TWI618683B - Tempered glass and glass for tempering - Google Patents

Tempered glass and glass for tempering Download PDF

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TWI618683B
TWI618683B TW103125332A TW103125332A TWI618683B TW I618683 B TWI618683 B TW I618683B TW 103125332 A TW103125332 A TW 103125332A TW 103125332 A TW103125332 A TW 103125332A TW I618683 B TWI618683 B TW I618683B
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glass
item
tempered glass
compressive stress
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TW201509853A (en
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川本浩佑
村田
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日本電氣硝子股份有限公司
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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
    • C03C3/083—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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • 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)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

本發明是一種於表面具有壓縮應力層的強化玻璃，其特徵在於：作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、10%~30%的Al2O3、0%~6%的B2O3、5%~25%的Na2O、0%~10%的MgO，且實質上不含As2O3、Sb2O3、PbO以及F。 The present invention is a strengthened glass having a compressive stress layer on the surface, which is characterized in that, as a glass composition, it contains 50% to 80% of SiO 2 and 10% to 30% of Al 2 O 3 in terms of mole%. % To 6% of B 2 O 3 , 5% to 25% of Na 2 O, 0% to 10% of MgO, and substantially free of As 2 O 3 , Sb 2 O 3 , PbO, and F.

Description

強化玻璃及強化用玻璃 Tempered glass and tempered glass

本發明是有關於一種強化玻璃以及強化用玻璃，尤其是有關於一種適合於行動電話、數位相機、個人數位助理(Personal Digital Assistant，PDA)(行動終端機)、太陽電池等的蓋玻璃，或者顯示器、特別是觸控面板顯示器的玻璃基板的強化玻璃以及強化用玻璃。 The present invention relates to a strengthened glass and a strengthened glass, and more particularly, to a cover glass suitable for a mobile phone, a digital camera, a personal digital assistant (PDA) (mobile terminal), a solar cell, or the like, or A tempered glass and a tempered glass of a glass substrate of a display, particularly a touch panel display.

行動電話、數位相機、PDA、觸控面板顯示器、大型電視、非接觸供電等裝置(device)存在日益普及的傾向。 Devices such as mobile phones, digital cameras, PDAs, touch panel displays, large televisions, and non-contact power supplies tend to become increasingly popular.

於該些用途中使用藉由離子交換處理等進行了強化處理的強化玻璃(參照專利文獻1、非專利文獻1)。 For these applications, a tempered glass that has been tempered by an ion exchange process or the like is used (see Patent Document 1, Non-Patent Document 1).

而且，近年來將強化玻璃用於數位看板(Digital signage)、滑鼠(mouse)、智慧型手機等的外部裝飾零件中的情況不斷增加。 Furthermore, in recent years, the use of tempered glass in exterior decoration parts such as digital signage, mouse, and smartphone has been increasing.

作為強化玻璃的主要要求特性，可列舉：(1)高機械強度、(2)高耐刮傷性、(3)輕量、(4)低成本等。尤其於智慧型手機的用途中，輕量化即薄型化的要求不斷提高。 The main required characteristics of tempered glass include (1) high mechanical strength, (2) high scratch resistance, (3) light weight, (4) low cost, and the like. Especially in the use of smart phones, the demand for weight reduction, that is, thinning, is constantly increasing.

現有技術文獻 Prior art literature

專利文獻 Patent literature

專利文獻1：日本專利特開2006-83045號公報 Patent Document 1: Japanese Patent Laid-Open No. 2006-83045

非專利文獻 Non-patent literature

非專利文獻1：泉谷徹郎等、「新型玻璃與其物性」、初版、經營系統研究所股份有限公司、1984年8月20日、頁451-498 Non-Patent Document 1: Izumi Tetsuro, etc., "New Glass and Its Physical Properties", First Edition, Management Systems Research Corporation, August 20, 1984, pages 451-498

但，若將現有的強化玻璃薄型化，則有內部的拉伸應力變得過大，於強化玻璃破損時碎片飛散，或強化玻璃自我斷裂之虞。因此於使壓縮應力層的壓縮應力值或厚度增加，提高強化玻璃的機械強度的方面而言，自然存在界限。故有效的是盡可能地抑制於強化玻璃表面產生刮傷且抑制機械強度的降低。 However, if the conventional tempered glass is made thin, the internal tensile stress becomes too large, and when the tempered glass is broken, fragments may be scattered, or the tempered glass may break by itself. Therefore, there is naturally a limit in terms of increasing the compressive stress value or thickness of the compressive stress layer and improving the mechanical strength of the strengthened glass. Therefore, it is effective to suppress the occurrence of scratches on the surface of the tempered glass as much as possible and to suppress the decrease in mechanical strength.

作為難以產生刮傷的強化用玻璃即裂紋產生率低的強化用玻璃，提出有B2O3含量高的玻璃。然而B2O3含量高的玻璃難以獲得高的強化特性。 As a glass for tempering, which is a glass for tempering that is hard to cause scratches, and has a low crack generation rate, a glass with a high B 2 O 3 content has been proposed. However, glass with a high B 2 O 3 content is difficult to obtain high strengthening characteristics.

進而，B2O3含量越多，強化用玻璃的應變點越容易降低。低應變點的強化用玻璃存在強化特性容易因KNO3熔融鹽的溫度變化而發生變化的問題。尤其，若推進薄型化，則會產生如下問題：因強化用玻璃面內的強化特性的稍許不均，而導致強化玻璃的翹曲量變大。為了解決該問題，必須嚴格控制強化用玻璃面內的強化特性，於該方面而言，有效的是實現強化用玻璃的高應變點化。 Furthermore, as the content of B 2 O 3 increases, the strain point of the glass for tempering tends to decrease. The low strain point strengthening glass has a problem that the strengthening characteristics are liable to change due to a temperature change of the KNO 3 molten salt. In particular, if the reduction in thickness is promoted, a problem arises in that the amount of warping of the strengthened glass increases due to slight unevenness in the strengthening characteristics within the surface of the glass for strengthening. In order to solve this problem, it is necessary to strictly control the strengthening characteristics in the plane of the glass for strengthening. In this respect, it is effective to increase the strain point of the glass for strengthening.

因此，本發明鑒於所述情況而成，其技術性課題在於創 造一種強化玻璃以及強化用玻璃，所述強化玻璃以及強化用玻璃即便不過剩地含有B2O3，裂紋產生率亦低，並且強化特性或應變點充分地高且適於薄型化。 Therefore, the present invention has been made in view of the above-mentioned circumstances, and a technical problem thereof is to create a strengthened glass and a strengthened glass which have a low crack generation rate even if B 2 O 3 is not excessively contained, and The strengthening characteristics or strain points are sufficiently high and suitable for thinning.

本發明者等人進行了各種研究，結果發現藉由嚴格地規定玻璃組成可解決所述技術性課題，從而作為本發明而提出。即本發明的強化玻璃於表面具有壓縮應力層，其特徵在於：作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、10%~30%的Al2O3、0%~6%的B2O3、5%~25%的Na2O以及0%~10%的MgO，且實質上不含As2O3、Sb2O3、PbO以及F。此處，所謂「實質上不含As2O3」為以下主旨：雖不積極地添加As2O3作為玻璃成分，但容許雜質水準的添加，具體而言是指As2O3的含量小於0.1莫耳%的情形。所謂「實質上不含Sb2O3」為以下主旨：雖不積極地添加Sb2O3作為玻璃成分，但容許雜質水準的添加，具體而言是指Sb2O3的含量小於0.1莫耳%的情形。所謂「實質上不含PbO」為以下主旨：雖不積極地添加PbO作為玻璃成分，但容許雜質水準的添加，具體而言是指PbO的含量小於0.1莫耳%的情形。所謂「實質上不含F」為以下主旨：雖不積極地添加F作為玻璃成分，但容許雜質水準的添加，具體而言是指F的含量小於0.1莫耳%的情形。 The present inventors have conducted various studies, and as a result, have found that the above technical problems can be solved by strictly specifying the glass composition, and have been proposed as the present invention. That is, the tempered glass of the present invention has a compressive stress layer on the surface, which is characterized in that as a glass composition, it contains 50% to 80% of SiO 2 , 10% to 30% of Al 2 O 3 , and 0% in terms of mole%. ~ 6% of B 2 O 3 , 5% ~ 25% of Na 2 O, and 0% ~ 10% of MgO, and are substantially free of As 2 O 3 , Sb 2 O 3 , PbO, and F. Here, the so-called "substantially free of As 2 O 3 " is the following gist: Although As 2 O 3 is not actively added as a glass component, the addition of an impurity level is allowed, specifically, the content of As 2 O 3 is less than 0.1 mol%. The so-called "substantially free of Sb 2 O 3 " is the following purpose: Although Sb 2 O 3 is not actively added as a glass component, the addition of an impurity level is allowed, specifically, the content of Sb 2 O 3 is less than 0.1 mol % Of cases. The so-called "substantially free of PbO" is the main idea: although PbO is not actively added as a glass component, the addition of an impurity level is allowed. Specifically, it refers to a case where the content of PbO is less than 0.1 mole%. The so-called "substantially free of F" is the main idea: although F is not actively added as a glass component, the addition of an impurity level is allowed, specifically, a case where the content of F is less than 0.1 mol%.

本發明的強化玻璃的特徵在於：作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、12%~18%的Al2O3、0%~3%的B2O3、12%~18%的Na2O、0%~2%的K2O、0.1%~4%的MgO以 及0%~2%的CaO，莫耳比Na2O/Al2O3為0.6~1.6。 The tempered glass of the present invention is characterized in that as a glass composition, it contains 50% to 80% of SiO 2 , 12% to 18% of Al 2 O 3 , and 0% to 3% of B 2 O 3 in terms of mole%. , 12% ~ 18% Na 2 O, 0% ~ 2% K 2 O, 0.1% ~ 4% MgO, and 0% ~ 2% CaO, the molar ratio Na 2 O / Al 2 O 3 is 0.6 ~ 1.6.

本發明的強化玻璃較佳為強化處理前的裂紋產生率為80%以下。此處，「裂紋產生率」是指如下般測定而得的值。首先，於保持為濕度30%、溫度25℃的恆溫恆濕槽內，對玻璃表面(光學研磨面)實施15秒的設定為載荷1000gf的維氏壓頭(Vickers indenter)的楔入，實施15秒後，對自壓痕的4角產生的裂紋數進行計數(針對1個壓痕而言最大值為4)。如上所述將壓頭楔入50次並求出總裂紋產生數，之後藉由(總裂紋產生數/200)×100的式子而求出所述裂紋產生率。 The tempered glass of the present invention preferably has a crack generation rate before tempering of 80% or less. Here, the "crack generation rate" means a value measured as follows. First, wedge a Vickers indenter set at a load of 1000 gf to a glass surface (optical polishing surface) for 15 seconds in a constant temperature and humidity tank maintained at a humidity of 30% and a temperature of 25 ° C. for 15 seconds. After 2 seconds, the number of cracks generated from the 4 corners of the indentation was counted (the maximum value is 4 for one indentation). As described above, the indenter was wedged 50 times to obtain the total number of cracks, and then the crack generation rate was determined by the formula (total number of cracks / 200) × 100.

本發明的強化玻璃較佳為壓縮應力層的壓縮應力值為900MPa以上且1500MPa以下，並且壓縮應力層的厚度為10μm以上且60μm以下。此處，「壓縮應力層的壓縮應力值」及「壓縮應力層的厚度」是指使用表面應力計(例如東芝股份有限公司製造的FSM-6000)對試樣進行觀察時，根據所觀察到的干涉條紋的根數與其間隔而算出的值。 The tempered glass of the present invention preferably has a compressive stress layer having a compressive stress value of 900 MPa to 1500 MPa and a thickness of the compressive stress layer of 10 μm to 60 μm. Here, the "compressive stress value of the compressive stress layer" and the "thickness of the compressive stress layer" refer to the observation of a sample using a surface stress meter (such as FSM-6000 manufactured by Toshiba Corporation). A value calculated by the number of interference fringes and the interval between them.

本發明的強化玻璃較佳為應變點為590℃以上。此處，所謂「應變點」是指基於美國試驗材料學會(American Society for Testing Material，ASTM)C336的方法進行測定而得的值。 The tempered glass of the present invention preferably has a strain point of 590 ° C or higher. Here, the "strain point" is a value measured by the method of the American Society for Testing Material (ASTM) C336.

本發明的強化玻璃較佳為液相溫度為1250℃以下。此處，所謂「液相溫度」是設為如下溫度：將通過標準篩30目(500μm)而殘留於50目(300μm)的玻璃粉末裝入鉑舟，於溫度梯度爐中保持24小時後，將鉑舟取出，藉由顯微鏡觀察而確認到於玻 璃內部失透(結晶異物)的最高溫度。 The tempered glass of the present invention preferably has a liquidus temperature of 1250 ° C or lower. Here, the "liquid phase temperature" is set to a temperature in which a glass powder which passes through a standard sieve of 30 mesh (500 μm) and remains in 50 mesh (300 μm) is loaded into a platinum boat and held in a temperature gradient furnace for 24 hours. Take out the platinum boat and observe the glass by microscope observation. Maximum temperature of devitrification (crystalline foreign matter) inside the glass.

本發明的強化玻璃較佳為液相黏度為104.5dPa．s以上。此處，所謂「液相黏度」是指利用鉑球提拉法對液相溫度下的黏度進行測定而得的值。 The tempered glass of the present invention preferably has a liquid phase viscosity of 10 4.5 dPa. s or more. Here, the "liquid phase viscosity" refers to a value obtained by measuring a viscosity at a liquid phase temperature by a platinum ball pulling method.

