JP3878792B2 - Protruded substrate, method of manufacturing the same, and flat display - Google Patents

Description

【００７９】
【表２】

【００８０】
表１、２から、所定の金属を添加しない試料Ｎｏ．１、２０では、焼成による収縮率が大きく絶縁基板から剥離してしまった。また、ＺｎＯまたはＳｎＯ_２を添加しない試料Ｎｏ．８では、スペーサが緻密化せず、スペーサ強度が低くなった。
【００８１】
これに対して、本発明に従い、特定の金属およびＺｎＯまたはＳｎＯ_２を添加した試料Ｎｏ．２〜７、９〜１９、２１〜３８では、スペーサの焼成収縮率が小さく、絶縁基板から剥離することなく形成することができ、かつスペーサ強度を１ＭＰａ以上、特に１．５ＭＰａ以上、さらに２ＭＰａ以上と高めることができた。
【００８２】
【発明の効果】
以上詳述したとおり、本発明を構成する磁器組成物は、原料中に特定の金属を添加して焼成により酸化させることにより、焼成による収縮を抑制でき、高いスペーサであっても変形や絶縁基板からの剥離のないスペーサを精度良く作製することができるとともに、ＺｎＯまたはＳｎＯ_２を添加することによって、ガラス中のＰｂＯまたはＢｉ_２Ｏ_３成分がＰｂＯまたはＢｉ_２Ｏ_３として解離することを防止できることから、ガラス中のＰｂＯまたはＢｉ_２Ｏ_３が特定の金属の酸化によって還元され磁器外部に蒸発、揮散することを防止してボイドの発生を抑制して磁器密度を高めることができる。
【００８３】
また、スペーサ中に特定の金属が残存するため、スペーサに導電性を付与することができ、スペーサ表面での帯電を防止することができる。
【００８８】
【発明の効果】
以上詳述したとおり、本発明の磁器組成物は、原料中に特定の金属を添加して焼成により酸化させることにより、焼成による収縮を抑制でき、高いスペーサであっても変形や絶縁基板からの剥離のないスペーサを精度良く作製することができるとともに、ＺｎＯまたはＳｎＯ2を添加し、ＴｉＯ_２を含有しないことによって、ガラス中のＰｂＯまたはＢｉ2Ｏ3成分がＰｂＯまたはＢｉ2Ｏ3として解離することを防止できることから、ガラス中のＰｂＯまたはＢｉ2Ｏ3が特定の金属の酸化によって還元され磁器外部に蒸発、揮散することを防止してボイドの発生を抑制して磁器密度を高めることができる。
【図面の簡単な説明】
【図１】 本発明のスペーサ付基板を用いて構成された平面型ディスプレイの一例を示す概略断面図である。
【符号の説明】
１：平面型ディスプレイ
２：背面板
３：正面板
４：スペーサ
６：電子放出素子
７：拡散防止層
８：蛍光体
１０：ＩＴＯ膜
１１：ブラックマトリックス
１２：枠体
１３：ガス排気口[0001]
BACKGROUND OF THE INVENTION
The present invention includes, for example, a spacer incorporated in a flat display such as a plasma display and a field emission display, an insulating substrate for a wiring board, a ferrule for connecting between optical fibers and optical components, various sealing members, etc. The present invention relates to a porcelain composition suitable as a substrate, a substrate with protrusions using the porcelain, and a flat display.
[0002]
[Prior art]
In recent years, a pair of parallel facing substrates such as a plasma display panel (PDP), a plasma addressed liquid crystal panel (PALC), a field emission display (hereinafter referred to as FED), etc. A flat panel display having a structure in which a space is separated by a spacer (protrusion) has been developed.
[0003]
In the above flat display, it is necessary to keep the inside of the display in a vacuum state, and in order to prevent the substrate from being bent due to an external atmospheric pressure, a plurality of surfaces having a predetermined height on the surface of an insulating substrate such as a glass substrate are provided. A substrate with a projection on which a spacer (projection) is formed is preferably used.
[0004]
In the field emission display panel, a plurality of electron-emitting devices are formed on one of the pair of substrates to generate and accelerate an electron beam, thereby emitting a phosphor formed on the other substrate. However, in order to prevent abnormal discharge between the electron-emitting device and the phosphor, and to obtain a desired luminance by controlling the current density and acceleration state of the electron beam, the distance between the pair of substrates is It is necessary to form a spacer having a high height for separating the spacers by 500 μm or more.
[0005]
On the other hand, in a plasma display panel that is one type of the above flat display, as a method of forming spacers on the substrate surface, conventionally, for example, glass containing PbO on a glass substrate surface made of alkali borosilicate glass, glass ZrO as an improvement in softening point, adjustment of thermal expansion coefficient, or pigment ₂ , SiO ₂ Add a ceramic filler, etc., and then add and mix an organic resin and organic solvent consisting of an acrylic binder, dispersant, etc. to make a paste, and then apply this paste to a predetermined substrate surface by printing and forming a projection Forming a substrate or forming a substrate having a projection-shaped molded body with a molding die, heating the substrate to a temperature at which the substrate does not thermally deform, for example, 550 ° C., and firing the projection to obtain a thickness of 40 μm and a height A spacer of about 150 μm has been formed integrally.
