KR100453919B1 - Coating composition having high heat-resistance coloring and antistatic properties - Google Patents

Abstract

The present invention relates to a coating composition having a high heat-resistant coloring and antistatic properties, in particular, applied to a flat panel display in the field of display to achieve excellent wear resistance, and coating to impart colorability for contrast control with antistatic properties of static electricity To a composition.

The present invention provides a coating composition for a display panel comprising: a) an inorganic colorant having a particle diameter of 5 to 200 nm dispersed in an aqueous solution or an organic solvent; b) a silicate binder comprising i) an organosilane compound, ii) an acid catalyst, and v) water alone or a mixture of water and an organic solvent; And c) inorganic conductive fine particles having a particle diameter of 5 to 200 nm.

The coating composition of the present invention has an economical advantage in that it is possible to use low-cost transparent flat glass instead of expensive tint and semi-tint colored glass panels in the development of flat panel displays by forming a coating film having colorability and antistatic properties. In addition, the image contrast can be improved by controlling the transmittance by controlling the content of the colorant, and a stable color can be obtained when the display coating is cured at a high temperature, thereby greatly contributing to high quality flattening and large size.

Description

Coating composition with high heat-resistant coloring and antistatic properties {COATING COMPOSITION HAVING HIGH HEAT-RESISTANCE COLORING AND ANTISTATIC PROPERTIES}

The present invention relates to a coating composition having high heat-resistant coloring and antistatic properties, and in particular, to a coating composition which is applied to a flat panel display to realize excellent wear resistance and imparts colorability for controlling contrast with antistatic property of static electricity. will be.

Electrostatic charging on the front of the display panel facilitates the attachment of dust and foreign materials, which may cause deterioration of image quality, device damage, and damage to human body. Therefore, in order to suppress such a phenomenon, an antistatic function is provided in the diffuse reflection antiwear coating composition applied to a display surface.

The prior art for forming the antistatic film is conductive to the coating composition, such as antimony tin oxide (antimony tin oxide), antimony zinc oxide (antimony zinc oxide), tin oxide, indium tin oxide (Indium tin oxide) Particles are used, and as mentioned above, in order to maintain high transmittance when applied to a display panel, an average particle size of 150 nm or less, preferably less than 100 nm, is used in a solution phase. This is because, as the particle size in the coating increases, the phenomenon of whitening due to light scattering is likely to be found.

In Japanese Patent Laid-Open No. 238279, Japanese Laid-Open Patent No. 181302, Japanese Laid-Open Patent No. 86967, Japanese Laid-Open Patent No. 54613, US Pat. No. 5,256,484, US Pat. The implementation of this is introduced.

One of the major changes in the recent display is the development of flat panel displays such as LCD, PDP, flat panel type CDT, CPT has also been developed in the CDT, CPT which occupies the largest portion of the conventional display.

Since the conventional round panel uses tint and semi tint glass, that is, colored glass panel, coating compositions having functions of antistatic property and antireflection are applied.

At present, small colored panels having a small size of flat CPT and CDT of 17 "or more and less than 40" are used in some small colored panels, but in most cases, transparent colorless panels are used. This is because the glass panel becomes thicker as the display is enlarged. Therefore, since the thickness of the glass inside the panel is not uniform at the center and the outside, it is difficult to realize uniform transmittance with colored glass. As a result, when using a color panel such as tint and semi tint in a flat panel display, a problem arises that the cost is high and uniform transparency and contrast control are not easy. In addition, due to limitations in the design of the CRT, a coating composition capable of forming a uniform colored coating on a colorless transparent panel and controlling transmittance is required.

In addition, in order to improve the image contrast, it is necessary to use a colorant capable of controlling the transmittance in the wear resistant antistatic coating composition, as shown in Equation 1 below, and in particular, in the transparent flat panel glass panel, the transmittance and optical properties of the coating composition It is even more important because it is affected a lot.

