JP3878790B2 - Protruded substrate and method for manufacturing the same, flat display and method for manufacturing the same - Google Patents

Description

【００９３】
表１から、所定の金属を添加しない試料Ｎｏ．１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、ＴｉＯ₂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。
【００９４】
これに対して、本発明に従い、特定の金属およびＴｉＯ₂を添加した試料Ｎｏ．２〜７、９〜２３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２ＭＰａ以上と高めることができた。
【００９５】
（実施例２）
実施例１のルチル型ＴｉＯ₂をアナターゼ型ＴｉＯ₂に代える以外は、実施例１と同様に磁器を作製し、同様に評価した。焼成開始温度についても図３の試料Ｎｏ．２７についてのＴＧ−ＤＴＡ曲線から実施例１同様に算出した。結果は表２に示した。
【００９６】
【表２】

【００９７】
表２の結果から明らかなように、所定の金属を添加しない試料Ｎｏ．２４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。
【００９８】
これに対して、本発明に従い、特定の金属およびＴｉＯ₂を添加した試料Ｎｏ．２５〜４７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２ＭＰａ以上と高めることができた。
【００９９】
【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、ＴｉＯ₂を添加することによって、特定金属の酸化開始温度を低めることができることから、磁器の焼成温度を低めることができる。
【０１００】
特に、アナターゼ型ＴｉＯ₂はガラスを還元することなく、金属の酸化温度を低下させることができることから、ガラス中の成分が流失して磁器密度を低下させることなく低温焼成での磁器の緻密化を促進することができる。
【０１０１】
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。
【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。
【図２】試料Ｎｏ．４のスペーサ原料の大気中での熱重量分析（ＴＧ）、示差熱分析（ＤＴＡ）の結果および焼結開始温度を算出する方法を示すグラフである。
【図３】試料Ｎｏ．２７のスペーサ原料の大気中での熱重量分析（ＴＧ）、示差熱分析（ＤＴＡ）の結果および焼結開始温度を算出する方法を示すグラフである。
【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 relates to a substrate with protrusions used in, for example, a plasma display and a manufacturing method thereof, and a flat display and a manufacturing method thereof.
[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 protrusions on which the spacers (protrusions) are 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 which is one type of the above flat display, as a method of forming a spacer on the substrate surface, conventionally, for example, a glass softening point is formed on a glass substrate surface made of alkali borosilicate glass. ZrO to increase or as a 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 body or forming a substrate having a projection-shaped molded body by a molding die, heating the substrate to a temperature at which the substrate does not shrink, for example, 550 ° C., and firing the projection to obtain a thickness of 40 μm and a height of 150 μm. It has been practiced to integrally form spacers of a certain degree.
[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, but the dimensions and position accuracy are low, and it takes time and effort. In addition, it is not suitable for miniaturization of spacer thickness and interval.
[0009]
In the FED, electrons emitted from the electron-emitting device collide with a 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 with respect to the above-mentioned problems, and it is possible to reduce the thickness and interval of a porcelain composition and porcelain that can suppress shrinkage due to firing, a substrate with a projection using the same, and a substrate with a projection. In addition, an object of the present invention is to provide a flat display including a substrate with a spacer that can prevent deformation of the spacer and separation of the spacer accompanying firing, and can prevent charging of the spacer.
[0011]
[Means for Solving the Problems]
As a result of studying the above problems, the present inventors have found that at least one metal of Zn, Al, Sn, Cu, Mg and TiO ₂ After 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. And a fine spacer can be formed with high accuracy, and the TiO ₂ Lowers the oxidation start temperature of the specific metal, so that the sintering temperature of the porcelain can be lowered, and further, by leaving the metal in the porcelain, desired conductivity can be imparted to the porcelain. It has been found that the spacer can be prevented from being charged when used as a spacer for a flat display.
[0019]
Furthermore, the substrate with protrusions of the present invention is a substrate with protrusions formed by integrally forming protrusions on the surface of the substrate, wherein the protrusions are made of the above-mentioned porcelain. Average linear expansion coefficient at 3 ° C. is 3-9 × 10 ^-6 / ° C is desirable.
[0020]
In particular, it is effective for the protrusion having a thickness of 200 μm or less and a height of 300 μm or more, and a plurality of the protrusions are formed on the surface of the substrate substantially in parallel at a predetermined interval in the thickness direction. It is desirable that
[0021]
Moreover, the manufacturing method of the board | substrate with a protrusion of this invention is (a) glass with an average particle diameter of 5 micrometers or less, at least 1 type of metal among Si, Zn, Al, Sn, Cu, and Mg, and TiO. 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 by the above in an oxidizing atmosphere to oxidize at least a part of the metal in the molded body.
