KR100663413B1 - A composite brightness insulator film for Flat Panel Display and the same composite method - Google Patents

Abstract

The present invention relates to a composition of a transparent insulating film of a large screen display device that does not contain lead, which is environmentally friendly, and improves production efficiency and quality, minimizes color temperature drop of the large display device, and improves color purity. It is an object to provide a composition of a blue-type transparent insulating film.

In order to achieve the above object, the composition of the transparent insulating film of the large-screen display device of the present invention is Bi ₂ O ₃ 15-50wt%, B ₂ O ₃ 15-50wt%, BaO 1-20wt%, ZnO 5-40wt%, CaO 0.1- In the main composition composed of 15 wt%, at least one oxide selected from SiO ₂ , Al ₂ O ₃ , P ₂ O ₅ , MgO, and SrO is 0.1-10 wt%, CuO, CeO ₂ , CoO, V ₂ O ₅ , At least one oxide selected from La ₂ O ₃ and Nd ₂ O ₃ is 0.1-10 wt%.

Description

A composite brightness insulator film for Flat Panel Display and the same composite method

1 is a diagram showing the structure of a large-screen display device of a general PDP having a transparent insulating film.

* Description of the symbols for the main parts of the drawings *

1,11-Transparent glass substrate 2-Bus electrode (ITO electrode)

3,13-transparent insulation film 4-protective film

12-address electrode (Ag electrode)

14-Crosstalk preventive cell material

15-fluorescent material

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition of a transparent insulating film used for a large screen display device such as a plasma display panel (PDP), and the like, and particularly, a composition of a transparent insulating film having improved quality without containing lead (Pb) harmful to humans It is about providing a composition method.

In general, the PDP constituting the large-screen display device is configured as shown in FIG. 1 as an example.

In the upper plate 1 made of a transparent glass substrate, an indium tin oxide (ITO) electrode 2 connected to a bus electrode is formed in a predetermined pattern, and a transparent insulating film 3 and a protective film 4 made of a dielectric layer covering the ITO electrode. ) Is configured.

On the other hand, on the lower plate 11 made of a transparent glass substrate, an address electrode 12 made of silver (Ag) electrode or the like is formed in a predetermined pattern, and the address electrode is covered by a transparent insulating film 13 made of a dielectric layer. On the dielectric layer, a crosstalk preventing cell material 14 is formed in the boundary region of each cell in order to prevent crosstalk of pixels. Each pixel region partitioned by the crosstalk preventing cell material is formed to apply a fluorescent material 15, and plasma gas is injected into an enclosed space region of each pixel.

The PDP configured as described above has a plasma gas discharged under the control of a voltage applied to the bus electrode connected to the ITO electrode of the upper plate 1 of the transparent organic substrate and the address electrode 12 of the lower plate. Ultraviolet rays generated at (Xe, Ne, etc.) excite the fluorescent substance 15 to cause the corresponding pixel region to emit light.

The transparent insulating film (3) (13) of the glass composition used in the large-screen display device of the PDP is important to protect the electrode from ion bombardment during plasma discharge, to maintain discharge, to improve luminous efficiency, and to prevent diffusion. The element has a light transmittance of 80% or more, a dielectric constant in the range of 10-15, and a breakdown voltage of 1.1 KV. The coefficient of thermal expansion should be similar to that of a glass substrate to prevent thermal stress between adhesives. It should be possible.

As the dielectric layer of the conventional transparent insulating film requiring the above characteristic condition, a PbO-B ₂ O ₃ -SiO ₂ system containing a large amount of Pb (lead) was mainly used to obtain a low firing temperature.

The PbO has been generally added to a glass composition for low temperature baking because it is effective in lowering the melting point of the glass composition, that is, the transparent insulating film, and is excellent in improving wettability with an oxide such as alumina.

However, when the glass composition containing PbO is discarded, it may easily cause a chemical reaction with an acid or an alkali solution even in a natural state, thereby causing environmental problems such as soil and water pollution.

In addition, SiO ₂ -P ₂ O ₅ -ZnO-BaO-based, SiO ₂ -B ₂ O ₃ -ZnO-BaO-based, etc. have been studied as a glass composition of a transparent insulating film containing no PbO, but in order to lower the melting point of the glass composition. Alkali metal oxides, such as Li, Na, and K, are added. However, since the alkali metal ions added have a high moving speed in the glass composition, when the composition is fired, ion exchange occurs with a metal film, such as an Ag electrode (address electrode), of a PDP formed adjacent to the metal composition, such as an Ag electrode. There is a problem of causing discoloration of the film and lowering the luminance of the PDP.

In addition, when discharging the large screen display device of the PDP, Ne in the discharge gas acts as a factor of reducing the color purity of the large screen display device by emitting visible light of orange color, and the color purity is deteriorated due to the intrinsic optical properties of the phosphor material. There is a problem that the luminance is lowered due to reflection of external light.

