JP4106766B2 - Display substrate manufacturing method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for manufacturing a display substrate in which partition walls are formed on a dielectric layer. The display substrate of the present invention can be used in plasma display panels, plasma addressed liquid crystal displays, image display devices using electron-emitting devices, and the like.
[0002]
[Prior art]
As an image forming apparatus replacing a large and heavy cathode ray tube, a light and thin so-called flat display attracts attention. As a flat display, a liquid crystal display has been actively developed, but this still has problems such as a dark image and a narrow viewing angle. As an alternative to this liquid crystal display, a plasma display panel, which is a self-luminous discharge type display, and an image forming apparatus using an electron-emitting device can provide a brighter image and a wider viewing angle than a liquid crystal display. The need is increasing because it can meet the demands for screen and high definition.
[0003]
The electron-emitting device includes a thermal electron-emitting device and a cold cathode electron-emitting device. Cold cathode electron-emitting devices include field emission type (FE type), metal / insulating layer / metal type (MIM type), and surface conduction type. An image forming apparatus using such a cold cathode electron source displays an image by irradiating a phosphor with an electron beam emitted from each type of electron-emitting device to generate fluorescence. In this apparatus, a front glass substrate (also referred to as a face plate) and a back glass substrate (also referred to as an element substrate) are provided with respective functions, and the back glass substrate includes a plurality of electron-emitting devices and elements of those elements. Matrix wiring for connecting the electrodes is provided. Since these wirings intersect at the electrode portion of the electron-emitting device, an insulating layer (dielectric layer) for insulation is provided. Further, a spacer (also referred to as a barrier or a partition wall) is formed between the two substrates as an atmospheric pressure resistant support member.
[0004]
The plasma display panel generates plasma discharge between the anode and cathode electrodes facing each other in the discharge space provided between the front glass substrate and the rear glass substrate having the respective functions, and is enclosed in the discharge space. The display is performed by irradiating the phosphor in the discharge space with the ultraviolet rays generated from the flowing gas. Electrodes are formed on the front glass substrate and the back glass substrate, respectively, and an insulating layer (dielectric layer) is formed so as to cover them. In addition, the rear glass substrate is provided with barrier ribs (also referred to as barriers or ribs) in order to suppress the spread of discharge to a certain area and perform display in a prescribed cell, while ensuring a uniform discharge space. ing.
[0005]
The partition wall of the plasma display panel is usually printed and dried with an insulating paste containing glass powder on the back glass substrate by a screen printing method, and this printing and drying process is repeated 10 to 15 times to a predetermined height, followed by firing. Is formed. However, in the normal screen printing method, particularly when the panel size is increased, it is difficult to align the discharge electrode formed on the substrate in advance with the printing place of the insulating glass paste, and it is difficult to obtain the position accuracy. There is.
[0006]
With the increase in area and resolution of plasma display panels, it is becoming increasingly technically difficult and costly to produce high aspect ratio, high-definition barriers using such screen printing methods. ing.
[0007]
As methods for improving these problems, JP-A-1-296534, JP-A-2-165538, JP-A-5-342992, JP-A-6-295676, and JP-A-8-50811 A method has been proposed in which the partition walls are formed by a photolithography technique using a photosensitive paste.
[0008]
A data electrode for writing display data is formed on the rear glass substrate using a silver paste, and a dielectric layer is provided thereon to cover the electrode, and a partition is formed thereon. A phosphor layer is formed by applying, drying, and firing phosphors that emit red, green, and blue light on the side surfaces of the partition walls and the bottom surface surrounded by the partition walls.
[0009]
The plasma display panel is formed by sealing the rear glass substrate and the front glass substrate having a plurality of transparent electrodes formed in a strip shape so that matrix driving is possible, and then mixing He-Xe, Ne-Xe, or the like. It is manufactured by enclosing gas and mounting a drive circuit. When a pulsed alternating voltage is applied between adjacent transparent electrodes, a gas discharge occurs and plasma is formed. The ultraviolet rays generated here excite the phosphor to emit visible light, and display light is emitted through the front glass substrate.
[0010]
Thus, although a plasma display panel is produced, the glass substrate may be warped or cracked during processing, and there is a problem that the yield decreases. In addition, it was necessary to improve the yield reduction due to peeling or the like occurring between the dielectric layer and the partition wall. In particular, when the partition walls were formed by the photosensitive glass paste method, peeling due to the difference in polymerization and hardening between the upper and lower partition walls was likely to occur.
[0011]
[Problems to be solved by the invention]
The present invention eliminates the warping and cracking of a substrate that occurs when a dielectric layer and a partition are formed on a glass substrate on which an electrode is formed, and further eliminates peeling between the dielectric layer and the partition. An object is to provide a manufacturing method.
[0012]
[Means for Solving the Problems]
An object of the present invention is to form a dielectric paste coating film by applying a dielectric paste made of an inorganic powder and an organic component on a glass substrate on which an electrode is formed, and a partition made of an inorganic powder and an organic component thereon A method of manufacturing a display substrate in which a partition pattern is formed by a paste and then the dielectric paste coating film and the partition pattern are fired simultaneously, wherein the firing shrinkage ratio t1 of the dielectric paste coating film and the partition pattern firing The shrinkage rate t2 is achieved by a method for manufacturing a display substrate, which satisfies the following formula.
[0013]
t1 ≦ 0.4
t2 ≦ 0.4
| T1-t2 | ≦ 0.03
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The display substrate of the present invention has a configuration in which an electrode is formed on a glass substrate, a dielectric layer is formed thereon, and a partition is further formed thereon. As the glass substrate, high strain point glass such as soda glass or PD-200 manufactured by Asahi Glass Co., Ltd. is usually used.
[0015]
In the present invention, a dielectric paste comprising an inorganic powder and an organic component is applied on a glass substrate on which an electrode is formed to form a dielectric paste coating film, and a partition paste comprising an inorganic powder and an organic component is formed thereon. After the barrier rib pattern is formed, the dielectric paste coating film and the barrier rib pattern are fired simultaneously.
[0016]
The paste is composed of an inorganic powder and an organic component, and is prepared so as to have an appropriate viscosity using a solvent or the like in order to obtain coating processing characteristics. After coating to form a coating film or forming a pattern, the solvent is removed by drying. In the firing process, organic components are thermally decomposed or oxidized to be removed from the coating film or pattern, and the low softening point glass powder components constituting the inorganic powder are melted and sintered to form an integrated inorganic layer. Will do. That is, the organic component is removed from the coating film or pattern, and the glass component having a low softening point is melted, resulting in a decrease in volume. These firing shrinkages appear mainly as changes in thickness in the case of a coating film, and appear as changes in height and line width in the case of a stripe pattern.
