JP4874895B2 - Antistatic coating composition, method for producing antistatic coating film using the same, and coating film therefor - Google Patents

Description

  The present invention relates to an antistatic coating composition, a method for producing an antistatic coating film using the same, and an antistatic coating film produced thereby, and more particularly, the polymer aggregation phenomenon in the coating composition. The present invention relates to a removed antistatic coating composition, a method for producing a transparent antistatic coating film using the same, and an antistatic coating film produced thereby.

  With the miniaturization and high integration of various semiconductors and electronic devices, the generation of static electricity has various effects on products. In order to effectively remove such static electricity, an antistatic coating method using a conductive material has been proposed. At present, such a coating technique is applied to an antistatic coating film on the outer glass of a display element, a tray for transporting a semiconductor element, a protective film for a polarizing plate and a backlight unit, and a coating film for a transparent lens.

  Such an antistatic coating film includes metal particles such as aluminum, carbon black, a non-conductive polymer containing a conductive additive such as a surfactant that has ionic conductivity when reacted with moisture, And a conductive polymer having conductivity, such as polythiophene, polypyrrole, and polyaniline.

  Among various conductive materials, conductive polymer materials that are transparent and have good adhesion to the substrate have recently attracted attention in various industrial fields. However, when coating is performed with a coating composition containing a conductive polymer, a phenomenon in which the polymer is aggregated at the metal portion of the coating device tends to occur. Such agglomeration causes a defect in the coating process, and if the process is interrupted to remove the agglomerated part, the productivity is lowered and the manufacturing cost is increased.

  The object of the present invention is to provide an antistatic coating composition that effectively removes the polymer agglomeration phenomenon that occurs in the metal part of the equipment and improves the efficiency of the coating operation when performing the antistatic coating operation. It is to be.

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

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

In order to achieve the above object, the present invention provides a conductive polymer aqueous dispersion containing a polythiophene-based, polypyrrole-based, polyaniline-based polymer compound or a mixture thereof, a water-soluble polyurethane, a water-soluble polyacrylate, and a water-soluble polyvinyl. One or more water-soluble binder resins selected from the group consisting of alcohol, water-soluble polyvinyl acetal, and mixtures thereof , alcohol solvents, dimethyl sulfoxide, propylene glycol methyl ether, N-methylpyrrolidone, ethyl-3 A functional organic solvent selected from the group consisting of ethoxypropionate, propylene glycol monomethyl ether acetate, butyl carbitol and mixtures thereof, water, ethylenediamine, dimethylethylenediamine, 2-butylamine, triethanol One or more polymer aggregates selected from the group consisting of ruamine, benzotriazole, benzothiazole, pyridine, tolyltriazole, quinoline, imidazole, benzimidazole, 5-methyl-1H-benzotriazole, polyvinylpyrrolidone, N-phenylthiourea A coating composition comprising an inhibitor is provided.

  In order to achieve the other object, the present invention provides a method for producing an antistatic coating film, comprising: a step of coating a substrate with the coating composition; and a step of drying the coated composition. provide.

In the coating composition according to an embodiment of the present invention, the coating composition is 1 to said conductive polymer aqueous dispersion 30 wt%, and 5 to 25% by weight of the binder resin, 5 to 40 wt% It is preferable to contain 5 to 30% by weight of the functional organic solvent, 10 to 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 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 a step of coating a substrate with the coating composition and a step of drying the coated composition.

  If an antistatic coating film is formed using the antistatic coating composition manufactured by the above method, the polymer agglomeration phenomenon generated in the metal part of the coating device is effectively removed, and the efficiency of the coating operation is reduced. And can increase productivity.

  If the antistatic coating film is formed using the antistatic coating composition of the present invention, the polymer agglomeration phenomenon generated in the metal part of the device is effectively removed, and the efficiency and productivity of the coating operation are improved. Can be increased.

  The antistatic coating film produced by the present invention has an excellent antistatic function and transparency, and can be applied to various fields in the semiconductor and display industries.

