JP4062557B2 - Plasma display substrate - Google Patents

Description

【０１００】
【発明の効果】
本発明によれば、蛍光体のハガレが生じないため、高精細のＰＤＰを歩留まりよく製造できるプラズマディスプレイ用基板が得られる。これにより高精細のプラズマディスプレイを提供することができる。本発明のプラズマディスプレイ用基板は、ガラス基板上に、電極、誘電体および隔壁を設けた上に蛍光体層を設けた背面用のプラズマディスプレイ用基板において特に有効である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a substrate used in a plasma display panel (hereinafter abbreviated as PDP). More specifically, the present invention relates to a plasma display substrate for producing a PDP with a high yield when producing a PDP substrate.
[0002]
[Prior art]
In recent years, plasma displays have attracted attention as large displays. The PDP used for this is capable of high-speed display compared to a liquid crystal panel and is easy to increase in size, so that it has penetrated into the fields of OA equipment and public information display devices, and further, the field of high-definition television. Progress is expected. Along with such expansion of applications, a color PDP having a fine and large number of display cells and capable of high-definition display is particularly attracting attention.
[0003]
The PDP has a configuration in which a front plate and a back plate are bonded together. First, a plurality of transparent electrodes made of ITO or tin oxide are formed on the back surface of a glass substrate on the back plate of a glass substrate. A pulse AC voltage of 10 kHz to several tens of kHz is usually applied between the adjacent transparent electrodes to obtain a display discharge. The sheet resistance of the transparent electrode is several tens of ohms / cm.²Since the electrode resistance is about several tens of kΩ and the drive voltage is not sufficiently raised and driving becomes difficult, a metal bus electrode is usually formed on the transparent electrode to lower the resistance value. .
[0004]
Next, these electrodes are covered with a transparent dielectric layer using a low melting point glass or the like, and further MgO is formed as a protective layer by an electron beam evaporation method. Such a dielectric layer has a role as a capacitor for accumulating electric charges for discharge.
[0005]
On the other hand, for the back plate, a data electrode for writing display data on a glass substrate is produced using a photosensitive silver paste or the like, and covered with a dielectric layer. A white or black barrier rib is formed thereon, and a phosphor layer that emits red, green, and blue light is formed. Here, in order to increase the definition of the PDP, it is necessary to reduce the pitch between the partition walls.
[0006]
The front plate and the back plate as described above are sealed together so that matrix driving is possible, then exhausted, mixed with a mixed gas of He, Ne, and Xe, and a drive circuit is mounted to produce a PDP. .
[0007]
In PDP display, when a pulsed alternating voltage is first applied between adjacent transparent electrodes, gas discharge is generated and plasma is formed. The generated ultraviolet light excites the phosphor to emit visible light before it is emitted. Display emission is obtained through the faceplate. The transparent electrode that generates discharge is composed of a scan electrode and a sustain electrode. In actual panel driving, a sustain discharge pulse is applied to the transparent electrode, which is the discharge electrode, and when generating a discharge, a voltage is applied to the data electrode on the back plate to cause a counter discharge, This discharge is maintained between the discharge electrodes by the sustain pulse.
Conventionally, when a PDP as described above is manufactured, there is a problem in that the yield is lowered due to a part of the substrate generated during processing being warped or broken. In particular, when the phosphor layer is formed, there is a problem that the phosphor is likely to be warped or broken, or the phosphor may be peeled off due to them.
[0008]
[Problems to be solved by the invention]
The object of the present invention is to suppress phosphor warpage and cracks that occur when a phosphor layer is formed on a glass substrate, and to prevent phosphor peeling caused by them, thereby creating a PDP with high yield.To doCanRupuThe object is to provide a substrate for a laser display.
[0009]
[Means for Solving the Problems]
In order to achieve the above object, a plasma display substrate of the present invention is a plasma display substrate in which an electrode, a dielectric layer and a partition are provided on a glass substrate, and a phosphor layer is provided thereon. However, the coefficient of thermal expansion at 50 to 400 ° C. is 70 to 85 × 10^-7/ ° K glass, and the surface of the partition wall has an arithmetic average roughness Ra of 0.1 μm or more.0.31μm or less, Maximum height Rt is 1.0μm or more3.0 μm or lessIn the present invention, the partition wall has an arithmetic average roughness Ra of 0.2 μm or more.0.31μm or lessMaximum height Rt is 2.0μm or more3.0 μm or lessIt is preferable to have a surface roughness of
[0010]
DETAILED DESCRIPTION OF THE INVENTION
As a substrate used for the plasma display substrate of the present invention, general soda lime glass, glass obtained by annealing soda lime glass, or high strain point glass (for example, “PD-200” manufactured by Asahi Glass Co., Ltd.), etc. Can be used. The size of the glass substrate is not particularly limited, and glass having a thickness of 1 to 5 mm can be used.
[0011]
In the present invention, an electrode is formed on the glass substrate as described above. When an electrode is formed on a glass substrate, an electrode material containing 50% by weight or more, more preferably 90 to 99% by weight of silver is preferably used from the viewpoint of resistance and adhesion to the glass substrate. If the silver content is less than 50% by weight, the resistance value is low, and if it exceeds 99% by weight, the adhesion to the glass substrate becomes poor, such being undesirable. Moreover, the electrode layer excellent in adhesiveness with substrate glass can be obtained by containing 1 to 10 weight% of a glass component in an electrode.
[0012]
As a method for forming an electrode on a glass substrate, a screen printing method, a photosensitive paste method, or the like is used. Among these, the photosensitive paste method is preferably used because fine processing is possible. Examples of the photosensitive paste method include silver powder having an average particle size of 1 to 4 microns and an average particle size of 0.1 to 2 microns. A photosensitive silver paste obtained by kneading a glass frit with a photosensitive organic component is coated on a glass substrate, dried, and then subjected to exposure, development, and firing steps to form an electrode.
