JP4747603B2 - Method for manufacturing member for plasma display panel and plasma display using the same - Google Patents

Description

The present invention relates to a manufacturing method and plasma display Lee plasma display panel member.

  Plasma display panels (hereinafter sometimes referred to as PDPs) can display at a higher speed than liquid crystal panels, and are easy to increase in size, so that they have penetrated into fields such as OA equipment and public information display devices. . Furthermore, progress in the field of high-definition television is highly expected. Accompanying such expansion of applications, a fine color PDP having a large number of display cells has attracted attention.

  The PDP generates a plasma discharge between electrodes in a discharge space provided between a front glass substrate and a back glass substrate, and emits ultraviolet rays generated from the gas enclosed in the discharge space to fluoresce in the discharge space. The display is performed by touching the body. In a typical PDP, the front glass substrate has scan electrodes, sustain electrodes, and dielectric layers on the substrate, and the back glass substrate has address electrodes, dielectric layers, barrier ribs, and phosphor layers on the substrate. Yes. In driving the PDP, scan pulses are sequentially applied to the scan electrodes, and in accordance with this timing, data pulses having a polarity opposite to the scan pulse corresponding to the display data are applied to the address electrodes of the display cells corresponding to the scan electrodes. The discharge is maintained by the sustain pulse applied to the sustain electrode.

  In recent years, in order to improve the performance of PDP, a reflective layer made of a white pigment is provided between the phosphor layer and the barrier rib (for example, Patent Documents 1 and 2), and the purity of the inert gas around the PDP phosphor is increased. In order to improve light emission luminance, it has been proposed to provide a gas adsorption layer made of white porous inorganic powder for adsorbing moisture generated from the substrate and carbon dioxide (for example, Patent Document 3).

  Further, a phosphor made of a compound containing magnesium oxide is provided on the phosphor layer in order to avoid phosphor deterioration (sputtering or alteration of the phosphor surface) due to plasma damage of the PDP and to realize a long-life PDP. Providing a protective layer has also been proposed (for example, Patent Document 4).

However, when a reflective layer made of a white inorganic powder is provided between the phosphor layer and the barrier layer, the reflective layer and the phosphor layer are usually white. Until it was seen, it could not be found, and there was a problem that the production yield of PDP was lowered. Even when a phosphor protective layer is formed on the phosphor layer, since the layer usually contains magnesium oxide, the phosphor protective layer is also white, and there is no means for easily confirming defects. It has been difficult to produce a PDP with a high yield.
In order to solve such a problem, it is known that the phosphor layer is colored with an organic dye (Patent Document 5). However, since the phosphor powder, particularly the blue phosphor powder for PDP, is prone to thermal degradation, a problem has been pointed out that it deteriorates to lower the luminance (Non-patent Document 1). That is, when the paste forming the phosphor layer contains an organic dye, the phosphor deteriorates due to rapid heat generation when the organic dye is burned off in the firing step, causing a reduction in the luminous efficiency of the PDP. Since this tendency is particularly remarkable in a blue phosphor, the color balance may be lowered.
Japanese Patent No. 3196665 Japanese Patent No. 2815012 JP 2002-324492 A JP 2004-179099 A JP 2000-104052 A J. et al. Electrochem. (Journal of the Electrochemical Society), 145, 3903 (1998)

  In view of the above-described prior art, an object of the present invention is to provide a method for manufacturing a high-quality, high-quality member for a plasma display panel.

If the paste material used for forming layers other than the phosphor layer is optically distinguishable from the paste used for the phosphor layer, the present inventors can solve the above problem, and the phosphor ( It was found that high-performance and high-yield manufacturing of the PDP can be realized without causing any deterioration in luminance (especially blue). That is, the gist of the present invention is that a phosphor layer and a layer other than the phosphor layer are formed between the side wall and / or between the barrier ribs on a member having at least an electrode and barrier ribs formed on a substrate. At this time, these layers are formed by applying a paste material, drying and / or firing, and the paste used for forming the layers other than the phosphor layer includes a paste used for forming the phosphor layer and Are colored in different colors and are titanium oxide, zinc oxide, zinc sulfide, barium oxide, magnesium oxide, calcium oxide, zirconia, tin oxide, glass powder having a melting point of 620 ° C. or higher, lithium fluoride, calcium fluoride, alumina and includes at least one selected from the group consisting of silica, the use of paste containing a coloring agent selected from the further organic dyes and pigments A method for manufacturing a plasma display panel member according to symptoms, also proposes various preferred embodiments.

  According to the present invention, there is little deterioration of the phosphor, and a high-quality PDP member can be obtained with a high yield.

  Below, this invention is demonstrated along the preparation procedure of PDP.

  As a substrate used for manufacturing the plasma display panel member of the present invention, in addition to soda glass, “PD200” manufactured by Asahi Glass Co., Ltd., which is a high strain point glass with little thermal deformation and thermal shrinkage for PDP, manufactured by Nippon Electric Glass Co., Ltd. “PP8” or the like can be used. Note that the material is not limited to glass as long as it has heat resistance and dimensional stability and has a high volume resistivity, and ceramic, metal, or the like can also be used.

  Address electrodes are formed on the substrate with a metal such as silver, aluminum, chromium, or nickel. As a method for forming an electrode, a metal paste mainly composed of these metal powders and an organic binder is printed in an electrode pattern by screen printing, or a photosensitive metal paste using a photosensitive organic component as an organic binder. A photosensitive paste method in which an electrode pattern is exposed to light using a photomask, unnecessary portions are dissolved and removed in a development process, and further heated and baked at 400 to 600 ° C. to form an electrode pattern. Can be used. Further, after sputtering a metal such as chromium or aluminum on a glass substrate, a resist is applied, the resist is exposed to an electrode pattern, and after development, an etching method is used to remove unnecessary portions of the metal by etching. it can. The electrode thickness is preferably 1 to 10 μm, and more preferably 2 to 5 μm. If the electrode thickness is too thin, the resistance value tends to be large and accurate driving tends to be difficult. If it is too thick, a large amount of material is required, which tends to be disadvantageous in terms of cost. The width of the address electrode is preferably 20 to 200 μm, more preferably 30 to 100 μm. If the width of the address electrode is too thin, the resistance value tends to be high and accurate driving tends to be difficult, and if it is too thick, the distance between adjacent electrodes tends to be small, so that a short defect tends to occur. Further, the address electrodes are formed at a pitch corresponding to the display cell (region where each RGB of the pixel is formed). The pitch is preferably 100 to 500 μm for a normal PDP and 100 to 250 μm for a high definition PDP.

