1276615 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關化學強化玻璃，特別是使用於電子材料 領域之觸摸面板，汽車用及建築用等領域使用之化學強化 玻璃及其製造方法。 【先前技術】 由省資源•省能源之觀點或社會需要之變化，強化玻 璃朝薄板化或提高強化度進展。一般所使用之風冷強化法 生產3 mm以下，特別是2 mm以下玻璃板厚有困難，2 mm以下之玻璃多數使用化學強化法。又，化學強化法可 得到比一般風冷強化法之強化玻璃更高的強度爲其優點。 化學強化玻璃爲多數市場所接受之理由，係上述之薄 板玻璃除了強化性及高強度化以外，在一定的條件下亦可 截切之強化玻璃。風冷強化玻璃爲切斷而導入裂痕時粉碎 斷裂不能截切。 此係如圖5 (參閱非專利文獻1 )所示，化學強化玻 璃與風冷強化（物理強化）玻璃，於玻璃內部所形成之應 力模式大不相同。風冷強化玻璃爲利用表層與內層之溫度 差及黏性流動性，其應力模式槪略爲近似2次曲線形狀。 相對於此，化學強化玻璃係利用表層之離子交換，嚴密的 依存Fick之擴散法則，多數大部份接近直線。風冷強化 玻璃爲得到所定表面壓縮力値，內層之拉伸應力必然變大 。由於玻璃之破壞係依存此內層之拉伸應力，在大拉伸應 -4- (2) 1276615 力下細片化現象爲必然。一方面，化學化玻璃時，壓縮應 力値變大時，在一般條件下，內層之拉伸應力値並未顯著 變大。化學強化玻璃之拉伸應力値，大部份依表面壓縮力 値及壓縮力層厚度之函數。 即不論風冷強化玻璃，或化學強化玻璃，其玻璃之破 壞強度大。一方面，風冷強化玻璃時截切爲不可能，化學 強化玻璃時截切有可能性亦倂持截切不易的問題。 又，化學強化玻璃之製造方法，考慮種種的方法。例 如以離子半徑小的原子取代離子半徑大的原子的方法，利 用玻璃黏性流動離子半徑大的原子取代離子半徑小的原子 的方法，利用熱膨脹率差的方法，析出結晶的方法，組合 上述方法之方法等多數之方法。一般，鹼石灰系玻璃多數 使用以離子半徑小的原子取代離子半徑大的原子的方法， 其中，多數之化學強化玻璃於化學強化處理槽中浸漬，以 所謂浸漬法製造。即，玻璃以高溫之化學強化處理液，例 如浸漬於硝酸鉀溶液中，玻璃中之鈉離子由硝酸鉀溶液中 之鉀離子所取代，於表層形成壓縮應力層。又，玻璃中含 鋰時作爲化學強化處理液，多數使用硝酸鈉，或硝酸鈉與 硝酸鉀之混合鹽。 依公知之技術，例如，以切斷之玻璃使用於化學強化 時（參閱專利文獻1 )，切截條件之重要因素之表面應力 之測定技術（參閱專利文獻2 )已有揭示。 又，硬碟驅動化學強化有關之步驟： 1)於預備加熱槽之預備加熱（0.5〜2小時程度昇溫至 -5- 1276615 (3) 380 〜500 °C ) 2 )以硝酸鉀或硝酸鈉溶融鹽溶液之化學強化處理（ 0.5〜6小時程度） 3 )於送風冷卻槽之冷卻（5〜25m3/分之冷卻風面內之 溫度差爲5 °C以下由溶融鹽溶液之融點以下強制冷卻至室 溫） 更詳細之說明例如（參閱專利文獻3 )。 專利文獻1 :日本特開2002- 1 60932號公報 專利文獻2:日本特公昭59-37451號公報 專利文獻3 :日本特開2000-3445 5 0號公報 非專利文獻 1 : H.M. Garfinkel，其他 The Glass Industry, 5 0( 1 969), p.76 【發明內容】 〔發明之揭示〕 本發明之目的爲提供可具有指定強度且可截切之化學 強化玻璃。 本發明之另一目的爲提供上述化學強化玻璃之製造方 法。 依本發明之第1特徵，可提供由離子交換於表層形成 應力層之化學強化玻璃，壓縮應力層中接近玻璃表面具有 壓縮應力模式A與玻璃內層側之壓縮應力模式B之2種 類應力模式之化學強化玻璃。 依本發明之第2特徵，有關由離子交換處理於表層形 -6- (4) 1276615 成應力壓縮層製造化學強化玻璃之方法，離子交換浸漬處 理後保持於高於該浸漬液1 0 t以上之環境下，爲其特徵 之化學強化玻璃製造方法（第1方法）。 更依本發明之第2特徵，可提供以第2特徵之方法製 造之化學強化玻璃。 依本發明之第3特徵，有關由離子交換處理於表層形 成應力壓縮層製造化學強化玻璃之方法，係於離子交換之 第〗浸漬處理後以高於該浸漬液2 0 °C以上5 0 °C以下溫度 ，1 〇分鐘以上60分鐘以下作第2浸漬處理爲其特徵之化 學強化玻璃製造方法（第2方法）。 更依本發明之第3特徵，可提供以第3特徵之方法製 造之化學強化玻璃。 依本發明第1特徵之化學強化玻璃，可由上述第1或 第2方法而製造。 〔發明之實施型態〕 以下詳細說明本發明上述第1特徵。依此第1特徵， 提供可定安截切之化學強化玻璃。 爲改善玻璃之截切性，玻璃中持有2種類應力模式時 變爲有用。由持有2種類應力模式，可持有指定之壓縮應 力層厚度，成爲可容易截切之化學強化玻璃。以另外一種 方式說’非依存向來Fick法則之應力模式之化學強化玻 璃，不依存Fick法則，特別在表層附近發生之應力係依 另外之函數表示之化學強化玻璃。 -7- (5) 1276615 又’應力模式A及應力模式B自各爲近似1次函數 時’應力模式A及應力模式B爲持有不同斜率之上述化 學強化玻璃。不具其他應力模式，即，僅有1種類之向來 之化學強化玻璃，持有大破壞強度値，有不容易截切之問 題。 又’由應力模式A所求得之表面應力値，爲小於應 力模式B至玻璃表面之延伸線所求出之假表面應力値之化 學強化玻璃。若爲較大之値時，截切變難。 更又’相對於應力模式B延伸至玻璃表面所求出之假 表面應力値’與應力模式A所求得之表面應力値之比爲 0 · 8以上0.9 5以下之上述化學強化玻璃爲更合適。相對於 應力模式B延伸至玻璃表面所求出之假表面應力値之比爲 0.8以上0.95以下，低於〇·8時表面壓縮應力變小，事實 上之玻璃強度降低。又，超過0.95時，截切性下降。合 適爲0.85以上0.93以下。 此時’依條件，如圖6所示之應心力模式A之斜度 與模式B爲相反的情形。即，向來之化學強化玻璃係表面 之壓縮應力極端大於內層之應力値，本發明之化學強化玻 璃顯不稍爲進入內層部份之應力値比表面壓縮應力大。具 有如此之應力模式之化學強化玻璃當然屬於本發明之範圍 〇 更又’應力模式A之壓縮應力層厚度爲2//m以上5 "m以下。應力模式a之壓縮應力層厚度低於2#111時， 其相對之截切性效果小，應力模式A之壓縮應力層厚度 -8- 1276615 (6) 大於1 5 /i m時，化學強化玻璃性質之破壞度實質上變小 。以3 // m以上9 // m以下爲理想。 又，化學強化玻璃之生產管理能簡單進行，化學強化 玻璃內之應力模式己說明爲近似1次。但是，嚴格的述叙 時應力當然亦不爲近似1次函數。如上述離子交換本質上 依從Fick之擴散法則，擴散法則不爲〗次函數，嚴格的 說超出近似直線爲必然現象。又，玻璃內產生應力，除離 子交換以外，亦受溫度分佈，變形，板厚等項因素的影響 。如此不能爲近似直線或不容易近似時，產生之應力模式 可依1個函數表示，或必要以2個以上函數可回歸至原則 ，不使用近似3次以上之函數。近似係使用具有1極點或 無極點之函數。使用此函數爲近似時，可用1個函數表示 時，爲向來之化學強化玻璃。一方面，必要使用2個函數 時即爲本發明之強化玻璃。又，考慮近似函數之領域爲壓 縮應力所有之範圍。玻璃之截切性及破壞強度係依頼壓縮 應力値，及延伸應力爲一定値者，開始之範圍其應力之生 成有不安定者，有產生誤判之顧慮。 化學強化玻璃之壓縮應力層之厚度及壓縮應力値，係 受化學強化時之處理溫度及處理時間，更受處理液之選擇 及其活性特性之影響大，並不單純。又，依玻璃內之離子 交換狀況或晶化狀況而異。但，可得到破壞強度保持實用 水準，且截切性提高之化學強化玻璃。 以下詳述發明第2特徵。依此第2特徵可提供具強度 及截切性之化學強化玻璃之製造方法（第1方法）。 -9-1276615 (1) Technical Field of the Invention The present invention relates to chemically strengthened glass, particularly to a touch panel used in the field of electronic materials, chemically strengthened glass used in the fields of automobiles and construction, and a method for producing the same . [Prior Art] Enhance the progress of glass growth or enhancement by changing resources or energy-saving perspectives or changes in social needs. Generally, the air-cooling method used for the production of 3 mm or less, especially the glass plate thickness of 2 mm or less is difficult, and most of the glass of 2 mm or less is chemically