[0013]
In the present invention, a dielectric layer made of an insulator is then formed on the glass substrate on which the electrodes as described above are formed. The thickness of the dielectric layer is preferably 3 to 20 μm, more preferably 6 to 15 μm, for the formation of a uniform buffer layer. When the thickness exceeds 20 μm, it is difficult to remove the solvent during firing, cracks are likely to occur, and the stress applied to the glass substrate is large, so that problems such as warping of the substrate may occur. If the thickness is less than 3 μm, it is difficult to maintain uniformity of thickness. The dielectric material has a dielectric constant of 7 to 13, more preferably 7 to 10. A material having a dielectric constant of 7 or less is difficult to be baked on a glass substrate, and a material of 13 or more is not preferable because a discharge voltage becomes high when displaying a PDP.
[0014]
The dielectric layer has a thermal expansion coefficient α50 to 400 in the range of 50 to 400 ° C. and a value of 70 to 85 × 10.^-7/ ° K, or 72-80 × 10^-7It is preferable that the glass is made of glass at a temperature of / ° K. This is consistent with the thermal expansion coefficient of the substrate glass and reduces the stress applied to the glass substrate during firing. 85 × 10^-7If it exceeds / ° K, a stress is applied such that the substrate is warped on the surface on which the dielectric layer is formed.^-7If it is less than / ° K, a stress is applied so that the substrate is warped on the surface without the dielectric layer.
[0015]
If heating and cooling of the substrate are repeated while the substrate is warped, the substrate may break. Also, when sealing the front and back plates, there is a gap between the bulkhead head and the front plate surface, causing erroneous discharge between the cells, and sealing the two substrates so that they are not parallel. There is a problem that it cannot be performed or the substrate is damaged.
[0016]
The warping and cracking of the substrate during firing as described above can also be suppressed by making the total content of alkali metals contained in the dielectric layer preferably 5% by weight or less. Even if the thermal expansion coefficient matches that of the substrate glass, when it contains an alkali metal, specifically, 5% by weight or more of sodium, lithium, potassium, ion exchange with the glass component in the glass substrate or electrode is performed during firing. As a result, the surface portion of the substrate glass and the characteristics of the dielectric glass change, so that they do not coincide with the thermal characteristics of the substrate glass and heat deformation occurs. In particular, when lithium is contained, thermal deformation is likely to occur, and the total content of lithium contained in the dielectric layer is preferably 3% by weight or less.
[0017]
Furthermore, the use of glass containing 10 to 60% by weight of at least one of bismuth oxide, lead oxide and zinc oxide for the dielectric layer makes it easy to control the thermal softening temperature and the thermal expansion coefficient. In particular, the use of glass containing 10 to 60% by weight of bismuth oxide has advantages such as maintaining the stability of the dielectric paste. If the added amount of bismuth oxide, lead oxide, or zinc oxide exceeds 60% by weight, the heat-resistant temperature of the glass becomes too low and baking onto the glass substrate becomes difficult. As a suitable glass composition, the following compositions can be illustrated, for example by the oxide conversion description.
[0018]
10 to 40 parts by weight of bismuth oxide
3-50 parts by weight of silicon oxide
10 to 40 parts by weight of boron oxide
5-20 parts by weight of barium oxide
10-20 parts by weight of zinc oxide
The dielectric layer can be formed by applying a dielectric paste composed of an inorganic powder containing a glass powder having the glass composition as described above and an organic binder on a glass substrate and baking it. The amount of the glass powder used for the dielectric paste is preferably 50 to 90% by weight based on the sum of the glass powder and the organic component. If it is less than 50% by weight, the dielectric layer lacks denseness and surface flatness, and if it exceeds 90% by weight, the paste viscosity increases and the thickness unevenness at the time of application becomes large, which is not preferable.
[0019]
Here, the firing temperature is preferably 500 to 600 ° C. in order to suppress deformation of the glass substrate. For this reason, as an inorganic powder used for the dielectric paste, glass powder having a glass transition temperature (Tg) of 430 to 500 ° C. and a load thermal softening temperature (Ts) of 470 to 580 ° C. is 30% by weight or more, and further 60% by weight. % Or more is preferable. When the glass transition temperature (Tg) is lower than 430 ° C. or when the load thermal softening temperature (Ts) is lower than 470 ° C., the glass melts during the subsequent process, and the thickness uniformity and characteristics of the dielectric are When the glass transition temperature (Tg) is lower than 500 ° C. or when the load heat softening temperature (Ts) is higher than 580 ° C., firing on the glass substrate becomes insufficient, and the dielectric layer is peeled off. It is not preferable because it is easy to cause omission.
[0020]
In the present invention, a partition is formed on the dielectric layer as described above. As a method for forming the partition pattern, a screen printing method, a photosensitive paste method, or the like is used. Of these, the photosensitive paste method is preferably used because it enables high definition and a reduction in manufacturing steps. In the photosensitive paste method, a photosensitive paste composed mainly of an inorganic component composed of glass powder and an organic component having photosensitivity is applied onto a glass substrate, a photomask pattern is printed by exposure, and a partition pattern is formed by development. Thereafter, the partition wall is obtained by firing. As a method of applying, a method of transferring a photosensitive sheet (green tape) obtained by applying a photosensitive paste on a film onto a glass substrate can also be used.
[0021]
Since the partition pattern formed by the photosensitive paste method tends to generate distortion stress due to non-uniformity of photocuring in the thickness direction, peeling may occur during firing. When the barrier ribs are peeled off, color mixture occurs at the peeled portions, and the peeled barrier ribs leave the remaining pixels on the panel, resulting in a decrease in yield. Here, when the barrier ribs are formed, after the dielectric paste is applied, the barrier rib pattern is formed using the barrier rib paste, and the dielectric layer and the barrier rib pattern are fired at the same time, so that there is no peeling or collapse. A partition layer can be formed.
[0022]
As a partition material used in the present invention, a glass material having a glass transition point of 430 to 500 ° C. and a heat softening temperature of 470 to 580 ° C. is used for pattern formation on a glass substrate having a low glass transition point and a low thermal softening point. It is preferable to use it. In particular, in the photosensitive paste method, by using a glass having an average refractive index of 1.5 to 1.7, the refractive index of the glass powder in the paste is brought close to the refractive index of the organic component, and light scattering in the paste is reduced. It can be suppressed and the number of coating and exposure can be reduced.
