KR100404874B1 - Conductive polymer cathode ray tube black coating layer and method for producing thereof - Google Patents

Abstract

The present invention relates to a conductive polymer black-colored CRT (cathod ray tube) coating layer and a method for forming the same, and more particularly, to PEDT, high refractive inorganic sol, C _{1 to} C ₃ alcohol solvent, amide solvent, water soluble or alcohol soluble resin. A first coating layer formed using a first composition comprising a binder and a sulfonic acid monomer dopant and a PEDT, silica sol or alkylsilica sol, a C _{1 to} C ₃ alcohol solvent, an amide solvent, and a sulfonic acid monomer dopant. In a conductive polymer black-colored CRT coating layer consisting of a second coating layer formed using the second composition, a water-dispersible carbon black, a water-dispersible color pigment, and a water-soluble or alcohol-soluble colored dye are added to at least one of the first composition and the second composition. It relates to a conductive polymer black-colored CRT coating layer, characterized in that the coating layer is formed as a low, by the present invention Genie while the four and contrast enhancement characteristics can provide a conductive polymer CRT black colored coating layer that can be an electromagnetic wave shielding function.

Description

Conductive polymer cathode ray tube black coating layer and method for producing etc

The present invention relates to a conductive polymer black colored CRT (cathod ray tube) coating layer and a method for forming the same, and more particularly, to a conductive polymer black colored CRT coating layer having low reflection and contrast enhancement properties and capable of electromagnetic shielding. It relates to a formation method.

As a conductive polymer compound, polyaniline, polypyrrol, polythiophene, and the like are widely used. These polymer compounds have attracted attention as synthetic metals because of their easy polymerization and excellent electrical conductivity, and have been proposed for their application as various conductive materials such as electromagnetic wave materials, secondary battery electrodes and transparent electrodes. However, due to the difficulty in processing and instability in heat, air and ultraviolet light, only a few examples of actual commercialization have been achieved.

In order to solve the above problems and the like of the conventional conductive polymer, poly (3), which is an alcohol-soluble polythiophene conductive polymer described in US Pat. Nos. 5,035,926 and 5,391,472, has recently been attracting attention. , 4-dioxyethylene) -thiophene (poly (3,4-dioxyethylene) thiophene, hereinafter referred to as PEDT). The conductive polymer has excellent solubility, excellent air, heat and UV resistance as well as polyaniline and polypyrrole, as well as other conductive polymers of the same polythiophene type, so that the externally exposed area has been rarely used due to durability problems. It became possible to use as a conductive coating film. In particular, since the transmittance is excellent when forming a thin film, the use of CRT glass surface, transparent plastic surface (panel, film) and other transparent substrates, such as electromagnetic shielding material, antistatic material, has been proposed for use as a conductive coating material.

In the case of the metal oxide-based inorganic ITO (indiumtinoxide) thin film and PEDT thin film containing high refractive index (formerly Korean Patent Publication No. 2000-040197), which is used as the electromagnetic shielding coating material of CRT outer glass, it has high conductivity and less than 1%. In addition to having a low reflectivity function that reflects reflectivity and exhibits excellent coating properties such as very high transmittance (over 98%), it is pointed out that it is not suitable as a coating material for color plane CRT, which has recently been in the spotlight. The reason for this is that the transmittance of the outer surface glass itself for color plane CRT is more than 83%, so that the contrast of the flat CRT screen is reduced when the existing high-permeability, inorganic oxide-based oxide film of metal oxide type or PEDT film containing high refractive index is applied. Because it becomes. Therefore, in recent years, black colored coating liquids having low transmittance have been used for the outer glass of the color flat CRT. In the case of coating liquids developed for this purpose, carbon black is mostly dispersed in a transparent conductive solution. Typical examples thereof include black coating liquids (US Pat. No. 5,681,885) in which carbon powder is dispersed in an ATO (antimonytinoxide) sol and a silica sol solution. In this case, the color is dark black or black brown, which is not excellent in appearance color characteristics, and not only deteriorates the sense of quality, but also uses non-conductive colorant so that the surface resistance of the film is about 10 ¹⁰ ~ 10 ¹¹ Ω / □, which is used only for antistatic. It cannot be used for electromagnetic shielding.

The present invention is to solve the problems of the prior art as described above, by improving the low-reflection coating liquid composition using a high refractive material and a conductive polymer disclosed in the Korean Patent Publication No. 2000-040197 filed by the present inventors low reflection and An object of the present invention is to provide a conductive polymer black-colored CRT coating layer having contrast enhancement properties and also capable of shielding electromagnetic waves.

Another object of the present invention is to provide a method for forming the conductive polymer black-colored CRT coating layer.

