JPH10114538A - Alkali-free glass and its production - Google Patents
Alkali-free glass and its productionInfo
- Publication number
- JPH10114538A JPH10114538A JP9116464A JP11646497A JPH10114538A JP H10114538 A JPH10114538 A JP H10114538A JP 9116464 A JP9116464 A JP 9116464A JP 11646497 A JP11646497 A JP 11646497A JP H10114538 A JPH10114538 A JP H10114538A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- alkali
- free glass
- sample
- free
- 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
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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Liquid Crystal (AREA)
- Glass Compositions (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、無アルカリガラス、特
にディスプレイ等の透明ガラス基板として使用される無
アルカリガラスとその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkali-free glass, particularly to an alkali-free glass used as a transparent glass substrate for a display or the like, and a method for producing the same.
【０００２】[0002]
【従来の技術】従来、液晶ディスプレイ等の透明ガラス
基板として、無アルカリガラスが使用されている。ディ
スプレイ用途に用いられる無アルカリガラスには、耐熱
性、耐薬品性等の特性の他に、表示欠陥となる泡のない
ことが要求される。2. Description of the Related Art Conventionally, non-alkali glass has been used as a transparent glass substrate for a liquid crystal display or the like. Alkali-free glass used for display applications is required to be free from bubbles that cause display defects, in addition to properties such as heat resistance and chemical resistance.
【０００３】このような無アルカリガラスとして、従来
より種々のガラスが提案されており、本出願人も特開昭
６３−７４９３５号においてＳｉＯ2 −Ａｌ2 Ｏ3 −Ｂ
2 Ｏ 3 −ＣａＯ−ＢａＯ系の無アルカリガラスを提案し
ている。[0003] As such an alkali-free glass,
More various glasses have been proposed, and the present applicant has
No. 63-74935, SiOTwo -AlTwo OThree -B
Two O Three -Propose alkali-free glass based on CaO-BaO
ing.
【０００４】[0004]
【発明が解決しようとする課題】泡のないガラスを得る
ためには、ガラス化反応時から均質化溶融時にかけての
温度域で清澄ガスを発生する清澄剤を使用することが重
要である。つまりガラスの清澄は、ガラス化反応時に発
生するガスを清澄ガスによってガラス融液中から追い出
し、さらに均質化溶融時に残った微小な泡を再び発生さ
せた清澄ガスによって泡径を大きくして浮上させて除去
する。In order to obtain a bubble-free glass, it is important to use a fining agent that generates a fining gas in the temperature range from the vitrification reaction to the homogenization and melting. In other words, the fining of the glass drives out the gas generated during the vitrification reaction from the glass melt by the fining gas, and further increases the diameter of the bubbles by the fining gas that regenerated the fine bubbles remaining during homogenization and melting, and floats the glass. To remove.
【０００５】ところで液晶ディスプレイ用ガラス基板に
使用されるような無アルカリガラスでは、ガラス融液の
粘度が高く、アルカリ成分を含有するガラスに比べて溶
融がより高温で行われる。このため、清澄剤には幅広い
温度域（１２００〜１６００℃程度）で清澄ガスを発生
することができるＡｓ2 Ｏ3 が広く使用されている。By the way, in alkali-free glass used for a glass substrate for a liquid crystal display, the viscosity of a glass melt is high, and melting is performed at a higher temperature than glass containing an alkali component. For this reason, As 2 O 3 that can generate a fining gas in a wide temperature range (about 1200 to 1600 ° C.) is widely used as a fining agent.
【０００６】しかしながらＡｓ2 Ｏ3 は毒性が非常に強
く、ガラスの製造工程や廃ガラスの処理時等に環境を汚
染する可能性があり、その使用が制限されつつある。However, As 2 O 3 is very toxic, and may pollute the environment during the glass manufacturing process or the treatment of waste glass, and its use is being restricted.
