JPH09110460A - Alkali-free glass - Google Patents
Alkali-free glassInfo
- Publication number
- JPH09110460A JPH09110460A JP26960295A JP26960295A JPH09110460A JP H09110460 A JPH09110460 A JP H09110460A JP 26960295 A JP26960295 A JP 26960295A JP 26960295 A JP26960295 A JP 26960295A JP H09110460 A JPH09110460 A JP H09110460A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- alkali
- free glass
- range
- weight
- 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
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
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐熱性、耐薬品
性、光学的均質性に優れ、電子工業分野における電子部
品素材として多用され、特に薄膜半導体 (TFT)形のアク
ティブマトリックス液晶ディスプレイ用基板として有用
で、かつフロート法による成形 (製板) が容易な無アル
カリガラスに関する。TECHNICAL FIELD The present invention has excellent heat resistance, chemical resistance, and optical homogeneity, and is widely used as a material for electronic parts in the field of electronic industry. In particular, it is a thin film semiconductor (TFT) type active matrix liquid crystal display substrate. The invention relates to an alkali-free glass which is useful as a glass and is easy to form (plate) by the float method.
【０００２】[0002]
【従来技術】近年、ディスプレイ等の基板として、ガラ
スの表面に金属や金属酸化物等の薄膜を形成した無アル
カリガラス基板が多く使用されている。これらの無アル
カリガラス基板は、電子部品素材、殊に TFT用基板とし
て採用するうえで、また製造上各種の特性が必要とされ
る。2. Description of the Related Art In recent years, a non-alkali glass substrate having a thin film of a metal or a metal oxide formed on the surface of glass has been widely used as a substrate for a display or the like. These non-alkali glass substrates are required to have various characteristics when they are used as electronic component materials, especially as TFT substrates, and in manufacturing.
【０００３】すなわちガラス基板上への成膜工程におい
て高温での熱処理が施されるが、それに耐え得る高耐熱
性が必要であり、歪点において約 650℃以上であること
が、また、基板上に形成される薄膜、特にSi系薄膜は、
熱膨張率が約36〜39×10-7／℃であり、膜を歪や亀裂等
が生ずることなく密着させるためにはそれに近似した熱
膨張率が、また薄膜のパターニング工程において酸やア
ルカリ等の薬液によってエッチングされるが、基板ガラ
ス自体が浸食されないだけの耐薬品性が、さらにガラス
中に気泡、分相、脈理が存在すると、ディスプレイ等の
光学的欠陥となるため光学的均質性等が要求される。That is, a heat treatment at a high temperature is performed in a film forming process on a glass substrate, but high heat resistance capable of withstanding the heat treatment is required, and the strain point is about 650 ° C. or higher. The thin film formed in, especially the Si-based thin film,
The coefficient of thermal expansion is about 36 to 39 × 10 -7 / ° C, and the coefficient of thermal expansion is close to that in order to bring the film into close contact without causing distortion or cracks. Although it is etched by the chemical solution, the substrate glass itself is not chemically eroded, and if bubbles, phase separation, or striae are present in the glass, it will cause optical defects in displays, etc. Is required.
【０００４】加えて工業的に生産するうえで、溶融が容
易であり、成形し易いものでなければならず、特に雰囲
気、炉材等による汚染が少なく連続溶融可能な直接通電
法による電気溶融、表面平滑性に優れ連続成形に適した
フロート法成形が適用できるガラス組成物であることが
望まれる。In addition, for industrial production, it must be easy to melt and easy to mold, and in particular, electric melting by the direct energization method that can be continuously melted with little pollution by atmosphere, furnace material, etc., It is desired that the glass composition has excellent surface smoothness and is suitable for continuous molding by the float molding.
