JP4790300B2 - Glass - Google Patents

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JP4790300B2
JP4790300B2 JP2005116966A JP2005116966A JP4790300B2 JP 4790300 B2 JP4790300 B2 JP 4790300B2 JP 2005116966 A JP2005116966 A JP 2005116966A JP 2005116966 A JP2005116966 A JP 2005116966A JP 4790300 B2 JP4790300 B2 JP 4790300B2
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glass
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thermal expansion
temperature
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JP2006290704A (en
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素之 宮田
修 塩野
隆 村田
晋吉 三和
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Hitachi Ltd
Nippon Electric Glass Co Ltd
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Hitachi Ltd
Nippon Electric Glass Co Ltd
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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
    • 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
    • C03C3/083—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
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Description

本発明はクラック発生率の低いガラスに関するものである。   The present invention relates to a glass having a low crack generation rate.

ガラスは任意の形状に成形しやすく、光透過率や強度が高いことなどから、ディスプレイ用ガラス基板、ブラウン管、航空機用のディスプレイ、建築用部材等様々な分野で使用されている。しかしガラス製品の割れ・破壊の問題はいまだ解決されておらず、このような破壊を防ぐため化学的、あるいは物理的にガラスを強化する方法や、ガラスを結晶化させる方法が用いられている。（例えば特許文献１〜３）
特公平０６−０５３５９２ 特公平０８−０１８８５０ 特開平０８-１５１２２８ Glass is easily formed into an arbitrary shape, and has high light transmittance and high strength. Therefore, it is used in various fields such as a glass substrate for display, a cathode ray tube, a display for aircraft, and a building member. However, the problem of breakage / breakage of glass products has not been solved yet, and a method of chemically or physically strengthening glass or a method of crystallizing glass is used to prevent such breakage. (For example, Patent Documents 1 to 3)
JP 06-053592 JP08-018850 JP 08-151228

しかしながら上記のような強化ガラスでは、風冷、イオン交換、熱処理といった余分な工程が増える上、一旦割れてしまうと爆発的に破壊したり、強化できる板厚や組成が制限されたりするといった問題がある。   However, in the tempered glass as described above, extra steps such as air cooling, ion exchange, and heat treatment increase, and once it breaks, there is a problem that it is destroyed explosively or the thickness and composition that can be strengthened are limited. is there.

本発明の目的は、強化しなくても割れや破壊の起こりにくいガラスを提供することである。   An object of the present invention is to provide a glass that is not easily broken or broken without being strengthened.

ガラスの理論強度は本来非常に高いのであるが、理論強度よりもはるかに低い応力でも破壊に至ること多い。これはガラス表面にグリフィスフローと呼ばれる小さな欠陥が成形後の工程、例えば研磨や他物体との接触により発生してしまうためである。   Although the theoretical strength of glass is inherently very high, it often leads to fracture even at a stress much lower than the theoretical strength. This is because a small defect called Griffith flow occurs on the glass surface due to a post-molding process, for example, polishing or contact with another object.

本発明者らは、ガラス中に発生した微細なクラックがガラスの割れ・破壊に至る致命的な欠点になりやすく、ガラスの強度を向上させる根本的対策としてクラックを発生しにくくすればよいことに着目した。そして種々の実験を繰り返した結果、クラック発生率が低いガラスを見いだし、本発明として提案するものである。   The present inventors are prone to minute cracks occurring in the glass, which is likely to be a fatal defect leading to cracking / breaking of the glass, and it is only necessary to make cracks difficult to generate as a fundamental measure to improve the strength of the glass. Pay attention. As a result of repeating various experiments, a glass with a low crack generation rate is found and proposed as the present invention.

