TWI675893B - Antistatic coating composition with various surface resistance according to the dilution - Google Patents

Abstract

The present invention is an antistatic coating mixture containing an anionic surfactant containing water-dispersible polyethylene (3,4-ethylenedioxythiophene), which can achieve various surface resistance properties at a dilution rate, and is excellent in durability and transparency Antistatic coating mixture.

Description

Antistatic coating mixture with various surface resistance properties at the dilution rate

The invention is a mixture containing polyethylene (3,4-ethylenedioxy thiophen) aqueous solution and an antistatic coating, and realizes a variety of surface resistances according to the dilution rate. It has durability, excellent electrical properties, and antistatic. Outstanding performance.

With the miniaturization and high density of various semiconductors and electronic devices, the occurrence of static electricity brings many problems to the products. Therefore, in order to effectively remove static electricity, we propose an antistatic coating method by using a conductive substance. Such coating technology has been used on antistatic coating films and protective films for display screen elements, and transportation plates for semiconductor elements.

The charged substance is composed of metal oxide particles and CNTs, ionic liquids, surfactants, conductive polymers, and the like. The present invention has advantages over metals in terms of special adjustments to processability, weight, and chemical reforming. A conductive polymer material with good adhesion to the equipment produces a charged coating composition.

Well-known conductive polymers are polypyrrole, polythiophene, polyaniline, polyacetylene, etc., which are widely used in industry. In particular, the commonly used polythiophene is made of polyethylene (3,4-ethylenedioxythiophene) (PEDOT) and a chemical polymerization method relying on 3,4-ethylenedioxythiophene (EDOT). Its oxidized form is It is well known for its very high electrical conductivity. (Published invention patent EP0339340)

In the present invention, the conductive polymer used makes use of the surface of anions in an aqueous solution The active agent, by means of a water-soluble p-conjugated polymer relying on a chemical polymerization reaction, relates to a method and invention for manufacturing a solution of an aqueous dispersion antistatic coating composition that can be diluted at a high rate.

Examples of well-known p-conjugated polymers are polypyrrole, polythiophene, polyaniline, polyacetylene, polybenzene. These can be produced using various chemical and electrochemical polymerization methods. Generally, the conductive polymer undergoes a doping process, and although it can be adjusted from an insulator to a conductive conductor, it has the characteristic of very low solubility in solvents due to the strong interaction of non-localized dual bonding. However, the use of dopants can improve the conductivity and solubility in solvents. In order to commercialize the use of antistatic products and electromagnetic shielding materials in such a process, it must have the property of being soluble in order to mix with the coating liquid used.

In order to achieve such a purpose, phosphoric acid, carboxylate and sulfonic acid functional groups are often used as conductive polymers to replace doping, and in particular, compounds having a sulfonic acid functional group are often used for high conductivity and excellent dopability.

However, although the substitution group of the sulfonic acid contains a monomer-type dopant, although it has the characteristics of easy doping, the dopant may fall off in the main chain of the conductive polymer under long-term use or high temperature conditions. In addition, the polymer dopant contained in the sulfonic acid substitution body is connected to the main chain of the sulfonated styrene polymer with a large molecular weight, and exists in a doped form. At this time, the polarity of the 100% sulfonated polymer is increased, and it only dissolves in water. When the conductive polymer is synthesized, it has physical properties that are dispersed only in aqueous solution. In addition, the sulfonic acid functional group of the anionic surfactant used as a dopant is relatively small at the same molecular weight compared with the sulfonic acid functional group of sodium polystyrene sulfonate, and it is very difficult to achieve lower resistivity.

In this regard, the applicant proposed a solution of an aqueous dispersion of polyethylene (3,4-ethylenedioxythiophene) using an anionic surfactant proposed in the registered patent 10-0933441 (registered date December 15, 2009), Together with the resistance polyurethane adhesive and additives, it has excellent manufacturing durability, and realizes a coating mixture with multiple surface resistances at a dilution rate, and finally completed the present invention.

As described above, the present invention utilizes an aqueous dispersion of polyethylene (3,4-ethylenedioxythiophene) using an anionic surfactant as proposed in the registered patent of the Republic of Korea 10-0933441 (registration date December 15, 2009). It is an object of the present invention to provide a coating mixture that is excellent in durability, realizes various surface resistances at a dilution rate, and has excellent transparency and adhesion on equipment.

