JP2004067443A - Process for treating glass - Google Patents
Process for treating glass Download PDFInfo
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- JP2004067443A JP2004067443A JP2002228704A JP2002228704A JP2004067443A JP 2004067443 A JP2004067443 A JP 2004067443A JP 2002228704 A JP2002228704 A JP 2002228704A JP 2002228704 A JP2002228704 A JP 2002228704A JP 2004067443 A JP2004067443 A JP 2004067443A
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- glass
- electron beam
- crack resistance
- crack
- irradiated
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- 239000011521 glass Substances 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000010894 electron beam technology Methods 0.000 claims abstract description 31
- 230000001133 acceleration Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 238000003672 processing method Methods 0.000 claims description 4
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 238000007373 indentation Methods 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000002360 explosive Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
- C03C23/004—Other surface treatment of glass not in the form of fibres or filaments by irradiation by electrons, protons or alpha-particles
-
- 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
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
-
- 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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
-
- 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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- 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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- 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
-
- 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
- C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
-
- 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
- C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
- C03C3/105—Glass compositions containing silica with 40% to 90% silica, by weight containing lead 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
- C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
- C03C3/108—Glass compositions containing silica with 40% to 90% silica, by weight containing lead containing boron
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Surface Treatment Of Glass (AREA)
- Glass Compositions (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、各種ガラスのクラック抵抗を向上させる方法に関するものである。
【０００２】
【従来の技術】
ガラスは脆性材料であり、その加工工程や搬送工程で他の部材と軽く接触しただけでも、微少なクラックが発生したり、割れたりしやすい。特にブラウン管用パネル、フラットディスプレイ用基板、光学レンズ、光通信等に用いられるガラスは、表面に僅かなクラックが発生しただけでも、製品としての機能が失われるため、これらのガラスのクラック抵抗を向上させることは非常に重要である。
【０００３】
