JPH10231328A - Antistatic agent for resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain antistatic agent for a resin comprising an aromatic polymer containing a specific sulfonic acid base salt, hardly causing a color problem, capable of manifesting excellent antistatic properties by a small adding amount within a short time, and maintaining the antistatic properties for a long time and excellent in resistance to washing. SOLUTION: This antistatic agent for a resin comprises a polymer consisting essentially of a repeating unit 1 of formula I (X is H or methyl; M is an organic amines or an organic phosphorus; SO3 M group is positioned at 3- to 5-positions of a benzene ring) and a repeating unit 2 of formula II [M is a basic organic group of at least one of organic amines and organic phosphoruses; (n) is 0 or 1; at least one of SO3 M group exists at the ortho-position of the benzene ring] regulated so that the molar ratio of the unit 1 to the unit 2 may be within the range of (98/2) to (80/20), and having 1,000-1,000,000 weight average molecular weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Plastic (resin) 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 describes a technique for imparting an antistatic property by adding an epihalohydrin-based polymer such as epichlorohydrin rubber to a plastic. Japanese Patent Application Laid-Open No. 58-18836 describes a technique for adding an antistatic property by adding a polyetheresteramide to a plastic. However, with these technologies,
If the conductive polymer is not added in a large amount, sufficient antistatic properties cannot be imparted, and if added in a large amount, there is a problem that the mechanical properties of the plastic deteriorate.

In addition, JP-A-48-65237 describes a method of adding a tertiary amine salt of polystyrenesulfonic acid to plastic. According to this method, it is possible to impart an antistatic property to plastic by adding a relatively small amount of the conductive polymer, but the antistatic property after washing with water is maintained to some extent, but it is still insufficient. In addition, there is a problem that it takes some time until the antistatic property is developed.

Further, JP-A-8-104787 describes that a tertiary amine salt of polystyrenesulfonic acid and an amine sulfate salt are used in combination, but the antistatic ability is not yet sufficient. In addition, Japanese Patent Publication No. 45-2924
No. 0 describes a method in which a sulfonated polystyrene and a fixing agent are used in combination for the purpose of improving the washing resistance. 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. JP-A-59-36159 describes that sodium polystyrene sulfonate having a sulfonic acid group introduction ratio of 40 to 100 mol% is used as a kneading type antistatic agent. The antistatic agent does not have sufficient antistatic properties after washing with water.

[0008]

Therefore, the present invention has no problem of coloring, can exhibit excellent antistatic properties in a short time with a small amount of addition, and can maintain it for a long period of time. Moreover, it is an object of the present invention to provide a kneading-type resin antistatic agent having excellent washing resistance.

[0009]

In order to achieve the above object, an antistatic agent for a resin according to the present invention is represented by the repeating unit 1 represented by the above formula (Chemical Formula 1) and the formula (Chemical Formula 2). The repeating unit 2 is an essential component, the molar ratio of the repeating unit 1 and the repeating unit 2 is in the range of repeating unit 1 / repeating unit 2 = 98/2 to 80/20, and the weight average molecular weight is 1,000 to 1,000,000. Consisting of a polymer in the range of

As described above, the antistatic agent for a resin according to the present invention comprises an aromatic polymer containing a special sulfonate group, and the polymer has a sulfonic acid at a meta-position or a para-position of a benzene ring. The repeating unit 1 having a base bonded thereto and the repeating unit 2 having a sulfonate group bonded to the ortho position of the benzene ring are contained in a specific ratio, and the weight average molecular weight is in a specific range. Such a resin antistatic made of a specific polymer can be used by kneading it into the resin, and there is no problem of coloring. Further, the polymer has a short electrostatic voltage decay time. Therefore, the resin antistatic agent of the present invention comprising the polymer has excellent antistatic properties, can exhibit excellent antistatic properties in a short time with a small amount of addition, and can maintain it for a long time. In addition, it has excellent washing resistance.

In the antistatic agent for a resin according to the present invention, the M ₃ of the SO ₃ M group in the above formulas (1) and (2)
Is preferably a primary amine. That is, the resin antistatic agent comprising the aromatic polymer containing a sulfonic acid primary amine base is particularly excellent in antistatic performance and water washing resistance.

