JP6596894B2 - Tempered glass plate and manufacturing method thereof - Google Patents

Tempered glass plate and manufacturing method thereof Download PDF

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JP6596894B2
JP6596894B2 JP2015081311A JP2015081311A JP6596894B2 JP 6596894 B2 JP6596894 B2 JP 6596894B2 JP 2015081311 A JP2015081311 A JP 2015081311A JP 2015081311 A JP2015081311 A JP 2015081311A JP 6596894 B2 JP6596894 B2 JP 6596894B2
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tempered glass
glass plate
compressive stress
mpa
thickness
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JP2016000682A (en
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清貴 木下
睦 深田
隼人 奥
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Priority to TW104116096A priority patent/TW201600475A/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B27/00—Tempering or quenching glass products
    • 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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass (AREA)

Description

本発明は、強化ガラス板及びその製造方法に関する。   The present invention relates to a tempered glass sheet and a method for producing the same.

従来、スマートフォンやタブレットパーソナルコンピューター（タブレットＰＣ）等のディスプレイの前面板として、強化ガラス板が用いられている。ディスプレイの前面板として用いられる強化ガラス板には、強度が高いことが求められている。例えば、強化ガラス板の表層に設けられた圧縮応力層を貫通して内部の引張応力層に至るクラック（破壊起点）が形成されると、引張応力層の引張応力によってクラックが進展する。それによって強化ガラス板が破断する場合がある。これに鑑み、特許文献１では、サンドペーパー落球試験において、破壊時の平均落球高さが１７ｃｍ以上である強化ガラス板をカバーガラスとして用いることが提案されている。特許文献１に記載の強化ガラス板では、落下衝撃により発生するスロークラックに起因する破壊が生じにくい。   Conventionally, a tempered glass plate is used as a front plate of a display such as a smartphone or a tablet personal computer (tablet PC). A tempered glass plate used as a front plate of a display is required to have high strength. For example, when a crack (breaking origin) that penetrates the compressive stress layer provided on the surface layer of the tempered glass plate and reaches the internal tensile stress layer is formed, the crack develops due to the tensile stress of the tensile stress layer. Thereby, the tempered glass plate may break. In view of this, Patent Document 1 proposes to use a tempered glass plate having an average falling ball height of 17 cm or more as a cover glass in a sandpaper falling ball test. In the tempered glass plate described in Patent Document 1, breakage due to slow cracks generated by a drop impact is unlikely to occur.

国際公開第２０１３／０５１５１４号公報International Publication No. 2013/051514

ディスプレイの前面板として用いられる強化ガラス板には、耐衝撃性が優れていることが好ましいのみならず、鋭利な部材により引っ掻かれたときの加傷強度が高いことがさらに好ましいことが分かった。   It was found that the tempered glass plate used as the front plate of the display not only has excellent impact resistance, but also preferably has a high scratch strength when scratched by a sharp member. .

本発明の主な目的は、引っ掻き等に対する加傷強度が高い強化ガラス板を提供することにある。   A main object of the present invention is to provide a tempered glass sheet having high scratch strength against scratches and the like.

本発明に係る強化ガラス板は、圧縮応力を有する表層と、引張応力を有する内層とを有する強化ガラス板である。本発明に係る強化ガラス板の厚み（ｔ）は、０．４ｍｍ以下である。本発明に係る強化ガラス板において、内層における引張応力（ＣＴ）が、ＣＴ≦１９５０ｔ２−１４７０ｔ＋３３６を満たす。 The tempered glass sheet according to the present invention is a tempered glass sheet having a surface layer having a compressive stress and an inner layer having a tensile stress. The tempered glass sheet according to the present invention has a thickness (t) of 0.4 mm or less. In the tempered glass sheet according to the present invention, the tensile stress (CT) in the inner layer satisfies CT ≦ 1950t 2 −1470t + 336.

