JP2705503B2 - Sealing glass - Google Patents
Sealing glassInfo
- Publication number
- JP2705503B2 JP2705503B2 JP5042935A JP4293593A JP2705503B2 JP 2705503 B2 JP2705503 B2 JP 2705503B2 JP 5042935 A JP5042935 A JP 5042935A JP 4293593 A JP4293593 A JP 4293593A JP 2705503 B2 JP2705503 B2 JP 2705503B2
- Authority
- JP
- Japan
- Prior art keywords
- pbo
- glass
- tio
- sealing
- sealing glass
- 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
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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、低融点ガラスと、熱膨
張率を調整するために添加するチタン酸鉛からなる封着
ガラスに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealing glass comprising low-melting glass and lead titanate added for adjusting the coefficient of thermal expansion.
【０００２】[0002]
【従来の技術】一般に蛍光表示管の組立てにおいてガラ
ス基板とガラスの容器部を封着するには、ＰｂＯを主成
分とする低融点ガラス粉末が使用されている。しかし低
融点ガラスの熱膨張率は１１０×１０-7／℃前後であ
り、ガラス基板の９０×１０-7／℃前後に較べて大き
く、封着時にクラックが発生してしまう。その防止策と
して、特公昭６３−１９４５６号公報で開示されている
ように、低融点ガラス粉末にフィラーとしてチタン酸鉛
を添加すれば、熱膨張率が小さくなると共に、粘性流動
が確保されて粘度が上がらない性質を持たせることがで
きる。即ち、熱膨張率の小さいチタン酸鉛（−１０〜１
５×１０-7／℃）を３０〜４０ｗｔ％加えることによ
り、低融点ガラスの熱膨張率をガラス基板の熱膨張率に
近づけることができる。2. Description of the Related Art Generally, in assembling a fluorescent display tube, a low melting point glass powder containing PbO as a main component is used for sealing a glass substrate and a glass container. However, the thermal expansion coefficient of the low-melting glass is about 110 × 10 −7 / ° C., which is larger than that of the glass substrate of about 90 × 10 −7 / ° C., and cracks occur during sealing. As a preventive measure, as disclosed in JP-B-63-19456, if lead titanate is added as a filler to a low-melting glass powder, the coefficient of thermal expansion is reduced and the viscous flow is ensured. However, it is possible to have a property that does not rise. That is, lead titanate having a small coefficient of thermal expansion (−10 to 1
By adding (5 × 10 −7 / ° C.) 30 to 40% by weight, the coefficient of thermal expansion of the low-melting glass can be made closer to the coefficient of thermal expansion of the glass substrate.
【０００３】[0003]
【発明が解決しようとする課題】蛍光表示管の製造工程
において、封着ガラスは、低融点ガラスとフィラーとし
てのチタン酸鉛とビークルを混合してなる封着ペースト
の形態で基板周囲に塗布され、その後、仮焼成されて基
板に固着し、後工程の作業をやり易くしている。その
後、絶縁層や陽極導体、蛍光体等をスクリーン印刷法等
で基板上に被着した後、再び焼成して固着させる。最後
に、前面板と側面板からなる容器部と前記基板を加熱封
着する。このように封着ガラスを塗布した後、封着する
までに焼成工程を数回行うことになる。In the manufacturing process of the fluorescent display tube, the sealing glass is applied around the substrate in the form of a sealing paste obtained by mixing a low melting glass, a lead titanate as a filler and a vehicle. Thereafter, it is pre-baked and fixed to the substrate, thereby facilitating the work in the post-process. After that, an insulating layer, an anode conductor, a phosphor, and the like are applied on the substrate by a screen printing method or the like, and then fired again to be fixed. Lastly, the substrate is heat-sealed to the container portion including the front plate and the side plate. After the application of the sealing glass, the firing step is performed several times before the sealing is performed.
