JPH11180728A - Substrate glass composition for display device - Google Patents

Substrate glass composition for display device

Info

Publication number
JPH11180728A
JPH11180728A JP9352646A JP35264697A JPH11180728A JP H11180728 A JPH11180728 A JP H11180728A JP 9352646 A JP9352646 A JP 9352646A JP 35264697 A JP35264697 A JP 35264697A JP H11180728 A JPH11180728 A JP H11180728A
Authority
JP
Japan
Prior art keywords
glass
temperature
coefficient
thermal expansion
melting
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.)
Pending
Application number
JP9352646A
Other languages
Japanese (ja)
Inventor
Nobuya Kuriyama
延也 栗山
Hiroshi Machishita
汎史 町下
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central Glass Co Ltd
Original Assignee
Central Glass Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Central Glass Co Ltd filed Critical Central Glass Co Ltd
Priority to JP9352646A priority Critical patent/JPH11180728A/en
Publication of JPH11180728A publication Critical patent/JPH11180728A/en
Pending legal-status Critical Current

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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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum

Abstract

PROBLEM TO BE SOLVED: To produce the substrate glass for the display device suitable to a melting and floating forming method including a directly energizing melting having a moderate heat performance, being a low density glass and suitable for PDP especially. SOLUTION: The glass is incorporated with 60-63 SiO2 , 9-13 Al2 O3 , 0.5-3.5 ZrO2 , 0.5-2 P2 O5 , 71-78 SiO2 +Al2 O3 +ZrO+P2 O5 , 1-5 MgO, 4-9 CaO, 1-5 SrO, 0-4 BaO, 11-14 MgO+CaO+SrO+BaO, 0-2 Li2 O, 7-9 Na2 O, 2-5 K2 O, 9-14 Li2 O+ Na2 +K2 O by wt.%, and the glass has a specific density of <=2.60, a distortion point of >=570 deg.C, 10<4> poise temp. of <=1200 deg.C, a temp. difference of poise temp.- devitrification temp. of >=50 deg.C and a coefficient of thermal expansion from room temp. to 300 deg.C of >=80×10<-7> / deg.C.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、各種ディスプレイ
装置用基板ガラス、特にプラズマディスプレイパネル
(ＰＤＰ) 用基板ガラスとして好適なガラス組成物であ
って、電気溶融法を含めた溶融、およびフロート法によ
る成形 (製板) が容易なディスプレイ装置用基板ガラス
組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate glass for various display devices, and particularly to a plasma display panel.
The present invention relates to a glass composition suitable for a substrate glass for (PDP), which is easy to be formed by melting including an electric melting method and forming (plate making) by a float method.

【０００２】[0002]

【従来技術および解決すべき課題】従来、ディスプレイ
装置用基板ガラスとしては、ソーダ石灰シリカ系ガラス
が用いられるケースが多い。一例としてＰＤＰ用ガラス
基板においては、ガラス基板にニッケルやアルミニウム
等の電極や絶縁塗膜等をスクリーン印刷などにより施
し、 500℃を越える温度での焼成を繰返してパネルを製
作する。基板ガラスは電極や塗膜との熱膨張率が異なる
とそれらの亀裂や剥離を生じ易いので、熱膨張率を整合
させる必要があり、前記ソーダ石灰シリカ系ガラスにお
いては熱膨張率が90×10-7／℃近くと、電極や塗膜との
熱膨張率に近い点において有用であるが、歪点が 510℃
近辺の温度であるため繰返し焼成に際して熱変形を生じ
易く、製作歩留りを著しく悪化させるという問題があ
る。2. Description of the Related Art Conventionally, soda-lime-silica glass is often used as a substrate glass for display devices. As an example, in the case of a glass substrate for PDP, an electrode such as nickel or aluminum, an insulating coating film or the like is applied to the glass substrate by screen printing or the like, and firing at a temperature exceeding 500 ° C. is repeated to produce a panel. If the substrate glass has a different coefficient of thermal expansion from the electrodes and the coating film, cracks and peeling are liable to occur.Therefore, it is necessary to match the coefficients of thermal expansion.In the soda-lime-silica glass, the coefficient of thermal expansion is 90 × 10 -7 / ° C is useful in that it has a coefficient of thermal expansion close to that of electrodes and coatings, but the strain point is 510 ° C.
Since the temperature is in the vicinity, there is a problem that thermal deformation is apt to occur during repeated firing, and the production yield is remarkably deteriorated.

【０００３】特開平３−40933 号公報には、SiO2成分、
Al2O3 成分、CaO 等の２価金属酸化物、Na2O等のアルカ
リ金属酸化物、ZrO2成分等よりなる基板用ガラス組成物
であって、600 ℃付近の熱処理においても殆ど変形せ
ず、また熱膨張率もソーダ石灰シリカ系ガラスと殆ど変
わらないガラスが開示されている。概してこの成分系で
は２価金属酸化物が過多で、ガラスの比重を増大させる
上に、ガラス融液の高温粘度を上昇し、均質化、清澄性
を悪化し、また、成形性も難化するという危惧がある。
均質化、清澄性を改善するためには溶融促進・清澄剤と
してのNa2SO3 、Sb2O3 、またはAs2O3 を過剰に添加す
る必要があるが、例えば直接通電溶融の場合においては
それらが電極と反応して電極を変質劣化させたり、ガラ
スに着色を与えたりするという危惧がある。[0003] JP-A-3-40933 discloses a SiO 2 component,
A glass composition for substrates consisting of Al 2 O 3 components, divalent metal oxides such as CaO, alkali metal oxides such as Na 2 O, ZrO 2 components, etc., which are almost deformed even at a heat treatment at around 600 ° C. A glass having a coefficient of thermal expansion almost equal to that of soda-lime-silica glass is disclosed. In general, this component system contains an excess of divalent metal oxides, which increases the specific gravity of the glass, increases the high-temperature viscosity of the glass melt, deteriorates homogeneity and clarity, and makes molding difficult. There is a fear that.
In order to improve homogenization and fining, it is necessary to add Na 2 SO 3 , Sb 2 O 3 , or As 2 O 3 in excess as a melting accelerator and fining agent. There is a fear that they may react with the electrodes to deteriorate and deteriorate the electrodes or to give coloring to the glass.