即ち、本発明のガラスは、質量百分率で、ＳｉＯ２ ５５〜７２％、Ａｌ２Ｏ３ １２〜２０％、Ｂ２Ｏ３ ０〜３％、ＭｇＯ ０〜１２％、ＣａＯ ０〜１２％、ＢａＯ ０〜１２％、ＳｒＯ ０〜１２％、Ｎａ２Ｏ ６〜１５％、Ｋ２Ｏ ２〜１５％、Ｌｉ２Ｏ ２〜１５％、ＺｎＯ ０〜１０％、ＴｉＯ ２ ０〜０．５％、希土類元素 ０．０１％以下であり、且つＬｉ２Ｏ／（Ｎａ２Ｏ＋Ｋ２Ｏ）の値がモル比で０．５〜１．３、（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／（Ｌｉ ２ Ｏ＋Ｎａ ２ Ｏ＋Ｋ ２ Ｏ）の値が０．４以下の範囲にあることを特徴とする。 That is, the glass of the present invention, by mass percentage, SiO 2 55~72%, Al 2 O 3 12 ~20%, B 2 O 3 0~ 3%, 0~12% MgO, CaO 0~12%, BaO 0~12%, SrO 0~12%, Na 2 O 6~15%, K 2 O 2 ~15%, Li 2 O 2~15%, 0~10% ZnO, TiO 2 0~0.5%, The rare earth element is 0.01% or less, and the value of Li 2 O / (Na 2 O + K 2 O) is 0.5 to 1.3 in molar ratio , (MgO + CaO + SrO + BaO) / (Li 2 O + Na 2 O + K 2 O) The value is in the range of 0.4 or less .

本発明のガラスは、クラックの発生率が低く、ガラス製品の割れや破壊が起こりにくい。また液相温度を低く設定することによって優れた成形性を得ることができ、安価に多量生産を行うことができる。また歪点を高く設定することで、高い耐熱性を得ることが可能になる。それゆえ本発明のガラスは、窓ガラス、食器、ディスプレイ用基板、ハードディスク基板等の各種の電子部品用途等への応用が期待できる。   The glass of the present invention has a low occurrence rate of cracks, and it is difficult for glass products to break or break. Further, by setting the liquidus temperature low, excellent moldability can be obtained, and mass production can be performed at low cost. Moreover, high heat resistance can be obtained by setting the strain point high. Therefore, the glass of the present invention can be expected to be applied to various electronic parts such as window glass, tableware, display substrates, and hard disk substrates.

本発明においてガラス組成を上記のように限定した理由を以下に述べる。なお以下の説明では、特に断りがない限り“％”は“質量％”を意味する。   The reason why the glass composition is limited as described above in the present invention will be described below. In the following description, “%” means “mass%” unless otherwise specified.

ＳｉＯ2の含有量は５５〜７２％である。ＳｉＯ2の含有量が多くなると、ガラスの溶融、成形が難しくなったり、熱膨張係数が小さくなりすぎて周辺材料との整合性が取り難くなったりするので７２％以下、７０％以下、特に６９％以下であることが望ましい。一方、含有量が少なくなると、熱膨張係数が大きくなりガラスの耐熱衝撃性が低下する。またガラス化しづらく失透性が悪化するため、５５％以上、５８％以上、特に６０％以上であることが望ましい。 The content of SiO 2 is 55 to 72%. When the content of SiO 2 increases, it becomes difficult to melt and mold the glass, or the coefficient of thermal expansion becomes too small to make it difficult to match the surrounding materials. Therefore, it is 72% or less, 70% or less, especially 69. % Or less is desirable. On the other hand, when the content decreases, the thermal expansion coefficient increases and the thermal shock resistance of the glass decreases. Moreover, since it is hard to vitrify and devitrification deteriorates, it is desirable that it is 55% or more, 58% or more, especially 60% or more.

Ａｌ２Ｏ３の含有量は１２〜２０％である。Ａｌ２Ｏ３の含有量が多くなると、ガラスに失透結晶が析出しやすくなったり、ガラスの高温粘度が高くなって溶融、成形が難しくなったり、熱膨張係数が小さくなり周辺材料との整合性が取り難くなるので、１８％以下、特に１６％以下であることが望ましい。一方ガラスの歪点を高めるという観点からは１２％以上含有することが望ましい。 The content of Al 2 O 3 is 12 to 20%. When the content of Al 2 O 3 increases, devitrification crystals tend to precipitate on the glass, the high-temperature viscosity of the glass increases, making it difficult to melt and mold, and the coefficient of thermal expansion decreases to match the surrounding materials. Therefore, it is desirable that it is 18% or less, particularly 16% or less. On the other hand, from the viewpoint of enhancing the strain point of the glass desirably contains more than 1 2%.

