WO2021149633A1 - Sealing/coating glass with low thermal expandability - Google Patents

Sealing/coating glass with low thermal expandability Download PDF

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Publication number
WO2021149633A1
WO2021149633A1 PCT/JP2021/001458 JP2021001458W WO2021149633A1 WO 2021149633 A1 WO2021149633 A1 WO 2021149633A1 JP 2021001458 W JP2021001458 W JP 2021001458W WO 2021149633 A1 WO2021149633 A1 WO 2021149633A1
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Prior art keywords
glass
mol
sealing
sio
mgo
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PCT/JP2021/001458
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French (fr)
Japanese (ja)
Inventor
浩三 前田
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日本山村硝子株式会社
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Priority to JP2021572715A priority Critical patent/JPWO2021149633A1/ja
Priority to CN202180009687.3A priority patent/CN115038674A/en
Publication of WO2021149633A1 publication Critical patent/WO2021149633A1/en

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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
    • 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
    • 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
    • C03C3/089—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
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form

Definitions

  • the present invention relates to a sealing / coating material, more specifically for sealing between members in the manufacture of articles such as electronic devices, and for each part such as electrodes and resistors of electronic parts such as silicon diodes.
  • a sealing / coating material more specifically for sealing between members in the manufacture of articles such as electronic devices, and for each part such as electrodes and resistors of electronic parts such as silicon diodes.
  • sealing and covering glasses that can be used to coat their surfaces for protection and insulation, especially for such glasses that do not contain lead and alkali metal oxides.
  • the sealing material used in the manufacture of articles such as electronic devices must be able to seal the target articles at the lowest possible temperature, be close to the coefficient of thermal expansion of those articles, and be fired for reliable sealing. Sometimes it is required to show sufficient liquidity.
  • the coefficient of thermal expansion is close to the surface to be coated, (2) the alkali metal component is small, and (3) acid is used in the process. Therefore, it has necessary properties such as acid resistance and (4) firing at a relatively low temperature (particularly 900 ° C or lower) so that the heat during firing does not adversely affect electronic parts and the like.
  • Glass that is used for sealing or coating in the above article generally is of PbO-SiO 2 -B 2 O 3 system, also for the purpose of close to that of the semiconductor to lower the thermal expansion coefficient thereof, Cody Materials whose coefficient of thermal expansion has been adjusted by adding a low-expansion ceramic such as Elite have also been used.
  • Patent Document 1 ZnO-B 2 O 3- SiO 2 glass
  • Patent Document 2 ZnO-Bi 2 O 3- SiO 2 glass
  • the lead-free glass that has been developed so far has a problem that the softening temperature is high and therefore a high firing temperature, and that if the ZnO content is increased so as to lower the softening temperature, the acid resistance is inferior.
  • An object of the present invention is a glass that does not contain lead oxide and alkali metal oxides, can be fired at a relatively low temperature of 900 ° C. or lower, and has excellent acid resistance, and has a coefficient of thermal expansion of 40 to 70 ⁇ 10-7.
  • the purpose is to provide a sealing / coating material that is in a relatively low range for glass at / ° C.
  • the present inventor has made glass produced by combining components in a specific range at a ratio in a specific range to have fluidity at a temperature of 900 ° C. or lower. Based on this finding, we found that the glass can be suitably used for sealing and coating objects, has excellent acid resistance, and has a coefficient of thermal expansion in the range of about 40 to 70 ⁇ 10-7 / ° C. Further studies have led to the completion of the present invention. That is, the present invention provides the following.
  • SiO 2 31-53% Al 2 O 3 : 3 to 15% B 2 O 3 : 4-24% ZnO: 1 to 14% At least one of MgO and CaO: 5-20% total Bi 2 O 3 : Greater than 0 to 11% Contains, The total content of SiO 2 and B 2 O 3 is 50 mol% or more.
  • SiO 2 36-51% Al 2 O 3 : 5 to 15% B 2 O 3 : 6-22% ZnO: 5-14% At least one of MgO and CaO: 5-18% total Bi 2 O 3 : 0.5-11% Contains, The total content of SiO 2 and B 2 O 3 is 50 mol% or more.
  • a glass for sealing and covering which is characterized by. 4. The sealing / coating glass according to any one of 1 to 3 above, which contains 5 mol% or more of MgO. 5. It contains virtually no lead oxide or alkali metal oxide, and is in mol%.
  • SiO 2 33-43% Al 2 O 3 : 3 to 15% B 2 O 3 : 13-28% ZnO: 0 to less than 10%
  • At least one of MgO and CaO: 10 to 25% in total Bi 2 O 3 : 0-5% Contains, The total content of SiO 2 and B 2 O 3 is 50 mol% or more.
  • SiO 2 35-42% Al 2 O 3 : 8 to 15% B 2 O 3 : 15-22% ZnO: 3 to less than 10%
  • At least one of MgO and CaO: 15 to 23% in total Contains, Bi 2 O 3 : 0 to less than 1%
  • the total content of SiO 2 and B2O 3 is 50 mol% or more.
  • a glass for sealing and covering which is characterized by. 7. Molar ratio of SiO 2 to the total of MgO, CaO and Bi 2 O 3: [SiO 2 / (MgO + CaO + Bi 2 O 3 )]
  • the sealing / covering glass according to any one of 1 to 6 above, wherein the number is 1 to 5. 8.
  • the sealing / coating glass according to any one of 1 to 5 above which is in the form of powder.
  • the sealing / coating paste according to 7 above which contains an organic binder and a solvent.
  • the sealing / coating material of the present invention having the above structure can be fired at 900 ° C. or lower. Further, since the glass powder of the present invention does not react with the filler when it is mixed with the ceramic filler and fired, crystals hardly precipitate during firing, and even if it precipitates, only a very small amount of precipitation occurs. Therefore, it has excellent fluidity during firing, has high mechanical strength after cooling and solidification, and can be used as a sealing material with excellent durability. Further, in the sealing / coating material of the present invention, the coefficient of thermal expansion can be easily adjusted in the range of about 40 to 70 ⁇ 10 -7 / ° C. Therefore, the sealing / coating material of the invention can be used as a material particularly suitable for sealing / coating.
  • the components constituting the sealing / coating glass of the present invention and their content ranges suitable for achieving the object of the present invention are as follows.
  • SiO 2 is a component that forms glass, and is preferably contained in the range of 30 to 55 mol%. This is because if the content of SiO 2 is less than 30 mol%, the glass may not be obtained, and even if it is obtained, the glass may have a coefficient of thermal expansion so high that it cannot be used for sealing. This is because if the content of SiO 2 is more than 55 mol%, it becomes difficult for the glass to melt, and in particular, SiO 2 may remain unmelted as an unmelted substance. Considering the stable achievement of glass formability, desired coefficient of thermal expansion and meltability, the content of SiO 2 is more preferably 31 to 53 mol%, still more preferably 36 to 51 mol%.
  • Al 2 O 3 is a component that forms glass, and is preferably contained in the range of 1 to 17 mol%. This is because if the content of Al 2 O 3 is less than 1 mol%, glass may not be obtained, and if the content of Al 2 O 3 is more than 17 mol%, it may remain undissolved as an unmelted substance. Because there is. Considering the stable achievement of glass formability and meltability, the content of Al 2 O 3 is more preferably 3 to 15 mol%, still more preferably 5 to 15 mol%.
  • B 2 O 3 is a component that forms glass, and is preferably contained in the range of 2 to 28 mol%. This is because if the content of B 2 O 3 is less than 2 mol%, the glass may not be obtained, and even if it is obtained, the glass may have a softening temperature so high that it cannot be used for sealing. If the content of B 2 O 3 is more than 28 mol%, the glass may have a high coefficient of thermal expansion so that it cannot be used for sealing or coating. Considering the formability of the glass, the desired softening temperature and the stable achievement of the coefficient of thermal expansion , the content of B 2 O 3 is more preferably 4 to 24 mol%, still more preferably 6 to 22 mol%.
  • the total content of SiO 2 and B 2 O 3 in the sealing and coating glass of the present invention is preferably 50 mol% or more. This is because if the total content of SiO 2 and B 2 O 3 is less than 50 mol%, glass may not be obtained. Considering the stable achievement of glass formability, the total content of SiO 2 and B 2 O 3 is more preferably 55 mol% or more, still more preferably 57 mol% or more.
  • the content is preferably 14 mol% or less. This is because if the ZnO content is more than 14 mol%, glass having poor acid resistance may be produced. Considering the stable achievement of the formability and acid resistance of the obtained glass, the ZnO content is more preferably 1 to 14 mol%, still more preferably 5 to 14 mol%. However, not limited to these ranges, the ZnO content may be, for example, less than 10 mol%, or 9.5 mol% or less, 9 mol% or less, that is, 0 to less than 10 mol%, 0 to 9.5. It may be in the range of mol%, 0 to 9 mol%, and the like. Further, the lower limit of these ranges may be 1 mol%, 3 mol%, or the like instead of 0 mol% as described above.
  • MgO and CaO are components that enhance the formability of glass, and it is preferable to contain at least one of them in the range of 5 to 25 mol% in total. This is because if the total amount of MgO and CaO is less than 5 mol%, the glass may have a softening temperature so high that it cannot be sealed in the desirable temperature range of the present invention, and the total content thereof is more than 25 mol%. This is because if there are many, glass may not be obtained. Considering the stable achievement of glass formability and fluidity, the total content of MgO and CaO is more preferably 5 to 20 mol%, still more preferably 5 to 18 mol%.
