KR100554248B1 - Glass ceramic composition and thick-film glass paste composition - Google Patents

Abstract

The plasma-display panel includes a front plate 10a provided to cover the bus electrode 12 with the dielectric film 15, a back plate 10b provided to cover the address electrode with the dielectric film 15, and a partition 16. And the dielectric film 15 and the partition 16 consist essentially of SiO ₂ -B ₂ O ₃ -ZnO-R ₂ O-based glass powder having a softening point of 520 to 580 ° C. Composition, and at least one inorganic oxide selected from the group of alumina, silica, olivine, zirconia, zircon, titania and heat resistant inorganic pigments.

Description

Glass ceramic composition and thick film glass paste composition {GLASS CERAMIC COMPOSITION AND THICK-FILM GLASS PASTE COMPOSITION}

1 is a partial cutaway perspective view showing the structure of a general AC type PDP, specifically, a front plate and a back plate.

2 is a partial cutaway perspective view showing the configuration of the VFD.

3 is a cross-sectional view of part of the configuration of the FED.

The present invention relates to glass-ceramics used to form dielectrics and partitions of plasma-display panels (hereinafter referred to as PDPs), fluorescent display tubes (hereinafter referred to as VFDs) and field-emitting displays (hereinafter referred to as FEDs). A thick film paste composition comprising the composition and the glass-ceramic composition.

PDPs are currently in the spotlight as large flat-panel displays that make large television sets. VFDs are used as display devices for text and symbols, and in particular as display devices in automobiles, audio devices and measurement devices such as digital multimeters. FED is attracting attention as a display device to replace the conventional CRT display.

1 is a partial cutaway perspective view showing the structure of a typical AC PDP. For illustration, one corner was cut and partially cut to separate the top and bottom from the center.

The PDP has a pair of glass plates 10a and 10b which are in contact with each other through a small gap, which is surrounded by a sealing material to form a discharge space, which is excited by ultraviolet rays and generated by the discharge to emit an image by a phosphor that emits light. Is projected. In the PDP, the glass plate 10a on which an image is displayed is called a front plate, and the glass plate 10b on the opposite side is called a back plate.

A stripe-shaped partition 16 is formed on the back plate 10b, and a single electrode (hereinafter referred to as address electrode) 13 is formed between each of these partitions 16 so that the address electrode is parallel to the partition 16. It is formed on the bottom surface of the groove, and the dielectric film 15 is formed to cover the surface of the address electrode 13. In addition, the phosphor 17 which is excited by ultraviolet rays is coated on the wall surface of this partition 16.

The stripe transparent electrode 11 is formed on the front plate 10a by ITO or the like, and the bus electrode 12 made of silver or the like is formed on the upper surface of the transparent electrode. A dielectric film 15 such as glass transparent to visible light is formed to cover the bus electrode 12. In addition, the MgO film 14 is formed to cover the dielectric film 15 by vapor deposition.

In the method of forming the PDP having the above-described configuration, conventional thick film technology is used as an electrode made of silver and a method of forming a dielectric and a partition.

2 is a partial cutaway perspective view showing the configuration of the VFD. For illustration purposes, some cuts were made.

A typical VFD has a vacuum container defined by the surface glass 21 and the glass substrate 22, and electrons emitted from the filament 26 inside the vacuum container impinge on the fragment electrode 24 by hitting the segment electrode 24. Controlled by the grating electrode 23 to excite the phosphors on 24 to cause them to emit light, so that a text or symbol is displayed. In order for the engraving electrode 24 to be a display, a wire 27 for transmitting a signal from the terminal 28 to the engraving electrode 24, and an insulating layer for insulating between the wire 27 and the engraving electrode 24. 25 is formed on the glass substrate 22.

In the method of forming the VFD having the above-described configuration, a conventional thick film technique is widely used as a method of forming the electrode and the insulating layer. The wire 27 to the piece electrode 24 is often made of thick film silver paste, and the insulating layer 25 covering the wire 27 is a dielectric material made of thick film glass paste. The piece electrode 24 is made of a thick film glass paste having graphite as a main component. In order to maintain the electrical conduction of the piece electrode 24 and the wire 27, the insulating layer 25 is printed so that a through hole can be formed through the insulating layer 25.

