WO2008007504A1 - Composition de verre pour l'étanchéité et matériau étanche - Google Patents

Composition de verre pour l'étanchéité et matériau étanche Download PDF

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Publication number
WO2008007504A1
WO2008007504A1 PCT/JP2007/061265 JP2007061265W WO2008007504A1 WO 2008007504 A1 WO2008007504 A1 WO 2008007504A1 JP 2007061265 W JP2007061265 W JP 2007061265W WO 2008007504 A1 WO2008007504 A1 WO 2008007504A1
Authority
WO
WIPO (PCT)
Prior art keywords
sealing
glass
glass composition
sealing material
atmosphere
Prior art date
Application number
PCT/JP2007/061265
Other languages
English (en)
Japanese (ja)
Inventor
Takemi Kikutani
Junichi Iseki
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
Priority claimed from JP2007127853A external-priority patent/JP5703535B2/ja
Application filed by Nippon Electric Glass Co., Ltd. filed Critical Nippon Electric Glass Co., Ltd.
Priority to CN2007800256622A priority Critical patent/CN101484396B/zh
Publication of WO2008007504A1 publication Critical patent/WO2008007504A1/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
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • 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
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • 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
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
    • 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
    • H01J9/24—Manufacture or joining of vessels, leading-in conductors or bases
    • H01J9/26—Sealing together parts of vessels
    • 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
    • H01J9/24—Manufacture or joining of vessels, leading-in conductors or bases
    • H01J9/26—Sealing together parts of vessels
    • H01J9/261—Sealing together parts of vessels the vessel being for a flat panel display
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2217/00—Gas-filled discharge tubes
    • H01J2217/38—Cold-cathode tubes
    • H01J2217/49—Display panels, e.g. not making use of alternating current
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2329/00—Electron emission display panels, e.g. field emission display panels

Definitions

  • the present invention relates to a glass composition for sealing and a sealing material using the same, a plasma display panel (hereinafter referred to as PDP), a field emission display (hereinafter referred to as FED), a fluorescent display tube.
  • PDP plasma display panel
  • FED field emission display
  • VFD fluorescent display tube
  • sealing of flat display devices sealing of optical components such as lens caps, LD caps, etc., electronic components such as IC packages, piezoelectric resonators such as crystal resonators and surface acoustic wave devices
  • the present invention relates to a sealing glass composition and a sealing material suitable for sealing (including electronic component storage containers).
  • glass has been used as a sealing material for flat display devices and the like.
  • Glass has superior chemical durability and heat resistance compared to resin adhesives, and is suitable for ensuring airtightness of flat display devices.
  • the sealing material used for the PDP undergoes the following heat treatment process.
  • primary firing also referred to as glaze process or temporary firing process
  • the primary firing is performed under a temperature condition in which the resin contained in the vehicle is completely pyrolyzed.
  • secondary firing of the sealing material also referred to as a sealing process or a sealing process
  • the required amount of rare gas is injected and the exhaust pipe is sealed. In this way, the PDP is produced.
  • FED is a display device in which the inside of the device is kept in a high vacuum, and a phosphor is excited by an electron beam generated by applying an electric field in the high vacuum to emit visible light. is there . Even in FED, there is a process of sealing the exhaust pipe after exhausting the inside of the apparatus to a high vacuum through the exhaust pipe in the final manufacturing process after primary firing and secondary firing.
  • Patent Document 1 Japanese Patent Laid-Open No. 2-2229738
  • Patent Document 2 JP-A-7-69672
  • Patent Document 3 Japanese Patent Laid-Open No. 9-227154
  • tin phosphate glass described in Patent Documents 2 and 3 contains 25 mol% or more of PO.
  • the Po content is the main factor that determines the water resistance of the glass.
  • the water resistance can be improved, since the glass constituents are reduced, the thermal stability of the glass tends to be impaired, especially when firing in an air atmosphere, and it should be used as a sealing material. It becomes difficult.
  • the PDP is manufactured through a primary firing process, a secondary firing process, and a vacuum exhaust process.
  • the primary firing process and the secondary firing process are performed in the atmosphere, and the vacuum exhaust process is performed.
  • the process is performed in a high vacuum reduced pressure atmosphere.
  • the evacuation process is a process that requires a high temperature and a long period of time (usually 5 hours or more) to make the inside of the apparatus into a high vacuum, which is a cause of lowering the production efficiency of PDP and the like. Under these circumstances, various attempts have been made to shorten the evacuation process. However, an effective improvement measure has yet to be found.
  • FED also has a process of keeping the inside of the apparatus in a high vacuum, if it can be sealed under reduced pressure as in the case of PDP, the manufacturing efficiency can be dramatically increased and the product cost can be reduced. Can be cheap.
  • FED is required to be sealed at a low temperature of 490 ° C or lower because the heat resistance of phosphors, devices, etc. is poor compared to PDP.
  • the present invention improves the water resistance of tin phosphate glass and at the same time improves the production efficiency of PDP and the like, and can be well sealed in a low oxygen atmosphere, particularly under reduced pressure, and has a low temperature of 490 ° C or lower. It is a technical problem to obtain a sealing glass composition and a sealing material which can be sealed with a good thermal stability.
  • SnO in terms of mol% as follows: SnO 30-80%, PO 10-25% (however, 25% not included), BO 0-20% ZnO 0-20%,
  • the present invention proposes that the present invention can solve the above problems by regulating the glass composition to 0 to 20%. That is, first, book
  • the glass composition for sealing of the invention is a glass composition, expressed in mol% in terms of the following oxides.
  • the “low oxygen atmosphere” in the present invention means an atmosphere having an oxygen concentration of 15% by volume or less (preferably 10% by volume or less, more preferably 5% by volume or less, and further preferably 1% by volume or less).