In the present invention, the content of the repeating unit 1 and the repeating unit 2 in the polymer is as follows:
For example, it can be obtained as follows. First,
The content of all sulfonate groups in the polymer is calculated from the ratio of carbon atoms to sulfur atoms measured by an elemental analyzer.
Also, by measurement of NMR (nuclear magnetic resonance) spectrum,
The amount of the sulfonate group bonded to the para position of the benzene ring is
It is calculated from the proton ratio of the aromatic ring. Then, the amount of the sulfonic acid group bonded to the para-position of the benzene ring was subtracted from the total sulfonic acid group content to obtain a sulfonic acid group bonded to the ortho-position of the benzene ring. And the remaining amount of the deduction is the repetition unit 1, and the ratio can be calculated from these values. In the production of the antistatic agent for a resin of the present invention, a sulfonate group is hardly introduced at the meta position of the benzene ring, and therefore can be ignored in this measurement.

In the present invention, the weight average molecular weight can be measured, for example, by gel permeation chromatography.

[0014]

Next, an embodiment of the present invention will be described.

The repeating unit 2 has the following modes. First, in the above formula (Formula 2), when n is 0,
The SO ₃ M group is located at the ortho position (position 2 or 6) of the benzene ring.
And n is 1, (1) two SO ₃ M groups are in the ortho position (positions 2 and 6) of the benzene ring, and (2) one SO ₃ M group is in the benzene ring. Is in the ortho position (position 2 or 6) and the other SO ₃ M group is in the meta or para position (any of positions 3 to 5) of the benzene ring
There are times when there is.

The essential monomer units constituting the sulfonic acid group-containing aromatic polymer according to the present invention include styrene sulfonic acid or a salt thereof, α-methylstyrene sulfonic acid or a salt thereof, vinyl toluene sulfonic acid or a salt thereof, and the like. These can be used alone or in combination of two or more. Of these, 2 to 20 mol%, preferably 5 to 15 mol%, are the repeating unit 2 having a sulfonate group at the ortho position, and the remainder is the repeating unit 1.
If the amount of the repeating unit 2 is less than 2 mol%, the antistatic ability is insufficient, while if it exceeds 20 mol%, the performance may not be similarly satisfied.

In the sulfonic acid group-containing aromatic polymer, the salt constituting the sulfonic acid salt group is at least one of an organic amine and an organic phosphorus.

Examples of the organic amine include primary amines such as butylamine, hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine and monoethanolamine, dibutylamine and dihexylamine. , Dioctylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine,
Secondary amines such as dioctadecylamine, diethanolamine and morpholine, and tertiary amines such as tributylamine, trihexylamine, trioctylamine, tridecylamine, tridodecylamine, tritetradecylamine, trihexadecylamine and trioctadecylamine Secondary amines. Also, mixtures thereof can be used. Of these, primary amines are preferred from the viewpoints of antistatic properties and washing resistance as described above, and particularly preferred are n-dodecylamine, n-tetradecylamine, and n-hexadecylamine. Is a monoalkylamine.

Examples of the organic phosphorus include tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, tetraoctylphosphonium,
Examples thereof include tetraphenylphosphonium, methyltriphenylphosphonium, benzyltriphenylphosphonium, and methyltri (m-tolyl) phosphonium. Of these, tetraphenylphosphonium and benzyltriphenylphosphonium are preferred from the viewpoints of antistatic properties and heat resistance.

The polymer according to the present invention can be composed of only the repeating unit 1 and the repeating unit 2, but may be a copolymer obtained by copolymerizing another repeating unit as desired. Such other repeating units include the following monomers. For example, styrene,
Aromatic hydrocarbon monomers such as α-methylstyrene, vinyltoluene, vinylnaphthalene, etc., aromatic sulfonic acid monomers such as vinyltoluenesulfonic acid or a salt thereof, vinylnaphthalenesulfonic acid or a salt thereof, butadiene, isoprene, pentadiene, cyclopentadiene, etc. Conjugated dienes, butadiene, isoprene, pentadiene, sulfonated conjugated dienes such as cyclopentadiene or salts thereof, olefins such as ethylene, propylene, butene and isobutylene, acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid And itaconic acid, citraconic acid or organic amine salts of these acids, 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.

