JPH10139478A - Composition for sealing - Google Patents
Composition for sealingInfo
- Publication number
- JPH10139478A JPH10139478A JP2940697A JP2940697A JPH10139478A JP H10139478 A JPH10139478 A JP H10139478A JP 2940697 A JP2940697 A JP 2940697A JP 2940697 A JP2940697 A JP 2940697A JP H10139478 A JPH10139478 A JP H10139478A
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- JP
- Japan
- Prior art keywords
- sealing
- weight
- low
- glass
- composition
- 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.)
- Granted
Links
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- Glass Compositions (AREA)
- Gas-Filled Discharge Tubes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、低温度の熱処理に
より封着できるブラウン管（ＣＲＴ）のパネルとファン
ネルとを封着するための封着用組成物、およびプラズマ
ディスプレイパネル（ＰＤＰ）または蛍光表示管（ＶＦ
Ｄ）を封着するための封着用組成物に関する。The present invention relates to a sealing composition for sealing a panel of a cathode ray tube (CRT) and a funnel which can be sealed by a low-temperature heat treatment, and a plasma display panel (PDP) or a fluorescent display tube. (VF
The present invention relates to a sealing composition for sealing D).
【０００２】[0002]
【従来の技術】従来、カラーＣＲＴのパネルとファンネ
ルとの封着には、特公昭３６−１７８２１に開示される
タイプのＰｂＯ−Ｂ2 Ｏ3 −ＺｎＯ−ＳｉＯ2 系結晶性
低融点ガラスを用い、４４０〜４５０℃の温度に３０〜
４０分程度保持して封着していた。かくして封着された
パネルとファンネルはその内部を１０-6Ｔｏｒｒ以下の
高真空を得るため３００〜３８０℃に加熱されつつ排気
される。Conventionally, the sealing of the color CRT panel and funnel, using a type of PbO-B 2 O 3 -ZnO- SiO 2 based crystalline low melting glass disclosed in JP-B 36-17821 , At a temperature of 440-450 ° C, 30-
Sealing was maintained for about 40 minutes. The panel and the funnel thus sealed are evacuated while being heated to 300 to 380 ° C. in order to obtain a high vacuum of 10 −6 Torr or less.
【０００３】また、従来、ＰＤＰまたはＶＦＤにおける
ガラス基板の封着には、低融点ガラスを用い、４４０〜
５００℃の温度で保持することにより封着していた。か
くして、封着されたパネルはＰＤＰの場合は２５０〜３
８０℃に加熱されつつ排気され、１００〜５００Ｔｏｒ
ｒになるようにＮｅ、Ｈｅ−Ｘｅ等の放電ガスが封入さ
れて、またＶＦＤの場合は真空を得るため２５０〜３８
０℃に加熱されつつ排気されて封止される。[0003] Conventionally, a glass substrate of PDP or VFD is sealed with a low melting point glass, and 440-400 is used.
It was sealed by holding at a temperature of 500 ° C. Thus, the sealed panel is 250-3 for PDP.
Exhausted while being heated to 80 ° C, 100 to 500 Torr
r, a discharge gas such as Ne or He-Xe is sealed, and in the case of VFD, 250 to 38
It is evacuated while being heated to 0 ° C. and sealed.
【０００４】[0004]
【発明が解決しようとする課題】従来の封着用ガラス粉
末は、鉛成分を含有するガラスが用いられていたが、鉛
成分を含有しないガラスを用いるとリサイクルなどの点
で有利である。また、従来の非鉛の封着用ガラス粉末
は、封着対象物であるガラスと熱膨張率がマッチングせ
ず、パネルが割れたり、排気のときの加熱によりガラス
基板にハンダが流動したり、発泡したり、封着部分が割
れたりしていた。Conventional glass powder for sealing uses a glass containing a lead component, but using a glass containing no lead component is advantageous in terms of recycling and the like. In addition, the conventional lead-free glass powder for sealing does not match the coefficient of thermal expansion with the glass to be sealed, so that the panel is broken, solder flows on the glass substrate due to heating during exhaust, or foaming occurs. Or the seal was cracked.
【０００５】本発明は、鉛成分を含有しないガラス粉末
を用い、ＣＲＴ、ＰＤＰおよびＶＦＤを封着するのに適
したガラスセラミックス組成物の提供を目的とする。An object of the present invention is to provide a glass-ceramic composition suitable for sealing CRT, PDP and VFD using glass powder containing no lead component.