strengthened. Further, the chemical strengthening method can obtain a higher strength than the tempered glass of the general air-cooling strengthening method. The reason why the chemically strengthened glass is accepted by most markets is the tempered glass which can be cut under certain conditions in addition to the strengthening and high strength of the above-mentioned thin glass. The air-cooled tempered glass is pulverized when it is cut into a crack, and the fracture cannot be cut. As shown in Fig. 5 (see Non-Patent Document 1), the chemically strengthened glass and the air-cooled reinforced (physically strengthened) glass have a very different stress pattern formed inside the glass. The air-cooled tempered glass utilizes the temperature difference between the surface layer and the inner layer and the viscous fluidity, and the stress mode is approximately twice the curve shape. In contrast, chemically strengthened glass utilizes ion exchange on the surface layer, and closely adheres to the diffusion rule of Fick, and most of it is close to a straight line. Air-cooled tempered glass In order to obtain a given surface compression force, the tensile stress of the inner layer is inevitably increased. Since the destruction of the glass depends on the tensile stress of the inner layer, it is inevitable that the filming under the force of -4- (2) 1276615 is large. On the one hand, when the chemical stress is increased, the tensile stress 内 of the inner layer is not significantly increased under normal conditions. The tensile stress of chemically strengthened glass is mostly based on the surface compressive force and the thickness of the compressive layer. That is, regardless of the air-cooled tempered glass or the chemically strengthened glass, the glass is broken in strength. On the one hand, it is impossible to cut the air-cooled tempered glass, and it is possible to cut the cut when chemically tempered glass. Moreover, various methods of manufacturing a chemically strengthened glass are considered. For example, a method in which an atom having a large ionic radius is substituted by an atom having a small ionic radius, a method in which an atom having a small ionic radius is replaced by an atom having a large viscous flow ionic radius, and a method of precipitating crystallization by a method of a difference in thermal expansion ratio is used. Most methods such as methods. In general, a soda lime-based glass is a method in which an atom having a large ionic radius is replaced by an atom having a small ionic radius. Among them, a large number of chemically strengthened glass is immersed in a chemical strengthening treatment tank and produced by a so-called impregnation method. That is, the glass is chemically strengthened with a high temperature chemical treatment solution, for example, immersed in a potassium nitrate solution, and the sodium ions in the glass are replaced by potassium ions in the potassium nitrate solution to form a compressive stress layer on the surface layer. Further, when lithium is contained in the glass, as a chemical strengthening treatment liquid, sodium nitrate or a mixed salt of sodium nitrate and potassium nitrate is often used. According to a known technique, for example, when the cut glass is used for chemical strengthening (see Patent Document 1), a technique for measuring the surface stress which is an important factor of the cutting condition (see Patent Document 2) has been disclosed. Also, the hard disk drive chemical strengthening related steps: 1) Preheating in the preliminary heating bath (0.5 to 2 hours to -5 to 1476615 (3) 380 to 500 °C) 2) Melting with potassium nitrate or sodium nitrate Chemical strengthening treatment of salt solution (about 0.5 to 6 hours) 3) Cooling in air supply cooling tank (the temperature difference in the cooling air surface of 5~25m3/min is 5 °C or less and forced cooling below the melting point of molten salt solution To the room temperature) A more detailed description is for example (see Patent Document 3). Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 59-37451. Patent Document 3: Japanese Patent Publication No. 2000-3445 No. 5 No. Patent Publication No. 1: HM Garfinkel, Other The Glass Industry, 5 0 (1 969), p. 76 [Disclosure of the Invention] [Disclosure of the Invention] An object of the present invention is to provide a chemically strengthened glass which can have a specified strength and can be cut. Another object of the present invention is to provide a method for producing the above chemically strengthened glass. According to the first feature of the present invention, it is possible to provide a chemically strengthened glass in which a stress layer is formed by ion exchange on a surface layer, and a type of stress mode in a compressive stress layer having a compressive stress pattern A close to the glass surface and a compressive stress pattern B on the inner layer side of the glass is obtained. Chemically strengthened glass. According to a second aspect of the present invention, a method for producing a chemically strengthened glass by ion exchange treatment in a surface layer of -6-(4) 1276615 stress-compressed layer is maintained at a temperature higher than 10 t above the immersion liquid after ion exchange immersion treatment A chemically strengthened glass manufacturing method (first method) characterized by the environment. Further, according to the second feature of the present invention, the chemically strengthened glass produced by the method of the second feature can be provided. According to a third aspect of the present invention, a method for producing a chemically strengthened glass by forming a stress-compressed layer on a surface layer by ion exchange treatment is performed at a temperature higher than 20 ° C and above 50 ° after the immersion treatment of ion exchange. A method of producing a chemically strengthened glass (second method) characterized by a second immersion treatment at a temperature of C or less and a temperature of 1 minute or more and 60 minutes or less. Further, according to the third feature of the present invention, the chemically strengthened glass produced by the method of the third feature can be provided. The chemically strengthened glass according to the first feature of the present invention can be produced by the above first or second method. [Embodiment of the Invention] The above first feature of the present invention will be described in detail below. According to the first feature, there is provided a chemically strengthened glass which can be cut and cut. In order to improve the cut-off property of the glass, it becomes useful to hold two kinds of stress modes in the glass. It holds two types of stress modes and can hold the specified thickness of the compressive stress layer to become a chemically strengthened glass that can be easily cut. In another way, the chemically strengthened glass of the stress mode of the non-dependent Fick rule does not depend on the Fick rule, and the stress occurring in the vicinity of the surface layer is chemically strengthened glass expressed by another function. -7- (5) 1276615 Further, when the stress mode A and the stress mode B are approximate first-order functions, the stress mode A and the stress mode B are the above-described chemically strengthened glass having different slopes. There is no other stress mode, that is, there is only one type of chemically strengthened glass, which has a large damage strength and is not easily cut. Further, the surface stress 求 obtained by the stress mode A is a chemically strengthened glass which is smaller than the pseudo surface stress 求出 obtained by the stress pattern B to the extension line of the glass surface. If it is larger, the cutting becomes difficult. Further, the above chemically strengthened glass having a ratio of the surface stress 値 obtained by extending