One aspect of the present invention for achieving the above object is a first comprising a PEDT, high refractive inorganic sol, C ₁ ~ C ₃ alcohol solvent, amide solvent, water-soluble or alcohol-soluble resin binder and sulfonic acid monomer dopant A second coating layer formed using the first coating layer formed using the composition and a second composition comprising PEDT, silica sol or alkylsilica sol, a C _{1 to} C ₃ alcohol solvent, an amide solvent, and a sulfonic acid monomer dopant. A conductive polymer black-colored CRT coating layer comprising: a water-dispersible carbon black, a water-dispersible color pigment, and a water-soluble or alcohol-soluble color dye, in addition to at least one of the first composition and the second composition, wherein the coating layer is formed. It relates to a polymer black-colored CRT coating layer.

Another aspect of the present invention for achieving the above object is to form a first coating layer using the first composition, and then to form a second coating layer using a second composition thereon for 30 minutes at 150 ~ 200 ℃ It relates to a method of forming a CRT coating layer comprising the step of heat firing for about 1 hour.

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

The first composition of the present invention comprises a PEDT, a high refractive inorganic sol, an alcohol solvent, an amide solvent, a water-soluble or alcohol-soluble resin binder and a sulfonic acid monomer dopant, the second composition is a silica sol or alkyl silica produced from PEDT, silane A water-dispersible carbon black, a water-dispersible colored pigment, and a water-soluble or alcohol-soluble colored dye containing a sol, an alcohol solvent, an amide solvent, and a sulfonic acid monomer dopant, wherein a hydrophilic group is covalently bonded to at least one of the first or second compositions. Characterized in that it is included.

When the composition coating liquid of the present invention is coated on a transparent substrate such as CRT outer glass, the reflectance is 0.3 to 0.8%, the surface resistance is 2X10 ³ to 10 ⁵ Ω / □, low reflection of 40% to 80%, hardness 4H to 8H And a conductive polymer black colored film for flat color TV electronic shielding having contrast enhancement properties.

The component which comprises the composition of this invention is demonstrated in detail as follows.

In the present invention, a polythiophene-based water-soluble PEDT is used as the conductive polymer, and in particular, the dopant-doped polystyrene sulfonate (PSS) is well soluble in water and has excellent thermal stability, moisture stability, and UV stability. desirable. Hereinafter, PEDT used in the composition of the present invention refers to a state containing a dopant. This PEDT can be easily coated by diluting with these solvents because it is well mixed with solvents having a high dielectric constant such as water, alcohol and amide solvents, and polyaniline and polypyrrole, which are other conductive polymers when the coating film is formed It shows excellent transparency compared with that.

The content of the PEDT is 0.02 to 0.4% by weight in the first or second composition, it is applied in the aqueous state. If the content is less than 0.02% by weight, there is a problem that the surface resistance exceeds 10 ⁸ Ω / □, which is the minimum conductivity value of the commercially available conductive thin film, and when the content exceeds 0.4% by weight, the conductivity is excellent. However, because gelation occurs in PEDT and high refractive inorganic sol solution, it is not suitable for CRT exterior glass coating which requires high uniform thin film. The aqueous solution is preferably adjusted to 2 to 25% by weight.

Hereinafter, a high refractive inorganic sol which is a metal oxide used in one layer for the purpose of increasing the refractive index of the conductive polymer thin film transparent film will be described.

The high refractive inorganic sol has a refractive index of RI = 1.6 or more when forming its own thin film. Examples thereof include TiO ₂ sol (hydrolysis in methanol from TYZOR TE from Dupont, a 10% solids solution), and CeO ₂ sol (colo of Nyacol). Ceria sol, 20% solids aqueous solution), TiO ₂ -Fe ₂ O ₃ -SiO ₂ sol (e.g. Catalytic Optolake 1130F-2 (A-8), solids concentration 30% by weight, dispersed in methanol), TiO _2- CeO ₂ -SiO ₂ sol (e.g. Catalytic Optolake 1130A (A-8), solids concentration 30%, dispersed in methanol), TiO ₂ -ZrO ₂ -SiO ₂ sol (e.g. Catalytic Optolake 1130Z, solids concentration 10% , Dispersed in water), TiO ₂ -CeO ₂ sol (e.g. catalyzed products, 20% solids concentration, dispersed in methanol) and CeO ₂ -SiO ₂ sol (hydrolyzed tetraethoxysilane in CeO ₂ aqueous solution and methanol, CeO ₂ / SiO ₂ = 85/15% by weight, solid content concentration 15%).

The high refractive sol inorganic sol used in the present invention is preferably diluted with a solvent so that the solid content concentration is 14 to 16% by weight. The reason is that when the solid content concentration exceeds 16% by weight, the high refractive inorganic sol is used as the conductive polymer. This is because gelation often occurs when added to the included coating liquid without careful and very slow addition. The content of the high refractive inorganic sol is preferably 0.5 to 20% by weight of the solid content concentration of 14 to 16% by weight. If the high refractive inorganic sol solution is used at less than 0.5% by weight, the high refractive index conductive polymer thin film transparent film of 1.6 or more desired in the present invention cannot be prepared, and when used in excess of 20% by weight, the refractive index of the film is very excellent, but the non-conductive material As the surface resistance increases, the conductivity is very low, which is not more than 10 ⁸ Ω / □, which is not suitable for the purpose of the present invention, and also is not suitable because gelation easily occurs in the conductive polymer and the solution and a high uniform film cannot be produced.