Hereinafter, one embodiment of the present invention will be described in more detail.
Antistatic coating composition according to one embodiment of the present invention, a conductive polymer aqueous dispersion, and Ba Indah resin, an alcohol solvent, a functional organic solvent, water, a polymeric aggregation inhibitor, including.

  The conductive polymer is used to remove a contamination source such as dust by generating an antistatic effect on the surface of the coating film. In the coating composition according to one embodiment of the present invention, the conductive polymer aqueous dispersion is obtained by dispersing or dissolving the conductive polymer compound in water, and the concentration of the polymer compound is the total dispersion. 0.1 to 10% by weight based on the above. The conductive polymer compound is preferably a polythiophene-based, polypyrrole-based, or polyaniline-based polymer compound, more preferably a double polythiophene-based compound, and particularly preferably polyethylene dioxythiophene (PEDOT).

On the other hand, as the conductive polymer aqueous dispersion, commercially available product names Baytron P and Baytron PH manufactured by Bayer may be used. Baytron
P is a product obtained by adding polystyrene sulfonic acid (PSS) as a dopant to an aqueous dispersion in which PEDOT is dispersed in water. Of the Baytron P, the content of PEDOT is about 1.4%.

  The content of the conductive polymer aqueous dispersion is preferably 1 to 30% by weight based on the entire coating composition. If the content of the conductive polymer aqueous dispersion is less than 1% by weight, there is a problem that the surface resistance of the coating film is increased and the antistatic performance is deteriorated. There is a problem that the coating property of the coating composition is lowered and the manufacturing cost is increased without special improvement of the shielding performance.

Among the antistatic coating compositions according to an embodiment of the present invention, the water-soluble binder resin improves the dispersibility of the conductive polymer and improves the film uniformity, adhesion, and film strength of the coating film to be produced. Have a role to improve. As the binder resin, ordinary photo-curing or thermosetting binders can be used in a wide range, for example, water-soluble polyurethane, water-soluble polyacrylate, water-soluble polyvinyl alcohol, water-soluble polyvinyl acetal , or a mixture thereof. Although it is mentioned, it is not limited to these. Of these, use of a water-soluble thermosetting polyurethane resin is desirable because it improves the adhesion and film strength characteristics and antistatic performance of the coating film to be formed.

Content in the pre fangs Indah resin is preferably 5 to with respect to the total coating composition is 25% by weight. If it is less than before Kiba Indah content of the resin is 5 wt%, the uniformity of the coating film, there is a problem that adhesion and film strength is lowered, if it exceeds 25 wt%, the dispersibility of the conductive polymer As a result, the antistatic performance deteriorates, and the frequency of occurrence of contamination increases when a large area is coated.

  Among the antistatic coating compositions according to one embodiment of the present invention, the alcohol solvent plays a role of improving coating properties such as drying properties of the coating composition. As the alcohol solvent, alcohol compounds commonly used in polymer coating compositions are used in a wide range, and preferably one or more aliphatic alcohols having 1 to 5 carbon atoms are selected and used. Desirably, methanol, ethanol, isopropyl alcohol (IPA) or a mixture thereof may be used. Desirably, a solvent mixture prepared by mixing ethanol and isopropyl alcohol may be used.

  The content of the alcohol solvent is 5 to 40% by weight, preferably 10 to 30% by weight, based on the entire coating composition. If the content of the alcohol solvent is less than 5% by weight with respect to the total coating composition, the drying property may be lowered. If the content exceeds 40% by weight, the dispersibility of the conductive polymer is lowered and the surface resistance is lowered. There is a problem of rising.

  The antistatic coating composition according to an embodiment of the present invention is a functional organic material that further improves the coating properties such as solubility, dispersibility, drying property, and film uniformity of the coating composition together with the aliphatic alcohol solvent. Contains solvent. Examples of the functional organic solvent include dimethyl sulfoxide (DMSO), propylene glycol methyl ether (PGME), N-methylpyrrolidone (NMP), ethyl-3-ethoxypropionate (EEP), propylene glycol monomethyl ether acetate (PGMEA). , Butyl carbitol (BC), or a mixture thereof, preferably dimethyl sulfoxide.