特にＰＤＰ用ガラス基板のクラック抵抗を向上させることは、極めて重要な技術課題となっている。すなわち、ＰＤＰ用ガラス基材の材質としては、従来から主にソーダライムガラスが使用されてきたが、熱処理工程で変形や収縮が起こり、寸法が変化しやすいという問題があるため、近年では、高歪点ガラスに置き換わりつつある。しかしながら高歪点ガラスは、ソーダライムガラスに比べてクラックが発生しやすいという欠点がある。そのため高歪点ガラス基板を用いたＰＤＰ装置の歩留まりは低く、生産性向上を妨げる原因の一つとなっている。
【０００４】
このような事情から、高歪点ガラスからなるＰＤＰ用ガラス基板の材質を改良し、クラック抵抗を向上させる試みがなされているが、未だ商品化に至っていないのが実状である。
【０００５】
【発明が解決しようとする課題】
一般にガラスのクラック抵抗を向上させる方法としては、物理（風冷）強化法やイオン交換強化法が知られている。これらの強化法は、ガラス表面に圧縮強化層を形成し、ガラスの実用強度を増大させるものであるが、圧縮強化層で耐えることができないような大きな力がガラスに加わった場合には、爆発的な著しい破損が起こるため、その取り扱いには細心の注意を払う必要がある。また風冷強化法の場合は、形状が複雑であったり、肉厚の薄いガラスには効果が小さいという問題もある。
【０００６】
本発明は上記事情に鑑みてなされたものであって、その目的とするところは、形状や肉厚に制限されることなく、効果的にガラスのクラック抵抗を向上することができ、爆発的な破損も起こらないガラスの処理方法を提供することである。
【０００７】
【課題を解決するための手段】
本発明者等は、上記目的を達成すべく鋭意検討を行った結果、ガラス表面に所定条件で電子線を照射すると、ガラスの構造変化が起こり、クラック抵抗が向上すること、こうして得られたガラスは、物理強化やイオン交換強化法によって処理されたガラスのように爆発的な破損は起こらないことを見いだし、本発明を提案するに至った。
【０００８】
すなわち本発明のガラスの処理方法は、下記方法によって測定されるクラック抵抗が向上するように、ガラス表面に電子線を照射することを特徴とする。
【０００９】
（方法）ガラスをビッカース硬度計のステージに置き、ガラス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。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ケ）に対する割合を求め、クラック発生率とする。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する。
【００１０】
【発明の実施の形態】
ガラス表面に所定の条件で電子線を照射すると、ガラスのクラック抵抗が向上する。しかも、この電子線照射によるガラスのクラック抵抗向上方法は、形状が複雑なガラスや肉厚の薄いガラスにも効果がある。
【００１１】
ガラス表面に電子線を照射すると、ガラスのクラック抵抗が向上する理由は、定かでないが、次のように推察される。
【００１２】
一般にガラスは、ＳｉとＯの網目構造を有するが、網目の隙間にアルカリ土類金属イオンやアルカリ金属イオン等が入ると、非架橋酸素が存在することになり、網目構造が切断される箇所が発生する。ところがガラスに電子線を照射すると、ガラスの表面層に位置するアルカリ土類金属イオンやアルカリ金属イオン等がガラスの内部に移動し、ガラス表面層の網目構造は、網目構造の隙間に空洞ができた状態となる。その結果、ガラス表面層の網目構造に柔軟性が増し、ガラスのクラック抵抗が向上する。
【００１３】
こうして得られるガラスは、表面に圧縮強化層が形成されないため、大きな力が加わって破損しても、爆発的な破損とはならない。
【００１４】
本発明においてガラスのクラック抵抗を向上させるために必要な電子線の照射条件は、ガラス材質によって異なるが、（加速電圧（ｋＶ））２×電流密度（μＡ／ｃｍ２）×電子線照射時間（分）が１０００以上の電子線を照射すると、特にアルカリ土類金属酸化物（Ｒ′Ｏ）やアルカリ金属酸化物（Ｒ２Ｏ）を多量に（例えば、合量で３５質量％以上）含むガラスについて、クラック抵抗の向上効果が得られる。（加速電圧（ｋＶ））２×電流密度（μＡ／ｃｍ２）×電子線照射時間（分）の値が高いほど、ガラスのクラック抵抗は向上しやすく、好ましくは３０００以上、より好ましくは１００００以上とすることが望ましい。
【００１５】
本発明において、ガラスに電子線を照射するために使用する装置は、特に限定されないが、生産性を考えると、電子線を広範囲に亘って均一に照射できる装置が適している。また照射時間を短縮するためには、加速電圧と照射量の大きい装置が望ましい。
【００１６】
またガラスの材質は、特に限定されないが、質量百分率で、ＳｉＯ２ ４０〜７５％、Ａｌ２Ｏ３ ０〜２５％、アルカリ土類金属酸化物Ｒ′Ｏ（Ｒ′は、Ｍｇ、Ｃａ、Ｓｒ、ＢａまたはＺｎである） ４〜３５％、アルカリ金属酸化物Ｒ２Ｏ（Ｒは、Ｎａ、ＫまたはＬｉである） ０〜２４％、Ｂ２Ｏ３ ０〜３０％、ＰｂＯ ０〜５０％の組成を有するガラスを処理すると、クラック抵抗の向上がより顕著に現れるため好適である。
【００１７】
【実施例】
以下、本発明のガラスの処理方法を実施例に基づき詳細に説明する。
【００１８】
（実施例１）
ガラス試料として、ＰＤＰ基板用ガラスを準備した。このガラスは、質量百分率で、ＳｉＯ２ ５５％、Ａｌ２Ｏ３ ７％、Ｒ′Ｏ ２２％、Ｒ２Ｏ １１％、ＺｒＯ２ ５％の組成を有し、歪点が５８０℃、３０〜３８０℃における平均熱膨張係数が８３×１０−７／℃である。
【００１９】
次いで電子線照射装置を用い、以下に示す条件でガラス試料（寸法：３０φｍｍ×２ｍｍ）に電子線照射を行った。
加速電圧：１０ｋＶ、２０ｋＶ、３０ｋＶ
電流密度：３μＡ／ｃｍ２
照射時間：１０分間
処理雰囲気：真空（１０−７Ｔｏｒｒ）
こうして得られたガラス試料（Ｎｏ．２〜４）と、電子線照射を行わなかったガラス試料（Ｎｏ．１）について、クラック抵抗を測定し、その結果を表１に示した。
【００２０】
【表１】
表１から明らかなように、加速電圧１０ｋＶで電子線照射したＮｏ．２のガラス試料のクラック抵抗は、電子線を照射していないＮｏ．１のガラス試料のクラック抵抗と同レベルであったが、加速電圧２０ｋＶ以上で電子線照射したＮｏ．３、４のガラス試料は、電子線を照射していないＮｏ．１のガラス試料に比べて、クラック抵抗が１０％以上向上した。
【００２２】
（実施例２）
