WO2008050772A1 - Composition de verre à base de bismuth et matière à base de bismuth - Google Patents

Composition de verre à base de bismuth et matière à base de bismuth Download PDF

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Publication number
WO2008050772A1
WO2008050772A1 PCT/JP2007/070661 JP2007070661W WO2008050772A1 WO 2008050772 A1 WO2008050772 A1 WO 2008050772A1 JP 2007070661 W JP2007070661 W JP 2007070661W WO 2008050772 A1 WO2008050772 A1 WO 2008050772A1
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WO
WIPO (PCT)
Prior art keywords
bismuth
glass
tablet
based material
exhaust pipe
Prior art date
Application number
PCT/JP2007/070661
Other languages
English (en)
Japanese (ja)
Inventor
Masayuki Horimoto
Kentaro Ishihara
Original Assignee
Nippon Electric Glass Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Electric Glass Co., Ltd. filed Critical Nippon Electric Glass Co., Ltd.
Priority to CN200780039316XA priority Critical patent/CN101528621B/zh
Priority to KR1020127007999A priority patent/KR101163002B1/ko
Publication of WO2008050772A1 publication Critical patent/WO2008050772A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J17/00—Gas-filled discharge tubes with solid cathode
    • H01J17/02—Details
    • H01J17/16—Vessels; Containers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/34—Vessels, containers or parts thereof, e.g. substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J17/00—Gas-filled discharge tubes with solid cathode
    • H01J17/02—Details
    • H01J17/18—Seals between parts of vessels; Seals for leading-in conductors; Leading-in conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/86—Vessels; Containers; Vacuum locks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/86—Vessels; Containers; Vacuum locks
    • H01J29/864—Spacers between faceplate and backplate of flat panel cathode ray tubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/38—Exhausting, degassing, filling, or cleaning vessels

Definitions

  • the present invention relates to a flat display device such as a plasma display panel (hereinafter referred to as PDP), various types of field emission displays (hereinafter referred to as FED) having various electron-emitting devices, and a fluorescent display tube (hereinafter referred to as VFD), and the like.
  • PDP plasma display panel
  • FED field emission displays
  • VFD fluorescent display tube
  • the present invention relates to a bismuth-based glass composition and a bismuth-based material that are suitable for sealing electronic parts (including electronic parts storage containers) such as crystal resonators and IC packages, forming partition walls, and forming side frames.
  • glass has been used as a sealing material for flat display devices and the like.
  • Glass is superior in chemical durability and heat resistance compared to resin adhesives, and is suitable for ensuring airtight reliability of flat display devices and the like.
  • these glasses require various properties such as mechanical strength, fluidity, and electrical insulation, but at least deteriorate the fluorescent properties of phosphors used in flat display devices, etc. It is required to be usable at a temperature that does not allow them to be used. Therefore, as a glass that satisfies the above characteristics, a lead borate glass (see, for example, Patent Document 1) containing a large amount of PbO and having an extremely large effect of lowering the melting point of the glass has been widely used.
  • the glass used for the sealing material is selected to be crystalline or non-crystalline depending on the application.
  • crystalline glass is selected for applications where the sealing material should not soften and flow after the sealing process, for example, sealing of exhaust pipes for PDP.
  • the heat treatment temperature rises to near the softening point, for example, 400 to 420 ° C.
  • the power evacuation process There is a power evacuation process.
  • amorphous glass is used, the glass is softened again in the evacuation process, and as a result, an airtight leak is likely to occur in a flat display device or the like. Therefore, in order to prevent such a situation, it is considered preferable to select crystalline glass in this application (see, for example, Patent Documents 3 and 4).
  • Patent Document 1 Japanese Patent Laid-Open No. 63-315536
  • Patent Document 2 JP-A-6-24797
  • Patent Document 3 Japanese Patent Laid-Open No. 2001-122640
  • Patent Document 4 Japanese Patent Laid-Open No. 2001-10843
  • the bismuth-based glass described in Patent Document 2 is capable of obtaining crystalline glass by selecting a glass composition.
  • this crystalline glass contains 13% by mass or more of B 2 O, which is a glass constituent component (a component not constituting a crystal), in the glass composition, and constitutes a crystal.
  • bismuth-based glass has poor thermal stability as compared with lead borate-based glass, that is, it is difficult to control the precipitation of crystals immediately after devitrification at a high temperature. Therefore, if the crystallinity of the bismuth glass is to be strengthened, the glass is often crystallized before the glass flows sufficiently in the sealing process, and the function as a sealing material is often not exhibited.
