JP3079581B2 - Sealing glass - Google Patents
Sealing glassInfo
- Publication number
- JP3079581B2 JP3079581B2 JP02414823A JP41482390A JP3079581B2 JP 3079581 B2 JP3079581 B2 JP 3079581B2 JP 02414823 A JP02414823 A JP 02414823A JP 41482390 A JP41482390 A JP 41482390A JP 3079581 B2 JP3079581 B2 JP 3079581B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- sealing
- temperature
- thermal expansion
- coefficient
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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- Glass Compositions (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、主に気密端子の圧縮封
着に用いられる封着ガラスに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealing glass mainly used for compression sealing of hermetic terminals.
【０００２】[0002]
【従来の技術】気密端子の圧縮封着に用いられる封着ガ
ラスは、通常、以下のようにして作製、使用される。2. Description of the Related Art A sealing glass used for compression sealing of hermetic terminals is usually prepared and used as follows.
【０００３】まずガラス原料を溶融、成形し、その成形
体をボールミルで粉砕した後、所定の篩を通過させるこ
とによって微粉末にし、次いでこの微粉末を水溶性バイ
ンダーと混合して造粒し、顆粒を作製する。その後、こ
の顆粒を打錠成形して金属リード線用の孔を有する所定
形状のタブレットを作製し、これを常温から６５０〜６
６０℃まで昇温させて、バインダーの分解除去と仮焼結
を行う。次にこのタブレットの孔に金属リード線を挿入
し、これを環状の外環金属（通常は、鉄）の封着部に挿
入した後、カーボン治具にセットし、次いで電気炉に入
れ、窒素雰囲気下、ガラスの封着温度で熱処理して封着
する。この結果、膨張差によってガラスが外環金属に圧
縮された状態となる。[0003] First, a glass raw material is melted and molded, the molded body is pulverized by a ball mill, and then finely divided by passing through a predetermined sieve. Then, the fine powder is mixed with a water-soluble binder and granulated. Make granules. Thereafter, the granules are tablet-molded to prepare a tablet having a predetermined shape having a hole for a metal lead wire.
The temperature is raised to 60 ° C., and the binder is decomposed and removed and pre-sintered. Next, a metal lead wire is inserted into the hole of the tablet, and this is inserted into the annular outer ring metal (usually iron) sealing portion. Under an atmosphere, heat treatment is performed at the sealing temperature of the glass for sealing. As a result, the glass is compressed by the outer ring metal due to the difference in expansion.
【０００４】この用途のガラスに要求される特性として
は、（１）外環金属と、金属リード線とを絶縁するた
め、１５０℃で１０11Ω−ｃｍ、３５０℃で１０6.5 Ω
−ｃｍ以上の体積固有抵抗を有すること、（２）高温で
封着すると、カーボン治具や電気炉の炉芯管の劣化が早
く、しかも消費電力が大きくなるため、低い温度で封着
が可能であること、（３）熱膨張係数が小さすぎると、
封着後、ガラスに圧縮歪がかかりすぎて破損する恐れが
あり、一方熱膨張係数が大きすぎると、圧縮歪が不足
し、後工程で気密端子を半田付けする際に外環金属との
間に間隙が生じやすくなるため、０℃から固着温度まで
の温度範囲における熱膨張係数が９５〜１１０×１０-7
／℃であること、（４）粉末状にして、これを水溶性バ
インダーと混合した後、品質が低下しないように、アル
カリ溶出量が０．８ｍｇ以下であること等が挙げられ、
従来よりこの用途のガラスとしては、Ｎａ2 Ｏ−ＢａＯ
−ＳｉＯ2 系の封着ガラスが用いられている。[0004] The properties required of the glass for this application are as follows: (1) To insulate the outer ring metal from the metal lead wire, 10 11 Ω-cm at 150 ° C and 10 6.5 Ω at 350 ° C.
(2) When sealed at high temperature, carbon jigs and furnace core tubes of electric furnaces deteriorate quickly and consume more power, so sealing can be performed at lower temperatures. (3) If the coefficient of thermal expansion is too small,
After sealing, the glass may be damaged due to excessive compressive strain, while if the coefficient of thermal expansion is too large, the compressive strain will be insufficient and the outer ring metal will be soldered when soldering the hermetic terminal in a later process. Since a gap is likely to be formed, the coefficient of thermal expansion in the temperature range from 0 ° C. to the fixing temperature is 95 to 110 × 10 −7.
/ 4 ° C., and (4) after powdering and mixing this with a water-soluble binder, the alkali elution amount is 0.8 mg or less so that the quality is not deteriorated.