【０００４】しかしながら従来の封着ガラスの中には、
塗布した後の仮焼成時に透明なガラス状にならず、表面
が白くなり、再び加熱しても溶融しないものが現れるこ
とがあった。この白化したものを顕微鏡で観察すると、
ガラス中に六角形の板状結晶が認められた。そして白化
したものは、板状結晶ができてしまうために、加熱して
も流れが悪くなる現象がある。However, some conventional sealing glasses include:
At the time of calcination after application, the glass did not become a transparent glass, the surface became white, and there was a case where some did not melt even when heated again. Observing this whitened thing with a microscope,
Hexagonal plate-like crystals were observed in the glass. Then, since the whitened one forms plate-like crystals, there is a phenomenon that the flow becomes poor even when heated.
【０００５】そこで、封着ガラスを一定の円柱形、例え
ばφ２０ｍｍの円柱形に成形し、この成形した封着ガラ
スを炉中で封着温度で１時間加熱した後の円柱の形を測
定して、流れの状態や、表面状態を観察し、評価してい
た。[0005] Therefore, the sealing glass is formed into a fixed cylindrical shape, for example, a cylindrical shape of φ20 mm, and the formed sealing glass is heated in a furnace at a sealing temperature for one hour, and the shape of the cylindrical shape is measured. The state of the flow and the surface state were observed and evaluated.
【０００６】その結果、流れの悪い原因はフィラーとし
て入れるチタン酸鉛にあることを知見した。特にチタン
酸鉛（ＰｂＴｉＯ3 ）の中に原料である酸化鉛（Ｐｂ
Ｏ）が未反応物質として残っている場合に、このＰｂＯ
が結晶核となって板状結晶ができると推察した。[0006] As a result, it has been found that the cause of poor flow is lead titanate inserted as a filler. In particular, lead oxide (Pb) as a raw material is contained in lead titanate (PbTiO 3 ).
O) remains as unreacted material, this PbO
Was assumed to be a crystal nucleus to form a plate crystal.
【０００７】そこで、本発明者らは、低融点ガラスに、
遊離のＰｂＯやＴｉＯ2 のないＰｂＴｉＯ3 にＰｂＯを
添加して焼成する実験と、遊離のＰｂＯやＴｉＯ2 のな
いＰｂＴｉＯ3 にＴｉＯ2 を添加して焼成する実験を行
った結果、ＰｂＯを添加した方は流れが悪く、白化して
板状結晶が発生したが、ＴｉＯ2 を添加した方は、流れ
は悪くならず、板状結晶も発生しなかった。Therefore, the present inventors have developed a low melting point glass.
Experiments and firing into the free PbO and TiO 2 with no PbTiO 3 by addition of PbO, results of experiments firing by adding TiO 2 to the free PbO and TiO 2 with no PbTiO 3, was added PbO In the case of TiO 2 , the flow did not worsen and no plate-like crystal was generated.
【０００８】本発明は、以上の実験から得た知見に基づ
いて成されたものであり、焼成後に白化しない封着ガラ
スを提供することを目的としている。The present invention has been made based on the findings obtained from the above experiments, and has as its object to provide a sealing glass which does not whiten after firing.
【０００９】[0009]
【課題を解決するための手段】本発明の封着ガラスは、
低融点ガラスにチタン酸鉛（ＰｂＴｉＯ3 ）を含有する
封着ガラスにおいて、チタン酸鉛が実質的に一酸化鉛
（ＰｂＯ）と二酸化チタン（ＴｉＯ2 ）のみから合成さ
れ、かつ両者のモル比ＰｂＯ／ＴｉＯ2 を０．９５以上
１未満として合成されたことを特徴としている。Means for Solving the Problems The sealing glass of the present invention comprises:
In a sealing glass containing low-melting glass containing lead titanate (PbTiO 3 ), lead titanate is substantially synthesized from only lead monoxide (PbO) and titanium dioxide (TiO 2 ).
And a mole ratio PbO / TiO 2 of 0.95 or more and less than 1.