[0006]
[Problems to be solved by the invention]
However, as a method for producing a spacer having a high height on the substrate surface as in the FED, in the method for firing the above-described glass, ceramic filler, and spacer molded body containing an organic resin, the spacer is subjected to firing shrinkage. Therefore, the spacer cannot be formed with high accuracy, and there is a problem that a large firing shrinkage difference is generated between the spacer and the spacer is deformed or the spacer is peeled off from the substrate.
[0007]
That is, since the substrate hardly shrinks during firing of the spacer molded body, a large shrinkage difference occurs between the substrate and the spacer that shrinks during firing. At this time, when the height of the spacer is low, the contraction of the spacer is suppressed by the restraining force of the insulating substrate. In particular, the field emission for forming a high spacer having a thickness of 200 μm or less and a height of 500 μm or more on the substrate surface. In the case of the type display (FED), the contraction force of the spacer is greater than the restraining force of the substrate, and the contraction of the spacer cannot be suppressed, and there is a problem that the spacer is peeled off or deformed.
[0008]
Therefore, in FED, glass and ceramics after firing are processed into a spacer shape by cutting and affixed to the substrate surface to form the spacer. In addition, it is not suitable for miniaturization of spacer thickness and interval.
[0009]
In the FED, the electrons emitted from the electron-emitting device collide with the spacer wall surface existing in the vicinity of the device and the spacer wall surface is charged. As a result, the electron beam emitted from the electron-emitting device is bent, It is impossible to accurately reach a predetermined position on the front plate, the display image is distorted, or abnormal discharge occurs between the electron-emitting device and the spacer, resulting in a decrease in the density of electron beams reaching the phosphor. Thus, there is a problem that a desired luminance cannot be obtained.
[0010]
The present invention has been made to solve the above problems, and is provided with a substrate having a protrusion using a porcelain capable of suppressing shrinkage due to firing as a protrusion, and further, the thickness and interval can be reduced. An object of the present invention is to provide a flat display including a substrate with a spacer that can prevent deformation and separation of the spacer and can prevent the spacer from being charged.
[0011]
[Means for Solving the Problems]
As a result of examining the above problems, the present inventors have found that PbO and / or Bi. ₂ O ₃ For glass containing Si and / or Sn and ZnO and / or SnO ₂ After the molding, the mixture is fired in an oxidizing atmosphere, and as a result, at least a part of the metal is oxidized and volume-expanded. As a result, the shrinkage of the porcelain can be suppressed as a whole, and the spacer is deformed or peeled off. In addition, the spacer having a fine thickness can be formed with high accuracy, and the ZnO and / or SnO. ₂ Is PbO or Bi in the glass ₂ O ₃ Dissociates and PbO or Bi ₂ O ₃ Has been found to be able to increase the density of the porcelain and increase the strength of the spacer since it can be reduced along with the oxidation of the metal and can be prevented from evaporating and volatilizing out of the porcelain.
[0012]
That is, the porcelain composition of the present invention contains at least PbO and / or Bi2O3, and contains, as fillers, metal Si and / or metal Sn, ZnO and / or SnO2, and TiO2. ₂ It is characterized by not containing.
[0013]
Here, the average linear expansion coefficient at 15 to 450 ° C. of the protrusion is 3 to 9 × 10. ^-6 / ° C., the thickness of the projections is 200 μm or less and the height is 300 μm or more, and a plurality of the projections are formed on the surface of the substrate substantially in parallel at a predetermined interval in the thickness direction. It is desirable.
[0014]
Furthermore, the manufacturing method of the board | substrate with a protrusion of this invention is (a) At least PbO and / or Bi. ₂ O ₃ Containing glass, metal Si and / or metal Sn, ZnO and / or SnO ₂ (B) a step of forming a protrusion-shaped molded body by applying and forming the paste obtained in the step (a) on the substrate surface; and (c) the step (b). And baking the substrate obtained in the above in an oxidizing atmosphere to oxidize at least a part of the metal Si and / or the metal Sn in the molded body.
[0015]
Here, the total amount of the metal Si and / or metal Sn is 5 to 70 parts by weight with respect to 100 parts by weight of the glass, and the ZnO and / or SnO. ₂ It is desirable that the metal Si and / or the metal Sn is made of a powder having an average particle size of 6 μm or less.
[0016]
Furthermore, the flat display of the present invention is a flat display in which a plurality of protrusions are disposed between two substrates formed in parallel and spaced apart at a predetermined interval, and the protrusions are made of the above porcelain. It is characterized by.