Ｂ２Ｏ３の含有量は０〜３％である。Ｂ２Ｏ３の含有量が高くなると歪点が低下するため、３％以下、２．５％以下、特に２％以下であることが望ましい。一方ガラスの密度や高温粘度を低下させるために０．１％以上、０．５％以上、１％以上含有させても良い。 The content of B 2 O 3 is 0 to 3 %. When the content of B 2 O 3 is increased, the strain point is lowered. Therefore, the content is preferably 3 % or less, 2.5% or less, particularly 2% or less. On the other hand, 0.1% or more, 0.5% or more, 1% or more may be contained in order to reduce the density or high temperature viscosity of the glass.

ＺｎＯの含有量は０〜１０％である。ＺｎＯの含有量が多くなると熱膨張係数が高くなる。またガラスが失透しやすくなったり、クラック発生率が高くなったりする傾向にあるため８％以下、５％以下、３％以下、特に２．５％以下であることが望ましい。   The content of ZnO is 0 to 10%. As the ZnO content increases, the thermal expansion coefficient increases. Further, since the glass tends to be devitrified and the crack generation rate tends to increase, it is preferably 8% or less, 5% or less, 3% or less, particularly 2.5% or less.

ＭｇＯは、ガラスの高温粘度を低下させて溶融性や成形性を高める成分である。その含有量は０〜１２％である。ＭｇＯの含有量が多くなると、密度や熱膨張係数が高くなったり、ガラスが失透しやすくなったりする傾向にあるため６．５％以下、５％以下、特に４％以下が望ましい。   MgO is a component that lowers the high-temperature viscosity of glass and improves meltability and formability. Its content is 0-12%. If the content of MgO increases, the density and thermal expansion coefficient tend to increase, and the glass tends to be devitrified. Therefore, it is preferably 6.5% or less, 5% or less, particularly 4% or less.

ＣａＯは、ガラスの高温粘度を低下させて溶融性や成形性を高める成分である。その含有量は０〜１２％である。ＣａＯの含有量が多くなると、密度や熱膨張係数が高くなる傾向にあるため９％以下、５％以下、３％以下、特に２．５％以下であることが望ましい。   CaO is a component that lowers the high-temperature viscosity of the glass and improves the meltability and moldability. Its content is 0-12%. When the content of CaO increases, the density and the coefficient of thermal expansion tend to increase. Therefore, the content is preferably 9% or less, 5% or less, 3% or less, particularly 2.5% or less.

ＳｒＯは、ガラスの高温粘度を低下させて溶融性や成形性を高める成分である。その含有量は０〜１２％である。ＳｒＯの含有量が多くなると、密度や熱膨張係数が高くなる傾向にあるため８％以下、５％以下、３％以下、特に２．５％以下であることが望ましい。   SrO is a component that lowers the high-temperature viscosity of the glass and improves meltability and formability. Its content is 0-12%. When the SrO content increases, the density and the thermal expansion coefficient tend to increase. Therefore, it is desirable that the SrO content is 8% or less, 5% or less, 3% or less, particularly 2.5% or less.

ＢａＯは、ガラスの高温粘度を低下させて溶融性や成形性を高める成分である。その含有量は０〜１２％である。ＢａＯの含有量が多くなると、密度や熱膨張係数が高くなる傾向にあるため１０％以下、５％以下、３％以下、特に２．５％以下であることが望ましい。   BaO is a component that lowers the high-temperature viscosity of the glass and improves meltability and moldability. Its content is 0-12%. When the content of BaO increases, the density and the coefficient of thermal expansion tend to increase. Therefore, the content is preferably 10% or less, 5% or less, 3% or less, particularly 2.5% or less.

またＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの合量が多くなると密度や熱膨張係数が高くなったり失透性が悪化したりする傾向がある。そのためこれらの成分の合量は１０％以下、９％以下、５％以下、特に４％以下であることが好ましい。   Moreover, when the total amount of MgO + CaO + SrO + BaO increases, the density and thermal expansion coefficient tend to increase or the devitrification tends to deteriorate. Therefore, the total amount of these components is preferably 10% or less, 9% or less, 5% or less, particularly 4% or less.

