201213261 六、發明說明： 【發明所屬之技術領域】 [0001] 本揭示是關於一種用以製作具有抗反射（AR)塗層之強化 玻璃的製程，以及根據該製程所製作的玻璃。尤其，本 揭示是關於一種用以在玻璃上沉積抗反射塗層，並且在 設置該抗反射塗層之後藉由離子交換處理以化學強化該 玻璃的製程。 【先前技術】 [0002] 可利用離子交換製程以對玻璃進行化學強化。在該製程 中，出現在位於或鄰近於玻璃表面之範圍内的金屬離子 會由大型金屬離子所交換，這通常是藉由將該玻璃浸沒 在熔化浸浴之内的方式進行。出現於該玻璃内的大型離 子可藉由在靠近該表面的範圍内產生壓縮應力來強化該 玻璃。而在該玻璃的中央範圍内則會引入拉張應力以均 衡該壓縮應力。 [0003] 化學強化玻璃近來既經公認為適用於手持式裝置，像是 行動電話、媒體播放器和其他裝置，以及其他要求透明 性、高強度與抗磨損的應用項目。然而，對於此等應用 項目，當撞擊時容易產生碎裂或破損的玻璃並非所樂見 ° Gorilla® Glass (Corning Incorporated)是一種 經離子交換玻璃，此者具有高抗損傷、熔融汲拉薄型玻 璃和天然表面品質的優點，使其對於作為消費性電子應 用項目，例如平面螢幕電視、電腦和監視器螢幕以及像 是電子書閱讀器、行動電話、音樂播放器之手持式裝置 ，的覆蓋玻璃而言極具吸引力。對於許多該等裝置，抗 100117131 表單編號A0101 第4頁/共30頁 1003391833-0 201213261 反射（AR)塗層為必要，藉以降低來自基板之可見光線的 反射度並且提高光線的穿透度。AR塗層可藉由許多方法 以沉積於表面玻璃基板上，例如溶凝膠方法以及像是傳 統沉積（CD)的真空沉積方法，其中待予沉積的材料是藉 由電阻加熱方法或電子轟炸（電子射束）、化學汽相沉積 (CVD)、離子輔助沉積（IAD)，此方式類似於CD而其另增 特性為所予沉積的膜層在沉積過程中會被轟炸以惰性氣 體（即如氬氣）的能量離子再加上當沉積氧化物膜層時的 一些離子化氧氣（藉以改善化學計量），以及離子射束濺 鍍（IBS)，其中是將能量離子射束導引至目標材料，以及 其他的真空方法，俾加熱至熔化狀態。不過，要利用CD 、CVD、IAD、I SB或其他真空方法以大量生產大型尺寸 AR塗層基板會需要昂貴的真空室設備。就以經濟的立場 而言（設備成本、操作塗層、所能生產之產品的體積）， 通常是保留真空方法以運用在高價值產品上，像是著眼 於雷射系統的光學元件。 [0004] 相對於前揭方法，溶凝膠塗層對於消費性產品大量生產 而言就是一種為眾人所關注的替代性塗層技術。溶凝膠 方法使用的是低成本材料及設備，並且運作於室溫（例如 18-25°C)和週遭壓力處或附近。一般說來，溶凝膠塗層 需要進行固化，這可藉由施用熱能[D. Chen, “Anti-ref1ect ion coatings made by sol-gel process : a review，” Solar Energy Materials&So1ar Cells, Vol. 68 (2001 )，pp. 31 3-336 ]，以自附著 層中汽化該溶液的殘餘有機物或其他液體化合物；藉由 100117131 表單編號A0101 第5頁/共30頁 1003391833-0 201213261 在氨質大氣中進行固化[U.s. PatentNo. 7,642，199 and £P patent N〇. 1 902 023];或者是UV固化 [U.S. Patent No. 6,942,924 and article by P. Belleville et al, “A UV cured sol-gel broadband antiref 1ective and scratch-resistance coating for CRTM ,S〇-Ge! Optics V, Proceed I rigs of SFME, Vol. 3943 (2000), PP. 67-71 ]以緻密化該塗層結構而達成。然而，高溫固 化，尤其是在高於約300 °C的溫度處進行固化，可能會犧 牲該離子交換（I0X)玻璃獲自於離子交換製程的高抗損傷 度，該製程會藉由令壓縮應力鬆弛而經由交換動作，例 如來自玻璃的鈉離子交換為來自KN〇浸浴的鉀離子’而 Ο 產生高壓縮應力《另一項對於溶凝膠塗層的關注因素是 來自溶凝膠塗層製程的”邊緣效應，，會導致在沿該玻璃 邊緣上具有不令人滿意品質的塗層區域’這將需要予以 裁除或切斷俾製作最終產品。該，’邊緣效應，，在溶凝膠 製程禋為本質性，並且，除非採取步驟以移除該效應， 否則會沿该邊緣上產生不符合該塗層及/或產品之典型規 格的溶凝膠塗層區域。若離子交換是在溶凝膠塗層之前 完成，則在化學強化玻璃上進行，，邊緣效應，，區域裁修 確實困難重重且成本昂貴。美國專利第6,656 522號（該 ‘522號利：)案文中揭示一種’於進行溶凝膠塗層和固 化處理後，在經由熱性回火所強化之玻璃上的多層式、 溶凝膠AR塗層。該‘522號專利案文雖保留其在〇塗層、 固化以及減时之後的光學„，然必齡意到熱性 1003391833-0 回火並不同於I0X (化學強化處理）製程。美國專利第 100117131 表單編號A0101 第6頁/共30頁 201213261 4, 168，113號（該113號專利）案文評估經選定之金屬氧 化物的真空室、電子射束沉積塗層以及該等對於ιοχ製 程的反應性。不過，欲對此項，113號專利的真空沉積作 業/IOX製程進行比例調整以供生產例如鹼石灰玻璃片的 大型玻璃片確為昂責且高難度。從而本揭示呈現一種簡 易且價廉製程，藉以能夠依便捷且低成本方式來生產經 化學強化（藉由IOX)及AR塗層的玻璃物品。 【發明内容】 [0005] Ο ο 本揭示是針對於一種用以生產抗反射（AR)及/或抗眩光 (AG)塗層、經離子交換之玻璃物品的方法，該等物品是 藉由一製程所生產，該製程包含提供其内含有可離子交 換離子之選定玻璃材料的薄片；洗淨該玻璃片；對該玻 璃塗覆溶凝膠以產生AR及/或AG塗層；固化該AR及/或AG 塗層以提供具有其上附著有AR及/或AG塗層的玻璃；以及 令該玻璃片内的可離子交換離子作離子交換於較大離子 ，俾藉此在該玻璃内構成至少一經離子交換層而且在該 玻璃内傳授壓縮應力俾藉此予以強化。例如，然非受限 於此，含有鈉及/或鋰的玻璃可為由鉀離子或铯離子所離 子交換。該離子交換作業可在單一步驟中，或是在利用 一或更多具有相同或不同組成成份之離子交換浸浴的複 數個步驟中，所完成，例如，然非限制，可在第一步驟 中利用含κ離子浸浴並且在第二步驟中利用含K/Cs離子浸 浴以交換玻璃内的Na/Li離子；或是兩者浸浴皆可含有尺 離子。 [0006] 即以AR塗層作為範例，本揭所述方法的優點，其中是在 100117131 表單编號A0101 第7頁/共30頁 1003391833-0 201213261 構成該AR塗層之後，包含固化處理，才進行ΐοχ，在於能 夠獲得最大壓縮應力。當離子交換玻璃是在既已進行過 離子交換之後才進行AR塗層時，會有必要審慎地控制該 AR塗層的任何固化處理。必須避免高於300 ° C的溫度，理 由是，若高於此溫度，由離子交換所產生而對該玻璃引 致強化結果的壓縮應力鬆弛會被釋放。其結果為壓縮應 力消減，並且抗撞擊與震盪性出現損失。即如本揭所示 ，既已將在該示範性AR塗層之後的離子交換施用於玻璃 並予適當固化，則該玻璃可為離子交換以獲致高壓縮應 力，然不致顯著地損失AR性質。即如附圖3所示並如表3 所述，3及4層經AR塗層且後續地離子交換的玻璃可產生 具有高於620MPa之壓縮應力以及大於23μιη之覆層深度的 AR/I0X玻璃。在一具體實施例裡，該壓縮應力是大於 660Mpa並且該覆層深度為大於30_。在進一步具體實施 例裡，該壓縮應力是大於700Mpa並且該覆層深度為大於 35μιη。在其他的具鱧實施例裡，該壓縮應力是大於 720Mpa並且該覆層深度為大於38μιη。 【實施方式】 [0007] 100117131 在此是利用AR塗層以示範說明本揭示。然應瞭解確能根 據本揭示施用其他塗層，例如抗眩光塗層。抗眩光及抗 反射處理二者是代表改善或優化可讀性的方式。然該等 是按照不同方式達此目的。抗眩光塗層是利用散光機制 以打斷來自外部來源（例如太陽或室内光照）而自物品表 面所反射的光線。抗反射則是處理經由顯示器窗口所傳 透的内部及外部來源兩者。當光線自一媒體通行至另一 者時’例如從空氣通行至固體層或是多個固體層之間’ 表單塢號Α0101 第8頁/共30頁 1003391833-0 201213261 該等覆層間之覆層内的折射指數差或材料（空氣/固體或 固體/固體）會產生移位相位差’如此而提高所反射之光 線的量值。這些反射為累集性並且可能”沖除”顯示畫 面，使得影像無法讀知而不會增加該顯示器的光線輸出 ，如此為非所樂見者，原因是這會需要提高供應給該顯 示器的電力’並且對於可攜式顯示器項目而言，這種電 力增加將導致再充電或更換作業之間的電池壽命縮短。 此外，在固化後的抗反射或抗眩光塗層雖並未含有可交 換離子，例如鋰及/或鈉，然而在如本揭所述的離子交換 步驟之後，該塗層確含有至少5wt%可交換至該經施以塗 層之玻璃内的’’較大”鹼金屬離子。在多層塗層中，可 將抗反射及抗眩光塗層施用於相同的玻璃物品。 [0008]圖la為說明現存用以備製經AR塗層、離子交換玻璃之溶 凝膠方法/製程10的主要步驟之略圖。該方法1〇牵涉到如 下步驟序列，即對所提供之_進行離子交換12 ;洗淨 該經離子交換玻賴；溶凝膠塗覆該所洗淨離子交換玻 璃16 ;以及固化該溶凝膠塗層，並且切割及裁修該所固 化溶凝膠塗層18。在此方法中，可對含有像是以及/或“ 離子之可交換離子的玻璃進行離子交換，故而將Li及/或 Na離子替換為較大離子，例如κ離子◊在離子交換之後’ 將該玻璃洗淨益塗覆溶凝膠AR塗層混合物，然後令此者 乾燥以部分地移除流體且予固化，藉此在該經離子交換 玻璃的表面上構成AR塗層。該固化可為熱性方式完成， 然必須謹慎以確保該固化溫度並非完成於該離子交換破 璃内之壓縮應力不會鬆弛的溫度處。若確出現這種鬆弛 100117131 表單煸號A0101 $ 9頁/共30頁 1003391833-0 201213261 情況，則玻璃會損失一部分藉由離子交換製程所獲致的 強度。對於熱性固化處理的精確最大溫度可為逐一玻璃 組成分而改變，然通常會是低於350 °C，並且最好是低於 300 °C。在既已固化該溶凝膠AR塗層之後，接著可將該經 塗層玻璃切割且裁修至所欲尺寸。利用UV固化來取代熱 性固化可避免對該塗層基板過度加熱，然問題在於經IOX 處理玻璃塗層之後的切割及裁修處理可能會將微型碎裂 引入至該等所切割及裁修表面内，這些微型碎裂在使用 過程中可能成長，從而在最終產品内導致碎裂或破損玻 璃。 [0009] 圖lb為說明本揭示用以備製經AR塗層、離子交換玻璃之 製程20的主要步驟之略圖。該方法20牽涉到如下步驟序 列，即洗淨未經離子交換玻璃22 ;溶凝膠塗覆該所洗淨 玻璃24 ;以及固化該溶凝膠塗層，並且切割及裁修該所 固化溶凝膠塗層26 ;以及對該經塗層、切割及裁修之玻 璃進行離子交換28。在此方法中，會洗淨含有像是Li及/ 或Na離子之可交換離子的玻璃22，對其塗覆溶凝膠AR塗 層，並且該玻璃上的AR塗層可為熱性或UV固化。在一具 體實施例裡，該塗層係經UV固化。在既已固化該AR塗層 之後，該塗層玻璃係經切割且裁修成所欲尺寸，同時進 行任何必要的邊緣完工處理，像是研磨或磨光。在次一 步驟中，將該經尺寸切定且邊緣完工玻璃放置在離子交 換介質内以供將像是Li及/或Na的離子交換成即如K離子 的較大離子。在離子交換之後，該玻璃係經洗淨並且可 進行任何額外的製程步驟，例如在該玻璃的表面上列印 100117131 表單編號A0101 第10頁/共30頁 1003391833-0 201213261 ° _ 多項特性（商標或撰文），或是將抗油性及/或抗水性塗層 施用於該玻璃’·然不限於此4本製程中，該玻填所有3 表面皆經離子交換且強化。由於能夠在離子交換之前先 完成任何必要的固化、裁修、研磨及磨光處理，因而不 致引入於使用過程中可能會在該玻螭内成長並造成碎裂 的表面缺陷。所獲結果為一種能夠保留藉由該玻螭内之 高壓縮應力所產生的高抗損性之經AR塗層、離子交換玻 璃。此外，該製程可供使用熱性或uv固化該…塗層而無 須擔憂該玻璃内的壓縮應力輸出現損失。 在根據本揭示的方法中，I0X作業是在溶凝膠脯塗層固化 於破璃表面上之後才進行，並且所固化的溶_AR塗層 應擁有足夠硬度，使得在牽涉到像是切割、磨光、裁修 、離子交換、洗料㈣後續程相餘，財限於此 ，不會被例如到痕所損傷》一種決定塗層是否擁有足夠 硬度的簡易方式為對塗層進行，，鉛筆硬度，，測試。亦可 在既已對難層玻璃進行離子交換之後利用該㈣硬度 ϋ [0011] 測试來決定塗層的硬度。 該鉛筆硬度測試是利用硬度9H (最硬)、8H、7H、叩、 5H、4H、3H、2H、F、hb、b、2B、3b、4b、5b、6b、、 7B、8B及9B (最軟）的鉛筆級度集合。字母” η”及，，b ”分別地代表”硬度，，和，’黑度”。錯筆材料含有黏土 及石墨。硬度會隨著黏土含量提高而增加並且黑度降低 二因此，對於所有的錯筆而言，黏土愈多，錯筆就會變 得愈硬。賴表面應為潔淨，並且無含任何塵土以及來 自AR及/或ιοχ製程的遺留殘餘物。 100117131 表單編號A0101 第11頁/共30頁 1003391833-0 201213261 [0012] 該鉛筆測試為簡單且方便執行、提供均勻結果並具有可 靠性，原因是鉛筆在其等級上為均勻。為進行測試，選 擇一支鉛筆，並且沿該測試片件的表面劃出一條至少一 英吋（~ 2. 5cm)的直線。若此鉛筆留下刮痕，則利用下一 種較軟鉛筆並且重複此程序。在使用產生刮痕的鉛筆之 後第一種不會造成刮痕之鉛筆的編號會被視為是該塗層 的”鉛筆硬度”。