  • MgO in particular acts in the direction of lowering the coefficient of thermal expansion while maintaining the formability of the glass, and therefore, it is preferable to contain at least 5 mol%. Considering that the coefficient of thermal expansion of the obtained glass is lowered, it is more preferable that CaO is not used in combination and only MgO is contained in any of the above ranges.
  • Bi 2 O 3 is a component that stabilizes the glass state and lowers the softening temperature of the glass, and is not an essential component, but it is preferably contained, and in that case, the content is preferably 12 mol% or less. This is because if the content of Bi 2 O 3 exceeds 12 mol%, the formability of the glass is lowered, or crystals are likely to be precipitated during firing, which may cause sealing or coating failure. Considering the formability, sealing, and coating performance of the obtained glass, the content of Bi 2 O 3 is more preferably greater than 0 to 11 mol%, and further preferably 0.5 to 11 mol%.
  • the content of Bi 2 O 3 may be, for example, less than 5 mol%, or 3 mol% or less, 1 mol% or less, that is, 0 to less than 10 mol%, 0 to 3 mol. It may be in the range of less than%, less than 0 to less than 1 mol%, and the like. Further, the lower limit of these ranges may be 0.5 mol% instead of 0 mol% as described above.
  • ZrO 2 is not an essential component, it is preferably contained because it acts to improve the acid resistance of the glass, and in that case, the content is preferably 7 mol% or less. This is because if the content of ZrO 2 exceeds 7 mol%, the formability of the glass deteriorates, or crystals tend to precipitate during firing, which may cause sealing and coating defects. Forming and sealing of the glass content of ZrO 2 is obtained, in consideration of the securing of the coating performance, the content of ZrO 2 is preferably 0.1 to 5 mol%, more preferably 1 to 5 mol%.
  • the ratio of the content of SiO 2 (mol%) to the total content (mol%) of MgO, CaO, and Bi 2 O 3 is 1. It is preferably ⁇ 5. If this ratio is less than 1, the acid resistance of the obtained glass may decrease, and if this ratio exceeds 5, the softening temperature may become high enough to require an excessively high temperature for firing. be. Considering acid resistance and ensuring an appropriate softening temperature, the ratio [SiO 2 / (MgO + CaO + Bi 2 O 3 )] is more preferably 2 to 4.
  • La 2 O 3 , Nb 2 O 5 , TeO 2 , CeO 2 , TiO 2, etc. are used for the purpose of improving the stability of glass during manufacturing, suppressing crystallization, and adjusting the coefficient of thermal expansion.
  • a total of up to 5 mol% can be added.
  • the sealing / coating glass of the present invention is preferably fired at 900 ° C. or lower so that the heat during firing does not adversely affect electronic parts and the like, its softening point is an approximate guideline. , It is preferably in the range of about 600 ° C. to 750 ° C., and more preferably in the range of about 650 ° C. to 730 ° C.
  • the glass powder of the present invention may be blended with a ceramic filler as necessary for the purpose of adjusting the coefficient of thermal expansion and improving the strength when used as a sealing / coating material. can.
  • the blending amount of the ceramic filler can be appropriately set to be 40% by weight or less of the total amount with the glass.
  • Examples of the ceramic filler to be blended include cordierite, zircon, zirconium phosphate, aluminum titanate, mullite, alumina, willemite, and silica ( ⁇ -quartz, cristobalite, tridimite).
  • the sealing / covering glass of the present invention can be used as a sealing / covering material in the form of a powder or in the form of a mixed powder of this and ceramic powder. Further, for example, it is used as a sealing / covering material in a form more convenient to be applied to the surface of a sealing / covering object such as a paste or a sheet in which a binder or a solvent is further mixed with these powders. You can also.
  • those powders may be mixed with at least one of a solvent and an organic binder.
  • a paste can be prepared by mixing a powder of the glass of the present invention in powder form, a solvent and an organic binder.
  • the average particle size of the sealing / coating glass in the form of powder is not particularly limited, but is usually preferably 1 to 10 ⁇ m, and more preferably 2 to 8 ⁇ m.
  • organic binder is not particularly limited, and can be appropriately adopted from known binders according to the specific use of the sealing / coating material.
  • examples include, but are not limited to, cellulose resins such as ethyl cellulose.
  • the solvent may be appropriately selected depending on the organic binder used, for example, alcohols such as ethanol, methanol and isopropanol; terpineol ( ⁇ -terpineol, or ⁇ -terpineol and ⁇ -terpineol containing ⁇ -terpineol as a main component).
  • Organic solvents such as (mixture with), but are not limited to these.
  • the solvent may be used alone or in combination of two or more.
  • additives such as a plasticizer, a thickener, a sensitizer, a surfactant, and a dispersant can be appropriately added as needed.
  • additives such as a solvent and an organic binder are appropriately selected and added to the sealing / coating glass powder of the present invention or a mixed powder with a ceramic filler.
  • the mixture may be mixed, the mixture may be applied onto the substrate, and the coating may be dried at room temperature or under heating.
  • Ceramic filler powder was mixed with the glass powders of four examples randomly selected from the above examples at the ratios shown in Examples 50 to 53 of Table 10 so as to have the contents shown in the same table, and the mixed powder was prepared. Each was prepared.
  • Glass transition temperature, softening temperature, crystallization temperature Approximately 60 to 80 mg of glass powder is filled in a platinum cell, and using a DTA measuring device (Thermo Plus EVO2 TG-DTA8122 manufactured by Rigaku Co., Ltd.), 20 ° C. The temperature was raised in 1 and the glass transition temperature (Tg), softening temperature (Ts), and crystallization temperature (Tp) were measured.
  • Tg glass transition temperature
  • Ts softening temperature
  • Tp crystallization temperature
  • the softening temperature of the glasses of Examples 1 to 49 is in the range of 615 ° C. to 767 ° C., all of them are in a state of having sufficient fluidity at a temperature not exceeding 900 ° C. Can be fired in. Further, the glasses of Examples 1 and 39 having a crystallization temperature of less than 900 ° C. have a sufficiently large difference between the softening temperature and the crystallization temperature (the differences are 185 ° C. and 246 ° C., respectively) and do not cause crystallization. It is possible to fire at a temperature, and in the remaining glasses of the examples, crystallization is not detected, or the crystallization temperature exceeds 900 ° C.
  • the glass of each example shows an expansion coefficient in the range of 40 to 70 ⁇ 10-7 / ° C, which is preferable in the present invention.
  • the glasses of Comparative Examples 1 and 2 having a low SiO 2 content (15.3 and 25.0 mol%, respectively) showed a remarkable weight loss in the acid resistance test, as seen in Examples 31 and 32.
  • the glass of the present invention has excellent acid resistance.
  • the glass of Comparative Example 2 is not suitable for the object of the present invention in that the coefficient of thermal expansion is as large as 71 ⁇ 10 -7 / ° C.
  • the glass of Comparative Example 3 has a considerably low crystallization temperature (777 ° C.) and a small difference between the softening temperature and the crystallization temperature (the difference is 167 ° C.), which causes a decrease in fluidity. It is difficult to control the temperature so that the glass is fired while suppressing crystallization, and the glass of Comparative Example 4 has a very narrow difference between the softening temperature and the crystallization temperature (the difference is 118 ° C.), so that the glass is fired. It is even more difficult to suppress crystallization in.
  • the glasses of Examples 54 to 69 were produced in the same manner as in Examples 1 to 53 so that the glass compositions shown in Tables 11 to 13 were obtained, and powders and glass blocks were prepared, respectively. The crystallization temperature and the coefficient of thermal expansion were measured (some have not been measured). The results are shown in Tables 11-13.
  • the glass of the present invention is suitable for sealing articles such as semiconductors in terms of softening temperature and coefficient of thermal expansion, and can be provided as having excellent acid resistance. Therefore, a wide variety of electronic devices can be provided. It can be used for sealing and bonding of various parts of electronic parts.
  • the glass of the present invention in the form of a powder, can be used alone or as a mixed powder with a ceramic filler powder for sealing with excellent fluidity at a temperature of 900 ° C. or lower, and for sealing electronic devices and other articles as a coating material. Can be used for coating.
  • the filler and glass will react, the coefficient of thermal expansion is close to that of semiconductors used in articles such as electronic devices, and the problem of thermal stress is unlikely to occur. Further, since it can be provided even if it has excellent acid resistance, it can be advantageously used as a material for sealing and coating those articles.

Abstract

Disclosed is a sealing/coating material which is free of lead oxides and alkali metal oxides, which can be fired at a comparatively low temperature, which has excellent acid resistance, and which has a comparatively low thermal expansion coefficient. The material is sealing/coating glass characterized by: being substantially free of lead oxides and alkali metal oxides; containing, in terms of mol%, 30-55% SiO2, 1-17% Al2O3, 2-28% B2O3, 0-14% ZnO, a combined amount of 5-25% of at least one of MgO and CaO, and 0-12% Bi2O3; and having a combined amount of SiO2 and B2O3 which is not less than 50 mol%.