  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 property of the coating composition is deteriorated and a non-uniform film is formed. There is a problem that the drying property is lowered without being improved.

  The antistatic coating composition according to an embodiment of the present invention further includes an additive that suppresses polymer aggregation on the metal surface. The polymer aggregation inhibitor used is ethylenediamine, dimethylethylenediamine, 2-butylamine, triethanolamine, benzotriazole, benzothiazole, pyridine, tolyltriazole, quinoline, imidazole, benzimidazole, 5-methyl-1H- as amine compounds. 1 or more types selected from the group which consists of benzotriazole, polyvinylpyrrolidone, and N-phenylthiourea are included.

  The content of the polymer aggregation inhibitor is preferably 0.001 to 10% by weight based on the total coating composition. If the amount is less than 0.001% by weight, the effect of the polymer aggregation inhibitor is minute and the polymer aggregation cannot be effectively suppressed. If the amount is 10% by weight or more, the dispersibility of the coating liquid and the antistatic performance. Reduce.

  The polymer aggregation inhibitor may be added after first being dissolved in a solvent, or may be added after any remaining composition is mixed.

When producing the coating composition by mixing the components sequentially, the water may be added to the dispersion Bas Indah and conductive polymer aqueous dispersion. The content of water to be added is preferably 10 to 50% by weight based on the whole composition.

Hereinafter, the manufacturing method of the antistatic coating film which concerns on one Embodiment of this invention is demonstrated.
The manufacturing method of the coating film which concerns on one Embodiment of this invention includes the process of coating the board | substrate with the coating composition which concerns on one Embodiment of this invention, and the process of drying the said coated composition.

  In the method for producing an antistatic coating film according to one embodiment of the present invention, as a substrate on which the coating composition is coated, polyester, polystyrene, polyimide, polyamide, polysulfonic acid, polycarbonate, polyacrylic acid, polyethylene, polypropylene, or the like is used. Organic polymer substrates may be used.

  Desirable coating methods include a gravure method, a reverse coating method, and a roll coating method.

  In the method for producing an antistatic coating film according to an embodiment of the present invention, the drying and curing conditions for the coating film are selected according to the respective coating methods, but a temperature of 60 to 120 ° C. that is normally used. For 5 to 120 seconds, more preferably at a temperature of 80 to 120 ° C. for 10 to 60 seconds.

  When the drying and curing temperature is less than 60 ° C., the drying is insufficient. Even if the drying and curing is performed at a temperature exceeding 120 ° C., compared with the case of drying and curing at 120 ° C. or less, the coating film There is not only an advantage in terms of performance, but also there is a problem that the cost increases and the danger of work due to high temperature heating increases.

  When the drying and curing time is less than 5 seconds, the drying is insufficient. Even if the drying and curing is performed for more than 120 seconds, there is no advantage in the performance of the coating film. The cost of forming will increase.

  Hereinafter, although one embodiment of the present invention will be described more specifically through examples and comparative examples, the present invention is not limited to the following examples. In the following examples and comparative examples, percentages and mixing ratios are based on weight unless otherwise noted.

(Comparative Example 1)
Production of Antistatic Coating Composition and Coating Film 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 placed in a mixing container and stirred for 1 hour. To this was added 15 parts by weight of water-soluble polyurethane resin, and the mixture was further stirred for 1 hour. 20 parts by weight of PEDOT aqueous dispersion was added and stirred for another hour to prepare a coating composition. As the PEDOT aqueous dispersion, Baytron manufactured by Bayer, doped with sulfonic acid polystyrene.
P (PEDOT concentration of 1.4% by weight) was used.

  Using the obtained coating composition, it was coated on polyethylene terephthalate resin (PET) by a gravure coating method and dried at 110 ° C. for 10 seconds.

