JP2005082621A - Antistatic coating composition and material using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high mol. wt. anionic antistatic coating composition which exhibits an antistatic property even under a low humidity condition, does not contain a halogen compound producing dioxins, when burned, and acts, even when an antistatic coating layer is placed between laminated plastic film layers, and to provide various plastic materials each having a laminated plastic film using the composition. <P>SOLUTION: This antistatic coating composition is characterized by neutralizing a carboxy group-having polymer with one or more quaternary ammonium hydroxide compounds selected from tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide) and then adding a cross-linking agent capable of reacting with the carboxy group to the neutralized product. And, an antistatic plastic film and a material each having the composition between the layers. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an anionic antistatic coating agent composition that does not contain a halogen compound that contributes to the generation of dioxins at the time of incineration, and is highly effective even under low humidity, and a coating layer formed from this composition is made of plastic. By forming on film and plastic moldings, etc., the generation of static electricity on these films and moldings is suppressed, and many packaging materials, information recording materials, building materials, printing materials, electronic materials, automobile parts, electrical equipment parts, etc. The present invention relates to a material that is effective in the field where static electricity damage is a problem.

Plastic films, laminates thereof, and plastic moldings are charged by contact, peeling, friction, etc. due to the dielectric properties of the material itself, and antistatic agents are widely applied or kneaded as a prevention method. However, since these methods have a relatively low molecular weight liquid antistatic agent on the film surface, there are problems such as transfer of the antistatic agent to the contents, decrease in adhesive strength due to breathing, surface stickiness, and poor sustainability. There was a point.
There are the following proposals regarding an adhesive primer and a film whose outer surface is a base film itself that does not contain an antistatic agent and can maintain high antistatic performance for a long time.
Japanese Patent No. 2608383 gazette This patent invention provides: Claim 1 In the adhesive primer comprising a crosslinkable polymer having antistatic properties, the crosslinkable polymer has at least a carboxyl group and a quaternary ammonium base in the side chain. An adhesion primer, which is a cross-linkable copolymer. 2. An electrostatic induction-preventing laminated film having a primer layer comprising the adhesive primer according to claim 1 on a plastic film substrate. 3. An electrostatic induction-preventing laminated film comprising a plastic film substrate layer, a primer layer comprising the adhesive primer according to claim 1, an adhesive layer, and another plastic film layer. The above-mentioned patented invention has an excellent feature that antistatic properties can be obtained even when a coating layer is present between layers of a laminated plastic film. In the embodiment specifically described in this patent, a compound containing chlorine is used. Since it is used, a film using this generates dioxins depending on the conditions during incineration. Next, as an example not containing a halogen compound, there are the following known examples. Patent No. 3207757 This patent invention relates to an adhesive primer made of a crosslinkable polymer having anti-static properties, wherein the crosslinkable polymer is a side chain, a carboxyl group, and the counter ion is an aliphatic sulfonate ion. It is a cross-linkable copolymer having a secondary ammonium base. JP, 2001-262047, A The invention concerning this application is an acrylate monomer of a non-halogen quaternary ammonium alkyl sulfate salt, an acrylate monomer having an OH group at the terminal, and a part of the skeleton composition of a styrene monomer and an alkyl acrylate. It features a non-halogen antistatic adhesive primer that is a copolymer. However, the copolymers disclosed in Patent Documents 2 and 3 are all cationic. This cationic coating material has a strong tendency to gel when mixed with an anionic material, and care must be taken when sharing equipment. In addition, when an anionic material is repeatedly applied to the application surface of the cationic material, problems such as whitening of the coated surface and generation of a gel-like material are likely to occur. Accordingly, since many of the commercially available coating materials are anionic, it is easier to handle if the antistatic coating agent is also anionic. Next, an anionic antistatic coating agent composition obtained by partially or completely neutralizing an unsaturated carboxylic acid copolymer with an alkali metal hydroxide, ammonia and amines is inferred from the following patent publication. Is done. The invention according to this application is an organic solution containing a metal ion neutralized ethylene / unsaturated carboxylic acid copolymer, an alcohol-based additive and an organic solvent, wherein the metal ion neutralized ethylene The unsaturated carboxylic acid copolymer is an ethylene / unsaturated carboxylic acid copolymer (A) having an unsaturated carboxylic acid content of 10 to 35% by weight based on the carboxyl group of the copolymer. % Of the resin neutralized with potassium ions in an amount corresponding to the percentage, and the alcohol additive is selected from the group consisting of alkanolamine, glycerin and polyethylene glycol having a molecular weight of 250 or less, and the alcohol additive is a copolymer ( It is contained in the range of 0.1 to 9% by weight per A). However, in the case of the invention of this application, there is a problem that the performance is inferior to that of the cationic material under a low humidity condition such as a relative humidity of 20% or less at 23 ° C. The following Patent Document 5 and Patent Document 6 are recognized as materials that can solve the various problems described above. JP, 09-187638, A The invention concerning this application consists of a polymer which has a quaternary ammonium base obtained by making a copolymer of a monomer which has an acid group, and a nonionic monomer react with a quaternary ammonium compound. High molecular surface activity. Japanese Patent No. 3038542 This patent invention is a pressure-sensitive adhesive comprising an alkyl (meth) acrylate copolymer having at least one quaternary ammonium / organic acid group in the molecular side chain. However, the invention of the former Patent Document 5 states that “a polymer comprising a polymer having a quaternary ammonium base obtained by reacting a copolymer of a monomer having an acid group and a nonionic monomer with a quaternary ammonium compound. ”Surfactant” is disclosed, but since the polymeric surfactant is assumed to be used in a non-aqueous system, quaternary ammonium carbonate must be synthesized under pressure and then reacted with a polymer having an acid group. The process must be complicated and dangerous. Next, the invention of Patent Document 6 discloses a “pressure-sensitive adhesive comprising an alkyl (meth) acrylate copolymer having at least one quaternary ammonium / organic acid group in the molecular side chain”. However, since it is intended as a pressure-sensitive adhesive, problems such as blocking occur when it is used as an antistatic coating agent for plastic films. Moreover, the quaternary ammonium salt used in these inventions has a concern about toxicity.