The alkoxy silane included in the preparation of the second composition in the present invention is to give adhesion to the CRT outer glass and the hardness of the coating film, and to give a tetraalkoxysilane (Si (OR ') ₄ which is preferably R' = methyl group or ethyl group). Or alkyltrialkoxysilane (RSi (OR ') ₃ , preferably R = methyl group, R' = methyl group or ethyl group) may be used. These alkoxysilanes are reacted with water or additionally added alcohol solvents in the aqueous solution of PEDT to undergo hydrolysis and condensation reactions, followed by silica sol (-SiO ₂ -SiO _2- ) and alkylsilazole (R-SiO ₂ -SiO _2- ) When the silica sol is coated with a thin film and then thermally cured to form polysilicate crystals, the silica sol has adhesiveness with the CRT outer glass and increases the film hardness.

The content of the alkoxy silane is suitably 3 to 10% by weight. If the content is less than 3% by weight, hardness of 5H or more cannot be achieved. If the content is more than 10% by weight, the hardness becomes very good, but the amount of polysilicate that adversely affects the conductivity increases relatively to 10 ³ Surface resistance of ˜10 ⁵ Ω / □ (measured value after formation of the first and second coating layers) cannot be achieved.

In the present invention, as the dispersion solvent of the PEDT conductive polymer solution and the high refractive sol solution, an amide solvent is mixed with the alcohol solvent. This is because the conductivity of the coating film tends to be very low when used only with the alcohol solvent, which is not preferable. When the alcohol and amide solvents are mixed and used, the conductivity of the coating film is excellent. Therefore, even though the PEDT conductive polymer aqueous solution is used, it shows a sufficient film conductivity desired in the present invention. As a result, the occurrence of gelation problem is reduced, so the long-term storage stability of the solution is also excellent.

As the alcohol solvent used in the present invention, alcohols having 1 to 3 carbon atoms such as methanol, ethanol, and isopropanol are suitable, and methanol is more preferable. In the case of mixing two or more kinds of the alcohol, at least 50% of methanol should be included to have good dispersibility.

The content of the alcohol solvent is suitably 50 to 99.3 wt% in the first composition and 55 to 94.8 wt% in the second composition.

Specific examples of the amide solvent used in the present invention include formamide (formamide = FA), N-methylformamide (N-methylformamide = MFA), N, N-dimethylformamide (N, N-dimethylformamide = DMF), Acetamide (acetamide = AA), N-methylacetamide (MAA), N, N-dimethylacetamide (N-, N-dimethylacetamide = DMA), N-methylpropionamide (N-methylpropion amide = MPA), N-methylpyrrolidone (N-methylpyrrolidone = NMP), and the like.

In the present invention, the content of the amide solvent is appropriately 0.1 to 10% by weight regardless of the first composition or the second composition. If the amide solvent is used at less than 0.1% by weight, the sufficient conductivity desired by the present invention cannot be achieved. If the amide solvent is used at more than 10% by weight, the conductivity is high, but the boiling point is high, and thus remains even after high temperature baking of 150 ° C. or higher. The amide solvents adversely affect long-term stability, and also cause problems such as delay in subsequent processes such as secondary coating due to the amide solvent remaining after coating.

PEDT conductive polymer is doped with polystyrenesulfonic acid (-SO ₃ H, -SO ₃ -Na), which serves as a dispersant, to help disperse the conductive polymer itself, but when the amount of the aqueous solution of PEDT conductive polymer is less than 10% by weight And when the surface is not clean when the CRT panel outer glass surface is coated, the first composition includes a water-soluble or alcohol-soluble resin binder because the PEDT conductive polymer itself does not have sufficient dispersibility and adhesion to the substrate surface.

Specific examples of such water-soluble or alcohol-soluble resin binders include polymethyl methacrylate (PMMA), polyacrylate (PA), polyvinyl alcohol (PVOH), polyvinyl acetal (PVAT), polyvinylbutylal (PVB), methyl Cellulose (MC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), polyvinylacetate (PVAc), hydroxypropylmethylcellulose (HPMC) and the like. Such resin binders are preferably added in the form of a solution (alcohol or aqueous solution), and the amount of the binder is preferably 0.005 to 0.1% by weight based on solids. If the content is less than 0.005% by weight does not exhibit the effect of the substrate adhesion desired in the present invention, the dispersibility is inhibited, if the content exceeds 0.1% by weight the viscosity of the composition is increased, the comb pattern after spin coating, such as a uniform film It is not preferable because a problem occurs that is not formed.