Next, a dielectric layer is formed as necessary. The dielectric layer can be formed by applying a glass paste containing glass powder and an organic binder as main components so as to cover the address electrodes and then baking at 400 to 600 ° C. The glass powder used for the glass paste used for forming the dielectric layer contains at least one of lead oxide, bismuth oxide, zinc oxide and phosphorus oxide, and these are 20% by mass or more based on the whole glass powder. By doing so, firing at 600 ° C. or less becomes easy, and by setting it to 80% by mass or less, crystallization can be prevented and a decrease in transmittance can be prevented. Examples of the organic binder that can be used include cellulose compounds such as ethyl cellulose and methyl cellulose, and acrylic compounds such as methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, methyl acrylate, ethyl acrylate, and isobutyl acrylate. Moreover, you may add additives, such as a solvent and a plasticizer. As the solvent, a solvent such as terpineol, butyrolactone, toluene, or methyl cellosolve can be used. As the plasticizer, dibutyl phthalate, diethyl phthalate, or the like can be used. By adding a filler component in addition to the glass powder, a PDP having a high reflectance and a high luminance can be obtained. As the filler, titanium oxide, aluminum oxide, zirconium oxide and the like are preferable, and it is particularly preferable to use titanium oxide having a center particle diameter (D ₅₀ ) of 0.05 to 3 μm. The filler content is preferably a glass powder: filler ratio of 1: 1 to 10: 1. The brightness can be improved by setting the filler content to 1/10 or more of the glass powder. Moreover, sinterability can be maintained by setting it as below equal amount of glass powder. Further, by adding conductive fine particles, a PDP with high reliability during driving can be manufactured. The conductive fine particles are preferably metal powders such as nickel and chromium, and the center particle diameter (D ₅₀ ) is preferably 1 to 10 μm. When the thickness is 1 μm or more, a sufficient effect can be exhibited, and when the thickness is 10 μm or less, unevenness on the dielectric can be suppressed and partition formation can be facilitated. As content in which these electroconductive fine particles are contained in a dielectric material layer, 0.1-10 mass% is preferable. Effectiveness can be obtained when the content is 0.1% by mass or more, and short-circuiting between adjacent address electrodes can be prevented when the content is 10% by mass or less. The thickness of the dielectric layer is preferably 3 to 30 μm, more preferably 3 to 15 μm. If the thickness of the dielectric layer is too thin, pinholes tend to occur frequently, and if it is too thick, the discharge voltage tends to be high and the power consumption tends to increase. The glass paste used to form the dielectric layer can be prepared by kneading the above-described glass powder and components such as an organic binder.

  In the member for a plasma display panel according to the present invention, a partition wall for partitioning discharge cells is formed on a substrate on which an electrode is formed or a substrate on which an electrode or a dielectric layer is formed. In addition to the main partition provided substantially parallel to the address electrode, the partition can form an auxiliary partition. By forming the auxiliary barrier rib, a phosphor layer can also be formed on the surface of the auxiliary barrier rib, and the light emitting area can be increased. Accordingly, it is possible to increase the luminance because the ultraviolet rays efficiently act on the phosphor screen. Further, the presence of the auxiliary partition wall increases the bonding area of the entire partition wall, and the structural strength of the member can be obtained. As a result, the width of the barrier ribs and auxiliary barrier ribs can be reduced, the discharge volume in the display cell portion can be increased, and the discharge efficiency can be further improved.

  The height of the main partition wall is suitably 80 μm to 200 μm. By setting the thickness to 80 μm or more, the phosphor and the scan electrode can be prevented from being too close to each other, and the phosphor can be prevented from being deteriorated by discharge. Moreover, sufficient brightness | luminance can be obtained by setting it as 200 micrometers or less. The pitch (P) of the main partition walls is often 100 μm ≦ P ≦ 500 μm. In the high-definition plasma display, the main partition pitch (P) is 100 μm ≦ P ≦ 250 μm. By setting the thickness to 100 μm or more, the discharge space can be widened and sufficient luminance can be obtained, and by setting the thickness to 500 μm or less, a fine image with fine pixels can be displayed. By setting it to 250 μm or less, it is possible to display a beautiful video of HDTV (high definition) level. The width (L) of the main partition wall is preferably 10 μm ≦ L ≦ 50 μm as a half-value width (width at 50% height of the partition wall). By setting the thickness to 10 μm or more, strength can be maintained, and damage can be prevented from occurring when the front plate and the back plate are sealed. Moreover, the area | region which can form a fluorescent substance layer can be taken widely by setting it as 50 micrometers or less, and high brightness | luminance can be obtained.

  The height of the auxiliary partition is preferably lower than the height of the main partition, and more preferably 1/2 to 5/6 of the height of the main partition. By setting the height of the auxiliary partition wall to ½ or more of the height of the main partition wall, the light emission area can be increased and the luminance can be improved. In addition, the phosphor layer can be easily formed by making it lower than the main barrier rib.