  The problem imposed on the present invention is that it exhibits an antistatic property even under low humidity conditions, does not contain a halogen compound, and functions even when an antistatic coating layer is present between the layers of the laminated plastic film. An object of the present invention is to provide various plastic materials including a preventive coating agent composition and a laminated plastic film using the composition.

Invention of Claim 1 One or more quaternary ammonium hydroxide compounds selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide) as a polymer containing a carboxylic acid group. By neutralizing with, an antistatic polymer can be obtained. This polymer composition is anionic and does not contain a halogen compound. By using these quaternary ammonium hydroxide compounds, low humidity performance comparable to that of a cationic material is obtained. This polymer can also be obtained by copolymerizing a monomer having a carboxylic acid group partially or completely neutralized with these quaternary ammonium hydroxide compounds. By adding a crosslinking agent capable of reacting with carboxylic acid to this polymer, an antistatic coating agent composition having water resistance can be obtained. Examples of the functional group of the crosslinking agent include isocyanate, epoxy, alkoxysilane, carbodiimide, N-methylol nitrogen, polyvalent metal (salt), aziridine, oxazoline, hydrazide and the like. Of these, the toxicity to the human body and the odor during use are mild, and when used in the form of a water-containing solution or dispersion at room temperature, the coating solution is stable and has a pot life of 2 hours or more. Then, as a crosslinking agent capable of undergoing a crosslinking reaction under curing conditions of 40 ° C. or lower, a functional group of the crosslinking agent is preferably one or more selected from isocyanate, epoxy, alkoxysilane, and carbodiimide. Alkoxysilane is useful for improving adhesion to metal oxide vapor deposition films such as silica and alumina.
Patent Document 5 discloses a “polymer surfactant comprising a polymer having a quaternary ammonium base obtained by reacting a copolymer of a monomer having an acid group and a nonionic monomer with a quaternary ammonium compound”. However, since the polymer surfactant is assumed to be used in a non-aqueous system, the quaternary ammonium carbonate must be reacted with a polymer having an acid group after being synthesized under pressure. And dangerous. The polymer surfactant is used after being dissolved in a solvent because of its use, and it is expected that the physical properties as a coating agent, particularly water resistance, is poor as it is.
In contrast, the present invention uses a quaternary ammonium hydroxide compound as described above to neutralize a polymer containing a carboxylic acid group, so that the process is simple. Further, these aqueous quaternary ammonium hydroxide compounds are widely available as high-purity photoresist developing solutions for semiconductors, and are easily available. Furthermore, it becomes suitable as an antistatic coating agent by adding a crosslinking agent capable of reacting with a carboxylic acid to a polymer containing a carboxylic acid group neutralized with a quaternary ammonium hydroxide compound.