例如，若令僅AR塗層的片件經鉛筆測 試並且3H鉛筆留下刮痕，但是2H鉛筆不會留下刮痕，則 該塗層的鉛筆硬度為2H。任何不會被9H鉛筆留下刮痕的 塗層都被視為是具有9H硬度評級。 [0013] 可對一系列經AR塗層且離子交換的樣本進行鉛筆測試。 該等AR塗層可為單層式、3層式及4層式塗層，這些是利 用含有Si09、Al9Oq、！409及/或過渡金屬氧化物，例如201213261 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present disclosure relates to a process for producing a tempered glass having an anti-reflection (AR) coating, and a glass produced according to the process. In particular, the present disclosure relates to a process for depositing an anti-reflective coating on glass and chemically strengthening the glass by ion exchange treatment after the anti-reflective coating is disposed. [Prior Art] [0002] An ion exchange process can be utilized to chemically strengthen the glass. In this process, metal ions present in or adjacent to the surface of the glass are exchanged by large metal ions, typically by immersing the glass in a molten bath. Large ions present in the glass can strengthen the glass by creating compressive stresses in the vicinity of the surface. Tensile stress is introduced in the center of the glass to balance the compressive stress. [0003] Chemically strengthened glass has recently been recognized as being suitable for use in handheld devices such as mobile phones, media players and other devices, as well as other applications requiring transparency, high strength and wear resistance. However, for these applications, glass that is prone to cracking or breakage when impacted is not a pleasure. Gorilla® Glass (Corning Incorporated) is an ion-exchanged glass with high damage-resistant, fused, thin-drawn glass. And the advantages of natural surface quality, making it a cover glass for consumer electronic applications such as flat screen TVs, computer and monitor screens, and handheld devices such as e-book readers, mobile phones, and music players. The words are very attractive. For many of these devices, anti-100117131 Form No. A0101 Page 4 of 30 1003391833-0 201213261 Reflection (AR) coating is necessary to reduce the reflectance of visible light from the substrate and increase the penetration of light. The AR coating can be deposited on a surface glass substrate by a number of methods, such as a lyogel method and a vacuum deposition method such as conventional deposition (CD), in which the material to be deposited is subjected to resistance heating or electron bombardment ( Electron beam), chemical vapor deposition (CVD), ion-assisted deposition (IAD), which is similar to CD and has the additional property that the deposited layer will be bombarded with an inert gas during deposition (ie Energy ions of argon) plus some ionized oxygen (to improve stoichiometry) when depositing an oxide film, and ion beam sputtering (IBS), which directs the energy ion beam to the target material, As well as other vacuum methods, the crucible is heated to a molten state. However, the use of CD, CVD, IAD, I SB or other vacuum methods to mass produce large size AR coated substrates would require expensive vacuum chamber equipment. From an economic standpoint (equipment cost, operating coating, volume of product that can be produced), vacuum methods are often used to apply to high-value products, such as optical components that focus on laser systems. [0004] Compared to the prior methods, sol-gel coatings are an alternative coating technique of interest for mass production of consumer products. The lyophilized process uses low cost materials and equipment and operates at or near room temperature (e.g., 18-25 ° C) and ambient pressure. In general, sol-gel coatings require curing, which can be achieved by applying thermal energy [D. Chen, "Anti-ref1 cation coatings made by sol-gel process : a review," Solar Energy Materials & So1ar Cells, Vol. 68 (2001), pp. 31 3-336 ], a residual organic or other liquid compound that vaporizes the solution in a self-adhesive layer; by means of 100117131 Form No. A0101 Page 5 of 30 1003391833-0 201213261 in an ammonia atmosphere Curing is carried out [Us Patent No. 7,642,199 and £P patent N〇. 1 902 023]; or UV curing [US Patent No. 6,942,924 and article by P. Belleville et al, "A UV cured sol-gel broadband antiref 1ective and scratch-resistance coating for CRTM, S〇-Ge! Optics V, Proceed I rigs of SFME, Vol. 3943 (2000), PP. 67-71] is achieved by densifying the coating structure. However, high temperature curing Curing, especially at temperatures above about 300 °C, may sacrifice the high degree of damage resistance of the ion exchange (I0X) glass from the ion exchange process, which is exchanged by relaxing the compressive stress. Action, for example The sodium ion exchange from the glass is the potassium ion from the KN〇 bath and the high compressive stress is produced. Another factor of concern for the sol gel coating is the edge effect from the sol-gel coating process. This results in a coating area with unsatisfactory quality along the edge of the glass. This will require cutting or cutting the crucible to make the final product. Thus, the 'edge effect, 禋 is essential in the sol-gel process, and unless steps are taken to remove the effect, a condensation will occur along the edge that does not meet the typical specifications of the coating and/or product. Glue coated area. If the ion exchange is done before the sol gel coating, then on chemically strengthened glass, edge effects, and area trimming are indeed difficult and costly. U.S. Patent No. 6,656,522 (the '522 patent:) discloses a multi-layer, lyotropic AR coating on a glass reinforced by thermal tempering after sol gel coating and curing treatment. Floor. The '522 patent text retains its optical properties after enamel coating, curing, and time lapse, but it is tempered to heat 1003391833-0 and is different from the I0X (chemical strengthening treatment) process. US Patent No. 100117131 Form No. A0101 Page 6 of 30 201213261 4, 168, 113 (the '113 patent) text