JPH0525463A - Antistatic agent - Google Patents

Abstract

PURPOSE:To obtain a polymeric antistatic agent having high antistatic properties, not causing surface staining due to bleed-out and having persistent performances by forming a copolymer comprising specified repeating units each having a polyester structure as a side chain and specified ionic repeating units. CONSTITUTION:The objective polymeric antistatic agent which is a copolymer comprising repeating units of formulas I and II, having a weight ratio of [I] to [II] in a range of 10:90 to 90:10 and an intrinsic viscosity etainh of 0.02 or above. In formula I, R<1> is a 1-20C alkyl group or an aralkyl group; R<2> is an aliphatic hydrocarbon group; R<3> is a group of formula III (wherein R<5> is a 1-20C alkyl group, a hydrogen atom or a halogen atom; and (m) is an integer of 1-4) or the like; R<4> is a hydrogen atom or a methyl group; and (n) is 2-200. In formula II, R<6> is a hydrogen atom or a methyl group; and X is an ionic residue containing an ammonium salt or a metal salt.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel antistatic agent. In particular, it relates to a novel high molecular weight antistatic agent which exhibits excellent antistatic performance for a long period of time by kneading or coating with a resin, and an antistatic resin composition using the same.

[0002]

2. Description of the Related Art Generally, polymer materials are excellent in electrical insulation and thus are easily charged, and dust is attached to molded products to impair the appearance. Trouble occurs. In addition, when it is used in electric products, it has major problems such as malfunction caused by accumulated static electricity.

In order to solve such a problem, conventionally, various surfactants have often been applied to the surface of a molded article so as to have an antistatic property.
However, although this method is simple and quick-acting, it has serious problems in durability such as stickiness remaining on the surface of the resin and the antistatic agent easily peeling off. On the other hand, as a method of obtaining stable antistatic performance for a longer period of time, a method of kneading an antistatic agent into the resin itself in advance is often employed. Unlike the coating method, the kneading method prevents long-term antistatic because even if the surface antistatic agent layer is lost, the concentration gradient causes the internal antistatic agent to diffuse to the surface and form a new layer. It is said to maintain performance.
However, also in this case, since it is premised that the antistatic agent bleeds out to the surface, problems similar to those caused by coating often occur. That is, even a molded product in which an antistatic agent is kneaded in advance often has a problem of surface contamination, and the antistatic agent layer on the surface is easily lost by wiping with water, so that the antistatic property is temporarily lost. The phenomenon of being seen is seen.

In order to solve these various problems, a high molecular weight antistatic agent has been proposed in which a monomer having an antistatic property is used alone or is copolymerized with various monomers and macromonomers. However, even in these methods, it is difficult to achieve a high level of adhesion to the resin that is the base material, compatibility and antistatic properties, so the surface resistance is sufficiently reduced,
The goal of maintaining its performance over a long period of time is not completely satisfied, and further improvements have been desired.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an antistatic agent having a high antistatic property, no surface contamination due to bleed-out, and whose performance does not change over a long period of time. To do.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a repeating unit represented by the following general formula [I] having a polyester structure as a side chain and a main chain We have developed a copolymer consisting of an ionic repeating unit represented by the following general formula [II] and found that this structure exhibits excellent performance as an antistatic agent.

[0007]

[Chemical 5]

(In the formula, R ¹ is an alkyl group having 1 to 20 carbon atoms or an aralkyl group, R ² is an aliphatic hydrocarbon group, and R ^{3 is}
Is

[0009]

[Chemical 6]

Or --CO-- (wherein R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom, m = 1 to an integer of 4 and L = 1 to an integer of 10), R ³ In

[0011]

[Chemical 7]

A urethane bond is formed adjacent to -O-.

R ⁴ is a hydrogen atom or a methyl group, and n is 2 to
200. )

[0014]

[Chemical 8]

(In the formula, R ⁶ is a hydrogen atom or a methyl group, and X is an ionic residue containing a quaternary ammonium salt or a metal salt.) The present invention will be described in more detail below.

