JP3669022B2 - Substrate glass composition and plasma display substrate using the same - Google Patents
Substrate glass composition and plasma display substrate using the same Download PDFInfo
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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
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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Description
【０００１】
【発明の属する技術分野】
本発明は、フラットディスプレイ、特にプラズマディスプレイ（ＰＤＰ）用基板ガラスとして有用で、フロート法成形による大板の製造に好適な基板用ガラス組成物に関する。
【０００２】
【従来の技術】
ＰＤＰは、一般的に、基板ガラス上に金属電極、絶縁ペースト、リブペースト等を５５０〜６００℃程度の最高温度で焼成した後、対向板をフリットシールすることにより製造される。従来、このための基板ガラスとしては、建築用あるいは自動車用として広く用いられるソーダライムシリカガラスが一般的に用いられてきた。
【０００３】
しかし、ソーダライムシリカガラスのガラス転移点は５３０〜５５０℃であるため、上記の最高温度で熱処理を受けると、基板が変形する、あるいは基板ガラスの寸法が著しく変化するため、対向板との電極位置合わせを精度良く実現しがたい等の課題があった。このような課題は、パネルの大きさが例えば呼称４０インチのような大型なものになるとより顕著になり、耐熱性のより高い基板用ガラスが必要となる。
【０００４】
現在、ソーダライムシリカガラスよりも耐熱性に優れ、ディスプレイ用ガラスとして広く使われている基板ガラスに、例えば特開平４−３２５４３４（米国特許明細書５３４８９１６号）に代表される液晶用の無アルカリガラスがある。しかし、これらのガラスの熱膨張係数は３５〜５０×１０-7℃-1の範囲にあり、ソーダライムシリカガラスの熱膨張係数８０〜９０×１０-7℃-1よりもはるかに小さい。このため液晶用の無アルカリガラスをＰＤＰに使用するためには各種のフリット・ペースト材料を基板ガラスの熱膨張率に合致したものを使用しなければならず、上記の温度範囲でそれらを選定することは非常に困難である。
【０００５】
一方、特開平３−４０９３３には、熱膨張係数がソーダライムシリカガラスのそれと同程度で、６００℃での熱変形が小さいガラス組成物が開示されている。しかし、ここに示されている組成物は、次のいずれかの点で充分に満足できるものでなかった。
【０００６】
（１）ガラス転移点が６００℃以下であるため、熱処理によるガラスの収縮量が呼称４０インチのような大きなパネルに対しては充分に小さくない。
（２）ＣａＯの含有量が６％以上であるため失透温度が高く、品質、生産性に優れたフロート法による成形が困難である。
【０００７】
【発明が解決しようとする課題】
本発明の目的は、上記欠点を解決し、ソーダライムシリカガラスと同様の熱膨張係数を有し、大型ＰＤＰの製造に適するよう、高いガラス転移点を有し、フロート法成形に適した基板用ガラス組成物を提供することにある。
【０００８】
【課題を解決するための手段】
本発明は、重量％表示で実質的に、
ＳｉＯ２ ５２〜６２％、
Ａｌ２Ｏ３ ５〜１２％、
ＭｇＯ ０〜 ４％、
ＣａＯ ３〜 ５．５％、
ＳｒＯ ６〜 ９％、
ＢａＯ ０〜１３％、
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ １７〜２７％、
Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ ７〜１４％、
ＺｒＯ２ ０．２〜 ６％、
ＳＯ３ ０〜 ０．６％、
からなり、
ガラス転移点が６００℃以上であり、
失透温度が、粘度が１０ ４ ポイズとなる温度よりも低く、
熱膨張係数が７５〜９５×１０ −７ ℃ −１ の範囲にある基板用ガラス組成物である。
【０００９】
