JPH10140142A - Antistatic agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a built-in antistatic agent nonproblematic in discoloration, capable of exhibiting excellent antistatic properties for a long term even when used in a small amount and excellent in water washing resistance. SOLUTION: This agent comprises an aromatic polymer having at least either type of sulfo group and sulfonate group. Its weight-average molecular weight should be in the range of 1,000-500,000, and the rate of the total of the introduced sulfo and sulfonate groups should be in the range of 3-38mol%. This is obtained by polymerizing a monomer containing at least either a sulfo group or a sulfonate group, such as styrenesulfonic acid, its salt, α- methylstyrenesulfonic acid or its salt with a comonomer such as styrene according to a usual method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic agent, and more particularly, to an antistatic agent which can be used by being kneaded into plastic and has excellent washing resistance and the like.

[0002]

2. Description of the Related Art Plastic materials have been used in a wide range of fields due to their excellent properties, but have the property of being electrically insulating and easily charged by static electricity. For this reason, dust adheres to the plastic molded product and impairs its appearance, and when used for cases or parts of electric / electronic equipment, static electricity discharge causes malfunction of equipment or failure of electronic parts such as ICs. May cause. For this reason, various techniques have been developed for preventing static charge of plastics.

For example, it is common practice to add a surfactant type antistatic agent to plastics. However, in this method, although the antistatic property is excellent in a short term, the antistatic property cannot be maintained in a long term, and the antistatic property rapidly decreases after washing with water.

There is a method of kneading a conductive inorganic substance such as carbon fiber or carbon black into a plastic in order to impart a sustained antistatic property. However, there is a problem in that the color tone of the usable plastic is limited to black because of the coloration.

On the other hand, recently, using a conductive polymer,
A technique has been proposed in which this and a plastic are used as a polymer alloy to impart a persistent antistatic property to the plastic. For example, JP-A-61-185557,
JP-A-62-25164 and JP-A-64-17
No. 48, JP-A-58-18836 discloses a technique for adding an antihalohydrin-based polymer such as epichlorohydrin rubber to impart antistatic properties. Each of the techniques for imparting properties has been disclosed. However, in these techniques, sufficient antistatic properties cannot be imparted unless a large amount of the conductive polymer is added, and if added in a large amount, there is a problem that the mechanical properties of the plastic deteriorate.

[0006] In addition, the third of polystyrene sulfonic acid
There is a method of adding a quaternary amine salt to plastics (Japanese Patent Application Laid-Open No. 48-65237). In this method, an antistatic property can be imparted with a relatively small amount of addition, but the antistatic property after washing with water is provided. There is a problem that the properties are maintained to some extent but are still insufficient. Also,
Japanese Patent No. 29240 discloses, with the aim of improving the washing resistance,
A method using a combination of a sulfonated polystyrene and a fixing agent is disclosed. However, this method is not a kneading method, but a method of coating on a plastic surface, and requires a heat treatment after coating, so that the implementation is complicated and not an efficient method. And JP-A-59-36.
No. 159, the introduction rate of sulfonic acid groups is 40 to 10
It is disclosed that 0 mol% of sodium polystyrene sulfonate is used as a kneading type antistatic agent, but this antistatic agent does not yet have sufficient antistatic properties after washing with water.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and has no coloring problem, and can exhibit excellent antistatic properties for a long time with a small amount of addition. It is an object of the present invention to provide a kneading type antistatic agent which is possible and has excellent washing resistance.

[0008]

In order to achieve the above object, the present invention provides an antistatic agent comprising an aromatic polymer containing at least one of a sulfonic acid group and a sulfonate group. The weight average molecular weight is in the range of 1,000 to 500,000, and the total introduction ratio of the sulfonic acid groups and sulfonic acid groups is in the range of 3 to 38 mol%.

That is, the present inventors have conducted a series of studies focusing on conductive polymers in order to solve the above problems. As a result, in an aromatic polymer containing at least one of a sulfonic acid group and a sulfonic acid group (hereinafter, referred to as “sulfonic acid group or the like”) (hereinafter referred to as “aromatic polymer containing sulfonic acid group or the like”), When the molecular weight and the introduction ratio of the sulfonic acid group and the like are specified in the above range, and the aromatic polymer containing the sulfonic acid group and the like is used as an antistatic agent, it can be used by kneading into plastic,
The present inventors have found that a small amount of addition exhibits excellent antistatic properties over a long period of time, has no coloring problem, and maintains excellent antistatic properties even after washing with water.