When the other monomer is introduced, the total content of the repeating unit 1 and the repeating unit 2 in the polymer according to the present invention is usually 50% by weight or more, preferably 70 to 98% by weight. is there. If the amount is less than 50% by weight, the antistatic ability may be insufficient.

The weight average molecular weight of the polymer according to the present invention is in the range of 1,000 to 100,000,000, and if the weight average molecular weight is out of the range, the antistatic ability becomes insufficient. The preferred weight average molecular weight is 2000
It is in the range of ５００500,000.

Next, the polymer according to the present invention is:
It is obtained by polymerizing a monomer capable of deriving the repeating unit 1 and the repeating unit 2 and, if necessary, the other monomer by a known method, for example, radical polymerization, anionic polymerization, cationic polymerization or the like. Examples of the method for producing the polymer include the following method. (1) A method in which a monomer corresponding to the repeating unit 1 having no sulfonic acid group is polymerized and then sulfonated. (2) A method in which a monomer corresponding to the repeating unit 1 having no sulfonic acid group is copolymerized with another monomer and then sulfonated. (3) A method of copolymerizing monomers containing sulfonic acid groups of repeating units 1 and 2. (4) A method of copolymerizing a monomer containing a sulfonic acid group of repeating units 1 and 2 with another monomer.

Of these methods, it is economically preferable to carry out the above methods (1) and (2) industrially.

In the present invention, the amount (molar ratio) of the repeating unit 1 and the repeating unit 2 in the obtained polymer is set in the above-mentioned specific range, for example, by adding sodium p-styrenesulfonate and sodium m-styrenesulfonate. It is preferable to adopt a method such as a method of copolymerizing at least one of the above and o-styrenesulfonic acid at a predetermined ratio or a method of sulfonating polystyrene with sulfuric anhydride under predetermined conditions.

Next, the antistatic agent for a resin 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), Examples include vinyl chloride resin, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), polyethylene terephthalate resin, polyamide resin, polycarbonate resin, polyphenylene ether 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 with respect to 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 the antistatic agent for a resin of the present invention is added to various plastics, if necessary, a lubricant such as a higher alcohol, a fatty acid amide, a fatty acid metal soap, an antioxidant, an ultraviolet absorber, a silicon derivative, An antiblocking agent, a coloring agent, a filler, a plasticizer, other known antistatic agents, and other additives can be used in combination.

The form of the antistatic agent for resin of the present invention is not particularly limited, and may be, for example, any of powder, wax, and paste.

In the molding of plastics using the resin antistatic agent of the present invention, for example, first, the resin antistatic agent and pellets or powdered plastics are uniformly mixed with a Henschel mixer or the like. Alternatively, it can be carried out by preparing an antistatic agent-added compound using an extruder or the like, and then supplying the mixture or the compound to various molding machines and molding. 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 for resin of the present invention is added can be formed into various kinds of plastics such as sheets and films by a general plastic molding method such as press molding, injection molding, extrusion molding, blow molding, and calendar molding. It can be processed into a shaped molded product.

[0032]

Next, examples will be described together with comparative examples.

First, according to the following Synthesis Examples 1, 2, and 3, the polymers (A to L) of the examples and the polymers (a to
D) were synthesized respectively. In addition, the said polymer (A ~)
The measurement of the weight average molecular weight of L, a to d) and the ratio between the repeating unit 1 and the repeating unit 2 were performed by the following methods, respectively.

(Weight average molecular weight of polymer) Standard polystyrene was used as a standard substance, and TSK was used as a separation column.
-G4000HXL and G2500HXL (7.8 mmI
(D × 30 cm, manufactured by Tosoh Corporation) and gel permeation chromatography (GPC) using an ultraviolet detector (measuring wavelength: 266 nm).

(Measurement of Ratio of Repeating Unit 1 to Repeating Unit 2 in Polymer) When the polymer is a sulfonated homopolymer of an aromatic hydrocarbon monomer, an elemental analyzer (E
A-1108 type (manufactured by Carlo Elba) was used to calculate the sulfonic acid group introduction rate per unit of aromatic ring from the ratio of carbon atoms to sulfur atoms. When a sulfate was contained in the water-soluble polymer, the amount was determined by ion chromatography, and the amount of sulfur was subtracted from the amount of sulfur obtained by an elemental analyzer.