  • the present invention provides bismuth that is softened well in a heat treatment step, for example, a sealing step, and crystals are sufficiently precipitated after softening, and that is not easily re-softened in a heat treatment step after crystal precipitation, for example, a vacuum evacuation step.
  • the technical challenge is to obtain glass-based glass compositions and bismuth-based materials.
  • the present inventors as a result of extensive studies, the glass composition range of the bismuth glass, the mass 0/0, as a glass composition, in terms of mass 0/0, Bi O 60-84% , BO 5. 4 —15%, ZnO 10— 27%, CuO 0-7%, FeO 0-5%, BaO + SrO + MgO + CaO 0—10%, Si
  • bismuth glass composition of the present invention has a glass composition, in terms of mass 0/0, Bi O 60-84% , BO
  • substantially free of PbO in the present invention refers to a case where the content of PbO in the glass composition is lOOOppm or less.
  • the glass composition range of the bismuth-based glass composition of the present invention is regulated as described above, the precipitation of crystals (the amount of precipitated crystals, the timing of crystal precipitation, the crystallization temperature, etc.) is easily controlled. be able to. That is, the bismuth-based glass composition of the present invention exhibits good fluidity at low temperatures and can be sealed well at low temperatures. In addition, since a sufficient amount of crystals are precipitated after the glass is softened, it is difficult for the glass to be re-softened in the heat treatment process after crystallization. Reliability can be ensured.
  • Bismuth-based glass compositions of the present invention the content of Bi O is restricted to 60 to 84 weight 0/0
  • the glass has a low melting point and can be sealed at a low temperature.
  • the glass softens.
  • the content of ZnO is restricted to 10 to 27 weight 0/0. If the ZnO content is 10% by mass or more, it is possible to easily control the precipitation of crystals, and in particular, it is possible to increase the crystallinity of the glass by precipitating low expansion crystals. it can. On the other hand, if the ZnO content is 27% by mass or less, the crystal precipitation time can be delayed, so that it is easy to deposit crystals on the glass while ensuring the desired fluidity in the sealing step.
  • the precipitated crystal is Bi 2 O—B 2 O
  • the bismuth-based glass composition of the present invention contains substantially no PbO in the glass composition. In this way, it is possible to accurately meet recent environmental demands.
  • bismuth glass composition of the present invention has a glass composition, in terms of mass 0/0, Bi O
  • the bismuth-based glass composition of the present invention has a glass composition with a mass percentage of BiO
  • bismuth glass composition of the present invention has a glass composition, in terms of mass 0/0, Bi O
  • the bismuth-based material of the present invention contains 40% to 100% of a glass powder made of the bismuth-based glass composition described above by volume%; 100%, 0 to 60% of a refractory filler powder, and has a crystal structure. Characterized by sex.
  • the bismuth-based material of the present invention is a refractory filler. You may comprise only the glass powder which does not add powder.
  • “crystallinity” means 600 ° C., preferably 570, as measured by a differential thermal analysis (DTA) apparatus (in the atmosphere, the temperature rising rate is 10 ° C./min, starting from the room temperature). This refers to a crystallizing peak that develops up to ° C, more preferably 550 ° C, and even more preferably 530 ° C.
  • DTA differential thermal analysis
  • the bismuth-based material of the present invention is characterized by a crystallization temperature of 490 to 570 ° C.
  • the “crystallization temperature” in the present invention refers to a temperature at which a crystallization peak appears in the measurement with a DTA apparatus (in the atmosphere, the heating rate is 10 ° C./min, starting from room temperature).
  • the bismuth-based material of the present invention is characterized in that the refractory filler powder is a ZnO-containing refractory filler powder.
  • the refractory filler powder is one or more selected from the group of willemite, zinc oxide, garnite, and ZnO—Al 2 O—SiO.
  • the bismuth-based material of the present invention is characterized by being used for sealing.
  • the bismuth-based material of the present invention is characterized by being used for a flat panel display or a partition wall of an electronic component.
  • the bismuth-based material of the present invention is characterized by being used for a side display of a flat display device or an electronic component.
  • the tablet of the present invention is a tablet obtained by sintering a bismuth-based material into a predetermined shape, and the bismuth-based material is the bismuth-based material described above.
  • the shape of the tablet of the present invention is not particularly limited, but it is preferably a ring shape when fixing the exhaust pipe is assumed.
  • the tablet-integrated exhaust pipe of the present invention is characterized in that the above tablet is attached to the distal end portion of the expanded exhaust pipe.
  • the “tip portion of the exhaust pipe” refers to a surface portion of the exhaust pipe having an enlarged diameter, and the exhaust pipe bottom surface or the exhaust pipe outer peripheral side surface on the side in contact with the panel in the enlarged diameter portion.
