JPH0717404B2 - Composition for sealing - Google Patents
Composition for sealingInfo
- Publication number
- JPH0717404B2 JPH0717404B2 JP61101060A JP10106086A JPH0717404B2 JP H0717404 B2 JPH0717404 B2 JP H0717404B2 JP 61101060 A JP61101060 A JP 61101060A JP 10106086 A JP10106086 A JP 10106086A JP H0717404 B2 JPH0717404 B2 JP H0717404B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- glass powder
- sealing
- composition
- parts
- 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 - Lifetime
Links
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、封着用組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a composition for sealing.
［従来の技術］ PbO-B2O3-ZnO系低融点ガラス粉末は、CRTの気密封止あ
るいはアルミナ製ICパッケージシール用として使用さ
れ、その際該ガラス粉末は有機バインダーとの混合し、
スラリー法あるいは印刷法等により塗布形成され焼成さ
れる。ここで、通常有機バインダーはアクリル樹脂、ニ
トロセルロース、エチルセルロース等をブチルカルビト
ールアセテート、酢酸イソアミルあるいはα−テルピネ
オール等の溶剤に溶かして用いる。[Prior Art] PbO-B 2 O 3 -ZnO-based low-melting glass powder is used for hermetic sealing of CRT or alumina IC package seal, in which the glass powder is mixed with an organic binder,
It is applied and formed by a slurry method or a printing method, and then baked. Here, the organic binder is usually used by dissolving acrylic resin, nitrocellulose, ethyl cellulose or the like in a solvent such as butyl carbitol acetate, isoamyl acetate or α-terpineol.
しかしながら、この有機バインダーの空気中における分
解温度は350℃〜500℃前後であり、低融点ガラス粉末の
軟化点は340〜480℃と同等であるため、焼成の際未分解
有機物の存在下でガラスの軟化が生じ、ガラスと反応し
発泡したり、黒化したり、濡れ性あるいは電気特性の低
下を生ずるという問題点があった。However, the decomposition temperature of this organic binder in air is around 350 ° C to 500 ° C, and the softening point of the low melting point glass powder is equivalent to 340 ° C to 480 ° C. However, there is a problem in that it softens and reacts with glass to cause foaming, blackening, and deterioration of wettability or electrical characteristics.
さらに、アルミナ製のICパッケージのシールの如く電極
材等に使用される金属と同時に焼成する場合には、その
材料の酸化防止上、酸素濃度をより低く、（例えば100p
pm以下：O2濃度）する必要があり、その場合には有機バ
インダーの除去は一層困難となっている。Furthermore, when firing at the same time as the metal used for the electrode material such as the seal of the IC package made of alumina, in order to prevent the oxidation of the material, lower the oxygen concentration (for example, 100p
pm or less: O 2 concentration), and in that case, removal of the organic binder becomes more difficult.
［発明が解決しようとする問題点］ 本発明は、空気中は勿論のこと低酸素濃度においても低
温度で焼成することにより前述の問題点を生じない封着
用組成物の提供を目的とする。[Problems to be Solved by the Invention] An object of the present invention is to provide a sealing composition which does not cause the above-mentioned problems by firing at a low temperature not only in the air but also at a low oxygen concentration.
［問題点を解決するための手段］ 本発明は、重量％で低融点ガラス粉末60〜100％と耐火
物フィラー０〜40％とからなる無機成分100重量部に対
し、酸化剤としてMnO2を0.05〜５重量部添加してなる封
着用組成物であって、低融点ガラス粉末は重量％表示で
実質的に、PbO 65〜85、B2O3 5〜13、ZnO 1〜13、SiO2
0.3〜３、Al2O3 0〜５、BaO＋CaO＋MgO 0〜10、CuO 0〜
２、からなる封着用組成物を提供する。[Means for solving the problems] The present invention is, relative to the inorganic component 100 parts by weight consisting of 60 to 100% and 0-40% refractory filler low-melting glass powder in wt%, the MnO 2 as oxidant A sealing composition comprising 0.05 to 5 parts by weight, wherein the low melting point glass powder is substantially expressed in terms of% by weight, PbO 65 to 85, B 2 O 3 5 to 13, ZnO 1 to 13, SiO 2
0.3-3, Al 2 O 3 0-5, BaO + CaO + MgO 0-10, CuO 0-
A sealing composition comprising 2.
