JP2871115B2 - Antistatic agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel antistatic agent. In particular, the present invention relates to a novel high molecular weight antistatic agent that exhibits excellent antistatic performance over a long period of time by kneading or applying to a resin, and an antistatic resin composition using the same.

[0002]

2. Description of the Related Art In general, a polymer material is excellent in electric insulation, so that it is easily charged, dust not only adheres to a molded product and impairs the appearance, but also various kinds of static electricity are generated during the production of films and fibers. Trouble occurs. In addition, when used for electric appliances, there is a big problem such as malfunction caused by accumulated static electricity.

[0003] In order to solve such a problem, it has heretofore been often practiced to apply various surfactants to the surface of a molded article so as to have an antistatic property.
However, although this method is simple and has a quick effect, it has a serious problem in durability such that stickiness remains on the surface of the resin and the antistatic agent easily peels 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. The kneading method differs from the coating method in that even if the antistatic agent layer on the surface is lost, the internal antistatic agent diffuses to the surface due to the concentration gradient and a new layer is formed, so long-term antistatic effect 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. In other words, molded articles in which an antistatic agent is preliminarily kneaded often cause a problem of surface contamination, and the antistatic agent layer on the surface is easily lost by wiping with water, and the antistatic property is temporarily lost. Is observed.

In order to solve these problems, there has been proposed a high molecular weight antistatic agent comprising a monomer having an antistatic property alone or copolymerized with various monomers and macromonomers. However, these methods are also difficult to achieve a high level of adhesion to the resin serving as the base material, compatibility and antistatic properties, so that the surface resistance is sufficiently reduced,
The goal of maintaining its performance for a long time was not completely satisfied, and further improvement was desired.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an antistatic agent which has high antistatic properties, does not cause surface contamination due to bleed-out, and whose performance does not change over a long period of time. I do.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, a repeating unit represented by the following general formula [I] having a polyester structure as a side chain and a main chain comprising: A copolymer comprising an ionic repeating unit represented by the following general formula [II] was developed, and it was found that this structure exhibited excellent performance as an antistatic agent.

[0007]

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Wherein R ¹ is an alkyl or aralkyl group having 1 to 20 carbon atoms, R ² is an aliphatic hydrocarbon group, R ³
Is

[0009]

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[0010] or -CO- (wherein, R ⁵ represents an alkyl group, a hydrogen atom or a halogen atom having 1 to 20 carbon atoms, m = 1 to 4 integer, El = integer of 1 to 10), R ³ In

[0011]

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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]

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(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.) Hereinafter, the present invention will be described in more detail.

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

[0017]

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The polyester macromonomer represented by the general formula [III] will be described in detail. [III] R ¹ in the formula 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 straight-chain C 3-8 aliphatic hydrocarbon group. Specifically, it corresponds to an aliphatic hydrocarbon group of the polyester by ring-opening polymerization of a lactone compound described below, preferably,

[0019]

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[0020]

Preferred as R ³ are:

[0022]

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Or -CO-.

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, and more preferably 2 to 50.

As described above, preferable polyester macromonomers include the following.

[0026]

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[0027]

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The production of the polyester macromonomer [III] usually comprises 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]

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(R ² has the same meaning as in the above formula [I]) by ring-opening polymerization of the lactone compound to obtain the following polyester alcohol.

[0031]

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The initiator R ¹ —OH is preferably methanol, n-butanol, n-hexanol,
n-octanol, 2-ethylhexanol and the like. 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. Examples of the catalyst include known catalysts used for ring-opening polymerization of lactones, for example, mineral acids such as sulfuric acid and phosphoric acid, and lithium, sodium and potassium. 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 solvent, but a solvent may be used in some cases. As the solvent, toluene,
Xylene, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, chloroform, carbon tetrachloride and the like can be used. The reaction can be suitably performed at a temperature between 0 ° C. and 200 ° C. for a reaction time of 10 minutes to 30 hours.

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

[0036]

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([V] wherein R ⁷ is

[0038]

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(However, R ⁵ , m and L are the same as those of the above general formula.
It is synonymous with [I]. R ⁴ is a hydrogen atom or a methyl group. )

[0040]

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

[0042]

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And the above-mentioned general formula
A specific example of [VI]

[0044]

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And the like.