[0022]
Here, the glass is 50 to 75 wt%, the metal is 3 to 35 wt% in total, and the TiO ₂ Is contained in a ratio of 3 to 35% by weight, and the glass is at least PbO, Bi. ₂ O _Three And B ₂ O _Three It is desirable that the material contains at least one selected from the above, further contains another inorganic filler, and the metal is made of a powder having an average particle size of 6 μm or less.
[0023]
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. The volume specific resistance value of the protrusion at 25 ° C. is 1 × 10 ⁸ ~ 1x10 ¹⁴ It is desirable that it is Ω · cm.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
The porcelain composition of the present invention includes glass, at least one metal selected from Si, Zn, Al, Sn, Cu, and Mg, and TiO. ₂ It contains.
[0025]
Among the above components, as the glass, PbO-based glass, Bi ₂ O _Three Glass, SiO ₂ -B ₂ O _Three Glass, soda glass, silica glass, etc. can be used, but PbO, SiO in particular in terms of low-temperature sintering and wettability with metal particles, and also in terms of bondability with other substrates of porcelain. ₂ , Bi ₂ O _Three And B ₂ O _Three Containing at least one selected from, more specifically, PbO-SiO. ₂ -B ₂ O _Three Glass and Bi ₂ O _Three -B ₂ O _Three Glass, B ₂ O _Three It is desirable to contain -PbO-ZnO glass and PbO-ZnO glass.
[0026]
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.
[0027]
According to the present invention, the specific metal oxidizes with volume expansion by heating to a temperature of 350 to 490 ° C. in an oxidizing atmosphere, so that the glass powder shrinks by firing. Even so, 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.
[0028]
The specific metal has an average particle size of 6 μm or less, particularly 2 μm or less in terms of efficient volume expansion and conductivity control in porcelain, and 0.5 to 6 μm, particularly in terms of adjusting the viscosity of the paste. It is desirable that it is 0.8-2 micrometers. Further, the metal may be coated on the surface of glass particles.
[0029]
Further, according to the present invention, as described above, by adding TiO 2, the firing temperature of the spacer can be lowered by 5 ° C. or more, particularly 10 ° C. or more, further 20 ° C. or more, and further 30 ° C. or more. Even when an electron-emitting device, a phosphor or the like formed on the back plate or front plate to be sintered and integrated are fired at the same time, they can be prevented from being altered or deteriorated by firing.
[0030]
Here, the TiO ₂ As rutile TiO ₂ And / or anatase TiO ₂ Can be used. Of these, rutile TiO ₂ Is another structure of TiO ₂ Since it exhibits a stronger catalytic action than the above, the effect of lowering the sintering start temperature of the porcelain is large, and the sintering temperature of the porcelain can be lowered, for example, by 10 ° C. or more, particularly 20 ° C. or more, and further by 30 ° C.
[0031]
Rutile TiO ₂ Has a strong catalytic action to promote the oxidation of the specific metal described above and has a large effect of lowering the firing temperature of the porcelain. However, since the glass is reduced, the anatase TiO has a moderate catalytic action and does not reduce the glass. ₂ It is desirable to use In addition, when glass is reduced, for example, components in the glass such as lead flow out of the porcelain and the porcelain density decreases, resulting in a decrease in porcelain strength.
[0032]
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, and further 75% or more at 480 ° C. or lower, more preferably 460 ° C. or lower, the total amount of the metal is 50 to 75% by weight as a whole. 3 to 35% by weight and the TiO ₂ The TiO 2 content is preferably 3 to 35% by weight, and the TiO is added to 100 parts by weight of the specific metal. ₂ It is desirable to add 16 to 600 parts by weight.
[0033]
TiO ₂ May be coated on the surface of glass particles or metal particles. However, in order to efficiently reduce the sintering start temperature of the porcelain, the average particle diameter of the TiO2 is 0.05 to 10 μm, particularly 0. It is desirable to be a powder of 05-2 μm.
[0034]
Furthermore, to improve porcelain strength, to control thermal expansion coefficient, to color, to control dielectric constant, to control resistivity, and further to SiO ₂ , ZrO ₂ , Al ₂ O _Three Such as ceramic filler, SiO ₂ -Al ₂ O _Three -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 desirably contained in a total amount of 30% by weight or less, particularly 20% by weight.