  For example, the main partition wall and the auxiliary partition wall may be formed by applying and drying a photosensitive paste made of an organic component including inorganic fine particles and a photosensitive component on the substrate, exposing and developing the pattern of the partition walls, and then baking. Can be formed. In addition, glass paste is printed and dried by screen printing, this process is repeated many times, and after a predetermined height, it is fired, formed by sand blasting or liquid honing via a subtractive mask layer formed by photolithography You can also

  In the present invention, the phosphor layer and the layer other than the phosphor layer are formed on the side surface of the barrier rib and / or the member having the electrode, the dielectric layer if necessary, and the barrier rib at least formed on the substrate. Alternatively, it is formed between the partition walls.

The phosphor layer is formed by alternately arranging three layers each containing phosphors that usually emit red, green, and blue light. Here, when the thickness of the red phosphor layer is Tr, the thickness of the green phosphor layer is Tg, and the thickness of the blue phosphor layer is Tb,
10 μm ≦ Tr <Tb ≦ 50 μm
10 μm ≦ Tg <Tb ≦ 50 μm
Thus, the thickness of the blue light emitting luminance is made thicker than that of green and red, so that a plasma display panel having a better color balance (high color temperature) can be produced. When the thickness of the phosphor layer is 10 μm or more, sufficient luminance can be obtained. Further, by setting the thickness to 50 μm or less, a wide discharge space can be obtained and high luminance can be obtained. In the present invention, the phosphor layer is not limited to a combination of three colors of red, green, and blue.
The phosphor layer can be formed by applying a phosphor paste prepared by using a phosphor as an organic binder and an organic solvent as main components, and between the side walls of the barrier ribs and / or between the barrier ribs. Examples of the method for applying the phosphor paste include a screen printing method, a method for ejecting the phosphor paste from the die, and a photosensitive paste method. Among these, the method for ejecting the phosphor paste from the die is simple and low. It is preferable because a member for plasma display can be obtained at low cost.

  In the present invention, layers other than the phosphor layer formed between the partition walls and / or between the partition walls may be formed below or above the phosphor layer. Of course, it can be formed on both the upper and lower sides. In addition, it is permissible to form two or more layers for each (in this case, the paste is preferably colored so that the color of the paste used in forming each layer is different).

  Examples of the case where it is formed on the lower side of the phosphor layer include a case where it is formed as a reflection layer for reflecting generated fluorescence in a visually recognizable direction and a gas adsorption layer for adsorbing water vapor generated from the substrate.

  The paste used to form such a reflective layer or gas adsorption layer usually contains at least an inorganic powder, a binder resin, and a solvent.

Examples of the inorganic powder include titanium oxide, zinc oxide, zinc sulfide, barium oxide, magnesium oxide, zirconia, calcium oxide, tin oxide, glass powder having a melting point of 620 ° C. or higher, lithium fluoride, calcium fluoride, alumina, and silica. An inorganic powder containing at least one of the group can be preferably used. The particle diameter is such that the center particle diameter (D ₅₀ ) is in the range of 0.05 to 5 μm, and the maximum particle diameter is 10 μm or less. More preferably, the center particle diameter (D ₅₀ ) is in the range of 0.1 to 3 μm, and the maximum particle diameter is 8 μm or less. When the center particle size and the maximum particle size are within this range, a smooth surface can be obtained. When the average particle size is larger than this range, the surface irregularities become large. When the average particle size is smaller than this range, the flow characteristics of the paste may be poor, and the application may not proceed smoothly.

  Moreover, the denseness of a reflective layer or a gas adsorption layer can be improved by using a glass powder having a softening point of 350 to 600 ° C. as an inorganic powder other than the above. The softening point is preferably 400 to 550 ° C. As a glass powder having a softening point of 350 to 600 ° C., the composition containing 20 to 90% by mass of at least one of bismuth oxide, lead oxide, and zinc oxide as its composition is easy to control the softening point and the thermal expansion coefficient. It is preferably used in terms of points. When the content of these components exceeds 90% by mass, the heat-resistant temperature of the glass is lowered, which is not preferable in terms of baking onto a glass substrate, and when the content is less than 20% by mass, the baking temperature and the softening point are not achieved. The control effect tends to be small. It is also effective to contain silicon oxide, boron oxide, zirconium oxide, etc. as other components contained in this glass powder.

  It is preferable that silicon oxide is contained in the range of 5-40 mass% as a composition in glass powder. If it is less than 5% by mass, the denseness, strength and stability of the layer formed below the phosphor layer (for example, the reflective layer or the gas adsorbing layer) are lowered, and the thermal expansion coefficient is out of the preferred range. And thermal expansion coefficient mismatch, which may cause defects such as bending of the substrate and cracking of the formed layer. If it exceeds 40% by mass, the softening point and glass transition point will rise, making it difficult to form a dense layer, and bubbles will remain, which tends to lower the electrical insulation.

  Boron oxide is preferably contained in the glass powder in the range of 5 to 30% by mass as its composition. By setting it within this range, electrical, mechanical and thermal characteristics such as electrical insulation, strength, thermal expansion coefficient, and denseness can be improved. If it exceeds 30% by mass, the stability of the glass tends to decrease.

  Zirconium oxide is preferably contained in the glass powder in the range of 3 to 10% by mass as its composition. By including zirconium oxide in such a range, the acid resistance of a layer (for example, a reflective layer or a gas adsorption layer) formed under the phosphor layer can be improved, so that the storage stability of the glass paste can be improved. If it is less than 3% by mass, the effect of improving the storage stability is small, and if it exceeds 10% by mass, it becomes difficult to form the layer as a dense layer, and baking onto a glass substrate becomes difficult.

  In addition to the above, the glass powder may contain phosphorus oxide, lithium oxide, potassium oxide, sodium oxide, barium oxide, aluminum oxide, magnesium oxide, and the like as necessary.