[0017]
The firing shrinkage t in the present invention represents the ratio of the thickness before and after the firing treatment in the case of a coating film, and the ratio of the line width before and after the firing treatment in the case of a striped pattern. is there. That is, the numerical value before the firing treatment is L₀And when the numerical value after firing is L, t = (L₀-L) / L₀Is defined by
[0018]
The present invention pays attention to the difference between the firing shrinkage rate t1 as a change in the thickness of the dielectric paste coating film and the firing shrinkage rate t2 as a change in the line width of the stripe pattern of the partition wall pattern. 03 (3%) or less is preferable, and 0.015 (1.5%) or less is more preferable.
[0019]
By controlling the firing shrinkage rate in this way, it is possible to obtain a method for manufacturing a display substrate in which defects such as peeling and cracking between the formed dielectric layer and the partition are eliminated. When there is a difference greater than 0.03 between the two, separation / cracking of the partition walls cannot be avoided.
[0020]
The details of the mechanism are not clear, but are estimated as follows. That is, at the time of co-firing, most of the organic components in the dielectric paste coating film and the barrier rib pattern are debindered (a phenomenon in which organic components are removed by decomposition) in a temperature range of about 300 to 500 ° C. Next, when the heating temperature is set to 500 ° C. or higher, rearrangement and fluidization of the glass powder occurs, and densification is promoted simultaneously with softening of the glass. At this time, although different depending on the case, at a firing temperature of 550 to 580 ° C., densification is almost completed and firing shrinkage of 20 to 40% occurs. In simultaneous firing, each of the dielectric layer and the barrier ribs shrinks, but if the difference in shrinkage exceeds 0.03 (3%), the shear stress between the dielectric layer and the barrier ribs increases and peeling occurs.・ It is considered to cause cracks. In addition, after firing the dielectric layer in advance without co-firing, a barrier rib paste is applied on the dielectric layer to form a barrier rib pattern. Becomes larger and causes peeling and cracking.
[0021]
If the firing shrinkage rate of the dielectric paste coating film and the barrier rib pattern exceeds 40%, the glass substrate may be warped or cracked, so both t1 and t2 are set to 0.4 or less.
[0022]
The dielectric layer has an effect of covering and protecting and insulating the electrode formed on the glass substrate, and also has an effect of improving the formability of the partition wall formed thereon. The thickness of the dielectric layer is preferably 4 to 18 μm, more preferably 8 to 15 μm after firing, in order to form a uniform and dense dielectric layer. When the thickness exceeds 18 μm, it is difficult to remove the binder during firing, cracks are likely to occur, and the stress applied to the glass substrate is so great that the substrate may be warped. If the thickness is less than 4 μm, it is difficult to form a flat, uniform and dense dielectric layer, and the dielectric layer may be cracked by unevenness of the electrode portion.
[0023]
The dielectric layer formed from the dielectric paste of the present invention is formed on a glass substrate on which electrodes are formed. Therefore, in order to prevent problems such as yellowing due to an ion exchange reaction between the components of the inorganic powder constituting the dielectric layer and the silver ions of the silver electrode used in many cases and the components of the glass substrate. Is preferably substantially free of alkali metals. In the present invention, substantially free means that the total content of alkali metals is 0.5% by weight or less, preferably 0.1% by weight or less.
[0024]
The inorganic powder is preferably composed mainly of glass powder having a glass transition point of 400 to 500 ° C and a softening point of 430 to 530 ° C. The main component means that 50% by weight or more of the glass powder is contained in the inorganic powder. If the glass transition point of the glass powder forming the dielectric layer is 500 ° C. and the softening point is higher than 530 ° C., high-temperature firing is required, and the glass substrate is distorted during firing. In addition, a material having a glass transition point lower than 400 ° C. and a softening point lower than 430 ° C. causes distortion in the dielectric layer during the formation and sealing of the phosphor layer in a later process, and the film thickness accuracy cannot be maintained. This is not preferable because it causes problems.
[0025]
The glass powder that is the main component of the inorganic powder blended in the dielectric paste is expressed in terms of oxide,
Bismuth oxide 20-70% by weight
3-30% by weight of silicon oxide
Boron oxide 10-30% by weight
Zinc oxide 2-40% by weight
Barium oxide 8-20% by weight
The thing containing is preferable. With this composition range, a dielectric paste that can be baked on a glass substrate at 530 to 580 ° C. is obtained.
[0026]
The bismuth oxide in the glass powder is blended in the range of 20 to 70% by weight. By setting it to 20% by weight or more, an effect of controlling the baking temperature and the softening point appears. By setting it to 70% by weight or less, the heat-resistant temperature of the glass is prevented from becoming too low, so that baking onto the glass substrate is performed appropriately.
[0027]
Silicon oxide can be blended in the range of 3 to 30% by weight, but by setting it to 3% by weight or more, the denseness, strength and stability of the glass layer are improved, and the thermal expansion coefficient is close to the value of the glass substrate. Therefore, mismatch with the glass substrate can be prevented. When the content is 30% by weight or less, the softening point and the glass transition point are lowered, and the glass substrate can be densely baked at 580 ° C. or less.
[0028]
By blending boron oxide in the range of 10 to 30% by weight, it is possible to improve electrical, mechanical and thermal characteristics such as electrical insulation, strength, thermal expansion coefficient, and denseness. The stability of the glass can be maintained by setting it to 30% by weight or less.
[0029]
Zinc oxide is preferably added in the range of 2 to 40% by weight. By making it 2% by weight or more, the effect of improving the density appears, and by making it 40% by weight or less, it is possible to prevent the baking temperature from becoming too low to be controlled and to maintain the insulation resistance.
[0030]
Barium oxide is blended in the range of 8 to 20% by weight. The glass baking temperature and electrical insulation can be controlled by setting it as 8 weight% or more. By making it 20% by weight or less, the stability and denseness of the glass layer can be maintained.
[0031]
The inorganic component A of the dielectric paste may be used by adding 10 to 50% by weight of a filler, that is, one containing 50 to 90% by weight of the glass powder and 10 to 50% by weight of the filler. . Adding a filler has effects such as reducing the shrinkage rate during firing and reducing the stress applied to the substrate. By making the filler addition amount 10% by weight or more, it is possible to obtain an effect of reducing the firing shrinkage rate or controlling the thermal expansion coefficient. Further, when the filler addition amount is 50% by weight or less, it becomes possible to maintain the denseness and strength of the dielectric layer after firing, and at the same time, it is possible to prevent defects such as cracks.
