KR20070103986A - Dielectric glass material for high-intensity display - Google Patents

Abstract

A colored glass powder for a display upper dielectric is provided to have a high dielectric constant and a low melting point, to improve the color purity and luminescent efficiency of plasma display panels by brightness of blue color, and to prevent a coefficient of heat expansion from become larger by adjusting properly composition of glass components. A colored glass powder for a display upper dielectric includes a base glass composition and 0.001-5 parts by weight, based on 100 parts by weight of the base glass composition, of a colorant. The base glass composition comprises Bi2O3 30-60wt%, BaO 10-20wt%, ZnO 10-20wt%, B2O3 10-20wt%, SiO2 1-5wt%, and Al2O3 1-5wt%. The colorant is selected from CuO, Co3O4, NiO, MnO, MnO2, Mn2O3, and mixtures thereof. The colored glass powder has an average particle size of 1-10 micron.

Description

Dielectric Glass Material for high-intensity display

Figure 1 shows the structure of the AC-PDP as an example of the structure of the display used in the prior art,

Figure 2 shows the spectral transmittance of the upper dielectric layer according to Example 1 of the present invention.

<Explanation of symbols for main parts of the drawings>

1-Lower substrate 2-Address electrode 3-Lower dielectric layer

4-Bulkhead 5-Phosphor 6-Shield

7-Upper dielectric layer 8-Discharge sustaining electrode 8a, 8b-Transparent electrode

8a ＇, 8b＇-Bus electrode 9-Upper board

The present invention relates to a transparent dielectric for a display (eg, AC-PDP, SED, etc.) and a display panel using the same. Specifically, a mother glass containing Bi ₂ O ₃ as a main component instead of PbO which is harmful to humans and the environment. The present invention relates to a colored glass powder obtained by mixing a component and a colorant capable of increasing color purity and brightness of a display panel, a method of manufacturing the same, and a method of manufacturing a display panel using the same.

Figure 1 shows the structure of the AC-PDP as an example of the structure of the display used in the prior art. As shown, the lower substrate 1, the address electrode 2 formed on the lower substrate 1, the lower dielectric layer 3 formed on the address electrode 2, and the lower dielectric layer 3 It is formed on the top to maintain a discharge distance and includes a partition wall (4) for receiving the phosphor layer (5).

In addition, a discharge sustaining electrode 8 consisting of two electrodes is formed on the upper substrate 9 of the PDP, and the discharge sustaining electrode 8 is a transparent electrode 8a, so as not to inhibit light transmission of the upper substrate 9. 8b) and an indium-tin-oxide (ITO) electrode. In order to prevent the voltage drop of the discharge holding electrode 8, bus electrodes 8a 'and 8b', which are metal electrodes having a smaller area, are provided.

In addition, a protective film 6 is formed on the upper dielectric layer 7 to prevent sputtering of the upper dielectric layer 7 by gas ions during discharge and to lower the discharge start voltage by secondary electron emission. The space between the protective film 6 and the phosphor layer 5 is filled with an inert gas such as Ne + Xe, He + Xe.

Referring to Fig. 1, the operation principle of the PDP is as follows. First, a voltage corresponding to the discharge sustain voltage is applied between the two electrodes 8a and 8b constituting the discharge sustain electrode 8 to accumulate charge in the upper dielectric layer 7.

Subsequently, when a voltage corresponding to the discharge start voltage is applied to the address electrode 2, an inert gas is separated into electrons and ions by a glow discharge, and the plasma is formed, and the phosphor is emitted by ultraviolet rays generated at the moment when the electrons and ions are recombined. Visible light is generated when the layer 5 is excited.

In order to prevent the accelerated gas ions from colliding and deteriorating the dielectric or the phosphor, the discharge gas reduces the ion collision by using Ne gas having a large molecular weight as a main component. However, Ne gas has a disadvantage of lowering the color purity of the PDP by generating orange visible light by discharge. In addition, poor color purity of the phosphor, surface reflection of external light, and the like also have a problem of lowering the contrast ratio of the PDP.

In order to compensate for such a decrease in color purity characteristics and low contrast ratio characteristics, a method of forming a separate color filter or a black stripe on the PDP top plate has been proposed. However, when the black stripe is formed, another problem occurs that the aperture ratio is reduced by the area of the black stripe, and the luminous efficiency is lowered due to the decrease in the aperture ratio. In the case of introducing the color filter, the upper plate process is complicated by the manufacturing process of the color filter, and another problem occurs that the luminance is lowered by the color filter.