In the present invention, the total introduction ratio of sulfonic acid groups and the like refers to the introduction ratio of the aromatic polymer containing sulfonic acid groups and the like to the aromatic ring, and the measurement is carried out, for example, by the method described later. Can be. The weight average molecular weight can be measured, for example, by gel permeation chromatography.

[0011]

Next, the present invention will be described in detail. Examples of the monomer containing a sulfonic acid group or the like constituting the aromatic polymer containing a sulfonic acid group or the like according to the antistatic agent of the present invention include, for example, styrene sulfonic acid or a salt thereof, α-methylstyrene sulfonic acid or a salt thereof, vinyl Examples thereof include toluenesulfonic acid or a salt thereof, vinylnaphthalenesulfonic acid or a salt thereof, and these may be used alone or in combination of two or more. In this,
From the viewpoint of antistatic properties, styrenesulfonic acid or a salt thereof, and α-methylstyrenesulfonic acid or a salt thereof are preferred.

The aromatic polymer containing a sulfonic acid group or the like may contain another monomer in addition to the monomer containing a sulfonic acid group or the like. The other monomer is not particularly limited as long as it can be copolymerized with the sulfonic acid group-containing monomer and the like, for example, styrene,
Aromatic hydrocarbon monomers such as α-methylstyrene, vinyltoluene, and vinylnaphthalene, conjugated dienes such as butadiene, isoprene, pentadiene, and cyclopentadiene; sulfonated products of conjugated dienes such as butadiene, isoprene, pentadiene, and cyclopentadiene or salts thereof Olefins such as ethylene, propylene, butene, isobutylene, acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid or monovalent metal salts, divalent metal salts, ammonium salts of these acids And organic amine salts, and esters of these acids with hydroxyl-containing compounds such as alcohols, polyethylene glycols and isethionic acid. These monomers can be used alone or in combination of two or more. Among them, butadiene, isoprene, an ester of acrylic acid and polyethylene glycol, and an ester of methacrylic acid and polyethylene glycol are preferred from the viewpoints of antistatic properties and compatibility with a resin. In addition, the content ratio of the other monomer unit in the sulfonic acid group-containing aromatic polymer is usually 1 to 50 mol%, preferably 3 to 40 mol%.

The content of the aromatic monomer unit in the sulfonic acid group-containing aromatic polymer according to the present invention is usually at least 50 mol%, preferably at least 60 mol%. In addition, the total introduction ratio of sulfonic acid groups and sulfonic acid groups to the aromatic ring of the aromatic polymer in the sulfonic acid group-containing polymer is in the range of 3 to 38 mol%. When the amount is less than 3 mol%, the antistatic property becomes insufficient. On the contrary, when the amount exceeds 38 mol%, the compatibility with the plastic becomes inferior, so that the kneading is hindered and the antistatic property is also inferior. That is because A preferable range of the total introduction ratio of the sulfonic acid groups and the sulfonic acid groups is 3 to 35 mol%.

In the aromatic polymer containing a sulfonic acid group or the like, the basic substance constituting the sulfonic acid salt includes:
For example, lithium hydroxide, sodium hydroxide, alkali metal hydroxides such as potassium hydroxide, calcium hydroxide,
Magnesium hydroxide, alkaline earth metal hydroxides such as barium hydroxide, calcium oxide, barium oxide, magnesium oxide, metal oxides such as zinc oxide, ammonia or aqueous ammonia, or monoethanolamine, diethanolamine, triethanolamine, Morpholine,
Organic bases such as ethylamine, butylamine, coconut oil amine and tallow amine are exemplified. Among them, lithium, potassium, zinc, and coconut oil amine are preferred from the viewpoint of antistatic properties.

The weight average molecular weight of the aromatic polymer containing a sulfonic acid group or the like ranges from 1,000 to 500,000. That is, when the weight average molecular weight is out of the range,
This is because the antistatic property becomes insufficient. The preferred range of the weight average molecular weight is in the range of 2,000 to 200,000.

The aromatic polymer containing a styrene group or the like according to the antistatic agent of the present invention can be produced, for example, by the following two methods (A and B). (A) A method of polymerizing the monomer containing a sulfonic acid group or the like and the other copolymerizable monomer by a conventional method. (B) The aromatic hydrocarbon monomer and the other copolymerizable monomer are copolymerized by an ordinary method to produce an aromatic polymer, and then sulfonated by an ordinary method, and if necessary, by the basic substance. How to neutralize.