3 is a cross-sectional view of the configuration of the FED. 3 shows only a part of the interior continuing in the left and right directions.

In the FED, the glass plates 31a and 31b are provided facing each other to define a vacuum container, and together with the two glass plates 31a and 31b, the electron-emitting element 36 emitting electrons is emitted electrons. Is formed on the glass substrate 31b to strike the phosphor 33 on the glass substrate 31a to excite the phosphor 33 to emit light. The wire 38 that signals to the electron-emitting element 36, the dielectric material covering the wire 38, and the gate electrode 34 formed over the spacer 35 are formed with the electron-emitting element 36. It is formed on the glass substrate 31b. The electron-emitting element 36 is located in the absence of the spacer 36.

Thin film technology is often used in the method of forming the components of the FED, and the dielectric material is formed using the thick film technology.

In PDP, VFD and FED, high strain glass (eg PD-200 manufactured by Asahi Glass Co.) or soda lime glass is used as the glass substrate, and in terms of the dimensional stability of the device, The sintering temperature for the thick film should be 600 ° C. or lower, mill preferably 580 ° C. or lower.

In addition, for PDP, VFD, and FED, there is a process of sealing a manufactured and processed glass substrate to form a vacuum container. In this process, the glass substrate is heated to 450 ° C. to melt the glass-ceramic material used for sealing and perform sealing. However, in view of maintaining the dimensional stability of the device, deformation due to softening of partitions and dielectric materials is not tolerated. Therefore, by setting the glass transition temperature of the glass component of the thick film to 450 ° C. or higher, and preferably 470 ° C. or higher, deformation due to softening of partitions and / or dielectric materials can be prevented. However, when the sintering temperature of the thick film containing the glass component having the above glass transition temperature is not higher than 500 ° C, or preferably higher than 520 ° C, fine and precise sintered film cannot be obtained.

Therefore, the sintering temperature of the thick film is 500 ° C to 600 ° C, and preferably 520 ° C to 580 ° C, and when the transition point of the glass component in the thick film is not within this temperature range, a fine and precise sintered film suitable for partitions and dielectric materials is produced. Can not get

Typically, the thick film contained lead, bismuth, or barium as dangerous substances to maintain softening temperatures within this temperature range. For example, the glass-ceramic composition disclosed in Japanese Patent Application Laid-open No. Hei 8-119725, the partition-forming material for plasma display panel disclosed in Japanese Patent Laid-Open No. Hei 11-60273, or Japanese Patent Laid-Open No. 2000-001334 The glass-paste composition disclosed in the head contains lead. In addition, bismuth is contained in the insulating glass composition disclosed in Japanese Patent Laid-Open No. Hei 9-268026, and the plasma display disclosed in Japanese Patent Laid-Open No. Hei 9-283035.

Dangerous substances contained in the glass composition are released into the environment as waste materials not only at the time of disposal of the display device including the glass composition, but also at the time of manufacturing the display device, causing environmental problems such as contamination of soil, groundwater, river, etc. .

In addition, glass substrates made of glass-ceramic materials are widely used as insulating materials, but they also function as dielectric materials that act as capacitors by being placed between electrodes.

In PDPs, there may be places where glass-ceramic materials are used in dielectric materials to actively accumulate charge, but there are only a few areas of this kind, and the charge accumulated in most other insulating materials contributes to no light emission. Without it, power is wasted. Thus, in terms of power consumption of the device, it is desirable that the charging of the insulating material be kept to a minimum in areas not intended to carry charge. The same is true for the VFD and FED materials.

