite, and surface treatment products thereof can be cited. For example, TIPAQUER-680 (titanium oxide: Ishihara Industry (stock) system), KYOWAMAG150 (magnesium oxide: Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite: Kyowa Chemical Industry Co., Ltd.), ALCAMIZER4 (zinc-modified hydrotalcite: Kyowa Chemical Industry Co., Ltd.) ) System) and other commercially available products. Moreover, as another organic flame-retardant auxiliary agent, pentaerythritol can be mentioned, for example.

Examples of anti-aging agents include naphthylamine series, diphenylamine series, p-phenyldiamine series, quinoline series, hydroquinone derivatives, monophenol series, thiobisphenol series, hindered phenol series , Phosphite series, etc.

As crystal nucleating agents, inorganic crystal nucleating agents and organic crystal nucleating agents can be cited. Specific examples of inorganic crystal nucleating agents include kaolinite, synthetic mica, clay, zeolite, silica, graphite, carbon black, Metal salts of magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, aluminum oxide, neodymium oxide, and phenyl phosphate. In order to improve the dispersibility in the composition, these inorganic crystal nucleating agents can be modified with organic substances.

Specific examples of organic crystal nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, and terephthalic acid. Potassium, calcium oxalate, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octadecanoate, calcium octadecanoate, sodium stearate, potassium stearate, Lithium stearate, calcium stearate, magnesium stearate, barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum dibenzoate , Potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexane carboxylate and other organic carboxylic acid metal salts, sodium p-toluenesulfonate, sodium sulfoisophthalate, etc. Organic sulfonates, amide stearate, ethylene dilaurate amide, palmitate amide, hydroxystearate amide, erucamide, mesylic acid (t-butylamide) ) And other carboxylic acid amides, benzylidene sorbitol and its derivatives, sodium-2,2'-methylene bis(4,6-di-t-butylphenyl) phosphate and other phosphorus compounds Metal salts, and 2,2-methylbis(4,6-di-t-butylphenyl) sodium, etc.

The neutralizer is added to neutralize the residue catalyst in the synthetic resin. Examples include fatty acid metal salts such as calcium stearate, lithium stearate, and sodium stearate, or ethylene bis(stearylamine) , Ethylene bis (12-hydroxystearyl amide), stearic acid amide and other fatty acid amide compounds.

As the lubricant, for example, pure hydrocarbon lubricants such as fluid paraffin, natural paraffin, micro wax, synthetic paraffin, low molecular weight polyethylene, polyethylene wax, etc.; halogenated hydrocarbon lubricants; higher fatty acids, oxy fatty acids, etc. Fatty acid lubricants; fatty acid amides, difatty acid amides and other fatty acid amides lubricants; lower alcohol esters of fatty acids, polyglycerol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids (Ester wax) and other ester lubricants; metal soap, fatty alcohol, polyol, polyglycol, polyglycerol (Glycerol), partial esters of fatty acid and polyol, fatty acid and polyglycol, polyglycerol (Glycerol) Some ester lubricants or silicone oil, mineral oil, etc.

Examples of the processing aids include acrylic processing aids, and the acrylic processing aids may be one type of polymerized (meth)acrylate or two or more types of copolymerized ones. Examples of (meth)acrylates for polymerization or copolymerization include methacrylate, methacrylate, ethylacrylate, ethylmethacrylate, n-propyl acrylate, isopropyl Acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, isobutyl acrylate, t-butyl methacrylate, n-hexyl acrylate, n-hexyl (Meth)acrylates such as methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, etc. Moreover, in addition to the above, (meth)acrylic acid and hydroxyl group-containing (meth)acrylate can also be mentioned.

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

As the reinforcing material, for example, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, silica-based whisker, diatomaceous earth, sepiolite, Inorganic fibrous reinforcement of asbestos, slag fiber, zeolite, silicoapatite, gypsum fiber, silica fiber, silica, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber Material, polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, kenaf, ramie, cotton, jute, hemp, sisal, flax, linen, silk, manila hemp, sugar cane, wood pulp Organic fibrous reinforcing materials such as, paper scraps, waste paper and wool, glass flakes, non-swelling mica, graphite, metal foil, ceramic beads, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, micronized silicic acid , Feldspar powder, potassium titanate, Shirasu Balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, alumina, titanium oxide, aluminum silicate, silica, gypsum, microcrystalline quartz flint rock, Plate-like or granular strengthening materials such as sodium stone and white clay. These reinforcing materials can be coated or bundled with thermoplastic resins such as ethylene/vinyl acetate copolymers, or thermosetting resins such as epoxy resins. They can also be treated with coupling agents such as aminosilane or siloxane oxide. .

In the antistatic resin composition of the present invention, as other additives, in a range that does not impair the effects of the present invention, if necessary, additives commonly used in synthetic resins, such as crosslinking agents, anti-fogging agents, and anti-fogging agents, can be used as additives. Plate-out prevention agents, surface treatment agents, fluorescent agents, antifungal agents, fungicides, metal deactivators, and mold release agents are blended in a range that does not impair the effects of the present invention.