The above polyester alcohol and the above [V]
Is a urethane bond formation reaction, and these may be reacted in equimolar amounts. Although the reaction proceeds without a catalyst, a tin catalyst such as dibutyltin dilaurate, dibutyltin dioctoate, or dibutyltin mercaptide may be used to increase 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 equimolar amounts. When a condensation reaction is employed, a hydrogen halide is produced as a by-product, so that a deoxidizing agent such as a tertiary amine may be used, or the reaction may be performed in an inert gas stream. When an ester exchange reaction is employed, a known ester exchange catalyst such as a mineral acid such as hydrochloric acid or sulfuric acid, a metal salt such as zinc, calcium, or magnesium, or a metal alkoxide such as titanium tetrabutoxide may be used.

In these reactions, a catalyst may be used. As the solvent, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, chloroform, carbon tetrachloride and the like can be used. The reaction can be suitably performed at a temperature between 0 ° C and 200 ° C for 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. R ⁶ in the formula is a hydrogen atom or a methyl group, and X is a compound having an anionic or cationic ionic residue or a compound capable of easily introducing an ionic group after polymerization. No restrictions. To give a specific example, as the monomer having a cationic group, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylamino (meth) acrylate, dibutylaminoethyl ( And quaternized nitrogen-containing monomers such as meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminovinyl sulfide, diethylaminoethyl vinyl ether, vinylbenzyl-N, N'-dimethylamine, vinylpyridine, and vinylquinoline. This quaternization is carried out by a known method by adding an inorganic acid such as hydrogen chloride, hydrogen bromide, sulfuric acid, benzyl chloride, benzyl bromide, or the like to a tertiary amino group.
It can be carried out by reacting a quaternizing agent such as methyl chloride and methyl bromide. The quaternization step may be performed in the state of the monomer before the copolymerization or at any stage after the copolymerization.

Examples of the monomer having an anionic group include:
(Meth) acrylic acid, α-chloro (meth) acrylic acid,
Vinylsulfonic acid, sulfonated styrene, 2-acrylamide-2-methylpropanesulfonic 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-
Vinyl monomers having a carboxyl group, a sulfonic acid group, a phosphoric acid group, such as amidophosphooxypropyl (meth) acrylate and acid phosphooxypropyl (meth) acrylate, or alkali metal salts, ammonium salts, or dimethyl thereof Examples thereof include organic amine salts such as amine, triethylamine, and triethanolamine, and tetrabutylphosphonium salts. When a metal salt or an organic salt is used, the corresponding monomer may be used for direct polymerization, or after polymerization at the stage of an organic acid monomer,
Neutralization may be performed.

Particularly preferred as these monomers having an ionic residue are dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dipropylaminoethyl (meth) acrylate.
Quaternary ammonium salts and metal salts of (meth) acrylic acid.

The copolymerization of the polyester macromonomer [III] and the vinyl monomer [IV] can be easily carried out by a usual radical polymerization method. That is, a polyester macromonomer [III] and a vinyl monomer [IV] are usually added with an azo compound or a radical polymerization initiator such as a peroxide in an amount of 0.1 to 10% by weight, and 0 ° C to 200 ° C. At a temperature of 1 hour to 24 hours. Here, in order to adjust the degree of polymerization, a chain transfer agent such as an alkyl mercaptan may be added. 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 ratio of the polyester macromonomer [III] to the vinyl monomer [IV] is 10:90 to 90:10 by weight, preferably 20:80 to 80: 2.
It is in the range of 0. When the ratio of the vinyl monomer [IV] is 10
If the ratio is smaller, it is difficult to exhibit antistatic properties, and if the ratio of the polyester macromonomer [III] is smaller than 10, the affinity at the time of coating or mixing with another resin is unfavorably deteriorated. The copolymer as the antistatic agent of the present invention was prepared by adding methyl ethyl ketone / methanol (7 /
3) Dissolve in the mixed solvent to a concentration of 0.5 g / dl;
The intrinsic viscosity ηinh measured at 5 ° C is 0.02 or more. When ηinh is lower than 0.02, the advantage of the high molecular weight is lost, and not only bleeding out from the base material is facilitated, but also the antistatic performance is lowered.

The polymer antistatic agent obtained in the present invention can be kneaded with various resins or applied to the surface thereof,
Lowers the electrical resistance of the resin and exhibits excellent antistatic properties. Further, since it has a side chain having high compatibility with various resins, it has excellent adhesion to the resin and compatibility, and its performance does not change over a long period of time. 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 in combination as a binder in order to improve the texture and strength of the coating film. That is, if the antistatic resin composition obtained by mixing the copolymer of the present invention in an amount of 0.1 to 200 parts by weight to 100 parts by weight of a thermoplastic or thermosetting resin as described below is applied as a solution, the two are uniform. And a dispersed coating film is obtained, and a film having further improved strength and adhesion as a coating film can be obtained. The antistatic agent containing these binders can form a uniform and transparent film by selecting an appropriate binder and a proper blending ratio. An antistatic effect equivalent to that of the coated product can be obtained.