[0023]
Here, the refractive index measurement of the glass material is accurate in confirming the effect of measuring at the wavelength of the light to be exposed, particularly when the photosensitive paste method is used. In particular, it is preferable to measure with light having a wavelength in the range of 350 to 650 nm. Furthermore, refractive index measurement with i-line (365 nm) or g-line (436 nm) is preferable. As for the light transmittance, an ellipso method, a V-block method, or a Becke method can be used as a spectrophotometer and a refractive index measurement method.
[0024]
In order to obtain a glass having a heat softening temperature that can be baked on a glass substrate and an average refractive index of 1.5 to 1.7, at least one of lithium oxide, sodium oxide, and potassium oxide is used in an amount of 2-20. It is a simple method to use glass fine particles containing wt%. The total content of alkali metal oxides such as sodium oxide, lithium oxide and potassium oxide is 2 to 20% by weight, which makes it easy to control the thermal softening temperature and the coefficient of thermal expansion. Since a refractive index can be made low, it is preferable from the point which can make a refractive index difference with organic substance small. When the content of the alkali metal oxide is less than 2%, it is difficult to control the heat softening temperature, and when it exceeds 20%, the paste stability is lowered, which is not preferable.
[0025]
Here, when an alkali metal is contained in the partition wall material, an ion exchange reaction occurs between the three layers of the partition wall layer / dielectric layer / glass substrate when the dielectric layer also contains an alkali metal or an oxide thereof. Problems such as warping and cracking of the substrate, and yellowing of the substrate due to reaction with the silver electrode may occur. In order to solve such a problem, the total content of alkali metals contained in the dielectric layer is preferably 5% by weight or less, more preferably 0.5% by weight or less.
[0026]
As a composition of the partition material used in the present invention, silicon oxide is preferably blended in the range of 3 to 60% by weight in glass. When the content of silicon oxide is 60% by weight or less, there is an advantage that the thermal softening point becomes low and baking onto a glass substrate becomes possible. When the content of silicon oxide is less than 3% by weight, it is preferable from the viewpoint that the denseness, strength and stability of the glass layer are reduced, or that the thermal expansion coefficient is out of the desired value and mismatching with the glass substrate is likely to occur. Absent.
[0027]
Furthermore, it is possible to improve electrical, mechanical and thermal properties such as electrical insulation, strength, thermal expansion coefficient, and denseness of the insulating layer by blending boron oxide in the glass in the range of 5 to 50% by weight. preferable. If it exceeds 50% by weight, the stability of the glass decreases, such being undesirable.
[0028]
In addition, by adding aluminum oxide, barium oxide, calcium oxide, magnesium oxide, zinc oxide, zirconium oxide, etc., especially aluminum oxide, barium oxide, zinc oxide, etc., it is possible to improve hardness and workability. it can. The content is preferably 40% by weight or less, more preferably 25% by weight or less, from the viewpoint of control of the thermal softening point, thermal expansion coefficient, and refractive index.
As a glass composition containing lithium oxide, in oxide conversion notation,
2-15 parts by weight of lithium oxide
15-50 parts by weight of silicon oxide
Boron oxide 15-40 parts by weight
2-15 parts by weight of barium oxide
6-25 parts by weight of aluminum oxide
It is preferable to contain 50% by weight or more of the composition containing
[0029]
In the above composition, sodium oxide or potassium oxide may be used instead of lithium oxide, but lithium oxide is preferable in terms of paste stability.
[0030]
The amount of the glass powder used for the partition wall paste is preferably 65 to 85% by weight based on the sum of the glass powder and the organic component. If the amount of the glass powder is less than 65% by weight, the shrinkage rate during firing increases, causing disconnection and peeling of the partition walls. In the photosensitive paste method, etc., pattern thickening and residual film during development are generated. It is not preferable because it is likely to occur. When the amount of the glass powder exceeds 85% by weight, particularly in the photosensitive paste method, since the photosensitive component is small, the pattern formability becomes poor, which is not preferable.
[0031]
In the present invention, after the barrier ribs are formed, a phosphor layer is further formed. As a method for forming the phosphor pattern, a screen printing method, a photosensitive paste method, or the like is used. Of these, the photosensitive paste method is preferably used because it enables high definition and a reduction in manufacturing steps. In the photosensitive paste method, a photosensitive paste composed mainly of an inorganic component composed of inorganic phosphor powder and a photosensitive organic component is applied onto a glass substrate, a photomask pattern is baked by exposure, and a phosphor pattern is developed by development. It is a method of forming. Thereafter, the phosphor layer is formed by baking and degreasing.
[0032]
It does not specifically limit as fluorescent substance powder used by this invention, A well-known fluorescent substance powder can be used. For example, in red, Y₂O_Three: Eu, YVO_Four: Eu, (Y, Gd) BO_Three: Eu, Y₂O_ThreeS: Eu, γ-Zn_Three(PO_Four)₂: Mn, (ZnCd) S: Ag + In₂O_Three, Y₂SiO_Five: Eu, Y₂Al_FiveO₁₂: Eu, Zn_Three(PO_Four)₂: Mn, YBO_Three: Eu, (Y, Gd) BO_Three: Eu, GdBO_Three: Eu, ScBO_ThreeP: Eu, LuBO_Three: Eu etc. In green, Zn₂GeO₂: Mn, BaAl₁₂O₁₉: Mn, Zn₂SO_Four: Mn, LaPO_Four: Tb, ZnS: Cu, Al, ZnS: Au, Cu, Al, (ZnCd) S: Cu, Al, Zn₂SiO_Four: Mn, As, AsY_ThreeAl_FiveO₁₂: Ce, CeMgAl₁₁O₁₉: Tb, Gd₂O₂S: Tb, Y_ThreeAl_FiveO₁₂: Tb, ZnO: Zn and the like. In blue, Y₂SiO_Five: Ce, CaWO_Four: Pb, BaMgAl₁₄O_{twenty three}: Eu, Sr_Five(PO_Four)_ThreeCl: Eu, BaMgAl₁₆O₂₇: Eu, BaMg₂Al₁₄O_{twenty four}: Eu, ZnS: Ag + pigment (red), Y₂SiO_Three: Ce and the like.