[0032]
As the filler, it is preferable to use at least one selected from the group consisting of silica, titania, alumina, barium titanate, cordierite, mullite and zirconia.
[0033]
The amount of the inorganic powder in the dielectric paste of the present invention is preferably 65 to 85% by weight. If it is less than 65% by weight, the shrinkage rate during firing becomes large, and it becomes difficult to obtain a dense dielectric layer. On the other hand, if it exceeds 85% by weight, the viscosity of the paste increases, the thickness unevenness during application increases, and it becomes difficult to obtain a flat film.
[0034]
The organic component of the dielectric paste is a component that serves as a binder for constituting the paste, but is preferably a component having good debinding properties in the firing step. In the present invention, since the co-firing with the barrier rib pattern is performed, it is preferable that the binder removal property is equivalent to the organic component of the barrier rib paste and the influence on the firing shrinkage rate is also equal. From these viewpoints, it is preferable to use an acrylic resin or a cellulose resin as the organic component. In addition, when an acrylic photosensitive organic component is used as the organic component of the barrier rib paste, an acrylic resin similar to the photosensitive organic component of the barrier rib paste may be used as the organic component in order to match the binder removal property. preferable.
[0035]
The dielectric paste has a state in which an inorganic powder is mixed and dispersed in an organic component, and the one in which the inorganic powder A is uniformly mixed and dispersed in the organic component has good coatability. In order to obtain such a paste, it is important that the average particle size, maximum particle size, tap density, and the like of the inorganic powder are in an appropriate range.
[0036]
The average particle size of the inorganic powder is 1 to 4 μm, the maximum particle size is 10 μm or less, and the tap density is 0.6 g / cm.^ThreeIt is preferable that Those having such a range of particle size and distribution, and powder mass per unit volume have good filling and dispersibility in the paste, and thus a paste with excellent coating properties can be prepared, so that it is dense and uniform. It becomes possible to obtain a simple coating film.
[0037]
The particle size is a value measured by a laser scattering / diffraction method, the average particle size is 50% volume particle size, and the maximum particle size is the maximum value of the particle size. Since the cohesive force of the particles depends on the surface area, if the average particle diameter is less than 1 to 4 μm, the dispersibility in the paste is improved and a dense and uniform coating film is obtained. It is also important to make the maximum particle size 10 μm or less in order to prevent the generation of voids inside the surface and unnecessary irregularities on the surface.
[0038]
Tap density of inorganic powder 0.6g / cm^ThreeOr more, preferably 0.7 g / cm^ThreeBy setting it as the above, the filling property and dispersibility of powder improve, and it becomes difficult to produce a bubble and an aggregate.
[0039]
A display substrate used in a plasma display panel is such that a dielectric layer is formed on an electrode as described above, and a partition is further formed thereon. In the present invention, a stripe-shaped barrier rib pattern is mainly formed on a dielectric paste coating film, and the coating film and the barrier rib pattern are simultaneously fired to form a dielectric layer and barrier ribs. Therefore, for the formation of the barrier rib pattern, either the barrier rib paste is applied in a pattern on the dielectric paste coating film, or the pattern is formed after being applied to the entire surface.
[0040]
Regardless of the method of forming the partition wall pattern, it is preferable that the partition wall end portion be tapered in order to prevent the partition wall end portion from jumping or rising during firing of the partition wall pattern. Such a defect is caused by jumping away from the lower part due to a difference in firing shrinkage between the upper part and the lower part of the partition wall, or by raising only the upper part while adhering to the lower part. If such a defect exists at both ends of the stripe-shaped barrier rib, a gap occurs between the top of the barrier rib on the back plate and the front plate when the substrate is sealed, and crosstalk occurs during discharge. Several countermeasures for this problem have been proposed, but the most effective method is to keep at least a part of the partition wall end in a tapered shape. By doing in this way, it is estimated that the force resulting from the shrinkage stress and the adhesive force at the upper part of the partition wall can be relaxed along the taper shape, and the jumping and bulging can be prevented.
[0041]
The taper shape may be any shape such as a straight line, an upwardly convex curve, a downwardly convex curve, and a plurality of straight lines connected to each other. A combination of a stepped shape and a tapered shape can be used, but it is preferable to provide the tapered shape at the uppermost part of the partition wall. Swelling can be eliminated by having the tapered portion at the top.
[0042]
The tapered portion is lower than the desired partition wall height and causes image disturbance, so it is formed at the end of the striped partition wall. As a method for forming the tapered shape, the following method is used, but is not limited thereto.
[0043]
This phenomenon is used because barrier rib paste is applied by screen printing method, slit die coater method, doctor blade method, etc., because the taper shape with a thin film thickness tends to be formed at the beginning and end of coating. Thus, the coating direction and the longitudinal direction of the stripe-shaped partition wall can be made to coincide with each other so that the end portion can be tapered. When a barrier rib pattern is formed using a photosensitive barrier rib paste, the pattern is exposed and developed with the opening length of the barrier rib pattern of the photomask slightly longer than the coating length in the longitudinal direction of the barrier rib, and the edges are tapered. It can be shaped. This method is preferable because an end-tapered partition wall pattern can be formed without increasing the number of steps. Further, the end portion of the partition wall paste coating film can be mechanically scraped off by a cutting tool or spraying, or the end portion can be processed into a tapered shape by processing such as melting with a solvent. It is also possible to process a taper shape by pressing a wedge-shaped stamp on the edge of the partition wall paste coating film. The partition wall pattern may be formed after the coating film is processed into a tapered shape, or the end portion may be tapered after the partition wall pattern is formed.
[0044]
The partition intended to be formed on the display substrate of the present invention usually has a pitch of 100 to 250 μm, a height of 60 to 170 μm, and a width of 15 to 60 μm, and is mainly formed in a stripe shape. It may have a lattice shape. In order to form such high-aspect-ratio, high-definition patterned partition walls, it is compatible with glass substrates, adherence to dielectric paste coating film, support for subsequent processes, and durability during display operation The thermal characteristics of the inorganic powder constituting the partition wall are important factors in terms of properties.
[0045]
In order to perform dielectric layer formation and barrier rib formation by simultaneous firing without adversely affecting the glass plate as a substrate, the thermal characteristics of the inorganic powder in the barrier rib paste should be similar to the inorganic powder in the dielectric paste. preferable.