本発明に係る強化ガラス板において、圧縮応力を有する表層の深さである圧縮応力深さ（ＤＯＬ）が１０μｍ以上であることが好ましい。この場合、尖鋭な突起物が強化ガラス板に食い込んだ場合においても、クラックが生じにくい。圧縮応力深さ（ＤＯＬ）は、３５μｍ以下であることが好ましい。   In the tempered glass sheet according to the present invention, the compressive stress depth (DOL), which is the depth of the surface layer having compressive stress, is preferably 10 μm or more. In this case, even when a sharp protrusion bites into the tempered glass plate, cracks are unlikely to occur. The compressive stress depth (DOL) is preferably 35 μm or less.

本発明に係る強化ガラス板において、表層の圧縮応力（ＣＳ）が６００ＭＰａ以上であることが好ましい。そうすることにより、強化ガラス板の曲げ強度を向上することができる。圧縮応力（ＣＳ）は、２０００ＭＰａ以下であることが好ましい。圧縮応力（ＣＳ）を２０００ＭＰａ以下にすることで、高い加傷強度を維持できる程度に引張応力（ＣＴ）を保ちつつ、最低限の圧縮応力深さ（ＤＯＬ）を確保することができる。   In the tempered glass sheet according to the present invention, the compressive stress (CS) of the surface layer is preferably 600 MPa or more. By doing so, the bending strength of a tempered glass board can be improved. The compressive stress (CS) is preferably 2000 MPa or less. By setting the compressive stress (CS) to 2000 MPa or less, the minimum compressive stress depth (DOL) can be secured while maintaining the tensile stress (CT) to such an extent that high scratch strength can be maintained.

本発明に係る強化ガラス板において、厚み（ｔ）が０．２ｍｍ以上であることが好ましい。   In the tempered glass sheet according to the present invention, the thickness (t) is preferably 0.2 mm or more.

本発明に係る強化ガラス板は、ガラス組成として、質量％で、ＳｉＯ２を５０％〜８０％、Ａｌ２Ｏ３を５％〜３５％、Ｂａ２Ｏ３を０％〜１５％、Ｎａ２Ｏを１％〜２０％、Ｋ２Ｏを０％〜１０％及びＭｇＯを０％〜１０％含有することが好ましい。 The tempered glass plate according to the present invention has, as a glass composition, mass%, SiO 2 50% to 80%, Al 2 O 3 5% to 35%, Ba 2 O 3 0% to 15%, Na 2. It is preferable to contain 1% to 20% of O, 0% to 10% of K 2 O, and 0% to 10% of MgO.

本発明に係る強化ガラス板の製造方法は、厚み（ｔ）が０．４ｍｍ以下のガラス板を化学強化処理して表層に圧縮応力付与する一方、内層に引張応力を付与する強化ガラス板の製造方法である。本発明に係る強化ガラス板の製造方法では、内層における引張応力（ＣＴ）が、ＣＴ≦１９５０ｔ２−１４７０ｔ＋３３６を満たすように化学強化処理を行う。 The method for producing a tempered glass plate according to the present invention is a method for producing a tempered glass plate in which a compressive stress is applied to the surface layer by chemically strengthening a glass plate having a thickness (t) of 0.4 mm or less and a tensile stress is applied to the inner layer. Is the method. In the method for producing a tempered glass sheet according to the present invention, the chemical strengthening treatment is performed so that the tensile stress (CT) in the inner layer satisfies CT ≦ 1950t 2 −1470t + 336.

本発明によれば、引っ掻き等に対する加傷強度が高い強化ガラス板を提供することができる。   According to the present invention, it is possible to provide a tempered glass plate having high scratch strength against scratches and the like.

