KR100371516B1 - Antistatic transparent black coating composition, producing method thereof, and coating method of glass surface using thereof - Google Patents

Abstract

The present invention is a coating composition for coating the surface of the CRT (Cathod Ray Tube) glass, especially polyethylene dioxythiophene aqueous solution, alcohol and amide mixed solvent, alkoxysilane, water-soluble polymer, sulfonic acid monomer dopant, water dispersible carbon black, water An antistatic colored coating composition comprising an acidic colored pigment and an alcohol-soluble colored dye, a method for preparing the same, and a coating method for a glass surface using the same, wherein the coating composition of the present invention is coated on a CRT glass surface to have a good appearance and charge Provide a CRT with protection.

Description

Antistatic coloring coating composition, its manufacturing method and coating method of glass surface using the same {ANTISTATIC TRANSPARENT BLACK COATING COMPOSITION, PRODUCING METHOD THEREOF, AND COATING METHOD OF GLASS SURFACE USING THEREOF}

The present invention relates to an antistatic colored coating composition used for coating CRT (Cathod Ray Tube) glass of a television, a production method thereof, and a coating method of a glass surface using the same. Antistatic coloring coating composition comprising alcohol and amide mixed solvent, alkoxysilane, water soluble polymer, sulfonic acid monomer dopant, water dispersible carbon black, water dispersible color pigment and alcohol soluble color dye, method for producing the same, and glass using the same It relates to the coating method of the surface.

Color television's flat glass tube outer glass is used with antistatic coloring coating to improve contrast and prevent electrostatic shock. Coating liquids developed for this purpose are mostly those in which carbon black is dispersed in a transparent conductive solution, and representative examples thereof are coating liquids in which carbon powder is dispersed in an antimontinoxide sol and a silica sol solution. Patent No. 5,681,885) and a conductive coating and a coating liquid in which carbon powder is dispersed in a silazazole solution. However, these coating liquids are dark or dark brown in color, so they do not have an excellent appearance color characteristic, and do not give a high-quality feeling, and the surface resistance is also 10 ¹⁰ to 10 ¹¹ Ω / □, which is not good in antistatic properties.

Accordingly, an object of the present invention is to provide an antistatic coloring coating composition which improves the antistatic properties by improving the color conductivity and the film conductivity while solving the problems of the coating solution for CRT described above.

Still another object of the present invention is to provide a method for preparing the antistatic colored coating composition and a method for coating a glass surface using the same.

That is, one aspect of the present invention is 6 to 26% by weight polyethylene dioxythiophene aqueous solution having a solid content of 0.6 to 3.0% by weight; 64 to 90 wt% of an alcohol and amide mixed solvent; 3-10% by weight of alkoxysilane; 0.005 to 0.1% by weight of a water-soluble polymer; 0.005 to 0.05% by weight of sulfonic acid monomer dopant; 0.1 to 0.30% by weight of water-dispersible carbon black; Water dispersible colored pigments 0.05 to 0.25 wt%; And it provides an antistatic colored coating composition comprising 0.05 to 0.25% by weight of azochrome complex-based or anthraquinone-based alcohol-soluble colored dyes.

Another aspect of the present invention relates to a method for preparing the antistatic coloring coating composition, comprising the steps of: (a) adding a polyethylenedioxythiophene aqueous solution to a reactor to start stirring; (b) sequentially adding alcohol and an amide mixed solvent, an alkoxysilane, a sulfonic acid monomer dopant and a water-soluble polymer while continuing to stir, followed by stirring for 6 hours or more; (c) adding water-dispersible carbon black, water-dispersible colored pigments, and alcohol-soluble colored dyes, followed by stirring for 2 hours or more.

Another aspect of the present invention is characterized in that the glass composition is coated with a spin method over 80 to 150 seconds at a speed of 80 to 150 rpm on the glass surface, and then heat-fired at 150 to 200 ° C. for 30 minutes to 1 hour. It relates to a coating method of the glass surface.