[0017]
Here, the volume resistivity value of the protrusion at 25 ° C. is 1 × 10. ⁸ ~ 1x10 ¹⁴ It is desirable that it is Ω · cm.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
The porcelain composition constituting the present invention contains PbO and / or Bi. ₂ O ₃ Containing glass, as filler, metal Si and / or metal Sn, ZnO and / or SnO ₂ It contains.
[0019]
Among the above components, as the glass, specifically, PbO—SiO ₂ -B ₂ O ₃ Glass and Bi ₂ O ₃ -B ₂ O ₃ Glass, B ₂ O ₃ At least one selected from the group of -PbO-ZnO glass and PbO-ZnO glass can be used.
[0020]
Further, the softening temperature of the glass is preferably 370 to 850 ° C., particularly 370 to 430 ° C. in terms of low-temperature baking, and the average particle size of the glass is 5 μm or less in terms of forming dense porcelain. In particular, it is desirable that it is 3 μm or less.
[0021]
According to the above configuration, the specific metal of the metal Si and / or the metal Sn is oxidized with volume expansion by heating to a temperature of 350 to 490 ° C. in an oxidizing atmosphere, for example. Thereby, even if the glass powder shrinks due to firing, shrinkage due to firing of the porcelain can be reduced as a whole. For example, metal Si has an oxidation start temperature of about 450 ° C. in the atmosphere. The oxidation start temperature in the present invention means the lowest temperature at which an endotherm accompanying the softening of the glass and an exotherm accompanying the oxidation of the metal occur in the TG-DTA curve and an increase in weight is observed.
[0022]
The specific metal is 5 to 70 parts by weight, particularly 30 to 60 parts by weight in total with respect to 100 parts by weight of the glass in terms of efficient volume expansion and control of conductivity in the porcelain. The average particle size is preferably 6 μm or less, particularly 2 μm or less, and 0.5 to 6 μm, particularly 0.8 to 3 μm, and more preferably 1 to 2 μm in terms of adjusting the viscosity of the paste. Further, the metal may be coated on the glass particle surface.
[0023]
DETAILED DESCRIPTION OF THE INVENTION
The porcelain composition of the present invention contains glass containing PbO and / or Bi2O3, and contains, as a filler, metal Si and / or metal Sn, ZnO and / or SnO2, and TiO2. ₂ It does not contain.
[0024]
The above ZnO and / or SnO ₂ The addition amount of PbO and Bi in the glass ₂ O ₃ The total amount is 10 to 150 parts by weight, particularly 20 to 100 parts by weight, and the total amount of glass is 100 to 50 parts by weight, and the total amount is 5 to 50 parts by weight, especially 10 to 30 parts by weight. Part is desirable.
[0025]
In order to set the shrinkage ratio due to firing of the porcelain to 2% or less, particularly 1% or less, further 0.5% or less, further 0.3% or less, the porcelain is 1000 ° C. or less, particularly 500 ° C. or less, In order to increase the relative density to 65% or more, particularly 70% or more, further 75% or more at 450 to 480 ° C., more preferably 460 to 480 ° C., the glass as a whole is 50 to 75% by weight, The total amount is 3 to 35% by weight, ZnO and / or SnO ₂ The content of is desirably contained in a proportion of 3 to 35% by weight.
[0026]
ZnO and / or SnO ₂ May be coated on the surface of glass particles or metal particles, but in terms of ease of production and cost, the average particle size is 0.05 to 10 μm, particularly 0.1 to 3 μm, and further 0.5 A powder of ˜2 μm is desirable.
[0027]
Furthermore, for the composition described above, for example, TiO having an average particle size of 0.05 to 10 μm. ₂ Is added at a ratio of 16 to 600 parts by weight with respect to 100 parts by weight of the specific metal and 5 to 50 parts by weight with respect to 100 parts by weight of the glass, so that the firing temperature of the spacer is 5 ° C. or more, particularly 10 ° C. As described above, since the temperature can be further lowered by 20 ° C. or more, and further by 30 ° C. or more, even when the electron-emitting device or the phosphor formed on the back plate or the front plate to be sintered and integrated with the spacer is simultaneously fired. These can be prevented from being altered or deteriorated by firing.
[0028]
Furthermore, in order to improve porcelain strength, for controlling the thermal expansion coefficient, for coloring, for controlling the dielectric constant, for controlling the resistivity, further for SiO ₂ , ZrO ₂ , Al ₂ O ₃ Such as ceramic filler, SiO ₂ -Al ₂ O ₃ -MgO system (glass softening point 760 ° C., thermal expansion coefficient 2.8 × 10 ^-6 Other inorganic fillers such as glass such as glass can be added in a total amount of preferably 30% by weight or less, particularly 20% by weight or less.
[0029]
Next, in order to produce a porcelain using the above composition, for example, an organic binder is optionally added to the powdery composition such as a spherical shape, a needle shape, an indeterminate shape, and a hollow shape, and after mixing, A molded body is produced by a known molding method such as press molding, roll molding, extrusion molding, injection molding, or casting.