【０００６】[0006]
【課題を解決するための手段】本発明は、実質的にビス
マス系の低融点ガラスの粉末６０〜９９重量％と低膨張
セラミックスフィラーの粉末１〜４０重量％とからなる
組成物であり、該低融点ガラスの組成が実質的に重量表
示で、Ｂｉ2 Ｏ3 ：７７〜９５％、ＭｇＯ＋ＺｎＯ：１
〜２０％、Ｂ2 Ｏ3 ：２〜１０％、ＳｉＯ2 ：０〜１
％、ＣｅＯ2 ：０〜１０％、からなることを特徴とする
封着用組成物を提供する。According to the present invention, there is provided a composition comprising 60 to 99% by weight of substantially bismuth-based low melting glass powder and 1 to 40% by weight of low expansion ceramic filler powder. the composition of the low melting point glass is substantially the weight display, Bi 2 O 3: 77~95% , MgO + ZnO: 1
~20%, B 2 O 3: 2~10%, SiO 2: 0~1
%, CeO 2 : 0 to 10%.
【０００７】[0007]
【発明の実施の形態】本発明におけるビスマス系の低融
点ガラスの組成範囲について、以下に説明する。本発明
においては、比較的低温の４００〜５５０℃、かつ短時
間（６分〜１時間）で充分に流動して、封着できるよう
に、軟化点が５００℃以下の低融点ガラスを用いる。本
発明の低融点ガラスはＣＲＴを封着する場合のように、
短時間で封着することが必要な場合には、結晶性である
ことが好ましい。一方、複数回の加熱を経て封着する用
途の場合には、非結晶性であることが好ましい場合もあ
る。BEST MODE FOR CARRYING OUT THE INVENTION The composition range of a bismuth-based low-melting glass according to the present invention will be described below. In the present invention, a low-melting glass having a softening point of 500 ° C. or less is used so that the material can sufficiently flow and seal at a relatively low temperature of 400 to 550 ° C. and a short time (6 minutes to 1 hour). The low-melting glass of the present invention, as in the case of sealing a CRT,
When sealing is required in a short time, it is preferably crystalline. On the other hand, in the case of an application in which sealing is performed after heating a plurality of times, it may be preferable that the material be non-crystalline.
【０００８】ここでいう結晶性のガラスとは、１０℃／
分で昇温し、封着温度（４００〜５００℃）で２時間保
持したとき、示差熱分析（ＤＴＡ）で発熱ピークが生じ
るものをいう。[0008] The crystalline glass referred to herein is 10 ° C /
When the temperature is raised in minutes and maintained at a sealing temperature (400 to 500 ° C.) for 2 hours, an exothermic peak is generated in differential thermal analysis (DTA).
【０００９】低融点ガラスは重量％表示で以下のような
組成範囲を持つ。 Ｂｉ2 Ｏ3 ７７〜９５％、 ＭｇＯ＋ＺｎＯ １〜２０％、 Ｂ2 Ｏ3 ２〜１０％、 ＳｉＯ2 ０〜 １％、 ＣｅＯ2 ０〜１０％。The low melting point glass has the following composition range in terms of% by weight. Bi 2 O 3 77~95%, MgO + ZnO 1~20%, B 2 O 3 2~10%, SiO 2 0~ 1%, CeO 2 0~10%.
【００１０】Ｂｉ2 Ｏ3 の含有量が７７重量％（以下、
ガラス組成の説明において、単に％という。）未満で
は、軟化点が高くなりすぎ、流動性が悪く、封着部の強
度、気密性が損なわれ、４００〜５５０℃では封着でき
ないおそれがある。その含有量が９５％超では、ガラス
化が困難になる。好ましくは７９％以上であり、また９
３％以下である。When the content of Bi 2 O 3 is 77% by weight (hereinafter referred to as
In the description of the glass composition, it is simply referred to as%. If it is less than (), the softening point will be too high, the fluidity will be poor, the strength and airtightness of the sealed portion will be impaired, and sealing may not be possible at 400 to 550 ° C. If the content exceeds 95%, vitrification becomes difficult. It is preferably at least 79%, and 9
3% or less.
【００１１】ＺｎＯとＭｇＯとは少なくとも一方が含有
されればよく、この合計の含有量が１％未満では、該低
融点ガラスの加熱時の結晶化が激しくなりすぎ、流動性
が悪くなる。また合計の含有量が２０％超では、軟化点
が高くなりすぎ、流動性が悪くなる。どちらの場合も、
封着部の強度、気密性が損なわれ、４００〜５５０℃で
は封着できないおそれがある。好ましくは２％以上であ
り、また１５％以下である。It is sufficient that at least one of ZnO and MgO is contained. If the total content is less than 1%, the crystallization of the low-melting glass at the time of heating becomes too severe, and the fluidity becomes poor. If the total content is more than 20%, the softening point becomes too high, and the fluidity becomes poor. In both cases,
The strength and airtightness of the sealing portion are impaired, and there is a possibility that sealing cannot be performed at 400 to 550 ° C. It is preferably at least 2% and at most 15%.