Ｎａ2Ｏの含有量は６〜１５％である。Ｎａ2Ｏはガラスの高温粘度を低下させて溶融性や成形性を高めたり、クラック発生率を低減させたりする効果がある。また失透性を改善する成分でもあり、６％以上、７％以上、特に８％以上含有させることが望ましい。しかしＮａ2Ｏの含有量が多くなると熱膨張係数が大きくなりすぎて、ガラスの耐熱衝撃性が低下したり、周辺材料の熱膨張係数と整合し難くなったりする。また歪点も低下する傾向にある。更に１５％以上となると失透性が悪化する傾向にあるため１２％以下、１１％以下、特に１０％以下であることが好ましい。 The content of Na 2 O is 6 to 15%. Na 2 O has the effect of reducing the high temperature viscosity of the glass to improve the meltability and formability, and to reduce the crack generation rate. It is also a component that improves devitrification, and it is desirable to contain 6% or more, 7% or more, and particularly 8% or more. However, when the content of Na 2 O increases, the thermal expansion coefficient becomes too large, and the thermal shock resistance of the glass is lowered, or it becomes difficult to match the thermal expansion coefficient of the surrounding materials. Also, the strain point tends to decrease. Further, when it is 15% or more, devitrification tends to deteriorate, so it is preferably 12% or less, 11% or less, and particularly preferably 10% or less.

Ｋ２Ｏの含有量は２〜１５％である。Ｋ２Ｏはガラスの高温粘度を低下させて溶融性や成形性を高めたり、クラック発生率を低減させたりする効果がある。また失透性を改善する成分でもあり、２％以上含有させることが好ましい。しかしＫ２Ｏの含有量が多くなると熱膨張係数が大きくなりすぎて、ガラスの耐熱衝撃性が低下したり、周辺材料の熱膨張係数と整合し難くなったりする。また歪点も低下する傾向にある。更に１５％以上となると失透性が悪化する傾向にあるため１３％以下、１０％以下、８％以下、特に６％以下であることが好ましい。 The content of K 2 O is 2 to 15%. K 2 O has the effect of reducing the high temperature viscosity of the glass to improve the meltability and formability, and to reduce the crack generation rate. Moreover, it is also a component which improves devitrification, and it is preferable to make it contain 2 % or more. However, when the content of K 2 O increases, the thermal expansion coefficient becomes too large, and the thermal shock resistance of the glass is lowered, or it becomes difficult to match the thermal expansion coefficient of the surrounding materials. Also, the strain point tends to decrease. Further, when it is 15% or more, devitrification tends to deteriorate, so it is preferably 13% or less, 10% or less, 8% or less, and particularly preferably 6% or less.

Ｌｉ2Ｏの含有量は２〜１５％である。Ｌｉ2Ｏの含有量が多くなりすぎると、ガラスが失透しやすくなる上、熱膨張係数が大きくなりすぎて、ガラスの耐熱衝撃性が低下したり、周辺材料の熱膨張係数と整合し難くなったりする。また歪点も低下する傾向にあるため、１５％以下、１３％以下、１０％以下、８％以下、特に６％以下であることが望ましい。その一方で、ガラスの高温粘度を低下させて溶融性や成形性を高める成分である。また、クラック発生率を低減させる効果が大きいために２％以上、特に２．５％以上含有させることが好ましい。 The content of Li 2 O is 2 to 15%. If the Li 2 O content is too high, the glass tends to devitrify, the thermal expansion coefficient becomes too large, and the thermal shock resistance of the glass is lowered, or it is difficult to match the thermal expansion coefficient of the surrounding materials. It becomes. Further, since the strain point tends to decrease, it is desirable that the strain point is 15% or less, 13% or less, 10% or less, 8% or less, and particularly 6% or less. On the other hand, it is a component that lowers the high-temperature viscosity of glass and improves meltability and moldability. Moreover, since the effect of reducing the crack generation rate is great, it is preferable to contain 2% or more, particularly 2.5% or more.

Ｎａ2Ｏ＋Ｋ2Ｏ＋Ｌｉ2Ｏの合量が多くなりすぎるとガラスが失透しやすくなる上、熱膨張係数が大きくなりすぎて、ガラスの耐熱衝撃性が低下したり、周辺材料の熱膨張係数と整合し難くなったりする。また歪点も低下する傾向にある。それゆえこれらの成分の合量は、２０％以下、１８％以下、特に１６％以下であることが望ましい。一方Ｎａ2Ｏ＋Ｋ2Ｏ＋Ｌｉ2Ｏの合量が少なすぎると溶融性が悪化し、クラック発生率が高くなる。それゆえ合量で０．１％以上、３％以上、５％以上、特に９％以上であることが望ましい。 If the total amount of Na 2 O + K 2 O + Li 2 O is too large, the glass tends to devitrify, the thermal expansion coefficient becomes too large, the thermal shock resistance of the glass decreases, and the thermal expansion coefficient of the surrounding materials It becomes difficult to align. Also, the strain point tends to decrease. Therefore, the total amount of these components is desirably 20% or less, 18% or less, and particularly 16% or less. On the other hand, if the total amount of Na 2 O + K 2 O + Li 2 O is too small, the meltability deteriorates and the crack generation rate increases. Therefore, the total amount is preferably 0.1% or more, 3% or more, 5% or more, particularly 9% or more.