In addition, as the dielectric constant of the insulating material increases, the amount of charge accumulation in the insulating material increases. As mentioned above, glass-ceramic materials have been known as dielectric materials, in particular glass-ceramic materials containing lead, bismuth or barium have a high dielectric constant due to the lead, bismuth or barium contained therein, and lead, bismuth Or the dielectric constant of conventional glass-ceramic materials containing barium easily exceeds the value of 10. Typically, this high dielectric constant could not be lowered, and as a result, there was a problem that the power consumption of the display device was increased.

In order to solve this problem, P ₂ O ₅ -SiO ₂ -ZnO type glass as a glass-ceramic composition containing no lead and bismuth has been disclosed in Japanese Patent Application Laid-Open Nos. 8-301631 and 2000-12857. However, there is a problem that the glass has low water resistance and chemical resistance and is not suitable for practical application.

In addition, although SiO ₂ -B ₂ O ₃ -ZnO type glass is disclosed in Japanese Patent Laid-Open No. 9-283035 as a glass containing no lead and bismuth and having a reduced dielectric constant, the water resistance within the disclosed composition range is extremely good. There is a problem that there is an unranged portion, which is not suitable for application.

SiO ₂ -B ₂ O ₃ -ZnO-type glass is also disclosed in Japanese Patent Laid-Open No. 2000-226232, but too much ZnO is contained, making it difficult to obtain uniform glass. If a uniform glass cannot be obtained, a uniform composition material for the display device cannot be formed, and there is a problem that the display device is malfunctioning.

In addition, Japanese Patent Laid-Open No. 2000-313635 that it is a poor water resistance in the polar SiO ₂ -B ₂ O ₃ -ZnO type glass composition range of the range disclosed in part to the presence, the problem is not suitable for practical application.

In addition, while the ₂ -B ₂ O ₃ -ZnO type SiO glass also is disclosed in Japanese Patent Laid-Open No. 2001-163635, because the range is not specified it is is difficult to obtain the desired glass.

Although SiO ₂ -B ₂ O ₃ -BaO type glass is disclosed in Japanese Patent Laid-Open No. 2000-327367 as a glass containing no lead, bismuth, and no alkali metal oxide, the softening point of the glass is so high that it is used for PDP. There is a problem that is not suitable for.

The amount of inorganic oxide suitable for the partition material is disclosed in Japanese Patent Laid-Open No. 2000-001334, but the glass used therewith contains lead, and the most suitable combination with glass free of lead and bismuth is not disclosed. .

Japanese Patent Laid-Open No. 2002-1902255 discloses inorganic oxides suitable for glass free of lead and bismuth, and a mixed amount of such inorganic oxides, wherein α-quartz and cristobalite are essential components of the inorganic oxide. Cristobalite has a coefficient of thermal expansion that is one digit higher than that of glass substrates. It is also known that α-quartz and cristobalite undergo a phase change between them, and the phase change is accompanied by a sudden change in the coefficient of thermal expansion. Thus, the coefficient of thermal expansion of partitions and / or dielectric materials may not follow the coefficient of thermal expansion of the substrate, resulting in defects such as cracks in the display device, which is not suitable.

It is an object of the present invention to provide a fine sintered film on the upper surface of soda lime glass and to provide a glass-ceramic composition containing no dangerous lead and bismuth, and a thick film glass paste composition containing no dangerous substances.

In one embodiment of the invention, the glass-ceramic composition comprises from 5 to 30% by weight of inorganic oxide powder and the remaining glass powder, which inorganic oxide powder comprises alumina, silica, forsterite, zirconia, zircon , Titania, and at least one material selected from heat resistant inorganic pigments, and the glass powder is essentially 3 to 30% by weight of SiO ₂ , 20 to 45% by weight of B ₂ O ₃ , 20 to 45% by weight of oxide conversion. ZnO, and from 5 to 20% by weight of alkali metal oxide. Alkali metal oxides are one or more materials selected from the group of K ₂ O, Na ₂ O and Li ₂ O.

In addition, the glass powder preferably contains 10 wt% or less of ZrO ₂ by oxide conversion.

Further, the glass powder preferably contains Al ₂ O ₃ of not more than 10 wt% by oxide conversion.