  • the residual oxygen concentration in the atmosphere can be measured with, for example, LC-750 manufactured by Toray Engineering Co., Ltd.
  • the glass composition for sealing of the present invention can obtain desired characteristics by strictly regulating the glass composition range as described above. Specifically, by regulating the SnO content within a predetermined range, low-temperature sealing properties can be secured, and even when sealed during decompression, the airtight reliability of the flat panel display device is ensured. Can be maintained. P O
  • the water resistance of the glass can be remarkably improved. If the P 2 O content is restricted to less than 25 mol%, the glass is thermally stable.
  • the reliability of the flat display device can be ensured. Therefore, if the glass composition for sealing of the present invention is used as a sealing material, sealing can be performed under reduced pressure, so that the manufacturing cost of a flat display device such as a PDP can be reduced.
  • the glass composition for sealing of the present invention can be satisfactorily sealed in a low oxygen atmosphere (depressurized atmosphere, neutral atmosphere, reducing atmosphere, etc.).
  • a low oxygen atmosphere depressurized atmosphere, neutral atmosphere, reducing atmosphere, etc.
  • the reason is as follows.
  • Sn becomes a stable glass forming component when the valence is divalent.
  • the valence of Sn becomes tetravalent, the glass tends to devitrify and become thermally unstable. Therefore, in a low-oxygen atmosphere, tin phosphate glass is less susceptible to devitrification because SnO in the glass composition is oxidized during firing and the reaction to become SnO hardly proceeds.
  • the sealing of the present invention The glass composition for low-oxygen has a low oxygen content because the PO content is regulated to less than 25 mol%.
  • a sealing glass composition of the present invention in addition to the above glass composition, in mole 0/0 in terms of oxide, MoO, Nb O, TiO, ZrO, CuO, MnO, MgO , CaO, S
  • the glass composition for sealing of the present invention is represented by MoO 0-5%, NbO 0-15%, TiO 0- 15%, ZrO
  • R 3 ⁇ 4Mg refers to at least one of Ca ⁇ Sr ⁇ Ba) 0-15%.
  • the sealing glass composition of the present invention has a glass composition, in molar 0/0 in terms of oxide, SnO 30 ⁇ 80%, PO 10 ⁇ 25% ( however, 25% Not included), BO
  • R O (R is at least l of Li, Na, K, Cs) 0-2
  • R indicates at least one of Mg ⁇ Ca ⁇ Sr ⁇ Ba) 0-15%.
  • the sealing glass composition of the present invention is characterized by containing F in an amount of 0 to 10% in terms of the following oxide% in addition to the above glass composition.
  • the sealing material of the present invention is characterized in that it contains 50 to 100% by volume of a glass powder comprising the above glass composition for sealing and 0 to 50% by volume of a refractory filler powder. It is possible.
  • the sealing material of the present invention is characterized in that when fired in a reduced pressure atmosphere, the surface of the fired body is bright and devitrification is not observed.
  • the suitability is judged by the following procedure. First, dry seal the sealing material to 2cm ⁇ to make a button-shaped sample. Next, after placing the prepared sample on a high strain point glass substrate, 1. OX IOTorrd. 33kPa) under reduced pressure (soft spot of the sealing material + 30 °) Bake for 30 minutes at the temperature of C).
  • the heating / cooling speed is 5 ° CZ
  • Samples are loaded into and removed from the reactor at room temperature.
  • the gloss is evaluated by measuring the average surface roughness Ra of the prepared button-shaped sample surface.
  • the average surface roughness Ra is measured by a method based on JIS-R 3502. When the average surface roughness Ra of the button surface is 100 ⁇ m or less, it is evaluated as “shiny”. Further, the sample after firing was observed, and crystals were deposited on the surface of the button-shaped sample produced, and the product was evaluated as “no devitrification”. Devitrification is evaluated by observing crystals on the button surface using a stereomicroscope.
  • the sealing material of the present invention is characterized in that the surface of the fired body is glossy and devitrification is not observed when fired in a neutral or reducing atmosphere.
  • the suitability is determined by the following procedure. To do. First, dry-press the sealing material to 2cm ⁇ to make a button-shaped sample. Next, after placing the prepared sample on a high strain point glass substrate, using an atmosphere firing furnace, N
  • the temperature raising and lowering speed is 5 ° CZ, and the sample is put into and out of the firing furnace at room temperature.
  • the gloss is evaluated by measuring the average surface roughness Ra of the prepared button-shaped sample surface.
  • the average surface roughness Ra of the button surface is 100 m or less, it is evaluated as “shiny”.
  • the average surface roughness Ra is measured by a method based on JIS-R3502.
  • the fired sample is observed, and if no crystal is deposited on the surface of the button-shaped sample produced, it is evaluated that “devitrification is not observed”. Devitrification is evaluated by observing crystals on the button surface using a stereomicroscope.
  • the refractory filler contains tin oxide, niobium oxide, zirconium phosphate, cordierite, Na Nb Zr (PO 4), KZr (PO 4), Ca N
  • the sealing material of the present invention includes PDP, FED, VFD, CRT (Cathode Ray Tube
  • the sealing tablet of the present invention is a sealing tab in which a sealing material is sintered into a predetermined shape.
  • the sealing material is characterized by the aforementioned sealing material.
  • the sealing paste of the present invention is characterized in that the sealing material is the aforementioned sealing material in the sealing paste in which the sealing material is dispersed in a vehicle.
  • the “vehicle” in the present invention is a constituent material of a sealing paste containing a solvent, a resin binder, and the like, and the solvent is an essential component, but the resin binder is an optional component.
  • the sealing paste of the present invention comprises vehicle toluene, N, N, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, dimethyl carbonate, butyl carbitol acetate, isoamyl acetate, propylene.
