JP2000128572A - Borosilicate glass and its production - Google Patents

Borosilicate glass and its production

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Publication number
JP2000128572A
JP2000128572A JP30443598A JP30443598A JP2000128572A JP 2000128572 A JP2000128572 A JP 2000128572A JP 30443598 A JP30443598 A JP 30443598A JP 30443598 A JP30443598 A JP 30443598A JP 2000128572 A JP2000128572 A JP 2000128572A
Authority
JP
Japan
Prior art keywords
glass
borosilicate glass
sno
sample
chloride
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
JP30443598A
Other languages
Japanese (ja)
Inventor
Toshiji Narita
利治 成田
Hiroki Yamazaki
博樹 山崎
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.)
Nippon Electric Glass Co Ltd
Original Assignee
Nippon Electric 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 Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Priority to JP30443598A priority Critical patent/JP2000128572A/en
Publication of JP2000128572A publication Critical patent/JP2000128572A/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
    • C03C3/089—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
    • 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
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen

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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

PROBLEM TO BE SOLVED: To provide borosilicate glass containing no As2O3 as a clarificant and having no bubbles which may cause defective display, and to provide its producing method. SOLUTION: Borosilicate glass is obtd. by preparing a glass source material which gives a glass having a compsn. by weight of, 60 to 80% SiO2, 2 to 10% Al2O3, 3 to 20% B2O3, 0 to 10% MgO, 0 to 10% CaO, 0 to 10% BaO, 1 to 12% Na2O, 0 to 10% K2O and 3 to 15% Na2O+K2O, adding 0.1 to 1 wt.% Sb2O3 as a clarificant and 0.01 to 1 wt.% chlorides calculated as Cl and/or 0.01 to 1 wt.% SnO2 to the source material, and melting and forming the source material.

Description

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

【０００１】[0001]

【産業上の利用分野】本発明は、液晶ディスプレイ等の
透明ガラス基板として使用される硼珪酸ガラスとその製
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 a borosilicate glass used as a transparent glass substrate for a liquid crystal 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、低アルカリ硼珪酸ガラスや無アルカリガラ
スが使用されている。ディスプレイ用途に用いられるガ
ラスには、耐熱性、耐薬品性、アルカリ溶出等の特性の
他に、表示欠陥となる泡がないことが要求される。2. Description of the Related Art Conventionally, low alkali borosilicate glass and non-alkali glass have been used as transparent glass substrates for liquid crystal displays and the like. Glass used for display applications is required to be free from bubbles that cause display defects in addition to properties such as heat resistance, chemical resistance, and alkali elution.

【０００３】このようなガラスとして、従来より種々の
ガラスが提案されており、本出願人も特開平３−１４６
４３５号において液晶基板等に用いられる硼珪酸ガラス
を提案している。[0003] As such a glass, various glasses have been conventionally proposed, and the present applicant has also disclosed in Japanese Patent Application Laid-Open No. 3-146.
No. 435 proposes a borosilicate glass used for a liquid crystal substrate or the like.

【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、ガラス化反応が始まる比較的低い温度域と、
ガラス融液の脱泡、均質化が起こる比較的高い温度域の
両方で清澄ガスを発生する清澄剤を選択することが重要
である。これは、原料がガラス化反応を起こすときに発
生するガスを追い出すとともに、脱泡、均質化過程でガ
ラス融液中に残った微小な泡を大きくすることにより浮
上させて除去するためである。In order to obtain a bubble-free glass, a relatively low temperature range at which the vitrification reaction starts,
It is important to select a fining agent that generates fining gas both in the relatively high temperature range where defoaming and homogenization of the glass melt occurs. This is because the gas generated when the raw material undergoes a vitrification reaction is expelled, and the fine bubbles remaining in the glass melt during the defoaming and homogenization processes are increased to remove them by floating.