本發明的強化玻璃較佳為104.0dPa．s的黏度下的溫度為1400℃以下。此處，所謂「104.0dPa．s的黏度下的溫度」是指利用鉑球提拉法進行測定而得的值。 The tempered glass of the present invention is preferably 10 4.0 dPa. The temperature at the viscosity of s is 1400 ° C or lower. Here, the "temperature at a viscosity of 10 4.0 dPa · s" means a value measured by a platinum ball pulling method.

本發明的強化玻璃較佳為於以104.5dPa．s的黏度與氧化鋁耐火物接觸48小時的時候，接觸界面所產生的失透結晶為1個/mm2以下。 The tempered glass of the present invention is preferably at 10 4.5 dPa. When the viscosity of s is in contact with the alumina refractory for 48 hours, the devitrification crystal generated at the contact interface is 1 or less per mm 2 .

本發明的強化玻璃較佳為平板形狀。 The tempered glass of the present invention preferably has a flat plate shape.

本發明的強化玻璃較佳為厚度為0.3mm~2.0mm。 The tempered glass of the present invention preferably has a thickness of 0.3 mm to 2.0 mm.

本發明的強化玻璃較佳為利用溢流下拉法成形而得。此處，「溢流下拉法」為自成形體耐火物的兩側使熔融玻璃溢出，一邊於成形體耐火物的下端使所溢出的熔融玻璃合流，一邊向下方進行延伸成形而製造玻璃板的方法。於溢流下拉法中，應成為玻璃板的表面的面不與成形體耐火物的表面接觸而以自由表面的狀態成形。因此，可廉價地製造未研磨且表面品質良好的玻璃板。 The tempered glass of the present invention is preferably formed by an overflow down-draw method. Here, the "overflow down-draw method" is a method of manufacturing a glass plate by making molten glass overflow from both sides of a refractory body of a formed body, and merging the overflowed molten glass at the lower end of the formed body refractory body, while performing extension molding downward. method. In the overflow down-draw method, the surface to be the surface of the glass plate is formed in a free surface state without contacting the surface of the refractory body of the formed body. Therefore, an unpolished glass plate with good surface quality can be manufactured at low cost.

本發明的強化玻璃較佳為用於觸控面板顯示器。 The tempered glass of the present invention is preferably used for a touch panel display.

本發明的強化玻璃較佳為用於行動電話的蓋玻璃。 The tempered glass of the present invention is preferably a cover glass for a mobile phone.

本發明的強化玻璃較佳為用於太陽電池的蓋玻璃。 The tempered glass of the present invention is preferably a cover glass for a solar cell.

本發明的強化玻璃較佳為用於顯示器的保護構件。 The tempered glass of the present invention is preferably a protective member for a display.

本發明的強化玻璃的特徵在於：作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、12%~18%的Al2O3、0%~3%的B2O3、12%~18%的Na2O、0%~2%的K2O、0.1%~4%的MgO以及0%~2%的CaO，莫耳比Na2O/Al2O3為0.6~1.6，且實質上不含As2O3、Sb2O3、PbO以及F；壓縮應力層的壓縮應力值為900MPa以上且1500MPa以下，壓縮應力層的厚度為10μm以上且60μm以下；應變點為590℃以上；液相溫度為1250℃以下；液相黏度為104.5dPa．s以上；強化處理前的裂紋產生率為80%以下；於以104.5dPa．s的黏度與氧化鋁耐火物接觸48小時的時候，接觸界面所產生的失透結晶為1個/mm2以下；厚度為0.3mm~2.0mm；並且為平板形狀。 The tempered glass of the present invention is characterized in that as a glass composition, it contains 50% to 80% of SiO 2 , 12% to 18% of Al 2 O 3 , and 0% to 3% of B 2 O 3 in terms of mole%. , 12% ~ 18% Na 2 O, 0% ~ 2% K 2 O, 0.1% ~ 4% MgO, and 0% ~ 2% CaO, the molar ratio Na 2 O / Al 2 O 3 is 0.6 ~ 1.6, and does not substantially contain As 2 O 3 , Sb 2 O 3 , PbO, and F; the compressive stress value of the compressive stress layer is 900 MPa to 1500 MPa, and the thickness of the compressive stress layer is 10 μm to 60 μm; the strain point It is above 590 ℃; liquid temperature is below 1250 ℃; liquid viscosity is 10 4.5 dPa. above s; crack generation rate before strengthening treatment is below 80%; at 10 4.5 dPa. When the viscosity of s is in contact with the alumina refractory for 48 hours, the devitrification crystals generated at the contact interface are 1 or less per mm 2 ; the thickness is 0.3 mm to 2.0 mm; and the shape is flat.

本發明的強化用玻璃的特徵在於：作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、10%~30%的Al2O3、0%~6%的B2O3、5%~25%的Na2O以及0%~10%的MgO，且實質上不含As2O3、Sb2O3、PbO以及F。 The strengthening glass of the present invention is characterized in that, as a glass composition, it contains 50% to 80% of SiO 2 , 10% to 30% of Al 2 O 3 , and 0% to 6% of B 2 O in terms of mole%. 3 , 5% to 25% Na 2 O, and 0% to 10% MgO, and are substantially free of As 2 O 3 , Sb 2 O 3 , PbO, and F.

本發明的強化用玻璃較佳為裂紋產生率為80%以下。 The tempering glass of the present invention preferably has a crack generation rate of 80% or less.

本發明的強化用玻璃的特徵在於：厚度為0.3mm~2.0mm，壓縮應力層的壓縮應力值為900MPa以上且1500MPa以下，壓縮應力層的厚度為10μm以上且60μm以下，應變點為590℃以上，並且裂紋產生率為80%以下。 The tempering glass of the present invention is characterized in that the thickness is 0.3 mm to 2.0 mm, the compressive stress layer has a compressive stress value of 900 MPa to 1500 MPa, the compressive stress layer has a thickness of 10 μm to 60 μm, and a strain point of 590 ° C. And the crack generation rate is 80% or less.

本發明的強化用玻璃的特徵在於：厚度為0.7mm~2.0mm，壓縮應力層的壓縮應力值為1000MPa以上，壓縮應力層的 厚度為40μm以上，應變點為620℃以上，並且裂紋產生率為80%以下。 The strengthening glass of the present invention is characterized in that the thickness is 0.7 mm to 2.0 mm, the compressive stress value of the compressive stress layer is 1000 MPa or more, The thickness is 40 μm or more, the strain point is 620 ° C. or more, and the crack generation rate is 80% or less.

本發明的強化用玻璃較佳為△CS為100MPa以下。此處，「△CS」是指測定於400℃的KNO3熔融鹽中浸漬4小時的時候的壓縮應力值CS400、與於430℃的KNO3熔融鹽中浸漬4小時的時候的壓縮應力值CS430後，藉由△CS=CS400-CS430的式子進行計算所得的值。 The tempering glass of the present invention preferably has a ΔCS of 100 MPa or less. Here, "△ CS" means the compressive stress value CS 400 when immersed in a KNO 3 molten salt at 400 ° C for 4 hours, and the compressive stress value when immersed in a KNO 3 molten salt at 430 ° C for 4 hours. After CS 430 , the value calculated by the formula of ΔCS = CS 400 -CS 430 .

本發明的強化玻璃於其表面具有壓縮應力層。作為於表面形成壓縮應力層的方法，存在物理強化法與化學強化法。本發明的強化玻璃較佳為利用化學強化法製作而成。化學強化法為如下方法：於玻璃的應變點以下的溫度下，藉由離子交換處理將離子半徑大的鹼離子導入至玻璃表面。若利用化學強化法形成壓縮應力層，即便於玻璃的厚度薄的情況下，亦可適當地形成壓縮應力層，而且形成壓縮應力層後，即使將強化玻璃切斷亦如風冷強化法等物理強化法般，強化玻璃不容易斷裂。 The tempered glass of the present invention has a compressive stress layer on its surface. As a method for forming a compressive stress layer on the surface, there are a physical strengthening method and a chemical strengthening method. The tempered glass of the present invention is preferably produced by a chemical tempering method. The chemical strengthening method is a method in which alkali ions having a large ionic radius are introduced to the glass surface by an ion exchange process at a temperature below the strain point of the glass. If the compressive stress layer is formed by a chemical strengthening method, even if the thickness of the glass is thin, the compressive stress layer can be appropriately formed, and after the compressive stress layer is formed, even if the strengthened glass is cut, physical properties such as air-cooled strengthening method can be used. Tempered glass is not easy to break.

關於本發明的強化玻璃，以下示出限定各成分的含有範圍的理由。再者，於各成分的含有範圍的說明中，%的表示只要無特別說明，是指莫耳%。 The reason for limiting the content range of each component with respect to the tempered glass of this invention is shown below. In addition, in the description of the content range of each component, unless otherwise indicated,% means the Molar%.

SiO2為形成玻璃的網狀結構的成分。SiO2的含量較佳為 50%~80%、55%~76%、56%~75%、57%~73%、58%~72%或59%~71%，特佳為60%~70%。若SiO2的含量過少，則變得難以玻璃化，且熱膨脹係數過高，耐熱衝擊性容易降低。另一方面，若SiO2的含量過多，則熔融性或成形性容易降低，且熱膨脹係數過低，難以與周邊材料的熱膨脹係數相匹配。 SiO 2 is a component that forms the network structure of glass. The content of SiO 2 is preferably 50% to 80%, 55% to 76%, 56% to 75%, 57% to 73%, 58% to 72%, or 59% to 71%, and particularly preferably 60% to 70. %. When the content of SiO 2 is too small, it becomes difficult to vitrify, and the thermal expansion coefficient is too high, and the thermal shock resistance is liable to decrease. On the other hand, if the content of SiO 2 is too large, meltability or formability tends to decrease, and the thermal expansion coefficient is too low, making it difficult to match the thermal expansion coefficient of the surrounding material.

Al2O3為提高離子交換性能、應變點、楊氏模量的成分且為使裂紋產生率降低的成分。Al2O3的含量為10%~30%。若Al2O3的含量過少，則產生無法充分發揮離子交換性能之虞。另外，若Al2O3的含量過少，則有裂紋產生率變高之虞。故，Al2O3的較佳的下限範圍為10%以上、10.5%以上、11%以上、11.5%以上、12%以上、12.5%以上、13%以上、14%以上、14.5%以上、15%以上、15.5%以上、16.0%以上或16.1%以上，特佳為16.3%以上。另一方面，若Al2O3的含量過多，則於玻璃上容易析出失透結晶，難以利用溢流下拉法等將玻璃板成形，尤其於使用氧化鋁耐火物作為成形體耐火物，並利用溢流下拉法將玻璃板成形時，在與氧化鋁耐火物的界面容易析出尖晶石的失透結晶。另外，若Al2O3的含量過多，則熱膨脹係數過低，難以與周邊材料的熱膨脹係數相匹配，而且耐酸性亦降低，難以適用於酸處理步驟，進而高溫黏性變高，熔融性容易降低。故，Al2O3的較佳上限範圍為25%以下、20%以下、19%以下、18.5%以下、18%以下或17.5%以下，特佳為17%以下。 Al 2 O 3 is a component that improves ion exchange performance, strain point, and Young's modulus, and is a component that reduces crack generation rate. The content of Al 2 O 3 is 10% to 30%. When the content of Al 2 O 3 is too small, there is a possibility that the ion exchange performance cannot be fully exhibited. In addition, if the content of Al 2 O 3 is too small, the crack generation rate may increase. Therefore, the preferred lower range of Al 2 O 3 is 10% or more, 10.5% or more, 11% or more, 11.5% or more, 12% or more, 12.5% or more, 13% or more, 14% or more, 14.5% or more, 15 % Or more, 15.5% or more, 16.0% or more, or 16.1% or more, particularly preferably 16.3% or more. On the other hand, if the content of Al 2 O 3 is too large, devitrified crystals are easily precipitated on the glass, and it is difficult to shape the glass plate by an overflow down-draw method or the like. In particular, alumina refractory is used as a molded body refractory, and is used. When the glass sheet is formed by the overflow down-draw method, devitrified crystals of spinel are easily precipitated at the interface with the alumina refractory. In addition, if the content of Al 2 O 3 is too large, the thermal expansion coefficient is too low, it is difficult to match the thermal expansion coefficient of the surrounding materials, and the acid resistance is also reduced. It is difficult to apply it to the acid treatment step, and the high-temperature viscosity becomes high, and the meltability is easy. reduce. Therefore, the preferred upper range of Al 2 O 3 is 25% or less, 20% or less, 19% or less, 18.5% or less, 18% or less, or 17.5% or less, and particularly preferably 17% or less.

B2O3為使高溫黏度或密度降低且使玻璃穩定化、使結晶 難以析出、使液相溫度降低的成分。另外，B2O3為降低裂紋產生率、提高耐刮傷性的成分。但，若B2O3的含量過多，則難以獲得高的強化特性，或尤其是壓縮應力層的厚度變小，或因離子交換而產生稱為泛黃的玻璃表面的著色，或耐水性容易降低。故，B2O3的較佳範圍為0%~6%、0%~5%、0%~4%、0%~3.5%、0%~3%、0%~2.5%、0%~2%、0%~1.5%或0%~1%，特佳為0%~小於1%。 B 2 O 3 is a component that lowers the high-temperature viscosity or density, stabilizes the glass, makes it difficult to precipitate crystals, and lowers the liquidus temperature. In addition, B 2 O 3 is a component that reduces the crack generation rate and improves the scratch resistance. However, if the content of B 2 O 3 is too large, it is difficult to obtain high strengthening characteristics, or particularly the thickness of the compressive stress layer becomes small, or the coloration of a glass surface called yellowing due to ion exchange occurs, or the water resistance becomes easy. reduce. Therefore, the preferred ranges of B 2 O 3 are 0% ~ 6%, 0% ~ 5%, 0% ~ 4%, 0% ~ 3.5%, 0% ~ 3%, 0% ~ 2.5%, 0% ~ 2%, 0% ~ 1.5% or 0% ~ 1%, especially preferred is 0% ~ less than 1%.