【００１２】具体的にはＭｇＯは０〜８％とされるのが
好ましい。８％超では、ガラス化しにくくなり、安定し
たガラスができなくなるおそれがある。また、ＺｎＯは
０〜２０％とされるのが好ましい。２０％超では、軟化
点が高くなる。Specifically, the content of MgO is preferably 0 to 8%. If it exceeds 8%, vitrification becomes difficult and stable glass may not be obtained. Further, ZnO is preferably set to 0 to 20%. If it exceeds 20%, the softening point will be high.
【００１３】また、Ｂｉ2 Ｏ3 とＺｎＯとの合量は８５
〜９８％とすることが好ましい。８５％未満では封着温
度が高くなりすぎる場合があるためである。特に好まし
くは８７％以上である。The total amount of Bi 2 O 3 and ZnO is 85
It is preferable to set it to 98%. If it is less than 85%, the sealing temperature may be too high. It is particularly preferably at least 87%.
【００１４】Ｂ2 Ｏ3 の含有量が２％未満では、ガラス
の流動性が悪くなり、封着部の強度、気密性が損なわれ
るおそれがある。その含有量が１０％超では、ガラスの
軟化点が高くなり、４００〜５５０℃では封着できなく
なるおそれがある。好ましくは３％以上であり、また８
％以下である。If the content of B 2 O 3 is less than 2%, the fluidity of the glass becomes poor, and the strength and airtightness of the sealed portion may be impaired. If the content is more than 10%, the softening point of the glass will be high, and at 400 to 550 ° C, sealing may not be possible. It is preferably at least 3%, and 8
% Or less.
【００１５】ＳｉＯ2 は必須成分ではないが、含有させ
ることによって、該低融点ガラスの結晶化を抑制し、流
動性を高めうる。ただし、含有量が１％超では、軟化点
が高くなりすぎるおそれがある。特に低い温度で封着す
る必要のある場合は、実質的に含有しないことが好まし
い。Although SiO 2 is not an essential component, its inclusion can suppress crystallization of the low-melting glass and increase the fluidity. However, if the content exceeds 1%, the softening point may be too high. Particularly when it is necessary to seal at a low temperature, it is preferable that the resin is not substantially contained.
【００１６】ＣｅＯ2 も必須成分ではないが、ガラス組
成中のＢｉ2 Ｏ3 がガラス融解中に金属ビスマスとして
析出することを抑制し、該封着用組成物の電気絶縁性の
低下を抑止できる。ただし、含有量が１０％超では、軟
化点が高くなりすぎ、４００〜５５０℃では封着できな
いおそれがある。好ましくは０．０１％以上であり、ま
た５％以下である。Although CeO 2 is not an essential component, Bi 2 O 3 in the glass composition can be prevented from depositing as metallic bismuth during melting of the glass, and a decrease in the electrical insulation of the sealing composition can be suppressed. However, if the content is more than 10%, the softening point becomes too high, and there is a possibility that sealing cannot be performed at 400 to 550 ° C. Preferably it is 0.01% or more and 5% or less.
【００１７】この他にも、ＣａＯ、ＳｒＯ、ＢａＯも、
該封着用組成物の熱膨張係数を、大幅に増大させない範
囲で添加できる。また、Ｉｎ2 Ｏ3 、ＴｉＯ2 、ＳｎＯ
2 、ＺｒＯ2 も、軟化点を大幅に増大させない範囲で添
加してもよく、Ｌｉ2 Ｏ、Ｎａ2 Ｏ、Ｋ2 Ｏ、Ｃｌ、Ｆ
も、ＣＲＴ、ＰＤＰ、ＶＦＤの特性に悪影響を与えない
範囲で添加してもよい。これらの成分は添加された場合
でも、合量で１０％以下とすることが好ましく、特に好
ましくは５％以下である。In addition, CaO, SrO, and BaO also include
The thermal expansion coefficient of the sealing composition can be added within a range that does not significantly increase. In addition, In 2 O 3 , TiO 2 , SnO
2 and ZrO 2 may be added within a range that does not greatly increase the softening point, and Li 2 O, Na 2 O, K 2 O, Cl, F
May be added in a range that does not adversely affect the characteristics of CRT, PDP, and VFD. Even when these components are added, the total amount is preferably 10% or less, particularly preferably 5% or less.
【００１８】なお、ＣｕＯは、電子部品用途では、蛍光
体を劣化させることがあるため、添加を避ける場合があ
る。かかる場合はＣｕＯは実質的に含有されないことが
好ましい。[0018] In addition, CuO may be used in electronic parts, which may degrade the phosphor, and thus may not be added. In such a case, it is preferable that CuO is not substantially contained.
【００１９】かくして得られるガラスのガラス転移点は
適当な封着温度を得るために２８０〜３６０℃であるこ
とが好ましい。特にＣＲＴなどのより低い封着温度が要
求される分野に用いる封着用組成物として用いるために
は、ガラス転移点は２８０〜３５０℃、特に２８０〜３
４０℃であることが好ましい。The glass transition temperature of the glass thus obtained is preferably from 280 to 360 ° C. in order to obtain an appropriate sealing temperature. In particular, for use as a sealing composition used in a field where a lower sealing temperature is required, such as a CRT, the glass transition point is 280-350 ° C., particularly 280-3 ° C.