【０００５】ところで液晶ディスプレイ用ガラス基板に
使用されるような硼珪酸ガラスは、ガラス融液の粘度が
高く、高温で溶融が行われる。この種の硼珪酸ガラスで
は、通常１２００〜１３００℃でガラス化反応が起こ
り、１４００℃以上の高温で脱泡、均質化が行われる。
このため清澄剤には幅広い温度域（１２００〜１６００
℃程度）で清澄ガスを発生させることができるものが必
要とされ、現在ではＡｓ 2 Ｏ3 が広く使用されている。By the way, for a glass substrate for a liquid crystal display,
Borosilicate glass, as used, has a viscosity of the glass melt.
High and melting at high temperature. This kind of borosilicate glass
Means that a vitrification reaction usually occurs at 1200 to 1300 ° C.
And defoaming and homogenizing at a high temperature of 1400 ° C. or more.
For this reason, the fining agent has a wide temperature range (1200 to 1600).
Must be able to generate a fining gas at
It is important, now As Two OThree Is widely used.

【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硼珪
酸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.
An object of the present invention is to provide a borosilicate glass and a method for producing the borosilicate glass, which does not use any of the above, and which does not have bubbles that cause display defects.

【０００８】[0008]

【課題を解決するための手段】本発明者等は、種々の実
験を行った結果、清澄剤としてＡｓ2 Ｏ3 の代わりにＳ
ｂ2 Ｏ3 、塩化物、ＳｎＯ2 を組み合わせて使用するこ
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。As a result of various experiments, the present inventors have found that as a fining agent, S 2 O 3 is substituted for As 2 O 3.
The inventors have found that the above object can be achieved by using a combination of b 2 O 3 , chloride and SnO 2, and propose the present invention.

【０００９】即ち、本発明の硼珪酸ガラスは、重量百分
率でＳｉＯ2 ６０〜８０％、Ａｌ 2 Ｏ3 ２〜１０
％、Ｂ2 Ｏ3 ３〜２０％、ＭｇＯ ０〜１０％、Ｃａ
Ｏ ０〜１０％、ＢａＯ ０〜１０％、Ｎａ2 Ｏ １〜
１２％、Ｋ2 Ｏ ０〜１０％、Ｎａ2 Ｏ＋Ｋ2 Ｏ ３〜
１５％、Ｓｂ2 Ｏ3 ０．０１〜１％、Ｃｌ ０．００
５〜０．５％及び／又はＳｎＯ2 ０．０１〜１％の組
成を有することを特徴とする。That is, the borosilicate glass of the present invention has a weight percentage of
SiO at the rateTwo 60-80%, Al Two OThree 2-10
%, BTwo OThree 3-20%, MgO 0-10%, Ca
O 0-10%, BaO 0-10%, NaTwo O 1
12%, KTwo O 0-10%, NaTwo O + KTwo O 3 ~
15%, SbTwo OThree 0.01-1%, Cl 0.00
5 to 0.5% and / or SnOTwo 0.01-1% set
It is characterized by having a composition.

【００１０】また本発明の硼珪酸ガラスの製造方法は、
重量百分率でＳｉＯ2 ６０〜８０％、Ａｌ2 Ｏ3 ２
〜１０％、Ｂ2 Ｏ3 ３〜２０％、ＭｇＯ ０〜１０
％、ＣａＯ ０〜１０％、ＢａＯ ０〜１０％、Ｎａ2
Ｏ １〜１２％、Ｋ2 Ｏ ０〜１０％、Ｎａ2 Ｏ＋Ｋ2
Ｏ ３〜１５％の組成を有する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、成形する硼珪酸ガ
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、Ｓｂ2Ｏ3を０．０１〜１重量％と、塩化物をＣｌ
換算で０．０１〜１重量％及び／又はＳｎＯ2を０．０
１〜１重量％添加することを特徴とする。[0010] The method for producing a borosilicate glass according to the present invention comprises:
60-80% of SiO 2 by weight percentage, Al 2 O 3 2
~10%, B 2 O 3 3~20 %, MgO 0~10
%, CaO 0-10%, BaO 0-10%, Na 2
O 1-12%, K 2 O 0-10%, Na 2 O + K 2
In a method for producing a borosilicate glass to be molded after melting a glass raw material mixture prepared so as to obtain a glass having a composition of O 3 to 15%, Sb 2 O 3 is added as a fining agent to the glass raw material mixture. 0.11 to 1% by weight and chloride to Cl
0.01-1% by weight and / or SnO 2 in 0.0
It is characterized by adding 1 to 1% by weight.

