JP2004075494A - Glass substrate and its manufacturing method - Google Patents
Glass substrate and its manufacturing method Download PDFInfo
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- JP2004075494A JP2004075494A JP2002241449A JP2002241449A JP2004075494A JP 2004075494 A JP2004075494 A JP 2004075494A JP 2002241449 A JP2002241449 A JP 2002241449A JP 2002241449 A JP2002241449 A JP 2002241449A JP 2004075494 A JP2004075494 A JP 2004075494A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—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
- C03C3/089—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
-
- 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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- 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
Description
【０００１】
【産業上の利用分野】
本発明は、液晶ディスプレイ、エレクトロルミネッセンスディスプレイ、フィールドエミッションディスプレイ等のフラットパネルディスプレイ基板及びハードディスク基板等に用いられるガラス基板に関するものである。
【０００２】
【従来の技術】
従来より、フラットパネルディスプレイ基板やハードディスク基板としては、ガラス基板が広く使用されている。
【０００３】
特に、フラットパネルディスプレイに用いられるガラス基板の表面には、透明導電膜、絶縁膜、半導体膜、金属膜等が成膜され、しかもフォトリソグラフィーエッチング（フォトエッチング）によって種々の回路やパターンが形成される。これらの成膜、フォトエッチング工程において、ガラス基板には、種々の熱処理や薬品処理が施される。
【０００４】
従って、フラットパネルディスプレイに使用されるガラス基板には、以下のような特性が要求される。
（１）ガラス中にアルカリ金属酸化物が含有されていると、熱処理中にアルカリイオンが成膜された半導体物質中に拡散し、膜特性の劣化を招くため、実質的にアルカリ金属酸化物を含有しないこと。
（２）フォトエッチング工程において使用される種々の酸、アルカリ等の薬品によって劣化しないような耐薬品性を有すること。
（３）ガラスの歪点が低いと、成膜等の熱処理工程でガラス基板が熱収縮してパターンずれを起こすため、高い歪点を有すること。
（４）製造工程において、自重によってガラス基板がたわみ、装置と接触してガラス基板が破損するのを防止するために、高い比ヤング率（ヤング率／密度）を有すること。
【０００５】
また、フラットパネルディスプレイは、モバイル分野への応用が進められており、機器の軽量化が要求されている。これに伴ってガラス基板にも軽量化が要求されている。
【０００６】
【発明が解決しようとする課題】
ガラス基板の軽量化のために、ガラス基板の薄肉化が検討されている。
【０００７】
しかしながら、ガラス基板の肉厚が薄くなる程、ガラス基板の強度が低下するため割れやすくなるといった問題が生じる。
【０００８】
本発明の目的は、ガラス基板を薄肉化しても、割れ難いガラス基板及びその製造方法を提供することである。
【０００９】
【課題を解決するための手段】
本発明者は、種々の実験を繰り返した結果、ガラス基板に微小な分相構造を意図的に導入することで、ガラス基板の強度が向上することを見いだし、本発明として提案するものである。
【００１０】
すなわち、本発明のガラス基板は、質量百分率で、ＳｒＯ＋ＢａＯ ０〜６．５％の組成を有するアルミノシリケートガラスであって、且つ、２〜１００ｎｍの粒子サイズの分相構造を有することを特徴とする。
【００１１】
また、本発明のガラス基板の製造方法は、質量百分率で、ＳｉＯ２ ５０〜７０％、Ａｌ２Ｏ３ １０〜２０％、Ｂ２Ｏ３ ７〜１５％、ＭｇＯ＋ＣａＯ ０〜２０％、ＳｒＯ＋ＢａＯ ０〜６．５％の組成を有するアルミノシリケートガラスを、２〜５０ｎｍの粒子サイズの分相構造が得られるように、熱処理を行うことを特徴とする。
【００１２】
【作用】
ガラス基板の割れは、ガラス基板の表面に傷が付き、それが伸展することにより発生する。従って、ガラス基板の耐クラック性を向上させてクラックの発生を抑制すればガラス基板の強度は飛躍的に向上することになる。
【００１３】