Na2O為離子交換成分，且為使高溫黏度降低、提高熔融性或成形性的成分。另外，Na2O為改善耐失透性、且改善與成形體耐火物特別是與氧化鋁耐火物的反應失透性的成分。若Na2O的含量過少，則熔融性降低，或熱膨脹係數降低，或離子交換性能容易降低。故，Na2O的較佳下限範圍為5%以上、7%以上、大於7%、8%以上、9%以上、10%以上或11%以上，特佳為12%以上。另一方面，若Na2O的含量過多，則熱膨脹係數變得過高，耐熱衝擊性降低，或難以與周邊材料的熱膨脹係數相匹配。另外，若Na2O的含量過多，則應變點過於降低，或玻璃組成的成分失衡，反而有耐失透性降低的情況。故，Na2O的較佳上限範圍為25%以下、23%以下、21%以下、20%以下、19.5%以下、19%以下、18.5%以下、18.2%以下、18%以下或17.5%以下，特佳為17%以下。 Na 2 O is an ion exchange component, and is a component that lowers the viscosity at high temperatures and improves the meltability or moldability. In addition, Na 2 O is a component that improves the devitrification resistance and improves the devitrification resistance by reacting with the molded article refractory, particularly with the alumina refractory. When the content of Na 2 O is too small, the meltability is lowered, the thermal expansion coefficient is lowered, or the ion exchange performance is liable to decrease. Therefore, the preferred lower range of Na 2 O is more than 5%, more than 7%, more than 7%, more than 8%, more than 9%, more than 10%, or more than 11%, particularly preferably more than 12%. On the other hand, if the content of Na 2 O is too large, the thermal expansion coefficient becomes too high, the thermal shock resistance decreases, or it becomes difficult to match the thermal expansion coefficient of the surrounding material. In addition, if the content of Na 2 O is too large, the strain point is too low, or the components of the glass composition are out of balance, and devitrification resistance may be reduced. Therefore, the preferred upper range of Na 2 O is 25% or less, 23% or less, 21% or less, 20% or less, 19.5% or less, 19% or less, 18.5% or less, 18.2% or less, 18% or less, or 17.5% or less. Especially good is below 17%.

若莫耳比Na2O/Al2O3過小，則熔融性降低，或耐失透性降低，或與成形體耐火物特別是與氧化鋁耐火物的反應失透性降低，或玻璃組成的成分失衡，離子交換性能容易降低。故，莫耳 比Na2O/Al2O3的較佳下限範圍為0.5以上、0.6以上、0.7以上、0.8以上、0.9以上、0.95以上或0.98以上，特佳為1.00以上。另一方面，若莫耳比Na2O/Al2O3過大，則有離子交換性能降低，或裂紋產生率變高之虞。故，莫耳比Na2O/Al2O3的較佳上限範圍為2.0以下、1.9以下、1.8以下、1.7以下、1.6以下、1.5以下、1.4以下、1.3以下、1.2以下、1.18以下、1.15以下或1.13以下，特佳為1.1以下。 If the molar ratio is too small compared to Na 2 O / Al 2 O 3 , the meltability is reduced, or the devitrification resistance is reduced, or the reaction with the shaped body refractory, especially the alumina refractory, is reduced, or the glass composition is degraded. The composition is unbalanced, and the ion exchange performance is easily reduced. Therefore, the preferable lower limit range of the molar ratio Na 2 O / Al 2 O 3 is 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 0.95 or 0.98 or more, and particularly preferably 1.00 or more. On the other hand, if the molar ratio is too large, Na 2 O / Al 2 O 3 may reduce the ion exchange performance or increase the crack generation rate. Therefore, the preferred upper ranges of the Mohr ratio Na 2 O / Al 2 O 3 are 2.0 or less, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.18 or less, and 1.15. Below or 1.13, particularly preferably below 1.1.

B2O3+Na2O-Al2O3的較佳含量為-1.7%~2.7%、0%~2.55%或0.5%~2.4%，特佳為0.8%~2.2%。據此，容易使熔融性、應變點、離子交換性能以及裂紋產生率最佳化。再者，「B2O3+Na2O-Al2O3」為自B2O3與Na2O的合量減去Al2O3的含量而得者。 The preferred content of B 2 O 3 + Na 2 O-Al 2 O 3 is -1.7% to 2.7%, 0% to 2.55%, or 0.5% to 2.4%, particularly preferably 0.8% to 2.2%. According to this, it is easy to optimize meltability, strain point, ion exchange performance, and crack generation rate. The "B 2 O 3 + Na 2 O-Al 2 O 3 " is obtained by subtracting the content of Al 2 O 3 from the total amount of B 2 O 3 and Na 2 O.

K2O為促進離子交換的成分，且為鹼金屬氧化物中容易增大壓縮應力層的厚度的成分。另外，K2O為使高溫黏度降低、提高熔融性或成形性的成分，且進而亦為改善耐失透性的成分。但，若K2O的含量過多，則熱膨脹係數變得過高，耐熱衝擊性降低，或難以與周邊材料的熱膨脹係數相匹配。而且，若K2O的含量過多，則應變點過於降低，或玻璃組成的成分欠缺平衡，反而有耐失透性降低的傾向。故，K2O的較佳上限範圍為10%以下、9%以下、8%以下、7%以下、6%以下、5%以下、4%以下、3%以下或2%以下，特佳為小於2%。再者，添加K2O時，較佳的添加量為0.1%以上、0.5%以上、1%以上或1.5%以上，特佳為2%以上。 另外，於盡可能回避K2O的添加時，K2O的較佳含量為0%~1%或0%~小於1%，特佳為0%~0.05%。 K 2 O is a component that promotes ion exchange and is a component that easily increases the thickness of the compressive stress layer in the alkali metal oxide. In addition, K 2 O is a component that lowers the high-temperature viscosity, improves the meltability or moldability, and is also a component that improves the devitrification resistance. However, if the content of K 2 O is too large, the thermal expansion coefficient becomes too high, the thermal shock resistance decreases, or it is difficult to match the thermal expansion coefficient of the surrounding material. When the content of K 2 O is too large, the strain point is too low, or the components of the glass composition are not balanced, and the devitrification resistance tends to decrease. Therefore, the preferred upper range of K 2 O is 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or 2% or less, particularly preferred is Less than 2%. When K 2 O is added, the preferred amount is 0.1% or more, 0.5% or more, 1% or more, or 1.5% or more, particularly preferably 2% or more. In addition, when the addition of K 2 O is avoided as much as possible, the preferred content of K 2 O is 0% to 1% or 0% to less than 1%, particularly preferably 0% to 0.05%.

MgO為使高溫黏度降低、提高熔融性或成形性、或提高應變點或楊氏模量的成分，且為鹼土金屬氧化物中提高離子交換性能的效果大的成分。故，MgO的較佳下限範圍為0%以上、0.1%以上、0.5%以上、1%以上、1.5%以上、2%以上、2.5%以上、3%以上或3.5%以上，特佳為3.7%以上。但，若MgO的含量過多，則有密度或熱膨脹係數容易變高，且玻璃容易失透的傾向，尤其於使用氧化鋁耐火物作為成形體耐火物，並利用溢流下拉法將玻璃板成形時，在與氧化鋁耐火物的界面容易析出尖晶石的失透結晶。故，MgO的較佳上限範圍為10%以下、9%以下、8%以下、7%以下、6%以下或5%以下，特佳為4%以下。 MgO is a component that lowers the high-temperature viscosity, improves the meltability or formability, or increases the strain point or Young's modulus, and is a component that has a large effect of improving ion exchange performance among alkaline earth metal oxides. Therefore, the preferred lower range of MgO is 0% or more, 0.1% or more, 0.5% or more, 1% or more, 1.5% or more, 2% or more, 2.5% or more, 3% or more, or 3.5% or more, and 3.7% is particularly preferred. the above. However, if the content of MgO is too large, the density or the coefficient of thermal expansion tends to increase and the glass tends to devitrify, especially when alumina refractory is used as the shaped body refractory and the glass plate is formed by the overflow down-draw method. Devitrification crystals of spinel are easily precipitated at the interface with the alumina refractory. Therefore, the preferred upper range of MgO is 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, or 5%, and particularly preferably 4% or less.

除所述成分以外，例如亦可添加以下成分。 In addition to the above components, for example, the following components may be added.

Li2O為離子交換成分，且為使高溫黏度降低、提高熔融性或成形性的成分，而且為提高楊氏模量的成分。進而，一般而言，Li2O於鹼金屬氧化物中，提高壓縮應力值的效果大，但於含有7%以上的Na2O的玻璃系統中，若Li2O的含量變得極多，反而有壓縮應力值降低的傾向。另外，若Li2O的含量過多，則液相黏度降低、玻璃容易失透，此外，熱膨脹係數變得過高、耐熱衝擊性降低，或難以與周邊材料的熱膨脹係數相匹配。進而，若Li2O的含量過多，則低溫黏性過於降低，容易引起應力緩和，反而有壓縮應力值降低的情形。因此，作為難以產生刮傷的強化用玻璃、 即裂紋產生率低的強化用玻璃，提出有Li2O含量高的玻璃。但，若使用KNO3熔融鹽對Li2O含量高的玻璃進行離子交換處理，則Li離子容易混入KNO3熔融鹽中。若使用混入有Li離子的KNO3熔融鹽，則會產生強化用玻璃的強化特性變得不充分的問題。故，Li2O的較佳含量為0%~2%、0%~1.7%、0%~1.5%、0%~1%、0%~小於1%、0%~0.5%、0%~0.3%或0%~0.1%，特佳為0%~0.05%。 Li 2 O is an ion exchange component, a component that lowers the high-temperature viscosity, improves the meltability or moldability, and is a component that increases the Young's modulus. Furthermore, generally speaking, Li 2 O is effective in increasing the compressive stress value in alkali metal oxides. However, if the content of Li 2 O becomes extremely large in a glass system containing Na 2 O of 7% or more, Instead, the compressive stress value tends to decrease. When the content of Li 2 O is too large, the liquid phase viscosity decreases and the glass is liable to devitrify. In addition, the thermal expansion coefficient becomes too high, the thermal shock resistance decreases, or it is difficult to match the thermal expansion coefficient of the surrounding material. Further, if the content of Li 2 O is too large, the low-temperature viscosity is too low, and stress relaxation is likely to occur, but the compressive stress value may decrease. Therefore, as a strengthening glass that is less likely to be scratched, that is, a strengthening glass having a low crack generation rate, a glass having a high Li 2 O content has been proposed. However, if a glass with a high Li 2 O content is subjected to ion exchange treatment using a KNO 3 molten salt, Li ions are easily mixed into the KNO 3 molten salt. When a KNO 3 molten salt mixed with Li ions is used, there is a problem that the strengthening characteristics of the glass for strengthening become insufficient. Therefore, the preferred content of Li 2 O is 0% ~ 2%, 0% ~ 1.7%, 0% ~ 1.5%, 0% ~ 1%, 0% ~ less than 1%, 0% ~ 0.5%, 0% ~ 0.3% or 0% ~ 0.1%, especially preferred is 0% ~ 0.05%.

CaO為與其他成分相比較，不會伴有耐失透性的降低地使高溫黏度降低、提高熔融性或成形性，或提高應變點或楊氏模量的效果大的成分。但，若CaO的含量過多，則密度或熱膨脹係數變高，且玻璃組成的成分失衡，反而有耐失透性容易降低，或離子交換性能降低，或容易使離子交換溶液劣化的傾向。故，CaO的較佳含量為0%~6%、0%~5%、0%~4%、0%~3.5%、0%~3%、0%~2%或0%~1%，特佳為0%~0.5%。 CaO is a component that is more effective than other components in reducing high-temperature viscosity without increasing devitrification resistance, improving meltability or formability, or increasing strain point or Young's modulus. However, if the content of CaO is too large, the density or the coefficient of thermal expansion becomes high, and the components of the glass composition become unbalanced. On the contrary, the devitrification resistance tends to decrease, the ion exchange performance decreases, or the ion exchange solution tends to deteriorate. Therefore, the preferred content of CaO is 0% ~ 6%, 0% ~ 5%, 0% ~ 4%, 0% ~ 3.5%, 0% ~ 3%, 0% ~ 2% or 0% ~ 1%. Especially good is 0% ~ 0.5%.

SrO為使高溫黏度降低、提高熔融性或成形性，或提高應變點或楊氏模量的成分，但若其含量過多，則容易阻礙離子交換反應，此外，密度或熱膨脹係數變高，或玻璃容易失透。故，SrO的較佳含量為0%~2%、0%~1.5%、0%~1%、0%~0.5%或0%~0.1%，特佳為0%~小於0.1%。 SrO is a component that lowers the viscosity at high temperatures, improves the meltability or formability, or increases the strain point or Young's modulus. However, if it is contained in an excessive amount, SrO tends to hinder the ion exchange reaction. In addition, the density or thermal expansion coefficient becomes high, or glass Easy to devitrify. Therefore, the preferred content of SrO is 0% ~ 2%, 0% ~ 1.5%, 0% ~ 1%, 0% ~ 0.5% or 0% ~ 0.1%, particularly preferably 0% ~ less than 0.1%.