Meanwhile, techniques for forming an upper dielectric layer by mixing blue pigments are disclosed in Korean Patent Laid-Open Publication Nos. 2005-0019289, 2004-0068773, and Korean Patent Publication No. 524777, but the glass component forming the dielectric layer is PbO. There is a problem of environmental pollution because it contains a system glass, or there is a possibility that the coefficient of thermal expansion increases or the hardness withstand and the withstand voltage due to the internal pores may occur due to the mixing of the components of the glass component and the colorant, which needs improvement. It is true.

Accordingly, an object of the present invention is to provide a colored glass powder for display dielectric having a high dielectric constant and a low melting point in which a glass component containing Bi as a main component and a colorant component are mixed instead of Pb-based glass harmful to humans and the environment.

Moreover, another object of this invention is to provide the coloring glass powder for display dielectrics which adjusts the composition of a glass component suitably, suppresses a raise of a thermal expansion coefficient, and is excellent in hardness characteristic.

In addition, an object of the present invention is to control the composition and content of the Bi-based glass component and the color purity of the plasma display panel containing one or more colorants of CuO, Co ₃ O ₄ , NiO, MnO, MnO ₂ , Mn ₂ O ₃ To provide a colored glass powder and a manufacturing method thereof that can increase the contrast ratio, comprising the step of forming an upper dielectric layer using the colored glass powder, to provide a method of manufacturing a plasma display panel having a high brightness and high contrast ratio There is another purpose.

The present inventors have made an effort to achieve the above object, as a result, Bi ₂ O ₃ 30 to 60% by weight, BaO 10 to 20% by weight, ZnO 10 to 20% by weight, B ₂ O ₃ 10 to 20% by weight, SiO ₂ 1 To prepare a colored glass powder containing a parent glass component consisting of ~ 5% by weight and 1 to 5% by weight of Al ₂ O ₃ and 0.001 to 5 parts by weight of the coloring agent based on 100 parts by weight of the mother glass component, the colored glass When the powder is used for the upper dielectric of the display, it was confirmed that the plasma display panel having high brightness and high contrast ratio could be manufactured, and the present invention was completed.

Accordingly, the present invention relates to a colored glass powder for the upper dielectric of a display panel having a high brightness and high contrast ratio, and a method for manufacturing the same. The present invention relates to Bi ₂ O ₃ 30 to 60% by weight, BaO 10 to 20% by weight, ZnO 10 to 20% by weight, B ₂ O ₃ 10 to 20% by weight, SiO ₂ 1 to 5% by weight and Al ₂ O ₃ 1 to 5% by weight based on the mother glass component and 0.001 to 100 parts by weight of the mother glass component A colored glass powder containing 5 parts by weight of a colorant is provided, wherein the colorant is selected from CuO, Co ₃ O ₄ , NiO, MnO, MnO ₂ , Mn ₂ O _3, or mixtures thereof.

In addition, the present invention relates to a method for manufacturing a plasma display panel including forming a display panel upper dielectric layer using the colored glass powder, and a plasma display panel manufactured thereby.

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

The colored glass powder for the upper dielectric of the display panel of the present invention is a mother glass component using Bi-based glass, not Pb-based glass, and CuO, Co ₃ O ₄ , NiO, MnO, MnO ₂ , Mn ₂ O _3, or It contains a colorant selected from the mixture. Bi-based mother glass components include 30 to 60% by weight of Bi ₂ O ₃ , 10 to 20% by weight of BaO, 10 to 20% by weight of ZnO, 10 to 20% by weight of B ₂ O ₃ , SiO ₂ 1 to 5% by weight and Al ₂ O _{3 It} is characterized by consisting of 1 to 5% by weight. When using the mother glass component adjusted to the composition and content of the above has a low melting point glass transition temperature, the transmittance is less than 5% at 550 ~ 580 ℃, it is suitable because the yellowing phenomenon hardly occurs. In addition, the colored glass powder according to the present invention solves the problem of environmental pollution, which is a problem in the conventional Pb-based glass by using Bi-based glass as a mother glass component, and also 1 to 5% by weight of SiO ₂ in the mother glass component It also has the advantage of suppressing the increase in the coefficient of thermal expansion that can be caused by the mixing of the various parent glass components and the mixing of the colorant, and also has the advantage of preventing the decrease in hardness.

When the content of Bi ₂ O ₃ constituting the mother glass component is used in more than 60% by weight, the coefficient of thermal expansion is increased to increase the thermal stress to decrease the stability of the product, if less than 30% by weight Softening point is not appropriate.

BaO is suitable for 10 to 20% by weight because it lowers the softening point of glass but may affect its durability, and B ₂ O ₃ has a softening point of less than 10% by weight, making it difficult to process due to thermal characteristics. In the case of% or more, the coefficient of thermal expansion decreases and the softening point is increased, so it is preferable to use it in the range of 10 to 20% by weight.