Description

低熱膨張性封着・被覆用ガラスLow thermal expansion sealing / covering glass
　本発明は封着・被覆用材料に関し，より具体的には電子デバイス等の物品の製造に際した部材間の封着のために，また例えばシリコンダイオード等の電子部品の電極や抵抗体等各部の保護・絶縁用にそれらの表面を被覆するのに使用できる封着・被覆用ガラスに関し，特に，鉛及びアルカリ金属酸化物を含有しないそのようなガラスに関する。 The present invention relates to a sealing / coating material, more specifically for sealing between members in the manufacture of articles such as electronic devices, and for each part such as electrodes and resistors of electronic parts such as silicon diodes. For sealing and covering glasses that can be used to coat their surfaces for protection and insulation, especially for such glasses that do not contain lead and alkali metal oxides.
　電子デバイス等の物品の製造において使用される封着材料には，できるだけ低温で対象物品を封着できること，それらの物品の熱膨張係数に近似していること，及び確実な封着のための焼成時に十分な流動性を示すこと等が求められている。 The sealing material used in the manufacture of articles such as electronic devices must be able to seal the target articles at the lowest possible temperature, be close to the coefficient of thermal expansion of those articles, and be fired for reliable sealing. Sometimes it is required to show sufficient liquidity.
　また，電子部品の各部の表面に使用される被覆材料においても，（１）被覆対象面と熱膨張係数が近いこと，（２）アルカリ金属成分が少ないこと，（３）工程で酸を使用するため耐酸性があること，（４）焼成時の熱で電子部品等に悪影響を及ぼすことがないよう比較的低温（特に，９００℃以下）で焼成できること等必要な特性がある。 Also, in the coating material used for the surface of each part of electronic parts, (1) the coefficient of thermal expansion is close to the surface to be coated, (2) the alkali metal component is small, and (3) acid is used in the process. Therefore, it has necessary properties such as acid resistance and (4) firing at a relatively low temperature (particularly 900 ° C or lower) so that the heat during firing does not adversely affect electronic parts and the like.
　上記の物品において封着や被覆用として使用されているガラスは，一般にＰｂＯ－ＳｉＯ２－Ｂ２Ｏ３系のものであり，またそれらの熱膨張係数を下げて半導体のそれに近づける目的で，コーディエライトのような低膨張性セラミックを添加して熱膨張係数を調整した材料も使用されてきた。 Glass that is used for sealing or coating in the above article, generally is of PbO-SiO 2 -B 2 O 3 system, also for the purpose of close to that of the semiconductor to lower the thermal expansion coefficient thereof, Cody Materials whose coefficient of thermal expansion has been adjusted by adding a low-expansion ceramic such as Elite have also been used.
　しかし，鉛を含むガラスは，近年，環境上の観点から使用が避けられてきており，鉛を含有しないガラスの開発が行われている。鉛を含まないガラスとしては，ＺｎＯ－Ｂ２Ｏ３－ＳｉＯ２系ガラス（特許文献１），ＺｎＯ－Ｂｉ２Ｏ３－ＳｉＯ２系ガラス（特許文献２）等が知られている。 However, in recent years, the use of lead-containing glass has been avoided from the viewpoint of the environment, and lead-free glass is being developed. As lead-free glass, ZnO-B 2 O 3- SiO 2 glass (Patent Document 1), ZnO-Bi 2 O 3- SiO 2 glass (Patent Document 2) and the like are known.
　しかし，これまで開発されてきた無鉛ガラスには，軟化温度が高くそのため焼成温度が高いという問題点や，軟化温度を下げるようＺｎＯの含量を高めたものでは耐酸性に劣るという問題点がある。 However, the lead-free glass that has been developed so far has a problem that the softening temperature is high and therefore a high firing temperature, and that if the ZnO content is increased so as to lower the softening temperature, the acid resistance is inferior.
特開２０１１－１５３０４９JP 2011-153049 ＷＯ２０１８／０２６４０２WO2018 / 026402
　本発明の目的は，酸化鉛及びアルカリ金属酸化物を含有せず，９００℃以下という比較的低温で焼成でき，耐酸性に優れるガラスであって，熱膨張係数が，４０～７０×１０－７／℃というガラスとしては比較的低い範囲にある封着・被覆用材料を提供することにある。 An object of the present invention is a glass that does not contain lead oxide and alkali metal oxides, can be fired at a relatively low temperature of 900 ° C. or lower, and has excellent acid resistance, and has a coefficient of thermal expansion of 40 to 70 × 10-7. The purpose is to provide a sealing / coating material that is in a relatively low range for glass at / ° C.
　本発明者は，上述の従来技術の問題点の解決に向けて研究を重ねた結果，ある特定範囲の成分を特定範囲の割合で組み合わせて製造したガラスは，９００℃以下の温度で流動性を有して対象物の封着・被覆に好適に使用でき，耐酸性に優れ，熱膨張係数が約４０～７０×１０－７／℃の範囲に入るガラスとなることを見出し，この知見に基づき更に検討を重ねて本発明を完成させるに至った。すなわち，本発明は以下を提供する。 As a result of repeated research aimed at solving the above-mentioned problems of the prior art, the present inventor has made glass produced by combining components in a specific range at a ratio in a specific range to have fluidity at a temperature of 900 ° C. or lower. Based on this finding, we found that the glass can be suitably used for sealing and coating objects, has excellent acid resistance, and has a coefficient of thermal expansion in the range of about 40 to 70 × 10-7 / ° C. Further studies have led to the completion of the present invention. That is, the present invention provides the following.
　１．実質的に酸化鉛もアルカリ金属酸化物も含有せず，モル％で，
ＳｉＯ２　　　 ：　３０～５５％
Ａｌ２Ｏ３　　　：　１～１７％
Ｂ２Ｏ３　　　　：　２～２８％
ＺｎＯ 　　　　：　０～１４％
ＭｇＯとＣａＯのうち少なくとも１種：　合計５～２５％
Ｂｉ２Ｏ３　　　：　０～１２％
を含有し，
ＳｉＯ２とＢ２Ｏ３の合計含量が５０モル％以上であること，
を特徴とする，封着・被覆用ガラス。
　２．実質的に酸化鉛，アルカリ金属酸化物を含有せず，モル％で，
ＳｉＯ２　　　 ：　３１～５３％
Ａｌ２Ｏ３　　　：　３～１５％
Ｂ２Ｏ３　　　　：　４～２４％
ＺｎＯ 　　　　：　１～１４％
ＭｇＯとＣａＯのうち少なくとも１種：　合計５～２０％
Ｂｉ２Ｏ３　　　：　０より大～１１％
を含有し，
ＳｉＯ２とＢ２Ｏ３の合計含量が５０モル％以上であること，
を特徴とする，封着・被覆用ガラス。
　３．実質的に酸化鉛，アルカリ金属酸化物を含有せず，モル％で，
ＳｉＯ２　　　 ：　３６～５１％
Ａｌ２Ｏ３　　　：　５～１５％
Ｂ２Ｏ３　　　　：　６～２２％
ＺｎＯ 　　　　：　５～１４％
ＭｇＯとＣａＯのうち少なくとも１種：　合計５～１８％
Ｂｉ２Ｏ３　　　：　０．５～１１％
を含有し，
ＳｉＯ２とＢ２Ｏ３の合計含量が５０モル％以上であること，
を特徴とする，封着・被覆用ガラス。
　４．ＭｇＯを５モル％以上含有する，上記１～３の何れかの封着・被覆用ガラス。
　５．実質的に酸化鉛，アルカリ金属酸化物を含有せず，モル％で，
ＳｉＯ２　　　 ：　３３～４３％
Ａｌ２Ｏ３　　　：　３～１５％
Ｂ２Ｏ３　　　　：　１３～２８％
ＺｎＯ 　　　　：　０～１０％未満
ＭｇＯとＣａＯのうち少なくとも１種：　合計１０～２５％
Ｂｉ２Ｏ３　　　：　０～５％
を含有し，
ＳｉＯ２とＢ２Ｏ３の合計含量が５０モル％以上であること，
を特徴とする，封着・被覆用ガラス。
　６．実質的に酸化鉛，アルカリ金属酸化物を含有せず，モル％で，
ＳｉＯ２　　　 ：　３５～４２％
Ａｌ２Ｏ３　　　：　８～１５％
Ｂ２Ｏ３　　　　：　１５～２２％
ＺｎＯ 　　　　：　３～１０％未満
ＭｇＯとＣａＯのうち少なくとも１種：　合計１５～２３％
を含有し，
Ｂｉ２Ｏ３　　　：　０～１％未満
ＳｉＯ２とＢ２Ｏ３の合計含量が５０モル％以上であること，
を特徴とする，封着・被覆用ガラス。
７．ＭｇＯ，ＣａＯ及びＢｉ２Ｏ３の合計に対するＳｉＯ２のモル比：
［ＳｉＯ２／（ＭｇＯ＋ＣａＯ＋Ｂｉ２Ｏ３）］
が１～５である，上記１～６の何れかの封着・被覆用ガラス。
　８．粉末の形態である上記１～５の何れかの封着・被覆用ガラス。
　９．上記６の粉末とフィラー粉末とを含んでなる封着・被覆用材料であって，両粉末の合計量に対する該フィラー粉末の含量が４０重量％を超えないものである封着・被覆用材料。
　１０．上記７の封着・被覆用材料であって，有機バインダー及び溶剤を含んでなるものである，封着・被覆用ペースト。 1. 1. It contains virtually no lead oxide or alkali metal oxides and is in mol%.
SiO 2 : 30-55%
Al 2 O 3 : 1 to 17%
B 2 O 3 : 2-28%
ZnO : 0-14%
At least one of MgO and CaO: 5-25% total
Bi 2 O 3 : 0-12%
Contains,
The total content of SiO 2 and B 2 O 3 is 50 mol% or more.
A glass for sealing and covering, which is characterized by.
2. It contains virtually no lead oxide or alkali metal oxide, and is in mol%.
SiO 2 : 31-53%
Al 2 O 3 : 3 to 15%
B 2 O 3 : 4-24%
ZnO: 1 to 14%
At least one of MgO and CaO: 5-20% total
Bi 2 O 3 : Greater than 0 to 11%
Contains,
The total content of SiO 2 and B 2 O 3 is 50 mol% or more.
A glass for sealing and covering, which is characterized by.
3. 3. It contains virtually no lead oxide or alkali metal oxide, and is in mol%.
SiO 2 : 36-51%
Al 2 O 3 : 5 to 15%
B 2 O 3 : 6-22%
ZnO: 5-14%
At least one of MgO and CaO: 5-18% total
Bi 2 O 3 : 0.5-11%
Contains,
The total content of SiO 2 and B 2 O 3 is 50 mol% or more.
A glass for sealing and covering, which is characterized by.
4. The sealing / coating glass according to any one of 1 to 3 above, which contains 5 mol% or more of MgO.
5. It contains virtually no lead oxide or alkali metal oxide, and is in mol%.
SiO 2 : 33-43%
Al 2 O 3 : 3 to 15%
B 2 O 3 : 13-28%
ZnO: 0 to less than 10% At least one of MgO and CaO: 10 to 25% in total
Bi 2 O 3 : 0-5%
Contains,
The total content of SiO 2 and B 2 O 3 is 50 mol% or more.
A glass for sealing and covering, which is characterized by.
6. It contains virtually no lead oxide or alkali metal oxide, and is in mol%.
SiO 2 : 35-42%
Al 2 O 3 : 8 to 15%
B 2 O 3 : 15-22%
ZnO: 3 to less than 10% At least one of MgO and CaO: 15 to 23% in total
Contains,
Bi 2 O 3 : 0 to less than 1% The total content of SiO 2 and B2O 3 is 50 mol% or more.
A glass for sealing and covering, which is characterized by.
7. Molar ratio of SiO 2 to the total of MgO, CaO and Bi 2 O 3:
[SiO 2 / (MgO + CaO + Bi 2 O 3 )]
The sealing / covering glass according to any one of 1 to 6 above, wherein the number is 1 to 5.
8. The sealing / coating glass according to any one of 1 to 5 above, which is in the form of powder.
9. A sealing / coating material containing the powder of 6 and the filler powder, wherein the content of the filler powder with respect to the total amount of both powders does not exceed 40% by weight.
10. The sealing / coating paste according to 7 above, which contains an organic binder and a solvent.
