TW201825434A - Reinforced glass plate and method for producing reinforced glass plate - Google Patents

Reinforced glass plate and method for producing reinforced glass plate Download PDF

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Publication number
TW201825434A
TW201825434A TW106140426A TW106140426A TW201825434A TW 201825434 A TW201825434 A TW 201825434A TW 106140426 A TW106140426 A TW 106140426A TW 106140426 A TW106140426 A TW 106140426A TW 201825434 A TW201825434 A TW 201825434A
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Taiwan
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glass plate
compressive stress
ion exchange
strengthened glass
ion
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TW106140426A
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Chinese (zh)
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木下清貴
深田睦
梶岡利之
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日商日本電氣硝子股份有限公司
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Publication of TW201825434A publication Critical patent/TW201825434A/en

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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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • 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

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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)
  • Surface Treatment Of Glass (AREA)

Abstract

This method for producing a reinforced glass plate includes forming a compressive stress layer by carrying out ion exchange on at least a portion of the surface of a glass plate to be reinforced. The method is characterized by comprising an ion exchange step for carrying out ion exchange until compressive stress becomes at least 200 MPa at a position 50 [mu]m deep from the surface of the compressive stress layer.

Description

強化玻璃板、強化玻璃板之製造方法Strengthened glass plate, manufacturing method of strengthened glass plate

[0001] 本發明係關於強化玻璃板及其之製造方法，更具體地說，係關於藉由離子交換法而化學強化之強化玻璃板及其製造方法。[0001] The present invention relates to a strengthened glass plate and a method for manufacturing the same, and more particularly, to a strengthened glass plate chemically strengthened by an ion exchange method and a method for manufacturing the same.

[0002] 從前，於被搭載於智慧型手機或是平板個人電腦等電子機器之觸控面板顯示器，作為覆蓋玻璃板使用化學強化之強化玻璃板。 　　[0003] 這樣的強化玻璃板，一般，係藉由把鹼金屬包含作為組成之玻璃板以強化液化學處理，於表面形成壓縮應力層而製造的(例如，專利文獻1、2)。 　　[0004] 表面具有壓縮應力層的強化玻璃以調和應力平衡的方式在內部形成拉伸應力層。拉伸應力層的拉伸應力(CT)在壓縮應力層的深度(DOL)及壓縮應力(CS)越大時變得越大。 　　[0005] 例如，專利文獻1那樣設想起因於尖銳壓子工具的點衝突之破壞的場合，或是如專利文獻2那樣設想彎曲導致地破壞的場合，拉伸應力(CT)過大的話，強化玻璃應會變得容易破損。因此，從前，壓縮應力層的深度(DOL)以控制為一定值以下為較佳。例如，於專利文獻2，DOL以35μm以下為較佳。 [先前技術文獻] [專利文獻] 　　[0006] 　　[專利文獻1]日本特表2015-523310號公報 　　[專利文獻2]日本特開2014-001124號公報[0002] In the past, a chemically strengthened glass plate was used as a cover glass for a touch panel display mounted on an electronic device such as a smart phone or a tablet personal computer. [0003] Generally, such a strengthened glass plate is produced by chemically treating a strengthening liquid by containing a glass plate having a composition as an alkali to form a compressive stress layer on the surface (for example, Patent Documents 1 and 2). [0004] Tempered glass with a compressive stress layer on the surface forms a tensile stress layer in the interior in a manner that harmonizes the stress balance. The tensile stress (CT) of the tensile stress layer becomes larger as the depth of the compressive stress layer (DOL) and the compressive stress (CS) become larger. [0005] For example, when the damage caused by the point collision of a sharp plunger is conceived as in Patent Document 1, or the damage caused by bending is conceived as in Patent Document 2, if the tensile stress (CT) is too large, the glass is strengthened. Should become easily broken. Therefore, in the past, it is better to control the depth (DOL) of the compressive stress layer to a certain value or less. For example, in Patent Document 2, the DOL is preferably 35 μm or less. [Prior Art Document] [Patent Document] [0006] [Patent Document 1] Japanese Patent Publication No. 2015-523310 [Patent Document 2] Japanese Patent Publication No. 2014-001124

[發明所欲解決之課題] 　　[0007] 然而，實際上被搭載於智慧型手機或平板電腦等的強化玻璃的破損態樣(破損模式)有各種各樣，特定的破損態樣不一定是使拉伸應力(CT)或壓縮應力層的深度(DOL)如從前那樣限制為較小為較佳。 　　[0008] 本發明係考慮這種情形而完成的發明，課題在於提供具有高強度的強化玻璃板及其製造方法。 [供解決課題之手段] 　　[0009] 本發明之強化玻璃板之製造方法，特徵係把強化用玻璃板的表面之至少一部分離子交換形成壓縮應力層，具備進行離子交換直到壓縮應力層由表面起算深度50μm的位置之壓縮應力成為200MPa以上為止之離子交換步驟。 　　[0010] 在本發明之強化玻璃板之製造方法，較佳為在離子交換步驟，進行離子交換處理直到壓縮應力層之壓縮應力的最大值成為400MPa以上，且由該層的外表面起算的深度(DOL_Z)比100μm更深為止。 　　[0011] 在本發明之強化玻璃板之製造方法，較佳為離子交換步驟，包含使強化用玻璃板接觸於第一溫度的熔鹽進行離子交換之第一離子交換步驟，與使強化用玻璃板接觸於第二溫度的熔鹽進行離子交換的第二離子交換步驟；進而具備：於第一離子交換步驟前，於強化用玻璃的表面之至少一部分預先設置防止離子交換之防離子交換膜的成膜步驟，以及於第一離子交換步驟後，除去防離子交換膜的除去步驟；於除去步驟後實施第二離子交換步驟。 　　[0012] 本發明之強化玻璃板之製造方法，較佳為第二溫度比第一溫度更低；第一離子交換步驟之離子交換處理時間，比第二離子交換步驟之離子交換處理時間更長。 　　[0013] 在本發明之強化玻璃板之製造方法，第一溫度超過430℃，第二溫度為430℃以下為較佳。 　　[0014] 在本發明之強化玻璃板之製造方法，第一溫度與第二溫度之差為±5℃以內為較佳。 　　[0015] 在本發明之強化玻璃板之製造方法，於離子交換步驟，使強化用玻璃板連續10個小時以上接觸於鈉離子濃度為50000ppm以下的硝酸鉀熔鹽進行離子交換為較佳。 　　[0016] 本發明之強化玻璃板，特徵為於外表面之至少一部份具有深度50μm之壓縮應力為200MPa以上的壓縮應力深層。 　　[0017] 在本發明之強化玻璃板，較佳為壓縮應力深層之壓縮應力的最大值成為400MPa以上且其深度比100μm更深。 　　[0018] 本發明之強化玻璃板，沿著周緣部具備壓縮應力深層為較佳。 　　[0019] 本發明之強化玻璃板，於表面之中未被形成壓縮應力深層的區域之至少一部分具有比壓縮應力深層更淺的壓縮應力淺層為較佳。 　　[0020] 於本發明之強化玻璃板，壓縮應力淺層，深度為35～60μm，壓縮應力的最大值為600～1500MPa為較佳。 [發明之效果] 　　[0021] 根據以上這樣的本發明，可以得到具有高強度之強化玻璃板。[Problems to be Solved by the Invention] 000 [0007] However, in fact, there are various damage patterns (breakage modes) of tempered glass mounted on smartphones, tablets, and the like, and specific damage patterns are not necessarily used. The tensile stress (CT) or compressive stress layer depth (DOL) is preferably limited to a smaller value as before. [0008] The present invention has been made in consideration of such a situation, and an object thereof is to provide a strengthened glass plate having high strength and a method for manufacturing the same. [Means for Solving the Problems] [0009] The method for manufacturing a strengthened glass plate of the present invention is characterized in that at least a part of the surface of the strengthened glass plate is ion-exchanged to form a compressive stress layer, and the method includes ion exchange until the compressive stress layer is counted from the surface. The compressive stress at a depth of 50 μm is an ion exchange step up to 200 MPa or more. [0010] In the method for manufacturing a strengthened glass plate of the present invention, it is preferable to perform an ion exchange process in the ion exchange step until the maximum value of the compressive stress of the compressive stress layer becomes 400 MPa or more, and the depth from the outer surface of the layer (DOL_Z) is deeper than 100 μm. [0011] In the method for manufacturing a strengthened glass plate of the present invention, the ion-exchange step preferably includes a first ion-exchange step of bringing the glass plate for tempering into contact with a molten salt at a first temperature for ion exchange, and bringing the glass for tempering A second ion-exchange step in which the plate is in contact with the molten salt at a second temperature for ion exchange; and further comprising: before the first ion-exchange step, at least a part of a surface of the strengthening glass is provided with an ion-exchange-preventive membrane preventing ion exchange in advance A film forming step, and a removing step of removing the anti-ion exchange membrane after the first ion exchange step; and performing a second ion exchange step after the removing step. [0012] In the method for manufacturing a strengthened glass plate of the present invention, the second temperature is preferably lower than the first temperature; the ion exchange processing time in the first ion exchange step is longer than the ion exchange processing time in the second ion exchange step . [0013] In the method for manufacturing a strengthened glass sheet of the present invention, it is preferable that the first temperature exceeds 430 ° C and the second temperature is 430 ° C or lower. [0014] In the method for manufacturing a strengthened glass sheet of the present invention, it is preferable that the difference between the first temperature and the second temperature is within ± 5 ° C. [0015] In the method for manufacturing a strengthened glass plate of the present invention, in the ion exchange step, it is preferable that the strengthened glass plate is contacted with a molten potassium nitrate having a sodium ion concentration of 50,000 ppm or less for 10 hours or more for ion exchange. [0016] The tempered glass plate of the present invention is characterized in that at least a part of the outer surface has a deep layer of compressive stress with a compressive stress of 200 MPa or more at a depth of 50 μm. [0017] In the strengthened glass sheet of the present invention, it is preferable that the maximum value of the compressive stress of the compressive stress deep layer is 400 MPa or more and the depth thereof is deeper than 100 μm. [0018] It is preferable that the strengthened glass plate of the present invention includes a deep layer of compressive stress along the peripheral edge portion. [0019] It is preferable that the strengthened glass plate of the present invention has a shallow compressive stress shallow layer at least in a part of the surface in which no deep compressive stress deep layer is formed. [0020] In the strengthened glass sheet of the present invention, the shallow layer of compressive stress has a depth of 35 to 60 μm, and the maximum value of the compressive stress is preferably 600 to 1500 MPa. [Effects of the Invention] [0021] According to the present invention as described above, a strengthened glass plate having high strength can be obtained.