サンプル１〜１０における引張応力（ＣＴ）と限界荷重（ＬＬ）との関係を表すグラフである。It is a graph showing the relationship between the tensile stress (CT) and the limit load (LL) in samples 1 to 10. サンプル１〜１０のそれぞれの引張応力（ＣＴ）に対する限界荷重（ＬＬ）の傾き（α）と、サンプル１〜１０の厚み（ｔ）との関係を表すグラフである。It is a graph showing the relationship between the inclination ((alpha)) of the limit load (LL) with respect to each tensile stress (CT) of samples 1-10, and the thickness (t) of samples 1-10. 限界荷重（ＬＬ）が６Ｎとなるときの強化ガラス板の厚み（ｔ）と引張応力（ＣＴ）との関係を表すグラフである。It is a graph showing the relationship between the thickness (t) and tensile stress (CT) of a tempered glass board when a limit load (LL) will be 6N. クラックレジスタンス（ＣＲ）を表す模式図である。It is a schematic diagram showing crack resistance (CR). 実験例２における圧縮応力深さ（ＤＯＬ）とクラックレジスタンス（ＣＲ）との関係を示すグラフである。It is a graph which shows the relationship between the compressive-stress depth (DOL) in Example 2, and a crack resistance (CR).

以下、本発明を実施した好ましい形態の一例について説明する。但し、下記の実施形態は、単なる例示である。本発明は、下記の実施形態に何ら限定されない。   Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiment is merely an example. The present invention is not limited to the following embodiments.

本実施形態の強化ガラス板は、例えば、スマートフォンやタブレットパーソナルコンピューター（タブレットＰＣ）、ノート型パソコン等のディスプレイの前面板として好適に用いられる。   The tempered glass plate of the present embodiment is suitably used as a front plate of a display such as a smartphone, a tablet personal computer (tablet PC), or a notebook computer.

本実施形態の強化ガラス板は、少なくとも一方の主面に、圧縮応力層を有している。本実施形態の強化ガラス板は、両方の主面に、圧縮応力層を有していることが好ましい。   The tempered glass sheet of this embodiment has a compressive stress layer on at least one main surface. The tempered glass sheet of this embodiment preferably has a compressive stress layer on both main surfaces.

圧縮応力層は、例えば、イオン交換による化学強化により形成されたものであってもよいし、風冷等により急冷することにより形成されたものであってもよい。本実施形態では、圧縮応力層が、イオン交換による化学強化により形成されたものである例について説明する。   The compressive stress layer may be formed, for example, by chemical strengthening by ion exchange, or may be formed by quenching by air cooling or the like. In the present embodiment, an example in which the compressive stress layer is formed by chemical strengthening by ion exchange will be described.

本実施形態に係る強化ガラス板は、例えば、ガラス組成として、質量％で、ＳｉＯ２を５０％〜８０％、Ａｌ２Ｏ３を５％〜３５％、Ｂ２Ｏ３ ０〜１５％、Ｎａ２Ｏを１％〜２０％、Ｋ２Ｏを０％〜１０％及びＭｇＯを０％〜１０％を含有することが好ましい。このような組成を有する強化ガラス板であれば、化学強化処理によってディスプレイ用途等に好適な強化特性を容易に得られる。なお、上記組成は、一例であり、任意の組成のガラス板を用いて本発明の強化ガラス板を構成してよい。 The tempered glass plate according to the present embodiment is, for example, in terms of glass composition, mass%, SiO 2 50% to 80%, Al 2 O 3 5% to 35%, B 2 O 3 0-15%, Na 1% to 20% of the 2 O, it is preferable that the K 2 O containing 10% 0% 0% to 10% and MgO. If it is the tempered glass board which has such a composition, the tempering characteristic suitable for a display use etc. will be easily acquired by a chemical strengthening process. In addition, the said composition is an example and you may comprise the tempered glass board of this invention using the glass plate of arbitrary compositions.

本実施形態の強化ガラス板の厚み（ｔ）は、０．４ｍｍ以下である。そして、本実施形態の強化ガラス板においては、引張応力（ＣＴ）が、ＣＴ≦１９５０ｔ２−１４７０ｔ＋３３６を満たしている。このため、本実施形態の強化ガラス板は、引っ掻き等に対する高い加傷強度を有する。 The thickness (t) of the tempered glass plate of this embodiment is 0.4 mm or less. In the tempered glass plate of this embodiment, the tensile stress (CT) satisfies CT ≦ 1950t 2 −1470t + 336. For this reason, the tempered glass plate of this embodiment has high scratch strength against scratches and the like.