フロート法成形は粘度が１０4 ポイズ程度で行われるため、失透温度が１０4 ポイズに相当する温度より低いガラスでないとフロート法による成形が実質的に困難になる。
【００１０】
本発明による組成の限定理由は以下の通りである。
【００１１】
ＳｉＯ2 : ガラスの骨格を形成する成分で、その含有量が５２重量％未満では、ガラスの耐熱性が悪くなる。他方、６２重量％超では熱膨張係数が低下する。ＳｉＯ2 は５４〜６０重量％の範囲がより好ましい。
【００１２】
Ａｌ2 Ｏ3 ：ガラス転移点を上げ、耐熱性を向上させる効果があり、その含有量が５重量％未満ではこの効果があらわれず、他方、１２重量％超ではガラスの熱膨張係数が低くなりすぎる。Ａｌ2 Ｏ3 は６〜１１重量％の範囲がより好ましい。
【００１３】
ＭｇＯ：必須成分ではないが、含有することによりガラスの転移点の向上と熱膨張係数の増大がはかれる。しかし、その含有量が、４重量％超では失透が生成しやすくなる。
【００１４】
ＣａＯ：ガラスの転移点の向上と熱膨張係数の増大の作用がある。その含有量が３重量％未満ではガラスの熱膨張係数が小さくなりすぎる。他方、５．５重量％超では失透温度がフロート法の成形温度より高くなり、フロート法の成形が困難になる。
【００１５】
ＳｒＯ：ＣａＯと同様にガラスの転移点の向上と熱膨張係数の増大の作用がある。その含有量が６重量％未満ではガラスの熱膨張係数が小さくなりすぎる。他方、９重量％超では失透温度がフロート法の成形温度より高くなり、フロート法の成形が困難になる。
【００１６】
ＢａＯ：ＭｇＯと同様に、必須成分ではないが、含有することによりガラスの転移点の向上と熱膨張係数の増大がはかれる。しかし、その含有量が、１３重量％超では失透が生成しやすくなる。
【００１７】
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ：これらの合量が１７重量％未満ではガラスの耐熱性が低下し、熱膨張係数が小さくなりすぎる。他方、２７重量％超では失透温度が高くなりすぎる。ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯは１８〜２５重量％の範囲がより好ましい。
【００１８】
Ｌｉ2 Ｏ、Ｎａ2 Ｏ、Ｋ2 Ｏ：ガラスの熱膨張係数を大きくするために少なくとも一種は必須である。これらの合量が７重量％未満ではガラスの熱膨張係数が小さすぎる。他方、合量が１４重量％超ではガラスの耐熱性が低下する。Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏは８〜１３重量％の範囲がより好ましい。
【００１９】
このなかでＫ2 Ｏはガラスの熱膨張係数を大きくするため、４重量％以上含まれることが好ましい。一方、これらの成分は過度に添加するとガラスの耐熱性低下の傾向が大きい。かかる観点から、Ｎａ2 Ｏは０〜６重量％、Ｋ2 Ｏは４〜１２重量％、Ｌｉ2 Ｏは０〜１重量％の範囲とすることがより好ましい。
【００２０】
ＺｒＯ2 : ガラスの耐熱性及び化学的耐久性の向上のために使用する。０．２重量％未満では添加の効果がなく、好ましくは０．５重量％以上添加する。一方で、その含有量が６重量％超ではガラスの失透温度が高くなりすぎる。
【００２１】
ＳＯ3 ：必須成分ではないが、通常清澄剤として用いられる。しかし、その含有量が０．６重量％超では製造時にガラスが再沸するなどしてガラス中に気泡が残存する。
【００２２】
かくして、本発明においてより望ましいガラス組成の一例は、重量％表示で実質的に以下の如くなる。
ＳｉＯ2 ５４〜６０％、
Ａｌ2 Ｏ3 ６〜１１％、
ＭｇＯ ０〜 ４％、
ＣａＯ ３〜 ５．５％、
ＳｒＯ ６〜 ９％、
ＢａＯ ０〜１３％、
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ １８〜２５％、
Ｌｉ2 Ｏ ０〜 １％、
Ｎａ2 Ｏ ０〜 ６％、
Ｋ2 Ｏ ４〜１２％、
Ｌｉ2 Ｏ＋Ｎａ2 Ｏ＋Ｋ2 Ｏ ８〜１３％、
ＺｒＯ2 ０．５〜 ６％、
ＳＯ3 ０〜 ０．６％。
【００２３】
本発明によるガラスは上記成分以外にガラスの溶解性、清澄性、成形性を改善するため、Ａｓ2 Ｏ3 、Ｓｂ2 Ｏ3 、Ｐ2 Ｏ5 、Ｆ、Ｃｌを合量で２重量％以下添加できる。また、ガラスの化学的耐久性の向上のため、Ｌａ2 Ｏ3 、ＴｉＯ2 、ＳｎＯ2 、ＺｎＯを合量で５重量％以下添加できる。さらに、Ｆｅ2 Ｏ3 、ＣｏＯ、ＮｉＯ、Ｎｄ2 Ｏ3 等の着色剤を添加してガラスの色調を調整できる。この着色剤の含有量は合量で１重量％以下が好ましい。