The additive blended in the antistatic resin composition of the present invention can be directly added to the synthetic resin, or it can also be blended in the antistatic agent of the present invention, namely the polymer compound (C) or the antistatic agent composition, and then added to the synthetic resin. Resin.

Next, the molded product of the present invention will be described. The molding system 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 body having antistatic properties can be obtained. The molding method is not particularly limited. Examples include extrusion processing, calender processing, injection molding, rolls, compression molding, blow molding, rotary molding, etc., and can produce resin plates, sheets, films, bottles, and fibers. , Shaped products and other shaped products.

The molded body obtained from the antistatic resin composition of the present invention has excellent antistatic performance and durability.

The antistatic resin composition of the present invention and the molded body using the resin composition can be used in electrical, electronics, communications, agriculture, forestry and fisheries, mining, construction, food, fiber, clothing, medical, carbon, petroleum, rubber, leather , Automobiles, precision machinery, wood, building materials, civil engineering, furniture, printing, musical instruments, etc.

More specifically, the resin composition of the present invention and its molding system are used in printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, photocopiers, fax machines, ECR (electronic money) Registration machine), computers, electronic notebooks, cards, holders, stationery and other business, OA machines, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting appliances, game consoles, irons, kotatsu and other household appliances, TV, VTR, video recorders , Audio cassettes, tape recorders, mini-discs, CD players, speakers, liquid crystal displays and other AV equipment, connectors, relays, regulators, switches, printed base plates, coil bobbins, semiconductor sealing materials, LED sealing materials, wires, cables , Transformers, deflection yokes, distribution boards, clocks and other electrical and electronic parts and communication equipment, automotive interior and exterior decorative materials, plate-making films, adhesive films, bottles, food containers, food packaging films, pharmaceuticals and pharmaceuticals Applications such as packaging film, product packaging film, agricultural film, agricultural sheet, and greenhouse film.

Furthermore, the resin composition of the present invention and its molded body can be used in seats (fillers, exterior materials, etc.), seat belts, ceilings, convertible tops, armrests, door trims, and rear storage panels. (rear package tray), carpets, mats, sun visors, wheel covers, cushion covers, air bags, insulating materials, rings, straps, wire covering materials, electrical insulating materials, paints, coating materials, bedding materials, floor materials, walls Corners, carpets, wallpapers, wall decoration materials, exterior decoration materials, interior decoration materials, roofing materials, deck materials, wall materials, pillar materials, planking, enclosure materials, frameworks and decorative slats, window and door profiles, shingles Boards, siding, terraces, terraces, sound insulation boards, heat insulation boards, window materials and other materials for automobiles, vehicles, ships, aircrafts, buildings, housing and construction or civil materials, clothing, curtains, bed sheets, non-woven fabrics, plywood, synthetic fibers Boards, blankets, porch mats, sheets, buckets, hoses, containers, glasses, bags, boxes, goggles, skis, rackets, tents, musical instruments and other daily necessities, sporting goods, etc. Example

Hereinafter, although the present invention will be described in further detail using examples, the present invention is not limited to these.

According to the following production examples, the antistatic agent of the present invention, which is the polymer compound (C), was produced. In the following production examples, the number average molecular weight of the compound (b) is calculated by the following <Method for calculating the number average molecular weight derived from the hydroxyl value>, and the number average molecular weight of the compound (b) other than that of the compound (b) is calculated by the following <By polyphenylene The method of measuring the number average molecular weight in terms of ethylene>calculate.

＜Calculation method of number average molecular weight derived from hydroxyl valence＞ The hydroxyl value is measured by the following hydroxyl value measurement method, and the number average molecular weight (hereinafter, also referred to as "Mn") is determined by the following formula. Number average molecular weight = (56110×2)/hydroxyl value ＜Measurement method of hydroxyl value＞ ・Reagent A (acetylation agent) (1) Triethyl phosphate 1560mL (2) Acetic anhydride 193mL (3) Perchloric acid (60%) 16g Mix the above reagents in the order of (1)→(2)→(3). ・Reagent B Mix pyridine and pure water at a volume ratio of 3:1. ・Reagent C Add 2 to 3 drops of phenolphthalein solution to 500 mL of isopropyl alcohol, and make it neutral with 1N-KOH aqueous solution.

First, measure 2 g of a sample in a 200 mL Erlenmeyer flask, add 10 mL of triethyl phosphate, and heat to dissolve it. Add 15mL of reagent A, cover with stopper and shake vigorously. Add reagent B20mL, cover with stopper and shake vigorously. Add reagent C50mL. Titrate with 1N-KOH aqueous solution and calculate with the following formula. Hydroxyl value [mgKOH/g]=56.11×f×(T-B)/S f: the factor of 1N-KOH aqueous solution B: Empty test titration [mL] T: Titration of this test [mL] S: sample size [g]

＜Measuring method of number average molecular weight converted from polystyrene＞ The number average molecular weight (hereinafter, also referred to as "Mn") is measured by the gel permeation chromatography (GPC) method. The measurement conditions of Mn are as follows. Device: GPC device manufactured by Japan Spectroscopy Co., Ltd. Solvent: chloroform Reference material: Polystyrene Detector: UV detector Column stationary phase: Shodex LF-804 manufactured by Showa Denko Co., Ltd. Column temperature: 40℃ Sample concentration: 1mg/1mL Flow rate: 0.5mL/min. Injection volume: 30μL

