JPH05205632A - Method for forming fluorescent screen of plasma display panel - Google Patents

Abstract

PURPOSE:To form accurately and easily a fluorescent screen irrespective of material used to an electrode or a cell barrier. CONSTITUTION:A phosphor slurry 3 consisting of photosensitive resin compound with a phosphor dispersed is applied to a surface on which fluorescent screen is to be formed, wherein the resin compound is formed from gelatin and organic hardening agent. This is subjected to the exposure, development, and baking processes and a fluorescent screen 7 is formed in the specified place. Thereby the photolithographic process for formation of fluorescent screen can be done without being affected by the material to electrode 2 or cell barrier. This permits the use of a conventional paste for electrode or one for cell barrier which has been resiricted for the reason of difficulty in formation of fluorescent screen due to products or residues. When a low melting point glass is included in the phosphor slurry 3, no limitation is imposed on its sort to be selected.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a fluorescent screen on a plasma display panel (hereinafter referred to as PDP) which is a self-luminous flat panel display using gas discharge.

[0002]

2. Description of the Related Art FIG. 2 shows one configuration example of a conventional DC PDP. As shown in the figure, in this DC type PDP, a flat plate-shaped front plate 11 and a rear plate 12 made of glass are arranged in parallel and opposite to each other, and both are provided between them. It is held at a constant interval by the cell barrier 13. Further, an anode 14 is formed on the back side of the front plate 11, a cathode 15 is formed on the front side of the back plate 12 so as to be orthogonal to the anode 14, and a fluorescent screen is provided on both sides of the anode 14. 16 are formed adjacent to each other. In this DC type PDP, the anode 14
By applying a predetermined voltage from a DC power supply between the cathode 15 and the cathode 15 to form an electric field, each cell 17 as a display element including the front plate 11, the rear plate 12, and the cell barrier 13 is formed.
The discharge is performed inside the. Then, the fluorescent surface 16 on the back side of the front plate 11 is caused to emit light by the ultraviolet rays generated by this discharge, and the observer visually recognizes this light transmitted through the front plate 11.

FIG. 3 shows an example of the structure of a conventional AC type PDP. As shown in FIG.
As in the case of the DC type PDP, the C type PDP has a flat plate-like front plate 21 and a rear plate 22 made of glass, which are arranged in parallel and opposite to each other, and are provided between them. The cell barrier 23 holds the cells at regular intervals. Further, in this AC type PDP, two electrodes 24 and 25 orthogonal to each other are formed on the front surface side of the back plate 22 with the dielectric layer 26 interposed therebetween, and further on the front surface side thereof, the dielectric layer 27 and the protective layer 28. And a fluorescent screen 29 is formed on the back side of the front plate 21. In this AC type PDP, two electrodes 2
By applying a predetermined voltage from an AC power supply between 4 and 25 to form an electric field, the front plate 21 is discharged inside each cell 30 as a display element composed of the back plate 22 and the cell barrier 23. Done. Then, the fluorescent surface 29 on the back side of the front plate 21 is caused to emit light by the ultraviolet rays generated by this discharge, and the observer visually recognizes this light transmitted through the front plate 21.

Here, there are a matrix shape and a line shape as the shape of the cell barrier, for example, DC.
In the case of the type PDP, FIG. 4 shows a matrix and FIG. 5 shows a line. 4 and 5, 31 is a front plate arranged on the observer side, 32 is a rear plate, 33 is a cell barrier, 34 is an anode, and 35 is a cathode. Further, although those shown in these figures are examples in which the cell barrier 33 is formed on the back plate 32 when forming the PDP, the cell barrier 33 may be formed on the front plate 31 in some cases.

The DC type or A having the above-mentioned structure
The phosphor screen of the C-type PDP is generally formed by a photolithography method. Specifically, after applying a photosensitive phosphor slurry to the back surface of the front plate, a photomask corresponding to the pattern of the phosphor screen is used. It is formed by exposing it to light, developing it, and baking it. As the phosphor slurry, a mixture containing a phosphor and polyvinyl alcohol (PVA) and a diazonium compound as a photosensitive resin, or a mixture containing a phosphor and PVA and a dichromic acid compound as a photosensitive resin is mainly used. The antifoaming agent and the surfactant may be added depending on the case.