  • the sealing paste of the present invention is characterized in that it contains one or more selected from the group consisting of vehicle nitrocellulose, polyethylene glycol derivatives, and polyethylene carbonate.
  • the PDP or FED manufacturing method of the present invention is a PDP or FED manufacturing method including a sealing step using the sealing material, and is a whole or a part of the sealing step. Is characterized in that it is carried out in a reduced pressure atmosphere.
  • the “reduced pressure atmosphere” as used in the present invention refers to the case where the atmospheric pressure is 1. O X IOTorrd.
  • the method for manufacturing an optical component or electronic component according to the present invention is a method for manufacturing an optical component or electronic component having a sealing step using the above-mentioned sealing material. All or part of the process is characterized by being carried out in a neutral or reducing atmosphere.
  • neutral atmosphere refers to a neutral gas atmosphere such as an Ar atmosphere or an N atmosphere.
  • reducing atmosphere refers to an atmosphere in which 11% by volume of 11 gas is mixed in an N atmosphere.
  • the glass composition for sealing of the present invention has significantly improved water resistance, and at the same time, can be sealed well even under reduced pressure, thus greatly improving the production efficiency of flat display devices such as PDPs. Can do. That is, in the case of a flat display device such as a PDP, if it can be sealed in a reduced pressure, it is not necessary to evacuate the inside of the device for a long time of 5 hours or more through the exhaust pipe. The manufacturing efficiency of the display device can be dramatically increased. Furthermore, the sealing glass composition of the present invention has an advantage of good thermal stability even though it can be sealed at a low temperature of 490 ° C. or lower. Generally, low temperature of glass and thermal stability of glass are characteristics that are difficult to achieve at the same time, but the glass composition for sealing of the present invention can achieve both at a high level.
  • FIG. 1 is an explanatory view showing a configuration of an optical cap component.
  • SnO is an essential component that lowers the melting point of glass, and its content is 30 to 80%, preferably 40 to 70%, more preferably 50 to 66%.
  • SnO is 40% or more, the glass has excellent fluidity and high airtightness can be secured. If SnO is less than 30%, the viscosity of the glass becomes too high, and the sealing temperature may be increased. If SnO is more than 80%, vitrification tends to be difficult.
  • tin phosphate glass if SnO exceeds 70%, the ability of the glass to be easily altered when fired in an air atmosphere, and in a low oxygen atmosphere, even if SnO is in the range of 70-80%, Glass is difficult to change during firing.
  • PO is a glass-forming oxide and is an essential component. Its content is 10-25% ( ⁇
  • the thermal stability of the glass will be poor.
  • the glass-forming oxide Po is low.
  • the glass composition for sealing of the present invention regulates the glass composition within a predetermined range, even if PO is less than 25%,
  • B 2 O is a glass-forming oxide and is a component that stabilizes the glass. Its content
  • the glass when performing low-temperature sealing, can be cooled at a low temperature if the content of BO is 1 to 5%.
  • the stability will be poor, but if the firing atmosphere is a low oxygen atmosphere, the content of B 2 O will be low.
  • ZnO is an intermediate oxide and a component that stabilizes the glass.
  • the content is 0 to 20%, preferably 0 to 15%, more preferably 0 to 10%, still more preferably 3 to 10%.
  • the thermal stability of the glass can be improved, and devitrification hardly occurs on the glass surface during sealing.
  • ZnO is more than 20%, the balance of the glass composition is lacking, and conversely, the thermal stability of the glass tends to decrease.
  • SiO is a glass-forming oxide and is a component that stabilizes the glass. Its content
  • a small amount of SiO added for example about 0.5%
  • the thermal stability of the glass is improved, and the glass becomes difficult to devitrify during sealing. If SiO is 5% or less, the soft temperature of the glass will not rise so much, and low-temperature sealing can be performed.
  • Al O is an intermediate oxide, a component that stabilizes the glass, and heat of the glass.
  • the soft temperature of the glass rises, making it difficult to seal at low temperatures and impairing the fluidity of the glass.
  • WO is not an essential component, it has an effect of improving the adhesive force with an object to be sealed.
  • 3 Content is 0 to 20%, preferably 0 to 15%, more preferably 1.2 to 15%, still more preferably 3 to 10%.
  • WO should be 0.1%, especially 3% or less.
  • R 2 O is not an essential component, but at least one of R 2 O is glass.
  • the adhesive strength with a glass substrate or the like can be increased. Its content is
  • R O when considering the thermal stability of the glass, such as surface devitrification at the time of sealing and the fluidity of the glass, R O
  • the total amount of 2 is preferably 10% or less. If the total amount of R 2 O exceeds 20%, the glass tends to devitrify during sealing. In addition,
  • Li O has the highest ability to improve adhesion to glass substrates, etc.
  • the Li O content is 3% or less
  • MoO, NbO, TiO, ZrO, CuO, MnO, MgO, CaO, SrO, BaO are glass
  • MoO is not an essential component, but if it is added in a small amount to the glass composition, it will wet with the material to be sealed.
  • Nb 2 O, TiO and ZrO are components that improve the stability of the glass.
  • the content of these components is 0 to 15%, preferably 0 to 10%. If these components exceed 15%, the glass will melt and the glass tends to become unstable.
  • the CuO content is preferably 0 to 10%, particularly preferably 0 to 5%. If CuO exceeds 10%, the glass tends to become thermally unstable.
  • the MnO content is preferably 0 to 15%, particularly preferably 0 to 8%. If MnO exceeds 15%, the glass tends to become thermally unstable. In addition, it is possible to use both MnO and MnO as the raw material for introducing MnO. When MnO is used as the raw material for introduction, the thermal stability of the glass is improved. preferable.