Invention of Claim 2 When the coating film in this invention shows adhesiveness, when it uses as an antistatic coating agent of a plastic film, since problems, such as blocking, arise, it is said that this coating film is non-adhesive. It is essential. Here, non-adhesive means that when a 25 μm thick coating film is formed on a polyethylene terephthalate film as a sample, the adhesive strength test or holding strength test of the JIS Z 0237 adhesive tape / adhesive sheet test method is performed. It means that measurement is not possible because it does not adhere even if it is crimped.
More preferably, the coating film is anti-blocking. Here, blocking resistance refers to a state in which a film having a thickness of 0.3 μm formed on a polyethylene terephthalate film is used as a sample, and the films are not easily adhered to each other when the following test is performed. Say. The test method consisted of three or more samples arranged in a certain shape, which were placed in one method so that the coated surface and back surface were in contact with each other and sandwiched between smooth glass plates, and in a 40 ° C. oven at a pressure of 196 kPa (2 kgf / cm ² ) After pressing for 24 hours, the pressure is released and the state of the sample is observed.

Invention of Claim 3 The composition of this invention may be used for the plastic film for food packaging, In this case, consideration to safety is needed. Many tetramethylammonium salts are acutely toxic, and the toxicity is likely to decrease with increasing carbon chain length. In contrast, choline salts, which are bio-related substances, have relatively low acute toxicity. When compared with chloride, it is as follows.
Tetramethyl chloride
Ammonium: Oral, Rat, LD50: 50mg / kg (RTECS)
Trioctylmethyl chloride
Ammonium: Oral, Rat, LD50: 223mg / kg (RTECS)
Stearyl trimethyl chloride
Ammonium: Oral, rat, LD50: 1015 mg / kg (male)
Choline chloride: Oral, rat, LD50: 3400mg / kg (RTECS)
By limiting the quaternary ammonium hydroxide compound used for neutralization to choline, it becomes safer as an antistatic coating agent.

Invention of Claim 4 The quantity of the quaternary ammonium hydroxide compound used for neutralization is 2.4 mol or more with respect to 1 kg of polymers containing a carboxylic acid group, and is below the equivalent of the carboxylic acid group which a polymer contains. Is a quantitative limitation characterized by The amount of the quaternary ammonium hydroxide compound used for neutralization does not have to be equimolar with the carboxylic acid group contained in the polymer, but if it is less than 2.4 mol per 1 kg of the polymer, the antistatic effect is low. Moreover, when it uses exceeding the equivalent of the carboxylic acid group which a polymer contains, excess quaternary ammonium hydroxide compound decomposes | disassembles and volatilizes in a drying process, and does not contribute to the antistatic effect.

Invention of Claim 5 By providing the coating layer which consists of a composition of Claim 2 on a plastic film base material, the film which shows favorable antistatic property under low humidity is obtained. The antistatic property is evaluated by the surface resistance of the coat layer surface.