　上記構成になる本発明の封着・被覆用材料は，９００℃以下で焼成することができる。また本発明のガラスの粉末は，セラミックフィラーと混合して焼成した際にフィラーと反応することがないため，焼成時に結晶が析出することが殆どなく，仮に析出してもごく僅かな析出に止まるため，焼成時の流動性に優れており，冷却固化後の機械的強度が高く耐久性に優れた封着，被覆材として使用することができる。また本発明の封着・被覆用材料は，熱膨張係数を約４０～７０×１０-7／℃の範囲で容易に調節することができる。従って，発明の封着・被覆用材料は，封着，被覆に特に適した材料として使用することができる。 The sealing / coating material of the present invention having the above structure can be fired at 900 ° C. or lower. Further, since the glass powder of the present invention does not react with the filler when it is mixed with the ceramic filler and fired, crystals hardly precipitate during firing, and even if it precipitates, only a very small amount of precipitation occurs. Therefore, it has excellent fluidity during firing, has high mechanical strength after cooling and solidification, and can be used as a sealing material with excellent durability. Further, in the sealing / coating material of the present invention, the coefficient of thermal expansion can be easily adjusted in the range of about 40 to 70 × 10 -7 / ° C. Therefore, the sealing / coating material of the invention can be used as a material particularly suitable for sealing / coating.
　本発明の封着・被覆用ガラスを構成する各成分と，本発明の目的の達成に適したそれらの含量範囲は以下の通りである。 The components constituting the sealing / coating glass of the present invention and their content ranges suitable for achieving the object of the present invention are as follows.
　ＳｉＯ２はガラスを形成する成分であり，３０～５５モル％の範囲で含有させることが好ましい。これは，ＳｉＯ２の含量が３０モル％より少ない場合，ガラスが得られないおそれがあり，また得られたとしても封着に使用できない程熱膨張係数が高いガラスとなるおそれがあるのと，ＳｉＯ２の含量が５５モル％より多くなるとガラスが溶融し難くなり，特にＳｉＯ２が未溶融物として溶け残るおそれがあるからである。ガラスの形成性，望ましい熱膨張係数及び溶融性の安定した達成を考慮すると，ＳｉＯ２の含量は，より好ましくは３１～５３モル％，更に好ましくは３６～５１モル％である。 SiO 2 is a component that forms glass, and is preferably contained in the range of 30 to 55 mol%. This is because if the content of SiO 2 is less than 30 mol%, the glass may not be obtained, and even if it is obtained, the glass may have a coefficient of thermal expansion so high that it cannot be used for sealing. This is because if the content of SiO 2 is more than 55 mol%, it becomes difficult for the glass to melt, and in particular, SiO 2 may remain unmelted as an unmelted substance. Considering the stable achievement of glass formability, desired coefficient of thermal expansion and meltability, the content of SiO 2 is more preferably 31 to 53 mol%, still more preferably 36 to 51 mol%.
　Ａｌ２Ｏ３はガラスを形成する成分であり，１～１７モル％の範囲で含有させることが好ましい。これは，Ａｌ２Ｏ３の含量が１モル％より少ない場合，ガラスが得られないおそれがあるのと，Ａｌ２Ｏ３は，含量が１７モル％より多い場合，未溶融物として溶け残るおそれがあるからである。ガラスの形成性及び溶融性の安定した達成を考慮すると，Ａｌ２Ｏ３の含量は，より好ましくは３～１５モル％，更に好ましくは５～１５モル％である。 Al 2 O 3 is a component that forms glass, and is preferably contained in the range of 1 to 17 mol%. This is because if the content of Al 2 O 3 is less than 1 mol%, glass may not be obtained, and if the content of Al 2 O 3 is more than 17 mol%, it may remain undissolved as an unmelted substance. Because there is. Considering the stable achievement of glass formability and meltability, the content of Al 2 O 3 is more preferably 3 to 15 mol%, still more preferably 5 to 15 mol%.
　Ｂ２Ｏ３はガラスを形成する成分であり，２～２８モル％の範囲で含有させることが好ましい。これは，Ｂ２Ｏ３の含量が２モル％より少ない場合，ガラスが得られないおそれがあり，また得られたとしても封着に使用できない程軟化温度が高いガラスとなるおそれがあるのと，Ｂ２Ｏ３の含量が２８モル％より多いと，封着，被覆に使用できない程熱膨張係数が高いガラスとなるおそれがあるからである。ガラスの形成性，望ましい軟化温度及び熱膨張係数の安定した達成を考慮すると，Ｂ２Ｏ３の含量は，より好ましくは４～２４モル％，更に好ましくは６～２２モル％である。 B 2 O 3 is a component that forms glass, and is preferably contained in the range of 2 to 28 mol%. This is because if the content of B 2 O 3 is less than 2 mol%, the glass may not be obtained, and even if it is obtained, the glass may have a softening temperature so high that it cannot be used for sealing. If the content of B 2 O 3 is more than 28 mol%, the glass may have a high coefficient of thermal expansion so that it cannot be used for sealing or coating. Considering the formability of the glass, the desired softening temperature and the stable achievement of the coefficient of thermal expansion , the content of B 2 O 3 is more preferably 4 to 24 mol%, still more preferably 6 to 22 mol%.
　本発明の封着，被覆用ガラスにおけるＳｉＯ２とＢ２Ｏ３の合計含量は，５０モル％以上であることが好ましい。ＳｉＯ２とＢ２Ｏ３の合計含量が５０モル％未満であると，ガラスが得られないおそれがあるためである。ガラスの形成性の安定した達成を考慮すると，ＳｉＯ２とＢ２Ｏ３の合計含量は，より好ましくは５５モル％以上，更に好ましくは５７モル％以上である。 The total content of SiO 2 and B 2 O 3 in the sealing and coating glass of the present invention is preferably 50 mol% or more. This is because if the total content of SiO 2 and B 2 O 3 is less than 50 mol%, glass may not be obtained. Considering the stable achievement of glass formability, the total content of SiO 2 and B 2 O 3 is more preferably 55 mol% or more, still more preferably 57 mol% or more.
　ＺｎＯは，必須成分ではないが，ガラスの形成性を高めるように作用するから，含有させることが好ましく，その場合含量は１４モル％以下とすることが好ましい。ＺｎＯの含量が１４モル％より多い場合，耐酸性が悪いガラスを生じるおそれがあるからである。得られるガラスの形成性及び耐酸性の安定した達成を考慮すると，ＺｎＯの含量は，より好ましくは１～１４モル％であり，更に好ましくは５～１４モル％である。但しこれらの範囲に限らず，ＺｎＯの含有量は，例えば１０モル％未満，或いは９．５モル％以下，９モル％以下等としてもよく，即ち０～１０モル％未満，０～９．５モル％，０～９モル％等といった範囲であってよい。また，これらの範囲の下限も，前記と同様，０モル％の代わりに１モル％，３モル％等としてもよい。 Although ZnO is not an essential component, it acts to enhance the formability of glass, so it is preferable to include it. In that case, the content is preferably 14 mol% or less. This is because if the ZnO content is more than 14 mol%, glass having poor acid resistance may be produced. Considering the stable achievement of the formability and acid resistance of the obtained glass, the ZnO content is more preferably 1 to 14 mol%, still more preferably 5 to 14 mol%. However, not limited to these ranges, the ZnO content may be, for example, less than 10 mol%, or 9.5 mol% or less, 9 mol% or less, that is, 0 to less than 10 mol%, 0 to 9.5. It may be in the range of mol%, 0 to 9 mol%, and the like. Further, the lower limit of these ranges may be 1 mol%, 3 mol%, or the like instead of 0 mol% as described above.
　ＭｇＯ及びＣａＯはガラスの形成性を高める成分であり，少なくともいずれか１種類を合計で５～２５モル％の範囲で含有させることが好ましい。これはＭｇＯとＣａＯの合計量が５モル％より少ない場合，本発明の望ましい温度範囲では封着ができない程軟化温度が高いガラスとなるおそれがあるのと，それらの合計含量が２５モル％より多い場合，ガラスが得られないおそれがあるからである。ガラスの形成性及び流動性の安定した達成を考慮すると，ＭｇＯとＣａＯの合計含量は，より好ましくは５～２０モル％，更に好ましくは５～１８モル％である。ＭｇＯとＣａＯのうち，特にＭｇＯは，ガラスの形成性を維持したまま熱膨張係数を下げる方向に作用するため，少なくとも５モル％含有させることが好ましい。得られるガラスの熱膨張係数を低くすることも考慮すると，ＣａＯは併用せずＭｇＯのみを上記の何れかの範囲で含有させることがより好ましい。 MgO and CaO are components that enhance the formability of glass, and it is preferable to contain at least one of them in the range of 5 to 25 mol% in total. This is because if the total amount of MgO and CaO is less than 5 mol%, the glass may have a softening temperature so high that it cannot be sealed in the desirable temperature range of the present invention, and the total content thereof is more than 25 mol%. This is because if there are many, glass may not be obtained. Considering the stable achievement of glass formability and fluidity, the total content of MgO and CaO is more preferably 5 to 20 mol%, still more preferably 5 to 18 mol%. Of MgO and CaO, MgO in particular acts in the direction of lowering the coefficient of thermal expansion while maintaining the formability of the glass, and therefore, it is preferable to contain at least 5 mol%. Considering that the coefficient of thermal expansion of the obtained glass is lowered, it is more preferable that CaO is not used in combination and only MgO is contained in any of the above ranges.
　Ｂｉ２Ｏ３はガラス状態を安定させ，且つガラスの軟化温度を下げる成分であり，必須成分ではないが，含有させることが好ましく，その場合含量は１２モル％以下とすることが好ましい。これはＢｉ２Ｏ３の含量が１２モル％を超えるとガラスの形成性が低下するかあるいは焼成時に結晶が析出し易くなり，封着，被覆不良が発生するおそれがあるからである。得られるガラスの形成性及び封着，被覆性能の確保を考慮すると，Ｂｉ２Ｏ３の含量は，より好ましくは０より大～１１モル％，更に好ましくは０．５～１１モル％である。但しこれらの範囲に限らず，Ｂｉ２Ｏ３の含有量は，例えば５モル％未満，或いは３モル％以下，１モル％以下等としてもよく，即ち０～１０モル％未満，０～３モル％未満，０～１モル％未満等といった範囲であってよい。また，これらの範囲の下限も，前記と同様，０モル％の代わりに０．５モル％としてもよい。 Bi 2 O 3 is a component that stabilizes the glass state and lowers the softening temperature of the glass, and is not an essential component, but it is preferably contained, and in that case, the content is preferably 12 mol% or less. This is because if the content of Bi 2 O 3 exceeds 12 mol%, the formability of the glass is lowered, or crystals are likely to be precipitated during firing, which may cause sealing or coating failure. Considering the formability, sealing, and coating performance of the obtained glass, the content of Bi 2 O 3 is more preferably greater than 0 to 11 mol%, and further preferably 0.5 to 11 mol%. However, not limited to these ranges, the content of Bi 2 O 3 may be, for example, less than 5 mol%, or 3 mol% or less, 1 mol% or less, that is, 0 to less than 10 mol%, 0 to 3 mol. It may be in the range of less than%, less than 0 to less than 1 mol%, and the like. Further, the lower limit of these ranges may be 0.5 mol% instead of 0 mol% as described above.