クラック発生率を低減するためには、アルカリ成分の含有に加え、それらの割合を適切な範囲に調整することが非常に重要である。具体的にはモル比でＬｉ２Ｏ／（Ｎａ２Ｏ＋Ｋ２Ｏ）の値が０．５以上とすることが重要であり、特に０．６以上とすることが望ましい。ただしこの値が大きくなりすぎるとＬｉ２Ｏに起因する失透が起こりやすくなる。それゆえＬｉ２Ｏ／（Ｎａ２Ｏ＋Ｋ２Ｏ）の値の上限は１．３以下、特に１．１以下であることが望ましい。 In order to reduce the crack generation rate, it is very important to adjust the ratio of these components to an appropriate range in addition to the inclusion of alkali components. Specifically it is important to Li 2 O / (Na 2 O + K 2 O) value of 0.5 or more in molar ratio, it is desirable that the Japanese 0.6 or more. However, if this value becomes too large, devitrification due to Li 2 O tends to occur. Therefore, the upper limit of the value of Li 2 O / (Na 2 O + K 2 O) is 1 . It is desirable that it is 3 or less, especially 1.1 or less.

また本発明においては、モル比で（Ｌｉ2Ｏ＋Ａｌ2Ｏ3）／（Ｎａ2Ｏ＋Ｋ2Ｏ）の値を４以下に設定することが失透性を改善する上で重要である。（Ｌｉ2Ｏ＋Ａｌ2Ｏ3）／（Ｎａ2Ｏ＋Ｋ2Ｏ）の値は３．０以下、２．５以下、特に１．９以下とすることが望ましい。ただし（Ｌｉ2Ｏ＋Ａｌ2Ｏ3）／（Ｎａ2Ｏ＋Ｋ2Ｏ）の値が小さくなりすぎると失透性や溶融性の悪化、及びクラック発生率の上昇が懸念されるため、０．５以上、０．７以上、特に０．９以上であることが好ましい。 In the present invention, it is important to improve devitrification by setting the value of (Li 2 O + Al 2 O 3 ) / (Na 2 O + K 2 O) to 4 or less in terms of molar ratio. The value of (Li 2 O + Al 2 O 3 ) / (Na 2 O + K 2 O) is preferably 3.0 or less, 2.5 or less, particularly 1.9 or less. However, if the value of (Li 2 O + Al 2 O 3 ) / (Na 2 O + K 2 O) is too small, devitrification and meltability are deteriorated, and an increase in crack generation rate is concerned. It is preferably 0.7 or more, particularly 0.9 or more.

更に、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯの合量をＮａ２Ｏ＋Ｋ２Ｏ＋Ｌｉ２Ｏの合量で除した値が大きくなるとクラック発生率が高くなったり失透性が悪化したりする傾向が現れる。それゆえこの値が０．４以下、特に０．３以下であることが望ましい。 Furthermore, when the value obtained by dividing the total amount of MgO + CaO + SrO + BaO by the total amount of Na 2 O + K 2 O + Li 2 O increases, the tendency for crack generation to increase or devitrification to deteriorate appears. Therefore this value is 0 . It is desirable that it is 4 or less, particularly 0.3 or less.

本発明におけるガラスにおいてＣｏ、Ｎｉ等のガラスを強く着色するような遷移金属元素は、透過率を低下させるため０．５％以下、０．１％、特に０．０５％以下となるよう、原料あるいはカレットの使用量を調整することが望ましい。   In the glass according to the present invention, the transition metal element that strongly colors the glass such as Co and Ni is 0.5% or less, 0.1%, particularly 0.05% or less in order to reduce the transmittance. Alternatively, it is desirable to adjust the amount of cullet used.