Using the glass-ceramic composition of the present invention, dielectric materials or partitions or both for plasma displays, dielectric materials or partitions or both for fluorescent display tubes, or dielectric materials or partitions or both for field-emitting displays Form all branches.

The thick film glass paste composition of the present invention is obtained by mixing into a glass-ceramic composition in a vehicle.

Partitions and dielectric materials for display devices require extreme precision, and if there are a large number of voids in the partition, problems arise in air tightness and mechanical strength of the display device. Through an in-depth study of the glass-ceramic materials in which they are formed, the inventors have found that they can achieve fine and precise partitions and dielectric materials, and have come to the present invention.

In glass powder compositions, SiO ₂ is an essential component and a network former of the glass-ceramic composition. If the amount of SiO ₂ is 3% by weight or less, the water-resistance and chemical resistance of the glass-ceramic composition are not good, and if it exceeds 30% by weight, the softening point becomes high, so that a desired softening point cannot be obtained.

In glass powder compositions, the essential component B ₂ O ₃ has the effect of lowering the softening point, increasing the fluidity and stabilizing the glass-ceramic composition. If the amount of B ₂ O ₃ is less than 20% by weight, the softening point is increased to obtain the desired softening point. If the amount is more than 45% by weight, the softening point is lowered to obtain the desired softening point. Tolerance worsens.

In the glass powder composition, ZnO, an essential component, has the effect of lowering the softening point and appropriately adjusting the coefficient of thermal expansion. If the amount of ZnO is 20% by weight or less, the desired softening point cannot be obtained, and when the amount exceeds 45% by weight, it is difficult to obtain uniform glass.

In glass powder compositions, alkali metal oxides, which are an essential component, have the effect of lowering the softening point and increasing the fluidity as well as increasing the coefficient of thermal expansion. If the amount of alkali metal oxide is 5% by weight or less, the softening point is increased to obtain a desired softening point. If the amount is more than 20% by weight, the coefficient of thermal expansion is increased, which is used to make the glass-ceramic composition on a substrate such as soda-lime glass. Not only are they unsuitable, but the glass transition point and softening point are lowered to obtain the desired ceramic composition.

In glass powder compositions, ZrO ₂ is an essential component, but it has the effect of increasing water resistance and chemical resistance. However, if the amount of ZrO ₂ exceeds 10% by weight, this increases the softening point and thus cannot obtain the desired softening point.

In the glass powder composition, alkaline earth metal oxides (CaO, SrO) have the effect of lowering the softening point, increasing the fluidity and appropriately adjusting the coefficient of thermal expansion. If the amount of the alkaline earth metal oxide is 3% by weight or less, the above-described effect is not obtained, and thus the desired softening point cannot be obtained. If the amount exceeds 40% by weight, the coefficient of thermal expansion increases. Among alkaline earth metal oxides, BaO has the effect of increasing the dielectric constant, but it is preferably not included in the composition because it is a dangerous substance.

In glass-powder compositions, Al ₂ O ₃ is not an essential component, but has the effect of improving water resistance and chemical resistance. However, when the amount of Al ₂ O ₃ exceeds 10% by weight, the softening point becomes high and a desired softening point cannot be obtained.

The particle size of the glass powder by D ₅₀ is preferably 10 μm or less, and more preferably 5 μm or less. If the particle size by D ₅₀ is larger than 10 μm, fine partitions and / or dielectrics will not be obtained. In order to obtain glass particles having a desired particle size, known crushing methods such as ball mills or jet mills can be used. Known particle-size analyzers (eg, Microtrack®) can be used to determine the particle size of the glass powder. D ₅₀ is specified as representing the particle size where the accumulated particle-size frequency is 50% in the relationship between the accumulated particle size frequency distribution and the particle size, which is an intermediate particle size value.

The inorganic oxide powder is one or more materials selected from alumina, silica, goblet, zirconia, zircon, titania, and heat resistant inorganic pigments, and the addition of inorganic oxides improves the mechanical strength of the glass-ceramic composition.