引張応力（ＣＴ）は、公知の応力測定装置を用いて測定した値でも良いし、圧縮応力ＣＳ（ＭＰａ）、圧縮応力深さＤＯＬ（ｍｍ）およびガラス板の厚みｔ（ｍｍ）を用いて下式（１）に基づき算出した値でも良い。なお、圧縮応力ＣＳ（ＭＰａ）、圧縮応力深さＤＯＬ（ｍｍ）は、公知の応力測定装置を用いて測定して良い。   The tensile stress (CT) may be a value measured using a known stress measuring device, or may be calculated using a compressive stress CS (MPa), a compressive stress depth DOL (mm), and a thickness t (mm) of the glass plate. The value calculated based on the formula (1) may be used. The compressive stress CS (MPa) and the compressive stress depth DOL (mm) may be measured using a known stress measuring device.

ＣＴ＝（ＣＳ×ＤＯＬ）／（ｔ−２ＤＯＬ） …（１） CT = (CS × DOL) / (t− 2 DOL) (1)

強化ガラス板の圧縮応力ＣＳは、好ましくは６００ＭＰａ〜２０００ＭＰａ、より好ましくは８００ＭＰａ〜１４００ＭＰａ、さらに好ましくは９００ＭＰａ〜１３００ＭＰａ、もっとも好ましくは９５０ＭＰａ〜１１００ＭＰａである。強化ガラス板の引張応力ＣＴは、好ましくは２５ＭＰａ〜３００ＭＰａ、より好ましくは４０ＭＰａ〜２００ＭＰａ、さらに好ましくは６０ＭＰａ〜１５０ＭＰａ、もっとも好ましくは７０ＭＰａ〜１００ＭＰａである。   The compressive stress CS of the tempered glass plate is preferably 600 MPa to 2000 MPa, more preferably 800 MPa to 1400 MPa, still more preferably 900 MPa to 1300 MPa, and most preferably 950 MPa to 1100 MPa. The tensile stress CT of the tempered glass plate is preferably 25 MPa to 300 MPa, more preferably 40 MPa to 200 MPa, still more preferably 60 MPa to 150 MPa, and most preferably 70 MPa to 100 MPa.

上述した本発明の強化ガラス板は、例えば、以下のようにして得られる。まず、上述したガラス組成となるようにガラス原料を計量及び調合し、溶融窯で溶融して溶融ガラスを得る。次いで、溶融ガラスをオーバーフローダウンドロー法やフロート法などの成形方法を用いてガラス板に成形する。次いで、得られたガラス板の表面に強化液を接触させてイオン交換を行うことにより化学強化処理して強化ガラス板を得る。具体的には、３００℃〜６００℃の硝酸カリウム溶液などの強化液に満たされた強化槽にガラス板を０．５時間〜８時間浸漬させることにより化学強化処理を行う。この際、得られる強化ガラス板の引張応力（ＣＴ）がＣＴ≦１９５０ｔ２−１４７０ｔ＋３３６を満たすように処理時間や強化液の温度、強化液の濃度等を調整する。 The above-mentioned tempered glass sheet of the present invention is obtained as follows, for example. First, a glass raw material is measured and prepared so as to have the glass composition described above, and melted in a melting furnace to obtain a molten glass. Next, the molten glass is formed into a glass plate using a forming method such as an overflow downdraw method or a float method. Next, a tempered glass plate is obtained by chemical strengthening treatment by bringing the reinforcing liquid into contact with the surface of the obtained glass plate and performing ion exchange. Specifically, the chemical strengthening treatment is performed by immersing the glass plate in a strengthening tank filled with a strengthening solution such as a potassium nitrate solution at 300 to 600 ° C. for 0.5 to 8 hours. At this time, the treatment time, the temperature of the reinforcing liquid, the concentration of the reinforcing liquid, and the like are adjusted so that the tensile stress (CT) of the obtained tempered glass plate satisfies CT ≦ 1950t 2 −1470t + 336.