[0035]
Next, in order to produce the porcelain of the present invention using the composition, for example, an organic binder is added to the powdery composition such as a spherical shape, a needle shape, an indeterminate shape, and a hollow shape, if desired. After mixing, a molded body is produced by a known molding method such as press molding, roll molding, extrusion molding, injection molding, or cast molding.
[0036]
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.
[0037]
Next, the porcelain obtained by the above method will be described.
The porcelain of the present invention includes glass, a metal oxide formed by oxidizing at least one metal of Si, Zn, Al, Sn, Cu, and Mg added as a raw material, and the remaining metal, TiO 2 It contains.
[0038]
Here, the volume resistivity of the porcelain is 10 ⁸ -10 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.
[0039]
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 protrusion of such a substrate with protrusions, it can be suitably used as a flat display having the protrusion.
[0040]
Therefore, 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.
[0041]
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 and silica, Si substrate, etc. can be used. And low soda glass with low lead content is desirable.
[0042]
On the other hand, the front plate 3 is made of a glass substrate such as quartz glass, soda lime glass, low soda glass, lead alkali silicate glass or borosilicate glass, or a transparent substrate mainly composed of sapphire, quartz, single crystal zirconia, diamond or the like. Is formed.
[0043]
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.
[0044]
The spacer 4 is made of glass and / or ceramics, for example, lead glass (PbO-B ₂ O _Three -SiO ₂ ), Alkali silicate glass, bismuth glass (Bi-B) ₂ O _Three ) And other known glasses are used, but lead-based glass (PbO-B) in terms of mechanical strength, adhesion to insulating substrates, and long-term chemical stability of the material. ₂ O _Three -SiO ₂ ), Bismuth-based glass (Bi-B) ₂ O _Three ) Is desirable.
[0045]
According to the present invention, the spacer 4 is characterized in that at least one metal among Si, Zn, Al, Sn, Cu, and Mg is dispersed in a sintered body mainly composed of glass.
[0046]
As a result, the volume resistivity 1 × 10 × 10 at 25 ° C. is applied to the spacer 4. ⁸ ~ 1x10 ¹⁴ The conductivity of Ω can be imparted, and the spacer 4 can be prevented from being charged.
[0047]
Here, among the above metals, Si, Zn, and Sn are more compatible with glass and adhesion in terms of conductivity imparting effect, oxidation start temperature, and rate of increase in volume expansion due to metal oxidation. Metal Si is optimal.
[0048]
Of the oxides formed by oxidation of the metal, for example, SnO ₂ , ZnO, CuO, and the like have an effect of increasing conductivity.
[0049]
The spacer 4 is made of, for example, lead-based glass (PbO-B ₂ O _Three -SiO ₂ System), alkali silicate glass, bismuth glass (Bi-B) ₂ O _Three ) And other known glasses are used, but lead glass (PbO-B) is used in terms of mechanical strength, adhesion to insulating substrates, and long-term chemical stability of the material. ₂ O _Three -SiO ₂ System), bismuth-based glass (Bi-B) ₂ O _Three ) Is desirable.
[0050]
Further, in the spacer 4, as desired, as a ceramic filler, TiO ₂ , ZrO ₂ , ZnO, SiO ₂ , BN, Al ₂ O _Three 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.
[0051]
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.
[0052]
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.
[0053]
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.
[0054]
In addition, even when the substrate with spacers is heated and cooled again in the manufacturing process, the spacer 4 does 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 ppm / ° C., In particular, it is desirable to be 7.5 to 8.2 ppm / ° C.
[0055]
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.
[0056]
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.
[0057]
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.
[0058]
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.
[0059]
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.
[0060]
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.
[0061]
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.
[0062]
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.
[0063]
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.
[0064]
(Production 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.
[0065]
On the other hand, at least one metal selected from the group consisting of chromium, molybdenum, iron, silicon, zircon, zinc, copper, aluminum, and tin, and an average particle size of 0. A paste is prepared by adding 3 to 3 μm of rutile TiO 2 and, if desired, an acrylic binder or the like, an organic resin such as a plasticizer or a dispersant, and an organic solvent, and kneading them.
[0066]
The metal has a spherical shape, an indeterminate shape, a hollow shape, a flake shape such as a powder shape or a fiber shape, and has an average particle size of 0.5 to 6 μm, particularly 1.0 to 3.0 μm. This is desirable in that the metal remains in the sintered body, and in that the specific surface area of the metal is increased and the volume expansion effect due to oxidation of the metal is promoted.