[0046]
The inorganic powder in the partition wall paste preferably contains glass powder having a glass transition point of 400 to 520 ° C. and a softening point of 420 to 560 ° C. as a main component. The main component means that 50% by weight or more of the glass powder is contained in the inorganic powder.
[0047]
It is preferable that the glass powder used as the main component of the inorganic powder in a partition wall paste contains the following composition in oxide conversion description.
[0048]
Lithium oxide 3-15% by weight
10-30% by weight of silicon oxide
Boron oxide 20-40% by weight
2-15% by weight of barium oxide
Aluminum oxide 10-25% by weight
By containing 3 to 15% by weight of lithium oxide, not only the softening point and thermal expansion coefficient can be easily controlled, but the average refractive index of the glass can be lowered, so that the difference in refractive index from the organic substance is reduced. Easy to do. The addition amount of the alkali metal oxide is preferably 15% by weight or less, more preferably 10% by weight or less in order to improve the stability of the paste.
[0049]
The silicon oxide is preferably blended in the range of 10 to 30% by weight. By setting the content to 10% by weight or more, the denseness, strength and stability of the glass layer are improved, and the thermal expansion coefficient is close to the value of the glass substrate, so that it is possible to prevent peeling due to mismatch with the glass substrate. . By setting it to 30% by weight or less, there are advantages such that the softening point is lowered and baking onto a glass substrate becomes possible.
[0050]
Boron oxide is preferably blended in the range of 20 to 40% by weight. The stability of glass can be maintained by setting it as 40 weight% or less. By setting it as 20 weight% or more, intensity | strength and stability of glass can be improved.
[0051]
Barium oxide is preferably used in the range of 2 to 15% by weight. The glass baking temperature and electrical insulation can be controlled by setting it as 2 weight% or more. Moreover, the stability and denseness of a partition can be maintained by setting it as 15 weight% or less.
[0052]
Aluminum oxide is preferably used at 10 to 25% by weight, and is added to increase the strain point of the glass, stabilize the glass composition, and extend the pot life of the paste. By setting it as 10 weight% or more, the intensity | strength of a partition can be improved. By setting the content to 25% by weight or less, it is possible to prevent the heat-resistant temperature of the glass from becoming too high and difficult to bake on the glass substrate, and to obtain a dense partition at a temperature of 600 ° C. or less.
[0053]
Although not described in the above composition, zinc oxide, calcium oxide or magnesium oxide may be added. Zinc oxide is preferably blended in the range of 2 to 15% by weight. By setting it to 2% by weight or more, it is effective for improving the denseness of the partition walls. By setting it as 15 weight% or less, it can prevent that the temperature baked on a glass substrate becomes low too much, and can keep insulation resistance high.
[0054]
It is preferable to mix calcium oxide in the range of 2 to 13% by weight. By adding within this range, the glass can be easily melted and the thermal expansion coefficient can be controlled. Moreover, it is preferable to mix | blend magnesium oxide in 1-15 weight%. By adding 1% by weight or more, the glass can be easily melted and the thermal expansion coefficient can be controlled. Moreover, devitrification of glass can be suppressed by setting it as 15 weight% or less.
[0055]
The glass powder can contain titanium oxide, zirconium oxide, etc., but the amount is preferably 5% by weight or less. Zirconium oxide is effective in controlling the softening point, glass transition point, and electrical insulation.
[0056]
It is also preferable to add 10 to 50% by weight of filler to the inorganic powder of the partition wall paste. That is, it is also preferable to contain 50 to 90% by weight of glass powder having a glass transition point of 400 to 520 ° C. and a softening point of 420 to 560 ° C. and 10 to 50% by weight of filler.
[0057]
By adding 10% by weight or more of the filler, the firing shrinkage rate can be lowered and the thermal expansion coefficient can be controlled, and the shape retention and accuracy of the partition walls are improved. Furthermore, the addition of these fillers is preferable for maintaining the strength of the obtained partition walls. On the other hand, by setting the filler content to 50% by weight or less, it is possible to maintain the denseness of the partition walls after firing, maintain the strength of the partition walls, and prevent defects such as peeling and dropping. Further, it is possible to prevent the adsorption of a trace amount of moisture and the remaining organic components in the partition wall, and thus prevent the discharge characteristics from deteriorating.
[0058]
The filler is preferably made of at least one selected from the group consisting of titania, alumina, zirconia, cordierite, mullite, spinel and high melting point glass. As high melting glass, what contains the following compositions in oxide conversion description is preferable.
[0059]
Silicon oxide 15-50% by weight
Boron oxide 5-20% by weight
Aluminum oxide 15-50% by weight
Barium oxide 2-10% by weight
The high melting point glass preferably has a composition containing 15% by weight or more of silicon oxide and aluminum oxide, respectively, and the total content thereof is 50% by weight or more in the glass in order to provide necessary thermal characteristics. It is effective for. High melting point glass is preferable because the average refractive index, softening point, and thermal expansion coefficient can be controlled by changing the composition.
[0060]
The barrier rib pattern is formed by applying a barrier rib paste in a pattern (screen printing method), etching a paste film applied to the entire surface using a photoresist, or forming a pattern by a photolithography method using a photosensitive paste ( It is formed by a photosensitive paste method).
[0061]
The display substrate of the present invention is also applied to a large-area, high-definition image display apparatus, and the partition wall pattern to be formed has a high aspect ratio and high-definition. It is preferable to form by an adhesive paste method. That is, the organic component is a photosensitive organic component, and a barrier rib pattern is formed by photolithography after applying barrier rib paste.
[0062]
When the height of the partition walls after firing is 60 to 170 μm, the partition paste coating film applied for partition pattern formation needs to have a thickness of 100 to 220 μm in consideration of firing shrinkage. In order to expose a high-definition pattern on the partition wall paste coating film having such a thickness and form a high aspect ratio pattern with high resolution, the actinic ray for exposure is as straight as possible to the bottom of the coating film. Must be transparent. For this reason, it is important that both the inorganic powder B and the organic component B, which are blended in the barrier rib paste, have high light transmission properties and are mixed uniformly. Furthermore, in a mixture system in which inorganic powder is dispersed in a photosensitive organic component such as a barrier rib paste, the average refractive index of each of these components is most approximate to increase the light transmittance. Become important.
[0063]
Generally, the refractive index of the organic component is 1.45 to 1.7. The refractive index of the inorganic component is usually higher than this, but in order to match both refractive indexes, the average refractive index of the inorganic component is 1.5 to 1.8, preferably 1.5 to 1.65. Most preferably, the difference from the average refractive index of the organic component is about 0.05. That is, the inorganic powder of the partition wall paste preferably has an average refractive index of 1.5 to 1.8.