In order to achieve the above object, the present invention provides 30 to 80 wt% of an aqueous conductive polymer dispersion, 10 to 30 wt% of a water-soluble binder, 1 to 5 wt% of an alkaline additive, 1 to 10 wt% of an ethanol solvent, and 5 to 10 15wt% organic solvent to improve wetting and balance additives antistatic coating mixture consisting of a mixture 0.1 ~ 5wt%, and 2.9 ~ 20wt% of water (H ₂ O).

In addition, the above-mentioned conductive polymer aqueous dispersion liquid will be selected from polythiophene-based, polypyrrole-based, polyaniline-based polymer compounds, or mixtures thereof. The above aqueous solution of polyethylene (3,4-ethylenedioxythiophene) is a monomer selected from the following chemical formula 1, 3,4-ethylenedioxythiophene, anionic surfactant, P-toluene iron (III) sulfate One or two or more oxidants among iron (III) benzene sulfate, iron (III) sulphate, iron (III) triple trisulphate and iron (III) sulfate, and they are 300 ~ 1,000 rpm at 25 ° C The polyethylene solution of the aqueous solution of the following chemical formula 10 was produced by polymerization at a high stirring rate. The above-mentioned anionic surfactant was 5 to 95% in water as a whole, and the acidity was 6.5 to 5.0. The following chemical formulas are characterized by 2 to 9.

LAS：Linear Alkylbenzene Sulfonate [Chemical Formula 2]

LAS: Linear Alkylbenzene Sulfonate

AOS：α-Olefin Sulfonate

AOS: α-Olefin Sulfonate

AES：Alkyl Ether Sulfate(n=1~20)

AES: Alkyl Ether Sulfate (n = 1 ~ 20)

AAES：Ammonium Alkyl Ether Sulfate(n=1~20)

AAES: Ammonium Alkyl Ether Sulfate (n = 1 ~ 20)

AS：Alkyl Sulfate

AS: Alkyl Sulfate

[Chemical Formula 7]

The discharge-charged coating composition of the present invention realizes a variety of surface charges at a dilution rate. Resistance (surface resistance 104 ~ 108), safe for storage, and a single coating composition, which not only shortens the engineering time and improves the engineering productivity, because it is composed of a water-soluble solvent, it also has the advantage of environmental protection.

In addition, the present invention is a coating mixture, which is transparent and excellent in light transmittance when a coating film is formed on a PET film or the like. Due to the conductivity of a protective film used on a display screen, a liquid crystal protective film on a mobile phone, PDP and LCD panel protection It is very useful as a transparent antistatic coating protective film on various display devices such as films.

The antistatic coating mixture of the present invention is composed of 30-80wt% conductive polymer aqueous dispersion and 10-30wt% water-soluble binder; 1-5wt% alkaline additive; 1-10wt% ethanol solvent; 5 ~ 15wt% organic solvent; an antistatic coating mixture composed of 0.1 ~ 5wt% additive to improve wettability and balance with 2.9 ~ 20wt% water (H ₂ O).

The conductive polymer constituting the above-mentioned antistatic coating composition will be selected from polythiophene, polypyrrole, polyaniline polymer compounds, or one or more of them selected from a mixture thereof, so that polythiophene can be used more appropriately. Based polymer compound.

The above polythiophene-based polymer compound will be selected from the following monomeric types of 3,4-ethylenedioxythiophene of Chemical Formula 1, and one or two or more of the following anionic surfactants of Chemical Formulas 2 to 9. For the dopant, select one or more of P-toluene iron (III) sulfate, ferrous (III) benzene sulfate, ferrous (III) sulfate, triple iron (III) sulfate and iron (III) sulfate. The oxide is produced by stirring and polymerizing at a high speed of 300 to 1,000 rpm at 25 ° C. The oxide is a polyethylene solution of the following chemical formula 10, and an aqueous solution of polyethylene 3,4-ethylenedioxythiophene in water dispersion.

The anionic surfactant is water-soluble in the above-mentioned chemical formula 10. The liquid polyethylene solution as a whole has a water concentration range of 5 to 95% and is characterized by the following chemical formulas 2 to 9 having an acidity of 6.5 to 5.0.