Conventionally, as glass for this use, Na 2 O—BaO
-SiO 2 system sealing glass is used.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら従来の封
着ガラスの場合、体積固有抵抗、熱膨張係数、アルカリ
溶出量については、比較的良好な特性値を示すが、封着
温度が９８０〜１０５０℃と高いため、省資源、省エネ
ルギーの面から好ましくなかった。However, in the case of the conventional sealing glass, the volume resistivity, the coefficient of thermal expansion, and the alkali elution amount show relatively good characteristic values, but the sealing temperature is 980 to 1050 ° C. Therefore, it was not preferable in terms of resource saving and energy saving.
【０００６】本発明の目的は、上記した要求特性の全て
を満足し、特に８８０℃以下の低い温度で封着すること
が可能な封着ガラスを提供することである。An object of the present invention is to provide a sealing glass which satisfies all of the above-mentioned required characteristics and which can be sealed at a low temperature of 880 ° C. or less.
【０００７】[0007]
【課題を解決するための手段】本発明の封着ガラスは、
重量百分率で、ＳｉＯ2 ５５．０〜６５．０％、Ａｌ
2 Ｏ3 ２．０〜５．０％、Ｂ2 Ｏ3 １０．５〜１
５．０％、ＣａＯ＋ＢａＯ ７．０〜１２．０％、Ｌｉ
2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏ １０．０〜１８．０％、Ｔｉ
Ｏ2 ０．５〜７．０％、Ｆ2 ０〜２．５からなるこ
とを特徴とする。Means for Solving the Problems The sealing glass of the present invention comprises:
In weight percent, SiO 2 55.0~65.0%, Al
2 O 3 2.0 to 5.0%, B 2 O 3 10.5 to 1
5.0%, CaO + BaO 7.0-12.0%, Li
2 O + Na 2 O + K 2 O 10.0~18.0%, Ti
O 2 0.5 to 7.0%, F 2 0 to 2.5.
【０００８】[0008]
【作用】本発明の封着ガラスの構成成分の作用及びその
含有量の限定理由は、以下のとおりである。The effects of the constituents of the sealing glass of the present invention and the reasons for limiting the content thereof are as follows.
【０００９】ＳｉＯ2 は、ガラス骨格を形成するための
主成分であり、その含有量は、５５．０〜６５．０％で
ある。５５．０％より少ないと、熱膨張係数が大きくな
りすぎると共にアルカリ溶出量が多くなり、一方６５．
０％より多いと、封着温度が高くなる。[0009] SiO 2 is a main component for forming a glass skeleton, and its content is 55.0 to 65.0%. If it is less than 55.0%, the coefficient of thermal expansion becomes too large and the amount of alkali elution increases, while 65.
If it is more than 0%, the sealing temperature becomes high.
【００１０】Ａｌ2 Ｏ3 は、化学的耐久性を向上する成
分であり、その含有量は、２．０〜５．０％である。
２．０％より少ないと、アルカリ溶出量が多くなり、一
方５．０％より多いと、封着温度が高くなる。[0010] Al 2 O 3 is a component for improving the chemical durability, and its content is 2.0 to 5.0%.
If it is less than 2.0%, the amount of alkali elution increases, while if it is more than 5.0%, the sealing temperature increases.
【００１１】Ｂ2 Ｏ3 は、ガラスの粘度を低下して、溶
融性を良くすると共に封着温度を低下する成分であり、
その含有量は、１０．５〜１５．０％である。１０．５
％より少ないと、上記効果が得られず、一方１５．０％
より多いと、アルカリ溶出量が多くなる。B 2 O 3 is a component that lowers the viscosity of the glass, improves the meltability, and lowers the sealing temperature.
Its content is from 10.5 to 15.0%. 10.5
%, The above effect cannot be obtained, while 15.0%
If it is larger, the alkali elution amount increases.
【００１２】ＣａＯ及びＢａＯは、高温の粘性を低下
し、熱膨張係数を調整する成分であり、その含有量は、
合量で７．０〜１２．０％である。７．０％より少ない
と、封着温度が高くなり、一方１２．０％より多いと、
熱膨張係数が大きくなりすぎる。CaO and BaO are components that reduce the viscosity at high temperatures and adjust the coefficient of thermal expansion.
The total amount is 7.0 to 12.0%. If it is less than 7.0%, the sealing temperature will be high, while if it is more than 12.0%,
Thermal expansion coefficient is too large.
【００１３】アルカリ金属酸化物であるＬｉ2 Ｏ、Ｎａ
2 Ｏ及びＫ2 Ｏの各成分は、封着温度を低下すると共に
熱膨張係数を調整する成分であり、その含有量は、合量
で１０．０〜１８．０％である。１０．０％より少ない
と、上記効果が得られ難くなり、一方１８．０％より多
いと、アルカリ溶出量が多くなると共に体積固有抵抗が
低くなる。Li 2 O, Na which is an alkali metal oxide
Each component of 2 O and K 2 O is a component that lowers the sealing temperature and adjusts the coefficient of thermal expansion, and the total content thereof is 10.0 to 18.0%. If it is less than 10.0%, it is difficult to obtain the above effects, while if it is more than 18.0%, the alkali elution amount increases and the volume resistivity decreases.