以下、本発明の強化ガラス板の特性について、具体的な実験例に基づいてより具体的に説明する。   Hereinafter, the characteristics of the tempered glass sheet of the present invention will be described more specifically based on specific experimental examples.

（実験例１）
先ず、表１に記載の特性を有する強化ガラス板のサンプルを用意した。具体的にはガラス組成として、質量％で、ＳｉＯ２を６６％、Ａｌ２Ｏ３を１４．２％、Ｎａ２Ｏを１３．４％、Ｋ２Ｏを０．６％、Ｌｉ２Ｏを０．１％、Ｂ２Ｏ３を２．３％、ＭｇＯを３．０％及びＳｎＯ２を０．４％含有する組成の複数の板ガラスを表１に記載の厚み（ｔ）となるように研磨した。その後、得られたガラス板を、表１に記載の強化温度の硝酸カリウム溶液に表１に記載の強化時間浸漬することによりサンプルを作製した。 (Experimental example 1)
First, the sample of the tempered glass board which has the characteristic of Table 1 was prepared. Specifically, as a glass composition, by mass%, SiO 2 is 66%, Al 2 O 3 is 14.2%, Na 2 O is 13.4%, K 2 O is 0.6%, Li 2 O is A plurality of plate glasses having a composition containing 0.1%, B 2 O 3 2.3%, MgO 3.0% and SnO 2 0.4% so as to have the thickness (t) described in Table 1. Polished. Then, the sample was produced by immersing the obtained glass plate in the potassium nitrate solution of the tempering temperature described in Table 1 for the tempering time described in Table 1.

次に、ヌープ硬度の測定に用いられるダイヤモンド製ヌープ圧子を所定の荷重でサンプル１〜１０のそれぞれに押し込んだ後に、０．５ｍｍ／秒の速度で５ｍｍヌープ圧子をサンプルの主面と平行に走査させる加傷試験を、各５枚のサンプル１〜１０に対して行った。その結果、５枚の全てが２枚以上に分断されたときのヌープ圧子の荷重を、限界荷重（ＬＬ）として求めた。結果を図１に示す。なお、図１の縦軸は、限界荷重（ＬＬ）を示す。図１の横軸は、強化ガラス板の内層における引張応力（ＣＴ）を示す。図１には、厚み（ｔ）が０．２ｍｍ、０．３ｍｍ、０．４ｍｍ、０．５ｍｍ及び０．７ｍｍのそれぞれのデータの近似直線を示している。   Next, after a diamond Knoop indenter used for Knoop hardness measurement was pushed into each of the samples 1 to 10 with a predetermined load, the 5 mm Knoop indenter was scanned in parallel with the main surface of the sample at a speed of 0.5 mm / second. The wound test to be performed was performed on each of five samples 1 to 10. As a result, the load of the Knoop indenter when all of the five sheets were divided into two or more sheets was determined as the limit load (LL). The results are shown in FIG. In addition, the vertical axis | shaft of FIG. 1 shows a limit load (LL). The horizontal axis of FIG. 1 shows the tensile stress (CT) in the inner layer of the tempered glass sheet. FIG. 1 shows approximate straight lines of data with thicknesses (t) of 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, and 0.7 mm.

図１に示す結果から、サンプルの厚み（ｔ）が大きいほど、引張応力（ＣＴ）と限界荷重（ＬＬ）との相関を示すグラフの傾き（α）が大きくなり、逆に、サンプルの厚み（ｔ）が小さいほど、傾き（α）が小さくなる傾向にあることが分かる。すなわち、強化ガラス板の厚み（ｔ）が薄いほど、引張応力（ＣＴ）が高くなっても、加傷強度が低下しにくい。換言すれば、強化ガラス板の厚み（ｔ）が厚いほど、引張応力（ＣＴ）が高くなった際に、加傷強度が低下しやすい。   From the results shown in FIG. 1, as the sample thickness (t) increases, the slope (α) of the graph indicating the correlation between the tensile stress (CT) and the limit load (LL) increases. It can be seen that the smaller the t), the smaller the inclination (α) tends to be. That is, as the thickness (t) of the tempered glass plate is thinner, even if the tensile stress (CT) is higher, the scratch strength is less likely to decrease. In other words, the greater the thickness (t) of the tempered glass plate, the more easily the scratch strength decreases when the tensile stress (CT) increases.

