JP4132119B2 - Heat resistant glass - Google Patents
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- JP4132119B2 JP4132119B2 JP4346597A JP4346597A JP4132119B2 JP 4132119 B2 JP4132119 B2 JP 4132119B2 JP 4346597 A JP4346597 A JP 4346597A JP 4346597 A JP4346597 A JP 4346597A JP 4132119 B2 JP4132119 B2 JP 4132119B2
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- resistant glass
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- 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
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- Geochemistry & Mineralogy (AREA)
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- Organic Chemistry (AREA)
- Glass Compositions (AREA)
- Gas-Filled Discharge Tubes (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は耐熱性ガラスに関する。本発明の耐熱性ガラスは、例えばプラズマディスプレイ等の画像表示装置のガラス製パネルに好ましく用いられる。
【０００２】
【従来の技術】
プラズマディスプレイの製造工程では、電極上に誘電体層を形成するときと、Ｈｅ−Ｎｅガスを封止するときに焼成を行い、その温度は６００℃付近まで昇温することになる。そのため基板ガラスは６００℃の温度においても変形しない熱的特性が要求される。またプラズマディスプレイの製造に用いられる誘電体材料や封止用のガラスフリットは８２×１０-7／℃程度の膨張係数を有するために焼成中に反りやクラックが生じないように基板ガラスの方も同程度の膨張係数が要求される。またガラス製パネルの電気絶縁性確保のためその体積抵抗率を大きくする必要もある。
【０００３】
従来のプラズマディスプレイ用基板としては特開平７−１０１７４８号公報および米国特許第５，４５９，１０９号明細書に記載のものがあるが、特開平７−１０１７４８号公報に記載のガラスはＬｉ2Ｏ、Ｎａ2Ｏ、Ｋ2Ｏのアルカリ成分をその合量で９〜１６％含んでいるためガラス屈伏点（Ｔｓ）が６００℃以下で耐熱性が充分とはいえない。また米国特許第５，４５９，１０９号明細書に記載のガラスはＭｇＯが０〜１．５％、ＣａＯが０〜２．５％、ＭｇＯとＣａＯの合量が０〜４％であり、比較的に少量であるので、液相温度が高く、失透しやすく大量生産に不向きである。
【０００４】
また特開平４−４６０３５号公報には、ＳｉＯ2−Ｂ2Ｏ3−Ａｌ2Ｏ3−ＣａＯ−ＢａＯ系のグレースガラスが開示されているが、このグレースガラスは、セラミック基板に塗布されるものであり、基板ガラスの製法に用いられるものではない。このガラスはＢａＯを３５wt％以上含んでいるため耐失透性が不充分でフロート成型等の板状成型を必須とするガラスディスプレイ製造工程には適さない。
【０００５】
また特開平４−１４９０３９号公報には、ＳｉＯ2−Ａｌ2Ｏ3−Ｂ2Ｏ3−ＣａＯ−ＢａＯ−Ｙ2Ｏ3−ＺｒＯ2系のグレースガラスが開示されているが、このガラスもセラミック基板に塗布されるものであり、基板ガラスの製造に用いられるものではない。またこのガラスは、Ｙ2Ｏ3を必須成分としているため、熱膨張係数が小さく、封止用ガラスフリットとの間にかなりの膨張係数差が生じることになるため、焼成中にクラックが入るという欠点を有する。
【０００６】