evaluates the selected metal oxide vacuum chamber, electron beam deposition coating and the reactivity of the process for the ιοχ process. However, in order to this, the vacuum deposition/IOX process of the 113th patent is scaled for the production of large glass sheets such as soda lime glass sheets. This disclosure presents a simple and inexpensive process. Therefore, it is possible to produce chemically strengthened (by IOX) and AR coated glass articles in a convenient and low-cost manner. [Invention] [0005] The present disclosure is directed to a method for producing anti-reflection (AR) And/or an anti-glare (AG) coating, an ion exchanged glass article, the article being produced by a process comprising providing an ion-exchangeable ion therein Forming a sheet of glass material; washing the glass sheet; applying a sol gel to the glass to produce an AR and/or AG coating; curing the AR and/or AG coating to provide an AR and/or attached thereto AG coated glass; and ion-exchangeable ions in the glass sheet for ion exchange to a larger ion, thereby forming at least one ion exchange layer in the glass and imparting compressive stress within the glass For example, it is not limited thereto, and the glass containing sodium and/or lithium may be ion-exchanged by potassium ions or cesium ions. The ion exchange operation may be performed in a single step or in the use of one or more In a plurality of steps of ion exchange bathing of the same or different constituents, such as, but not limited to, utilizing a κ-containing ion bath in the first step and utilizing K/Cs ion immersion in the second step Bath to exchange Na/Li ions in the glass; or both baths may contain ruler ions. [0006] That is, the AR coating is taken as an example, the advantages of the method described in the figure is 100117131 Form No. A0101 Page 7 of 30 Page 1003391833- 0 201213261 After the AR coating is formed, it contains the curing treatment before it can be used to obtain the maximum compressive stress. When the ion exchange glass is subjected to the AR coating after the ion exchange has been performed, it is necessary to carefully control it. Any curing treatment of the AR coating must avoid temperatures above 300 ° C, on the grounds that if it is higher than this temperature, the compressive stress relaxation generated by ion exchange and causing the strengthening effect on the glass will be released. For compressive stress reduction, and loss of impact and shock resistance. As shown in the present disclosure, the ion exchange after the exemplary AR coating has been applied to the glass and properly cured, the glass may be ion exchanged. In order to achieve high compressive stress, the AR properties are not significantly lost. That is, as shown in FIG. 3 and as described in Table 3, 3 and 4 layers of AR-coated and subsequently ion-exchanged glass can produce AR/I0X glass having a compressive stress higher than 620 MPa and a coating depth greater than 23 μm. . In a specific embodiment, the compressive stress is greater than 660 MPa and the coating depth is greater than 30 Å. In a further embodiment, the compressive stress is greater than 700 MPa and the coating depth is greater than 35 μιη. In other embodiments, the compressive stress is greater than 720 MPa and the coating depth is greater than 38 πη. [Embodiment] [0007] 100117131 The present disclosure is exemplified by the use of an AR coating. It will be appreciated that other coatings, such as anti-glare coatings, can be applied in accordance with the present disclosure. Both anti-glare and anti-reflective treatments are representative of ways to improve or optimize readability. However, this is done in different ways. Anti-glare coatings use an astigmatism mechanism to interrupt light reflected from the surface of the object from an external source such as the sun or indoor light. Anti-reflection deals with both internal and external sources that are transmitted through the display window. When light travels from one medium to another 'for example, from air to solid layer or between multiple solid layers' Form Dock No. 1010101 Page 8 of 30 Page 1003391833-0 201213261 Cover between these layers The difference in refractive index within the material or the material (air/solid or solid/solid) produces a shift phase difference' which increases the amount of reflected light. These reflections are additive and may "flush" the display so that the image is unreadable without increasing the light output of the display, which is unpopular because it would require increased power to the display. And for portable display projects, this increase in power will result in a shortened battery life between recharging or replacement operations. In addition, the antireflective or anti-glare coating after curing does not contain exchangeable ions, such as lithium and/or sodium, however, after the ion exchange step as described herein, the coating does contain at least 5% by weight. Exchanging to the ''larger' alkali metal ions in the coated glass. In the multilayer coating, the anti-reflective and anti-glare coatings can be applied to the same glass article. [0008] Figure la is an illustration An outline of the main steps for preparing a lyogel method/process 10 for AR coating and ion exchange glass. This method involves the following sequence of steps, ie ion exchange 12 is provided; The ion exchanged glass is coated with the washed ion exchange glass 16; and the sol gel coating is cured, and the cured sol gel coating 18 is cut and trimmed. In this method, The glass may be ion-exchanged with and/or "ion exchangeable ions, so Li and/or Na ions may be replaced by larger ions, such as κ ions after ion exchange". Solubilizing the gel AR coating mixture, then This was dried by the fluid and removed to partially curing it, whereby the switching configuration of an AR coating on the glass surface