WO2016017732A1 - Composition de verre a base de bismuth, matiere pulverulente et pâte de matiere pulverulente - Google Patents

Composition de verre a base de bismuth, matiere pulverulente et pâte de matiere pulverulente Download PDF

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Publication number
WO2016017732A1
WO2016017732A1 PCT/JP2015/071601 JP2015071601W WO2016017732A1 WO 2016017732 A1 WO2016017732 A1 WO 2016017732A1 JP 2015071601 W JP2015071601 W JP 2015071601W WO 2016017732 A1 WO2016017732 A1 WO 2016017732A1
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Prior art keywords
powder material
mass
content
glass composition
powder
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Application number
PCT/JP2015/071601
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English (en)
Japanese (ja)
Inventor
久美子 姫井
Original Assignee
日本電気硝子株式会社
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Publication of WO2016017732A1 publication Critical patent/WO2016017732A1/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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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

Definitions

  • the present invention relates to a bismuth-based glass composition, a powder material, and a powder material paste.
  • the present invention relates to a bismuth-based glass composition, a powder material, and a powder material paste suitable for forming an insulating protective layer on a varistor element body and an electronic circuit.
  • the insulating protective layer is formed to protect and insulate electrodes, resistors, etc. formed on a soda lime glass substrate, an alumina substrate or the like. It is also formed to protect and insulate the varistor element body.
  • a powder material paste has been used to form an insulating protective layer. This powder material paste is generally a mixture of glass powder and vehicle, and ceramic powder may be added as necessary.
  • the insulating protective layer is formed by applying a powder material paste on an electrode or the like and then baking it.
  • the firing temperature is limited to 800 ° C. or less in order to prevent a situation where the properties of the electrode and the like deteriorate due to the reaction between the electrode and the powder material.
  • the powder material (powder material paste) is required to be able to be fired at a temperature of 800 ° C. or lower.
  • the powder material is required not to cause warping of the substrate or the varistor element body after firing and not to be easily peeled off from the substrate or varistor element body.
  • Patent Document 1 PbO—B 2 O 3 —SiO 2 -based glass has been used as a powder material that satisfies the above required characteristics (see Patent Document 1).
  • Patent Documents 2 to 4 describe Bi 2 O 3 —B 2 O 3 —ZnO-based glasses.
  • the electronic circuit on which the insulating protective layer is formed may be subjected to a plating treatment in order to impart characteristics such as corrosion resistance, optical characteristics, mechanical characteristics, and electrical characteristics.
  • the insulating protective layer is immersed in the plating solution.
  • the plating solution is usually an acidic solution. For this reason, when plating is performed, the insulating protective layer is required to have acid resistance. That is, acid resistance is required for the powder material.
  • the Bi 2 O 3 —B 2 O 3 —ZnO-based glasses described in Patent Documents 2 to 4 have low acid resistance, so that they are easily eroded by the plating solution, and it is difficult to maintain characteristics such as insulation. Have.
  • the present invention has been made in view of the above circumstances, and its technical problem is that it can be fired at a temperature of 800 ° C. or less without containing PbO, and warps from the substrate or the like from the substrate or the like. It is to create a bismuth-based glass composition, a powder material, and a powder material paste that do not easily peel and are not easily eroded by a plating solution.
  • the present inventor adopted bismuth-based glass as a glass system and strictly controlled the content ratio of SiO 2 , ZrO 2 , and Al 2 O 3 in the glass composition, thereby The present inventors have found that technical problems can be solved and propose the present invention. That is, the bismuth-based glass composition of the present invention has a glass composition of Bi 2 O 3 40 to 55%, SiO 2 28 to 40%, ZrO 2 over 5 to 9%, Al 2 O 3 2 to 10%, B 2 O 3 0 to 5%, and the mass ratio (SiO 2 + ZrO 2 ) / Al 2 O 3 is smaller than 15.
  • Bismuth glass generally has low acid resistance.
  • the content of SiO 2 is restricted to 25% by mass or more, and the content of ZrO 2 is restricted to more than 5% by mass. By doing so, acid resistance is improved.
  • the content of ZrO 2 is excessive when the content of SiO 2 is large, zircon (ZrSiO 4 ) crystals that reduce acid resistance during molding are precipitated, making it difficult to ensure desired acid resistance. There is. Further, the glass may be phase-divided during molding, and it may be difficult to ensure desired acid resistance.
  • the content of Al 2 O 3 in the glass composition is 2% by mass or more and the mass ratio (SiO 2 + ZrO 2 ) / Al 2 O 3 is regulated to less than 15.
  • the precipitation of zircon crystals and the phase separation of glass during molding are suppressed.
  • the content of MgO is 5% by mass or less
  • the content of CaO is 5% by mass or less
  • the content of SrO is 5% by mass or less
  • the content of ZnO is 5% by mass or less. It is preferable that
  • the bismuth-based glass composition of the present invention does not substantially contain PbO.
  • substantially free of PbO means that PbO is allowed to be mixed in at an impurity level, but avoids aggressive introduction. Specifically, the content of PbO in the glass composition Is less than 1000 ppm.
  • the powder material of the present invention preferably has a softening point of 800 ° C. or lower.
  • the “softening point” refers to the temperature at the fourth inflection point measured with a macro-type differential thermal analyzer (DTA).