そこで、本発明のガラス基板では、粒子サイズが２〜１００ｎｍである分相構造をガラス基板に意図的に導入して、クラックの発生を抑制してガラス基板の強度を飛躍的に向上させている。
【００１４】
ガラス基板中に２〜１００ｎｍの微小な分相構造を導入することで、クラックが分相粒子の界面で停止する、または、クラックが界面で停止しない場合でも、粒子を迂回するのに余分なエネルギーが必要となるため、クラックが伸展しにくくなり割れを抑えることができると考えられる。
【００１５】
尚、分相の粒子サイズが２ｎｍより小さいと、クラックの発生を抑制する効果が得られないため好ましくない。一方、分相の粒子サイズが１００ｎｍより大きくなると、熱処理に時間が掛かり生産性が悪化するため好ましくない。好ましくは２〜９０ｎｍであり、更に好ましくは、５〜８０ｎｍである。
【００１６】
また、分相の粒子サイズが５０ｎｍより大きくなると、光の散乱により、ガラス基板が白濁する傾向にあり、ガラス基板の透過率が低下する可能性がある。このため、ガラス基板をフラットパネルディスプレイ基板に用いる場合、分相の粒子サイズは５０ｎｍ以下であることが望ましい。
【００１７】
また、ガラス基板に粒子サイズが２〜１００ｎｍのサイズの分相構造を導入するには、ガラス基板を５００℃〜ガラスの徐冷点＋６０℃の温度で０．５〜３００時間保持するような熱処理を行えばよい。尚、熱処理は、溶融ガラスの冷却工程で行ってもよいし、溶融ガラスを一旦冷却し、ガラス基板に加工成形した後に行っても良い。また、熱処理温度を高くすれば、熱処理時間を短縮することもできる。
【００１８】
更に、本発明のガラス基板の好適な組成範囲は、質量百分率で、ＳｉＯ２ ５０〜７０％、Ａｌ２Ｏ３ １０〜２０％、Ｂ２Ｏ３ ７〜１５％、ＭｇＯ＋ＣａＯ ０〜２０％、ＳｒＯ＋ＢａＯ ０〜６．５％である。
【００１９】
尚、本発明においてガラスの組成を上記のように限定した理由は、ガラスの分相傾向、密度、耐薬品性、熱収縮性、ヤング率等を考慮したものであり、各成分の限定理由は、次のとおりである。
【００２０】
ＳｉＯ２は、ガラスのネットワークフォーマーとなる成分であり、ガラスの耐酸性を向上させたり、ガラスの歪点を上昇させてガラス基板の熱収縮を小さくする効果がある。含有量が多くなると、ガラスの高温粘度が高くなり、溶融性が悪化する傾向にあるが、含有量が５０〜７０％であれば、ガラスの溶融性を悪化させることなく、耐酸性が高く、熱収縮の小さいガラス基板を得ることができる。好ましい範囲は、５８〜６７％である。
【００２１】
Ａｌ２Ｏ３は、ガラスのネットワークフォーマーとなる成分であると共に、ガラスのヤング率を高める成分であり、ガラス基板がたわむのを抑制する効果がある。含有量が多くなると、液相温度が上昇して成形しにくくなる傾向にあるが、含有量が１０〜２０％であれば、液相温度が低く、たわみの小さいガラス基板を得ることができる。好ましい範囲は、１２〜１８％である。
【００２２】
Ｂ２Ｏ３は、融剤として作用し、ガラスの粘性を下げ、溶融性を改善する成分であり、且つガラスの密度を下げる成分である。含有量が多くなると、ガラスの歪点が低下する傾向にあるが、含有量が７〜１５％であれば、ガラスの歪点を低下させることなく、上記効果を得ることができる。好ましい範囲は、７〜１３％である。
【００２３】
ＭｇＯとＣａＯは、高温粘度を下げる成分であり、ガラスの溶融性を改善する効果がある。含有量が多くなると、ガラスの耐薬品性、特に耐バッファードフッ酸性が悪化する傾向にあるが、ＭｇＯとＣａＯが合量で１５％以下であれば、耐バッファードフッ酸性を特に悪化させることはない。好ましい範囲は、合量で０〜１０％である。
【００２４】
ＳｒＯとＢａＯは、ガラスの耐薬品性を向上させる成分であるが、これら成分が多くなると、ガラスの分相傾向が小さくなり、短時間の熱処理で分相を形成することができなくなる。このため、合量で６．５％より多く含有させるべきではない。好ましい範囲は、合量で０〜５％である。
【００２５】
尚、本発明においては、上記の成分以外にも、特性を損なわない範囲で他の成分、例えば、清澄剤としてＡｓ２Ｏ３、Ｓｂ２Ｏ３、ＳｎＯ２、Ｃｌ２、ＳＯ３等をそれぞれ３％まで、ガラスの耐薬品性、耐失透性を向上させるために、ＺｒＯ２、ＴｉＯ２、Ｙ２Ｏ３、Ｌａ２Ｏ３、Ｐ２Ｏ５をそれぞれ５％まで添加しても良い。
【００２６】
更に、前記した理由から、アルカリ金属酸化物（Ｎａ２Ｏ、Ｋ２Ｏ、Ｌｉ２Ｏ）の添加も避けるべきである。また、一般に融剤として使用されるＰｂＯもガラスの耐薬品性を著しく低下させたり、ガラス溶融時に融液の表面から揮発し、環境を汚染する虞れもあるため好ましくない。
【００２７】
また、本発明のガラス基板は、板ガラスの成形方法として知られているスロットダウンドロー法、オーバーフローダウンドロー法、フロート法、ロールアウト法等の方法によって製造できる。
【００２８】
【実施例】
以下、本発明を実施例に基づいて詳細に説明する。
【００２９】
表１〜６は本発明の実施例（試料Ｎｏ．１〜２７）を、表７は比較例（試料Ｎｏ．２８及び２９）をそれぞれ示している。
【００３０】
【表１】
【表２】
【表３】
【表４】
【表５】
【表６】
【表７】
表中の各試料は、次のようにして作製した。
【００３８】
