KR101311876B1 - Electroconductive coating composition for glass and preparation method thereof - Google Patents

Abstract

The present invention relates to a conductive coating liquid composition for glass and a method for preparing the same, and more specifically, (i) 80-95% by weight of a carbon nanotube dispersion, and (ii) a polyacrylic acid resin solution, a silane sol and a dispersant solution. By including 5-20% by weight of the binder solution, the coating film not only has excellent uniformity, chemical stability, strength, and electrical conductivity, but also satisfies the adhesion and permeability to the glass at the same time. It also relates to a conductive coating liquid composition for glass that can be preferably applied to the upper glass for the protection of various functional materials such as touch screen panels and the like and a method of manufacturing the same.

Description

Conductive coating liquid composition for glass and manufacturing method thereof {ELECTROCONDUCTIVE COATING COMPOSITION FOR GLASS AND PREPARATION METHOD THEREOF}

The present invention relates to a coating composition, chemical stability, electrical conductivity, as well as a conductive coating liquid composition for glass excellent in strength and permeability when applied to glass and a method for producing the same.

Recently, the liquid crystal display (LCD) has been widely used not only for indoor use but also for outdoor advertisement, interior use, electronic blackboard, and three-dimensional image display. For example, indoor or outdoor for corporate advertising or promotion; Activation of advertising through billboards; For publicity in hospitals, shopping malls, hotels, etc .; The demand is increasing in various fields such as geographic information at airports, terminals, railway stations, and the like. As the use thereof expands, the risk of damage to the liquid crystal panel due to weather changes or external shocks or damage due to external pollutants increases, and a protective glass for preventing this is applied.

In addition, the LCD has various functional materials such as a touch screen panel for inputting various information on the liquid crystal panel, and a transparent protective plate such as high strength glass is applied to protect the functional material.

On the other hand, LCDs are susceptible to static electricity during the production process, which may damage the thin film transistor line as well as the problem of contamination of the surface by foreign matter adsorbed to the optical member, staining due to the distortion of the liquid crystal alignment. .

In order to solve this problem, a conductive coating film is formed on the surface of the LCD exterior glass to prevent damage due to scratches and foreign contamination, while at the same time solving the electrostatic problem.

Conductive polymers such as polythiophene, polypyrrole, and polyaniline are used as conductive materials for forming the conductive coating film, but these have low solubility, permeability, and thermal stability, and thus have low physical properties such as coating properties, adhesion, and strength when applied to glass. There is a limit. In addition, the electrical conductivity of the coating film is increased in proportion to the thickness. In the case of the conductive polymer absorbs light in the visible region, it is difficult to satisfy the transmittance when the thickness is increased.

In consideration of this, recently, carbon nanotubes have been used as conductive materials. Carbon nanotubes are physically robust, have excellent chemical stability, have excellent mechanical properties, high thermal conductivity, and have electrical selectivity and field emission characteristics. However, in the case of carbon nanotubes, it is difficult to obtain a uniform coating film due to poor dispersibility in the coating solution, which is easily damaged by the external environment, and needs to be improved.

Korean Patent Publication No. 2009-75360 (2009. 7. 8)

The present invention is capable of forming a coating film having excellent antistatic properties and excellent strength and permeability due to external damage, so as to protect various functional materials such as touch screen panels as well as exterior glass of various image display apparatuses including LCDs. An object of the present invention is to provide a conductive coating liquid composition for glass, which can be preferably applied to the upper glass.

In addition, another object of the present invention is to provide a method for preparing the conductive coating liquid composition for glass.

In addition, another object of the present invention is to provide a conductive glass having a conductive coating film formed of the conductive coating liquid composition for glass.

1. (i) 80-95% by weight of carbon nanotube dispersion, and (ii) 5-20% by weight of a binder liquid in which a polyacrylic acid resin solution, a silane sol and a dispersant solution are mixed, and the carbon nanotube dispersion is carbon nano A conductive coating liquid composition for glass, comprising 0.21-0.5% by weight of a tube, 0.21-1.5% by weight of a dispersant, and a balance of water.

2. In the above 1, wherein the dispersing agent is sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate or a mixture thereof for the conductive coating liquid composition.