　ＺｒＯ２は必須成分ではないが，ガラスの耐酸性を向上させるように作用するから含有させることが好ましく，その場合含量は７モル％以下とすることが好ましい。これはＺｒＯ２の含量が７モル％を超えるとガラスの形成性が悪くなるかあるいは焼成時に結晶が析出し易くなり，封着，被覆不良が発生するおそれがあるからである。ＺｒＯ２の含量は得られるガラスの形成性及び封着，被覆性能の確保を考慮すると，ＺｒＯ２の含量は，好ましくは０．１～５モル％，より好ましくは１～５モル％である。 Although ZrO 2 is not an essential component, it is preferably contained because it acts to improve the acid resistance of the glass, and in that case, the content is preferably 7 mol% or less. This is because if the content of ZrO 2 exceeds 7 mol%, the formability of the glass deteriorates, or crystals tend to precipitate during firing, which may cause sealing and coating defects. Forming and sealing of the glass content of ZrO 2 is obtained, in consideration of the securing of the coating performance, the content of ZrO 2 is preferably 0.1 to 5 mol%, more preferably 1 to 5 mol%.
　本発明の封着，被覆用ガラスでは，ＭｇＯ，ＣａＯ，Ｂｉ２Ｏ３の合計含量（モル％）に対するＳｉＯ２の含量（モル％）の比〔ＳｉＯ２／（ＭｇＯ＋ＣａＯ＋Ｂｉ２Ｏ３）〕が１～５であることが好ましい。この比が１未満の場合，得られるガラスの耐酸性が低下するおそれがあるのと，この比が５を超える場合，焼成に過剰な高温を要する程に軟化温度が高くなるおそれがあるからである。耐酸性及び適切な軟化温度の確保を考慮すると，比〔ＳｉＯ２／（ＭｇＯ＋ＣａＯ＋Ｂｉ２Ｏ３）〕は２～４であることがより好ましい。 In the sealing and coating glass of the present invention, the ratio of the content of SiO 2 (mol%) to the total content (mol%) of MgO, CaO, and Bi 2 O 3 [SiO 2 / (MgO + CaO + Bi 2 O 3 )] is 1. It is preferably ~ 5. If this ratio is less than 1, the acid resistance of the obtained glass may decrease, and if this ratio exceeds 5, the softening temperature may become high enough to require an excessively high temperature for firing. be. Considering acid resistance and ensuring an appropriate softening temperature, the ratio [SiO 2 / (MgO + CaO + Bi 2 O 3 )] is more preferably 2 to 4.
　上記成分に加えて，製造時におけるガラスの安定性の向上，結晶化の抑制，熱膨張係数の調整の目的で，Ｌａ２Ｏ３，Ｎｂ２Ｏ５，ＴｅＯ２，ＣｅＯ２，ＴｉＯ２等を合計で５モル％まで加えることができる。 In addition to the above components, La 2 O 3 , Nb 2 O 5 , TeO 2 , CeO 2 , TiO 2, etc. are used for the purpose of improving the stability of glass during manufacturing, suppressing crystallization, and adjusting the coefficient of thermal expansion. A total of up to 5 mol% can be added.
　本発明の封着・被覆用ガラスは，焼成時の熱で電子部品等に悪影響を及ぼすことがないよう９００℃以下で焼成されることが好ましいため，その軟化点は，おおよその目安ではあるが，約６００℃～７５０℃の範囲にあることが好ましく，約６５０℃～７３０℃の範囲にあることがより好ましい。 Since the sealing / coating glass of the present invention is preferably fired at 900 ° C. or lower so that the heat during firing does not adversely affect electronic parts and the like, its softening point is an approximate guideline. , It is preferably in the range of about 600 ° C. to 750 ° C., and more preferably in the range of about 650 ° C. to 730 ° C.
（２）セラミックフィラー
　本発明のガラスからなる粉末には，封着・被覆用材料として使用する際の熱膨張係数の調整及び強度の向上の目的で，必要に応じてセラミックスフィラーを配合することができる。セラミックスフィラーの配合量は，ガラスとの合計量の４０重量％以下で適宜設定することができる。配合するセラミックフィラーの例としては，コーディエライト，ジルコン，リン酸ジルコニウム，チタン酸アルミニウム，ムライト，アルミナ，ウィレマイト，シリカ（α―クォーツ，クリストバライト，トリジマイト）が挙げられる。 (2) Ceramic filler The glass powder of the present invention may be blended with a ceramic filler as necessary for the purpose of adjusting the coefficient of thermal expansion and improving the strength when used as a sealing / coating material. can. The blending amount of the ceramic filler can be appropriately set to be 40% by weight or less of the total amount with the glass. Examples of the ceramic filler to be blended include cordierite, zircon, zirconium phosphate, aluminum titanate, mullite, alumina, willemite, and silica (α-quartz, cristobalite, tridimite).
　本発明の封着・被覆用ガラスは，粉末の形で又はこれとセラミック粉末との混合粉末の形で，封着・被覆用材料として使用することができる。また例えば，これらの粉末に，バインダーや溶剤を更に配合したペーストやシート等のような，封止・被覆対象物の表面に適用するのにより便利な形態の封着・被覆用材料として使用することもできる。 The sealing / covering glass of the present invention can be used as a sealing / covering material in the form of a powder or in the form of a mixed powder of this and ceramic powder. Further, for example, it is used as a sealing / covering material in a form more convenient to be applied to the surface of a sealing / covering object such as a paste or a sheet in which a binder or a solvent is further mixed with these powders. You can also.
　本発明の封着・被覆用ガラスからなる粉末又はこれとセラミックフィラーとの混合粉末をペーストの形態とするには，それらの粉末を溶剤及び有機バインダーの少なくとも１種と混合すればよい。例えば，粉末形態の本発明のガラスからなる粉末，溶剤及び有機バインダーを混合することによってペーストを調製することができる。ペーストの調製に際し，粉末の形態の封着・被覆用ガラスの平均粒径は，特に限定されないが，通常は１～１０μｍとするのが好ましく，２～８μｍとするのがより好ましい。 In order to form the powder made of the sealing / coating glass of the present invention or the mixed powder of this and the ceramic filler in the form of a paste, those powders may be mixed with at least one of a solvent and an organic binder. For example, a paste can be prepared by mixing a powder of the glass of the present invention in powder form, a solvent and an organic binder. When preparing the paste, the average particle size of the sealing / coating glass in the form of powder is not particularly limited, but is usually preferably 1 to 10 μm, and more preferably 2 to 8 μm.
　前記有機バインダーとして何を用いるかについては特に制限されず，封着・被覆用材料の具体的用途に応じて，公知のバインダーの中から適宜採用することができる。例えば，エチルセルロース等のセルロース樹脂が挙げられるが，これらに限定されない。 What is used as the organic binder is not particularly limited, and can be appropriately adopted from known binders according to the specific use of the sealing / coating material. Examples include, but are not limited to, cellulose resins such as ethyl cellulose.
前記溶剤としては，用いる有機バインダーに応じて適宜選択すればよく，例えばエタノール，メタノール，イソプロパノール等のアルコール類；テルピネオール（α－テルピネオール，又はα－テルピネオールを主成分としたβ－テルピネオール及びγ－テルピネオールとの混合物）等の有機溶剤が挙げられるが，これらに限定されない。なお溶剤は，単独で用いてもよく，２種以上を併用してもよい。 The solvent may be appropriately selected depending on the organic binder used, for example, alcohols such as ethanol, methanol and isopropanol; terpineol (α-terpineol, or β-terpineol and γ-terpineol containing α-terpineol as a main component). Organic solvents such as (mixture with), but are not limited to these. The solvent may be used alone or in combination of two or more.
　ペーストの調製においては，上記以外にも，必要に応じて，例えば可塑剤，増粘剤，増感剤，界面活性剤，分散剤等の公知の添加剤を適宜配合することができる。 In the preparation of the paste, in addition to the above, known additives such as a plasticizer, a thickener, a sensitizer, a surfactant, and a dispersant can be appropriately added as needed.
　シートの形態の封着・被覆用材料の製造は，例えば，溶剤，有機バインダー等の添加剤を適宜選択して本発明の封着・被覆用ガラスの粉末又はセラミックフィラーとの混合粉末に添加，混合し，混合物を基材上に塗布し，塗膜を室温又は加熱下に乾燥させればよい。 In the production of the sealing / coating material in the form of a sheet, for example, additives such as a solvent and an organic binder are appropriately selected and added to the sealing / coating glass powder of the present invention or a mixed powder with a ceramic filler. The mixture may be mixed, the mixture may be applied onto the substrate, and the coating may be dried at room temperature or under heating.
　以下，実施例を挙げて本発明を更に詳細に説明するが，本発明がこれらの実施例により限定されることは意図しない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not intended to be limited by these examples.
〔ガラス及びガラス粉末の製造〕
　表１～７の実施例１～４９及び及び表８の比較例１～４に示すガラス組成（成分含量はモル％表示）となるように原料を調合，混合し，該混合物を白金るつぼに入れ，１４００～１５００℃の温度で１時間溶融した後，双ロール法で急冷してガラスフレークを得ると共に，ガラス融液の一部は予め加熱しておいたカーボン板に流し出してガラスブロックを作製した。得られたガラスフレークは，ポットミルを用いて粉砕しガラス粉末とした。また，ガラスブロックは，後述のようにしてＤＴＡ測定装置を用いてガラス粉末について測定されたガラス転移温度より約５０℃高い温度に設定した電気炉に入れて徐冷を行った。 [Manufacturing of glass and glass powder]
The raw materials were prepared and mixed so as to have the glass composition (component content is expressed in mol%) shown in Examples 1 to 49 of Tables 1 to 7 and Comparative Examples 1 to 4 of Table 8, and the mixture was placed in a platinum crucible. After melting at a temperature of 1400 to 1500 ° C. for 1 hour, the glass flakes are obtained by quenching by the twin roll method, and a part of the glass melt is poured onto a preheated carbon plate to prepare a glass block. did. The obtained glass flakes were crushed using a pot mill to obtain glass powder. Further, the glass block was slowly cooled by being placed in an electric furnace set to a temperature about 50 ° C. higher than the glass transition temperature measured for the glass powder using a DTA measuring device as described later.
