WO2015019935A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2015019935A1 WO2015019935A1 PCT/JP2014/070200 JP2014070200W WO2015019935A1 WO 2015019935 A1 WO2015019935 A1 WO 2015019935A1 JP 2014070200 W JP2014070200 W JP 2014070200W WO 2015019935 A1 WO2015019935 A1 WO 2015019935A1
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- bismuth
- glass composition
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Classifications
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- 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
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- 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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
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 for forming an overcoat layer on an electronic circuit or the like.
- the overcoat layer is formed to protect and insulate electrodes, resistors, etc. formed on a soda lime glass substrate, an alumina substrate, or the like.
- a powder material paste has been used to form an overcoat layer.
- This powder material paste is generally a mixture of glass powder and vehicle, and ceramic powder may be added as necessary.
- the overcoat layer is formed by applying a powder material paste to an electrode or the like and then baking it.
- the firing temperature is limited to 600 ° C. or less in order to prevent a situation in which the characteristics 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 600 ° C. or lower.
- the powder material is required not to be warped in the substrate and not easily peeled off from the substrate after firing.
- 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 overcoat layer is formed may be subjected to a plating treatment in order to impart characteristics such as anticorrosion, optical characteristics, mechanical characteristics, and electrical characteristics.
- the overcoat layer is immersed in a plating solution.
- the plating solution is usually an acidic solution. For this reason, when a plating process is performed, the overcoat 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 baked at a temperature of 600 ° C. or less without containing PbO, and warpage of the substrate and peeling from the substrate can be prevented. It is to create a bismuth-based glass composition, a powder material, and a powder material paste that are unlikely to occur and that are not easily eroded by a plating solution.
- the inventor adopts bismuth-based glass as a glass system and can regulate the above technical problems by regulating the contents of SiO 2 and ZrO 2 in the glass composition. It is discovered and proposed as the present invention. That is, the bismuth-based glass composition of the present invention has, as a glass composition, Bi 2 O 3 55 to 80%, SiO 2 15 to 35%, ZrO 2 0 to less than 3%, B 2 O 3 0 to 3% by mass. 5%, ZnO 0 to less than 8%, mass ratio SiO 2 / ZrO 2 is larger than 6.7.
- Bismuth glass generally tends to have low acid resistance, but in the present invention, acid resistance is enhanced by regulating the SiO 2 content to 15% by mass or more. Furthermore, the present inventor found that ZrO 2 itself is a component that enhances acid resistance. However, when the content of ZrO 2 is excessive when the content of SiO 2 is large, zircon ( It has been found that ZrSiO 4 ) crystals are precipitated, making it difficult to ensure desired acid resistance. Furthermore, when the bismuth-based glass has a high SiO 2 content, scum or the like is likely to be generated at the time of melting. I found it.
- the content of ZrO 2 is less than 3% by mass and the mass ratio SiO 2 / ZrO 2 is restricted to more than 6.7, so that the precipitation of zircon crystals is suppressed, and the acid resistance and solubility are reduced. Are compatible.
- the bismuth-based glass composition of the present invention preferably further contains 1 to 9% by mass of BaO.
- the bismuth-based glass composition of the present invention preferably further contains 0.5 to 5% by mass of Al 2 O 3 .
- 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 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 powder material of the present invention preferably has a softening point of 600 ° C or lower.
- the powder material of the present invention is preferably used for forming an overcoat layer.
- 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 powder material paste of the present invention preferably contains substantially no phthalic acid compound.
- substantially does not contain a phthalic acid compound refers to a case where the content of the phthalic acid compound in the powder material paste is less than 1000 ppm.
- the powder material paste of the present invention preferably contains one or more of adipic acid compounds, sebacic acid compounds, and citric acid compounds.
- the bismuth-based glass composition of the present invention has, as a glass composition, Bi 2 O 3 55 to 80%, SiO 2 15 to 35%, ZrO 2 0 to less than 3%, B 2 O 3 0 to 5% by mass. ZnO 0 to less than 8%, and the mass ratio SiO 2 / ZrO 2 is greater than 6.7.
- the reason why the content range of each component is regulated as described above will be described below.
- % display means the mass%.
- 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 55 to 80%, preferably 57 to 77%, 60 to 75%, particularly 65 to 70%.
- the softening point is unreasonably raised and it becomes difficult to fire at a temperature of 600 ° C. or lower.
- the content of Bi 2 O 3 is increased, the acid resistance is likely to be lowered, and the overcoat layer is easily eroded by the plating solution, and as a result, it is difficult to ensure the protection and insulation of the electrodes of the electronic circuit. .
- the material cost increases.
- SiO 2 is a component that forms a glass skeleton and a component that increases acid resistance.
- the content of SiO 2 is 15 to 35%, preferably 17 to 33%, particularly preferably 20 to 30%.
- the acid resistance is likely to be lowered, and the overcoat layer is easily eroded by the plating solution, and as a result, it is difficult to ensure the protection and insulation of 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 600 ° C. or lower.
- ZrO 2 is a component that increases acid resistance.