3. In the above 1, the polyacrylic acid resin solution is 0.001-1% by weight of polyacrylic acid resin, 0.003-5% by weight of water and 94-99.9% by weight of the alcohol-based solvent coating composition for a glass composition.

4. In the above 1, the silane sol is 30-40% by weight of a tetraalkoxysilane compound having 1 to 20 carbon atoms of the alkoxy group, and different from the tetraalkoxysilane compound and having an alkoxy group having 20 to 20 carbon atoms of the alkoxy group. A conductive coating liquid composition for glass, comprising 30% by weight, 1-5% by weight of acid catalyst, 20-35% by weight of alcohol solvent, and residual amount of water.

5. In the above 4, the tetraalkoxysilane compound is at least one conductive coating liquid composition selected from the group consisting of tetraethoxysilane, tetramethoxysilane, tetra-n-propoxysilane and oligomers thereof.

6. In the above 4, the alkoxysilane compound is methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, methyltripropoxysilane, methyltributoxysilane, propyltrimeth At least one selected from the group consisting of methoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, isobutyltrimethoxysilane, octyltriethoxysilane, octyltrimethoxysilane and methacryloxydecyltrimethoxysilane Conductive coating liquid composition for glass.

7. In the above 1, the dispersant solution is a conductive coating liquid composition for glass containing 0.1-5% by weight and 95-99.9% by weight of the dispersant selected from sodium dodecyl sulfonate, sodium dodecylbenzenesulfonate or a mixture thereof.

8. according to the above 1, the mixing ratio of the polyacrylic acid resin solution, silane sol and dispersant solution is 25-35: 12-25: 40-60 conductive coating liquid composition.

9. In the above 1, the mixing ratio of the polyacrylic acid resin solution, silane sol and dispersant solution is 30-35: 15-20: 45-55 conductive coating liquid composition.

10. A first step of preparing a carbon nanotube dispersion by mixing 0.21-0.5% by weight of carbon nanotubes, 0.21-1.5% by weight of a dispersant and the balance of water; A second step of preparing a polyacrylic acid resin solution, a silane sol and a dispersant solution, respectively; A third step of preparing a binder liquid by mixing the polyacrylic acid resin solution prepared in the second step with the silane sol, and then mixing the dispersant solution with the mixed solution; And a fourth step of mixing 80-95% by weight of the carbon nanotube dispersion prepared in the first step and 5-20% by weight of the binder solution prepared in the second step.

11. In the above 10, the third step is a method for producing a conductive coating liquid composition for glass is carried out so that the mixing ratio of the polyacrylic acid resin solution, silane sol and dispersant solution is 25-35: 12-25: 40-60.

12. Conductive glass with a conductive coating film formed of a conductive coating liquid composition for glass of any one of the above 1 to 9 on one side.

13. The conductive glass according to the above 12, which is an exterior glass for protecting a liquid crystal display or a touch screen panel.

The present invention can greatly improve the dispersibility and coating properties of the carbon nanotubes to form a uniform coating film, excellent chemical stability and electrical conductivity of the formed coating film as well as the strength and permeability for appearance damage when applied to glass At the same time it can provide a conductive coating liquid for glass and a method for producing the same.

In addition, the conductive coating solution of the present invention can be preferably applied to the protective glass provided on top of various functional materials such as a touch screen panel as well as the appearance glass for protecting the display screen of various image display devices such as LCD.

The present invention relates to a coating composition, chemical stability, electrical conductivity, as well as a conductive coating liquid composition for glass excellent in strength and permeability when applied to glass and a method for producing the same.

Hereinafter, the present invention will be described in detail.

The conductive coating liquid composition for glass of the present invention comprises (i) 80-95% by weight of carbon nanotube dispersion, and (ii) 5-20% by weight of a binder liquid in which a polyacrylic acid resin solution, a silane sol and a dispersant solution are mixed. It features.

The conductive coating liquid composition of the present invention is a composition in the form of an aqueous dispersion in which water is used as a solvent and a hydrophilic alcohol solvent is mixed thereto.

(Iii) A carbon nanotube dispersion is a mixture of 0.21-0.5% by weight of carbon nanotubes, 0.21-1.5% by weight of a dispersant, and a balance of water.

In the present invention, a carbon nanotube (CNT), which is a nanometer-sized structure composed of carbon atoms, is used as the conductive material.