Invention of Claim 6 The coating which consists of a composition of Claim 1 or 2 is provided in a plastic film base material, and another plastic film is laminated | stacked through the adhesive agent or the thermoplastic resin melt-extruded on this coating layer. The composite film is a base film itself whose outer surface does not contain an antistatic agent, and is a material that can maintain high antistatic performance for a long time. Antistatic properties are evaluated by the frictional voltage on the outer surface of the film.

  According to the above invention, the antistatic property is exhibited even under a low humidity condition, and there is no concern that dioxin is generated depending on the incineration condition by not containing a halogen compound. Further, even if the coating composition according to the present invention is present between the layers of the laminated plastic film or the plastic material, the film performance is not deteriorated. Moreover, since the coating composition is not toxic, safety is ensured particularly in a laminated plastic film for food packaging.

In the antistatic coating composition, 210 g of ethyl acetate, 90 g of methyl methacrylate (MMA), 120 g of n-butyl methacrylate (BMA), acrylic, are added to a 1500 ml reactor equipped with a stirrer, thermometer and reflux condenser. Charge 90 g of acid (AA) and heat to 75 ° C. in a water bath. All reactions are carried out under a nitrogen stream. A solution prepared by dissolving 0.9 g of 2,2′-azobis (2,4-dimethylvaleronitrile) in 30 g of ethyl acetate is dropped into the reactor over 15 minutes to start the reaction. After an additional hour, 0.9 g of 2,2′-azobis (2,4-dimethylvaleronitrile) dissolved in 50 g of ethyl acetate is dropped into the reactor over 60 minutes. Stirring is continued at 80 ° C. for 2 hours, followed by cooling and adding 160 g of ethyl acetate to obtain a base polymer. Resins such as polyester, rosin ester, and terpene phenol can be optionally added to the base polymer, and low molecular quaternary ammonium compounds and inorganic salts can be optionally added as an antistatic aid.
To 100 g of the base polymer, 52 g of a 25% aqueous solution of tetramethylammonium hydroxide (TMAH) is added and stirred for neutralization reaction. Diluted by adding 84 g of distilled water and 200 g of ethyl acetate to make the coating stock solution.
A crosslinking agent capable of reacting with carboxylic acid groups is added to the coating stock solution, and diluted with ethyl acetate twice to obtain an antistatic coating agent. The functional group of the crosslinking agent is preferably at least one selected from isocyanate, epoxy, alkoxysilane, and carbodiimide.

Next, in the laminated plastic film using the above composition, an antistatic coating agent is applied to the polyethylene terephthalate film that has been subjected to corona discharge treatment. 3 is coated, dried at 80 ° C. for 20 seconds, and then cured at 40 ° C. for 24 hours to form an antistatic film.
A linear low-density polyethylene film coated with an adhesive for urethane-based solvent-based dry laminating on the antistatic film so that the coating amount after drying is 3 g / m ² , dried at 80 ° C. for 20 seconds and then subjected to corona discharge treatment. Are bonded and pressure-bonded, and cured at 40 ° C. for 24 hours to form an antistatic laminated film.
The coating method is not limited to the above, and any known coating apparatus and printing machine such as various roll coaters, gravure coaters, knife coaters, and die coaters can be used. Moreover, when applying to a plastic molding etc., well-known methods, such as the method of making it pass through a spin coat, dipping, spray application, and the fine mist atmosphere, can be used.
First, the evaluation method is demonstrated about each Example and comparative example which are demonstrated below.

Surface resistance
In 23 ℃ 20% RH environment, the surface resistance of the coating layer of the antistatic film is set to a high resistance meter (Hewlett Packard 4339A) with a resistance cell (dedicated measurement box, Hewlett Packard 16008B, inner electrode diameter 50 mm, outer electrode inner diameter Measure using a connected 70mm outer diameter 71mm).

Friction band voltage
A frictional voltage measuring machine defined in JIS L 1094 method B was used. Cotton cloth (Kanakin No. 3) is used for the friction cloth. The measurement is performed by rubbing the outer surface of the antistatic laminated film in an environment of 23 ° C. and 20% RH. Set the sample on the tester, rub for 60 seconds, rotate for 60 seconds without rubbing, and record the sample surface voltage at the end of friction and after idling for 60 seconds.