  As the binder resin, it can be mixed with the inorganic powder to the extent that it can be applied to the substrate, there is no problem in fluidity when applied to the substrate, and the shape retention when applied to the substrate. As long as there is no problem in properties, there is no particular limitation, but it is preferable that no carbon-containing substance remains after firing. Specifically, ethyl cellulose, methyl cellulose, nitrocellulose, cellulose acetate, cellulose propionate , Cellulose resins such as cellulose butyrate, hydroxypropyl cellulose, or methyl (meth) acrylate, ethyl (meth) acrylate, normal butyl (meth) acrylate, isobutyl (meth) acrylate, isopropyl (meth) acrylate, 2-ethyl Methyl (meth) acrylate, 2-hydroxylethyl Acrylic resin comprising a polymer or copolymer of meth) acrylate, poly -α- methyl sulfone, polyvinyl alcohol, polybutene, and the like.

  The organic solvent is not particularly limited as long as it dissolves or disperses the binder resin. For example, diethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol mono- 2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, 2-ethyl-1,3-hexanediol, terpineol, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol-n-propyl ether , Dipropylene glycol-n-propyl ether, propylene glycol-n Butyl ether, propylene glycol methyl ether acetate, propylene glycol diacetate, propylene glycol phenyl ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentane Diol diisobutyrate, dipropylene glycol-n-butyl ether, tripropylene glycol-n-butyl ether, dipropylene glycol dimethyl ether and the like and isopropyl alcohol, n-propyl alcohol, sec-butyl alcohol, isobutyl alcohol, 3-pentanol, n- Butyl alcohol, sec-butyl alcohol, isoamyl alcohol, methyl amyl alcohol, n-amyl alcohol, methyl n-butyl ether, 1,4-dioxa , Diethyl cellosolve, n-butyl ether, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, diethyl carbonate, isoamyl acetate, methyl cellosolve acetate, methyl amyl acetate, ethyl lactate, propylene glycol methyl ether, propylene glycol propyl ether, Examples include 2-hydroxy-4-methyl-2-pentanone, 2-methyl-1-butanol, 3-methyl-2-butanol, and γ-butyllactone.

  Moreover, as an example in the case of forming on the upper side of the phosphor layer, there is a case in which it is formed as a phosphor protective layer that protects the phosphor from the discharge generated in the discharge space.

  The paste used for forming such a phosphor protective layer usually contains at least an inorganic powder, a binder resin, and a solvent.

Examples of the inorganic powder include magnesium oxide, calcium oxide, calcium fluoride, and lithium fluoride. The particle diameter is such that the center particle diameter (D ₅₀ ) is in the range of 0.05 to 5 μm, and the maximum particle diameter is 10 μm or less. More preferably, the center particle diameter (D ₅₀ ) is in the range of 0.1 to 3 μm, and the maximum particle diameter is 8 μm or less. When the center particle size and the maximum particle size are within this range, a smooth surface can be obtained. When the maximum particle size is larger than this range, the surface unevenness becomes large, and when the center particle size is smaller than this range, the flow characteristics of the paste become poor, which may cause a problem during application.

  Moreover, the denseness of a fluorescent substance protective layer can be improved by containing glass powder with a softening point of 350-600 degreeC other than said inorganic powder. Preferably, the softening point is 400 to 550 ° C. The glass powder having a softening point of 350 to 600 ° C. contains 20 to 90% by mass of at least one of bismuth oxide, lead oxide, and zinc oxide as its composition. It is preferably mentioned in terms of easy control. When the content of these components exceeds 90% by mass, the heat-resistant temperature of the glass is lowered, which is not preferable in terms of baking onto a glass substrate, and when the content is less than 20% by mass, the baking temperature and the softening point are not achieved. It is less effective to control. It is also effective to contain silicon oxide, boron oxide, zirconium oxide, etc. as other components contained in this glass powder.

  It is preferable that silicon oxide is contained in the range of 5-40 mass% as a composition in glass powder. If the amount is less than 5% by mass, the denseness, strength and stability of the layer formed on the upper side of the phosphor layer (for example, the phosphor protective layer) will be reduced, causing a mismatch between the glass substrate and the coefficient of thermal expansion, and bending the substrate. Defects such as cracks in the formed layer may occur. If it exceeds 40% by mass, the softening point and glass transition point will rise and it will be difficult to form a dense layer, and bubbles will remain and electrical insulation will tend to be reduced.

  Boron oxide is preferably contained in the glass powder in the range of 5 to 30% by mass as its composition. By setting it within this range, electrical, mechanical and thermal characteristics such as electrical insulation, strength, thermal expansion coefficient, and denseness can be improved. If it exceeds 30% by mass, the stability of the glass tends to decrease.

  Zirconium oxide is preferably contained in the range of 3 to 10% by mass as the composition of the element in the glass powder. By including zirconium oxide in such a range, the acid resistance of a layer (for example, phosphor protective layer) formed on the upper side of the phosphor layer can be improved, so that the storage stability of the glass paste can be improved. If it is less than 3% by mass, the effect of improving the storage stability is small, and if it exceeds 10% by mass, it becomes difficult to form the layer as a dense layer, and baking onto a glass substrate becomes difficult.

  In addition to the above, the glass powder may contain phosphorus oxide, lithium oxide, potassium oxide, sodium oxide, barium oxide, aluminum oxide, magnesium oxide, and the like as necessary.

  The binder resin can be mixed with the inorganic powder to the extent that it can be applied to the substrate, there is no problem with the fluidity when applied to the substrate, and the shape retention when applied to the substrate. If there is no problem, there is no particular limitation, but after firing, it is preferable that the carbon-containing substance does not remain in the inorganic material, specifically, ethyl cellulose, methyl cellulose, nitrocellulose, cellulose acetate, Cellulose resins such as cellulose propionate, cellulose butyrate, hydroxypropyl cellulose, or methyl (meth) acrylate, ethyl (meth) acrylate, normal butyl (meth) acrylate, isobutyl (meth) acrylate, isopropyl (meth) acrylate 2-ethylmethyl (meth) acrylate, 2-hydroxy Ruechiru (meth) acrylate polymer or copolymer made of acrylic resin, polymethyl -α- methyl sulfone, polyvinyl alcohol, polybutene, and the like.