Next, the antistatic agent of the present invention can be applied to a wide variety of plastics, and can exhibit excellent antistatic properties. Examples of applicable plastics include, for example, polyethylene resin, polypropylene resin, acrylic resin, polystyrene resin, polyacrylonitrile resin, acrylonitrile-styrene copolymer resin (AS resin), methyl methacrylate-styrene copolymer resin (MS resin), Vinyl chloride resin, acrylonitrile-styrene-butadiene copolymer (ABS resin), polyethylene terephthalate resin (PET resin), polyamide resin (PA resin), polycarbonate resin (PC resin), polyphenylene ether resin (PPE resin), nylon 66 Resins, poly p-phenylene terephthalamide resin (TPA resin), polybutylene terephthalate resin (PBT resin) and the like.

The compounding ratio of the antistatic agent of the present invention is usually 0.1 to 20 parts by weight, preferably 0.3 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of plastics. Weight. That is, if it is less than 0.1 part by weight, sufficient antistatic properties cannot be obtained, and if it exceeds 20 parts by weight, the physical properties inherent in plastics may be reduced.

When adding the antistatic agent of the present invention to various plastics, if necessary, lubricants such as higher alcohols, fatty acid amides, fatty acid metal soaps, antioxidants, ultraviolet absorbers, silicone derivatives, antiblocking agents Agents, coloring agents, fillers, plasticizers, other known antistatic agents, and other additives can be used in combination.

The form of the antistatic agent of the present invention is not particularly limited, and may be, for example, any of powder, wax, and paste. The plastic molding using the antistatic agent of the present invention is performed by first uniformly mixing with a pellet or powdered plastics using a Henschel mixer or preparing an antistatic agent-added compound using an extruder or the like. After that, the mixture or compound can be supplied to various molding devices and molded. It is also possible to prepare a masterbatch to which the antistatic agent of the present invention is added at a high concentration and dilute the masterbatch before use.

The plastics to which the antistatic agent of the present invention is added can be molded into various shapes such as sheet films by a general plastic molding method such as press molding, injection molding, extrusion molding, blow molding, or calendar molding. Can be processed.

[0022]

Next, examples will be described together with comparative examples. First, the polymers (A to L) of the examples and the polymers (I to D) of the comparative examples were synthesized according to Synthesis Examples 1 and 2 below.

The methods for measuring the weight average molecular weights of the polymers (A to L, I to D) and the introduction ratios of sulfonic acid groups and the like are described below. (1) Weight average molecular weight of polymer Standard sodium polystyrene sulfonate is used as a standard substance, and TSK-G6000PWXL is used as a separation column.
And G3000PWXL (7.8 mm ID × 30 cm, manufactured by Tosoh Corporation) using an ultraviolet detector (measuring wavelength 238 n)
m) by gel permeation chromatography (GPC). (2) Introduction rate of sulfonic acid group When the polymer is a sulfonated product of a homopolymer of an aromatic hydrocarbon monomer, an elemental analyzer (EA-1108 type,
The sulfonic acid group introduction rate per aromatic ring unit was calculated from the ratio of carbon atoms to sulfur atoms measured by Carroelba Co.). When a sulfate was contained in this polymer, the amount was quantified by ion chromatography, and the amount of sulfur was subtracted from the amount of sulfur obtained by an elemental analyzer.

When the polymer is a sulfonated copolymer of an aromatic hydrocarbon monomer and a conjugated diene, the sulfonic acid group introduction ratio of the conjugated diene monomer unit is set to 100%, and the sulfonic acid group introduction of the aromatic hydrocarbon monomer is set to 100%. Rate,
The sulfonic acid group introduction ratio per aromatic ring unit was calculated from the ratio of carbon atoms to sulfur atoms measured by an element analyzer. When a sulfate was contained in this polymer, the amount was quantified by ion chromatography, and the amount of sulfur was subtracted from the amount of sulfur obtained by an elemental analyzer.

The value calculated in the measurement of the introduction rate of the sulfonic acid group is the total introduction rate of the sulfonic acid group and the sulfonate group. (Synthesis Example 1) A solution of 180 parts by weight of benzoic acid dissolved in 540 parts by weight of 1,2-dichloroethane was cooled in an ice bath, and 65 parts by weight of sulfuric anhydride was added dropwise thereto to prepare a benzoic acid-sulfuric anhydride complex. . This complex solution was treated with a weight average molecular weight of 60.
Of polystyrene (240 parts by weight) in a solution of 1,000 parts by weight of 1,2-dichloroethane. The reaction was stirred for 1 hour while cooling in an ice bath,
The temperature was further raised to 60 ° C., and the mixture was stirred for 1 hour to complete the reaction. The reaction solution was extracted with water, the aqueous phase was washed several times with ether, neutralized with an aqueous potassium hydroxide solution, and dried to obtain a partially sulfonated polystyrene (Polymer A) in powder form. The sulfonic acid group introduction ratio of the polymer A to the styrene unit was 30 mol%.