  • the tablet includes an aspect in which the tablet is adhered to a part of the distal end portion of the exhaust pipe as well as an aspect in which the tablet is adhered only to the distal end portion of the exhaust pipe.
  • the tablet-integrated exhaust pipe of the present invention is provided at the tip of the expanded exhaust pipe.
  • the tablet described above and a high melting point tablet are attached, and the above tablet is attached to the front end side of the exhaust pipe whose diameter has been expanded, and the high melting point tablet is attached to the rear end side of the above tablet.
  • the “high melting point tablet” in the present invention refers to a tablet that does not soften and deform at less than 520 ° C.
  • a glass tablet it refers to a tablet having a softening point measured by a DTA apparatus of 520 ° C. or higher.
  • BiO is a main component for lowering the softening point of glass, and the crystal structure of precipitated crystals.
  • the content of Bi O is less than 60%, the softening point is increased, 500 ° C below the temperature
  • B 2 O is an essential component for constituting a glass network of bismuth-based glass.
  • ZnO has an effect of suppressing devitrification of the glass during melting, and is an essential component for increasing the crystallinity of the glass by precipitating low expansion crystals. Its content is 10-27%, preferably 12-24%, more preferably 12-22%. If the ZnO content is less than 10%, it is difficult for the low expansion crystal to precipitate on the glass during the heat treatment process. If the content of ZnO is more than 27%, the time of crystal precipitation is advanced, and it becomes difficult to secure desired fluidity in the sealing process. Furthermore, if the content of BiO is less than 60-77%, the content of ZnO is 10--15% Less than 12%; less than 15% is particularly preferred 13.5 ⁇ ; less than 15% is most preferred
  • CuO is a component that suppresses devitrification at the time of glass melting, and its content is 0 to 7%, preferably 0 to 5%, more preferably 0 to 3%, and still more preferably 0 .; ! ⁇ 2%. If the CuO content is higher than 7%, the glass composition is not balanced and the glass becomes devitrified when melted.
  • Fe O is a component that suppresses devitrification of the glass during melting, and its content is 0 to 5%,
  • Preferably it is 0 to 3%, more preferably 0.;! To 3%. If the content of Fe O is more than 5%
  • the glass becomes thermally unstable.
  • BaO, SrO, MgO and CaO have an effect of suppressing devitrification at the time of melting of the glass, and the content is 0 to 10% in total amount (BaO + SrO + MgO + CaO), preferably Is 0-7%, more preferably 0.;!-5%. If the total amount of these components is more than 10%, the softening point of the glass will rise and it will be difficult to seal at a low temperature of 500 ° C or lower.
  • SiO and Al 2 O have the effect of increasing the weather resistance of the glass, and the content thereof is the total amount (Si
  • the softening point of the glass becomes high and it becomes difficult to seal at a low temperature of 500 ° C or lower.
  • the bismuth-based glass composition of the present invention is treated with a force S including, for example, the following components in addition to the above components.
  • MoO and WO are components that make it easy to control the timing of crystal precipitation.
  • the total content (Mo 0 + WO) is 0-5%, preferably 0-3%, more preferably 0-1
  • Sb 2 O is a component that makes it easy to control the time of crystal precipitation, and its content is 0
  • the total content (In 2 O 3 + Ga 2 O 3) is 0 to 5%, preferably 0 to 3%, more preferably 0 to
  • the bismuth-based glass composition of the present invention can further add various components as optional components.
  • various components for example, Li 0, Na 0, K 0, Cs 0, La O, Gd O, Y O,
  • CeO etc. can be added up to 10%.
  • Alkali such as Li 0, Na 0, K 2 O and Cs 2 O
  • Metal oxide is a component that lowers the softening point of glass. However, since the alkali metal oxide has an action of promoting devitrification of the glass, the total amount is preferably limited to 2% or less. Rare earth oxides such as La O, Gd O, Y O and CeO
  • a suitable content range of each component can be appropriately selected to obtain a preferable glass composition range.
  • a preferable glass composition range As a more preferable glass composition range,
  • Examples thereof include glass containing Al 0 to 5% and substantially free of PbO.
  • B O ZnO-based crystals can be sufficiently precipitated, and as a result, before and after crystal precipitation
  • Bismuth-based glass composition having the above glass composition exhibits good fluidity at below 500 ° C, 90 to the thermal expansion coefficient in a temperature range of 30 to 300 ° C approximately; 110 X 10- 7 / ° C.