  The organic solvent is not particularly limited as long as it dissolves the binder resin. For example, diethylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol mono-2 -Ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, 2-ethyl-1,3-hexanediol, terpineol, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol-n-propyl ether, Dipropylene glycol-n-propyl ether, propylene glycol-n-butyl Ether, propylene glycol methyl ether acetate, propylene glycol diacetate, propylene glycol phenyl ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentane Diol diisobutyrate, dipropylene glycol-n-butyl ether, tripropylene glycol-n-butyl ether, dipropylene glycol dimethyl ether and the like and isopropyl alcohol, n-propyl alcohol, sec-butyl alcohol, isobutyl alcohol, 3-pentanol, n- Butyl alcohol, sec-butyl alcohol, isoamyl alcohol, methyl amyl alcohol, n-amyl alcohol, methyl n-butyl ether, 1,4-dioxane, die Lucerosolve, n-butyl ether, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, diethyl carbonate, isoamyl acetate, methyl cellosolve acetate, methyl amyl acetate, ethyl lactate, propylene glycol methyl ether, propylene glycol propyl ether, 2- Examples include hydroxy-4-methyl-2-pentanone, 2-methyl-1-butanol, 3-methyl-2-butanol, and γ-butyllactone.

  In the present invention, the paste used for forming layers other than the phosphor layer is colored in a different color from the paste used for forming the phosphor layer. The paste can be colored by adding a colorant to the paste containing at least the above-described inorganic powder, binder resin and solvent. Examples of the colorant include organic dyes and pigments.

  The organic dye is not particularly limited as long as it can be colored so as to be optically distinguishable with respect to the paste used for forming the phosphor layer, but is preferably identifiable under visible light, Those that do not remain after are preferred. For example, it is preferable to use a material having a weight retention at 500 ° C. of 1% by mass or less measured under the following conditions. This weight retention rate was raised from 30 ° C. to 500 ° C. at 10 ° C./min under an air atmosphere (flow rate: 20 ml / min) using a thermogravimetric measuring device (“TGA50” manufactured by Shimadzu Corporation). Measure the weight at temperature. Weight retention at 500 ° C. by determining the ratio ((weight at 30 ° C.) / (Weight at 500 ° C.) × 100 (%)) of weight at 500 ° C. to weight at 30 ° C. Calculate the rate. By using a material having a weight retention of 1% or less, it is possible to reduce firing residue and to suppress problems such as abnormal discharge and reduced brightness such as abnormal discharge. The weight retention at 500 ° C. is preferably 0.5% or less, more preferably 0.2% or less.

  Specific examples of organic dyes include nitro and nitroso dyes, azo dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, quinoline dyes, benzoquinone dyes, naphthoquinone dyes, phthalicid dyes, and perinone dyes. Can be mentioned. It is preferable from the point that the weight retention at 500 ° C. is 1% or less, and at least one selected from nitro and nitroso dyes, azo dyes, indigoid dyes, phthalocyanine dyes, carbonium dyes, and methine dyes can be used.

In order to prevent the organic dye from remaining after firing, it is preferable to use as small an amount as possible. However, in order to detect defects in an image inspection apparatus, a phosphor paste is applied, a dried film, and a phosphor layer A paste colored in a color different from that of the paste used to form the phosphor used to form the layers other than the above was applied, and the dried films were obtained from the L ^* a ^* b ^* color system color coordinates of these films. The color difference (ΔE ^* _ab ) is preferably added so as to satisfy the following conditions. That is,
ΔE ^* _ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2 > 1.5
And more preferably
ΔE ^* _ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2 > 6.0
It is.

Here, ΔL *, Δa *, and Δb * are the L * value, a * value, and b * value of the film after applying and drying the paste for forming the phosphor layer, and the formation of layers other than the phosphor layer, respectively. This represents the difference between the L * value, a * value, and b * value of the film after application and drying of the paste used in the above. That is,
ΔL * = L * value (film after application / drying of paste used for forming phosphor layer) −L * value (film after application / drying of paste used for forming layers other than phosphor layer),
Δa * = a * value (film after application / drying of paste used to form phosphor layer) −a * value (film after application / drying of paste used to form layers other than phosphor layer),
Δb * = b * value (film after application / drying of paste used for forming phosphor layer) −b * value (film after application / drying of paste used for forming layers other than phosphor layer) .

  Examples of a method for applying a paste used for forming a layer other than the phosphor layer to the side surfaces of the partition walls and / or between the partition walls include a screen printing method, a method of discharging the phosphor paste from the base, and the like. A method of discharging a paste, particularly a method of applying with a dispenser is simple and preferable.

  The thickness of the layers other than the phosphor layer formed between the partition wall surface and / or the partition wall according to the present invention is not particularly limited, but when it is formed below the phosphor layer such as a reflective layer or a gas adsorption layer, It is preferable that it is -50 micrometers, More preferably, it is 1-15 micrometers. By setting it as this range, a desired effect can be acquired, without affecting a fluorescent substance layer. When formed on the top of a phosphor layer such as a phosphor protective layer, the thickness thereof is preferably in the range of 1 to 20 μm, more preferably 1 to 5 μm. By setting it as this range, while transmitting the light emission of fluorescent substance with sufficient intensity | strength, effects, such as protecting a fluorescent substance layer effectively, can be acquired.

  The layers other than the phosphor layer and the phosphor layer are formed by applying a layer used for forming the layer and then drying and / or firing. This drying and / or calcination may be performed together after applying these layers, or may be performed separately. Drying is sufficient as long as the solvent can be sufficiently removed, and is usually performed in the range of −50 ° C. to + 50 ° C. of the boiling point of the solvent. Examples of the firing conditions include a temperature of 400 ° C. to 550 ° C. to 600 ° C.