  • R'O is an alkaline earth oxide, and is a network-modified acid oxide. These components are not essential components, but their total content is preferably 0 to 15%, particularly preferably 0 to 5%. If R'O exceeds 15%, the glass tends to become thermally unstable. In particular, among R'O, MgO and BaO are preferred because they have a high effect of low temperature in addition to stabilizing the glass.
  • O is a component that improves the weather resistance of glass, and its content is preferably 0 to 10%.
  • the In O force is more than 10%.
  • the lanthanoid acid oxide is a network-modified oxide, and is not an essential component in the present invention! / Reinforcement
  • a lanthanoid acid oxide is contained in a glass component in a total amount of 0.1% or more. By doing so, the weather resistance of the glass is improved. On the other hand, if the lanthanoid oxide exceeds 15%, the sealing temperature tends to increase. Therefore, considering the balance between weather resistance and sealing temperature, the content of the lanthanoid compound is 0 to 15% in total, preferably 0.5 to 15%, more preferably 1 to 15%.
  • the lanthanoid oxide La 2 O, CeO, Nd 2 O and the like can be used.
  • the addition of other rare earth oxides such as Yo
  • the weather resistance of the glass can be further improved.
  • the rare earth oxide content excluding the lanthanoid oxide is preferably 0 to 5%.
  • Ta 2 O has an effect of improving weather resistance, and its content is preferably 0 to 10%.
  • TeO is a component that has an effect of lowering the soft saddle point, and its content is preferably 0 to 15%.
  • F may adversely affect the fluorescence characteristics of phosphors included in flat display devices and the like.
  • the content is preferably 0 to 10%, more preferably 0 to 5%, and even more preferably 0 to 3%. If F exceeds 10%, there is a high possibility that the fluorescent properties of the phosphor will be adversely affected.
  • the sealing glass composition of the present invention does not substantially contain PbO.
  • substantially does not contain PbO means that the PbO content contained in the glass composition is 100 Oppm or less. If the glass composition for sealing does not contain PbO, it can accurately meet recent environmental demands.
  • the glass composition for sealing of the present invention may further contain up to 10% of other components in addition to the above components as long as the effects of the present invention are not impaired.
  • composition range it is naturally possible to select a preferred composition range by arbitrarily combining the preferred and range of each component.
  • a more preferable composition range it is expressed in mol% in terms of the following oxides: SnO 30 to 80%, PO 10-25% (however, 25% is not included), BO 0.1 to 10% ( However, 10%
  • R 0 (R indicates at least one of Li ⁇ Na, K, Cs) 0-20%, MoO 0-5%, Nb
  • composition range of the glass composition is regulated as described above, the water resistance of the glass can be greatly improved, and the thermal stability of the glass can be greatly improved.
  • the glass composition is more suitable for sealing in a low oxygen atmosphere than in an atmospheric oxygen atmosphere. However, since the thermal stability of glass is greatly improved, it can be sealed even in an air atmosphere.
  • various raw materials such as oxides, hydroxides, nitrates, and phosphates can be used as glass raw materials.
  • the glass melt during melting can be blown out and foaming of the glass during firing can be suppressed, which is preferable.
  • a sealing glass composition having the above composition has a glass transition point of about 250 to 400 ° C, a softening point of about 360 to 440 ° C, and a temperature range of about 400 to 600 ° C. Good fluidity. In addition, it has a coefficient of thermal expansion of about 80 to 150 X 10 _7 Z ° C in the temperature range of 30 to 250 ° C.
  • the glass composition for sealing of the present invention having such properties can be used alone as a sealing material for a material having a suitable thermal expansion coefficient.
  • the glass composition for sealing of the present invention can be processed into a powder form by a ball mill, a jet mill or the like and used as a sealing material. Moreover, if the glass composition for sealing is made of glass powder, it becomes easy to adjust the mechanical strength and thermal expansion coefficient by mixing with a refractory filler powder, etc., and is mixed with a vehicle etc. It becomes easy to use as a material.
  • the coefficient of thermal expansion does not fit! Encapsulate materials such as alumina (70 X 10 "V ° O, high strain point glass (85 X 10" V ° O or soda flat glass (90 X 10 "V ° O)) In the case of wearing, it can be used appropriately by adding a fireproof filler powder, which is a low expansion material, and combining it.
  • the thermal expansion coefficient of the composite (composite) is 10 ⁇ It is important to design it as low as 30 X 10 _7 Z ° C.
  • the sealing material of the present invention preferably contains 50 to 50% by volume of glass powder and 0 to 50% by volume of refractory filler powder, in particular, FED, PDP, VFD, In the case of CRT sealing, it is preferable to contain 60 to 80% by volume of glass powder and 20 to 40% by volume of refractory filler powder.
  • the thermal expansion coefficient is about 60 to 90 ⁇ 10 _7 Z ° C.
  • the amount of the refractory filler powder is more than 50 volume%, the ratio of the glass powder becomes relatively low, and it becomes difficult to obtain the desired fluidity.
  • the particle size of the glass powder and refractory filler powder is determined by the average particle size D using a laser diffraction particle size distribution analyzer (SALD-2000J, manufactured by Shimadzu Corporation).
  • the average particle size D is less than 1 ⁇ O / z m
  • the fluidity of the material is obstructed and the airtight reliability of the flat display device or the like is obtained.
  • the glass composition for sealing may be formed into a predetermined shape, for example, a ball shape, a rod shape or a plate shape, and used as a sealing material.
  • the sealing material of the present invention When the sealing material of the present invention is fired in a reduced-pressure atmosphere, it is preferable that the surface of the fired body is glossy and devitrification is not observed.