The present invention has been made to solve the above problems,

A blue-type transparent insulating film of a low melting point dielectric, which does not contain harmful lead substances to humans or the environment, and does not easily diffuse into adjacent metal films during the firing process. The purpose of the present invention is to improve the quality of panels of large screen displays such as PDPs and to apply environmentally friendly materials to the production of panels by developing glass compositions.

In order to achieve the above object, the composition of the transparent insulating film of the large-screen display device of the present invention is Bi ₂ O ₃ 15-50wt%, B ₂ O ₃ 15-50wt%, BaO 1-20wt%, ZnO 5-40wt%, CaO 0.1- In the main composition composed of 15wt%, at least one oxide selected from SiO ₂ , Al ₂ O ₃ , P ₂ O ₅ , MgO, SrO is 0.1-10wt%, CuO, CeO ₂ , CoO, V ₂ O ₅ , At least one oxide selected from La ₂ O ₃ and Nd ₂ O ₃ is characterized in that the auxiliary composition consisting of 0.1-10wt% is mixed.

Example

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative example Bi ₂ O ₃ (wt%) 38.8 36.2 29.6 45 45.2 11.8 36.6 35.2 PbO (wt%) 45 B ₂ O ₃ (wt%) 16 19.7 21.4 14 15.1 25.4 20.1 19.2 25 BaO (wt%) 15.5 12.4 17.1 13.3 17.4 19 12.7 12.1 15 ZnO (wt%) 18.5 27.8 20.3 16 16.4 36 24.3 27 CaO (wt%) 3 2.4 5.1 3 One 3 4 2.3 Al ₂ O ₃ (wt%) 2 2 5 P ₂ O ₅ (wt%) 4 4.9 MgO (wt%) One 2.7 SiO ₂ (wt) 1.2 1.3 1.5 4.9 2.5 3 1.3 1.5 10 SrO (wt%) 1.5 CuO (wt%) 0.2 0.5 0.4 0.5 CeO ₂ (wt%) 0.1 CoO (wt%) 0.6 0.3 La ₂ O ₃ (wt%) 0.5 Nd ₂ O ₃ (wt%) 2.7 Transition point Tg (℃) 476 480 485 475 480 493 478 483 475 Softening Point Ts (℃) 50 505 515 497 498 530 513 523 496 Linear expansion coefficient TEC (x10 ^-7 79 71.6 78.6 77.9 72.3 69 74.3 71.6 75.3 permittivity 12-12.5 11-12 11.5-12 11-12 11-11.5 10.5-11.5 11.5-12 11.5-12 10-11 Water resistance Good Good Good Good Good Good Good Good Good Ag electrode discoloration U radish radish radish radish radish radish radish U Transmittance (%) 80 80 81 48 80 82 81 80 77 Crystallization presence radish radish radish radish radish radish radish radish U Withstand voltage (Kv) 2.2 2.3 3.3 2.5 2.7 2.9 2.6 2.7 1.8

Each of the eight sample samples at the mixing ratio of the composition shown in Table 1 was put into an electric furnace and melted for about one hour to about 1200-1350 ° C., followed by dry quenching using a twin roll. The crude powder was pulverized with a disk and finely pulverized with a dry pulverizer to prepare a glass powder for a transparent insulating film for PDP having an average particle diameter of 2.5 mu m.

 70 wt% of the glass powder prepared above and 30 wt% of alpha-terpineol, which is an ethyl cellulose-based vehicle, were mixed and milled in three rolls, followed by degassing to prepare a glass composition paste. On the formed transparent glass substrate was coated with a screen printing method to a thickness of 100-150㎛ and dried by applying heat of 120-180 ℃.

It is preferable that the compounding ratio of the composition and the ethyl cellulose-based vehicle is blended at about 7: 3% by weight, but since the ethyl cellulose-based vehicle is volatilized, it is within the compounding ratio range of 6: 4-9: 1 depending on the viscosity of the paste. You may mix and adjust suitably.

In addition, the ethyl cellulose-based vehicle may be BCA (Butyl Carbinol Acetate), DBP (De-butyl Phthalate) in addition to alpha-terpineol (α-Terpinol), and these materials may be used alone or as appropriately mixed You may also

Subsequently, the dried glass composition paste was calcined at a temperature of about 570 ° C. to prepare eight sample samples as shown in Table 1, and a transparent insulating film of a glass composition containing a conventional PbO component was prepared in order to contrast with the sample of the sample. One was manufactured on the same conditions as the Example of this invention, and was made into the comparison object. The paste was fired at a temperature of 570 ° C., but should be within a temperature range of 500-600 ° C.

In addition to the screen printing method, the method of manufacturing the transparent insulating film may be a method such as a thick film coating method or a laminating method.

The transition point (Tg), softening point (Ts), crystallization, linear expansion coefficient, dielectric constant, water resistance, yellowing phenomenon, transmittance, crystallization, withstand voltage, and the like of each blue-type transparent insulating film were measured using the samples prepared as described above. It is shown in Table 1 in preparation.