LAS：Linear Alkylbenzene Sulfonate

LAS: Linear Alkylbenzene Sulfonate

AOS：α-Olefin Sulfonate

AOS: α-Olefin Sulfonate

AES：Alkyl Ether Sulfate(n=1~20)

AES: Alkyl Ether Sulfate (n = 1 ~ 20)

AAES：Ammonium Alkyl Ether Sulfate(n=1~20) [Chemical Formula 5]

AAES: Ammonium Alkyl Ether Sulfate (n = 1 ~ 20)

AS：Alkyl Sulfate

AS: Alkyl Sulfate

AAS：Ammonium Alkyl Sulfate

AAS: Ammonium Alkyl Sulfate

XS：Xylene Sulfonate

XS: Xylene Sulfonate

[Chemical Formula 9]

The above-mentioned conductive polymer aqueous dispersion liquid accounts for 30 to 80% by weight of the total weight of the antistatic coating mixture, and the use amount is limited. When the use amount is less than 30% by weight, the antistatic performance will be lowered. When it exceeds 80% by weight, there is a problem of a sudden increase in viscosity. Therefore, it is appropriate to limit the use amount of the above-mentioned conductive polymer aqueous dispersion liquid to 30 to 80% by weight of the total weight of the antistatic coating mixture.

The above water-soluble adhesive is more preferably selected from one or two or more of fluorinated polyurethane, tetrafluoroethylene, hexafluoropropylene, ethylene-trifluoro, polyurethane, polyurethane-acrylic acid, and polyester composed of a copolymer. The method is to use at least one water-dispersed polyurethane adhesive or water-dispersed acrylic adhesive to strengthen the durability of the protective film, the characteristics of the film and the adhesion of the device to the device.

In addition, there are coatings for conductive polymers that improve the use of anionic surfactants. Film uniformity, adhesion, and enhance the hardness and solvent resistance of the coating.

The range of the above-mentioned water-soluble binder resin in the total weight of the antistatic coating mixture is limited to 10 to 30% by weight. At this time, when the content range is less than 10% by weight, the uniformity, hardness and The problem of reduced solvent resistance. When the content exceeds 30% by weight, the electrical properties of the conductive polymer using an anionic surfactant will be lowered, and a problem arises that the antistatic performance will deteriorate. Therefore, it is appropriate to limit the total weight of the water-soluble binder resin in the antistatic coating film mixture to 10-30% by weight.

The above-mentioned alkaline additives are used to neutralize the dispersion, and play a role of adjusting the pH of the solution to 4-10.

The alkaline additives are alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal hydroxides such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; magnesium hydroxide and hydroxide Alkali metal hydroxides such as calcium and barium hydroxide; alkali metal hydroxides such as magnesium carbonate, calcium carbonate, and barium carbonate; ammonia; methylamine, dimethylthiamine, trimethylamine, ethylamine, diethylamine, and triethyl Amines, ethanolamines, dimethylethanolamines, or aliphatic alkylamines selected from monoalkylamines, dialkylamines, and trialkylamines are substituted in alkyl groups such as triethanolamine carbons from 1 to 20.

The above-mentioned alkaline additives should be constantly monitored with a pH meter, and the alkaline additives should be added while stirring. After adding the above-mentioned alkaline additives, the pH value of the solution should be adjusted to 4-10, and the more appropriate pH value should be 6-8.

The range of the above-mentioned alkaline additive in the total weight of the antistatic coating mixture is limited to 1 to 5 wt%. When its usage is less than 1% by weight, the pH value of the antistatic mixture will lower the dispersibility problem; when it exceeds 5% by weight, the performance of the antistatic mixture will decrease, and there will also be a problem that the viscosity will increase greatly. Therefore, it is appropriate to limit the proportion of the above-mentioned alkaline additive in the total weight of the antistatic coating mixture to 1 to 5 wt%.

A suitable solvent in the present invention is a solvent that can be easily mixed with water. Specific examples The child image uses an alcohol solvent such as alcohol, ethylene glycol, or a glycol ether (ethylene glycol, diethylene glycol, propane-1,2-diol, and propane-1,3-diol).

It is appropriate to use a fatty alcohol having a carbon content of 1 to 5 as the alcohol solvent. Because if the carbon is increased, the intermolecular gravitational force becomes larger and the dispersion force to water will decrease. Therefore, in consideration of the dispersing power, it is appropriate to use a fatty alcohol having a carbon of 1 to 5, such as methanol, ethanol, n-propanol, isopropanol, or n-butanol.

The weight range of the above-mentioned alcohol solvent in the total weight of the antistatic coating mixture is limited to 1 to 10% by weight. When its usage is less than 1% by weight, there will be problems of drying and coating properties. When it exceeds 10% by weight, the dispersibility of the conductive polymer will increase or the surface resistance will increase. Therefore, the use of the above-mentioned alcohol solvent It is appropriate to limit the amount to 1 to 10% by weight of the antistatic coating mixture.