ZnO is used in the range of 10 to 20% by weight, but if it exceeds 20% by weight, the coefficient of thermal expansion is not good and the glass is easily crystallized at 10% by weight or less.

Al ₂ O ₃ lowers the coefficient of thermal expansion and improves acid resistance, but when 5 wt% or more is used, the viscosity and softening point are not high, and when 1 wt% or less is used, the acid resistance is not good.

SiO ₂ increases the mechanical strength and lowers the coefficient of thermal expansion, 1 ~ 5% by weight is suitable. If it is less than 1% by weight, the above effect is insignificant, and if it exceeds 5% by weight, the softening point is increased, which is not preferable.

In addition, the colorant contained in the colored glass powder according to the present invention is selected from CuO, Co ₃ O ₄ , NiO, MnO, MnO ₂ , Mn ₂ O ₃ or a mixture thereof, and 0.001 to 100 parts by weight of the base glass component It is added within the range of 5 parts by weight. When the colorant content is less than 0.001 parts by weight, the effect of the colorant is insignificant, and when the content is more than 5 parts by weight, there is a problem in that an opaque glass having a transmittance of 50% or less is disadvantageous.

The present inventors have conducted a lot of research to improve the brightness and contrast ratio of the plasma display panel (PDP), and found that the blue-based dielectric may play a role of improving color purity and contrast ratio among the colored dielectrics using the colored glass powder. . The blue-based colored dielectric absorbs 585 nm of orange light generated by Ne when discharged, and has an optical characteristic of transmitting red light near 620 nm, green light of 525 nm, and blue light of 460 nm, and absorbs external light to improve color purity and contrast ratio of PDP. Can act as a color filter.

Colorants suitable for the present invention can be selected from CuO, Co ₃ O ₄ , NiO, MnO, MnO ₂ , Mn ₂ O ₃ or mixtures thereof, containing MnO, MnO ₂ , Mn ₂ O ₃ or mixtures thereof. In this case, the color characteristics of the green are dissipated to efficiently express the color temperature characteristics, and the bright room contrast ratio (BRCR) is more excellent. Therefore, the colorant contained in the colored glass powder according to the present invention is a manganese oxide selected from MnO, MnO ₂ , Mn ₂ O ₃ or a mixture thereof, More preferably, it is a mixture with at least one component selected from CuO, Co ₃ O ₄ or NiO, and manganese oxide selected from MnO, MnO ₂ , Mn ₂ O ₃ or a mixture thereof, and CuO, Co ₃ O ₄ And when using a colorant consisting of NiO was excellent in color temperature characteristics, the color purity and contrast ratio of PDP was the best.

In addition, the colorant contained in the colored glass powder according to the present invention is preferably adjusted to an appropriate content because the difference in the chromaticity depending on the content of each component, in the case of CuO content is 0.005 to 100 parts by weight of the mother glass component 1.0 parts by weight is preferable, and 0.01 to 1.5 parts by weight is preferable for Co ₃ O ₄ . In the case of NiO, 0.005 to 0.8 parts by weight is preferable, and in the case of manganese oxide selected from MnO, MnO ₂ , Mn ₂ O ₃ or a mixture thereof, 0.01 to 0.5 parts by weight is preferable.

The reason for limiting the content of each colorant constituent is that in the case of CuO, the light absorbing ability is too small in the visible light region at less than 0.005 parts by weight, and when it exceeds 1.0 parts by weight, the absorption of light is too large and the color is green. to be. In addition, when Co ₃ O ₄ is less than 0.01 part by weight, the light absorbing ability is too small in the visible light region, and when it exceeds 1.5 parts by weight, the absorption of light is severe and the light emitted from the phosphor is absorbed. If it is less than the portion, the light absorbing ability is too small in the visible light region, and if it exceeds 0.8 parts by weight, the absorption of the light beams is severe and the luminance may decrease. Also, manganese oxide selected from MnO, MnO ₂ , Mn ₂ O _3, or mixtures thereof is less than 0.01 parts by weight of light absorbing ability in the visible region is too small, when the color is more than 0.8 parts by weight the color is red Symptoms may occur.

It is preferable that it is 1-10 micrometers, and, as for the average particle diameter of the colored glass powder which concerns on this invention, it is more preferable that it is 2-5 micrometers. It is preferable that the largest particle diameter is 15 micrometers or less, ie, it belongs to the range of 1-15 micrometers, and it is more preferable that the largest particle diameter is 10 micrometers or less, ie, it belongs to the range of 1-10 micrometers. The average particle diameter of the glass powder is related to the transmittance and the adhesion between the electrode and the glass substrate. If the average particle diameter is larger than 10 µm, printing problems occur on the glass substrate. Lowers.