Carbon nanotubes (CNT) may be prepared by a method such as a conventional arc discharge method, laser deposition method, plasma chemical vapor deposition method, gas phase synthesis method, thermal decomposition method and the like and then heat treated. In the product prepared by the above synthesis method, carbon impurities such as amorphous carbon or crystalline graphite particles, catalyst transition metal particles, etc. are present together with the synthesized carbon nanotubes. For example, when produced by the arc discharge method, 15-30 wt% of carbon nanotubes, 45-70 wt% of carbon impurities, and 5-25 wt% of catalyst transition metal particles are included in 100 wt% of the product. As such, when carbon nanotubes containing impurities are directly applied to the coating liquid without refining, the dispersibility and coating properties of the coating liquid are lowered, and the unique physical properties unique to the carbon nanotubes are difficult to be properly expressed. Therefore, the present invention uses carbon nanotubes in which impurities are removed as much as possible by heat-treating the products prepared by the arc discharge method. Specifically, the product prepared by the above synthesis method is made into a sheet or a granule having an average diameter of 2 to 5 mm, and then the granular product is fed into a rotatable reactor inclined downward at an angle of 1-5 degrees with respect to the traveling direction , The rotary reactor is heated to 350-500 캜, and the oxidizing gas is supplied at a rate of 200-500 cc / min to 1 g of the charged product, followed by heat treatment for 60-150 minutes. At this time, the tilted rotary reactor rotates at a speed of 5-20 rpm to disperse the product, thereby maximizing the contact surface area and automatically moving in the traveling direction to maximize the contact surface area with the oxidizing gas and to prevent local oxidation Heat treated. According to this method, the weight of the charged product is reduced by 60-85% to obtain high purity carbon nanotubes.

Carbon nanotubes containing 40% by weight or less, more preferably 25% by weight or less of carbon impurities in the total 100% by weight is good in ensuring the electrical conductivity and permeability of the coating film as well as dispersibility and stability of the coating solution.

The carbon nanotubes may be single-walled carbon nanotubes, double-walled carbon nanotubes, or multi-walled carbon nanotubes, which may be used alone or in combination of two or more.

The carbon nanotubes may be included in an amount of 0.21-0.5% by weight based on 100% by weight of the carbon nanotube dispersion. If the content is contained in 0.21-0.5% by weight, the dispersibility, coating properties, scratch resistance, permeability, etc. are maintained to a certain level or more, it is advantageous because the electrical conductivity is also excellent.

The dispersant is not particularly limited as long as it is an anionic surfactant, but sodium dodecylsulfonate (SDS) or sodium dodecyl benzene sulfonate (NaDDBS) is compatible with polyacrylic resins and carbon nanotubes. It is preferable in that the excellent coating properties can be obtained by maximizing the dispersibility of the coating liquid to obtain a uniform coating film.

The dispersant may be included as 0.21-1.5% by weight based on 100% by weight of the carbon nanotube dispersion. If the content is less than 0.21% by weight, the effect of improving dispersibility may be insufficient. If the content is more than 1.5% by weight, the conductivity and the adhesion may be reduced.

(Ii) The binder liquid is a mixture of a polyacrylic acid resin solution, a silane sol and a dispersant solution.

The polyacrylic acid resin solution is a solution in which 0.001-1% by weight of polyacrylic acid resin (based on solid content), 0.003-5% by weight of water and 94-99.9% by weight of an alcohol solvent are mixed.

The alcohol solvent is preferably a hydrophilic alcohol solvent in consideration of the fact that the coating liquid of the present invention is a coating liquid containing water as a solvent. Specifically, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1-ethyl -1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol, etc. are mentioned, These can be used individually or in combination of 2 or more types. In the case of the hydrophilic alcohol-based solvent, it is good to ensure the physical properties of the coating liquid because of good mixing properties with the carbon nanotube dispersion as well as polyacrylic acid resin.

Polyacrylic acid resin is a component that improves the adhesion to the substrate and prevents deformation of the coating film, and carbon nanotubes are attached to the substrate to realize sufficient electrical conductivity properties. In particular, the polyacrylic acid resin is more preferable in that it is possible to control the pH of the coating liquid in dispersing the carbon nanotubes, which greatly contributes to dispersion stability.