The polymer antistatic agent of the present invention comprises a polyester macromonomer represented by the following general formula [III] and a vinyl-based monomer represented by the following general formula [IV] as an ordinary radical initiator. It is obtained by copolymerizing in the presence.

[0017]

[Chemical 9]

The polyester macromonomer represented by the general formula [III] will be described in detail. [III] In the formula, R ¹ is an alkyl group having 1 to 20 carbon atoms or an aralkyl group.
R ² is an aliphatic hydrocarbon group, preferably a branched or linear aliphatic hydrocarbon group having 3 to 8 carbon atoms. Specifically, it corresponds to the aliphatic hydrocarbon group of the polyester obtained by ring-opening polymerization of the lactone compound described below, and preferably,

[0019]

[Chemical 10]

And the like.

Preferred as R ³ is

[0022]

[Chemical 11]

Or --CO-- Is mentioned.

R ⁴ is a hydrogen atom or a methyl group,
When R ³ has a —CO—NH— group, it is preferably a methyl group. N representing the degree of polymerization of the polyester structure is
It is usually 2 to 200, preferably 2 to 100, more preferably 2 to 50.

As described above, the preferred polyester macromonomers include the following.

[0026]

[Chemical 12]

[0027]

[Chemical 13]

The polyester macromonomer [III] is usually produced by the following two steps. That is, in the first step, R ¹ —OH (R ¹ is as defined in the above general formula [I])
With an alcohol compound represented by

[0029]

[Chemical 14]

(R ² is synonymous with the above-mentioned general formula [I]) is subjected to ring-opening polymerization to obtain the following polyester alcohol.

[0031]

[Chemical 15]

The initiator R ¹ --OH is preferably methanol, n-butanol, n-hexanol,
Examples include n-octanol and 2-ethylhexanol. As the lactone compound, a lactone having 3 to 8 carbon atoms is preferable, and ε-caprolactone, β-methyl-δ-valerolactone, and β-ethyl-δ-valerolactone are particularly preferable.

This reaction is usually carried out in the presence of a catalyst, and as the catalyst, known catalysts used for ring-opening polymerization of lactones such as mineral acids such as sulfuric acid and phosphoric acid, lithium, sodium, potassium and the like can be used. Alkali metals, alkyl metal compounds such as n-butyl lithium, metal alkoxides such as titanium tetrabutoxide, and the like can be used.

This reaction can be carried out without a solvent, but a solvent may be used depending on the case. As the solvent, toluene,
Xylene, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, chloroform, carbon tetrachloride, etc. can be used. The reaction conditions can be suitably carried out at a temperature between 0 ° C. and 200 ° C. with a reaction time of 10 minutes to 30 hours.

The number n of repeating units can be controlled by the molar ratio of the initiator to the lactone compound, and is about 2 to about 200. Next, the second step consists of reacting the produced polyester alcohol with the following [V] or [VI].

[0036]

[Chemical 16]

([V] In the formula, R ⁷ is

[0038]

[Chemical 17]

(However, R ⁵ , m and L are the above-mentioned general formulas.
Synonymous with [I]. ) R ⁴ is a hydrogen atom or a methyl group. )

[0040]

[Chemical 18]

(R ⁴ is a hydrogen atom or a methyl group, Y is a halogen atom, an alkoxy group having 1 to 8 carbon atoms or an acyloxy group.) Specific examples of the above general formula [V] are, for example,

[0042]

[Chemical 19]

And the like, and the above general formula
As a concrete example of [VI], for example,

[0044]

[Chemical 20]

And the like.

The polyester alcohol and the above [V]
The reaction with is a urethane bond formation reaction, and these may be reacted in an equimolar manner. Although the reaction proceeds even without a catalyst, a tin catalyst such as dibutyltin dilaurate, dibutyltin dioctoate, or dibutyltin mercaptide may be used to accelerate the reaction rate.