The thermoplastic resins usable here include:
There is no particular limitation as long as it is soluble in the solvent, and it may be appropriately selected according to the type of the substrate to be coated. For example, polyvinyl chloride, polyester, polyamide, polyacrylate, polyurethane and the like can be mentioned. By dissolving these resins and the high molecular weight antistatic agent of the present invention in a common solvent for both, coating and drying on a substrate, an antistatic film can be easily formed.

When high strength and chemical resistance are required for the coating film, a thermosetting resin may be used as the binder. That is, the high molecular weight antistatic agent of the present invention is mixed with polyols generally used in the urethane industry, and further mixed with a curing agent containing an isocyanate compound, applied to a substrate, cured, and dried, A highly durable coating film having more excellent wear resistance can be formed. 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 and high-hardness coating film is required, it is effective to use an ultraviolet curing resin in combination. That is, the high molecular weight antistatic agent of the present invention is blended with a known ultraviolet-curable resin composition, applied to a substrate, and then cured by ultraviolet rays according to a conventional method, thereby obtaining a coating film having a good surface property 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 robust, has excellent durability, and its surface resistance does not change even by washing with water.

[0059]

As described above, the high molecular weight antistatic agent obtained by the present invention has not only excellent antistatic properties but also high compatibility with various resins, and therefore has high durability. Further, the resin composition comprising the high molecular weight antistatic agent of the present invention and various resins is applied to a base material such as various plastic materials so that the resin composition is not sticky, and has excellent coating strength, adhesion and antistatic properties. The film is easily formed, and its antistatic property is not deteriorated even by wiping with water. Therefore, it can be used for all products that do not want to be affected by static electricity, such as electrical product housings, flooring materials, and various film products, and can provide a stable antistatic property for a long period of time.

[0060]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In addition, the measurement of the surface resistance value is performed by Yokogawa-HEWLETT-PACKARD 232
The measurement was performed using a 9A type insulation resistance meter at a measurement voltage of 100 V, under measurement conditions of 25 ° C., and 50% RH.

Reference Example A Synthesis of Polyester Alcohol A flask equipped with a stirring blade, a dropping funnel and a gas inlet was sufficiently replaced with dry nitrogen, and 5.7 g of 2-ethylhexanol and 0.1 g of metallic sodium were charged and stirred. To dissolve the metallic sodium. Next, the flask was immersed in an oil bath at 40 ° C., and 50 g of β-methyl-δ-valerolactone was dropped from the dropping funnel while stirring. After one hour, stirring was stopped, the contents of the flask were taken out, and dissolved in 500 ml of purified chloroform. Add this solution to 50
It was poured into 0 ml of deionized water, washed, and the chloroform layer was separated. After repeating this washing 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 KOH mg / g and the acid value was 0.03 KOH mg / g.

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

[0063]

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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
Hmg / g and acid value were 0.50 KOHmg / g.

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

Reference Example E Synthesis of Random Copolymer In a flask equipped with a stirring blade, a reflux condenser, and a gas inlet, methyl methacrylate 10.0 g methacryloyloxyethyltrimethylammonium chloride 10.0 g azobisisobutyronitrile 0 Then, 13 g of toluene and 7 g of n-hexane were added as a solvent to form a uniform solution, and then the solution was added under a nitrogen stream.
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 sufficiently washed with methanol and dried. The yield was almost 100%.

Example 1 A 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-dodecylmercaptan 0.4 g and 40 g of isopropyl alcohol are charged, and at 70 ° C. for 7 hours under a nitrogen stream, and further at 95 ° C. For 2 hours. After the polymerization, isopropanol was distilled off and dried under reduced pressure. The ηinh of the copolymer obtained here is 0.15 dl
/ G.

This copolymer was dissolved in a mixture of methyl ethyl ketone / methanol at a weight ratio of 7/3 to a concentration of 1 wt%, and a soft vinyl chloride sheet (Mitsubishi Kasei Vinyl Co., Ltd.) was used using a # 8 bar coater. (GA-450). After heating the sheet at 110 ° C. for 2 minutes to dry the solvent, the surface resistance was measured to be 8.5.
× 10 ⁸ Ω.