[0030]
Then, by firing the molded body in an oxidizing atmosphere, the glass in the molded body is sintered and contracted, and at least the surface of a specific metal is oxidized and volume-expanded. The dimensional change rate can be reduced. In addition, although all the specific metals can be oxidized, if a part is left as a metal, electroconductivity can be provided to the porcelain.
[0031]
Next, the porcelain obtained by the above method will be described. The porcelain having the above-described structure is made of PbO and / or Bi. ₂ O ₃ A metal oxide formed by oxidizing metal Si and / or metal Sn added as a raw material and the remaining metal, ZnO and / or SnO ₂ It contains. In the porcelain, in addition to the above components, metals such as Zn, Al, Cu, Mg, and oxides obtained by firing these oxides, TiO ₂ , ZrO ₂ , SiO ₂ Other ceramic fillers such as SiO ₂ -Al ₂ O ₃ -Other inorganic fillers, such as high softening point glass, such as MgO, may be contained.
[0032]
Here, the volume resistivity of the porcelain is 1 × 10 ⁸ ~ 1x10 ¹⁴ In the case of Ω · cm, the metal content in the porcelain is 34% by weight or less, particularly 1.5 to 34% by weight, and the metal particle size is 5.9 μm or less, particularly 0.3 to 5. It is desirable that it is 9 micrometers, and also 0.3-3 micrometers.
[0033]
Since the above porcelain can suppress shrinkage due to firing, it can be used, for example, as a ferrule for an optical fiber connector, an insulating substrate for a wiring substrate with high dimensional accuracy, and further as a sealing member. As a projection of the substrate with the projection, it can be suitably used as a flat display having the projection.
[0034]
Next, a description will be given based on FIG. 1 which is a schematic sectional view of a field emission display (FED) which is an example of the flat display according to the present invention. In FIG. 1, the flat display 1 is provided with a spacer 4 at a predetermined position between two substrates of a back plate 2 and a front plate 3 which are formed in parallel at a predetermined interval.
[0035]
As the back plate 2, a glass substrate such as quartz glass, soda lime glass, low soda glass, lead alkali silicate glass, borosilicate glass, ceramic substrate such as alumina or silica, Si substrate, etc. can be used. And low soda glass with low lead content is desirable.
[0036]
Next, the porcelain obtained by the above method will be described.
The porcelain of the present invention comprises a glass containing PbO and / or Bi2O3, a metal oxide formed by oxidation of metal Si and / or metal Sn added as a raw material and the remaining metal, ZnO and / or SnO2 and TiO ₂ It does not contain. In the porcelain, in addition to the above components, metals such as Zn, Al, Cu, and Mg, oxides thereof oxidized by firing, other ceramic fillers such as TiO2, ZrO2, and SiO2, SiO2-Al2O3-MgO Other inorganic fillers such as high softening point glass, etc. may be contained.
[0037]
The spacer 4 is formed in a rib shape, a lattice shape, a column shape, a frame shape, or the like. For example, in the case of a rib shape, it is desirable that the spacer 4 be formed in parallel with a predetermined interval. The spacer 4 is made of lead glass (PbO-B) in terms of mechanical strength, adhesion to an insulating substrate, and long-term chemical stability of the material. ₂ O ₃ -SiO ₂ ), Bismuth-based glass (Bi-B) ₂ O ₃ However, according to the present invention, the spacer 4 is characterized in that metal Si and / or metal Sn is dispersed in a sintered body mainly composed of glass. The spacer 4 has a volume resistivity of 1 × 10 at 25 ° C. ⁸ ~ 1x10 ¹⁴ Conductivity of Ω · cm can be imparted and the spacer 4 can be prevented from being charged.
[0038]
Here, among the metals, metal Si is most suitable in terms of conductivity imparting effect, oxidation start temperature, increase rate of volume expansion coefficient due to metal oxidation, familiarity with glass, and adhesion. In addition to the metal Si or metal Sn, the metal may contain at least one selected from the group consisting of Zn, Al, Cu, and Mg, and an oxide in which some of these are oxidized is contained. May be. Of the oxides formed by oxidation of the metal, for example, SnO ₂ , ZnO, CuO, and the like have an effect of increasing conductivity.
[0039]
Further, in the spacer 4, as desired, as a ceramic filler, TiO ₂ , ZrO ₂ ZnO, SnO ₂ , SiO ₂ , BN, Al ₂ O ₃ Etc. are used, and the glass strain point is adjusted to prevent deformation of the burning spacer, control of the thermal expansion coefficient of the spacer 4, coloring, and the like.
[0040]
Furthermore, according to the present invention, even when the spacer 4 has a thickness of 200 μm or less, particularly 100 μm or less, and a height of 500 μm or more, particularly 1500 μm or more, the spacer 4 is shrunk by firing and deforms and does not peel off. In addition, it is possible to form spacers having a fine interval of 400 μm or more, particularly 5 mm or less, and further 1 mm or less.