Further, in the PDP as described above, there is also known one in which a fluorescent screen is formed on the wall surface of the cell barrier, and one in which the fluorescent screen is formed across both the front plate and the wall surface of the cell barrier. The fluorescent screen in this case is also formed by the photolithography method.

[0007]

However, when the phosphor screen is formed by the photolithography method described above, Ni electrodes formed by thick film printing (for example, when using 9535 or 9536D manufactured by DuPont as a paste) Is formed on a glass substrate, a PVA-based phosphor slurry is formed due to boric acid generated by oxidation of boron in the electrode paste during firing, particularly sodium borate formed by reaction with sodium contained in the glass substrate or paste. Was solidified into a gel, and patterning could not be performed accurately.

Further, as materials for forming electrodes and cell barriers, boron, copper, aluminum, titanium, zirconium,
When tin, vanadium, chromium, etc. are contained, or when aldehydes, methylol compounds, activated vinyl groups, epoxy compounds, esters, diisocyanates, etc. remain in the electrodes and cell barriers, PVA-based The phosphor slurry solidifies at the time of application, which may prevent accurate patterning or a uniform film thickness.

Further, powdered glass (generally lead borosilicate glass) having a low melting point has been mixed in the phosphor slurry in order to improve the adhesive force between the phosphor and the glass substrate. When powdered glass having a ratio of 1.5% or more is used, the PVA-based phosphor slurry causes gelation, and therefore, the low melting point glass that can be used is very limited.

As described above, there is a problem that the photolithography process for forming the fluorescent screen is obstructed depending on the type of the low melting point glass in the PVA type phosphor slurry or the material forming the electrodes and cell barriers.

The present invention has been made in order to solve such a problem, and can accurately and irrespective of the kind of the material used in the previous step and the kind of the low melting point glass mixed with the phosphor slurry. It is an object of the present invention to provide a method for forming a fluorescent screen of a PDP that can easily form a fluorescent screen.

[0012]

In order to achieve the above object, the present invention applies a phosphor slurry prepared by dispersing a phosphor in a photosensitive resin composition onto a surface on which a phosphor screen is to be formed. Then, in the method of forming a fluorescent screen of a PDP which forms a fluorescent screen at a predetermined place through exposure, development and baking steps, the photosensitive resin composition is composed of gelatin and an organic curing agent. Is.

The organic curing agent is preferably a diazonium type or bisazide type curing agent, and it is particularly desirable to use a formaldehyde condensate of p-diazodiphenylamine among diazonium type curing agents.

In the above method, the phosphor slurry is preferably applied by a doctor blade coating method.

When a color PDP is formed by the above method, phosphors having red, green and blue emission colors are coated with phosphor slurry, selectively exposed through a mask, and developed. Just repeat.

[0016]

According to the above-described phosphor screen forming method of the present invention, the phosphor screen is not affected by the material of the electrode or cell barrier formed on the substrate or the low melting point glass mixed in the phosphor slurry. The photolithography process of formation is favorably performed.

[0017]

FIG. 1 is a process chart showing an embodiment of a method for forming a phosphor screen of a PDP according to the present invention, in which a phosphor screen is formed on the same surface as an electrode formed on a front plate of a DC type PDP. Is shown. Hereinafter, each step shown in FIGS. 1A to 1E will be described step by step.

First, as shown in FIG. 1A, an anode 2 is formed in a thick film or thin film state on a substrate 1 made of ceramic such as glass. Then, as shown in (b),
A phosphor slurry 3 made of a photosensitive resin composition in which a phosphor is dispersed is applied to the surface of the substrate 1 on which the phosphor surface is to be formed by an arbitrary coating method and dried. Then, as shown in (c), pattern exposure is performed with ultraviolet rays 5 through the mask 4 having a phosphor pattern, and then, as shown in (d), the phosphor layer 6 that has been developed and patterned is left, and the unexposed portion is exposed. Remove layers and dry.