The transition point was recorded by measuring the temperature at which the transition (points of mass transfer) occurred while heating the temperature of the blue-type transparent insulating film to 800 ° C. at a temperature increase rate of 10 ° C./min, and the softening point was melted glass. After the mass was prepared and polished to a size of 3mm x 3mm x 19mm, the temperature at which softening (points of transition from the solid phase to the liquid phase) was recorded by measuring the temperature while raising the temperature to 500 ° C at a heating rate of 10 ° C / min.

And, crystallization is recorded by visually inspecting whether or not crystallization occurs on the basis of 700 ℃ in the process of measuring the transition point, and the water resistance is 24 mm in distilled water at 30 ℃ after polishing the sample sample to a size of 4mm x 4mm It was recorded by observing with an optical microscope whether a water film was formed on the surface after time deposition.

The coefficient of linear expansion (TEC) is made of molten glass in the form of a mass, polished to a size of 3mm x 3mm x 15mm, and then the specimen is expanded between 50 ° C and 350 ° C while heating up to 500 ° C at a heating rate of 10 ° C / min. The degree was measured.

In addition, the yellowing phenomenon was recorded by cutting each sample to a size of 100mm x 50mm, evaluating the diffusion degree of Ag (silver) metal electrode with a color limiter and comparing with the color index.

In addition, the withstand voltage was measured by cutting each transparent insulating film into a size of 100 mm x 50 mm, attaching an electrode to the upper and lower portions of the specimen, and then applying a DC voltage to measure the voltage at which dielectric breakdown occurred.

In addition, the dielectric constant is measured by cutting the specimen into a size of 100 mm x 50 mm, attaching electrodes to the upper and lower portions of the specimen, and measuring the capacitance at 1 KHz with an LCR meter to measure the dielectric constant (capacitance (C) x (thickness) of the specimen. / Area) (1 / 8.842x10 ^-12 ) was calculated.

As can be seen from the experimental results recorded in Table 1, B ₂ O ₃ is an essential component for forming the glass composition of the blue-type transparent insulating film. As the content of B ₂ O ₃ increases in general borosilicate glass, The transition point and softening point of the glass is lowered, but in the low-temperature fired material, on the contrary, as the B ₂ O ₃ content increases, the transition point and softening point increase.

In addition, BaO / CaO acts as a modifying agent for glass, lowers the transition point and softening point of the glass, and increases the dielectric constant.

In addition, CuO / CeO ₂ / CoO / La ₂ O ₃ / Nd ₂ O ₃ is an additive, which acts to suppress yellowing with Ag ions moving in the Ag electrode through a redox reaction. If exceeded, the mother glass is colored, which significantly reduces the transmittance.

Compared with the glass composition containing the conventional PbO component, the glass composition of the present invention showed 75% transmittance, 1.8 KV withstand voltage and yellowing of the Ag electrode, whereas Example 2-8 of the present invention 80% transmittance of silver, withstand voltage over 2.3KV and yellowing of Ag electrode were not found.

The glass composition of the blue-type transparent insulating film used for the large screen display device of the present invention is not only superior in quality compared to the glass composition of the conventional transparent insulating film containing PbO, and in particular, does not contain a lead component. It is possible to realize the light weight of the product and to be environmentally friendly, thereby reducing the cost of the environmental treatment cost. In addition, compared with the glass composition of the conventional transparent insulating film, the effect of remarkably improving the yellowing phenomenon and the effect of efficiently absorbing unnecessary light deteriorating external light and color purity can be obtained.

Claims (4)

In the main composition consisting of Bi ₂ O ₃ 36-50wt%, B ₂ O ₃ 15-50wt%, BaO 1-20wt%, ZnO 5-24wt%, CaO 0.1-15wt%, SiO ₂ , Al ₂ O ₃ , At least one oxide selected from P ₂ O ₅ , MgO, and SrO is 0.1-10 wt%, and at least one oxide selected from CuO, CeO ₂ , CoO, V ₂ O ₅ , La ₂ O ₃ , and Nd ₂ O ₃ is selected. A composition of a transparent insulating film of a large screen display device, characterized in that the auxiliary composition consisting of 0.1-1wt% is mixed. The method of claim 1, The composition is a composition of a transparent insulating film of a large screen display device, characterized in that the melt is melted at 1200-1350 ℃ and then pulverized into a powder form through a cooling process. The method of claim 2, The powder and the ethyl cellulose-based vehicle are blended at a blending ratio of 6: 4-9: 1 to prepare a paste, and the paste is baked at a temperature of about 500-600 ° C. A composition of a transparent insulating film. The method of claim 3, The ethyl cellulose-based vehicle is a composition of a transparent insulating film of a large screen display device, characterized in that consisting of any one selected from alpha-terpineol, BCA, DBP.

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