(Examples 1 to 7)
Production of Antistatic Coating Composition and Coating Film An antistatic coating composition was produced with the same composition as Comparative Example 1, but 0.5 parts by weight of the polymer aggregation inhibitor shown in Table 1 below was further added. The polymer aggregation inhibitor was added after being mixed with isopropyl alcohol, and then stirred for another hour. The obtained coating composition was coated on a polyethylene terephthalate resin (PET) by a gravure coating method and dried at 110 ° C. for 10 seconds.

(Comparative Example 2)
Production of antistatic coating composition and coating film An antistatic coating composition was produced in the same manner as in Example 2, except that 20 parts by weight of 2-butylamine was added as a polymer aggregation inhibitor.

Physical Property Evaluation (1) Degree of Aggregation The degree of aggregation of the conductive polymer generated on the doctor blade during the coating process was observed with the naked eye and evaluated as follows.
○: A lot of aggregation occurs.
Δ: Some aggregation occurs.
X: Aggregation does not occur.
(2) Surface resistance The surface resistance of the coating film was measured using ST-3 which is a surface resistance measuring instrument manufactured by SIMCO. It represents that it is excellent in the antistatic effect, so that a surface resistance value is small.

  When the polymer aggregation inhibitor is added as in Examples 1 to 7 in Table 2, the coating property is excellent, the surface resistance does not increase much compared to the comparative example, and the polymer aggregation phenomenon occurs in the coating process. Did not occur. As in Examples 2 to 5, when triethanolamine, 2-butylamine, quinoline, benzotriazole, and polyvinylpyrrolidone were used as the polymer aggregation inhibitor, the aggregation prevention effect was particularly remarkable.

  As in Comparative Example 2, when the content of the additive is increased, the surface resistance is increased, the antistatic performance is lowered, and the dispersibility of the coating liquid is lowered.

  Although one embodiment of the present invention has been described above through preferred examples and comparative examples, those skilled in the art will recognize that various modifications and other equivalent examples are possible. Therefore, the true technical protection scope of the present invention must be determined by the technical idea of the claims.

  The present invention is applicable to various parts of the semiconductor and display industries.

Claims (6)

In the antistatic coating composition, the composition comprises:
1 to 30% by weight of a conductive polymer aqueous dispersion,
5 to 25% by weight of a binder resin that is one or more selected from the group consisting of water-soluble polyurethane, water-soluble polyacrylate, water-soluble polyvinyl alcohol, water-soluble polyvinyl acetal, and mixtures thereof ;
5 to 40% by weight alcohol solvent,
5 to 30 weights of functional organic solvent 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 %When,
10 to 50% by weight of water,
Consists of ethylenediamine, dimethylethylenediamine, 2-butylamine, triethanolamine, benzotriazole, benzothiazole, pyridine, tolyltriazole, quinoline, imidazole, benzimidazole, 5-methyl-1H-benzotriazole, polyvinylpyrrolidone, and N-phenylthiourea From 0.001 to 10% by weight of one or more polymer aggregation inhibitors selected from the group;
Including
The conductive polymer aqueous dispersion contains a polythiophene-based, polypyrrole-based, polyaniline-based polymer compound or a mixture thereof in an amount of 0.1 to 10% by weight based on the total weight of the conductive polymer aqueous dispersion. Antistatic coating composition.   The antistatic coating composition according to claim 1, wherein the conductive polymer contained in the conductive polymer aqueous dispersion is polyethylene dioxythiophene (PEDOT). The antistatic coating composition according to claim 1, wherein the alcohol solvent is an aliphatic alcohol having 1 to 5 carbon atoms. 4. The antistatic coating composition according to claim 3, wherein the alcohol solvent is methanol, ethanol, isopropyl alcohol, or a mixture thereof. Coating a substrate with the coating composition of claim 1;
Drying the coated composition;
A method for producing an antistatic coating film, comprising: An antistatic coating film produced by the method according to claim 5.