WO2008007596A1 - VERRE SANS PLOMB à bas point de fusion - Google Patents

VERRE SANS PLOMB à bas point de fusion Download PDF

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Publication number
WO2008007596A1
WO2008007596A1 PCT/JP2007/063418 JP2007063418W WO2008007596A1 WO 2008007596 A1 WO2008007596 A1 WO 2008007596A1 JP 2007063418 W JP2007063418 W JP 2007063418W WO 2008007596 A1 WO2008007596 A1 WO 2008007596A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
lead
free low
melting point
range
Prior art date
Application number
PCT/JP2007/063418
Other languages
English (en)
Japanese (ja)
Inventor
Nobuyuki Nakai
Taishin Shimooka
Original Assignee
Central Glass Company, Limited
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 Central Glass Company, Limited filed Critical Central Glass Company, Limited
Publication of WO2008007596A1 publication Critical patent/WO2008007596A1/fr

Links

Classifications

    • 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
    • H01J11/38—Dielectric or insulating layers
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • 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
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • 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
    • H01J11/10—AC-PDPs with at least one main electrode being out of contact with the plasma

Definitions

  • the present invention is for an electronic material substrate typified by a plasma display panel, a liquid crystal display panel, an electo-luminescence panel, a fluorescent display panel, an electo-chromic display panel, a light-emitting diode display panel, a gas discharge display panel, etc.
  • the present invention relates to a low melting glass used as an insulating coating material and a sealing material.
  • PDPs plasma display panels
  • An electrode for discharging plasma is formed on the front glass plate of the plasma display panel, and thin linear silver is often used as the electrode.
  • a highly transparent insulating material is arranged around the electrode. This insulating material is preferably excellent in plasma durability and transparent. For this reason, dielectric glass is often used as an insulating material.
  • dielectric glass is often used as an insulating material.
  • this dielectric glass is naturally required to have a lower melting point than that of the glass plate serving as the substrate in the process, a low-melting glass is used.
  • the dielectric glass and the silver of the bus electrode react with each other at a low temperature firing of 450 to 600 ° C, and the dielectric glass is colored yellow ( (Yellowing) occurred, and there was a big problem that high transmittance could not be obtained.
  • Patent Document 3 limited content of SiO, B 2 O, ZnO, Bi 2 O, BaO, Al 2 O
  • a material for plasma display (for example, see Patent Document 4) is disclosed.
  • Patent Document 1 Japanese Patent Laid-Open No. 2001-52621
  • Patent Document 2 Japanese Patent Laid-Open No. 2001-80934
  • Patent Document 3 Japanese Patent Laid-Open No. 2001-48577
  • Patent Document 4 Japanese Patent Laid-Open No. 2003-226549
  • a conventional dielectric material (insulating material) has a problem in that the glass layer and the silver electrode react with each other to cause the dielectric layer to be colored yellow (yellowing), resulting in a decrease in visible light transmittance. It is difficult to respond to this yellowing phenomenon, but it has not yet been achieved to the level desired by the market.
  • lead-based glass has been employed for low-melting glass, for example, low-melting glass for substrate coating.
  • the lead component is an important component for lowering the melting point of glass, it has a tendency to avoid its adoption in recent years because it has a great negative impact on the human body and the environment.
  • Lead-free electronic materials such as PDP are being studied. Being sung.
  • the 01-48577 gazette has the basic problem of containing lead, which is a significant improvement against yellowing. Furthermore, Japanese Patent Application Laid-Open No. 2003-226549 does not contain lead, and a considerable improvement against yellowing is recognized. However, as with lead, it contains bismuth that tends to be avoided from an environmental point of view. RU
  • the lead-free low-melting glass can be used as an insulating coating material and a sealing material for an electronic material substrate or a PDP panel.
  • Insulation for electronic material substrates typified by plasma display panels, liquid crystal display panels, electoric luminescence panels, fluorescent display panels, electoric chromic display panels, light emitting diode display panels, gas discharge display panels, etc.
  • a low melting point glass used as a coating material and a sealing material can reduce the phenomenon that the dielectric layer is colored yellow (yellowing) by the reaction between the glass and the silver electrode. .
  • SiO is a glass-forming component and coexists with another glass-forming component, B 2 O.
  • B 2 O is a glass forming component similar to SiO, facilitating glass melting, and thermal expansion of glass
  • the flowability of the glass becomes insufficient and the sinterability is impaired.
  • it exceeds 55% the stability of the glass is lowered. More preferably, it is 38 to 52% of range.
  • ZnO lowers the soft spot of the glass and adjusts the thermal expansion coefficient to an appropriate range, and is preferably contained in the glass in a range of 5 to 12%. If it is less than 5%, the above-mentioned action cannot be exhibited. On the other hand, if it exceeds 12%, the glass becomes unstable and devitrification tends to occur. More preferably, it is in the range of 6 to 11%.