【０００４】特開平７−257937号公報には、SiO2成分、
Al2O3 成分、CaO 等２価金属酸化物、K2O 等アルカリ金
属酸化物、ZrO2成分等よりなり、ＰＤＰ用基板に適用す
るガラス組成物が開示されている。しかし、ネットワー
クフォーマーとしてのSiO2成分が低く、その分ガラス形
成が不安定で、失透が生じ易い。またガラス比重を増大
し易く、特に大サイズのディスプレイ装置においては装
置の重量が増大し、その取扱を困難とするという危惧が
ある。Japanese Patent Application Laid-Open No. 7-257937 discloses an SiO 2 component,
A glass composition comprising an Al 2 O 3 component, a divalent metal oxide such as CaO, an alkali metal oxide such as K 2 O, a ZrO 2 component, and the like, and applied to a PDP substrate is disclosed. However, since the SiO 2 component as a network former is low, glass formation is correspondingly unstable, and devitrification tends to occur. Further, there is a concern that the specific gravity of the glass is easily increased, and especially in the case of a large-sized display device, the weight of the device is increased, which makes it difficult to handle.

【０００５】特表平９−507207号公報には、ネットワー
クフォーマーであるSiO2成分や、Al 2O3 成分、B2O3成
分、ZrO2成分と、２価金属酸化物、およびアルカリ金属
酸化物を含み、歪点がソーダ石灰系ガラスより高く、熱
膨張率がソーダ石灰系ガラス並に高い、基板ガラスや耐
火ガラスとして好適なガラス組成物が開示されている。
しかし、SiO2成分等の割合が低く、相対的に２価金属酸
化物、アルカリ金属酸化物等が高く、前記同様ガラス形
成が不安定で、失透が生じ易く、またガラス比重を増大
する。[0005] Japanese Patent Publication No. 9-507207 discloses a network.
SiO, the performerTwoIngredients and Al TwoOThree Ingredient, BTwoOThreeSuccess
Min, ZrOTwoComponent, divalent metal oxide, and alkali metal
Contains oxides, has a higher strain point than soda-lime glass,
The expansion coefficient is as high as soda-lime glass.
A glass composition suitable as fire glass is disclosed.
However, SiOTwoLow ratio of components, etc., relatively divalent metal acid
Oxides, alkali metal oxides, etc.
Unstable in composition, easy to devitrify, and increased glass specific gravity
I do.

【０００６】本発明はそれら従来技術における問題点に
鑑みて種々検討の末、完成に達したものであり、直接通
電溶融を含めた溶融、フロート法成形に適し、適度な熱
特性を有し、比較的低比重のガラスであって、特にＰＤ
Ｐ用として好適なディスプレイ装置用基板ガラス組成物
を提供するものである。The present invention has been accomplished after various studies in view of the problems in the prior art, and has been completed. The present invention is suitable for melting including direct electric current melting and float molding, and has appropriate thermal characteristics. A glass with relatively low specific gravity, especially PD
It is intended to provide a substrate glass composition for a display device suitable for P.

【０００７】[0007]

【課題を解決するための手段】本発明は、wt％で、SiO2
60〜63、Al2O3 ９〜13、ZrO2 0.5〜3.5 、P2O5 0.5〜
２、SiO2＋Al2O3 ＋ZrO2＋P2O5 71〜78、MgO １〜５、
CaO ４〜９、SrO １〜５、BaO ０〜４、MgO ＋CaO ＋Sr
0 ＋BaO 11〜14、Li2O ０〜２、Na2O ７〜９、K2O ２
〜５、Li2O＋Na2O＋K2O ９〜14の範囲で含有し、ガラス
比重が2.60以下、ガラスの歪点が 570℃以上、ガラスの
104 ポイズ温度（ガラス粘度が104 ポイズになる温度で
成形作業をするうえで基準となる）が1200℃以下であ
り、104 ポイズ温度−失透温度の温度差が50℃以上、か
つガラスの室温から 300℃における熱膨張率が80×10-7
／℃以上であるディスプレイ装置用基板ガラス組成物で
ある。SUMMARY OF THE INVENTION The present invention relates to a method for producing SiO 2 by wt.
60~63, Al 2 O 3 9~13, ZrO 2 0.5~3.5, P 2 O 5 0.5~
2, SiO 2 + Al 2 O 3 + ZrO 2 + P 2 O 5 71-78, MgO 1-5,
CaO 4-9, SrO 1-5, BaO 0-4, MgO + CaO + Sr
0 + BaO 11-14, Li 2 O 0-2, Na 2 O 7-9, K 2 O 2
5, contained in a range of Li 2 O + Na 2 O + K 2 O 9~14, glass specific gravity of 2.60 or less, the strain point of the glass is 570 ° C. or higher, the glass
10 4 poise temperature (the standard for molding at a temperature at which the glass viscosity becomes 10 4 poise) is 1200 ° C or less, and the temperature difference of 10 4 poise temperature-devitrification temperature is 50 ° C or more, and glass Has a coefficient of thermal expansion from room temperature to 300 ° C of 80 × 10 -7
/ ° C or higher is a substrate glass composition for a display device.