  • the bismuth-based glass composition of the present invention can adjust the crystallization temperature by adjusting the particle size, and can cope with a two-stage heat treatment process (when the heat treatment process is performed twice). it can. For example, in the primary heat treatment performed at a low temperature of about 460 ° C, in order to complete the crystallization of glass while ensuring fluidity, it is sufficient to reduce the particle size.
  • the average particle size D should be more than 10 to 100 m, preferably 15 to 70.
  • average particle diameter D indicates a value measured by laser diffraction method.
  • the bismuth-based glass composition of the present invention can be crystallized even with a glass powder alone, and since a Bi 2 O 3 —B 2 O—ZnO-based crystal or the like is precipitated, the thermal expansion coefficient of the glass is reduced.
  • the bismuth-based glass composition of the present invention can be suitably used as a sealing material with glass powder alone. Further, the bismuth-based glass composition of the present invention can also be used as a partition wall forming material, a side frame forming material, etc. by itself with a glass powder when the difference in thermal expansion coefficient from the glass substrate is appropriate.
  • a refractory filler powder to the glass powder made of the bismuth-based glass composition of the present invention to obtain a composite material.
  • Glass powder and The mixing ratio of the refractory filler powder is preferably a bismuth-based glass powder 40-99 9 vol%, the refractory filler powder 0.5;.! ⁇ 60 volume 0/0, more preferably bismuth glass powder 40-99 volume 0 / 0, refractory filler powder;!
  • the refractory filler powder 5-45 volume 0/0, particularly preferably a bismuth-based glass More than 60 volume% and less than 90 volume% of powder, more than 10 volume% and less than 40 volume% of refractory filler powder.
  • the content of the refractory filler powder is less than 0.1% by volume, the effect of adding the refractory filler powder becomes poor.
  • the content of the refractory filler powder is more than 60% by volume, the content of the glass powder is relatively decreased, and the fluidity of the bismuth-based material tends to be impaired.
  • willemite, ⁇ -eucryptite, zircon, tin oxide, mullite, quartz glass, alumina and the like can be used singly or in combination of two or more as the refractory filler powder. .
  • ⁇ -containing refractory filler powder can increase the crystallinity without changing the crystal seeds of the bismuth-based material.
  • refractory fillers containing ⁇ include willemite (2ZnO'SiO), garnite ( ⁇ ⁇ ⁇ 1 ⁇ ), zinc oxide ( ⁇
  • ZnO′Al 2 O 3 —SiO, etc. may be used alone or in combination of two or more. Special
  • the glass powder preferably has a ⁇ content of 6.5% or more in the glass composition. ⁇ The content of ⁇ is less than 6.5%
  • the crystallization temperature tends to shift to the low temperature side, and it becomes difficult to ensure the desired fluidity.
  • a refractory filler powder that acts as a crystal nucleus such as titanium oxide or iron oxide
  • the crystallinity of the bismuth glass can be increased.
  • refractory filler powders such as silica and zirconia
  • the glass powder should contain 6.5% or more in the glass composition.
  • the crystallization temperature is preferably 490 to 570 ° C.
  • 540 ° C is more preferred 510-530 ° C is even more preferred.
  • the crystallization temperature is lower than 490 ° C.
  • the crystal precipitation time becomes too early, and it becomes difficult to secure desired fluidity in the sealing step.
  • the crystallization temperature is higher than 570 ° C, a sufficient amount of crystals are difficult to precipitate in the sealing process, and the glass is easily re-softened in the heat treatment process after crystallization, for example, the vacuum evacuation process. It becomes difficult to ensure airtight reliability.
  • thermal expansion coefficient of the bismuth-based material 5 ⁇ 30 X 10_ 7 / ° C with respect to the article to be sealed, preferably important to design 7 ⁇ 20 X 10- 7 / ° C of about less. This is to prevent the sealing layer from being broken by setting the force and strain on the sealing layer after the sealing process to the compression side.
  • thermal expansion coefficient of the sealing material is 55 ⁇ 80 X 10_ 7 / ° C.
  • VFD soda glass substrate thermal expansion coefficient 85 ⁇ ; 100 X 10- 7 / ° C
  • For a suitable thermal expansion coefficient of the sealing material is 70 ⁇ 90 X 10- 7 / ° C.
  • the bismuth-based material may be used as it is, but it is easy to handle if it is kneaded uniformly with a vehicle and used as a paste.
  • the vehicle mainly consists of an organic solvent and a resin, and the resin is added for the purpose of adjusting the viscosity of the paste.
  • a surfactant, a thickener and the like can be added as necessary.
  • the prepared paste is applied using a dispenser such as a dispenser screen printer.