まず、表の組成となるようにガラス原料を調合し、白金ポットで１６００℃で２４時間溶融した。続いて、溶融ガラスをカーボン板上に流し出して板状に成形し、徐冷後、板厚が０．７ｍｍになるように両面研磨して、得られた板ガラスを２００ｍｍ角の大きさに切断加工した。その後、表中の条件で熱処理を施し分相させることで試料を作製した。
【００３９】
このようにして作製した各試料について、各種の特性を評価した。結果を表に示す。
【００４０】
表１〜表７から明らかなように、試料Ｎｏ．１〜２７は、粒子サイズが２ｎｍ以上の分相構造を有しているため、クラック抵抗が８．８Ｎ以上と高かった。また、密度は２．４６６ｇ／ｃｍ３以下であり、熱膨張係数は３０．０〜３６．５×１０−７／℃で耐熱衝撃性に優れ、歪点は６５６℃以上で熱収縮は小さく、比ヤング率は２７．５ＧＰａ／ｇ・ｃｍ−３以上でたわみ量は小さくなることが予想される。更に耐酸性、耐ＢＨＦ性にも優れていた。
【００４１】
これに対し、比較例である試料Ｎｏ．２８、２９は、熱処理を行ったものの、分相しなかったため、クラック抵抗が７．４Ｎと低かった。
【００４２】
次に、Ｎｏ．１のガラス組成を用い、熱処理条件を変えて、様々な大きさの粒子を有するガラス基板を作製し、分相の粒子サイズと耐クラック性の関係について調査した。結果を表８及び図１に示す。尚、図１において、縦軸はガラス基板の耐クラック性を表すクラックの発生率、横軸はダイヤモンド圧子に加える荷重を示している。図中、Ａは分相構造を有していないガラス基板、Ｂは粒子サイズが２ｎｍの分相構造を有するガラス基板（試料Ｎｏ．１）、Ｃは粒子サイズが１０ｎｍの分相構造を有するガラス基板、Ｄは粒子サイズが２０ｎｍの分相構造を有するガラス基板、Ｅは粒子サイズが５０ｎｍの分相構造を有するガラス基板、Ｆは粒子サイズが１００ｎｍの分相構造を有するガラス基板、Ｇは粒子サイズが１１０ｎｍの分相構造を有するガラス基板を表している。
【００４３】
【表８】
表８及び図１から明らかなように、分相構造を有していないガラス基板（試料Ａ）と、分相構造を有するガラス基板（試料Ｂ〜Ｇ）のクラック発生率を比較すると、分相構造を有するガラス基板の方が、クラックは発生しにくくなり耐クラック性が向上することが判る。また、粒子サイズが１００ｎｍまでは、粒子サイズが大きくなる程、クラックは発生しにくくなり耐クラック性は向上するが、１００ｎｍより大きくなると、徐々に耐クラック性は低下する傾向にあることが判る。
【００４５】
尚、分相の粒子サイズはＴＥＭ（透過型電子顕微鏡）で観察することによって測定した。
【００４６】
また、ガラスの耐クラック性の評価は、和田らが提案した方法（Ｍ．Ｗａｄａｅｔ ａｌ． Ｐｒｏｃ．， ｔｈｅ Ｘｔｈ ＩＣＧ， ｖｏｌ．１１， Ｃｅｒａｍ． Ｓｏｃ．， Ｊａｐａｎ， Ｋｙｏｔｏ， １９７４， ｐ３９）を用いた。この方法は、ビッカース硬度計のステージに試料ガラスを置き、試料ガラスの表面に菱形状のダイヤモンド圧子を種々の荷重で１５秒間押し付ける。そして、除荷後１５秒までに圧痕の四隅から発生するクラック数をカウントし、最大発生しうるクラック数（４ヶ）に対する割合を求め、クラック発生率とした。また、クラック発生率が５０％になるときの荷重を「クラック抵抗」とした。クラック抵抗が大きいということは、高い荷重でもクラックが発生しにくい、つまり、耐クラック性に優れているということである。尚、クラック発生率の測定は、同一荷重で２０回測定し、その平均値を求めた。また、測定条件は、気温２５℃、湿度３０％の条件で行った。
【００４７】
密度は、周知のアルキメデス法によって測定し、熱膨張係数は、ディラトメーターを用いて、３０〜３８０℃における平均熱膨張係数を測定したものである。
【００４８】
歪点及び徐冷点は、ＡＳＴＭ Ｃ３３６−７１の方法に基づいて、軟化点は、ＡＳＴＭ Ｃ３３８−７３の方法に基づいて測定した。１０４．０〜１０２．５ｄＰａ・ｓの粘度は、白金球引き上げ法により測定した。
【００４９】
ヤング率は、曲げ共振法により測定し、比ヤング率は、ヤング率と密度の測定値から算出した。
【００５０】
耐塩酸性は、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、それらの表面状態を目視で観察することによって評価した。耐ＢＨＦ性は、各試料を２０℃に保持された３０質量％弗化アンモニウム、６質量％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、それらの表面状態を目視で観察することによって評価した。ガラス基板の表面が白濁したものは×、全く変化のないものは○で示した。
【００５１】
液相温度の測定は、ガラスを粉砕し、標準篩３０メッシュ（５００ｎｍ）を通過し、５０メッシュ（３００ｎｍ）に残るガラス粉末を白金ボートに入れ、温度勾配炉中に２４時間保持して、結晶の析出する温度を測定したものである。
【００５２】
【発明の効果】
以上のように本発明のガラス基板は、優れた耐クラック性を有するため、薄型、軽量化が要求されているフラットパネルディスプレイ基板及びハードディスク基板等に用いられるガラス基板として好適である。
【図面の簡単な説明】
【図１】分相の粒子サイズとクラック発生率の関係を示すグラフである。[0001]
[Industrial applications]