  This plasma display member is sealed with a member that forms another surface, and then a discharge gas composed of helium, neon, xenon, etc. is sealed in a space formed between these members, and a drive circuit is mounted. Can produce plasma displays. When the plasma display member of the present invention is used as a back plate, a member forming another surface (that is, a front plate) is, for example, a transparent electrode, a bus electrode, a dielectric, a protective film in a predetermined pattern on the substrate. It is a member formed with (MgO).

  In the method for producing a member for a plasma display according to the present invention, the electrode layer, the dielectric layer, the barrier rib, the side wall of the barrier rib, and / or the layers other than the phosphor layer formed between the barrier ribs and / or the barrier ribs. In addition, other configurations such as a color filter layer and a black stripe may be formed. The color reproducibility is improved by forming the color filter layer, and the contrast can be improved by forming the black stripe.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples.

Example 1
First, a front plate was produced. A scan electrode having a pitch of 375 μm and a line width of 150 μm was formed on a glass substrate PD200 manufactured by Asahi Glass Co., Ltd. using indium tin oxide (ITO). Further, after applying a photosensitive silver paste on the substrate, mask exposure through a photomask, development using a 0.3 mass% sodium carbonate aqueous solution, and a baking process at 580 ° C. for 15 minutes, a line width of 50 μm. A bus electrode having a thickness of 3 μm was formed.

  Next, a glass paste obtained by kneading 70% by mass of a low-melting glass powder containing 75% by mass of lead oxide, 20% by mass of ethyl cellulose, and 10% by mass of terpineol is screen-printed to obtain a bus electrode for the display portion. After coating to a thickness of 50 μm, firing was performed at 570 ° C. for 15 minutes to form a front dielectric layer.

  A front plate was prepared by forming a 0.5 μm thick magnesium oxide layer as a protective film by electron beam evaporation on the substrate on which the dielectric layer was formed.

  Next, a back plate was produced. Address electrodes were formed on the glass substrate PD200 described above using a photosensitive silver paste. A photosensitive silver paste was applied, dried, exposed, developed, and baked to form address electrodes having a line width of 50 μm, a thickness of 3 μm, and a pitch of 250 μm.

Next, 60% by mass of low melting point glass powder containing 75% by mass of bismuth oxide, 10% by mass of titanium oxide powder having a center particle diameter (D ₅₀ ) of 0.3 μm, 15% by mass of ethyl cellulose, and 15% by mass of terpineol. The glass paste obtained by kneading was applied with a thickness of 50 μm by screen printing so as to cover the address electrodes of the display portion, and then baked at 570 ° C. for 15 minutes to form a dielectric layer.

A first photosensitive paste was applied on the dielectric layer. The photosensitive paste is composed of glass powder and an organic component containing a photosensitive component. As glass powder, lithium oxide 10% by mass, silicon oxide 25% by mass, boron oxide 30% by mass, zinc oxide 15% by mass, aluminum oxide 5% by mass. %, And a glass powder having a center particle diameter (D ₅₀ ) of 2 μm obtained by pulverizing glass having a composition of 15% by mass of calcium oxide. As an organic component containing a photosensitive component, acrylic polymer (APX-714, manufactured by Toray Industries, Inc.) 30% by mass, trimethylolpropane triacrylate 30% by mass, “Irgacure 369” (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator ) 10% by mass and 30% by mass of γ-butyrolactone were used.

  The photosensitive paste was prepared by mixing the glass powder and the organic component containing the photosensitive component at a mass ratio of 70:30, and then kneading them with a roll mill. Next, this photosensitive paste was applied to a thickness of 90 μm after drying using a die coater. Drying was performed using a clean oven (manufactured by Yamato Scientific Co., Ltd.).

  After drying, exposure was performed using a photomask having a stripe pattern with a pitch of 250 μm and a line width of 30 μm so that the stripe pattern was perpendicular to the address electrodes.

  After the exposure, the photosensitive paste was further applied and dried to obtain a 90 μm coating film.

  Next, using a photomask having a stripe pattern with a pitch of 250 μm and a line width of 30 μm, exposure was performed so that the stripe pattern was parallel to the address electrodes.

  After the exposure, development is performed in a 0.5% by mass aqueous ethanolamine solution, and further baking is performed at 560 ° C. for 15 minutes, whereby a main partition wall having a pitch of 250 μm, a line width of 30 μm, and a height of 130 μm, a pitch of 250 μm, a line width of 30 μm, An auxiliary partition wall having a height of 65 μm was formed.

Next, 70 mass% of titanium oxide (TIPAQUE CR-90, manufactured by Ishihara Sangyo Co., Ltd.), ethyl cellulose (manufactured by Hercules Co., Ltd.), and organic dye (Sudan III, C ₂₂ H ₁₆ N ₄ O) dissolved in terpineol Dispensing the paste obtained by mixing 30% by mass of vehicle (solid content concentration: 10% by mass, organic dye concentration: 0.1% by mass when the organic vehicle is 100 parts by mass) and kneading with three rollers Using the method, a paste layer serving as a reflective layer was formed by discharging between the side walls and the partition walls of the main partition wall and the auxiliary partition wall. The paste layer was formed to have a thickness after firing of 8 μm on the side wall of the partition and 6 μm on the dielectric layer. After formation, inspection was performed using an image inspection apparatus (Neptune 900, manufactured by V Technology Co., Ltd.), and coating omission defects could be detected at three locations. The defective part was repaired.

The pastes for forming the phosphor layers are red, blue and green phosphor powders, respectively, red phosphor powder: (Y, Gd, Eu) BO ₃ (BO ₃ salt matrix with Y, Gd, Eu) Activated substance), blue phosphor powder: (Eu) BaMgAl ₁₀ O ₁₇ (a substance obtained by activating Eu in a BaMgAl ₁₀ O ₁₇ salt matrix), green phosphor powder: (Mn) Zn ₂ SiO ₄ (Zn ₂ SiO ₍₄ ) A substance in which Mn is activated in a salt matrix), and a paste for forming phosphor layers of each color is an organic vehicle in which ethyl cellulose (manufactured by Hercules Co.) is dissolved in terpineol with respect to 70 parts by mass of the phosphor powder. A solid content concentration of 10% by mass) was prepared by kneading 30 parts by mass with three rollers.