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

Preferred antistatic coloring coating composition of the present invention is 6 to 26% by weight polyethylene dioxythiophene aqueous solution having a solid content of 0.6 to 3.0% by weight; 64 to 90 wt% of an alcohol and amide mixed solvent; 3-10% by weight of alkoxysilane; 0.005 to 0.1% by weight of a water-soluble polymer; 0.005 to 0.05% by weight of sulfonic acid monomer dopant; 0.1 to 0.30% by weight of water-dispersible carbon black; Water dispersible colored pigments 0.05 to 0.25 wt%; And 0.05 to 0.25 wt% of an azochrome complex-based or anthraquinone-based alcohol-soluble colored dye.

Polyethylenedioxythiophene aqueous solution is used as a conductive high molecular compound in the antistatic coloring coating composition of this invention.

As a conductive polymer compound, polyaniline, polypyrrol, polythiophene, and the like are widely used. These polymer compounds have been attracting attention as synthetic metals for a long time due to 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, transparent electrodes, and the like. However, since they are difficult to process and are extremely inferior in safety against heat, air, and ultraviolet light, only a few have actually been commercialized.

In order to solve the above problems of the existing conductive polymers, a polythiophene-based polyethylenedioxythiophene (PEDT) as described in US Pat. Nos. 5,035,926 and 5,391,472 has recently been attracting attention as a conductive material. Polyethylenedioxythiophene has excellent solubility, excellent air, heat, and UV resistance stability compared to polyaniline-based, polypyrrole-based, and polythiophene-based conductive polymers. It can also be applied to the formation of the conductive coating film of the exposed area. Also, since polyethylenedioxythiophene is doped with a high molecular acid (polystyrene sulfonic acid), it can be produced in an aqueous solution. Since this high aqueous polymer solution is easily mixed with an alcohol solvent, it exhibits excellent solvent processing characteristics which are rare for a conductive polymer.

Polyethylenedioxythiophene can be used as a conductive coating such as electromagnetic shielding materials, antistatic agents applied to substrates such as CRT glass surface, transparent plastic surface (panel, film).

The amount of the polyethylenedioxythiophene aqueous solution (solid content of 0.6 to 3.0% by weight) in the antistatic coloring coating composition of the present invention is preferably 6 to 26% by weight. More preferably, an aqueous polyethylenedioxythiophene having a solid content of 1.2 to 1.5% by weight is used. Polyethylene dioxythiophene is less than 6 wt% of thiophene solution a surface resistance of ¹⁰ 10 Ω / □ and at least greater than the commercial level of ^{10 8} ~ 10 10 Ω / target value of the □ to mothamyeo antistatic properties sufficient, the amount is 26% by weight In the case of exceeding the surface resistance of 10 ⁶ Ω / □ excellent antistatic properties, but the viscosity of the composition is high, there is a problem that can not produce a uniform coating film. In the present invention, the viscosity of PEDT is important. That is, in order to form a uniform coating film of the CRT outer glass, the viscosity of the PEDT aqueous solution should be in the range of 10 to 50cp. When the viscosity exceeds 50cp, the appearance after the coating is very poor, such as comb teeth, when the viscosity is less than 10cp is excellent in coating properties, but the molecular weight is low, so the film conductivity is not appropriate.

The composition of the present invention uses an alcohol and an amide mixed solvent to improve the conductivity of the coating film, and to maintain excellent dispersibility and film uniformity. By mixing the two solvents, the conductivity of the coating film is improved, so that the antistatic property is improved, and the dispersibility of the carbon black is also improved, thereby preventing appearance defects due to comb teeth on the coating film.

As the alcohol solvent, one or more selected from the group consisting of methanol, ethanol, propanol and isopropanol may be used.

As the amide solvent, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone One or more selected from the group consisting of can be used.

The amount of the alcohol and amide mixed solvent is suitably 64 to 90% by weight. Specifically, the mixing ratio of the solvent is preferably 94 to 99% by weight of the alcohol solvent, 1 to 6% by weight of the amide solvent, and more preferably at least 50% by weight of the methanol content of the total solvent mixture. If it is out of this content ratio, either film uniformity or film conductivity will worsen and become undesirable.