【発明が解決しようとする課題】
本発明は、上記の問題点を解消し、例えば６００℃以上という温度でも粘性流動を起こさない耐熱性とガラス製パネル製造可能な耐失透性とを有し、従来のガラスよりも、さらに優れた電気絶縁性を持ちながら、膨張係数は誘電体材料や封止用ガラスフリットと同一ないし近似した熱的特性を有し、例えばガラス基板等のガラス板状製品の製造に好ましく用いられる耐熱性ガラスを提供することを目的とする。
【０００７】
【課題を解決するための手段】
本発明の耐熱性ガラスは、ガラス成分として重量％で表示して
ＳｉＯ2 ３０〜４５％
Ｂ2Ｏ3 １〜１０％
Ａｌ2Ｏ3 １〜 ７％
ＳｒＯ １〜１７％
ＢａＯ ２２〜３５％未満
ＭｇＯ ０〜 ５％
ＣａＯ ０〜１４％
ＭｇＯ＋ＣａＯ ４％を超え１６％以下
を含むことを特徴とする。
【０００８】
本発明の耐熱性ガラスは更に、Ｌａ2Ｏ3、ＺｒＯ2、ＺｎＯ、ＴｉＯ2、Ａｓ2Ｏ3、Ｓｂ2Ｏ3、ＳｎＯ2、ＳＯ3のうち少なくとも１種を含むこともできる。これらの成分の含量は、重量％で表示してそれぞれＬａ2Ｏ3が０〜１４％、ＺｒＯ2が０〜８％、ＺｎＯが０〜５％、ＴｉＯ2が０〜５％、Ａｓ2Ｏ3が０〜２％、Ｓｂ2Ｏ3が０〜２％、ＳｎＯ2が０〜２％、ＳＯ3が０〜２％である。
【０００９】
さらに本発明は、上記本発明の耐熱性ガラスを板状に成型することにより得られる、プラズマディスプレイ用基板等に用いられるガラス板製品に関する。
【００１０】
【発明を実施ための形態】
本発明の耐熱性ガラスにおける各成分およびその含量の限定理由を以下に説明する。
【００１１】
ＳｉＯ2はガラス形成成分であるため本発明には欠かせない成分である。そのためＳｉＯ2が３０％未満になるとガラスの液相温度（Ｌ.Ｔ.）が上昇する。またＳｉＯ2が４５％を超えると膨張係数が小さくなる。そのためＳｉＯ2の含量は３０〜４５％に限定される。好ましいＳｉＯ2の含量は３２〜４３％の範囲である。
【００１２】
Ｂ2Ｏ3は硅酸塩ガラスに添加することにより液相温度を下げる効果があるため本発明には欠かせない成分である。そのためＢ2Ｏ3が１％未満になるとガラスの液相温度が上昇する。また１０％を超えると膨張係数が小さくなる。そのためＢ2Ｏ3の含量は１〜１０％に限定される。好ましいＢ2Ｏ3の含量は３〜８％の範囲である。
【００１３】
Ａｌ2Ｏ3はガラスの化学的耐久性を良くする効果と液相温度（Ｌ.Ｔ.）を下げる効果があるため本発明には欠かせない成分である。そのためＡｌ2Ｏ3が１％未満になると化学的耐久性が悪化し、液相温度が上昇する。また７％を超えると膨張係数が小さくなる。そのためＡｌ2Ｏ3の含量は１〜７％に限定される。好ましいＡｌ2Ｏ3の含量は３〜５％である。
【００１４】
ＢａＯ、ＳｒＯは適量添加によりガラスの液相温度を下げる効果があるため本発明には欠かせない成分である。そのためＳｒＯが１％未満または１７％を超えた場合、ＢａＯが２２％未満または３５％以上の場合は液相温度が上昇する。従ってＳｒＯは１〜１７％に限定され、ＢａＯは２２％以上３５％未満に限定される。好ましいＳｒＯの含量は３〜１５％であり、好ましいＢａＯの含量は２６〜３３％である。
【００１５】
ＭｇＯ、ＣａＯは適量添加によりガラスの液相温度を下げ、膨張係数を上げる効果があるため本発明においてどちらか少なくとも１成分は欠かせない成分である。ＭｇＯが５％、ＣａＯが１４％を超えると液相温度が上がるため、ＭｇＯの含量は０〜５％、ＣａＯの含量は０〜１４％に限定される。ＭｇＯは０〜４％であるが好ましく、０〜３％が特に好ましい。ＣａＯは０〜１０％未満が好ましく、０．５〜９．５％が特に好ましい。
【００１６】
また、ＭｇＯとＣａＯの合量が４％以下になると、液相温度（Ｌ.Ｔ.）が上昇し、膨張係数が小さくなる。また１６％を超えても液相温度が上昇するため、ＭｇＯとＣａＯの合量は４％を超え１６％以下に限定される。好ましくは４．５〜１４％である。
【００１７】
Ｌａ2Ｏ3は任意成分として適量添加により液相温度の低下やガラス屈伏点（Ｔｓ）の調整が可能である。ただし１４％を超えると液相温度が上昇するため、Ｌａ2Ｏ3は０〜１４％の範囲に限定される。好ましくは０〜１２％の範囲である。