  • acrylic ester (acrylic resin), ethyl cellulose, polyethylene glycol derivative, nitrocellulose, polymethylstyrene, polyethylene carbonate, methacrylic ester and the like can be used.
  • acrylic acid esters and nitrocellulose are preferable because of their good thermal decomposability.
  • Examples of the organic solvent include N, N, -dimethylformamide (DMF), a terbinol, higher alcohol, ⁇ - butyl rataton ( ⁇ BL), tetralin, butyl carbitol phosphate, ethyl acetate, isoamyl acetate, diethylene glycol monomer.
  • DMF N, N, -dimethylformamide
  • ⁇ BL terbinol
  • ⁇ BL ⁇ - butyl rataton
  • tetralin butyl carbitol phosphate
  • ethyl acetate isoamyl acetate
  • diethylene glycol monomer diethylene glycol monomer
  • Chill ether diethylene glycol monoethyl ethinoreate acetate, pendinoleanolo cornore, tonoleen, 3-methoxy-3-methylbutanol, water, triethylene glycol monomethyl ether, Reethylene glycolenoresimethylenoateol, dipropyleneglycololemonomethinoatenore, dipropyleneglycololemonobutinoreatenore, tripropyleneglycololemonomethinoate ether, tripropyleneglycolmonobutylether, propylenecarbonate, dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidone, etc.
  • DMSO dimethylsulfoxide
  • N-methyl-2-pyrrolidone etc.
  • DMSO dimethylsulfoxide
  • ⁇ -terpineol is preferable because it is highly viscous and has good solubility in resins and the like.
  • the bismuth-based material of the present invention is preferably sintered into a predetermined shape to form a tablet.
  • tablets also called press frit glass sintered bodies and glass molded bodies
  • the tablet has an insertion hole for inserting the exhaust pipe. Insert the exhaust pipe into this insertion hole, align the tip of the exhaust pipe with the position of the exhaust hole on the panel, and clip It is fixed with. After that, heat treatment is performed at the sealing temperature of the tablet, and the tablet is softened to attach the exhaust pipe to the panel.
  • the exhaust pipe can be easily connected to the exhaust equipment and the inclination of the exhaust pipe can be reduced with respect to the panel, that is, on the panel surface. It can be mounted vertically, and further, it can be mounted so that airtight reliability is maintained while maintaining the light emission capability of the flat display device.
  • the tablet of the present invention is suitable for fixing an exhaust pipe of a PDP because desired fluidity can be secured in the sealing step and heat resistance after crystallization is good.
  • the tablet of the present invention is produced through a plurality of independent heating processes as follows. First, a binder or solvent is added to a bismuth-based material to form a slurry. Thereafter, this slurry is put into a granulator such as a spray dryer to produce granules. At that time, the granules are heat-treated at a temperature at which the solvent volatilizes (about 100 to 200 ° C). Further, the produced granule is put into a mold designed to have a predetermined size and is dry-pressed into a ring shape to produce a pressed body.
  • a binder or solvent is added to a bismuth-based material to form a slurry. Thereafter, this slurry is put into a granulator such as a spray dryer to produce granules. At that time, the granules are heat-treated at a temperature at which the solvent volatilizes (about 100 to 200 ° C). Further, the produced granul
  • the binder remaining in the pressed body is decomposed and volatilized and sintered at a temperature about the softening point of the bismuth-based glass to produce a tablet.
  • sintering in a heat treatment furnace may be performed multiple times. When the sintering is performed a plurality of times, the strength of the tablet is improved and the tablet can be effectively prevented from being broken or broken.
  • the tablet of the present invention is used as a tablet-integrated exhaust pipe by being attached to the tip of the expanded exhaust pipe.
  • the tablet of the present invention can ensure desired fluidity in the sealing step and has good sealing strength between the material to be sealed and the tablet. Furthermore, since a sufficient amount of crystals precipitates after the tablet flows in the sealing process, it is possible to ensure airtight reliability of a flat panel display device or the like in which the tablet is difficult to be softened again in the subsequent heat treatment process.
  • the exhaust pipe has a thermal expansion coefficient is 85 X 10- 7 / ° C, heat resistant temperature 550 ° C, size, for example, an outer diameter of 5 mm, an inner diameter of 3. 5 mm. Further, it is preferable to form a flare portion or a flange portion at the tip portion where it is preferable to enlarge the tip portion of the exhaust pipe.
  • Various methods can be adopted as a method of expanding the diameter of the distal end portion of the exhaust pipe. In particular, a method of heating using a gas burner while rotating the tip of the exhaust pipe and processing it into a predetermined shape using several kinds of jigs is preferable because it is excellent in mass productivity.