【０００５】従来SiO2−Al2O3 −B2O3系−RO (二価成分
酸化物：MgO 、caO 、SrO 、BaO 等) よりなる成分系の
ガラスは公知であり、その幾つかは市場に供されてい
る。特開平4-325434号、特開平4-325436号に開示される
ガラスは概してSiO2をはじめとするガラスの網目構造形
成用酸化物が過少で相対的にRO成分が多く、歪点が低く
熱膨張率が高いという点でTFT 用基板として適当とはい
えない。特開平4-325435号に開示されるガラスは歪点は
高いが、CaO 、SrO が過多、B2O3が過少であり熱膨張率
が大きい点でTFT 用基板として不適当である。Conventionally, glass of a component system composed of SiO 2 —Al 2 O 3 —B 2 O 3 system —RO (divalent component oxides: MgO, caO, SrO, BaO, etc.) is known, and some of them are known. It is offered to the market. The glasses disclosed in JP-A-4-325434 and JP-A-4-325436 generally have a small amount of oxides for forming a network structure of glass such as SiO 2 and have a relatively large amount of RO component, a low strain point and a low thermal temperature. It is not suitable as a TFT substrate because of its high expansion coefficient. Although the glass disclosed in Japanese Patent Laid-Open No. 4-325435 has a high strain point, it is unsuitable as a TFT substrate because it has too much CaO 2 and SrO 2 and too little B 2 O 3 and has a large coefficient of thermal expansion.
【０００６】また、特開平4-160030号には高歪点で低熱
膨張率のガラスが開示されているがZnO 、PbO 、La2O
3 、As2O3 、またはSb2O3 の少なくとも一種を含んでお
り、フロート法成形には適さず、さらに比較的B2O3が多
い等耐酸性に劣る傾向にある。Further, Japanese Patent Laid-Open No. 4-160030 discloses a glass having a high strain point and a low coefficient of thermal expansion, but ZnO, PbO, La 2 O
Since it contains at least one of 3 , As 2 O 3 , and Sb 2 O 3 , it is not suitable for float molding, and tends to be inferior in acid resistance such as having a relatively large amount of B 2 O 3 .
【０００７】加えて特開平6-263473号には高歪点で低熱
膨張率のガラスが開示されているが、作業温度 (粘度10
4 ポイズを示す温度) が高い等フロート法成形に適当と
はいえない。該成分系をベースとする市販のガラスには
As2O3 等の溶融助剤の含有が不可避であるが先述のごと
くフロート法成形には忌避されるべきものである。In addition, JP-A-6-263473 discloses a glass having a high strain point and a low coefficient of thermal expansion.
It cannot be said to be suitable for iso-float molding, which has a high temperature of 4 poise). Commercially available glasses based on this component system
The inclusion of a melting aid such as As 2 O 3 is unavoidable, but as described above, it should be avoided in the float molding.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、上記した不
都合点を解消し、歪点が 660℃以上、熱膨張率が36〜39
(×10-7／℃) 、作業温度 (粘度104 ポイズを示す温度)
が1290℃以下、かつ失透温度が1290℃未満のフロート
法成形に適した無アルカリガラスを提供することを目的
とする。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned disadvantages and has a strain point of 660 ° C. or higher and a coefficient of thermal expansion of 36 to 39.
(× 10 -7 / ℃), working temperature (temperature showing viscosity of 10 4 poise)
It is an object of the present invention to provide an alkali-free glass having a devitrification temperature of 1290 ° C. or lower and a devitrification temperature of less than 1290 ° C., which is suitable for float forming.
【０００９】[0009]
【課題を解決するための手段】本発明は重量％表示で、
SiO2 60.5 〜62、Al2O3 13.5〜16.5、B2O3 6.5〜8.5、Z
rO2 0.3〜2 、MgO 0.5 〜2 、CaO 5 〜7 、SrO 5 〜7
、およびBaO 1 〜4 の範囲で含有し、かつ実質的にア
ルカリ金属酸化物並びにPbO 、ZnO 、As2O3 、およびSb
2O3 を含有しない無アルカリガラスであって、該無アル
カリガラス 100重量％に対し、調製時にフッ化物を F換
算で 0.5重量％以下の範囲で外挿添加したこと、前記無
アルカリガラスにおいて、CaO 、MgO 、BaO 、およびSr
O の和を14.5〜17.5重量％の範囲としたこと、さらに調
製時にフッ化物を F換算で 0.1〜 0.5重量％の範囲で外
挿添加したこと、加えて歪点が 660℃以上、熱膨張率が
36〜39 (×10-7／℃) であること、からなる。The present invention is based on the weight percentage,
SiO 2 60.5 to 62, Al 2 O 3 13.5 to 16.5, B 2 O 3 6.5 to 8.5, Z
rO 2 0.3 to 2 , MgO 0.5 to 2, CaO 5 to 7, SrO 5 to 7
, And BaO 1 to 4 and substantially containing alkali metal oxides and PbO 2 , ZnO 2 , As 2 O 3 , and Sb.