- the content of SiO 2 is large as in the present invention, if the content of ZrO 2 is excessive, zircon crystals are likely to precipitate, and acid resistance and solubility are likely to be reduced. Therefore, the content of ZrO 2 is less than 3%, preferably less than 2%, particularly preferably less than 1%.
- B 2 O 3 is a component that forms a glass skeleton and further expands the vitrification range. However, when its content increases, the acid resistance may be significantly reduced. Therefore, the content of B 2 O 3 is 0 to 5%, preferably 0 to 4% or 0 to 3.5%, particularly preferably 0.5 to 3%.
- ZnO is a component that lowers the softening point but is a component that reduces acid resistance.
- the content of ZnO is 0 to less than 8%, preferably 0 to 5% or 0 to 4%, particularly preferably 0 to 3%.
- the content of ZnO is increased, the acid resistance is significantly reduced, and the overcoat layer is easily eroded by the plating solution, and as a result, it is difficult to ensure protection and insulation of the electrodes of the electronic circuit.
- the mass ratio SiO 2 / ZrO 2 is greater than 6.7, preferably 7 or more, 12 or more or 18 or more, particularly preferably 25 or more. When the mass ratio SiO 2 / ZrO 2 is too small, zircon crystals are likely to precipitate, and acid resistance and solubility are likely to be reduced.
- BaO is a component that lowers the softening point and is a component that stabilizes the glass, particularly a component that suppresses phase separation.
- the content of BaO is preferably 0 to 9%, 1 to 9% or 2 to 8%, particularly preferably 3 to 7%.
- the content of BaO decreases, the glass tends to become unstable.
- the content of BaO is increased, the acid resistance tends to be lowered, and the overcoat layer is easily eroded by the plating solution. As a result, it is difficult to ensure protection and insulation of the electrodes of the electronic circuit.
- Al 2 O 3 is a component that increases acid resistance, and is a component that stabilizes glass, particularly a component that suppresses phase separation.
- the content of Al 2 O 3 is preferably 0 to 5%, 0.5 to 5% or 0.5 to 3%, particularly preferably 0.5 to 2.5%.
- the content of Al 2 O 3 decreases, the glass tends to become unstable.
- 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 600 ° C. or lower.
- MgO is a component that lowers the softening point and is a component that stabilizes the glass.
- the content of MgO is preferably 0 to 5% or 0 to 4%, particularly preferably 0 to 3%.
- the acid resistance tends to decrease, and the overcoat layer is easily eroded by the plating solution. As a result, it becomes difficult to ensure protection and insulation of the electrodes of the electronic circuit.
- 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% or 0 to 4%, particularly preferably 0 to 3%.
- the acid resistance is likely to be lowered, and the overcoat layer is easily eroded by the plating solution, and as a result, it is difficult to ensure protection and insulation of the electrodes of the electronic circuit.
- SrO is a component that lowers the softening point and is a component that stabilizes the glass.
- the content of SrO is preferably 0 to 5% or 0 to 4%, particularly preferably 0 to 3%.
- 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, it is also an environmental load 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 soot ceramic powder is preferably 40% by volume or less, 30% by volume or less, 20% by volume or less, 10% by volume or less, or 5% by volume or less, particularly preferably less than 1% by volume.
- the content of soot ceramic powder is preferably 40% by volume or less, 30% by volume or less, 20% by volume or less, 10% by volume or less, or 5% by volume or less, particularly preferably less than 1% by volume.
- the ceramic powder can be used as the ceramic powder.
- alumina, zircon, zirconia, mullite, silica, cordierite, titania, tin oxide, and the like can be added.
- the softening point is preferably 600 ° C. or less, particularly preferably 595 ° C. or less. If the softening point is too high, in order to obtain a dense overcoat layer, the firing temperature must be increased. In this case, the electrode and the powder material react with each other and the characteristics of the electrode and the like are likely to deteriorate. .
- the “softening point” refers to the value of the fourth inflection point measured with a macro-type differential thermal analyzer (DTA).
- the thermal expansion coefficient is preferably 65 to 85 ⁇ 10 ⁇ 7 / ° C., particularly preferably 72 to 80 ⁇ 10 ⁇ 7 / ° C. If it does in this way, after forming an overcoat layer on a soda-lime glass substrate or an alumina substrate, it will become easy to prevent curvature of a substrate and exfoliation of an overcoat layer.
- 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.
- the plasticizer is a component that controls the drying speed and imparts flexibility to the dry film.
- the content of the plasticizer in the powder material paste is preferably 0 to 10% by mass, particularly preferably 0.1 to 10% by mass. It is preferable that the plasticizer is substantially free of phthalic acid compounds such as butylbenzyl phthalate, dioctyl phthalate, diisooctyl phthalate, dicapryl phthalate, and dibutyl phthalate. In this way, the environmental load can be reduced.
- adipic acid compounds such as diisobutyl adipate and dibutoxyethyl adipate
- sebacic acid compounds such as dibutyl sebacate and di-2-ethylhexyl sebacate
- citric acid compounds such as tributyl acetylene citrate Etc.
- 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.
- the powder material paste is applied 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 overcoat layer (baked film) can be formed by baking the dried film at a temperature of 500 to 600 ° 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.