ガラス試料として、ブラウン管用パネルガラスを使用した。このブラウン管用パネルガラスは、質量百分率で、ＳｉＯ２ ５６％、Ａｌ２Ｏ３ ０．５％、Ｒ′Ｏ ２８％、Ｒ２Ｏ １３．５％、ＴｉＯ２ ０．５％、ＣｅＯ２ ０．５％、ＺｒＯ２ １％の組成を有する。
【００２３】
このガラス試料（寸法：３０φｍｍ×２ｍｍ）に電子線の照射を行った。照射条件は、実施例１と同様である。
【００２４】
こうして得られた各ガラス試料（Ｎｏ．６〜８）と、電子線照射を行わなかったガラス試料（Ｎｏ．５）について、クラック抵抗を測定し、その結果を表２に示した。
【００２５】
【表２】
表２から明らかなように、加速電圧１０ｋＶ以上で電子線照射したＮｏ．６〜８のガラス試料は、電子線を照射していないＮｏ．５のガラス試料に比べて、クラック抵抗が１０％以上向上した。
【００２７】
（実施例３）
表３に示す組成を有するガラス試料（Ｎｏ．９〜１５）を準備し、電子線照射装置を用い、各ガラス試料（寸法：３０φｍｍ×２ｍｍ）に対して、以下の条件で電子線を照射した。
加速電圧：３０ｋＶ
電流密度：３μＡ／ｃｍ２
照射時間：４８時間
処理雰囲気：真空（１０−７Ｔｏｒｒ）
また各ガラス試料について、電子線照射前後のクラック抵抗を測定し、その結果も表３に示した。
【００２８】
【表３】
表３から明らかなように、上記の条件で電子線を照射したガラス試料Ｎｏ．９〜１５は、いずれも電子線を照射することによってクラック抵抗が向上した。特に試料Ｎｏ．９〜１２のガラス試料については、著しい効果が見られた。
【００３０】
また実施例２のガラス試料についても、上記の条件で電子線を照射したところ、クラック抵抗が１５００ｍＮとなり、やはり著しい効果が見られた。
【００３１】
尚、上記のクラック抵抗は、和田らが提案した方法（Ｍ．Ｗａｄａ ｅｔａｌ．Ｐｒｏｃ．， ｔｈｅ Ｘｔｈ ＩＣＧ，ｖｏｌ．１１，Ｃｅｒａｍ．
Ｓｏｃ．，Ｊａｐａｎ，Ｋｙｏｔｏ，１９７４，ｐ３９）によって求めた。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、徐荷後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ケ）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。
【００３２】
【発明の効果】
以上説明したように、本発明のガラスの処理方法によると、形状や肉厚に制限されることなく、効果的にガラスのクラック抵抗を向上することが可能であり、またガラス表面に圧縮応力層が形成されないため、爆発的な破損も起こらない。よって本発明の処理方法は、クラック抵抗の向上が要求される各種ガラス、例えばブラウン管用ガラス、フラットディスプレイ用基板、光学レンズ、光通信に用いられるガラスに適用することができ、特にクラック抵抗の向上が大きな課題であるＰＤＰ基板に用いられる高歪点ガラスに有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for improving crack resistance of various glasses.
[0002]
[Prior art]
Glass is a brittle material, and even if it comes into slight contact with other members in the processing step or the transport step, minute cracks are likely to occur or break. In particular, the glass used for CRT panels, flat display substrates, optical lenses, optical communications, etc. loses its function as a product even if a slight crack occurs on the surface, so the crack resistance of these glasses is improved. It is very important to do so.
[0003]
In particular, improving the crack resistance of a glass substrate for PDP is a very important technical problem. That is, as a material of the glass substrate for PDP, soda lime glass has been mainly used in the past, but there is a problem that deformation and shrinkage occur in the heat treatment step and the dimensions are easily changed. It is being replaced by strain point glass. However, high strain point glass has a disadvantage that cracks are more likely to occur than soda lime glass. Therefore, the yield of a PDP device using a high-strain-point glass substrate is low, which is one of the factors that hinder improvement in productivity.
[0004]
Under these circumstances, attempts have been made to improve the crack resistance by improving the material of the glass substrate for PDP made of glass with a high strain point, but the reality is that it has not yet been commercialized.