On the other hand, polymers C, D, H, I, J, K,
The synthesis of L, b and c was carried out in the same manner as for the polymer A, except that the raw materials shown in Tables 1 and 2 below were used in the proportions shown in the same table.

(Synthesis Example 2) 104 parts by weight of styrene and 200 parts by weight of sodium styrenesulfonate were added to 100 parts of purified water.
It was suspended in 0 parts by weight. After purging with nitrogen, 6 parts by weight of potassium persulfate was added and polymerized at 60 ° C. for 6 hours to obtain a copolymer (polymer B). The weight average molecular weight of the obtained copolymer was 85,000.

On the other hand, the synthesis of the polymers E, F, G, A and D was carried out by the same operation as the polymer B, except that the raw materials shown in Tables 1 and 2 below were used in the proportions shown in the same table. Was.

[0029]

Table 1 Polymer Monomer composition (mol%) Mw Mw / Mn Type (× 10 ³ ) (Polymer A) Styrene --7 2.5 (100) (Polymer B) Styrene Styrene sulf (80) Na-100 fonate 3.5 (20) (Polymer C) Styrene isoprene-20 2.1 (80) (20) (Polymer D) Styrene PEG200 ester of α-methyl methacrylic acid-152.0 (90) (10) (Polymer E) Styrene Styrene Sulfur Isoprene Sulfate (75) Na Fonate Na Sulfonate Na Salt 35 3.0 (5) (20) (Polymer F) Styrene Styrene sulphate Na (92) Nafonate (5) 80 3.5 (3) (Polymer G) Styrene Styrene sulf (65) K-200 fonate 3.0 (35) (Polymer H) Styrene of α-methyl isoprene methacrylic acid (25) PEG400 ester 30 2.5 (70) (5) (Polymer I) Styrene butadiene methacrylic acid 50 2.8 (70) (15) (15) (Polymer J) Styrene Maleic anhydride-40 2.2(90) (10) (Polymer K) Styrene --10 2.7(100) (Polymer L) Styrene --20 3.0(100)

[0030]

TABLE 2 Polymer monomer composition (mol%) Mw Mw / Mn Type (× 10 ³ ) (Polymer) Styrene Styrene sulf (50) Na-100 fonate 3.5(50) (Polymero) Styrene isoprene-20 2.1(80) (20) (Polymer) Styrene PEG200 ester of α-methyl methacrylic acid-152.0(90) (10) (Polymer) Styrene Styrene sulphate Na (25) Nafonate (5) 80 3.5(70)

The sulfonic acid group introduction rate, weight average molecular weight (Mw), and weight average molecular weight of the polymers (A to L) of Examples and Comparative Examples (I to D) thus obtained were introduced. Table 3 below shows the ratio (Mw / Mn) between the number average molecular weight and the number average molecular weight.

[0032]

Table 3 Polymer Sulfonic acid group to aromatic ring Mw Mw / Mn type Introduction rate (mol%) (× 10 ³ ) A 30 5.0 2.6 B 20 100 3.5 C 10 15 2.3 D 5 16 2.1 E 6.25 35 3.0 F 3.15 80 3.5 G 35 200 3.0 H 35 35 2.8 I 15 52 3.0 J 27 4.5 2.5 K 3 10 2 0.7 L 35 1.8 3.2 a 50 100 3.5 b 80 22 2.4 c 1 15 2.0 d 73.7 80 3.5

Next, the polymers (A to L) of the examples and the polymers (A to D) of the comparative examples were evaluated for performance when used in the following three types of resins. (Polystyrene resin) To 100 parts by weight of polystyrene, 10 parts by weight of each of the polymer of the example and the polymer of the comparative example shown in Table 4 below were added, kneaded with a roll at 200 ° C. for 5 minutes, and then press-formed. A polystyrene plate was obtained. Each of these polystyrene plates was 25
℃ 60% (relative humidity) RH and 25 ° C 40% RH
After controlling the humidity for 24 hours in the atmosphere described above, the surface specific resistance value after applying the voltage for 1 minute at an applied voltage of 500 V was measured using a Hirester type resistance measuring apparatus (manufactured by Mitsubishi Yuka Co., Ltd., the same applies hereinafter). Next, the polystyrene plate was subjected to ultrasonic cleaning for 30 minutes, the surface moisture was wiped off, the humidity was adjusted in an atmosphere of 25 ° C. and 60% RH for 24 hours, and the surface resistivity was measured in the same manner as described above. . The results are also shown in Table 4 below.
In the same table, the smaller the numerical value of the surface specific resistance value, the higher the antistatic effect, and the same applies to the following tables. As a control, a polystyrene plate without an antistatic agent was prepared in the same manner as described above, and evaluated in the same manner as described above.