2 Al is a non-alkali glass containing no O 3, and 100% by weight of the non-alkali glass, fluoride was extrapolated in the range of 0.5% by weight or less in terms of F at the time of preparation, in the non-alkali glass, CaO, MgO, BaO, and Sr
The sum of O was set in the range of 14.5 to 17.5% by weight, and the fluoride was extrapolated in the range of 0.1 to 0.5% by weight in terms of F during preparation. In addition, the strain point was 660 ° C or higher, and the coefficient of thermal expansion was But
36 to 39 (× 10 -7 / ° C).
【００１０】本発明の成分系において、SiO2はガラスの
主成分であり、重量％において60.5％未満ではガラスの
耐酸、耐フッ酸性が低下する。62％を越えるとガラス融
液の高温粘度が高くなり、溶融性が劣り、またガラスの
失透傾向が増大し、特にSiO2系結晶が析出し易くなる。
従って 60.5 〜62％の範囲がよい。In the component system of the present invention, SiO 2 is the main component of glass, and if it is less than 60.5% by weight, the acid resistance and hydrofluoric acid resistance of the glass decrease. If it exceeds 62%, the high temperature viscosity of the glass melt becomes high, the meltability deteriorates, the devitrification tendency of the glass increases, and particularly SiO 2 -based crystals tend to precipitate.
Therefore, the range of 60.5 to 62% is preferable.
【００１１】Al2O3 はSiO2に対し適宜範囲で導入するこ
とによりガラス融液の高温下の粘度の上昇を抑え、歪点
を上昇させる効果を奏する。またSiO2系とB2O3−RO系の
分相の起生を抑制して均質化し、さらにSiO2−CaO(−Mg
O)系の失透を抑制する作用を有するが、13.5％未満では
それら作用効果が不充分であり、16.5％を越えると溶融
性を悪化し、かつガラスの耐酸性が低下する。従って1
3.5〜16.5％の範囲がよい。By introducing Al 2 O 3 with respect to SiO 2 in an appropriate range, it is possible to suppress the increase in viscosity of the glass melt at high temperature and to increase the strain point. In addition, the phase separation of the SiO 2 and B 2 O 3 -RO systems is suppressed and homogenized, and the SiO 2 -CaO (-Mg
Although it has an effect of suppressing devitrification of the O) type, if it is less than 13.5%, these effects are insufficient, and if it exceeds 16.5%, the meltability is deteriorated and the acid resistance of the glass is lowered. Therefore 1
The range of 3.5 to 16.5% is good.
【００１２】B2O3はガラス融液の高温粘度を下げ、溶融
性を向上させる。またこれを含むガラスはフッ酸に対し
て耐久性を示す。 6.5％未満ではそれらの効果が小さ
く、 8.5％を越えるとガラスの耐熱性が低下し、また耐
酸性も低下する。従って 6.5〜8.5％の範囲がよい。B 2 O 3 lowers the high temperature viscosity of the glass melt and improves the meltability. Further, the glass containing this exhibits durability against hydrofluoric acid. If it is less than 6.5%, these effects are small, and if it exceeds 8.5%, the heat resistance of the glass is lowered and the acid resistance is also lowered. Therefore, the range of 6.5 to 8.5% is preferable.
【００１３】ZrO2はそれ自体SiO2より高融点であるが、
CaO 、MgO 、BaO 、SrO 等の共存により低い温度で共融
する。また、ガラスの歪点を上昇させ、耐酸. 耐アルカ
リ性を向上するのでガラス中に含有せしめることが望ま
しい。ただし0.3 ％未満ではそれらの効果が充分得られ
ず、 2％を越えると脈理が発生し易く、またZrO2に起因
する失透を生じ易く溶融性を悪化する。従って0.3 〜 2
％の範囲とするのが好ましい。ZrO 2 itself has a higher melting point than SiO 2 ,
Eutectic at a low temperature due to the coexistence of CaO, MgO, BaO, SrO, etc. In addition, since it increases the strain point of the glass and improves acid resistance and alkali resistance, it is desirable to include it in the glass. However, if it is less than 0.3%, these effects cannot be sufficiently obtained, and if it exceeds 2%, striae are likely to occur, and devitrification due to ZrO 2 is likely to occur and the meltability is deteriorated. Therefore 0.3 to 2
It is preferably in the range of%.