It is preferable to use polyacrylic acid resin in the form of an aqueous solution having a solid content of 20-50% by weight, and it is preferable that the weight average molecular weight (in terms of polystyrene) of GPC method is 1,000 to 700,000.

The polyacrylic acid resin is preferably included as 0.001-1% by weight (based on the solid content) based on 100% by weight of the total acrylic acid resin solution. If the content is less than 0.001% by weight, it may be difficult to secure dispersion stability and coating property, and when the content is more than 1% by weight, electrical conductivity may be lowered.

When the polyacrylic acid resin is used in an aqueous solution, water may be included therein or may be included in a small amount separately, and its content may be 0.003-5% by weight.

The silane sol is 30-40% by weight of a tetraalkoxysilane compound having 1-20 carbon atoms in the alkoxy group; 20-30% by weight of the alkoxysilane compound different from the tetraalkoxysilane compound having 1-20 carbon atoms of the alkoxy group, 1-5% by weight of the acid catalyst, 20-35% by weight of the alcohol solvent, and the remaining amount of water are mixed with the sol-gel. It is obtained by reaction. When mixed in this content range, the sol-gel reaction occurs well, so that the physical properties of the obtained silane sol are good, particularly when applied to a glass substrate to ensure strength, that is, hardness against external damage.

The tetraalkoxysilane compound is a component for forming a silane sol, and the alkoxy group may be linear or branched, and preferably has 1-20 carbon atoms. Especially, tetraethoxysilane, tetramethoxysilane, tetra-n-propoxysilane, these oligomers, etc. are preferable, These can be used individually or in mixture of 2 or more types.

The alkoxysilane compound is a component for forming a silane sol together with the tetraalkoxysilane compound, and is not particularly limited as long as the alkoxysilane compound is different from the above tetraalkoxysilane compound, and the alkoxy group may be linear or branched and has 1-20 carbon atoms. Can be mentioned. Specifically, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, methyltripropoxysilane, methyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane Carbon number of a substituted or unsubstituted linear or branched alkyl group, such as isobutyltriethoxysilane, isobutyltrimethoxysilane, octyltriethoxysilane, octyltrimethoxysilane and methacryloxydecyltrimethoxysilane Alkylalkoxysilanes of 1-20; Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminoethyl-3-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N- (n-butyl) -3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane; Dimethyldimethoxysilane, Diethyldiethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mer Captopropyltrimethoxysilane; Tridecafluoro-1,1,2,2-tetrahydrooctylfreeethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriisopropoxysilane, etc. And fluoroalkylsilanes having 1 to 20 carbon atoms in the alkyl group of the above, and these may be used alone or in combination of two or more thereof. Among these, alkyl alkoxysilanes having 1 to 20 carbon atoms are preferable.

The acid catalyst is for imparting an appropriate degree of crosslinking to the silane sol, and may include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, diluted hydrofluoric acid, and the like, and these may be used alone or in combination of two or more thereof.

The alcohol solvent and water are used to influence the hydrolysis upon formation of the silane sol, and the above-described conventional hydrophilic alcohol solvents may be used alone or in combination of two or more thereof.

By mixing the above components for a certain time, it becomes possible to obtain a silane sol by a sol-gel reaction. The silane sol, in particular, when the coating liquid is applied to the glass substrate, can provide strong adhesion to secure excellent strength characteristics.

The dispersant solution is a solution in which 0.1-5% by weight of the dispersant selected from sodium dodecyl sulfonate, sodium dodecylbenzenesulfonate, or a mixture thereof and 95-99.9% by weight of water are mixed to uniformly mix the polyacrylic acid resin solution and the silanazole. In addition, it is possible to improve the coating property by facilitating the mixing even when mixing with the (i) carbon nanotube dispersion.

The polyacrylic acid resin solution, the silane sol and the dispersant solution may be mixed in a weight ratio of 25-35: 12-25: 40-60 to constitute a binder solution, preferably a weight ratio of 30-35: 15-20: 45-55 It is good to mix with. In the case of mixing in this weight ratio, it is possible to obtain a uniform coating film with good compatibility and compatibility with the carbon nanotube dispersion, as well as to satisfy the strong adhesion to the glass, strength and permeability at the same time.