  • the sealing material When sealing in a reduced pressure atmosphere, the sealing material is more easily foamed than in the atmosphere, but the sealing material of the present invention regulates the glass composition of the glass powder to a predetermined range. Therefore, it can be fired well in this atmosphere. As a result, even if the PDP secondary firing process and the vacuum exhaust process are performed simultaneously, the sealing layer is not devitrified, and foaming that impairs the hermeticity of the PDP can be suppressed, improving the production efficiency of the PDP, This can contribute to cost reduction.
  • the atmospheric pressure is preferably 1. OX 10 _1 Torr or less (13.3 Pa or less) as a reduced pressure atmosphere, and 1. OX 10 _3 Torr or less (0.133 Pa or less) is more preferable 1.0 X 10 _5 Torr or less (0. 00133Pa hereinafter) is more preferable.
  • the sealing material of the present invention is fired in a neutral atmosphere or a reducing atmosphere, it is preferable that the surface of the fired body is glossy and devitrification is not observed.
  • the sealing glass composition of the present invention does not impair the fluidity and wettability even when sealed in a reducing atmosphere, but rather when sealed in a reducing atmosphere, the atmosphere contains a certain amount of oxygen. Fluidity and wettability are improved as compared to sealing in an atmosphere. This is because the tin contained as the main component of the glass composition is more divalent (SnO) than tetravalent (SnO).
  • the thermal stability of the glass is maintained. Furthermore, since the sealing material of the present invention regulates the glass composition of the glass powder within a predetermined range, the glass has good thermal stability and low-temperature sealing properties. Can be fired well.
  • refractory filler powder examples thereof include cordierite, zircon (zirconium silicate), tin oxide, niobium oxide, zirconium phosphate, willemite, and mullite. Also, use a fireproof filler with the basic structure of [AB (MO)].
  • elements such as Li, Na, K, Mg, Ca, Sr, Ba, Zn, Cu, Ni, and Mn are suitable for A.
  • B is compatible with elements such as Zr, Ti, Sn, Nb, Al, Sc, and Y.
  • M is compatible with elements such as P, Si, W, and Mo.
  • a refractory white pigment e.g. TiO
  • a refractory black pigment e.g.
  • Fe-Mn, Fe-Co-Cr, and Fe-Mn-Al pigments can be added.
  • the sealing material of the present invention does not substantially contain PbO. If the sealing material does not contain PbO, it can accurately meet recent environmental requirements.
  • the object to be sealed is a metal (for example, stainless steel, Kovar, etc.), that is, It is preferably used for metal sealing.
  • the sealing material of the present invention can be satisfactorily sealed without oxidizing the metal in the sealing step because it can be used favorably in a low oxygen atmosphere.
  • the sealing material of the present invention can be processed into a sealing tablet sintered in a predetermined shape and used.
  • a sealing tablet With a sealing tablet, it is possible to accurately seal desired parts such as optical components, and to reduce the number of manufacturing processes that do not require the application of sealing paste with a dispenser or screen printer. This can contribute to lower product costs.
  • Sealed tablets are manufactured through multiple independent thermal processes as follows. First, a solvent resin binder is added to the glass powder to form a slurry. Then, this slurry is put into a granulator such as a spray dryer to produce glass powder granules. At this time, the glass powder granules are heat-treated at a temperature at which the solvent volatilizes (about 100 to 200 ° C.).
  • the produced glass powder granules are put into a mold designed to have a predetermined size and, for example, dry press-molded into a ring shape to produce a pressed body.
  • the resin binder remaining in the pressed body is decomposed and volatilized in a baking furnace such as a belt furnace and sintered at a temperature of about the soft point of the glass powder to produce a sealed tablet.
  • the firing in the firing furnace may be performed a plurality of times. When the firing is performed a plurality of times, the sintering strength of the glass tablet is improved, and the glass tablet can be prevented from being broken or broken.
  • the shape of the tablet is not particularly limited. For example, ring shapes, plate shapes, columnar shapes, frame shapes, tubular shapes, and the like can be used.
  • the below-mentioned thing can be used for a solvent and a resin binder.
  • the sealing material of the present invention is preferably mixed with a vehicle and used as a sealing paste. If the sealing material is processed into a sealing paste, a sealing pattern can be formed with high accuracy by a coating machine such as a dispenser or a screen printer.
  • a vehicle is a material containing components such as a solvent, a resin binder, a surfactant, a pigment, a thickener, and a plasticizer.
  • the glass powder according to the present invention is a tin phosphate glass mainly containing SnO.
  • tin phosphate glass reacts with the resin binder contained in the vehicle during firing due to its low melting point. Specifically, SnO is oxidized and becomes SnO. ,Liquidity
  • the vehicle according to the present invention is a solvent that volatilizes at a low temperature, a resin fat resin.
  • a binder it is highly necessary to use a solvent and a resin binder that do not alter the tin phosphate glass.
  • the solvent is preferably a solvent that does not denature the tin phosphate glass having a low boiling point and a small amount of residue after firing. That is, it is preferable to use a solvent having a boiling point of 300 ° C. or less.
  • a solvent having a boiling point of 300 ° C. or less Specifically, toluene, N, N, -dimethylformamide (DMF), 1,3 dimethyl-2 imidazolidinone (DMI), dimethyl carbonate, butyl carbitol acetate (BCA), isoamyl acetate, propylene carbonate, N-methyl 2-Pyrrolidoneacetonitrile, dimethyl sulfoxide, acetone, methyl ethyl ketone and the like can be preferably used.
  • a higher alcohol as the solvent.
  • Higher alcohols can be used as sealing pastes without adding a resin binder to the vehicle because the solvent itself has viscosity.
  • the vehicle does not contain a resin binder, it is possible to suppress the situation where SnO is oxidized and SnO is formed, and the glass is denatured during sealing.
  • Isoeicosyl alcohol can be used.