BaO為使高溫黏度降低、提高熔融性或成形性，或提高應變點或楊氏模量的成分。但，若BaO的含量過多，則容易阻礙離子交換反應，此外，密度或熱膨脹係數變高，或玻璃容易失透。 故，BaO的較佳含量為0%~6%、0%~3%、0%~1.5%、0%~1%、0%~0.5%或0%~0.1%，特佳為0%~小於0.1%。 BaO is a component that lowers the viscosity at high temperatures, improves the meltability or formability, or increases the strain point or Young's modulus. However, if the content of BaO is too large, the ion exchange reaction is likely to be hindered, and the density or thermal expansion coefficient becomes high, or the glass is easily devitrified. Therefore, the preferred content of BaO is 0% ~ 6%, 0% ~ 3%, 0% ~ 1.5%, 0% ~ 1%, 0% ~ 0.5%, or 0% ~ 0.1%, and particularly preferred is 0% ~ Less than 0.1%.

ZnO為提高離子交換性能的成分，且為尤其提高壓縮應力值的效果大的成分。另外，ZnO為不會降低低溫黏性而使高溫黏性降低的成分。但，若ZnO的含量過多，則有玻璃分相，或耐失透性降低，或密度變高，或壓縮應力層的厚度變小的傾向。故，ZnO的較佳含量為0%~6%、0%~5%或0%~3%，特佳為0%~1%。 ZnO is a component that improves ion exchange performance, and is a component that has a particularly large effect of increasing the compressive stress value. In addition, ZnO is a component that does not lower the low-temperature viscosity but lowers the high-temperature viscosity. However, if the content of ZnO is too large, there is a tendency that the glass is phase-separated, devitrification resistance is reduced, the density is increased, or the thickness of the compressive stress layer is reduced. Therefore, the preferred content of ZnO is 0% to 6%, 0% to 5%, or 0% to 3%, and particularly preferred is 0% to 1%.

B2O3+MgO+ZnO的較佳含量為0.03%~3.94%、0.1%~3.8%、0.5%~3.7%或1%~3.5%，特佳為2%~3.4%。據此，容易使熔融性、耐失透性以及壓縮應力層的厚度最佳化。再者，「B2O3+MgO+ZnO」為B2O3、MgO以及ZnO的合量。 The preferred content of B 2 O 3 + MgO + ZnO is 0.03% ~ 3.94%, 0.1% ~ 3.8%, 0.5% ~ 3.7% or 1% ~ 3.5%, particularly preferably 2% ~ 3.4%. This makes it easy to optimize the meltability, devitrification resistance, and thickness of the compressive stress layer. In addition, "B 2 O 3 + MgO + ZnO" is the total amount of B 2 O 3 , MgO, and ZnO.

TiO2為提高離子交換性能的成分，且為使高溫黏度降低的成分，但若其含量過多，則玻璃容易著色，或容易失透。故，TiO2的含量較佳為0%~4.5%、0%~小於1%或0%~0.5%，特佳為0%~0.3%。 TiO 2 is a component that improves the ion exchange performance and is a component that lowers the viscosity at high temperatures. However, if the content is too large, the glass is likely to be colored or devitrified. Therefore, the content of TiO 2 is preferably 0% to 4.5%, 0% to less than 1%, or 0% to 0.5%, and particularly preferably 0% to 0.3%.

ZrO2為顯著提高離子交換性能的成分，而且為提高液相黏度附近的黏性或應變點的成分，但若其含量過多，則有耐失透性顯著降低之虞，且亦有密度變得過高之虞。故，ZrO2的較佳含量為0%~5%、0%~4%或0%~3%，特佳為0.001%~2%。 ZrO 2 is a component that significantly improves the ion exchange performance, and is a component that increases the viscosity or strain point near the viscosity of the liquid phase. However, if the content of ZrO 2 is too large, the devitrification resistance may be significantly reduced, and the density may be changed. Excessive risk. Therefore, the preferred content of ZrO 2 is 0% to 5%, 0% to 4%, or 0% to 3%, particularly preferably 0.001% to 2%.

SnO2為提高離子交換性能的成分，但若其含量過多，則耐失透性容易降低。故，SnO2的較佳含量為0%~3%、0.01%~3%、0.05%~3%或0.1%~3%，特佳為0.2%~3%。 SnO 2 is a component that improves ion exchange performance, but if the content is too large, devitrification resistance is liable to decrease. Therefore, the preferred content of SnO 2 is 0% to 3%, 0.01% to 3%, 0.05% to 3%, or 0.1% to 3%, particularly preferably 0.2% to 3%.

P2O5為提高離子交換性能的成分，且為尤其增大壓縮應力層的厚度的成分。但，若P2O5的含量過多，則玻璃分相，或耐水性容易降低。故，P2O5的較佳含量為0%~10%、0%~3%或0%~1%，特佳為0%~0.5%。 P 2 O 5 is a component that improves the ion exchange performance and is a component that increases the thickness of the compressive stress layer in particular. However, if the content of P 2 O 5 is too large, the glass may be phase-separated or the water resistance may be easily reduced. Therefore, the preferred content of P 2 O 5 is 0% to 10%, 0% to 3%, or 0% to 1%, and particularly preferred is 0% to 0.5%.

作為澄清劑，可添加0%~3%的選自Cl、SO3、CeO2的組群(較佳為Cl、SO3的組群)中的一種或兩種以上。 As a clarifying agent may be added from 0% to 3% selected from Cl, SO 3, CeO 2 group (preferably Cl, SO 3 groups) one or two or more kinds.

自同時享有澄清效果與提高離子交換性能的效果的觀點而言，SnO2+SO3+Cl的較佳含量為0.01%~3%、0.05%~3%或0.1%~3%，特佳為0.2%~3%。再者，「SnO2+SO3+Cl」為SnO2、Cl以及SO3的合量。 From the viewpoint of enjoying both the clarifying effect and the effect of improving the ion exchange performance, the preferred content of SnO 2 + SO 3 + Cl is 0.01% to 3%, 0.05% to 3%, or 0.1% to 3%, particularly preferably 0.2% ~ 3%. In addition, "SnO 2 + SO 3 + Cl" is the total amount of SnO 2 , Cl, and SO 3 .

Fe2O3的較佳含量為小於1000ppm(小於0.1%)、小於800ppm、小於600ppm或小於400ppm，特佳為小於300ppm。進而，較佳為將Fe2O3的含量限制為所述範圍，並且將莫耳比Fe2O3/(Fe2O3+SnO2)限制為0.8以上或0.9以上，特佳為限制為0.95以上。據此，板厚1mm的透過率(400nm~770nm)容易提高(例如90%以上)。 The preferred content of Fe 2 O 3 is less than 1000 ppm (less than 0.1%), less than 800 ppm, less than 600 ppm, or less than 400 ppm, and particularly preferably less than 300 ppm. Furthermore, it is preferable to limit the content of Fe 2 O 3 to the above-mentioned range, and to limit the molar ratio Fe 2 O 3 / (Fe 2 O 3 + SnO 2 ) to 0.8 or more or 0.9 or more, particularly preferably to 0.95 or more. According to this, the transmittance (400 nm to 770 nm) with a thickness of 1 mm is easily improved (for example, 90% or more).

Nd2O3、La2O3等稀土氧化物為提高楊氏模量的成分。但，原料自身的成本高，且若大量添加，則耐失透性容易降低。故，稀土氧化物的較佳含量為3%以下、2%以下、1%以下或0.5%以下，特佳為0.1%以下。 Rare earth oxides such as Nd 2 O 3 and La 2 O 3 are components that increase the Young's modulus. However, the cost of the raw material itself is high, and if it is added in a large amount, devitrification resistance is liable to decrease. Therefore, the preferred content of the rare earth oxide is 3% or less, 2% or less, 1% or less, or 0.5% or less, and particularly preferably 0.1% or less.

關於本發明的強化玻璃，自環境方面考慮，作為玻璃組成，較佳為實質上不含As2O3、Sb2O3、PbO以及F。另外，自環 境方面考慮，亦較佳為實質上不含Bi2O3。所謂「實質上不含Bi2O3」為以下主旨：雖不積極地添加Bi2O3作為玻璃成分，但容許雜質水準的添加；具體而言是指Bi2O3的含量小於0.05%的情形。 Regarding the tempered glass of the present invention, from the viewpoint of environment, it is preferable that the glass composition is substantially free of As 2 O 3 , Sb 2 O 3 , PbO, and F. In addition, in terms of environment, it is also preferable that it is substantially free of Bi 2 O 3 . The so-called "substantially free of Bi 2 O 3 " is the following purpose: Although Bi 2 O 3 is not actively added as a glass component, the addition of impurity levels is allowed; specifically, the content of Bi 2 O 3 is less than 0.05%. situation.

本發明的強化玻璃中，可適宜取捨選擇各成分的較佳含有範圍而設為較佳的玻璃組成範圍。其中，特佳的玻璃組成範圍如下所述。 In the tempered glass of the present invention, a preferable content range of each component can be appropriately selected and set to a preferable glass composition range. Among them, particularly preferable glass composition ranges are as follows.

(1)作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、10%~30%的Al2O3、0%~6%的B2O3、5%~25%的Na2O、0%~10%的MgO，且實質上不含As2O3、Sb2O3、PbO以及F。 (1) As a glass composition, it contains 50% to 80% of SiO 2 , 10% to 30% of Al 2 O 3 , 0% to 6% of B 2 O 3 , and 5% to 25% in terms of mole. Na 2 O, 0% to 10% MgO, and substantially free of As 2 O 3 , Sb 2 O 3 , PbO, and F.

(2)作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、10%~30%的Al2O3、0%~6%的B2O3、5%~25%的Na2O、0%~10%的MgO、0%~5%的CaO，且實質上不含As2O3、Sb2O3、PbO以及F。 (2) As a glass composition, it contains 50% to 80% of SiO 2 , 10% to 30% of Al 2 O 3 , 0% to 6% of B 2 O 3 , and 5% to 25% in terms of mole%. Na 2 O, 0% to 10% MgO, 0% to 5% CaO, and substantially free of As 2 O 3 , Sb 2 O 3 , PbO, and F.

(3)作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、10%~30%的Al2O3、0%~6%的B2O3、5%~25%的Na2O、0%~10%的K2O、0%~10%的MgO、0%~5%的CaO，且實質上不含As2O3、Sb2O3、PbO以及F。 (3) As a glass composition, it contains 50% to 80% of SiO 2 , 10% to 30% of Al 2 O 3 , 0% to 6% of B 2 O 3 , and 5% to 25% in terms of mole. Na 2 O, 0% to 10% K 2 O, 0% to 10% MgO, 0% to 5% CaO, and substantially free of As 2 O 3 , Sb 2 O 3 , PbO, and F.

(4)作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、12%~18%的Al2O3、0%~3%的B2O3、12%~18%的Na2O、0%~2%的K2O、0.1%~4%的MgO、0%~2%的CaO，且實質上不含As2O3、Sb2O3、PbO以及F。 (4) As a glass composition, it contains 50% to 80% of SiO 2 , 12% to 18% of Al 2 O 3 , 0% to 3% of B 2 O 3 , and 12% to 18% in terms of mole%. Na 2 O, 0% to 2% K 2 O, 0.1% to 4% MgO, 0% to 2% CaO, and substantially free of As 2 O 3 , Sb 2 O 3 , PbO, and F.

(5)作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、 12%~18%的Al2O3、0%~3%的B2O3、12%~18%的Na2O、0%~8%的K2O、0.1%~4%的MgO、0%~2%的CaO，莫耳比Na2O/Al2O3為0.6~1.6，且實質上不含As2O3、Sb2O3、PbO以及F。 (5) As a glass composition, it contains 50% to 80% of SiO 2 , 12% to 18% of Al 2 O 3 , 0% to 3% of B 2 O 3 , and 12% to 18%. Na 2 O, 0% to 8% K 2 O, 0.1% to 4% MgO, 0% to 2% CaO, the molar ratio Na 2 O / Al 2 O 3 is 0.6 to 1.6, and substantially Does not contain As 2 O 3 , Sb 2 O 3 , PbO, and F.

本發明的強化玻璃較佳為例如具有下述特性。 The tempered glass of the present invention preferably has the following characteristics, for example.