【００１１】[0011]

【作用】本発明において使用するＳｂ2Ｏ3とＳｎＯ
2は、ＳｂイオンやＳｎイオンの価数変化による化学反
応により多量の清澄ガス（酸素ガス）を発生する。即
ち、Ｓｂ2Ｏ3（３価）は、数１００℃の低温域で一旦Ｓ
ｂ2 Ｏ5（５価）に変化した後、１２００〜１３００℃
付近で再びＳｂ2Ｏ3（３価）に戻る際に多量の清澄ガス
を放出し、ＳｎＯ2（４価）は１４００℃以上でＳｎＯ
に（２価）変化する際に多量の清澄ガスを放出する。ま
た塩化物は、１２００℃以上の温度域で分解、揮発して
清澄ガス（塩素ガス等）を発生するが、特に１４００℃
以上の高温域で分解、揮発が激しくなり、多量の清澄ガ
スを発生する。Sb 2 O 3 and SnO used in the present invention
2 generates a large amount of fining gas (oxygen gas) by a chemical reaction due to a change in the valence of Sb ions or Sn ions. That is, Sb 2 O 3 (trivalent) is once S in a low temperature range of several hundred degrees Celsius.
After changing to b 2 O 5 (pentavalent), 1200 to 1300 ° C.
When returning to Sb 2 O 3 (trivalent) again in the vicinity, a large amount of fining gas is released, and SnO 2 (tetravalent) releases SnO 2
Release a large amount of fining gas when changing to (divalent). Chloride is decomposed and volatilized in a temperature range of 1200 ° C. or more to generate a fining gas (such as chlorine gas).
Decomposition and volatilization become severe in the above high temperature range, and a large amount of fining gas is generated.

【００１２】従って清澄剤としてＳｂ2Ｏ3と、塩化物及
び／又はＳｎＯ2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硼珪酸ガラスを得ることができ
る。Therefore, by using Sb 2 O 3 together with chloride and / or SnO 2 as a fining agent, high fining can be achieved over a wide temperature range from the vitrification reaction occurring at a relatively low temperature to the homogenization melting at a high temperature. Since the effect is obtained, it is possible to obtain a borosilicate glass free of bubbles serving as display defects.

【００１３】次に、本発明の硼珪酸ガラスの製造方法を
述べる。Next, a method for producing the borosilicate glass of the present invention will be described.

【００１４】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.

【００１５】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６０〜８０％、好ましくは６５
〜７５％である。ＳｉＯ2が６０％より少ないとアルカ
リ溶出量が多くなるとともに、耐薬品性や耐熱性が低く
なって耐熱性が悪化する。一方、８０％より多いとガラ
スの溶融性が悪化する。[0015] SiO 2 is a component that forms a glass network, and its content is 60 to 80%, preferably 65 to 80%.
~ 75%. If the content of SiO 2 is less than 60%, the amount of alkali eluted will increase, and the chemical resistance and heat resistance will decrease, resulting in deterioration of the heat resistance. On the other hand, if it is more than 80%, the melting property of the glass deteriorates.

【００１６】Ａｌ2Ｏ3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２〜１０％、好ましくは
３〜８％である。Ａｌ2 Ｏ3 が２％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、ま
たガラスのアルカリ溶出量が多くなる。一方、１０％よ
り多いとガラスの溶融性が悪くなる。Al 2 O 3 is a component for improving the heat resistance and devitrification resistance of the glass, and its content is 2 to 10%, preferably 3 to 8%. If the content of Al 2 O 3 is less than 2%, the devitrification temperature rises remarkably, devitrification easily occurs in the glass, and the alkali elution amount of the glass increases. On the other hand, if the content is more than 10%, the melting property of the glass deteriorates.