Preferably it is 40 ° C.
【００２０】本発明でいう低膨張セラミックスフィラー
とは、室温〜３００℃における熱膨張係数が７０×１０
-7／℃以下であるセラミックスフィラーをいう。かかる
低膨張セラミックスフィラーとしては、ジルコン、コー
ジェライト、チタン酸アルミニウム、アルミナ、ムライ
ト、シリカ、β−ユークリプタイト、β−スポジュメン
およびβ−石英固溶体から選ばれる１種以上が好まし
く、特に、コージェライト、ジルコンは封着強度に優れ
るため、望ましい。The low-expansion ceramic filler referred to in the present invention is a material having a thermal expansion coefficient of 70 × 10 at room temperature to 300 ° C.
-7 / ° C or lower. The low expansion ceramic filler is preferably at least one selected from zircon, cordierite, aluminum titanate, alumina, mullite, silica, β-eucryptite, β-spodumene, and β-quartz solid solution, and particularly cordierite. Zircon is desirable because of its excellent sealing strength.
【００２１】本発明において、低融点ガラス粉末の含有
量は、低融点ガラス粉末と低膨張セラミックスフィラー
粉末との総量に対して６０〜９９重量％の範囲であり、
低膨張セラミックスフィラー粉末の含有量は低融点ガラ
ス粉末と低膨張セラミックスフィラーとの総量に対して
１〜４０重量％の範囲である。In the present invention, the content of the low melting point glass powder is in the range of 60 to 99% by weight based on the total amount of the low melting point glass powder and the low expansion ceramic filler powder.
The content of the low expansion ceramic filler powder is in the range of 1 to 40% by weight based on the total amount of the low melting glass powder and the low expansion ceramic filler.
【００２２】低融点ガラス粉末が９９重量％超では、低
膨張セラミックスフィラー粉末の量が少ないため、封着
用組成物の焼成後の熱膨張係数が大きくなりすぎ、封着
される対象物のガラスと熱膨張係数が合わず、割れやす
い。その含有量が６０重量％未満では、ガラス分が少な
く流動性が悪くなり、封着部の気密性が損なわれるおそ
れがある。When the content of the low-melting glass powder exceeds 99% by weight, the amount of the low-expansion ceramic filler powder is small, so that the thermal expansion coefficient of the sealing composition after firing becomes too large, and the glass to be sealed has Coefficient of thermal expansion does not match and is easily broken. If the content is less than 60% by weight, the glass content is small and the fluidity is poor, and the airtightness of the sealing portion may be impaired.
【００２３】かくして得られる封着用組成物の焼成後の
室温〜２５０℃の平均熱膨張係数は６５×１０-7〜１０
０×１０-7／℃となることが好ましい。平均熱膨張係数
が、この範囲をはずれると、封着対象物のガラスと熱膨
張係数のマッチングが困難になる。The thus obtained sealing composition has an average coefficient of thermal expansion from room temperature to 250 ° C. after firing of 65 × 10 -7 to 10
It is preferably 0 × 10 −7 / ° C. If the average coefficient of thermal expansion is out of this range, it becomes difficult to match the glass to be sealed with the coefficient of thermal expansion.
【００２４】本発明の封着用組成物をＣＲＴのパネルと
ファンネルとを封着するために適用する場合には、ビス
マス系の低融点ガラス粉末７０〜９９重量％と低膨張セ
ラミックスフィラー粉末１〜３０重量％とからなり、焼
成後の室温〜３００℃の平均熱膨張係数が８０×１０-7
〜１００×１０-7／℃であることが好ましい。When the sealing composition of the present invention is applied for sealing a CRT panel and a funnel, 70 to 99% by weight of a bismuth-based low melting glass powder and 1 to 30 of a low expansion ceramic filler powder are used. % And an average coefficient of thermal expansion from room temperature to 300 ° C. after firing is 80 × 10 −7.
It is preferable that it is 100-100-7 / degreeC.
【００２５】かかる封着用組成物は、４００〜５００℃
の温度に５分〜１時間保持することにより、ＣＲＴのパ
ネルとファンネルとを封着でき、封着後の３００〜３８
０℃の排気時の加熱により、流動したり、発泡したり、
機械的強度が損なわれたりすることがない。The sealing composition is used at a temperature of 400 to 500 ° C.
CRT panel and funnel can be sealed by holding at a temperature of 5 minutes to 1 hour.
By heating at the time of exhaustion of 0 ° C, it flows, foams,
There is no loss of mechanical strength.