[Manufacturing Example 1] In a separable flask, put 90.1g (1.0 mol) of 1,4-butanediol as (a1), 33g (0.22 mol) of adipic acid as (a2) and 102g of dimethyl terephthalate (0.52 mol), antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionoxymethyl]methane, ADEKA STAB AO-60 (stock) ADEKA product) 0.24 g. 0.27 g of tetraisopropyl titanate was polymerized under normal pressure while slowly raising the temperature from 25°C to 195°C for 6 hours to obtain polyester (A')-1 having hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-1 was 3,300.

Next, 160g of polyester (A')-1 obtained, 1.9g (0.01 mol) of trimellitic anhydride as polycarboxylic acid compound (a3)-1, number average molecular weight of polyethylene glycol 3300, ethyleneoxy The number of repeating units = 75 polyethylene glycol (b)-98g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.2g, and at 220 ℃ for 10 hours, reduced pressure After lowering polymerization, using LABO PLASTOMILLμ (manufactured by Toyo Seiki Seisakusho Co., Ltd.), extruded at 230°C, and cut into 5mm square particles to obtain particles of the antistatic agent of the present invention, namely the polymer compound (C)-1 200g (antistatic agent (C)-1). The melting point of the obtained pellets was measured by the following <Melting Point Measuring Method>. The results are shown in Table 1.

In addition, 15g of the obtained pellets (the number of pellets is about 2000) were sampled, and the particles of good shape (5mm square shape) and other poorly-shaped particles were visually confirmed, and the ratio (mass) to the total of the good-shaped particles was calculated. %), evaluate <Productivity (cutting)>. The poor shape of the particles also includes those where a part of the particles cannot be cut, the shape where several particles are connected, the state where the surface of the particles is jagged, and the particles have burrs or cracks observed. It can be said that the smaller the proportion of poorly shaped particles, the better the cutting performance and the higher the productivity. In addition, the storage stability of the obtained granules was evaluated by the following <Test Method for Storage Stability of Antistatic Agent>. The results are shown in Table 1.

＜Melting point measurement method＞ A differential scanning calorimeter (Diamond DSC manufactured by Perkin) was used to measure the melting point. That is, the particles of the sample are finely cut, and 3±1 mg is weighed in an aluminum pan. The temperature is increased from 50°C to 250°C at 10°C/min, and then the temperature is reduced from 250°C to -20°C at 10°C/min. The peak top of the melting peak at the second temperature rise when the temperature is raised from 10°C/min to 250°C is taken as the melting point.

＜Test method for storage stability of antistatic agent＞ Put 5g of pellets in a 130mL glass sample bottle, and place it in an oven at 100°C for 3 hours. After 3 hours, after taking out the sample bottle, attach the lid, and put the sample bottle upside down calmly, from the falling of the antistatic agent particles, as shown in Figure 1 below to evaluate the blocking performance.

○: The antistatic agent particles will not adhere to the bottom of the bottle and all fall off. The storage stability was evaluated as excellent. △: A part of the antistatic agent particles is directly attached to the bottom of the bottle. The storage stability was evaluated as slightly poor. ×: All of the antistatic agent particles directly adhere to the bottom of the bottle and remain. The storage stability was evaluated as poor.

[Manufacturing Example 2] In a separable flask, put 90.1g (1.0 mol) of 1,4-butanediol as (a1), 62g (0.42 mol) of adipic acid as (a2) and 67g of dimethyl terephthalate (0.35 mol), antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionoxymethyl]methane, ADEKA STAB AO-60 (stock) ADEKA product) 0.24 g. 0.27 g of tetraisopropyl titanate was polymerized at normal pressure for 6 hours while slowly raising the temperature from 25°C to 195°C to obtain polyester (A')-2 with hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-2 was 3100.

Next, 160g of polyester (A')-2 obtained, 1.9g (0.01 mol) of trimellitic anhydride as polycarboxylic acid compound (a3)-1, number average molecular weight of polyethylene glycol 3300, ethyleneoxy The number of repeating units = 75 polyethylene glycol (b)-98g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.2g, and at 220 ℃ for 16 hours, and After polymerization under reduced pressure, the same procedure as in Production Example 1 was carried out to obtain 200 g of particles of the polymer compound (C)-2 (antistatic agent (C)-2), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-2 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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, put 90.1g (1.0 mol) of 1,4-butanediol as (a1), 56g (0.38 mol) of adipic acid as (a2) and 74g of dimethyl terephthalate (0.38 mol), antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionoxymethyl]methane, ADEKA STAB AO-60 (stock) ADEKA product) 0.24 g. 0.27 g of tetraisopropyl titanate was polymerized at normal pressure for 5 hours while slowly raising the temperature from 25°C to 195°C to obtain polyester (A')-3 with hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-3 was 2,900.