  • FIG. Fig. 1 is a cross-sectional view of a tablet-integrated exhaust pipe.
  • the tip of the exhaust pipe 1 has an enlarged diameter, and the tablet 2 is bonded to the tip of the exhaust pipe on the panel side.
  • the tablet-integrated exhaust pipe of the present invention has a tablet and a high-melting-point tablet attached to the tip of the expanded exhaust pipe, and the tablet is connected to the tip of the exhaust pipe whose diameter is expanded. It is preferable to attach and attach a high melting point tablet to the rear edge side of the tablet. That's right. If the tablet-integrated exhaust pipe is configured in this way, the tablet is attached to the front end of the exhaust pipe, so when attaching the exhaust pipe to the panel, etc., the area that contacts the panel is only the exhaust pipe. This makes it easier to install the exhaust pipe on a panel, etc., and it can be installed vertically without tilting to the panel.
  • the tablet-integrated exhaust pipe is configured as described above, a high melting point tablet can be placed between the jig and the tablet when the tablet is fixed to the exhaust pipe in the process of manufacturing the tablet-integrated exhaust pipe.
  • a high melting point tablet can be placed between the jig and the tablet when the tablet is fixed to the exhaust pipe in the process of manufacturing the tablet-integrated exhaust pipe.
  • the tablet is preferably fixed to the outer peripheral surface of the front end portion of the glass tube, and more preferably fixed only to the outer peripheral surface of the front end portion of the glass tube. It is not fixed to the tip surface of the panel, that is, the surface to be bonded to the panel or the like. In this way, it is possible to easily prevent the glass from flowing into the exhaust holes formed in the panel or the like.
  • the high melting point tablet is not directly bonded to the exhaust pipe, it can be pressure sealed with the high melting point tablet part secured with a clip in the sealing process if it is fixed to the exhaust pipe through the tablet. ,preferable.
  • the high melting point tablet it is preferable to use product grades "ST-4" and "F N-13" manufactured by Nippon Electric Glass Co., Ltd. as materials.
  • a high-melting-point tablet can be produced by the above method.
  • ceramics, metals, etc. can be used as the material for high melting point tablets.
  • FIG. 2 shows an example of the tablet-integrated exhaust pipe having such a configuration.
  • Fig. 2 is a cross-sectional view of the tablet-integrated exhaust pipe, where the tip of the exhaust pipe 1 has an enlarged diameter, and the tablet 2 is bonded to the tip of the exhaust pipe 1 on the outer peripheral surface side. Yes.
  • the high melting point tablet 3 is not bonded to the outer peripheral surface side of the exhaust pipe 1.
  • the tablet 2 is attached to the front end side of the flange portion la, and the high melting point tablet 3 is attached to the rear end portion side of the flange portion la rather than the tablet 2.
  • the bismuth-based material of the present invention is preferably used as a sealing material.
  • the bismuth-based material of the present invention since the bismuth-based material of the present invention can be sealed at a low temperature, it is a feature of a member having poor heat resistance. It can be sealed without degrading the properties.
  • the bismuth-based material of the present invention is preferably used for sealing a flat display device or an electronic component. If the flat display device can be sealed at a low temperature, the manufacturing efficiency can be improved and the deterioration of the characteristics of other members such as a phosphor can be prevented. On the other hand, a member whose characteristics deteriorate at high temperatures (for example, a conductive adhesive for a crystal resonator package) may be used for an electronic component. Therefore, the bismuth-based material of the present invention can be sealed at a low temperature and is suitable for these applications.
  • the bismuth-based material of the present invention is preferably used for sealing PDP.
  • the inside of the PDP is evacuated through the exhaust pipe, and then the required amount of rare gas is injected to seal the exhaust pipe.
  • This evacuation process is preferably performed at as high a temperature as possible in order to increase the exhaust efficiency.
  • the bismuth-based material of the present invention is capable of increasing the exhaust temperature, which is difficult to be re-softened in the subsequent vacuum exhaust process, because many crystals are precipitated after the glass flows.
  • the bismuth-based material of the present invention is also suitable as a sealing material for the front glass substrate and the back glass substrate.
  • the bismuth-based material of the present invention is preferably used as a partition wall forming material for a flat display device or an electronic component.
  • the bismuth-based material of the present invention precipitates a sufficient amount of crystals after sintering, so that dimensional change is less likely to occur in the subsequent heat treatment step.
  • the mechanical strength and dimensional stability of the partition walls can be further enhanced.