[0034]

[Table 4] Polymer surface specific resistance (Ω) type 25 ° C 60% RH 25 ° C 40% RH After washing, 25 ° C 60% RH non-added product 10 ¹⁶ or more 10 ¹⁶ or more-A 2 × 10 ¹¹ 3 × 10 ¹² 3 × 10 ¹¹ C 8 × 10 ¹² 7 × 10 ¹³ 8.6 × 10 ¹² D 3 × 10 ¹² 5 × 10 ¹³ 3.5 × 10 ¹² K 1 × 10 ¹³ 9 × 10 ¹³ 1.3 × 10 ¹³ a 9 × 10 ¹⁴ 3 × 10 ¹⁵ 2 × 10 ¹⁵

From Table 4, it can be seen that in the polystyrene plate using the antistatic agent (Polymer A, C, D, K) of the Examples, excellent antistatic properties can be obtained with a small amount of addition even when the humidity conditions are changed. This shows that this effect was maintained even after washing with water. On the other hand, the polystyrene plate using the antistatic agent (Polymer A) of Comparative Example had poor antistatic properties.

(ABS resin) To 100 parts by weight of the ABS resin, 10 parts by weight of each of the polymer of the example and the polymer of the comparative example shown in Table 5 below were added, kneaded with a roll at 220 ° C. for 5 minutes, and then press-molded. Thus, six ABS resin plates were obtained. Each of these ABS resin plates was heated at 25 ° C.
2 in an atmosphere of 60% RH and 25 ° C. and 40% RH
After humidifying for 4 hours, the surface specific resistance value was measured at an applied voltage of 500 V for 1 minute after the application of the voltage using a Hirester resistance measuring apparatus. Next, the sample was subjected to ultrasonic cleaning for 30 minutes, then the surface was wiped off, the humidity was adjusted in an atmosphere of 25 ° C. and 60% RH for 24 hours, and the surface resistivity was measured in the same manner as described above. The results are also shown in Table 5 below.
As a control, an ABS resin plate without an antistatic agent was prepared in the same manner as described above, and the same evaluation as above was performed.

[0037]

[Table 5] Polymer surface specific resistance (Ω) type 25 ° C 60% RH 25 ° C 40% RH After washing, 25 ° C 60% RH additive-free product 10 ¹⁶ or more 10 ¹⁶ or more-B 5 × 10 ¹¹ 3 × 10 ¹² 6.5 × 10 ¹¹ E 4 × 10 ¹² 2 × 10 ¹³ 4.7 × 10 ¹² F 7 × 10 ¹³ 1 × 10 ¹⁴ 7.2 × 10 ¹³ I 2 × 10 ¹¹ 6 × 10 ¹² 3 × 10 ¹¹ B 5 × 10 ¹⁴ 7 × 10 ¹⁵ 8 × 10 ¹⁵ C 8 × 10 ¹⁵ 9 × 10 ¹⁶ 8 × 10 ¹⁶

From Table 5, it can be seen that the ABS resin plate using the antistatic agent (polymers B, E, F, I) of the examples exhibits excellent antistatic properties with a small amount of addition even when the humidity conditions are changed. It can be seen that this effect was maintained even after washing with water. In contrast, the antistatic agents of Comparative Examples (Polymer B,
The antistatic property of the ABS resin plate using (c) was poor.

(Acrylic Resin) 10 parts by weight of each of the polymers of Examples and Comparative Examples shown in Table 6 below were added to 100 parts by weight of an acrylic resin (ER, manufactured by Kuraray Co., Ltd.) and rolled at 200 ° C. for 5 minutes. After kneading, press molding was performed to obtain five acrylic resin plates. These acrylic resin plates were subjected to 25 ° C./60% RH and 25%, respectively.
After conditioning for 24 hours in an atmosphere of 40 ° C. and 40% RH, the surface specific resistance value was measured at an applied voltage of 500 V for 1 minute after the application of the voltage using a Hirester resistance measuring apparatus. Next,
After the acrylic resin plate was subjected to ultrasonic cleaning for 30 minutes, the surface moisture was wiped off and the acrylic resin plate was dried under an atmosphere of 25 ° C. and 60% RH.
After conditioning for 4 hours, the surface resistivity was measured in the same manner as described above. The results are also shown in Table 6 below. As a control, an acrylic resin plate without an antistatic agent was prepared in the same manner as described above, and the same evaluation as described above was performed.