In the present invention, the composition of the above-mentioned PEDT conductive polymer aqueous solution, high refractive inorganic sol solution, alcohol and amide solvent, water-soluble or alcohol-soluble resin binder shows the effect of the present invention, PEDT conductive polymer aqueous solution is less than 10% by weight When the concentration is low, the conductivity of the coating film tends to be low, so the composition of the present invention further improves the film conductivity by using a monomer dopant having a sulfonic acid group. Specific examples of the monomer dopant that can be used include p-toluenesulfonic acid (p-TSA), dodecylbenzenesulfonic acid (DDBSA), 1,5-anthraquinonedisulfonic acid (1,5-AQSA), 2,6-anthriqui Nondisulfonic acid (2,6-AQSA), anthraquinonesulfonic acid (AQSA), 4-hydroxybenzenesulfonic acid (4-HBSA), methylsulfonic acid (MSA), nitrobenzenesulfonic acid (NBSA) and the like. In the case of an acid form among these, it is used as it is, and when it exists in the form of a sodium (Na) salt, it replaces and uses it with the form of an acid using aqueous solution of nitric acid (pH = 2).

The sulfonic acid monomer dopant is preferably added in the form of an aqueous solution for dispersibility and the amount is preferably 0.005 to 0.05% by weight based on solid content. If the solid content is less than 0.005% by weight does not exhibit the desired conductivity synergistic effect in the present invention, if it exceeds 0.05% by weight dispersibility becomes bad, rather it is not preferable because it lowers the conductivity.

Hereinafter, the water dispersible carbon black and the water dispersible colored pigment used as the colorant in the present invention will be described. These colorants may be included in the first and / or second composition.

In the present invention, the water-dispersible carbon black uses a water-dispersed carbon that is surface-modified (covalently bonded) with a sulfonate and carboxylate group which are completely different from the conventional ones. When the water-dispersible carbon black is used, a stable dispersion state is maintained in water or an alcohol solvent without adding organic substances such as surfactants, dispersants, or polymers that are commonly used to maintain stable dispersibility of carbon. Therefore, when the antistatic black coating film is formed of such a material, excellent film hardness and high optical density can be obtained, and there is little elution of black color from the film surface. In particular, sulfonates and carboxylates present in these carbon powders can act as a doping agent for PEDT conductive polymers such as monomer dopants, which are the aforementioned conduction aids. Since it maintains a stable dispersion state in water or alcohol, there is almost no appearance defect due to the radial pattern of the coating film which is often found in the case of carbon dispersed with ordinary organic materials even when a high content of carbon is used. Appearance properties are good and can exhibit very low permeability.

In the present invention, when the water-dispersible carbon alone is used, the color characteristics have a dark brown color, and thus the color characteristics are not high-grade, and thus are not suitable where a high quality texture and color such as CRT is desired. Therefore, in order to overcome these disadvantages, water-dispersible colored pigments are mixed and used in a dispersed state. As an example of such a water-dispersible colored pigment used in the present invention, a conventional one can be used. That is, blue, violet, red, and yellow pigments in a form dispersed in water may be used. These are conventionally prepared using methods of dispersing pigments. That is, it is the form disperse | distributed to the beads etc. using water-soluble dispersing agents, such as polystyrene sulfonate, and a normal water-soluble surfactant. Since these water-dispersible colored pigments are used to reinforce the color of the water-dispersible carbon black mentioned above, the amount used is equal to or less than that of the water-dispersible carbon black.

The amount of water-dispersible carbon black used in the present invention is appropriately 0.01 to 0.3 parts by weight relative to 100 parts by weight of the coating liquid composition, and 0.01 to 0.25 parts by weight of the water-dispersible colored pigment. When it is out of the above range, not only the target transmittance of 40 to 80% can be achieved, but also precipitation and unevenness occur, which is not preferable because the black characteristics of the present invention become weak colors.

In the present invention, when only the water-dispersible carbon and colored pigments are used, the color properties are excellent, but the conductivity is lowered by increasing the surface resistance of the coating. In the present invention, by developing colorants to improve conductivity, not only have a colored color, which is the object of the present invention, but also improve the film conductivity. These colored dyes are azochrome complex dyes and anthraquinone dyes having a hydrophilic group having an alcohol-soluble property and excellent compatibility with the conductive solution of the present invention. These colored dyes are those having excellent compatibility with the conductive solutions of the present invention, and representative examples of these include PC-Black 006P (azochrome complex dye) and PC-Black 206P (azochrome complex dye) of Nippon Gunpowder. And PC-Blue 43P (anthraquinone dye).

The content of the colored dye in the composition of the present invention is 0.01 to 0.25 parts by weight relative to 100 parts by weight of the coating liquid composition. The use of less than 0.01 parts by weight does not lead to an improvement in conductivity, which is an object of the present invention, and when it exceeds 0.25 parts by weight, the black color property is very weak, which is not preferable.