【０００８】[0008]

【発明の実施の形態】以下の各成分において‘％’表示
はwt％のことをあらわす。本発明の成分系において、Si
O2はガラスのネットワークフォーマーとして作用する主
要成分であり、ガラス中60％未満ではガラスを安定して
形成し難く、失透を生じさせ易く、またガラスの歪点が
低下し、耐水性、耐薬品性を悪化させ、ガラス比重を増
大する傾向にある。他方63％を越えるとガラス融液の高
温粘度が高くなり、フロート法成形が困難になる。従っ
て60〜63％の範囲で導入する。BEST MODE FOR CARRYING OUT THE INVENTION In the following components, "%" indicates wt%. In the component system of the present invention, Si
O 2 is a main component acting as a network former of glass, and if it is less than 60% in the glass, it is difficult to form the glass stably, easily causing devitrification, and lowering the strain point of the glass, It tends to deteriorate chemical resistance and increase glass specific gravity. On the other hand, if it exceeds 63%, the high temperature viscosity of the glass melt becomes high, and it becomes difficult to form by a float method. Therefore, it is introduced in the range of 60 to 63%.

【０００９】Al2O3 はガラスネットワークの一翼を担う
もので、ガラスを安定して形成でき、ガラスの歪点、粘
度を上昇して耐熱性を向上し、またガラスの耐薬品性、
耐水性を向上する。Al2O3 がガラス中に９％未満である
とガラスの歪点が低下し、他方13％を超えるとガラス融
液の高温粘度が高くなり、失透傾向が増大し、フロート
法成形が困難になる。従って９〜13％の範囲で導入す
る。Al 2 O 3 plays a role in the glass network and can form the glass in a stable manner, raises the strain point and viscosity of the glass to improve the heat resistance, and also improves the chemical resistance of the glass,
Improves water resistance. If Al 2 O 3 is less than 9% in the glass, the strain point of the glass decreases, while if it exceeds 13%, the high-temperature viscosity of the glass melt increases, the tendency to devitrify increases, and it is difficult to form by the float method. become. Therefore, it is introduced in the range of 9 to 13%.

【００１０】P2O5はそれ自体ネットワークフォーマーで
あり、少量の導入でガラス歪点や粘度等を大きく変える
ことなく、失透温度を大幅に低下させ、特に成形作業温
度付近での失透の発生を抑制するうえで重要な成分であ
る。P2O5がガラス中 0.5％未満では上記作用が不充分で
あり、２％を越えるとガラスの分相傾向を増大しガラス
の耐水性、耐薬品性を損なう傾向にある。従って 0.5〜
２％の範囲で導入する。P 2 O 5 itself is a network former, and when introduced in a small amount, greatly reduces the devitrification temperature without greatly changing the glass strain point, viscosity, and the like. It is an important component for suppressing the generation of odor. If the content of P 2 O 5 is less than 0.5% in the glass, the above effect is insufficient, and if it exceeds 2%, the tendency of phase separation of the glass is increased, and the water resistance and chemical resistance of the glass tend to be impaired. Therefore 0.5 ~
Introduce in the range of 2%.

【００１１】ZrO2はガラスの耐水性、耐薬品性を向上す
る。またガラスの歪点を上昇させ、失透の発生を抑える
作用を有するのでガラス中に 0.5％以上含有させるのが
よく、他方 3.5％を超えると逆に失透傾向が増大し、ガ
ラスの溶融およびフロート法成形を困難とすると同時に
比重を大幅に増大する。従って 0.5〜 3.5％の範囲で導
入する。ZrO 2 improves the water resistance and chemical resistance of glass. Also, it has the effect of raising the strain point of the glass and suppressing the occurrence of devitrification. Therefore, it is better to contain 0.5% or more in the glass. On the other hand, if it exceeds 3.5%, the tendency of devitrification increases, and the melting and melting of the glass This makes the float molding difficult and at the same time greatly increases the specific gravity. Therefore, it is introduced in the range of 0.5 to 3.5%.

【００１２】なお、ガラス中SiO2＋Al2O3 ＋ZrO2＋P2O5
を71％未満とし、相対的に２価成分酸化物やアルカリ金
属酸化物を過量に含ませると、ガラス比重が増大するの
で好ましくない。またSiO2＋Al2O3 ＋ZrO2＋P2O5を78％
を越えて含有すると、熱膨張率が低下する上に、ガラス
融液の高温粘度が高くなり、フロート法成形が困難にな
る。従って71〜78wt％の範囲とし、好適には74〜77％の
範囲とする。In the glass, SiO 2 + Al 2 O 3 + ZrO 2 + P 2 O 5
Is less than 71%, and if the bivalent component oxide or alkali metal oxide is excessively contained, the glass specific gravity increases, which is not preferable. 78% of SiO 2 + Al 2 O 3 + ZrO 2 + P 2 O 5
If the content exceeds the above range, the coefficient of thermal expansion decreases, and the high-temperature viscosity of the glass melt increases, making it difficult to form by a float method. Therefore, it is in the range of 71 to 78% by weight, preferably in the range of 74 to 77%.

【００１３】本成分系において、SiO2同様のネットワー
クフォーマーであり、ガラスを安定して形成するB2O3を
適宜導入することができる。B2O3は高温粘度を下げてガ
ラス溶融を容易にする。ただし歪点と熱膨張率を低下す
る傾向にあり、導入量は２％以下とすべきである。This component system is a network former similar to SiO 2 , and B 2 O 3 for stably forming glass can be appropriately introduced. B 2 O 3 lowers the high temperature viscosity and facilitates glass melting. However, the strain point and the coefficient of thermal expansion tend to decrease, and the amount to be introduced should be 2% or less.

【００１４】MgO は失透温度を低下させ、また他の二価
成分酸化物に比べガラスの歪点を上昇させ、適度に調整
するうえで有用であるが、ガラス中１％未満であると上
記作用に乏しく、５％を越えて含有すると、ガラスの熱
膨張率を低下させ、失透傾向が大きくなる。従って１〜
５％の範囲で導入する。MgO lowers the devitrification temperature and raises the strain point of glass as compared with other divalent component oxides. MgO is useful for moderate adjustment. The effect is poor, and if the content exceeds 5%, the coefficient of thermal expansion of the glass is reduced and the tendency to devitrify is increased. Therefore 1
Introduce in the range of 5%.