[0023] ＜第一實施形態＞ 　　以下，說明本發明的實施形態之強化玻璃板之製造方法。圖1a～圖1e係顯示本發明的強化玻璃板的製造方法之一例之圖。 　　[0024] 首先，實施圖1a所示的準備步驟之處理。準備步驟，係準備強化用玻璃板G1的步驟。強化用玻璃板G1，是可使用離子交換法來強化的板狀的玻璃板。本實施形態之強化用玻璃板G1，如圖1a及圖2所示，是具有主表面S與端面E的約略矩形狀的玻璃板。又，圖2為板厚方向平面觀看強化用玻璃板G1之圖。此外，圖1a，為圖2之強化用玻璃板G1的AA向剖面視圖。強化用玻璃板G1被倒角加工，在主表面S與端面E之間具有倒角面B。亦即，於強化用玻璃板G1的外表面，包含主表面S、端面E、及倒角面B。 　　[0025] 強化用玻璃板G1，以質量百分比表示玻璃板組成，以含有SiO2 45～75%、Al2 O3 1～30%、Na2 O 0～20%、及K2 O 0～20%為佳。如前所述限制玻璃板的組成範圍的話，更容易在很高的程度上兼顧離子交換性能以及耐失透性。 　　[0026] 強化用玻璃板G1的板厚，例如為1.5mm以下，較佳為1.3mm以下、1.1mm以下、1.0mm以下、特別是0.9mm以下更佳。又，強化玻璃板的板厚越小，越可以使強化玻璃板輕量化，結果可以謀求裝置的薄型化、輕量化。在這樣的場合，強化用玻璃板G1的板厚，為0.7mm以下、0.6mm以下、0.5mm以下、0.4mm以下、0.3mm以下、0.2mm以下、特別是0.1mm以下為更佳。此外，考慮到生產性等的話，強化用玻璃板G1的板厚以0.01mm以上為較佳。 　　[0027] 強化用玻璃板G1的平面橫視尺寸可任意設定，例如10×10mm～3350×3950mm。 　　[0028] 強化用玻璃板G1，例如係使用溢流下拉法(overflow downdraw method)被成形的玻璃。又，強化用玻璃板G1之成形方法或加工狀態亦可任意選擇。例如，強化用玻璃板G1，亦可為使用浮法成形的玻璃。此外，主表面S、端面E、及倒角面B亦可為被研磨加工者。 　　[0029] 接著，前述準備步驟之後，實施圖1b所示之成膜步驟之處理。成膜步驟，是在強化用玻璃板G1表面之至少一部份形成防離子交換膜M而得到附膜強化用玻璃板G1m的步驟。在本實施形態，以如圖3所示那樣把強化用玻璃板G1的主表面的中央部S1被形成防離子交換膜M。又，圖1b相當於圖3之AA向剖面視圖。強化用玻璃板G1的表面之中，中央部S1以外的周緣部為露出的狀態。又，周緣部，是表背主表面S之中包含包圍中央部S1之外周區域S2、倒角面B、及端面E的部位。防離子交換膜M，係於後述之第一離子交換步驟，在進行強化用玻璃板G1表層的離子交換時抑制或者遮斷離子的透過之膜層。 　　[0030] 防離子交換膜M的材質，只要是可以抑制或者遮斷被離子交換之離子的透過即可，可使用任意的材質。被交換的離子為鹼金屬離子的場合，防離子交換膜M例如為金屬氧化物、金屬氮化物、金屬碳化物、金屬氧氮化物、金屬氧碳化物、金屬碳氮化物等為佳。此外，耐熱性或化學耐久性優異的碳材料或金屬、合金也可以作為防離子交換膜M使用。更詳細地說，作為防離子交換膜M的材質，例如可以為包含由SiO2 、Al2 O3 、SiN、SiC、AlN、ZrO2 、TiO2 、Ta2 O5 、Nb2 O5 、HfO2 、SnO2 、奈米碳管、石墨烯(graphene)、類金剛石碳、不鏽鋼之中選擇1種以上之膜。此外，防離子交換膜M，以在離子交換處理中，結晶性不容易變動的非晶質膜為佳。 　　[0031] 又，於防離子交換膜M也包含抑制離子透過的，亦為不完全遮斷的膜。這樣的防離子交換膜M的材質，例如可以使用ZrO2 、SnO2 、ITO膜、AlN。但是，由這些材質構成的膜在高溫下結晶性容易改變，所以離子交換處理中會有離子透過性變成容易變動的場合。 　　[0032] 考慮到機械強度或成本的場合，使用以SiO2 為主成分，包含Al2 O3 的膜作為防離子交換膜M是適宜的。在此場合，防離子交換膜M為以質量百分比表示具有含SiO2 20～99%，Al2 O3 1～80%之組成為佳。 　　[0033] 防離子交換膜M的厚度，只要是可以達成離子透過的遮斷或抑制即可，可為任意厚度。但是，防離子交換膜M的厚度過大的話，成膜時間或材料成本等會增大，所以在可達成離子透過的遮斷及抑制的範圍內以薄薄地形成為佳。具體而言，防離子交換膜M的膜厚，例如以1～5000nm為佳，更佳為50～4000nm。 　　[0034] 防離子交換膜M的成膜方法，可以使用濺鍍法或真空蒸鍍法等PVD法(物理氣相沉積法)、熱CVD法或電漿CVD法等CVD法(化學氣相沈積法)、浸沾塗佈法或狹縫塗佈法等濕式塗佈法。特別以濺鍍法為佳。使用濺鍍法的場合，可容易且均勻的形成防離子交換膜M。防離子交換膜M的成膜處所可以任意的手法設定。例如，可以在將周緣部遮罩住的狀態下進行成膜。此外，把預先成形為薄片狀的防離子交換膜M接合於強化用玻璃板G1的主表面而成膜亦可。 　　[0035] 又，在本實施形態，以形成含有SiO2 及Al2 O3 ，膜厚為100nm以上，可遮斷鹼金屬離子的透過之防離子交換膜M的場合為一例進行說明。 　　[0036] 接著，前述成膜步驟之後，進行離子交換步驟的處理。離子交換步驟，於強化用玻璃板G1的表面之至少一部分，進行離子交換直到由表面起算深度50μm的位置之壓縮應力成為200MPa以上為止，是形成壓縮應力深層C(C1、C2)的處理。本實施形態之離子交換步驟，包含圖1c所示的第一離子交換步驟，及圖1e所示的第二離子交換步驟。 　　[0037] 首先，實施圖1c所示的第一離子交換步驟之處理。第一離子交換步驟，是把強化用玻璃板G1藉由離子交換法得到部分化學強化之強化玻璃板G2的步驟。具體而言，浸漬強化用玻璃板G1於包含鹼金屬離子的熔鹽T1進行離子交換。本實施形態之熔鹽T1，例如為硝酸鉀熔鹽。 　　[0038] 在此，強化用玻璃板G1的表面之中在被形成防離子交換膜M的區域(中央部S1)不進行離子交換，所以未被形成壓縮應力層。另一方面，強化用玻璃板G1的表面之中在未被形成防離子交換膜M的區域(周緣部)進行離子交換，被形成壓縮應力深層C1。 　　[0039] 壓縮應力深層C1，為深度50μm之壓縮應力CS(50)為200MPa以上之壓縮應力層。此外，於壓縮應力深層C1，壓縮應力的最大值CSmax為400MPa以上，且該層的深度DOL_Z比100μm更深為佳。 　　[0040] 第一離子交換步驟之熔鹽T1的溫度超過430℃，較佳為440～500℃，更佳為450～490℃。此外，把附膜強化用玻璃板G1m浸漬於熔鹽T1中的時間，例如為10～200小時，較佳為12～170小時，更佳為24～100小時。藉由如此以比較高的溫度進行離子交換處理，可以短時間把深的壓縮應力層形成於周緣部。 　　[0041] 又，熔鹽T1在反覆使用時鈉離子濃度會增加，有離子交換特性變動的場合。亦即，熔鹽T1的鈉離子濃度以維持在一定範圍內為佳。此外，為了效率佳地增大壓縮應力深層C1、C2的深度，熔鹽T1的鈉離子濃度較佳為限制在50000ppm以下，更佳為30000ppm以下、進而又更佳為20000ppm以下。熔鹽T1之鈉離子濃度，可以進行添加硝酸鉀等而調整。 　　[0042] 又，結束第一離子交換步驟的處理之時間點所得到的具備防離子交換膜M的強化玻璃板G2，稱為附膜強化玻璃板G2m。 　　[0043] 接著，前述第一離子交換步驟之後，實施圖1d所示的除膜步驟的處理。除膜步驟，係從附膜強化玻璃板G2m除去防離子交換膜M的步驟。作為防離子交換膜M的除去方法，例如可以使用研磨或蝕刻等方法。 　　[0044] 作為使用於研磨的研磨裝置，可以使用週知的雙面研磨機或單面研磨機。又，藉由研磨除去防離子交換膜M的場合，僅研磨防離子交換膜M亦可，同時研磨防離子交換膜M與玻璃板部分亦可。 　　[0045] 蝕刻方法可以使用乾式蝕刻或濕式蝕刻等方法。 　　[0046] 使用乾式蝕刻的場合，特別以使用Ar、O2 、CH4 、BC13 、C12 、SF6 等之電漿為佳。 　　[0047] 使用於濕式蝕刻的蝕刻液，例如可以使用含氟、TMAH(四甲基氫氧化銨)、EDP、KOH、NaOH等的溶液作為蝕刻液使用，特別是把氟酸溶液作為蝕刻液使用為佳。又，使用氟酸溶液，不變更玻璃尺寸而僅除去防離子交換膜M的場合，使該氟酸溶液之HF濃度為10%以下為佳。 　　[0048] 如前所述進行而得到的強化玻璃板G2a，於周緣部具有壓縮應力深層C1。亦即，強化玻璃板G2a，係於周緣部具有高耐破損性的玻璃。 　　[0049] 接著，前述除膜步驟之後，實施圖1e所示的第二離子交換步驟的處理。第二離子交換步驟，係在第一離子交換步驟未被形成壓縮應力層的區域，形成相對較淺的壓縮應力淺層D而得到強化玻璃板G2b的步驟。在本實施形態，如圖1e所示，把強化玻璃板G2浸漬到含鹼金屬離子的熔鹽T2，在被形成了防離子交換膜M的區域(中央部S1)的全體形成壓縮應力淺層D。熔鹽T2，例如為硝酸鉀熔鹽。 　　[0050] 被形成於周緣部的壓縮應力深層C1，藉由在前述處理與熔鹽T2接觸而使特性多少有所改變而成為壓縮應力深層C2。在本實施形態，於變動後，壓縮應力深層C2，為深度50μm之壓縮應力CS(50)為200MPa以上之壓縮應力層。壓縮應力深層C2的深度50μm之壓縮應力CS(50)，較佳為200～500MPa，更佳為220～450MPa，進而更佳為250～400MPa。 　　[0051] 第二離子交換步驟之熔鹽T2的溫度，以比前述之第一離子交換步驟使用的熔鹽T1的溫度更低之溫度為較佳。藉由如此以比較低的溫度進行離子交換處理，變得容易防止中央部S1所形成的壓縮應力淺層D的深度變得過大。熔鹽T2的溫度例如為430℃以下，更佳為390～430℃，進而更佳為400～425℃。 　　[0052] 強化玻璃板G2浸漬於熔鹽T2中的時間，例如為0.1～72小時，較佳為0.3～50小時，更佳為0.5～24小時。 　　[0053] 又，熔鹽T2的鈉離子濃度也與熔鹽T1同樣以維持在一定範圍內為佳。此外，熔鹽T2的鈉離子濃度較佳為限制在30000ppm以下，更佳為20000ppm以下、進而又更佳為10000ppm以下。藉由如此調整熔鹽T2的鈉離子濃度，可以容易使壓縮應力深層G2及壓縮應力淺層D之壓縮應力的最大值成為較大之值。 　　[0054] 壓縮應力深層C2之壓縮應力的最大值，較佳為400MPa以上，更佳為450～1500MPa，進而更佳為500～1200MPa。此外，壓縮應力深層C2之深度，較佳為100μm以上，更佳為100～300μm，進而更佳為100～250μm。 　　[0055] 如前所述藉由進行二度之離子交換步驟的處理，可以得到使相對深的壓縮應力層之壓縮應力深層C2及相對淺的壓縮應力層之壓縮應力淺層D分別具有於不同的區域之強化玻璃板G2b。根據這樣的強化玻璃板G2b，例如於容易成為破損的起點的周緣部形成深的壓縮應力深層C2而可得到高耐破損性，同時，於中央部S1形成淺的壓縮應力淺層D抑制內部拉伸應力的增大而抑制被形成於強化玻璃板G2內部的拉伸應力的增大。此外，在中央部S1因為拉伸應力被減低，破損時與周緣部相比難以形成細的破片。亦即，例如強化玻璃板G2使用於顯示器等的場合，即使破損之後，也容易維持顯示器的辨識性。 　　[0056] 強化玻璃板G2(G2a、G2b)，藉由具有如前所述的壓縮應力深層C(C1、C2)，於該層的形成部位，在特定的破損模式下具有高的強度。所謂特定的破損模式，是指在強化玻璃板G2的落下處存在著銳利的突起物，該突起物突破表面的壓縮應力層，到達至內部的拉伸應力層因而發生龜裂，該龜裂因內部拉伸應力而進展、破損之破損模式。 　　[0057] 又，前述第一離子交換步驟之熔鹽T1的溫度或浸漬時間、第二離子交換步驟之熔鹽T2的溫度或浸漬時間等處理條件僅為一例，可以使被形成的壓縮應力深層C成為深度50μm之壓縮應力CS(50)為200MPa以上的應力層之方式任意調整。 　　[0058] 此外，為了抑制強化玻璃板的製造成本，例如，使前述第一離子交換步驟與第二離子交換步驟在同一強化槽(熔鹽)進行。在此場合，進行第一離子交換步驟時之熔鹽的溫度與進行第二離子交換步驟時之熔鹽的溫度之差，容易收窄於±5℃之範圍內。 　　[0059] 又，在前述實施形態，以在第一離子交換步驟的處理被形成的壓縮應力深層C1，具有深度50μm之壓縮應力CS(50)為200MPa以上的強化特性的場合作為一例來說明，但如果經過第二離子交換步驟的處理成為壓縮應力深層C2的時間點具有該特性的話，在經過第一離子交換步驟的處理之時間點還不具有前述特性亦可。 　　[0060] 此外，第二離子交換步驟之後，進而實施精加工步驟之處理亦可(未圖示)。在精加工步驟，把強化玻璃板G2b的表面，例如主表面S及端面E之至少任一予以研磨加工。由於第二離子交換步驟之處理使強化玻璃板G2b的尺寸或表面狀態不是製品規格等所要的狀態的場合，藉由實施這樣的精加工步驟之處理可以使成為所要的狀態。 　　[0061] 如以上所說明的，根據相關於本發明的實施形態之強化玻璃板之製造方法，可以安定而效率佳地製造於前述特定的破損模式具有很高的強度之強化玻璃板G2(G2m,G2b)。 　　[0062] 又，亦可於前述所示之任意步驟的前後，加設實施切斷加工、開孔加工、研磨加工、石刻加工等的加工之加工步驟。此外，於前述所示之任意步驟的前後，適當對玻璃板進行洗淨及乾燥處理亦可。 　　[0063] 此外，在前述實施形態，以熔鹽T1、T2為硝酸鉀熔鹽的場合為一例進行說明，但不限於此，替代或者組合使用用於玻璃板的離子交換之習知的熔鹽亦可。 　　[0064] 此外，離子交換的處理不限於如前所述之往熔鹽的浸漬，例如塗佈熔鹽而進行亦可。 　　[0065] 此外，前述之壓縮應力深層C1、C2及壓縮應力淺層D之壓縮應力的大小及各層的深度，例如，可以用應力計(折原製作所製造之FSM-6000LE及FsmV)來測定。 　　[0066] ＜第二實施形態＞ 　　在前述第一實施形態係以僅在強化玻璃板G2的周緣部被形成壓縮應力深層C(C1、C2)的場合為一例進行說明，但在強化玻璃板G2之外表面全面形成壓縮應力深層C亦可。圖4a及圖4b係顯示相關於本發明之第二實施形態的強化玻璃板之製造方法的概略之圖。 　　[0067] 圖4a與第一實施形態同樣是準備強化用玻璃板G1的準備步驟。其後，在第二實施形態，成膜步驟的處理被省略，如圖4b所示，對於不具有防離子交換膜M的強化用玻璃板G1實施離子交換步驟之處理。根據這樣的處理，可以容易地製造於外表面全面被形成壓縮應力深層C(C3)的強化玻璃板G2(G2c)。 [實施例] 　　[0068] 以下根據實施例，說明本發明之強化玻璃板G2(G2b或G2c)。於表1，No.1～6為本發明之實施例，No.7～9為比較例。又，以下之實施例僅為例示，本發明並不以下列實施例為限。 　　[0069] 首先，如以下所示製作各試樣No.1～9。以莫耳百分比表示玻璃組成，以成為含SiO2 66.3%、Al2 O3 11.4%、Na2 O 15.2%、B2 O3 0.5%、Li2 O 0.2%、K2 O 1.4%、MgO 4.8%、SnO2 0.2%的玻璃的方式，調和玻璃原料，使用白金罐在1600℃熔融21小時。其後，把得到的熔融玻璃，使用溢流下拉法由耐火物成形體留下成形，成形為厚度0.4mm的板狀，得到強化用玻璃板。 　　[0070] 接著，得到的強化用玻璃板之中，針對試樣No.1～3、5、7，依據圖1b所示的步驟，以質量百分比表示組成形成了含SiO2 70%、Al2 O3 30%的防離子交換膜。接著，以表1所示的條件把各試樣No.1～9浸漬於硝酸鉀熔鹽進行了離子交換處理(第一離子交換步驟)。接著，具有防離子交換膜的試樣No.1～3、5、7藉由研磨除去該膜(除去步驟)。其後，以表1所示的條件再度把No.1～3、5、7、8之試樣浸漬於硝酸鉀熔鹽進行了離子交換處理(第二離子交換步驟)。 　　[0071] 針對如前所述得到的各資料，進行了以下的特性測定及強度試驗。 　　[0072][0073] 表1所示的周緣部及中央部之壓縮應力的最大值CSmax，各壓縮應力層的計算上的深度DOL_C、實際上壓縮應力為零的深度DOL_Z、50μm深度之壓縮應力CS(50)、拉伸應力CT，都是使用折原製作所製造的表面應力計FSM-6000LE以及應用程式FsmV來測定的。又，DOL_C，是假設壓縮應力為線性比例於深度方向上改變而計算出的假想計算值，DOL_Z則是視為壓縮應力屈曲於深度方向上改變而測定之測定值。此外，CS(50)以負數來表示的場合，表示該數值於深度50μm不是產生壓縮應力而是拉伸應力。 　　[0074] 破損高度fb，使用圖5所示的試驗裝置J來進行。試驗裝置J，具備與測試試樣之強化玻璃板G2衝突的鎚H，以及支撐測定試樣的支撐裝置L。 　　[0075] 支撐裝置L，為支撐強化玻璃板G2的構件。支撐裝置L，例如由具有傾斜面的支撐台、及由該傾斜面突出的栓所構成。強化玻璃板G2，以傾斜面與主表面S抵接，栓與強化玻璃板G2的端面E抵接的方式支撐於支撐裝置L。 　　[0076] 鎚H，具備臂部及頭部。臂部，為伸長方向上具有一定的剖面形狀的長尺寸構件。具體而言，臂部為長度500mm程度的鋁製棒狀構件。臂部，藉由螺栓等固定具以一端為中心可自由旋轉的方式配置。頭部，是與設於臂部的另一端之側面部而與強化玻璃板G2接觸的構件。具體而言，頭部為不鏽鋼合金製的構件。頭部，具備延伸於臂部的伸長方向之凸部，於該凸部的先端與強化玻璃板G2的端面部分接觸。 　　[0077] 以下，說明使用試驗裝置J之試驗方法。首先，把強化玻璃板G2設置於支撐裝置L。此時，以鎚H的頭部衝突於強化玻璃板G2的周緣部，更特定地說是衝突於倒角面B的方式來設置強化玻璃板G2。接著，在強化玻璃板G2表面之中鎚H的頭部所衝突的位置，以研磨面與強化玻璃板G2抵接的方式載置100號砂紙SP。接著，把鎚H轉動抬高到特定的高度。接著使抬高的鎚H落下而使頭部與強化玻璃板G2衝突。接著，直到強化玻璃板G2破損為止徐徐提高鎚H的抬高高度f同時反覆進行前述試驗。如此進行，測定強化玻璃板G2破損時之抬高高度f之值作為破損高度fb。又，砂紙SP在每1次鎚H落下後都換新。 　　[0078] 根據使用前述試驗裝置J之試驗，可以測定周緣部之前述特定模式之耐破損性。又，對試樣施加的衝突能量的大小因應於抬高高度f而變大，所以破損高度fb之值越大，於該模式就有越高的耐破損性。 　　[0079] No.1～6之試樣，周緣部的深度50μm之壓縮應力CS(50)為200MPa以上，所以其破損高度fb都在50mm以上，是具有高耐破損性的玻璃。另一方面，No.7～9之試樣，周緣部的深度50μm之壓縮應力CS(50)未滿200MPa，所以其破損高度fb都很低，是耐破損性低的玻璃。特別是No.7、9，因為第一離子交換步驟之處理時間很短，所以壓縮應力CS(50)為很小的值。此外，No.8，因為第一離子交換步驟之熔鹽T1的鈉離子濃度很高，所以壓縮應力CS(50)成為很小的值。 　　[0080] 在此，前述No.1～9之中，為了參考，將No.2～4、6、7之各個，把強化玻璃板的周緣部之由表面起算的深度與壓縮應力的大小的關係顯示於圖6。又，在該圖的縱軸，應力值為正值的場合，顯示是壓縮應力作用，負值的場合，為拉伸應力在作用。如由該圖所可理解的，在No.2～4、6，與No.7相比，可知壓縮應力之值相對於深度和緩地變小。接著，可知在No.2～4、6，壓縮應力作用到比No.7還要深的位置。 [產業上利用可能性] 　　[0081] 本發明之強化玻璃板及其製造方法，作為用於觸控面板顯示器等之玻璃基板以及其製造方法等是有用的。[0023] <First Embodiment> Hereinafter, a method for manufacturing a strengthened glass plate according to an embodiment of the present invention will be described. 1a to 1e are diagrams showing an example of a method for manufacturing a tempered glass sheet according to the present invention. [0024] First, the processing of the preparation step shown in FIG. 1a is performed. The preparation step is a step of preparing a glass plate G1 for strengthening. The strengthening glass plate G1 is a plate-shaped glass plate that can be strengthened using an ion exchange method. As shown in FIGS. 1 a and 2, the strengthening glass plate G1 of this embodiment is a substantially rectangular glass plate having a main surface S and an end surface E. In addition, FIG. 2 is a plan view of the glass plate G1 for tempering viewed in a plane direction of the plate thickness. In addition, FIG. 1 a is a cross-sectional view taken along the line AA of the tempered glass plate G1 of FIG. 2. The reinforcing glass plate G1 is chamfered and has a chamfered surface B between the main surface S and the end surface E. That is, the outer surface of the strengthening glass plate G1 includes a main surface S, an end surface E, and a chamfered surface B. [0025] The glass sheet G1 for strengthening is a glass sheet composition expressed in mass percentage, and contains SiO 2 45 to 75%, Al 2 O 3 1 to 30%, Na 2 O 0 to 20%, and K 2 O 0 to 20 % Is better. When the composition range of the glass plate is limited as described above, it is easier to achieve both ion exchange performance and devitrification resistance to a high degree. [0026] The thickness of the glass plate G1 for strengthening is, for example, 1.5 mm or less, preferably 1.3 mm or less, 1.1 mm or less, 1.0 mm or less, and particularly preferably 0.9 mm or less. In addition, the smaller the thickness of the tempered glass plate, the more the tempered glass plate can be made lighter, and as a result, the device can be made thinner and lighter. In such a case, the thickness of the strengthening glass plate G1 is preferably 0.7 mm or less, 0.6 mm or less, 0.5 mm or less, 0.4 mm or less, 0.3 mm or less, 0.2 mm or less, and particularly preferably 0.1 mm or less. In addition, considering productivity and the like, the thickness of the glass plate G1 for strengthening is preferably 0.01 mm or more. [0027] The planar transverse dimension of the strengthening glass plate G1 can be arbitrarily set, for example, 10 × 10 mm to 3350 × 3950 mm. [0028] The glass sheet for strengthening G1 is, for example, a glass formed by using an overflow downdraw method. Moreover, the shaping | molding method and working state of the glass plate G1 for tempering can also be selected arbitrarily. For example, the glass plate G1 for strengthening may be a glass formed by a float process. In addition, the main surface S, the end surface E, and the chamfered surface B may be those to be polished. [0029] Next, after the foregoing preparation step, the processing of the film formation step shown in FIG. 1b is performed. The film formation step is a step of forming an ion exchange membrane M on at least a part of the surface of the glass plate G1 for strengthening to obtain a glass plate G1m for film strengthening. In this embodiment, as shown in FIG. 3, the central part S1 of the main surface of the glass plate G1 for tempering is formed with the ion exchange prevention membrane M. As shown in FIG. FIG. 1b corresponds to a cross-sectional view taken along the line AA in FIG. 3. Among the surfaces of the glass plate for strengthening G1, peripheral portions other than the central portion S1 are exposed. The peripheral edge portion is a portion of the front and back main surfaces S including the outer peripheral area S2 surrounding the central portion S1, the chamfered surface B, and the end surface E. The ion exchange prevention membrane M is a membrane layer that suppresses or blocks the transmission of ions when performing ion exchange on the surface layer of the glass plate G1 