In the case of the first composition of the present invention, an aqueous solution of a monomer dopant having an alcohol solvent, a high refractive inorganic sol solution, an amide solvent, and a sulfonic acid group is added while adding vigorously stirring a PEDT conductive polymer aqueous solution to a predetermined amount of a container. An alcohol-soluble resin binder solution, a water-dispersible carbon black having a hydrophilic group covalently bonded, a water-dispersible colored pigment, and a water / alcohol-soluble colored dye are added in order, and then sufficiently stirred at room temperature for about 2 to 4 hours to complete the preparation of the coating solution of the present invention. The addition order may be different, but when added and mixed in the above order, it exhibits the best solubility and dispersibility, thereby producing a highly uniform coating film.

In the case of the second composition, as a first step, a monomer plate having an alcohol solvent, an amide solvent, a tetraalkoxysilane or an alkyltrialkoxysilane, and a sulfonic acid is added to a predetermined amount of a container with an aqueous polythiophene conductive polymer solution and vigorously stirred. An aqueous dopant solution is added sequentially and stirred for at least 6 hours to prepare a SiO ₂ sol solution. This SiO ₂ sol forms an organic-inorganic hybrid with a polythiophene-based conductive polymer to increase the conductivity and hardness in the coating after the coating film is formed. As a second step, water-dispersible carbon black, water-dispersible colored pigment aqueous solution and water / alcohol-soluble colored dye are added to the solution thus prepared and stirred for at least 2 hours to complete the preparation of the coating solution of the present invention.

Only when manufactured in the above-described order, it is possible to produce a highly uniform coating film having excellent film dispersibility and solution dispersibility. In preparing the first and second compositions, the water-dispersible carbon black, the water-dispersible colored pigment, and the water / alcohol-soluble colored dye covalently bonded to the hydrophilic group may be added only to the first composition or only to the second composition. You may add together to 1st and 2nd composition.

Hereinafter, a method of manufacturing a conductive polymer black colored coating film for electromagnetic shielding having low reflection and contrast enhancement characteristics on CRT outer glass using the first and second compositions will be described.

1) The CRT outer glass is polished with CeO ₂ , washed with ethanol and dried.

2) The first composition of the present invention is coated on the CRT outer glass surface by spin coating or other method and dried to form a first coating layer. The rotation speed is suitably 80 to 150 rpm, and the time is suitably 80 to 150 seconds.

3) The second composition of the present invention is coated and dried on the first coating layer by spin coating or other method to form a second coating layer. The rotation speed is suitably 80 to 150 rpm, and the time is suitably 80 to 150 seconds.

4) Finally, in order to form a hard film, it may be dried at 150 to 200 ° C. for 30 minutes to 1 hour to form the conductive polymer black-colored CRT coating layer of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are for the purpose of explanation and are not intended to limit the present invention.

Example 1-10 and Comparative Example 1-2

In Examples 1 to 10 and Comparative Examples 1 to 2 of Tables 1a to 1c, the coating film properties of the representative compositions of the first and second layers of the present invention are shown. The illustrated aqueous solution of PEDT conductive polymer used Baytron P (trade name) 4071 (solid content 1.3% by weight) of Bayer, and the high refractive solution was TiO ₂ -Fe ₂ O ₃ -SiO ₃ sol (catalyzed Optolake 1130F-2 ( A-8), dispersed in methanol), TiO ₂ -CeO ₂ -SiO ₃ sol (catalyzed Optolake 1130A (A-8), dispersed in methanol), TiO ₂ -ZrO ₂ -SiO ₃ sol (catalyzed Optolake 1130Z, dispersed in water), TiO ₂ -CeO ₃ sol (catalyzed product, dispersed in methanol), CeO ₂ -SiO ₃ sol (produced by hydrolyzing TEOS in aqueous CeO ₂ solution and methanol solvent, ratio CeO ₂ / SiO ₃ = 85/15 wt%) of the product. These high refractive solutions were used to adjust the solid content concentration of all 15% by weight. MeOH, EtOH and amide solvents, NMAA, NMP, DMF, Tetraethoxysilane (TEOS), methyltriethoxysilane (mTEOS), sulfonic acid monomer dopants (p-TSA, MSA, NBSA, 4-HBSA), water-soluble polymer dispersants (HPC, MC, PAA, PMAA, PVB) were all used as Aldrich Co. without special purification, sulfonic acid monomer dopant and water-soluble polymer dispersants were used in 1% aqueous solution to facilitate the addition and dispersion. As the water-dispersible carbon black, CABOT Co., Ltd. was used (CB200: sulfonate carbon black, CB300: carboxylate carbon black). Disperse color pigments were all made from Mikuni Color (GA Blue 1, GA violet 1, GA Red 1, Yellow yellow, GA green). . These water-dispersible carbon blacks and color pigments were used in 5% aqueous solution to facilitate dispersion. The water-soluble or alcohol-soluble colored dyes used PC-Black 006P (Azochrome complex system), PC-Black 206P (Azochrome complex system) (above Bluish Black), and PC-Blue43P (Anthraquinone system) of Nippon Gunpowder. This case was also prepared by using a 4% solution dissolved in methanol for ease of dispersion.