The present invention relates to a glass substrate used for a flat panel display substrate such as a liquid crystal display, an electroluminescence display, and a field emission display, and a hard disk substrate.
[0002]
[Prior art]
Conventionally, glass substrates have been widely used as flat panel display substrates and hard disk substrates.
[0003]
In particular, a transparent conductive film, an insulating film, a semiconductor film, a metal film, and the like are formed on the surface of a glass substrate used for a flat panel display, and various circuits and patterns are formed by photolithography etching (photo etching). You. In these film forming and photo-etching steps, the glass substrate is subjected to various heat treatments and chemical treatments.
[0004]
Therefore, the glass substrate used for the flat panel display is required to have the following characteristics.
(1) When an alkali metal oxide is contained in glass, alkali ions diffuse into a formed semiconductor material during heat treatment, causing deterioration of film characteristics. Do not contain.
(2) It has chemical resistance such that it is not deteriorated by various acids, alkalis, and other chemicals used in the photoetching step.
(3) If the strain point of the glass is low, the glass substrate is thermally contracted in a heat treatment step such as film formation to cause a pattern shift, so that the glass substrate has a high strain point.
(4) In the manufacturing process, the glass substrate has a high specific Young's modulus (Young's modulus / density) in order to prevent the glass substrate from bending due to its own weight and being damaged by contact with the device.
[0005]
In addition, the application of the flat panel display to the mobile field has been promoted, and the weight of the device has been required to be reduced. Along with this, the weight of the glass substrate is also required to be reduced.
[0006]
[Problems to be solved by the invention]
In order to reduce the weight of the glass substrate, thinning of the glass substrate has been studied.
[0007]
However, as the thickness of the glass substrate becomes thinner, the strength of the glass substrate decreases, so that there is a problem that the glass substrate is more easily broken.