【００１８】
ＺｒＯ2、ＺｎＯ、ＴｉＯ2は任意成分として適量添加により液相温度を下げ化学的耐久性を上げることができる成分である。ただし、ＺｒＯ2が８％を超え、ＺｎＯ2またはＴｉＯ2が５％を超えると、熱膨張係数（α）が小さくなり、目的とする熱膨張特性が得られなくなる。よって、ＺｒＯ2は０〜８％、ＺｎＯは０〜５％、ＴｉＯ2は０〜５％の範囲に限定される。好ましくは、ＺｒＯ2が０〜６％、ＺｎＯが０〜４％、ＴｉＯ2が０〜４％の範囲である。
【００１９】
Ａｓ2Ｏ3、Ｓｂ2Ｏ3、ＳｎＯ2、ＳＯ3は任意成分として適量添加により、清澄剤として有効である。しかしいずれも２％を超えて添加すると耐失透性を悪くする。そのためＡｓ2Ｏ3、Ｓｂ2Ｏ3、ＳｎＯ2、ＳＯ3はの含量はそれぞれ０〜２％の範囲に限定される。
【００２０】
さらにＮｂ2Ｏ5、Ｔａ2Ｏ5、ＷＯ3、Ｇｄ2Ｏ3、ＰｂＯ、Ｂｉ2Ｏ3、ＴｅＯ2、Ｐ2Ｏ5等の成分も本発明の目的を損なわない程度であれば添加可能である。
【００２１】
本発明の耐熱性ガラスの原料としては、いずれの成分も水酸化物、炭酸塩、硝酸塩、硫化物、酸化物等を適宜用いることが可能である。これらの原料を所望の割合に秤取し、混合して調合原料とし、これを１２００℃〜１５００℃に加熱した熔解炉に投入し、熔解・清澄後撹拌し、均一化してから鋳型に鋳込み徐冷することにより、本発明の耐熱性ガラスを得ることができる。
【００２２】
本発明の耐熱性ガラスは、そのガラス屈伏点（Ｔｓ）が６７０℃以上で、１００℃〜３００℃の熱膨張係数（α）が７８×１０-7／℃〜９２×１０-7／℃の範囲にあるのが好ましい。
【００２３】
また本発明の耐熱性ガラスの液相温度は１０２０℃以下又は認めずであり、また体積抵抗率は４０．０〜３００．０×１０14Ωｃｍであるのが好ましい。
【００２４】
上記本発明の耐熱性ガラスを板状成型することにより、例えばプラズマディスプレイ等の画像表示装置用の基板ガラスが得られる。板状成型の方法は公知のフロート法やダウンドロー法等のいずれの成型方法でもガラスを失透させずに成型することが可能である。得られた板状ガラスの用途は上記に限定されず、他のガラスディスプレイ方式にも用いることができる。
【００２５】
【実施例】
以下、実施例により本発明を説明する。
【００２６】
実施例１〜５
表１に示す組成となるように各ガラス原料を調合した。このガラス原料を白金坩堝に入れ電気熔融炉を用いて１４００℃に加熱熔融し、型枠に鋳込み徐冷して実施例１〜５の試料ガラスを得た。得られたガラスの液相温度（Ｌ.Ｔ.）、ガラス屈伏点（Ｔｓ）、熱膨張係数（α）、体積抵抗率（ρＶ）の測定を行った。
【００２７】
液相温度（Ｌ.Ｔ.）は６００℃〜１１００℃の温度勾配のついた失透試験炉に１時間保持し、保持後、倍率１００倍の顕微鏡により結晶の有無を観察し、結晶が存在する温度と結晶が存在しない温度の境目を液相温度とした。なお液相温度認めずとは、６００℃〜１１００℃の全温度域において、１時間保持で結晶が存在しなかったということである。
【００２８】
ガラス屈伏点（Ｔｓ）と熱膨張係数（α）は径４ｍｍ、長さ１５〜２０ｍｍの円柱状サンプルを熱膨張測定機を用いて、サンプルに１０ｇの荷重をかけながら、８℃／ｍｉｎで昇温し、ガラス屈伏点は荷重によりガラスの膨張が止まったときの温度、熱膨張係数は、１００℃〜３００℃の範囲における平均線膨張係数を１０-7／℃を単位として示してある。
【００２９】
体積抵抗率ρＶ（Ω・ｃｍ）は、径２６．５ｍｍ、厚み１ｍｍの両面研磨試料について、アドバンテスト社Ｒ８３４０Ａを用いて、温度２０℃、湿度５０％で測定した。これらの測定結果を表１に示した。
【００３０】
比較例１〜６
特開平７−１０１７４８号公報の実施例の記載に従って、アルカリ分を高含量で含むガラス試料を作製し、前記実施例１〜５と同様にして液相温度、ガラス屈伏点、熱膨張係数、体積抵抗率を測定した。これらの測定結果を表２に示した。
【００３１】
比較例７〜８
特開平４−４６０３５号公報の実施例１および６の記載に従って、ＢａＯを３５wt％以上含むガラス試料を作製し、実施例１〜５と同様にして液相温度、ガラス屈伏点、熱膨張係数、体積抵抗率を測定した結果を表３に示す。