【００２４】
さらに、溶解性を向上するためにＢ2 Ｏ3 を添加できる。ただし、過度の添加は、熱膨張係数を低下させるので１．５重量％未満とすることが好ましい。
【００２５】
かくして得られるガラスのガラス転移点は６００℃以上、好ましくは、６１０℃以上である。また、本発明で得られるガラスの失透温度は、粘度が１０4 ポイズとなる温度よりも低い。その差は好ましくは４０℃以上である。さらに本発明で得られるガラスの熱膨張係数は７５〜９５×１０-7℃-1の範囲、好ましくは８０〜９０×１０-7℃-1の範囲にある。
【００２６】
本発明のガラスは、プラズマディスプレイ用基板として好適である。その分光透過率は４２５〜４７５ｎｍ、５１０〜５６０ｎｍ、６００〜６５０ｎｍの範囲でそれぞれ８５％以上となっていることが好ましい。
【００２７】
本発明のガラスは、例えば次のような方法で製造できる。すなわち、通常使用される各成分の原料を目標成分になるように調合し、これを溶解炉に連続的に投入し、１５００〜１６００℃に加熱して溶融する。この溶融ガラスをフロート法により所定の板厚に成形し、徐冷後切断することによって、透明なガラス基板を得る。
【００２８】
【実施例】
例１〜１０（表１）に実施例を、例１１〜１８（表２）に比較例を示す。
各成分の原料を目標組成になるように調合し、白金坩堝を用いて、１５００〜１６００℃の温度で４時間加熱し溶解した。溶解にあたっては、白金スターラーを挿入し２時間撹拌しガラスの均質化を行った。次いで溶解ガラスを流し出し、板状に成形後徐冷した。
【００２９】
こうして得られたガラスについて、組成（表１、表２の上段部、単位：重量％）、熱膨脹係数、ガラス転移点、粘性温度及び失透温度を測定し、表の各欄に示した。熱膨脹係数はα欄に単位：１０-7℃-1で示し、ガラス転移温度はＴg 欄に単位：℃で示し、失透温度はＣ欄に単位：℃で示した。粘性温度は、粘度が１０2 ポイズに相当する温度をＡ欄に単位：℃で示し、粘度が１０4 ポイズに相当する温度をＢ欄に単位：℃で示した。
【００３０】
ガラス転移点は、次のようにして求めた。ガラスを徐冷点の温度で３０分間保持した後、６０℃／分の速度で冷却し徐冷した。次いでこの徐冷したガラスについて、示差式熱膨張計を使用し室温から屈伏点まで温度に対する熱膨張率の曲線を求めた。この曲線の最初に屈曲する点の前後で接線を引き、接線の交点に対応する温度をガラス転移点とした。
【００３１】
表１より明らかなように、本発明によるガラス組成物の熱膨張係数は、８０〜９０×１０-7℃-1の範囲にあり、従来のソーダライムシリカガラスのそれと全く同等である。また、ガラス転移点はいずれも６１０℃以上であり、大型ＰＤＰの製造においてガラスが収縮してしまう等の問題がない。さらに、失透温度は、フロート法の成形粘度である１０4 ポイズに相当する温度よりも４０℃以上低く、フロート法による大板の製造に好適であることがわかる。
【００３２】
一方、表２には比較例として、特開平３−４０９３３に開示されているガラス組成物について同様の測定を行った結果を示す。比較例のうち、例１３及び例１４のガラスはガラス転移点が６００℃以下であるため、耐熱性が不充分で、大型のＰＤＰの製造においてはガラス収縮の問題が起こることが予想される。
【００３３】
また、例１１〜１２、１５〜１８のガラスは、いずれも失透温度が１０4 ポイズに相当する温度よりも高いため、フロート法による成形では失透が生じる恐れがある。
【００３４】
【表１】
【表２】
【発明の効果】
本発明によるガラスは、フロート法による成形ができ、また、ガラス転移点が高く、かつソーダライムシリカガラスと同等の熱膨脹係数を有しているので、プラズマディスプレイ用基板等、かかる特性を要求する用途に好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a glass composition for a substrate that is useful as a substrate glass for a flat display, particularly a plasma display (PDP), and that is suitable for production of a large plate by float forming.