  This phosphor layer forming paste is ejected from the tip of a nozzle having 256 holes (caliber: 130 μm) using a dispenser method so that the thickness after firing is 20 μm on the paste film to be a reflective layer. Thus, a paste layer serving as a phosphor was formed. After the application, inspection was performed using an image inspection apparatus (Neptune 900, manufactured by V Technology Co., Ltd.). As a result, 8 coating defect defects of the phosphor layer forming paste could be detected. The defective part was repaired.

Note that ΔE ^* ab is measured with a spectrocolorimeter (CM-2002, manufactured by MINOLTA) for the film after application / drying of the paste for forming the reflective layer and the film after application / drying of the paste for forming the phosphor layer. It was 12.0 when measured using.

Then, it baked for 30 minutes at 500 degreeC, and produced the backplate as a member for PDP.
The produced front plate and back plate were sealed using sealing glass, and neon gas containing 5% xenon was sealed so as to have an internal gas pressure of 66500 Pa. Further, a driving circuit was mounted to produce a PDP. When light was emitted by applying a voltage to the scan electrode of the PDP, display characteristics could be obtained uniformly within the substrate surface.

Example 2
First, the front plate was produced in the same manner as in Example 1, and the back plate was produced in the same manner as in Example 1 until the partition walls were formed.

Next, a phosphor layer was formed on the partition walls by discharging a phosphor paste between the side walls and the partition walls of the main partition walls and the auxiliary partition walls using a dispenser method. The paste for forming the phosphor layer is red phosphor powder: (Y, Gd, Eu) BO ₃ , blue phosphor powder: (Eu) BaMgAl ₁₀ O ₁₇ , green phosphor powder: (Mn) Zn ₂ SiO ₄ , the paste for forming phosphor layers of each color is 30 masses of organic vehicle (solid content concentration 10%) in which ethylcellulose (manufactured by Hercules Co.) is dissolved in terpineol for 70 mass parts of the phosphor powders. The parts were mixed and adjusted with three rollers. The paste for forming the phosphor layer is discharged from the tip of a nozzle having 256 holes (caliber: 130 μm) using a dispenser method so that the thickness after firing becomes 20 μm, and becomes a phosphor that becomes a phosphor A layer was formed. After the formation, an inspection was performed using an image inspection apparatus (Neptune 900, manufactured by V Technology Co., Ltd.). As a result, repair defects were detected for the defects in which four coating defects were detected in the phosphor layer.

As a paste for forming the phosphor protective layer, a glass composed of 60 parts by mass of magnesium oxide (2000A, manufactured by Ube Materials Co., Ltd.), bismuth oxide, silicon oxide, boron oxide, zirconium oxide, zinc oxide, and aluminum oxide is used. Organic vehicle in which crushed center particle diameter (D ₅₀ ) 0.8 μm, softening temperature 455 ° C. glass powder, ethyl cellulose (manufactured by Hercules) and organic dye (Sudan III, C ₂₂ H ₁₆ N ₄ O) are dissolved in terpineol (Solid content concentration: 10% by mass, organic dye concentration: 0.1% by mass when the organic vehicle is 100% by mass)) 30% by mass was mixed and kneaded with three rollers.

  The phosphor protective layer forming paste is discharged from a nozzle tip having 256 holes (caliber: 130 μm) using a dispenser method so that the thickness after firing becomes 3 μm, and becomes a phosphor. Formed on the paste layer. After the application, an inspection was performed using an image inspection apparatus (Neptune 900, manufactured by V Technology Co., Ltd.). As a result, it was possible to detect a coating defect in one phosphor protective layer forming paste. The defective part was repaired.

Note that ΔE ^* _ab is a spectrocolorimeter (CM-2002, manufactured by MINOLTA) for the film after application and drying of the phosphor protective layer paste and the film after application and drying of the phosphor layer forming paste. It was 13.0 when measured using.

  Then, it baked for 30 minutes at 500 degreeC, and produced the backplate as a member for PDP.

  The produced front plate and back plate were sealed using sealing glass, and neon gas containing 5% xenon was sealed so as to have an internal gas pressure of 66500 Pa. Further, a driving circuit was mounted to produce a PDP. When light was emitted by applying a voltage to the scan electrode of the PDP, display characteristics could be obtained uniformly in the plane.

Example 3
The organic dye concentration was the same as in Example 1 except that the organic dye concentration was 0.01% by mass when the organic vehicle was 100% by mass.

Note that ΔE ^* _ab is a spectrocolorimeter (CM-2002, manufactured by MINOLTA) for the film after application / drying of the paste for forming the reflective layer and the film after application / drying of the paste for forming the phosphor layer. It was 5.5 when measured using the above.

  After applying the phosphor layer forming paste, an inspection was performed using an image inspection apparatus (Neptune 900, manufactured by V Technology Co., Ltd.). A coating omission defect was confirmed. The defective part was repaired.

  The produced front plate and back plate were sealed using sealing glass, and neon gas containing 5% xenon was sealed so as to have an internal gas pressure of 66500 Pa. Further, a driving circuit was mounted to produce a PDP. When light was emitted by applying a voltage to the scan electrode of the PDP, display characteristics could be obtained uniformly within the substrate surface.

Example 4
The organic dye concentration was the same as in Example 2 except that the organic dye concentration was 0.01 parts by mass when the organic vehicle was 100% by mass.

In addition, ΔE ^* _ab is a spectrocolorimeter (CM-2002, manufactured by MINOLTA) for the film after application / drying of the paste for forming the phosphor protective layer and the film after application / drying of the paste for forming the phosphor layer ) Was 4.5.