Next, 160g of polyester (A')-3 obtained, 1.9g (0.01 mol) of trimellitic anhydride as polycarboxylic acid compound (a3)-1, number average molecular weight of polyethylene glycol 3300, ethyleneoxy The number of repeating units = 75 polyethylene glycol (b)-98g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.2g, at 220 ℃ for 15 hours, under reduced pressure After the lower polymerization, the same procedure as in Production Example 1 was carried out to obtain 200 g of particles of the polymer compound (C)-3 (antistatic agent (C)-3), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-3 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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] In a separable flask, put 90.1g (1.0 mol) of 1,4-butanediol as (a1), 50g (0.34 mol) of adipic acid as (a2) and 81g of dimethyl terephthalate (0.42 mol), antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionoxymethyl]methane, ADEKA STAB AO-60 (stock) ADEKA product) 0.24 g. 0.27 g of tetraisopropyl titanate was polymerized under normal pressure for 7 hours while slowly raising the temperature from 25°C to 195°C to obtain polyester (A')-4 with hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-4 was 3,000.

Next, 160g of polyester (A')-4 obtained, 1.9g (0.01 mol) of trimellitic anhydride as polycarboxylic acid compound (a3)-1, number average molecular weight of polyethylene glycol 3300, ethyleneoxy The number of repeating units = 75 polyethylene glycol (b)-98g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.2g, and at 220 ℃ for 12 hours, then reduce After the reduction polymerization, the same procedure as in Production Example 1 was carried out to obtain 200 g of particles of the polymer compound (C)-4 (antistatic agent (C)-4), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-4 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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, put 90.1g (1.0 mol) of 1,4-butanediol as (a1), 44g (0.30 mol) of adipic acid as (a2) and 88g of dimethyl terephthalate (0.45 mol), antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionoxymethyl]methane, ADEKA STAB AO-60 (stock) ADEKA product) 0.24 g. 0.27 g of tetraisopropyl titanate was polymerized at normal pressure for 11 hours while slowly raising the temperature from 25°C to 195°C to obtain polyester (A')-5 with hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-5 was 3100.

Next, 160g of polyester (A')-5 obtained, 1.9g (0.01 mol) of trimellitic anhydride as polycarboxylic acid compound (a3)-1, number average molecular weight of polyethylene glycol 3300, ethyleneoxy The number of repeating units = 75 polyethylene glycol (b)-98g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.2g, and at 220 ℃ for 8 hours, then reduce After the reduction polymerization, the same procedure as in Production Example 1 was carried out to obtain 200 g of particles of the polymer compound (C)-5 (antistatic agent (C)-5), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-5 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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, put 90.1g (1.0 mol) of 1,4-butanediol as (a1), 22g (0.15 mol) of adipic acid as (a2) and 115g of dimethyl terephthalate (0.59 mol), antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionoxymethyl]methane, ADEKA STAB AO-60 (stock) ADEKA product) 0.24 g. 0.27 g of tetraisopropyl titanate was polymerized at normal pressure for 9 hours while slowly raising the temperature from 25°C to 195°C to obtain polyester (A')-6 having hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-6 was 3,000.

Next, 160g of polyester (A')-6 obtained, 1.9g (0.01 mol) of trimellitic anhydride as polycarboxylic acid compound (a3)-1, number average molecular weight of polyethylene glycol 3300, ethyleneoxy The number of repeating units = 75 polyethylene glycol (b)-98g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.2g, and at 220 ℃ for 9 hours, then reduce After the reduction polymerization, the same procedure as in Production Example 1 was carried out to obtain 200 g of particles of the polymer compound (C)-6 (antistatic agent (C)-6), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-6 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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, put 90.1g (1.0 mol) of 1,4-butanediol as (a1), 11g (0.073 mol) of adipic acid as (a2) and 128g of dimethyl terephthalate (0.66 mol), antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionoxymethyl]methane, ADEKA STAB AO-60 (share) manufactured by ADEKA) 0.24 g. 0.27 g of tetraisopropyl titanate was polymerized at normal pressure for 8 hours while slowly raising the temperature from 25°C to 195°C to obtain polyester (A')-7 with hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-7 was 3,000.

Next, 160g of polyester (A')-7 obtained, 1.9g (0.01 mol) of trimellitic anhydride as polycarboxylic acid compound (a3)-1, number average molecular weight of polyethylene glycol 3300, ethyleneoxy The number of repeating units = 75 polyethylene glycol (b)-98g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.2g, and at 220 ℃ for 9 hours, then reduce After the reduction polymerization, the same procedure as in Production Example 1 was carried out to obtain 200 g of particles of the polymer compound (C)-7 (antistatic agent (C)-7), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-7 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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, put 69 g (1.11 mol) of ethylene glycol as (a1), 38 g (0.26 mol) of adipic acid as (a2) and 118 g (0.61 mol) of dimethyl terephthalate , Antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionoxymethyl]methane, ADEKA STAB AO-60 (stock) ADEKA product) 0.24g, tetraisopropyl 0.27 g of base titanate was polymerized at normal pressure for 4 hours while slowly raising the temperature from 25°C to 195°C, to obtain polyester (A')-8 with hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-8 was 3,000.