〔ガラス及びフィラーの混合粉末の調製〕
　表１０の実施例５０～５３に示す割合で，上記実施例からランダムに選択した４通りの実施例のガラス粉末に，セラミックフィラー粉末を同表に示す含量となるように調合し，混合粉末をそれぞれ調製した。 [Preparation of mixed powder of glass and filler]
Ceramic filler powder was mixed with the glass powders of four examples randomly selected from the above examples at the ratios shown in Examples 50 to 53 of Table 10 so as to have the contents shown in the same table, and the mixed powder was prepared. Each was prepared.
〔評価１〕
　実施例１～４９，比較例１～４の各ガラスにつき，ガラス粉末を用いてガラス転移温度，軟化温度，及び結晶化温度を，並びにガラスブロックを用いて熱膨張係数を，次の方法によりそれぞれ測定した。結果は表１～８に示す。 [Evaluation 1]
For each of the glasses of Examples 1 to 49 and Comparative Examples 1 to 4, the glass transition temperature, softening temperature, and crystallization temperature were determined by using glass powder, and the coefficient of thermal expansion was determined by using a glass block by the following methods. It was measured. The results are shown in Tables 1-8.
（１）ガラス転移温度，軟化温度，結晶化温度
　ガラス粉末約６０～８０ｍｇを白金セルに充填し，ＤＴＡ測定装置（リガク社製Ｔｈｅｒｍｏ　Ｐｌｕｓ　ＥＶＯ２　ＴＧ－ＤＴＡ８１２２）を用いて，室温から２０℃／分で昇温させてガラス転移温度（Ｔｇ），軟化温度（Ｔｓ），及び結晶化温度（Ｔｐ）を測定した。 (1) Glass transition temperature, softening temperature, crystallization temperature Approximately 60 to 80 mg of glass powder is filled in a platinum cell, and using a DTA measuring device (Thermo Plus EVO2 TG-DTA8122 manufactured by Rigaku Co., Ltd.), 20 ° C. The temperature was raised in 1 and the glass transition temperature (Tg), softening temperature (Ts), and crystallization temperature (Tp) were measured.
（２）熱膨張係数
　上記のガラスブロックを約５×５×１５ｍｍに切り出し，研磨して測定用のサンプルとした。ＴＭＡ測定装置を用いて，室温から１０℃／分で昇温したときに得られる熱膨張曲線から，５０℃と３００℃の２点に基づく熱膨張係数（α）を求めた。 (2) Coefficient of thermal expansion The above glass block was cut out to a size of about 5 × 5 × 15 mm and polished to prepare a sample for measurement. Using a TMA measuring device, the coefficient of thermal expansion (α) based on two points of 50 ° C. and 300 ° C. was obtained from the thermal expansion curve obtained when the temperature was raised from room temperature at 10 ° C./min.
〔評価２〕
　耐酸性
　実施例３１，３２，及び比較例１～４の各ガラスについて，次の方法により耐酸性を測定した。即ち，上記のガラスブロックを約５×５×１５ｍｍに切り出し，７０％硝酸に浸漬させて室温で２時間静置させた。浸漬前に対する浸漬後のガラスブロックの重量変化の割合（％）を求めた。結果は表９に示す。 [Evaluation 2]
Acid resistance The acid resistance of each of the glasses of Examples 31 and 32 and Comparative Examples 1 to 4 was measured by the following method. That is, the above glass block was cut into a size of about 5 × 5 × 15 mm, immersed in 70% nitric acid, and allowed to stand at room temperature for 2 hours. The rate (%) of the weight change of the glass block after immersion with respect to that before immersion was determined. The results are shown in Table 9.
〔評価３〕
　流動性（９００℃焼成）
　実施例３１，３２，及び比較例１～４の各ガラスについて，次の方法により９００℃で焼成した際の流動性を調べた。即ち，各ガラス粉末約５ｇを内径２０ｍｍの金型に入れ，プレス成形して圧粉体にし，それらを昇温速度２００℃／時間で９００℃まで昇温し，その温度に１時間保持した後，それらの焼成状態を観察した。結果を表９に示す。表面にガラス光沢があり，流動したものを○，表面にガラス光沢がなく，流動性がなかったものを×とした。 [Evaluation 3]
Fluidity (baked at 900 ° C)
The fluidity of each of the glasses of Examples 31 and 32 and Comparative Examples 1 to 4 when fired at 900 ° C. was examined by the following method. That is, about 5 g of each glass powder is placed in a mold having an inner diameter of 20 mm, press-molded into a green compact, heated to 900 ° C. at a heating rate of 200 ° C./hour, and held at that temperature for 1 hour. ， The firing state of them was observed. The results are shown in Table 9. Those having glass gloss on the surface and flowing were marked with ◯, and those having no glass gloss on the surface and having no fluidity were marked with x.
〔評価４〕
　混合粉末の圧粉体の熱膨張係数
　実施例５０～５３に混合粉末約５ｇを内径２０ｍｍの金型に入れ，プレス成形して圧粉体とした。各圧粉体を９００℃で１時間焼成し，得られた焼結体を約５×５×１５ｍｍに切り出し，試験体を作製した。試験体につき，ＴＭＡ測定装置を用いて，室温から１０℃／分で昇温したときに得られる熱膨張曲線から５０℃と３００℃の２点に基づく熱膨張係数（α）を求めた。結果を表１０に示す。 [Evaluation 4]
Thermal expansion coefficient of green compact of mixed powder In Examples 50 to 53, about 5 g of the mixed powder was placed in a mold having an inner diameter of 20 mm and press-molded to obtain a green compact. Each green compact was fired at 900 ° C. for 1 hour, and the obtained sintered body was cut out to about 5 × 5 × 15 mm to prepare a test body. For the test piece, the coefficient of thermal expansion (α) based on two points of 50 ° C. and 300 ° C. was obtained from the thermal expansion curve obtained when the temperature was raised from room temperature to 10 ° C./min using a TMA measuring device. The results are shown in Table 10.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　上記の表に見られるように，実施例１～４９のガラスは，軟化温度が６１５℃～７６７℃の範囲にあるため，何れも９００℃を超えない温度において十分な流動性を持たせた状態での焼成が可能である。また，９００℃未満に結晶化温度を有する実施例１及び３９のガラスは，軟化温度と結晶化温度との差が十分に大きく（差は，それぞれ１８５℃及び２４６℃），結晶化を起こさない温度での焼成が可能であり，残りの実施例のガラスは，何れも結晶化が検出されないか，或いは結晶化温度が９００℃を超えているため，９００℃未満の温度における焼成時に結晶化が起こるおそれはない。また，何れの実施例のガラスも，本発明における好ましい４０～７０×１０－７／℃の範囲内の膨張係数を示している。更に，ＳｉＯ２含量が低い（それぞれ１５．３及び２５．０モル％）比較例１及び２のガラスは，耐酸性試験での重量減少が顕著であるのに比べ，実施例３１及び３２に見られるように本発明のガラスは耐酸性に優れている。また比較例２のガラスは更に，熱膨張係数が７１×１０－７／℃と大きい点でも本発明の目的には適さない。また，比較例３のガラスは，結晶化温度がかなり低い（７７７℃）ことに加えて軟化温度と結晶化温度との差が小さい（差は１６７℃）ため，流動性低下の原因となる実質的な結晶化を抑制しつつ焼成するように温度制御するのが困難であり，比較例４のガラスは，軟化温度と結晶化温度との差が非常に狭い（差は１１８℃）ため，焼成における結晶化の抑制は尚更困難である。 As can be seen in the above table, since the softening temperature of the glasses of Examples 1 to 49 is in the range of 615 ° C. to 767 ° C., all of them are in a state of having sufficient fluidity at a temperature not exceeding 900 ° C. Can be fired in. Further, the glasses of Examples 1 and 39 having a crystallization temperature of less than 900 ° C. have a sufficiently large difference between the softening temperature and the crystallization temperature (the differences are 185 ° C. and 246 ° C., respectively) and do not cause crystallization. It is possible to fire at a temperature, and in the remaining glasses of the examples, crystallization is not detected, or the crystallization temperature exceeds 900 ° C. Therefore, crystallization occurs when firing at a temperature lower than 900 ° C. There is no danger of it happening. In addition, the glass of each example shows an expansion coefficient in the range of 40 to 70 × 10-7 / ° C, which is preferable in the present invention. Further, the glasses of Comparative Examples 1 and 2 having a low SiO 2 content (15.3 and 25.0 mol%, respectively) showed a remarkable weight loss in the acid resistance test, as seen in Examples 31 and 32. As can be seen, the glass of the present invention has excellent acid resistance. Further, the glass of Comparative Example 2 is not suitable for the object of the present invention in that the coefficient of thermal expansion is as large as 71 × 10 -7 / ° C. Further, the glass of Comparative Example 3 has a considerably low crystallization temperature (777 ° C.) and a small difference between the softening temperature and the crystallization temperature (the difference is 167 ° C.), which causes a decrease in fluidity. It is difficult to control the temperature so that the glass is fired while suppressing crystallization, and the glass of Comparative Example 4 has a very narrow difference between the softening temperature and the crystallization temperature (the difference is 118 ° C.), so that the glass is fired. It is even more difficult to suppress crystallization in.
　表１１～１３に示すガラス組成となるように，実施例１～５３と同様にして，実施例５４～６９のガラスを製造し，それぞれ粉末及びガラスブロックを作製し，ガラス転移温度，軟化温度，結晶化温度，及び熱膨張係数を測定した（一部は未測定）。結果は表１１～１３に示す。 The glasses of Examples 54 to 69 were produced in the same manner as in Examples 1 to 53 so that the glass compositions shown in Tables 11 to 13 were obtained, and powders and glass blocks were prepared, respectively. The crystallization temperature and the coefficient of thermal expansion were measured (some have not been measured). The results are shown in Tables 11-13.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
  