[0041]
The spacer 4 has a thickness of 100 to 200 μm from the viewpoint of strength and downsizing and an improvement in display brightness, and the spacer 4 has a height of no short-circuit discharge between the electron-emitting device and the phosphor. In view of controlling the electron beam density reaching the desired amount to 500 to 4000 μm, it is desirable.
[0042]
Further, the back plate 2 or the front plate 3 and the spacer 4 are firmly joined and integrated by firing the spacer 4, and are bonded and fixed to the other substrate by an adhesive or the like.
[0043]
In addition, even when the substrate with spacers is heated and cooled again in the manufacturing process, the spacers 4 do not generate defects such as cracks, so that the average thermal expansion coefficient of the spacers 4 at 15 to 450 ° C. is 7 to 9 × 10. ^-6 / ° C, especially 7.5 to 8.2 × 10 ^-6 / ° C is desirable.
[0044]
On the other hand, an electron-emitting device 6 is formed on the surface of the back plate 2. The specific structure of the electron-emitting device 6 is, for example, formed such that a plurality of line-like positive electrode layers and negative electrode layers arranged in parallel with a predetermined distance therebetween intersect, and the positive electrode layer and the negative electrode layer An MIM type structure in which an insulator is interposed at the intersection of electrode layers, a surface conductive type in which a positive electrode layer and a negative electrode layer are separated by a predetermined distance with an insulating layer interposed therebetween, and between a positive electrode layer and a negative electrode layer A field emission type or the like in which an insulator is interposed and the positive electrode layer and the insulator are partially cut out at a predetermined position and a protruding insulator is provided at the cutout portion can be suitably used.
[0045]
As the positive electrode layer and the negative electrode layer, at least one metal or alloy selected from the group of silver, aluminum, nickel, platinum, gold, palladium, amorphous silicon, polysilicon, graphite, and the like can be used. Moreover, as an insulator, what mainly has at least 1 sort (s) of oxides, nitrides, etc. selected from the group of Si, Ti, Ga, W, Al, and Pd can be used conveniently.
[0046]
Further, a diffusion prevention layer 7 made of silica, silicon nitride, or the like is formed between the back plate 2 and the electron emitter 6 in order to prevent diffusion of impurities into the electron emitter 6.
[0047]
On the other hand, a phosphor 8 is deposited on the surface of the front plate 3 on the spacer 4 formation side. A plurality of sets of phosphors 8 are regularly arranged with at least three types of phosphors 8 emitting at least one of red (R), green (G), and blue (B) as one set, The electron-emitting device 6 is formed at a position facing each phosphor 8, and an electron beam is emitted from the electron-emitting device 6 and collides with the phosphor 8 at a position facing the phosphor 8. Make it emit light.
[0048]
Further, according to FIG. 1, transparent ITO (indium-tin oxide) is interposed between the front plate 3 and the phosphor 8 in order to accelerate the electron beam emitted from the electron-emitting device 6 toward the phosphor 8. ) The film 10 is formed, but the present invention is not limited to this. In order to accelerate the electron beam and reflect the scattered light emitted from the phosphor 8 to increase the light emission luminance, the ITO film is formed. Instead, a metal back (not shown) made of a metal layer such as a metal foil of 100 to 300 nm of aluminum, silver, nickel, platinum or the like is deposited on the surface of the phosphor 8 formed on the front plate 3 surface. Is desirable.
[0049]
Further, in order to obtain a sharp image on the portion of the front plate 3 other than the phosphor 8 forming portion on the surface side where the phosphor 8 is formed, by preventing color bleeding in the flat display 1 and increasing the contrast of the display screen. Further, for example, a black or dark black matrix 11 made of a mixture of an oxide such as iron, nickel, copper, or manganese and a low-melting glass, or metallic chromium or graphite is deposited.
[0050]
Further, a frame body 12 is disposed on the outer peripheral portion of the back plate 2 and the front plate 3, and the back plate 2, the front plate 3 and the frame body 12 are bonded and sealed with an adhesive such as frit glass. Thus, the flat display 1 can be manufactured. Further, a gas exhaust port 13 for evacuating the flat display 1 is provided at an end of the back plate 2, and the inside of the flat display is vacuum-sealed by the gas exhaust port 13.
[0051]
According to FIG. 1, the spacers 4 are arranged for each of the three groups of R, G, and B of the phosphor 8, but the present invention is not limited to this, It may be arranged for each phosphor 8 or may be arranged for each of a plurality of sets of the phosphors 8.
[0052]
Further, the present invention is not limited to the FED shown in FIG. 1, and is a plane in which a display such as a plasma display panel (PDP) or a plasma addressed liquid crystal panel (PALC) is sealed with a vacuum or a gas at a predetermined atmospheric pressure. Any type display can be suitably applied.