【０００７】本発明の目的は、清澄剤としてＡｓ2 Ｏ3
を使用せず、しかも表示欠陥となる泡が存在しない無ア
ルカリガラスとその製造方法を提供することである。An object of the present invention is to provide As 2 O 3 as a fining agent.
It is an object of the present invention to provide a non-alkali glass and a method for producing the same, which do not use any of them, and which do not have bubbles serving as display defects.
【０００８】[0008]
【課題を解決するための手段】本出願人は、種々の実験
を行った結果、清澄剤としてＡｓ2 Ｏ3 の代わりにＳｎ
Ｏ2 とＳｂ2 Ｏ3 を併用することによって上記目的が達
成できることを見いだし、本発明として提案するもので
ある。The present applicant has conducted various experiments and found that Sn was used as a fining agent instead of As 2 O 3.
The inventors have found that the above object can be achieved by using O 2 and Sb 2 O 3 together, and propose the present invention.
【０００９】即ち、本発明の無アルカリガラスは、重量
百分率でＳｉＯ2 ４０〜７０％、Ａｌ2 Ｏ3 ６〜２
５％、Ｂ2 Ｏ3 ５〜２０％、ＭｇＯ ０〜１０％、Ｃ
ａＯ０〜１５％、ＢａＯ ０〜３０％、ＳｒＯ ０〜１
０％、ＺｎＯ ０〜１０％、ＳｎＯ2 ０．０５〜２
％、Ｓｂ2 Ｏ3 ０．０５〜３％の組成を有し、本質的
にアルカリ金属酸化物を含有しないことを特徴とする。That is, the alkali-free glass of the present invention comprises 40 to 70% of SiO 2 and 6 to 2 of Al 2 O 3 by weight percentage.
5%, B 2 O 3 5~20 %, 0~10% MgO, C
aO 0 to 15%, BaO 0 to 30%, SrO 0 to 1
0%, ZnO 0-10%, SnO 2 0.05-2
%, Has a composition of Sb 2 O 3 0.05 to 3%, essentially characterized in that it does not contain alkali metal oxides.
【００１０】また本発明の無アルカリガラスの製造方法
は、重量百分率でＳｉＯ2 ４０〜７０％、Ａｌ2 Ｏ3
６〜２５％、Ｂ2 Ｏ3 ５〜２０％、ＭｇＯ ０〜１
０％、ＣａＯ ０〜１５％、ＢａＯ ０〜３０％、Ｓｒ
Ｏ ０〜１０％、ＺｎＯ ０〜１０％の組成を有し、本
質的にアルカリ金属酸化物を含有しないガラスとなるよ
うに調合したガラス原料調合物を溶融した後、成形する
無アルカリガラスの製造方法において、ガラス原料調合
物に清澄剤としてＳｎＯ2 を０．０５〜２重量％及びＳ
ｂ2 Ｏ3 を０．０５〜３重量％添加することを特徴とす
る。[0010] manufacturing method of alkali-free glass of the present invention, SiO 2 40 to 70% by weight percentage, Al 2 O 3
6~25%, B 2 O 3 5~20 %, MgO 0~1
0%, CaO 0-15%, BaO 0-30%, Sr
Production of alkali-free glass which has a composition of 0 to 10% of O and 0 to 10% of ZnO and which is formed by melting a glass raw material mixture prepared so as to be essentially free of an alkali metal oxide and then molding. In the method, 0.05 to 2 % by weight of SnO2 as a fining agent and S
The b 2 O 3, characterized in that the addition of 0.05 to 3 wt%.