Further, the polyester alcohol and the above
The reaction with [VI] is a condensation reaction or a transesterification reaction, and these may be reacted in an equimolar manner. When a condensation reaction is adopted, a hydrogen halide is produced as a by-product, so a deoxidizing agent such as a tertiary amine may be used, or the reaction may be carried out under an inert gas stream. When the transesterification reaction is adopted, known transesterification catalysts such as mineral acids such as hydrochloric acid and sulfuric acid, metal salts such as zinc, calcium and magnesium, metal alkoxides such as titanium tetrabutoxide may be used.

A catalyst may be used in these reactions. As the solvent, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, chloroform, carbon tetrachloride, etc. can be used. The reaction conditions can be suitably carried out at a temperature between 0 ° C and 200 ° C and a reaction time of 30 minutes to 50 hours.

Next, the vinyl monomer represented by the general formula [IV] will be described in detail. The vinyl monomer represented by the general formula [IV] is a conventionally known radically polymerizable monomer. In the formula, R ⁶ is a hydrogen atom or a methyl group, and X is particularly a group having an anionic or cationic ionic residue, or a group capable of easily introducing an ionic group after polymerization. There is no limit. Specific examples of the monomer having a cationic group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylamino (meth) acrylate, dibutylaminoethyl ( Examples thereof include quaternary compounds of nitrogen-containing monomers such as (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminovinyl sulfide, diethylaminoethyl vinyl ether, vinylbenzyl-N, N'-dimethylamine, vinylpyridine and vinylquinoline. This quaternization can be carried out by a known method by adding an inorganic acid such as hydrogen chloride, hydrogen bromide or sulfuric acid, benzyl chloride or benzyl bromide to the tertiary amino group.
It can be carried out by acting a quaternizing agent such as methyl chloride or methyl bromide. The quaternization step may be performed in the state of the monomer before the copolymerization or at any stage after the copolymerization.

As the monomer having an anionic group,
(Meth) acrylic acid, α-chloro (meth) acrylic acid,
Vinyl sulfonic acid, sulfonated styrene, 2-acrylamido-2-methylpropane sulfonic acid, sulfomethyl (meth) acrylate, 2-sulfoethyl (meth) acrylate, 3-sulfoethyl (meth) acrylate, 3
-Sulfopropyl (meth) acrylate, allylsulfonic acid, 1-phenylvinylsulfonic acid, acid phosphooxyethyl (meth) acrylate, 3-chloro-2-
Amidophosphooxypropyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, and other vinyl-based monomers having a carboxyl group, a sulfonic acid group, a phosphoric acid group, or their alkali metal salts, ammonium salts, or dimethyl. Examples thereof include organic amine salts such as amine, triethylamine and triethanolamine, and tetrabutylphosphonium salt. When using a metal salt or an organic salt, even if the corresponding monomer is directly used in the polymerization, or after the polymerization at the stage of the organic acid monomer,
Neutralization may be performed.

Particularly preferred as the monomer having these ionic residues are dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dipropylaminoethyl (meth) acrylate.
A primary ammonium salt and a metal salt of (meth) acrylic acid.

The copolymerization of the polyester macromonomer [III] and the vinyl-based monomer [IV] can be easily carried out by an ordinary radical polymerization method. That is, the polyester macromonomer [III] and the vinyl-based monomer [IV] are usually added with a radical polymerization initiator such as an azo compound or a peroxide in an amount of 0.1 to 10% by weight, and the mixture is added at 0 ° C to 200 ° C. It can be suitably carried out at the temperature of 1 hour to 24 hours. Here, a chain transfer agent such as alkyl mercaptan may be added to adjust the degree of polymerization. As the polymerization method, any of bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization and the like, which are usually employed in radical polymerization, may be used.