  • an appropriate viscosity is secured and it is immediately preferred.
  • pentanediol and its derivatives can also be used as a solvent.
  • jetylpentanediol (C 3 H 2 O 3) has excellent viscosity characteristics.
  • the resin binder in addition to a low decomposition temperature, a resin that does not denature the tin phosphate glass with few residues after firing is preferable.
  • Nitrocellulose, polyethylene glycol derivatives, and polyethylene carbonate are suitable as resin binders because they do not alter the tin phosphate glass, which has low decomposition temperature and little residue after firing. Excellent degradability and viscosity characteristics.
  • dimethyl carbonate, propylene carbonate, and N-methyl-2-pyrrolidone are preferable because they do not dry in a short time and the coating workability is excellent in leveling.
  • polyethylene carbonate When polyethylene carbonate is used by dissolving it in DMF, it must be dissolved at a higher concentration than the polyethylene glycol derivative, and the optimum concentration is 10 to 30% by weight.
  • the optimal concentration when dissolved in dimethyl carbonate is 5 to 10 weight 0/0.
  • propylene carbonate or N-methyl-2-pyrrolidone is used, the content is 10 to 30% by weight.
  • Polyethylene glycol derivatives are HOCH CH 0 ⁇ (CH CH O) NCO [X] —CO
  • Polyethylene render derivatives having the above skeleton structure exhibit excellent viscosity characteristics in a small amount and have low-temperature decomposability characteristics.
  • polyethylene glycol derivatives having a molecular weight of 100,000 to 500,000 have good low-temperature decomposability.
  • polyethylene glycol derivative strength is suitable because of its low cost and availability.
  • Polyethylene glycol derivatives dissolve well in N, N'-dimethylformamide (DMF), 1,3-dimethyl-2-imidazolidinone (DMI) and the like. These solvents are preferable because they do not dry in a short time at room temperature.
  • DMF N'-dimethylformamide
  • DMI 1,3-dimethyl-2-imidazolidinone
  • the optimum concentration is 0.5 to 5% by weight. Note that the use of DMI rather than DMF is suitable for cases where volatility is kept low and comparative work time is increased.
  • Nitrocellulose has low-temperature decomposability and can be mixed with isoamyl acetate and used as a vehicle.
  • the vehicle and the sealing material can be kneaded using a kneader such as a three-roll mill.
  • the glass composition for sealing of the present invention can also be used as a binder for conductive powder.
  • the glass powder comprising the glass composition for sealing of the present invention 10 to 60% by weight And a conductive material containing 40 to 90% by weight of metal powder and 0 to 20% by weight of refractory filler powder. This is because if the amount of the metal powder is more than 90% by weight, the ratio of the glass powder becomes relatively low and it becomes difficult to obtain the required fluidity, and if it is less than 40% by weight, the conductivity cannot be secured. Also, if the amount of the refractory filler powder is more than 20% by weight, the ratio of the glass powder becomes relatively low, and the necessary sealing properties can be obtained.
  • examples of the metal powder include Ag, Pd, Al, Ni, Cu, Au, and a mixture thereof.
  • the refractory filler powder the same refractory filler as described above can be used.
  • a refractory white pigment eg TiO
  • a refractory black pigment e.g., TiO
  • the conductive paste thus obtained can be formed into a conductive pattern by baking in a vacuum at 400 to 900 ° C. for about 5 minutes to 1 hour.
  • a method for producing a PDP or FED of the present invention is a method for producing a PDP or FED having a sealing step using the above-mentioned sealing material, wherein a part or all of the sealing step is a reduced-pressure atmosphere. It is executed with care.
  • the sealing process is performed in a reduced pressure atmosphere, as described above, the secondary firing process and the vacuum exhaust process can be performed simultaneously, which contributes to a low product cost.
  • the sealing material of the present invention can be sealed at a low temperature and has good thermal stability, troubles caused by the properties of the sealing material can also be suppressed.
  • VFD and CRT have the same or similar manufacturing processes as PDP and FED, and have the benefit of diverting the above manufacturing method.
  • the optical component or electronic component manufacturing method of the present invention is a method for manufacturing an optical component or an electronic component having a sealing process using the above-described sealing material, wherein all or part of the sealing step is performed. It is carried out in a neutral or reducing atmosphere. If the sealing process is a neutral atmosphere or a reducing atmosphere, the metal members used in the optical component are not oxidized, and the elements such as the electronic component are not easily deteriorated. As a result, the manufacturing cost of the optical component is reduced. The reliability of electronic parts can be improved. In addition to being capable of being sealed at low temperatures, the sealing material of the present invention also has good thermal stability, so that it is due to the thermal characteristics of the sealing material. Rubble can be suppressed.
  • An optical cap component 1 shown in FIG. 1 is a metal having a cylindrical side wall portion 5 and an end wall portion 6 provided at the tip of the side wall portion 5 and having a lens holding hole at the center thereof. It is composed of a shell 2 made of light and a light-transmitting glass member (spherical lens member) 4 fixed to the lens holding hole of the metal shell 2 with a sealing material 3.
  • the light-transmissive glass member and the metal shell are sealed with a sealing material.
  • the sealing process is generally performed at a low temperature for the purpose of maintaining the product characteristics of the optical cap component.
  • the sealing temperature is not higher than the soft melting point of the light-transmitting glass member and not higher than the Curie point of the metal shell, and is normally set to a temperature of 550 ° C. or lower. Therefore, when the sealing material of the present invention is used, it can be satisfactorily sealed at a low temperature even in a reducing atmosphere or a neutral atmosphere, and it can suppress the oxidation of the metal shell, so that a special plating treatment is performed. The cost of the optical cap part which is not necessary can be reduced.