【００１０】[0010]
【作用】一酸化鉛（ＰｂＯ）と二酸化チタン（Ｔｉ
Ｏ2 ）から封着ガラス用フィラーとしてのチタン酸鉛
（ＰｂＴｉＯ3 ）を合成する際、両原料物質のモル比Ｐ
ｂＯ／ＴｉＯ2 を０．９５以上１未満とすれば、すなわ
ちＰｂＯをＴｉＯ2 より少ないモル数で合成すれば、未
反応ＰｂＯがなくなり、合成されたＰｂＴｉＯ3 中に遊
離のＰｂＯを含まないので封着ガラス中において結晶化
を促進することがなくなり、封着ガラスは安定であり機
械的衝撃等にも強い。[Action] Lead monoxide (PbO) and titanium dioxide (Ti)
When synthesizing lead titanate (PbTiO 3 ) as a filler for sealing glass from O 2 ), the molar ratio of both raw materials P
If bO / TiO 2 is 0.95 or more and less than 1, that is, if PbO is synthesized in a smaller number of moles than TiO 2 , unreacted PbO is eliminated, and free PbO is not contained in the synthesized PbTiO 3. The crystallization is not promoted during the glass deposition, and the sealing glass is stable and resistant to mechanical shocks and the like.
【００１１】[0011]
【実施例】未反応のＰｂＯを生じさせないために、Ｐｂ
ＴｉＯ3 の原料成分の好ましい混合割合を、次に示すよ
うな実験により確認した。本例においては、原料物質を
実質的に一酸化鉛（ＰｂＯ）と二酸化チタン（Ｔｉ
Ｏ 2 ）のみとして合成した。なお、「実質的に一酸化鉛
（ＰｂＯ）と二酸化チタン（ＴｉＯ 2 ）のみとして合
成」とは、積極的には他の成分を加えず、純度の関係で
やむを得ず不純物を微量に含む場合を除き、一酸化鉛
（ＰｂＯ）と二酸化チタン（ＴｉＯ 2 ）のみから合成す
ることを意味する。 EXAMPLES In order not to generate unreacted PbO, Pb
The preferable mixing ratio of the raw material components of TiO 3 was confirmed by the following experiment. In this example, the raw material is
Substantially lead monoxide (PbO) and titanium dioxide (Ti
O 2 ) alone. In addition, "substantially lead monoxide
(PbO) and titanium dioxide (TiO 2 )
`` Naturally '' means that the other ingredients are not added
Unless unavoidably contains trace amounts of impurities, lead monoxide
(PbO) and titanium dioxide (TiO 2 ) only
Means that
【００１２】ＰｂＯとＴｉＯ2 の混合割合を、図１の試
料〜のように定める。各試料〜における原料の
混合割合は、モル比でＰｂＯ／ＴｉＯ2 の値が０．９５
〜１．０４となっている。そして各試料ごとにこれを混
合し、８００〜１２００℃で焼成してＰｂＴｉＯ3 を得
る。The mixing ratio of PbO and TiO 2 is determined as shown in FIG. The mixing ratio of the raw materials in each sample was as follows: the molar ratio of PbO / TiO 2 was 0.95.
１．０1.04. Then, this is mixed for each sample, and fired at 800 to 1200 ° C. to obtain PbTiO 3 .
【００１３】前記〜のＰｂＴｉＯ3 を入れた封着ガ
ラスで構成したφ２０ｍｍの円柱を封着温度で１時間加
熱した。〜は、ＰｂＯ／ＴｉＯ2 のモル比が１．０
４０〜１．０００のものであり、円柱の直径は２４〜２
６ｍｍと流れが悪く、六角形の板状結晶が生じて表面が
白化した状態となった。〜は、ＰｂＯ／ＴｉＯ2の
モル比が０．９９５〜０．９５０のものであり、円柱の
直径は２７〜２９ｍｍと流れも良好であり、白化現象は
現れなかった。以上の結果からわかるように、ＰｂＯ／
ＴｉＯ2 のモル比が１未満であれば良好な結果が得られ
る。A φ20 mm cylinder made of the above sealing glass containing PbTiO 3 was heated at the sealing temperature for 1 hour. Indicates that the molar ratio of PbO / TiO 2 is 1.0
40-1.000, and the diameter of the cylinder is 24-2
The flow was poor at 6 mm, and hexagonal plate-like crystals were formed and the surface was whitened. ~ Is intended molar ratio of PbO / TiO 2 is 0.995 to 0.950, the diameter of the cylinder is better 27~29mm and flow, whitening phenomenon did not appear. As can be seen from the above results, PbO /
Good results are obtained if the molar ratio of TiO 2 is less than 1.