The introduction ratio of the sulfonic acid group at the para position of the aromatic ring is as follows:
¹ H-NMR spectrum (measurement machine: JNM-EX270
And the peak intensity (a) around 7.6 ppm and the peak intensity (b) around 8.1 ppm, and (b / 2) / (a / 3 + b / 2) × 100 It was determined by the formula. The introduction rate of the sulfonic acid group at the ortho position of the aromatic ring was defined as the value obtained by subtracting the introduction rate of the para-position from the introduction rate of the sulfonic acid group obtained by the elemental analyzer.

When the polymer is a sulfonated copolymer of an aromatic hydrocarbon monomer and a conjugated diene, the sulfonic acid group introduction rate of the conjugated diene monomer unit is set to 100%, and the sulfonic acid group of the aromatic hydrocarbon monomer unit is set to 100%. The introduction rate was calculated from the ratio of carbon atoms to sulfur atoms measured by an element analyzer. In this case, when a sulfate was contained in the water-soluble polymer, the amount was determined by ion chromatography, and the amount of sulfur was subtracted from the amount of sulfur obtained by an elemental analyzer. The sulfonic acid group introduction rate at the para-position of the aromatic ring was determined by measuring the ¹ H-NMR spectrum (the measuring device was the same as described above), and the peak intensity around 7.6 ppm (a)
From the peak intensity (b) around 8.1 ppm, (b /
2) It was obtained from the equation of (a / 3 + b / 2) × 100. The introduction rate of the sulfonic acid group at the ortho position of the aromatic ring was defined as the value obtained by subtracting the introduction rate of the para-position from the introduction rate of the sulfonic acid group obtained by the elemental analyzer.

(Synthesis Example 1) 100 parts by weight of polystyrene having a weight average molecular weight of 7000 was added to 1,2-dichloroethane 40
0 parts by weight, and 1.0 part by weight of acetophenone was further added to prepare a raw material solution. This raw material solution was continuously supplied to a sulfonation reactor equipped with a turbine-type stirrer together with SO _{3 as} a sulfonating agent, and a sulfonation reaction was performed at 45 ° C. In this case, the feed rate is 24 g of the raw material solution.
/ Min, SO ₃ 4.25 g / min. The molar ratio of SO _{3 to} styrene units in polystyrene is 1.15.
It is. The reactor is equipped with a jacket and has a capacity of 40.
0 ml. After distilling off the solvent from the obtained sulfonated product, it was further dried to obtain a powdery polystyrenesulfonic acid. This was dissolved in ethanol, neutralized with dodecylamine, concentrated and dried to obtain polydecylamine dodecylamine salt [Polymer (A)] as a solid.

The weight average molecular weight of the obtained polystyrene dodecylamine salt was 28,000. Further, as a result of analyzing the obtained polystyrene sulfonate, the total sulfonate group introduction rate to the styrene unit was 102%, the sulfonate group introduction rate to the para position was 90%, and the sulfonate group introduction rate to the ortho position was 90%. It was 12%.

On the other hand, polymers (C), (D), (H),
The synthesis of (I), (J), (K) and (L) was carried out in exactly the same manner as the synthesis of the polymer (A), except that the raw materials shown in Table 1 below were used in the proportions shown in the same table. went.

In Table 1 below, as the organic amine and organic phosphorus neutralizing sulfonic acid, (A) is dodecylamine, and (C) is dodecylamine / ethanol octadecylamine = 8/2 (weight). Mixture),
(D) is tridodecylamine, (H) is tetradecylamine, (I) is tritetradecylamine, (J) is dioctadecylamine, (K) is tetrabutylphosphonium, (L) is didecylmethylamine, (B) is dodecylamine.

(Synthesis example 2) 10 parts by weight of styrene, neutralized salt of p-styrenesulfonic acid with tetradecylamine 80
Parts by weight, 10 parts by weight of a neutralized salt of o-styrenesulfonic acid with tetradecylamine were dissolved in 400 parts by weight of toluene. After this dissolved product was replaced with nitrogen, 1.5 parts by weight of benzoyl peroxide was added, and the mixture was polymerized at 90 ° C. for 6 hours. The obtained polystyrene sulfonic acid tetradecylamine salt [Polymer (B)] had a weight average molecular weight of 200,000.