  • the powder material paste of the present invention is a powder material paste containing a powder material and a vehicle, wherein the powder material is the powder material described above.
  • Bi 2 O 3 is a component that lowers the softening point, but is a component that lowers acid resistance.
  • the content of Bi 2 O 3 is 40 to 55%, preferably 41 to 54%, 42 to 53%, particularly 43 to 52%.
  • the softening point is unduly raised and it becomes difficult to fire at a temperature of 800 ° C. or lower.
  • the content of Bi 2 O 3 increases, the acid resistance tends to decrease, and the insulating protective layer is easily eroded by the plating solution, and as a result, it becomes difficult to insulate and protect the electrodes of the electronic circuit.
  • the raw material cost is likely to increase.
  • SiO 2 is a component that forms a glass skeleton and a component that increases acid resistance.
  • the content of SiO 2 is 28 to 40%, preferably 29 to 38%, in particular 30 to 36%.
  • the acid resistance is likely to be lowered, and the insulating protective layer is easily eroded by the plating solution. As a result, it is difficult to insulate and protect the electrodes of the electronic circuit.
  • the content of SiO 2 is increased, the softening point is unreasonably raised and it becomes difficult to fire at a temperature of 800 ° C. or lower.
  • Al 2 O 3 is a component that enhances acid resistance and is a component that stabilizes glass, particularly a component that suppresses the precipitation of zircon crystals.
  • the content of Al 2 O 3 is 2 to 10%, preferably 2.5 to 9%, particularly 3 to 8%.
  • the content of Al 2 O 3 is reduced, the glass becomes unstable and zircon crystals are likely to precipitate during molding.
  • the content of Al 2 O 3 is increased, the softening point is unreasonably raised and it becomes difficult to fire at a temperature of 800 ° C. or lower.
  • the mass ratio (SiO 2 + ZrO 2 ) / Al 2 O 3 is 15 or less, preferably 14 or less, 13 or less, 12 or less, 11 or less, 10 or less, particularly 9 or less.
  • the mass ratio (SiO 2 + ZrO 2 ) / Al 2 O 3 is excessive, zircon crystals are likely to precipitate during molding, and the glass is likely to be phase-separated.
  • CaO is a component that lowers the softening point and is a component that stabilizes the glass.
  • the content of CaO is preferably 0 to 5%, 0 to 4%, particularly 0 to 3%.
  • the content of CaO is increased, the acid resistance is likely to be lowered, and the insulating protective layer is easily eroded by the plating solution. As a result, it is difficult to insulate and protect the electrodes of the electronic circuit.
  • ZnO is a component that lowers the softening point but is a component that reduces acid resistance.
  • the content of ZnO is 0 to 5%, preferably 0 to 4%, particularly 0 to 3%.
  • the content of ZnO is increased, the acid resistance is significantly reduced, and the insulating protective layer is easily eroded by the plating solution, and as a result, it becomes difficult to insulate and protect the electrodes of the electronic circuit.
  • Cs 2 O, Rb 2 O, or the like may be introduced up to 5%, particularly up to 1%, alone or in total.
  • Y 2 O 3 , La 2 O 3 , Ta 2 O 5 , SnO 2 , TiO 2 , Nb 2 O 5 , P 2 O 5 , CuO , CeO 2 , V 2 O 5, etc. may be introduced in a total amount or independently up to 10%, particularly up to 1%.
  • PbO is a component that lowers the softening point, but it is also an environmentally hazardous substance, so it is preferable to avoid substantial introduction.
  • the powder material of the present invention is a powder material containing a glass powder made of the bismuth-based glass composition and a ceramic powder, wherein the glass powder content is 50 to 100% by mass, and the ceramic powder content is 0. It is characterized by ⁇ 50 mass%.
  • the glass powder can be produced, for example, by forming molten glass into a film and then crushing and classifying the obtained glass film.
  • the average particle diameter D 50 of the glass powder is preferably 3.0 ⁇ m or less, and the maximum particle diameter D max is preferably 20 ⁇ m or less.
  • the “average particle diameter D 50 ” refers to a value measured with a laser diffractometer, and in an accumulated particle size distribution curve based on volume when measured by a laser diffraction method, the accumulated amount is accumulated from the smaller particle.
  • the particle diameter is 50%.
  • Maximum particle size D max refers to a value measured by a laser diffractometer, and in the volume-based cumulative particle size distribution curve measured by the laser diffraction method, the accumulated amount is accumulated from the smaller particle.
  • the particle size is 99%.
  • the content of the ceramic powder is preferably 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, and particularly less than 1% by mass. If the ceramic powder is too much, the proportion of the glass powder becomes relatively small, and it becomes difficult to form a dense insulating protective layer, so that the insulating protective layer is easily eroded by the plating solution. It becomes difficult to insulate and protect the electrodes. If ceramic powder is added, the thermal expansion coefficient, mechanical strength, and acid resistance of the powder material can be adjusted.
  • the ceramic powder can be used as the ceramic powder.
  • alumina, zirconia, mullite, silica, cordierite, titania, tin oxide, and the like can be added.
  • the softening point is preferably 800 ° C. or lower, 790 ° C. or lower, particularly 680 to 780 ° C. If the softening point is too high, in order to obtain a dense insulating protective layer, the firing temperature must be increased, in which case the electrode and the powder material react and the characteristics of the electrode and the like are likely to deteriorate. .
  • the thermal expansion coefficient is preferably 45 to 65 ⁇ 10 ⁇ 7 / ° C., particularly 50 to 60 ⁇ 10 ⁇ 7 / ° C. If it does in this way, it will become easy to prevent the curvature of a board