Coating method of the present Example and Comparative Examples was as follows. In the case of the first composition, a high refractive sol solution, an alcoholic solvent, and an amide solvent, dispersed in methanol or water, first of all, in a 1 L glass container at the mixing ratio illustrated in Tables 1a to 1c, with the addition of an aqueous solution of PEDT and vigorously stirring. A hydrophilic group covalently bonded water-dispersible carbon black, water-disperse color pigments, water-soluble or alcohol-soluble color dyes were added in sequence and stirred sufficiently for 2 to 4 hours at room temperature to complete the first composition.

In the case of the second composition, a monomer dopant having an alcohol and an amide solvent, TEOS (or MTEOS), sulfonic acid group, was first added to the mixed ratio shown in Tables 1a to 1c in a 1L glass container, followed by vigorous stirring. A water-soluble polymer dispersant is added sequentially and stirred for about 8 hours at room temperature. The water-dispersible carbon black, water-dispersible colored pigment, and water-soluble or alcohol-soluble colored dye solution were added to the solution thus prepared, and stirred for about 4 hours to complete the second composition. The second layer composition of Comparative Example 1 was prepared in the same manner as above, but did not use a PEDT conductive polymer.

Preparation of the coating film for physical property evaluation is as follows. The coating liquids prepared according to the compositions of the present examples were washed with acid, coated on a dried glass surface by a spin method, and dried. The speed of rotation is suitably 80 to 150 rpm, and the time is suitably 80 to 150 seconds. The second composition described in the present invention was formed by spin coating on the surface of the first coating layer. The speed of rotation is suitably 80 to 150 rpm, and the time is suitably 80 to 150 seconds. Finally it was dried for 30 minutes to 1 hour at 150 to 200 ℃ to form a hard film. The thickness of the dried coating film was about 50-400 nm in total of the 1st coating layer and the 2nd coating layer.

The physical properties were evaluated for surface resistance per unit area using Loresta (4-point probe) manufactured by Mitsubishi Chemical Co., Ltd., and the transmittance was evaluated at 550 nm using UV-visibleSpectrometer, and the film hardness was measured using pencil hardness meter. Measured. The film uniformity was visually evaluated, and the evaluation criteria were evaluated whether the coating film state was good or bad. That is, when the state of the coating film is uneven due to gelation or the gelation is still present in the coating film was evaluated as poor.

In the following examples, when a monomer dopant having a sulfonic acid group, a water-soluble polymer dispersant, a water-dispersible carbon black, a water-disperse color pigment, a water-soluble or alcohol-soluble color dye solution is added to the first composition and to the first composition There was almost no difference (membrane appearance, membrane performance).

Example Furtherance Film properties Conductivity (Ω / □) Permeability (T%) reflectivity(%) Membrane uniformity Example 1 Article 1 Composition PEDT (aq) / TiO ₂ -CeO ₂ -SiO ₂ Sol (MeOH) / MeOH / NMAA (10/2/86/2) CB200 (5%, aq) = 2% GA green (5%, aq) = 3 % PC-Blue43P (5%, MeOH) = 3% 16K 57 0.71 Good Article 2 Composition PEDT (1.3%, aq) = 12% MeOH / NMAA = 75% / 2% p-TSA (1%, aq) = 2% MC (1%, MeOH) = 3% TEOS = 6% Example 2 Article 1 Composition PEDT (aq) / TiO ₂ -CeO ₂ Sol (MeOH) / MeOH / NMAA (10 / 1.5 / 81 / 0.5) CB300 (5%, aq) = 3% GA blue (5%, aq) = 2% GA violet (5%, aq) = 1% PC-Black206P (5%, MeOH) = 1% 4K 44 0.78 Good Article 2 Composition PEDT (1.3%, aq) = 24% MeOH / NMP = 63% / 3% MSA (1%, aq) = 1% PAA (1%, aq) = 1% TEOS = 8% Example 3 Article 1 Composition PEDT (aq) / TiO ₂ -CeO ₂ -SiO ₂ Sol (MeOH) / MeOH / NMAA (6 / 1.2 / 88.8 / 4) CB200 (5%, aq) = 2% GA violet (5%, aq) = 3 % PC-Blue43P (5%, MeOH) = 4% 83 K 52 0.80 Good Article 2 Composition PEDT (1.3%, aq) = 12% MeOH / NMAA = 74% / 3% p-TSA (1%, aq) = 2% MC (1%, MeOH) = 3% TEOS = 6% Example 4 Article 1 Composition PEDT (aq) / CeO ₂ -SiO ₂ Sol (MeOH) / MeOH / NMAA (8 / 1.5 / 89.5 / 1) CB200 (5%, aq) = 1% GA blue (5%, aq) = 1% GA violet (5%, aq) = 2% PC-Black206P (5%, MeOH) = 2% 6K 62 0.74 Good Article 2 Composition PEDT (1.3%, aq) = 22% MeOH / IPA / DMF = 60% / 5% / 3% NBSA (1%, aq) = 1% HEC (1%, MeOH) = 1% TEOS = 8%