本發明的強化玻璃於表面具有壓縮應力層。壓縮應力層的壓縮應力值較佳為300MPa以上、400MPa以上、500MPa以上、600MPa以上、700MPa以上、800MPa以上、900MPa以上、950MPa以上、1000MPa以上、1100MPa以上、1150MPa以上、1200MPa以上、1250MPa以上或1300MPa以上，特佳為1350MPa以上。壓縮應力值越大，強化玻璃的機械強度越高。另一方面，若於表面形成極大的壓縮應力，則有強化玻璃內部所存在的拉伸應力變得極高，強化處理前後的尺寸變化變大之虞。因此，壓縮應力層的壓縮應力值較佳為1500MPa以下或1450MPa以下，特佳為1400MPa以下。再者，若增加玻璃組成中的Al2O3、TiO2、ZrO2、MgO、ZnO的含量，或減少SrO、BaO的含量，則有壓縮應力值變大的傾向。另外，若縮短離子交換時間，或降低離子交換溶液的溫度，則有壓縮應力值變大的傾向。 The tempered glass of the present invention has a compressive stress layer on the surface. The compression stress value of the compressive stress layer is preferably 300 MPa or more, 400 MPa or more, 500 MPa or more, 600 MPa or more, 700 MPa or more, 800 MPa or more, 900 MPa or more, 950 MPa or more, 1000 MPa or more, 1100 MPa or more, 1150 MPa or more, 1200 MPa or more, 1250 MPa or more, or 1300 MPa. Above, particularly preferred is 1350 MPa or more. The larger the compressive stress value, the higher the mechanical strength of the strengthened glass. On the other hand, if a large compressive stress is formed on the surface, the tensile stress existing in the strengthened glass may become extremely high, and there is a possibility that the dimensional change before and after the strengthening treatment becomes large. Therefore, the compressive stress value of the compressive stress layer is preferably 1500 MPa or less or 1450 MPa or less, and particularly preferably 1400 MPa or less. Furthermore, if the contents of Al 2 O 3 , TiO 2 , ZrO 2 , MgO, and ZnO are increased, or the contents of SrO and BaO are decreased, the compressive stress value tends to increase. In addition, if the ion exchange time is shortened or the temperature of the ion exchange solution is lowered, the compressive stress value tends to increase.

壓縮應力層的厚度較佳為10μm以上、15μm以上、20μm以上、25μm以上、30μm以上、35μm以上或40μm以上，特佳為45μm以上。即便壓縮應力層的厚度越大，強化玻璃產生的刮傷越深，強化玻璃亦難以破裂，而且機械強度的不均變小。另一方面，壓縮應力層的厚度越大，越難以切斷強化玻璃。另外， 有強化玻璃內部所存在的拉伸應力變得極高，強化處理前後的尺寸變化變大之虞。因此，壓縮壓力層的厚度較佳為80μm以下或70μm以下，特佳為60μm以下。再者，若增加玻璃組成中的K2O、P2O5的含量，或減少SrO、BaO的含量，則有壓縮壓力層的厚度變大的傾向。另外，若延長離子交換時間，或提高離子交換溶液的溫度，則有壓縮壓力層的厚度變大的傾向。 The thickness of the compressive stress layer is preferably 10 μm or more, 15 μm or more, 20 μm or more, 25 μm or more, 30 μm or more, 35 μm or more, or 40 μm or more, particularly preferably 45 μm or more. Even if the thickness of the compressive stress layer is larger, the scratches generated by the strengthened glass are deeper, the strengthened glass is less likely to be broken, and the unevenness in mechanical strength is reduced. On the other hand, the larger the thickness of the compressive stress layer, the more difficult it is to cut the strengthened glass. In addition, there is a possibility that the tensile stress existing in the strengthened glass becomes extremely high, and the dimensional change before and after the strengthening treatment becomes large. Therefore, the thickness of the compression pressure layer is preferably 80 μm or less or 70 μm or less, and particularly preferably 60 μm or less. Furthermore, if the content of K 2 O and P 2 O 5 in the glass composition is increased, or the content of SrO and BaO is decreased, the thickness of the compression pressure layer tends to increase. In addition, if the ion exchange time is extended or the temperature of the ion exchange solution is increased, the thickness of the compression pressure layer tends to increase.

內部的拉伸應力值較佳為150MPa以下、140MPa以下、130MPa以下、120MPa以下、110MPa以下、100MPa以下、90MPa以下或80MPa以下，特佳為70MPa以下。若內部的拉伸應力值過高，則藉由物理衝突等，強化玻璃容易自我斷裂。另一方面，若內部的拉伸應力值過低，則難以確保強化玻璃的機械強度。內部的拉伸應力值較佳為1MPa以上、5MPa以上或7MPa以上，特佳為10MPa以上。再者，內部的拉伸應力可藉由下述數式1來計算。 The internal tensile stress value is preferably 150 MPa or less, 140 MPa or less, 130 MPa or less, 120 MPa or less, 110 MPa or less, 100 MPa or less, 90 MPa or less, or 80 MPa or less, and particularly preferably 70 MPa or less. If the internal tensile stress value is too high, the tempered glass is liable to self-break due to physical conflicts and the like. On the other hand, if the internal tensile stress value is too low, it becomes difficult to secure the mechanical strength of the strengthened glass. The internal tensile stress value is preferably 1 MPa or more, 5 MPa or more, or 7 MPa or more, and particularly preferably 10 MPa or more. The internal tensile stress can be calculated by the following Equation 1.

[數式1]CT=(CS×DOL)/[t-2×DOL] [Numerical formula 1] CT = (CS × DOL) / [t-2 × DOL]

[CT：內部的拉伸應力(MPa)] [CT: Internal tensile stress (MPa)]

[CS：壓縮應力層的壓縮應力值(MPa)] [CS: compressive stress value of the compressive stress layer (MPa)]

[DOL：壓縮應力層的厚度(μm)] [DOL: thickness of compressive stress layer (μm)]

[t：厚度(μm)] [t: thickness (μm)]

密度較佳為2.6g/cm3以下、2.55g/cm3以下、2.50g/cm3以下、2.48g/cm3以下或2.46g/cm3以下，特佳為2.45g/cm3以下。密度越小，越可使強化玻璃輕量化。再者，若增加玻璃組成中的SiO2、B2O3、P2O5的含量，或減少鹼金屬氧化物、鹼土金屬氧化物、ZnO、ZrO2、TiO2的含量，則密度容易降低。 Density is preferably 2.6g / cm 3 or less, 2.55g / cm 3 or less, 2.50g / cm 3 or less, 2.48g / cm 3 or less, or 2.46g / cm 3 or less, particularly preferably 2.45g / cm 3 or less. The smaller the density, the more lightweight the tempered glass. Furthermore, if the content of SiO 2 , B 2 O 3 , P 2 O 5 in the glass composition is increased, or the content of alkali metal oxide, alkaline earth metal oxide, ZnO, ZrO 2 , and TiO 2 is decreased, the density is liable to decrease. .

應變點較佳為550℃以上、580℃以上、590℃以上、600℃以上、610℃以上、615℃以上、620℃以上、625℃以上、630℃以上、640℃以上或650℃以上，特佳為660℃以上。應變點越高，強化特性越難以因KNO3熔融鹽的溫度變化而發生變化。尤其是即便薄型化，亦容易嚴格地控制面內的強化特性。再者，若增加玻璃組成中的B2O3、鹼金屬氧化物的含量，則應變點容易降低，反之，若增加SiO2、Al2O3的含量，則應變點容易上升。 The strain point is preferably 550 ° C, 580 ° C, 590 ° C, 600 ° C, 610 ° C, 615 ° C, 620 ° C, 625 ° C, 630 ° C, 640 ° C, or 650 ° C. It is preferably 660 ° C or more. The higher the strain point, the harder it is for the strengthening characteristics to change due to the temperature change of the KNO 3 molten salt. In particular, even if the thickness is reduced, it is easy to strictly control the in-plane strengthening characteristics. Furthermore, if the contents of B 2 O 3 and alkali metal oxides in the glass composition are increased, the strain point is liable to decrease. Conversely, if the contents of SiO 2 and Al 2 O 3 are increased, the strain point is liable to rise.

104.0dPa．s的黏度下的溫度較佳為1400℃以下。104.0dPa．s的黏度下的溫度越低，越能減輕對成形設備的負擔，成形設備的壽命變得越長，結果，容易使強化玻璃的製造成本低廉化。若增加鹼金屬氧化物、鹼土金屬氧化物、ZnO、B2O3、TiO2的含量，或減少SiO2、Al2O3的含量，則104.0dPa．s的黏度下的溫度容易降低。 10 4.0 dPa. The temperature at the viscosity of s is preferably 1400 ° C or lower. 10 4.0 dPa. The lower the temperature under the viscosity of s, the more the burden on the molding equipment can be reduced, and the life of the molding equipment becomes longer. As a result, it is easy to reduce the manufacturing cost of the tempered glass. If the content of alkali metal oxide, alkaline earth metal oxide, ZnO, B 2 O 3 , TiO 2 is increased, or the content of SiO 2 and Al 2 O 3 is decreased, 10 4.0 dPa. The temperature at the viscosity of s is easy to decrease.

102.5dPa．s的黏度下的溫度較佳為1700℃以下、1680℃以下或1650℃以下，特佳為1600℃以下。102.5dPa．s的黏度下的溫度越低，越能實現低溫熔融，越能減輕對熔融窯等玻璃製造設備的負擔，而且容易提高氣泡品質。即，102.5dPa．s的黏度下的溫 度越低，越容易使強化玻璃的製造成本低廉化。此處，「102.5dPa．s的黏度下的溫度」例如可利用鉑球提拉法進行測定。再者，102.5dPa．s的黏度下的溫度相當於熔融溫度。另外，若增加玻璃組成中的鹼金屬氧化物、鹼土金屬氧化物、ZnO、B2O3、TiO2的含量，或減少SiO2、Al2O3的含量，則102.5dPa．s的黏度下的溫度容易降低。 10 2.5 dPa. The temperature at s of the viscosity is preferably 1700 ° C or lower, 1680 ° C or lower, or 1650 ° C or lower, and particularly preferably 1600 ° C or lower. 10 2.5 dPa. The lower the temperature under the viscosity of s, the more low-temperature melting can be achieved, the more it can reduce the burden on glass manufacturing equipment such as melting kiln, and the easier it is to improve the bubble quality. That is, 10 2.5 dPa. The lower the temperature under the viscosity of s, the easier it is to reduce the manufacturing cost of tempered glass. Here, the "temperature at a viscosity of 10 2.5 dPa · s" can be measured by, for example, a platinum ball pulling method. Furthermore, 10 2.5 dPa. The temperature at the viscosity of s corresponds to the melting temperature. In addition, if the content of alkali metal oxides, alkaline earth metal oxides, ZnO, B 2 O 3 , and TiO 2 is increased, or the content of SiO 2 and Al 2 O 3 is decreased, it is 10 2.5 dPa. The temperature at the viscosity of s is easy to decrease.

熱膨脹係數較佳為50×10-7/℃~100×10-7/℃、70×10-7/℃~100×10-7/℃或75×10-7/℃~95×10-7/℃，特佳為80×10-7/℃~90×10-7/℃。若將熱膨脹係數限制為所述範圍，則玻璃難以因熱衝擊而破損，因此可縮短強化處理前的預熱或強化處理後的緩冷所需的時間。結果，可使強化玻璃的製造成本低廉化。另外，若將熱膨脹係數限制為所述範圍，則容易與金屬、有機系接著劑等周邊構件的熱膨脹係數相匹配，可防止周邊構件的剝離。再者，若增加玻璃組成中的鹼金屬氧化物、鹼土金屬氧化物的含量，則熱膨脹係數變高，反之，若降低鹼金屬氧化物、鹼土金屬氧化物的含量，則熱膨脹係數變低。此處，「熱膨脹係數」是指使用膨脹計，對25℃~380℃的溫度範圍的平均熱膨脹係數進行測定而得的值。 The thermal expansion coefficient is preferably 50 × 10 -7 / ℃ ~ 100 × 10 -7 / ℃, 70 × 10 -7 / ℃ ~ 100 × 10 -7 / ℃ or 75 × 10 -7 / ℃ ~ 95 × 10 -7 / ° C, particularly preferably 80 × 10 -7 / ° C to 90 × 10 -7 / ° C. When the thermal expansion coefficient is limited to the above range, the glass is less likely to be damaged by thermal shock, and therefore the time required for preheating before tempering or slow cooling after tempering can be shortened. As a result, the manufacturing cost of tempered glass can be reduced. In addition, if the coefficient of thermal expansion is limited to the above range, it is easy to match the coefficient of thermal expansion of peripheral members such as metals and organic adhesives, and it is possible to prevent peeling of the peripheral members. In addition, if the content of the alkali metal oxide and the alkaline earth metal oxide in the glass composition is increased, the thermal expansion coefficient becomes higher, whereas if the content of the alkali metal oxide and the alkaline earth metal oxide is decreased, the thermal expansion coefficient becomes lower. Here, the "thermal expansion coefficient" refers to a value obtained by measuring an average thermal expansion coefficient in a temperature range of 25 ° C to 380 ° C using a dilatometer.

液相溫度較佳為1300℃以下、1280℃以下、1250℃以下或1230℃以下，特佳為1200℃以下。再者，液相溫度越低，越能提高耐失透性或成形性。另外，若增加玻璃組成中的Na2O、K2O、B2O3的含量，或減少Al2O3、Li2O、MgO、ZnO、TiO2、ZrO2的含量，則液相溫度容易降低。 The liquidus temperature is preferably 1300 ° C or lower, 1280 ° C or lower, 1250 ° C or lower or 1230 ° C or lower, and particularly preferably 1200 ° C or lower. Furthermore, the lower the liquidus temperature, the more the devitrification resistance or moldability can be improved. In addition, if the content of Na 2 O, K 2 O, B 2 O 3 in the glass composition is increased, or the content of Al 2 O 3 , Li 2 O, MgO, ZnO, TiO 2 , ZrO 2 is decreased, the liquidus temperature Easy to lower.