of the ion. This curing can be done thermally, but care must be taken to ensure that the curing temperature is not at a temperature at which the compressive stress within the ion exchange glass does not relax. If such a relaxation occurs, 100117131 forms the nickname A0101 $9 page/total 30 pages 1003391833-0 201213261, the glass will lose some of the strength obtained by the ion exchange process. The precise maximum temperature for the thermal cure treatment may vary from one glass component to one component, and will typically be below 350 °C, and preferably below 300 °C. After the lyogel AR coating has been cured, the coated glass can then be cut and tailored to the desired size. The use of UV curing instead of thermal curing avoids overheating the coated substrate, but the problem is that the cutting and trimming process after the IOX treatment of the glass coating may introduce micro-cracks into the cut and cut surfaces. These micro-cracks may grow during use, causing cracking or broken glass in the final product. [0009] FIG. 1b is a schematic diagram illustrating the main steps of the process for preparing an AR-coated, ion-exchanged glass process 20 of the present disclosure. The method 20 involves a sequence of steps of washing without ion exchange glass 22; sol gel coating the cleaned glass 24; and curing the lyogel coating, and cutting and tailoring the cured gel a glue coating 26; and ion exchange 28 of the coated, cut and trimmed glass. In this method, glass 22 containing exchangeable ions such as Li and/or Na ions is washed, coated with a lyogel AR coating, and the AR coating on the glass can be thermally or UV cured. . In a specific embodiment, the coating is UV cured. After the AR coating has been cured, the coated glass is cut and tailored to the desired size while performing any necessary edge finishing operations, such as grinding or buffing. In the next step, the size-cut and edge-finished glass is placed in an ion exchange medium for exchanging ions such as Li and/or Na into larger ions such as K ions. After ion exchange, the glass is washed and any additional processing steps can be performed, such as printing 100117131 on the surface of the glass. Form No. A0101 Page 10 / Total 30 Page 1003391833-0 201213261 ° _ Multiple Features (Trademarks Or the author), or apply an oil-repellent and/or water-resistant coating to the glass'. However, it is not limited to the four processes, and all three surfaces of the glass-filled are ion-exchanged and strengthened. Since any necessary curing, trimming, grinding, and buffing can be performed prior to ion exchange, it is not introduced into surface defects that may grow in the glass during use and cause chipping. The result obtained was an AR-coated, ion-exchanged glass capable of retaining the high damage resistance caused by the high compressive stress in the glass. In addition, the process can be used to cure the coating using heat or uv without worrying about the loss of compressive stress output within the glass. In the method according to the present disclosure, the IOX operation is performed after the sol-gel coating is cured on the glass surface, and the cured _AR coating should have sufficient hardness to be involved in cutting, Polishing, cutting, ion exchange, washing (4) follow-up process, the wealth is limited to this, will not be damaged, for example, to the mark. A simple way to determine whether the coating has sufficient hardness is the coating, pencil hardness, test. The (4) hardness ϋ [0011] test can also be used to determine the hardness of the coating after the ion exchange of the hard glass. The pencil hardness test uses hardness 9H (hardest), 8H, 7H, 叩, 5H, 4H, 3H, 2H, F, hb, b, 2B, 3b, 4b, 5b, 6b, 7B, 8B and 9B ( The softest set of pencil scales. The letters "η" and, "b" respectively represent "hardness," and "blackness." The wrong material contains clay and graphite. The hardness increases as the clay content increases and the blackness decreases. Therefore, for all In the erroneous pen, the more clay there is, the harder the pen will become. The surface should be clean and free of any dust and residual residues from the AR and/or ιοχ process. 100117131 Form No. A0101 Page 11 / Total 30 pages 1003391833-0 201213261 [0012] The pencil test is simple and convenient to perform, provides uniform results and is reliable because the pencil is uniform in its grade. For testing, select a pencil and follow the test A line of at least one inch (~2.5 cm) is drawn on the surface of the piece. If the pencil leaves a scratch, use the next softer pencil and repeat the procedure. After using the pencil that produces the scratch, first The number of the pencil that will not cause scratches will be considered as the "pencil hardness" of the coating. For example, if only the AR coated piece is pencil tested and the 3H pencil leaves a scratch, 2H pencil The scratch will be left and the pencil hardness of the coating will be 2 H. Any coating that will not be scratched by the 9H pencil is considered to have a 9H hardness rating. [0013] A series of AR coatings are available. The ion-exchanged samples are subjected to pencil testing. The AR coatings can be single-layer, 3-layer and 4-layer coatings, which utilize Si09, Al9Oq, !409 and/or transition metal oxides, for example