  • sealing glass composition and sealing material of the present invention will be described in detail based on examples.
  • Tables 1 to 3 show examples of the glass composition for sealing of the present invention (samples a to n), and Table 4 shows comparative examples (samples P and q).
  • Each glass sample was prepared as follows. First, the notch raw materials were prepared so as to have the glass compositions shown in Tables 1 to 4, and N gas for a flow rate of 3 LZ was flown into the electric furnace, and then the flow rate was 1 LZ.
  • Tin monoxide was used as a batch raw material of SnO.
  • Orthophosphoric acid as a batch raw material for PO (
  • Strong phosphoric acid (105 wt% phosphoric acid) was used without using (orthophosphoric acid). The reason for this is that strong phosphoric acid has a lower moisture content than normal phosphoric acid, which can be accompanied by a reduction in the moisture content of the glass batch, and glass melt spills during melting. ⁇ N Reagent grade oxides were used as raw materials for the other components.
  • the molten glass was passed through a water-cooled roller, formed into a thin plate shape, pulverized with a ball mill, passed through a sieve with a mesh size of 105 m, and a laser diffraction particle size distribution analyzer (Shimadzu Corporation). Glass powder with an average particle size of about 10 m was obtained at SALD-2000J
  • the glass transition point and the coefficient of thermal expansion were determined after pressing the molten glass into 20 X 5mm ⁇ . It measured with the rod-type thermal expansion meter (TMA) (made by Rigaku Corporation).
  • TMA rod-type thermal expansion meter
  • the softening point was measured by a macro-type differential thermal analysis (DTA) apparatus (manufactured by Rigaku Corporation) while flowing nitrogen gas at a flow rate of lOOccZ during measurement.
  • DTA differential thermal analysis
  • a powder having a weight corresponding to the true specific gravity of the material was dry-pressed into a button shape of ⁇ 2 cm with a mold to obtain a button-shaped powder compact.
  • this compact was placed on a soda glass substrate, and then heated in N to a firing temperature of 450 ° C at a rate of 10 ° CZ and held for 10 minutes. That
  • the surface of the fired body was glossy and observed with a stereomicroscope, and no crystal was observed.
  • a crystal was observed and evaluated as “X”.
  • the diameter of the fired body was measured with a digital caliper to evaluate its fluidity.
  • a button-like powder compact was obtained. Next, after placing this compact on the various substrates in the table, 1. In a reduced pressure of OX 10 _1 Torr, the temperature was raised to a firing temperature of 470 ° C at a rate of 10 ° CZ and held for 10 minutes. did. Thereafter, the surface of the fired body was glossy and observed with a stereomicroscope. The surface of the fired body was not glossy or was observed with a stereomicroscope, and the crystal observed was evaluated as “X”. Further, the diameter of the fired body was measured with a digital caliper, and the fluidity (under reduced pressure) was evaluated.
  • the samples a to n of the examples have a thermal expansion coefficient of 106 to 118 ⁇ 10 ”V ° C glass transition point of 302 to 355 ° C., and have good characteristics as a sealing material.
  • the samples a to n of the examples also had good surface conditions after firing, while the samples p and q of the comparative examples had poor surface conditions after firing (during decompression). Yes, function as a sealing material in a reduced-pressure atmosphere It is thought that it cannot be demonstrated.
  • the samples p and q of the comparative example have poor water resistance, and it is considered that long-term reliability of a flat display device or the like cannot be ensured.
  • Tables 5 and 6 show examples (sample Nos. 1 to 8) of the sealing material of the present invention.
  • NZP listed in the table is NbZr (PO),
  • ZWP3 ⁇ 4Zr WO PO
  • KZP3 ⁇ 4KZr PO
  • KNbZPi KNbZPi or Na Nb Zr (PO)
  • NbZr (PO) filler powder was produced as follows. First, niobium phosphate: NbPO
  • NbZr (PO 4) filler powder having an average particle size of 14 / z m was obtained.
  • KZr (PO 4) filler powder having an average particle size of 14 / z m was obtained.
  • the temperature was raised to the 480 ° C firing temperature at a rate of 10 ° CZ, held at the firing temperature for 10 minutes, and then cooled to room temperature at the rate of 10 ° CZ. Thereafter, the surface of the fired body was glossy and observed with a stereomicroscope, and no crystal was observed. The surface of this fired body When the crystal was not glossy and observed with a Z or a stereomicroscope, crystals were observed and evaluated as “ ⁇ ”. In addition, the diameter of this fired body is measured with a digital caliper.
  • the surface condition after firing was evaluated by the following method. First, a powder having a weight corresponding to the true specific gravity of each sample was dry-pressed into a 2 cm button shape using a die to obtain a button-shaped powder compact. Next, this molded body was placed on the soda glass substrate in the table, 1. In a reduced pressure of OX 10 _1 Torr, the temperature was raised to a 490 ° C firing temperature at a rate of 10 ° C / min, After holding at the firing temperature for 10 minutes, the temperature was lowered to room temperature at a rate of 10 ° CZ. Thereafter, the surface of the fired body was glossy and observed with a stereomicroscope, and no crystal was observed. When the surface of the fired body was not glossy or was observed with a stereomicroscope, crystals that were observed were evaluated as “X”. Further, the diameter of the fired body was measured with a digital caliper, and the fluidity (under reduced pressure) was evaluated.
  • Sample Nos. 1 to 8 in the examples have a thermal expansion coefficient of 68.9 to 77 X 10 _7 Z ° C, and a flow diameter (in N) of 22.8 to 24.2 mm.