- a 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 overcoat layer of a chip resistor.
- a chip resistor an electrode, a resistor, and the like are formed on an alumina substrate, and an overcoat layer is formed thereon. Then, after the overcoat layer is formed, a plating process using 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 600 ° C. or less without containing PbO, and the substrate is warped or peeled off from the substrate. This is particularly suitable for this application because it hardly occurs and is not easily eroded by the plating solution.
- Tables 1 and 2 show examples of the present invention (sample Nos. 1 to 11) and comparative examples (sample No. 12).
- 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 1250 to 1350 ° C. for 2 hours, and then formed into a film. The solubility was evaluated using the obtained glass film. “ ⁇ ” indicates that no devitrification crystal or phase separation was observed on the surface of the glass film, “ ⁇ ” indicates that the devitrification crystal or phase separation was slightly observed, and noticeable irregularities or phase separation was observed. Things were evaluated as “x”.
- 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.
- the softening point was the value 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. Further, after applying the powder material paste on the alumina substrate by screen printing so that a fired film (overcoat layer) of about 10 ⁇ m is obtained, the coated film is dried and (softening point + 10) ° C. in an electric furnace. Firing was performed for 10 minutes at a temperature to form a fired film. 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 1 hour, washed with water, dried, then measured for mass reduction, and the mass reduction ratio before and after immersion was evaluated. In addition, it means that acid resistance is so low that the ratio of mass reduction is large.
- sample No. Nos. 1 to 9 had low softening points and good solubility and acid resistance.
- Sample No. In No. 10 since the phase separation tendency was slightly recognized, the solubility and acid resistance were lowered accordingly.
- Sample No. 10 and 11 also showed a slight tendency to phase separation, so that the solubility and acid resistance decreased accordingly.
- Sample No. No. 12 had poor solubility.
- the bismuth-based glass composition, the powder material and the powder material paste of the present invention are particularly suitable for the formation of an overcoat layer, particularly for the formation of an overcoat layer of a chip resistor. It can also be applied to uses such as binders for sealing and sealing materials.
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Abstract
Description
Claims (11)
- ガラス組成として、質量%で、Bi2O3 55~80%、SiO2 15~35%、ZrO2 0~3%未満、B2O3 0~5%、ZnO 0~8%未満を含有し、質量比SiO2/ZrO2が6.7より大きいことを特徴とするビスマス系ガラス組成物。
- 更にBaOを1~9質量%含むことを特徴とする請求項1に記載のビスマス系ガラス組成物。
- 更にAl2O3を0.5~5質量%含むことを特徴とする請求項1又は2に記載のビスマス系ガラス組成物。
- MgOの含有量が5質量%以下、CaOの含有量が5質量%以下、SrOの含有量が5質量%以下、且つZnOの含有量が5質量%以下であることを特徴とする請求項1~3の何れかに記載のビスマス系ガラス組成物。
- 実質的にPbOを含まないことを特徴とする請求項1~4の何れかに記載のビスマス系ガラス組成物。
- 請求項1~5の何れかに記載のビスマス系ガラス組成物からなるガラス粉末とセラミック粉末とを含有する粉末材料であって、
ガラス粉末の含有量が50~100質量%、セラミック粉末の含有量が0~50質量%であることを特徴とする粉末材料。 - 軟化点が600℃以下であることを特徴とする請求項6に記載の粉末材料。
- オーバーコート層の形成に用いることを特徴とする請求項6又は7に記載の粉末材料。
- 粉末材料とビークルとを含有する粉末材料ペーストにおいて、
粉末材料が請求項6~8の何れかに記載の粉末材料であることを特徴とする粉末材料ペースト。 - 実質的にフタル酸系化合物を含有しないことを特徴とする請求項9に記載の粉末材料ペースト。
- アジピン酸系化合物、セバシン酸系化合物、クエン酸系化合物の内、一種又は二種以上を含むことを特徴とする請求項9又は10に記載の粉末材料ペースト。
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CN201480032421.0A CN105307994B (zh) | 2013-08-09 | 2014-07-31 | 铋系玻璃组合物、粉末材料及粉末材料糊剂 |
US14/910,725 US10011519B2 (en) | 2013-08-09 | 2014-07-31 | Bismuth-based glass composition, powder material, and powder material paste |
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JP2013165757A JP6206832B2 (ja) | 2013-08-09 | 2013-08-09 | 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 |
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CN106517795A (zh) * | 2016-12-29 | 2017-03-22 | 广东羚光新材料股份有限公司 | 一种低熔点玻璃浆料及其制备方法 |
US10115505B2 (en) * | 2017-02-23 | 2018-10-30 | E I Du Pont De Nemours And Company | Chip resistor |
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US10011519B2 (en) | 2018-07-03 |
US20160185650A1 (en) | 2016-06-30 |
JP6206832B2 (ja) | 2017-10-04 |
CN105307994B (zh) | 2019-01-15 |
CN105307994A (zh) | 2016-02-03 |
TWI625317B (zh) | 2018-06-01 |
TW201512133A (zh) | 2015-04-01 |
JP2015034109A (ja) | 2015-02-19 |
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