L L 6 L T i、H f、G d和Z r之氧化物，然不限於此，的溶凝膠所沉 積。該溶凝膠可為利用已知方法，例如利用酸性酒精介 質内的Si及/或Ti烷氧化物，該介質含有Ti及/或A1或其 他金屬的鹼金屬鹽類（通常為氣化物、硝酸鹽或醋酸）， 然不限於此，所製作。該溶凝膠可為搖變性或非搖變性 ，並可藉由浸沾、喷灑或其他業界眾知方式以按如單一 或複數個疊層方式所施用。當欲以鍍於玻璃物品的僅單 一側上時，可藉由將該溶凝膠噴灑於該所欲侧上，或是 利用像是可移除聚合物薄膜的保護性材料，藉由保護該 非予塗層的一側並且藉由浸沾方式以將該塗層施用於該 所欲側，來施用該塗層。塗層的厚度可有所變化。在一 具體實施例裡，該AR塗層具有50nm至350nm範圍的厚度 100117131 表單編號A0101 第12頁/共30頁 1003391833-0 201213261 在另具體實施例裡，該AR塗層具有1〇〇11„1至25〇11111範 圍的厚度。在®1已將該AR賴膠塗層施用於該（等）所欲 灸會藉由熱性或是UV固化處理以於含氡大氣中（ 氣或者空氣混合以其他氡氣）令其 固化。熱性固化 通常疋在150 (：至6〇〇。(：或低於玻璃軟化點，取其較低者 。的'皿度範圍處進行2G分鐘至1 2小時範圍的選定時間。 ^ 〜’、f生固化是在350 °C至6〇〇。（：溫度範圍處進行1 Ο =時至5f時範圍的時間。在-具體實施例裡，當出現臭 3) π可在較低溫度處進行熱性固化，例如者出現有 選定量值的臭氣以促進任何有機殘餘物的燃燒時，可在 170 C至250 C的溫度範圍内進行熱性固化。表1棄整對 於經AR塗層然後Ι〇χ處理之樣本的錯筆硬度。 [0014]表 1 [0015]The oxide of L L 6 L T i, H f, G d and Z r is not limited thereto, and the sol gel is deposited. The lyophile may be a known method, for example, using Si and/or Ti alkoxide in an acidic alcohol medium containing an alkali metal salt of Ti and/or A1 or other metals (usually a vapor, nitric acid). Salt or acetic acid), which is not limited to this, is produced. The lyotropic gel may be shaken or non-shaken and may be applied in a single or multiple laminates by dipping, spraying or other means known in the art. When it is desired to be plated on only a single side of the glass article, by spraying the lyophile on the desired side, or by using a protective material such as a removable polymer film, by protecting the non- The coating is applied by coating one side of the coating and applying the coating to the desired side by dipping. The thickness of the coating can vary. In a specific embodiment, the AR coating has a thickness in the range of 50 nm to 350 nm. 100117131 Form No. A0101 Page 12/Total 30 Page 1003391833-0 201213261 In another embodiment, the AR coating has 1 〇〇 11 „ a thickness in the range of 1 to 25 〇 11111. The application of the AR lacquer coating to the (1) moxibustion in the ® 1 will be treated by heat or UV curing in a sputum-containing atmosphere (gas or air mixing Other helium) cures it. Thermal curing usually simmers at 150 (: to 6 〇〇. (: or below the softening point of the glass, taking the lower one. The range of 2G minutes to 12 hours) The selected time. ^ ~ ', f raw curing is in the range of 350 ° C to 6 〇〇. (: temperature range is 1 Ο = hour to 5f time range. In the specific embodiment, when the smell is 3) π can be thermally cured at lower temperatures, such as when a odor of a selected amount is present to promote combustion of any organic residue, which can be thermally cured at temperatures ranging from 170 C to 250 C. Table 1 Wrong pen hardness for samples treated with AR coating and then treated. [0014]Table 1 [00 15]
[0016] 100117131 單層溶凝膠AR ------ 3層溶凝膠… 4層溶凝膠AR 只塗覆AR ------- 塗覆AR及AR 後作IOX ~~—---------- 塗膜 ~~~~——-_ 塗膜 —---. 塗膜 6H ~-—---— 6H 7H 8-9H ------- 9H --- 9H 測試結果表示，當利用溶凝膠以對玻蹲進行AR塗層 再進行離子交換時，_子交錢之表面的硬度會提高 〇 即如表1所示，這些AR塗層可為單層式覆層或多層式塗層 。圖2a至2c顯示對於一系列，在進行離子交換之前或之 後，以溶凝膠施用AR塗層之玻璃物品的光學效能，反射 度相對於波長，測試結果。表23至2(3描述單層、3層及4 表單蝙號A0101 第13頁/共30頁 1003391833-0 201213261 層AR塗層經Ι0Χ處理的玻璃樣本，而依反射度相對於波長 以評估其光學效能。在所有情況下，離子交換都是在AR 塗層既已完全固化之後進行。表2a至2c分別地對應於圖 2a至2c ° [0017] 表2a圖2 Ι0Χ對1-層固化溶凝膠塗膜影響[0016] 100117131 Single layer lyotropic gel AR ------ 3 layers of lyotropic gel... 4 layers of lyotropic gel AR coated only AR ------- After coating AR and AR for IOX ~~- ---------- Coating film~~~~——-_ Coating film----. Coating film 6H ~------ 6H 7H 8-9H ------- 9H --- 9H test results show that when using lyogel to carry out AR coating on glass bottles and then ion exchange, the hardness of the surface of _ paying money will increase, as shown in Table 1, these AR coatings can be It is a single-layer coating or a multi-layer coating. Figures 2a through 2c show the optical performance, reflectance versus wavelength, test results for a series of glass articles coated with an AR coating before or after ion exchange. Tables 23 to 2 (3 describes single layer, 3 layers, and 4 forms bat number A0101 page 13 / total 30 pages 1003391833-0 201213261 layer AR coating treated with Χ0Χ glass samples, and the reflectance is relative to the wavelength to evaluate Optical performance. In all cases, ion exchange is carried out after the AR coating has been fully cured. Tables 2a to 2c correspond to Figures 2a to 2c, respectively. [0017] Table 2a Figure 2 Ι0Χ for 1-layer curing solution Gel coating effect
試樣編號 反射光線波長 I0X溫度，° I0X時間， nm C hrs. 34 490 無I0X,只 無I0X只塗 塗覆AR 覆AR 36 “ 410塗覆AR 6塗覆AR 30 535 無I0X,只 無I0X只塗 塗覆AR 覆AR 32 “ 410塗覆AR 6塗覆AR 表2b, I0X對4-層固化溶凝膠AR塗膜影響Sample number reflects light wavelength I0X temperature, ° I0X time, nm C hrs. 34 490 No I0X, only I0X only coated AR coated AR 36 "410 coated AR 6 coated AR 30 535 No I0X, only I0X Application only AR coated AR 32 "410 coated AR 6 coated AR Table 2b, I0X effect on 4-layer cured lyophilized AR coating
試樣編號 I0X溫度，。C I0X 時間，hrs. A4 無I0X，只塗覆AR 無I0X只塗覆AR B4 390塗覆AR 12塗覆AR C4 390塗覆AR 16塗覆AR D4 400塗覆AR 10塗覆AR E4 400塗覆AR 8塗覆AR 表2c，I0X對3-層固化溶凝膠AR塗膜影響 [0020] !試樣編號 丨I0X溫度，°C 丨I0X時間，hrs. j---------1----------L________________________________」Sample number I0X temperature,. C I0X time, hrs. A4 No I0X, only AR coated No I0X only AR B4 390 coated AR 12 coated AR C4 390 coated AR 16 coated AR D4 400 coated AR 10 coated AR E4 400 coated AR 8 coated AR Table 2c, I0X effect on 3-layer curing lysate AR coating [0020] ! Sample number 丨I0X temperature, °C 丨I0X time, hrs. j-------- -1----------L________________________________"
ί A3 I無I0X，只塗覆AR!無I0X只塗覆AR ,__________________________________[_______—_________________________________|_____________________________________ 」 丨 B3 ： 390 1 6 ： . 100117131 表單編號A0101 第14頁/共30頁 1003391833-0 201213261 C3 390 16 — Ο 圖2a至2c顯示對於具有不同覆層ar塗層之光學效能所產 生的IOX效應。圖2(a)為單層式AR塗層光學效能。該等 樣本的次序是在最小反射度之兩侧上所給定。在49〇nm或 535nm波長處的最小反射度會自劣化至q. 5%，並且 據信此係肇因於經IOX處理所引生的溶凝膠結構緻密化 。不同的IOX製程會對AR塗層反射度產生不同的影響。圖 2(b)及2(c)分別地表示經ΙΟχ之後的4層式及3層式溶凝 膠塗層，並且顯示反射度位移或變形兩者，而這又再度 地顯示IOX製程會對反射度的位移/變形程度造成影響。 在圖2b裡，由括號40所涵蓋之樣本次序自圖式的上方至 下方為A4、C4、B4、D4和E4 ;並且由括號42所涵蓋之次 序自圖式的上方至下方為E4、B4、D4、C4和A4。在圖2c 裡，位在由箭頭44所標位置處之曲線的次序自圖式的上 方至下方為C3、B3和A3 ;並且位在由箭頭46所標位置處 的次序自圖式的上方至下方為A3和B3，這些是彼此重合 ，以及在46處的最下方曲線C3。 Ο [0021] 圖3為說明經光學測量之壓縮應力，以及在對經Ar塗層 Gorilla®玻璃進行IOX後之κ離子覆層深度，的圖形。該 圖表示按選定時間及溫度處所固化的不同溶凝膠AR塗層（ 單層式、3層式及4層式）會對ΐοχ製程產生不同的回應。 例如，單層式溶凝缪AR比起多層式AR塗層玻璃具有較快 速的擴散速率，從而導致較短的I0X時間。此外，圖3指 出欲優化10X製程俾符合在經AR塗層Gor i 11 a®玻璃上的 所選定目標”壓縮應力（CS)”和，，覆層深度（dol)，，確 100117131 表單編號A0101 第15頁/共30頁 1003391833-0 201213261 為可行。表5描述藉由編號所表示的各項玻蹲樣本。 [0022]表 3 [0023] 數字ί A3 I No I0X, only AR! No I0X only AR, __________________________________[_________________________________________|_____________________________________ 丨B3 : 390 1 6 : . 100117131 Form No. A0101 Page 14 of 30 1003391833-0 201213261 C3 390 16 — Ο Figures 2a to 2c show the IOX effect produced by the optical performance of coatings with different cladding layers. Figure 2(a) shows the optical performance of a single layer AR coating. The order of the samples is given on both sides of the minimum reflectance. The minimum reflectance at a wavelength of 49 〇 nm or 535 nm will self-degrade to q. 5%, and it is believed that this 致 is densified by the sol-gel structure induced by the IOX treatment. Different IOX processes have different effects on the AR coating reflectivity. Figures 2(b) and 2(c) show the 4-layer and 3-layer sol coatings after warping, respectively, and show both reflectance displacement or deformation, which again shows the IOX process The degree of displacement/deformation of the reflection affects. In Figure 2b, the sample order covered by brackets 40 is A4, C4, B4, D4, and E4 from the top to the bottom of the figure; and the order covered by parentheses 42 is E4, B4 from the top to the bottom of the figure. , D4, C4 and A4. In Figure 2c, the order of the curves at the position indicated by arrow 44 is C3, B3 and A3 from the top to the bottom of the figure; and the order from the position indicated by arrow 46 is from the top of the figure to Below are A3 and B3, which are coincident with each other, and the lowest curve C3 at 46. [0021] FIG. 3 is a graph illustrating the optically measured compressive stress and the kappa ion cladding depth after IOX on Ar-coated Gorilla® glass. The figure shows that different lyogel AR coatings (single layer, 3-layer and 4-layer) cured at selected times and temperatures will respond differently to the ΐοχ process. For example, a single layer lysate AR has a faster diffusion rate than a multilayer AR coated glass, resulting in a shorter IOX time. In addition, Figure 3 indicates that the 10X process is to be optimized to meet the selected target "compressive stress (CS)" and, on the AR coated Gor i 11 a® glass, and the coating depth (dol), indeed 100117131 Form No. A0101 Page 15 of 30 Page 1003391833-0 201213261 is feasible. Table 5 describes the various glass samples represented by the numbers. Table 3 [0023] Numbers
"----- 試樣 ~ 50 '- ------ 51 - 3-層，41〇。(：，6 小時 IOX ^ ^ —~~-_______ ---—— ----. ___ ^~J 3-層，390 °C，12 小時 ΙΟχ O C ------ rQ ^--~~~ 4 層，40 0 °C，8 小時IOX 5 〇 —----— 4-層，400 °C，1〇 小時ιοχ 54 --—-- ----- 4-層，390 °C，12 小時 IOX 55 1-層，400 °C，6 小時 IOX 56 1-層，390 °C，8 小時 IOX 圖4為說明在首先經AR塗層然後再進行ΐοχ處理之c〇r-i 1 la®玻璃上進行電子微探針分析（ΕΡΜΑ)所測得的K及Na 離子深度廓型之圖形；其結果確認在AR塗層玻璃上的光 學測得DOL為令人信服。底下表4描述由圖4編號所識別的 玻璃樣本。 [0024]表 4 100117131 [0025] 數字 試樣 60 底線，Na/無AR塗膜 62 39(TC, 16 小時Na2〇 含Ar 塗膜 64 390 °C，12 小時Na2〇 含Ar 塗膜 ---------- — ------1 丨66 底線，NaJ無AR '玄膜 2 ------------------- 1--------------- I 68 39(TC，16 小時K2〇 含Ar 表單编號A0101 第16頁/共30頁 1003391833-0 201213261"----- Sample ~ 50 '- ------ 51 - 3-layer, 41〇. (:, 6 hours IOX ^ ^ —~~-_______ ---—— ----. ___ ^~J 3-layer, 390 °C, 12 hours ΙΟχ OC ------ rQ ^--~ ~~ 4 layers, 40 0 °C, 8 hours IOX 5 〇----- 4- layer, 400 °C, 1 hour ιοχ 54 ----- ----- 4-layer, 390 ° C, 12 hours IOX 55 1-layer, 400 °C, 6 hours IOX 56 1-layer, 390 °C, 8-hour IOX Figure 4 shows the c〇ri 1 la after first coating with AR and then ΐοχ The pattern of the K and Na ion depth profiles measured by electronic microprobe analysis (ΕΡΜΑ) on the glass; the results confirmed that the optical measured DOL on the AR coated glass was convincing. Figure 4 identifies the identified glass samples. [0024] Table 4 100117131 [0025] Digital Sample 60 Bottom Line, Na/AR-Free Coating 62 39 (TC, 16 Hours Na2〇 Containing Ar Coating Film 64 390 °C, 12 hours Na2〇 contains Ar film----------——------1 丨66 bottom line, NaJ no AR 'Xuan film 2 --------------- ---- 1--------------- I 68 39(TC, 16 hours K2〇Ar Form No. A0101 Page 16/Total 30 Page 1003391833-0 201213261
1塗膜 390。 C, 12小時K2〇含Ar ： j塗膜 1 FSM 量測 D0L 於41μπι , FSM 量測 D0L 於48μιη | Ο 固化然後才進行ι0χ· •‘疋會先將該溶凝膠塗層徹底地 程所產生的所有殘餘有程，並且尤其是自該溶凝膠沉積製 固化步驟過程t將殘餘=料都會魏化料。若未在 當在〇〇3浸浴中進行^材料予以氧化並移除，則 導致溶凝膠塗層效能劣化=時該等將成為氧化，從而 玻璃的範例可如圖5所亍：經適當固化之溶凝膠塗層 日肺中顯示AR塗層的去彩化結果 AGG’而在該方盒區域内出現斑駁變色。 當溶凝細塗層既經適當固化後，就不會出現去彩化， 同時玻璃清晰且透明而無含色彩或其他缺陷，即如圖51) 所示，不會展現出圖5a中的斑驳變色情況。 [_]任何能夠被離子交換的玻璃組成分皆可根據本揭示加以 運用。此等玻璃或玻璃陶瓷成分含有較小離子，通常為 Na及Li離子，而能夠由例如K、Rb及Cs離子的較大離子 所交換。這些玻璃成分包含鹼石灰、鹼矽酸鋁和驗紗酸 硼鋁玻璃。能夠運用於本揭示内之鹼矽酸鋁玻璃的其一 範例，然不限於此，可為共同授予之美國專利申請案第 2010/ 0009154號案文所描述並且具備下列概略成分者 ：66mol% Si〇2 ; 14mol% Na2〇 ； lOmol% 〇 · 0. 6mol% B2〇3 ; 2. 5mol% K2〇 ; 5. 7raol% Mg〇 ; 100117131 表單編號A0101 第17頁/共30 1 1003391833-0 201213261 0· 6mol°/。CaO ; 0. 2mol% Sn〇2 ;以及〇. 〇2mol% Zr〇 。此玻璃内的鈉質可為由鉀、铷或鉋所交換，藉以 2 近其表面處產生高壓縮應力的範圍’並且在玻螭部分< 内部或中央範圍裡產生在中央張力下的範圍《除另予〜、 明外，應瞭解該等詞彙”鋰”，”鈉”，”鉀” ” ’ 絶 ”及”铷”的使用在此是指這些鹼金屬的個別單價陽離 子。若是使用#〇和绝，則該等亦可接著與玻璃内的却離 子以及鈉離子交換。在一具體實施例裡，部分或所有的 鈉及鉀會被玻璃内的鋰所取代。然後鋰可與鈉、钟、細 或铯交換，藉以獲得高表面壓縮應力以及在張力下的内 部體積。為產生表面壓縮應力（即相對於張力），就必須 由鹽類溶液内具有較高原子數的離子來取代玻璃内的— 或更多離子；例如鈉取代玻璃内的鋰，鉀取代玻螭内的 鈉及/或鋰’铷取代玻璃内的鉀及/或鈉及/或鋰等等。 [0027] 如此，在一具體實施例裡，本揭示是針對於一種化學強 化玻璃物品’其中包含具有第·^和第—面以及選疋厚度 的玻璃物品，該玻璃物品具有多個壓力外部層’此等延 伸進入該等第一和第二面的一選定深度’以及張力内部 層，此者構成於該等壓力外部層之間，以及所選定塗層 ，此者位在該玻璃物品之該等第一和第二面的至少一者 上。該塗層係自含有抗反射及抗眩光塗層的群組中所選 定’並且該塗層含有至少5wt%的氧化鉀。在—具體實施 例裡為根據申請專利範圍第1項所述的化學強化破螭，其 中該選定塗層含有至少l〇wt%的氧化鉀。該選定塗層可為 由2-4個覆層所組成的多層式塗層。