[0064]
As in the case of the dielectric paste, in the inorganic powder constituting the barrier rib paste, appropriate ranges of average particle diameter, maximum particle diameter and tap density are present in order to obtain barrier rib paste with good coatability.
[0065]
The average particle size of the inorganic powder is preferably 1.5 to 6 μm, and the maximum particle size is preferably 30 μm or less. When the average particle size is 1.5 μm or more, a dense coating film can be formed and a high-definition pattern can be obtained. In addition, when the average particle size is 6 μm and the maximum particle size is 30 μm or less, the formed partition walls are sufficiently dense, and voids and the like are generated inside, thereby adversely affecting the mechanical strength. It is preferable that an unnecessary unevenness is generated on the surface of the partition wall without causing any trouble at the time of sealing.
[0066]
The tap density of inorganic powder is 0.6 g / cm^ThreeOr more, preferably 0.7 g / cm^ThreeThe above is preferable because the powder filling properties and dispersibility are improved, and bubbles and aggregates are less likely to be produced, so that it is possible to obtain a photosensitive partition paste having high light transmittance and excellent pattern characteristics. .
[0067]
As a method for producing glass powder, the glass powder in the dielectric paste and the glass powder in the partition wall paste are common. For example, a compound such as lithium, silicon, aluminum, boron, and barium as raw materials has a predetermined composition. After mixing at 900 to 1200 ° C., the mixture is rapidly cooled, made into a glass frit, and pulverized into a fine powder. The average particle size, maximum particle size, and particle size distribution of the powder to be used have important effects on the filling property, dispersibility, and paste application property of the paste, and therefore it is important to control them within an appropriate range. High purity carbonates, oxides, hydroxides and the like can be used as raw materials. Depending on the type and composition of the glass powder, high-resistance and dense pores can be obtained by using powders that are made of ultra-pure alkoxide and organometallic materials with a purity of 99.99% or more, and that are homogeneously produced by the sol-gel method. This is preferable because a high-strength insulating layer with a small amount is obtained.
[0068]
The barrier rib paste can be formed by pattern printing using a screen printing plate using an organic binder similar to that of the dielectric paste. However, in a more preferable method of the present invention, the organic component is photosensitive organic. A photosensitive partition paste using the components is used. That is, an inorganic powder is kneaded with a photosensitive organic component to prepare a photosensitive partition paste.
[0069]
The photosensitive organic component undergoes a change due to a light reaction when exposed to light, and a pattern is formed using this. There are known a photo-dissolving type (positive type) in which a portion subjected to light is dissolved in a solvent and a photo-insolubilizing type (negative type) in which a portion subjected to light is insoluble in a solvent. Any type can be used for the photosensitive partition paste, but in order to form a firm pattern by mixing with inorganic components, a negative type that is photocured by polymerization and crosslinking reaction and becomes insoluble in the solvent. It is preferable to use the photosensitive organic component.
[0070]
The photosensitive organic component of the barrier rib paste is mainly composed of a photosensitive monomer and an oligomer or polymer, and contains a photopolymerization initiator and an ultraviolet absorber. If necessary, additives such as a sensitizer, a polymerization inhibitor, a dispersant, a stabilizer, and a solvent can be added to the photosensitive paste.
[0071]
As the photosensitive monomer, a compound having an active carbon-carbon double bond is preferable, and monofunctional and polyfunctional compounds having a vinyl group, an allyl group, an acrylate group, a methacrylate group, or an acrylamide group as functional groups are used.
[0072]
In particular, the polyfunctional acrylate compound and / or polyfunctional methacrylate compound is preferably contained in the organic component in an amount of 10 to 80% by weight. Since various types of compounds have been developed as the polyfunctional acrylate compound and the polyfunctional methacrylate compound, it is possible to select them in consideration of reactivity, refractive index, and the like.
[0073]
As a method of controlling the refractive index of the photosensitive organic component, a photosensitive monomer having a refractive index of 1.55 to 1.8 is selected and contained, and the average refractive index of the photosensitive organic component is changed to the average refractive index of the inorganic material. The approaching method is simple. The photosensitive monomer having such a high refractive index can be selected from an aromatic ring such as a benzene ring and a naphthalene ring, and an acrylate or methacrylate monomer containing a sulfur atom.
[0074]
In the photosensitive organic component, an oligomer or a polymer serves as a component that functions to improve the physical properties of the cured product formed by photoreaction and to adjust the viscosity of the paste, and to control the developability of the unexposed area. Added.
[0075]
These oligomers or polymers can be obtained by polymerization or copolymerization of components selected from compounds having a carbon-carbon double bond. In particular, an oligomer or polymer having a weight average molecular weight of 2000 to 60,000, more preferably 3000 to 40,000 having a carboxyl group and an unsaturated double bond in the molecular side chain is preferably used. For introduction, an oligomer or polymer having a carboxyl group in the side chain is preferably subjected to an addition reaction with an ethylenically unsaturated compound having glycidyl group or isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride.
[0076]
The acid value of the oligomer or polymer is preferably from 50 to 160, particularly preferably from 70 to 140, from the viewpoint of development tolerance and solubility in a developer in an unexposed area.
[0077]
In the photosensitive organic component, a photopolymerization initiator is further added to initiate a photoreaction, and a sensitizer may be added to assist the effect of the photopolymerization initiator in some cases. Since the preferred photosensitive functional group in the present invention is a radical polymerizable group, the photopolymerization initiator is preferably selected from those that generate radical species.
[0078]
There are different types of photopolymerization initiators, such as single molecule direct cleavage type, ion-pair electron transfer type, hydrogen abstraction type, and two-molecule complex system. Compounds selected from direct cleavage types are preferred. Examples include benzoin alkyl ethers, α, α-dimethoxy-α-morpholinoacetophenone, α, α-dimethoxy-α-phenylacetophenone, and the like. Moreover, a peroxide, a phosphine oxide, a sulfur compound, a halogen compound, etc. may be used, and these may be used alone or in combination.
[0079]
The photopolymerization initiator is generally blended in an amount of 0.05 to 10% by weight based on the photosensitive component, but in the case of the photosensitive partition paste, the amount of inorganic powder is taken into consideration and 2 to 30% based on the photosensitive component. It is preferable to blend by weight%.
[0080]
By blending a sensitizer with a photopolymerization initiator, the sensitivity can be improved (chemical sensitization) or the wavelength range effective for the reaction can be expanded (spectral sensitization).