In the composition of the present invention, a water-soluble polymer is used as a dispersant to help disperse polyethylenedioxythiophene. Polyethylenedioxythiophene is dispersed in the conductive polymer itself by doping with polystyrene sulfonic acid (-SO ₃ H, -SO ₃ ^- Na), which serves as a dispersant, but the concentration of the aqueous solution of polyethylene dioxythiophene is 10 wt% or less. In this case, since the dispersibility and adhesion to the surface of the substrate is not sufficient, a water-soluble or alcohol-soluble polymer is used as a dispersant and a resin binder.

The water-soluble polymer used as a dispersant in the composition of the present invention is polymethacrylic acid (PMAA), polyacrylic acid (PAA), polyvinyl alcohol (PVOH), polyvinyl butyral (PVB), methylcellulose (MC), hydroxypropyl It is 1 type chosen from the group which consists of cellulose (HPC), hydroxyethyl cellulose (HEC), and polyvinylacetate (PVAc).

The water-soluble polymer is preferably added in the form of an alcohol solution or an aqueous solution, and the amount of the water-soluble polymer is preferably 0.005 to 0.1% by weight based on solid content. If the solid content is less than 0.005% by weight, the effect of improving the adhesion to the substrate is not sufficient, the dispersibility is inhibited, if the content exceeds 0.1% by weight, the viscosity of the composition is increased to inhibit the formation of a uniform coating film, resulting in poor appearance.

In the composition of the present invention, a sulfonic acid monomer dopant is used as a conduction aid. Polyethylenedioxythiophene uses a sulfonic acid monomer dopant as a conduction aid because the conductivity property is very degraded by silica sol as a binder in a coating film state. The sulfonic acid monomer dopant is further doped into the polyethylenedioxythiophene molecule to serve to increase the conductivity of the coating film.

The sulfonic acid monomer dopants include p-toluenesulfonic acid (p-TSA), dodecylbenzenesulfonic acid, 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), and nitrobenzenesulfonic acid (NBSA) are used. Among them, the acid form is used as it is, and when present in the form of sodium (Na) salt, it is used by replacing with an acid form using an aqueous solution of nitric acid at pH 2.

The sulfonic acid monomer dopant is preferably added in the form of an aqueous solution in terms of dispersibility. The amount of addition 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 is more than 0.05% by weight dispersibility becomes bad, rather it lowers the conductivity is not preferred.

In the composition of the present invention, the alkoxysilane is used to increase the adhesion to the CRT glass and to give the hardness of the coating film when the composition is coated. Such alkoxysilanes are selected from the group consisting of tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane and methyltriethoxysilane, and water contained in aqueous polyethylenedioxythiophene solution during the manufacturing process. Or react with the additionally added water to form a silica sol (-SiO ₂ -SiO _2- ) and an alkylsilica sol (R-SiO ₂ -SiO _2- ) through a hydrolysis reaction and a condensation reaction. The silica sol forms a polysilicate crystal during thermosetting coating, thereby increasing the adhesion between the coating film and the CRT outer glass and at the same time increasing the film hardness.

In the composition of the present invention, it is preferable to use 3 to 10 wt% of the alkoxysilane. When the amount of the alkoxysilane is less than 3% by weight, the hardness of 5H or more cannot be achieved, and when the amount of the alkoxysilane is more than 10% by weight, the hardness becomes very good, but the amount of polysilicate that adversely affects the conductivity is relatively increased. There is a problem that the surface resistance of about 10 ⁶ ~ 10 ⁸ Ω / □ can not be achieved.

In the composition of the present invention, water-dispersible carbon black is used as a colorant. In the present invention, the surface-modified water-dispersible carbon covalently bonded to sulfonate and carboxylate groups is used. In this case, a stable dispersion state is maintained in water or an alcohol solvent without adding organic substances such as surfactants, dispersants or polymers, which are usually used to maintain stable dispersibility of carbon. When the coating film is formed using the carbon black, it is possible to achieve excellent film hardness and high optical density, and also has the advantage that little black color is eluted on the film surface. In addition, since the sulfonate and carboxylate groups present in the carbon powder can also act as a doping agent for polyethylenedioxythiophene, they also play a role in improving the film conductivity to improve the antistatic properties. In addition, due to the stable dispersibility in water or alcohol solvents when using a high content of carbon also brings the effect of preventing the appearance defects due to the comb teeth of the coating film that occurs frequently.