for strengthening, in a first ion exchange step described later. [0030] The material of the ion exchange membrane M may be any material as long as it can suppress or block the transmission of ions that are ion-exchanged. When the ion to be exchanged is an alkali metal ion, the ion exchange prevention membrane M is preferably a metal oxide, a metal nitride, a metal carbide, a metal oxynitride, a metal oxycarbide, a metal carbonitride, or the like. In addition, a carbon material, a metal, or an alloy excellent in heat resistance or chemical durability can also be used as the ion-exchange membrane M. In more detail, the material of the ion exchange prevention membrane M may be, for example, SiO 2 , Al 2 O 3 , SiN, SiC, AlN, ZrO 2 , TiO 2 , Ta 2 O 5 , Nb 2 O 5 , HfO. 2 , SnO 2 , nano carbon tube, graphene, diamond-like carbon, stainless steel, more than one kind of film is selected. The ion-exchange membrane M is preferably an amorphous membrane that does not easily change crystallinity during the ion-exchange process. [0031] The ion-exchange membrane M also includes a membrane that inhibits ion transmission and is not completely blocked. The material of such an ion exchange membrane M can be, for example, ZrO 2 , SnO 2 , ITO membrane, or AlN. However, since the crystallinity of a film made of these materials is easily changed at high temperatures, the ion permeability may be easily changed during the ion exchange process. [0032] When mechanical strength or cost is considered, it is suitable to use a membrane containing SiO 2 as a main component and containing Al 2 O 3 as the ion-exchange prevention membrane M. In this case, it is preferable that the ion exchange prevention membrane M has a composition containing 20 to 99% of SiO 2 and 1 to 80% of Al 2 O 3 in terms of mass percentage. [0033] The thickness of the ion exchange membrane M may be any thickness as long as it can block or suppress ion transmission. However, if the thickness of the ion exchange membrane M is too large, the film formation time, material cost, and the like may increase. Therefore, it is preferable to use a thin topography within a range that can block and suppress ion transmission. Specifically, the film thickness of the anti-ion exchange membrane M is, for example, preferably 1 to 5000 nm, and more preferably 50 to 4000 nm. [0034] As the film formation method of the ion exchange membrane M, a PVD method (physical vapor deposition method) such as a sputtering method or a vacuum evaporation method, a CVD method (chemical vapor deposition method) such as a thermal CVD method, or a plasma CVD method can be used. Method), wet coating methods such as dip coating method or slit coating method. Particularly preferred is sputtering. When a sputtering method is used, the ion exchange membrane M can be formed easily and uniformly. The film formation location of the ion exchange prevention membrane M can be set by arbitrary methods. For example, film formation can be performed while the peripheral edge portion is covered. In addition, the ion exchange membrane M formed in a sheet shape in advance may be bonded to the main surface of the reinforcing glass plate G1 to form a film. [0035] In this embodiment, an example will be described in the case of forming an ion-exchange prevention film M containing SiO 2 and Al 2 O 3 with a film thickness of 100 nm or more and capable of blocking the transmission of alkali metal ions. [0036] Next, after the aforementioned film formation step, a process of an ion exchange step is performed. The ion exchange step is a process of forming a compressive stress deep layer C (C1, C2) by performing ion exchange on at least a part of the surface of the glass plate G1 for strengthening until the compressive stress at a position at a depth of 50 μm from the surface becomes 200 MPa or more. The ion exchange step in this embodiment includes a first ion exchange step shown in FIG. 1c and a second ion exchange step shown in FIG. 1e. [0037] First, the processing of the first ion exchange step shown in FIG. 1c is performed. The first ion exchange step is a step of obtaining a partially strengthened glass plate G2 chemically strengthened by a glass plate G1 for strengthening by an ion exchange method. Specifically, the glass plate G1 for immersion strengthening is ion-exchanged with the molten salt T1 containing an alkali metal ion. The molten salt T1 in this embodiment is, for example, a potassium nitrate molten salt. [0038] Here, among the surfaces of the glass plate G1 for strengthening, ion exchange is not performed in the region (central portion S1) where the ion exchange membrane M is formed, so no compressive stress layer is formed. On the other hand, among the surfaces of the glass plate G1 for strengthening, ion exchange is performed in a region (peripheral edge portion) where the ion exchange membrane M is not formed, and a compressive stress deep layer C1 is formed. [0039] The compressive stress deep layer C1 is a compressive stress layer with a compressive stress CS (50) of 50 μm in depth of 200 MPa or more. In addition, in the compressive stress deep layer C1, the maximum value of the compressive stress CSmax is 400 MPa or more, and the depth DOL_Z of the layer is preferably deeper than 100 μm. [0040] The temperature of the molten salt T1 in the first ion exchange step exceeds 430 ° C, preferably 440 to 500 ° C, and more preferably 450 to 490 ° C. The time for immersing the glass plate G1m for film strengthening in the molten salt T1 is, for example, 10 to 200 hours, preferably 12 to 170 hours, and more preferably 24 to 100 hours. By performing the ion exchange treatment at a relatively high temperature in this manner, a deep compressive stress layer can be formed on the peripheral portion in a short time. [0041] In addition, when the molten salt T1 is repeatedly used, the concentration of sodium ions increases, and the ion exchange characteristics may change. That is, the sodium ion concentration of the molten salt T1 is preferably maintained within a certain range. In order to increase the depth of the compressive stress deep layers C1 and C2 efficiently, the sodium ion concentration