KR20080018674A - Antistatic coating composition, antistatic coating film production method using same and coating film - Google Patents

Abstract

In the antistatic coating process using a conductive polymer, there is disclosed a coating composition and a method for producing an antistatic coating film using the same that can improve the aggregation phenomenon of the polymer caused by contact with the metal part of the coating machine. The coating composition is a conductive polymer aqueous dispersion; Water-soluble binder resins; Alcohol solvents; Functional organic solvents; water; And polymer aggregation inhibitors. In addition, the method for producing a coating film may include coating the conductive coating composition on a substrate; And drying the coated composition.

Description

Antistatic coating composition and method for producing antistatic coating film using same and coating film thereof {Anti-static coating composition, preparation method of coating film using the same and the coating film}

 The present invention relates to an antistatic coating composition, a method for preparing an antistatic coating film using the same, and an antistatic coating film prepared thereby, and more particularly, to an antistatic coating composition which removes a polymer agglomeration phenomenon in the coating composition, a transparent antistatic material using the same It relates to a method for producing a coating film and an antistatic coating film produced thereby.

As various semiconductors and electronic devices are miniaturized and highly integrated, the generation of static electricity causes various problems in the product. In order to effectively remove such static electricity, an antistatic coating method using a conductive material has been proposed. Currently, such a coating technology is used in an antistatic coating film of the outer glass of the display device, a tray for transporting semiconductor devices, a protective film of a polarizing plate and a backlight unit, a coating film of a transparent lens, and the like.

Such an antistatic coating film is a non-conductive polymer containing a conductive additive such as metal particles such as aluminum, carbon black, and a surfactant which reacts with moisture to have ion conductivity, or polythiopene, polypyrrole, polyaniline It may be made of a conductive polymer having conductivity itself, such as (polyaniline).

Among various conductive materials, conductive polymer materials, which are transparent and have good adhesion to substrates, have recently been spotlighted in various industrial fields. However, when coating is performed with a coating composition including a conductive polymer, the polymers tend to aggregate in the metal part of the coater. Such agglomeration causes defects in the coating process, and if the process is stopped to remove the agglomerated portion, productivity is lowered, thereby increasing manufacturing costs.

Accordingly, it is an object of the present invention to provide an antistatic coating composition that can effectively remove the agglomeration phenomenon of the polymer generated in the metal part of the device when performing the antistatic coating operation to increase the efficiency of the coating operation.

Another object of the present invention is to provide a method for producing a transparent and antistatic coating film having excellent antistatic performance using the composition.

Still another object of the present invention is to provide an antistatic coating film prepared by the above method.

The present invention to achieve the above object,

Conductive polymer aqueous dispersions containing polythiophene-based, polypyrrole-based, polyaniline-based high molecular compounds or mixtures thereof;

Water-soluble binder resins;

Alcohol solvents;

Functional organic solvents selected from the group consisting of dimethyl sulfoxide, propylene glycol methyl ether, N-methylpyrrolidone, ethyl-3-ethoxypropionate, propylene glycol monomethyl ether acetate, butyl carbitol and mixtures thereof;

water; And

Ethylene diamine, dimethyl ethylene diamine, 2-butylamine, triethanolamine, benzotriazole, benzothiazole, pyridine , Tolyltriazole, quinoline, imidazole, benzimidazole, 5-methyl-1H-benzotriazole, polyvinylpyrrolidone It provides a coating composition comprising at least one polymer aggregation inhibitor selected from the group consisting of (polyvinylpyrrolidone), N-phenylthiourea (N-phenylthiourea).

In addition, the present invention to achieve another object,

Coating the coating composition on a substrate; And it provides a method for producing an antistatic coating film comprising the step of drying the coated composition.

In the coating composition according to an embodiment of the present invention, the coating composition is 1 to 30% by weight of the conductive polymer aqueous dispersion; 5 to 25% by weight of the water-soluble binder resin; 5-40% by weight of alcohol solvent; 5-30% by weight of the functional organic solvent; 10-50% by weight of water; And 0.001 to 10% by weight of the polymer aggregation inhibitor.

In the coating composition according to an embodiment of the present invention, the water-soluble binder resin is a group consisting of polyurethane, polymethyl methacrylate, polyacrylate, polyvinyl alcohol, polyvinyl acetal, polyvinylacetate, and mixtures thereof It is preferable that it is 1 or more types chosen from.

In the coating composition according to an embodiment of the present invention, the alcohol solvent is preferably an aliphatic alcohol having 1 to 5 carbon atoms.