In the sintering process, when sintering is performed at a temperature higher than the temperature for forming a fine and precise sintered film, excessive sintering occurs and bubbles (voids) easily occur. The generation of voids is thought to be caused by a decrease in viscosity due to melting of the glass powder. The added inorganic oxide tends to prevent sintering of the glass powder in the sintering process, which makes it possible to suppress the formation of voids such as bubbles, and even at this time, the sintering of the glass powder becomes excessive. However, the temperature range that can be sintered without generating voids is narrow.

In particular, large amounts of B ₂ O ₃ or alkali metal oxides that lower the viscosity of the glass-ceramic glass compositions above glass compositions containing lead or bismuth may be contained in compositions such as the compositions in the glass powders of the glass-ceramic compositions of the invention. In this case, the temperature range in which sintering is possible without the occurrence of voids is much narrower.

In addition, in the case of a firing furnace for a large display panel such as a PDP or FED, it is difficult to make the temperature inside the firing furnace completely uniform. Thus, when using such a kiln to sinter the material to the optimum region within the very narrow sintering temperature, which is only the dropping point of optimum sintering, there will be excessive sintering and insufficient sintering, and consequently excessive sintering in the sintering film. There will be a large number of voids due to sintering, and there will be a large number of voids due to insufficient sintering, and generally fine and precise sintered films will not be obtained.

As described above, according to the present invention, it is possible to provide a partition material and a dielectric material which can obtain a wide temperature range capable of fine and precise sintering and no voiding, so that it is possible to improve the productivity of the display device. Suitable. In addition, by suppressing the occurrence of voids and improving mechanical strength, the present invention has the effect of improving the withstand voltage characteristic of the dielectric.

In the glass-ceramic composition, when the amount of the inorganic oxide powder is 5% by weight or less, the above effects cannot be expected. In addition, when the amount exceeds 30% by weight, sintering of the glass is prevented too much by the inorganic oxide, and a large number of voids are generated, and fine and precise partitions or dielectrics cannot be obtained.

Silica and gotoolives are known to have low dielectric constants, and by adding such materials it is possible to improve characteristics and lower dielectric constants.

Black pigments such as Fe-Co-Cr compounds can be used as heat resistant pigments.

The particle size of the inorganic oxide powder is preferably 10 μm or less and more preferably 5 μm or less by D ₅₀ . If the particle size of the inorganic oxide powder is larger than 10 mu m, fine and precise partitions and dielectrics cannot be obtained.

The coefficient of thermal expansion of the glass-ceramic composition is set according to the composition ratio of the glass powder and the inorganic oxide powder. The coefficient of thermal expansion of the glass-ceramic composition is preferably from 50 × 10 ⁻⁷ to 87 × 10 ⁻⁷ . The coefficient of thermal expansion of substrates, such as soda-lime glass, is 83 x 10 ^-7 to 87 x 10 ^-7 and if the value of the glass-ceramic composition is not near this range, warping of the display device may occur during sintering. will be. In addition, when the value of the glass-ceramic composition is less than or equal to this range, compression is applied to the substrate, which makes it difficult to break.

The glass powder may be combined with the inorganic oxide powder to adjust the coefficient of thermal expansion of the glass-ceramic composition. The coefficient of thermal expansion of silica is 55 × 10 ⁻⁷ , which has the effect of lowering the coefficient of thermal expansion of the glass-ceramic composition, while the coefficient of thermal expansion of goblet is 95 × 10 ⁻⁷ , which is the thermal expansion of the glass-ceramic composition. Has the effect of raising the coefficient.

Quartz glass powder can be used as silica. In silica, α-quartz is known to undergo a phase transition, and when it undergoes a phase transition with cristobalite or the like, the coefficient of thermal expansion changes rapidly, and a change in the coefficient of thermal expansion may cause a crack in the partition or the dielectric. This does not occur for quartz glass powders. Even if quartz glass powder is used, it has the same effect as other inorganic oxide powders of the present invention, and the effect of the quartz glass powder on the coefficient of thermal expansion and the dielectric constant is not different from that of silica (α-quartz).