如根據申請專利範園 100117131 表單編號A0101 第18頁/共30頁 1〇0咖1833~0 2012132611 coating film 390. C, 12 hours K2〇 containing Ar: j film 1 FSM measuring D0L at 41μπι, FSM measuring D0L at 48μιη | 固化 curing before proceeding with ι0χ· • '疋 will first completely coat the sol gel coating All of the residuals produced are, and especially from the lyophilic gel deposition curing step t, the residue = material will be chemicalized. If the material is not oxidized and removed in the 〇〇3 bath, the sol gel coating performance is degraded = when it will become oxidized, so the glass example can be as shown in Figure 5: The cured sol gel coating showed the decolorization result of the AR coating in the day lungs and the mottled discoloration occurred in the box area. When the condensed fine coating is properly cured, no decolorization occurs, and the glass is clear and transparent without color or other defects, as shown in Figure 51), and does not exhibit the mottle in Figure 5a. Discoloration situation. [_] Any glass component that can be ion exchanged can be used in accordance with the present disclosure. These glass or glass ceramic components contain smaller ions, typically Na and Li ions, which can be exchanged by larger ions such as K, Rb and Cs ions. These glass components include soda lime, aluminum citrate and yttrium borosilicate glass. An example of an alkali aluminosilicate glass that can be used in the present disclosure is not limited thereto, and can be described in the commonly assigned U.S. Patent Application Serial No. 2010/0009154 and having the following general composition: 66 mol% Si〇 2; 14 mol% Na2〇; lOmol% 〇·0. 6mol% B2〇3; 2. 5mol% K2〇; 5. 7raol% Mg〇; 100117131 Form No. A0101 Page 17 of 30 1 1003391833-0 201213261 0· 6mol ° /. CaO; 0.2 mol% Sn〇2; and 〇. 〇2 mol% Zr〇. The sodium in the glass can be exchanged by potassium, strontium or planer, whereby the range of high compressive stress is generated near the surface of the glass and the range under the central tension is generated in the inner or central range of the glass portion. Unless otherwise stated, the terms "lithium", "sodium", "potassium", "absolute" and "铷" are used herein to mean the individual monovalent cations of these alkali metals. If #〇 and 绝 are used, they can then be exchanged with the ions and sodium ions in the glass. In one embodiment, some or all of the sodium and potassium are replaced by lithium in the glass. Lithium can then be exchanged with sodium, bell, fine or ruthenium to achieve high surface compressive stress and internal volume under tension. In order to generate surface compressive stress (ie, relative to tension), it is necessary to replace - or more ions in the glass with ions having a higher atomic number in the salt solution; for example, lithium in the sodium-substituted glass, potassium in the glass The sodium and/or lithium '铷 replaces potassium and/or sodium and/or lithium in the glass and the like. [0027] Thus, in one embodiment, the present disclosure is directed to a chemically strengthened glass article comprising a glass article having a first and a first surface and a thickness selected from the group, the glass article having a plurality of pressure outer layers 'These extend into a selected depth of the first and second faces' and the inner layer of tension, which is formed between the outer layers of the pressure, and the selected coating, which is located in the glass article Waiting for at least one of the first and second faces. The coating is selected from the group comprising an anti-reflective and anti-glare coating and the coating contains at least 5 wt% potassium oxide. In a specific embodiment, the chemically strengthened celluloid according to claim 1, wherein the selected coating layer contains at least 1% by weight of potassium oxide. The selected coating can be a multilayer coating consisting of 2-4 coatings. For example, according to the application for patent garden 100117131 Form No. A0101 Page 18 / Total 30 pages 1〇0咖1833~0 201213261
[0028] Ο [0029] 第1項所述的化學強化玻璃，其中該選定塗層具有在5〇nm 至350nm範圍内的厚度。在一具體實施例裡，該選定塗層 具有100nm至250nm範圍的厚度《在一具體實施例裡，該 玻璃在經塗層及離子交換之後具有至少620MPa的壓縮應 力以及至少23um的覆層深度。在另一具體實施例裡，該 玻璃具有至少660MPa的壓縮應力以及至少30μιη的覆層深 度。在進一步具體實施例裡，該玻璃具有至少700MPa的 壓縮應力以及至少35|jm的覆層深度。 在本揭所述方法中，可在未經離子交換玻璃上構成一經 固化AR塗層，並且接著利用鉀離子離子交換浸浴以對含 有鈉離子（及/或鋰離子）的AR塗層玻璃進行離子交換，且 既已發現所獲之離子交換玻璃在該AR塗層裡含有至少 5wt%的氧化鉀。在一具體實施例裡，該AR塗層内的鉀離 子量值為至少1 Owt%的氧化鉀。這是由於例如鈉離子（及/ 或鋰離子）的遷移之故，該等離子是經由從該玻璃至該AR 塗層的遷移進入到該AR塗層内。然後所遷移的鈉（及/或 鋰）離子會藉由離子交換浸浴内的鉀離子所離子交換。該 AR塗層内的所獲離子交換會將額外硬度傳授至該固化AR 塗層。 從而，本揭示是針對於一種用以製作其上具有選定塗層 之化學強化玻璃物品的方法。該方法包含提供具有選定 組成分的經成形玻璃物品’此者具有第一和第二面以及 選定厚度’該玻璃物品含有鈉及/或鋰離子；將選定溶凝 膠塗層施用於該玻璃物品的第一和第二面；藉由自包含 熱性固化及UV固化之群組所選定的方法以固化該物品之 100117131 表單編號A0101 第19頁/共30頁 1003391833-0 201213261 表面上的溶凝膠；提供其中含有大於鋰及/或鈉離子之選 定鹼金屬離子的離子交換浸浴，並且以該等大於鋰及/或 鈉離子之選定鹼金屬離子來對該選定塗層内的鋰及/或鈉 離子進行離子交換，該離子交換的離子取代延伸穿過該 選定塗層並深至距該等第一和第二面的表面一選定深度 ，俾藉此產生壓縮應力。該溶凝膠塗層是自包含抗反射 及抗眩光塗層的群組所選定，並且該塗層在經離子交換 之後是以氧化物形式含有至少5wt%大於链及/或鈉離子的 鹼金屬離子。該選定塗層可為具有50nm至350nm厚度範 圍内之單層式塗層或2-4層式的多層抗反射或抗眩光塗層 。在該方法的一具體實施例裡，所施用塗層具有在ΙΟΟμιη 至250μπι範圍内的厚度。在該方法中，該離子交換進行一 段時間而使得該玻璃具有至少620MPa的壓縮應力以及至 少23μιη的覆層深度。在一具體實施例裡，進行該離子交 換而使得該玻璃具有至少660MPa的壓縮應力以及至少30 μιπ的覆層深度。在一具體實施例裡，進行該離子交換而 使得該玻璃具有至少700MPa的壓縮應力以及至少35μπι的 覆層深度。該等大於鋰及/或鈉離子的選定鹼金屬離子係 自包含鉀、铷及铯離子，以及其等之混合物，的群組所 選定。 [0030] 雖既已為敘釋之目的而陳述多項典型具體實施例，然前 揭說明不應被視為限制本揭示或後載申請專利範圍的範 疇。可運用其他像是替代性化學方法或者熱性回火的方 式以進行玻璃強化。此外，可將不同的玻璃強化方式彼 此併同運用以達到所欲的壓縮應力位準或廓型。在替代 100117131 表單編號Α0101 第20頁/共30頁 1003391833-0 201213261 *! 生具體實施例裡，可在該離子交換製程中利用像是銀等 等的金屬離子以取代’或組合於’驗金屬離子。從而， 熟諸本項技術之人士即可構思各種修改、調適及替代項 目’而不致悚離由本揭示或後載申請專利範圍的精神與 範疇。 【圖式簡單說明】 [0031]圖ia及113為略圖’其中分別地說明對於溶凝膠塗層之 現有及本揭示製程以產生經AR塗層、 化學強化玻璃物品 的主要製程步驟。 〇 师]® 2a為其巾說明對於單層AR塗層反射度之IQX效應的圖形 [剛圖2b為其巾說明對於四層溶麟AR塗層反射度之Ι〇χ效應 的圖形。 [0034]圖2c為其中說明對於三層溶凝膠AR塗層反射度之ΙΟΧ效應 的圖形。 [0035] 圖3為圖表，其中說明，以表丨的各種經…塗層離子交換 玻璃，對於壓縮應力的IOX效應以及K離子擴散深度。 [0036] 圖4為其中說明離子交換玻璃中藉由電子微探針分析 (ΕΡΜΑ)所獲得之κ及Na深度廓型的圖形。 [0037] 圖5a說明，由於溶凝膠AR塗層在進行IOX之前未先予徹底 固化，因與IOX鹽類反應所致生的玻璃樣本去彩化。 [0038] 圖5b說明在進行IOX之前先經適當固化的溶凝膠ar塗層。 【主要元件符號說明】 1003391833-0 100117131 表單編號A0101 第21頁/共30頁 201213261 [0039] AR塗層離子交換玻璃之溶凝膠方法10 ;玻璃進行離子交 換12;洗淨經離子交換玻璃14;溶凝膠塗覆所洗淨離子 交換玻璃16;切割及裁修所固化溶凝膠塗層18;AR塗層 離子交換玻璃之製程20;洗淨未經離子交換玻璃22;溶 凝膠塗覆所洗淨玻璃24;切割及裁修所固化溶凝膠塗層 26;玻璃進行離子交換28。 