[0040]

[Table 6] Polymer surface specific resistance (Ω) type 25 ° C 60% RH 25 ° C 40% RH After washing, 25 ° C 60% RH non-added product 10 ¹⁶ or more 10 ¹⁶ or more-G 5 × 10 ¹¹ 3 × 10 ¹² 6.4 × 10 ¹¹ H 4 × 10 ¹² 2 × 10 ¹³⁵ 5 × 10 ¹² J 7 × 10 ¹² 1 × 10 ¹³ 7.2 × 10 ¹² L 2 × 10 ¹¹ 6 × 10 ¹² 3.6 × 10 ¹¹ d 5 × 10 ¹⁴ 7 × 10 ¹⁵ 4 × 10 ¹⁵

From Table 6, it can be seen that the acrylic resin plate using the antistatic agent (polymers G, H, J, L) of the examples exhibits excellent antistatic properties with a small amount of addition even when the humidity conditions are changed. It can be seen that this effect was maintained even after washing with water. On the other hand, the acrylic resin plate using the antistatic agent (Polymer D) of the comparative example had poor antistatic properties.

(Polycarbonate resin) To 100 parts by weight of polycarbonate, 5 parts by weight of each of the polymers of Examples and Comparative Examples shown in Table 7 below were added.
After roll kneading at 300 ° C for 5 minutes, press molding,
Six polycarbonate plates were obtained. These polycarbonate plates were subjected to 25 ° C./60% RH and 25 ° C., respectively.
-After humidifying for 24 hours in an atmosphere of 40% RH, the surface specific resistance value was measured one minute after the application of the voltage at a voltage of 500 V using a Hirester resistance measuring apparatus. Next, the polycarbonate plate was subjected to ultrasonic cleaning for 30 minutes, then the surface was wiped off, the humidity was adjusted in an atmosphere of 25 ° C. and 60% RH for 24 hours, and the surface resistivity was measured in the same manner as described above. . The results are also shown in Table 7 below. As a control, a polycarbonate plate without an antistatic agent was prepared in the same manner as described above, and evaluated in the same manner as described above.

[0043]

[Table 7] Polymer surface resistivity (Ω) type 25 ° C 60% RH 25 ° C 40% RH After washing, 25 ° C 60% RH additive-free product 10 ¹⁶ or more 10 ¹⁶ or more-A 2 × 10 ¹¹ 7 × 10 ¹¹ 3 × 10 ¹¹ K 5 × 10 ¹² 1 × 10 ¹³ 7 × 10 ¹² J 7 × 10 ¹¹ 4 × 10 ¹² 1 × 10 ¹² L 5 × 10 ¹¹ 2 × 10 ¹² 5 × 10 ¹¹ B 3 × 10 ¹⁴ 1 × 10 ¹⁵ 3 × 10 ¹⁵ C 7 × 10 ¹⁵ 4 × 10 ¹⁶ 4 × 10 ¹⁶

As shown in Table 7, in the polycarbonate plate using the antistatic agent (Polymer A, K, J, L) of the examples, excellent antistatic properties were obtained with a small amount of addition even when the humidity conditions were changed. This shows that this effect was maintained even after washing with water. On the other hand, the polycarbonate plate using the antistatic agent (Polymer B, C) of Comparative Example had poor antistatic properties.

(Polyethylene terephthalate resin) To 100 parts by weight of polyethylene terephthalate, 5 parts by weight of each of the polymers of Examples and Comparative Examples shown in Table 8 below were added, roll-kneaded at 280 ° C for 5 minutes, and then press-molded. Thus, six polyethylene terephthalate plates were obtained. These polyethylene terephthalate plates were subjected to 25 ° C./60% RH and 25 ° C./40%, respectively.
After humidifying for 24 hours in an atmosphere of RH, a voltage of 1 was applied at an applied voltage of 500 V using a high-resistor resistance measuring apparatus.
After a minute, the surface specific resistance was measured. Next, after ultrasonically cleaning this polyethylene terephthalate plate for 30 minutes,
The surface moisture was wiped off, the humidity was adjusted in an atmosphere of 25 ° C. and 60% RH for 24 hours, and the surface resistivity was measured in the same manner as described above. The results are also shown in Table 8 below. As a control, a polyethylene terephthalate plate without an antistatic agent was prepared in the same manner as described above, and evaluated in the same manner as described above.