The weight ratio of the polyester macromonomer [III] to the vinyl monomer [IV] is 10:90 to 90:10, preferably 20:80 to 80: 2.
The range is 0. The ratio of vinyl monomer [IV] is 10
If the ratio is smaller, the antistatic property is less likely to be exhibited, and if the ratio of the polyester macromonomer [III] is less than 10, the affinity for coating or mixing with other resins is deteriorated, which is not preferable. The copolymer, which is the antistatic agent of the present invention, is converted into methyl ethyl ketone / methanol (7 /
3) Dissolve it in the mixed solvent so that the concentration becomes 0.5 g / dl, and
The intrinsic viscosity ηinh measured at 5 ° C is 0.02 or more. When ηinh is lower than 0.02, not only the advantage of having a high molecular weight is lost, bleeding out from the substrate becomes easy, but also the antistatic performance is deteriorated.

The polymer antistatic agent obtained in the present invention can be kneaded with various resins or applied to the surface thereof to
It lowers the electrical resistance of the resin and exhibits excellent antistatic properties. Further, since it has a side chain that is highly compatible with various resins, it has excellent adhesiveness and compatibility with the resin, and its performance does not change over a long period of time. Further, when the copolymer of the present invention is applied to a resin, it can be used as a solution as it is, but various resins can be used together as a binder in order to improve the texture and strength of the coating film. That is, when an antistatic resin composition prepared by mixing 0.1 to 200 parts by weight of the copolymer of the present invention with 100 parts by weight of a thermoplastic or thermosetting resin as described below is applied as a solution, both are uniformly A coating film that is compatible with or dispersed in is obtained, and a coating film having further improved strength and adhesiveness can be obtained. Antistatic agents containing these binders form a uniform and transparent film by selecting an appropriate binder and compounding ratio, and even though the ion concentration is substantially lowered, only the copolymer is formed. The same antistatic effect as that of the applied one can be obtained.

The thermoplastic resin that can be used here is
There is no particular limitation as long as it is soluble in the solvent, and it may be appropriately selected depending on the type of the substrate to be coated. For example, polyvinyl chloride, polyester, polyamide, polyacrylic acid ester, polyurethane and the like can be mentioned. An antistatic film can be easily formed by dissolving these resins and the high molecular weight antistatic agent of the present invention in a solvent common to both, coating and drying on a substrate.

When the coating film is required to have high strength and chemical resistance, a thermosetting resin can be used as a binder. That is, the high molecular weight antistatic agent of the present invention is mixed with polyols commonly used in the urethane industry, further mixed with a curing agent containing an isocyanate compound, then applied to a substrate, cured, if dried, It is possible to form a highly durable coating film having more excellent abrasion resistance. At this time, a solvent generally used in the urethane industry and additives such as a curing catalyst may be used.

Further, when a quick-drying coating film having a high hardness is required, it is effective to use an ultraviolet curable resin in combination. That is, a high-molecular-weight antistatic agent of the present invention is added to a known ultraviolet-curable resin composition, and the composition is applied to a substrate and then cured by ultraviolet rays according to a conventional method to obtain a coating film having good surface properties in a short time. be able to. The UV-curable resin that can be used here is not particularly limited, and monofunctional monomers such as butyl acrylate, tetrahydrofurfuryl acrylate and vinylpyrrolidone, and polyfunctional oligomers such as polyurethane acrylate and polyester acrylate are appropriately mixed according to a conventional method. And use it.

Since the copolymer of the present invention has high compatibility with these various binder resins, it forms a uniform coating film. The thus-obtained coating film comprising the antistatic resin composition of the present invention has no stickiness, is transparent and tough, has excellent durability, and its surface resistance value does not change even by washing with water.

[0059]

INDUSTRIAL APPLICABILITY As described above, the high molecular weight antistatic agent obtained according to the present invention is not only excellent in antistatic property but also has high compatibility because it has good compatibility with various resins. In addition, the resin composition comprising the high molecular weight antistatic agent of the present invention and various resins can be applied to a substrate such as various plastic materials without stickiness and has excellent coating strength, adhesion and antistatic property. The film is easily formed, and its antistatic property is not deteriorated even by wiping with water. Therefore, it can be applied to all products such as housings of electric products, flooring materials, various film products, and the like that do not want to be adversely affected by static electricity, and can provide stable antistatic properties for a long period of time, which is extremely important industrially.