【００１４】しかしながら、ＰｂＯ／ＴｉＯ2 のモル比
が０．９４以下の場合にはＰｂＴｉＯ3 の結晶成長がし
にくくなり、ＰｂＴｉＯ3 の結晶粒径が小さくなって、
スクリーン印刷に適する粘度を得るには低融点ガラス粉
末に対してビークル量を多くしなければならない。この
ため封着ガラスとして適しなくなるのでフィラーとして
使用できない。[0014] However, hardly the crystal growth of PbTiO 3 in the case the molar ratio of PbO / TiO 2 is 0.94 or less, the crystal grain size of PbTiO 3 becomes small,
In order to obtain a viscosity suitable for screen printing, the amount of the vehicle must be increased with respect to the low melting point glass powder. For this reason, it is not suitable as a sealing glass and cannot be used as a filler.
【００１５】[0015]
【発明の効果】本発明によれば、原料物質を実質的に一
酸化鉛（ＰｂＯ）と二酸化チタン（ＴｉＯ 2 ）のみと
し、ＰｂＯ／ＴｉＯ2 のモル比を０．９５以上１未満に
規定してＰｂＴｉＯ3 を製造するようにしたので、これ
を封着ガラスにフィラーとして添加してもガラス中に板
状結晶が生じることはなく、封着ガラスの流れが良く、
封着不良がでなくなった。 According to the present invention, the raw material is substantially reduced.
Only lead oxide (PbO) and titanium dioxide (TiO 2 )
And. Thus the production of PbTiO 3 defines the molar ratio of PbO / TiO 2 less than 1 or greater than 0.95, plate crystals occurs during the glass be added to this as a filler in the sealing glass Nothing, the flow of the sealing glass is good,
Bad sealing is gone.
【図１】本発明の一実施例において行なわれた実験の内
容及び結果等を示す表図である。FIG. 1 is a table showing the contents and results of an experiment conducted in one example of the present invention.
Claims (1)
3 ）を含有する封着ガラスにおいて、チタン酸鉛が実質
的に一酸化鉛（ＰｂＯ）と二酸化チタン（ＴｉＯ2 ）の
みから合成され、かつ両者のモル比ＰｂＯ／ＴｉＯ2 を
０．９５以上１未満として合成されたことを特徴とする
封着ガラス。A low melting point glass is made of lead titanate (PbTiO).
In the sealing glass containing 3), lead titanate is substantially
To lead monoxide (PbO) and titanium dioxide (TiO 2)
Synthesized from only, and sealing glass, characterized in that the molar ratio PbO / TiO 2 both synthesized as less than 1 or greater than 0.95.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5042935A JP2705503B2 (en) | 1993-03-03 | 1993-03-03 | Sealing glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5042935A JP2705503B2 (en) | 1993-03-03 | 1993-03-03 | Sealing glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06256040A JPH06256040A (en) | 1994-09-13 |
| JP2705503B2 true JP2705503B2 (en) | 1998-01-28 |
Family
ID=12649877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5042935A Expired - Lifetime JP2705503B2 (en) | 1993-03-03 | 1993-03-03 | Sealing glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2705503B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04160035A (en) * | 1990-10-22 | 1992-06-03 | Nippon Electric Glass Co Ltd | Low-melting point sealing composition |
-
1993
- 1993-03-03 JP JP5042935A patent/JP2705503B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06256040A (en) | 1994-09-13 |
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