【００１４】上記SiO2、B2O3、Al2O3 およびZrO2等の酸
性ないし中性酸化物、特にSiO2、Al 2O3 、ZrO2に対し、
以下に述べる塩基性酸化物であるCaO 、MgO 、BaO 、Sr
O 等を共存させガラス溶融時の媒溶剤として作用させる
ことにより、溶融を容易とする。すなわち、CaO はガラ
ス融液の高温粘性を下げ、溶融性を向上させ、かつ失透
傾向を抑制する。 5％未満ではそれらの効果が不充分で
あり、 7％を越えるとガラスの歪点を低下させ、また前
記分相が発生し易い。従って 5〜 7％の範囲とするもの
である。The above SiOTwo, BTwoOThree, AlTwoOThree And ZrOTwoAcid such as
Or neutral oxides, especially SiOTwo, Al TwoOThree , ZrOTwoAgainst
The following basic oxides CaO, MgO, BaO, Sr
Coexist with O, etc. to act as a solvent when melting glass
This facilitates melting. That is, CaO is
Reduces the high temperature viscosity of the melt, improves the meltability, and devitrifies
Suppress the tendency. If it is less than 5%, those effects are insufficient.
Yes, exceeding 7% lowers the strain point of the glass,
The phase separation is likely to occur. Therefore, the range of 5 to 7%
It is.
【００１５】SrO はCaO 同様にガラス融液の高温粘性を
下げ、溶融性を向上させ、かつ失透傾向を抑制する。ま
た、CaO に比べガラスの歪点、耐薬品性を向上する。 5
％未満ではそれらの効果が不充分であり、 7％を越える
とガラスの歪点を低下させ、また熱膨張率を増大させ
る。従って 5〜 7％の範囲とするものである。Like CaO, SrO lowers the high temperature viscosity of the glass melt, improves the meltability, and suppresses the tendency of devitrification. It also improves the strain point and chemical resistance of glass compared to CaO. Five
If it is less than%, the effects are insufficient, and if it exceeds 7%, the strain point of the glass is lowered and the coefficient of thermal expansion is increased. Therefore, the range is 5 to 7%.
【００１６】MgO はガラスの熱膨張係数を増大させずに
溶融性を向上させ、失透の抑制に効果があるが、0.5 ％
未満ではその効果が小さく 2％を越えると特にフッ酸系
液により点食を受け白濁を生じ易く、またSiO2−Al2O3
−MgO 系結晶が析出し易くなりガラスの失透傾向が大き
くなる。従って0.5 〜2 ％の範囲とする。MgO improves the meltability without increasing the coefficient of thermal expansion of glass and is effective in suppressing devitrification, but 0.5%
Tend to cause white turbidity subjected to pitting in particular hydrofluoric acid solution exceeds 2% smaller, the effect is less than, also SiO 2 -Al 2 O 3
-MgO-based crystals tend to precipitate and the glass tends to devitrify. Therefore, the range is 0.5 to 2%.
【００１７】BaO はCaO およびMgO との共存下で溶融性
を向上させ、ガラスの失透傾向を抑制するが、1 ％未満
ではその効果が不充分である。 4％を越えるとガラスの
耐酸性が低下し、またガラスの熱膨張率が増大する。従
って 1〜 4％の範囲とするのがよい。BaO improves the meltability in the presence of CaO and MgO and suppresses the devitrification tendency of the glass, but if it is less than 1%, its effect is insufficient. If it exceeds 4%, the acid resistance of the glass decreases and the coefficient of thermal expansion of the glass increases. Therefore, it is better to set it in the range of 1 to 4%.