液相黏度較佳為104.0dPa．s以上、104.4dPa．s以上、104.8dPa．s以上、105.0dPa．s以上、105.3dPa．s以上、105.5dPa．s以上、105.7dPa．s以上或105.8dPa．s以上，特佳為106.0dPa．s以上。再者，液相黏度越高，越能提高耐失透性或成形性。另外，若增加玻璃組成中的Na2O、K2O的含量，或減少Al2O3、Li2O、MgO、ZnO、TiO2、ZrO2的含量，則液相黏度容易變高。 The liquid viscosity is preferably 10 4.0 dPa. s or more, 10 4.4 dPa. s or more, 10 4.8 dPa. s or more, 10 5.0 dPa. Above s, 10 5.3 dPa. s above, 10 5.5 dPa. Above s, 10 5.7 dPa. above s or 10 5.8 dPa. Above s, especially good is 10 6.0 dPa. s or more. Furthermore, the higher the liquid phase viscosity, the more the devitrification resistance or moldability can be improved. In addition, if the content of Na 2 O, K 2 O in the glass composition is increased, or the content of Al 2 O 3 , Li 2 O, MgO, ZnO, TiO 2 , or ZrO 2 is decreased, the liquid phase viscosity tends to increase.

楊氏模量較佳為65GPa以上、69GPa以上、71GPa以上或75GPa以上，特佳為77GPa以上。楊氏模量越高，強化玻璃越難以撓曲，於用於觸控面板顯示器等時，即便用筆等強力按壓強化玻璃的表面，強化玻璃的變形量亦小。結果，容易防止強化玻璃與位於背面的液晶元件接觸而造成顯示不良的情況。另外，楊氏模量越高，相對於強化處理時所產生的應力的變形量變得越小，因此，可降低強化處理前後的尺寸變化。 The Young's modulus is preferably 65 GPa or more, 69 GPa or more, 71 GPa or more, or 75 GPa or more, and particularly preferably 77 GPa or more. The higher the Young's modulus, the more difficult it is for the tempered glass to flex. When it is used in a touch panel display or the like, even if the surface of the tempered glass is strongly pressed with a pen or the like, the amount of deformation of the tempered glass is small. As a result, it is easy to prevent display defects caused by contact between the tempered glass and the liquid crystal element on the back surface. In addition, the higher the Young's modulus, the smaller the amount of deformation with respect to the stress generated during the strengthening treatment. Therefore, the dimensional change before and after the strengthening treatment can be reduced.

強化處理前的裂紋產生率、即強化用玻璃的裂紋產生率較佳為99%以下、98%以下、95%以下、90%以下、85%以下、80%以下、70%以下、60%以下、50%以下或40%以下，特佳為30%以下。裂紋產生率越低，越難以於強化玻璃的表面產生刮傷，因此強化玻璃的機械強度難以降低，且機械強度難以產生不均。 The crack generation rate before the strengthening treatment, that is, the crack generation rate of the strengthening glass is preferably 99% or less, 98%, 95% or less, 90% or less, 85% or less, 80% or less, 70% or less, and 60% or less. , Below 50% or below 40%, particularly preferred below 30%. The lower the crack generation rate, the more difficult it is to cause scratches on the surface of the strengthened glass, so it is difficult to reduce the mechanical strength of the strengthened glass, and it is difficult to cause unevenness in the mechanical strength.

於以104.5dPa．s的黏度與氧化鋁耐火物接觸48小時的時候，接觸界面所產生的失透結晶較佳為1個/mm2以下、0.1個/mm2以下、0.01個/mm2以下或0.001個/mm2以下，特佳為0.0001個/mm2以下。據此，於使用氧化鋁耐火物作為成形體耐火物，並 利用溢流下拉法將玻璃板成形時，玻璃難以於耐火物界面失透，可進行大量生產。 At 10 4.5 dPa. When the viscosity of s is in contact with the alumina refractory for 48 hours, the devitrification crystal generated at the contact interface is preferably 1 or less per mm 2 , 0.1 or less per mm 2 , 0.01 or less per mm 2, or 0.001 or less per mm. 2 or less, particularly preferably 0.0001 pieces / mm 2 or less. Accordingly, when an alumina refractory is used as a formed body refractory and a glass plate is formed by an overflow down-draw method, it is difficult for the glass to devitrify the refractory interface, and mass production is possible.

本發明的強化玻璃較佳為平板形狀。據此，容易適用於行動電話、數位相機、PDA(行動終端機)、太陽電池的蓋玻璃，或顯示器、特別是觸控面板顯示器的玻璃基板。再者，為了提高設計性，本發明的強化玻璃可為具有屈曲部及/或彎曲部的形狀。此種形狀可藉由對玻璃進行加熱使其變形而形成，且亦可藉由將熔融玻璃流入成型模具中，視需要進行壓製而形成。 The tempered glass of the present invention preferably has a flat plate shape. According to this, it can be easily applied to a cover glass of a mobile phone, a digital camera, a PDA (mobile terminal), a solar cell, or a glass substrate of a display, particularly a touch panel display. Furthermore, in order to improve designability, the tempered glass of the present invention may have a shape having a buckled portion and / or a bent portion. Such a shape can be formed by heating the glass to deform it, and it can also be formed by pouring molten glass into a molding die and pressing it if necessary.

本發明的強化玻璃中，厚度(平板形狀時為板厚)較佳為2.0mm以下、1.5mm以下、1.3mm以下、1.1mm以下、1.0mm以下或0.8mm以下，特佳為0.7mm以下。另一方面，若厚度過薄，則難以獲得所需的機械強度。故，厚度較佳為0.1mm以上、0.2mm以上、0.3mm以上或0.4mm以上，特佳為0.5mm以上。 In the tempered glass of the present invention, the thickness (thickness in a flat plate shape) is preferably 2.0 mm or less, 1.5 mm or less, 1.3 mm or less, 1.1 mm or less, 1.0 mm or 0.8 mm or less, and particularly preferably 0.7 mm or less. On the other hand, if the thickness is too thin, it is difficult to obtain the required mechanical strength. Therefore, the thickness is preferably 0.1 mm or more, 0.2 mm or more, 0.3 mm or more, or 0.4 mm or more, and particularly preferably 0.5 mm or more.

本發明的強化玻璃的強化特性的面內不均小，因此可較佳地於表面形成各種功能膜。作為功能膜，例如較佳為：用以賦予導電性的透明導電膜，用以降低反射率的抗反射膜，用以賦予防眩功能、提高圖像可視性、或提高利用觸控筆等的運筆感受的防眩膜，用以防止指紋的附著且賦予撥水性、撥油性的防污膜等。透明導電膜發揮出作為觸控感測器用的電極的功能，例如較佳為形成於應成為顯示器裝置側的表面。作為透明導電膜，例如使用錫摻雜氧化銦(氧化銦錫(Indium Tin Oxide，ITO))、氟摻雜氧化錫(Fluorine-doped Tin Oxide，FTO)、銻摻雜氧化錫 (Antimony-doped Tin Oxide，ATO)等。尤其，因ITO的電阻低，故而較佳。ITO例如可藉由濺鍍法而形成。另外，FTO、ATO可藉由化學氣相沈積(Chemical Vapor Deposition，CVD)法而形成。抗反射膜形成於應成為觀察者側的表面。另外，當於觸控面板與強化玻璃(蓋玻璃)之間存在空隙時，較佳為於應成為強化玻璃的背面側(顯示器裝置側的相反側)的表面亦形成抗反射膜。抗反射膜例如較佳為折射率相對較低的低折射率層與折射率相對較高的高折射率層交互積層而成的電介質多層膜。抗反射膜例如可藉由濺鍍法、CVD法等而形成。防眩膜於將強化玻璃用作蓋玻璃時，形成於應成為觀察者側的表面。防眩膜較佳為具有凹凸結構。凹凸結構亦可為部分地覆蓋強化玻璃的表面的島狀結構。另外，凹凸結構較佳為不具規則性。藉此，可提高防眩功能。防眩膜例如可藉由利用噴霧法來塗布SiO2等透光性材料並使其乾燥而形成。防污膜於將強化玻璃用作蓋玻璃時，形成於應成為觀察者側的表面。防污膜較佳為包含主鏈中含有矽的含氟聚合物。作為含氟聚合物，較佳為主鏈中具有-O-Si-O-單元、且側鏈具有含有氟的撥水性官能基的聚合物。含氟聚合物例如可藉由將矽烷醇脫水縮合而合成。形成抗反射膜與防污膜時，較佳為於抗反射膜之上形成防污膜。進而，形成防眩膜時，較佳為首先形成防眩膜，而於其上形成抗反射膜及/或防污膜。 The in-plane unevenness of the strengthening characteristics of the strengthened glass of the present invention is small, so various functional films can be formed on the surface. As the functional film, for example, a transparent conductive film for imparting conductivity, an anti-reflection film for reducing reflectance, an anti-glare function, improving image visibility, or using a stylus pen or the like are preferred. An anti-glare film that feels like a pen, is used to prevent fingerprints from attaching, and to provide water repellent and oil repellent antifouling films. The transparent conductive film functions as an electrode for a touch sensor, and is preferably formed on a surface to be a display device side, for example. As the transparent conductive film, for example, tin-doped indium oxide (Indium Tin Oxide (ITO)), fluorine-doped tin oxide (FTO), or antimony-doped tin (Antimony-doped Tin) are used. Oxide, ATO) and so on. In particular, ITO is preferred because of its low resistance. ITO can be formed by a sputtering method, for example. In addition, FTO and ATO can be formed by a chemical vapor deposition (Chemical Vapor Deposition, CVD) method. The anti-reflection film is formed on a surface to be the observer's side. In addition, when there is a gap between the touch panel and the tempered glass (cover glass), it is preferable that an anti-reflection film is also formed on a surface that should be the tempered glass on the back side (opposite to the display device side). The antireflection film is preferably a dielectric multilayer film in which a low refractive index layer having a relatively low refractive index and a high refractive index layer having a relatively high refractive index are alternately laminated. The antireflection film can be formed by, for example, a sputtering method, a CVD method, or the like. The anti-glare film is formed on a surface to be an observer's side when tempered glass is used as a cover glass. The anti-glare film preferably has an uneven structure. The uneven structure may be an island structure that partially covers the surface of the strengthened glass. The irregular structure is preferably irregular. This can improve the anti-glare function. The anti-glare film can be formed, for example, by applying a spray method to a light-transmitting material such as SiO 2 and drying it. When a tempered glass is used as a cover glass, the antifouling film is formed on a surface to be an observer side. The antifouling film preferably contains a fluoropolymer containing silicon in the main chain. As the fluoropolymer, a polymer having -O-Si-O- units in the main chain and a fluorine-containing water-repellent functional group in the side chain is preferred. The fluoropolymer can be synthesized, for example, by dehydrating and condensing silanol. When forming the antireflection film and the antifouling film, it is preferable to form an antifouling film on the antireflection film. Furthermore, when forming an anti-glare film, it is preferable to form an anti-glare film first, and to form an anti-reflection film and / or an antifouling film thereon.

本發明的強化玻璃中，可適宜取捨選擇各成分的較佳含有範圍、較佳特性而製成較佳的強化玻璃。其中，特佳的強化玻 璃如下所述。 In the tempered glass of the present invention, a better tempered glass can be made by properly selecting and selecting the preferred content range and preferred characteristics of each component. Among them, the best strengthened glass The glass is described below.

(1)作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、12%~19%的Al2O3、0%~3%的B2O3、12%~19%的Na2O、0%~8%的K2O、0.1%~3%的MgO、0%~2%的CaO，莫耳比Na2O/Al2O3為0.6~1.6，且實質上不含As2O3、Sb2O3、PbO以及F；壓縮應力層的壓縮應力值為900MPa以上且1500MPa以下，壓縮應力層的厚度為10μm以上且60μm以下；應變點為620℃以上；液相溫度為1250℃以下；液相黏度為104.5dPa．s以上；於以104.5dPa．s的黏度與氧化鋁耐火物接觸48小時的時候，接觸界面所產生的失透結晶為1個/mm2以下；厚度為0.3mm~2.0mm；並且為平板形狀。 (1) As a glass composition, it contains 50% to 80% of SiO 2 , 12% to 19% of Al 2 O 3 , 0% to 3% of B 2 O 3 , and 12% to 19% in terms of mole%. Na 2 O, 0% to 8% K 2 O, 0.1% to 3% MgO, 0% to 2% CaO, the molar ratio Na 2 O / Al 2 O 3 is 0.6 to 1.6, and substantially Does not include As 2 O 3 , Sb 2 O 3 , PbO, and F; the compressive stress value of the compressive stress layer is 900 MPa to 1500 MPa, the thickness of the compressive stress layer is 10 μm to 60 μm; the strain point is 620 ° C or higher; The phase temperature is below 1250 ℃; the liquid viscosity is 10 4.5 dPa. s above; at 10 4.5 dPa. When the viscosity of s is in contact with the alumina refractory for 48 hours, the devitrification crystals generated at the contact interface are 1 or less per mm 2 ; the thickness is 0.3 mm to 2.0 mm; and the shape is a flat plate.

關於本發明的強化用玻璃，作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、10%~30%的Al2O3、0%~6%的B2O3、5%~25%的Na2O、0%~10%的MgO，且實質上不含As2O3、Sb2O3、PbO以及F。故，本發明的強化用玻璃的技術特徵(較佳的特性、較佳的成分範圍等)與本發明的強化玻璃的技術特徵重複，其重複部分已記載於本發明的強化玻璃的說明部分中。故，關於其重複部分，省略詳細的說明。 Regarding the strengthening glass of the present invention, as a glass composition, it contains 50% to 80% SiO 2 , 10% to 30% Al 2 O 3 , 0% to 6% B 2 O 3 , 5% to 25% Na 2 O, 0% to 10% MgO, and substantially free of As 2 O 3 , Sb 2 O 3 , PbO, and F. Therefore, the technical characteristics (preferred characteristics, preferred composition range, etc.) of the tempered glass of the present invention are the same as those of the tempered glass of the present invention, and the overlapping portions are described in the description of the tempered glass of the present invention. . Therefore, detailed descriptions thereof will be omitted.