  • R 2 O Li 0, Na 0, K 2 O
  • the coefficient is adjusted to an appropriate range, and it is preferably contained in the range of 10 to 18%. If it is less than 10%, the above-mentioned action cannot be exerted. On the other hand, if it exceeds 18%, the thermal expansion coefficient is excessively increased. More preferably, it is 11 to 17% of range.
  • BaO has an effect of imparting moderate fluidity to glass and increasing transparency, and has a content of 0.1 to 3%. It is contained in a box. If it exceeds 3%, the above effect cannot be exhibited. More preferably, it is in the range of 1 to 2%.
  • ZrO has the effect of increasing the water resistance of the glass, and is contained in the range of 0.1 to 7%.
  • it is in the range of 1% to 6%.
  • CuO has the effect of mitigating the coloration of silver colloid (yellowing) due to the reaction between the silver electrode used as the bus electrode wire and the dielectric layer, and the diffusion of silver into the dielectric layer. It is preferably contained in the range of ⁇ 2%. If the content is less than 1%, the above-mentioned effect cannot be exhibited. If the content exceeds 2%, the glass is colored and the transparency is lowered. More preferably, it is in the range of 0.1 to 1%.
  • MnO reacts with a silver electrode used as a bus electrode wire and a dielectric layer, and in the dielectric layer
  • It has the effect of mitigating silver diffusion and color development (yellowing) of silver colloid, and it is preferably contained in the range of 0 to 2%. If it exceeds 2%, the glass is colored and the transparency is lowered. More preferably, it is in the range of 0 to 1%.
  • RO MgO + CaO + SrO
  • substantially not containing PbO By substantially not containing PbO, it is possible to eliminate the influence on the human body and the environment.
  • substantially free of PbO means that PbO may be contained up to an amount enough to be mixed as an impurity in the glass raw material. For example, if it is in the range of 0.3 wt% or less in the low-melting glass, the above-mentioned adverse effects, that is, the influence on the human body and the environment, the influence on the insulation characteristics, etc., are hardly affected by PbO. It becomes.
  • the thermal expansion coefficient of 65 at 30 ° C ⁇ 300 ° C X 10 " V ° C ⁇ 95 X 10- 7 Z ° C, further ⁇ I ⁇ is 500 ° It may be C or more and 630 ° C or less. If the tension coefficient is out of this range, problems such as film peeling and substrate warping may occur during thick film formation. Preferably, in the range of 75 X 10- 7 Z ° C ⁇ 85 X 10- 7 Z ° C. In addition, if the soft spot exceeds 630 ° C, problems such as soft deformation of the substrate may occur.
  • the temperature is preferably 500 ° C or higher and 590 ° C or lower.
  • the lead-free low melting point glass of the present invention can be used as an insulating coating material and a sealing material for a substrate for electronic materials. Thereby, it can be set as the board
  • the lead-free low-melting glass of the present invention can be used as an insulating coating material and a sealing material for PDP panels. As a result, a PDP panel in which yellowing is suppressed can be obtained.
  • the present invention is a disclosure of a low-melting-point glass corresponding to a yellowing phenomenon caused by a reaction with silver, and the object is not limited to a silver electrode.
  • the lead-free low melting point glass of the present invention can be used for, for example, both the front plate and the back plate of PDP glass.
  • a back plate When used as a back plate, it is often used as a sealing material or covering material, and is used in powder form.
  • This powdered glass is mixed with a low-expansion ceramics filler such as muraite or alumina, heat-resistant pigments, etc., if necessary, at a ratio of 0.6 ⁇ glass Z (glass + filler) weight ratio ⁇ or more. Then, it is generally kneaded with organic oil to form a paste.
  • the glass substrate is a transparent glass substrate, particularly soda-lime-silica glass, or similar glass (high strain point glass), or an alumino-lime borosilicate-based glass with little (or little) alkalinity. Glass is frequently used.
  • Acid zinc white as ZnO source
  • lithium carbonate as Li O source
  • sodium carbonate as Na O source
  • a part of the glass was poured into a mold and made into a block shape for use in measuring thermal properties (thermal expansion coefficient, softening point).
  • the remaining glass was flaked with a rapid cooling twin roll molding machine and sized with a pulverizer into a powder with an average particle size of 1 to 3 ⁇ m and a maximum particle size of less than 10 ⁇ m.
  • a paste oil composed of ⁇ -terpineol and butyl carbitol acetate is mixed with ethylcellulose as a binder and the above glass powder, and the viscosity is 300 ⁇ 50 parts.
  • a paste of the same size was prepared.
  • the thermal expansion coefficient was determined from the amount of elongation at 30 to 300 ° C when the temperature was raised at 5 ° C / min using a thermal dilatometer.
  • Tables 1 and 2 show the low melting point glass composition and various test results.
  • Comparative Examples 1 to 4 in Table 2 outside the composition range of the present invention show significant yellowing, or do not show favorable physical properties, and are suitable for coating substrates such as PDP Cannot be applied as low melting point glass.