【００１７】Ｂ2Ｏ3は融剤として働き、溶融を容易にす
る成分であり、その含有量は３〜２０％、好ましくは８
〜１５％である。Ｂ2Ｏ3が３％より少ないと融剤として
の効果が不十分となり、２０％より多いと耐酸性や耐熱
性が悪化する。B 2 O 3 is a component that functions as a flux and facilitates melting, and its content is 3 to 20%, preferably 8%.
~ 15%. When B 2 O 3 is less than 3%, the effect as a flux becomes insufficient, and when it is more than 20%, acid resistance and heat resistance deteriorate.

【００１８】ＭｇＯ、ＣａＯ及びＢａＯは高温域の粘度
を下げてガラスの溶融を容易にする成分であり、その含
有量はそれぞれ０〜１０％、好ましくはそれぞれ０〜５
％である。これら各成分が１０％より多いと高温粘度が
低下しすぎて相対的に液相粘度が低くなるため、結晶が
析出し易くなり、成型温度が著しく制限される。MgO, CaO and BaO are components that lower the viscosity in the high temperature range and facilitate melting of the glass, and their contents are each 0 to 10%, preferably 0 to 5%.
%. If the content of each of these components is more than 10%, the high temperature viscosity is too low and the liquidus viscosity is relatively low, so that crystals are easily precipitated, and the molding temperature is significantly restricted.

【００１９】Ｎａ2Ｏは融剤として働き、ガラスの溶融
を容易にする成分であり、その含有量は１〜１２％、好
ましくは３〜１０％である。Ｎａ2Ｏが１％より少ない
とガラスの溶融性が悪化し、１２％より多いとガラスの
アルカリ溶出量が多くなる。Na 2 O is a component which functions as a flux and facilitates melting of the glass, and its content is 1 to 12%, preferably 3 to 10%. If Na 2 O is less than 1%, the melting property of the glass is deteriorated, and if it is more than 12%, the alkali elution amount of the glass is increased.

【００２０】Ｋ2ＯはＮａ2Ｏと同様の効果があり、その
含有量は０〜１０％、好ましくは０〜５％である。Ｋ2
Ｏが１０％より多いとガラスのアルカリ溶出量が多くな
る。K 2 O has the same effect as Na 2 O, and its content is 0 to 10%, preferably 0 to 5%. K 2
When O is more than 10%, the alkali elution amount of the glass increases.

【００２１】Ｎａ2ＯとＫ2Ｏの含有量は合量で３〜１５
％に制限される。その理由はこれら成分の合量が３％よ
り少ないとガラスの溶融性が悪化し、１５％より多いと
ガラスのアルカリ溶出量が多くなるためである。The content of Na 2 O and K 2 O is 3 to 15 in total.
%. The reason is that if the total amount of these components is less than 3%, the meltability of the glass deteriorates, and if the total amount is more than 15%, the alkali elution amount of the glass increases.

【００２２】また上記成分の他に、ＺｎＯ、ＴｉＯ2、
Ｆｅ2Ｏ3等を合量で５％まで添加することができる。In addition to the above components, ZnO, TiO 2 ,
Fe 2 O 3 and the like can be added up to 5% in total.