[0060]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples without departing from the gist thereof. The surface resistance is measured by Yokogawa-HEWLETT-PACKARD 232
Using a 9A type insulation resistance meter, measurement was performed at a measurement voltage of 100 V, measurement conditions of 25 ° C. and 50% RH.

Reference Example A Polyester alcohol synthesis A flask equipped with a stirring blade, a dropping funnel and a gas inlet was sufficiently replaced with dry nitrogen, and then 5.7 g of 2-ethylhexanol and 0.1 g of metallic sodium were charged and stirred. The metallic sodium was dissolved. Next, this flask was immersed in an oil bath at 40 ° C., and 50 g of β-methyl-δ-valerolactone was added dropwise from a dropping funnel while stirring. After 1 hour, the stirring was stopped and the contents of the flask were taken out and dissolved in 500 ml of purified chloroform. 50 this solution
The mixture was poured into 0 ml of deionized water, washed, and the chloroform layer was separated. After repeating this washing once again, the solvent was distilled off from the chloroform solution under reduced pressure to obtain a colorless and transparent polyester alcohol. The hydroxyl value of this product is 5
The acid value was 8.6 KOHmg / g and 0.03 KOHmg / g.

Reference Example B Synthesis of Polyester Macromonomer Polyester alcohol 20.00 synthesized in (A) in a reactor equipped with a stirring blade and a reflux condenser.
g m-isopropenyl-α, α′-dimethylbenzylisocyanate 4.25 g dibutyltin dioctoate (1% toluene solution)
0.12 g was charged, heated to 80 ° C., and reacted for 9 hours. The IR spectrum and H-NMR of the product were measured, and it was confirmed that a polyester macromonomer having the following structure was obtained.

[0063]

[Chemical 21]

Reference Example C Synthesis of Polyester Alcohol A polyester alcohol was obtained in the same manner as in Reference Example A except that β-methyl-δ-valerolactone was changed to ε-caprolactone. The hydroxyl value of this product is 56.78 KO
The Hmg / g and the acid value were 0.50 KOHmg / g.

Reference Example D Polyester Macromonomer Synthesis Using the polyester alcohol synthesized in (C), m
Reference Example B except that the charge amount of -isopropenyl-α-α'-dimethylbenzyl isocyanate was 4.11 g.
A macromonomer based on caprolactone was synthesized in exactly the same manner as in.

Reference Example E Synthesis of Random Copolymer Methyl methacrylate 10.0 g Methacryloyloxyethyl trimethylammonium chloride 10.0 g Azobisisobutyronitrile 0 in a flask equipped with a stirring blade, a reflux condenser and a gas inlet. .9 g was charged, 13 g of toluene and 7 g of n-hexane were added as a solvent to make a uniform solution, and then 8
Polymerization was carried out at 0 ° C. for 8 hours. After the polymerization, the reaction solution was poured into methanol to precipitate a product, which was thoroughly washed with methanol and dried. The yield was almost 100%.

Example 1 Polyester macromonomer synthesized in Reference Example (B) in a flask equipped with a stirring blade, a reflux condenser and a gas inlet.
10.0 g methacryloyloxyethyltrimethylammonium chloride 10.0 g azobisisobutyronitrile 0.2 g n-dodecyl mercaptan 0.4 g and isopropyl alcohol 40 g were charged, and under a nitrogen stream at 70 ° C. for 7 hours and further 95 ° C. It was polymerized for 2 hours. After the polymerization, isopropanol was distilled off and the residue was dried under reduced pressure. Ηinh of the copolymer obtained here is 0.15 dl
/ G.