[0033]
In particular, as an inorganic phosphor powder, [(Y, Gd, Eu) BO as red_Three], As green [(Zn, Mn)₂SiO_Four], As blue [(Ba, Eu) MgAl_TenO₁₇], A phosphor layer having a high luminance and a long life can be formed. And at least one element selected from the group consisting of thulium (Tm), terbium (Tb) and europium (Eu), and at least one element selected from yttrium (Y), gadolinium (Gd) and lutetium (Lu). A tantalate rare earth phosphor substituted with a matrix rare earth element can be used. Preferably, the rare earth phosphor of tantalate is represented by the formula Y_1-xEu_xTaO_Four(Wherein x is approximately 0.005 to 0.1). The europium activated yttrium tantalate phosphor. Europium activated yttrium tantalate is preferred for the red phosphor, and tantalate rare earth phosphor is the composition formula Y for the green phosphor._1-xTb_xTaO_Four(Wherein x is approximately 0.001 to 0.2), terbium activated yttrium tantalate is preferred. For blue phosphor, tantalate rare earth phosphor is Y_1-xTb_xTaO_FourThulium activated yttrium tantalate represented by the formula (wherein x is approximately 0.001 to 0.2) is preferred.
[0034]
In the green phosphor, Mn is zinc silicate (ZnSiO_Four) Manganese-activated zinc phosphor (Zn) having an average particle diameter of 2 to 8 μm activated by 0.2% by weight or more and less than 0.1% by weight based on the base amount₂SiO_Four: Mn) and the general formula is (Zn_2-xMn_x) O ・ αSiO₂A manganese-activated zinc silicate phosphor represented by the formula (wherein x and α are values in the range of 0.01 ≦ x ≦ 0.2 and 0.5 <α ≦ 1.5) is preferable.
[0035]
The amount of the phosphor powder is preferably 40 to 85% by weight. If the amount is less than 40% by weight, the shrinkage rate is too large, and peeling or cracking is likely to occur. If the amount exceeds 85% by weight, the shrinkage rate is too small, so that the phosphor layer becomes 50 μm or more.
[0036]
The phosphor powder particle size used in the present invention is selected in consideration of the line width, width interval (space) and thickness of the phosphor layer pattern to be produced. 15 μm, specific surface area 0.1-2m²/ G is preferable. More preferably, the particle diameter is 2 to 10 μm and the specific surface area is 0.2 to 1 m.²/ G. In this range, the luminous efficiency of the phosphor is good and the lifetime is long, and particularly when the photosensitive paste method is used, light is sufficiently transmitted at the time of ultraviolet exposure, and a highly accurate pattern shape is obtained. Powder particle size is less than 1.5μm, specific surface area is 2m²If it exceeds / g, the luminous efficiency and life of the phosphor will be reduced. Furthermore, in the photosensitive paste method and the like, the powder becomes too fine and light is scattered outside the desired part during exposure, so that the remaining film of the pattern during development (excess phosphor remains in the part to be developed originally) Occurs) and a high-definition pattern cannot be obtained.
[0037]
As the shape of the phosphor powder, a polyhedral (granular) one can be used, but a powder without aggregation is preferable. Among these, spherical powder is more preferable because it can reduce the influence of scattering during exposure in the photosensitive paste method. The spherical powder preferably has a particle shape with a sphericity of 80% by number or more. More preferably, the sphericity is 90% by number or more. When the sphericity is less than 80% by number, it is difficult to obtain a high-definition pattern due to the influence of scattering by the phosphor powder during ultraviolet exposure. The spherical ratio is measured by photographing the phosphor powder with an optical microscope at a magnification of 300, and counting the particles that can be counted, and the ratio of the spherical particles is defined as the spherical ratio.
[0038]
One of the features of the present invention is that the surface of the partition wall has a surface roughness with Ra of 0.1 μm or more and Rt of 1.0 μm or more. Furthermore, it is preferable that Ra is 0.2 μm or more and Rt is 2.0 μm or more.
[0039]
Here, the surface roughness is a physical property obtained on the basis of a “roughness curve” of the surface of an object (hereinafter referred to as an object surface), and the “roughness curve” is symmetrical on a plane perpendicular to the object surface. A curve obtained by removing the undulation component of the surface from the contour that appears at the cut end when the surface is cut. Ra means arithmetic average roughness, and Rt means maximum height, and the definition conforms to JIS B 0601.
[0040]
When the surface of the partition wall has such a surface roughness, when the phosphor layer is formed, the number of portions where the phosphor particles come into contact with the surface of the partition wall increases, and the phosphor particles are likely to be caught on the partition wall. Adhesive strength between the phosphor layer and the phosphor layer formed thereon increases, and even when the phosphor is warped, it is possible to suppress phosphor peeling.
[0041]
Here, the surface roughness of the partition surface such that Ra is less than 0.1 μm and / or Rt is less than 1.0 μm by firing at a firing temperature equal to or higher than the thermal softening temperature of the glass material used is defined as Ra. Is controlled to be 0.1 μm or more and Rt is 1.0 μm or more, specifically, for example, the partition wall pattern is fired at a firing temperature lower than the thermal softening temperature of the glass material to be used, and the glass is sintered. Although the method of suppressing etc. is mentioned, when this degree of unsintering becomes high, there exists a problem that the intensity | strength of the partition formed is reduced.
[0042]
Moreover, it is also a preferable means to make the partition wall material contain a filler having a heat softening temperature of 650 to 850 ° C. The inclusion of the filler in the partition wall material means that Ra is less than 0.1 μm and / or Rt is less than 1.0 μm by firing at a firing temperature equal to or higher than the thermal softening temperature, and as described above, the thermal softening temperature. When firing at the following firing temperature, Ra is less than 0.1 μm and / or Rt is less than 1.0 μm as a result of balancing the degree of unsintering in order to maintain the strength of the partition walls and the like. In the case where a glass material is used as the partition wall material, the filler has a high melting point, so that it does not sinter under the firing conditions of the partition wall, and the formed partition wall can have the above surface roughness. It is valid. Moreover, in the photosensitive paste method, the shrinkage rate at the time of baking after pattern formation becomes small, and it is preferable also from the point that pattern formation becomes easy.
[0043]
As the filler, refractory glass or ceramics having a heat softening temperature of 600 ° C. or higher can be preferably used.