【００２６】本発明の封着用組成物をＣＲＴのパネルと
ファンネルとを封着するために適用する場合において、
低融点ガラス粉末の含有量が９９重量％超では、低膨張
セラミックスフィラー粉末の量が少ないため、熱膨張係
数が大きくなりすぎ、パネルおよびファンネルと熱膨張
係数が合わず、割れやすい。その含有量が７０重量％未
満では、ガラス分が少なく流動性が悪くなり、ＣＲＴと
して充分な真空が得られにくい。When the sealing composition of the present invention is applied to seal a panel of a CRT and a funnel,
When the content of the low-melting glass powder exceeds 99% by weight, the amount of the low-expansion ceramic filler powder is small, so that the thermal expansion coefficient becomes too large, and the panel and the funnel do not have the same thermal expansion coefficient and are easily cracked. If the content is less than 70% by weight, the glass content is small and the fluidity is poor, and it is difficult to obtain a sufficient vacuum as a CRT.
【００２７】また、室温〜３００℃における焼成後の封
着用組成物の平均熱膨張係数が８０×１０-7〜１００×
１０-7／℃の範囲外になると、封着後のパネルガラスま
たはファンネルガラスまたは封着部に引張応力が働き、
バルブの耐圧強度が低下する。The average thermal expansion coefficient of the sealing composition after firing at room temperature to 300 ° C. is 80 × 10 −7 to 100 ×.
When the temperature is out of the range of 10 −7 / ° C., tensile stress acts on the panel glass or funnel glass or the sealed portion after sealing,
The pressure resistance of the valve decreases.
【００２８】本発明の封着用組成物をＰＤＰ封着用また
はＶＦＤ封着用に適用する場合は、ビスマス系の低融点
ガラス粉末６０〜９８重量％と低膨張セラミックスフィ
ラー粉末２〜４０重量％とからなり、焼成後の室温〜２
５０℃の平均熱膨張係数が６５×１０-7〜９０×１０-7
／℃であることが好ましい。When the sealing composition of the present invention is applied to PDP sealing or VFD sealing, the composition comprises 60 to 98% by weight of a bismuth-based low melting glass powder and 2 to 40% by weight of a low expansion ceramic filler powder. Room temperature after firing, 2
The average thermal expansion coefficient at 50 ° C. is 65 × 10 −7 to 90 × 10 −7.
/ ° C.
【００２９】かかる封着用組成物は、４００〜５００℃
の温度で５分〜１時間保持することにより、ＰＤＰまた
はＶＦＤを封着でき、封着後に２８０〜３８０℃で排気
する際に、加熱により流動したり、発泡したり、機械的
強度が損なわれたりすることがない。Such a sealing composition is used at a temperature of 400 to 500 ° C.
By holding at a temperature of 5 minutes to 1 hour, PDP or VFD can be sealed, and when evacuated at 280 to 380 ° C. after sealing, it flows by heating, foams, or impairs mechanical strength. Or not.
【００３０】本発明の封着用組成物をＰＤＰ封着用また
はＶＦＤ封着用に適用する場合において、低融点ガラス
粉末の含有量が９８重量％超では、低膨張セラミックス
フィラー粉末量が少ないため、焼成後の熱膨張係数が大
きくなりすぎて基板ガラスと熱膨張係数が合わず、封着
後のシールフリット部に引張応力が残り割れやすい。６
０重量％未満では、ガラス分が少なく流動性が悪くな
り、ＰＤＰやＶＦＤとして充分な封着部の気密性が得ら
れない。When the sealing composition of the present invention is applied to PDP sealing or VFD sealing, if the content of the low-melting glass powder exceeds 98% by weight, the amount of the low-expansion ceramic filler powder is small. Has an excessively large coefficient of thermal expansion and does not match the coefficient of thermal expansion of the substrate glass. 6
If the amount is less than 0% by weight, the glass content is small and the fluidity is poor, so that the hermeticity of the sealed portion sufficient as PDP or VFD cannot be obtained.
【００３１】また、室温〜２５０℃における焼成後の封
着用組成物の平均熱膨張係数が６５×１０-7〜９０×１
０-7／℃の範囲外になると、封着後に基板ガラスまたは
封着部に引張応力が働き、耐圧強度が低下する。The average thermal expansion coefficient of the sealing composition after firing at room temperature to 250 ° C. is 65 × 10 −7 to 90 × 1.
If the temperature is outside the range of 0 -7 / ° C, tensile stress acts on the substrate glass or the sealed portion after sealing, and the pressure resistance decreases.
【００３２】この組成物に、着色のために顔料などの着
色剤を添加し使用することもできる。A coloring agent such as a pigment may be added to the composition for coloring.