【００１８】さらに、上記組成範囲内において、CaO ＋
MgO ＋BaO ＋SrO を14.5〜17.5％の範囲にすることによ
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、耐
酸性等に優れ、失透傾向の小さい無アルカリガラスを得
ることができる。CaO ＋MgO ＋BaO ＋SrO が17.5％を越
えると、溶融性は向上するが、特に熱膨張率が増大し、
耐薬品性が低下する。14.5％未満では、熱膨張率は低下
するが高温粘度が上昇して溶融および成形を困難とし、
失透傾向も増大し、さらに溶融時の電気抵抗が高くなり
直接通電による電気溶融に適さない。従って14.5〜17.5
％の範囲とするのが望ましい。Further, within the above composition range, CaO +
By keeping MgO + BaO + SrO in the range of 14.5 to 17.5%, while maintaining the meltability of the glass in a good range, the viscosity-temperature gradient is moderate and the formability is good, and the heat resistance and acid resistance are excellent. It is possible to obtain an alkali-free glass having a low devitrification tendency. When CaO + MgO + BaO + SrO exceeds 17.5%, the meltability improves, but the thermal expansion coefficient increases in particular,
Chemical resistance decreases. If it is less than 14.5%, the coefficient of thermal expansion decreases, but the high temperature viscosity increases, making melting and molding difficult,
The devitrification tendency also increases, and the electric resistance during melting increases, which is not suitable for electric melting by direct current application. Therefore, 14.5 to 17.5
It is desirable to set it in the range of%.
【００１９】F分はCaF2、MgF2等の金属フッ化物として
導入するもので F分の過半は溶融段階で蒸発するが、本
成分系においては F分がガラス融液の粘性、表面張力を
降下させ溶融、清澄性に顕著な作用を呈し、ひいては欠
陥のきわめて少ないガラス成形品を得ることができると
いう点において含有せしめることが望ましい。具体的に
は上記した酸化物ガラス 100重量％に対して、調製時の
Fの導入量が0.5 重量％を越える場合はガラスの分相傾
向が増大しまた炉材の浸食等に問題を有するので、0.5
重量％以下の範囲で導入するのが好ましい。更に好まし
くは0.1 〜0.5％の範囲とすることにより前記作用効果
を充分に発揮せしめる。The F content is the majority of the F content in those introduced as metal fluoride CaF 2, MgF 2 or the like evaporates melt stage, F content in this component is a glass melt viscosity, surface tension It is desirable to contain it in the point that it can be lowered to have a remarkable effect on melting and clarifying properties, and that a glass molded product having extremely few defects can be obtained. Specifically, for 100% by weight of the above oxide glass,
If the amount of F introduced exceeds 0.5% by weight, the phase separation tendency of the glass increases and there is a problem with erosion of the furnace material.
It is preferably introduced in the range of not more than wt%. More preferably, by setting it in the range of 0.1 to 0.5%, the above-mentioned effects can be sufficiently exhibited.
【００２０】本発明においてはアルカリ金属酸化物はガ
ラスの耐熱性を低下させ、特に電子部品素材としてガラ
スに金属薄膜等を形成させる場合にアルカリ金属イオン
が表面湧出し膜特性が劣化するので、実質的に存在して
はならない。In the present invention, the alkali metal oxide lowers the heat resistance of the glass, and particularly when forming a metal thin film or the like on the glass as an electronic component material, the alkali metal ion deteriorates the surface seepage film property, so that it is substantially Must not exist.
【００２１】また直接通電による電気溶融を可能とする
ために、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
反応性を有するZnO や清澄剤としてのAs2O3 、Sb2O3 を
含有してはならない。Further, in order to enable electric fusion by direct energization, it is necessary to avoid reacting with a commonly used electrode such as molybdenum to form an alloy, and therefore reactive ZnO or fining is used. It should not contain As 2 O 3 and Sb 2 O 3 as agents.
【００２２】さらにフロート法成形による量産を容易と
し、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
の揮発成分やAs2O3 、Sb2O3 等の反応着色成分も実質的
に含有してはならない。Further, in order to facilitate mass production by the float molding and to prevent volatilization in a reducing atmosphere such as nitrogen and hydrogen and not coloring the glass, volatile components such as PbO and ZnO and As 2 O 3 , Sb 2 O 3 etc. should not be contained substantially.