[0005]
[Problems to be solved by the invention]
Generally, as a method for improving the crack resistance of glass, a physical (air cooling) strengthening method and an ion exchange strengthening method are known. These tempering methods form a compression-strengthened layer on the glass surface and increase the practical strength of the glass.However, when a large force that cannot be withstood by the compression-strengthened layer is applied to the glass, the explosion occurs. Great care must be taken when handling it, as it can cause significant damage. In the case of the air-cooling tempering method, there is also a problem that the shape is complicated or the effect is small for thin glass.
[0006]
The present invention has been made in view of the above circumstances, and the object thereof is to be able to effectively improve the crack resistance of glass without being limited by the shape and thickness, and to provide an explosive An object of the present invention is to provide a method for treating glass that does not break.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object.As a result, when irradiating the glass surface with an electron beam under predetermined conditions, the structural change of the glass occurs, the crack resistance is improved, and the glass thus obtained is improved. Has found that explosive breakage does not occur unlike glass treated by physical strengthening or ion exchange strengthening, and has led to the present invention.
[0008]
That is, the glass treatment method of the present invention is characterized in that the glass surface is irradiated with an electron beam so that the crack resistance measured by the following method is improved.
[0009]
(Method) The glass is placed on a stage of a Vickers hardness tester, and a diamond-shaped diamond indenter is pressed against the glass surface with various loads for 15 seconds. By 15 seconds after unloading, the number of cracks generated from the four corners of the indentation is counted, and the ratio to the maximum number of possible cracks (four) is determined to be the crack occurrence rate. The load at which the crack occurrence rate becomes 50% is defined as crack resistance.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Irradiating the glass surface with an electron beam under predetermined conditions improves the crack resistance of the glass. Moreover, the method for improving the crack resistance of glass by electron beam irradiation is also effective for glass having a complicated shape and thin glass.
[0011]
The reason why the glass surface is irradiated with an electron beam to improve the crack resistance of the glass is not clear, but is presumed as follows.
[0012]
Generally, glass has a network structure of Si and O. However, if alkaline earth metal ions or alkali metal ions enter into the gaps of the network, non-crosslinked oxygen will be present, and a portion where the network structure is cut will be present. appear. However, when the glass is irradiated with an electron beam, alkaline earth metal ions and alkali metal ions located in the surface layer of the glass move into the glass, and the network structure of the glass surface layer forms cavities in the gaps of the network structure. State. As a result, the flexibility of the network structure of the glass surface layer increases, and the crack resistance of the glass improves.
[0013]
The glass thus obtained does not have a compression-strengthened layer on its surface, so that even if it is broken by applying a large force, it does not become explosive.
[0014]
In the present invention, the irradiation conditions of the electron beam necessary for improving the crack resistance of the glass differ depending on the glass material, but (acceleration voltage (kV)) 2 × current density (μA / cm 2 ) × electron beam irradiation time ( When the divided) is irradiated more than 1000 electron beam, in particular an alkaline earth metal oxide (R'O) or alkali metal oxides (R 2 O) a large amount (e.g., more than 35 mass% in total) containing glass The effect of improving the crack resistance can be obtained. (Acceleration voltage (kV)) The higher the value of 2 × current density (μA / cm 2 ) × electron beam irradiation time (minute), the more easily the crack resistance of the glass is improved, preferably 3000 or more, more preferably 10,000 or more. It is desirable that
[0015]
In the present invention, the device used to irradiate the glass with an electron beam is not particularly limited, but in view of productivity, a device capable of uniformly irradiating an electron beam over a wide range is suitable. In order to shorten the irradiation time, an apparatus having a large acceleration voltage and a large dose is desirable.
[0016]
The material of the glass is not particularly limited. However, in terms of mass percentage, SiO 2 is 40 to 75%, Al 2 O 3 is 0 to 25%, and alkaline earth metal oxide R′O (R ′ is Mg, Ca, Sr , Ba or Zn) 4 to 35%, alkali metal oxide R 2 O (R is Na, K or Li) 0 to 24%, B 2 O 3 0 to 30%, PbO 0 to 50% It is preferable to treat the glass having the following composition, since the improvement in crack resistance appears more remarkably.
[0017]
【Example】
Hereinafter, the glass processing method of the present invention will be described in detail based on examples.
[0018]
(Example 1)
Glass for a PDP substrate was prepared as a glass sample. The glass, by mass percentage, SiO 2 55%, Al 2 O 3 7%, R'O 22%, R 2 O 11%, has a composition of ZrO 2 5%, the strain point is 580 ° C.,. 30 to The average coefficient of thermal expansion at 380 ° C. is 83 × 10 −7 / ° C.