[Equation 1]

Cr = (πB / RTgL) + 1

In Equation 1,

Cr: Contrast

B: fluorescent surface luminance

Tg: light transmittance of glass

L: external light intensity

R: fluorescent surface reflectance

In order to improve the contrast by Equation 1, Japanese Patent Application Laid-open No. Hei 10-53758 tried to control the colorability of the coating film using carbon black or titanium black, and the color tone and light absorption In order to improve, Japanese Patent Laid-Open No. 1-275664 used a water-soluble phthalocyanine compound. In Japanese Patent Laid-Open No. 1-251545, methyl violet was used as a colorant. However, in the aforementioned antistatic properties, the colorants of the patent, in particular, the materials of the colorant have a disadvantage in that the antistatic properties are deteriorated because they essentially act as an insulator. In addition, in the formation of the coating film, the organic dye and the colorants derived therefrom when cured at a high temperature undergo a curing process, causing deformation and color change, and may also cause a poor appearance of the coating film.

Therefore, the present invention used an inorganic colorant and an inorganic conductive material to achieve stable colorability and antistatic properties at high temperatures. An example of the preparation of the inorganic pigment composition is shown in Japanese Patent Laid-Open No. 10-175660.

Composite oxide pigments include Ti-Sb-Ni, Ti-Sb-Cr, Zn-Fe, Zn-Fe-Cr, Co-Zn-Ni-Ti, Co-Al-Cr, Co-Al, Cu-Cr, Cu- Various components such as Cr-Mn and Cu-Fe-Mn may be used, and the antistatic property may be maintained or reduced depending on the compatibility with an inorganic conductive material, a binder, and an acid, which implements antistatic properties in the coating film.

In view of the problems in the prior art, an object of the present invention is to provide a coating composition which forms a stable coloring at a high temperature and an antistatic film.

Another object of the present invention is to provide a coating composition having improved color purity and high quality.

Another object of the present invention is to provide a coating composition capable of improving the slipperiness decrease and the film strength decrease phenomenon of the coating film surface due to the compatibility of the colorant and the raw material properties.

The present invention to achieve the above object,

In the coating composition for a display panel,

a) an inorganic colorant having a particle diameter of 5 to 200 nm dispersed in an aqueous solution or an organic solvent;

b) i) organosilane compounds,

Ii) an acid catalyst, and

Iii) water alone or a mixture of water and organic solvent

A silicate binder comprising a; And

c) inorganic conductive fine particles having a particle diameter of 5 to 200 nm

It provides a composition comprising a.

Hereinafter, the present invention will be described in detail.

In recent years, as the popularity of flat panel displays has increased, the use of transparent colorless glass panels instead of conventional colored glass panels has led to the necessity of coating compositions capable of controlling transmittance. In addition, since it is common to cure the coating composition at a high temperature of 150 to 300 ° C. in order to obtain an excellent film strength in the display field, the present invention has developed a coating composition having stable coloring property at high temperature and excellent wear resistance and antistatic property.

The present invention relates to a coating composition for a display panel for the purpose of improving image contrast and antistatic to flat glass. The present invention provides a coating composition comprising an inorganic composite metal pigment dispersed in an organic solvent that realizes high heat resistance coloration and antistatic properties, conductive fine particles of a metal alkoxide type, a silicate binder that implements abrasion resistance and chemical resistance, and an organic solvent. to provide. In particular, the coating composition of the present invention is to reduce the color uniformity, surface scratch resistance, lowering the film strength and the like, which may be caused by the use of a colorant for producing a coating composition having high color purity and high user preference, and a colorant for improving quality. Polydimethyl siloxane-based or polyether siloxane-based additives for improvement are further included as sleeping and leveling agents.

The coating composition of the present invention includes an inorganic colorant, an inorganic conductive material and a silicone binder and an organic solvent which are stable at high temperature, and has coloring property applied to a display and implements antistatic properties.