【００２３】なお、前記アルカリ金属酸化物や通電溶融
用電極との反応性成分、還元雰囲気との反応、揮発性成
分およびFe2O3 、MnO2、SO3 その他不純物としての極微
量の混入は本発明を妨げるものではない。It should be noted that the reactive component with the alkali metal oxide or the electrode for electric current melting, the reaction with the reducing atmosphere, the volatile component and the trace amount of Fe 2 O 3 , MnO 2 , SO 3 and other impurities are not mixed. It does not hinder the present invention.
【００２４】[0024]
【実施例】珪砂、水酸化アルミニウム、ホウ酸、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、亜砒酸およびフッ化カルシウ
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1630℃、約６時間加熱溶融した。次に溶融ガラスを鋳
型に流込み、約 200mm□×35mm厚の大きさのガラスブロ
ックとし、 700℃に保持した電気炉に移入して炉内で徐
冷した。[Examples] Platinum refractory crucible was filled with a compounding material consisting of silica sand, aluminum hydroxide, boric acid, magnesium carbonate, calcium carbonate, barium carbonate, strontium carbonate, zircon sand, arsenous acid and calcium fluoride, and the mixture was filled in an electric furnace at 1630. It was melted by heating at ℃ for about 6 hours. Next, the molten glass was poured into a mold to form a glass block having a size of about 200 mm □ × 35 mm, and the glass block was transferred to an electric furnace maintained at 700 ° C. and gradually cooled in the furnace.
【００２５】原料調合に基づくガラス (酸化物) 組成を
表１に示す。なおCaF2のかたちで導入されるF 分につい
ては酸化物組成計100 重量％に対する外挿添加量 (重量
％)で示した。The glass (oxide) composition based on the raw material formulation is shown in Table 1. The F content introduced in the form of CaF 2 is shown as the extrapolated amount (wt%) with respect to 100 wt% of the total oxide composition.
【００２６】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) 、溶融温度 (102 ポイズ
の温度) 、および作業温度(104ポイズの温度) 、失透温
度を測定した。また耐酸性 (1/100N HNO3 水溶液に95
℃、20時間浸漬し減量mg/cm2を測定) について調査し
た。それらの結果を表１に示す。For these glass samples, room temperature to 300
Average coefficient of thermal expansion at 10 ° C X 10 -7 / ° C), strain point (temperature at which glass exhibits a viscosity of 10 14.5 poise), melting temperature (temperature of 10 2 poise), and working temperature (temperature of 10 4 poise), devitrification The temperature was measured. Acid resistance (95% in 1 / 100N HNO 3 aqueous solution)
It was soaked at 20 ° C. for 20 hours, and the weight loss mg / cm 2 was measured). Table 1 shows the results.
【００２７】[0027]
【表１】 [Table 1]
【００２８】表1 中実施例NO.1〜NO.8は本発明によるガ
ラスであり、歪点は660 ℃以上で耐熱性に優れる。熱膨
張率もSi薄膜の熱膨張率36×10-7／℃に近似しており、
作業温度は1290℃以下で失透温度は作業温度を下回って
おり、フロート成形が可能である。耐酸減量も0.14mg/c
m2以下であり液晶ディスプレイ用等の基板として充分な
耐酸性を有する。In Table 1, Examples No. 1 to No. 8 are the glasses according to the present invention and have a strain point of 660 ° C. or higher and excellent heat resistance. The coefficient of thermal expansion is also close to the coefficient of thermal expansion of the Si thin film, 36 × 10 -7 / ° C,
The working temperature is 1290 ° C or less, and the devitrification temperature is lower than the working temperature, so float molding is possible. Acid loss resistance is also 0.14mg / c
It has m 2 or less and has sufficient acid resistance as a substrate for liquid crystal displays and the like.
【００２９】他方、比較例NO.1においては歪点が低く、
熱膨張率が高すぎ、またNO.2においては作業温度が高
く、フロート法成形には適さない。On the other hand, in Comparative Example No. 1, the strain point is low,
The coefficient of thermal expansion is too high, and the working temperature is high for NO.2, which is not suitable for float molding.