【００１４】これらのアルカリ金属酸化物はの作用は、
Ｌｉ2 Ｏ〉Ｎａ2 Ｏ〉Ｋ2 Ｏの順に大きく、好ましく
は、Ｌｉ2Ｏ １．０〜３．０％、Ｎａ2 Ｏ ２．０〜
８．０％、Ｋ2Ｏ ４．０〜１０．０％となるように各
成分を調整する。The action of these alkali metal oxides is
Li 2 O> Na 2 O> K 2 O increases in the order of, preferably, Li 2 O 1.0~3.0%, Na 2 O 2.0~
8.0%, to adjust the components for the K 2 O 4.0~10.0%.
【００１５】ＴｉＯ2 は、アルカリ溶出量を少なくする
成分であり、その含有量は、０．５〜７．０％である。
０．５％より少ないと、上記効果が得られず、一方７．
０％より多いと、封着温度が高くなる。TiO 2 is a component that reduces the alkali elution amount, and its content is 0.5 to 7.0%.
If it is less than 0.5%, the above effects cannot be obtained, while 7.
If it is more than 0%, the sealing temperature becomes high.
【００１６】Ｆ2 は、ガラスの融剤として使用されると
共に封着温度を低下する成分であるが、２．０％より多
いと、ガラスが分相しやすくなって安定生産が困難にな
る。F 2 is used as a flux for glass and is a component that lowers the sealing temperature. However, if it is more than 2.0%, the glass is likely to separate phases, making stable production difficult.
【００１７】尚、ＺｒＯ2 は、アルカリ溶出量を少なく
する効果が大であるが、封着温度を高くするため、本発
明においては含有しないほうが好ましい。Although ZrO 2 has a great effect of reducing the alkali elution amount, it is preferably not contained in the present invention in order to increase the sealing temperature.
【００１８】[0018]
【実施例】以下、本発明の封着ガラスを実施例に基づい
て詳細に説明する。EXAMPLES Hereinafter, the sealing glass of the present invention will be described in detail based on examples.
【００１９】表１は、本発明の実施例（試料Ｎｏ．１〜
３）及び比較例（試料Ｎｏ．４〜７）を各々示すもので
ある。Table 1 shows examples of the present invention (samples No. 1 to No. 1).
3) and Comparative Examples (Sample Nos. 4 to 7) are shown respectively.
【００２０】[0020]
【表１】 [Table 1]
【００２１】表に示した各試料は、表の酸化物組成にな
るように原料を調合し、白金ルツボに入れ、１４５０℃
で４時間溶融した後、カーボン板上に流し出すことによ
って作製した。For each sample shown in the table, raw materials were prepared so as to have the oxide composition shown in the table, put in a platinum crucible, and placed at 1450 ° C.
For 4 hours, and then poured out onto a carbon plate.
【００２２】表から明らかなように、本発明の実施例で
あるＮｏ．１〜３の各試料は、封着温度が８７７℃以
下、０℃から固着温度までの温度範囲における熱膨張係
数が９９〜１０９×１０-7／℃、アルカリ溶出量が０．
６９ｍｇ以下、体積固有抵抗が１５０℃で１０12.0Ω−
ｃｍ以上、３５０℃で１０7.0 Ω−ｃｍ以上であり、い
ずれも良好な値を示した。As can be seen from the table, No. 1 which is an embodiment of the present invention. Each of the samples 1 to 3 has a sealing temperature of 877 ° C. or lower, a coefficient of thermal expansion in the temperature range from 0 ° C. to the fixing temperature of 99 to 109 × 10 −7 / ° C., and an alkali elution amount of 0.
69 mg or less, volume resistivity is 10 12.0 Ω- at 150 ° C
cm or more and 10 7.0 Ω-cm or more at 350 ° C., all showing good values.
【００２３】それに対し、比較例であるＮｏ．４の試料
は、Ｂ2 Ｏ3 が少ないため、またＮｏ．６の試料は、Ｚ
ｒＯ2 を含有するため、封着温度が高く、Ｎｏ．５の試
料は、ＴｉＯ2 が少ないため、アルカリ溶出量が多く、
さらにＮｏ．７の試料は、アルカリ金属酸化物が多いた
め、アルカリ溶出量が多いと共に、体積固有抵抗が低か
った。On the other hand, the comparative example No. The sample of No. 4 has a small amount of B 2 O 3 , and Sample No. 6 is Z
Since rO 2 is contained, the sealing temperature is high. The sample No. 5 has a small amount of TiO 2 , so the amount of alkali elution is large,
In addition, No. The sample No. 7 contained a large amount of alkali metal oxides, so that the alkali elution amount was large and the volume resistivity was low.