The present invention uses inorganic colorants such that there is no or very slight change in color before and after curing at high temperatures. The inorganic colorants include silicon (Si), titanium (Ti), zirconium (Zr), copper (Cu), cerium (Ce), aluminum (Al), manganese (Mn), zinc (Zn), and iron (Fe). Preference is given to using oxidizing compounds selected from the group consisting of one or two or more thereof. The present invention is used by dispersing the inorganic colorant in an aqueous solution or an organic solvent. The particle diameter of the inorganic colorant is preferably 5 to 200 nm, more preferably 10 to 100 nm. If the particle size of the inorganic colorant is less than 5 nm, the ability to control color and transmittance, called coloring power, may be reduced. This can be lowered and leads to a lower dispersibility. At this time, the content of the solid content of the dispersion is adjusted to 0.1 to 20% by weight, preferably adjusted to less than 15% by weight. And it is used at 0.1 to 8% by weight in the total coating composition.

The silicate binder may be prepared using a general organosilane compound as a starting material, preferably 10 to 60% by weight of the following organosilane compound, 0.1 to 10% by weight of an acid catalyst, and water alone or a mixture of water and an organic solvent. The silicate binder solution is prepared using 10 to 70 wt%. Specific examples of the organosilane compound include tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane and vinyltriethoxy Silane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane mercaptopropyltrimethoxysilane, [gamma- (triethoxy) propyltetrasulfane], phenyl-gammaaminopropyltrimethoxysilane, glycidoxypropyltri Methoxysilane, glycidoxypropylethyldiethoxysilane, isocyanatepropyltriethoxysilane, methacryloxypropyltriethoxysilane, methylsilicate oil, and ethyl silicate oil can be selected one or more selected from the group consisting of Can be. The acid catalyst may be hydrochloric acid, nitric acid, sulfuric acid, acetic acid, trichloroacetic acid, phosphoric acid, or the like. The silicate binder solution thus prepared has a molecular weight structure that has a degree of adhesion to glass or plastics, and is prepared from a solution of 1 to 20% by weight of solids to be 0.5 to 10% by weight based on the total coating composition. At this time, the molecular weight can generally be appropriately selected in consideration of the coating property and the thickness of the coating film within the range of Mw = 1,000 to 20,000.

The particle diameter of the inorganic conductive particles used in the present invention is preferably 5 to 200 nm, more preferably 5 to 200 nm. At this time, the form of the inorganic conductive particles is spherical or amorphous, in the case of the spherical primary particle size is less than 50 nm, preferably less than 30 nm is good, in the solution phase is less than 200 nm, preferably less than 150 nm Good to do. In this case, when the inorganic conductive particle size is less than 5 nm, it is impossible to manufacture the inorganic conductive particles, and when the inorganic conductive particle size exceeds 200 nm, problems may occur in whitening and permeability due to light scattering during coating film formation. The inorganic conductive fine particles are selected from the group consisting of antimonitin oxide, antimony zinc oxide, indium tin oxide, tin oxide, and conductive polymer. The inorganic conductive fine particles are used in an amount of 1 to 40% by weight, preferably 5 to 20% by weight, based on the solid content of the coating composition.

In addition, the present invention can further implement a high quality by further comprising 0.01 to 3% by weight of various colorants to the total coating composition that does not cause a decrease in resistance, film strength. The colorant is preferably a copper phthalocyanine derivative pigment or cobalt oxide derivative pigment having a particle diameter of 5 to 200 nm. In addition, violet pigments or quinacridone derivative pigments may be used in an amount of 0.01 to 3% by weight based on the total coating composition in order to improve color purity in addition to the high quality of the panel through the coating film on the front surface of the panel.

At this time, the compatibility and dispersibility in the coating composition of the colorant may reduce the uniformity of color and the scratch resistance of the film surface when the coating composition is applied.