【００３０】[0030]
【発明の効果】本発明の無アルカリガラスは、耐熱性、
耐薬品性等に優れ、熱膨張率も適度であるため、ガラス
表面に金属や金属酸化物の薄膜を形成し、該薄膜をエッ
チングしてパターンを形成させるためのガラス基板、特
にTFT 用基板として好適であり、またガラスの直接通電
法による溶融性およびフロート法による成形性に適し、
均質なガラスを連続的に低いコストで製造することが可
能であり、量産に適するという効果を奏する。The alkali-free glass of the present invention has heat resistance,
Since it has excellent chemical resistance and an appropriate coefficient of thermal expansion, it is used as a glass substrate for forming a thin film of metal or metal oxide on the glass surface and etching the thin film to form a pattern, especially as a TFT substrate. It is suitable, and also suitable for the meltability of glass by the direct current method and the moldability of the float method,
Homogeneous glass can be continuously produced at low cost, which is suitable for mass production.
Claims (4)
3.5〜16.5、B2O3 6.5〜8.5 、ZrO2 0.3〜2 、MgO 0.5
〜2 、CaO 5 〜7 、SrO 5 〜7 、およびBaO 1 〜4 の範
囲で含有し、かつ実質的にアルカリ金属酸化物並びにPb
O 、ZnO 、As2O3 、およびSb2O 3 を含有しない無アルカ
リガラスであって、該無アルカリガラス 100重量％に対
し、調製時にフッ化物を F換算で 0.5重量％以下の範囲
で外挿添加したことを特徴とする無アルカリガラス。1. SiO in weight%Two 60.5 ~ 62, AlTwoOThree 1
3.5 ~ 16.5, BTwoOThree 6.5 to 8.5, ZrOTwo 0.3-2, MgO 0.5
~ 2, CaO 5-7, SrO 5-7, and BaO 1-4.
And Pb contained in
O, ZnO, AsTwoOThree , And SbTwoO Three Alkaline free of
Reglass, which is 100% by weight of the alkali-free glass
When prepared, the fluoride content in the range of 0.5% by weight or less in terms of F
Alkali-free glass characterized by being extrapolated in.
〜17.5重量％の範囲としたことを特徴とする請求項１記
載の無アルカリガラス。2. The sum of CaO, MgO, BaO, and SrO is 14.5.
The alkali-free glass according to claim 1, wherein the content is in the range of -17.5% by weight.
量％の範囲で外挿添加したことを特徴とする請求項１ま
たは２記載の無アルカリガラス。3. The alkali-free glass according to claim 1, wherein a fluoride is extrapolated in the range of 0.1 to 0.5% by weight in terms of F at the time of preparation.
10-7／℃) であることを特徴とする請求項１ないし３記
載の無アルカリガラス。4. A strain point of 660 ° C. or higher and a coefficient of thermal expansion of 36 to 39 (×
10. The alkali-free glass according to claim 1, wherein the alkali-free glass is 10 −7 / ° C.).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26960295A JPH09110460A (en) | 1995-10-18 | 1995-10-18 | Alkali-free glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26960295A JPH09110460A (en) | 1995-10-18 | 1995-10-18 | Alkali-free glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09110460A true JPH09110460A (en) | 1997-04-28 |
Family
ID=17474656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26960295A Pending JPH09110460A (en) | 1995-10-18 | 1995-10-18 | Alkali-free glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09110460A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11292563A (en) * | 1998-04-03 | 1999-10-26 | Nippon Electric Glass Co Ltd | Alkali-free glass substrate |
| EP1152990A1 (en) * | 1998-11-30 | 2001-11-14 | Corning Incorporated | Glasses for flat panel displays |
| DE10064804A1 (en) * | 2000-12-22 | 2002-07-11 | Schott Glas | Alkali-free aluminoborosilicate glasses and their use |
| JP2008069021A (en) * | 2006-09-12 | 2008-03-27 | Nippon Electric Glass Co Ltd | Alkali-free glass and alkali-free glass substrate using the same |
| US7833919B2 (en) | 2006-02-10 | 2010-11-16 | Corning Incorporated | Glass compositions having high thermal and chemical stability and methods of making thereof |
| US8007913B2 (en) | 2006-02-10 | 2011-08-30 | Corning Incorporated | Laminated glass articles and methods of making thereof |