When the water-dispersible carbon black alone is used, since the color characteristics have a blackish brown color, the color does not give a sense of quality, and therefore, it is not suitable where a high quality texture and color such as CRT is desired. In order to overcome this disadvantage, water-dispersible colored pigments are mixed and used. It is preferable to use a water-dispersible colored pigment in the form of beads dispersed in a water-soluble dispersant such as polystyrene sulfonate and a conventional water-soluble surfactant. Since the water-dispersible colored pigment is used to reinforce the color of the water-dispersible carbon black, it is preferable to use the same amount or less than that of the water-dispersible carbon black.

In the present invention, the water dispersible carbon black is preferably 0.1 to 0.3% by weight, and the water dispersible colored pigment is preferably 0.05 to 0.25% by weight. When carbon black and pigment are used below the minimum weight, the minimum permeability of 80% or less desired in the present invention cannot be achieved, and the black color as required by the CRT cannot be obtained. In addition, when the maximum weight is exceeded, the permeability is good, but the pigment solid content is too high, resulting in poor appearance such as precipitation and staining, which is not good.

When only the water-dispersible carbon and colored pigments are used, the color characteristics are excellent, but the surface resistance is in the range of 10 ⁸ to ^{10 10} Ω / □, and in most cases, the commercial value characteristic standard shows values close to 10 ¹⁰ . This is not so good. In the present invention, the electroconductivity of the coating film by the composition of the present invention is achieved by blending the colorants to improve the conductivity to about 10 ⁶ ~ 10 ⁸ Ω / □. Such colored dyes use azochrome complex dyes and anthraquinone dyes having a hydrophilic group having an alcohol-soluble property and excellent hydrophilic group compatibility with the conductive solution of the present invention.

The colored dyes are preferably used in 0.05 to 0.25% by weight. If it is used less than 0.05% by weight can not lead to an improvement in conductivity for the purpose of the present invention, when the content is more than 0.25% by weight black color properties are weak, which is not preferable.

Hereinafter, the manufacturing method of the antistatic coloring coating composition of this invention is demonstrated.

First, the aqueous solution of polyethylene dioxythiophene is added to the reactor to start stirring, and the stirring is continued, and then alcohol and amide mixed solvent, alkoxysilane, sulfonic acid monomer dopant and water-soluble polymer are sequentially added, followed by stirring for 6 hours or more. Prepares an offen and silica sol solution.

Next, water-dispersible carbon black, water-dispersible colored pigments, and alcohol-soluble colored dyes are added to the polyethylene dioxythiophene and silica sol solution produced above, and stirred for 2 hours or more to prepare an antistatic colored coating composition of the present invention.

If the order of addition of the constituents in the preparation or the manufacturing method is different, the desired effect may not be sufficiently exhibited in the present invention.

Hereinafter, a method of coating on a glass surface using the antistatic coloring coating composition of the present invention will be described.

The glass surface is first polished with cellum oxide, then washed with ethanol and dried.

Next, the antistatic coloring coating composition of the present invention is coated on the glass surface by a spin method and dried. The coating is preferably carried out over 80 to 150 seconds at a speed of 80 to 150 rpm.

Finally, heat curing is performed at 150 to 200 ° C. for about 30 minutes to 1 hour to form a hard film.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are only for explaining the present invention and are not intended to limit the claims of the present invention.

Examples 1-8 and Comparative Examples 1-8

Aqueous polyethylene dioxythiophene solution was added to a 1 L glass container, followed by vigorous stirring to add alcohol, an amide solvent, an alkoxysilane, a sulfonic acid monomer dopant, and a water-soluble polymer in a mixing ratio as shown in Tables 1 and 2 below. And stirred at room temperature for about 8 hours. Next, the water-dispersible carbon black aqueous solution, the water-dispersible colored pigment aqueous solution and the alcohol-soluble colored dye were added to the composition, followed by stirring for about 4 hours to complete the coating composition.