Example Furtherance Film properties Conductivity (Ω / □) Permeability (T%) reflectivity(%) Membrane uniformity Example 5 Article 1 Composition PEDT (aq) / TiO ₂ -Fe ₂ O ₃ -SiO ₂ Sol (MeOH) / MeOH / NMAA (10/2/74/2) CB200 (5%, aq) = 2% GA blue (5%, aq) = 2% GA red (5%, aq) = 1% PC-Black6P (5%, MeOH) = 1% 19K 53 0.71 Good Article 2 Composition PEDT (1.3%, aq) = 12% MeOH / NMAA = 74% / 3% p-TSA (1%, aq) = 2% MC (1%, MeOH) = 3% TEOS = 6% Example 6 Article 1 Composition PEDT (aq) / TiO ₂ -ZrO ₂ -SiO ₂ Sol (MeOH) / MeOH / NMP (10 / 1.8 / 74.7 / 6) CB200 (5%, aq) = 2% GA blue (5%, aq) = 2 % GA violet (5%, aq) = 0.5% PC-Black206P (5%, MeOH) = 1% 8K 40 0.68 Good Article 2 Composition PEDT (1.3%, aq) = 8% MeOH / NMP = 81.5% / 3.5% 4-HBSA (1%, aq) = 2% PMAA (1%, aq) = 2% TEOS = 3% Example 7 Article 1 Composition PEDT (aq) / TiO ₂ -ZrO ₂ -SiO ₂ Sol (MeOH) / MeOH / NMAA (10 / 1.5 / 80.5 / 4) CB300 (5%, aq) = 3% GA blue (5%, aq) = 1 % GA violet (5%, aq) = 0.5% PC-Black206P (5%, MeOH) = 2% 17K 48 0.75 Good Article 2 Composition PEDT (1.3%, aq) = 18% MeOH / EtOH / NMP = 58% / 8% / 3.5% MSA (1%, aq) = 1% MC (1%, aq) = 1% TEOS = 8% GA violet (5%, aq) = 0.5% PC-Black6P (5%, MeOH) = 2% Example 8 Article 1 Composition PEDT (aq) / TiO ₂ -CeO ₂ -SiO ₂ Sol (MeOH) / MeOH / NMAA (15/3/81/1) 9K 53 0.49 Good Article 2 Composition PEDT (1.3%, aq) = 12% MeOH / NMAA = 68% / 2% p-TSA (1%, aq) = 2% MC (1%, MeOH) = 3% TEOS = 6% CB200 (5%, aq) = 2% GA blue (5%, aq) = 2% GA violet (5%, aq) = 1% PC-Blue43P (5%, MeOH) = 2%

Example Furtherance Film properties Conductivity (Ω / □) Permeability (T%) reflectivity(%) Membrane uniformity Example 9 Article 1 Composition PEDT (aq) / TiO ₂ -CeO ₂ -SiO ₂ Sol (MeOH) / MeOH / NMAA (18 / 3.6 / 77.9 / 0.5) 7K 55 0.31 Good Article 2 Composition PEDT (1.3%, aq) = 8% MeOH / NMP = 77% / 3% p-TSA (1%, aq) = 1% HPC (1%, MeOH) = 1% TEOS = 5% CB200 (5%, aq) = 2% GA blue (5%, aq) = 1% GA violet (5%, aq) = 1% PC-Blue43P (5%, MeOH) = 1 = 1% Comparative Example 1 Article 1 Composition PEDT (aq) / TiO ₂ -CeO ₂ -SiO ₂ Sol (MeOH) / MeOH / NMAA (18 / 3.6 / 77.9 / 0.5) 780K 59 1.2 Good Article 2 Composition MeOH / NMP = 85% / 3% p-TSA (1%, aq) = 1% HPC (1%, MeOH) = 1% TEOS = 5% CB200 (5%, aq) = 2% GA blue (5% , aq) = 1% GA violet (5%, aq) = 1% PC-Blue43P (5%, MeOH) = 1% Comparative Example 2 Single layer composition PEDT (1.3%, aq) = 8% MeOH / NMP = 76% / 3% p-TSA (1%, aq) = 1% HPC (1%, MeOH) = 1% TEOS = 5% CB200 (5%, aq) = 3% GA blue (5%, aq) = 1% GA violet (5%, aq) = 1% PC-Blue43P (5%, MeOH) = 1% 80,000K 55 3.0 Good

* K = 1000

** Film properties of Comparative Example 2 are measured after single coating.

According to the present invention, it is possible to provide a conductive polymer coating film for a CRT, which can have an electromagnetic shielding function while having low reflection and contrast enhancement characteristics.