Here, in the case of a color PDP, phosphors having red, green, and blue emission colors are selectively applied by coating a photosensitive resin composition containing the phosphors and through a mask of a phosphor pattern. The steps of exposing and developing to remove the unexposed portion and excess phosphor are repeated.

Finally, the phosphor layer 6 thus formed is fired to burn off the resin component of the phosphor slurry and the organic curing agent, and the desired pattern of fluorescence as shown in FIG. Form surface 7.

In addition to the front plate on which the phosphor screen 7 is formed in this manner, a back plate on which a cathode and a cell barrier are formed is prepared, and a PDP is formed by combining these front and back plates. It

The above manufacturing steps themselves may be the same as those in the conventional method, and therefore, the electrode forming method, substrate material, coating method, developing method and baking method used may be the same as those in the conventional method. However, in the present invention,
A photosensitive resin composition containing gelatin and an organic curing agent is used.

As the above-mentioned gelatin, any conventionally known gelatin can be used.

On the other hand, examples of the organic curing agent include diazonium salts, phenyl azides, o-quinone azides,
Although any conventionally known organic curing agent such as bisazide can be used, a diazonium type curing agent is suitable from the viewpoint of curability, developability, baking property, etc., and particularly useful is p-diazodiphenylamine. Formaldehyde condensate of (condensation degree 2 to 3).

The amount of such an organic curing agent added to gelatin is preferably 20 wt% or more of gelatin.
That is, when the content is 20 wt% or less, the hardening of gelatin becomes insufficient and the film may float during development. Further, when the amount of the curing agent is too large, only the surface layer is cured due to the coloring of the curing agent and curing failure occurs as a whole, or the sensitivity is remarkably lowered and the film thickness cannot be earned for the exposure amount. The phenomenon occurs.

The photosensitive resin composition used in the present invention contains the above-mentioned gelatin and an organic curing agent as essential components, but any other conventionally known additives can be incorporated as required. In the present invention, the above essential components and optional additives are mixed with water or water and a water-soluble organic solvent such as alcohol to prepare a coating liquid. The amount of the solvent used varies depending on the type of gelatin used, the concentration of the phosphor and the coating method, but in general, a range of 20 to 80 wt% is good.

Phosphors that can be used in the present invention include red as Y ₂ O ₃ : Eu, Y ₂ SiO ₅ : Eu,
_{Y 3 Al 5 O 12: Eu} , Zn 3 (PO 4) 2: Mn, Y
BO ₃ : Eu, (Y, Gd) BO ₃ : Eu, GdB
O ₃ : Eu, ScBO ₃ : Eu, LuBO ₃ : Eu and the like, and Y ₂ SiO ₅ : Ce, CaWO ₄ : P as blue
b, BaMgAl ₁₄ O ₂₃ : Eu, etc., and Z as green
n ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, SrAl
_{13 O 19: Mn, CaAl 12} O 19: Mn, YBO 3: T
b, BaMgAl ₁₄ O ₂₃ : Mn, LuBO ₃ : Tb, G
dBO ₃ : Tb, ScBO ₃ : Tb, Sr ₆ Si ₃ O ₃
Cl ₄ : Eu, etc.

Such a phosphor may be added in an amount of about 10 to 100 parts by weight per 1 part by weight of the above gelatin.
More preferably, it is added in a proportion of 33 to 80 parts by weight. At this time, it should be noted that a large amount of resin causes an extremely large amount of exposure required for curing, resulting in deterioration of shape and insufficient film thickness.

To disperse the phosphor in the photosensitive resin composition, for example, a ball mill, a sand mill, a roll mill, a speed line mill or the like can be used, and the ball mill is particularly useful in the present invention.

As a method for applying a phosphor slurry composed of a photosensitive resin composition in which the above phosphor is dispersed on a substrate provided with a desired electrode, there are a doctor blade coating method, a myer bar coating method and a roll coating method. Known coating methods such as a screen coating method, a screen printing method, and a spinner coating method can be used, but the inclusion of air bubbles, the prevention of sedimentation of the phosphor, the prevention of the electrode damage due to the uneven electrode substrate, The doctor blade coating method is most suitable from the viewpoints of inclusion of bubbles and uniformity of coating amount. In particular, the electrodes on the substrate are generally formed in a stripe shape, and during coating, it is preferable to move the doctor blade along the stripes for coating. A smooth coating with a uniform film thickness can be realized without problems such as air bubble mixing, electrode damage, and coating unevenness.
The coating film formed as described above varies depending on the thickness of the electrode, but generally it is about 5 to 50 μm when dried.
A degree is preferable.