The organic solvent used in the present invention includes a functional organic solvent used for improving coating properties such as solubility, dispersibility, drying property, film uniformity, etc. of the coating mixture.

In order to give the above-mentioned functional organic solvents, there are dimethyl sulfoxide (DMSO), dimethyl aceton (N-methylpyrrolidone; NMP), ethylene glycol (Ethylene glycol), propylene glycol methyl ether (Propylene glycol methyl ether (PGME), etc., in which the use of dimethyl sulfene is more appropriate.

The use amount of the above-mentioned organic solvent in the total weight of the antistatic coating mixture is limited to 5 to 15% by weight. If the amount used is less than 5 wt%, the dispersibility and coating properties of the antistatic mixture will be deteriorated, and there will be a problem of forming an uneven film during coating. When it exceeds 15 wt%, the coating property is not particularly improved, and there is a problem that the drying property is deteriorated. Therefore, it is appropriate to limit the amount of the organic solvent used in the entire antistatic coating mixture to 5-15% by weight.

The additive used in the present invention is used to improve the physical properties of the film during coating, and can improve wettability and balance. After applying the coating mixture, the surface tension of the film surface will be locally different. Such problems can be solved by improving the surface tension difference after the additives are distributed on the surface of the film. The additive used at this time is selected from one or two or more kinds of fluorinated, silicone, or non-siloxane (polymer type).

The range of the above additives in the total weight of the antistatic coating mixture is limited to 0.1 to 5 wt%. When the amount of the additive is less than 0.5 wt%, the coating properties will be deteriorated and a problem that a uniform film cannot be formed will occur. When it exceeds 5 wt%, the uniformity does not particularly improve, and there is a problem that the antistatic performance is reduced. Therefore, it is appropriate to limit the proportion of the above additives to the total weight of the antistatic coating mixture to 0.1 to 5 wt%.

In the following, specific content will be explained through comparison and implementation examples of the above technical structure. However, these do not limit the technical scope of the present invention.

[Manufacturing example 1]

Conductive polymer composite material using anionic surfactant

2.0 L of distilled water and 70% SLES (Sodium Lauryl Ether Sulfate) 56 g were placed in a 5 L reactor equipped with a stirrer and a nitrogen filling device at 25 ° C., and stirred at a speed of 300 rpm. After 30 minutes of nitrogen bubbling, 22.48 g (0.16 mol) of 3,4-ethylenedioxythiophene and 52.8 g (0.22 mol) of sodium persulfate and 0.4 g (1.00 mol) of iron sulfate were added dropwise, and then high Molecular reaction. After the mixture was stirred at 25 ° C. for 24 hours, the remaining initiator and oxide ions were removed by two ion exchange resins (300 mL Lewatit ™ S100MB + 500 mL Lewatit ™ M600MB). Then, after stirring at 90 ° C. for 1 hour, a high-shear macroscopic fluidizer was used, and dispersion treatment was performed under the condition of 15 MPa to produce a conductive polymer aqueous dispersion.

[Manufacturing Example 2]

Conductive polymer composition using an anionic surface active (SLS) agent

2.5 L of distilled water and 31% SLS (Sodium Lauryl Sulfate) 145 g were placed in a 5 L reactor equipped with a stirrer and a nitrogen filling device at 25 ° C., and the mixture was stirred at a speed of 300 rpm. After 30 minutes of nitrogen bubbling, 28.1 g (0.2 mol) of 3,4-ethylenedioxythiophene and 66 g (0.27 mol) of sodium persulfate and 0.5 g (125 mmol) of ferric sulfate were added dropwise for polymer reaction. After the mixture was stirred at 25 ° C. for 24 hours, the remaining initiator and oxide ions were removed by two ion exchange resins (300 mL Lewatit ™ S100MB + 500 mL Lewatit ™ M600MB). In addition, after further stirring at 90 ° C for 1 hour, a high-shear macrofluidizing agent was used, and dispersion treatment was performed under the conditions of 15 MPa to produce a conductive polymer aqueous dispersion.