[0053]
<Manufacturing method>
Next, a method for manufacturing the above-described FED will be described. First, a back plate made of the above-described material is prepared, cut into a predetermined shape, and a diffusion prevention layer is formed on one surface of the back plate by sputtering, CVD, ion beam, vapor deposition, MBE, etc. After that, the surface of the electron-emitting device is masked by a photolithography method or the like on the surface, and the electron-emitting device is formed by a known thin film forming method such as a sputtering method, a vapor deposition method, an ion beam method, a CVD method, or an MBE method. An insulator is formed to form an electron-emitting device.
[0054]
On the other hand, for glass having an average particle size of 0.5 to 6 μm, at least one metal selected from the group consisting of chromium, molybdenum, iron, silicon, zircon, zinc, copper, aluminum, and tin, and ZnO and / or SnO ₂ If necessary, an acrylic binder or the like, an organic resin such as a plasticizer or a dispersant, and an organic solvent are added and kneaded to prepare a paste.
[0055]
In addition, the said metal consists of shapes, such as spherical shape, indefinite shape, a hollow shape, powder shape, such as flake shape, or fiber shape, and an average particle diameter of 0.5-6 micrometers, Especially 0.8-3.0 micrometers, Furthermore, 1. The thickness of 0 to 2.0 μm is desirable in that the metal remains in the sintered body and the specific surface area of the metal is increased to promote the volume expansion effect due to metal oxidation.
[0056]
Further, the amount of the metal added is that the specific metal is added to 100 parts by weight of the glass in terms of suppressing the firing shrinkage, improving the dispersibility of the spacer paste, and improving the strength of the spacer. The total amount is preferably 5 to 70 parts by weight, more preferably 20 to 60 parts by weight, and further ZnO and / or SnO. ₂ The amount of addition is preferably 5 to 50 parts by weight, particularly 10 to 30 parts by weight, from the viewpoint of densification of the spacer and improvement of the spacer strength. Furthermore, for example, ZrO may be added to the paste as desired. ₂ , Al ₂ O ₃ , SiO ₂ And other fillers are added.
[0057]
Then, a plurality of spacer molded bodies having a thickness of 100 to 200 μm and a height of 500 to 4000 μm are formed on the surface of the insulating substrate using the paste at intervals of 400 μm or more.
[0058]
Then, a plurality of the spacer moldings are produced on the surface of the back plate using the paste. According to the present invention, for example, a spacer molded body having a thickness of 100 to 200 μm and a height of 500 to 4000 μm can be produced at a pitch of 400 μm or more.
[0059]
As a specific method for forming the spacer molded body, (a) a method of forming the spacer molded body by printing and applying the paste a plurality of times, and (b) the mold in a mold made of rubber, metal, ceramics, etc. After filling the spacer paste, the mold is brought into contact with the insulating substrate, and then the mold is removed. (C) A sheet having a desired thickness is formed on the surface of the insulating substrate using the paste. (D) A method for removing a spacer-shaped groove on the surface of the sheet after placing and pressing a rigid plate-shaped mold having a spacer-shaped groove formed on the surface of the sheet and pressing it. A roll-shaped mold having a high rigidity is placed and rotated while pressing to form a spacer molding, (e) a sandblasting method, (f) a spacer is separately formed, processed, and processed into a glass frit Contact And a method of bonding at a predetermined position of the back plate can be used by the agent.
[0060]
As a method for forming the spacer molded body, a method (b) for making it possible to easily form a high spacer having a height of 1000 μm or more and making the porosity of the spacer within a predetermined range, or a method other than the above After forming the groove by pressing and releasing with the above-mentioned mold in which the resin layer is formed on the substrate surface and the spacer-shaped protrusion is formed, the above-described slurry for forming the spacer is filled in the groove Then, a method of curing and removing the resin layer is preferable.
[0061]
Then, the board | substrate with a protrusion which integrated the backplate and the spacer is produced by baking the board | substrate with which the molded object for spacers was formed, for example at 420-480 degreeC.
[0062]
If the firing is performed in an oxidizing atmosphere such as air or oxygen, the glass in the spacer molded body sinters and shrinks, but the metal oxidizes from the surface and expands in volume. Baking shrinkage of the molded body is suppressed, a spacer with a small dimensional change rate can be manufactured, and a spacer with high dimensional accuracy without deformation or peeling from the insulating substrate can be formed.
[0063]
Moreover, according to the present invention, as described above, ZnO and / or SnO. ₂ Is added to the spacer, the relative density of the spacer can be improved to 65% or more, particularly 68% or more, and further 70% or more. Therefore, the spacer is formed on the back plate or the front plate to be integrated with the spacer. Even when the electron-emitting device and the phosphor are simultaneously fired, they can be prevented from being altered or deteriorated by firing, and the load resistance (strength) of the spacer is increased to 1 MPa or more, particularly 1.5 MPa or more, and further 2 MPa or more. Can do.