[0081]
There are various mechanisms of action of sensitizers, but what is called a triplet sensitizer is most often used. Among these are hydrocarbon compounds, amino / nitro compounds, quinones, xanthones, anthrones, ketones, and organic dyes. Some of these have a function as a photopolymerization initiator.
[0082]
As a sensitizer used in combination with a monomolecular direct cleavage type photopolymerization initiator, a compound selected from xanthones is preferable, and specific examples thereof include 2,4-diethylthioxanthone and isopropylthioxanthone. These may be used alone or in combination of two or more.
[0083]
It is effective for blending a photosensitive paste with an ultraviolet absorber for pattern processing with an excellent shape. By adding these ultraviolet absorbers to the photosensitive paste, light having a wavelength in the vicinity of h-line (405 nm) and i-line (365 nm) in the wavelength range of light from an ultra-high pressure mercury lamp most often used as an exposure light source. To the lower layer of the photosensitive paste coating film by reducing the amount of light in the vicinity of the h-line and i-line absorbed by the photopolymerization initiator and sensitizer and increasing the transmittance of light of the g-line wavelength. It can be sufficiently photocured.
[0084]
The ultraviolet absorber has an absorption maximum in a wavelength range of 350 to 400 nm, and is, for example, at least one selected from the group consisting of azo dyes, benzophenone compounds, cyanoacrylate compounds, benzotriazole compounds, and indole compounds. It is.
[0085]
Specific examples of these compounds include Sudan I, Sudan II, Sudan III, Sudan IV, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2, 2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy- 4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4 -Dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di) -T-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5' -Di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 2-ethyl-2-cyano-3,3-diphenyl acrylate, “BONASORB” UV-3901 (manufactured by Orient Chemical Co., Ltd.) , "BONASORB" UA-3902 (manufactured by Orient Chemical Co.), "SOM" -2-0008 (manufactured by Orient Chemical Industries, Ltd.) and the like can be mentioned, but not limited to.
[0086]
Furthermore, a methacryl group or the like may be introduced into the skeleton of these ultraviolet absorbers and used as a reaction type.
[0087]
The addition amount of the ultraviolet absorber is preferably in the range of 0.05 to 2% by weight in the photosensitive paste. By setting it within these ranges, the ultraviolet absorber absorbs wavelengths in the vicinity of h-line and i-line and increases the transmittance of g-line, thereby improving the effect of improving the shape of the pattern to be formed.
[0088]
As a compounding ratio of the inorganic powder of the photosensitive partition paste and the photosensitive organic component, 60/40 to 90/10 (parts by weight) is preferable. Furthermore, 65/35 to 85/15 (parts by weight) is also preferable from the viewpoint of shrinkage due to firing.
[0089]
The photosensitive partition paste can be usually produced by preparing various components so as to have a predetermined composition and then uniformly mixing and dispersing them with a three roller or a kneader.
[0090]
The viscosity of the photosensitive partition paste is adjusted to about 10,000 to 200,000 cps (centipoise) with an organic solvent. Examples of the organic solvent used at this time include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, and the like. The organic solvent mixture containing 1 or more types of them is mentioned.
[0091]
For example, 50,000 to 200,000 cps is preferable in order to obtain a coating film having a thickness of 10 to 20 μm by coating the glass substrate once by a screen printing method. When using a blade coater method or a die coater method, 10,000 to 20,000 cps is preferable.
[0092]
After applying the photosensitive partition paste, pattern exposure is performed using an exposure apparatus. For this purpose, various exposure apparatuses are known and can be used. The exposure is generally mask exposure through a photomask, as is done by ordinary photolithography techniques. There are two methods for performing exposure through the mask: a method in which the mask is in close contact with the surface of the photosensitive partition paste coating film, and a method in which the mask is slightly spaced. The latter is exposure using a so-called proximity exposure apparatus, and is performed for the purpose of forming a high-definition pattern with a high aspect ratio using a photosensitive partition paste. It is effective to prevent the defects of the baked partition wall from having an end portion of the partition pattern tapered, and it is preferable to set the pattern opening of the photomask to be used longer than the coating length of the partition paste.
[0093]
The actinic ray used for the exposure is most preferably ultraviolet light, and as its light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp or the like is used. An exposure machine using parallel rays using an ultra-high pressure mercury lamp as a light source is common.
[0094]
After the exposure, development is performed using the difference in solubility between the exposed portion and the unexposed portion in the developer. In this case, an immersion method, a spray method, a brush method, or the like is used. As the developer, a solution in which an organic component in the photosensitive partition paste, particularly an oligomer or polymer, can be dissolved is preferably used.
[0095]
The oligomer or polymer preferably used in the present invention can be developed with an aqueous alkaline solution by having a carboxyl group in the side chain.
[0096]
As the aqueous alkaline solution, an aqueous solution of sodium hydroxide, sodium carbonate, calcium hydroxide, or the like can be used. However, it is preferable to use an organic alkaline aqueous solution because an alkaline component can be easily removed during firing.
[0097]
As the organic alkali, a general amine compound can be used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine, diethanolamine and the like.
[0098]
The concentration of the aqueous alkali solution is preferably 0.05 to 5% by weight, and preferably 0.1 to 1% by weight, with which there is no fear of peeling or eroding the pattern of the exposed part while completely removing the soluble part. More preferred. The temperature during development is preferably 20 to 50 ° C. for process control.
[0099]
The barrier rib pattern formed on the dielectric paste coating film is then baked simultaneously with the dielectric paste coating film in a baking furnace to remove organic components by thermal decomposition or oxidative decomposition, and at the same time in the dielectric paste. The glass powder and the glass powder in the barrier rib paste are melted to form the dielectric layer and the barrier ribs simultaneously. The firing atmosphere and temperature vary depending on the characteristics of the paste and the substrate, but are usually fired in air.
[0100]
As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used. In the case of batch-type firing, the glass substrate on which the partition pattern was formed on the dielectric paste coating film was heated from room temperature to about 500 ° C. over several hours at a substantially constant speed, and further set as the firing temperature. The temperature is raised to 520 to 610 ° C. over 30 to 40 minutes and held for 15 to 30 minutes for firing. These conditions are general, and when the thermal characteristics of the glass powder change, new conditions are set.
[0101]
Since the firing temperature must be lower than the glass transition point of the glass substrate used, there is an upper limit naturally. If the firing temperature is too high or the firing time is too long, defects such as sagging occur in the shape of the partition walls.