of the molten salt T1 is preferably limited to 50,000 ppm or less, more preferably 30,000 ppm or less, and still more preferably 20,000 ppm or less. The sodium ion concentration of the molten salt T1 can be adjusted by adding potassium nitrate or the like. [0042] The tempered glass plate G2 having the ion-exchange-preventive membrane M obtained at the time when the process of the first ion-exchange step is completed is referred to as a film-reinforced glass plate G2m. [0043] Next, after the aforementioned first ion exchange step, the processing of the film removing step shown in FIG. 1d is performed. The film removing step is a step of removing the ion-exchange-preventing membrane M from the film-reinforced glass plate G2m. As a method for removing the ion exchange membrane M, for example, a method such as polishing or etching can be used. [0044] As a polishing device used for polishing, a well-known double-side polishing machine or single-side polishing machine can be used. When the ion exchange membrane M is removed by polishing, only the ion exchange membrane M may be polished, and the ion exchange membrane M and the glass plate may be polished at the same time. [0045] As the etching method, a method such as dry etching or wet etching can be used. [0046] When dry etching is used, it is particularly preferable to use plasmas such as Ar, O 2 , CH 4 , BC 13 , C 12 , SF 6 and the like. [0047] As the etching solution used for wet etching, for example, a solution containing fluorine, TMAH (tetramethylammonium hydroxide), EDP, KOH, NaOH, etc. can be used as the etching solution, and in particular, a hydrofluoric acid solution can be used as the etching solution. Better to use. When a hydrofluoric acid solution is used, and only the ion exchange membrane M is removed without changing the glass size, the HF concentration of the hydrofluoric acid solution is preferably 10% or less. [0048] The tempered glass plate G2a obtained as described above has a compressive stress deep layer C1 at the peripheral portion. That is, the tempered glass plate G2a is a glass having high damage resistance at the peripheral portion. [0049] Next, after the aforementioned film removing step, the processing of the second ion exchange step shown in FIG. 1e is performed. The second ion exchange step is a step of forming a relatively shallow compressive stress shallow layer D in a region where the compressive stress layer is not formed in the first ion exchange step to obtain a strengthened glass plate G2b. In this embodiment, as shown in FIG. 1e, a tempered glass plate G2 is immersed in a molten salt T2 containing an alkali metal ion, and a shallow layer of compressive stress is formed in the entire area (central portion S1) where the ion exchange membrane M is formed. D. The molten salt T2 is, for example, a potassium nitrate molten salt. [0050] The compressive stress deep layer C1 formed at the peripheral portion becomes a compressive stress deep layer C2 by changing the characteristics somewhat by contacting the molten salt T2 in the aforementioned treatment. In this embodiment, after the change, the compressive stress deep layer C2 is a compressive stress layer having a compressive stress CS (50) having a depth of 50 μm of 200 MPa or more. The compressive stress CS (50) having a depth of 50 μm in the compressive stress deep layer C2 is preferably 200 to 500 MPa, more preferably 220 to 450 MPa, and even more preferably 250 to 400 MPa. [0051] The temperature of the molten salt T2 in the second ion exchange step is preferably lower than the temperature of the molten salt T1 used in the aforementioned first ion exchange step. By performing the ion exchange treatment at a relatively low temperature in this way, it becomes easy to prevent the depth of the compressive stress shallow layer D formed in the central portion S1 from becoming too large. The temperature of the molten salt T2 is, for example, 430 ° C or lower, more preferably 390 to 430 ° C, and even more preferably 400 to 425 ° C. [0052] The time for which the tempered glass plate G2 is immersed in the molten salt T2 is, for example, 0.1 to 72 hours, preferably 0.3 to 50 hours, and more preferably 0.5 to 24 hours. [0053] Also, the sodium ion concentration of the molten salt T2 is preferably maintained within a certain range similarly to the molten salt T1. The sodium ion concentration of the molten salt T2 is preferably limited to 30,000 ppm or less, more preferably 20,000 ppm or less, and still more preferably 10,000 ppm or less. By adjusting the sodium ion concentration of the molten salt T2 in this way, the maximum value of the compressive stress of the deep compressive stress layer G2 and the shallow compressive stress layer D can be made larger. [0054] The maximum value of the compressive stress of the compressive stress deep layer C2 is preferably 400 MPa or more, more preferably 450 to 1500 MPa, and even more preferably 500 to 1200 MPa. The depth of the compressive stress deep layer C2 is preferably 100 μm or more, more preferably 100 to 300 μm, and even more preferably 100 to 250 μm. [0055] As described above, by performing the second-degree ion exchange step processing, the compressive stress deep layer C2 of the relatively deep compressive stress layer and the compressive stress shallow layer D of the relatively shallow compressive stress layer can be obtained respectively. Area of the strengthened glass plate G2b. According to such a strengthened glass plate G2b, for example, a deep compressive stress deep layer C2 is formed at the peripheral edge portion that is likely to be the starting point of damage, and high breakage resistance can be obtained. At the same time, a shallow compressive stress shallow layer D is formed in the central portion S1 to suppress internal tension An increase in the tensile stress suppresses an increase in the tensile stress formed inside the tempered glass sheet G2. In addition, since the tensile stress is reduced in the central portion S1, it is difficult to form a thin fragment when compared with the peripheral portion when broken. That is, when the tempered glass plate G2 is used in a display or the