  • the bismuth-based material of the present invention can be sintered at a low temperature and has excellent heat resistance after crystallization. Therefore, the bismuth-based material is used for the purpose of forming a part of the partition wall, that is, for repairing the defective part of the partition wall. You can also
  • the bismuth-based material of the present invention is preferably used as a material for forming a side frame (support frame, side spacer) of a flat display device or an electronic component.
  • the bismuth-based material of the present invention regulates the glass composition of the bismuth-based glass composition within the above range! /, The ability to do so, crystals precipitate after the side frame sintering step, The side frame can be formed stably, and the dimensional accuracy of the side frame can be easily improved.
  • the addition of refractory filler powder to bismuth-based glass powder makes it easier to adjust the thermal expansion coefficient of the side frame and increases the mechanical strength of the side frame. It becomes easy to raise.
  • the inside of the flat display device can be reliably supported even when the inside of the flat display device is in a vacuum state, and cracks are generated from the side frame even when a mechanical shock is applied to the flat display device. It becomes difficult to do.
  • the bismuth-based material of the present invention is densely sintered at a temperature below the strain point of the high strain point glass substrate (eg, 570 ° C. or less).
  • the side frame can be formed at a temperature below the strain point of the high strain point glass substrate.
  • the bismuth-based material of the present invention is preferably used for an FED side frame. Since the bismuth-based material of the present invention can easily control the precipitation of crystals, the dimensional accuracy of the side frame can be easily improved. As a result, the distance between the front glass substrate and the rear glass substrate can be made uniform, the accelerating voltage applied between the front plate and the back plate inside the FED device varies, and the velocity of electrons that collide with the phosphors. It is difficult to cause a situation in which the brightness characteristics of the FED are adversely affected.
  • Table 14 shows examples of the present invention (sample at), and Table 5 shows comparative examples (sample ux) of the present invention.
  • TMA push rod thermal expansion coefficient measurement
  • the softening point was determined by a DTA apparatus. The measurement was performed in the atmosphere at a heating rate of 10 ° C / min and started from room temperature.
  • the crystallization temperature was measured with a DTA apparatus. Measurement is performed in the air at a heating rate of 10 ° C.
  • Measurement was started at room temperature.
  • the presence or absence of a glass transition point and the thermal expansion coefficient in a temperature range of 500 ° C or lower were measured with a TMA apparatus using a calcined body heat-treated at a temperature 20 ° C lower than the crystallization temperature as a sample.
  • the crystallinity was evaluated by measuring with a TMA apparatus after a crystallization peak appeared at a temperature of 570 ° C or lower with a DTA apparatus and heat-treated at a temperature 20 ° C lower than the crystallization temperature.
  • Tables 6 to 9 show examples of the present invention (sample No .;! To 20), and Table 10 shows comparative examples of the present invention (sample No. 2;! To 24).
  • Tables 6 to 10 Glass powder and refractory filler powder are mixed in the proportions shown in 10, and bismuth-based materials are mixed.
  • Willemite and tin dioxide (tin stone) were used as the refractory filler. Willemite had an average particle size D of 11 m, and tin dioxide had an average particle size D of 8 Hm.
  • the softening point was measured with a DTA apparatus. The measurement was performed in the atmosphere at a heating rate of 10 ° C / min and started from room temperature. The crystallization temperature was measured with a DTA apparatus. The measurement was carried out in the atmosphere at a heating rate of 10 ° C / min and started from room temperature.
  • the flow diameter is a powder having a mass corresponding to the true specific gravity of a bismuth-based material, pressed into a button shape having an outer diameter of 20 mm by a mold, and then the obtained button sample is mounted on a high strain point glass substrate. After being placed, the temperature was raised at 10 ° C / min in an electric furnace, held at the heat treatment temperature shown in Table 6 to 10 for 10 minutes, and then lowered at a rate of 10 ° C / min. The diameter was measured with a digital caliper and evaluated.
  • Sample No.;! ⁇ 20 uses willemite or tin dioxide as refractory filler powder, and the button surface after heat treatment is sufficiently crystallized, which is a characteristic characteristic of non-crystalline glass. No glass transition point was observed in the temperature range below 500 ° C. Therefore, it can be considered that Sample Nos. 1 to 20 are crystallized with high density (high crystallinity).
  • Sample No. 21 shown in Table 10 uses willemite as a refractory filler powder, and although the button surface was in a matte state, the glass transition point could be confirmed at a temperature lower than the softening point, and low. It is thought that it is crystallized to a density (low crystallinity). Samples Nos. 22 to 24 use willemite as a refractory filler powder, have a flow diameter of 20 mm or more, and show good fluidity. The surface was not crystallized.