The carbon nanotube dispersion and (ii) the binder liquid as described above are preferably included in a ratio of 80-95% by weight: 5-20% by weight with respect to 100% by weight of the conductive coating liquid composition for glass, more preferably 85 The ratio is -93% by weight: 7-15% by weight. When mixed in this way, it is possible to obtain a uniform coating film by maximizing the dispersibility of the carbon nanotubes, while maintaining a strong adhesion and strength to the glass while maintaining a high permeability.

The conductive coating liquid composition may be preferably applied to a protective glass provided on top of various functional materials such as a touch screen panel as well as a protective appearance glass for protecting a display screen of various image display devices such as a glass, for example, an LCD. Specifically, the conductive glass may be provided with a conductive coating film formed by coating and drying the conductive coating liquid composition on one surface of the glass. In this case, the conductive coating film may be formed on the viewer side of various functional materials such as LCD or touch screen panel of glass.

The conductive coating liquid composition of the present invention can be prepared by the following method.

A first step of preparing a carbon nanotube dispersion; A second step of preparing a polyacrylic acid resin solution, a silane sol and a dispersant solution, respectively; A third step of preparing a binder liquid by mixing the polyacrylic acid resin solution prepared in the second step with the silane sol, and then mixing the dispersant solution with the mixed solution; And a fourth step of mixing 80-95 wt% of the carbon nanotube dispersion prepared in the first step and 5-20 wt% of the binder solution prepared in the second step.

The first step is to prepare a carbon nanotube dispersion, the carbon nanotube 0.21-0.5% by weight of the conductive material, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate or a mixture thereof 0.21-1.5% by weight and the balance of Water is mixed to prepare a carbon nanotube dispersion. In this case, an ultrasonic disperser or an ultrasonicizer may be used for good dispersion of the conductive material. For example, when using an ultrasonic disperser can be dispersed for 0.5-5 hours at 40 Hz, 150W. In addition, centrifugation may be performed after sonication.

The second step is to prepare a polyacrylic acid resin solution, a silane sol and a dispersant solution constituting the binder liquid, respectively.

The polyacrylic acid resin solution is prepared by mixing 0.001-1% by weight of polyacrylic acid resin (based on solids content), 0.003-5% by weight of water, and 94-99.9% by weight of an alcohol solvent. Mixing time is not specifically limited, It can carry out until each component mixes well. Moreover, in order to make mixing favorable, you may mix, heating in a thermostat.

The silane sol is 30-40% by weight of a tetraalkoxysilane compound having 1-20 carbon atoms in the alkoxy group, 20-30% by weight of an alkoxysilane compound having 1-20 carbon atoms different from the tetraalkoxysilane compound and an acid catalyst 1- Prepared by sol-gel reaction by mixing 5% by weight, 20-35% by weight of the alcohol solvent and the remaining amount of water. Mixing can be carried out at room temperature for 15-30 hours.

The dispersant solution is prepared by mixing 0.1-5% by weight of the selected dispersant and 95-99.9% by weight of water in sodium dodecylsulfonate, sodium dodecylbenzenesulfonate or mixtures thereof.

The third step is to prepare a binder liquid by mixing the polyacrylic acid resin solution, the silane sol and the dispersant solution prepared in the second step, respectively. In particular, the present invention is characterized in that the polyacrylic acid resin solution and the silane sol among the three components constituting the binder liquid are mixed first, and then the dispersant solution is mixed with the mixed solution. At this time, it may be performed while heating in a thermostat for uniform mixing. For example, the polyacrylic acid resin solution and the silane sol may be mixed for 10-30 minutes, and then the dispersant solution may be added to the mixed solution and mixed for 1-10 minutes. According to this method, the polyacrylic acid resin and the silane sol are uniformly mixed to maximize the effect of each component, and greatly improves dispersibility and coating property even when mixing with the carbon nanotube dispersion of the first step. You can do it. Through this, it is not only excellent in strength and good permeability but also excellent in adhesion when applied to glass. A good coating film can be obtained.

In the third step, the mixing ratio of the polyacrylic acid resin solution, the silane sol and the dispersant solution is preferably 25-35: 12-25: 40-60, more preferably 30-35: 15-20: 45 Mixing at a weight ratio of -55 is recommended.