[0002]
[Prior art]
In general, a PDP is manufactured by baking a metal electrode, an insulating paste, a rib paste, or the like on a substrate glass at a maximum temperature of about 550 to 600 ° C., and then frit-sealing a counter plate. Conventionally, as the substrate glass for this purpose, soda lime silica glass, which is widely used for construction or automobiles, has been generally used.
[0003]
However, since the glass transition point of soda lime silica glass is 530 to 550 ° C., when subjected to the heat treatment at the above-mentioned maximum temperature, the substrate is deformed, or the dimensions of the substrate glass are remarkably changed. There was a problem that it was difficult to achieve accurate alignment. Such a problem becomes more prominent when the size of the panel is large, for example, 40 inches, and a glass for a substrate having higher heat resistance is required.
[0004]
As a substrate glass that is superior in heat resistance to soda lime silica glass and is widely used as a display glass, an alkali-free glass for liquid crystal represented by, for example, JP-A-4-325434 (US Pat. No. 5,348,916). There is. However, the thermal expansion coefficient of these glasses is in the range of 35~50 × 10 -7 ℃ -1, much smaller than the thermal expansion coefficient of 80~90 × 10 -7 ℃ -1 soda-lime-silica glass. For this reason, in order to use non-alkali glass for liquid crystal for PDP, various frit paste materials that match the thermal expansion coefficient of the substrate glass must be used, and they are selected within the above temperature range. It is very difficult.
[0005]
On the other hand, Japanese Patent Laid-Open No. 3-40933 discloses a glass composition having a thermal expansion coefficient comparable to that of soda lime silica glass and having a small thermal deformation at 600 ° C. However, the composition shown here is not fully satisfactory in any of the following points.
[0006]
(1) Since the glass transition point is 600 ° C. or lower, the shrinkage amount of the glass due to heat treatment is not sufficiently small for a large panel having a nominal size of 40 inches.
(2) Since the content of CaO is 6% or more, the devitrification temperature is high, and it is difficult to form by the float method excellent in quality and productivity.
[0007]
[Problems to be solved by the invention]
The object of the present invention is to solve the above-mentioned drawbacks, have a thermal expansion coefficient similar to that of soda lime silica glass, have a high glass transition point, and be suitable for float process molding so as to be suitable for production of a large PDP. It is to provide a glass composition.
[0008]
[Means for Solving the Problems]
The present invention substantially represents the weight percentage,
SiO 2 52~62%,
Al 2 O 3 5-12%,
MgO 0-4%,
CaO 3 to 5.5%,
SrO 6-9%,
BaO 0-13%,
MgO + CaO + SrO + BaO 17-27%,
Li 2 O + Na 2 O + K 2 O 7-14%,
ZrO 2 0.2-6%,
SO 3 0~ 0.6%,
Tona is,
The glass transition point is 600 ° C. or higher,
The devitrification temperature is lower than the temperature at which the viscosity becomes 10 4 poise,
Thermal expansion coefficient of the glass composition for a substrate area by the near of 75~95 × 10 -7 ℃ -1.