Next, 160g of polyester (A')-8 obtained, 1.9g (0.01 mol) of trimellitic anhydride as polycarboxylic acid compound (a3)-1, number average molecular weight of polyethylene glycol 3300, ethyleneoxy The number of repeating units = 75 polyethylene glycol (b)-1 100g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.3g, and at 220 ℃ for 10 hours, reduced pressure After the lower polymerization, the same procedure as in Production Example 1 was carried out to obtain 200 g of particles of the polymer compound (C)-8 (antistatic agent (C)-8), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-8 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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, put 46g (0.51 mol) of 1,4-butanediol as (a1), 32g (0.51 mol) of ethylene glycol, and 35g (0.24 mol) of adipic acid as (a2) With 109g (0.56 mol) of dimethyl terephthalate, antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoxymethyl]methane, ADEKA STAB AO -60 (made by ADEKA) 0.24g, 0.27g of tetraisopropyl titanate, while slowly raising the temperature from 25°C to 195°C, polymerization was carried out at normal pressure for 5 hours to obtain a polyester ( A')-9. The number average molecular weight of the obtained polyester (A')-9 was 3,300.

Next, 160g of polyester (A')-9 obtained, 1.9g (0.01 mol) of trimellitic anhydride as polycarboxylic acid compound (a3)-1, number average molecular weight of polyethylene glycol 3300, ethyleneoxy The number of repeating units = 75 polyethylene glycol (b)-1 99g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.3g, and at 220 ℃ for 9 hours, then reduce After the reduction polymerization, the same procedure as in Production Example 1 was carried out to obtain 200 g of particles of the polymer compound (C)-9 (antistatic agent (C)-9), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-9 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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, put 71 g (0.79 mol) of 1,4-butanediol as (a1), 12 g (0.20 mol) of ethylene glycol, and 34 g (0.23 mol) of adipic acid as (a2) With dimethyl terephthalate 105g (0.54 mol), antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionoxymethyl]methane, ADEKA STAB AO -60 (Stock) ADEKA product) 0.24g, 0.27g tetraisopropyl titanate, while slowly raising the temperature from 25°C to 195°C, polymerization was carried out at normal pressure for 6 hours to obtain a polyester ( A')-10. The number average molecular weight of the obtained polyester (A')-10 was 3,300.

Next, 160g of the obtained polyester (A')-10, 1.9g (0.01 mol) of trimellitic anhydride as the polycarboxylic acid compound (a3)-1, number average molecular weight of 3300 as polyethylene glycol, and ethyleneoxy The number of repeating units = 75 polyethylene glycol (b)-98g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.3g, and at 220 ℃ for 11 hours, then reduce After polymerization under pressure, the same procedure as in Production Example 1 was carried out to obtain 200 g of particles of the polymer compound (C)-10 (antistatic agent (C)-10), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-10 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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] In 160 g of the polyester (A')-1 obtained in the same manner as in Production Example 1, 1.6 g (0.0075 mol) of pyromellitic anhydride as the polycarboxylic acid compound as (a3)-2 was placed as polyethylene glycol The number average molecular weight is 3300, the number of repeating units of ethyleneoxy group = 75 polyethylene glycol (b)-98g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.2g, After polymerization under reduced pressure at 220°C for 14 hours, the same procedure as in Production Example 1 was carried out to obtain particles of the polymer compound (C)-11 (antistatic agent (C)-11), which is the antistatic agent of the present invention 200g. The obtained pellets of the polymer compound (C)-11 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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 the polyester (A')-1 obtained in the same manner as in Production Example 1, put 1.5 of butane-1,2,3,4-tetracarboxylic dianhydride as the polycarboxylic acid compound (a3)-3 g (0.0075 mol), as the number average molecular weight of polyethylene glycol 3300, the number of repeating units of ethylene oxide = 75 polyethylene glycol (b)-98g, antioxidant (ADEKA STAB AO-60) 0.2 g. 1.2 g of tetraisopropyl titanate was polymerized at 220°C for 10 hours under reduced pressure, and then the same procedure as in Production Example 1 was carried out to obtain the antistatic agent of the present invention, which is the polymer compound (C)-12 ( Antistatic agent (C)-12) particles 200g. The obtained pellets of the polymer compound (C)-12 were performed in the same manner as in Production Example 1, and the melting point was measured. 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] In 160 g of polyester (A')-1 obtained in the same manner as in Production Example 1, 1.4 g (0.0075 mol) of citric acid as the polycarboxylic acid compound (a3)-4 was placed as the number of polyethylene glycols The average molecular weight is 3300, the number of repeating units of ethyleneoxy group=75 polyethylene glycol (b)-1 98g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.2g, and After polymerization at 220°C for 10 hours under reduced pressure, it was carried out in the same manner as in Production Example 1, to obtain 200 g of particles of the polymer compound (C)-13 (antistatic agent (C)-13), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-13 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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] To 160 g of polyester (A')-1 obtained in the same manner as in Production Example 1, 1.9 g (0.01 mol) of trimellitic anhydride as the polycarboxylic acid compound (a3)-1 was put into the number average of polyethylene glycol Polyethylene glycol (b)-2 30g with a molecular weight of 1000, the number of repeating units of ethyleneoxy group=22, 0.2g of antioxidant (ADEKA STAB AO-60), 1.2g of tetraisopropyl titanate, and a weight of 220 After polymerization under reduced pressure for 12 hours at C, the same procedure as in Production Example 1 was carried out to obtain 200 g of particles of the polymer compound (C)-14 (antistatic agent (C)-14), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-14 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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, 1.9 g (0.01 mol) of trimellitic anhydride as the polycarboxylic acid compound (a3)-1 was put into the number average of polyethylene glycol The molecular weight is 6000, the number of repeating units of ethyleneoxy group = 136 polyethylene glycol (b)-3 178g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.2g, and 220 After polymerizing at a temperature of 14 hours under reduced pressure, it was carried out in the same manner as in Production Example 1 to obtain 200 g of particles of the polymer compound (C)-15 (antistatic agent (C)-15), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-15 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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] In a separable flask, 170 g (1.9 mol) of 1,4-butanediol as (a1), 56 g (0.38 mol) of adipic acid as (a2), and 173 g ( 0.89 mol), antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionoxymethyl]methane, ADEKA STAB AO-60 (stock) ADEKA product) 0.84g , 0.95 g of tetraisopropyl titanate was polymerized at normal pressure for 3 hours while slowly raising the temperature from 25°C to 195°C to obtain polyester (A')-11 with hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-11 was 1,000.