【００１１】[0011]
【作用】本発明において使用するＳｎＯ2 とＳｂ2 Ｏ3
は、１２００℃以上の温度域でＳｎイオンとＳｂイオン
の価数変化による化学反応により多量の酸素ガスを発生
する。特にＳｎＯ2 は１４００℃以上で、Ｓｂ2 Ｏ3 は
１２００〜１３００℃付近で酸素ガスを多量に発生す
る。従って清澄剤としてＳｎＯ2 とＳｂ2 Ｏ3 を併用す
ることにより、比較的低温で起こるガラス化反応時から
高温の均質化溶融時にかけての広い温度域で高い清澄効
果が得られるため、表示欠陥となる泡が存在しない無ア
ルカリガラスを得ることができる。The SnO 2 and Sb 2 O 3 used in the present invention
Generates a large amount of oxygen gas by a chemical reaction due to a change in the valence of Sn ions and Sb ions in a temperature range of 1200 ° C. or higher. In particular, SnO 2 generates a large amount of oxygen gas at 1400 ° C. or higher, and Sb 2 O 3 generates a large amount of oxygen gas at around 1200 to 1300 ° C. Therefore, by using SnO 2 and Sb 2 O 3 together as a fining agent, a high fining effect can be obtained in a wide temperature range from the time of vitrification reaction occurring at a relatively low temperature to the time of homogenization melting at a high temperature. An alkali-free glass free from bubbles can be obtained.
【００１２】次に、本発明の無アルカリガラスの製造方
法を述べる。Next, a method for producing an alkali-free glass of the present invention will be described.
【００１３】まず、所望の組成を有するガラスとなるよ
うにガラス原料調合物を用意する。ガラスの組成範囲及
びその限定理由を以下に述べる。First, a glass raw material mixture is prepared so as to obtain a glass having a desired composition. The composition range of the glass and the reason for the limitation are described below.
【００１４】ＳｉＯ2 はガラスのネットワークとなる成
分であり、その含有量は４０〜７０％、好ましくは４５
〜６５％である。ＳｉＯ2 が４０％より少ないと耐薬品
性が悪化するとともに、歪点が低くなって耐熱性が悪く
なり、７０％より多いと高温粘度が大きくなって溶融性
が悪くなるとともに、クリストバライトの失透物が析出
し易くなる。[0014] SiO 2 is a component that forms a glass network, and its content is 40 to 70%, preferably 45 to 70%.
~ 65%. When the content of SiO 2 is less than 40%, the chemical resistance is deteriorated, and the strain point is lowered, whereby the heat resistance is deteriorated. When the content is more than 70%, the high-temperature viscosity is increased, the melting property is deteriorated, and the cristobalite is devitrified. It becomes easier for substances to precipitate.
【００１５】Ａｌ2 Ｏ3 はガラスの耐熱性、耐失透性を
高める成分であり、その含有量は６〜２５％、好ましく
は１０〜２０％である。Ａｌ2 Ｏ3 が６％より少ないと
失透温度が著しく上昇してガラス中に失透が生じ易くな
り、２５％より多いと耐酸性、特に耐バッファードフッ
酸性が低下してガラス基板表面に白濁が生じ易くなる。Al 2 O 3 is a component for improving the heat resistance and devitrification resistance of the glass, and its content is 6 to 25%, preferably 10 to 20%. If Al 2 O 3 is less than 6%, the devitrification temperature rises remarkably and devitrification tends to occur in the glass. If it is more than 25%, the acid resistance, especially the buffered hydrofluoric acid resistance, decreases and the glass substrate surface is deteriorated. Cloudiness is likely to occur.
【００１６】Ｂ2 Ｏ3 は融剤として働き、粘性を下げて
溶融を容易にする成分であり、その含有量は５〜２０
％、好ましくは６〜１５％である。Ｂ2 Ｏ3 が５％より
少ないと融剤としての効果が不十分となり、２０％より
多いと耐塩酸性が低下するとともに、歪点が低下して耐
熱性が悪化する。B 2 O 3 is a component that acts as a flux, lowers the viscosity and facilitates melting, and has a content of 5 to 20%.
%, Preferably 6 to 15%. If the content of B 2 O 3 is less than 5%, the effect as a flux will be insufficient, and if it is more than 20%, the hydrochloric acid resistance will be reduced, and the strain point will be lowered, thus deteriorating heat resistance.