This copolymer was dissolved in a mixed solution of methylethylketone / methanol in a weight ratio of 7/3 to a concentration of 1 wt%, and a soft vinyl chloride sheet (Mitsubishi Kasei Vinyl Co., Ltd.) was prepared using a # 8 bar coater. It was applied on GA-450 manufactured by the company. This sheet was heated at 110 ° C. for 2 minutes to dry the solvent, and then the surface resistance value was measured to be 8.5.
It was × 10 ⁸ Ω.

Example 2 Polyester macromonomer synthesized in Reference Example (D) in the flask used in Example 1
10.0 g methacryloyloxyethyltrimethylammonium chloride 10.0 g azobisisobutyronitrile 0.2 g and isopropyl alcohol 25 g were charged, and polymerization was carried out at 70 ° C. for 7 hours and further at 95 ° C. for 2 hours under a nitrogen stream. After the polymerization, isopropanol was distilled off and the residue was dried under reduced pressure. ηinh was 0.15 dl / g. This polymer was coated on a soft vinyl chloride sheet in the same manner as in Example 1 and the surface resistance was measured and found to be 8.0 × 10 ⁸ Ω.

Example 3 Polyester macromonomer synthesized in Reference Example (B) in the flask used in Example 1
40.0 g Methacrylic acid 17.0 g Azobisisobutyronitrile 0.6 g and isopropyl alcohol 85 g were charged, and polymerization was carried out at 70 ° C. for 8 hours under a nitrogen stream. After the polymerization, isopropanol was distilled off and the residue was dried under reduced pressure. ηinh is 0.11 dl
/ G. 20 g of this product was dissolved in 200 g of a mixed solvent of methyl ethyl ketone / methanol 7/3, and KO
41.6 g of a 5% methanol solution of H was added, and the mixture was stirred at room temperature for 1 hour. After the reaction, the solvent was distilled off under reduced pressure to obtain 22 g.
The product was obtained. This polymer was applied onto a soft vinyl chloride sheet in the same manner as in Example 1 and the surface resistance value was measured to be 6.5 × 10 ⁹ Ω.

Example 4 3 g of the copolymer obtained in Example 1 and 7 g of vinyl chloride resin powder (P-500 manufactured by Mitsubishi Kasei Vinyl Co., Ltd.) were added to a 9/1 mixture of methyl ethyl ketone / methanol to a concentration of 10 wt.
It melt | dissolved so that it might become%. This solution was cast on a glass plate and dried at 70 ° C. for 6 hours to obtain a 70 μm-thick blend film. This film was colorless and transparent, and the surface resistance value was 2.4 × 10 ⁷ Ω for both front and back surfaces. Furthermore, this film is washed with water for 5 minutes and then at 110 ° C.
Allow to dry for minutes. After leaving this film at room temperature for 1 day, the surface resistance was measured and found to be 3.4 × 10 ⁷ Ω.

Examples 5, 6 Using the copolymers obtained in Examples 2 and 3, Example 4
A blend film with a vinyl chloride resin was prepared in the same manner as in. The obtained films are all colorless and transparent, and have surface resistance values of 1.8 × 10 ⁷ Ω and 9.4, respectively.
It was × 10 ⁷ Ω.

Example 7 The copolymer synthesized in Example 1 and polyvinyl butyral resin (Sekisui Chemical S-REC BMS) were dissolved in ethanol at a mixing ratio of 2/8 to prepare a solution having a concentration of 10 wt%. From this solution, a film having a thickness of 70 μ was prepared in the same manner as in Example 4. This film was colorless and transparent, and had a surface resistance value of 6.0 × 10 ⁹ Ω.

Example 8 The copolymer synthesized in Example 1 and the polyester resin (Toyobo Byron 200) were used in a ratio of 3/7 tetrahydrofuran / methyl ethyl ketone / methanol 60/30 /
It was dissolved in 10 mixed solvents to prepare a solution having a concentration of 10 wt%. From this solution, a film having a thickness of 70 μ was prepared in the same manner as in Example 4. This film was colorless and transparent, and had a surface resistance value of 1.5 × 10 ⁷ Ω.