[0009]
Float molding is performed at a viscosity of about 10 4 poise, and therefore, molding by the float method is substantially difficult unless the glass has a devitrification temperature lower than a temperature corresponding to 10 4 poise.
[0010]
The reasons for limiting the composition according to the present invention are as follows.
[0011]
SiO 2 : A component that forms a glass skeleton. If the content is less than 52% by weight, the heat resistance of the glass deteriorates. On the other hand, if it exceeds 62% by weight, the thermal expansion coefficient decreases. SiO 2 is more preferably in the range of 54 to 60% by weight.
[0012]
Al 2 O 3 : has the effect of increasing the glass transition point and improving the heat resistance. If the content is less than 5% by weight, this effect does not appear. On the other hand, if it exceeds 12% by weight, the thermal expansion coefficient of the glass decreases. Too much. Al 2 O 3 is more preferably in the range of 6 to 11% by weight.
[0013]
MgO: Although not an essential component, inclusion thereof improves the glass transition point and increases the thermal expansion coefficient. However, if the content exceeds 4% by weight, devitrification tends to occur.
[0014]
CaO: Has the effect of improving the glass transition point and increasing the thermal expansion coefficient. If the content is less than 3% by weight, the thermal expansion coefficient of the glass becomes too small. On the other hand, if it exceeds 5.5% by weight, the devitrification temperature becomes higher than the molding temperature of the float process, which makes it difficult to mold the float process.
[0015]
Similar to SrO: CaO, it has the effect of improving the glass transition point and increasing the thermal expansion coefficient. If the content is less than 6% by weight, the thermal expansion coefficient of the glass becomes too small. On the other hand, if it exceeds 9% by weight, the devitrification temperature becomes higher than the molding temperature of the float process, and the float process is difficult to mold.
[0016]
Similar to BaO: MgO, it is not an essential component, but inclusion thereof improves the glass transition point and increases the thermal expansion coefficient. However, if the content exceeds 13% by weight, devitrification tends to occur.
[0017]
MgO + CaO + SrO + BaO: If the total amount is less than 17% by weight, the heat resistance of the glass is lowered and the thermal expansion coefficient is too small. On the other hand, if it exceeds 27% by weight, the devitrification temperature becomes too high. MgO + CaO + SrO + BaO is more preferably in the range of 18 to 25% by weight.
[0018]
Li 2 O, Na 2 O, K 2 O: At least one kind is essential for increasing the thermal expansion coefficient of glass. If the total amount is less than 7% by weight, the thermal expansion coefficient of the glass is too small. On the other hand, if the total amount exceeds 14% by weight, the heat resistance of the glass decreases. Li 2 O + Na 2 O + K 2 O is more preferably in the range of 8 to 13% by weight.
[0019]
Among these, K 2 O is preferably contained in an amount of 4% by weight or more in order to increase the thermal expansion coefficient of the glass. On the other hand, when these components are added excessively, the glass tends to be reduced in heat resistance. From this viewpoint, Na 2 O is more preferably 0 to 6% by weight, K 2 O is preferably 4 to 12% by weight, and Li 2 O is more preferably 0 to 1% by weight.
[0020]
ZrO 2 : Used for improving the heat resistance and chemical durability of glass. If it is less than 0.2% by weight, there is no effect of addition, preferably 0.5% by weight or more is added. On the other hand, if the content exceeds 6% by weight, the devitrification temperature of the glass becomes too high.
[0021]
SO 3 : Although not an essential component, it is usually used as a fining agent. However, if its content exceeds 0.6% by weight, bubbles remain in the glass due to, for example, re-boiling of the glass during production.
[0022]
Thus, an example of a more desirable glass composition in the present invention is substantially as follows in terms of% by weight.