【００１７】ＭｇＯは歪点を下げずに高温粘度を下げて
ガラスの溶融を容易にする成分であり、その含有量は０
〜１０％、好ましくは０〜７％である。ＭｇＯが１０％
より多いとガラスの耐バッファードフッ酸性が著しく低
下する。ＣａＯもＭｇＯと同様の働きをし、その含有量
は０〜１５％、好ましくは０〜１０％である。ＣａＯが
１５％より多いとガラスの耐バッファードフッ酸性が著
しく低下する。ＢａＯはガラスの耐薬品性を向上させる
とともに失透性を改善する成分であり、その含有量は０
〜３０％、好ましくは０〜２０％である。ＢａＯが３０
％より多いと歪点が低下して耐熱性が悪くなる。ＳｒＯ
はＢａＯと同様の効果があり、その含有量は０〜１０
％、好ましくは０〜７％である。ＳｒＯが１０％より多
いと失透性が増すため好ましくない。ＺｎＯは耐バッフ
ァードフッ酸性を改善するとともに失透性を改善する成
分であり、その含有量は０〜１０％、好ましくは０〜７
％である。ＺｎＯが１０％より多いと逆にガラスが失透
し易くなり、また歪点が低下して耐熱性が得られなくな
る。なおＭｇＯ、ＣａＯ、ＢａＯ、ＳｒＯ及びＺｎＯの
合量が５％より少ないと高温粘性が高くなって溶融性が
悪化するとともに、ガラスが失透し易くなり、３０％よ
り多いと耐熱性及び耐酸性が悪くなり好ましくない。MgO is a component that lowers the viscosity at high temperature without lowering the strain point and facilitates melting of the glass.
-10%, preferably 0-7%. MgO is 10%
If the amount is larger, the buffered hydrofluoric acid resistance of the glass is remarkably reduced. CaO also functions similarly to MgO, and its content is 0 to 15%, preferably 0 to 10%. When the content of CaO is more than 15%, the buffered hydrofluoric acid resistance of the glass is significantly reduced. BaO is a component that improves the chemical resistance of the glass and also improves the devitrification property.
-30%, preferably 0-20%. BaO is 30
%, The strain point is lowered and the heat resistance is deteriorated. SrO
Has the same effect as BaO, and its content is from 0 to 10
%, Preferably 0 to 7%. If the content of SrO is more than 10%, the devitrification will increase, which is not preferable. ZnO is a component that improves buffered hydrofluoric acid resistance and also improves devitrification, and its content is 0 to 10%, preferably 0 to 7%.
%. On the other hand, if the content of ZnO is more than 10%, the glass is liable to be devitrified, and the strain point is lowered, so that heat resistance cannot be obtained. If the total amount of MgO, CaO, BaO, SrO, and ZnO is less than 5%, the high-temperature viscosity becomes high and the melting property deteriorates, and the glass is easily devitrified. Becomes worse, which is not preferable.
【００１８】また上記成分の他に、ＺｒＯ2 、ＴｉＯ
2 、Ｆｅ2 Ｏ3 等を合量で５％まで添加することができ
る。In addition to the above components, ZrO 2 , TiO
2 , Fe 2 O 3 and the like can be added up to 5% in total.
【００１９】次にガラス原料調合物にＳｎＯ2 とＳｂ2
Ｏ3 を添加する。ＳｎＯ2 及びＳｂ2 Ｏ3 の添加量は、
ガラス原料調合物１００重量％に対して０．０５〜２重
量％及び０．０５〜３重量％である。その理由は、Ｓｂ
2 Ｏ3 が０．０５％より少ないとガラス化反応時に発生
したガスを追い出し難くなり、またＳｎＯ2 が０．０５
％より少ないと均質化溶融時にガラス融液中に残った泡
を除去し難くなる。またＳｎＯ2 が２％及びＳｂ2 Ｏ3
が３％より多いと揮発量が増えてガラスが変質し易くな
るためである。Next, SnO 2 and Sb 2 were added to the glass raw material mixture.