【００１５】CaO は主要な２価成分酸化物として、SiO2
やAl2O3 を主体とするガラスにおける融液の高温粘度を
下げ、またその適度な導入により失透の発生を抑制する
作用を有するが、ガラス中３％未満ではその作用が不充
分であり、他方９％を超えると失透傾向が大きくなり、
またガラス比重を増大する。従って３〜９％の範囲で導
入する。CaO is SiO 2 as a main divalent component oxide.
, Al 2 O 3, or the lower the high temperature viscosity of the melt in the glass mainly comprising, also has the effect of suppressing the occurrence of devitrification due to its moderate introduced, is insufficient its effect in the glass less than 3% On the other hand, if it exceeds 9%, the tendency of devitrification increases,
It also increases the glass specific gravity. Therefore, it is introduced in the range of 3 to 9%.

【００１６】SrO はCaO とともにガラス融液の高温粘度
を下げ、また失透の発生を抑制する作用を有し、ガラス
の熱膨張率、歪点を調整するうえで有用であるが、ガラ
ス中１％未満ではその作用が不充分であり、５％を越え
て導入すると比重が増大するので好ましくなく、従って
１〜５％の範囲で導入する。SrO has the effect of lowering the high-temperature viscosity of the glass melt together with CaO and suppressing the occurrence of devitrification, and is useful in adjusting the coefficient of thermal expansion and strain point of the glass. If it is less than 5%, its effect is insufficient, and if it exceeds 5%, the specific gravity increases, which is not preferable. Therefore, it is introduced in the range of 1 to 5%.

【００１７】BaO はCaO 等とともにガラス融液の高温粘
度を下げ失透の発生を抑制する作用を有するので適宜導
入することができるが、ガラス中４％を超えるとガラス
の歪点が低下し過ぎ、ガラスの比重を増大する。従って
４％以下の範囲で随時導入する。BaO, together with CaO and the like, has the effect of lowering the high-temperature viscosity of the glass melt and suppressing the occurrence of devitrification, so that it can be appropriately introduced. However, if it exceeds 4% in the glass, the strain point of the glass is too low. Increases the specific gravity of the glass. Therefore, it is introduced as needed in the range of 4% or less.

【００１８】さらに、上記組成範囲内において、２価金
属酸化物 (CaO 、MgO 、BaO 、SrO)の合計を11〜14％の
範囲とすることによって、ガラスの溶融性を良好な範囲
に維持しつつ、粘度−温度勾配を適度として成形性を良
好とし、耐熱性、化学的耐久性等に優れ、適切な範囲の
熱膨張率を有するガラスを得ることができる。２価金属
酸化物の合計が14％を越えると、ガラスの熱膨張率が上
昇するとともに失透傾向が増大し、化学的耐久性が低下
し、またガラス比重が増大する。11％未満では、高温粘
度が上昇して溶融および成形を困難とし、熱膨張率が低
下する。Further, the melting property of the glass is maintained in a good range by setting the total of the divalent metal oxides (CaO, MgO, BaO, SrO) in the range of 11 to 14% within the above composition range. In addition, it is possible to obtain a glass having an appropriate viscosity-temperature gradient, good moldability, excellent heat resistance, chemical durability and the like, and a thermal expansion coefficient in an appropriate range. When the total amount of the divalent metal oxides exceeds 14%, the coefficient of thermal expansion of the glass increases, the tendency of devitrification increases, the chemical durability decreases, and the specific gravity of the glass increases. If it is less than 11%, the high temperature viscosity increases to make melting and molding difficult, and the coefficient of thermal expansion decreases.

【００１９】Li2Oは強力なガラス溶融剤として作用する
が、ガラスの熱膨張率を低下させ、また歪点も低下させ
る傾向があるので、ガラス中３％以下の範囲で必要に応
じ適宜導入するものである。Although Li 2 O acts as a strong glass-melting agent, it tends to lower the coefficient of thermal expansion of the glass and the strain point. Is what you do.

【００２０】Na2OはK2O とともに主要なガラス溶融剤と
して作用し、またガラスの熱膨張率を適度な高さに維持
するうえで不可欠である。Na2Oがガラス中７％未満であ
ると、ガラス溶融が不充分となり、均質性、清澄性も損
なう。他方９％を超えるとガラスの歪点が低下し過ぎ、
耐水性、耐薬品性も劣化する。従って７〜９％の範囲で
導入する。Na 2 O, together with K 2 O, acts as a main glass melting agent, and is indispensable for maintaining the coefficient of thermal expansion of the glass at a moderate level. If Na 2 O is less than 7% in the glass, glass melting becomes insufficient, and homogeneity and clarity are also impaired. On the other hand, if it exceeds 9%, the strain point of the glass becomes too low,
Water resistance and chemical resistance also deteriorate. Therefore, it is introduced in the range of 7 to 9%.

【００２１】K2O は上記の如くガラス溶融剤であり、ガ
ラスの熱膨張率を適度に調整し、またNa2Oとの混合アル
カリ効果によりアルカリイオンのガラス中での移動を抑
制して、ガラスの体積抵抗率を高める。ガラス中２％未
満であるとそれら作用が不充分であり、５％を超えると
熱膨張率が過大となり、また歪点も低下し過ぎるため、
２〜５％の範囲とする。また、ガラス比重をより低くす
るうえでは、２〜４％の範囲とするのがよい。K 2 O is a glass melting agent as described above, and appropriately adjusts the coefficient of thermal expansion of the glass and suppresses the movement of alkali ions in the glass by the alkali effect of mixing with Na 2 O. Increase the volume resistivity of glass. If the content is less than 2% in the glass, their effects are insufficient, and if it exceeds 5%, the coefficient of thermal expansion becomes excessive, and the strain point is too low.
The range is 2 to 5%. In order to further reduce the glass specific gravity, it is preferable to set the range of 2 to 4%.