Using the composition described above to prepare a specimen in the following manner. The glass was first washed with acid, and the dried glass was preheated to 35 ° C., and then coated on the surface of the glass by spin coating for 120 rpm and 120 seconds. This was baked in 180 degreeC oven for 30 minutes, and the test piece was produced.

Conductive polymer 1.3%, aq. Alcohol and amide mixed solvent 1% sulfonic acid monomer dopant, aq. Water soluble polymer Alkoxysilane Water dispersible carbon black 5%, aq. 5% water-based pigments, aq. Alcohol soluble colored dye 5%, MeOH Example 1 PEDT8% MeOH / NMP75.9% / 3% p-TSA1% HPC (1%, MeOH) 1% TEOS5% CB2003% GA blue = 1% GA viloet = 1% Blue43P 1.1% Example 2 PEDT12% MeOH / NMAA71% / 2% p-TSA1% MC (1%, MeOH) 2% TEOS5% CB2003% GA blue = 1% GA violet = 1% Blue43P2% Example 3 PEDT12% MeOH / NMAA70% / 2% p-TSA1% MC (1%, MeOH) 2% TEOS5% CB2003% GA green = 2% Blue43P3% Example 4 PEDT12% MeOH / NMAA69.5% / 3% p-TSA1% MC (1%, MeOH) 1% TEOS5% CB2003% GA violet = 2% Blue43P3.5% Example 5 PEDT12% MeOH / NMAA69% / 3% p-TSA2% MC (1%, MeOH) 2% TEOS5% CB2003% GA blue = 1% GA red = 1% Black6P2% Example 6 PEDT15% MeOH / EtOH / NMP58 / 8% / 3.5% MSA1% MC (1%, aq.) 1% TEOS7% CB3003% GA blue = 1.0% GA violet = 0.5% Black6P2% Example 7 PEDT20% MeOH / NMP65.9% / 3% MSA1% PAA (1%, aq.) 1% TEOS4% CB3002.5% GA blue = 1.0% GA violet = 0.5% Black206P1.1% Example 8 PEDT18% MeOH / IPA / DMF62% / 5% / 3% NBSA1% HEC (1%, MeOH) 1% TEOS4% CB2002.5% GA blue = 1% GA violet = 0.5% Black206P2% Example 9 PEDT8% MeOH / NMP72% / 3% 4-HBSA2% PMAA (1%, aq.) 2% TEOS4% CB2005% GA blue = 2% GA violet = 0.5% Black206P1.5% Example 10 PEDT15% MeOH / NMAA65.7% / 3% p-TSA0.6% PVB (1%, MeOH) 0.6% mTEOS10% CB2002.5% GA blue = 1.0% GA violet = 0.5% Black206P1.1% Example 11 PEDT10% MeOH / NMP70.5% / 3% p-TSA2% HPC (1%, MeOH) 3% TEOS4% CB2002.5% GA blue = 1% GA violet = 1% Blue43P3%