The O 3 is added. The addition amounts of SnO 2 and Sb 2 O 3 are as follows:
It is 0.05 to 2% by weight and 0.05 to 3% by weight based on 100% by weight of the glass raw material preparation. The reason is Sb
2 O 3 is hard expel gas generated during the vitrification reaction with less than 0.05%, also SnO 2 0.05
%, It is difficult to remove bubbles remaining in the glass melt during homogenization and melting. Also, 2% of SnO 2 and Sb 2 O 3
If it exceeds 3%, the amount of volatilization increases and the glass is liable to deteriorate.
【００２０】続いて調合したガラス原料を溶融する。ガ
ラス原料を加熱していくとまずガラス化反応が起こる
が、このときＳｂ2 Ｏ3 の価数変化による化学反応によ
って多量の酸素ガスが発生し、ガラス化反応時に発生し
たガスが融液中から追い出される。さらにより高温の均
質化溶融時には、ＳｎＯ2 の価数変化による化学反応で
多量の酸素ガスが発生してガラス融液中に残存する微小
な泡が除去される。Subsequently, the prepared glass raw material is melted. When the glass raw material is heated, a vitrification reaction occurs first. At this time, a large amount of oxygen gas is generated by a chemical reaction due to a change in the valence of Sb 2 O 3 , and the gas generated during the vitrification reaction is removed from the melt. Get kicked out. Further, at the time of homogenization melting at a higher temperature, a large amount of oxygen gas is generated by a chemical reaction due to a change in the valence of SnO 2 , and fine bubbles remaining in the glass melt are removed.
【００２１】その後、溶融ガラスを所望の形状に成形す
る。ディスプレイ用途に使用する場合、フュージョン
法、ダウンドロー法、フロート法、ロールアウト法等の
方法を用いて薄板状に成形する。Thereafter, the molten glass is formed into a desired shape. When used for display applications, it is formed into a thin plate using a method such as a fusion method, a downdraw method, a float method, or a rollout method.
【００２２】このようにして、重量百分率でＳｉＯ2
４０〜７０％、Ａｌ2 Ｏ3 ６〜２５％、Ｂ2 Ｏ3 ５
〜２０％、ＭｇＯ ０〜１０％、ＣａＯ ０〜１５％、
ＢａＯ ０〜３０％、ＳｒＯ ０〜１０％、ＺｎＯ ０
〜１０％、ＳｎＯ2 ０．０５〜２％、Ｓｂ2 Ｏ3
０．０５〜３％の組成を有し、本質的にアルカリ金属酸
化物を含有しない本発明の無アルカリガラスを得ること
ができる。Thus, the weight percentage of SiO 2
40~70%, Al 2 O 3 6~25 %, B 2 O 3 5
-20%, MgO 0-10%, CaO 0-15%,
BaO 0-30%, SrO 0-10%, ZnO 0
-10%, SnO 2 0.05-2%, Sb 2 O 3
The alkali-free glass of the present invention having a composition of 0.05 to 3% and containing essentially no alkali metal oxide can be obtained.
【００２３】[0023]
【実施例】以下、実施例に基づいて本発明を説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.
【００２４】（実施例１）表１は、ＳｎＯ2 とＳｂ2 Ｏ
3 の効果を示したものであり、試料ａはＡｓ2 Ｏ3 を清
澄剤として添加した従来の無アルカリガラス、試料ｂは
試料ａからＡｓ2Ｏ3 を除いて作製した無アルカリガラ
ス、試料ｃはＳｎＯ2 のみを添加した無アルカリガラ
ス、試料ｄはＳｂ2 Ｏ3 のみを添加した無アルカリガラ
ス、試料ｅはＳｎＯ2 とＳｂ2 Ｏ3 を併用した本発明の
無アルカリガラスを示している。Example 1 Table 1 shows that SnO 2 and Sb 2 O
And shows a third effect, sample a is As 2 O 3 conventional alkali-free glass was added as a refining agent, the sample b is non-alkali glass was prepared except As 2 O 3 from the sample a, sample c Is an alkali-free glass to which only SnO 2 is added, sample d is an alkali-free glass to which only Sb 2 O 3 is added, and sample e is an alkali-free glass of the present invention in which both SnO 2 and Sb 2 O 3 are used.