The method for producing an antistatic coating film according to the present invention includes coating the coating composition on a substrate, and drying the coated composition.

If the antistatic coating film is formed using the antistatic coating composition prepared by the above method, it is possible to effectively remove the agglomeration phenomenon of the polymer generated in the metal part of the coating machine to increase the efficiency and productivity of the coating operation.

Hereinafter, the present invention will be described in detail.

As described above, the antistatic coating composition of the present invention is a conductive polymer aqueous dispersion; Water-soluble binder resins; Alcohol solvents; Functional organic solvents; water; And polymer aggregation inhibitors.

The conductive polymer has an antistatic effect on the surface of the coating film and is used to remove contaminants such as dust. The conductive polymer aqueous dispersion in the coating composition of the present invention is obtained by dispersing or dissolving the conductive polymer compound in water, wherein the concentration of the polymer compound is 0.1 to 10% by weight based on the total dispersion. The conductive polymer compound is preferably a polythiophene-based, polypyrrole-based or polyaniline-based high molecular compound, more preferably a polythiophene-based compound, and particularly preferably polyethylene dioxythiophene (PEDOT).

Meanwhile, as the conductive polymer aqueous dispersion, Bayer P or Baytron PH, which are commercially available, may be used. Baytron P is a product in which polystyrene sulfonic acid (PSS) is added as a dopant to an aqueous dispersion in which polyethylene dioxythiophene (PEDOT) is dispersed in water. The content of polyethylene dioxythiophene in the Baytron P is 1.4%.

The content of the conductive polymer aqueous dispersion is preferably 1 to 30% by weight based on the total coating composition. If the content of the conductive polymer aqueous solution is less than 1% by weight, there is a problem that the surface resistance of the coating film is increased to reduce the antistatic performance, if the content of more than 30% by weight coating of the coating composition without further improvement of the antistatic and electromagnetic shielding performance There is a problem that the properties are lowered and the manufacturing cost is increased.

The water-soluble binder resin in the antistatic coating composition according to the present invention improves the dispersibility of the conductive polymer, and serves to improve the film uniformity, adhesion, film strength, etc. of the resulting coating film. As the binder resin, a conventional photocurable or thermosetting binder can be widely used, and for example, polyurethane, polymethylmethacrylate, polyacrylate, polyvinyl alcohol, polyvinyl acetal, polyvinylacetate, or Mixtures thereof, but are not limited to these. Of these, when the polyurethane resin of water-soluble thermosetting type is used, the coating film to be formed is preferable because its adhesion property and film strength characteristics and antistatic performance are improved.

The content of the water-soluble binder resin is preferably 5 to 25% by weight based on the total coating composition. If the content of the water-soluble binder resin is less than 5% by weight, there is a problem that the uniformity, adhesion and film strength of the coating film is lowered, and when the content of the water-soluble binder resin is greater than 25% by weight, the dispersibility of the conductive polymer is lowered, the antistatic performance is lowered, and the large area. There is a problem that the frequency of occurrence of stains during coating increases.

Alcohol solvent in the antistatic coating composition according to the present invention serves to improve the coating properties, such as drying of the coating composition. As the alcohol solvent, an alcohol compound commonly used in the polymer coating composition may be widely used, and preferably one or more of aliphatic alcohols having 1 to 5 carbon atoms may be selected, and more preferably methanol, ethanol, Isopropyl alcohol (IPA) or a mixture thereof may be used, and preferably, a solvent mixture prepared by mixing ethanol and isopropyl alcohol may be used.

The content of the alcohol solvent is preferably 5 to 40% by weight, preferably 10 to 30% by weight of the alcohol solvent based on the total coating composition. If the content of the alcohol solvent is less than 5% by weight relative to the total coating composition, there is a fear that the dryability is lowered. If the content of the alcohol solvent exceeds 40% by weight, the dispersibility of the conductive polymer is lowered to increase the surface resistance.

The antistatic coating composition according to the present invention includes a functional organic solvent which further improves coating properties such as solubility, dispersibility, dryness, film uniformity, etc. of the coating composition together with the aliphatic alcohol solvent. The functional organic solvents include dimethyl sulfoxide (DMSO), propyleneglycol methylether (PGME), N-methylpyrrolidone (NMP), ethyl-3-ethoxypropionate (ethyl-3-ethoxypropionate; EEP), propyleneglycol monomethyl etheracetate (PGMEA), butyl carbitol (BC), or mixtures thereof, and preferably dimethyl sulfoxide use.