図２は、図１に示した各グラフの傾き（α）を縦軸に、板厚を横軸にとってプロットしたグラフである。図２に示す結果から、強化ガラス板のサンプルの厚み（ｔ）が０．４ｍｍ以下の場合には、０．４ｍｍより大きな場合と比較して、傾き（α）が小さくなることが分かる。このことから、強化ガラス板の厚み（ｔ）が０．４ｍｍ以下と薄い場合と、強化ガラス板の厚み（ｔ）が０．４ｍｍより大きい場合とでは、引張応力（ＣＴ）と加傷強度との関係が大きく異なることが分かる。特に０．４ｍｍ以下の厚み（ｔ）の強化ガラス板において引張応力（ＣＴ）が高くても、高い加傷強度を維持しやすいことが分かる。   FIG. 2 is a graph in which the slope (α) of each graph shown in FIG. 1 is plotted on the vertical axis and the thickness is plotted on the horizontal axis. From the results shown in FIG. 2, it can be seen that when the thickness (t) of the tempered glass plate sample is 0.4 mm or less, the inclination (α) is smaller than when the thickness is larger than 0.4 mm. From this, when the thickness (t) of the tempered glass plate is as thin as 0.4 mm or less and when the thickness (t) of the tempered glass plate is larger than 0.4 mm, the tensile stress (CT) and the scratch strength It can be seen that the relationship is greatly different. In particular, it can be seen that even when the tensile stress (CT) is high in a tempered glass plate having a thickness (t) of 0.4 mm or less, high scratch strength is easily maintained.

図３は、限界荷重（ＬＬ）が６Ｎとなるときの強化ガラス板の厚み（ｔ）と引張応力（ＣＴ）との関係を表すグラフである。図３の縦軸は引張応力（ＣＴ）を示す。図３の横軸は、限界荷重（ＬＬ）が６Ｎとなるときの強化ガラス板の厚み（ｔ）を示す。図３に示す結果から、強化ガラス板の厚み（ｔ）が０．４ｍｍ以下の場合は、ＣＴ≦１９５０ｔ２−１４７０ｔ＋３３６とすることにより、６Ｎの引っ掻き等に耐え得る強化ガラス板を実現し得ることが分かる。 FIG. 3 is a graph showing the relationship between the thickness (t) of the tempered glass sheet and the tensile stress (CT) when the limit load (LL) is 6N. The vertical axis | shaft of FIG. 3 shows tensile stress (CT). The horizontal axis of FIG. 3 shows the thickness (t) of the tempered glass sheet when the limit load (LL) is 6N. From the results shown in FIG. 3, when the thickness (t) of the tempered glass plate is 0.4 mm or less, it is possible to realize a tempered glass plate that can withstand 6N scratching and the like by setting CT ≦ 1950t 2 −1470t + 336. I understand.

なお、上述した強化ガラス板の組成は一例である。ＳｉＯ２を６１．５％、Ａｌ２Ｏ３を１８．０％、Ｎａ２Ｏを１４．５％、Ｋ２Ｏを２．０％、Ｌｉ２Ｏを０．１％、Ｂ２Ｏ３を０．５％、ＭｇＯを３．０％及びＳｎＯ２を０．４％含有する組成の強化ガラス板においても同様の試験を行ったところ、同様の傾向が観察された。また、ＳｉＯ２を６１．２％、Ａｌ２Ｏ３を２０．１％、Ｎａ２Ｏを１５．９％、ＭｇＯを２．６％及びＳｎＯ２を０．２％含有する組成の強化ガラス板においても同様の試験を行ったところ、同様の傾向が観察された。 In addition, the composition of the tempered glass plate mentioned above is an example. SiO 2 61.5%, Al 2 O 3 18.0%, Na 2 O 14.5%, K 2 O 2.0%, Li 2 O 0.1%, B 2 O 3 When the same test was performed on a tempered glass plate having a composition containing 0.5%, MgO 3.0% and SnO 2 0.4%, the same tendency was observed. Further, a tempered glass plate having a composition containing 61.2% SiO 2 , 20.1% Al 2 O 3 , 15.9% Na 2 O, 2.6% MgO and 0.2% SnO 2 A similar tendency was observed when a similar test was conducted in No. 1.