| WO2013047586A1 (en) * | 2011-09-30 | 2013-04-04 | ＡｖａｎＳｔｒａｔｅ株式会社 | Glass substrate for flat panel display |
| US8713967B2 (en) | 2008-11-21 | 2014-05-06 | Corning Incorporated | Stable glass sheet and method for making same |
| DE19840113B4 (en) * | 1998-09-03 | 2016-07-07 | Eglass Asia Ltd. | Alkali-free glass composition for the production of flat glass |
| JP2020503239A (en) * | 2016-12-30 | 2020-01-30 | ドンシュー グループ カンパニー，リミテッド | Composition, glassware and use thereof for preparing glass |
-
1995
- 1995-10-18 JP JP26960295A patent/JPH09110460A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11292563A (en) * | 1998-04-03 | 1999-10-26 | Nippon Electric Glass Co Ltd | Alkali-free glass substrate |
| DE19840113B4 (en) * | 1998-09-03 | 2016-07-07 | Eglass Asia Ltd. | Alkali-free glass composition for the production of flat glass |
| DE19840113B9 (en) * | 1998-09-03 | 2016-10-13 | Eglass Asia Ltd. | Alkali-free glass composition for the production of flat glass |
| EP1152990A1 (en) * | 1998-11-30 | 2001-11-14 | Corning Incorporated | Glasses for flat panel displays |
| US6319867B1 (en) | 1998-11-30 | 2001-11-20 | Corning Incorporated | Glasses for flat panel displays |
| EP1152990A4 (en) * | 1998-11-30 | 2004-11-10 | Corning Inc | Glasses for flat panel displays |
| US6831029B2 (en) | 1998-11-30 | 2004-12-14 | Corning Incorporated | Glasses for flat panel displays |
| US7365038B2 (en) | 1998-11-30 | 2008-04-29 | Corning Incorporated | Glasses for flat panel displays |
| US7524784B2 (en) | 1998-11-30 | 2009-04-28 | Corning Incorporated | Glasses for flat panel displays |
| DE10064804A1 (en) * | 2000-12-22 | 2002-07-11 | Schott Glas | Alkali-free aluminoborosilicate glasses and their use |
| DE10064804C2 (en) * | 2000-12-22 | 2003-03-20 | Schott Glas | Alkali-free aluminoborosilicate glasses and their use |
| US7833919B2 (en) | 2006-02-10 | 2010-11-16 | Corning Incorporated | Glass compositions having high thermal and chemical stability and methods of making thereof |
| US8753993B2 (en) | 2006-02-10 | 2014-06-17 | Corning Incorporated | Glass compositions having high thermal and chemical stability and methods of making thereof |
| US8763429B2 (en) | 2006-02-10 | 2014-07-01 | Corning Incorporated | Glass compositions having high thermal and chemical stability and methods of making thereof |
| US8007913B2 (en) | 2006-02-10 | 2011-08-30 | Corning Incorporated | Laminated glass articles and methods of making thereof |
| US10364177B2 (en) | 2006-02-10 | 2019-07-30 | Corning Incorporated | Glass compositions having high thermal and chemical stability and methods of making thereof |
| JP2008069021A (en) * | 2006-09-12 | 2008-03-27 | Nippon Electric Glass Co Ltd | Alkali-free glass and alkali-free glass substrate using the same |
| US8713967B2 (en) | 2008-11-21 | 2014-05-06 | Corning Incorporated | Stable glass sheet and method for making same |
| WO2013047586A1 (en) * | 2011-09-30 | 2013-04-04 | ＡｖａｎＳｔｒａｔｅ株式会社 | Glass substrate for flat panel display |
| JPWO2013047586A1 (en) * | 2011-09-30 | 2015-03-26 | ＡｖａｎＳｔｒａｔｅ株式会社 | Glass substrate for flat panel display |
| JP2020503239A (en) * | 2016-12-30 | 2020-01-30 | ドンシュー グループ カンパニー，リミテッド | Composition, glassware and use thereof for preparing glass |
| US11319241B2 (en) | 2016-12-30 | 2022-05-03 | Tunghsu Group Co., Ltd. | Composition for preparing glass, glass article and use thereof |
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