The colored glass powder for display panel upper dielectric according to the present invention is produced by a manufacturing method comprising the following steps.

30 to 60 wt% Bi ₂ O ₃ , 10 to 20 wt% BaO, 10 to 20 wt% ZnO, 10 to 20 wt% B ₂ O ₃ , 1 to 5 wt% SiO _{2 and} 1 to 5 wt% Al ₂ O ₃ A glass mixture manufacturing step of mixing a 0.001 to 5 parts by weight of a colorant based on 100% by weight of the mother glass component and the mother glass component in a dry ball mill;

A glass mixture melting step of melting the glass mixture at 800 to 1600 ° C; And

Powder manufacturing step of pulverizing after cooling the molten glass mixture.

It is preferable that the said melting temperature is 800-1600 degreeC, More preferably, it is 1000-1400 degreeC. In addition, the pulverizing step is more preferably made of coarsely pulverized and finely pulverized to advantageously control the size of the particles.

If the firing temperature is too low, uniform mixing of the raw materials is not performed, and thus it is difficult to exhibit the same characteristics. If the firing temperature is too high, some elements such as boron and bismuth are volatilized to secure reproducible characteristics. Difficult problems can arise.

The present invention provides a method for manufacturing a plasma display panel using the colored glass powder to produce an upper dielectric layer of the plasma display panel, the plasma display panel having a high brightness and high contrast ratio manufactured by the method To provide.

In the method of manufacturing a plasma display panel using the colored glass powder, the colored glass powder according to the present invention is mixed with an ethyl cellulose resin solution to prepare a paste solution, and the paste solution is applied to the upper glass substrate on which the discharge sustaining electrode is formed. And drying and firing the glass substrate to which the paste solution is applied.

Hereinafter, the present invention will be described in more detail with reference to examples, and the present invention is not limited to the following examples, but it is well known that various modifications can be made within the scope of the technical idea of the present invention. to be.

[Examples 1-3]

Manufacture of colored glass

After mixing the dielectric having the composition shown in Table 1 below for 2 hours in a dry ball-mill, the mixed powder was placed in a Pt-crucible, melted at 1000 to 1400 ° C. for 2 hours, cooled and pulverized. After the glass was prepared.

Preparation of colored glass powder

After preparing the glass, the glass powder was coarsely pulverized and finely pulverized to prepare a pulverized product having an average particle diameter of 2 μm (maximum particles: 8 μm) of the glass material having the composition shown in Table 1 above. Was reproducible by appropriate adjustment.

Preparation of Dielectric Using Colored Glass Powder

Ethyl cellulose resin and ethylene glycol propyl ether were mixed in a weight ratio of 3.5: 6.5 to prepare a resin solution, and then the glass powder prepared in Example was mixed in a weight ratio of 30:70 (glass powder: resin solution). A paste solution is prepared by mixing and dispersing in a mixer, which is applied onto a glass substrate by a blade coating method. Thereafter, the coated glass substrate was dried at 100 ° C. for 30 minutes, and then calcined at 570 ° C. for 6 minutes. The obtained thickness was 30-40 micrometers.

[Comparative Examples 1 and 2]

As shown in Table 1, a dielectric glass powder containing only a mother glass component and not containing a colorant and a dielectric using the same were prepared.

TABLE 1 Composition of colored glass powder

[Test Example]

The film thickness in each example was measured by SEM, and the dielectric materials prepared in Examples 1 to 3 were measured at 460 nm (blue), 550 nm (green), and 620 nm (red) using a spectrophotometer <Perkin-Elmer Lambda 35>. Spectral transmittances at each wavelength of) are measured and shown in Table 2, and a graph of spectral transmittances of the dielectric prepared in Example 1 is shown in FIG. 2 and Table 2 shows that the dielectric using the colored glass powder according to the present invention has a transmittance of 460 nm (blue) higher than that of 550 nm (green) and 620 nm (red). And improvement in contrast ratio can be expected.

In addition, as shown in Table 2, the samples of Examples 1 to 3 had a coefficient of thermal expansion of 8.7 to 8.9 × 10 ⁻⁷ / ° C., with little change in the coefficient of thermal expansion due to the use of a colorant, and a softening point of 490 to 500 ° C. in a range of suitable values. Since it was a transparent glass film which has the chromaticity of a blue system, all were suitable as a transparent dielectric formation material. On the other hand, the samples of Comparative Examples 1 and 2 exhibited the same characteristics as in Example, but since they were colorless and transparent glass films, there was no change in chromaticity and improvement in color temperature and contrast ratio were difficult to expect.