  • the bismuth-based material of the present invention includes PDP, FED, VFD and cathode ray tube (CRT) sealing material, PDP partition wall forming material, PDP, FED and VFD side frame forming material, (II) Quartz vibration It is suitable as a sealing material for electronic parts such as cores and IC packages, and (III) magnetic head as a sealing material between cores or between a core and a slider.
  • CRT cathode ray tube
  • FIG. 1 is a cross-sectional view showing a tablet-integrated exhaust pipe of the present invention.
  • FIG. 2 is a cross-sectional view showing a tablet-integrated exhaust pipe of the present invention.

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Abstract

[PROBLÈMES] Proposer une composition de verre à base de bismuth qui peut être bien ramollie en traitement thermique tel qu'un scellement et peut cristalliser de façon satisfaisante après avoir été ramollie et qui est peu re-ramollie après cristallisation par un traitement thermique, par exemple un traitement sous vide. [MOYENS POUR RÉSOUDRE LES PROBLÈMES] Les problèmes sont résolus par une composition de verre à base de bismuth caractérisée par le fait qu'elle a une composition qui comprend en masse 60 à 84 % de Bi2O3, 5,4 à 15 % de B2O3, 10 à 27 % de ZnO, 0 à 7 % de CuO et 0 à 5 % de Fe2O3 et contient BaO, SrO, MgO et CaO dans une quantité totale de 0 à 10 % et SiO2 et Al2O3 dans une quantité totale de 0 à 5 % et qu'elle est sensiblement exempte de PbO.
PCT/JP2007/070661 2006-10-24 2007-10-23 Composition de verre à base de bismuth et matière à base de bismuth WO2008050772A1 (fr)

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CN104086197A (zh) * 2014-07-12 2014-10-08 瑞泰科技股份有限公司 一种玻璃窑用红柱石堇青石耐火材料及其制品

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JP5779922B2 (ja) * 2011-03-16 2015-09-16 日本電気硝子株式会社 耐火性フィラー及びこれを用いた封着材料
JP5773128B2 (ja) * 2010-05-10 2015-09-02 日本電気硝子株式会社 耐火性フィラーの製造方法
US8871664B2 (en) 2010-05-10 2014-10-28 Nippon Electric Glass Co., Ltd. Refractory filler, sealing material using same, and manufacturing method for refractory filler
CN102757182B (zh) * 2012-08-06 2014-12-10 西安创联宏晟电子有限公司 低温低膨胀系数高硬度无铅电子玻璃粉及其制备方法
KR101252179B1 (ko) * 2012-09-27 2013-04-05 주식회사 정관 무기용매를 포함하는 배기관 실링 소자용 슬러리 조성물과, 그 과립 제조 방법 및 이를 이용한 배기관 실링 소자의 제조 방법
CN103880287B (zh) * 2012-12-21 2015-11-25 辽宁法库陶瓷工程技术研究中心 一种低温封接微晶玻璃材料及制备方法
JP2015199629A (ja) * 2014-04-08 2015-11-12 旭硝子株式会社 封着材料、封着体
CN104445919B (zh) * 2014-11-27 2016-10-05 华南理工大学 应用于表面改性的低熔点低膨胀系数光学玻璃及其制备方法
CN105417954A (zh) * 2015-12-14 2016-03-23 周妙思 一种无铅玻璃粉
CN105502952A (zh) * 2015-12-14 2016-04-20 周妙思 一种玻璃粉
CN105502949A (zh) * 2016-01-14 2016-04-20 中澳科创（深圳）新材料有限公司 铜-铝间封接用氧化铋系低熔点玻璃及其制备方法
CN106946461B (zh) * 2017-04-25 2019-07-09 福州大学 一种CeO2改性的低温封接玻璃及其制备与使用方法
CN107200482B (zh) * 2017-05-25 2020-05-12 佛山市三水区康立泰无机合成材料有限公司 一种掺杂型可见光催化自洁膜、喷墨打印自洁玻璃及其制备方法
CN110217993B (zh) * 2019-06-26 2022-05-27 鲁米星特种玻璃科技股份有限公司 一种环保型低温封接玻璃及其制备方法
CN112499978A (zh) * 2020-12-24 2021-03-16 陕西科技大学 一种低熔点电子浆料用玻璃粉及其制备方法

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CN104086197A (zh) * 2014-07-12 2014-10-08 瑞泰科技股份有限公司 一种玻璃窑用红柱石堇青石耐火材料及其制品
CN104086197B (zh) * 2014-07-12 2016-06-08 瑞泰科技股份有限公司 一种玻璃窑用红柱石堇青石耐火材料及其制品

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