[0102]
The present invention aims at making the difference between the firing shrinkage rate of the dielectric paste coating film and the firing shrinkage rate of the barrier rib pattern 0.03 or less, preferably 0.015 or less. Items related to the firing shrinkage ratio are the ratio of the organic component to the inorganic powder in the paste, the composition of the organic component, the blending amount of the filler in the inorganic powder, and the like. If they are exactly the same, the firing shrinkage should be the same, but in practice the dielectric paste and the barrier rib paste have different required characteristics, so it is difficult to use the same paste. For example, the dielectric paste does not require pattern formation, and as the inorganic powder, a bismuth oxide-containing glass that does not substantially contain an alkali metal and can be baked on a glass substrate at a low temperature is suitable. On the other hand, patterning properties are required for the barrier rib paste, and lithium oxide-containing glass is suitable as the inorganic powder. Therefore, while satisfying the characteristics required for each, the difference between the firing shrinkage rate of the dielectric paste coating film and the firing shrinkage rate of the barrier rib pattern is 0.03 or less, preferably 0.015 or less. It is important to prepare the composition.
[0103]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to this. In addition, the density | concentration in an Example is weight%, when there is no notice.
[0104]
Example 1
A 300 mm square glass substrate (PD-200) on which a striped electrode pattern having a pitch of 150 μm and a line width of 40 μm is formed using a photosensitive silver paste is baked in air at 590 ° C. for 30 minutes to form a glass substrate. A substrate on which an electrode was formed was produced. The thickness of this electrode was 7 μm.
[0105]
Next, 60 g of ethyl cellulose as an organic component was dissolved in 940 g of terpineol at 80 ° C., and 200 g of binder solution stirred until the solid content disappeared (ethyl cellulose concentration 6%) was mixed with three rolls of glass powder A 50 g, filler A 10 g and thickener. A dielectric paste was prepared by kneading.
[0106]
Glass powder A has a composition of 38% bismuth oxide, 7% silicon oxide, 19% boron oxide, 4% aluminum oxide, 20% zinc oxide, 12% barium oxide, an average particle size of 2.5 μm, and a maximum particle size of 6. 5 μm, glass transition point 475 ° C., softening point 515 ° C., coefficient of thermal expansion 75 × 10^-7/ K. As the filler A, titania (Ishihara Sangyo TIPAQUE R550) was used.
[0107]
This dielectric paste was applied on a glass substrate on which an electrode was formed by a screen printing method so as to have a dry thickness of 20 μm, and dried at 80 ° C. for 40 minutes. When this was fired in air at 570 ° C. for 30 minutes, the firing shrinkage ratio was 0.22. However, in this embodiment, the partition paste is not applied after the dielectric layer is formed, but the partition paste pattern is formed on the dielectric paste coating film, and then the dielectric paste coating film and the partition pattern are fired simultaneously. Applied method.
[0108]
150 g of photosensitive polymer (X-4007), 150 g of photosensitive monomer (MGP400), 30 g of photopolymerization initiator (IC-369), 1 g of UV absorber (Sudan IV) were dissolved in 300 g of γ-butyrolactone with heating and stirring. For partition formation, 50 g of glass powder B and 10 g of filler B are mixed in 32 g of a photosensitive organic component solution (photosensitive organic component concentration: 47.4%) prepared by filtering through a 400 mesh filter, and kneaded with three rolls. A photosensitive paste was prepared.
[0109]
The composition of the glass powder B was 7% lithium oxide, 23% silicon oxide, 33% boron oxide, 4% barium oxide, 20% aluminum oxide, 2% zinc oxide, 6% magnesium oxide and 5% calcium oxide. Non-spherical powder having an average particle size of 2.5 μm and a maximum particle size of 22 μm. The glass transition point is 489 ° C., the softening point is 528 ° C., and the thermal expansion coefficient is 50 × 400 ° C.^-7/ K. As the filler B, high melting point glass was used, and the composition thereof was 38% silicon oxide, 10% boron oxide, 35% aluminum oxide, 2% zinc oxide, 5% magnesium oxide, 5% calcium oxide, 5% barium oxide. %Met. The average particle size is a non-spherical powder having a particle size of 1.5 μm. The glass transition point is 653 ° C., softening point is 778 ° C.^-7/ K.
[0110]
This barrier rib photosensitive paste was applied on the dielectric paste coating film by screen printing. In order to avoid the occurrence of pinholes or the like in the coating film, coating and drying were repeated several times, and coating was performed so that the dry thickness was 180 μm. The drying in the middle was performed at 80 ° C. for 10 minutes each, applied to a predetermined thickness, and then dried at 80 ° C. for 40 minutes. This photosensitive paste coating film was subjected to contact exposure through a photomask (striped pattern, pitch 150 μm, line width 20 μm) for the purpose of forming a PDP partition pattern. 20mW / cm²1J / cm with ultra high pressure mercury lamp²The exposure was performed. Thereafter, a 0.3% aqueous solution of monoethanolamine maintained at 35 ° C. was developed by showering for 120 seconds and washed with water by shower spray.
[0111]
A pattern opening portion formed in the photomask for forming the partition wall pattern was designed to be larger than the length in the partition wall longitudinal direction of the partition wall paste coating film. After development, when the partition wall edge was observed, it was confirmed that the edge was tapered.
[0112]
Subsequently, the dielectric paste coating film and the barrier rib pattern were simultaneously fired in air at 570 ° C. for 30 minutes to form a dielectric layer and barrier ribs. The height of the partition was 140 μm, and the line width at the center of the partition was 33 μm. The firing shrinkage ratio of the partition wall pattern was 0.24. The difference from the firing shrinkage rate of the dielectric paste was 0.02.
[0113]
The obtained barrier ribs did not bounce or bulge at the edges, and there were no defects such as peeling / cracking between the dielectric layer and the barrier ribs, and there were no problems such as substrate warpage. This display substrate was confirmed to function satisfactorily as a plasma display panel formed by applying a phosphor between the barrier ribs and sealing it with the front substrate.
[0114]
(Example 2)
Dielectric paste glass powder A was 40 g, and filler A was 20 g. A display substrate was prepared in the same manner as in Example 1 except that the partition wall paste glass powder B was 40 g and the filler B was 20 g. The firing shrinkage rates of the dielectric paste and the barrier rib paste were 0.21 and 0.22, respectively. In the obtained display substrate, no defect was observed between the dielectric layer and the partition wall, and there was no trouble such as warpage of the substrate. This display substrate was confirmed to function satisfactorily as a plasma display panel.