Example 9 The mixed solution of the copolymer prepared in Example 4 and the vinyl chloride resin was applied onto the soft vinyl chloride sheet used in Example 1 with a # 5 bar coater, and the mixture was heated at 110 ° C. for 2 hours. Dry for minutes. The resulting coating film was colorless and transparent and had a surface resistance value of 2.4.
It was × 10 ⁸ Ω. This value did not change after the film was washed with water for 5 minutes.

Example 10 3 g of the isopropanol solution of the copolymer obtained in Example 1 (resin solid content 10 wt%) and 7 g of polyurethane resin sampler IB-114B (resin solid content 30 wt%, Sanyo Chemical Co., Ltd.) were mixed. . Coronate E as a curing agent
After adding 0.14 g of H (manufactured by Nippon Polyurethane Co.),
It was coated on the soft vinyl chloride film used in Example 1 with a # 5 bar coater. After curing at 70 ° C. for 3 hours, the surface resistance was measured and found to be 6.2 × 10 ⁹ Ω. This value did not change even after washing with water for 5 minutes.

Example 11 Methyl ethyl ketone / methanol (7/3) solution of the copolymer obtained in Example 1 (resin solid content 10 wt%)
5g and urethane acrylate UV curable resin PR-
3.5 g of 202 (50% methyl ethyl ketone solution, manufactured by Mitsubishi Kasei Co., Ltd.) was mixed to obtain a solution having a resin solid content of 23 wt%. This solution was coated on the soft vinyl chloride film used in Example 1 with a # 5 bar coater to give 120 W / cm.
The UV lamp was irradiated for 12 seconds to cure. The coating film obtained was colorless and transparent, and had a surface resistance value of 7.5 × 10.
It was ⁷ Ω. This value did not change even after washing with water for 5 minutes.

Comparative Example 1 A blend film was prepared in the same manner as in Example 4 except that 4 g of the random copolymer obtained in Reference Example E and 6 g of vinyl chloride resin powder (P-500 manufactured by Mitsubishi Kasei Vinyl Co., Ltd.) were used. It was created. This film is slightly cloudy,
The surface resistance value was 4.1 × 10 ¹⁴ Ω.

Comparative Example 2 The same as Example 4 except that 1.5 g each of the macromonomer and the quaternary ammonium salt-based monomer used in Example 1 were used as they were in place of the copolymer synthesized in Example 1. Then, a vinyl chloride film containing a quaternary ammonium salt was prepared. The surface of this film was sticky, and the surface resistance value immediately after film formation was 1.3 × 10 ⁶ Ω, but after washing with water for 5 minutes, it increased to 2.6 × 10 ¹² Ω.

Claims (4)

[Claims] 1. A repeating unit represented by the following general formula [I] and a repeating unit represented by the following general formula [II], wherein the weight ratio of [I] to [II] is 10:90 to 90. Is in the range of 10 and the intrinsic viscosity ηinh is
A polymer antistatic agent, which is a copolymer of 0.02 or more. [Chemical 1] (In the formula, R ¹ is an alkyl group having 1 to 20 carbon atoms or an aralkyl group, R ² is an aliphatic hydrocarbon group, and R ³ is Or -CO- (wherein R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom, and m = an integer of 1 to 4, L =
An integer of 1 to 10) embedded image in R ³ A urethane bond is formed adjacent to —O—. R ⁴ is a hydrogen atom or a methyl group, and n is 2 to 200. ) [Chemical 4] (In the formula, R ⁶ is a hydrogen atom or a methyl group, and X is 4
It is an ionic residue containing a primary ammonium salt and a metal salt. ) 2. A thermoplastic resin having a content of 0.
The antistatic agent according to claim 1, which is used in an amount of 1 to 200 parts by weight. 3. The antistatic agent according to claim 1, which is used in an amount of 0.1 to 200 parts by weight based on 100 parts by weight of the urethane curable resin. 4. The antistatic agent according to claim 1, which is used in an amount of 0.1 to 200 parts by weight based on 100 parts by weight of the ultraviolet curable resin.