  • the “thermal expansion coefficient” is a value measured in a temperature range of 30 to 300 ° C. by a thermomechanical analyzer (TMA).
  • the powder material paste of the present invention is a powder material paste containing a powder material and a vehicle, wherein the powder material is the powder material described above.
  • the vehicle is a material for dispersing glass powder into a paste, and is usually composed of a thermoplastic resin, a plasticizer, a solvent, and the like.
  • the powder material paste can be prepared by preparing a powder material and a vehicle, and mixing and kneading them at a predetermined ratio.
  • Thermoplastic resin is a component that increases the film strength after drying and also a component that imparts flexibility.
  • the content of the thermoplastic resin in the powder material paste is preferably 0.1 to 20% by mass.
  • the thermoplastic resin polybutyl methacrylate, polyvinyl butyral, polymethyl methacrylate, polyethyl methacrylate, ethyl cellulose and the like are preferable, and it is preferable to use one or more of these.
  • Solvent is a component for dissolving the thermoplastic resin.
  • the content of the solvent in the powder material paste is preferably 10 to 30% by mass.
  • the solvent terpineol, diethylene glycol monobutyl ether acetate, 2,2,4-trimethyl-1,3-pentadiol monoisobutyrate and the like are preferable, and it is preferable to use one or more of these.
  • a powder material paste is applied on an electronic circuit on which electrodes, resistors, etc. are formed by a screen printing method, a batch coating method, After forming a coating layer having a predetermined thickness, it is dried to obtain a dry film. Thereafter, the predetermined insulating protective layer (baked film) can be formed by baking the dried film at a temperature of 700 to 800 ° C. for 5 to 20 minutes. If the firing temperature is too low or the firing time (holding time) is too short, the dried film will not sinter sufficiently, making it difficult to form a dense fired film. On the other hand, if the firing temperature is too high or the holding time is too long, the electrode and the powder material react with each other, and the characteristics of the electrode and the like easily deteriorate.
  • the method for forming the insulating protective layer the method using a powder material paste has been described as an example, but other methods may be adopted.
  • a method such as a green sheet method, a photosensitive paste method, or a photosensitive green sheet method may be adopted.
  • the bismuth-based glass composition, powder material and powder material paste of the present invention are preferably used for forming an insulating protective layer, and particularly preferably used for forming an insulating protective layer on a varistor element body.
  • electrodes, resistors, and the like are formed on the varistor element body made of ZnO oxide, and an insulating protective layer is formed thereon. Thereafter, a plating treatment with a plating solution is performed.
  • the bismuth-based glass composition, the powder material, and the powder material paste of the present invention can be fired at a temperature of 800 ° C. or less without containing PbO, and warp of the varistor element body and the varistor element body. It is particularly suitable for this application because it does not easily peel off from the film and is not easily eroded by the plating solution.
  • Table 1 shows examples (samples Nos. 1 to 4) and comparative examples (samples Nos. 5 and 6) of the present invention.
  • Each sample was prepared as follows. First, raw materials were prepared and mixed uniformly so as to have the glass composition shown in the table. Next, it was put in a platinum crucible and melted at 1350 to 1450 ° C. for 2 hours, and then formed into a film.
  • the above glass film was pulverized with a ball mill and then classified into an air stream to obtain a glass powder having an average particle size D 50 of 3.0 ⁇ m or less and a maximum particle size D max of 20 ⁇ m or less.
  • the softening point and thermal expansion coefficient were evaluated using the obtained glass powder.
  • Softening point is the temperature of the fourth inflection point measured with a macro-type differential thermal analyzer (DTA).
  • DTA differential thermal analyzer
  • the coefficient of thermal expansion was determined by pressing each glass powder and firing it at (softening point +10) ° C., then processing to a diameter of 5 mm and a length of 20 mm to obtain a measurement sample, and then a thermomechanical analyzer (TMA) ) Measured in a temperature range of 30 to 300 ° C.
  • TMA thermomechanical analyzer
  • the glass powder and the vehicle were mixed and kneaded in a three-roll mill to obtain a powder material paste.
  • the coated film is dried, and the temperature is (softening point + 10) ° C. in an electric furnace. Bake for 10 minutes at temperature. Acid resistance was evaluated using the obtained substrate with a fired film. Specifically, the substrate with the fired film was immersed in 5% by mass sulfuric acid at 40 ° C. for 5 hours, washed with water, dried, then measured for mass decrease, and evaluated the rate of mass decrease before and after immersion. In addition, it means that acid resistance is so low that the ratio of mass reduction is large.
  • sample No. Nos. 1 to 4 could be fired at a temperature of 800 ° C. or lower due to their low softening point, and further had good moldability and acid resistance.
  • Sample No. No. 5 had a low softening point, but a slight phase separation tendency was observed. As a result, moldability and acid resistance were low.
  • Sample No. No. 6 had poor moldability and acid resistance.
  • the bismuth-based glass composition, powder material, and powder material paste of the present invention are suitable for forming an insulating protective layer on a varistor element body and an electronic circuit. It can also be applied to uses such as wearing materials.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