【００２２】前記アルカリ金属酸化物 (Li2O、Na2O、K2
O ) の量に関し、そのガラス中の合計量を９〜14％とす
ることにより、ガラスの歪点、熱膨張率、高温粘度およ
び失透温度を適切な範囲に維することができる。アルカ
リ金属酸化物の合計量が９％未満では熱膨張率が低下
し、失透傾向が増大する。14％を越えるとガラスの歪点
が低下し過ぎるうえに、比重を増大し、体積抵抗率が低
下する。従って９〜14％の範囲とするものであるが、特
にガラスの易溶融性を考慮すれば、12〜14％の範囲がよ
い。The alkali metal oxides (Li 2 O, Na 2 O, K 2
By setting the total amount of O 2) in the glass to 9 to 14%, the strain point, the coefficient of thermal expansion, the high-temperature viscosity and the devitrification temperature of the glass can be kept in appropriate ranges. If the total amount of the alkali metal oxides is less than 9%, the coefficient of thermal expansion decreases, and the tendency to devitrify increases. If it exceeds 14%, the strain point of the glass will be too low, and the specific gravity will increase, and the volume resistivity will decrease. Accordingly, the range is set to 9 to 14%, but the range is preferably set to 12 to 14% in consideration of easy melting property of glass.

【００２３】本発明において、原料バッチ中に塩化物、
フッ化物を導入するのが望ましく、例えばCaF2、MgF2、
NaCl、CaCl2 等の金属フッ化物、塩化物を導入すること
により、ガラス融液の粘度、表面張力を降下させ溶融、
清澄性を向上し、かつ電気溶融法を採用した場合におい
ては電極を変質劣化させないうえで有効であるが、フッ
素、または塩素分として原料バッチのガラス換算量 (酸
化物)100wt％に対して0.5 wt％以下外挿添加するのが肝
要であり、0.5 wt％を超えると炉材の侵食等が激しくな
る傾向があるうえに、ガラスの歪点を低下させる。In the present invention, chloride,
It is desirable to introduce fluoride, for example CaF 2 , MgF 2 ,
By introducing metal fluorides and chlorides such as NaCl and CaCl 2 to lower the viscosity and surface tension of the glass melt,
It is effective to improve the clarity and to prevent the electrode from being deteriorated and deteriorated when the electro-melting method is used. It is important to add extra wt% or less, and if it exceeds 0.5 wt%, the erosion of the furnace material and the like tend to be severe and the strain point of the glass is lowered.

【００２４】さらにガラスの溶融、清澄性を向上させる
原料としては硝酸塩の導入が好ましい。すなわち例えば
硝酸バリウム、硝酸ナトリウム、硝酸カリウム等の原料
形態で原料バッチ中に導入するが、硝酸塩の殆どはガラ
スの初期溶融の過程で酸素を発生し、S 、FeおよびTiの
ようなガラス中の微量還元成分を酸化状態に維持するた
め、これら還元成分がモリブデン等の電極と反応して電
極が損耗するような弊害を抑制する。Further, as a raw material for improving the melting and clarity of the glass, it is preferable to introduce a nitrate. That is, for example, barium nitrate, sodium nitrate, and potassium nitrate are introduced into a raw material batch in the form of raw materials, but most of nitrates generate oxygen during the initial melting of the glass, and trace amounts of S, Fe, and Ti in the glass. In order to maintain the reduced components in an oxidized state, the adverse effects such that these reduced components react with an electrode of molybdenum or the like to wear the electrodes are suppressed.

【００２５】硝酸塩はNO3 として原料バッチのガラス換
算量 (酸化物)100wt％に対して４wt％以下、さらに望ま
しくは 1〜 4wt％の範囲で外挿添加するのが好ましい。
４wt％を超えると原料バッチの溶解速度が過大となり、
安定した溶融状態を得るのが困難となる。前記塩化物、
フッ化物または硝酸塩は必要に応じ適宜導入するもの
で、両者を併存させてもよい。The nitrate is preferably extrapolated as NO 3 in an amount of 4 wt% or less, more preferably in the range of 1 to 4 wt% based on 100 wt% of the glass equivalent (oxide) of the raw material batch.
If it exceeds 4 wt%, the dissolution rate of the raw material batch becomes excessive,
It is difficult to obtain a stable molten state. Said chloride,
Fluoride or nitrate is appropriately introduced as needed, and both may be used together.

【００２６】本発明において、直接通電による電気溶融
法を採用する場合は、汎用されるモリブデン等の電極と
反応して合金を形成したりするようなことは避けねばな
らず、従って原料バッチ中に清澄剤としてのAs2O3 、Sb
2O3 およびＳ分、硫酸塩（ガラス中に一部SO3 として残
留する) は少量(0.3％以下）に留めるべきである。ま
た、反応性を有するZnO 原料の混入は避けた方がよい。In the present invention, when the electric melting method by direct energization is adopted, it is necessary to avoid forming an alloy by reacting with a commonly used electrode such as molybdenum. As 2 O 3 , Sb as fining agent
The 2 O 3 and S content, sulfates (partially remaining as SO 3 in the glass) should be kept in small amounts (0.3% or less). It is better to avoid the incorporation of a reactive ZnO raw material.

【００２７】さらにフロート法成形による量産を容易と
し、成形時の窒素および水素等の還元雰囲気下で揮発し
たり、ガラスに着色を与えないようにするために、PbO
、ZnO 等の揮発成分の混入も避けるべきである。Furthermore, in order to facilitate mass production by float molding, and to prevent volatilization under a reducing atmosphere such as nitrogen and hydrogen during molding and to prevent coloring of the glass, PbO is used.
Volatile components such as ZnO and ZnO should be avoided.