本発明において、低融点ガラス粉末と耐火物フィラーと
からなる無機成分100重量部に対し、酸化剤としてMnO2
を添加する、その添加量が0.05重量部未満では添加によ
る効果が少なく、他方５重量部を越えると低融点ガラス
粉末の基本的特性（軟化点、結晶化特性等）が変化す
る。酸化剤の添加量は、上記範囲中0.1〜３重量部の範
囲がより望ましい。In the present invention, with respect to 100 parts by weight of an inorganic component consisting of a low melting point glass powder and a refractory filler, MnO 2 as an oxidizing agent
If the addition amount is less than 0.05 parts by weight, the effect due to the addition is small, while if it exceeds 5 parts by weight, the basic characteristics (softening point, crystallization characteristics, etc.) of the low melting point glass powder change. The addition amount of the oxidizing agent is more preferably 0.1 to 3 parts by weight in the above range.
本発明においては、上記酸化剤を除く無機成分が重量％
表示で低融点ガラス粉末60〜100％と耐火物フィラー０
〜40％とからなる。低融点ガラス粉末が60％未満では気
密性が損なわれたり接着強度が低下するので目的とする
封着を行なうことは難しい。一方耐火物フィラーは必須
成分ではないが、添加することにより、封着部目体の強
度を向上したり、熱膨張係を調整することができる。か
ゝる耐火物フィラーとしては、ジルコンコージェライ
ト、α−アルミナ、α−石英等が使用される。In the present invention, the inorganic components other than the above-mentioned oxidizer are% by weight.
Shows low melting glass powder 60-100% and refractory filler 0
It consists of ~ 40%. If the low melting point glass powder is less than 60%, the hermeticity is impaired and the adhesive strength is lowered, so that it is difficult to carry out the intended sealing. On the other hand, the refractory filler is not an essential component, but the addition of the refractory filler can improve the strength of the sealing body and adjust the coefficient of thermal expansion. As such a refractory filler, zircon cordierite, α-alumina, α-quartz or the like is used.
一方、上記低融点ガラス粉末としては重量％表示で実質
的に PbO 65〜85 B2O3 ５〜13 ZnO １〜13 SiO2 0.3〜3 Al2O3 ０〜5 BaO＋CaO＋NgO ０〜10 CuO ０〜2 からなる組成のものである。その理由は次の通りであ
る。On the other hand, as the low melting point glass powder, it is substantially expressed in weight% PbO 65 to 85 B 2 O 35 to 13 ZnO 1 to 13 SiO 2 0.3 to 3 Al 2 O 3 0 to 5 BaO + CaO + NgO 0 to 10 CuO 0 It has a composition of 2. The reason is as follows.
PbO:65％未満では、ガラス軟化温度が高くなり過ぎ所望
の400〜450℃で到着できない。一方85％より多いとガラ
スの化学的耐久性が著しく低下する。望ましくは68〜82
wt％。If the PbO content is less than 65%, the glass softening temperature becomes too high to reach the desired temperature of 400 to 450 ° C. On the other hand, if it is more than 85%, the chemical durability of glass is remarkably reduced. Preferably 68-82
wt%.
B2O3:5％未満では軟化温度が高くなる過ぎる。一方13％
より多いとガラスの化学的耐久性が低下する。望ましく
は７〜11wt％。B 2 O 3: too higher softening temperature is less than 5%. Meanwhile, 13%
If it is more, the chemical durability of the glass will be reduced. Desirably 7-11 wt%.
ZnO:1％未満では結晶化特性が発現されない。一方13％
より多いと逆にガラス溶融過程で矢透する。望ましくは
２〜12wt％。If the ZnO content is less than 1%, no crystallization property is exhibited. Meanwhile, 13%
On the contrary, when the amount is larger, the glass is transparent in the melting process. Desirably 2 to 12 wt%.
SiO2:0.3％未満ではガラスの結晶化が速くなり過ぎ、緻
密な焼結層が得られない。一方３％より多いとガラスの
軟化温度が高くなり過ぎる。望ましく0.5〜2.8wt％。If the SiO 2 content is less than 0.3%, the crystallization of the glass will be too fast and a dense sintered layer cannot be obtained. On the other hand, if it exceeds 3%, the softening temperature of the glass becomes too high. Desirably 0.5 to 2.8 wt%.