[Manufacturing example 3]

Conductive polymer composition using an anionic surface active (SLS) agent

2.5 L of distilled water and 240% of 40% SOS (Sodium Octyl Sulfate) were placed in a 5 L reactor equipped with a stirrer and a nitrogen filling device at 25 ° C., and the mixture was stirred at a speed of 300 rpm. After 30 minutes of nitrogen bubbling, 56.2 g (0.39 mol) of 3,4-ethylenedioxythiophene and 132 g (0.55 mol) of sodium persulfate and 1.0 g (2.5 mmol) of iron sulfate were added dropwise for polymer reaction. After the mixture was stirred at 25 ° C. for 24 hours, the remaining initiator and oxide ions were removed by two ion exchange resins (300 mL Lewatit ™ S100MB + 500 mL Lewatit ™ M600MB). In addition, after further stirring at 90 ° C for 1 hour, a high-shear macrofluidizing agent was used, and dispersion treatment was performed under the conditions of 15 MPa to produce a conductive polymer aqueous dispersion.

[Manufacturing example 4]

Conductive polymer mixture using poly (styrene sulfonate) [PSS]

At 25 ° C, put 71.4 g of 30% poly (styrene sulfonate) [PSS] (Mw = 290,000) solution in a suitable reaction vessel with a stirrer and a nitrogen inlet, and mix with 1 L of deionized water. . After bubbling nitrogen through this solution for 30 minutes, 10.7 g of EDOT was added. Fe ₂ (SO ₄ ) ₃ ˙H ₂ O and Na ₂ S ₂ O _{8 were} added at respective concentrations of 0.13 and 41.6 mM, and the polymerization reaction was started. Next, after the reaction mixture was stirred at 25 ° C., a predetermined type of PEDOT was added with a concentration of 6.95 mM and a corresponding amount of Na ₂ S ₂ O ₈ . After adding a 16-hour reaction, the reaction mixture was treated twice with an ion exchanger (1,000 mL of LewatitTM S100MB + 1,000 mL of LewatitTM M600MB). After the produced mixture was heat-treated at 95 ° C for 2 hours, the resulting black mixture was treated with a high-shear macrofluidizer under the conditions of 60 MPa.

[Example 1]

Conductive polymer aqueous dispersion 60wt%, water 6wt%, isopropyl alcohol 4wt%, 2-Amino-2-methyl-1-propanol 2wt%, waterborne polyurethane resin adhesive 20wt%, dimethyl sulfene 6wt %, Organic silicon wetted at a ratio of 2wt% to prepare an antistatic coating mixture. The conductive polymer aqueous dispersion (1.4% by weight of powder) of the above manufacturing example 1 was put into a mixing container for 1 hour. Stirring.

Add 2-Amino-2-methyl-1-propanol (Alfa aesar, 95%) to the mixing container and stir for 1 hour, then add water-based polyurethane resin adhesive (Neo Rez R-961 (powder powder) (32% by weight) After 30 minutes of re-stirring, add dimethyl sulfene in the mixing container, and then wet with silicone (BYK-333) for 1 hour to produce an antistatic coating. mixture.

In addition, a mixed solvent of distilled water and isopropyl alcohol (water: isopropanol = 3: 7 (weight ratio)) is used to dilute the above-mentioned primary antistatic coating mixture twice. At this time, the weight ratio of the diluted antistatic coating mixture and the above mixed solvent should be 1: 2 ~ 10.

[Example 2]

The antistatic coating mixture was produced in the same manner as in Example 1 above, but for the use of the conductive polymer dispersion, the conductive polymer aqueous dispersion (1.4% by weight of powder) of Production Example 2 was used once. Antistatic coating mixture.

In addition, the above-mentioned antistatic coating mixture was diluted twice by the same method as in Example 1 above.

[Example 3]

The antistatic coating mixture was carried out in the same manner as in Example 1 above, but for the use of the conductive aqueous dispersion, the antistatic polymer aqueous dispersion (1.4% by weight of powder) of Manufacturing Example 3 was used once to manufacture Antistatic coating mixture.

In addition, the above-mentioned primary antistatic coating mixture was used in the same manner as in Example 1 and diluted twice.

[Comparative Example 1]

The antistatic coating mixture was produced in the same manner as in Example 1 above, but for the use of the conductive polymer aqueous dispersion, the conductive polymer dispersion (1.4% by weight of powder) of the above Production Example 4 was used once. Antistatic coating mixture.

In addition, the above-mentioned antistatic coating mixture will be diluted twice by the same method as in Example 1 above.

[Experimental Example 1]

Production of the conductive layer using the diluted antistatic coating mixtures of Examples 1 to 3 and Comparative Example 1

The diluted antistatic coating mixtures of Examples 1 to 3 and Comparative Example 1 were coated with a bar thickness of 6.86 μm on a 210 × 297 mm poly (ethylene terephthalate) support, and then This conductive layer was produced after drying for 2 minutes at 105 ° C.