Therefore, the present invention further includes a sleeping enhancement and leveling agent as an additive in the coating composition to improve this. The sleeping enhancement and leveling agent is a polydimethyl siloxane-based additive or a polyether siloxane-based additive having excellent compatibility with solvents, and its amount is used so that the solid content of the dispersion is 0.01 to 3% by weight. Specific examples of the additives include BYK-300, BYK-306, BYK-307, BYK-320, BYK-335, and the like of BYK-Chemie, and specific examples of the polyether siloxane-based additives include Tego-Chemie, Tego. 400, Tego 410 and Tego 453.

In the present invention, the final coating composition is prepared by the following method.

In the present invention, the conductive fine particles and the inorganic colorant are weighed and diluted with an organic solvent or distilled water in consideration of coating property and coating thickness. At this time, the solvent is used by appropriately selecting a low boiling point, a middle boiling point, or a high boiling point solvent in consideration of the size, coating conditions, curing temperature of the subject to be coated. Such solvents include ketones including acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diacetone alcohol; Alcohols including methyl alcohol, ethyl alcohol, isopropanol, normal butanol and 2-butanol; Polyalcohol derivatives, including methylcellussolve, ethylcellussolve, isopropylcellussolve, butylcellussolve; And a high boiling point solvent including formamide, dimethylformamide, tetrahydropearlfilalcohol, ethylene glycol, and N-methylpyrrolidone. The final coating composition must contain at least one solvent having a low boiling point, a middle boiling point, or a high boiling point to achieve good coating properties, which greatly affects the final coating strength.

The present invention is prepared by coating a suitable amount of the silicate binder synthesized from the organosilane compound into the dispersion of the diluted inorganic colorant, inorganic conductive material and stirred so as to sufficiently mix.

In addition, the present invention further prepares a coating composition by using a colorant and a sleep enhancing and leveling agent as additives in the composition.

Application of the coating composition is a glass panel used for the display as a subject, in particular applied to a flat glass panel, but is not limited in the spin coating or spray coating application method.

Hereinafter, the following examples will be described in order to help the understanding of the present invention, but the scope of the present invention is not limited to the examples.

Example 1

The metal-based colorant was dispersed in alcohol with 10% sol, and then a solvent and a silicate binder were added so that the solid content in the coating composition was as shown in Table 1 below. Then, the mixture was sufficiently mixed to have uniformity, spin coated at 120 rpm for 25 seconds on a 29 "flat glass panel having a surface temperature of 40 ° C., and cured at 150 ° C. for 15 minutes. The physical properties of the coating film were measured, and the results are shown in Table 1. In this case, the physical properties of the formed coating film were measured as follows.

① Antistatic property: Measured using Mitsubishi Chemical's Hi-Resta surface ohmmeter, and the transmission property was PSI Darsa-2000 transmission / reflection measurement equipment.

② Strength of coating film: The resistance of the resistance value before and after the test was observed by reciprocating 200 times with a load of 1 kg / ㎠ using Lion Rubber.

③ Chemical resistance: The coating film immersed in boiling water at 100 ℃ for 30 minutes was dried to observe the adhesion.

[Comparative Examples 1 and 2]

In the same manner as in Example 1 and the composition and content of Table 1 below, carbon black and titanium black were dispersed in 10% sol in alcohol instead of the metal-based inorganic colorant and added to the coating composition. In addition, physical properties were measured by the physical property measurement method of Example 1, and the results are shown in Table 1 below.

Classification (% by weight) Example 1 Comparative Example 1 Comparative Example 2 Silicate binder 3.0 3.0 3.0 Inorganic colorants Cu-Fe Inductor 1.0 - - Carbon black - 0.7 - Titanium black - - 0.7 Conductive fine particles ATO 2.0 2.0 2.0 ethyl alcohol 55 55.3 55.3 Isopropyl Alcohol 20 20 20 2-butanol 10 10 10 Dimethylformamide 3.0 3.0 3.0 Cellosolve 3.0 3.0 3.0 Etc 3.0 3.0 3.0 Properties Permeability (%) 66 63 63 Resistance (Ω / □) <5 × 10 ¹⁰ <1 × 10 ¹¹ <18 × 10 ¹¹ Coating Great Good Good Hot water Attach Peeling Peeling

In Table 1, when various colorants (Cu-Fe derivatives) were used to obtain the same transmittance of Example 1, compared with Comparative Example 1 (carbon black) and Comparative Example 2 (titanium black), the resistance and coating properties are excellent. Excellent properties could be achieved in the hot water test.