【００２８】本発明においては、ガラス比重を2.60以下
としたことにより、特に大サイズ化しつつあるＰＤＰ等
のディスプレイ装置の軽量化、取扱容易性を高めること
ができる。また、ガラスの歪点 (ガラスが粘度1014.5ポ
イズを示す温度) を 570℃以上としたことにより、500
℃を越える各種繰返し熱処理に対しても基板ガラスが歪
んだりすることがなく、更に熱膨張率 (室温〜300 ℃)
を80×10-7／℃以上に、かつ90×10-7／℃付近まで調整
することができるので、厚膜等（熱膨張率は、その組成
にもよるが略80〜90×10-7／℃である) との熱膨張率差
を僅少とし、又は無くし、それらとの密着性を良好とし
たガラスが得られる。加えて成形作業をするうえで基準
となるガラス粘度である104 ポイズになる温度を、1200
℃以下とすることができ、失透温度を104 ポイズ温度よ
り50℃以上低くしたことにより、成形作業を容易とする
ものである。In the present invention, by setting the glass specific gravity to 2.60 or less, it is possible to increase the weight and the ease of handling of a display device such as a PDP, which is becoming particularly large in size. In addition, by setting the strain point of glass (the temperature at which the glass exhibits a viscosity of 10 14.5 poise) to 570 ° C or higher,
The substrate glass is not distorted by various heat treatments exceeding ℃, and the coefficient of thermal expansion (from room temperature to 300 ℃)
The above 80 × 10 -7 / ℃, and can be adjusted to around 90 × 10 -7 / ℃, thick like (coefficient of thermal expansion, depending on the composition substantially 80-90 × 10 - 7 / ° C.) is small or eliminated, and a glass having good adhesion to them is obtained. In addition, the temperature at which the glass viscosity becomes 10 4 poise, which is the standard for forming
° C. can be less, by which the devitrification temperature lower 50 ° C. or higher than 10 4 poise temperature, it is intended to facilitate the forming operation.

【００２９】[0029]

【実施例】珪砂、水酸化アルミニウム、無水硼酸、リン
酸、炭酸マグネシウム、炭酸カルシウム、炭酸バリウ
ム、炭酸ストロンチウム、ジルコン砂、炭酸リチウム、
炭酸ナトリウム、炭酸カリウム、フッ化カルシウムおよ
び硝酸バリウムよりなる調合原料を白金製耐火坩堝に充
填し電気炉内で1500℃、約 4時間加熱溶融した。次に溶
融ガラスを鋳型に流し込み、約 200mm□×35mm厚の大き
さのガラスブロックとし、 630℃に保持した電気炉に移
入して該炉内で徐冷した。[Examples] Silica sand, aluminum hydroxide, boric anhydride, phosphoric acid, magnesium carbonate, calcium carbonate, barium carbonate, strontium carbonate, zircon sand, lithium carbonate,
The prepared raw material consisting of sodium carbonate, potassium carbonate, calcium fluoride and barium nitrate was filled in a platinum refractory crucible and heated and melted at 1500 ° C. for about 4 hours in an electric furnace. Next, the molten glass was poured into a mold to form a glass block having a size of about 200 mm □ × 35 mm, transferred to an electric furnace maintained at 630 ° C., and gradually cooled in the furnace.

【００３０】原料調合に基づくガラス (酸化物) 組成を
表１、表２に示す。なおいずれのケースにおいても、Ca
F2のかたちで導入されるF 分、Ba(NO3)2のかたちで導入
されるNO3 分についてはガラス酸化物成分計100 wt％に
対する外挿添加・導入量 (wt％) としてF 0.2 ％、NO3
0.3 ％と共通とした。Tables 1 and 2 show the glass (oxide) composition based on the raw material preparation. In each case, Ca
Regarding the F component introduced in the form of F 2 and the NO 3 component introduced in the form of Ba (NO 3 ) 2 , the amount of extrapolated addition / introduction (wt%) relative to 100 wt% of the total glass oxide component is F 0.2 %, NO 3
Common with 0.3%.

【００３１】これらのガラス試料について、室温〜 300
℃における平均熱膨張率（ X10-7／℃) 、歪点 (ガラス
が粘度1014.5ポイズを示す温度) 、転移点（熱膨張率測
定に際する温度−膨張量勾配の変化 <転移> 点）、溶融
温度（ガラスが粘度102 ポイズを示す温度）、成形温度
(ガラスが粘度104 ポイズを示す温度＝104 ポイズ温
度）、失透温度（ガラスを一定温度に２時間維持して失
透が生ずる上限温度）、作業温度範囲（上記成形温度−
失透温度）、およびガラス比重を測定した。それらの結
果を表１（実施例）、表２（実施例、比較例）に示す。For these glass samples, room temperature to 300
Average coefficient of thermal expansion in ° C (X10 -7 / ° C), strain point (temperature at which glass exhibits a viscosity of 10 14.5 poise), transition point (change in temperature-expansion gradient when measuring thermal expansion coefficient <transition> point) , (the temperature at which the glass exhibits a viscosity of 10 2 poises) melt temperature, mold temperature
(Temperature glass exhibits a viscosity of 10 4 poise = 10 4 poise temperature), (upper limit temperature devitrification occurs maintained 2 hours glass at a constant temperature) the devitrification temperature, the working temperature range (the molding temperature -
Devitrification temperature), and glass specific gravity. The results are shown in Table 1 (Example) and Table 2 (Example, Comparative Example).

