JP3878958B2 - Porcelain composition - Google Patents

Description

  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. As a suitable porcelain composition.

  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.

  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 a spacer (protrusion) is formed is preferably used.

  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.

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. In order to increase or as a pigment, a ceramic filler such as ZrO ₂ or SiO ₂ is added, and an organic resin or an organic solvent composed of an acrylic binder or a dispersant is added and mixed to prepare a paste. The substrate surface is printed and applied to form a projection-shaped molded body, or a substrate having a projection-shaped molded body is formed by a molding die, and this is heated to a temperature at which the substrate does not shrink, for example, 550 ° C. The protrusions are baked to integrally form a spacer having a thickness of about 40 μm and a height of about 150 μm.

  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.

  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.

  Therefore, in FED, glass and ceramics after firing are processed into a spacer shape by cutting and are attached to the surface of the substrate to form the spacer. However, the size and position accuracy are low, and it takes time and effort. In addition, it is not suitable for miniaturization of spacer thickness and interval.

  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.

  The present invention has been made to solve the above-mentioned problems, using a porcelain composition capable of suppressing shrinkage due to firing, porcelain, and a substrate with a protrusion using the same as a protrusion, and further miniaturization of thickness and interval. 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 due to firing, and can prevent charging of the spacer.

As a result of examining the above-mentioned problems, the inventors of the present invention, after molding a mixture in which at least one metal of Si, Zn, Al, Sn and Mg and TiO ₂ are added to glass, By firing in an oxidizing atmosphere, 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 has a fine thickness without causing deformation or peeling of the spacer. The TiO ₂ reduces the oxidation start temperature of the specific metal, so that the sintering temperature of the porcelain can be lowered, and the metal is left in the porcelain so that it is desired for the porcelain. It has been found that the spacer can be prevented from being charged, particularly when used as a spacer for a flat display.

That is, the porcelain composition of the present invention contains glass, at least one metal of Si, Zn, Al, Sn, and Mg, and TiO _2, and the glass content is 50 to 75% by weight, The total content of the metal is 3 to 35% by weight, and the content of the TiO ₂ is 3 to 35% by weight.

Here, it is desirable that the glass contains at least one selected from PbO, Bi ₂ O ₃ and B ₂ O ₃ .

  The metal is preferably made of a powder having an average particle size of 6 μm or less.

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 by adding TiO ₂ , the oxidation start temperature of the specific metal can be lowered, so that the firing temperature of the porcelain can be lowered.

In particular, anatase-type TiO ₂ can reduce the oxidation temperature of the metal without reducing the glass, so that the components in the glass can be washed away and the porcelain can be densified at low temperature without lowering the porcelain density. Can be promoted.

  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.

The porcelain composition of the present invention contains glass, at least one metal among Si, Zn, Al, Sn and Mg, and TiO ₂ .

Among the above components, as the glass, PbO glass, Bi ₂ O ₃ glass, SiO ₂ —B ₂ O ₃ glass, soda glass, silica glass, etc. can be used. More specifically, it contains at least one selected from PbO, SiO ₂ , Bi ₂ O ₃ and B ₂ O ₃ in terms of wettability with particles and bondability with other substrates of porcelain. Specifically, it is desirable to contain PbO—SiO ₂ —B ₂ O ₃ glass, Bi ₂ O ₃ —B ₂ O ₃ glass, B ₂ O ₃ —PbO—ZnO glass, and PbO—ZnO glass. .

  Further, the softening temperature of the glass is preferably 370 to 850 ° C., particularly preferably 370 to 430 ° C. in terms of low-temperature firing, and further 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.

  According to the present invention, the specific metal is oxidized with volume expansion by heating to a temperature of 350 to 490 ° C. in an oxidizing atmosphere. However, 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.

  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.

Further, according to the present invention, by adding TiO ₂ as described above, 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 the electron-emitting device, the phosphor, etc. formed on the back plate or the front plate to be sintered and integrated with the spacer are simultaneously fired, they can be prevented from being altered or deteriorated by firing.

Here, as the TiO ₂ , rutile TiO ₂ and / or anatase TiO ₂ can be used. Among them, the rutile type TiO ₂ is because it exhibits a strong catalytic effect compared to TiO ₂ having another structure, a large lowering effect of the sintering initiation temperature of the porcelain, the sintering temperature of the ceramic for example 10 ° C. or more, in particular 20 The temperature can be lowered by 30 ° C. or more.