[0008]
An object of the present invention is to provide a glass substrate which is hardly broken even when the glass substrate is thinned, and a method for manufacturing the same.
[0009]
[Means for Solving the Problems]
As a result of repeating various experiments, the present inventor has found that the strength of the glass substrate is improved by intentionally introducing a minute phase separation structure into the glass substrate, and proposes the present invention.
[0010]
That is, the glass substrate of the present invention is aluminosilicate glass having a composition of SrO + BaO of 0 to 6.5% by mass percentage, and has a phase separation structure with a particle size of 2 to 100 nm. .
[0011]
Further, the method for producing a glass substrate of the present invention is characterized in that, in terms of mass percentage, 50 to 70% of SiO 2 , 10 to 20% of Al 2 O 3 , 7 to 15% of B 2 O 3 , 0 to 20% of MgO + CaO, 0 to 20% of SrO + BaO 0 A heat treatment is performed on an aluminosilicate glass having a composition of 6.5% so as to obtain a phase-separated structure having a particle size of 2 to 50 nm.
[0012]
[Action]
The cracks in the glass substrate occur when the surface of the glass substrate is scratched and extended. Therefore, if the crack resistance of the glass substrate is improved to suppress the occurrence of cracks, the strength of the glass substrate will be dramatically improved.
[0013]
Therefore, in the glass substrate of the present invention, a phase separation structure having a particle size of 2 to 100 nm is intentionally introduced into the glass substrate, thereby suppressing the occurrence of cracks and dramatically improving the strength of the glass substrate. .
[0014]
By introducing a fine phase separation structure of 2 to 100 nm in the glass substrate, the crack stops at the interface of the phase-separated particles, or even when the crack does not stop at the interface, extra energy to bypass the particles. Therefore, it is considered that the crack is difficult to extend and the crack can be suppressed.
[0015]
If the particle size of the phase separation is smaller than 2 nm, the effect of suppressing the generation of cracks cannot be obtained, which is not preferable. On the other hand, when the particle size of the phase separation is larger than 100 nm, heat treatment takes time and productivity is deteriorated, which is not preferable. Preferably it is 2-90 nm, More preferably, it is 5-80 nm.
[0016]
When the particle size of the phase separation is larger than 50 nm, the glass substrate tends to become cloudy due to light scattering, and the transmittance of the glass substrate may be reduced. Therefore, when a glass substrate is used for a flat panel display substrate, the particle size of the phase separation is desirably 50 nm or less.
[0017]
In order to introduce a phase-separated structure having a particle size of 2 to 100 nm into the glass substrate, a heat treatment in which the glass substrate is kept at a temperature of 500 ° C. to the annealing point of glass + 60 ° C. for 0.5 to 300 hours. Should be performed. The heat treatment may be performed in a cooling step of the molten glass, or may be performed after the molten glass is once cooled and formed into a glass substrate. In addition, if the heat treatment temperature is increased, the heat treatment time can be shortened.
[0018]
Further, a preferable composition range of the glass substrate of the present invention is, in terms of mass percentage, 50 to 70% of SiO 2 , 10 to 20% of Al 2 O 3 , 7 to 15% of B 2 O 3 , 0 to 20% of MgO + CaO, and SrO + BaO. 0 to 6.5%.
[0019]
The reason for limiting the composition of the glass as described above in the present invention is to take into account the phase separation tendency of glass, density, chemical resistance, heat shrinkage, Young's modulus, and the like. ,It is as follows.
[0020]
SiO 2 is a component that serves as a network former of glass, and has an effect of improving the acid resistance of glass and increasing the strain point of glass to reduce the thermal shrinkage of the glass substrate. When the content increases, the high-temperature viscosity of the glass increases, and the meltability tends to deteriorate. However, when the content is 50 to 70%, the acid resistance is high without deteriorating the meltability of the glass, A glass substrate with small heat shrinkage can be obtained. The preferred range is 58-67%.
[0021]
Al 2 O 3 is a component that serves as a network former of glass and is a component that increases the Young's modulus of the glass, and has an effect of suppressing bending of the glass substrate. When the content increases, the liquidus temperature rises and molding tends to be difficult. However, when the content is 10 to 20%, a glass substrate having a low liquidus temperature and small deflection can be obtained. The preferred range is 12-18%.
[0022]
B 2 O 3 is a component that acts as a flux, lowers the viscosity of the glass, improves the meltability, and lowers the density of the glass. When the content increases, the strain point of the glass tends to decrease, but when the content is 7 to 15%, the above effect can be obtained without lowering the strain point of the glass. The preferred range is 7-13%.