【００３３】[0033]
【実施例】表１、表２に示すガラス組成（単位：重量
％）となるように原料を調合・混合し、１０００〜１４
００℃の温度にて溶融しガラス化しガラスを得た。次い
でこのガラスをボールミルで粉砕し、低融点ガラス粉末
を得た。EXAMPLES Raw materials were prepared and mixed so that the glass composition (unit:% by weight) shown in Tables 1 and 2 was obtained.
It was melted and vitrified at a temperature of 00 ° C. to obtain glass. Next, this glass was pulverized with a ball mill to obtain a low-melting glass powder.
【００３４】これらの低融点ガラス粉末と低膨張セラミ
ックスフィラー粉末とを表１、表２の構成欄に示す重量
割合で混合し、封着用組成物を調製した。例１〜１７は
実施例、例１８〜２０は比較例である。また、例１〜
３、例１８はＣＲＴ用途、例４〜１６、１９はＰＤＰ用
途、例１７、２０はＶＦＤ用途に調製した例である。These low-melting glass powders and low-expansion ceramic filler powders were mixed at the weight ratios shown in the constitution columns of Tables 1 and 2 to prepare a sealing composition. Examples 1 to 17 are Examples and Examples 18 to 20 are Comparative Examples. Examples 1 to
Examples 3 and 18 are examples for CRT use, Examples 4 to 16 and 19 are examples for PDP use, and Examples 17 and 20 are examples for VFD use.
【００３５】この封着用組成物について、フローボタン
径、接着残留歪み、熱膨張係数を測定した結果を表１、
表２に示す。それぞれの測定法は以下のとおりである。Table 1 shows the results of measuring the flow button diameter, adhesive residual strain, and thermal expansion coefficient of this sealing composition.
It is shown in Table 2. Each measuring method is as follows.
【００３６】フローボタン径：封着時の組成物の流動性
を示すもので、封着用組成物の試料粉末（ＣＲＴ用は
８．０ｇ、ＰＤＰ、ＶＦＤ用は４．５ｇ）を、直径１
２．７ｍｍの円柱状に加圧成形後、表１、表２に記載し
た焼成温度に３０分間保持したとき、封着用組成物が流
動した直径（単位：ｍｍ）である。このフローボタンは
ＣＲＴ用は２６．５ｍｍ以上、ＰＤＰ、ＶＦＤ用は２０
ｍｍ以上が望ましい。Flow button diameter: Indicates the fluidity of the composition at the time of sealing. A sample powder of the sealing composition (8.0 g for CRT, 4.5 g for PDP and VFD) has a diameter of 1
It is the diameter (unit: mm) at which the sealing composition flows when pressed at a firing temperature described in Tables 1 and 2 for 30 minutes after being pressed into a 2.7 mm column. This flow button is 26.5 mm or more for CRT and 20 for PDP and VFD.
mm or more is desirable.
【００３７】接着残留歪み：封着用組成物とビヒクル
（酢酸イソアミルにニトロセルロース１．２％を溶解し
た溶液）とを重量比９．０：１．０の割合で混合してペ
ーストとした。このペーストを、ＣＲＴ用はファンネル
ガラス片の上、ＰＤＰ、ＶＦＤ用は基板ガラス片の上、
に塗布し、フローボタン径の場合と同条件で焼成後、ガ
ラス片と焼成後の封着用組成物との間に発生した残留歪
み（単位：ｎｍ／ｃｍ）をポーラリメーターを用いて測
定した。「＋」は焼成後の封着用組成物が圧縮歪みを受
けていること、また、「−」は焼成後の封着用組成物が
引張歪みを受けていることを示す。この残留歪みは−１
００〜＋５００ｎｍ／ｃｍの範囲が望ましい。Adhesive residual strain: A paste was prepared by mixing a sealing composition and a vehicle (a solution of 1.2% nitrocellulose in isoamyl acetate) at a weight ratio of 9.0: 1.0. Put this paste on a funnel glass piece for CRT, on a substrate glass piece for PDP and VFD,
And fired under the same conditions as for the flow button diameter, and the residual strain (unit: nm / cm) generated between the glass piece and the fired sealing composition was measured using a polarimeter. . “+” Indicates that the sealing composition after firing has undergone compressive strain, and “−” indicates that the sealing composition after firing has undergone tensile strain. This residual strain is -1
The range of 00 to +500 nm / cm is desirable.
【００３８】熱膨張係数：封着用組成物をフローボタン
径の場合と同条件で焼成後、所定寸法に研磨して、熱膨
張測定装置により昇温速度１０℃／分の条件で伸びの量
を測定し、室温〜３００℃（ＣＲＴ用途）または室温〜
２５０℃（ＰＤＰまたはＶＦＤ用途）までの平均熱膨張
係数（単位：×１０-7／℃）を算出した。Thermal expansion coefficient: After baking the sealing composition under the same conditions as in the case of the flow button diameter, it is polished to a predetermined size, and the amount of elongation is measured by a thermal expansion measuring device at a temperature rising rate of 10 ° C./min. Measure, room temperature to 300 ° C (for CRT use) or room temperature to
The average coefficient of thermal expansion up to 250 ° C. (for PDP or VFD use) (unit: × 10 −7 / ° C.) was calculated.