  After applying the phosphor protective layer forming paste, when an inspection was performed using an image inspection apparatus (Neptune 900, manufactured by V Technology Co., Ltd.), a coating omission defect of the phosphor protective layer could not be detected. The coating omission at one place was confirmed. The defective part was repaired.

  The produced front plate and back plate were sealed using sealing glass, and neon gas containing 5% xenon was sealed so as to have an internal gas pressure of 66500 Pa. Further, a driving circuit was mounted to produce a PDP. When light was emitted by applying a voltage to the scan electrode of the PDP, display characteristics could be obtained uniformly within the substrate surface.

Comparative Example 1
The same procedure as in Example 1 was performed except that no organic dye was used in the reflective layer forming paste. Application failure, defects could not be observed, and unlit portions were seen on the PDP.

Comparative Example 2
The same procedure as in Example 2 was performed, except that no organic dye was used in the phosphor protective layer paste. Application failure, defects could not be observed, and unlit portions were seen on the PDP.

Comparative Example 3
An organic dye is not used for the paste for forming the reflective layer, and as the paste for forming the phosphor layer, red phosphor powder: (Y, Gd, Eu) BO ₃ , blue phosphor powder: (Ba, Eu) MgAl ₁₀ O ₁₇ , green phosphor powder: (Zn, Mn) ₂ SiO ₄ , 70 parts by mass of each and organic dye (Sudan III, C ₂₂ H ₁₆ N ₄ O) dissolved in terpineol (solid content concentration 10% by mass) , Organic dye concentration: 0.1 parts by mass when the organic vehicle is 100% by mass))) The same procedure as in Example 1 was performed except that a paste obtained by kneading 30 parts by mass with a three-roller was used. .

Note that ΔE ^* _ab is measured with a spectrocolorimeter (CM-2002, manufactured by MINOLTA) for the film after application / drying of the paste for forming the reflective layer and the film after application / drying of the paste for forming the phosphor layer. It was 15.0 when measured using.

  After forming the phosphor layer, inspection was performed using an image inspection apparatus (Neptune 900, manufactured by V Technology Co., Ltd.). As a result, eight coating paste defects could be detected. The defective part was repaired.

  After the phosphor paste was repaired, it was baked at 500 ° C. for 30 minutes to produce a back plate as a member for PDP.

  The produced front plate and back plate were sealed using sealing glass, and neon gas containing 5% xenon was sealed so as to have an internal gas pressure of 66500 Pa. Further, a driving circuit was mounted to produce a PDP. When light was emitted by applying a voltage to the scan electrode of the PDP, the luminance of the blue phosphor was reduced by 10% compared to Example 1.

Comparative Example 4
An organic dye is not used for the phosphor protective layer paste, and as the phosphor layer forming paste, red phosphor powder: (Y, Gd, Eu) BO ₃ , blue phosphor powder: (Ba, Eu) MgAl ₁₀ O ₁₇ , green phosphor powder: (Zn, Mn) ₂ SiO ₄ , 70 parts by mass of each and organic dye (Sudan III, C ₂₂ H ₁₆ N ₄ O) dissolved in terpineol (solid content concentration 10% by mass) Organic dye concentration: 0.1 parts by mass when the organic vehicle is 100% by mass))) The same procedure as in Example 2 was performed, except that a paste obtained by kneading 30 parts by mass with three rollers was used. .

Note that ΔE ^* _ab is measured with a spectrocolorimeter (CM-2002, manufactured by MINOLTA) for the film after application / drying of the paste for forming the reflective layer and the film after application / drying of the paste for forming the phosphor layer. It was 13.0 when measured using.

  After forming the phosphor protective layer, inspection was performed using an image inspection apparatus (Neptune 900, manufactured by V Technology Co., Ltd.). As a result, eight coating defect defects of the phosphor protective layer paste could be detected. The defective part was repaired.

  After repairing the phosphor protective layer paste, baking was performed at 500 ° C. for 30 minutes to prepare a back plate as a member for PDP.

  The produced front substrate and back substrate were sealed using sealing glass, and neon gas containing 5% xenon was sealed so as to have an internal gas pressure of 66500 Pa. Further, a driving circuit was mounted to produce a PDP. When light was emitted by applying a voltage to the scan electrode of the PDP, the luminance of the blue phosphor was reduced by 9% compared to Example 1.

Claims (4)

When forming a layer other than the phosphor layer and the phosphor layer on the side surface of the partition and / or between the partitions on a member having at least an electrode and a partition formed on the substrate, these layers are provided with a paste material. The paste used for forming the layers other than the phosphor layer is colored in a color different from the paste used for forming the phosphor layer, and is formed by drying and / or firing , and titanium oxide. Includes at least one selected from the group consisting of zinc oxide, zinc sulfide, barium oxide, magnesium oxide, calcium oxide, zirconia, tin oxide, glass powder having a melting point of 620 ° C. or higher, lithium fluoride, calcium fluoride, alumina, and silica further plasma display panel unit which is characterized by using a paste containing a coloring agent selected from organic dyes and pigments The method of production. From the L ^* a ^* b ^* color system color coordinates of the film after application / drying of the paste used to form the phosphor layer and the film after application / drying of the paste used to form a layer other than the phosphor layer obtained the color difference (ΔE * _^ab) is the method according to claim 1 Symbol placement of a plasma display panel member and satisfies the following expression.
ΔE ^* _ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2 > 1.5
(Here, ΔL ^* , Δa ^* , and Δb ^* are the paste used for forming the L ^* value, a ^* value, and b ^* value of the film after applying and drying the phosphor paste, and layers other than the phosphor layer, respectively. The difference between the L ^* value, a ^* value, and b ^* value of the film after the application and drying of the film is expressed.) The process according to claim 1 or 2, wherein the plasma display panel member, characterized in that applied by a dispenser the paste used for forming the layers other than the phosphor layer. The plasma display which used the member for plasma display panels manufactured by the manufacturing method of the member for plasma display panels in any one of Claims 1-3 for the backplate.