本發明的強化用玻璃中，△CS較佳為100MPa以下、80MPa以下或60MPa以下，特佳為40MPa以下。據此，由強化溫度的不均引起的強化特性的不均得以減少，可將強化處理時的翹曲抑制得小。 In the tempering glass of the present invention, ΔCS is preferably 100 MPa or less, 80 MPa or less, or 60 MPa or less, and particularly preferably 40 MPa or less. Accordingly, unevenness in the strengthening characteristics due to unevenness in the strengthening temperature can be reduced, and warpage at the time of the strengthening treatment can be suppressed to be small.

於本發明的強化用玻璃於430℃的KNO3熔融鹽中浸漬4小時的情形下，表面的壓縮應力層的壓縮應力值較佳為成為300MPa以上、400MPa以上、500MPa以上、600MPa以上、700MPa以上、800MPa以上、900MPa以上、950MPa以上、1000MPa以上、1100MPa以上、1150MPa以上、1200MPa以上、1250MPa以上或1300MPa以上，特佳為成為1350MPa以上，壓縮應力層的厚度較佳為成為10μm以上、15μm以上、20μm以上、25μm以上、30μm以上、35μm以上或40μm以上，特佳為成為45μm以上。 When the tempering glass of the present invention is immersed in KNO 3 molten salt at 430 ° C for 4 hours, the compressive stress value of the surface compressive stress layer is preferably 300 MPa or more, 400 MPa or more, 500 MPa or more, 600 MPa or more, and 700 MPa or more. 800 MPa or more, 900 MPa or more, 950 MPa or more, 1000 MPa or more, 1100 MPa or more, 1150 MPa or more, 1200 MPa or more, 1250 MPa or more or 1300 MPa or more, particularly preferably 1350 MPa or more, and the thickness of the compression stress layer is preferably 10 μm or more, 15 μm or more, 20 μm or more, 25 μm or more, 30 μm or more, 35 μm or more, or 40 μm or more, particularly preferably 45 μm or more.

本發明的強化用玻璃中，可適宜取捨選擇各成分的較佳含有範圍、較佳特性而製成較佳的強化用玻璃。其中，特佳的強化用玻璃如下所述。 In the strengthening glass of the present invention, a preferable strengthening range of each component can be appropriately selected and selected to make a better strengthening glass. Among them, particularly preferred strengthening glasses are as follows.

(1)作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、10%~30%的Al2O3、0%~6%的B2O3、5%~25%的Na2O、0%~10%的MgO，實質上不含As2O3、Sb2O3、PbO以及F，且裂紋產生率為80%以下。 (1) As a glass composition, it contains 50% to 80% of SiO 2 , 10% to 30% of Al 2 O 3 , 0% to 6% of B 2 O 3 , and 5% to 25% in terms of mole. Na 2 O, 0% to 10% MgO, does not substantially contain As 2 O 3 , Sb 2 O 3 , PbO, and F, and the crack generation rate is 80% or less.

(2)厚度為0.3mm~2.0mm，壓縮應力層的壓縮應力值為900MPa以上且1500MPa以下，壓縮應力層的厚度為10μm以上且60μm以下，應變點為620℃以上，且裂紋產生率為80%以下。 (2) The thickness is 0.3mm ~ 2.0mm, the compressive stress layer has a compressive stress value of 900 MPa or more and 1500 MPa or less, the compressive stress layer has a thickness of 10 μm or more and 60 μm or less, the strain point is 620 ° C or more, and the crack generation rate is 80 %the following.

(3)厚度為0.7mm~2.0mm，壓縮應力層的壓縮應力值為1000MPa以上，壓縮應力層的厚度為40μm以上，應變點為620℃以上，裂紋產生率為80%以下，且△CS為100MPa以下。 (3) The thickness is 0.7mm ~ 2.0mm, the compressive stress layer has a compressive stress value of 1000 MPa or more, the compressive stress layer has a thickness of 40 μm or more, a strain point is 620 ° C or more, a crack generation rate is 80% or less, and △ CS is 100MPa or less.

進行離子交換處理時，KNO3熔融鹽的溫度較佳為390℃~550℃，離子交換時間較佳為0.5小時~10小時，特佳為1小時~8小時。據此，容易適當地形成壓縮應力層。再者，本發明的強化用玻璃具有所述玻璃組成，因此即便不使用KNO3熔融鹽與NaNO3熔融鹽的混合物等，亦可增大壓縮應力層的壓縮應力值或厚度。 When performing ion exchange treatment, the temperature of the KNO 3 molten salt is preferably 390 ° C. to 550 ° C., the ion exchange time is preferably 0.5 hour to 10 hours, and particularly preferably 1 hour to 8 hours. This makes it easy to form a compressive stress layer appropriately. Further, the present invention has a strengthened glass composition of the glass, so KNO 3 molten salt and the molten salt mixture of NaNO 3 without using, or may increase the thickness of the compression stress value of the compressive stress layer.

可如以下般製作本發明的強化玻璃(強化用玻璃)。 The tempered glass (glass for tempering) of this invention can be produced as follows.

首先，將以成為所述玻璃組成的方式進行調配而成的玻璃原料投入至連續熔融爐中，以1500℃~1700℃進行加熱熔融，澄清後，供給至成形裝置並成形為平板形狀等，進行緩冷，藉此可製作強化用玻璃。 First, a glass raw material prepared so as to have the above-mentioned glass composition is put into a continuous melting furnace, heated and melted at 1500 ° C to 1700 ° C, clarified, and then supplied to a molding apparatus and formed into a flat plate shape. Slow cooling can be used to produce tempered glass.

成形為平板形狀的方法較佳為採用溢流下拉法。溢流下拉法為可大量地製作高品質的玻璃板，而且亦可容易地製作大型的玻璃板的方法。進而，溢流下拉法中，使用氧化鋁或氧化鋯作為成形體耐火物。本發明的強化用玻璃與氧化鋁或氧化鋯、特別是與氧化鋁的相容性良好(與成形體反應而難以生成氣泡或渣子等)。 The method of forming into a flat plate shape is preferably an overflow down-draw method. The overflow down-draw method is a method in which high-quality glass plates can be produced in large quantities, and large-scale glass plates can also be easily produced. Furthermore, in the overflow down-draw method, alumina or zirconia is used as the shaped body refractory. The tempering glass of the present invention has good compatibility with alumina or zirconia, particularly with alumina (reacts with a molded body, making it difficult to form bubbles or slag, etc.).

除溢流下拉法外，還可採用各種成形方法。例如可採用：浮式法、下拉法(流孔下拉(slot down draw)法、再拉法等)、滾壓(rollout)法、壓製法等成形方法。 In addition to the overflow down-draw method, various forming methods can be used. For example, a forming method such as a float method, a down-draw method (slot down draw method, re-draw method, etc.), a rollout method, and a pressing method can be adopted.

接著，藉由對所得的強化用玻璃進行強化處理而可製作強化玻璃。將強化玻璃切斷為規定尺寸的時間可為強化處理之 前，亦可為強化處理之後。 Then, a tempered glass can be produced by tempering the obtained tempering glass. The time for cutting the tempered glass to a predetermined size can be a tempering process. Before or after the strengthening treatment.

作為強化處理，較佳為離子交換處理。離子交換處理的條件並無特別限定，只要考慮玻璃的黏度特性、用途、厚度、內部的拉伸應力、尺寸變化等而選擇最佳的條件即可。例如，離子交換處理可藉由於390℃~550℃的KNO3熔融鹽中浸漬1小時~8小時來進行。尤其，若將KNO3熔融鹽中的K離子與玻璃中的Na成分進行離子交換，則可效率良好地於玻璃的表面形成壓縮應力層。 The strengthening treatment is preferably an ion exchange treatment. The conditions of the ion exchange treatment are not particularly limited, and the optimum conditions may be selected in consideration of the viscosity characteristics, use, thickness, internal tensile stress, and dimensional change of the glass. For example, the ion exchange treatment can be performed by immersing in a KNO 3 molten salt at 390 ° C to 550 ° C for 1 to 8 hours. In particular, if K ions in the KNO 3 molten salt are ion-exchanged with Na components in the glass, a compressive stress layer can be efficiently formed on the surface of the glass.

實施例 Examples

以下，基於實施例對本發明加以說明。再者，以下的實施例僅為例示。本發明並不受以下的實施例任何限定。 Hereinafter, the present invention will be described based on examples. The following examples are merely examples. The present invention is not limited in any way by the following examples.

表1~表12表示本發明的實施例(試樣No.1~No.68)。 Tables 1 to 12 show examples of the present invention (Sample Nos. 1 to 68).

[表3] [table 3]

如下般製作表中的各試樣。首先，以成為表中的玻璃組成的方式調配玻璃原料，使用鉑罐(pot)以1600℃進行21小時 熔融。之後，將所得的熔融玻璃流出至碳板之上，而成形為平板形狀。對所得的玻璃板評價各種特性。 Each sample in the table was prepared as follows. First, a glass raw material was prepared so that it might become the glass composition in a table | surface, and it carried out for 21 hours at 1600 degreeC using a platinum pot (pot). Melting. After that, the obtained molten glass was poured onto a carbon plate and formed into a flat plate shape. Various characteristics were evaluated about the obtained glass plate.

密度ρ為藉由周知的阿基米德(Archimedes)法進行測定而得的值。 The density ρ is a value measured by a well-known Archimedes method.

應變點Ps、緩冷點Ta為基於ASTM C336的方法進行測定而得的值。 The strain point Ps and the slow cooling point Ta are values obtained by measuring based on the method of ASTM C336.

軟化點Ts為基於ASTM C338的方法進行測定而得的值。 The softening point Ts is a value measured in accordance with the method of ASTM C338.

高溫黏度104.0dPa．s、103.0dPa．s、102.5dPa．s下的溫度為利用鉑球提拉法進行測定而得的值。 High temperature viscosity 10 4.0 dPa. s, 10 3.0 dPa. s, 10 2.5 dPa. The temperature under s is a value measured by a platinum ball pulling method.

熱膨脹係數α為使用膨脹計，對25℃~380℃的溫度範圍的平均熱膨脹係數進行測定而得的值。 The thermal expansion coefficient α is a value obtained by measuring an average thermal expansion coefficient in a temperature range of 25 ° C. to 380 ° C. using a dilatometer.

楊氏模量E為利用周知的共振法進行測定而得的值。 The Young's modulus E is a value measured by a known resonance method.

液相溫度TL是設為如下溫度：將通過標準篩30目(500μm)而殘留於50目(300μm)的玻璃粉末裝入鉑舟，於溫度梯度爐中保持24小時後，將鉑舟取出，藉由顯微鏡觀察而確認到於玻璃內部失透(結晶異物)的最高溫度。 The liquid phase temperature TL was set as follows: a glass powder remaining through a standard sieve of 30 mesh (500 μm) and remaining in 50 mesh (300 μm) was loaded into a platinum boat, and after being held in a temperature gradient furnace for 24 hours, the platinum boat was taken out, The maximum temperature of devitrification (crystalline foreign matter) inside the glass was confirmed by microscope observation.

液相黏度logηTL為利用鉑球提拉法對液相溫度下的玻璃的黏度進行測定而得的值。 The liquid viscosity logη TL is a value obtained by measuring the viscosity of a glass at a liquid temperature using a platinum ball pulling method.

裂紋產生率為如下而得的值：首先，於保持為濕度30%、溫度25℃的恆溫恆濕槽內，對玻璃表面(光學研磨面)實施15秒的設定為載荷1000gf的維氏壓頭的楔入，實施15秒後， 對自壓痕的4角產生的裂紋數進行計數(針對1個壓痕而言最大值為4)，將該操作重複合計50次，求出總裂紋產生數後，藉由(總裂紋產生數/200)×100的式子而算出的值。 The crack generation rate is a value obtained by first applying a Vickers indenter set at a load of 1000 gf to a glass surface (optical polishing surface) for 15 seconds in a constant temperature and humidity tank maintained at a humidity of 30% and a temperature of 25 ° C. Wedge, after 15 seconds, The number of cracks generated at the four corners of the indentation was counted (the maximum value is 4 for one indentation). This operation was repeated 50 times, and the total number of cracks was obtained. / 200) × 100.

如下般評價與氧化鋁的相容性。於以104.5dPa．s的黏度使各試樣與氧化鋁耐火物接觸的狀態下保持48小時後，觀察各試樣與氧化鋁耐火物的接觸界面，測定失透渣子的數密度(個/mm2)。 The compatibility with alumina was evaluated as follows. At 10 4.5 dPa. After the viscosity of s was maintained for 48 hours in a state where each sample was in contact with the alumina refractory, the contact interface between each sample and the alumina refractory was observed, and the number density (pieces / mm 2 ) of devitrified slag was measured.