Ｓｃ、Ｙ、Ｌａ等の希土類元素やＴｉＯ2は失透性を悪化させるため０．５％以下、０．１％以下、特に０．０１％以下となるよう、原料あるいはカレットの使用量を調整することが好ましいが、それらの元素を含有しないことが理想である。
また本発明のガラスの特性を大きく損なわない範囲で他の成分を添加することが可能である。例えば清澄剤としてＳＯ3、Ｓｂ2Ｏ3、Ｓｂ2Ｏ5及びＳｎＯ2の群から選択された一種または二種以上を０〜３％含有させてもよい。 Since the rare earth elements such as Sc, Y, La and TiO 2 deteriorate the devitrification property, the amount of raw materials or cullet is adjusted so that it is 0.5% or less, 0.1% or less, particularly 0.01% or less. Ideally, it is ideal that they do not contain these elements.
Moreover, it is possible to add another component in the range which does not impair the characteristic of the glass of this invention largely. For example as a fining agent SO 3, Sb 2 O 3, Sb 2 O 5 and SnO 2 selected one or two or more from the group may be contained 0-3%.

以上の組成を有する本発明のガラスは、クラック発生率の低いものであるが、特にクラック発生率が６０％以下、５０％以下、４０％以下、３０％以下、特に２０％以下となるようにすることが望ましい。尚、本発明におけるクラック発生率とは、湿度３０％、温度２５℃に保持された恒温恒湿槽内において、荷重５００ｇに設定したビッカース圧子をガラス表面（光学研磨面）に１５秒間打ち込み、その１５秒後に圧痕の４隅から発生するクラックの数をカウント（１つの圧痕につき最大４とする）する。２０回圧子を打ち込み、総クラック発生数／８０×１００とするものである。   The glass of the present invention having the above composition has a low crack generation rate, and particularly the crack generation rate is 60% or less, 50% or less, 40% or less, 30% or less, particularly 20% or less. It is desirable to do. In the present invention, the crack occurrence rate means that a Vickers indenter set at a load of 500 g is driven into the glass surface (optical polishing surface) for 15 seconds in a constant temperature and humidity chamber maintained at a humidity of 30% and a temperature of 25 ° C. The number of cracks generated from the four corners of the indentation after 15 seconds is counted (maximum is 4 for each indentation). The indenter is driven 20 times to make the total number of cracks generated / 80 × 100.

また成形中にガラスが失透しないようガラスの液相温度を１０５０℃以下、１０００℃以下、特に９６０℃以下に調整することが望ましく、液相温度における粘度は１０4.0ｄＰａ・ｓ以上、１０4.3ｄＰａ・ｓ以上、１０4.5ｄＰａ・ｓ以上、１０4.7ｄＰａ・ｓ以上、特に１０5.0ｄＰａ・ｓ以上に調整することが望ましい。 Further, it is desirable to adjust the liquid phase temperature of the glass to 1050 ° C. or lower, 1000 ° C. or lower, particularly 960 ° C. or lower so that the glass does not devitrify during molding, and the viscosity at the liquid phase temperature is 10 4.0 dPa · s or higher and 10 4.3. It is desirable to adjust to dPa · s or more, 10 4.5 dPa · s or more, 104.7 dPa · s or more, particularly 10 5.0 dPa · s or more.

またＰＤＰ等のディスプレイ用基板での用途を考えた場合、他の部材の熱膨張係数との整合性から、熱膨張係数は３０〜３８０℃の温度範囲において５０×１０-7／℃〜９５×１０-7／℃、６０×１０-7／℃〜９０×１０-7／℃、７０×１０-7／℃〜９０×１０-7／℃、８０×１０-7／℃〜９０×１０-7／℃、８２×１０-7／℃〜８８×１０-7／℃となるよう調整することが望ましい。 Further, when considering use with a display substrate such as a PDP, the thermal expansion coefficient is 50 × 10 −7 / ° C. to 95 × in the temperature range of 30 to 380 ° C. from the consistency with the thermal expansion coefficient of other members. 10 −7 / ° C., 60 × 10 −7 / ° C. to 90 × 10 −7 / ° C., 70 × 10 −7 / ° C. to 90 × 10 −7 / ° C., 80 × 10 −7 / ° C. to 90 × 10 − 7 / ° C., it is desirable to adjust 82 × 10 -7 / ℃ ~88 × 10 -7 / ℃ become so.