[0067]
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, particularly 20 to 60 parts by weight. Further, the amount of TiO 2 added is 5 to 70 parts by weight, particularly 15 to 40 parts by weight in terms of low-temperature firing and low dielectric constant. Part is desirable.
[0068]
Furthermore, in the paste, for example, ZrO ₂ , Al ₂ O _Three , SiO ₂ And other fillers are added.
[0069]
Then, using the paste, for example, a plurality of spacer molded bodies having a thickness of 100 to 200 μm and a height of 500 to 1500 μm are produced on the surface of the insulating substrate at intervals of 400 μm or more.
[0070]
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.
[0071]
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 being pressed 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.
[0072]
As a method for forming the spacer molded body, a method (b) or a method other than the above can be used in order to easily form a spacer having a height of 1000 μm or more and make the porosity of the spacer within a predetermined range. 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.
[0073]
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.
[0074]
If the firing is performed in an oxidizing atmosphere such as air or oxygen, the glass in the spacer molding is sintered and shrinks, but the metal is oxidized from the surface and expands in volume. As a result, it is possible to produce a spacer with a small dimensional change rate, and to form a spacer with high dimensional accuracy without deformation or peeling from the insulating substrate.
[0075]
Further, according to the present invention, as described above, by adding TiO 2, the firing temperature of the spacer can be lowered by 5 ° C. or more, particularly 10 ° C. or more, further 20 ° C. or more, and further 30 ° C. or more. Even when an electron-emitting device, a phosphor or the like formed on the back plate or front plate to be sintered and integrated are fired at the same time, they can be prevented from being altered or deteriorated by firing.
[0076]
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.
[0077]
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.
[0078]
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.
[0079]
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.
[0080]
And after arrange | positioning a frame to the outer peripheral part of a backplate, and bonding together with adhesives, such as frit glass, frit glass is attached to 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.
[0081]
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.
[0082]
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. According to the present invention, since the spacer can be baked at a low temperature of 500 ° C. or less, particularly 460 ° C. or less, and further 450 ° C. or less, even when the spacer is formed after forming the phosphor, the phosphor is not altered. The spacer can be densified.
[0083]
【Example】
Example 1
The following two types of glasses A and B were prepared.
Glass A: PbO-B ₂ O _Three -SiO ₂ (Strain point is 410 ° C)
Glass B: Bi ₂ O _Three -B ₂ O _Three (Strain point is 420 ° C)
With respect to 100 parts by weight of the two types of glass, the metals shown in Table 1 and rutile TiO having an average particle diameter of 2 μm. ₂ Were added at a ratio shown in Table 1, and wet-mixed in IPA (isopropyl alcohol) for 18 hours in a ball mill using zirconia balls.
[0084]
Then, 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. 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, heat-treated at 110 ° C. for 30 minutes, and the silicone rubber mold is removed. Thus, a molded article for spacer was formed.
[0085]
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.
[0086]
The silicone rubber mold used had a recess depth (spacer height) of 1200 μm, a recess width (spacer thickness) of 200 μm, and a distance between the recesses (inter-spacer distance) of 800 μm.
[0087]
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 dimensional change rate.
[0088]
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.
[0089]
Further, the appearance of the spacer was observed with a stereomicroscope, and the presence / absence of peeling, warping, bending, or cutting was judged.
[0090]
Further, a part of the spacer was pulverized and X-ray diffraction measurement was performed to confirm the presence or absence of the added metal. 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 Table 1.
[0091]
In addition, (sample No. 4) thermogravimetric analysis (TG) and suggestive thermal analysis (DTA) as shown in FIG. 2 are measured in the atmosphere for the raw material mixed powder of each sample, and the weight of the sample increases. At the same time, the temperature at which the exothermic reaction proceeds due to metal oxidation and glass softening was determined as the oxidation start temperature. The results are shown in Table 1.
[0092]
[Table 1]

[0093]
From Table 1, sample No. to which a predetermined metal was not added was obtained. In No. 1, the shrinkage ratio due to firing was large, and the film was peeled off from the insulating substrate. TiO ₂ Sample No. without addition of In No. 8, the spacer was not densified and the spacer strength was low.
[0094]
In contrast, according to the present invention, certain metals and TiO ₂ Sample No. to which In Nos. 2 to 7 and 9 to 23, the firing shrinkage ratio of the spacer was small, the spacer could be formed without peeling from the insulating substrate, and the spacer strength could be increased to 1 MPa or more, particularly 2 MPa or more.