【００２５】[0025]
【表１】 [Table 1]
【００２６】各試料は次のようにして調製した。Each sample was prepared as follows.
【００２７】表の組成を有するようにガラス原料を調合
し、電気炉にて溶融した。このとき、ガラス化反応時の
清澄性を評価するために１５００℃で１時間溶融したも
のと、均質化溶融時の清澄性を評価するために１５５０
℃で１時間溶融したものの２種類を用意した。次いで、
溶融ガラスをカーボン台上に流しだし、徐冷した後、ガ
ラス中に残存している泡の個数を計数し、ガラス１００
ｇ中の泡が１０００個を越えるものを×、１０１〜１０
００個のものを△、１００個以下のものを○で評価し
た。結果を表１に示す。Glass raw materials were prepared to have the compositions shown in the table, and were melted in an electric furnace. At this time, one melted at 1500 ° C. for 1 hour to evaluate clarity during the vitrification reaction, and 1550 to evaluate clarity during homogenization and melting.
Two types were prepared which were melted at 1 ° C. for 1 hour. Then
After the molten glass was poured on a carbon table and cooled slowly, the number of bubbles remaining in the glass was counted, and the glass 100
g when the number of bubbles in g exceeds 1,000, x: 101 to 10
00 samples were evaluated as Δ, and 100 or less were evaluated as ○. Table 1 shows the results.
【００２８】表１から明らかなように、ＳｎＯ2 とＳｂ
2 Ｏ3 を添加しない試料ｂのガラスは清澄性が著しく悪
かった。ＳｎＯ2 のみを添加した試料ｃのガラスはガラ
ス化反応時の清澄性が良くなかった。Ｓｂ2 Ｏ3 のみを
添加した試料ｄのガラスはガラス化反応時及び均質化溶
融時の清澄性が良くなかった。一方、ＳｎＯ2 とＳｂ2
Ｏ3 の両方を添加した試料ｅのガラスは、Ａｓ2 Ｏ3 を
添加した試料ａのガラスと同様、ガラス化反応時及び均
質化溶融時の何れにおいても清澄性が良好であった。As is clear from Table 1, SnO 2 and Sb
The glass of sample b to which 2 O 3 was not added had extremely poor clarity. The glass of Sample c to which only SnO 2 was added had poor clarity during the vitrification reaction. The glass of Sample d to which only Sb 2 O 3 was added had poor clarity during the vitrification reaction and during homogenization and melting. On the other hand, SnO 2 and Sb 2
Glass samples e both added was the O 3 is similar to the glass of the sample a obtained by adding As 2 O 3, was good clarity in either the time during vitrification reaction and homogenizing the melt.
【００２９】（実施例２）表２は、本発明の方法により
得られる無アルカリガラスの実施例（試料Ｎｏ．１〜
６）を示している。Example 2 Table 2 shows examples of alkali-free glass obtained by the method of the present invention (sample Nos. 1 to 5).
6).
【００３０】[0030]
【表２】 [Table 2]
【００３１】各試料は次のようにして調製した。Each sample was prepared as follows.
【００３２】表の組成を有するガラスとなるようにガラ
ス原料を調合し、実施例１と同様にして清澄性を評価し
た。またこれらのガラス原料調合物を電気炉にて１５５
０〜〜１６００℃で１６〜２４時間溶融し、成型して試
料を得た。Glass raw materials were prepared so as to obtain a glass having the composition shown in the table, and the clarity was evaluated in the same manner as in Example 1. In addition, these glass raw material preparations were placed in an electric furnace for 155 hours.
The sample was melted at 0 to 1600 ° C. for 16 to 24 hours and molded to obtain a sample.