The content of the functional organic solvent is 5 to 30% by weight, preferably 10 to 30% by weight based on the total coating composition. If the content of the functional organic solvent is less than 5% by weight, there is a problem in that the coating composition of the coating composition is inferior and a non-uniform film is formed, and when the content of the functional organic solvent exceeds 30% by weight, there is a problem in that the drying performance is reduced without particularly improving the coating performance.

The antistatic coating composition of the present invention further comprises an additive for inhibiting polymer aggregation on the metal surface. Polymer aggregation inhibitors that can be used are amine compounds such as ethylene diamine, dimethyl ethylene diamine, 2-butylamine, triethanolamine, benzotriazole, benzo Benzothiazole, pyridine, tolyltriazole, quinoline, imidazole, benzimidazole, 5-methyl-1H-benzotriazole (5-methyl- 1H-benzotriazole), polyvinylpyrrolidone, and N-phenylthiourea (N-phenylthiourea).

The content of the polymer aggregation inhibitor is preferably 0.001 to 10% by weight based on the total coating composition. If it is less than 0.001% by weight, the effect of the polymer aggregation inhibitor is insignificant, so that the aggregation of the polymer cannot be effectively suppressed, and if it is 10% by weight or more, the dispersibility and antistatic performance of the coating liquid are reduced.

The polymer aggregation inhibitor may be added after dissolving in a solvent first, or after mixing all the remaining composition.

In the case of preparing the coating composition by mixing the components in turn, water may be added to disperse the water-soluble binder and the conductive polymer aqueous dispersion. The amount of water to be added is preferably 10 to 50% by weight based on the total composition.

Hereinafter will be described a method for producing an antistatic coating film of the present invention.

Method for producing a coating film according to the invention, the step of coating the coating composition according to the invention on a substrate; And drying the coated composition.

In the method for producing an antistatic coating film of the present invention, an organic material such as polyester, polystyrene, polyimide, polyamide, polysulfonate, polycarbonate, polyacrylate, polyethylene, or polypropylene as a substrate for coating the coating composition A polymeric substrate is used.

Preferred coating methods include gravure coating, reverse coating and roll coating.

In the method for producing an antistatic coating film according to the present invention, the conditions for drying and curing the coating film are selected according to the respective coating methods, but it is usually performed at a temperature of 60 to 120 ° C. for 5 to 120 seconds. Preferably, it is more preferable to carry out in 10 to 60 second at the temperature of 80-120 degreeC.

When the drying and curing temperature is less than 60 ° C, drying is insufficient, and even if drying and curing above 120 ° C, there is no advantage in terms of performance of the coating film as compared with drying and curing below 120 ° C. There is a problem such that the operation risk due to high temperature heating is increased.

If the drying and curing time is less than 5 seconds, the drying is insufficient, and if drying and curing for more than 120 seconds, there is no advantage in terms of the performance of the coating film, and the cost of forming the coating film is high.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples and comparative examples, percentages and mixing ratios are by weight unless otherwise indicated.

(Comparative Example 1)

Antistatic coating composition and Of coating film  Produce

20 parts by weight of water, 20 parts by weight of dimethyl sulfoxide, 10 parts by weight of ethanol and 15 parts by weight of isopropyl alcohol were added to the mixing vessel, followed by stirring for 1 hour. 15 parts by weight of a water-soluble polyurethane resin was added thereto and further stirred for 1 hour. 20 parts by weight of an aqueous polyethylene dioxythiophene (PEDOT) dispersion was added and stirred for 1 hour to prepare a coating composition. As the aqueous polyethylene dioxythiophene dispersion, Baytron P (PEDOT concentration 1.4 wt%) manufactured by Bayer, doped with polystyrene sulfonate, was used.

Using the obtained coating composition, it coated on polyethylene terephthalate resin (PET) by the gravure coat method, and dried at 110 degreeC for 10 second.

 (Examples 1 to 7)

Antistatic coating composition and Of coating film  Produce

An antistatic coating composition was prepared with the same composition as Comparative Example 1, but 0.5 parts by weight of the polymer aggregation inhibitor shown in Table 1 was further added. Polymer aggregation inhibitor was added in admixture with isopropyl alcohol and then further stirred for 1 hour. Using the obtained coating composition, it coated on polyethylene terephthalate resin (PET) by the gravure coat method, and dried at 110 degreeC for 10 second.

(Comparative Example 2)

Antistatic coating composition and Of coating film  Produce

An antistatic coating composition was prepared in the same manner as in Example 2, but 20 parts by weight of 2-butylamine was added as a polymer aggregation inhibitor.