[0023]
MgO and CaO are components that lower the high-temperature viscosity and have an effect of improving the melting property of glass. When the content increases, the chemical resistance of the glass, particularly the buffered hydrofluoric acid resistance, tends to deteriorate. However, if the total amount of MgO and CaO is 15% or less, the buffered hydrofluoric acid resistance is particularly deteriorated. There is no. A preferred range is 0 to 10% in total.
[0024]
SrO and BaO are components that improve the chemical resistance of glass. However, when these components are increased, the tendency of phase separation of the glass decreases, and it becomes impossible to form a phase separation by short-time heat treatment. For this reason, it should not be contained more than 6.5% in total. A preferred range is 0 to 5% in total.
[0025]
In the present invention, in addition to the above-mentioned components, other components such as As 2 O 3 , Sb 2 O 3 , SnO 2 , Cl 2 , SO 3 and the like are used as long as the properties are not impaired. Up to 3%, ZrO 2 , TiO 2 , Y 2 O 3 , La 2 O 3 , P 2 O 5 may be added up to 5% in order to improve the chemical resistance and devitrification resistance of the glass. .
[0026]
Furthermore, for the reasons described above, the addition of alkali metal oxides (Na 2 O, K 2 O, Li 2 O) should be avoided. In addition, PbO, which is generally used as a flux, is also not preferred because it may significantly lower the chemical resistance of the glass and may volatilize from the surface of the melt when the glass is melted, thus polluting the environment.
[0027]
Further, the glass substrate of the present invention can be manufactured by a method such as a slot down draw method, an overflow down draw method, a float method, or a roll out method which is known as a method for forming a sheet glass.
[0028]
【Example】
Hereinafter, the present invention will be described in detail based on examples.
[0029]
Tables 1 to 6 show examples of the present invention (samples Nos. 1 to 27), and Table 7 shows comparative examples (samples Nos. 28 and 29).
[0030]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
[Table 6]
[Table 7]
Each sample in the table was prepared as follows.
[0038]
First, a glass raw material was prepared so as to have the composition shown in the table, and was melted in a platinum pot at 1600 ° C. for 24 hours. Subsequently, the molten glass was poured onto a carbon plate, formed into a plate shape, cooled slowly, and polished on both sides so that the plate thickness became 0.7 mm, and the obtained plate glass was cut into a size of 200 mm square. processed. Thereafter, heat treatment was performed under the conditions shown in the table to separate the phases, thereby preparing a sample.
[0039]
Various characteristics were evaluated for each sample thus manufactured. The results are shown in the table.
[0040]
As is clear from Tables 1 to 7, the sample No. Nos. 1 to 27 had a phase separation structure with a particle size of 2 nm or more, and thus had a high crack resistance of 8.8 N or more. Further, the density is 2.466 g / cm 3 or less, the coefficient of thermal expansion is 30.0 to 36.5 × 10 −7 / ° C., which is excellent in thermal shock resistance, the strain point is 656 ° C. or more, and the thermal shrinkage is small, If the specific Young's modulus is 27.5 GPa / g · cm −3 or more, the amount of deflection is expected to be small. Furthermore, it was also excellent in acid resistance and BHF resistance.
[0041]
On the other hand, the sample No. In Nos. 28 and 29, although heat treatment was performed, no phase separation occurred, so that the crack resistance was as low as 7.4 N.
[0042]
Next, No. Using the glass composition of No. 1 and changing the heat treatment conditions, glass substrates having particles of various sizes were produced, and the relationship between the particle size of the phase separation and crack resistance was investigated. The results are shown in Table 8 and FIG. In FIG. 1, the vertical axis indicates the crack generation rate indicating the crack resistance of the glass substrate, and the horizontal axis indicates the load applied to the diamond indenter. In the figure, A is a glass substrate having no phase separation structure, B is a glass substrate having a phase separation structure with a particle size of 2 nm (sample No. 1), and C is a glass substrate having a phase separation structure with a particle size of 10 nm. Substrate, D is a glass substrate having a phase separation structure with a particle size of 20 nm, E is a glass substrate having a phase separation structure with a particle size of 50 nm, F is a glass substrate having a phase separation structure with a particle size of 100 nm, and G is a particle. The figure shows a glass substrate having a phase separation structure with a size of 110 nm.