Al2O3：必須成分ではないが、化学的耐久性向上用とし
て、５％まで導入可能。Al 2 O 3 : Not an essential component, but can be introduced up to 5% for improving chemical durability.
BaO,CaO,MgO:必須成分ではないが、Al2O3同様化学的耐
久性および結晶化速度調整用として使用する。その量は
10％までが限度。BaO, CaO, MgO: Although not an essential component, they are used for chemical durability and crystallization rate adjustment like Al 2 O 3 . The amount is
The limit is 10%.
CuO:必須成分ではないが、ガラスとの反応性up、結晶化
特性の調整用として使用する。２％までが限度。CuO: Although not an essential component, it is used to increase the reactivity with glass and adjust the crystallization characteristics. The limit is 2%.
使用に当っては、本発明の組成物は上記成分に有機バイ
ンダーを添加し、使用し易い粘度に調整される。この有
機バインダーとしては特に限定されず、例えばアクリル
樹脂、ニトロセルロース、エチルセルロースをブチルカ
ルビトールアセテートあるいはα−テルピネオールに溶
解したものが使用される。In use, the composition of the present invention is prepared by adding an organic binder to the above components and adjusting the viscosity so that it can be easily used. The organic binder is not particularly limited, and for example, an acrylic resin, nitrocellulose, ethyl cellulose dissolved in butyl carbitol acetate or α-terpineol is used.
［実施例］ 重量％表示でPbO 75,ZnO 11.5,B2O3 9.5,SiO2 2,BaO 2
からなる低融点ガラス粉末と耐火物フィラーと通常使用
されているニトロセルロース、ブチルカルビノールアセ
テート系のビヒクルと酸化剤とを所定割合によるよう調
合した。次いでこれを、ライカイ機及び３本ローラーに
より十分混練しスクリーン印刷用のペーストを得た。表
−１に耐火物フィラー、酸化剤及びこれらを低融点ガラ
ス粉末との混合割合を示す。表中低融点ガラス粉末と耐
火物フィラーとの数値はそれぞれの重量％を示し、酸化
剤の数値は低融点ガラス粉末と耐火物フィラーとの総量
100重量部に対する重量部である。[Example] PbO 75, ZnO 11.5, B 2 O 3 9.5, SiO 2 2, BaO 2 in weight%
A low-melting-point glass powder, a refractory filler, and a commonly used nitrocellulose or butylcarbinol acetate-based vehicle and an oxidizer were mixed at a predetermined ratio. Then, this was sufficiently kneaded with a liquor machine and three rollers to obtain a paste for screen printing. Table 1 shows the refractory filler, the oxidizer, and the mixing ratio of these with the low-melting glass powder. In the table, the numerical values of the low-melting glass powder and the refractory filler show the respective weight%, and the numerical values of the oxidizer are the total amount of the low-melting glass powder and the refractory filler.
This is parts by weight with respect to 100 parts by weight.
次いでこれらペーストを用い、200メッシュ、総厚105μ
ｍのスクリーンを用い印刷し、150℃、30分乾燥後450℃
１時間の焼成を行なった。焼成雰囲気中の酸素濃度は30
0℃まで20％、300℃以上および冷却工程での酸素濃度は
70ppmと酸素濃度を二段切り換えを施した。印刷層の厚
みは、乾燥時点で200±20μｍであった。Next, using these pastes, 200 mesh, total thickness 105μ
m screen, print at 150 ℃, dry for 30 minutes, then 450 ℃
Firing was performed for 1 hour. Oxygen concentration in the firing atmosphere is 30
20% up to 0 ℃, over 300 ℃ and oxygen concentration in the cooling process
The oxygen concentration was switched between 70 ppm and two levels. The thickness of the printed layer was 200 ± 20 μm when dried.
表−１より明らかな如く、本発明による組成物は、電気
特性に優れ、且つ黒化は大巾に低減できる良好なもので
ある。比較例としてMnO2以外の酸化剤を添加したものに
ついても同様なテストを行なったので併せて表−１に示
す。なお各特性の評価方法は次のとおりである。As is clear from Table 1, the composition according to the present invention is excellent in electrical characteristics and can significantly reduce blackening. As a comparative example, the same test was performed for those to which an oxidant other than MnO 2 was added, and the results are also shown in Table 1. The evaluation method of each characteristic is as follows.