また耐熱性が低いとガラスが熱間にさらされた際に、熱収縮と呼ばれる微小な寸法収縮が起こり、特にディスプレイ用の基板として使用する際に寸法ずれ不良を起こす恐れがある。従ってこれらの用途では高い耐熱性が必要であり、具体的には、耐熱性の指標である歪点温度が４５０℃以上、４６０℃以上、特に４７０℃以上となるように調整することが望ましい。   In addition, when the heat resistance is low, when the glass is exposed to heat, minute dimensional shrinkage called heat shrinkage occurs, and there is a possibility of causing a dimensional deviation defect particularly when used as a substrate for a display. Therefore, high heat resistance is required for these applications, and specifically, it is desirable to adjust the strain point temperature, which is an index of heat resistance, to be 450 ° C. or higher, 460 ° C. or higher, particularly 470 ° C. or higher.

またガラスの高温粘度が低いと製造設備への負担も小さく泡品位も良くなりやすいので、安価に製造するという観点からガラスの高温粘度は低いほうが良い。具体的には１０2.5ｄＰａ・ｓにおける温度が１６００℃以下、１５５０℃以下、特に１５００℃以下となるように調整することが望ましい。 In addition, if the high-temperature viscosity of the glass is low, the burden on the production equipment is small and the bubble quality is likely to be improved. Specifically, it is desirable to adjust so that the temperature at 10 2.5 dPa · s is 1600 ° C. or lower, 1550 ° C. or lower, particularly 1500 ° C. or lower.

本発明の実施例及び参考例を以下に記載する。Ｎｏ．１、Ｎｏ．２、Ｎｏ．４、Ｎｏ．６〜Ｎｏ．１０及びＮｏ．１３は参考例である。 Examples and reference examples of the present invention will be described below. No. 1, no. 2, no. 4, no. 6-No. 10 and no. Reference numeral 13 is a reference example.

まず、表１〜４の組成となるようにガラス原料を調合し、白金ポットを用いて１６００℃で４時間溶融した。その後、溶融ガラスをカーボン板の上に流し出して板状に成形した。   First, the glass raw material was prepared so that it might become a composition of Tables 1-4, and it melted at 1600 degreeC for 4 hours using the platinum pot. Thereafter, the molten glass was poured onto a carbon plate and formed into a plate shape.

表中の密度は、周知のアルキメデス法によって測定した。また、歪点は、ＡＳＴＭ Ｃ３３６−７１の方法に基づいて測定し、この値が高いほど、ガラスの耐熱性が高くなる。軟化点は ＡＳＴＭ Ｃ３３８−９３の方法に基づいて測定をおこなった。また粘度１０4.0、１０3.0、１０2.5のｄＰａ・ｓにおける温度は、白金球引き上げ法で測定した。この温度が低いほど、溶融性に優れていることになる。また、液相温度の測定は、ガラスを粉砕し、標準篩３０メッシュ（５００μｍ）を通過し、５０メッシュ（３００μｍ）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。液相粘度は液相温度における各ガラスの粘度を示す。液相粘度が高く、液相温度が低いほど、耐失透性に優れ、成形性に優れている。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。 The density in the table was measured by the well-known Archimedes method. Moreover, a strain point is measured based on the method of ASTM C336-71, and the higher the value, the higher the heat resistance of the glass. The softening point was measured based on the method of ASTM C338-93. The viscosity of 10 4.0, 10 3.0, 10 2.5 Temperature in dPa · s of was measured by a platinum ball pulling method. The lower this temperature, the better the meltability. The liquid phase temperature is measured by crushing the glass, passing through a standard sieve 30 mesh (500 μm), putting the glass powder remaining on 50 mesh (300 μm) into a platinum boat, and holding it in a temperature gradient furnace for 24 hours. The temperature at which crystals are deposited is measured. The liquid phase viscosity indicates the viscosity of each glass at the liquid phase temperature. The higher the liquidus viscosity and the lower the liquidus temperature, the better the devitrification resistance and the moldability. The thermal expansion coefficient is obtained by measuring an average thermal expansion coefficient at 30 to 380 ° C. using a dilatometer.