【００３２】
比較例９
米国特許第５，４５９，１０９号明細書の記載に従って、ＭｇＯとＣａＯの合量が４％以下（１．４％）であるガラス試料を作製し、実施例１〜５と同様にして液相温度、ガラス屈伏点、熱膨張係数、体積抵抗率を測定した結果を表３に示す。
【００３３】
【表１】
【表２】
【表３】
表１、表２、表３より次のことが明らかである。
【００３７】
表２に示すように比較例１〜６のガラスはアルカリ成分をその合量で９〜１６％含んでいるため、ガラス屈伏点（Ｔｓ）が６００℃以下で耐熱性が充分ではない。また体積抵抗率が小さく、絶縁性に劣っている。
【００３８】
比較例７〜８のガラスはＢａＯを３５wt％以上含んでいるため、液相温度が１０４０℃以上ある。このガラス組成でシート成型を行なうとするならば、いかなる方法を用いても成型作業温度は１０４０℃未満でなくてはガラスの粘性が低すぎて成型はできない。よって、比較例７〜８のガラスでは液相温度が高いことになる。
【００３９】
比較例９のガラスはＭｇＯとＣａＯが４％以下（１．４％）と少ないため液相温度が高く、失透し易く大量生産に向かないことが明らかである。
【００４０】
一方、表１に示すように実施例１〜５のガラスは、いずれもガラス屈伏点が６７０℃以上で液相温度は１０２０℃以下であるため、シート成型中でガラスが失透することは無く、得られた板を６００℃まで昇温しても板が変型しない耐熱特性を有している。また熱膨張係数も従来用いられた誘電体材料や封止用ガラスフリットがそのまま使えるように７８×１０-7／℃〜９２×１０-7／℃の範囲にあり、また比較例１〜６のガラスよりも体積抵抗率が大きく電気絶縁性にも優れている。
【００４１】
【発明の効果】
本発明によれば、耐熱性、耐失透性、電気絶縁性、熱膨張特性に優れ、プラズマディスプレイ用基板などのガラス板状製品に好ましく用いられるガラスが提供された。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a heat resistant glass. The heat-resistant glass of the present invention is preferably used for a glass panel of an image display device such as a plasma display.
[0002]
[Prior art]
In the manufacturing process of the plasma display, firing is performed when the dielectric layer is formed on the electrode and when the He—Ne gas is sealed, and the temperature is raised to around 600 ° C. Therefore, the substrate glass is required to have thermal characteristics that do not deform even at a temperature of 600 ° C. In addition, since the dielectric material used for manufacturing the plasma display and the glass frit for sealing have an expansion coefficient of about 82 × 10 −7 / ° C., the substrate glass is also used to prevent warping and cracks during firing. A similar expansion coefficient is required. It is also necessary to increase the volume resistivity in order to ensure the electrical insulation of the glass panel.