[0095]
(Example 2)
Rutile TiO of Example 1 ₂ Anatase TiO ₂ A porcelain was produced in the same manner as in Example 1 except that it was replaced with and evaluated in the same manner. Regarding the firing start temperature, the sample No. in FIG. The TG-DTA curve for No. 27 was calculated in the same manner as in Example 1. The results are shown in Table 2.
[0096]
[Table 2]

[0097]
As is apparent from the results in Table 2, the sample No. to which the predetermined metal was not added was added. In No. 24, the shrinkage ratio due to firing was large, and the film was peeled off from the insulating substrate.
[0098]
In contrast, according to the present invention, certain metals and TiO ₂ Sample No. to which In Nos. 25 to 47, the firing shrinkage ratio of the spacer was small, the spacer could be formed without peeling from the insulating substrate, and the spacer strength could be increased to 1 MPa or more, particularly 2 MPa or more.
[0099]
【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 TiO ₂ Since the oxidation start temperature of the specific metal can be lowered by adding, the firing temperature of the porcelain can be lowered.
[0100]
In particular, anatase TiO ₂ Can reduce the oxidation temperature of the metal without reducing the glass, and can promote densification of the porcelain during low-temperature firing without reducing the porcelain density due to loss of components in the glass.
[0101]
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.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an example of a flat display constructed using a substrate with spacers of the present invention.
FIG. 4 is a graph showing a method for calculating a result of thermogravimetric analysis (TG) in air and differential thermal analysis (DTA) of 4 spacer raw materials and a sintering start temperature.
FIG. It is a graph which shows the method of calculating the result of thermogravimetric analysis (TG) in air | atmosphere of 27 spacer raw materials, differential thermal analysis (DTA), and sintering start temperature.
[Explanation of symbols]
1 Flat display
2 Back plate
3 Front plate
4 Spacer
6 Electron emitter
7 Diffusion prevention layer
8 Phosphor
10 ITO film
11 Black matrix
12 Frame
13 Gas exhaust port

Claims (13)

A substrate with protrusions formed by integrally forming protrusions on a substrate surface, wherein the protrusions contain glass, at least one metal of Zn and Sn, an oxide of the metal, and TiO _2. A substrate with protrusions. The glass is _{PbO, SiO 2, Bi 2 O} 3 and B ₂ O with projection board according to claim 1, characterized in that it contains at least one ₃ selected from. 3. The substrate with protrusions according to claim 1, wherein an average linear expansion coefficient of the protrusions at 15 to 450 ° C. 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 at a predetermined interval in the thickness direction thereof. (A) a step of producing a paste containing glass having an average particle size of 5 μm or less, at least one metal of Zn and Sn, and TiO _2; and (b) obtained in the step (a) on the substrate surface. A step of applying and forming the obtained paste to form a protrusion-shaped molded body, and (c) firing the substrate obtained in the step (b) in an oxidizing atmosphere to form the metal in the molded body. And a step of oxidizing at least a part of the method. 7. The substrate with protrusions according to claim 6, wherein the glass contains 50 to 75% by weight, the metal in a total amount of 3 to 35% by weight, and TiO _{2 in} a proportion of ₃ to 35% by weight. Production method. The method for producing a substrate with protrusions according to claim 7, wherein the glass contains at least one selected from PbO, Bi ₂ O ₃ and B ₂ O ₃ . The method for manufacturing a substrate with protrusions according to claim 7 or 8, wherein the metal is made of powder having an average particle diameter of 6 µm or less. The protrusions of the substrate with protrusions formed integrally with the protrusions on the substrate surface are made of glass, at least one metal of Zn and Sn, an oxide of the metal, and TiO _2, and are separated at a predetermined interval. A flat display in which a plurality of protrusions are arranged between two parallel substrates, wherein the glass is at least one selected from PbO, SiO ₂ , Bi ₂ O ₃ and B ₂ O _3. A flat-panel display comprising: 11. The method for manufacturing a flat display according to claim 10, wherein a mixture of glass having an average particle diameter of 5 μm or less, at least one metal of Zn and Sn, and TiO ₂ is formed in an oxidizing atmosphere. A method for producing a flat display, comprising firing and oxidizing at least a part of the metal. 11. The planar type according to claim 10, wherein the glass contains 50 to 75% by weight, the metal in a total amount of 3 to 35% by weight, and the TiO _{2 in} a ratio of ₃ to 35% by weight. display. The flat display according to claim 10 or 12, wherein a volume specific resistance value of the protrusion at 25 ° C is 1 x 10 ⁸ to 1 x 10 ¹⁴ Ω · cm.

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