Figure 0004790300
Figure 0004790300

Figure 0004790300
Figure 0004790300

Figure 0004790300
Figure 0004790300

Figure 0004790300
Figure 0004790300

表から明らかなように、本発明の実施例は、いずれもクラック発生率が６０％以下と低く、破壊のオリジンとなりうる致命的なクラックが発生しにくい。また熱膨張係数が８１〜９０×１０-7／℃、歪点が４５０℃以上、液相温度が９６０℃以下であり、液相粘度も１０5.1ｄＰａ・ｓ以上と高いので、ディスプレイ用途の使用においては周辺部材との熱膨張係数の整合性がよく、また安価に製造できる。 As is clear from the table, all the examples of the present invention have a low crack generation rate of 60% or less, and it is difficult for fatal cracks that can be the origin of destruction to occur. In addition, the coefficient of thermal expansion is 81 to 90 × 10 −7 / ° C., the strain point is 450 ° C. or higher, the liquidus temperature is 960 ° C. or lower, and the liquid phase viscosity is 10 5.1 dPa · s or higher. Can be manufactured at low cost with good consistency of thermal expansion coefficient with peripheral members.

本発明のガラスは、高い機械的強度が要求される用途に適用可能であり、例えば窓ガラス、食器、ディスプレイ用基板への応用が期待できる。   The glass of the present invention can be applied to applications requiring high mechanical strength, and can be expected to be applied to, for example, window glass, tableware, and display substrates.

Claims (7)

質量百分率で、ＳｉＯ２ ５５〜７２％、Ａｌ２Ｏ３ １２〜２０％、Ｂ２Ｏ３ ０〜３％、ＭｇＯ ０〜１２％、ＣａＯ ０〜１２％、ＢａＯ ０〜１２％、ＳｒＯ ０〜１２％、Ｎａ２Ｏ ６〜１５％、Ｋ２Ｏ ２〜１５％、Ｌｉ２Ｏ ２〜１５％、ＺｎＯ ０〜１０％、ＴｉＯ ２ ０〜０．５％、希土類元素 ０．０１％以下であり、且つＬｉ２Ｏ／（Ｎａ２Ｏ＋Ｋ２Ｏ）の値がモル比で０．５〜１．３、（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）／（Ｌｉ ２ Ｏ＋Ｎａ ２ Ｏ＋Ｋ ２ Ｏ）の値が０．４以下の範囲にあることを特徴とするガラス。 By mass percentage, SiO 2 55~72%, Al 2 O 3 12 ~20%, B 2 O 3 0~ 3%, 0~12% MgO, CaO 0~12%, BaO 0~12%, SrO 0~ 12%, Na 2 O 6~15% , K 2 O 2 ~15%, Li 2 O 2~15%, 0~10% ZnO, TiO 2 0~0.5%, below 0.01% rare earth elements There, and in Li 2 O / (Na 2 O + K 2 O) values the molar ratio of 0.5~1.3, (MgO + CaO + SrO + BaO) / (Li 2 O + Na 2 O + K 2 O) range value is 0.4 or less in the Glass characterized by that. 質量百分率で、ＭｇＯ ０〜４％、ＣａＯ ０〜２．５％、ＢａＯ ０〜２．５％、ＳｒＯ ０〜２．５％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ ０〜４％であることを特徴とする請求項１に記載のガラス。   The mass percentage is MgO 0-4%, CaO 0-2.5%, BaO 0-2.5%, SrO 0-2.5%, MgO + CaO + SrO + BaO 0-4%. The glass described. クラック発生率が６０％以下であることを特徴とする請求項１または２に記載のガラス。 The glass according to claim 1 or 2 , wherein a crack occurrence rate is 60% or less. ３０〜３８０℃における熱膨張係数が５０×１０−７／℃〜９５×１０−７／℃であることを特徴とする請求項１〜３の何れか１項に記載のガラス。 30 to 380 glass according to any one of claim 1 to 3, the thermal expansion coefficient at ° C. is characterized in that it is a 50 × 10 -7 / ℃ ~95 × 10 -7 / ℃. 歪点が４５０℃以上であることを特徴とする請求項１〜４の何れか１項に記載のガラス。 The glass according to any one of claims 1 to 4 , wherein the strain point is 450 ° C or higher. 液相温度が１０５０℃以下であることを特徴とする請求項１〜５の何れか１項に記載のガラス。 Liquid phase temperature is 1050 degrees C or less, The glass of any one of Claims 1-5 characterized by the above-mentioned. 高温粘度１０２．５における温度が１６００℃以下であることを特徴とする請求項１〜６の何れか１項に記載のガラス。 Glass according to any one of claim 1 to 6, the temperature in the high temperature viscosity of 10 2.5 is characterized in that it is 1600 ° C. or less.
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