[0003]
Conventional plasma display substrates include those described in JP-A-7-101748 and US Pat. No. 5,459,109, but the glass described in JP-A-7-101748 is Li 2 O. , Na 2 O and K 2 O contain alkali components in a total amount of 9 to 16%, so that the glass yield point (Ts) is 600 ° C. or less, and the heat resistance is not sufficient. The glass described in US Pat. No. 5,459,109 has 0 to 1.5% MgO, 0 to 2.5% CaO, and 0 to 4% of the total amount of MgO and CaO. Therefore, the liquid phase temperature is high, and it is easy to devitrify and is not suitable for mass production.
[0004]
JP-A-4-46035 discloses a SiO 2 —B 2 O 3 —Al 2 O 3 —CaO—BaO-based grace glass, which is applied to a ceramic substrate. It is not used for the manufacturing method of substrate glass. Since this glass contains 35 wt% or more of BaO, it is not suitable for a glass display manufacturing process in which devitrification resistance is insufficient and plate-like molding such as float molding is essential.
[0005]
Japanese Patent Application Laid-Open No. 4-149039 discloses a grace glass of SiO 2 —Al 2 O 3 —B 2 O 3 —CaO—BaO—Y 2 O 3 —ZrO 2. It is applied to the substrate and is not used for manufacturing the substrate glass. In addition, since this glass has Y 2 O 3 as an essential component, the thermal expansion coefficient is small, and a considerable difference in expansion coefficient is generated between the glass frit for sealing, so that cracks occur during firing. Has drawbacks.
[0006]
[Problems to be solved by the invention]
The present invention solves the above-mentioned problems, has heat resistance that does not cause viscous flow even at a temperature of, for example, 600 ° C. or more, and devitrification resistance that can produce a glass panel, and is superior to conventional glass. In addition, it has the same thermal characteristics as the dielectric material and sealing glass frit, while having electrical insulation, and has a thermal characteristic that is preferably used for the production of glass plate products such as glass substrates. The purpose is to provide.
[0007]
[Means for Solving the Problems]
The heat-resistant glass of the present invention is expressed as% by weight as a glass component, and SiO 2 is 30 to 45%.
B 2 O 3 1-10%
Al 2 O 3 1-7%
SrO 1-17%
BaO 22-35% MgO 0-5%
CaO 0-14%
It is characterized by containing MgO + CaO over 4% and up to 16%.
[0008]
The heat-resistant glass of the present invention can further contain at least one of La 2 O 3 , ZrO 2 , ZnO, TiO 2 , As 2 O 3 , Sb 2 O 3 , SnO 2 , and SO 3 . The contents of these components are expressed in weight%, La 2 O 3 is 0 to 14%, ZrO 2 is 0 to 8%, ZnO is 0 to 5%, TiO 2 is 0 to 5%, As 2 O 3 is 0 to 2%, Sb 2 O 3 is 0 to 2%, SnO 2 is 0 to 2%, and SO 3 is 0 to 2%.
[0009]
Furthermore, this invention relates to the glass plate product used for the substrate for plasma displays etc. which are obtained by shape | molding the heat resistant glass of the said invention in plate shape.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
The reasons for limiting each component and its content in the heat-resistant glass of the present invention will be described below.
[0011]
Since SiO 2 is a glass forming component, it is an essential component for the present invention. Therefore SiO 2 is below 30%, the glass liquidus temperature (L.T.) is increased. If SiO 2 exceeds 45%, the expansion coefficient becomes small. Therefore the content of SiO 2 is limited to 30% to 45%. The content of the SiO 2 content is preferably in the range of 32-43%.
[0012]
B 2 O 3 is an indispensable component for the present invention because it has the effect of lowering the liquidus temperature when added to oxalate glass. Therefore, when B 2 O 3 is less than 1%, the liquidus temperature of the glass increases. If it exceeds 10%, the expansion coefficient becomes small. Therefore, the content of B 2 O 3 is limited to 1 to 10%. The preferred B 2 O 3 content is in the range of 3-8%.
[0013]
Al 2 O 3 is an indispensable component for the present invention because it has the effect of improving the chemical durability of the glass and the effect of lowering the liquidus temperature (LT). Therefore, when Al 2 O 3 is less than 1%, the chemical durability is deteriorated and the liquidus temperature is increased. If it exceeds 7%, the expansion coefficient becomes small. Therefore, the content of Al 2 O 3 is limited to 1 to 7%. A preferable content of Al 2 O 3 is 3 to 5%.