Figure JPOXMLDOC01-appb-T000013
  
　表１１～１３に見られる通り，実施例５４～６９のガラスは，実施例１～４９のガラスと同等の結果を示した。 As can be seen in Tables 11 to 13, the glasses of Examples 54 to 69 showed the same results as the glasses of Examples 1 to 49.
　このように，本発明のガラスは，軟化温度，熱膨張係数の点で半導体などの物品の封着に適しており，且つ耐酸性に優れたものとしても提供できるため，広範な種々の電子デバイスや電子部品各部の封着，接着に用いることが可能である。 As described above, the glass of the present invention is suitable for sealing articles such as semiconductors in terms of softening temperature and coefficient of thermal expansion, and can be provided as having excellent acid resistance. Therefore, a wide variety of electronic devices can be provided. It can be used for sealing and bonding of various parts of electronic parts.
　本発明のガラスは，粉末の形態で，単独あるいはセラミックフィラー粉末との混合粉末として，９００℃以下の温度での流動性に優れた封着，被覆用材料として電子デバイスその他の物品の封着・被覆に使用することができる。また，フィラーとガラスが反応する懸念がなく，電子デバイス等の物品に用いられる半導体と熱膨張係数が近く熱応力の問題も生じ難く，封着・被覆部分の機械的強度及び耐久性が高く，更に耐酸性に優れたものしても提供できるから，それらの物品の封着，被覆用材料として有利に使用することが可能である。 The glass of the present invention, in the form of a powder, can be used alone or as a mixed powder with a ceramic filler powder for sealing with excellent fluidity at a temperature of 900 ° C. or lower, and for sealing electronic devices and other articles as a coating material. Can be used for coating. In addition, there is no concern that the filler and glass will react, the coefficient of thermal expansion is close to that of semiconductors used in articles such as electronic devices, and the problem of thermal stress is unlikely to occur. Further, since it can be provided even if it has excellent acid resistance, it can be advantageously used as a material for sealing and coating those articles.