[0115]
(Example 3)
As glass powder used for the photosensitive paste for the partition, lithium oxide 9%, silicon oxide 20%, boron oxide 31%, barium oxide 4%, aluminum oxide 24%, zinc oxide 2%, magnesium oxide 6%, calcium oxide 4% A display substrate was prepared in the same manner as in Example 1 except that the glass powder C comprising: This glass powder C is a non-spherical powder having an average particle size of 2.5 μm and a maximum particle size of 18.5 μm, and has a glass transition point of 474 ° C., a softening point of 515 ° C., and a thermal expansion coefficient of 79 × 10 ° C.^-7/ K.
[0116]
The firing shrinkage rate of the barrier rib pattern was 0.245, and the difference from the firing shrinkage rate of the dielectric paste was 0.025. In the obtained display substrate, no defect was observed between the dielectric layer and the partition wall, and there was no trouble such as warpage of the substrate. This display substrate was confirmed to function satisfactorily as a plasma display panel.
[0117]
Comparative Example 1
In Example 1, instead of simultaneous firing, a process of firing the dielectric paste coating film in advance, coating the partition paste, forming a partition pattern, and firing was used. Other than that, the display substrate was prepared and evaluated in the same manner as in Example 1. The difference between the firing shrinkage rate of the dielectric paste and the firing shrinkage rate of the barrier rib pattern was 0.02, but as a result of applying different firing steps, it was observed that a part of the formed barrier ribs was peeled off.
[0118]
Comparative Example 2
A display substrate was prepared and evaluated in the same manner as in Example 1 except that the amount of the photosensitive organic component solution added was 55 g when preparing the partition wall paste. In this case, the firing shrinkage rate of the partition wall pattern was 0.26, and the difference from the firing shrinkage rate 0.22 of the dielectric paste coating film was 0.04. Peeling was observed on the formed dielectric layer and a part of the partition wall.
[0119]
Explanation of abbreviations
X-4007:
A photosensitive polymer having a weight average of 43,000 and an acid value of 95, obtained by addition-reacting 0.4 equivalent of glycidyl methacrylate to a carboxyl group of a copolymer comprising 40% methacrylic acid, 30% methyl methacrylate and 30% styrene.
[0120]
MGP400:
X₂N−CH (CH_Three) −CH₂− (OCH₂CH (CH_Three))_n−NX₂
X: -CH₂CH (OH) −CH₂O-CO-C (CH_Three) ＝ CH₂
n: 2 to 10
IC-369: Irgacure369: Ciba Geigy product
2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1
[0121]
【The invention's effect】
In the method for manufacturing a display substrate in which the dielectric paste coating film and the barrier rib pattern formed thereon are simultaneously fired, the difference between the firing shrinkage ratio t1 of the dielectric paste coating film and the firing shrinkage ratio t2 of the barrier rib pattern | t1− By setting t2 | to 0.03 or less, it is possible to obtain an excellent display substrate in which the problem of partition wall peeling is solved.
[0122]
The display substrate of the present invention can be used for a plasma display panel, a plasma addressed liquid crystal display, an image display device using an electron-emitting device, and the like, and can be particularly preferably used as a plasma display panel substrate.

Claims (14)

A dielectric paste made of an inorganic powder and an organic component is applied to a glass substrate on which electrodes are formed to form a dielectric paste coating film, and a barrier rib pattern is formed on the electrode by a barrier paste made of an inorganic powder and an organic component. After that, a method for manufacturing a display substrate in which the dielectric paste coating film and the barrier rib pattern are simultaneously fired, wherein the firing shrinkage ratio t1 of the dielectric paste coating film and the firing shrinkage ratio t2 of the barrier rib pattern are expressed by the following equations: A method for manufacturing a display substrate, wherein:
t1 ≦ 0.4
t2 ≦ 0.4
| T1-t2 | ≦ 0.03 2. The method for manufacturing a display substrate according to claim 1, wherein the inorganic powder in the dielectric paste does not substantially contain an alkali metal. 3. The display substrate according to claim 1, wherein the inorganic powder in the dielectric paste is mainly composed of glass powder having a glass transition point of 400 to 500 ° C. and a softening point of 430 to 530 ° C. 4. Production method. The inorganic powder in the dielectric paste contains 50 to 90% by weight of glass powder having a glass transition point of 400 to 500 ° C and a softening point of 430 to 530 ° C and 10 to 50% by weight of filler. Item 4. A method for manufacturing a display substrate according to Item 3. The said glass powder contains the following composition, The manufacturing method of the board | substrate for displays of Claim 3 characterized by the above-mentioned.
Bismuth oxide 20-70% by weight
3-30% by weight of silicon oxide
Boron oxide 10-30% by weight
Zinc oxide 2-40% by weight
Barium oxide 8-20% by weight 5. The method for producing a display substrate according to claim 4, wherein the filler is at least one selected from the group consisting of silica, titania, alumina, barium titanate, cordierite, mullite, and zirconia. The method for producing a display substrate according to claim 1, wherein the organic component in the dielectric paste contains an acrylic resin or a cellulose resin. The method for producing a display substrate according to claim 1, wherein the inorganic powder in the partition wall paste contains glass powder having a glass transition point of 400 to 520 ° C. and a softening point of 420 to 560 ° C. as a main component. The inorganic powder in the partition wall paste contains 50 to 90% by weight of glass powder having a glass transition point of 400 to 520 ° C and a softening point of 420 to 560 ° C and 10 to 50% by weight of filler. A method for producing a display substrate according to claim 8. The said glass powder contains the following composition, The manufacturing method of the board | substrate for displays of Claim 8 characterized by the above-mentioned.
Lithium oxide 3-15% by weight
10-30% by weight of silicon oxide
Boron oxide 20-40% by weight
2-15% by weight of barium oxide
Aluminum oxide 10-25% by weight 10. The method for manufacturing a display substrate according to claim 9, wherein the filler is at least one selected from the group consisting of titania, alumina, zirconia, cordierite, mullite, spinel, and refractory glass. 2. The method for manufacturing a display substrate according to claim 1, wherein the organic component in the barrier rib paste is a photosensitive organic component, and the barrier rib pattern is formed by photolithography after the barrier rib paste is applied. 13. The method for producing a display substrate according to claim 12, wherein the photosensitive organic component comprises a photosensitive monomer and an oligomer or polymer as main components, and contains a photopolymerization initiator and an ultraviolet absorber. The method for manufacturing a display substrate according to claim 1, wherein the display substrate is used for a plasma display panel.