【００２３】次にガラス原料調合物にＳｂ2Ｏ3と、塩化
物及び／又はＳｎＯ2を添加する。Ｓｂ2Ｏ3原料として
は、Ｓｂ2Ｏ3以外にもＳｂ2Ｏ5を使用することができ、
塩化物原料としては、ＮａＣｌ、ＫＣｌ、ＢａＣｌ2、
ＣａＣｌ2等が使用できる。Ｓｂ2Ｏ3、塩化物、ＳｎＯ2
の添加量は、何れもガラス原料調合物１００重量％に対
して０．０１〜１重量％である。Ｓｂ2Ｏ3が０．０１％
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、塩化物やＳｎＯ2が０．０１％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。一方、Ｓｂ 2Ｏ3、ＳｎＯ2が１％より多いとガラス
が失透し易くなり、また塩化物が１％より多いと揮発量
が多くなりすぎてガラスが変質し易くなる。なお塩化物
とＳｎＯ 2は、何れか一つを選択して使用しても良い
が、両者を併用するとさらに優れた清澄効果を得ること
ができる。Next, Sb was added to the glass raw material mixture.TwoOThreeAnd chloride
Object and / or SnOTwoIs added. SbTwoOThreeAs raw material
Is SbTwoOThreeBesides, SbTwoOFiveCan be used,
NaCl, KCl, BaClTwo,
CaClTwoEtc. can be used. SbTwoOThree, Chloride, SnOTwo
The amount of addition is based on 100% by weight of the glass raw material formulation.
From 0.01 to 1% by weight. SbTwoOThreeIs 0.01%
If it is less, the gas generated during the vitrification reaction is expelled.
Difficult, chloride and SnOTwoIs less than 0.01%
It is difficult to remove bubbles remaining in the glass melt during homogenization and melting.
You. On the other hand, Sb TwoOThree, SnOTwoIf more than 1% is glass
Is easily devitrified, and if the chloride is more than 1%, the amount of volatilization
And the glass is apt to deteriorate. In addition, chloride
And SnO TwoMay be used by selecting one of them
However, when both are used together, an even better fining effect is obtained.
Can be.

【００２４】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Ｓｂ2Ｏ3の価数変化による化学反応によっ
て酸素ガスが発生し、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、塩化物の分解、揮発によって塩素ガス等が発生
するとともに、ＳｎＯ2の価数変化による化学反応で酸
素ガスが発生してガラス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, 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 expelled from the melt. . Further, at the time of homogenization and melting at a higher temperature, chlorine gas and the like are generated by decomposition and volatilization of chloride, and oxygen gas is generated by a chemical reaction due to a change in the valence of SnO 2 , and minute gas remaining in the glass glass melt is generated. Bubbles are removed.

【００２５】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.

【００２６】このようにして、重量百分率でＳｉＯ2 ６
０〜８０％、Ａｌ2Ｏ3 ２〜１０％、Ｂ2Ｏ3 ３〜２０
％、ＭｇＯ ０〜１０％、ＣａＯ ０〜１０％、ＢａＯ
０〜１０％、Ｎａ2Ｏ １〜１２％、Ｋ2Ｏ ０〜１０
％、Ｎａ2Ｏ＋Ｋ2Ｏ ３〜１５％、Ｓｂ2Ｏ3 ０．０１
〜１％、Ｃｌ ０．００５〜０．５％及び／又はＳｎＯ
2 ０．０１〜１％の組成を有する本発明の硼珪酸ガラス
を得ることができる。In this way, SiO 2 6
0 to 80%, Al 2 O 3 2 to 10%, B 2 O 3 3 to 20
%, MgO 0-10%, CaO 0-10%, BaO
0~10%, Na 2 O 1~12% , K 2 O 0~10
%, Na 2 O + K 2 O 3~15%, Sb 2 O 3 0.01
１1%, Cl 0.005-0.5% and / or SnO
2 The borosilicate glass of the present invention having a composition of 0.01 to 1% can be obtained.

【００２７】[0027]

【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.