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

Example 3 The polyester macromonomer synthesized in Reference Example (B) was added to 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 polymerized at 70 ° C. for 8 hours under a nitrogen stream. After the polymerization, isopropanol was distilled off and dried under reduced pressure. ηinh is 0.11 dl
/ G. 20 g of this product was dissolved in 200 g of a 7/3 mixed solvent of methyl ethyl ketone / methanol,
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.
Was obtained. This polymer was applied on a soft vinyl chloride sheet in the same manner as in Example 1, and the surface resistance 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 at a concentration of 10 wt.
%. 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 had a surface resistance of 2.4 × 10 ⁷ Ω on both sides. The film was further washed with water for 5 minutes,
Dried for minutes. After leaving this film at room temperature for one day, the surface resistance was measured and found to be 3.4 × 10 ⁷ Ω.

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

Example 7 The copolymer synthesized in Example 1 and polyvinyl butyral resin (Sekisui Chemical Esrec 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 70 μm thick film was prepared in the same manner as in Example 4. This film was colorless and transparent, and had a surface resistance of 6.0 × 10 ⁹ Ω.

Example 8 The copolymer synthesized in Example 1 and a polyester resin (Toyobo Byron 200) were mixed in a ratio of 3/7 in 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 70 μm thick film was prepared in the same manner as in Example 4. This film was colorless and transparent, and had a surface resistance of 1.5 × 10 ⁷ Ω.

Example 9 The mixed solution of the copolymer and vinyl chloride resin prepared in Example 4 was applied to the soft vinyl chloride sheet used in Example 1 with a # 5 bar coater, Dried for minutes. The obtained coating film was colorless and transparent, and had a surface resistance of 2.4.
× 10 ⁸ Ω. This value did not change after washing the film for 5 minutes.

Example 10 3 g of an isopropanol solution of the copolymer obtained in Example 1 (resin solid content: 10 wt%) and 7 g of polyurethane resin SAMPLE IB-114B (resin solid content: 30 wt%, manufactured by Sanyo Chemical Co., Ltd.) were mixed. . Coronate E as curing agent
After adding 0.14 g of H (manufactured by Nippon Polyurethane),
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 for 5 minutes.

Example 11 A solution of the copolymer obtained in Example 1 in methyl ethyl ketone / methanol (7/3) (resin solid content: 10 wt%)
5g and urethane acrylate UV curable resin PR-
Then, 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 applied to the soft vinyl chloride film used in Example 1 with a # 5 bar coater, and was applied at 120 W / cm.
For 12 seconds to cure. The resulting coating film is colorless and transparent, and has a surface resistance of 7.5 × 10
⁷ Ω. This value did not change even after washing for 5 minutes.

Comparative Example 1 A blend film was prepared in exactly the same manner as in Example 4 except that 4 g of the random copolymer obtained in Reference Example E and 6 g of a 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 was 4.1 × 10 ¹⁴ Ω.

COMPARATIVE EXAMPLE 2 The same procedure as in Example 4 was repeated except that 1.5 g of each of the macromonomer and the quaternary ammonium salt monomer used in Example 1 were used instead of the copolymer synthesized in Example 1. Thus, a vinyl chloride film containing a quaternary ammonium salt was prepared. The surface of this film was sticky, and the surface resistance immediately after film formation was 1.3 × 10 ⁶ Ω, but increased to 2.6 × 10 ¹² Ω after washing for 5 minutes.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C09K 3/16 106 C08G 63/08 CA (STN)

Claims (4)

(57) [Claims] 1. It comprises a repeating unit represented by the following general formula [I] and a repeating unit represented by the following general formula [II], and the ratio of [I] to [II] is 10:90 to 90 by weight. 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. Embedded image (Wherein, R ¹ is an alkyl or aralkyl group having 1 to 20 carbon atoms, R ² is an aliphatic hydrocarbon group, and R ³ is Or —CO— (where R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom, m = 1 to 4;
## STR3 ## in an integer of 1 to 10) 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. ) (Wherein, R ⁶ is a hydrogen atom or a methyl group, and X is 4
It is an ionic residue containing a quaternary ammonium salt or a metal salt. ) 2. An amount of 0.1 to 100 parts by weight of the thermoplastic resin.
The antistatic agent according to claim 1, wherein the antistatic agent is used in an amount of 1 to 200 parts by weight. 3. The antistatic agent according to claim 1, wherein 0.1 to 200 parts by weight is used based on 100 parts by weight of the urethane-curable resin. 4. The antistatic agent according to claim 1, wherein the amount is 0.1 to 200 parts by weight based on 100 parts by weight of the ultraviolet curable resin.