On the other hand, polymers (E), (F), (G),
The synthesis of (a), (c) and (d) was performed in exactly the same manner as the synthesis of the monomer (B), except that the raw materials shown in Table 1 below were used in the proportions shown in the same table.

Synthesis Example 3 100 parts by weight of polystyrene having a weight average molecular weight of 20,000 was dissolved in 400 parts by weight of 1,2-dichloroethane, and 1000 parts by weight of concentrated sulfuric acid was added.
The reaction was carried out by stirring at 80 ° C. for 3 hours. Add 10 reaction mixtures
After dilution with 00 parts by weight of water, the mixture was neutralized with an aqueous sodium hydroxide solution. After concentration, sodium sulfate was removed by a recrystallization method to obtain an aqueous solution of sodium polystyrenesulfonate. This was treated with an ion exchange resin and converted into polystyrene sulfonic acid, and then neutralized with a solution of dodecylamine salt in ethanol to obtain polystyrenesulfonic acid dodecylamine salt [polymer (b)]. The weight average molecular weight was 80,000, the total sulfonic acid group introduction rate per styrene unit was 100%, and the sulfonic acid group introduction rate in the para position was 60%.
%, And the introduction ratio of the sulfonic acid group into the ortho position was 40%.

[0045]

[Table 1]

The polymers (A to L) of the examples thus obtained and the polymers (A to L) of the comparative examples were
Introduction rate of sulfonate group to aromatic ring, molar ratio of repeating unit 1 to repeating unit 2 (unit 1 / unit 2), weight average molecular weight (Mw), weight average molecular weight (Mw) and number average molecular weight (Mn) The ratio (Mw / Mn) is shown in Table 2 below.

[0047]

[Table 2]

Next, the performance of the polymers (A to L) of the examples and the polymers (A to D) of the comparative examples when used in the following three kinds of resins was evaluated.

(Polystyrene resin) Polystyrene 100
10 parts by weight of each of the polymers of Examples and Comparative Examples shown in Table 3 below were added to the parts by weight,
After roll kneading at 5 ° C. for 5 minutes, press molding was performed to obtain six polystyrene plates. Each of these polystyrene plates was placed in an atmosphere of 25 ° C. and 60% RH (relative humidity) for 2 hours.
After humidifying for 4 hours, the surface specific resistance value was measured at an applied voltage of 500 V for one minute after the application of the voltage using a Hirester type resistance measuring device (manufactured by Mitsubishi Yuka Co., Ltd., same hereafter). In addition, an electrostatic voltage decay characteristic measuring instrument (Type 406D, Electro
-Tech System. Inc., USA, the same applies hereinafter), and after applying a voltage of 5 KV, a 99% decay period (second) of the electrostatic voltage was measured. Next, this polystyrene plate was
After ultrasonic cleaning for 0 minutes, wipe off the surface moisture
After conditioning for 24 hours in an atmosphere of 60 ° C. and 60% RH, the surface resistivity and the static voltage 99% decay period (second) were measured in the same manner as described above. The results are also shown in Table 3 below. In the same table, the smaller the value of the surface specific resistance and the value of the static voltage 99% decay period, the higher the antistatic effect is, and the surface specific resistance is the same value and the electrostatic voltage 9
When the 9% decay periods are different, a smaller decay period value indicates a higher antistatic effect. This is shown in Table 4 below.
The same applies to Table 5 and Table 5. As a control, a polystyrene plate without an antistatic agent was prepared in the same manner as described above, and the same evaluation as described above was performed.

[0050]

[Table 3]

From the above Table 3, it can be seen that in the polystyrene plate using the antistatic agent for resin [Polymer (A), (D), (F), and (K) in Examples, excellent antistatic properties were obtained with a small amount of addition. It can be seen that this effect was maintained even after washing with water. On the other hand, in the polystyrene plate using the resin antistatic agent [Polymer (d), (b)] of the comparative example, compared with the polystyrene plate using the resin antistatic agent of the example, the electrostatic voltage decay period was reduced. And the antistatic ability was poor.