【００２８】（実施例１）表１、２は、Ｓｂ2Ｏ3、塩化
物及びＳｎＯ2の効果を示したものであり、試料ａはＡ
ｓ2Ｏ3を清澄剤として添加した従来の硼珪酸ガラス、試
料ｂは試料ａからＡｓ2Ｏ3を除いて作製した硼珪酸ガラ
ス、試料ｃはＳｂ2Ｏ3のみを添加した硼珪酸ガラス、試
料ｄは塩化物（ＮａＣｌ）のみを添加した硼珪酸ガラ
ス、試料ｅはＳｎＯ2のみを添加した硼珪酸ガラス、試
料ｆはＳｂ2Ｏ3及び塩化物を併用した本発明の硼珪酸ガ
ラス、試料ｇはＳｂ2Ｏ3及びＳｎＯ2を併用した本発明
の硼珪酸ガラス、試料ｈはＳｂ2Ｏ3、塩化物及びＳｎＯ
2を併用した本発明の硼珪酸ガラスを示している。Example 1 Tables 1 and 2 show the effects of Sb 2 O 3 , chloride and SnO 2.
conventional borosilicate glass to which s 2 O 3 was added as a fining agent, sample b: borosilicate glass prepared by removing As 2 O 3 from sample a, sample c: borosilicate glass to which only Sb 2 O 3 was added, Sample d is borosilicate glass to which only chloride (NaCl) is added, sample e is borosilicate glass to which only SnO 2 is added, sample f is borosilicate glass of the present invention in which Sb 2 O 3 and chloride are used together, and sample is g is the borosilicate glass of the present invention using both Sb 2 O 3 and SnO 2 , and sample h is Sb 2 O 3 , chloride and SnO 2
2 shows a borosilicate glass of the present invention in which No. 2 is used in combination.

【００２９】[0029]

【表１】 [Table 1]

【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原料調合物となる
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１５０
０℃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１６００℃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１００ｇ中の泡が１０００個を越える
ものを××、１０１〜１０００個のものを×、１１〜１
００個のものを△、１〜１０個のものを○、全く泡のな
いものを◎で示した。結果を表１に示す。なお表中のガ
ラス原料調合物組成は、各成分を酸化物換算した値であ
り、また塩化物はＣｌ換算した値で示す。Glass raw materials were prepared so as to obtain a glass raw material mixture having the composition shown in the table, and were melted in an electric furnace. At this time, in order to evaluate the clarity during the vitrification reaction, 150
Two types were prepared: one that was melted at 0 ° C. for one hour and one that was melted at 1600 ° C. for one hour in order to evaluate clarity during homogenization and melting. Next, the molten glass was poured out onto a carbon table and, after slow cooling, the number of bubbles remaining in the glass was counted. X, 11 to 1
00 samples were indicated by Δ, 1 to 10 samples were indicated by ○, and no bubbles were indicated by ◎. Table 1 shows the results. In addition, the glass raw material composition in the table is a value obtained by converting each component into an oxide, and the chloride is shown by a value obtained by converting into Cl.

【００３３】表から明らかなように、清澄剤を全く添加
しない試料ｂのガラスは清澄性が著しく悪かった。Ｓｂ
2Ｏ3のみを添加した試料ｃのガラスは、ガラス化反応時
に多量の清澄ガスが発生したものの、均質化溶融時に十
分な清澄ガスが発生せず、結果として清澄性が悪かっ
た。塩化物のみを添加した試料ｄのガラス及びＳｎＯ2
のみを添加した試料ｅのガラスは、均質化溶融時に多量
の清澄ガスを発生したものの、ガラス化反応時に十分な
ガスが発生しなかったため、結果として清澄性が不十分
であった。As is clear from the table, the glass of the sample b to which no fining agent was added had remarkably poor clarity. Sb
In the glass of sample c to which only 2 O 3 was added, although a large amount of fining gas was generated during the vitrification reaction, sufficient fining gas was not generated during homogenization and melting, resulting in poor fining properties. Sample d glass to which only chloride was added and SnO 2
Although the glass of sample e to which only glass was added generated a large amount of fining gas during homogenization and melting, sufficient gas was not generated during the vitrification reaction, resulting in insufficient fining.