[0014]
BaO and SrO are indispensable components for the present invention because they have the effect of lowering the liquidus temperature of the glass when added in appropriate amounts. Therefore, when SrO is less than 1% or exceeds 17%, the liquidus temperature rises when BaO is less than 22% or 35% or more. Therefore, SrO is limited to 1 to 17%, and BaO is limited to 22% or more and less than 35%. The preferred SrO content is 3 to 15%, and the preferred BaO content is 26 to 33%.
[0015]
Since MgO and CaO have the effect of lowering the liquidus temperature of the glass and increasing the expansion coefficient when added in appropriate amounts, at least one of them is an indispensable component in the present invention. If the MgO content exceeds 5% and the CaO content exceeds 14%, the liquidus temperature increases, so the MgO content is limited to 0-5% and the CaO content is limited to 0-14%. MgO is preferably 0 to 4%, particularly preferably 0 to 3%. CaO is preferably 0 to less than 10%, particularly preferably 0.5 to 9.5%.
[0016]
On the other hand, when the total amount of MgO and CaO is 4% or less, the liquidus temperature (LT) increases and the expansion coefficient decreases. Moreover, since liquid phase temperature rises even if it exceeds 16%, the total amount of MgO and CaO is limited to more than 4% and 16% or less. Preferably it is 4.5 to 14%.
[0017]
La 2 O 3 is possible to adjust the reduction and glass deformation point of the liquidus temperature (Ts) by adding an appropriate amount as an optional ingredient. However, if it exceeds 14%, the liquidus temperature rises, so La 2 O 3 is limited to the range of 0 to 14%. Preferably it is 0 to 12% of range.
[0018]
ZrO 2 , ZnO, and TiO 2 are components that can lower the liquidus temperature and increase the chemical durability by adding appropriate amounts as optional components. However, if ZrO 2 exceeds 8% and ZnO 2 or TiO 2 exceeds 5%, the thermal expansion coefficient (α) decreases, and the desired thermal expansion characteristics cannot be obtained. Therefore, ZrO 2 is limited to 0 to 8%, ZnO is limited to 0 to 5%, and TiO 2 is limited to 0 to 5%. Preferably, ZrO 2 is 0 to 6%, ZnO is 0 to 4%, and TiO 2 is 0 to 4%.
[0019]
As 2 O 3 , Sb 2 O 3 , SnO 2 , and SO 3 are effective as refining agents by adding appropriate amounts as optional components. However, if both are added in excess of 2%, the devitrification resistance is deteriorated. Therefore, the contents of As 2 O 3 , Sb 2 O 3 , SnO 2 and SO 3 are limited to the range of 0 to 2%, respectively.
[0020]
Furthermore, components such as Nb 2 O 5 , Ta 2 O 5 , WO 3 , Gd 2 O 3 , PbO, Bi 2 O 3 , TeO 2 , and P 2 O 5 can be added as long as the purpose of the present invention is not impaired. It is.
[0021]
As the raw material for the heat-resistant glass of the present invention, any component can be appropriately used hydroxide, carbonate, nitrate, sulfide, oxide and the like. These raw materials are weighed in a desired ratio, mixed to prepare a mixed raw material, which is put into a melting furnace heated to 1200 ° C. to 1500 ° C., stirred after melting and clarification, homogenized, and gradually poured into a mold. The heat-resistant glass of the present invention can be obtained by cooling.
[0022]
The heat resistant glass of the present invention has a glass yield point (Ts) of 670 ° C. or higher and a thermal expansion coefficient (α) of 100 ° C. to 300 ° C. of 78 × 10 −7 / ° C. to 92 × 10 −7 / ° C. Preferably it is in the range.
[0023]
Further, the liquidus temperature of the heat-resistant glass of the present invention is preferably 1020 ° C. or less, and the volume resistivity is preferably 40.0 to 300.0 × 10 14 Ωcm.
[0024]
By forming the heat-resistant glass of the present invention into a plate shape, for example, a substrate glass for an image display device such as a plasma display can be obtained. The plate-shaped molding method can be performed without devitrifying the glass by any known molding method such as a float method or a downdraw method. The use of the obtained sheet glass is not limited to the above, and can be used for other glass display systems.