Types and Contents of Polymer Aggregation Inhibitors Used in Coating Compositions Types of Polymer Aggregation Inhibitors Content of Polymer Aggregation Inhibitor (wt%) Comparative Example 1 none - Example 1 Triethanolamine 0.5 Example 2 2-butylamine 0.5 Example 3 Quinoline 0.5 Example 4 Benzotriazole 0.5 Example 5 Polyvinylpyrrolidone 0.5 Example 6 Benzimidazole 0.5 Example 7 Tolyltriazole 0.5 Comparative Example 2 2-butylamine 20

Property evaluation

(1) degree of aggregation

The degree of aggregation of the conductive polymer generated in the doctor blade during the coating process was visually observed and evaluated as follows.

○: a lot of aggregation occurs,

△: little aggregation occurs;

X: No aggregation occurs.

(2) surface resistance

The surface resistance of the coating film was measured using ST-3, a surface resistance measuring instrument of SIMCO. The smaller the surface resistance value, the better the antistatic effect.

Surface resistance and agglomeration degree of coating film Surface resistance (Ω / □) Coagulation degree Comparative Example 1 1.0 x 10 ⁶ ○ Example 1 1.2 x 10 ⁶ × Example 2 1.6 x 10 ⁶ × Example 3 2.0 x 10 ⁶ × Example 4 1.6 x 10 ⁶ × Example 5 1.2 x 10 ⁶ × Example 6 1.8 x 10 ⁶ △ Example 7 1.4 x 10 ⁶ △ Comparative Example 2 3.5 x 10 ⁷ △

When the polymer aggregation inhibitor was added as in Examples 1 to 7 of Table 2, the coating property was excellent, and the aggregation phenomenon of the polymer did not occur during the coating process without increasing the surface resistance as much as the comparative example. . As in Examples 2 to 5, when triethanolamine, 2-butylamine, quinoline, benzotriazole, and polyvinylpyrrolidone were used as the polymer aggregation inhibitor, the aggregation preventing effect was particularly excellent.

As in the case of Comparative Example 2, the content of the additive increases, the surface resistance increases, which lowers the antistatic performance and the dispersibility of the coating liquid worsens.

As described above, when the antistatic coating film is formed using the antistatic coating composition of the present invention, it is possible to effectively remove the agglomeration phenomenon of the polymer generated in the metal part of the device to increase the efficiency and productivity of the coating operation.

Therefore, the antistatic coating film prepared according to the present invention has excellent antistatic function and transparency, and can be applied to various parts of the semiconductor and display industries.

Claims (7)

In the antistatic coating composition, 1 to 30% by weight of a conductive polymer aqueous dispersion containing polythiophene, polypyrrole, polyaniline-based polymer compound or a mixture thereof; 5 to 25% by weight of the water-soluble binder resin; Alcohol solvent 5-40% by weight; Functional organic solvents selected from the group consisting of dimethyl sulfoxide, propylene glycol methyl ether, N-methylpyrrolidone, ethyl-3-ethoxypropionate, propylene glycol monomethyl ether acetate, butyl carbitol and mixtures thereof To 30% by weight; 10-50% by weight of water; And Ethylene diamine, dimethyl ethylene diamine, 2-butylamine, triethanolamine, benzotriazole, benzothiazole, pyridine , Tolyltriazole, quinoline, imidazole, benzimidazole, 5-methyl-1H-benzotriazole, polyvinylpyrrolidone (polyvinylpyrrolidone), and N-phenylthiourea (N-phenylthiourea) antistatic coating composition comprising 0.001 to 10% by weight of one or more polymer aggregation inhibitors selected from the group consisting of. According to claim 1, wherein the conductive polymer contained in the conductive polymer aqueous dispersion is antistatic coating composition, characterized in that the polyethylene dioxythiophene (polyethylen dioxithiophene; PEDOT). The method of claim 1, wherein the water-soluble binder resin is one or more selected from the group consisting of polyurethane, polymethyl methacrylate, polyacrylate, polyvinyl alcohol, polyvinyl acetal, polyvinylacetate, and mixtures thereof. Antistatic coating composition characterized in. The antistatic coating composition of claim 1, wherein the alcohol solvent is an aliphatic alcohol having 1 to 5 carbon atoms. The antistatic coating composition of claim 4, wherein the alcohol solvent is methanol, ethanol, isopropyl alcohol or a mixture thereof. Coating the coating composition according to claim 1 on a substrate; And Method of producing an antistatic coating film comprising the step of drying the coated composition. An antistatic coating film prepared by the method of claim 6.