The inorganic oxide powder is not limited to select only one type, and a plurality of types can be combined. If it is desired to make the color of the partition and dielectric white, TiO ₂ can be added. In addition, addition of TiO ₂ is effective when an increase in dielectric constant is desired.

If it is desired to keep the dielectric constant below 10 and to make the color of the partition and dielectric white, the amount of TiO ₂ added to the glass-ceramic composition should be 3% by weight or less, and an inorganic oxide such as silica or gobletite Can be used with powders. In this case, the object of the present invention is achieved by maintaining the total amount of inorganic oxide powder in the glass-ceramic composition at 30% by weight or less.

The thick film glass paste composition of the present invention contains a vehicle comprising a resin, a solvent, and other known additives added to the glass-ceramic composition of the present invention.

At least one type of resin selected from the group of ethyl cellulose, acrylic, and polyvinyl butyral, and terpinol, dihydroterpinol, butyl carbitol acetate, butyl carbitol, 2,2,4-trimethyl-1,3- At least one type of solvent selected from the group of pentane diol mono butyrate is an essential component of the vehicle.

Paste printing (coating) of PDP, VFD or FED can be carried out by known methods such as screen printing, dye coaters, or roll coaters.

The viscosity of the thick film glass paste should be suitable for such printing (coating) apparatus and can be controlled by the amount of resin and solvent.

Known additives for thick film glass pastes, such as antifoams or dispersants, may be added to the thick film glass paste composition.

Known methods, such as using a roll mill or ball mill, can be used for the preparation of thick film glass paste compositions.

Example

Examples and comparative examples of the present invention are described below, but the present invention is not limited to these examples.

Examples 1 to 10, Comparative Examples 1 to 4

Glass composition:

Glass powders A to F having the compositions shown in Table 1 were melted at 1300 ° C., rapidly cooled and ground using a ball mill. The particle size of the glass powder obtained using the Microtrack® model 9320-X100 was measured, and the glass transition point and softening point were measured using TG-DTA (Seiko Electronics, model TG / DTA320).

The glass transition point, softening point, coefficient of thermal expansion and particle size of the obtained glass powder are shown in Table 1.

Preparation of Glass Paste

10% by weight of ethyl cellulose (average molar weight 80,000) as resin, 50% by weight of terpinol as solvent and 30% by weight of butyl carbitol acetate and 10% by weight of dioctyl adipate as plasticizer and heated at 60 ° C to obtain a vehicle. .

Further, the glass powder and the inorganic oxide powder are mixed with the compositions shown in Tables 2a and 2b, and the vehicle is added to the obtained glass-ceramic composition in a weight ratio of 100 to 40, and then mixed in a roll mill to obtain a thick film glass paste composition. .

Evaluation of the precision of the sintered film of the partition

The thick film glass paste composition is coated onto soda lime glass with a gap-700 μm applicator and then dried in a belt dryer at 120 ° C. for 30 minutes to obtain a 150 μm thick dry film. This dry film is masked with a 200 μm wide photoresist and ground to a sandblaster (injector manufactured by Fuji Manufacturing Co.) using CaCO ₃ as the abrasive material. After sintering for 30 minutes at the maximum temperatures of 520 ° C., 540 ° C., 560 ° C. and 580 ° C. in the belt-type kiln, the cross section was observed by SEM to evaluate the precision of the sintered film. The measurement results are shown in Tables 2a and 2b.

Evaluation of dielectric constant

The thick film glass paste composition was printed on the soda-lime glass substrate previously printed with a silver electrode and then dried, and the process was repeated four times to obtain a 150 탆 thick dry film. This dry film was sintered for 30 minutes at a maximum temperature of 560 ° C. in a belt firing furnace, and then further sintered at 500 ° C. for 5 minutes in a belt firing furnace. The sample obtained consisted of a silver electrode and a glass-paste sintered film provided between the silver electrodes. The dielectric constant of the sample was measured and calculated using a Q metric (Yokogawa-Hewlett Packard Co., Model 4278A). The measurement results are shown in Tables 2a and 2b.