[0046]

[Table 8] Polymer surface resistivity (Ω) type 25 ° C 60% RH 25 ° C 40% RH After washing, 25 ° C 60% RH additive-free product 10 ¹⁶ or more 10 ¹⁶ or more-A 3 × 10 ¹¹ 5 × 10 ¹¹ 5 × 10 ¹¹ C 4 × 10 ¹² 7 × 10 ¹² 8 × 10 ¹² I 5 × 10 ¹² 9 × 10 ¹² 8 × 10 ¹² L 5 × 10 ¹¹ 1 × 10 ¹² 7 × 10 ^{11 A} 6 × 10 ¹⁴ 1 × 10 ¹⁵ 3 × 10 ¹⁵ B 6 × 10 ¹⁴ 2 × 10 ¹⁵ 4 × 10 ¹⁵

From the above Table 8, it can be seen that in the polyethylene terephthalate plate using the antistatic agent (Polymer A, C, I, L) of the Examples, excellent antistatic properties can be obtained with a small amount of addition even when the humidity conditions are changed. It can be seen that this effect was maintained even after washing with water. On the other hand, the polyethylene terephthalate plate using the antistatic agent (Polymer I or II) of Comparative Example had poor antistatic properties.

(Polyphenylene ether resin) For 100 parts by weight of polyphenylene ether, 1 part of each of the polymers of Examples and Comparative Examples shown in Table 9 below was used.
After adding 0 parts by weight and kneading the rolls at 300 ° C. for 5 minutes, press molding was performed to obtain six polyphenylene ether plates. Each of these polyphenylene ether plates was
After humidifying for 24 hours in an atmosphere of 5 ° C./60% RH and 25 ° C./40% RH, the surface specific resistance value is measured using a Hirester type resistance measuring apparatus at an applied voltage of 500 V and 1 minute after the voltage application. did. Next, the polyphenylene ether plate was subjected to ultrasonic cleaning for 30 minutes, the surface moisture was wiped off, the humidity was adjusted in an atmosphere of 25 ° C. and 60% RH for 24 hours, and the surface resistivity was measured in the same manner as described above. did. The results are also shown in Table 9 below. As a control, a polyphenylene ether plate without an antistatic agent was prepared in the same manner as described above, and the same evaluation as described above was performed.

[0049]

[Table 9] Polymer surface specific resistance (Ω) type 25 ° C 60% RH 25 ° C 40% RH After washing, 25 ° C 60% RH additive-free product 10 ¹⁶ or more 10 ¹⁶ or more-D 7 × 10 ¹² 9 × 10 ¹² 1 × 10 ¹³ E 2 × 10 ¹² 7 × 10 ¹² 7 × 10 ¹² F 5 × 10 ¹² 1 × 10 ¹³ 3 × 10 ¹³ G 8 × 10 ¹¹ 3 × 10 ¹² 1 × 10 ¹² C 7 × 10 ¹⁵ 2 × 10 ¹⁶ 2 × 10 ¹⁶ D 2 × 10 ¹⁴ 5 × 10 ¹⁴ 8 × 10 ¹⁵

As can be seen from Table 9, in the polyphenylene ether plate using the antistatic agent (polymers D, E, F, G) of the examples, excellent antistatic properties can be obtained with a small amount of addition even when the humidity conditions are changed. It can be seen that this effect was maintained even after washing with water. On the other hand, the polyphenylene ether plate using the antistatic agent (Polymer C, D) of Comparative Example had poor antistatic properties.

(Nylon 66 resin) Nylon 66 resin 1
To 100 parts by weight, 10 parts by weight of each of the polymers of Examples and Comparative Examples shown in Table 10 below were added,
After roll kneading at 280 ° C for 5 minutes, press molding,
Six nylon 66 plates were obtained. These nylon 66 plates were subjected to 25 ° C./60% RH and 25 ° C./40%, respectively.
After humidifying for 24 hours in an atmosphere of RH, a voltage of 1 was applied at an applied voltage of 500 V using a high-resistor resistance measuring apparatus.
After a minute, the surface specific resistance was measured. Next, the nylon 66 plate was subjected to ultrasonic cleaning for 30 minutes, then the surface moisture was wiped off, the humidity was adjusted in an atmosphere of 25 ° C. and 60% RH for 24 hours, and the surface resistivity was measured in the same manner as described above. did.
The results are also shown in Table 10 below. As a control, a nylon 66 plate without an antistatic agent was prepared in the same manner as described above, and evaluated in the same manner as described above.