[0064]
On the other hand, after producing a front plate made of the above-described material and processing it into a predetermined shape, a printing method such as a known printing method such as a screen printing method, a gravure printing method, an offset printing method, roll, etc. on one surface of the front plate After an ITO film is deposited by a paste application method such as a coater method or a vapor deposition method, a black matrix having a predetermined shape is applied by a known printing method such as a photolithography method, a screen printing method, a gravure printing method, or an offset printing method. It forms.
[0065]
Next, the phosphor paste is applied to a predetermined position of the area surrounded by the black matrix on the front plate by a photolithography method, a screen printing method, a gravure printing method, a printing method such as an offset printing method, an ink jet method or the like. Form. If the ITO film is not formed, a resin layer is formed on the front plate surface by a printing method such as a photolithography method, a screen printing method, a gravure printing method, and an offset printing method, if desired. Thereafter, a metal back is deposited on the predetermined position by vapor deposition or the like, and a resin layer is further formed on the metal back surface.
[0066]
Further, the phosphor paste or the paste and resin layer are heat-treated at 400 to 600 ° C., particularly 450 to 500 ° C., and the organic component and the resin layer in the phosphor are volatilized and removed to form a front plate.
[0067]
On the other hand, a frame body that is disposed on the outer periphery of the back plate and the front plate and seals the inside of the display is produced.
[0068]
And after arrange | positioning a frame to the outer peripheral part of a backplate, and bonding together with adhesives, such as frit glass, it is frit glass on the top of this frame, and the spacer top of the backplate which integrated the above-mentioned spacer by sintering. The phosphor forming surface of the front plate is aligned and bonded so that the top of the spacer is disposed at a predetermined position other than the phosphor forming portion.
[0069]
Furthermore, a gas exhaust port for exchanging gas with the inside of the display is formed in advance at the end of the back plate, and connected to an external gas exhaust pipe. Then, a vacuum pump is connected to the gas exhaust pipe provided in the frame body, and the inside of the panel is ^-Four The flat display of the present invention is manufactured by heating to 400 to 500 ° C. while reducing the pressure to about Pa to fix the adhesive between the front plate, the back plate and the frame, and sealing the gas exhaust port. can do.
[0070]
In the above flat display manufacturing method, the spacer is integrally formed on the back plate side. However, the present invention is not limited to this, and the spacer may be integrally formed on the front plate side. Good. In this case, it is desirable to form a spacer after forming the phosphor on the front plate surface in advance.
[0071]
【Example】
The following two types of glasses A and B were prepared. Glass A: PbO-SiO ₂ -B ₂ O ₃ (Softening point is 410 ° C.) Glass B: Bi ₂ O ₃ -B ₂ O ₃ (Softening point is 420 ° C.) With respect to 100 parts by weight of the above two types of glasses, the metals shown in Tables 1 and 2 and ZnO or SnO having an average particle diameter of 2 μm ₂ Were added in the proportions shown in Tables 1 and 2, and wet mixed in IPA (isopropyl alcohol) for 18 hours in a ball mill using zirconia balls.
[0072]
Then, with respect to 100 parts by weight of the obtained mixed powder, a binder, a polymerization initiator, and a dispersing agent are added so that the total amount is 42 parts by weight, and mixed in a carbitol solvent to produce a paste. Then, after filling the silicone rubber mold with the paste and sufficiently defoaming, it is in contact with the surface of the insulating substrate made of borosilicate glass, vacuum-sealed, and heat-treated at 110 ° C. for 30 minutes. By extracting, a molded article for spacer was formed.
The obtained molded body was measured for the thickness and height of the molded body spacer using a laser displacement meter (LC-2440 / 2400, manufactured by Keyence Corporation), and was confirmed to be the same size as the silicone rubber mold within the measurement accuracy. confirmed.
[0073]
The silicone rubber mold has a recess depth (spacer height) of 1200 μm, a recess width (spacer thickness) of 200 μm, a recess (spacer) length of 8 cm, and a distance between the recesses (inter-spacer distance). Of 800 μm was used.
[0074]
Further, the compact is fired in the atmosphere at 450 ° C. for 15 minutes, and the height of the spacer is measured with a laser displacement meter in the same manner as described above, and the ratio of the spacer height to the height of the spacer compact (( The height of the spacer / the height of the molded article for spacer) × 100 (%)) was calculated as the shrinkage rate, which is the dimensional change rate.
[0075]
In addition, another flat plate is placed on the spacer end of the obtained substrate with spacers, a force is applied to compress both the substrates in the spacer height direction, the load F at which the spacer breaks is measured, and the total spacers are measured. The pressure P (F / S) with respect to the cross-sectional area S was calculated as the spacer strength.
[0076]
Further, the appearance of the spacer was observed with a stereomicroscope, and the presence / absence of peeling, warping, bending, or cutting was judged.
[0077]
Furthermore, a part of the spacer was crushed and X-ray diffraction measurement was performed to confirm the constituent components. Sample No. It was confirmed that the oxide of the metal was present in any sample except 1. Furthermore, the volume specific resistance value (described as “resistance” in the table) was measured for a part of the spacer with an insulation meter. The results are shown in Tables 1 and 2.