In addition, rutile TiO ₂ has a strong catalytic action for promoting the oxidation of the above-mentioned specific metal and a large effect of lowering the firing temperature of the porcelain. However, since the glass is reduced, the catalytic action is moderate and the glass is reduced. It is desirable to use anatase type TiO ₂ that does not occur. 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.

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. and 3 to 35 wt%, it is desirable that the content of the TiO ₂ is contained in an amount of 3 to 35 wt%, also from 16 to 600 weight the TiO ₂ with respect to the particular metal 100 parts by weight It is desirable to add at a ratio of parts.

Further, TiO ₂ may be coated on the surface of glass particles or metal particles, but in order to efficiently reduce the sintering start temperature of the porcelain, the average particle diameter of TiO 2 is 0.05 to 10 μm. In particular, a powder of 0.05 to 2 μm is desirable.

In addition, for ceramic strength improvement, for thermal expansion coefficient control, for coloring, for dielectric constant control, for resistivity control, further ceramic fillers such as SiO ₂ , ZrO ₂ , Al ₂ O ₃ , Other inorganic fillers such as glass such as SiO ₂ —Al ₂ O ₃ —MgO (glass softening point 760 ° C., thermal expansion coefficient 2.8 × 10 ⁻⁶ / ° C.) are desirably 30% by weight or less in total. It can also be contained at 20% by weight.

  Next, in order to produce a porcelain using the porcelain composition of the present invention, 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.

  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.

  Next, the porcelain obtained by the above method will be described. The porcelain obtained from the porcelain composition of the present invention is glass, a metal oxide formed by oxidizing at least one metal of Si, Zn, Al, Sn, and Mg added as a raw material and the remainder. It contains a metal and TiO2.

Here, when the volume specific resistance value of the porcelain is in the range of 10 ⁸ to 10 ¹⁴ Ω · cm, the metal content in the porcelain is 34 wt% or less, particularly 1.5 to 34 wt%, The particle size is preferably 5.9 μm or less, particularly 0.3 to 5.9 μm, and more preferably 0.3 to 3 μm.

  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.

  Then, it demonstrates based on FIG. 1 which is a schematic sectional drawing about the field emission display (FED) which is an example of the flat type display using the porcelain obtained from the porcelain composition of this 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.

  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.

  On the other hand, the front plate 3 is a transparent substrate mainly composed of glass substrate such as quartz glass, soda lime glass, low soda glass, lead alkali silicate glass, borosilicate glass, sapphire, quartz, single crystal zirconia, diamond or the like. Is formed.

  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 glass and / or ceramics, for example, known glass such as lead glass (PbO—B ₂ O ₃ —SiO ₂ ), alkali silicate glass, bismuth glass (Bi—B ₂ O ₃ ). Although used, lead-based glass (PbO—B ₂ O ₃ —SiO ₂ ), bismuth-based glass (Bi—B ₂ O) in terms of mechanical strength, adhesion to insulating substrate, and long-term chemical stability of the material. ₃ ) is desirable.

  According to the present invention, the spacer 4 is characterized in that at least one metal among Si, Zn, Al, Sn, and Mg is dispersed in a sintered body mainly composed of glass.

As a result, the spacer 4 can be given conductivity with a volume resistivity of 1 × 10 ⁸ to 1 × 10 ¹⁴ Ω at 25 ° C., and the spacer 4 can be prevented from being charged.

  Here, among the metals, in terms of conductivity imparting effect, oxidation start temperature, and the rate of increase in volume expansion due to metal oxidation, Si, Zn and Sn are further compatible with glass and in terms of adhesion. Metal Si is optimal.

Of the oxides formed by oxidation of the above metals, for example, SnO ₂ , ZnO, and the like have an effect of increasing conductivity.

The spacer 4 may be a known glass such as a lead glass (PbO—B ₂ O ₃ —SiO ₂ system), an alkali silicate glass, or a bismuth glass (Bi—B ₂ O ₃ ). Lead glass (PbO—B ₂ O ₃ —SiO ₂ system) and bismuth glass (Bi—B ₂ O ₃ ) in terms of mechanical strength, adhesion to insulating substrate, and long-term chemical stability of the material. It is desirable.

Further, in the spacer 4, TiO ₂ , ZrO ₂ , ZnO, SiO ₂ , BN, Al ₂ O ₃ or the like is used as a ceramic filler, if desired. The effect of preventing the deformation of the spacer, the control of the thermal expansion coefficient of the spacer 4, the coloring, and the like are achieved.

  Furthermore, according to the porcelain composition of 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 shrinks due to firing and deforms and peels off. In addition, it is possible to form fine spacers, and to form spacers having a fine interval of 400 μm or more, particularly 5 mm or less, and further 1 mm or less.