【００３２】 〔表１・実施例〕 実 施 例 (wt%) １ ２ ３ ４ ５ ６ ７ SiO2* 61.7 62.2 62.3 62.4 61.0 60.5 60.5 Al2O3* 9.5 9.6 9.7 9.7 11.7 11.7 11.4 P2O5* 0.5 0.5 0.5 0.5 0.5 0.5 0.5 ZrO2* 2.5 2.5 2.5 2.5 2.5 2.5 2.5B2O3 0 0 0 0 0 0 0 *小計 74.2 74.8 75.0 75.1 75.7 75.2 74.9 Li2O 0 0 0 0 0.5 0 0 Na2O 8.1 8.2 8.2 8.2 8.2 8.1 8.1K2O 4.5 4.5 4.7 4.6 3.1 4.5 4.5 小計 12.6 12.7 12.7 12.8 11.8 12.6 12.6 MgO 2.0 2.0 2.5 3.1 2.0 2.6 2.0 CaO 7.6 7.7 7.0 6.1 7.7 6.7 7.6 SrO 1.6 3.1 3.1 3.1 3.1 3.0 3.0BaO 2.1 0 0 0 0 0 0 小計 13.3 12.7 12.5 12.3 12.7 12.4 12.6 熱膨張率(X10ー7/・c) 83 85 82 82 82 81 83 歪点 586 585 573 575 573 600 593 転移点 622 623 610 612 605 634 632 溶融温度 1570 1580 1579 1594 1596 1584 1594 成形温度 1156 1159 1157 1156 1160 1170 1152 失透温度 1100 1100 1103 1100 1110 1110 1100 作業温度範囲 56 59 54 56 50 60 52 比重 2.59 2.58 2.59 2.59 2.59 2.58 2.59 （注：各成分、小計のwt％表示において下位数値は四捨五入した）[Table 1 Example] Example (wt%) 1 2 3 4 5 6 7 SiO 2 * 61.7 62.2 62.3 62.4 61.0 60.5 60.5 Al 2 O 3 * 9.5 9.6 9.7 9.7 11.7 11.7 11.4 P 2 O 5 * 0.5 0.5 0.5 0.5 0.5 0.5 0.5 ZrO 2 * 2.5 2.5 2.5 2.5 2.5 2.5 2.5 B 2 O 3 0 0 0 0 0 0 0 * Subtotal 74.2 74.8 75.0 75.1 75.7 75.2 74.9 Li 2 O 0 0 0 0 0.5 0 0 Na 2 O 8.1 8.2 8.2 8.2 8.2 8.1 8.1 K 2 O 4.5 4.5 4.7 4.6 3.1 4.5 4.5 Subtotal 12.6 12.7 12.7 12.8 11.8 12.6 12.6 MgO 2.0 2.0 2.5 3.1 2.0 2.6 2.0 CaO 7.6 7.7 7.0 6.1 7.7 6.7 7.6 SrO 1.6 3.1 3.1 3.1 3.1 3.0 3.0 BaO 2.1 0 0 0 0 0 0 subtotal 13.3 12.7 12.5 12.3 12.7 12.4 12.6 thermal expansion coefficient (X10 over 7 / · c) 83 85 82 82 82 81 83 strain point 586 585 573 575 573 600 593 transition 622 623 610 612 605 634 632 Melting temperature 1570 1580 1579 1594 1596 1584 1594 Molding temperature 1156 1159 1157 1156 1160 1170 1152 Devitrification temperature 1100 1100 1103 1100 1110 1110 1100 Working temperature range 56 59 54 56 50 60 52 Specific gravity 2.59 2.58 2.59 2.59 2.59 2.58 2.59 (Note : Smell of wt% of each component and subtotal Lower values were rounded off)

【００３３】 〔表２・実施例、比較例〕 実 施 例 比 較 例 (wt%) ８ ９ １ ２ ３ ４ ５ ６ SiO2* 61.0 60.5 67.1 62.5 65.0 61.5 54.0 57.7 Al2O3* 10.0 11.7 6.1 9.6 12.0 9.5 9.0 6.5 P2O5* 0.5 0.5 0 0 0 0 0 0 ZrO2* 2.5 2.5 1.3 2.5 2.0 2.5 3.7 3.0 B2O3 1.3 0 0 0 0 0 0 0 *小計 75.3 75.2 74.5 74.6 79.0 73.5 66.7 67.2 Li2O 0 0 0 0 0 0 0 0 Na2O 7.6 8.1 7.3 8.2 7.0 8.0 4.0 4.5 K2O 4.7 4.5 2.7 4.5 2.0 4.5 9.0 6.6 小計 12.3 12.7 10.0 12.7 9.0 12.5 13.0 11.1 MgO 2.0 3.2 3.6 2 4.0 2.0 3.0 1.8 CaO 7.5 5.9 9.8 7.7 8.0 7.5 7.7 5.1 SrO 3.1 3.0 0 3.1 0 0 0 7.0 BaO 0 0 2.1 0 0 4.5 9.6 8.0 小計 12.6 12.2 15.5 12.7 12.0 14.0 20.3 21.9 熱膨張率(X10ー7/・c) 82 82 77 85 72 83 85 81 歪点 575 589 592 580 631 598 603 581 転移点 622 630 634 620 670 623 637 627 溶融温度 1575 1600 1590 1576 1650 1557 1506 1538 成形温度 1160 1180 1170 1142 1225 1130 1129 1135 失透温度 1109 1125 1175 1129 1202 1129 1115 1065 作業温度範囲 51 55 ー5 13 23 1 14 70 比重 2.59 2.58 2.62 2.58 2.52 2.59 2.74 2.77 （注：各成分、小計のwt％表示において下位数値は四捨五入した）[Table 2-Examples and Comparative Examples]Example Comparative example (wt%) 8 9 1 2 3 4 5 6 SiOTwo* 61.0 60.5 67.1 62.5 65.0 61.5 54.0 57.7 AlTwoOThree* 10.0 11.7 6.1 9.6 12.0 9.5 9.0 6.5 PTwoOFive* 0.5 0.5 0 0 0 0 0 0 ZrOTwo* 2.5 2.5 1.3 2.5 2.0 2.5 3.7 3.0 B 2 O 3 1.3 0 0 0 0 0 0 0 * Subtotal 75.3 75.2 74.5 74.6 79.0 73.5 66.7 67.2 LiTwoO 0 0 0 0 0 0 0 0 NaTwoO 7.6 8.1 7.3 8.2 7.0 8.0 4.0 4.5 K 2 O 4.7 4.5 2.7 4.5 2.0 4.5 9.0 6.6 Subtotal 12.3 12.7 10.0 12.7 9.0 12.5 13.0 11.1 MgO 2.0 3.2 3.6 2 4.0 2.0 3.0 1.8 CaO 7.5 5.9 9.8 7.7 8.0 7.5 7.7 5.1 SrO 3.1 3.0 0 3.1 0 0 0 7.0 BaO 0 0 2.1 0 0 4.5 9.6 8.0 Subtotal 12.6 12.2 15.5 12.7 12.0 14.0 20.3 21.9 Thermal expansion coefficient (X10-782 82 77 85 72 83 85 81 Strain point 575 589 592 580 631 598 603 581 Transition point 622 630 634 620 670 623 637 627 627 Melting temperature 1575 1600 1590 1576 1650 1557 1506 1538 Molding temperature 1160 1180 1170 1142 1225 1130 1129 1135 Devitrification temperature 1109 1125 1175 1129 1202 1129 1115 1065 Working temperature range 51 55 -5 13 23 1 14 70 Specific gravity 2.59 2.58 2.62 2.58 2.52 2.59 2.74 2.77 (Note: Lower numbers are rounded off in wt% of each component and subtotal) did)