like, it is easy to maintain the visibility of the display even after the glass is broken. [0056] The tempered glass plate G2 (G2a, G2b) has a compressive stress deep layer C (C1, C2) as described above, and has a high strength in a specific damage mode at a portion where the layer is formed. The so-called specific damage mode refers to the presence of sharp protrusions at the drop of the strengthened glass plate G2. The protrusions break through the surface compressive stress layer and reach the internal tensile stress layer, which causes cracking. The crack causes Damage mode in which internal tensile stress progresses and breaks. [0057] The processing conditions such as the temperature or immersion time of the molten salt T1 in the first ion exchange step and the temperature or immersion time of the molten salt T2 in the second ion exchange step are only examples, and the compressive stress to be formed can be deepened. C is arbitrarily adjusted so that the compressive stress CS (50) having a depth of 50 μm becomes a stress layer of 200 MPa or more. [0058] In order to suppress the manufacturing cost of the strengthened glass sheet, for example, the first ion exchange step and the second ion exchange step are performed in the same strengthening tank (molten salt). In this case, the difference between the temperature of the molten salt when the first ion-exchange step is performed and the temperature of the molten salt when the second ion-exchange step is performed is likely to narrow within a range of ± 5 ° C. [0059] In the foregoing embodiment, the case where the compressive stress deep layer C1 formed in the treatment of the first ion exchange step has a strengthening characteristic with a compressive stress CS (50) of 200 MPa or more at a depth of 50 μm will be described as an example. However, if the time point at which the processing in the second ion exchange step becomes the compressive stress deep layer C2 has this characteristic, the time point after the processing in the first ion exchange step may not have the aforementioned characteristics. [0060] In addition, after the second ion-exchange step, a process of performing a finishing step may be performed (not shown). In the finishing step, the surface of the strengthened glass plate G2b, for example, at least one of the main surface S and the end surface E is polished. When the size or surface state of the tempered glass plate G2b is not the desired state due to the processing of the second ion exchange step, the desired state can be achieved by performing the processing of such a finishing step. [0061] As described above, according to the method for manufacturing a strengthened glass sheet according to an embodiment of the present invention, it is possible to stably and efficiently manufacture the strengthened glass sheet G2 (G2m) having a high strength in the specific damage mode described above. , G2b). [0062] Furthermore, processing steps such as cutting processing, hole processing, grinding processing, and stone carving processing may be added before and after any of the steps shown above. In addition, before and after any of the steps shown above, the glass plate may be appropriately washed and dried. [0063] In the foregoing embodiment, the case where the molten salts T1 and T2 are potassium nitrate molten salts will be described as an example, but the invention is not limited to this, and conventional molten salts used for ion exchange of glass plates are used instead of or in combination. Yes. [0064] The ion exchange treatment is not limited to the immersion into a molten salt as described above, and may be performed by applying a molten salt, for example. [0065] In addition, the magnitude of the compressive stress and the depth of each layer of the compressive stress deep layers C1, C2, and the shallow compressive stress shallow layer D can be measured using, for example, a stress meter (FSM-6000LE and FsmV manufactured by Ohara Co., Ltd.). [Second Embodiment] In the first embodiment described above, the case where the compressive stress deep layer C (C1, C2) is formed only at the peripheral edge portion of the strengthened glass plate G2 is described as an example, but the strengthened glass plate G2 is described as an example. A deep layer C of compressive stress may be formed on the entire outer surface. 4a and 4b are diagrams showing the outline of a method for manufacturing a tempered glass sheet according to a second embodiment of the present invention. 4a is a preparation step for preparing a glass plate G1 for tempering, similarly to the first embodiment. Thereafter, in the second embodiment, the process of the film formation step is omitted. As shown in FIG. 4B, the process of the ion exchange step is performed on the glass plate G1 for strengthening without the ion exchange membrane M. According to such a process, the tempered glass plate G2 (G2c) having the compressive stress deep layer C (C3) formed on the entire outer surface can be easily manufactured. [Examples] [0068] The tempered glass sheet G2 (G2b or G2c) of the present invention will be described below based on examples. In Table 1, Nos. 1 to 6 are examples of the present invention, and Nos. 7 to 9 are comparative examples. In addition, the following examples are merely examples, and the present invention is not limited to the following examples. [0069] First, samples Nos. 1 to 9 were prepared as follows. The glass composition is expressed in mole percentages so as to contain SiO 2 66.3%, Al 2 O 3 11.4%, Na 2 O 15.2%, B 2 O 3 0.5%, Li 2 O 0.2%, K 2 O 1.4%, MgO 4.8 %, SnO 2 0.2% glass method, glass raw materials were blended, and a platinum can was used to melt at 1600 ° C for 21 hours. Thereafter, the obtained molten glass was left-molded from the refractory molded article using an overflow down-draw method, and formed into a plate shape having a thickness of 0.4 mm to obtain a glass plate for strengthening. [0070] Next, the resulting strengthened, for sample No.1 ~ 3,5,7, according to the step shown in FIG. IB, expressed as a percentage by mass composition is formed into a glass containing SiO 2 70%, Al 2 O 3 30% ion exchange