[0044]
Furthermore, as the high melting point glass powder, glass powder containing 15% by weight or more of silicon oxide and aluminum oxide is preferable. Further, the total content of these is preferably 50% by weight or more in the glass powder in order to provide necessary thermal characteristics. As an example, glass powder having the following composition is preferably used.
[0045]
Silicon oxide: 15-50% by weight
Boron oxide: 5 to 20% by weight
Aluminum oxide: 15-50% by weight
Barium oxide: 2 to 10% by weight
The filler content is preferably 5% to 90% by weight of the glass material used. When the filler content is less than 5% by weight, the effect of filler addition cannot be obtained. When the filler content exceeds 90% by weight, the strength of the partition walls is lowered, which is not preferable.
[0046]
In the present invention, a general organic binder, a solvent, or the like can be used as the organic component used in the paste for electrodes, dielectrics, barrier ribs, and phosphors. Specific examples of the organic binder include polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, cellulose polymers such as methyl hydroxyethyl cellulose, silicon polymers such as polymethylsiloxane and polymethylphenylsiloxane, polyethylene, Examples thereof include polyvinyl pyrrolidone, polystyrene, polyamide, high molecular weight polyether, methacrylic acid ester polymer, acrylic acid ester polymer, acrylic acid ester-methacrylic acid ester copolymer, α-methylstyrene polymer, and butyl methacrylate resin.
[0047]
Solvents used for adjusting the viscosity of the paste include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, butyl carbitol acetate. , Dimethyl sulfoxide, γ-butyrolactone, bromobenzene, chlorobenzene, dibromobenzene, dichlorobenzene, bromobenzoic acid, chlorobenzoic acid, and the like, and organic solvent mixtures containing one or more of these.
[0048]
In addition, a plasticizer can be added to the organic component. Specific examples include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like.
[0049]
As described above, patterning becomes easier by imparting photosensitivity to electrodes, dielectrics, barrier ribs and phosphor pastes, and in particular, the solubility of the dielectrics in solvents and developers is controlled. There are advantages you can do. The paste contains a photosensitive component selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer, and, if necessary, a photopolymerization initiator, an ultraviolet absorber, a sensitizer, and a sensitizer. Photosensitivity is imparted by adding additive components such as a sensitizer and a polymerization inhibitor. In such a case, after applying the paste on the glass substrate and drying it, pattern exposure is performed to develop and remove unnecessary portions to form a desired pattern.
[0050]
As the photosensitive component, there are a light-insolubilized type and a light-solubilized type,
(A) a functional monomer, oligomer or polymer containing one or more unsaturated groups in the molecule,
(B) those containing photosensitive compounds such as aromatic diazo compounds, aromatic azide compounds, organic halogen compounds,
(C) There are so-called diazo resins such as a condensate of diazo amine and formaldehyde.
[0051]
In addition, as a light-soluble type,
(D) Inorganic salts of diazo compounds and complexes with organic acids, those containing quinonediazos,
(E) For example, naphthoquinone-1,2-diazide-5-sulfonic acid ester of phenol, novolak resin, or the like in which quinonediazos are bonded to a suitable polymer binder.
[0052]
Among these, in particular, in the case of laminating and patterning, a photo-insolubilized type is one, and among them, the above-mentioned (A) is a photosensitive paste that can be easily used by mixing with inorganic fine particles. Preferably used.
[0053]
The sensitive monomer is a compound containing a carbon-carbon unsaturated bond. Specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate. , Isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol Acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate , Isobornyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phenoxyethyl acrylate, stearyl acrylate, Trifluoroethyl acrylate, allylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, di Pentaerythritol hexaac Rate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, triglycerol diacrylate, trimethylolpropane Triacrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, benzyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, bisphenol A diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, bisphenol A-propylene oxide Adjunct Acrylates such as diacrylates, thiophenol acrylates, benzyl mercaptan acrylates, and the like, monomers in which 1 to 5 of these aromatic ring hydrogen atoms are substituted with chlorine or bromine atoms, or styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, chlorinated styrene, brominated styrene, α-methylstyrene, chlorinated α-methylstyrene, brominated α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, carboxymethylstyrene, Vinyl naphthalene, vinyl anthracene, vinyl carbazole, and those in which some or all of the acrylates in the molecule of the above compounds are replaced with methacrylate, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, etc. It is. In the present invention, one or more of these can be used.
[0054]
In addition to these, by adding an unsaturated acid such as an unsaturated carboxylic acid, developability after pattern exposure can be imparted. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.
[0055]
The content of these monomers is preferably 5 to 30% by weight with respect to the sum of the inorganic fine particles and the photosensitive component. Outside this range, the pattern formability may deteriorate and the hardness after curing may be insufficient.
[0056]
As the binder, polyvinyl alcohol, polyvinyl butyral, methacrylic acid ester polymer, acrylic acid ester polymer, acrylic acid ester-methacrylic acid ester copolymer, α-methylstyrene polymer, butyl methacrylate resin and the like are used.
[0057]
Moreover, the oligomer and polymer obtained by superposing | polymerizing at least 1 type among the compounds which have the above-mentioned carbon-carbon double bond can be used. In the polymerization, it can be copolymerized with other photosensitive monomers so that the content of these photoreactive monomers is 10% by weight or more, more preferably 35% by weight or more.
[0058]
As the monomer to be copolymerized, the developability in forming a pattern can be improved by copolymerizing an unsaturated acid such as an unsaturated carboxylic acid. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof. The acid value (AV) of the polymer or oligomer having an acidic group such as a carboxyl group in the side chain thus obtained is preferably 50 to 180, more preferably 70 to 140. When the acid value is less than 50, the allowable development width becomes narrower, and when the acid value exceeds 180, the solubility of the unexposed area in the developing solution decreases. This is not preferable because it is difficult to obtain a high-definition pattern.
[0059]
By adding a photoreactive group to the side chain or molecular end of the polymer or oligomer shown above, it can be used as a photosensitive polymer or photosensitive oligomer having photosensitivity. Preferred photoreactive groups are those having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group.