Conductive polymer 1.3%, aq. Alcohol and amide mixed solvent 1% sulfonic acid monomer dopant, aq. Water soluble polymer Alkoxysilane Water dispersible carbon black 5%, aq. 5% water-based pigments, aq. Alcohol soluble colored dye 5%, MeOH Comparative Example 1 EDT12% MeOH / NMP68% / 3% p-TSA2% HPC (1%, MeOH) 3% TEOS6% CB2003% GA blue = 2% GA violet = 1% Comparative Example 2 EDT10% MeOH / NMP72% / 3% p-TSA4% HPC (1%, MeOH) 3% TEOS4% CB2002% GA blue = 1% GA violet = 1% Comparative Example 3 EDT22% MeOH / IPA / NMP55% / 5% / 3% NBSA1% HEC (1%, MeOH) 1% TEOS8% CB2002% GA blue = 1% GA violet = 2% Comparative Example 4 PEDT4% MeOH / NMP79% / 2% p-TSA4% HPC (1%, MeOH) 2% TEOS4% CB2002% GA blue = 1% GA violet = 1% Blue43P1% Comparative Example 5 PEDT30% MeOH / EtOH / NMP40% / 10% / 4% p-TSA1% HPC (1%, MeOH) 1% TEOS8% CB2002% GA blue = 1% GA violet = 1% Blue43P2% Comparative Example 6 PEDT8% MeOH / NMP77% / 2.9% p-TSA0.1% HPC (1%, MeOH) 2% TEOS4% CB3002% GA blue = 1% GA violet = 1% Black6P2% Comparative Example 7 PEDT8% MeOH / NMP65% / 4% p-TSA7% HPC (1%, MeOH) 2% TEOS6% CB3004% GA blue = 1% GA violet = 1% Black6P2% Comparative Example 8 PEDT10% MeOH / NMP74% / 2% p-TSA2% HPC (1%, MeOH) 2% TEOS2% CB3004% GA blue = 1% GA violet = 1% Black6P2% Comparative Example 9 PEDT12% MeOH / NMP55% / 2% p-TSA2% HPC (1%, MeOH) 2% TEOS12% CB2004% GA Blue = 4% GA Violet = 4% Black6P3% Comparative Example 10 PEDT22% MeOH / NMP65% / 2.5% p-TSA1% HPC (1%, MeOH) 1% TEOS6% CB2000.2% GA Blue = 0.15% GA Violet = 0.15% Black206P2% Comparative Example 11 PEDT12% MeOH / NMP62% / 2% p-TSA3% HPC (1%, MeOH) 3% TEOS5% CB3008% GA blue = 2% GA Violet = 2% Black206P1%

PEDT (polyethylenedioxythiophene); Baytron PH 4071 from Bayer

MeOH, EtOH, NMP (N-methylpyrrolidone), DMF (N, N-dimethylformamide), NMAA (N-methylacetamide); Aldrich

p-TSA (p-toluenesulfonic acid), MSA (methylsulfonic acid), NBSA (nitrobenzenesulfonic acid), 4-HBSA (4-hydroxybenzene sulfonic acid); Aldrich

HPC (hydroxypropylcellulose), MC (methylcellulose), PAA (polyacrylic acid), PMAA (polymethacrylic acid), PVB (polyvinylbutyral), HEC (hydroxyethylcellulose); Aldrich

TEOS (tetraethoxysilane), mTEOS (methyltriethoxysilane); Aldrich

CB200 (sulfonate carbon black), CB300 (carboxylate carbon black); Cabot

GA blue, GA violet, GA green, GA red, GA yellow; Mikuni Color

PC-Black 006P, PC-Black 206P (Azochrome Complex system), PC-Blue43P (Anthraquinone system); Japanese gunpowder

Resistance (Ω / □) Permeability (T%) Hardness (H) State Film color Example 1 8ｘ10 ⁷ 55 6 Good Black Blue Example 2 6ｘ10 ⁷ 50 6 Good Black Blue Example 3 5ｘ10 ⁷ 52 6 Good Black green Example 4 4ｘ10 ⁷ 48 6 Good dark mauve Example 5 4ｘ10 ⁷ 52 6 Good Black Blue Example 6 7ｘ10 ⁶ 51 7 Good Black Blue Example 7 2ｘ10 ⁶ 42 7 Good Black Blue Example 8 5ｘ10 ⁶ 70 5 Good Black Blue Example 9 3ｘ10 ⁷ 65 4 Good Black Blue Example 10 4ｘ10 ⁶ 68 6 Good Black Blue Example 11 4ｘ10 ⁷ 72 5 Good Black Blue Comparative Example 1 6ｘ10 ⁹ 50 6 Good Black Blue Comparative Example 2 8ｘ10 ⁹ 72 5 Good Black Blue Comparative Example 3 4ｘ10 ⁸ 70 5 Good Black Blue Comparative Example 4 1ｘ10 ¹¹ 65 5 Good Black Blue Comparative Example 5 2ｘ10 ⁶ 45 4 Bad Black Blue Comparative Example 6 2ｘ10 ¹⁰ 60 4 Good Black Blue Comparative Example 7 4ｘ10 ⁹ 55 5 Bad Black Blue Comparative Example 8 8ｘ10 ⁶ 56 2 Good Black Blue Comparative Example 9 2 × 10 ¹¹ 35 8 Bad Black Blue Comparative Example 10 4 × 10 ⁸ 85 6 Good Black Blue Comparative Example 11 2 × 10 ⁹ 38 5 Bad Black Blue