【００３３】このようにして得られた各試料について、
耐熱性及び耐薬品性を評価した。結果を表２に示す。For each sample thus obtained,
Heat resistance and chemical resistance were evaluated. Table 2 shows the results.
【００３４】表２から明らかなように、各試料とも清澄
性に優れ、しかも耐熱性、耐薬品性の特性についても良
好であった。As is clear from Table 2, each sample was excellent in clarity, and also excellent in heat resistance and chemical resistance.
【００３５】なお耐熱性は、歪点をＡＳＴＭ Ｃ３３６
−７１の方法に基づいて測定した。耐薬品性は、耐塩酸
性について各試料を８０℃に保持された１０重量％塩酸
水溶液に２４時間浸漬した後、ガラス基板の表面状態を
観察することによって評価し、ガラス基板表面の変色し
たものを×、全く変色のないものを○で示した。また耐
バッファードフッ酸性は、各試料を２０℃に保持された
３８．７重量％フッ化アンモニウムと１．６重量％フッ
酸からなるバッファードフッ酸に３０分間浸漬した後、
ガラス基板の表面状態を観察することによって評価し、
ガラス基板表面が白濁したものを×、全く変化しなかっ
たものを○で示した。The heat resistance was determined by setting the strain point to ASTM C336.
It measured based on the method of -71. Chemical resistance was evaluated by observing the surface condition of the glass substrate after immersing each sample in a 10% by weight aqueous hydrochloric acid solution maintained at 80 ° C. for 24 hours. X, those without any discoloration were indicated by o. The buffered hydrofluoric acid resistance was determined by immersing each sample in buffered hydrofluoric acid composed of 38.7% by weight ammonium fluoride and 1.6% by weight hydrofluoric acid kept at 20 ° C. for 30 minutes.
Evaluated by observing the surface condition of the glass substrate,
When the surface of the glass substrate became cloudy, the result was x, and when the surface did not change, the result was o.
【００３６】[0036]
【発明の効果】以上説明したように、本発明の方法によ
れば、清澄剤としてＳｎＯ2 とＳｂ2Ｏ3 を併用するた
めに清澄性に優れ、表示欠陥となる泡が存在しない無ア
ルカリガラスを製造することが可能である。As described above, according to the method of the present invention, since SnO 2 and Sb 2 O 3 are used in combination as fining agents, the fining properties are excellent, and the alkali-free glass free of bubbles that cause display defects does not exist. Can be manufactured.
【００３７】また、本発明の無アルカリガラスは、表示
欠陥となる泡がなく、かつ優れた耐熱性、耐薬品性を有
しており、特にディスプレイ用透明ガラス基板として好
適である。Further, the alkali-free glass of the present invention has no bubbles as display defects and has excellent heat resistance and chemical resistance, and is particularly suitable as a transparent glass substrate for a display.
Claims (2)
Ａｌ2 Ｏ3 ６〜２５％、Ｂ2 Ｏ3 ５〜２０％、Ｍｇ
Ｏ ０〜１０％、ＣａＯ ０〜１５％、ＢａＯ ０〜３
０％、ＳｒＯ ０〜１０％、ＺｎＯ ０〜１０％、Ｓｎ
Ｏ2 ０．０５〜２％、Ｓｂ2 Ｏ3 ０．０５〜３％の
組成を有し、本質的にアルカリ金属酸化物を含有しない
ことを特徴とする無アルカリガラス。1. 40% to 70% by weight of SiO 2 ,
Al 2 O 3 6~25%, B 2 O 3 5~20%, Mg
O 0-10%, CaO 0-15%, BaO 0-3
0%, SrO 0-10%, ZnO 0-10%, Sn
O 2 0.05 to 2%, has a composition of Sb 2 O 3 0.05~3%, essentially alkali-free glass, characterized in that does not contain an alkali metal oxide.