membrane. Next, each of the samples Nos. 1 to 9 was immersed in molten potassium nitrate under the conditions shown in Table 1 and subjected to ion exchange treatment (first ion exchange step). Next, samples Nos. 1 to 3, 5, and 7 having an ion exchange membrane were removed by polishing (removal step). Thereafter, the samples of Nos. 1 to 3, 5, 7, and 8 were again immersed in a molten potassium nitrate under the conditions shown in Table 1 and subjected to ion exchange treatment (second ion exchange step). [0071] With respect to each of the data obtained as described above, the following characteristic measurement and strength test were performed. [0072] [0073] The maximum value of the compressive stress CSmax of the peripheral portion and the central portion shown in Table 1, the calculated depth DOL_C of each compressive stress layer, the depth DOL_Z which is actually zero compressive stress, and the compressive stress CS (50 μm depth) ) And tensile stress CT are measured using a surface stress meter FSM-6000LE manufactured by Ohara Corporation and the application program FsmV. In addition, DOL_C is an imaginary calculation value calculated assuming that the compressive stress changes linearly in the depth direction, and DOL_Z is a measured value measured as the compressive stress buckling changes in the depth direction. In addition, when CS (50) is expressed as a negative number, it means that the value is not a compressive stress but a tensile stress at a depth of 50 μm. [0074] The damage height fb was performed using the test device J shown in FIG. 5. The test device J includes a hammer H that collides with the strengthened glass plate G2 of the test sample, and a support device L that supports the measurement sample. [0075] The support device L is a member that supports the strengthened glass plate G2. The support device L includes, for example, a support base having an inclined surface, and a peg protruding from the inclined surface. The tempered glass plate G2 is supported by the support device L so that the inclined surface abuts the main surface S, and the pin abuts the end surface E of the tempered glass plate G2. [0076] The hammer H includes an arm portion and a head portion. The arm portion is a long member having a constant cross-sectional shape in the elongation direction. Specifically, the arm portion is an aluminum rod-shaped member having a length of approximately 500 mm. The arm is rotatably arranged around one end by a fixture such as a bolt. The head portion is a member that comes into contact with the tempered glass plate G2 with a side surface portion provided on the other end of the arm portion. Specifically, the head is a member made of a stainless steel alloy. The head portion includes a convex portion extending in the elongation direction of the arm portion, and a tip end of the convex portion is in contact with an end surface portion of the tempered glass plate G2. [0077] A test method using the test device J will be described below. First, the tempered glass plate G2 is set on the support device L. At this time, the strengthened glass plate G2 is provided so that the head of the hammer H collides with the peripheral edge portion of the strengthened glass plate G2, more specifically, with the chamfered surface B. Next, on the surface of the strengthened glass plate G2 where the head of the hammer H collided, a 100-gauge sandpaper SP was placed so that the polishing surface abuts on the strengthened glass plate G2. Next, the hammer H is rotated and raised to a specific height. Next, the raised hammer H is dropped and the head collides with the tempered glass plate G2. Then, until the tempered glass plate G2 is broken, the raising height f of the hammer H is gradually increased, and the aforementioned test is repeatedly performed. In this way, the value of the raised height f when the tempered glass plate G2 was broken was measured as the broken height fb. In addition, the sandpaper SP is renewed after each drop of the hammer H. [0078] According to the test using the test device J described above, the breakage resistance of the specific mode in the peripheral portion can be measured. In addition, the magnitude of the collision energy applied to the sample increases in response to the raised height f. Therefore, the larger the value of the damage height fb, the higher the damage resistance in this mode. [0079] In the samples Nos. 1 to 6, the compressive stress CS (50) at a depth of 50 μm in the peripheral portion is 200 MPa or more, so the breakage heights fb are all 50 mm or more, and the glass has high breakage resistance. On the other hand, in the samples Nos. 7 to 9, the compressive stress CS (50) at a depth of 50 μm in the peripheral portion was less than 200 MPa, so the breakage height fb was low, and the glass had low breakage resistance. In particular, Nos. 7 and 9, because the processing time of the first ion exchange step is short, the compressive stress CS (50) is a small value. In addition, No. 8 has a high value of the compressive stress CS (50) because the sodium ion concentration of the molten salt T1 in the first ion exchange step is high. [0080] Here, among the aforementioned Nos. 1 to 9, for reference, each of Nos. 2 to 4, 6, and 7 is the depth from the surface of the peripheral edge portion of the strengthened glass plate and the magnitude of the compressive stress. The relationship is shown in Figure 6. In addition, when the vertical axis of the figure has a positive stress value, it shows that the compressive stress is acting, and when it is negative, it means that the tensile stress is acting. As can be understood from the figure, in Nos. 2 to 4, and 6, compared with No. 7, it can be seen that the value of the compressive stress gradually decreases with respect to the depth. Next, it can be seen that in Nos. 2 to 4, 6 the compressive stress is applied to a position deeper than that in No. 7. [Industrial Applicability] [0081] The strengthened glass plate and the manufacturing method thereof according to the present invention are useful as a glass substrate for a touch panel display and the like, and a manufacturing method thereof.