Abstract

L'invention concerne un verre à bas point de fusion sans plomb SiO2-B2O3-ZnO-R2O-BaO-ZrO2-CuO transparent et isolant. Le verre à bas point de fusion sans plomb contient un SiO2 de 25-40 % en poids, un B2O3 de 35-55 % en poids, un ZnO de 5-12 % en poids, un R2O(Li2O+Na2O+K2O) de 10-18 % en poids, un BaO de 0,1-3 % en poids, un ZrO2 de 0,1-7 % en poids, et un CuO de 0,1-2 % en poids. Le jaunissement dû à la réaction avec l'argent peut être supprimé et une transmissivité élevée de la lumière visible peut être obtenue en utilisant le verre à bas point de fusion sans plomb.
PCT/JP2007/063418 2006-07-14 2007-07-05 VERRE SANS PLOMB à bas point de fusion WO2008007596A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006194638A JP2008019147A (ja) 2006-07-14 2006-07-14 無鉛低融点ガラス
JP2006-194638 2006-07-14

Publications (1)

Publication Number Publication Date
WO2008007596A1 true WO2008007596A1 (fr) 2008-01-17

Family

ID=38923158

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/063418 WO2008007596A1 (fr) 2006-07-14 2007-07-05 VERRE SANS PLOMB à bas point de fusion

Country Status (2)

Country Link
JP (1) JP2008019147A (fr)
WO (1) WO2008007596A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008099916A1 (fr) * 2007-02-16 2008-08-21 Central Glass Company, Limited Verre sans plomb à point de fusion bas
JP5251376B2 (ja) * 2007-10-05 2013-07-31 旭硝子株式会社 電極被覆用無鉛ガラスおよびプラズマディスプレイ装置
WO2010050590A1 (fr) * 2008-10-30 2010-05-06 旭硝子株式会社 Pâte de verre

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11106234A (ja) * 1997-09-30 1999-04-20 Nippon Electric Glass Co Ltd 釉薬用ガラス組成物
JPH11157867A (ja) * 1997-11-21 1999-06-15 Sec Kk 情報記録ディスク基板用ガラス
WO2003045864A1 (fr) * 2001-11-30 2003-06-05 Asahi Glass Company, Limited Composition de scellement et materiau de scellement
JP2005343730A (ja) * 2004-06-02 2005-12-15 Central Glass Co Ltd 無鉛低融点ガラス
JP2006117440A (ja) * 2004-10-19 2006-05-11 Central Glass Co Ltd 無鉛低融点ガラス
JP2006151763A (ja) * 2004-11-30 2006-06-15 Central Glass Co Ltd 無鉛低融点ガラス
JP2006169047A (ja) * 2004-12-16 2006-06-29 Central Glass Co Ltd 無鉛低融点ガラス

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11106234A (ja) * 1997-09-30 1999-04-20 Nippon Electric Glass Co Ltd 釉薬用ガラス組成物
JPH11157867A (ja) * 1997-11-21 1999-06-15 Sec Kk 情報記録ディスク基板用ガラス
WO2003045864A1 (fr) * 2001-11-30 2003-06-05 Asahi Glass Company, Limited Composition de scellement et materiau de scellement
JP2005343730A (ja) * 2004-06-02 2005-12-15 Central Glass Co Ltd 無鉛低融点ガラス
JP2006117440A (ja) * 2004-10-19 2006-05-11 Central Glass Co Ltd 無鉛低融点ガラス
JP2006151763A (ja) * 2004-11-30 2006-06-15 Central Glass Co Ltd 無鉛低融点ガラス
JP2006169047A (ja) * 2004-12-16 2006-06-29 Central Glass Co Ltd 無鉛低融点ガラス

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