La présente invention vise à fournir une composition de verre à base de bismuth qui est apte à être cuite à une température égale ou inférieure à 800 °C et n'est pas susceptible à une déformation du substrat ou analogue et à une séparation à partir d'un substrat ou analogue, tout en n'étant pas susceptible à l'érosion par une solution de placage même dans les cas où la composition de verre à base de bismuth ne contient pas de l'oxyde de plomb; une matière pulvérulente; et une pâte de matière pulvérulente. Un composition de verre à base de bismuth selon la présente invention est caractérisée en ce qu'elle contient en tant que composition de verre, en pourcentage massique, 40 à 55 % de Bi2O3, 28 à 40 %SiO2, entre 5% et 9% de ZrO2, 2-10% de Al2O3 et 0-5% de B2O3, tout en ayant un rapport massique (SiO2 + ZrO2)/Al2O3 inférieur à 15.
PCT/JP2015/071601 2014-07-31 2015-07-30 Composition de verre a base de bismuth, matiere pulverulente et pâte de matiere pulverulente WO2016017732A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014155896A JP2016033094A (ja) 2014-07-31 2014-07-31 ビスマス系ガラス組成物、粉末材料及び粉末材料ペースト
JP2014-155896 2014-07-31

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WO2016017732A1 true WO2016017732A1 (fr) 2016-02-04

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Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
JP6418487B2 (ja) * 2014-07-31 2018-11-07 日本電気硝子株式会社 ビスマス系ガラス組成物、粉末材料及び粉末材料ペースト

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60251150A (ja) * 1984-05-25 1985-12-11 Okuno Seiyaku Kogyo Kk ガラスエナメル用粉末組成物
JPS6114151A (ja) * 1984-06-28 1986-01-22 オーエンス‐イリノイ・インコーポレーテツド 化学抵抗性の無鉛ガラスフリツト組成物
JPH05262536A (ja) * 1991-06-14 1993-10-12 Cookson Group Plc ガラス組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60251150A (ja) * 1984-05-25 1985-12-11 Okuno Seiyaku Kogyo Kk ガラスエナメル用粉末組成物
JPS6114151A (ja) * 1984-06-28 1986-01-22 オーエンス‐イリノイ・インコーポレーテツド 化学抵抗性の無鉛ガラスフリツト組成物
JPH05262536A (ja) * 1991-06-14 1993-10-12 Cookson Group Plc ガラス組成物

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