[0060]
Such a side chain can be added to an oligomer or polymer by using an ethylenically unsaturated compound having a glycidyl group or an isocyanate group relative to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. There is a method of making an acid chloride or allyl chloride by addition reaction.
[0061]
Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl crotonic acid ether, and glycidyl ether of isocrotonic acid.
[0062]
Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloylethyl isocyanate.
[0063]
In addition, the ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride is 0.05 to 1 molar equivalent with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. It is preferable to add.
[0064]
The amount of the polymer component consisting of the photosensitive polymer, photosensitive oligomer and binder in the photosensitive paste is excellent in terms of pattern formability and shrinkage after baking. On the other hand, it is preferably 5 to 30% by weight. Outside this range, pattern formation may not be possible or the pattern may become thicker.
[0065]
Specific examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4- Benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- t-Butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethylketanol, benzylmethoxyethyl acetal, benzoin, benzoin Ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p -Azidobenzylidene) cyclohexanone, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione- 2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Mihi L-ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl Photoreductive dyes such as disulfide, benzthiazole disulfide, triphenylformine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide and eosin, methylene blue, and reducing agents such as ascorbic acid and triethanolamine Examples include combinations. In the present invention, one or more of these can be used.
[0066]
The addition amount of the photopolymerization initiator is preferably 0.05 to 20% by weight, more preferably 0.1 to 15% by weight, based on the photosensitive component. If the amount of the photopolymerization initiator is less than 0.05% by weight, the photosensitivity becomes poor, and if it exceeds 20% by weight, the residual ratio of the exposed portion may become too small.
[0067]
It is also effective to add an ultraviolet absorber in the paste because a high aspect ratio, high definition and high resolution can be obtained. As the ultraviolet absorber, an organic dye, particularly an organic dye having a high UV absorption coefficient in a wavelength range of 350 to 450 nm is preferably used. Specifically, azo dyes, amino ketone dyes, xanthene dyes, quinoline dyes, amino ketone dyes, anthraquinone dyes, benzophenone dyes, diphenyl cyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes, and the like can be used. . Even when an organic dye is added as a light-absorbing agent, it is preferable because it does not remain in the insulating film after baking and the deterioration of the insulating film characteristics due to the light-absorbing agent can be reduced. Of these, azo dyes and benzophenone dyes are preferable.
[0068]
The addition amount of the organic dye is preferably 0.05 to 1 part by weight, more preferably 0.1 to 0.18% by weight with respect to the inorganic fine particles. If it is less than 0.05% by weight, the effect of adding an ultraviolet light absorber is reduced, and if it exceeds 1% by weight, the properties of the insulating film after firing are deteriorated.
[0069]
As a method for adding an ultraviolet light absorber composed of an organic dye, specifically, for example, a solution in which an organic dye is previously dissolved in an organic solvent is prepared and kneaded at the time of preparing the paste, or inorganic fine particles are added in the organic solvent. And a method of drying after mixing. By this method, so-called capsule-shaped fine particles in which the surface of each inorganic fine particle is coated with an organic film can be produced.
[0070]
Furthermore, the addition of a sensitizer is effective for improving sensitivity. Examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2 , 6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) -benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) Chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) -isonaphthothiazole, 1,3-bis (4-dimethylaminobenzal) acetone, 1,3-carbonyl-bis (4-diethylamino Benzal) acetone, 3,3-carbonyl-bis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate And isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole and the like. In the present invention, one or more of these can be used. Some sensitizers can also be used as photopolymerization initiators. When a sensitizer is added to the photosensitive paste, the addition amount is preferably 0.05 to 10% by weight, more preferably 0.1 to 10% by weight, based on the photosensitive component. If the amount of the sensitizer is less than 0.05% by weight, the effect of improving the photosensitivity is not exhibited, and if it exceeds 10% by weight, the residual ratio of the exposed portion may be too small, which is not preferable.
[0071]
The addition of a polymerization inhibitor is effective for improving the thermal stability during storage. Specific examples of the polymerization inhibitor include hydroquinone, monoester of hydroquinone, N-nitrosodiphenylamine, phenothiazine, pt-butylcatechol, N-phenylnaphthylamine, 2,6-di-tert-butyl-p- Examples include methylphenol, chloranil, and pyrogallol. When adding a polymerization inhibitor, the addition amount is 0.001 to 1 weight% normally in the photosensitive paste.
[0072]
Also, by adding a known radical polymerizable monomer and radical polymerization initiator to the dielectric layer paste, a thermopolymerizable paste can be obtained, and after applying the paste, it can be heated to obtain a crosslinked structure. it can. Specific examples of the radical polymerizable monomer in this case include ethylene, styrene, butadiene, vinyl chloride, vinyl acetate, acrylic acid, methyl acrylate, methyl vinyl ketone, acrylamide and acrylonitrile. Examples of the radical initiator include benzoyl peroxide, lauroyl peroxide, potassium persulfate, azobisisobutyronitrile, benzoyl peroxide-dimethylaniline, and the like.
[0073]
Furthermore, the addition of organic dyes and UV absorbers to the dielectric layer paste means that the pattern due to reflection / scattering from the dielectric surface during exposure when patterning the barrier ribs using the photosensitive paste method. This is effective in suppressing defects. That is, when the relationship of T1 <T2 is established between the total light transmittance T1 of the dielectric paste g-line and the total light transmittance T2 of the photosensitive paste for barrier ribs, the barrier rib pattern can be formed satisfactorily. As the organic dye and ultraviolet absorber used here, the compounds described above for the organic component materials can be used as appropriate.
[0074]
After mixing each of the above components, the paste for electrodes, dielectric layers, barrier ribs and phosphors in the present invention can be prepared by kneading with a planetary mixer or three rollers.
[0075]
Further, when each paste is applied onto the substrate, the substrate may be subjected to a surface treatment in order to improve the adhesion between the substrate and the coating film. Examples of the surface treatment agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, tris- (2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxysilane, and γ- (methacryloxypropyl) trimethoxy. Silane coupling agents such as silane, γ (2-aminoethyl) aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and γ-aminopropyltriethoxysilane, or organic titanium, organic Using organic metals such as aluminum and organic zirconium
wear.