Claims (10)

  1. 　実質的に酸化鉛もアルカリ金属酸化物も含有せず，モル％で，
    ＳｉＯ２　　　 ：　３０～５５％
    Ａｌ２Ｏ３　　　：　１～１７％
    Ｂ２Ｏ３　　　　：　２～２８％
    ＺｎＯ 　　　　：　０～１４％
    ＭｇＯとＣａＯのうち少なくとも１種：　合計５～２５％
    Ｂｉ２Ｏ３　　　：　０～１２％
    を含有し，
    ＳｉＯ２とＢ２Ｏ３の合計含量が５０モル％以上であること，
    を特徴とする，封着・被覆用ガラス。     It contains virtually no lead oxide or alkali metal oxides and is in mol%.
    SiO 2 : 30-55%
    Al 2 O 3 : 1 to 17%
    B 2 O 3 : 2-28%
    ZnO : 0-14%
    At least one of MgO and CaO: 5-25% total
    Bi 2 O 3 : 0-12%
    Contains,
    The total content of SiO 2 and B 2 O 3 is 50 mol% or more.
    A glass for sealing and covering, which is characterized by.
  2. 　実質的に酸化鉛，アルカリ金属酸化物を含有せず，モル％で，
    ＳｉＯ２　　　 ：　３１～５３％
    Ａｌ２Ｏ３　　　：　３～１５％
    Ｂ２Ｏ３　　　　：　４～２４％
    ＺｎＯ 　　　　：　１～１４％
    ＭｇＯとＣａＯのうち少なくとも１種：　合計５～２０％
    Ｂｉ２Ｏ３　　　：　０より大～１１％
    を含有し，
    ＳｉＯ２とＢ２Ｏ３の合計含量が５０モル％以上であること，
    を特徴とする，封着・被覆用ガラス。     It contains virtually no lead oxide or alkali metal oxide, and is in mol%.
    SiO 2 : 31-53%
    Al 2 O 3 : 3 to 15%
    B 2 O 3 : 4-24%
    ZnO: 1 to 14%
    At least one of MgO and CaO: 5-20% total
    Bi 2 O 3 : Greater than 0 to 11%
    Contains,
    The total content of SiO 2 and B 2 O 3 is 50 mol% or more.
    A glass for sealing and covering, which is characterized by.
  3. 　実質的に酸化鉛，アルカリ金属酸化物を含有せず，モル％で，
    ＳｉＯ２　　　 ：　３６～５１％
    Ａｌ２Ｏ３　　　：　５～１５％
    Ｂ２Ｏ３　　　　：　６～２２％
    ＺｎＯ 　　　　：　５～１４％
    ＭｇＯとＣａＯのうち少なくとも１種：　合計５～１８％
    Ｂｉ２Ｏ３　　　：　０．５～１１％
    を含有し，
    ＳｉＯ２とＢ２Ｏ３の合計含量が５０モル％以上であること，
    を特徴とする，封着・被覆用ガラス。     It contains virtually no lead oxide or alkali metal oxide, and is in mol%.
    SiO 2 : 36-51%
    Al 2 O 3 : 5 to 15%
    B 2 O 3 : 6-22%
    ZnO: 5-14%
    At least one of MgO and CaO: 5-18% total
    Bi 2 O 3 : 0.5-11%
    Contains,
    The total content of SiO 2 and B 2 O 3 is 50 mol% or more.
    A glass for sealing and covering, which is characterized by.
  4. 　ＭｇＯを５モル％以上含有する，請求項１～３の何れかの封着・被覆用ガラス。 The sealing / coating glass according to any one of claims 1 to 3, which contains 5 mol% or more of MgO.
  5. 　実質的に酸化鉛，アルカリ金属酸化物を含有せず，モル％で，
    ＳｉＯ２　　　 ：　３３～４３％
    Ａｌ２Ｏ３　　　：　３～１５％
    Ｂ２Ｏ３　　　　：　１３～２８％
    ＺｎＯ 　　　　：　０～１０％未満
    ＭｇＯとＣａＯのうち少なくとも１種：　合計１０～２５％
    Ｂｉ２Ｏ３　　　：　０～５％
    を含有し，
    ＳｉＯ２とＢ２Ｏ３の合計含量が５０モル％以上であること，
    を特徴とする，封着・被覆用ガラス。     It contains virtually no lead oxide or alkali metal oxide, and is in mol%.
    SiO 2 : 33-43%
    Al 2 O 3 : 3 to 15%
    B 2 O 3 : 13-28%
    ZnO: 0 to less than 10% At least one of MgO and CaO: 10 to 25% in total
    Bi 2 O 3 : 0-5%
    Contains,
    The total content of SiO 2 and B 2 O 3 is 50 mol% or more.
    A glass for sealing and covering, which is characterized by.
  6. 　実質的に酸化鉛，アルカリ金属酸化物を含有せず，モル％で，
    ＳｉＯ２　　　 ：　３５～４２％
    Ａｌ２Ｏ３　　　：　８～１５％
    Ｂ２Ｏ３　　　　：　１５～２２％
    ＺｎＯ 　　　　：　３～１０％未満
    ＭｇＯとＣａＯのうち少なくとも１種：　合計１５～２３％
    を含有し，
    Ｂｉ２Ｏ３　　　：　０～１％未満
    ＳｉＯ２とＢ２Ｏ３の合計含量が５０モル％以上であること，
    を特徴とする，封着・被覆用ガラス。     It contains virtually no lead oxide or alkali metal oxide, and is in mol%.
    SiO 2 : 35-42%
    Al 2 O 3 : 8 to 15%
    B 2 O 3 : 15-22%
    ZnO: 3 to less than 10% At least one of MgO and CaO: 15 to 23% in total
    Contains,
    Bi 2 O 3 : 0 to less than 1% The total content of SiO 2 and B 2 O 3 is 50 mol% or more.
    A glass for sealing and covering, which is characterized by.
  7. 　ＭｇＯ，ＣａＯ及びＢｉ２Ｏ３の合計に対するＳｉＯ２のモル比：
    ［ＳｉＯ２／（ＭｇＯ＋ＣａＯ＋Ｂｉ２Ｏ３）］
    が１～６である，請求項１～４の何れかの封着・被覆用ガラス。
          Molar ratio of SiO 2 to the total of MgO, CaO and Bi 2 O 3:
    [SiO 2 / (MgO + CaO + Bi 2 O 3 )]
    The sealing / covering glass according to any one of claims 1 to 4, wherein the number is 1 to 6.
  8. 　粉末の形態である請求項１～７の何れかの封着・被覆用ガラス。 Glass for sealing / coating according to any one of claims 1 to 7 in the form of powder.
  9. 　請求項８の粉末とフィラー粉末とを含んでなる封着・被覆用材料であって，両粉末の合計量に対する該フィラー粉末の含量が４０重量％を超えないものである封着・被覆用材料。 A sealing / coating material comprising the powder of claim 8 and a filler powder, wherein the content of the filler powder does not exceed 40% by weight based on the total amount of both powders. ..
  10. 　請求項９の封着・被覆用材料であって，有機バインダー及び溶剤を含んでなるものである，封着・被覆用ペースト。 A sealing / coating paste according to claim 9, which comprises an organic binder and a solvent.
PCT/JP2021/001458 2020-01-21 2021-01-18 Sealing/coating glass with low thermal expandability WO2021149633A1 (en)

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JPH0297435A (en) * 1988-10-03 1990-04-10 Tdk Corp Glass sealant for high temperature thermistor device
JPH06191885A (en) * 1992-12-22 1994-07-12 Asahi Glass Co Ltd Sealing glass and circuit parts
JPH10139477A (en) * 1996-11-13 1998-05-26 Nippon Electric Glass Co Ltd Highly expandable glass composition
JP2003267750A (en) * 2002-03-15 2003-09-25 Nihon Yamamura Glass Co Ltd Glass composition for coating resistive element
JP2011230973A (en) * 2010-04-30 2011-11-17 Nippon Electric Glass Co Ltd Bismuth-based non-lead glass and composite material
WO2013168521A1 (en) * 2012-05-08 2013-11-14 新電元工業株式会社 Resin-sealed semiconductor device and production method therefor
JP2018002491A (en) * 2016-06-27 2018-01-11 日本電気硝子株式会社 Wavelength conversion member and light-emitting device using the same
JP2018098412A (en) * 2016-12-15 2018-06-21 住友金属鉱山株式会社 Composition for thick film resistor, paste for thick film resistor, thick film resistor and manufacturing methods thereof

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Publication number Priority date Publication date Assignee Title
JP5877750B2 (en) * 2012-03-30 2016-03-08 日本山村硝子株式会社 Alkali-free glass filler

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4691142A (en) * 1984-09-19 1987-09-01 U.S. Philips Corporation Electric lamp and glass composition
JPH0297435A (en) * 1988-10-03 1990-04-10 Tdk Corp Glass sealant for high temperature thermistor device
JPH06191885A (en) * 1992-12-22 1994-07-12 Asahi Glass Co Ltd Sealing glass and circuit parts
JPH10139477A (en) * 1996-11-13 1998-05-26 Nippon Electric Glass Co Ltd Highly expandable glass composition
JP2003267750A (en) * 2002-03-15 2003-09-25 Nihon Yamamura Glass Co Ltd Glass composition for coating resistive element
JP2011230973A (en) * 2010-04-30 2011-11-17 Nippon Electric Glass Co Ltd Bismuth-based non-lead glass and composite material
WO2013168521A1 (en) * 2012-05-08 2013-11-14 新電元工業株式会社 Resin-sealed semiconductor device and production method therefor
JP2018002491A (en) * 2016-06-27 2018-01-11 日本電気硝子株式会社 Wavelength conversion member and light-emitting device using the same
JP2018098412A (en) * 2016-12-15 2018-06-21 住友金属鉱山株式会社 Composition for thick film resistor, paste for thick film resistor, thick film resistor and manufacturing methods thereof

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