  • the flow diameter (under reduced pressure) is 20. 0-21.7 mm
  • the sealing glass composition and sealing material of the present invention have a PDP and various electron-emitting devices. Sealing of flat display devices such as various FEDs and VFDs to be sealed, sealing of optical parts such as lens caps and LD caps, and electronics such as IC packages, piezoelectric vibrators such as crystal resonators and surface acoustic wave elements, etc. It is suitable for sealing parts (including electronic component storage containers).
  • the sealing glass composition and sealing material of the present invention can also be used in display devices such as CRTs and inorganic electoluminescence displays. It can also be used to seal lamps such as flat fluorescent lamps (FFL). Furthermore, it can be used for sealing optical components having optical fibers, ball lenses, and the like as constituent members.
  • display devices such as CRTs and inorganic electoluminescence displays. It can also be used to seal lamps such as flat fluorescent lamps (FFL). Furthermore, it can be used for sealing optical components having optical fibers, ball lenses, and the like as constituent members.
  • FTL flat fluorescent lamps
  • the sealing glass composition and the sealing material of the present invention can also be used in an organic electoluminescence display.
  • the sealing material of the present invention is processed into a sealing paste, a sealing tablet, a frit bar, etc., and the glass substrates are fixed to each other through these, and then a laser beam is applied to the sealing portion. By irradiating, the glass substrates are sealed together.
  • a laser beam an excimer laser, a YAG laser, or the like can be used.

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Abstract

On a cherché à produire une composition de verre pour l'étanchéité qui non seulement améliore l'imperméabilité à l'eau du verre au phosphate d'étain mais qui assure une étanchéité appropriée dans une atmosphère pauvre en oxygène, notamment une atmosphère de vide et qui en outre, assure une étanchéité à basse température, telle qu'une température inférieure ou égale à 490°C, qui présente une excellente stabilité à la chaleur et qui produit un matériau étanche approprié. On a donc préparé une composition de verre pour l'étanchéité qui se caractérise en ce qu'elle renferme, en pourcentage molaire en terme d'oxyde, de 30 à 80% SnO, de 10 à 25% (25% étant exclu) P2O5, 0 de 20% B2O3, 0 à 20% ZnO, 0 à 10% SiO2, 0 à 10% Al2O3, 0 à 20% WO3 et de 0 à 20% R2O (R représentant au moins un élément parmi Li, Na, K and Cs). Cette composition se caractérise en ce qu'elle est utilisée pour l'étanchéité dans une atmosphère pauvre en oxygène et plus particulièrement une atmosphère de vide.
PCT/JP2007/061265 2006-07-11 2007-06-04 Composition de verre pour l'étanchéité et matériau étanche WO2008007504A1 (fr)

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WO2010099381A1 (fr) * 2009-02-27 2010-09-02 Corning Incorporated Verre de phosphate de sn dopé avec des métaux de transition
JP2011225404A (ja) * 2010-04-22 2011-11-10 Nippon Electric Glass Co Ltd ＳｎＯ−Ｐ２Ｏ５系ガラス、封着材料及び封着ペースト
WO2012043787A1 (fr) * 2010-10-01 2012-04-05 日本電気硝子株式会社 Boîtier d'élément électrique
JP2012113968A (ja) * 2010-11-25 2012-06-14 Nippon Electric Glass Co Ltd 電気素子パッケージ
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WO2017061403A1 (fr) * 2015-10-07 2017-04-13 日本化学工業株式会社 Matériau à dilatation thermique négative et matériau composite le comprenant
WO2017061402A1 (fr) * 2015-10-07 2017-04-13 日本化学工業株式会社 Procédé de production de phosphate de tungstène et de zirconium
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WO2010099381A1 (fr) * 2009-02-27 2010-09-02 Corning Incorporated Verre de phosphate de sn dopé avec des métaux de transition
US8084380B2 (en) 2009-02-27 2011-12-27 Corning Incorporated Transition metal doped Sn phosphate glass
CN102414139A (zh) * 2009-02-27 2012-04-11 康宁股份有限公司 过渡金属掺杂的磷酸锡玻璃
CN102414139B (zh) * 2009-02-27 2015-07-22 康宁股份有限公司 过渡金属掺杂的磷酸锡玻璃
US9090498B2 (en) 2010-03-29 2015-07-28 Nippon Electric Glass Co., Ltd. Sealing material and paste material using same
JP2011225404A (ja) * 2010-04-22 2011-11-10 Nippon Electric Glass Co Ltd ＳｎＯ−Ｐ２Ｏ５系ガラス、封着材料及び封着ペースト
WO2012043787A1 (fr) * 2010-10-01 2012-04-05 日本電気硝子株式会社 Boîtier d'élément électrique
JP2012113968A (ja) * 2010-11-25 2012-06-14 Nippon Electric Glass Co Ltd 電気素子パッケージ
WO2017061403A1 (fr) * 2015-10-07 2017-04-13 日本化学工業株式会社 Matériau à dilatation thermique négative et matériau composite le comprenant
KR20180059784A (ko) * 2015-10-07 2018-06-05 니폰 가가쿠 고교 가부시키가이샤 인산텅스텐산지르코늄의 제조 방법
KR102611412B1 (ko) 2015-10-07 2023-12-07 니폰 가가쿠 고교 가부시키가이샤 인산텅스텐산지르코늄의 제조 방법
WO2017061402A1 (fr) * 2015-10-07 2017-04-13 日本化学工業株式会社 Procédé de production de phosphate de tungstène et de zirconium
JP6190023B1 (ja) * 2015-10-07 2017-08-30 日本化学工業株式会社 リン酸タングステン酸ジルコニウムの製造方法
JP2018002578A (ja) * 2015-10-07 2018-01-11 日本化学工業株式会社 リン酸タングステン酸ジルコニウムの製造方法
JP2018002577A (ja) * 2015-10-07 2018-01-11 日本化学工業株式会社 負熱膨張材及びそれを含む複合材料
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