[0043]
[Table 8]
As is clear from Table 8 and FIG. 1, when the crack generation rates of the glass substrate having no phase-separated structure (Sample A) and the glass substrate having the phase-separated structure (Samples BG) are compared. It can be seen that the glass substrate having the structure is less prone to cracks and has improved crack resistance. In addition, it is found that, as the particle size increases up to 100 nm, cracks are less likely to occur and the crack resistance improves as the particle size increases. However, when the particle size exceeds 100 nm, the crack resistance tends to gradually decrease.
[0045]
The particle size of the phase separation was measured by observation with a TEM (transmission electron microscope).
[0046]
The crack resistance of the glass was evaluated by the method proposed by Wada et al. (M. Wada et al. Proc., The Xth ICG, vol. 11, Ceram. Soc., Japan, Kyoto, 1974, p39). . In this method, a sample glass is placed on a stage of a Vickers hardness tester, and a diamond-shaped diamond indenter is pressed against the surface of the sample glass with various loads for 15 seconds. Then, the number of cracks generated from the four corners of the indentation by 15 seconds after unloading was counted, and the ratio to the maximum number of possible cracks (four) was determined to be the crack occurrence rate. The load at which the crack occurrence rate became 50% was defined as "crack resistance". The fact that the crack resistance is large means that a crack is hardly generated even under a high load, that is, the crack resistance is excellent. The crack occurrence rate was measured 20 times with the same load, and the average value was obtained. The measurement was performed at a temperature of 25 ° C. and a humidity of 30%.
[0047]
The density was measured by the well-known Archimedes method, and the coefficient of thermal expansion was obtained by measuring the average coefficient of thermal expansion at 30 to 380 ° C. using a dilatometer.
[0048]
The strain point and the annealing point were measured based on the method of ASTM C336-71, and the softening point was measured based on the method of ASTM C338-73. The viscosity of 10 4.0 ~10 2.5 dPa · s were measured by a platinum ball pulling method.
[0049]
The Young's modulus was measured by a bending resonance method, and the specific Young's modulus was calculated from the measured values of the Young's modulus and the density.
[0050]
Hydrochloric acid resistance was evaluated by immersing each sample in a 10% by weight aqueous hydrochloric acid solution maintained at 80 ° C. for 24 hours, and then visually observing the surface state thereof. The BHF resistance was determined by immersing each sample in buffered hydrofluoric acid composed of 30% by mass of ammonium fluoride and 6% by mass of hydrofluoric acid kept at 20 ° C. for 30 minutes, and then visually observing the surface condition thereof. evaluated. When the surface of the glass substrate became turbid, x was shown, and when there was no change, o was shown.
[0051]
The liquidus temperature was measured by crushing the glass, passing through a standard sieve 30 mesh (500 nm), placing the glass powder remaining on the 50 mesh (300 nm) in a platinum boat, and holding the glass powder in a temperature gradient furnace for 24 hours. Was measured at the temperature at which the precipitates formed.
[0052]
【The invention's effect】
As described above, since the glass substrate of the present invention has excellent crack resistance, it is suitable as a glass substrate used for a flat panel display substrate, a hard disk substrate, and the like, which are required to be thin and lightweight.
[Brief description of the drawings]
FIG. 1 is a graph showing a relationship between a particle size of a phase separation and a crack generation rate.