【００３４】表１、表２中実施例NO.1〜 NO.９は本発明
におけるガラスであり、102 ポイズ温度が1600℃以下で
あって、電気溶融等により、容易に溶融、清澄化でき
る。10 4 ポイズ温度を1200℃以下とし、失透温度を104
ポイズ温度より50℃以上低くしたことにより、成形性も
容易としフロート法成形に適する。ガラスの歪点は570
℃以上で耐熱性が良好である。熱膨張率は80×10-7／℃
以上で電極や厚膜との熱膨張率に近似している。またガ
ラス比重を2.60以下としたことにより、大サイズ化しつ
つあるディスプレイ装置の軽量化、取扱容易性を高める
ことができる。更に、表示しないが体積抵抗率も109
Ω.cm 以上で電気絶縁性に優れ、ディスプレイ装置用基
板ガラス、殊にＰＤＰ用の基板ガラスとして好適であ
る。Examples 1 to 9 in Tables 1 and 2 show the present invention.
Is the glass inTwo When poise temperature is below 1600 ℃
It can be easily melted and clarified by electric melting, etc.
You. Ten Four Poise temperature is 1200 ° C or less and devitrification temperature is 10Four 
Moldability is also reduced by lowering the poise temperature by 50 ° C or more.
Easy and suitable for float molding. The strain point of the glass is 570
Good heat resistance above ℃. The coefficient of thermal expansion is 80 × 10-7/ ℃
The above approximates the coefficient of thermal expansion with the electrode and the thick film. In addition
By reducing the specific gravity of the lath to 2.60 or less, the size has been increased.
Lightweight and easy handling of existing display devices
be able to. Furthermore, although not indicated, the volume resistivity is 109 
Excellent electrical insulation at Ω.cm or more,
It is suitable as a sheet glass, especially as a substrate glass for PDP.
You.

【００３５】[0035]

【発明の効果】本発明のガラスは、ガラスの熱膨張率、
歪点、ガラス比重等の点でディスプレイ装置用基板ガラ
ス、特にＰＤＰ用の基板ガラスとして好適であり、また
ガラスの溶融性も良好で、直接通電法による溶融および
フロート法による成形に適し、均質なガラスを連続的に
低いコストで製造することができ、量産に適するという
効果を奏する。The glass of the present invention has a coefficient of thermal expansion of glass,
In terms of strain point, glass specific gravity, etc., it is suitable as a substrate glass for display devices, in particular, a substrate glass for PDP, and has a good melting property of glass, and is suitable for melting by a direct current method and molding by a float method, and is homogeneous. Glass can be manufactured continuously at a low cost, which is advantageous for mass production.

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】wt％で、SiO2 60〜63、Al2O3 ９〜13、Zr
O2 0.5〜3.5 、P2O5 0.5〜２、SiO2＋Al2O3 ＋ZrO2＋P2
O5 71〜78、MgO １〜５、CaO ４〜９、SrO １〜５、Ba
O ０〜４、MgO ＋CaO ＋Sr0 ＋BaO 11〜14、Li2O ０〜
２、Na2O ７〜９、K2O ２〜５、Li2O＋Na2O＋K2O ９〜
14の範囲で含有し、ガラス比重が2.60以下、ガラスの歪
点が 570℃以上、ガラスの104 ポイズ温度が1200℃以下
であり、104 ポイズ温度−失透温度の温度差が50℃以
上、かつガラスの室温から 300℃における熱膨張率が80
×10-7／℃以上であることを特徴とするディスプレイ装
置用基板ガラス組成物。1. A in wt%, SiO 2 60~63, Al 2 O 3 9~13, Zr
O 2 0.5 to 3.5, P 2 O 5 0.5 to 2, SiO 2 + Al 2 O 3 + ZrO 2 + P 2
O 5 71-78, MgO 1-5, CaO 4-9, SrO 1-5, Ba
O 0~4, MgO + CaO + Sr0 + BaO 11~14, Li 2 O 0~
2, Na 2 O 7~9, K 2 O 2~5, Li 2 O + Na 2 O + K 2 O 9~
Containing 14 range, the glass specific gravity of 2.60 or less, the strain point of the glass is 570 ° C. or higher, 10 4 poise temperature of the glass is at 1200 ° C. or less, 10 4 poise temperature - temperature difference between liquidus temperature 50 ° C. or higher And the coefficient of thermal expansion of the glass from room temperature to 300 ° C is 80
A substrate glass composition for a display device having a temperature of at least × 10 −7 / ° C.
JP9352646A 1997-12-22 1997-12-22 Substrate glass composition for display device Pending JPH11180728A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Application Number Priority Date Filing Date Title
JP9352646A JPH11180728A (en) 1997-12-22 1997-12-22 Substrate glass composition for display device

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Publication Number Publication Date
JPH11180728A true JPH11180728A (en) 1999-07-06

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