[Test Example 1]

Using the coating composition of Example 1 (inorganic colorant, in particular, composite metal colorant) by comparing the change of the color coordinate system value with temperature and curing time is shown in Table 2 below, the equipment used is Minolta CM- In 2002, the value of Lab coordinate system was measured at light source D65 and measurement angle 2 degrees.

division L a ^* B ^* 150 ℃, 15 minutes 49.44 -3.13 -3.98 180 ℃, 10 minutes 52.23 -3.07 -3.41 180 ℃, 20 minutes 52.05 -2.97 -3.39 180 ℃, 30 minutes 51.86 -2.92 -3.48

In Table 2, it can be seen that the values of L and B vary about △ 0.3 and △ 0.6, respectively, at 150 ℃, 15 minutes and 180 ℃ due to the difference in the thickness of the coating film with temperature. According to the results, it can be seen that the colorant values are stable at high temperatures because the color coordinate values do not change significantly.

Example 2

In the same manner as in Example 1, indium tin oxide having high conductivity instead of antimony tin oxide (ATO) was surface-treated with a chelating agent and a dispersion stabilizer.

EXAMPLES 3 AND 4

In the same manner as in Example 1, but for the implementation of high quality, a coating composition was prepared using a colorant (Copper phtalocyanine derived pigment) as shown in Table 3 below, and the physical properties of the coating after the coating film was measured.

Comparative Example 3

In the same manner as in Example 1, the content of the colorant (copper phthalocyanine derivative pigment) used for high-quality in Example 3 was increased to 0.6% by weight in the total coating composition.

[Comparative Example 4]

In the same manner as in Example 1, the content of the colorant (cobalt oxide derivative blue pigment) used for high quality in Example 4 was increased to 0.6% by weight in the total coating composition.

Classification (% by weight) Example 3 Example 4 Comparative Example 3 Comparative Example 4 Silicate binder 3.0 3.0 3.0 3.0 Inorganic colorants Cu-Fe Inductor 2.0 2.0 2.0 2.0 Colorant Copper Phthacyanine Derivatives Pigments 0.3 - 0.6 - Cobalt Oxide Blue Pigment - 0.3 - 0.6 Conductive fine particles ATO ITO 1.0 2.0 2.0 2.0 ethyl alcohol 54.7 53.7 53.7 53.4 Isopropyl Alcohol 20 20 20 20 2-butanol 10 10 10 10 Dimethylformamide 3.0 3.0 3.0 3.0 Cellosolve 3.0 3.0 3.0 3.0 Etc 3.0 3.0 3.0 3.0 Properties Permeability (%) 60.8 60.4 61 60.7 Resistance (Ω / □) <3 × 10 ¹⁰ <5 × 10 ¹⁰ <8 × 10 ¹⁰ <5 × 10 ¹¹ Coating Great Great Good usually Hot water Attach Attach Peeling Peeling

As can be seen from the results of Table 3, in the case of using the colorant to improve the quality of the panel, especially in the case of increasing the blue color of Example 3 in the case of the copper-phthalocyanine derivative pigments in appearance and hot water There is no effect at all, and the change in resistance value is minimal. And in the case of the cobalt oxide blue pigment of Example 4, there is no influence of hot water. On the other hand, in the case of Comparative Example 3 using a copper-phthalocyanine derivative pigment outside the content of the present invention, the coating property is good, but the water resistance is poor and in the case of the cobalt oxide derivative derivative of Comparative Example 4 deterioration in appearance and hot water characteristics It can be seen that the change in resistance value increases greatly with the content. In the case of Example 2, in the case of ITO, the same resistance value can be obtained with a smaller content than the addition of ATO.