In addition, when the dielectric prepared in Examples 1 to 3 were cut and examined by SEM, the internal pore generation was excellent, and the hardness was also excellent. In particular, the dielectric materials of Examples 1 to 2 having a relatively high SiO ₂ content showed better results in terms of hardness and suppressing internal pore generation than Example 3. However, in terms of softening temperature, the result of Example 3 is excellent, so that the content of SiO ₂ is preferably controlled to 1 to 5% by weight based on the parent glass component.

[Table 2] Properties of Colored Glass Powders and Properties of Dielectrics Using the Same

Next, two board | substrates for PDP cut | disconnected to the predetermined magnitude | size were prepared. After forming a transparent electrode and a bus electrode on the upper glass substrate, the dielectric glass pastes of Examples and Comparative Examples were printed and baked to form a dielectric layer having a thickness of about 30 μm. On the other hand, an address electrode, a partition wall, and a phosphor were formed on the lower glass substrate, and the two glass substrates were thus sealed to a sealing glass, and then a mixed gas of Xe and Ne was sealed therein, followed by airtight packaging to produce an AC plasma display panel. It was. Among the AC type plasma display panels fabricated as described above, the panel using the dielectrics of Examples 1 to 3 showed higher luminance and higher contrast ratio than the panels formed of the dielectrics of Comparative Examples 1 and 2, It was confirmed that the formed panel did not have a halation phenomenon.

In addition, in Example 1, there is no difference in chromaticity compared to Example 3, which does not contain manganese oxide, but the bright room contrast ratio (BRCR) was better than that of Example 3.

Since the dielectric formed from the colored glass powder according to the present invention has a function of a color filter that emits blue, the dielectric absorbs orange light generated by the discharge of Ne out of the discharge gas injected into the PDP internal space to improve the color purity of the PDP. In addition, the PDP made of such a dielectric absorbs or blocks external light to decrease the reflectance of the external light, thereby increasing the contrast ratio, and increasing the luminance of blue to improve the luminous efficiency of the PDP.

Claims (8)

30 to 60 wt% Bi ₂ O ₃ , 10 to 20 wt% BaO, 10 to 20 wt% ZnO, 10 to 20 wt% B ₂ O ₃ , 1 to 5 wt% SiO _{2 and} 1 to 5 wt% Al ₂ O ₃ The colored glass powder for display upper dielectrics containing 0.001-5 weight part of coloring agents with respect to the mother glass component which consists of%, and 100 weight part of mother glass components. The method of claim 1, Wherein said colorant is selected from CuO, Co ₃ O ₄ , NiO, MnO, MnO ₂ , Mn ₂ O _3, or mixtures thereof. The method of claim 2, The colorant is manganese oxide selected from MnO, MnO ₂ , Mn ₂ O ₃ or a mixture thereof, A colored glass powder for display upper dielectric, which is a mixture with at least one component selected from CuO, Co ₃ O ₄ or NiO. The method of claim 3, wherein The colorant is 0.01 to 0.5 parts by weight of manganese oxide selected from MnO, MnO ₂ , Mn ₂ O ₃ or a mixture thereof with respect to 100 parts by weight of the mother glass component, 0.005 to 1.0 parts by weight CuO, 0.01 to 1.5 parts by weight of Co ₃ O ₄ and 0.005 to 0.8 parts by weight of NiO. The colored glass powder for display upper dielectric. The method of claim 1, The colored glass powder for display upper dielectric, characterized in that the average particle diameter of the colored glass powder is 1 to 10 ㎛. 30 to 60 wt% Bi ₂ O ₃ , 10 to 20 wt% BaO, 10 to 20 wt% ZnO, 10 to 20 wt% B ₂ O ₃ , 1 to 5 wt% SiO _{2 and} 1 to 5 wt% Al ₂ O ₃ A glass mixture manufacturing step of mixing a 0.001 to 5 parts by weight of a colorant based on 100% by weight of the mother glass component and the mother glass component in a dry ball mill; A glass mixture melting step of melting the glass mixture at 800 to 1600 ° C; And A powder manufacturing step of cooling and pulverizing the molten glass mixture; The manufacturing method of the colored glass powder of Claim 1 which consists of a 5th term | claim. A method of manufacturing a plasma display panel, wherein the upper dielectric layer of the plasma display panel is manufactured using the colored glass powder according to claim 1. A plasma display panel having high brightness and high contrast ratio manufactured according to the manufacturing method of claim 7.

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