[0025]
【Example】
Hereinafter, the present invention will be described by way of examples.
[0026]
Examples 1-5
Each glass raw material was prepared so that it might become a composition shown in Table 1. This glass raw material was put in a platinum crucible, heated and melted to 1400 ° C. using an electric melting furnace, cast into a mold and gradually cooled to obtain sample glasses of Examples 1 to 5. The liquid phase temperature (LT), glass yield point (Ts), thermal expansion coefficient (α), and volume resistivity (ρV) of the obtained glass were measured.
[0027]
The liquidus temperature (L.T.) is held in a devitrification test furnace with a temperature gradient of 600 ° C. to 1100 ° C. for 1 hour. After holding, the presence or absence of crystals is observed with a microscope at a magnification of 100 times. The boundary between the temperature at which the crystal is present and the temperature at which no crystal is present is defined as the liquidus temperature. In addition, that liquid phase temperature is not recognized means that the crystal | crystallization did not exist by hold | maintaining for 1 hour in the whole temperature range of 600 to 1100 degreeC.
[0028]
The glass yield point (Ts) and the coefficient of thermal expansion (α) were increased at 8 ° C./min while applying a 10 g load to a sample of a cylindrical sample having a diameter of 4 mm and a length of 15 to 20 mm using a thermal expansion measuring machine. raised, glass deformation point temperature at which expansion of the glass is stopped by the load, the thermal expansion coefficient is shown an average linear expansion coefficient in the range of 100 ° C. to 300 ° C. in units of 10 -7 / ° C..
[0029]
The volume resistivity ρV (Ω · cm) was measured on a double-sided polished sample having a diameter of 26.5 mm and a thickness of 1 mm using Advantest R8340A at a temperature of 20 ° C. and a humidity of 50%. These measurement results are shown in Table 1.
[0030]
Comparative Examples 1-6
According to the description of Examples in JP-A-7-101748, a glass sample containing a high content of alkali was prepared, and the liquidus temperature, glass yield point, thermal expansion coefficient, volume in the same manner as in Examples 1-5. The resistivity was measured. The measurement results are shown in Table 2.
[0031]
Comparative Examples 7-8
According to the description of Examples 1 and 6 of JP-A-4-46035, a glass sample containing 35 wt% or more of BaO was prepared, and the liquidus temperature, the glass yield point, the thermal expansion coefficient, The results of measuring the volume resistivity are shown in Table 3.
[0032]
Comparative Example 9
According to the description in US Pat. No. 5,459,109, a glass sample in which the total amount of MgO and CaO is 4% or less (1.4%) is prepared, and the liquid phase is obtained in the same manner as in Examples 1-5. Table 3 shows the results of measurement of temperature, glass yield point, thermal expansion coefficient, and volume resistivity.
[0033]
[Table 1]
[Table 2]
[Table 3]
From Table 1, Table 2, and Table 3, the following is clear.
[0037]
As shown in Table 2, since the glasses of Comparative Examples 1 to 6 contain 9 to 16% of the total amount of alkali components, the glass yield point (Ts) is 600 ° C. or less and the heat resistance is not sufficient. In addition, the volume resistivity is small and the insulating property is poor.
[0038]
Since the glasses of Comparative Examples 7 to 8 contain 35 wt% or more of BaO, the liquidus temperature is 1040 ° C. or more. If sheet molding is performed with this glass composition, the molding operation temperature must be less than 1040 ° C., and the viscosity of the glass is too low to be molded. Therefore, in the glasses of Comparative Examples 7 to 8, the liquidus temperature is high.
[0039]
It is clear that the glass of Comparative Example 9 has a high liquidus temperature because it contains less than 4% (1.4%) of MgO and CaO, is easily devitrified, and is not suitable for mass production.
[0040]
On the other hand, as shown in Table 1, since the glasses of Examples 1 to 5 all have a glass yield point of 670 ° C. or higher and a liquidus temperature of 1020 ° C. or lower, the glass is not devitrified during sheet molding. The obtained plate has heat resistance characteristics that do not deform even when the temperature is raised to 600 ° C. Also, the thermal expansion coefficient is in the range of 78 × 10 −7 / ° C. to 92 × 10 −7 / ° C. so that the conventionally used dielectric material and sealing glass frit can be used as they are. It has a larger volume resistivity than glass and is excellent in electrical insulation.