【００３９】また、これらの封着用組成物を用いて封着
を行ったＣＲＴ、ＰＤＰ、ＶＦＤの強度を測定した。Further, the strength of CRT, PDP and VFD which were sealed using these sealing compositions was measured.
【００４０】ＣＲＴについては、２５型のファンネルと
パネルの間に封着用組成物を介在させ、４００〜５００
℃に３０分間保持してファンネルとパネルを封着してバ
ルブを製造した。ＰＤＰについては、この封着用組成物
をあらかじめＰＤＰの基板の端部に介在させ、４００〜
５００℃で３０分間保持し封着して、パネルを製造し
た。ＶＦＤについては、電極等を形成したガラス基板の
端部の間にグリッドを設置して介在させ、４００〜５０
０℃で３０分間保持してガラス基板どうしを封着して、
パネルを製造した。For the CRT, a sealing composition is interposed between a 25-type funnel and a panel, and 400 to 500.
C. for 30 minutes to seal the funnel and panel to produce a valve. For PDP, the sealing composition was previously interposed at the edge of the PDP substrate,
The panel was held at 500 ° C. for 30 minutes and sealed to produce a panel. Regarding VFD, a grid is provided and interposed between the ends of the glass substrate on which electrodes and the like are formed, and 400 to 50
Hold at 0 ° C for 30 minutes to seal the glass substrates together,
Panels were manufactured.
【００４１】これらのバルブおよびパネルについて、耐
水圧強度を測定した結果を表１、表２に示す。耐水圧強
度の測定法は次のとおりである。Tables 1 and 2 show the results of measuring the water pressure resistance of these valves and panels. The measuring method of the water pressure resistance is as follows.
【００４２】耐水圧強度：バルブまたはパネルの内外に
水による圧力差を与えて破壊するときの圧力差を測定し
た（単位：ｋｇ／ｃｍ2 、５個の平均値）。バルブまた
はパネルとしての強度を保証するために、通常この耐水
圧強度は３ｋｇ／ｃｍ2 以上が望ましい。Water-proof pressure strength: The pressure difference when breaking by applying a pressure difference due to water to the inside or outside of the valve or panel was measured (unit: kg / cm 2 , average value of 5 pieces). In order to guarantee the strength as a valve or a panel, usually, the water pressure resistance is preferably 3 kg / cm 2 or more.
【００４３】また、それぞれの封着用組成物に用いたガ
ラスのガラス転移点（単位：℃）を記載した。ガラス転
移点はＤＴＡを用いて昇温速度１０℃／分で測定した。Further, the glass transition point (unit: ° C.) of the glass used for each sealing composition is described. The glass transition point was measured at a heating rate of 10 ° C./min using DTA.
【００４４】表１、表２から、本発明の封着用組成物
は、実用的に充分な特性を有することがわかる。また例
１８〜２０においては、フローボタン径が小さく、耐水
圧強度が低い。Tables 1 and 2 show that the sealing composition of the present invention has practically sufficient characteristics. In Examples 18 to 20, the flow button diameter was small and the water pressure resistance was low.
【００４５】[0045]
【表１】 [Table 1]
【００４６】[0046]
【表２】 [Table 2]
【００４７】[0047]
【発明の効果】本発明によれば、鉛を含まない、ＣＲ
Ｔ、ＰＤＰ、ＶＦＤなどの封着に好適な封着用組成物が
得られる。本発明の封着用組成物を用いて封着したＣＲ
Ｔ、ＰＤＰ、ＶＦＤは特に耐水圧強度に優れる。According to the present invention, lead-free CR
A sealing composition suitable for sealing such as T, PDP, and VFD is obtained. CR sealed using the sealing composition of the present invention
T, PDP, and VFD are particularly excellent in water pressure resistance.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田辺 隆一 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Ryuichi Tanabe 1150 Hazawacho, Kanagawa-ku, Yokohama-shi
Claims (6)
６０〜９９重量％と低膨張セラミックスフィラーの粉末
１〜４０重量％とからなる組成物であり、該低融点ガラ
スの組成が実質的に重量表示で、 Ｂｉ2 Ｏ3 ７７〜９５％、 ＭｇＯ＋ＺｎＯ １〜２０％、 Ｂ2 Ｏ3 ２〜１０％、 ＳｉＯ2 ０〜 １％、 ＣｅＯ2 ０〜１０％、 からなることを特徴とする封着用組成物。1. A composition comprising substantially bismuth-based low melting point glass powder of 60 to 99% by weight and low expansion ceramic filler powder of 1 to 40% by weight, wherein the composition of the low melting point glass is substantially by weight displayed, Bi 2 O 3 77~95%, MgO + ZnO 1~20%, B 2 O 3 2~10%, SiO 2 0~ 1%, CeO 2 0~10%, characterized in that it consists Sealing composition.