The characteristics of the conductive layer were prepared using the diluted antistatic coating mixtures of Examples 1 to 3 and Comparative Example 1

The surface resistance of the layer was measured under a room condition of a temperature of 25 ° C and a relative humidity of 37%. Surface resistance (Ω / □) will be measured using Probe (SRM-110) and Fluke (8846A) The results are shown in Table 1.

The light transmittance adopts uv-vis spectrometer from Sinco. Sampling 50mm x 50mm poly (ethylene terephthalate). The film adopts referance, so that light with a wavelength of 400 ~ 700nm passes through the above-mentioned embodiments in a level. The produced coating film was measured for its value.

The wet-heat durability characteristics of the conductive layer were prepared using the diluted antistatic coating mixtures of Examples 1 to 3 and Comparative Example 1.

In a constant temperature and humidity room, at 85 ° C and 85% relative humidity (Relative Humidity, RH), leave it for 168 hours (hr), and then take out the surface resistance and transmittance of each according to the above measurement method. Evaluation.

The antistatic coating mixture of the present invention realizes a variety of surface resistances (surface resistance: 10 ⁴ to 10 ⁸ ) at a dilution rate. It is a single liquid coating mixture with excellent antistatic performance, good transparency and safe storage, It shortens the engineering time and improves the productivity of the project. Because it is composed of water-soluble solvents, it is environmentally friendly.

When the corresponding coating mixture forms a coating film on a PET film, etc., it has excellent transparency and light transmittance, as well as conductivity. Films used on display screens, liquid crystal protective films for mobile phones, PDP and LCD panel protective films It is very useful as a transparent antistatic coating film on various display devices.

Claims (6)

A diluted antistatic coating mixture, comprising: an antistatic coating mixture with multiple surface resistance properties according to the dilution rate, which is composed of 30-80wt% conductive polymer aqueous dispersion and 10-30wt% water-soluble viscosity Mixture, 1-5wt% alkaline additives, 1-10wt% ethanol solvents, 5-15wt% organic solvents, 0.1-5wt% additives to improve wettability and balance, and 2.9-20wt% water (H ₂ O) A mixed solvent; and a mixed solvent containing water and isopropanol in a weight ratio of 3: 7; wherein the weight ratio of the antistatic coating mixture having multiple surface resistance properties at the dilution ratio to the mixed solvent is 1: 2-10; wherein the conductive polymer aqueous dispersion is a 3,4-ethylenedioxythiophene monomer of Formula 1, an anionic surfactant, and P-toluene iron (III) sulfate, phenylsulfite One or two or more oxides of iron (III), ferric (III) sulfate, triple iron (III) sulfate and iron (III) sulfate are prepared by stirring and polymerizing at 300-1,000 rpm at 25 ° C. The polyethylene (3,4-ethylenedioxythiophene) aqueous solution of formula 10; wherein the anionic surfactant is the whole of the aqueous solution of formula 10 The water concentration in the range of 5-95%, acidity is 6.5-5.0 of the formula according to any one of 2 to 9 wherein: [Chemical Formula 2] [Chemical Formula 7] The alkyl substituents R in the formulae 2 to 7 and 9 are an alkyl group, an isoalkyl group, an alkoxy group, an alkoxyalkyl group, an alkylsulfonic acid peonil, and an alkylsilane with 4 to 18 carbon atoms. And one of alkoxysilane; the metal ion M of the formulae 2 to 4, 6, 8, and 9 is a compound selected from Li, Na, Mg, K, Ca or neutralized with an amine. The diluted antistatic coating mixture as described in claim 1, wherein the water-soluble adhesive is a fluoropolyurethane, tetrafluoropropylene, trifluoroethylene, hexafluoropropylene, polyurethane, One or two or more of polyurethane-acrylic and polyester are selected. The diluted antistatic coating mixture as described in claim 1, wherein the alkaline additive is an ammonia, an aliphatic alkylamine, an alkali metal hydroxide, an alkali metal carbonate, or an alkaline earth metal hydroxide. , Alkaline earth metal carbonate is selected from one or two or more. The diluted antistatic coating mixture according to item 1 of the claim, wherein the ethanol solvent is one or two or more selected from methanol, ethanol, and isopropanol. The diluted antistatic coating mixture according to item 1 of the claim, wherein the organic solvent is selected from one or two or more of dimethyl sulfene, monoethylene glycol, and N-methylpyrrolidone. The diluted antistatic coating mixture according to claim 1, wherein the additive is one or two or more selected from polysiloxane, polyacrylate, and fluorine.