【００３４】一方、Ｓｂ2Ｏ3と、塩化物又はＳｎＯ2を
添加した試料ｆ、ｇのガラスは、Ａｓ2Ｏ3を添加した試
料ａのガラスと同様に清澄性が良好であった。またＳｂ
2Ｏ3、塩化物及びＳｎＯ2を添加した試料ｈのガラス
は、試料ａのガラスよりも優れた清澄性を示した。On the other hand, the glasses of Samples f and g to which Sb 2 O 3 and chloride or SnO 2 were added had good clarity, similarly to the glass of Sample a to which As 2 O 3 was added. Also Sb
The glass of sample h to which 2 O 3 , chloride and SnO 2 were added exhibited better clarity than the glass of sample a.

【００３５】（実施例２）表３〜６は、本発明の方法に
より得られる硼珪酸ガラスの実施例（試料Ｎｏ．１〜２
０）を示している。(Example 2) Tables 3 to 6 show examples of borosilicate glass obtained by the method of the present invention (samples Nos. 1 to 2).
0).

【００３６】[0036]

【表３】 [Table 3]

【００３７】[0037]

【表４】 [Table 4]

【００３８】[0038]

【表５】 [Table 5]

【００３９】[0039]

【表６】 [Table 6]

【００４０】各試料は次のようにして調製した。Each sample was prepared as follows.

【００４１】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６〜８時間溶融し、成型して試料を
得た。塩化物としてはＮａＣｌを使用した。このように
して得られた各試料について、耐薬品性及びアルカリ溶
出量を評価した。結果を各表に示す。なお表中のガラス
組成は、各成分を酸化物換算した値であり、また塩化物
はガラス中に残存する量をＣｌ換算した値で示してあ
る。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 6 to 8 hours and molded to obtain a sample. NaCl was used as the chloride. Each sample thus obtained was evaluated for chemical resistance and alkali elution amount. The results are shown in each table. In the table, the glass composition is a value obtained by converting each component into an oxide, and the chloride is a value obtained by converting the amount remaining in the glass into Cl.

【００４２】表から明らかなように、各試料とも清澄性
に優れ、しかも耐薬品性、アルカリ溶出の特性について
も良好であった。As is clear from the table, each sample was excellent in clarity, and also excellent in chemical resistance and alkali elution characteristics.

【００４３】なお耐薬品性は、各試料を８０℃に保持さ
れた１０重量％硫酸水溶液又は塩酸水溶液に８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、ガラス基板表面に全く変色がないものを○で示
した。またアルカリ溶出量は、ＪＩＳ−Ｒ３５０２に基
づいて測定した。The chemical resistance was evaluated by immersing each sample in a 10% by weight aqueous solution of sulfuric acid or hydrochloric acid kept at 80 ° C. for 8 hours, and then observing the surface condition of the glass substrate. Those without any discoloration were indicated by ○. The alkali elution amount was measured based on JIS-R3502.

【００４４】[0044]

【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Ｓｂ2Ｏ3と、塩化物及び／又はＳｎ
Ｏ2を使用するために清澄性に優れ、表示欠陥となる泡
が存在しない硼珪酸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, Sb 2 O 3 as a fining agent, chloride and / or Sn are used.
The use of O 2 makes it possible to produce a borosilicate glass which is excellent in clarity and free of bubbles which cause display defects.

【００４５】また、本発明の硼珪酸ガラスは、表示欠陥
となる泡がなく、かつ耐熱性や耐薬品性に優れ、またア
ルカリ溶出量が少ないため、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 borosilicate glass of the present invention has no bubbles as display defects, has excellent heat resistance and chemical resistance, and has a small amount of alkali elution. Therefore, it is particularly suitable as a transparent glass substrate for displays.