100117131 表單編號A0101 第22頁/共30頁 1003391833-0[0029] The chemically strengthened glass of item 1, wherein the selected coating has a thickness in the range of 5 〇 nm to 350 nm. In a specific embodiment, the selected coating has a thickness in the range of 100 nm to 250 nm. In one embodiment, the glass has a compressive stress of at least 620 MPa and a coating depth of at least 23 um after coating and ion exchange. In another embodiment, the glass has a compressive stress of at least 660 MPa and a coating depth of at least 30 μm. In a further embodiment, the glass has a compressive stress of at least 700 MPa and a coating depth of at least 35 | jm. In the method of the present invention, a cured AR coating can be formed on the non-ion exchange glass, and then a potassium ion ion exchange bath is used to perform AR coating glass containing sodium ions (and/or lithium ions). Ion exchange, and it has been found that the ion exchange glass obtained contains at least 5% by weight of potassium oxide in the AR coating. In one embodiment, the amount of potassium ions in the AR coating is at least 1% by weight potassium oxide. This is due to, for example, the migration of sodium ions (and/or lithium ions) that enter the AR coating via migration from the glass to the AR coating. The migrated sodium (and/or lithium) ions are then ion exchanged by potassium ions in the ion exchange bath. The resulting ion exchange within the AR coating imparts additional hardness to the cured AR coating. Accordingly, the present disclosure is directed to a method for making a chemically strengthened glass article having a selected coating thereon. The method includes providing a shaped glass article having a selected composition having a first and second side and a selected thickness 'the glass article containing sodium and/or lithium ions; applying a selected sol coating to the glass article The first and second sides; the method of curing the article by a method selected from the group consisting of heat curing and UV curing. 100117131 Form No. A0101 Page 19 of 30 1003391833-0 201213261 Solvent on the surface Providing an ion exchange bath containing selected alkali metal ions greater than lithium and/or sodium ions, and selecting lithium and/or sodium ions selected from the selected alkali metal ions to select lithium and/or The sodium ions undergo ion exchange, the ion exchanged ion extensions extending through the selected coating and deep to a selected depth from the surfaces of the first and second faces, thereby creating a compressive stress. The sol-gel coating is selected from the group consisting of anti-reflective and anti-glare coatings, and the coating contains at least 5% by weight of an alkali metal larger than the chain and/or sodium ion after ion exchange. ion. The selected coating can be a single layer coating having a thickness ranging from 50 nm to 350 nm or a 2-4 layer multilayer anti-reflective or anti-glare coating. In a specific embodiment of the method, the applied coating has a thickness in the range of from ΙΟΟμηη to 250μπι. In this method, the ion exchange is carried out for a period of time such that the glass has a compressive stress of at least 620 MPa and a coating depth of at least 23 μm. In a specific embodiment, the ion exchange is performed such that the glass has a compressive stress of at least 660 MPa and a coating depth of at least 30 μπ. In a specific embodiment, the ion exchange is performed such that the glass has a compressive stress of at least 700 MPa and a coating depth of at least 35 μm. The selected alkali metal ions greater than lithium and/or sodium ions are selected from the group consisting of potassium, cesium and strontium ions, and mixtures thereof. [0030] While a number of typical embodiments have been described for the purposes of the present disclosure, it should not be construed as limiting the scope of the disclosure or the scope of the appended claims. Other methods such as alternative chemical methods or thermal tempering can be used for glass strengthening. In addition, different glass reinforcement methods can be used together to achieve the desired compressive stress level or profile. In the alternative embodiment 100117131 Form No. 101 0101 Page 20 / Total 30 Page 1003391833-0 201213261 *! In the specific embodiment, metal ions such as silver may be used in the ion exchange process instead of 'or combined with 'metal ion. Accordingly, a person skilled in the art can devise various modifications, adaptations, and alternatives without departing from the spirit and scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS [0031] Figures ia and 113 are schematic diagrams which respectively illustrate the main process steps for the prior art and disclosed processes for lyotropic coatings to produce AR coated, chemically strengthened glass articles. 〇 ] ® ® a a a 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其 为其Figure 2c is a graph in which the effect of enthalpy on the reflectance of a three-layer lyogel AR coating is illustrated. [0035] FIG. 3 is a graph illustrating the IOX effect on compressive stress and the K ion diffusion depth for various coated ion exchange glasses of the surface. 4 is a graph in which the κ and Na depth profiles obtained by electron microprobe analysis (ΕΡΜΑ) in ion-exchanged glass are explained. [0037] FIG. 5a illustrates that the lyogel AR coating was de-colored due to the reaction with the IOX salt since the lyogel AR coating was not completely cured prior to the IOX. [0038] Figure 5b illustrates a lyogel ar coating that is suitably cured prior to performing IOX. [Description of main component symbols] 1003391833-0 100117131 Form No. A0101 Page 21 of 30 201213261 [0039] AR coating ion-exchange glass sol-gel method 10; glass ion exchange 12; washing by ion-exchange glass 14 Sol-gel coated washed ion exchange glass 16; cut and cut cured sol gel coating 18; AR coated ion exchange glass process 20; washed without ion exchange glass 22; The washed glass 24 is cut; the cured sol gel coating 26 is cut and cut; and the glass is ion exchanged 28. 100117131 Form No. A0101 Page 22 of 30 1003391833-0