[0041]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the glass which was excellent in heat resistance, devitrification resistance, electrical insulation, and a thermal expansion characteristic, and was preferably used for glass plate-shaped products, such as a substrate for plasma displays, was provided.
Claims (7)
ＳｉＯ２ ３０〜４５％
Ｂ２Ｏ３ １〜１０％
Ａｌ２Ｏ３ １〜 ７％
ＳｒＯ １〜１７％
ＢａＯ ２２〜３５％未満
ＭｇＯ ０〜 ５％
ＣａＯ ０〜１４％
ＭｇＯ＋ＣａＯ ４％を超え１６％以下
を含み、Ｌｉ２Ｏ，Ｎａ２ＯおよびＫ２Ｏを含まず、さらにＰｂＯ含まない（但し、ＣａＯ＋ＢａＯが４０重量％以上である場合を除く）ことを特徴とする耐熱性ガラス。As a glass component, expressed in weight%, SiO 2 30-45%
B 2 O 3 1~10%
Al 2 O 3 1-7%
SrO 1-17%
BaO 22-35% MgO 0-5%
CaO 0-14%
MgO + CaO more than 4% and less than 16%, Li 2 O, Na 2 O and K 2 O are not included, and PbO is not included (except when CaO + BaO is 40% by weight or more). Heat resistant glass.
ＳｉＯ２ ３０〜４５％
Ｂ２Ｏ３ １〜１０％
Ａｌ２Ｏ３ １〜 ７％
ＳｒＯ １〜１７％
ＢａＯ ２２〜３５％未満
ＭｇＯ ０〜 ５％
ＣａＯ ０〜１４％
ＭｇＯ＋ＣａＯ ４％を超え１６％以下
を含み、ＰｂＯを含まない（但し、ＣａＯ＋ＢａＯが４０重量％以上である場合を除く）ことおよびプラズマディスプレイ用基板に用いられることを特徴とする耐熱性ガラス。As a glass component, expressed in weight%, SiO 2 30-45%
B 2 O 3 1~10%
Al 2 O 3 1-7%
SrO 1-17%
BaO 22-35% MgO 0-5%
CaO 0-14%
A heat-resistant glass characterized in that it contains more than 4% MgO + CaO and less than 16% and does not contain PbO (except when CaO + BaO is 40% by weight or more) and is used for a substrate for plasma display.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4346597A JP4132119B2 (en) | 1996-03-13 | 1997-02-27 | Heat resistant glass |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8-56417 | 1996-03-13 | ||
| JP5641796 | 1996-03-13 | ||
| JP4346597A JP4132119B2 (en) | 1996-03-13 | 1997-02-27 | Heat resistant glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH101328A JPH101328A (en) | 1998-01-06 |
| JP4132119B2 true JP4132119B2 (en) | 2008-08-13 |
Family
ID=26383226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4346597A Expired - Lifetime JP4132119B2 (en) | 1996-03-13 | 1997-02-27 | Heat resistant glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4132119B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3800443B2 (en) * | 1996-10-22 | 2006-07-26 | 日本電気硝子株式会社 | Non-alkali glass substrate for display and method for producing the same |
| JP2003112942A (en) * | 2001-10-03 | 2003-04-18 | Nippon Electric Glass Co Ltd | Glass substrate for field emission type display |
| JP2006160546A (en) * | 2004-12-06 | 2006-06-22 | Hitachi Ltd | Flat surface-type display device |
| JP6175742B2 (en) * | 2011-05-18 | 2017-08-09 | 日本電気硝子株式会社 | High refractive index glass |
| JP6694229B2 (en) * | 2014-10-08 | 2020-05-13 | 株式会社オハラ | Glass |
| WO2016072241A1 (en) * | 2014-11-05 | 2016-05-12 | 日本電気硝子株式会社 | Glass |
| CN115180824B (en) * | 2022-07-05 | 2024-01-16 | 河北光兴半导体技术有限公司 | Fireproof glass composition, fireproof glass and preparation method thereof |
-
1997
- 1997-02-27 JP JP4346597A patent/JP4132119B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH101328A (en) | 1998-01-06 |
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