Water resistance A cross-linking agent is added to the coating stock solution, cast onto a polyethylene plate, dried and cured to produce a cured film. Immerse the cured film in hot water and observe the condition.

Blocking resistance Three or more antistatic films arranged in a certain shape are overlapped in one way so that the coated surface and the back surface are in contact with each other and sandwiched between smooth glass plates. In a 40 ° C oven, the pressure is 196 kPa (2 kgf / cm ² ) for 24 hours, then decompress and observe the condition of the sample

  The present Example 1 relates to a polymer containing a carboxylic acid group as a base of the coating agent composition, and a production example thereof will be described below.

Production Example 1
A 1500 ml reactor equipped with a stirrer, thermometer and reflux condenser was charged with 210 g of ethyl acetate, 90 g of methyl methacrylate (MMA), 120 g of n-butyl methacrylate (BMA), 90 g of acrylic acid (AA), in a water bath. Heat to 75 ° C. All reactions are carried out under a nitrogen stream. A solution prepared by dissolving 0.9 g of 2,2′-azobis (2,4-dimethylvaleronitrile) in 30 g of ethyl acetate is dropped into the reactor over 15 minutes to start the reaction. After an additional hour, 0.9 g of 2,2′-azobis (2,4-dimethylvaleronitrile) dissolved in 50 g of ethyl acetate is dropped into the reactor over 60 minutes. Stirring was continued at 80 ° C. for 2 hours, followed by cooling and adding 160 g of ethyl acetate to obtain a base polymer a. The carboxylic acid group content of the base polymer a is calculated to be 4.2 mol per kg of polymer.

Production Example 2
In a 1500 ml reactor equipped with a stirrer, thermometer, reflux condenser, ethyl acetate 210 g, 2-ethylhexyl acrylate (2EHA) 142.5 g, n-butyl acrylate (BA) 142.5 g, acrylic acid (AA) 12 g, acrylic acid Charge 3 g of 2-hydroxyethyl (2-HEA) and heat to 75 ° C. in a water bath. All reactions are carried out under a nitrogen stream. A solution prepared by dissolving 0.9 g of 2,2′-azobis (2,4-dimethylvaleronitrile) in 30 g of ethyl acetate is dropped into the reactor over 15 minutes to start the reaction. After an additional hour, 0.9 g of 2,2′-azobis (2,4-dimethylvaleronitrile) dissolved in 50 g of ethyl acetate is dropped into the reactor over 60 minutes. Stirring was continued at 80 ° C. for 2 hours, followed by cooling and addition of 160 g of ethyl acetate to obtain a base polymer b. The carboxylic acid group content of the base polymer b is a calculated value of 0.56 mol per kg of the polymer.

Example 2 relates to a coating agent composition and a laminated plastic film.
To 100 g of base polymer a, 52 g of a 25% aqueous solution of tetramethylammonium hydroxide (TMAH) is added and stirred to carry out a neutralization reaction, and then diluted by adding 84 g of distilled water and 200 g of ethyl acetate to obtain a coating stock solution. The amount of quaternary ammonium hydroxide compound used for neutralization is 3.6 mol per 1 kg of polymer in the calculated value.
Mix 40 g of the coating solution and 1 g of the isocyanate-based crosslinking agent “Aquanate AQ-200” (manufactured by Nippon Polyurethane Industry Co., Ltd.), and add 55 g of ethyl acetate to make an antistatic coating solution with a nonvolatile content of 6%. The coating solution was applied to the corona discharge treated surface of a PET film (S-25, manufactured by Unitika Ltd.) with a thickness of 25μm using Meyer bar coater # 3, dried at 80 ° C for 20 seconds and then aged at 40 ° C for 24 hours. An antistatic film was obtained.
Applying urethane solvent-type dry laminating adhesive to antistatic film so that the coating amount after drying is 3g / m ² , drying at 80 ° C for 20 seconds and then corona discharge treatment 60μm thick linear low density A polyethylene film (TUX-FCS, manufactured by Tosero Co., Ltd.) is bonded and pressure-bonded, and cured at 40 ° C. for 24 hours to form an antistatic laminated film. Urethane solvent type dry laminate adhesive is Takelac A-969V (Mitsui Takeda Chemical Co., Ltd.) and Takenate A-5 (Mitsui Takeda Chemical Co., Ltd.) mixed at a mass ratio of 3: 1. Used diluted.