［特性評価法］ ・体積抵抗率 タケダ理研製振動容量型微微小電流電
位計により、100VDC印加時の体積抵抗を測定した。[Characteristics evaluation method] -Volume resistivity The volume resistance when applying 100VDC was measured by a Takeda Riken vibration capacitance type micro current electrometer.
なお、評価基準として、log10ρν値が、13.0以上であ
ることが電気的寿命特性上要求される。In addition, as an evaluation criterion, a log 10 ρν value of 13.0 or more is required in terms of electrical life characteristics.
・黒化の度合 焼成体の色調を目視判定し、黒色、グ
レー色、白（乳白）色の３段階に分類し評価した。 -Degree of blackening The color tone of the fired product was visually evaluated and classified into 3 grades of black, gray and white (milky white) for evaluation.
［発明の効果］ 本発明によれば、低温度で焼成しても黒化を防止・抑制
し電気特性に優れた焼成体を形成することができる。特
に極めて酸素濃度の低い雰囲気中でも上記特性の焼成体
を形成できるので、電極等酸化され易い金属の封着等に
好適である。[Effects of the Invention] According to the present invention, it is possible to prevent or suppress blackening even when fired at a low temperature and form a fired body having excellent electrical characteristics. In particular, since a fired body having the above characteristics can be formed even in an atmosphere having an extremely low oxygen concentration, it is suitable for sealing metal such as electrodes that is easily oxidized.
Claims (1)
火物フィラー０〜40％とからなる無機成分100重量部に
対し、酸化剤としてMnO2を0.05〜５重量部添加してなる
封着用組成物であって、低融点ガラス粉末は重量％表示
で実質的に、PbO 65〜85、B2O3 5〜13、ZnO 1〜13、SiO
2 0.3〜３、Al2O3 0〜５、BaO＋CaO＋MgO 0〜10、CuO 0
〜２、からなる封着用組成物。1. MnO 2 as an oxidizer is added in an amount of 0.05 to 5 parts by weight to 100 parts by weight of an inorganic component consisting of 60 to 100% low melting point glass powder and 0 to 40% refractory filler. A composition for sealing, wherein the low melting point glass powder is substantially expressed as a weight percentage, PbO 65-85, B 2 O 3 5-13, ZnO 1-13, SiO 2.
2 0.3-3, Al 2 O 3 0-5, BaO + CaO + MgO 0-10, CuO 0
A sealing composition comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61101060A JPH0717404B2 (en) | 1986-05-02 | 1986-05-02 | Composition for sealing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61101060A JPH0717404B2 (en) | 1986-05-02 | 1986-05-02 | Composition for sealing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62260733A JPS62260733A (en) | 1987-11-13 |
| JPH0717404B2 true JPH0717404B2 (en) | 1995-03-01 |
Family
ID=14290569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61101060A Expired - Lifetime JPH0717404B2 (en) | 1986-05-02 | 1986-05-02 | Composition for sealing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0717404B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2002042232A1 (en) | 2000-11-22 | 2004-03-25 | 旭硝子株式会社 | Color cathode ray tube and glass frit for color cathode ray tube |
| DE102005044523A1 (en) * | 2005-09-16 | 2007-03-29 | Schott Ag | Connecting elements using a glass solder used in the manufacture of electronic components comprises soldering the elements together by fusing a glass solder and releasing the oxidant locally during soldering |
| CN104556680A (en) * | 2014-12-31 | 2015-04-29 | 贵州省轻工业科学研究所 | Glass for tailless sealing of stainless steel vacuum insulation container and preparation method for glass |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60221358A (en) * | 1984-04-13 | 1985-11-06 | 日本碍子株式会社 | Ceramic composition for electric insulator |
| JPS6140868A (en) * | 1984-07-31 | 1986-02-27 | 昭和電工株式会社 | Manufacture of sintered body |
| JPS6140867A (en) * | 1984-07-31 | 1986-02-27 | 昭和電工株式会社 | Readily sinterable composition |
| JPS628404A (en) * | 1985-07-03 | 1987-01-16 | 昭栄化学工業株式会社 | Insulating paste |
| JPH0740633B2 (en) * | 1985-12-12 | 1995-05-01 | 旭硝子株式会社 | Insulating layer composition |
-
1986
- 1986-05-02 JP JP61101060A patent/JPH0717404B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62260733A (en) | 1987-11-13 |
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