[0082][0082]

G1‧‧‧強化用玻璃板G1‧‧‧ Strengthened glass plate

G2(G2a、G2b、G2c)‧‧‧強化玻璃板G2 (G2a, G2b, G2c) ‧‧‧Tempered glass

M‧‧‧防離子交換膜M‧‧‧Anti-ion exchange membrane

T1‧‧‧第一熔鹽T1‧‧‧The first molten salt

T2‧‧‧第二熔鹽T2‧‧‧Second Molten Salt

[0022] 　　圖1a係顯示相關於本發明之第一實施形態的強化玻璃板的製造方法之圖。 　　圖1b係顯示相關於本發明之第一實施形態的強化玻璃板的製造方法之圖。 　　圖1c係顯示相關於本發明之第一實施形態的強化玻璃板的製造方法之圖。 　　圖1d係顯示相關於本發明之第一實施形態的強化玻璃板的製造方法之圖。 　　圖1e係顯示相關於本發明之第一實施形態的強化玻璃板的製造方法之圖。 　　圖2係顯示相關於本發明之實施形態的強化玻璃板之平面圖。 　　圖3係顯示具備相關於本發明之實施形態的防離子交換膜之強化用玻璃板之平面圖。 　　圖4a係顯示相關於本發明之第二實施形態的強化玻璃板的製造方法之圖。 　　圖4b係顯示相關於本發明之第二實施形態的強化玻璃板的製造方法之圖。 　　圖5係相關於本發明的實施形態之破損高度測定用試驗裝置之概要圖。 　　圖6係針對強化玻璃板顯示由表面起算的深度與壓縮應力的大小的關係之圖。[0022] FIG. 1a is a diagram showing a method for manufacturing a strengthened glass plate according to a first embodiment of the present invention. Fig. 1b is a view showing a method for manufacturing a tempered glass plate according to the first embodiment of the present invention. Fig. 1c is a view showing a method for manufacturing a tempered glass plate according to the first embodiment of the present invention. Fig. 1d is a view showing a method for manufacturing a tempered glass plate according to the first embodiment of the present invention. Fig. 1e is a view showing a method for manufacturing a tempered glass sheet according to the first embodiment of the present invention. Fig. 2 is a plan view showing a tempered glass plate according to an embodiment of the present invention. FIG. 3 is a plan view showing a reinforcing glass plate provided with an ion exchange membrane according to an embodiment of the present invention. Fig. 4a is a view showing a method for manufacturing a tempered glass plate according to a second embodiment of the present invention. Fig. 4b is a view showing a method for manufacturing a tempered glass plate according to a second embodiment of the present invention. FIG. 5 is a schematic diagram of a test apparatus for measuring a height of a damage according to an embodiment of the present invention. FIG. 6 is a diagram showing the relationship between the depth from the surface and the magnitude of the compressive stress for a tempered glass plate.

Claims (12)

一種強化玻璃板之製造方法，其特徵係 　　把強化用玻璃板的表面之至少一部分離子交換形成壓縮應力層， 　　具備進行前述離子交換直到前述壓縮應力層由表面起算深度50μm的位置之壓縮應力成為200MPa以上為止之離子交換步驟。A method for manufacturing a strengthened glass plate, characterized in that at least a part of the surface of a strengthened glass plate is ion-exchanged to form a compressive stress layer, and the compressive stress is provided so that the compressive stress at the position where the compressive stress layer has a depth of 50 μm from the surface becomes 200 MPa The ion exchange steps so far. 如申請專利範圍第1項之強化玻璃板之製造方法，其中 　　於前述離子交換步驟，進行離子交換處理直到前述壓縮應力層之壓縮應力的最大值成為400MPa以上，且由該層的外表面起算的深度比100μm更深為止。For example, the method for manufacturing a strengthened glass plate according to item 1 of the patent scope, wherein in the foregoing ion exchange step, ion exchange treatment is performed until the maximum value of the compressive stress of the compressive stress layer becomes 400 MPa or more, and it is calculated from the outer surface of the layer. The depth is deeper than 100 μm. 如申請專利範圍第1或2項之強化玻璃板之製造方法，其中 　　前述離子交換步驟，包含使前述強化用玻璃板接觸於第一溫度的熔鹽進行前述離子交換之第一離子交換步驟，與使前述強化用玻璃板接觸於第二溫度的熔鹽進行前述離子交換的第二離子交換步驟； 　　進而具備： 　　於前述第一離子交換步驟前，於前述強化用玻璃板的表面之至少一部分預先設置防止前述離子交換之防離子交換膜的成膜步驟，以及 　　於前述第一離子交換步驟後，除去前述防離子交換膜的除去步驟；於前述除去步驟後實施前述第二離子交換步驟。For example, the manufacturing method of a strengthened glass plate according to item 1 or 2 of the patent application scope, wherein the aforementioned ion exchange step includes a first ion exchange step of bringing the aforementioned strengthened glass plate into contact with a molten salt at a first temperature to perform the aforementioned ion exchange, and Performing the second ion exchange step of contacting the glass plate for tempering with a molten salt at a second temperature; and further comprising: (1) providing in advance at least a part of a surface of the glass plate for tempering before the first ion exchange step; The film-forming step of the ion-exchange-preventing membrane preventing the ion exchange, and the removing step of removing the ion-exchange preventing membrane after the first ion-exchanging step; and performing the second ion-exchanging step after the removing step. 如申請專利範圍第3項之強化玻璃板之製造方法，其中 　　前述第二溫度比前述第一溫度更低； 　　前述第一離子交換步驟之離子交換處理時間，比前述第二離子交換步驟之離子交換處理時間更長。For example, the method for manufacturing a strengthened glass plate according to item 3 of the patent application, wherein the aforementioned second temperature is lower than the aforementioned first temperature; The ion exchange processing time of the aforementioned first ion exchange step is longer than the ion exchange of the aforementioned second ion exchange step Processing time is longer. 如申請專利範圍第4項之強化玻璃板之製造方法，其中 　　前述第一溫度超過430℃，前述第二溫度為430℃以下。For example, the method for manufacturing a strengthened glass plate according to item 4 of the patent application, wherein: the first temperature exceeds 430 ° C, and the foregoing second temperature is 430 ° C or lower. 如申請專利範圍第3項之強化玻璃板之製造方法，其中 　　前述第一溫度與前述第二溫度之差為±5℃以內。For example, the method for manufacturing a strengthened glass plate according to item 3 of the patent application scope, wherein: 差 The difference between the first temperature and the second temperature is within ± 5 ° C. 如申請專利範圍第1或2項之強化玻璃板之製造方法，其中 　　於前述離子交換步驟，使前述強化用玻璃板連續10個小時以上接觸於鈉離子濃度為50000ppm以下的硝酸鉀熔鹽進行前述離子交換。For example, the method for manufacturing a strengthened glass plate according to item 1 or 2 of the patent application scope, wherein in the foregoing ion exchange step, the aforementioned strengthened glass plate is continuously contacted with a molten potassium nitrate having a sodium ion concentration of 50,000 ppm or less for more than 10 hours to perform the foregoing Ion exchange. 一種強化玻璃板，其特徵為 　　於外表面之至少一部份具有深度50μm之壓縮應力為200MPa以上的壓縮應力深層。A strengthened glass plate, characterized in that at least a part of the outer surface has a compressive stress deep layer with a compressive stress of 200 MPa or more at a depth of 50 μm. 如申請專利範圍第8項之強化玻璃板，其中 　　前述壓縮應力深層之壓縮應力的最大值為400MPa以上且深度比100μm更深。For example, the strengthened glass sheet according to item 8 of the scope of patent application, wherein the maximum value of the compressive stress of the aforementioned deep layer of compressive stress is 400 MPa or more and the depth is deeper than 100 μm. 如申請專利範圍第8或9項之強化玻璃板，其中 　　沿著周緣部具備前述壓縮應力深層。For example, the tempered glass sheet according to item 8 or 9 of the scope of patent application, wherein is provided with the aforementioned deep layer of compressive stress along the periphery. 如申請專利範圍第8或9項之強化玻璃板，其中 　　於表面之中未被形成前述壓縮應力深層的區域之至少一部分具有比前述壓縮應力深層更淺的壓縮應力淺層。For example, in the strengthened glass sheet according to item 8 or 9 of the scope of patent application, at least a part of the area where the aforementioned deep layer of compressive stress is not formed on the surface has a shallow shallow layer of compressive stress that is shallower than the deep layer of compressive stress. 如申請專利範圍第11項之強化玻璃板，其中 　　前述壓縮應力淺層之深度為35～60μm，且壓縮應力的最大值為600～1500MPa。For example, the strengthened glass sheet according to item 11 of the scope of patent application, wherein the depth of the aforementioned shallow layer of compressive stress is 35 to 60 μm, and the maximum value of the compressive stress is 600 to 1500 MPa.
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