The fourth step is to prepare a conductive coating solution composition by mixing 80-95% by weight of the carbon nanotube dispersion prepared in the first step and 5-20% by weight of the binder solution prepared in the third step. At this time, it may be performed for 1-5 minutes while heating in a thermostat in order to improve the mixing.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.

Example

Example 1

Carbon nanotubes (SA100, NanoSolution Co., Ltd.), synthesized by the arc discharge method, were rotated at a speed of 5-20 rpm, a temperature of 420 ° C., and an oxidizing gas of 250 mW / min using a rotary kiln rotary reactor having an inclination angle of 3 °. Heat treatment was performed for 100 minutes at a feed rate to use carbon nanotubes A having a carbon impurity content of 15%. 0.27 parts by weight of carbon nanotubes A, 0.27 parts by weight of sodium dodecyl sulfonate (SDS) and 99.46 parts by weight of water were mixed and treated with an ultrasonic disperser for 35 minutes. The treated solution was centrifuged at 6,000 rpm for 12 minutes to prepare a carbon nanotube dispersion.

0.4 parts by weight of an aqueous polyacrylic acid resin solution (solid content 25%) and 99.6 parts by weight of ethanol were mixed and stirred until well mixed to prepare a polyacrylic acid resin solution.

37 parts by weight of tetraethoxysilane, 24 parts by weight of methyltriethoxysilane, 27 parts by weight of ethanol, 4 parts by weight of hydrochloric acid (35%) and 8 parts by weight of water were mixed for 24 hours to prepare a silane sol. .

0.5 parts by weight of sodium dodecyl sulfonate (SDS) and 99.5 parts by weight of water were mixed for 5 minutes while heating in a thermostat to prepare a dispersant solution.

The binder solution was prepared by mixing the prepared polyacrylic acid resin solution, silane sol and dispersant solution in a weight ratio of 32.5: 17.5: 50. At this time, the polyacrylic acid resin solution and the silane sol were mixed for a total of 20 minutes while heating in a thermostat for 5 minutes, a dispersant solution was added to the mixture and mixed for 5 minutes in a thermostat.

The prepared carbon nanotube dispersion and the binder solution were added in a weight ratio of 90:10, and mixed with heating in a thermostat for 5 minutes to prepare a conductive coating solution composition.

Example 2-12, Comparative Example 1-5

The same process as in Example 1, except that the conductive coating solution was prepared in the composition as shown in Table 1.

Comparative Example 6

The same procedure as in Example 1 was carried out, but the polyacrylic acid resin solution, the silane sol and the dispersant solution were added at the same time, and mixed for 5 minutes while heating in a thermostat.

division Carbon Nanotube Dispersion Binder solution Kinds Mixing ratio Ⅰ Ⅱ Ⅲ Mixing ratio Example 1 A 90 32.5 17.5 50 10 Example 2 B 90 32.5 17.5 50 10 Example 3 A 85 32.5 17.5 50 15 Example 4 A 94 32.5 17.5 50 6 Example 5 A 90 27 17.5 55.5 10 Example 6 A 90 32.5 24 43.5 10 Example 7 A 90 24.5 17.5 58 10 Example 8 A 90 36 17.5 46.5 10 Example 9 A 90 32.5 10 57.5 10 Example 10 A 90 32.5 26 41.5 10 Example 11 A 90 42 18 37 10 Example 12 A 90 25.5 12.5 62 10 Comparative Example 1 A 90 50 - 50 10 Comparative Example 2 A 90 - 50 50 10 Comparative Example 3 A 90 70 30 - 10 Comparative Example 4 A 75 32.5 17.5 50 25 Comparative Example 5 A 97 32.5 17.5 50 3 Comparative Example 6 A 90 32.5 17.5 50 10 Carbon nanotube dispersion A: Contains carbon nanotube (carbon impurity content: 15%) after heat treatment of SA100
Carbon nanotube dispersion B: contains SA100 (carbon impurity content: 45-70%)
Binder solution I: polyacrylic acid resin solution
Binder solution II: silane sol
Biander liquid III: Dispersant solution

Test Example

Physical properties of the conductive coating liquids prepared in Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 2 below.

1. Dispersibility

A small amount of the prepared conductive coating liquid composition was dropped on the glass plate to determine whether the agglomerate was agglomerated, and the remaining coating liquid composition was stored in a glass bottle. In the same manner, it was confirmed whether the flocculation for 30 days, the results were evaluated based on the following criteria.