To 100 g of base polymer a, 60.6 g of a 25% aqueous solution of tetramethylammonium hydroxide (TMAH) is added and stirred for neutralization, and then diluted by adding 110 g of distilled water and 189 g of ethyl acetate to obtain a coating stock solution. The amount of quaternary ammonium hydroxide compound used for neutralization is 4.2 mol per 1 kg of polymer in the calculated value.
Mix 40 g of the coating solution and 1 g of the isocyanate-based crosslinking agent “Aquanate AQ-200” (manufactured by Nippon Polyurethane Industry Co., Ltd.), and add 55 g of ethyl acetate to make an antistatic coating solution with a nonvolatile content of 6%. Thereafter, the same procedure as in Example 2 was performed.

  The same procedure as in Example 3 was carried out except that a 33.3% choline aqueous solution was used instead of the 25% TMAH aqueous solution, and the ethyl acetate used in the preparation of the coating stock solution was changed to 231 g.

Tetramethylammonium hydroxide (TMAH) 25% aqueous solution 39.0g, distilled water 359g, ethylene-acrylic acid copolymer "Nukurel N5130H" (Mitsui / DuPont Polychemical Co., Ltd.) 40g was added and heated to a neutralization reaction. Disperse at the same time to make a coating stock solution. The carboxylic acid group content of Nucrel N5130H is calculated to be 2.7 mol per kg of polymer. The amount of quaternary ammonium hydroxide compound used for neutralization is 2.7 mol per 1 kg of polymer as a calculated value.
Mix 40 g of the coating solution and 1 g of the epoxy-based crosslinking agent “TETRAD-X” (Mitsubishi Gas Chemical Co., Ltd.), and add 55 g of methanol to make an antistatic coating solution with a nonvolatile content of 6%. Thereafter, the same procedure as in Example 2 was performed.

  The same procedure as in Example 3 was performed except that 84 g of a 25% aqueous solution of tetraethylammonium hydroxide (TEAH) was used instead of the 25% aqueous solution of TMAH, and the ethyl acetate used in the preparation of the coating stock solution was changed to 259 g.

Comparative Example 1
After adding 30.3 g of 25% aqueous solution of tetramethylammonium hydroxide (TMAH) to 100 g of the base polymer a and carrying out a neutralization reaction, it is diluted by adding 110 g of distilled water and 126 g of ethyl acetate to obtain a coating stock solution. The amount of the quaternary ammonium hydroxide compound used for neutralization is 2.1 mol per 1 kg of polymer as a calculated value.
Thereafter, the same procedure as in Example 2 was performed.

Comparative Example 2
The same procedure as in Example 3 was performed except that 4.68% aqueous ammonia was used instead of the 25% aqueous solution of TMAH, and the ethyl acetate used in the coating stock solution was changed to 86 g.

Comparative Example 3
The same procedure as in Example 3 was performed except that a 15.4% aqueous solution of potassium hydroxide was used instead of the 25% aqueous solution of TMAH, and the ethyl acetate used in the preparation of the coating stock solution was changed to 141 g.

Comparative Example 4
This was carried out in the same manner as in Example 3 except that a 11.0% aqueous solution of sodium hydroxide was used instead of the 25% aqueous solution of TMAH, and the ethyl acetate used in the preparation of the coating stock solution was changed to 118 g.