Example 5

In the same manner as in Example 1, in addition to the high quality of the panel in order to improve the color purity through the coating film on the front panel of the violet-based pigments, quinacridone derivative pigments as shown in Table 4 to improve the optical properties and quality It was.

Example 6

The coating composition was prepared by the same method as Example 1, but adding 0.1 wt% of polydimethyl siloxane-based sleeping and leveling enhancer BYK-307 as shown in Table 4 below.

Example 7

The coating composition was prepared by the same method as Example 1, but adding 0.1% by weight of Tego-ZG-400, a polyether siloxane-based sleeping and leveling enhancer, as shown in Table 4 below.

Classification (% by weight) Example 5 Example 6 Example 7 Silicate binder 3.0 3.0 3.0 Inorganic colorants Cu-Fe Inductor 2.0 1.0 1.0 Colorant Copper Phthalocyanine Derivatives Blue Pigment 0.3 - - Sleeping and Leveling Enhancers BYK-307 - 0.1 - Tego-zg-400 - 0.1 Conductive fine particles ATO 2.0 2.0 2.0 ethyl alcohol 53.7 54.9 54.9 Isopropyl Alcohol 20 20 20 2-butanol 10 10 10 Dimethylformamide 3.0 3.0 3.0 Cellosolve 3.0 3.0 3.0 Etc 3.0 3.0 3.0 Properties Permeability (%) 60.5 66.5 66 Resistance (Ω / □) <6 × 10 ¹⁰ <6 × 10 ¹⁰ <6 × 10 ¹⁰ Coating Great Great Great Hot water Attach Attach Attach

As described above, the coating composition of the present invention forms a coating film having colorability and antistatic properties, and thus, in the development of a flat panel display, low-cost transparent flat glass may be used instead of expensive tint and semi-tint colored glass panels. There is an economic advantage, and the image contrast can be improved by adjusting the transmittance by controlling the content of the colorant, and also stable color can be obtained when the display coating is cured at a high temperature can greatly contribute to high-quality flattening and enlargement.

Claims (10)

In the coating composition for a display panel, a) group consisting of silicon (Si), titanium (Ti), zirconium (Zr), copper (Cu), cerium (Ce), aluminum (Al), manganese (Mn), zinc (Zn), and iron (Fe) 0.1 to 8% by weight of an inorganic colorant having a particle diameter of 5 to 200 nm and dispersed in an aqueous solution or an organic solvent selected from one or two or more kinds thereof; b) 10 to 60% by weight of an organosilane compound, Ii) 0.1 to 10% by weight acid catalyst, and V) 10 to 70% by weight of water alone or a mixture of water and organic solvent 0.5 to 10% by weight of a silicate binder; And c) 1 to 40% by weight of inorganic conductive fine particles having a particle diameter of 5 to 200 nm selected from the group consisting of antimonitin oxide, tin oxide, antimony zinc oxide, and indium tin oxide. Composition comprising a. delete delete The organosilane compound according to claim 1, wherein the organosilane compound of b) iii) is tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane or vinyltri. Methoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane mercaptopropyltrimethoxysilane, [gamma- (triethoxy) propyltetrasulfane], phenyl-gammaaminopropyltrimeth 1 from the group consisting of oxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropylethyldiethoxysilane, isocyanatepropyltriethoxysilane, methacryloxypropyltriethoxysilane, methylsilicate oil, and ethyl silicate oil. Or a composition selected from two or more. delete The composition of claim 1, wherein said composition further comprises a colorant of 5 to 200 nm of particles. 7. The composition of claim 6 wherein said colorant is a copper phthalocyanine derivative pigment, a cobalt oxide derivative, a violet pigment or a quinacridone derivative pigment. The composition of claim 1, wherein said composition further comprises a sleeping and leveling agent. 9. The composition of claim 8 wherein said sleeping and leveling agent is a polydimethyl siloxane-based or polyethersiloxane-based additive. A display panel coated with the composition of claim 1.