[0078]
[Table 1]

[0079]
[Table 2]

[0080]
From Tables 1 and 2, sample no. In Nos. 1 and 20, the shrinkage ratio due to firing was large and the film was peeled off from the insulating substrate. ZnO or SnO ₂ Sample No. without addition of In No. 8, the spacer was not densified and the spacer strength was low.
[0081]
In contrast, according to the present invention, certain metals and ZnO or SnO ₂ Sample No. to which 2 to 7, 9 to 19, and 21 to 38, the firing shrinkage rate of the spacer is small, it can be formed without peeling from the insulating substrate, and the spacer strength is 1 MPa or more, particularly 1.5 MPa or more, and further 2 MPa or more. I was able to increase.
[0082]
【The invention's effect】
As described in detail above, the porcelain composition constituting the present invention can suppress shrinkage due to firing by adding a specific metal to the raw material and oxidizing it by firing. Can be manufactured with high accuracy, and ZnO or SnO ₂ By adding PbO or Bi in the glass. ₂ O ₃ Component is PbO or Bi ₂ O ₃ Can be prevented from dissociating as PbO or Bi in the glass. ₂ O ₃ Can be reduced by oxidation of a specific metal and evaporated and volatilized outside the porcelain, thereby suppressing the generation of voids and increasing the porcelain density.
[0083]
Further, since a specific metal remains in the spacer, conductivity can be imparted to the spacer and charging on the spacer surface can be prevented.
[0088]
【The invention's effect】
As described above in detail, the porcelain composition of the present invention can suppress shrinkage due to firing by adding a specific metal to the raw material and oxidizing it by firing. A spacer without peeling can be produced with high accuracy, and ZnO or SnO2 is added, and TiO 2 is added. ₂ By not containing PbO or Bi2O3 in the glass can be prevented from dissociating as PbO or Bi2O3, PbO or Bi2O3 in the glass is reduced by oxidation of a specific metal and evaporated and volatilized outside the porcelain. This can prevent the generation of voids and increase the porcelain density.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an example of a flat display configured using a substrate with spacers of the present invention.
[Explanation of symbols]
1: Flat panel display
2: Back plate
3: Front plate
4: Spacer
6: Electron emitting device
7: Diffusion prevention layer
8: Phosphor
10: ITO film
11: Black matrix
12: Frame
13: Gas exhaust port

Claims (10)

A substrate with protrusions formed by integrally forming protrusions on a substrate surface, wherein the protrusions include glass containing PbO and / or Bi ₂ O ₃ , metal Si and / or metal Sn, and an oxide of the metal , ZnO and / or SnO ₂ and comprising a porcelain containing no TiO ₂ . The porcelain, with projections substrate according to claim 1, volume resistivity at 25 ° C. is ^{1 × 10 8 ~1 × 10 14} Ω · cm. 3. The substrate with protrusions according to claim 1, wherein an average linear expansion coefficient at 15 to 450 ° C. of the protrusions is 3 to 9 × 10 ⁻⁶ / ° C. 3.   The substrate with protrusions according to claim 1, wherein the protrusion has a thickness of 200 μm or less and a height of 300 μm or more.   5. The substrate with protrusions according to claim 1, wherein a plurality of the protrusions are formed on the surface of the substrate substantially in parallel with a predetermined interval in the thickness direction. (A) producing a paste containing PbO and / or Bi ₂ O ₃ , metal Si and / or metal Sn, ZnO and / or SnO ₂ and not TiO ₂ ; A step of applying and forming the paste obtained in the step (a) on the surface of the substrate to form a protrusion-shaped molded body, and a step (c) firing the substrate obtained in the step (b) in an oxidizing atmosphere. And the process of oxidizing at least one part of the said metal in the said molded object is comprised, The manufacturing method of the board | substrate with a protrusion characterized by the above-mentioned. The paste in the step (a) is 5 to 70 parts by weight of the total amount of the metal Si and / or metal Sn and 5 to 50 parts by weight of the ZnO and / or SnO ₂ with respect to 100 parts by weight of the glass. The method for manufacturing a substrate with protrusions according to claim 6, wherein the substrate is contained in a proportion.   The method for manufacturing a substrate with protrusions according to claim 7, wherein the metal Si and / or the metal Sn is made of powder having an average particle diameter of 6 μm or less. A flat display in which a plurality of protrusions are disposed between two substrates formed in parallel and spaced apart at a predetermined interval, wherein the protrusions include glass containing PbO and / or Bi ₂ O ₃ and metal A flat display comprising a porcelain containing Si and / or metal Sn, an oxide of the metal, ZnO and / or SnO ₂ and not containing TiO ₂ . 10. The flat display according to claim 9, wherein the porcelain has a volume resistivity value at 25 ° C. of 1 × 10 ⁸ to 1 × 10 ¹⁴ Ω · cm.

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