the stress mode B to the glass surface to the surface stress 求 obtained by the stress mode A is preferably 0.8 or more and 0.9 5 or less. . The ratio of the pseudo surface stress 求出 obtained by extending the stress mode B to the surface of the glass is 0.8 or more and 0.95 or less, and the surface compressive stress is smaller than 〇·8, and the glass strength is actually lowered. Moreover, when it exceeds 0.95, the cutting property will fall. The suitability is 0.85 or more and 0.93 or less. At this time, depending on the condition, the slope of the stress mode A as shown in Fig. 6 is opposite to the mode B. That is, the compressive stress on the surface of the chemically strengthened glass system is extremely larger than the stress 内 of the inner layer, and the chemically strengthened glass of the present invention shows that the stress 进入 which enters the inner layer portion is larger than the surface compressive stress. It is of course within the scope of the present invention to have a chemically strengthened glass having such a stress mode. Further, the thickness of the compressive stress layer of the stress mode A is 2//m or more and 5 "m or less. When the thickness of the compressive stress layer of stress mode a is lower than 2#111, the relative cutting effect is small, and the thickness of the compressive stress layer of stress mode A is -8-1276615 (6) is greater than 1 5 /im, the properties of chemically strengthened glass The degree of damage is substantially reduced. It is ideal for 3 // m or more and 9 // m or less. Moreover, the production management of chemically strengthened glass can be easily carried out, and the stress mode in the chemically strengthened glass has been described as approximately one time. However, the stress at the time of rigorous remarks is of course not an approximate one-time function. If the above ion exchange essentially follows the diffusion rule of Fick, the diffusion rule is not a gradual function, and strictly speaking, it is an inevitable phenomenon that the approximate straight line is exceeded. In addition, stress is generated in the glass, and in addition to ion exchange, it is also affected by factors such as temperature distribution, deformation, and plate thickness. When this cannot be approximated or not easily approximated, the resulting stress pattern can be expressed as a function, or it is necessary to return to the principle with two or more functions, and a function of approximately three or more times is not used. The approximation uses a function with 1 pole or no pole. When this function is used for approximation, it can be represented by one function, which is chemically strengthened glass. On the one hand, it is necessary to use two functions as the tempered glass of the present invention. Also, the area in which the approximation function is considered is the range of the compressive stress. The cutting property and the breaking strength of the glass depend on the compressive stress 値, and the extension stress is a certain one. The initial range of the stress is unsettled, and there are concerns about misjudgment. The thickness and compressive stress of the compressive stress layer of the chemically strengthened glass are the processing temperature and the treatment time in the case of chemical strengthening, and are more affected by the selection of the treatment liquid and the active characteristics thereof, and are not simple. Further, it varies depending on the ion exchange state or the crystallization state in the glass. However, it is possible to obtain a chemically strengthened glass in which the breaking strength is maintained at a practical level and the cutting property is improved. The second feature of the invention will be described in detail below. According to the second feature, there is provided a method (first method) for producing a chemically strengthened glass having strength and cutting properties. -9-