The respective steps and conditions such as drying of the coating film, curing by patterning exposure, elution of unexposed portion by development, and baking are as described above and as exemplified in the specific examples described later. There is no limitation and it may be the same as in the prior art.

Although the planar substrate of the DC type PDP has been described above, it is obvious that the same can be applied to the AC type PDP.

Next, a specific example of the above embodiment will be described in detail below.

[Specific Example A] A Ni electrode (9536D manufactured by DuPont) was used to print Ni electrodes with a width of 150 μm and a pitch of 500 μm on a glass substrate to be a front plate by a screen printing method. Firing was performed at 580 ° C. to form an anode. After washing the substrate, a phosphor having a green emission color (Chemical Optonics, Zn ₂
SiO ₄ : Mn): 29.5 wt%, gelatin: 1.7
wt%, pure water: 54.1 wt%, ethanol: 14.7
Formaldehyde condensate of p-diazodiphenylamine (D-01, manufactured by Shinko Giken Co., Ltd.)
4) A phosphor slurry obtained by adding 60 wt% of gelatin was applied to the entire surface with a blade coater at 30 ° C. so as to cover the electrodes, dried at room temperature, and then applied through a mask.
Ultraviolet rays with a maximum wavelength of around 50 nm are 59.2 mJ /
Exposure was carried out by irradiating with a dose of cm ² . At this time, irradiation was performed from the back surface side of the substrate so that a fluorescent screen was not formed on the electrodes. Then, the substrate was spray-developed with water to remove the unexposed portion. Then, it dried at 120 degreeC and hardened. Subsequently, a cell having a blue emission color (phosphor: BaMgAl ₁₄ O ₂₃ : Eu) and a cell having a red emission color (phosphor: (Y, Gd) B)
The above steps are repeated for O ₃ : Eu) to give about 4
The resin component (gelatin) and the curing agent (formaldehyde condensate of p-diazodiphenylamine) in the slurry were burned off by baking at 40 ° C. for 30 minutes, and red, green and blue were separately painted on the substrate excluding the electrodes. A phosphor screen was formed.

By combining the front plate having the phosphor screen and the rear plate having the cathode and the cell barrier separately, a matrix color PDP in which the three primary colors of red, green and blue are visually recognized is formed. PD created in this way
In P, a phosphor screen is formed on the back side of the front plate, and this phosphor screen is excited by ultraviolet rays generated by plasma discharge to emit light, and an observer visually recognizes the transmitted light of the phosphor screen.

Needless to say, a PDP having a line-shaped cell barrier as shown in FIG. 5 can also be formed by the same process.

[Specific Example B] Ni paste (manufactured by DuPont, 9536) was applied on a glass substrate by a screen printing method.
In D), Ni electrodes were printed with a width of 150 μm and a pitch of 500 μm, and after drying, firing was performed at 580 ° C. in the atmosphere to form an anode. After cleaning the substrate, a phosphor having a green emission color (Chemical Optonics, Zn ₂ SiO ₄ : M
n): 29.5 wt%, gelatin: 1.5 wt%, pure water: 69.0 wt% in a mixture of 4.4'-Diazido sty
lbene-2.2'disulfonic acid (Shinko Giken Co., A-
066) is added to the phosphor slurry by adding 55 wt% of gelatin to the entire surface with a blade coater at 30 ° C. so as to cover the electrodes, and after drying at room temperature, the maximum wavelength is set to around 350 nm through a mask. 52.5m ultraviolet light
Exposure was performed by irradiating with a dose of J / cm ² . At this time, irradiation was performed from the back surface side of the substrate so that a fluorescent screen was not formed on the electrodes. Then, the substrate was spray-developed with water to remove the unexposed portion. Then, it dried at 120 degreeC and hardened. Subsequently, a cell having a phosphor screen having a blue emission color (phosphor: BaMgAl ₁₄ O ₂₃ : Eu),
Phosphor screen cell with red emission color (phosphor: (Y, Gd)
The above steps are similarly repeated for BO ₃ : Eu), and the resin component (gelatin) and the curing agent (4.4′-Diazido stylbene-) in the slurry are obtained by baking at about 440 ° C. for 30 minutes.
2.2'disulfonic acid) was burned off, and red, green, and blue phosphor screens were separately formed on the substrate excluding the electrodes.