[0019]
Next, the glass sample (dimensions: 30 mm × 2 mm) was irradiated with an electron beam using an electron beam irradiation apparatus under the following conditions.
Acceleration voltage: 10 kV, 20 kV, 30 kV
Current density: 3 μA / cm 2
Irradiation time: 10 minutes Processing atmosphere: Vacuum (10 -7 Torr)
The crack resistance of the glass sample (No. 2 to 4) thus obtained and the glass sample (No. 1) not subjected to the electron beam irradiation were measured, and the results are shown in Table 1.
[0020]
[Table 1]
As is evident from Table 1, No. 1 was irradiated with an electron beam at an acceleration voltage of 10 kV. The crack resistance of the glass sample of Sample No. 2 was not irradiated with the electron beam. No. 1 was the same level as the crack resistance of the glass sample, but was irradiated with an electron beam at an acceleration voltage of 20 kV or more. The glass samples of Nos. 3 and 4 were Nos. No. The crack resistance was improved by 10% or more as compared with the glass sample of No. 1.
[0022]
(Example 2)
A panel glass for a cathode ray tube was used as a glass sample. This CRT panel glass has a mass percentage of 56% SiO 2 , 0.5% Al 2 O 3 , 28% R'O, 13.5% R 2 O, 0.5% TiO 2, 0.5% CeO 2 . It has a composition of 5% and ZrO 2 1%.
[0023]
The glass sample (dimensions: 30 mm x 2 mm) was irradiated with an electron beam. Irradiation conditions are the same as in Example 1.
[0024]
Crack resistance was measured for each of the glass samples (Nos. 6 to 8) thus obtained and the glass sample (No. 5) that was not subjected to electron beam irradiation, and the results are shown in Table 2.
[0025]
[Table 2]
As is evident from Table 2, No. 1 was irradiated with an electron beam at an acceleration voltage of 10 kV or more. The glass samples Nos. 6 to 8 were Nos. No. As compared with the glass sample of No. 5, the crack resistance was improved by 10% or more.
[0027]
(Example 3)
Glass samples (Nos. 9 to 15) having the compositions shown in Table 3 were prepared, and each glass sample (dimensions: 30 mm × 2 mm) was irradiated with an electron beam under the following conditions using an electron beam irradiation apparatus. .
Acceleration voltage: 30 kV
Current density: 3 μA / cm 2
Irradiation time: 48 hours Processing atmosphere: vacuum (10 -7 Torr)
The crack resistance of each glass sample before and after electron beam irradiation was measured, and the results are also shown in Table 3.
[0028]
[Table 3]
As is clear from Table 3, the glass sample No. irradiated with the electron beam under the above conditions. In all of Nos. 9 to 15, crack resistance was improved by irradiation with an electron beam. In particular, the sample No. For glass samples 9 to 12, significant effects were observed.
[0030]
When the glass sample of Example 2 was irradiated with an electron beam under the above conditions, the crack resistance became 1500 mN, and a remarkable effect was also observed.
[0031]
The crack resistance is determined 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 the 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". High crack resistance means that cracks are unlikely to occur even under a high load, that is, they have excellent crack resistance. 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%.
[0032]
【The invention's effect】
As described above, according to the glass processing method of the present invention, it is possible to effectively improve the crack resistance of the glass without being limited by the shape and the wall thickness, and furthermore, it is possible to improve the compression stress layer on the glass surface. No explosive damage occurs because no is formed. Therefore, the processing method of the present invention can be applied to various glasses that require improvement in crack resistance, for example, glass for cathode ray tubes, substrates for flat displays, optical lenses, and glasses used for optical communication, and in particular, improvement in crack resistance. Is useful for high strain point glass used for PDP substrates, which is a major problem.
Claims (3)
（方法）ガラスをビッカース硬度計のステージに置き、ガラス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。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ケ）に対する割合を求め、クラック発生率とする。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する。A glass treatment method comprising irradiating a glass surface with an electron beam so that crack resistance measured by the following method is improved.
(Method) The glass is placed on a stage of a Vickers hardness tester, and a diamond-shaped diamond indenter is pressed against the glass surface with various loads for 15 seconds. By 15 seconds after unloading, the number of cracks generated from the four corners of the indentation is counted, and the ratio to the maximum number of possible cracks (four) is determined to be the crack occurrence rate. The load at which the crack occurrence rate becomes 50% is defined as crack resistance.
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