由表1~表12明確可知：試樣No.1~No.68的密度為2.46g/cm3以下、應變點為601℃以上、裂紋產生率為68%以下，適合作為強化玻璃的原材料、即強化用玻璃。另外，因液相黏度為105.2dPa．s以上，與氧化鋁耐火物的相容性良好，故而可利用溢流下拉法成形為平板形狀，並且，因102.5dPa．s的黏度下的溫度為1702℃以下，故而認為可廉價地製作大量的玻璃板。再者，於強化處理前後，玻璃的表層的玻璃組成雖於微觀而言不同，但就玻璃整體而言，玻璃組成並無實質不同。 It is clear from Tables 1 to 12 that Sample No. 1 to No. 68 have a density of 2.46 g / cm 3 or less, a strain point of 601 ° C or more, and a crack generation rate of 68% or less. They are suitable as raw materials for tempered glass, That is, glass for strengthening. In addition, the liquid viscosity is 10 5.2 dPa. Above s, it has good compatibility with alumina refractory, so it can be formed into a flat plate shape by the overflow down-draw method, and because of 10 2.5 dPa. Since the temperature at s is 1702 ° C. or lower, it is considered that a large number of glass plates can be produced inexpensively. Furthermore, although the glass composition of the surface layer of the glass before and after the strengthening treatment is microscopically different, the glass composition as a whole is not substantially different.

接著，對各試樣的兩表面實施光學研磨後，於400℃的KNO3熔融鹽中浸漬4小時，藉此進行離子交換處理。於離子交換處理後，對各試樣的表面進行洗滌。繼而，根據使用表面應力計(東芝股份有限公司製造的FSM-6000)所觀察到的干涉條紋的根數與其間隔而算出表面的壓縮應力層的壓縮應力值(CS400)與厚度(DOL400)。算出時，將各試樣的折射率設為1.50，將光學彈性常數設為30[(nm/cm)/MPa]。 Next, both surfaces of each sample were optically polished, and then immersed in a KNO 3 molten salt at 400 ° C. for 4 hours to perform an ion exchange treatment. After the ion exchange treatment, the surface of each sample was washed. Then, the compressive stress value (CS 400 ) and thickness (DOL 400 ) of the compressive stress layer on the surface were calculated based on the number of interference fringes and the interval between them observed using a surface stress meter (FSM-6000 manufactured by Toshiba Corporation). . At the time of calculation, the refractive index of each sample was set to 1.50, and the optical elastic constant was set to 30 [(nm / cm) / MPa].

進而，對各試樣的兩表面實施光學研磨後，於430℃的KNO3熔融鹽中浸漬4小時，藉此進行離子交換處理。於離子交換處理後，對各試樣的表面進行洗滌。繼而，根據使用表面應力計(東芝股份有限公司製造的FSM-6000)所觀察到的干涉條紋的根數與其間隔而算出表面的壓縮應力層的壓縮應力值(CS430)與厚度(DOL430)。算出時，將各試樣的折射率設為1.50，將光學彈性常數設為30[(nm/cm)/MPa]。 Furthermore, after optical polishing was performed on both surfaces of each sample, the sample was immersed in a KNO 3 molten salt at 430 ° C. for 4 hours to perform an ion exchange treatment. After the ion exchange treatment, the surface of each sample was washed. Then, the compressive stress value (CS 430 ) and thickness (DOL 430 ) of the compressive stress layer on the surface were calculated based on the number of interference fringes and the interval between them observed using a surface stress meter (FSM-6000 manufactured by Toshiba Corporation). . At the time of calculation, the refractive index of each sample was set to 1.50, and the optical elastic constant was set to 30 [(nm / cm) / MPa].

針對各試樣，根據△CS=CS400-CS430的式子算出△CS。 For each sample, ΔCS was calculated from the formula ΔCS = CS 400 -CS 430 .

由表1~表12明確可知：試樣No.1~No.68的CS430為1114MPa以上，DOL430為38μm以上，△CS小。 It is clear from Tables 1 to 12 that CS 430 of samples No. 1 to No. 68 is 1114 MPa or more, DOL 430 is 38 μm or more, and ΔCS is small.

本發明的強化玻璃以及強化用玻璃適合作為行動電話、數位相機、PDA等的蓋玻璃，或觸控面板顯示器等的玻璃基板。另外，本發明的強化玻璃以及強化用玻璃除所述用途以外，亦可期待應用於要求高機械強度的用途，例如：窗玻璃、磁碟用基板、平板顯示器用基板、太陽電池用蓋玻璃、固體攝像元件用蓋玻璃、餐具。 The tempered glass and tempered glass of the present invention are suitable as a cover glass for a mobile phone, a digital camera, a PDA, or the like, or a glass substrate such as a touch panel display. In addition, the tempered glass and tempered glass of the present invention can be expected to be used in applications requiring high mechanical strength in addition to the applications described above, such as window glass, substrates for magnetic disks, substrates for flat panel displays, cover glass for solar cells, Cover glass and tableware for solid-state imaging devices.

Claims (22)

一種強化玻璃，其於表面具有壓縮應力層，所述強化玻璃的特徵在於：作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、13.6%~30%的Al2O3、0%~6%的B2O3、5%~25%的Na2O以及0%~10%的MgO，且實質上不含As2O3、Sb2O3、PbO以及F。 A strengthened glass having a compressive stress layer on the surface. The strengthened glass is characterized in that as a glass composition, it contains 50% to 80% SiO 2 and 13.6% to 30% Al 2 O 3 in terms of mole%. 0% to 6% of B 2 O 3 , 5% to 25% of Na 2 O, and 0% to 10% of MgO, and substantially free of As 2 O 3 , Sb 2 O 3 , PbO, and F. 一種強化玻璃，其特徵在於：作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、13.6%~18%的Al2O3、0%~3%的B2O3、12%~18%的Na2O、0%~2%的K2O、0.1%~4%的MgO以及0%~2%的CaO，莫耳比Na2O/Al2O3為0.6~1.6。 A tempered glass, characterized in that as a glass composition, it contains 50% to 80% of SiO 2 , 13.6% to 18% of Al 2 O 3 , and 0% to 3% of B 2 O 3 in terms of mole%. 12% to 18% Na 2 O, 0% to 2% K 2 O, 0.1% to 4% MgO, and 0% to 2% CaO. The molar ratio Na 2 O / Al 2 O 3 is 0.6 to 1.6. 如申請專利範圍第1項或第2項所述的強化玻璃，其中，強化處理前的裂紋產生率為80%以下。 The tempered glass according to item 1 or 2 of the scope of patent application, wherein the crack generation rate before the tempering treatment is 80% or less. 如申請專利範圍第1項或第2項所述的強化玻璃，其中，壓縮應力層的壓縮應力值為900MPa以上且1500MPa以下，並且壓縮應力層的厚度為10μm以上且60μm以下。 The tempered glass according to item 1 or 2 of the scope of the patent application, wherein the compressive stress layer has a compressive stress value of 900 MPa to 1500 MPa, and a thickness of the compressive stress layer is 10 μm to 60 μm. 如申請專利範圍第1項或第2項所述的強化玻璃，其中，應變點為590℃以上。 The tempered glass according to item 1 or item 2 of the scope of patent application, wherein the strain point is 590 ° C or higher. 如申請專利範圍第1項或第2項所述的強化玻璃，其中，液相溫度為1250℃以下。 The tempered glass according to item 1 or item 2 of the scope of patent application, wherein the liquidus temperature is 1250 ° C or lower. 如申請專利範圍第1項或第2項所述的強化玻璃，其中，液相黏度為104.5dPa．s以上。 The tempered glass according to item 1 or 2 of the scope of patent application, wherein the liquid phase viscosity is 10 4.5 dPa. s or more. 如申請專利範圍第1項或第2項所述的強化玻璃，其中，104.0dPa．s的黏度下的溫度為1400℃以下。 The tempered glass according to item 1 or item 2 of the scope of patent application, wherein 10 4.0 dPa. The temperature at the viscosity of s is 1400 ° C or lower. 如申請專利範圍第1項或第2項所述的強化玻璃，其中，於以104.5dPa．s的黏度與氧化鋁耐火物接觸48小時的時候，接觸界面所產生的失透結晶為1個/mm2以下。 The tempered glass according to item 1 or item 2 of the scope of patent application, wherein 10 to 4.5 dPa. When the viscosity of s is in contact with the alumina refractory for 48 hours, the devitrification crystal generated at the contact interface is 1 or less per mm 2 . 如申請專利範圍第1項或第2項所述的強化玻璃，其為平板形狀。 The tempered glass according to item 1 or item 2 of the scope of patent application has a flat plate shape. 如申請專利範圍第1項或第2項所述的強化玻璃，其厚度為0.3mm~2.0mm。 The tempered glass according to item 1 or item 2 of the scope of patent application has a thickness of 0.3 mm to 2.0 mm. 如申請專利範圍第1項或第2項所述的強化玻璃，其為利用溢流下拉法成形而得。 The tempered glass according to item 1 or 2 of the scope of patent application, which is formed by the overflow down-draw method. 如申請專利範圍第1項或第2項所述的強化玻璃，其用於觸控面板顯示器。 The tempered glass according to item 1 or item 2 of the scope of patent application, which is used for a touch panel display. 如申請專利範圍第1項或第2項所述的強化玻璃，其用於行動電話的蓋玻璃。 The tempered glass according to item 1 or 2 of the scope of patent application, which is used for a cover glass of a mobile phone. 如申請專利範圍第1項或第2項所述的強化玻璃，其用於太陽電池的蓋玻璃。 The tempered glass according to item 1 or 2 of the scope of patent application, which is used for a cover glass of a solar cell. 如申請專利範圍第1項或第2項所述的強化玻璃，其用於顯示器的保護構件。 The tempered glass according to item 1 or 2 of the scope of patent application, which is used for a protective member of a display. 一種強化玻璃，其特徵在於：作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、13.6%~18%的Al2O3、0%~3%的B2O3、12%~18%的Na2O、0%~2%的K2O、0.1%~4%的MgO以及0%~2%的CaO，莫耳比Na2O/Al2O3為0.6~1.6，且實質上不含As2O3、Sb2O3、PbO以及F；壓縮應力層的壓縮應力值為900MPa 以上且1500MPa以下，壓縮應力層的厚度為10μm以上且60μm以下；應變點為590℃以上；液相溫度為1250℃以下；液相黏度為104.5dPa．s以上；強化處理前的裂紋產生率為80%以下；於以104.5dPa．s的黏度與氧化鋁耐火物接觸48小時的時候，接觸界面所產生的失透結晶為1個/mm2以下；厚度為0.3mm~2.0mm；並且為平板形狀。 A tempered glass, characterized in that as a glass composition, it contains 50% to 80% of SiO 2 , 13.6% to 18% of Al 2 O 3 , and 0% to 3% of B 2 O 3 in terms of mole%. 12% to 18% Na 2 O, 0% to 2% K 2 O, 0.1% to 4% MgO, and 0% to 2% CaO. The molar ratio Na 2 O / Al 2 O 3 is 0.6 to 1.6, and does not substantially include As 2 O 3 , Sb 2 O 3 , PbO, and F; the compressive stress value of the compressive stress layer is 900 MPa to 1500 MPa, and the thickness of the compressive stress layer is 10 μm to 60 μm; the strain point is Above 590 ℃; liquid temperature below 1250 ℃; liquid viscosity is 10 4.5 dPa. above s; crack generation rate before strengthening treatment is below 80%; at 10 4.5 dPa. When the viscosity of s is in contact with the alumina refractory for 48 hours, the devitrification crystals generated at the contact interface are 1 or less per mm 2 ; the thickness is 0.3 mm to 2.0 mm; and the shape is flat. 一種強化用玻璃，其特徵在於：作為玻璃組成，以莫耳%計，含有50%~80%的SiO2、13.6%~30%的Al2O3、0%~6%的B2O3、5%~25%的Na2O以及0%~10%的MgO，且實質上不含As2O3、Sb2O3、PbO以及F。 A glass for strengthening, characterized in that as a glass composition, it contains 50% to 80% of SiO 2 , 13.6% to 30% of Al 2 O 3 , and 0% to 6% of B 2 O 3 in mol%. , 5% to 25% Na 2 O, and 0% to 10% MgO, and substantially free of As 2 O 3 , Sb 2 O 3 , PbO, and F. 如申請專利範圍第18項所述的強化用玻璃，其中，裂紋產生率為80%以下。 The tempered glass according to claim 18, wherein the crack generation rate is 80% or less. 如申請專利範圍第18項所述的強化用玻璃，其厚度為0.3mm~2.0mm，壓縮應力層的壓縮應力值為900MPa以上且1500MPa以下，壓縮應力層的厚度為10μm以上且60μm以下，應變點為590℃以上，並且裂紋產生率為80%以下。 As described in the patent application No. 18, the glass for strengthening has a thickness of 0.3 mm to 2.0 mm, a compressive stress value of the compression stress layer of 900 MPa to 1500 MPa, a thickness of the compressive stress layer of 10 μm to 60 μm, strain The point is 590 ° C or higher, and the crack generation rate is 80% or lower. 如申請專利範圍第18項所述的強化用玻璃，其厚度為0.7mm~2.0mm，壓縮應力層的壓縮應力值為1000MPa以上，壓縮應力層的厚度為40μm以上，應變點為620℃以上，並且裂紋產生率為80%以下。 As described in the patent application No. 18, the tempering glass has a thickness of 0.7 mm to 2.0 mm, a compressive stress layer having a compressive stress value of 1000 MPa or more, a compressive stress layer having a thickness of 40 μm or more, and a strain point of 620 ° C. And the crack generation rate is 80% or less. 如申請專利範圍第18項至第21項中任一項所述的強化用玻璃，其中，△CS為100MPa以下。 The strengthened glass according to any one of claims 18 to 21 in the scope of patent application, wherein ΔCS is 100 MPa or less.
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