Next, put 100 g of the obtained polyester (A')-11, 3.8 g (0.02 mol) of trimellitic anhydride as the polycarboxylic acid compound (a3)-1, number average molecular weight of 3300 as polyethylene glycol, and ethyleneoxy The number of repeating units = 75 polyethylene glycol (b)-1 201g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.5g, and at 220 ℃ for 15 hours, then reduce After polymerization under pressure, the same procedure as in Production Example 1 was carried out to obtain 250 g of particles of the polymer compound (C)-16 (antistatic agent (C)-16), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-16 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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, 124g (1.4 mol) of 1,4-butanediol as (a1), 48g (0.33 mol) of adipic acid as (a2) and 150g ( 0.77 mol), antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionoxymethyl]methane, ADEKA STAB AO-60 (stock) ADEKA product) 0.29g 0.33 g of tetraisopropyl titanate was polymerized at normal pressure for 10 hours while slowly raising the temperature from 25°C to 195°C to obtain polyester (A')-12 with hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-12 was 6000.

Next, put 200 g of the obtained polyester (A')-12, 1.3 g (0.0068 mol) of trimellitic anhydride as the polycarboxylic acid compound (a3)-1, 3300 as the number average molecular weight of polyethylene glycol, and ethyleneoxy The number of repeating units = 75 polyethylene glycol (b) -1 68g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.3g, and at 220 ℃ 14 hours, then reduce After the polymerization under pressure, the same procedure as in Production Example 1 was carried out to obtain 230 g of particles of the polymer compound (C)-17 (antistatic agent (C)-17), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-17 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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 as (a2), and 121 g ( 0.62 mol), antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionoxymethyl]methane, ADEKA STAB AO-60 (share) ADEKA product) 0.39g 0.44 g of tetraisopropyl titanate was polymerized at normal pressure for 4 hours while slowly raising the temperature from 25°C to 195°C to obtain polyester (A')-13 with hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-13 was 2,000.

Next, put 130 g of the obtained polyester (A')-13, 1.9 g (0.01 mol) of trimellitic anhydride as the polycarboxylic acid compound (a3)-1, the number average molecular weight of 3300 as polyethylene glycol, and ethyleneoxy The number of repeating units = 75 polyethylene glycol (b)-1 148g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.4g, and at 220 ℃ for 13 hours, after reducing After the polymerization under pressure, the same procedure as in Production Example 1 was carried out to obtain 250 g of particles of the polymer compound (C)-18 (antistatic agent (C)-18), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-18 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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), antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionoxymethyl]methane, ADEKA STAB AO-60 (stock) ADEKA product) 0.29g 0.33 g of tetraisopropyl titanate was polymerized at normal pressure for 9 hours while slowly raising the temperature from 25°C to 195°C to obtain polyester (A')-14 with hydroxyl groups at both ends. The number average molecular weight of the obtained polyester (A')-14 was 5,000.

Next, 200 g of the obtained polyester (A')-14, 2.3 g (0.012 mol) of trimellitic anhydride as the polycarboxylic acid compound (a3)-1, number average molecular weight of 3300 as polyethylene glycol, and ethyleneoxy The number of repeating units = 75 polyethylene glycol (b)-1 61g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.2g, and at 220 ℃ for 8 hours, then reduce After polymerization under pressure, the same procedure as in Production Example 1 was carried out to obtain 220 g of particles of the polymer compound (C)-19 (antistatic agent (C)-19), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-19 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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] Placed in a polyethylene glycol (b) with 160 g of polyester (A')-1 obtained in the same manner as in Production Example 1, a number average molecular weight of 3300 as polyethylene glycol, and the number of repeating units of ethyleneoxy group = 75 -1 98g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 0.24g, polymerized at 195°C for 7.5 hours under reduced pressure to obtain a block polymer.