Ａｌ2 Ｏ3 ６〜２５％、Ｂ2 Ｏ3 ５〜２０％、Ｍｇ
Ｏ ０〜１０％、ＣａＯ ０〜１５％、ＢａＯ ０〜３
０％、ＳｒＯ ０〜１０％、ＺｎＯ ０〜１０％の組成
を有し、本質的にアルカリ金属酸化物を含有しないガラ
スとなるように調合したガラス原料調合物を溶融した
後、成形する無アルカリガラスの製造方法において、ガ
ラス原料調合物に清澄剤としてＳｎＯ2 を０．０５〜２
重量％及びＳｂ2 Ｏ3 を０．０５〜３重量％添加するこ
とを特徴とする無アルカリガラスの製造方法。2. SiO 2 40 to 70% by weight,
Al 2 O 3 6~25%, B 2 O 3 5~20%, Mg
O 0-10%, CaO 0-15%, BaO 0-3
After melting a glass raw material composition having a composition of 0%, SrO 0-10%, and ZnO 0-10% and containing essentially no alkali metal oxide, the mixture is melted and then molded. In the method for producing glass, 0.05 to 2 SnO2 is used as a fining agent in the glass raw material mixture.
Method for producing an alkali-free glass, which comprises adding weight% and Sb 2 O 3 0.05 to 3 wt%.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11646497A JP3861271B2 (en) | 1996-08-21 | 1997-04-18 | Alkali-free glass and method for producing the same |
| US08/911,945 US6508083B1 (en) | 1996-08-21 | 1997-08-20 | Alkali-free glass and method for producing the same |
| KR1019970039767A KR100406021B1 (en) | 1996-08-21 | 1997-08-21 | Alkali-free glass and method for producing the same |
| US09/907,288 US6546753B2 (en) | 1996-08-21 | 2001-07-17 | Method of producing an alkali-free glass |
| US10/298,811 US6933253B2 (en) | 1996-08-21 | 2002-11-18 | Alkali-free glass and method for producing the same |
| KR1020030042403A KR100424420B1 (en) | 1996-08-21 | 2003-06-27 | Alkali-free glass and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23971296 | 1996-08-21 | ||
| JP8-239712 | 1996-08-21 | ||
| JP11646497A JP3861271B2 (en) | 1996-08-21 | 1997-04-18 | Alkali-free glass and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10114538A true JPH10114538A (en) | 1998-05-06 |
| JP3861271B2 JP3861271B2 (en) | 2006-12-20 |
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ID=26454793
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11646497A Expired - Fee Related JP3861271B2 (en) | 1996-08-21 | 1997-04-18 | Alkali-free glass and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP3861271B2 (en) |
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| JPH1143350A (en) * | 1997-07-24 | 1999-02-16 | Nippon Electric Glass Co Ltd | Non-alkali glass and its production |
| EP1044932A1 (en) * | 1999-04-12 | 2000-10-18 | Schott Glas | Alkali-free aluminoborosilicate glass and its use |
| DE19939789A1 (en) * | 1999-08-21 | 2001-02-22 | Schott Glas | Alkali-free aluminoborosilicate glasses and their uses |
| DE10000839C1 (en) * | 2000-01-12 | 2001-05-10 | Schott Glas | Alkali-free aluminoborosilicate glass used as substrate glass in displays and in thin layer photovoltaics contains oxides of silicon, boron, aluminum, magnesium, calcium, strontium, barium and zinc |
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| DE10000836A1 (en) * | 2000-01-12 | 2001-07-26 | Schott Glas | Alkali-free aluminoborosilicate glass and its uses |
| DE10034985C1 (en) * | 2000-07-19 | 2001-09-06 | Schott Glas | Production of an alkali-free aluminosilicate glass used as a substrate glass for displays comprises adding tin oxide as refining agent to the starting materials, melting the glass and hot molding the glass |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001500098A (en) * | 1996-07-19 | 2001-01-09 | コーニング インコーポレイテッド | Arsenic-free glass |
-
1997
- 1997-04-18 JP JP11646497A patent/JP3861271B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001500098A (en) * | 1996-07-19 | 2001-01-09 | コーニング インコーポレイテッド | Arsenic-free glass |
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