【００２４】尚、表中の封着温度は、カーボン板上に流
し出した板状ガラスを粗砕し、これをアルミナルツボ中
で溶融し、白金引き上げ法によって１０4 ポアズに相当
する温度を測定し、また熱膨張係数は、上記板状ガラス
を直径約４ｍｍ、長さ約４５ｍｍの棒状に加工し、押棒
式熱膨張測定装置を用いて測定したものであり、熱膨張
係数を測定するために使用した固着温度は、ガラスの転
移点と屈伏点との中間の温度と規程した。The sealing temperature in the table is determined by measuring the temperature equivalent to 10 4 poise by a platinum pulling method by crushing a sheet glass poured onto a carbon plate, melting the glass in an alumina crucible. The coefficient of thermal expansion is obtained by processing the sheet glass into a rod having a diameter of about 4 mm and a length of about 45 mm, and measuring the same using a push-bar type thermal expansion measuring device. The fixing temperature used was defined as a temperature intermediate between the glass transition point and the yield point.
【００２５】アルカリ溶出量は、上記板状ガラスを粉砕
し、ＪＩＳ Ｒ−３５０２に基づいて測定し、さらに体
積固有抵抗は、上記板状ガラスを直径約３５ｍｍ、厚さ
約２ｍｍの円板状に研磨成形し、その上面に直径１８ｍ
ｍの主電極と内径２０ｍｍのガード電極を、また下面に
直径３０ｍｍの下電極を印刷によって形成し、メガオー
ムメーターを用いて１５０℃と３５０℃における値を測
定したものである。The alkali elution amount is measured according to JIS R-3502 by pulverizing the above-mentioned glass sheet. Further, the volume resistivity is obtained by measuring the above-mentioned glass sheet into a disk having a diameter of about 35 mm and a thickness of about 2 mm. Polished and formed on the upper surface with a diameter of 18m
A main electrode having a diameter of m and a guard electrode having an inner diameter of 20 mm, and a lower electrode having a diameter of 30 mm were formed on the lower surface by printing, and values at 150 ° C. and 350 ° C. were measured using a megohmmeter.
【００２６】[0026]
【発明の効果】以上のように、本発明の封着ガラスは、
封着温度が８８０℃以下と低く、外環金属によって適度
に圧縮されるような熱膨張係数を有し、アルカリ溶出量
が少なく、しかも体積固有抵抗が大きいため、気密端子
の封着ガラスに要求される特性を全て満足しており、特
に封着温度が非常に低いため、省資源、省エネルギーを
計ることが可能である。As described above, the sealing glass of the present invention
Since the sealing temperature is as low as 880 ° C or less, it has a thermal expansion coefficient that allows it to be appropriately compressed by the outer ring metal, has a small amount of alkali elution, and has a large volume specific resistance. Since all of the required characteristics are satisfied, and particularly the sealing temperature is very low, it is possible to save resources and energy.
Claims (1)
５．０％、Ａｌ2 Ｏ3 ２．０〜５．０％、Ｂ2 Ｏ3
１０．５〜１５．０％、ＣａＯ＋ＢａＯ ７．０〜１
２．０％、Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏ １０．０〜１
８．０％、ＴｉＯ2 ０．５〜７．０％、Ｆ2 ０〜
２．５％からなることを特徴とする封着ガラス。2. The method of claim 1, wherein the weight percentage of SiO 2 is 55.0-6.
5.0%, Al 2 O 3 2.0~5.0 %, B 2 O 3
10.5-15.0%, CaO + BaO 7.0-1
2.0%, Li 2 O + Na 2 O + K 2 O 10.0~1
8.0%, TiO 2 0.5-7.0%, F 20 0
Sealing glass comprising 2.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02414823A JP3079581B2 (en) | 1990-12-26 | 1990-12-26 | Sealing glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02414823A JP3079581B2 (en) | 1990-12-26 | 1990-12-26 | Sealing glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04228454A JPH04228454A (en) | 1992-08-18 |
| JP3079581B2 true JP3079581B2 (en) | 2000-08-21 |
Family
ID=18523262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02414823A Expired - Fee Related JP3079581B2 (en) | 1990-12-26 | 1990-12-26 | Sealing glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3079581B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113666766B (en) * | 2021-09-14 | 2022-11-22 | 长春工业大学 | Method for connecting zirconia ceramics by glass solder infiltration |
-
1990
- 1990-12-26 JP JP02414823A patent/JP3079581B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04228454A (en) | 1992-08-18 |
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