SiO 2 54~60%,
Al 2 O 3 6-11%,
MgO 0-4%,
CaO 3 to 5.5%,
SrO 6-9%,
BaO 0-13%,
MgO + CaO + SrO + BaO 18-25%,
Li 2 O 0-1%,
Na 2 O 0-6%,
K 2 O 4-12%,
Li 2 O + Na 2 O + K 2 O 8-13%,
ZrO 2 0.5-6%,
SO 3 0~ 0.6%.
[0023]
In addition to the above components, the glass according to the present invention improves As 2 O 3 , Sb 2 O 3 , P 2 O 5 , F, and Cl in a total amount of 2% by weight or less in order to improve the solubility, clarity and moldability of the glass. Can be added. Further, in order to improve the chemical durability of the glass, La 2 O 3 , TiO 2 , SnO 2 and ZnO can be added in a total amount of 5% by weight or less. Furthermore, the color tone of the glass can be adjusted by adding a colorant such as Fe 2 O 3 , CoO, NiO, or Nd 2 O 3 . The total content of the colorant is preferably 1% by weight or less.
[0024]
Furthermore, B 2 O 3 can be added to improve solubility. However, excessive addition reduces the thermal expansion coefficient, so it is preferable to make it less than 1.5% by weight.
[0025]
The glass transition point of the glass thus obtained is 600 ° C. or higher, preferably 610 ° C. or higher. The devitrification temperature of the glass obtained in the present invention is lower than the temperature at which the viscosity becomes 10 4 poise. The difference is preferably 40 ° C. or higher. Furthermore, the thermal expansion coefficient of the glass obtained by the present invention is in the range of 75 to 95 × 10 −7 ° C.− 1 , preferably in the range of 80 to 90 × 10 −7 ° C. −1 .
[0026]
The glass of the present invention is suitable as a substrate for plasma display. The spectral transmittance is preferably 85% or more in the range of 425 to 475 nm, 510 to 560 nm, and 600 to 650 nm.
[0027]
The glass of the present invention can be produced, for example, by the following method. That is, the raw material of each component normally used is mixed so that it may become a target component, this is continuously thrown into a melting furnace, and it heats to 1500-1600 degreeC and fuse | melts. The molten glass is formed into a predetermined plate thickness by a float method, and is cooled and then cut to obtain a transparent glass substrate.
[0028]
【Example】
Examples are shown in Examples 1 to 10 (Table 1), and Comparative Examples are shown in Examples 11 to 18 (Table 2).
The raw material of each component was prepared so that it might become a target composition, and it melt | dissolved by heating at the temperature of 1500-1600 degreeC for 4 hours using the platinum crucible. In melting, a platinum stirrer was inserted and stirred for 2 hours to homogenize the glass. Next, the molten glass was poured out, formed into a plate shape, and then slowly cooled.
[0029]
About the glass obtained in this way, the composition (the upper part of Table 1 and Table 2, unit: wt%), the coefficient of thermal expansion, the glass transition point, the viscosity temperature and the devitrification temperature were measured and shown in each column of the table. The coefficient of thermal expansion is indicated in the column α by the unit: 10 −7 ° C. −1 , the glass transition temperature is indicated in the T g column by the unit: ° C., and the devitrification temperature is indicated in the C column by the unit: ° C. As for the viscosity temperature, the temperature corresponding to a viscosity of 10 2 poise is indicated in the column A in units of ° C, and the temperature corresponding to a viscosity of 10 4 poise is indicated in the column B in units of ° C.
[0030]
The glass transition point was determined as follows. The glass was held at the temperature of the annealing point for 30 minutes, and then cooled and slowly cooled at a rate of 60 ° C./min. Next, for this slowly cooled glass, a differential thermal dilatometer was used to obtain a curve of thermal expansion coefficient with respect to temperature from room temperature to the yield point. A tangent line was drawn before and after the first bending point of this curve, and the temperature corresponding to the intersection of the tangent lines was taken as the glass transition point.