[0076]
As a method for applying the paste, known methods such as screen printing, bar coater, roll coater, die coater and blade coater can be used.
[0077]
Furthermore, the developer used for development when the photosensitive paste method is used is an organic solvent in which the organic components in the photosensitive paste can be dissolved, and water is added to the extent that the dissolving power is not lost in the organic solvent. Things can be used. When a compound having an acidic group such as a carboxyl group is present in the photosensitive paste, development can be performed with an aqueous alkaline solution. A metal alkali aqueous solution such as sodium hydroxide, sodium carbonate, calcium hydroxide aqueous solution or the like can be used as the alkali aqueous solution. However, it is preferable to use an organic alkali aqueous solution because an alkaline component can be easily removed during firing.
[0078]
As the organic alkali, an amine compound can be preferably used. Specific examples include tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, monoethanolamine and diethanolamine.
[0079]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited to these. The measurement of each physical property is as follows.
[0080]
(A) Refractive index: According to JIS K-0062.
[0081]
(B) Ts, Tg: 100 mg of a glass sample was collected and heated at 20 ° C. per minute while introducing air, and the differential thermal analysis (DTA) was performed by plotting the temperature on the horizontal axis and the amount of heat on the vertical axis. Read Ts and Tg from the DTA curve.
[0082]
(C) Thermal expansion coefficient: An average thermal expansion coefficient of 50 to 400 ° C. is determined according to JIS R-3102.
[0083]
Moreover, about the evaluation method, the surface roughness of the partition was measured using the surface roughness meter by Tokyo Seimitsu Co., Ltd. Regarding the peeling of the phosphor, the surface of the substrate was observed with an optical microscope after firing the phosphor, and evaluated as x when there was peeling and ◯ when there was no peeling.
[0084]
Example 1
(1) Preparation of paste
In a 40% γ-butyrolactone (γ-BL) solution of polymer A shown below, trimethylolpropane triacrylate (TMPTA) is 50% by weight as a monomer and Irgacure 907 (Ciba Geigy) 20% by weight, 2,4-diethylthioxanthone (DETX) 20% by weight, p-dimethylaminobenzoic acid ethyl ester (EPA) 10% by weight, and dibutyl plasticizer An organic vehicle A was obtained by adding 17 wt% of phthalate (DBP) and 100 wt% of γ-BL as a solvent and dissolving them. A dielectric layer paste was prepared by adding 65 g of the following glass powder A to 35 g of the obtained organic vehicle A and kneading the mixture with a kneader. The glass powder used was finely powdered with an attractor in advance.
[0085]
Next, in a 40% solution of polymer A, sensitization with 100% by weight of Compound A shown below as a monomer and 16% by weight of Irgacure 369 (manufactured by Ciba-Geigy) as a monomer with respect to resin solids An organic vehicle B was obtained by adding 16% by weight of 2,4-diethylthioxanthone (DETX) as an agent and 50% by weight of γ-BL as a solvent and dissolving them. Furthermore, the glass powder B shown below was immersed in a Sudan 4 acetone solution as an organic dye so that Sudan 4 was 0.08 part by weight with respect to 100 parts by weight of the glass powder, and dried. The glass powder used was finely powdered with an attractor in advance. Subsequently, 52 g of glass powder B treated with an organic dye was added to 48 g of the above-described organic vehicle B, and kneaded with a kneader to prepare a partition wall paste.
[0086]
Furthermore, 60% by weight of TMPTA as a monomer, 12% by weight of Irgacure 907 (manufactured by Ciba Geigy) as a monomer, and 120% of γ-BL as a solvent in a γ-BL 40% solution of polymer A with respect to the resin solid content. The organic vehicle C was obtained by adding and dissolving at a weight percentage. Subsequently, each color inorganic phosphor powder shown below was immersed in a Sudan 4 acetone solution as an organic dye so that Sudan 4 was 0.05 part by weight with respect to 100 parts by weight of the phosphor powder and dried. Next, 35 g of each color inorganic phosphor powder treated with an organic dye was added to 65 g of the obtained organic vehicle C, and kneaded with a kneader to prepare each color phosphor layer paste.
[0087]
Polymer A:
0.4 equivalent of glycidyl methacrylate (GMA) with respect to the carboxyl group of a copolymer consisting of 40% methacrylic acid (MAA), 30% methyl methacrylate (MMA) and 30% styrene (St). A photosensitive polymer having a weight-average molecular weight of 43,000 and an acid value of 95 subjected to addition reaction.
[0088]
Compound A:
Glass powder A: composition Bi₂O_Three  38%, SiO₂  7%, B₂O_Three  19%, BaO 12%, Al₂O_Three  3%, ZnO 21%. Non-spherical powder with an average particle size of 3.4 μm. Tg 476 ° C, Ts 525 ° C. Thermal expansion coefficient 77 × 10^-7/ ° K. Refractive index at g-line (436 nm) 1.75.
Glass powder B:
Composition Li₂O 9%, SiO₂  22%, B₂O_Three  33%, BaO 4%, Al₂O_Three  Non-spherical powder having 23%, ZnO 2%, MgO 7% and an average particle size of 2.6 μm. Tg (glass transition point) 472 ° C., Ts (softening point) 515 ° C. Thermal expansion coefficient 83 × 10^-7/ ° K. Refractive index 1.59 at g-line (436 nm).
[0089]
Green phosphor powder: (Zn, Mn)₂SiO_Four
Red phosphor powder: (Y, Gd, Eu) BO_Three
Blue phosphor powder: (Ba, Eu) MgAl_TenO₁₇
(2) Production of PDP substrate
Subsequently, the above dielectric layer paste is screen-printed on a 300 mm square glass substrate (PD-200 manufactured by Asahi Glass Co., Ltd.) on which striped electrodes having a pitch of 150 μm and a line width of 40 μm are formed using a photosensitive silver paste. The whole surface was applied to a thickness of 30 μm by drying, dried at 80 ° C. for 30 minutes, and then 3 J / cm with an ultrahigh pressure mercury lamp.²The light irradiation was performed with the exposure amount.