Comparative Example 5
The same procedure as in Example 3 was performed except that a 27.8% methanol solution of triethylamine was used instead of the 25% aqueous solution of TMAH, and the ethyl acetate used in the preparation of the coating stock solution was changed to 203 g.

Comparative Example 6
The same procedure as in Example 3 was performed except that a 24.5% aqueous solution of dimethylaminoethanol was used instead of the 25% aqueous solution of TMAH, and the ethyl acetate used in the preparation of the coating stock solution was changed to 186 g.

Comparative Example 7
The same procedure as in Example 3 was carried out except that a 20.1% aqueous solution of diethylamine was used instead of the 25% aqueous solution of TMAH, and the ethyl acetate used in the preparation of the coating stock solution was changed to 164 g.

Comparative Example 8
The same procedure as in Example 3 was performed except that a 20.1% aqueous solution of n-butylamine was used instead of the 25% aqueous solution of TMAH, and the ethyl acetate used in the preparation of the coating stock solution was changed to 164 g.

Comparative Example 9
Stir and mix 40 g of BONDEIP-PA100 main agent (manufactured by Konishi Co., Ltd.), 40 g of BONDEIP-PA100 curing agent (same), 80 g of isopropyl alcohol, and 100 g of distilled water to obtain an antistatic coating solution having a nonvolatile content of 6%. Thereafter, the same procedure as in Example 2 was performed.

Comparative Example 10
After adding 8.08 g of a 25% aqueous solution of tetramethylammonium hydroxide (TMAH) to 100 g of the base polymer b and stirring to neutralize it, 239 g of ethyl acetate is added to dilute to make a coating stock solution. The amount of quaternary ammonium hydroxide compound used for neutralization is 0.56 mol based on 1 kg of polymer in the calculated value.
Thereafter, the same procedure as in Example 2 was performed.

Comparative Example 11
The same procedure as in Example 3 was carried out except that a crosslinking agent was not used in the preparation of the antistatic coating solution, and 40 g of ethyl acetate was added to 40 g of the coating stock solution to obtain a nonvolatile content of 6%.
Table 1 shows the polymers used in Examples and Comparative Examples, the carboxylic acid group content of the polymers, the names of substances used for neutralization, the amounts of substances used for neutralization, and ionicity.

判定基準
表面抵抗：5.0×10¹¹ Ω未満＝○、5.0×10¹¹ Ω以上＝×
摩擦帯電圧：摩擦終了時に1000 V未満＝○、1000 V以上＝×
耐水性：皮膜が膨潤するのみ＝○、皮膜が溶解または乳化する＝×
耐ブロッキング性：抵抗なく剥がれる＝○、剥がす際に抵抗がある＝× Evaluation results Table 2 shows the evaluation results.

Judgment criteria Surface resistance: Less than 5.0 × 10 ¹¹ Ω = ○, 5.0 × 10 ¹¹ Ω or more = ×
Friction voltage: Less than 1000 V at the end of friction = ○, 1000 V or more = ×
Water resistance: only the film swells = ○, the film dissolves or emulsifies = ×
Blocking resistance: peeling without resistance = ○, resistance when peeling = ×

Claims (6)

  The polymer containing a carboxylic acid group is neutralized with one or more quaternary ammonium hydroxide compounds selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide). An antistatic coating composition comprising a crosslinking agent capable of reacting with a carboxylic acid.   The composition according to claim 1, wherein the coating film is non-tacky.   2. The composition according to claim 1, wherein the quaternary ammonium hydroxide compound used for neutralization is choline.   The composition according to claim 2, wherein the amount of the quaternary ammonium hydroxide compound used for neutralization is not less than 2.4 moles per 1 kg of the polymer containing carboxylic acid groups and not more than the equivalent of the carboxylic acid groups contained in the polymer. Stuff.   An antistatic film having a coating layer comprising the composition according to claim 2 on a plastic film substrate. An antistatic laminated film comprising a plastic film base layer, a coat layer comprising the composition according to claim 1, an adhesive layer or a melt-extruded thermoplastic layer, and another plastic film layer.