By combining the front plate having the phosphor screen and the rear plate having the cathode and the cell barrier separately, a matrix color PDP in which the three primary colors of red, green and blue are visually recognized is formed. PD created in this way
In P, a phosphor screen is formed on the back side of the front plate, and this phosphor screen is excited by ultraviolet rays generated by plasma discharge to emit light, and an observer visually recognizes the transmitted light of the phosphor screen.

[0039]

As described above, the method for forming a phosphor screen of a plasma display panel according to the present invention comprises a phosphor slurry prepared by dispersing a phosphor in a photosensitive resin composition containing gelatin and an organic curing agent. Since it was used to form a phosphor screen at a predetermined place by the photolithography method, regardless of the material of the electrode or cell barrier used in the previous step,
It is possible to form a fluorescent screen that is accurately patterned and has a uniform film thickness. Therefore, it becomes possible to use a ready-made electrode paste or cell barrier paste, the use of which has been restricted due to difficulty in forming a fluorescent screen due to products and residues.

Further, even when the low melting point glass is mixed with the phosphor slurry in order to improve the adhesive force between the fluorescent substance and the glass substrate, the photolithography process is not hindered by the components in the low melting point glass, so that it can be used. The range of low melting point glass is widened.

Further, by applying the phosphor slurry by the doctor blade coating method in combination with the above method, even if the substrate is a large size, for example, a meter size, and the surface of the substrate is roughened by electrodes, It is possible to realize a coating having a uniform film thickness over the whole.

Color display is also possible by selectively forming the phosphor screen with phosphors having red, green and blue emission colors.

[Brief description of drawings]

FIG. 1 is a process chart showing an embodiment of a phosphor screen forming method of a plasma display panel according to the present invention.

FIG. 2 is a partial cross-sectional view showing an example of a DC type plasma display panel.

FIG. 3 is a partial cross-sectional view showing an example of an AC type plasma display panel.

FIG. 4 is a partially cutaway perspective view showing a DC type plasma display panel in which a cell barrier has a matrix shape, with a front plate and a rear plate thereof being separated from each other.

FIG. 5 is a partially cutaway perspective view showing a DC type plasma display panel having linear cell barriers with a front plate and a rear plate separated from each other.

[Explanation of symbols]

 1 substrate 2 electrode 3 phosphor slurry 4 mask 5 ultraviolet ray 6 phosphor layer 7 phosphor surface

Claims (6)

[Claims] 1. A phosphor slurry in which a phosphor is dispersed in a photosensitive resin composition is applied to a surface on which a phosphor screen is to be formed, and the phosphor screen is exposed at a predetermined position through exposure, development and baking steps. A method for forming a phosphor screen of a plasma display panel, wherein the photosensitive resin composition is composed of gelatin and an organic curing agent. 2. The method for forming a phosphor screen of a plasma display panel according to claim 1, wherein the organic curing agent is a diazonium type curing agent. 3. The method for forming a phosphor screen of a plasma display panel according to claim 1, wherein the organic curing agent is a formaldehyde condensate of p-diazodiphenylamine. 4. The method for forming a phosphor screen of a plasma display panel according to claim 1, wherein the organic curing agent is a bisazide type curing agent. 5. The method according to claim 1, 2, 3 or 4, wherein the phosphor slurry is applied by a doctor blade coating method. 6. The phosphors having red, green and blue emission colors are repeatedly coated with phosphor slurry, selectively exposed through a mask, and developed, respectively. The method for forming a phosphor screen of a plasma display panel according to 3, 4, or 5.