Surface resistance; Evaluated by Ultrehigh resistance (Advantest)

* Permeability; Evaluated by ASTM D1003 method (transmittance of 550nm)

Pencil hardness; Evaluated by ASTM D3502 (pencil hardness tester, toyoseki)

Membrane state and membrane color; Evaluated by visual observation

The antistatic coloring coating composition of the present invention is coated on the CRT glass surface to provide a CRT glass having physical properties such as appearance and excellent antistatic properties to give a luxurious feeling.

Claims (11)

6 to 26 wt% of an aqueous polyethylenedioxythiophene solution having a solid content of 0.6 to 3.0 wt%; 64 to 90 wt% of an alcohol and amide mixed solvent; 3-10% by weight of alkoxysilane; 0.005 to 0.1% by weight of a water-soluble polymer; 0.005 to 0.05% by weight of sulfonic acid monomer dopant; 0.1 to 0.30% by weight of water-dispersible carbon black; Water dispersible colored pigments 0.05 to 0.25 wt%; And 0.05 to 0.25 wt% of an azochrome complex-based or anthraquinone-based alcohol-soluble colored dye. delete The antistatic coloring coating composition according to claim 1, wherein the concentration of the solid content of the polyethylenedioxythiophene aqueous solution is 1.2 to 1.5% by weight. The antistatic coloring coating composition according to claim 1, wherein the polyethylene dioxythiophene aqueous solution has a viscosity of 10 to 50 cp. The antistatic coloring coating composition according to claim 1, wherein the introduced alkoxysilane reacts with water to undergo a hydrolysis and condensation reaction to form a silica sol. The method of claim 1, wherein the alcohol solvent is one or more selected from the group consisting of methanol, ethanol, propanol, isopropanol, The amide solvent is formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrroli Is one or more selected from a crowd of money, The alkoxysilane is one kind selected from the group consisting of tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, The water-soluble polymer is one selected from the group consisting of polymethacrylic acid, polyacrylic acid, polyvinyl alcohol, polyvinyl butyral, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, polyvinylacetate, The sulfonic acid monomer dopant is p-toluenesulfonic acid, dodecylbenzenesulfonic acid, 1,5-anthraquinonedisulfonic acid, 2,6-anthraquinonedisulfonic acid, anthraquinonesulfonic acid, 4-hydroxybenzenesulfonic acid, methylsulfonic acid, nitrobenzenesulfonic acid 1 type is selected from the group consisting of The water dispersible carbon black is a water dispersible carbon surface-modified with sulfonate or carboxylate, The water-dispersible colored pigment is an antistatic colored coating composition, characterized in that it is prepared using a milling method using a polymer dispersant and a surfactant. The antistatic coloring coating composition according to claim 1, wherein the mixed solvent comprises 94 to 99% by weight of an alcohol solvent and 1 to 6% by weight of an amide solvent. The antistatic coloring coating composition according to claim 7, wherein the content of methanol is 50% by weight or more based on the entire mixed solvent. The antistatic colored coating composition according to claim 1, wherein the water dispersible carbon black is 50 wt% or more based on the total content of the water dispersible carbon black, the water dispersible colored pigment, and the alcohol-soluble colored dye. (a) adding a polyethylenedioxythiophene aqueous solution to the reactor to start stirring; (b) adding alcohol and an amide mixed solvent, an alkoxysilane, a sulfonic acid monomer dopant, and a water-soluble polymer sequentially and then stirring for 6 hours or more while continuing stirring; (c) adding a water-dispersible carbon black, a water-dispersible colored pigment, and an alcohol-soluble colored dye, followed by stirring for 2 hours or more. The glass surface is coated by using the composition of claim 1 at a speed of 80 to 150 rpm by spin method over 80 to 150 seconds and then thermally baked at 150 to 200 ° C. for 30 minutes to 1 hour. Way.