（実験例２）
表２に示す特性を有する強化ガラス板を６枚用意した。 (Experimental example 2)
Six tempered glass plates having the characteristics shown in Table 2 were prepared.

そのサンプルの主面に、先端角度が１１５°のダイヤモンド製ビッカース圧子を一定の荷重で押し込んだ。その後、ビッカース圧子を取り除き、圧痕を顕微鏡を用いて観察した。その結果、図４に示すように、圧痕１０には、
圧痕１０の４つの角部のいずれからもクラック１１が延びていない場合（クラック発生率：０％）、
圧痕１０の４つの角部のひとつのみからクラック１１が延びている場合（クラック発生率：２５％）、
圧痕１０の４つの角部の２つのみからクラック１１が延びている場合（クラック発生率：５０％）、
圧痕１０の４つの角部の３つのみからクラック１１が延びている場合（クラック発生率：７５％）、
圧痕１０の４つの角部の全てからクラック１１が延びている場合（クラック発生率：１００％）、
が存在する。 A diamond Vickers indenter with a tip angle of 115 ° was pushed into the main surface of the sample with a constant load. Thereafter, the Vickers indenter was removed, and the indentation was observed using a microscope. As a result, as shown in FIG.
When the crack 11 does not extend from any of the four corners of the indentation 10 (crack occurrence rate: 0%),
When the crack 11 extends from only one of the four corners of the indentation 10 (crack occurrence rate: 25%),
When the crack 11 extends only from two of the four corners of the indentation 10 (crack occurrence rate: 50%),
When the crack 11 extends from only three of the four corners of the indentation 10 (crack occurrence rate: 75%),
When the crack 11 extends from all four corners of the indentation 10 (crack occurrence rate: 100%),
Exists.

なお、当該試験においては、角部のみならず圧痕１０の周囲全体から微小クラックが多数進展して、全体的に破砕されたような状態になる場合があり、このような場合も（クラック発生率：１００％）とした。   In this test, a large number of microcracks may develop from not only the corners but also from the entire periphery of the indentation 10, resulting in a state of being crushed as a whole. : 100%).

上記のような圧痕試験で、徐々に圧子を押し込む荷重を増大させて、クラック発生率が５０％以上となったときのビッカース圧子の荷重をクラックレジスタンス（ＣＲ）として評価した。クラックレジスタンス（ＣＲ）の値が大きいほど、クラックが発生しがたく、高い耐加傷性を有する強化ガラス板であるといえる。上記の評価結果を、図５に示す。図５の縦軸は、クラック発生率が５０％以上となったときのビッカース圧子の荷重であるクラックレジスタンス（ＣＲ）を示す。図５の横軸は、圧縮応力深さ（ＤＯＬ）を示す。また、図５に示す曲線は、データの近似曲線である。   In the indentation test as described above, the load of the indenter was gradually increased, and the load of the Vickers indenter when the crack occurrence rate was 50% or more was evaluated as crack resistance (CR). It can be said that the larger the value of the crack resistance (CR), the harder a crack is generated and the tempered glass plate having high scratch resistance. The evaluation results are shown in FIG. The vertical axis in FIG. 5 shows the crack resistance (CR), which is the load of the Vickers indenter when the crack occurrence rate is 50% or more. The horizontal axis in FIG. 5 indicates the compressive stress depth (DOL). Moreover, the curve shown in FIG. 5 is an approximate curve of data.