[0031]
As is clear from Table 1, the thermal expansion coefficient of the glass composition according to the present invention is in the range of 80 to 90 × 10 −7 ° C. −1 , which is completely equivalent to that of the conventional soda lime silica glass. Further, the glass transition points are all 610 ° C. or higher, and there is no problem that the glass shrinks in the production of a large PDP. Furthermore, the devitrification temperature is lower by 40 ° C. or more than the temperature corresponding to 10 4 poise, which is the molding viscosity of the float process, and it can be seen that it is suitable for the production of large plates by the float process.
[0032]
On the other hand, as a comparative example, Table 2 shows the result of the same measurement performed on the glass composition disclosed in JP-A-3-40933. Among the comparative examples, the glass of Examples 13 and 14 has a glass transition point of 600 ° C. or lower, so that the heat resistance is insufficient, and it is expected that a problem of glass shrinkage will occur in the production of a large PDP.
[0033]
In addition, since the glasses of Examples 11 to 12 and 15 to 18 have a devitrification temperature higher than a temperature corresponding to 10 4 poise, devitrification may occur in molding by the float process.
[0034]
[Table 1]
[Table 2]
【The invention's effect】
The glass according to the present invention can be formed by a float process, has a high glass transition point, and has a thermal expansion coefficient equivalent to that of soda lime silica glass. It is suitable for.
Claims (6)
ＳｉＯ２ ５２〜６２％、
Ａｌ２Ｏ３ ５〜１２％、
ＭｇＯ ０〜 ４％、
ＣａＯ ３〜 ５．５％、
ＳｒＯ ６〜 ９％、
ＢａＯ ０〜１３％、
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ １７〜２７％、
Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ ７〜１４％、
ＺｒＯ２ ０．２〜 ６％、
ＳＯ３ ０〜 ０．６％、
からなり、
ガラス転移点が６００℃以上であり、
失透温度が、粘度が１０ ４ ポイズとなる温度よりも低く、
熱膨張係数が７５〜９５×１０ −７ ℃ −１ の範囲にある基板用ガラス組成物。Substantially in weight% display,
SiO 2 52~62%,
Al 2 O 3 5-12%,
MgO 0-4%,
CaO 3 to 5.5%,
SrO 6-9%,
BaO 0-13%,
MgO + CaO + SrO + BaO 17-27%,
Li 2 O + Na 2 O + K 2 O 7-14%,
ZrO 2 0.2-6%,
SO 3 0~ 0.6%,
Tona is,
The glass transition point is 600 ° C. or higher,
The devitrification temperature is lower than the temperature at which the viscosity becomes 10 4 poise,
Thermal expansion coefficient of 75 to 95 × 10 -7 ° C. range near Ru glass composition for substrates of -1.
ＳｉＯ２ ５４〜６０％、
Ａｌ２Ｏ３ ６〜１１％、
ＭｇＯ ０〜 ４％、
ＣａＯ ３〜 ５．５％、
ＳｒＯ ６〜 ９％、
ＢａＯ ０〜１３％、
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ １８〜２５％、
Ｌｉ２Ｏ ０〜 １％、
Ｎａ２Ｏ ０〜 ６％、
Ｋ２Ｏ ４〜１２％、
Ｌｉ２Ｏ＋Ｎａ２Ｏ＋Ｋ２Ｏ ８〜１３％、
ＺｒＯ２ ０．５〜 ６％、
ＳＯ３ ０〜 ０．６％、
からなる請求項１に記載の基板用ガラス組成物。Substantially in weight% display,
SiO 2 54~60%,
Al 2 O 3 6-11%,
MgO 0-4%,
CaO 3 to 5.5%,
SrO 6-9%,
BaO 0-13%,
MgO + CaO + SrO + BaO 18-25%,
Li 2 O 0-1%,
Na 2 O 0-6%,
K 2 O 4~12%,
Li 2 O + Na 2 O + K 2 O 8~13%,
ZrO 2 0.5-6%,
SO 3 0~ 0.6%,
The glass composition for a substrate according to claim 1 , comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26448695A JP3669022B2 (en) | 1994-10-14 | 1995-10-12 | Substrate glass composition and plasma display substrate using the same |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6-249781 | 1994-10-14 | ||
| JP24978194 | 1994-10-14 | ||
| JP26448695A JP3669022B2 (en) | 1994-10-14 | 1995-10-12 | Substrate glass composition and plasma display substrate using the same |