Next, put in 100 g of the block polymer obtained, 0.71 g (0.0037 mol) of trimellitic anhydride as the polycarboxylic acid compound (a3)-1, and 1.2 g of tetraisopropyl titanate, and place them at 220°C for 3 hours. After polymerization under reduced pressure, it was carried out in the same manner as in Production Example 1, to obtain 80 g of particles of the polymer compound (C)-20 (antistatic agent (C)-20), which is the antistatic agent of the present invention. The obtained pellets of the polymer compound (C)-20 were performed in the same manner as in Production Example 1, and the melting point was measured. 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 the separable flask, put 1,4-butanediol (equivalent to (a1)) 184g (2.0 mol), adipic acid 235g (1.6 mol), antioxidant (4[3-(3,5- Di-tert-butyl-4-hydroxyphenyl)propanoxymethyl]methane, ADEKA STAB AO-60 (manufactured by ADEKA) 0.48g, polymerize at normal pressure while slowly raising the temperature from 25°C to 195°C For 3 hours, a comparative polyester-1 with hydroxyl groups at both ends was obtained. The number average molecular weight of the obtained comparative polyester-1 was 3,300.

Next, put the obtained comparative polyester-1 160g, trimellitic anhydride (equivalent to (a3)) 1.9g (0.01 mol), the number average molecular weight of polyethylene glycol 3300, and the number of repeating units of ethylene oxide = 75 Polyethylene glycol (equivalent to (b)) 97g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.2g, and after polymerization under reduced pressure at 220 ℃ for 10 hours, and Production Example 1 was carried out in the same manner, and 200 g of particles of the comparative polymer compound (C')-1 (comparative antistatic agent (C')-1) were obtained. The obtained particles of the comparative antistatic agent (C')-1 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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 the separable flask, put 1,4-butanediol (equivalent to (a1)) 118g (1.3 mol), dimethyl terephthalate 198g (1.0 mol), antioxidant (4[3-( 3,5-Di-tert-butyl-4-hydroxyphenyl)propanoxymethyl]methane, ADEKA STAB AO-60 (manufactured by ADEKA) 0.34g, 0.38g of tetraisopropyl titanate, from one side The temperature was gradually raised from 25°C to 195°C, while polymerizing under normal pressure for 4 hours, to obtain a comparative polyester-2 with hydroxyl groups at both ends. The number average molecular weight of the obtained comparative polyester-2 was 3,000.

Next, put the obtained comparative polyester-2 160g, trimellitic anhydride (equivalent to (a3)) 1.9g (0.01 mol), the number average molecular weight of polyethylene glycol 3300, and the number of repeating units of ethyleneoxy group = 75 Polyethylene glycol (equivalent to (b)) 98g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.2g, and after polymerization under reduced pressure at 220 ℃ for 10 hours, and Production Example 1 was carried out in the same manner, and 240 g of particles of the comparative polymer compound (C')-2 (comparative antistatic agent (C')-2) were obtained. The obtained particles of the comparative antistatic agent (C')-2 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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 the separable flask, put 1,4-butanediol (equivalent to (a1)) 161g (1.8 mol), 84g (0.42 mol) of sebacic acid and 189g (0.97 mol) of dimethyl terephthalate ), antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoxymethyl]methane, ADEKA STAB AO-60 (stock) ADEKA product) 0.48g, four different 0.55 g of propyl titanate was polymerized at normal pressure for 7 hours while gradually raising the temperature from 25°C to 195°C, to obtain a comparative polyester-3 having hydroxyl groups at both ends. The number average molecular weight of the obtained comparative polyester-3 was 3,300.

Next, put the obtained comparative polyester-3 160g, trimellitic anhydride (equivalent to (a3)) 1.9g (0.01 mol), the number average molecular weight of polyethylene glycol 3300, and the number of repeating units of ethyleneoxy group = 75 Polyethylene glycol (equivalent to (b)) 99g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.3g, and after polymerization under reduced pressure at 220 ℃ for 10 hours, and Production Example 1 was carried out in the same manner, and 200 g of particles of the comparative polymer compound (C')-3 (comparative antistatic agent (C')-3) were obtained. The obtained particles of the comparative antistatic agent (C')-3 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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 the separable flask, put 1,4-butanediol (equivalent to (a1)) 173g (1.9 mol), 66g (0.45 mol) of adipic acid, and 204g (1.1 mol) of dimethyl phthalate ), antioxidant (4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoxymethyl]methane, ADEKA STAB AO-60 (stock) ADEKA product) 0.48g, four different 0.55 g of propyl titanate was 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 3,000.