(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 4 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.
After humidifying in an atmosphere of 60% RH for 24 hours, the surface specific resistance value was measured using an Hi-Rester type resistance measurement device at an applied voltage of 500 V and one minute after the voltage application. Further, after applying a voltage of 5 KV, a 99% decay period (second) of the electrostatic voltage was measured using an electrostatic voltage decay characteristic measuring device. Next, the sample was subjected to ultrasonic cleaning for 30 minutes, the surface moisture was wiped off, and the sample was conditioned in an atmosphere of 25 ° C. and 60% RH for 24 hours. 99%
The decay period (seconds) was measured. The results are also shown in Table 4 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.

[0053]

[Table 4]

From the above Table 4, it can be seen that in the ABS resin plate using the resin antistatic agent [Polymer (B), (C), (G), (I)] in Example, a small amount was obtained as in the case of the polystyrene plate. It can be seen that excellent antistatic properties were obtained with the addition amount of, and this effect was maintained even after washing with water. On the other hand, in the ABS resin plate using the resin antistatic agent [Polymer (a), (b)] of the comparative example, the electrostatic voltage decay period was shorter than that of the ABS resin plate using the resin antistatic agent in the example. And the antistatic ability was poor.

(Acrylic resin) To 100 parts by weight of an acrylic resin (ER, manufactured by Kuraray Co., Ltd.), 10 parts by weight of each of the polymers of Examples and Comparative Examples shown in Table 5 below were added and rolled at 200 ° C. for 5 minutes. After kneading, press molding was performed to obtain six acrylic resin plates. After humidifying these acrylic resin plates in an atmosphere of 25 ° C. and 60% RH for 24 hours, respectively, the surface specific resistance value after applying the voltage at an applied voltage of 500 V for 1 minute was measured using a Hirester-type resistance measuring apparatus. It was measured. Further, after applying a voltage of 5 KV, a 99% decay period (second) of the electrostatic voltage was measured using an electrostatic voltage decay characteristic measuring device. Next, this acrylic resin plate was
After ultrasonic cleaning for 25 minutes, wipe off the surface moisture and
After humidifying in an atmosphere of 60% RH for 24 hours, the surface resistivity and the static voltage 99% decay period (second) were measured in the same manner as described above. The results are also shown in Table 5 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.

[0056]

[Table 5]

From the above Table 5, the acrylic resin plate using the antistatic agent for resin [Polymer (E), (H), (J), (L)] of the example shows the polystyrene plate and ABS.
As in the case of the resin plate, excellent antistatic properties were obtained with a small amount of addition, and this effect was maintained even after washing with water. On the other hand, in the acrylic resin plate using the resin antistatic agent [Polymer (b), (c)] of the comparative example, the electrostatic voltage decay period was shorter than that of the acrylic resin plate using the resin antistatic agent in the example. And the antistatic ability was poor.

[0058]

As described above, the antistatic agent for resin of the present invention can be used by kneading it into plastic.
There is no problem of coloring, and excellent antistatic properties are quickly exhibited with a small amount of addition, and this effect is maintained for a long time, and the washing resistance is also excellent. For this reason, the use of the antistatic agent of the present invention makes it possible to easily and inexpensively, without impairing the characteristics of plastic, for various uses, especially for plastic molded products used for applications that come into contact with water. Excellent antistatic properties can be imparted for a long period of time. Also,
The plastic molded article provided with the antistatic property by the antistatic agent for resin of the present invention can be freely colored, and the degree of freedom in designing a product using the plastic molded article increases.

Claims (2)

[Claims] 1. A repeating unit 1 represented by the following formula (Formula 1) and a repeating unit 2 represented by the following formula (Formula 2)
Is an essential component, and the molar ratio of the repeating unit 1 and the repeating unit 2 is such that the repeating unit 1 / the repeating unit 2 = 9
8/2 to 80/20, and the weight average molecular weight is 1
An antistatic agent for a resin comprising a polymer in the range of 000 to 1,000,000. Embedded image Embedded image 2. The antistatic agent for a resin according to claim 1, wherein in the formulas (1) and (2), M in the SO ₃ M group is a primary amine.