<Evaluation Criteria>

○: Aggregation occurred after 30 days (good).

(Triangle | delta): Aggregation generate | occur | produces after 10 days (usually).

X: Aggregation generate | occur | produces within 2 days (defect).

2. Coating property

The prepared conductive coating solution was coated on a glass plate using a spin coater and dried at 80 ° C. for 15 minutes to form a conductive coating film. The surface uniformity of the formed conductive coating film was visually observed and evaluated based on the following criteria.

<Evaluation Criteria>

(Circle): A liquid film | membrane is apply | coated uniformly at the time of coating liquid application (good).

(Triangle | delta): There exist some parts to which a liquid film is apply | coated unevenly at the time of coating liquid application (usually).

X: A liquid film is not apply | coated uniformly at the time of coating liquid coating, and a uniform coating layer is not formed (defect).

3. Surface resistivity (Ω / □)

The surface resistivity of the conductive coating film formed in the above 2 was measured using a surface resistance meter. At this time, the surface resistivity measurement was carried out by adopting a 4-point probe method, the coating film surface was divided into three parts in the longitudinal direction and measured in the center portion of the coating film was evaluated based on the following criteria.

<Evaluation Criteria>

○: Surface specific resistance (Ω / □) ≤ 5 x 10 ⁵ (good).

Δ: 5 × 10 ⁵ <surface specific resistance (Ω / □) ≤ 5 × 10 ⁶ (normal).

X: 5 x 10 ⁶ <surface specific resistance (Ω / □) (bad).

4. Permeability (%)

The transmittance of the conductive coating film formed in the above 2 was measured at 550 nm using a spectrophotometer, and the results were compared based on 90.5%, the transmittance of the uncoated glass, as a reference value, and evaluated based on the following criteria.

<Evaluation Criteria>

○: 85.5 ≤ transmittance (%) (good).

Δ: 81.5 ≤ transmittance (%) <85.5 (typical).

X: Permeability (%) <81.5 (bad).

5. Scratch resistance (Pencil hardness)

The surface of the conductive coating film formed in the above 2 was measured by H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H pencil using a pencil hardness tester (221-D, Yoshimitsu).

division Dispersibility Coating property Surface resistivity Permeability Pencil hardness
(H) Measures
(Ω / □) Judgment Measures
(%) Judgment Example 1 ○ ○ 1.3 x 10 ⁵ ○ 87.6 ○ 9 Example 2 ○ ○ 3.2 × 10 ⁵ ○ 86.4 ○ 9 Example 3 ○ ○ 4.9 × 10 ⁵ ○ 88.1 ○ 9 Example 4 ○ ○ 1.0 × 10 ⁵ ○ 85.5 ○ 8 Example 5 ○ ○ 5.0 × 10 ⁵ ○ 87.6 ○ 9 Example 6 ○ △ 4.9 × 10 ⁵ ○ 87.6 ○ 8 Example 7 ○ △ 5.0 × 10 ⁵ ○ 85.9 ○ 9 Example 8 ○ ○ 2.0 × 10 ⁶ △ 85.3 △ 8 Example 9 ○ ○ 3.4 × 10 ⁶ △ 84.0 △ 6 Example 10 ○ ○ 4.6 × 10 ⁶ △ 86.9 ○ 9 Example 11 ○ ○ 5.0 × 10 ⁶ △ 85.5 ○ 6 Example 12 ○ ○ 4.8 × 10 ⁶ △ 85.1 △ 6 Comparative Example 1 ○ ○ 1.4 × 10 ⁵ ○ 87.1 ○ One Comparative Example 2 × △ 1.1 × 10 ⁷ × 75.9 × 7 Comparative Example 3 △ △ 7.5 × 10 ⁶ × 86.1 ○ 8 Comparative Example 4 × △ 7.6 × 10 ⁷ × 88.1 ○ 3 Comparative Example 5 ○ × 3.5 × 10 ⁷ × 84.2 △ - Comparative Example 6 △ △ 3.3 × 10 ⁷ × 81.9 △ -

As shown in Table 2, according to the present invention, the conductive coating solution of Example 1-12 including the binder solution in which the carbon nanotube dispersion, the polyacrylic acid resin solution, the silane sol and the dispersant solution is mixed in an optimal content ratio is Comparative Example 1-6. Dispersibility and coating properties of the coating solution is better than that of forming a uniform coating film, it was confirmed that not only has excellent electrical conductivity and permeability, but also particularly good adhesion to the glass plate to ensure sufficient hardness. In particular, it was more effective than the case where the mixing ratio of the three kinds of components constituting the binder liquid was optimized.