| EP95116500A EP0769481B1 (en) | 1994-10-14 | 1995-10-19 | Glass composition for a substrate, and substrate for plasma display made thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08165138A JPH08165138A (en) | 1996-06-25 |
| JP3669022B2 true JP3669022B2 (en) | 2005-07-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26448695A Expired - Fee Related JP3669022B2 (en) | 1994-10-14 | 1995-10-12 | Substrate glass composition and plasma display substrate using the same |
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| JP (1) | JP3669022B2 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5854153A (en) * | 1997-01-09 | 1998-12-29 | Corning Incorporated | Glasses for display panels |
| FR2758550B1 (en) * | 1997-01-17 | 1999-02-12 | Saint Gobain Vitrage | SILICO-SODO-CALCIUM GLASS COMPOSITIONS AND THEIR APPLICATIONS |
| KR100431728B1 (en) * | 1997-11-03 | 2004-09-08 | 삼성코닝 주식회사 | Substrate glass composition for plasma image display panel, improving contrast and having high deformation point and low expansibility |
| WO1999026269A1 (en) * | 1997-11-17 | 1999-05-27 | Nippon Electric Glass Co., Ltd. | Plasma display substrate glass |
| US5854152A (en) * | 1997-12-10 | 1998-12-29 | Corning Incorporated | Glasses for display panels |
| JP2002117778A (en) * | 2000-10-10 | 2002-04-19 | Toray Ind Inc | Substrate for display, member for display and display |
| JP4692915B2 (en) * | 2002-05-29 | 2011-06-01 | 日本電気硝子株式会社 | Front glass substrate for plasma display devices. |
| JP2005089286A (en) * | 2003-08-12 | 2005-04-07 | Nippon Electric Glass Co Ltd | Glass base plate for flat panel display device |
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| EP1961710A4 (en) * | 2005-12-07 | 2009-12-09 | Nippon Electric Glass Co | Outer container for external electrode fluorescent lamp |
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| JP5046176B2 (en) * | 2006-05-18 | 2012-10-10 | 日本電気硝子株式会社 | Glass for flat image display device, glass substrate using the same, and manufacturing method thereof |
| KR101231520B1 (en) | 2007-10-25 | 2013-02-07 | 아사히 가라스 가부시키가이샤 | Glass composition for substrate and method for producing the same |
| CN101959819A (en) | 2008-02-27 | 2011-01-26 | 旭硝子株式会社 | Glass composition for substrate |
| JP5671041B2 (en) * | 2009-09-25 | 2015-02-18 | ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ | Aluminosilicate glass with high heat resistance and low working temperature |
| JP5255611B2 (en) * | 2010-09-17 | 2013-08-07 | Ｈｏｙａ株式会社 | GLASS SUBSTRATE FOR DISPLAY, PROCESS FOR PRODUCING THE SAME AND DISPLAY USING THE SAME |
| JP5915891B2 (en) * | 2011-05-10 | 2016-05-11 | 日本電気硝子株式会社 | Glass |
| JP5002067B2 (en) * | 2011-07-01 | 2012-08-15 | Ｈｏｙａ株式会社 | GLASS SUBSTRATE FOR PORTABLE LIQUID CRYSTAL DISPLAY, ITS MANUFACTURING METHOD, AND PORTABLE LIQUID CRYSTAL DISPLAY USING THE SAME |
| JP5502937B2 (en) * | 2012-06-11 | 2014-05-28 | Ｈｏｙａ株式会社 | GLASS SUBSTRATE FOR DISPLAY, PROCESS FOR PRODUCING THE SAME AND DISPLAY USING THE SAME |
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-
1995
- 1995-10-12 JP JP26448695A patent/JP3669022B2/en not_active Expired - Fee Related
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| JPH08165138A (en) | 1996-06-25 |
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