Measurement of internal pressure

The thick film glass paste composition is printed on a soda lime glass substrate previously printed with a silver electrode and then dried using a screen printing, followed by sintering at a maximum temperature of 560 ° C. for 30 minutes in a belt-type kiln to sinter 20 μm of glass paste. A membrane was obtained. The silver paste was then further baked at 500 ° C. for 5 minutes in a belt kiln. The resulting sample consisted of a silver electrode and a glass-paste sintered film provided between the silver electrodes. A constant voltage power supply was used to investigate the pressure at which dielectric breakdown occurred while applying an electrical load to the sample and raising the voltage. The measurement results are shown in Tables 2a and 2b.

Measurement of thermal expansion coefficient

Only the inorganic components of the thick film glass paste composition are mixed, pressed into a die to form a green compact, and then the green compact is sintered at 570 ° C. for 30 minutes in a box firing furnace, having a diameter of 4 mm and a length of 10 mm. I got the cylinder. The thermal expansion coefficient of this cylinder was measured by TMA (Seiko Electronics, Co., model TMA320) (temperature: 50 degreeC-350 degreeC, temperature rising rate: 10 degreeC / min).

The measurement results are shown in Tables 2a and 2b.

[Note on table]: ◎ = fine and fine sintered body and excellent partition

              × = excessive sintering and numerous voids (voids)

              ×× = broken partition

       ▲ = not sintered, and maintains the shape of many voids, partitions

In Examples 1 to 10, the softening point for the glass powders A to D existed in the temperature range of 540 ° C to 580 ° C, and through firing, excellent partitions having fine and precise sintered bodies were obtained, and the dielectric constant of the obtained sintered film was obtained. Is less than 10, and the internal pressure can be maintained at 1000V.

On the other hand, in the case of Comparative Example 1, the amount of the inorganic oxide powder contained was so small that a suitable sintering temperature range was not confirmed and the internal pressure was also very poor. In the case of Comparative Example 2, the amount of the inorganic oxide powder contained was so large that fine and precise sintering was impossible. In Comparative Examples 3 and 4, the compositions of glass powders E and F were not suitable, and a fine and precise sintered film could not be obtained.

The glass-ceramic composition of the present invention makes it possible to obtain a fine and precise sintered film on a soda-lime glass substrate even when no dangerous substances such as lead or bismuth are included in the glass component.

Claims (7)

The inorganic oxide powder is at least one material selected from alumina, silica, forsterite, zirconia, zircon, titania, and heat resistant inorganic pigments, and the glass powder is essentially 3 to 30% by weight of SiO ₂ , by oxide conversion. 20 to 45 wt% B ₂ O ₃ , 20 to 45 wt% ZnO, and 5 to 20 wt% alkali metal oxide, the alkali metal oxide being K ₂ O, Na ₂ O and Li ₂ Glass-ceramic composition consisting essentially of 5 to 30% by weight of inorganic oxide powder and the remaining glass powder, characterized in that it is at least one material selected from the group of O. The method of claim 1, Glass-ceramic composition, characterized in that the glass powder contains up to 10% by weight of ZrO ₂ by oxide conversion. The method according to claim 1 or 2, The glass-ceramic composition, characterized in that the glass powder contains up to 10% by weight of Al ₂ O ₃ by oxide conversion. The method according to claim 1 or 2, And the composition is for forming at least one of a dielectric material and a partition for the plasma display. The method according to claim 1 or 2, And the composition is for forming at least one of a dielectric material and a partition for a fluorescent display tube. The method according to claim 1 or 2, And the composition is for forming at least one of a dielectric material and a partition for a field-emitting display. A thick film glass paste composition comprising a glass-ceramic composition and a vehicle mixed with the glass-ceramic composition.

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