  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.

  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.

  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.

  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 notch can be suitably used.

  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.

  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.

  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.

  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 to 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.

  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.

  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.

  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.

  In addition, the porcelain composition of the present invention is not limited to the FED shown in FIG. 1. For example, the inside of a display such as a plasma display panel (PDP) or a plasma addressed liquid crystal panel (PALC) is vacuum or gas at a predetermined pressure. Any of the sealed flat display can be suitably applied.

(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.

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, an organic resin such as a plasticizer and a dispersant, and an organic solvent, and kneading.

  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.

  In addition, 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.

Furthermore, other fillers such as ZrO ₂ , Al ₂ O ₃ , and SiO ₂ are added to the paste as desired.

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.

  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.

  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.

  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.

  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.

  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.

Further, according to the porcelain composition of the present invention, the calcination temperature of the spacer is lowered by 5 ° C. or more, particularly 10 ° C. or more, further 20 ° C. or more, further 30 ° C. or more by adding TiO ₂ as described above. Therefore, even when an electron-emitting device, a phosphor, or the like formed on the back plate or the front plate that is sintered and integrated with the spacer is fired at the same time, it can be prevented from being altered or deteriorated by firing.

  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.

  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.

  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.

  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.

  And after arrange | positioning a frame body to the outer peripheral part of a backplate and bonding together with adhesives, such as frit glass, it is frit glass on the top part of this frame, and the spacer top part 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.

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 heated to 400 to 500 ° C. while reducing the pressure to about 10 ⁻⁴ Pa. A flat display using the porcelain composition of the present invention can be produced by fixing between the frames and sealing the gas exhaust port.

  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.

Example 1
The following two types of glasses A and B were prepared.

Glass A: PbO—B ₂ O ₃ —SiO ₂ (strain point is 410 ° C.)
Glass B: Bi ₂ O ₃ —B ₂ O ₃ (strain point is 420 ° C.)
The metal shown in Table 1 and rutile TiO ₂ having an average particle diameter of 2 μm were added in a proportion shown in Table 1 to 100 parts by weight of the two types of glass, and IPA (isopropyl alcohol) was added using a ball mill using zirconia balls. ) For 18 hours.

  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.

  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.

  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.

  In addition, another flat plate is placed on the spacer end of the obtained substrate with spacers, a force is applied to compress both 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.

  Further, the appearance of the spacer was observed with a stereomicroscope, and the presence / absence of peeling, warping, bending, or cutting was judged.

  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.

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.

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. Further, the sample without the addition of TiO ₂ No. In No. 8, the spacer was not densified and the spacer strength was low.

On the other hand, sample No. ₁ to which a specific metal and TiO ₂ were added using the porcelain composition of the present invention was used. In 2-4, 9-11, 14, 15, 17, 18, 22, 23, 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, especially It could be increased to 2 MPa or more.

(Example 2)
A porcelain was produced in the same manner as in Example 1 except that the rutile TiO ₂ in Example 1 was replaced with anatase TiO ₂ 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.

  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 it was peeled off from the insulating substrate.

On the other hand, sample No. 1 using the porcelain composition of the present invention to which a specific metal and TiO ₂ were added. In 25-27, 31-33, 36-39, 41, 42, 46, 47, 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, in particular It could be increased to 2 MPa or more.

It is a schematic sectional drawing which shows an example of the flat type display comprised using the board | substrate with a spacer which consists of a ceramic composition of this invention. Sample No. 4 is a graph showing a method of calculating the results of thermogravimetric analysis (TG) in air and differential thermal analysis (DTA) of 4 spacer raw materials and sintering start temperature. Sample No. 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

DESCRIPTION OF SYMBOLS 1 Flat display 2 Back plate 3 Front plate 4 Spacer 6 Electron emission element 7 Diffusion prevention layer 8 Phosphor 10 ITO film 11 Black matrix 12 Frame 13 Gas exhaust port

Claims (3)

Glass, Si, Zn, Al, at least the one metal of Sn and Mg, containing the TiO _2, the content of the glass is 50 to 75 wt%, the content of said metal in total 3 to 35 A porcelain composition having a weight percentage of TiO ₂ of 3 to 35 wt% in total. The porcelain composition according to claim 1, wherein the glass contains at least one selected from PbO, Bi ₂ O ₃ and B ₂ O ₃ . The porcelain composition according to claim 1 or 2, wherein the metal is made of a powder having an average particle size of 6 µm or less.

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