[0052]

[Table 10] Polymer surface resistivity (Ω) type 25 ° C 60% RH 25 ° C 40% RH After washing, 25 ° C 40% RH additive-free product 10 ¹⁶ or more 10 ¹⁶ or more-B 6 × 10 ¹¹ 1 × 10 ¹² 9 × 10 ¹¹ H 4 × 10 ¹² 9 × 10 ¹² 9 × 10 ¹² J 5 × 10 ¹² 9 × 10 ¹² 8 × 10 ¹² L 3 × 10 ¹¹ 8 × 10 ¹¹ 1 × 10 ^{12 A} 4 × 10 ¹⁴ 9 × 10 ¹⁴ 2 × 10 ¹⁵ C 7 × 10 ¹⁵ 3 × 10 ¹⁶ 8 × 10 ¹⁶

As shown in Table 10, the nylon 66 plate using the antistatic agent (Polymer B, H, J, L) of the example is as follows.
It can be seen that excellent antistatic properties were obtained with a small amount of addition even when the humidity conditions were changed, and that this effect was maintained even after washing with water. On the other hand, the nylon 66 plate using the antistatic agent (Polymer I or C) of Comparative Example had poor antistatic properties.

(Poly-p-phenylene terephthalamide resin) To 100 parts by weight of poly-p-phenylene terephthalamide, 10 parts by weight of each of the polymers of Examples and Comparative Examples shown in Table 11 below were added. After roll kneading for minutes, press molding was performed to obtain six poly p-phenylene terephthalamide plates. Each of these poly p-phenylene terephthalamide plates was
After humidifying for 24 hours in an atmosphere of 60 ° C./60% RH and 25 ° C./40% RH, the surface specific resistance was measured at an applied voltage of 500 V for 1 minute after the application of the voltage using a Hirester resistance measuring apparatus. . Next, the poly p-phenylene terephthalamide plate was subjected to ultrasonic cleaning for 30 minutes, the surface moisture was wiped off, and the humidity was adjusted in an atmosphere of 25 ° C. and 60% RH for 24 hours. The resistance was measured. The results are also shown in Table 11 below. As a control, a poly p-phenylene terephthalamide plate without an antistatic agent was prepared in the same manner as described above, and the same evaluation as described above was performed.

[0055]

[Table 11] Polymer surface specific resistance (Ω) type 25 ° C 60% RH 25 ° C 40% RH After washing, 25 ° C 60% RH additive-free product 10 ¹⁶ or more 10 ¹⁶ or more-A 4 × 10 ¹¹ 9 × 10 ¹¹ 1 × 10 ¹² C 5 × 10 ¹² 8 × 10 ¹² 9 × 10 ¹² D 6 × 10 ¹² 9 × 10 ¹² 1 × 10 ¹³ J 3 × 10 ¹² 9 × 10 ¹² 9 × 10 ¹² B 5 × 10 ¹⁴ 2 × 10 ¹⁵ 3 × 10 ¹⁵ C 8 × 10 ¹⁵ 3 × 10 ¹⁶ 3 × 10 ¹⁶

As can be seen from Table 11, the poly-p-phenylene terephthalamide plate using the antistatic agent (Polymer A, C, D, J) of the example was excellent with a small amount of addition even when the humidity conditions were changed. Antistatic properties are obtained, even after washing with water
It can be seen that this effect was maintained. On the other hand, in the poly p-phenylene terephthalamide plate using the antistatic agent (Polymer B, C) of the comparative example, the antistatic property was poor.

[0057]

As described above, the antistatic agent of the present invention comprises:
It can be used by kneading it into plastic, has no coloring problem, quickly exhibits excellent antistatic properties with a small amount of addition, maintains this effect for a long period of time, and has excellent washing resistance. For this reason, by using the antistatic agent of the present invention, excellent antistatic properties can be easily provided at low cost for a long period of time to plastic molded articles for various uses.

Claims (1)

[Claims] 1. An antistatic agent comprising an aromatic polymer containing at least one of a sulfonic acid group and a sulfonic acid group, wherein the weight average molecular weight is 1,000 to 5
An antistatic agent, wherein the total introduction ratio of the sulfonic acid groups and the sulfonic acid groups is in the range of 3 to 38 mol%.