フロントページの続き Ｆターム(参考） 2H090 JB02 JC06 JC18 JD01 JD09 4G062 AA18 BB01 BB05 CC01 CC04 DA06 DA07 DB03 DC03 DC04 DD01 DE01 DF01 EA01 EB03 EB04 EC01 EC02 EC03 ED01 ED02 ED03 EE01 EE02 EE03 EF01 EG01 EG02 EG03 FA01 FA10 FB01 FC01 FD01 FE01 FE02 FF01 FG01 FH01 FJ01 FK01 FL01 GA01 GA10 GB01 GC01 GD01 GE01 HH01 HH03 HH05 HH07 HH09 HH11 HH13 HH15 HH17 HH20 JJ01 JJ03 JJ04 JJ05 JJ06 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM27 NN31 NN34 5G435 AA00 AA14 HH02 KK07 Continued on the front page F-term (reference) 2H090 JB02 JC06 JC18 JD01 JD09 4G062 AA18 BB01 BB05 CC01 CC04 DA06 DA07 DB03 DC03 DC04 DD01 DE01 DF01 EA01 EB03 EB04 EC01 EC02 EC03 ED01 ED02 ED03 EE01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 EF01 FE01 FE01 FE02 FF01 FG01 FH01 FJ01 FK01 FL01 GA01 GA10 GB01 GC01 GD01 GE01 HH01 HH03 HH05 HH07 HH09 HH11 HH13 HH15 HH17 HH20 JJ01 JJ03 JJ04 JJ05 JJ06 JJ07 JJ10 KK01 KK03 KK01 KK03 KK03 KK03 KK03 A07

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 重量百分率でＳｉＯ2 ６０〜８０％、
Ａｌ2 Ｏ3 ２〜１０％、Ｂ2 Ｏ3 ３〜２０％、Ｍｇ
Ｏ ０〜１０％、ＣａＯ ０〜１０％、ＢａＯ ０〜１
０％、Ｎａ2 Ｏ １〜１２％、Ｋ2 Ｏ ０〜１０％、Ｎ
ａ2 Ｏ＋Ｋ2Ｏ ３〜１５％、Ｓｂ2 Ｏ3 ０．０１〜
１％、Ｃｌ ０．００５〜０．５％及び／又はＳｎＯ2
０．０１〜１％の組成を有することを特徴とする硼珪
酸ガラス。1. 60 to 80% by weight of SiO 2 ,
Al 2 O 3 2 to 10%, B 2 O 3 3 to 20%, Mg
O 0-10%, CaO 0-10%, BaO 0-1
0%, Na 2 O 1~12% , K 2 O 0~10%, N
a 2 O + K 2 O 3~15 %, Sb 2 O 3 0.01~
1%, Cl 0.005 to 0.5% and / or SnO 2
A borosilicate glass having a composition of 0.01 to 1%. 【請求項２】 重量百分率でＳｉＯ2 ６０〜８０％、
Ａｌ2 Ｏ3 ２〜１０％、Ｂ2 Ｏ3 ３〜２０％、Ｍｇ
Ｏ ０〜１０％、ＣａＯ ０〜１０％、ＢａＯ ０〜１
０％、Ｎａ2 Ｏ １〜１２％、Ｋ2 Ｏ ０〜１０％、Ｎ
ａ2 Ｏ＋Ｋ2Ｏ ３〜１５％の組成を有するガラスとな
るように調合したガラス原料調合物を溶融した後、成形
する硼珪酸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、Ｓｂ2 Ｏ3 を０．０１〜１重量％
と、塩化物をＣｌ換算で０．０１〜１重量％及び／又は
ＳｎＯ2 を０．０１〜１重量％添加することを特徴とす
る硼珪酸ガラスの製造方法。2. SiO 2 60-80% by weight,
Al 2 O 3 2 to 10%, B 2 O 3 3 to 20%, Mg
O 0-10%, CaO 0-10%, BaO 0-1
0%, Na 2 O 1~12% , K 2 O 0~10%, N
After melting the glass raw material formulation which is prepared to have a glass having a 2 O + K 2 O 3~15 % of the composition, in the manufacturing method of the borosilicate glass molding, as a fining agent in a glass raw material formulation, Sb 2 O 3, 0.01 to 1 wt%
When manufacturing method of borosilicate glass, which comprises adding 0.01 to 1% by weight of chlorides Cl terms and / or the SnO 2 0.01 to 1 wt%.
JP30443598A 1998-10-26 1998-10-26 Borosilicate glass and its production Pending JP2000128572A (en)

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ID=17932980

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