ン、コージェライト、チタン酸アルミニウム、アルミ
ナ、ムライト、シリカ、β−ユークリプタイト、β−ス
ポジュメンおよびβ−石英固溶体からなる群より選ばれ
る１種以上である請求項１記載の封着用組成物。2. The low-expansion ceramic filler is at least one selected from the group consisting of zircon, cordierite, aluminum titanate, alumina, mullite, silica, β-eucryptite, β-spodumene and β-quartz solid solution. The sealing composition according to claim 1.
が６５×１０-7〜１００×１０-7／℃である請求項１ま
たは２記載の封着用組成物。3. The sealing composition according to claim 1, wherein an average coefficient of thermal expansion from room temperature to 250 ° C. after firing is 65 × 10 −7 to 100 × 10 −7 / ° C.
９重量％と低膨張セラミックスフィラーの粉末１〜３０
重量％とからなり、焼成後の室温〜３００℃の平均熱膨
張係数が８０×１０-7〜１００×１０-7／℃である、ブ
ラウン管のパネルとファンネルとを封着するための請求
項１、２または３記載の封着用組成物。4. Bismuth-based low melting glass powder 70 to 9
9% by weight and low expansion ceramic filler powder 1 to 30
2. A method for sealing a panel of a cathode ray tube and a funnel, wherein the panel comprises a weight percent and an average coefficient of thermal expansion from room temperature to 300 ° C. after firing is 80 × 10 −7 to 100 × 10 −7 / ° C. 4. The sealing composition according to 2 or 3.
６０〜９８重量％と低膨張セラミックスフィラー２〜４
０重量％とからなり、焼成後の室温〜２５０℃の平均熱
膨張係数が６５×１０-7〜９０×１０-7／℃である、プ
ラズマディスプレイまたは蛍光表示管を封着するための
請求項１、２または３記載の封着用組成物。5. A substantially bismuth-based low melting point glass powder of 60 to 98% by weight and a low expansion ceramic filler 2 to 4.
Claims for sealing a plasma display or a fluorescent display tube comprising 0% by weight and having an average coefficient of thermal expansion from room temperature to 250 ° C. after firing of 65 × 10 −7 to 90 × 10 −7 / ° C. 4. The sealing composition according to 1, 2, or 3.
で、 Ｂｉ2 Ｏ3 ７７〜９５％、 ＭｇＯ＋ＺｎＯ １〜２０％、 Ｂｉ2 Ｏ3 ＋ＺｎＯ ８５〜９８％、 Ｂ2 Ｏ3 ２〜１０％、 ＳｉＯ2 ０〜 １％、 ＣｅＯ2 ０〜１０％、 からなる請求項１、２、３、４または５記載の封着用組
成物。6. The composition of said low-melting glass is substantially in terms of weight: Bi 2 O 3 77-95%, MgO + ZnO 1-20%, Bi 2 O 3 + ZnO 85-98%, B 2 O 3 2 10%, SiO 2 0~ 1% , CeO 2 0~10%, claims 1, 2, 3, 4 or 5 sealing composition according consist.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02940697A JP4557314B2 (en) | 1996-02-15 | 1997-02-13 | Sealing composition and sealing low melting point glass |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2787296 | 1996-02-15 | ||
| JP8-240817 | 1996-09-11 | ||
| JP24081796 | 1996-09-11 | ||
| JP8-27872 | 1996-09-11 | ||
| JP02940697A JP4557314B2 (en) | 1996-02-15 | 1997-02-13 | Sealing composition and sealing low melting point glass |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007093223A Division JP4650444B2 (en) | 1996-02-15 | 2007-03-30 | Low melting glass for sealing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10139478A true JPH10139478A (en) | 1998-05-26 |
| JP4557314B2 JP4557314B2 (en) | 2010-10-06 |
Family
ID=27285983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02940697A Expired - Fee Related JP4557314B2 (en) | 1996-02-15 | 1997-02-13 | Sealing composition and sealing low melting point glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4557314B2 (en) |
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| US9048056B2 (en) | 2009-03-27 | 2015-06-02 | Hitachi Powdered Metals Co., Ltd. | Glass composition and covering and sealing members using same |
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| CN104412332A (en) * | 2013-03-27 | 2015-03-11 | 第一毛织株式会社 | Composition for forming solar cell electrode and electrode prepared using the same |
| JP2013177308A (en) * | 2013-05-28 | 2013-09-09 | Nippon Electric Glass Co Ltd | Crystalline bismuth-based material |
| WO2024057824A1 (en) * | 2022-09-14 | 2024-03-21 | 日本電気硝子株式会社 | Bismuth-based glass powder and composite powder including same |
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