Next, put the obtained comparative polyester-4 160g, trimellitic anhydride (equivalent to (a3)) 1.9g (0.01 mol), as the number average molecular weight of polyethylene glycol 3300, and the number of repeating units of ethyleneoxy group = 75 Polyethylene glycol (equivalent to (b)) 98g, antioxidant (ADEKA STAB AO-60) 0.2g, tetraisopropyl titanate 1.2g, and polymerized at 220°C for 15 hours under reduced pressure, The same procedure as in Production Example 1 was carried out to obtain 200 g of particles of the comparative polymer compound (C')-4 (comparative antistatic agent (C')-4). The obtained particles of the comparative antistatic agent (C')-4 were carried out in the same manner as in Production Example 1, and the melting point was measured. 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 antistatic agents (C)-1 to (C)-20 indicate the relative value of the monomer (a2) of the polymer compound (C) to adipic acid and terephthalic acid The ratio of terephthalic acid (including derivatives such as dimethyl terephthalate) in total moles (mol%). Regarding the comparative antistatic agents (C')-1 to (C')-3, the same applies to terephthalic acid (including derivatives of dimethyl terephthalate) in the total of the carboxylic acids used Proportion (mol%). For the comparison antistatic agent (C')-4, it does not mean relative to terephthalic acid, but relative to the total of phthalic acid (including derivatives of dimethyl phthalate) and adipic acid The ratio of phthalic acid (including derivatives such as dimethyl phthalate) in moles (mol%).

[Examples 1 to 53, Comparative Examples 1 to 20] Using the resin composition of each of the examples mixed in accordance with the blending amounts (parts by mass) described in Tables 2 to 11 below, test pieces were obtained in accordance with the test piece production 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. In the same manner, the resin composition of the comparative example was prepared with the blending shown in the following Tables 2 to 11, and each was evaluated. The results are shown in Tables 2-11.

<Conditions for preparing block polypropylene resin composition test piece> The block polypropylene resin composition mixed according to the blending amounts shown in the following Tables 2 to 11 was used with a 2-axis extruder made by Ikegai (put into PCM30, 60mesh) at 230°C, 6kg/ The granulation is performed under hourly conditions to obtain granules. The obtained pellets were molded using a horizontal injection molding machine (NEX80: manufactured by Nissei Plastic Industries Co., Ltd.) under processing conditions of a resin temperature of 230°C and a mold temperature of 40°C to obtain a test piece (100mm×100mm×3mm).

<Conditions for making test pieces of ABS resin composition> The ABS resin composition mixed according to the blending amounts shown in the following Tables 2 to 11 was used with a 2-axis extruder made by Ikegai (put into PCM30, 60mesh) at 230°C and 6kg/hour. Granulation is carried out to obtain granules. The obtained pellets were molded using a horizontal injection molding machine (NEX80: manufactured by Nissei Plastic Industries Co., Ltd.) under processing conditions of a resin temperature of 230°C and a mold temperature of 50°C to obtain a test piece (100mm×100mm×3mm).

＜Method of measuring surface resistivity (SR value)＞ After forming and processing the obtained test piece, immediately store it at a temperature of 25°C and a humidity of 50%RH. After 1 day of forming and 30 days of storage, use the R8340 resistance meter manufactured by Advantest in the same environment to apply The surface resistivity (Ω/□) was measured under the conditions of a voltage of 500V and an application time of 1 minute. The measurement was performed with 5 test pieces for each of 5 points, and the average value was calculated.

From the results shown in Tables 2 to 11, it is very clear that according to the present invention, an antistatic agent having excellent antistatic effect and durability, and excellent storage stability and productivity (cutting properties) can be obtained.

Claims (9)

An antistatic agent characterized by having a polyester segment (A) and a polyether segment (B), and The polyester segment (A) is composed of: (a1) At least one of 1,4-butanediol or ethylene glycol, (a2) Adipic acid and terephthalic acid and (a3) Polyester obtained from polycarboxylic acid compound, (A2) The ratio of terephthalic acid in adipic acid and terephthalic acid to the total moles of adipic acid and terephthalic acid is 40 mole% or more and less than 100 mole%, The polyether segment (B) is (b) polyethylene glycol, And it contains one or more polymer compounds (C) having a structure in which the polyester segment (A) and the polyether segment (B) are bonded through an ester bond. The antistatic agent of claim 1, wherein the ratio of the (a3) polycarboxylic acid compound of the polymer compound (C) to (a2) adipic acid and terephthalic acid, and (a3) the polycarboxylic acid compound The total number of moles is 0.05 to 5 mole%. Such as the antistatic agent of claim 1 or 2, wherein the mass ratio (A)/(B) of the polyester segment (A) of the polymer compound (C) to the polyether segment (B) is 0.1 to 4.0 . 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 more and 200°C or less. An antistatic agent composition characterized in that the antistatic agent described in any one of claims 1 to 4 is further blended with one selected from the group consisting of alkali metal salts and ionic liquids Made from above. An antistatic resin composition characterized by blending a synthetic resin with an antistatic agent as described in any one of claims 1 to 4. An antistatic resin composition characterized by blending a synthetic resin with an antistatic agent composition as described in claim 5. The antistatic resin composition according to claim 6 or 7, wherein the synthetic resin is one or more selected from the group consisting of polyolefin-based resins and polystyrene-based resins. A molded body characterized by being obtained from the antistatic resin composition described in any one of Claims 6 to 8.