[0090]
Next, the partition wall paste was applied to a thickness of 350 μm (after drying: 180 μm), dried at 80 ° C. for 40 minutes, and then passed through a striped negative mask with a pitch of 150 μm and a line width of 20 μm. To 50mW / cm²1.5 J / cm with an ultra-high pressure mercury lamp² It was irradiated with light at an exposure amount of.
[0091]
This was subjected to shower development with a 0.3% by weight aqueous solution of monoethanolamine maintained at 35 ° C. for 200 seconds, and then washed with water using a shower spray to remove the uncured space. A striped barrier rib pattern was formed. The glass substrate on which the dielectric layer and the partition walls thus obtained were formed was baked in air at 570 ° C. for 30 minutes to prepare the partition walls. The surface roughness of the produced partition was as shown in Table 1.
[0092]
Next, the red phosphor layer paste was applied on the entire surface of the substrate on which the barrier ribs were formed by screen printing, and dried at 80 ° C. for 40 minutes with the coated surface down. After drying, cool to room temperature, put a photomask and 100mJ / cm with ultra high pressure mercury lamp²It was irradiated with light at an exposure amount of. This was subjected to shower development with a 0.3 wt% aqueous solution of monoethanolamine maintained at 35 ° C. for 85 seconds, and then washed with water using a shower spray to remove the uncured space portion. And dried at 80 ° C. for 20 minutes to form a striped red phosphor pattern. The green phosphor layer paste and the blue phosphor layer paste were also patterned in the same manner as the red phosphor to form red, green and blue stripe patterns. Thus, the glass substrate on which each color phosphor was patterned was baked at 500 ° C. for 30 minutes to produce the PDP rear substrate of the present invention.
[0093]
The evaluation results of the substrate for PDP of the present invention produced as described above are as shown in Table 1, and there was no peeling of the phosphor.
[0094]
(Example 2)
A back substrate for PDP of the present invention was produced in the same manner as in Example 1 except that the following glass powder C was used as the partition wall glass powder. The evaluation results of the PDP substrate of the present invention thus produced were as shown in Table 1, and the phosphor was not peeled off.
[0095]
Glass powder C:
Composition Li₂O 7%, SiO₂  22%, B₂O_Three  32%, BaO 4%, Al₂O_Three  19%, ZnO 2%, MgO 6%, CaO 4%, ZrO₂  1% non-spherical powder with an average particle size of 2.9 μm. Tg (glass transition point) 497 ° C., Ts (softening point) 530 ° C. Thermal expansion coefficient 75 × 10^-7/ ° K. Refractive index 1.59 at g-line (436 nm).
[0096]
(Example 3)
The present invention was carried out in the same manner as in Example 1 except that the above-mentioned glass powder B (80 wt%) and the following glass powder D (20 wt%) were mixed as the partition glass powder.
A rear substrate for PDP was produced. The evaluation results of the substrate for PDP of the present invention produced as described above are as shown in Table 1, and there was no peeling of the phosphor.
[0097]
Glass powder D:
Composition SiO₂  38%, B₂O_Three  9%, BaO 5%, Al₂O_Three  Spherical powder with 35%, ZnO 3%, MgO 5%, CaO 5%, average particle size 2.7 μm. Tg (glass transition point) 652 ° C., Ts (softening point) 746 ° C. Thermal expansion coefficient 43 × 10^-7/ ° K. Refractive index at g-line (436 nm) of 1.58.
[0098]
(Comparative Examples 1 and 2)
About the back substrate for PDP in which the surface of the partition wall has the surface roughness as shown in Table 1, the result evaluated in the same manner as in Examples 1 to 3 is as shown in Table 1, and the peeling of the phosphor is observed. there were.
[0099]
[Table 1]

[0100]
【The invention's effect】
According to the present invention, since the peeling of the phosphor does not occur, a plasma display substrate capable of manufacturing a high-definition PDP with a high yield can be obtained. Thereby, a high-definition plasma display can be provided. The substrate for plasma display of the present invention is particularly effective in a substrate for plasma display for a back surface in which a phosphor layer is provided on a glass substrate on which electrodes, dielectrics and barrier ribs are provided.

Claims (11)

In a plasma display substrate in which an electrode, a dielectric layer and barrier ribs are provided on a glass substrate, and a phosphor layer is provided thereon, the dielectric layer has a thermal expansion coefficient of 70 to 85 × at 50 to 400 ° C. ^10-7 / ° K glass, and the surface of the partition wall has an arithmetic average roughness Ra of 0.1 μm to 0.31 μm and a maximum height Rt of 1.0 μm to 3.0 μm. A substrate for a plasma display characterized by having a thickness. 2. The plasma display substrate according to claim 1, wherein the arithmetic average roughness Ra is 0.2 μm or more and 0.31 μm or less , and the maximum height Rt is 2.0 μm or more and 3.0 μm or less . 3. The plasma display substrate according to claim 1, wherein the total content of sodium, lithium and potassium elements contained in the partition walls is 2.0 to 20.0 wt%. 4. The plasma display substrate according to claim 1, wherein the partition walls are made of glass having a refractive index of 1.5 to 1.7. The said partition contains the filler of load heat softening temperature (Ts) 650-850 degreeC, The board | substrate for plasma displays in any one of Claims 1-4 characterized by the above-mentioned. 6. The plasma display substrate according to claim 1, wherein the phosphor layer is made of an inorganic phosphor powder. The inorganic phosphor powder is one kind of phosphor powder of any one of [(Y, Gd, Eu) BO ₃ ], [(Zn, Mn) ₂ SiO ₄ ] and [(Ba, Eu) MgAl ₁₀ O ₁₇ ]. Or it contains 2 or more types, The board | substrate for plasma displays of Claim 6 characterized by the above-mentioned.  The plasma display substrate according to claim 1, wherein an alkali metal content of the dielectric layer is 5% by weight or less.  The plasma display substrate according to claim 1, wherein a content of lithium element in the dielectric layer is 3.0% by weight or less.  10. The plasma display according to claim 1, wherein the dielectric layer is made of glass having a glass transition temperature (Tg) of 430 to 500 ° C. and a load heat softening temperature (Ts) of 470 to 580 ° C. 10. Substrate.  The substrate for plasma display according to claim 1, wherein the dielectric layer is made of glass containing 10 to 60% by weight of bismuth oxide.