Claims (7)

PEDT content of the composition based on the total of 0.02~0.4% PEDT aqueous solution of 2-25% by weight, the high refractive index inorganic sol solution is 0.5~20% by weight of 50~97.3% by weight of an alcohol solvent of C ₁ ~C _3, amide-based solvent, 0.1 to 10 A first coating layer formed using a first composition composed of weight percent, 0.005 to 0.1 weight percent of water-soluble or alcohol-soluble resin binder, and 0.005 to 0.05 weight percent of sulfonic acid monomer dopant, and 2 to 25% by weight aqueous solution of PEDT having a PEDT content of 0.02 to 0.4% by weight based on the total composition, 3 to 10% by weight of tetraalkoxysilane or alkyltriethoxysilane, 55 to 94.8% by weight of C _{1 to} C ₃ alcohol solvent, amide In the conductive polymer black-colored CRT coating layer comprising a second coating layer formed by using a second composition consisting of 0.1 to 10% by weight of the solvent, and 0.005 to 0.05% by weight of the sulfonic acid monomer dopant. 0.01 to 0.3 parts by weight of water-dispersible carbon black, 0.01 to 0.25 parts by weight of water-dispersible color pigment, and 0.01 to 0.25 parts by weight of water-soluble or alcohol-soluble colored dye, are added to at least one of the first and second compositions. Conductive polymer black-colored CRT coating layer, characterized in that the coating layer is formed. delete The conductive polymer black-colored CRT layer according to claim 2, wherein the solid content concentration of the high refractive inorganic sol solution used is 14 to 16% by weight. The method of claim 1, The high refractive inorganic sol has TiO ₂ sol, CeO ₂ sol, TiO ₂ -Fe ₂ O ₃ -SiO ₂ sol, TiO ₂ -CeO ₂ -SiO ₂ sol, TiO ₂ having a refractive index of RI = 1.6 or more when forming a thin film of its own -ZrO ₂ -SiO ₂ sol, TiO ₂ -CeO ₂ sol, or CeO ₂ -SiO ₂ sol, The C _{1 to} C ₃ alcohol solvent is methanol, ethanol, isopropanol or a mixture thereof, The amide solvent is formamide (FA), N-methylformamide (MFA), N, N-dimethylformamide (DMF), acetamide (AA), N-methylacetamide (MAA), N, N- Dimethylacetamide (DMA), N-methylpropionamide (MPA), or N-methylpyrrolidone (NMP), The sulfonic acid monomer dopant is p-toluenesulfonic acid (p-TSA), dodecylbenzenesulfonic acid (DDBSA), 1,5-anthraquinone disulfonic acid (1,5-AQSA), 2,6- anthraquinone disulfonic acid (2 , 6-AQSA), anthraquinonesulfonic acid (AQSA), 4-hydroxybenzenesulfonic acid (4-HBSA), methylsulfonic acid (MSA), or nitrobenzenesulfonic acid (NBSA), The water-soluble or alcohol-soluble resin binder is polymethyl methacrylate (PMMA), polyacrylate (PA), polyvinyl alcohol (PVOH), polyvinyl acetal (PVAT), polyvinyl butylal (PVB), methyl cellulose (MC) ), Hydroxypropyl cellulose (HP, The conductive polymer black, wherein the silane is tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane or methyltriethoxysilane C), hydroxyethylcellulose (HEC), or polyvinylacetate (PVAc). Tinted CRT coating layer. The method of claim 1, The water-dispersible carbon black is a sulfonate group or a carboxylate group is covalently bonded, The water-dispersible colored pigments are water-dispersible blue pigments, water-dispersible violet pigments, water-dispersible green pigments, water-dispersible red pigments or mixtures thereof prepared using a milling method using a polymer dispersant and a surfactant. Conductive polymer black colored CRT coating layer, characterized in that the alcohol-soluble colored dye is an azochrome complex dye or an anthraquinone dye. The method of claim 1, wherein a surface resistance of the coating layer ^{2 x 10 3 ~10 5 Ω /} □, and the transmittance is 40-80%, the film hardness is 4~8H, characterized in that the reflectivity of 0.3~0.8% Conductive polymer black colored CRT coating layer. A method of forming the CRT coating layer according to claim 1, wherein a first coating layer is first formed using the first composition, and then a second coating layer is formed using the second composition thereon, and then 30 minutes to 1 minute at 150 to 200 ° C. CRT coating layer forming method comprising the step of thermally firing for about a time.