In addition, in the case of Comparative Example 6 in which the three components constituting the binder liquid were mixed at the same time, agglomeration occurred, resulting in inferior dispersibility and coating property as compared with the Examples, which was not good throughout other physical properties.

Claims (13)

(Iii) 80-95 wt% of carbon nanotube dispersion, and
(Ii) 5-20% by weight of a binder liquid in which a polyacrylic acid resin solution, a silane sol and a dispersant solution are mixed,
The carbon nanotube dispersion is a conductive coating liquid composition for glass comprising a carbon nanotube 0.21-0.5% by weight, a dispersant 0.21-1.5% by weight and the balance of water.
The conductive coating liquid composition for glass according to claim 1, wherein the dispersant is sodium dodecyl sulfonate, sodium dodecylbenzenesulfonate or a mixture thereof.
The conductive coating liquid composition for glass according to claim 1, wherein the polyacrylic acid resin solution contains 0.001-1% by weight of polyacrylic acid resin, 0.003-5% by weight of water, and 94-99.9% by weight of an alcohol solvent.
The silane sol is 30-40% by weight of a tetraalkoxysilane compound having 1-20 carbon atoms in the alkoxy group, and 20-30% by weight of an alkoxysilane compound different from the tetraalkoxysilane compound having 1-20 carbon atoms in the alkoxy group. %, Acid catalyst 1-5% by weight, alcohol-based solvent 20-35% by weight and the remaining amount of water conductive coating liquid composition.
The conductive coating liquid composition for glass according to claim 4, wherein the tetraalkoxysilane compound is at least one selected from the group consisting of tetraethoxysilane, tetramethoxysilane, tetra-n-propoxysilane and oligomers thereof.
The compound of claim 4, wherein the alkoxysilane compound is methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, methyltripropoxysilane, methyltributoxysilane, propyltrimethoxysilane For at least one glass selected from the group consisting of propyltriethoxysilane, isobutyltriethoxysilane, isobutyltrimethoxysilane, octyltriethoxysilane, octyltrimethoxysilane and methacryloxydecyltrimethoxysilane Conductive coating solution composition.
The conductive coating liquid composition for glass according to claim 1, wherein the dispersant solution comprises 0.1-5% by weight and 95-99.9% by weight of a dispersant selected from sodium dodecyl sulfonate, sodium dodecylbenzenesulfonate or a mixture thereof.
The conductive coating liquid composition for glass according to claim 1, wherein the mixing ratio of the polyacrylic acid resin solution, the silane sol and the dispersant solution is 25-35: 12-25: 40-60.
The conductive coating liquid composition for glass according to claim 1, wherein the mixing ratio of the polyacrylic acid resin solution, the silane sol and the dispersant solution is 30-35: 15-20: 45-55.
A first step of preparing a carbon nanotube dispersion by mixing 0.21-0.5% by weight of carbon nanotubes, 0.21-1.5% by weight of a dispersant, and a balance of water;
A second step of preparing a polyacrylic acid resin solution, a silane sol and a dispersant solution, respectively;
A third step of preparing a binder liquid by mixing the polyacrylic acid resin solution prepared in the second step with the silane sol, and then mixing the dispersant solution with the mixed solution; And
Method for producing a conductive coating liquid for glass comprising a fourth step of mixing 80-95% by weight of the carbon nanotube dispersion prepared in the first step and 5-20% by weight of the binder solution prepared in the second step.
The method of claim 10, wherein the third step is performed such that a mixing ratio of the polyacrylic acid resin solution, the silane sol, and the dispersant solution is 25-35: 12-25: 40-60.
Conductive glass having a conductive coating film formed on one surface of the conductive coating liquid composition of any one of claims 1 to 9.
The conductive glass according to claim 12, which is an exterior glass for protecting a liquid crystal display or a touch screen panel.