Claims (5)
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| JP2002241449A JP4168320B2 (en) | 2002-08-22 | 2002-08-22 | Manufacturing method of glass substrate |
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| JP2008124418A Division JP4862859B2 (en) | 2008-05-12 | 2008-05-12 | Glass substrate |
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Cited By (16)
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| JP2006269261A (en) * | 2005-03-24 | 2006-10-05 | Lintec Corp | Composition for forming dielectric layer or insulator layer, green sheet, and flat panel display substrate |
| JP2006347795A (en) * | 2005-06-15 | 2006-12-28 | Hoya Corp | Non-alkali glass, its production method, and glass substrate for forming tft (thin film transistor) of liquid crystal display |
| JP2006347796A (en) * | 2005-06-15 | 2006-12-28 | Hoya Corp | Glass member, product using the same, and method for production of the product |
| JP2007039316A (en) * | 2005-06-27 | 2007-02-15 | Nippon Electric Glass Co Ltd | Glass substrate for display |
| WO2008149888A1 (en) * | 2007-06-08 | 2008-12-11 | Nippon Electric Glass Co., Ltd. | Alkali-free glass and alkali-free glass substrate |
| JP2010105841A (en) * | 2008-10-29 | 2010-05-13 | Asahi Glass Co Ltd | Method for manufacturing flat display panel |
| JP2010535146A (en) * | 2007-07-31 | 2010-11-18 | コーニング インコーポレイテッド | Glass composition suitable for downdraw process and method for producing and using the same |
| JP2012176887A (en) * | 2012-04-23 | 2012-09-13 | Hoya Corp | Non-alkali glass, its production method, and glass substrate for forming tft (thin film transistor) of liquid crystal display |
| WO2015186606A1 (en) * | 2014-06-02 | 2015-12-10 | 日本電気硝子株式会社 | Phase-separated glass, phase-separable glass, organic el device, and method for producing phase-separated glass |
| JP2015227272A (en) * | 2014-06-02 | 2015-12-17 | 日本電気硝子株式会社 | Phase-split glass and composite substrate using the same |
| JP2016050155A (en) * | 2014-09-01 | 2016-04-11 | 国立大学法人 東京大学 | Glass material and method for producing the same |
| WO2016117406A1 (en) * | 2015-01-21 | 2016-07-28 | 日本電気硝子株式会社 | Phase-separated glass |
| JPWO2014058054A1 (en) * | 2012-10-12 | 2016-09-05 | 旭硝子株式会社 | Method for producing phase-separated glass and phase-separated glass |
| JP2016528152A (en) * | 2013-08-15 | 2016-09-15 | コーニング インコーポレイテッド | Alkali-doped and alkali-free boroaluminosilicate glass |
| CN108423985A (en) * | 2018-04-25 | 2018-08-21 | 成都光明光电股份有限公司 | Glass composition |
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| JP2006269261A (en) * | 2005-03-24 | 2006-10-05 | Lintec Corp | Composition for forming dielectric layer or insulator layer, green sheet, and flat panel display substrate |
| JP2006347795A (en) * | 2005-06-15 | 2006-12-28 | Hoya Corp | Non-alkali glass, its production method, and glass substrate for forming tft (thin film transistor) of liquid crystal display |
| JP2006347796A (en) * | 2005-06-15 | 2006-12-28 | Hoya Corp | Glass member, product using the same, and method for production of the product |
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| WO2008149888A1 (en) * | 2007-06-08 | 2008-12-11 | Nippon Electric Glass Co., Ltd. | Alkali-free glass and alkali-free glass substrate |
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| US8455378B2 (en) | 2007-06-08 | 2013-06-04 | Nippon Electric Glass Co., Ltd. | Alkali-free glass and alkali-free glass substrate |
| JP2010535146A (en) * | 2007-07-31 | 2010-11-18 | コーニング インコーポレイテッド | Glass composition suitable for downdraw process and method for producing and using the same |
| JP2010105841A (en) * | 2008-10-29 | 2010-05-13 | Asahi Glass Co Ltd | Method for manufacturing flat display panel |
| JP2012176887A (en) * | 2012-04-23 | 2012-09-13 | Hoya Corp | Non-alkali glass, its production method, and glass substrate for forming tft (thin film transistor) of liquid crystal display |
| JPWO2014058054A1 (en) * | 2012-10-12 | 2016-09-05 | 旭硝子株式会社 | Method for producing phase-separated glass and phase-separated glass |
| JP2016528152A (en) * | 2013-08-15 | 2016-09-15 | コーニング インコーポレイテッド | Alkali-doped and alkali-free boroaluminosilicate glass |
| US11168018B2 (en) | 2013-08-15 | 2021-11-09 | Corning Incorporated | Aluminoborosilicate glass substantially free of alkali oxides |
| USRE49307E1 (en) | 2013-08-15 | 2022-11-22 | Corning Incorporated | Alkali-doped and alkali-free boroaluminosilicate glass |
| WO2015186606A1 (en) * | 2014-06-02 | 2015-12-10 | 日本電気硝子株式会社 | Phase-separated glass, phase-separable glass, organic el device, and method for producing phase-separated glass |
| JP2015227272A (en) * | 2014-06-02 | 2015-12-17 | 日本電気硝子株式会社 | Phase-split glass and composite substrate using the same |
| JP2016050155A (en) * | 2014-09-01 | 2016-04-11 | 国立大学法人 東京大学 | Glass material and method for producing the same |
| WO2016117406A1 (en) * | 2015-01-21 | 2016-07-28 | 日本電気硝子株式会社 | Phase-separated glass |
| CN108423985A (en) * | 2018-04-25 | 2018-08-21 | 成都光明光电股份有限公司 | Glass composition |
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