図５に示すように、圧縮応力深さ（ＤＯＬ）が１０μｍとなるまでは、圧縮応力深さ（ＤＯＬ）が大きくなるほど、クラックレジスタンス（ＣＲ）が大幅に増加する。換言すれば、圧縮応力深さ（ＤＯＬ）が１０μｍ以下である場合、クラックレジスタンス（ＣＲ）は、圧縮応力深さ（ＤＯＬ）が小さくなるほど、対数関数的に低下する。従って、圧縮応力深さ（ＤＯＬ）を１０μｍ以上とすることにより、良好なクラックレジスタンス（ＣＲ）を得られることが分かる。   As shown in FIG. 5, until the compressive stress depth (DOL) reaches 10 μm, the greater the compressive stress depth (DOL), the greater the crack resistance (CR) increases. In other words, when the compressive stress depth (DOL) is 10 μm or less, the crack resistance (CR) decreases logarithmically as the compressive stress depth (DOL) decreases. Therefore, it can be seen that a good crack resistance (CR) can be obtained by setting the compression stress depth (DOL) to 10 μm or more.

Claims (4)

圧縮応力を有する表層と、引張応力を有する内層とを有する強化ガラス板であって、
厚み（ｔ）が０．４ｍｍ以下であり、
前記内層における引張応力（ＣＴ）が、
ＣＴ≦１９５０ｔ２−１４７０ｔ＋３３６
を満たし、
前記表層の圧縮応力（ＣＳ）が６００ＭＰａ以上であり、
前記圧縮応力を有する表層の深さである圧縮応力深さ（ＤＯＬ）が２０．６μｍ以上である、強化ガラス板。 A tempered glass sheet having a surface layer having compressive stress and an inner layer having tensile stress,
The thickness (t) is 0.4 mm or less,
The tensile stress (CT) in the inner layer is
CT ≦ 1950t 2 −1470t + 336
Meet the,
The compressive stress (CS) of the surface layer is 600 MPa or more,
The tempered glass board whose compressive stress depth (DOL) which is the depth of the surface layer which has the said compressive stress is 20.6 micrometers or more . 厚み（ｔ）が０．２ｍｍ以上である、請求項１に記載の強化ガラス板。 The tempered glass sheet according to claim 1 whose thickness (t) is 0.2 mm or more. ガラス組成として、質量％で、ＳｉＯ２を５０％〜８０％、Ａｌ２Ｏ３を５％〜３５％、Ｂａ２Ｏ３を０％〜１５％、Ｎａ２Ｏを１％〜２０％、Ｋ２Ｏを０％〜１０％及びＭｇＯを０％〜１０％含有する、請求項１又は２に記載の強化ガラス板。 As a glass composition, in mass%, a SiO 2 50% to 80%, the Al 2 O 3 5% ~35% , the Ba 2 O 3 0% ~15% , 1% ~20% of Na 2 O, K the 2 O containing 10% 0% 0% to 10% and MgO, tempered glass plate according to claim 1 or 2. 厚み（ｔ）が０．４ｍｍ以下のガラス板を化学強化処理して表層に圧縮応力付与する一方、内層に引張応力を付与する強化ガラス板の製造方法であって、
前記内層における引張応力（ＣＴ）が、
ＣＴ≦１９５０ｔ２−１４７０ｔ＋３３６
を満たし、前記表層の圧縮応力（ＣＳ）が６００ＭＰａ以上であり、前記圧縮応力を有する表層の深さである圧縮応力深さ（ＤＯＬ）が２０．６μｍ以上となるように前記化学強化処理を行う、強化ガラス板の製造方法。 A method for producing a tempered glass plate that imparts a compressive stress to a surface layer by chemically strengthening a glass plate having a thickness (t) of 0.4 mm or less, and imparts a tensile stress to an inner layer,
The tensile stress (CT) in the inner layer is
CT ≦ 1950t 2 −1470t + 336
Meets, the surface layer of the compressive stress (CS) is at least 600 MPa, the chemical strengthening treatment as the depth of the surface layer is compressive stress depth having a compressive stress (DOL) is equal to or greater than 20.6μm The manufacturing method of the tempered glass board to perform.
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