TW200948734A - Damage resistant glass article for use as a cover plate in electronic devices - Google Patents

Damage resistant glass article for use as a cover plate in electronic devices Download PDF

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Publication number
TW200948734A
TW200948734A TW98103588A TW98103588A TW200948734A TW 200948734 A TW200948734 A TW 200948734A TW 98103588 A TW98103588 A TW 98103588A TW 98103588 A TW98103588 A TW 98103588A TW 200948734 A TW200948734 A TW 200948734A
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TW
Taiwan
Prior art keywords
glass
fluorine
group
coating film
layer
Prior art date
Application number
TW98103588A
Other languages
Chinese (zh)
Inventor
Jaymin Amin
Adra Smith Baca
Lorrie Foley Beall
Robert Allan Morse
Xu Ouyang Ouyang
Robert Sabia
Original Assignee
Corning Inc
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Application filed by Corning Inc filed Critical Corning Inc
Publication of TW200948734A publication Critical patent/TW200948734A/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only

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  • Surface Treatment Of Glass (AREA)
  • Glass Compositions (AREA)

Abstract

An alkali aluminosilicate glass article, said alkali aluminosilicate glass having a surface compressive stress of at least about 200 MPa, a surface compressive layer having a depth of at least about 30 μ m, a thickness of at least about 0.3 mm and an amphiphobic fluorine-based surface layer chemically bonded to the surface of the glass. In one embodiment the glass has an anti-reflective coating applied to one surface of the glass between the chemically strengthened surface of the glass and the amphiphobic coating. In another embodiment the surface of the chemically strengthened glass is acid treated using a selected acid (e.g., HCL, H2SO4, HClO4, acetic acid and other acids as described) prior to placement of the amphiphobic coating or the anti-reflective coating.

Description

200948734 六、發明說明： 本發明一般係關於鹼金屬鋁矽酸鹽玻璃。特別是本發 明係關於高強度向下抽拉之驗金屬鋁石夕酸鹽玻璃玻璃物體 以使用作為保護性蓋板。尤其是，本發明係關於高強度向 下抽拉之驗金屬銘發酸鹽雙疏性(amphiph〇biC)玻璃玻璃 - 物體以使用作為移動電子裝置中蓋板。 【先前技術】 譬如個人資料輔助，手機，手錶，膝上型或筆記型電腦 專的移動式電子裝置通常會包含一個蓋板。蓋板的至少一 部分是透明的，讓使用者可看到顯示畫面。在某些應用上， 蓋板對使用者的觸摸很敏感。由於需要經常性接觸，這種 蓋板必須要有高強度和抗刮性。 - 本公司之美國第11/888213號申請專利揭示出鹼金屬 紹石夕酸鹽玻璃，其能夠利用化學地離子交換作加強以及呈200948734 VI. INSTRUCTIONS: The present invention generally relates to alkali metal aluminosilicate glasses. In particular, the present invention relates to a high-strength down-drawing test aluminite glass-glass object for use as a protective cover. In particular, the present invention relates to a high-strength down-drawing metal-detecting amphiph〇biC glass-object for use as a cover in a mobile electronic device. [Prior Art] For example, personal data assistance, mobile phones, watches, laptops, or notebook computers. Personalized mobile electronic devices usually include a cover. At least a portion of the cover is transparent so that the user can see the display. In some applications, the cover is sensitive to the user's touch. Due to the need for frequent contact, such a cover must have high strength and scratch resistance. - The Company's US Patent Application No. 11/888213 discloses an alkali metal sulphate glass which can be reinforced by chemical ion exchange.

H 現之組成份能夠向下為片狀物。玻璃熔融溫度小於165(TC 液相線黏滯係數為至少130千泊以及在一項實施例中大於 ^ 250千泊。玻璃能夠在相當低溫度下作離子交換以及深度 至少為3〇em。玻璃組成份以莫耳百分比表示包含 Si〇2^68%;12%^Na2〇^16°/〇；8%^Al2〇3^12%;0°/〇^B2〇3^ 30/〇;2%SK2〇S5%;4%SMg〇S6%;以及 0%SCaOS5%，其中 66% ‘ Si〇2+B2〇3+CaO $69%;Na2〇+K2〇+B2〇3+MgO+CaO+SrO> 10%; 5% ^ MgO+CaO+SrO ^ 8%; (Na2〇+B2〇3) ^ ΑΙ2Ο3 ^ 2%; 2% SNa2〇-Al2〇3$6%;以及 4%S(Na2〇+K2〇)SAl2〇3$10%。 3 200948734 銘石夕酸鹽玻璃可以在電子產品上用來做為防損傷的蓋 板玻璃。_的完成處建要成形厂接著祀_鍊:_—子交 換⑽)以形成壓縮表面層避免像是顺和磨損的機械性 傷害，因而提供抗損害的性質。處理是藉由在玻璃表面 上父換大购軒和小涵離子以處__和溫度控制 交換的深度並且提供魏深度層⑽L)，如果在產品使用期 間，比表面引發的損害還深就可以防止破裂。這種產品新 〇 增的優點是’離子交換驗辦酸紐射崎子交換交換 到比同類的玻璃更大的深度層，因而大幅減少損害並避免 破壞。 然而’有關其應用上的使用譬如做為媒體/電子裝置的 盍板玻璃，這種驗金屬紹發酸鹽玻璃（和所有同類的蓋板玻 璃製品)有幾項重要議題。第一個重要議題是無法轉移和 很難移除指Hp留在表面的油和油月旨。移除油和油脂的困難 在觸控螢幕的應用上是很重要的，因為在使用設備時，指印 ❿ 會重複施加在蓋板玻璃表面。指印和從其他來源產生的污 痕會顯示在螢幕上，尤其在設備不使用時背景呈暗或黑色 - 背景的時候。這會產生光學干擾的問題，因為指印/污痕會 影響圖像品質（降低其顯示功能），並造成客戶對設備負面 的感覺。包括在指印的油和油脂可能是灰塵，化妝品和乳 液。 第一項重要議題是可能來自表面反射的強光。強光來 自於光線的反射，沒有垂直於操作者的視野。強光的出現 會導致使用者傾斜設備並繼續調整螢幕角度，以得到較佳 200948734 的視野。必須不斷改變視野角度對使用者而言是很討厭的 。更者厂由'於菲抗反射塗膜表面的傾斜會因強光使指印無 效，任何包括抗反射(AR)特性顯示表面會使指印更明顯。 因此，抗指紋或易清洗的塗膜對抗反射表面是很需要的。 雖然目前已有的一些工業用塗膜提供了某種程度的保 濩’經由改善的油/水濕潤行為，大幅減少指印黏著性，但這 — 種塗膜沒施成功使用在觸控螢幕應用的化學性堅勃玻璃。° 【發明内容】 本發明的一項實施範例是關於由透明抗損害化學性 堅勒保護的蓋板玻璃(也稱為蓋板或蓋板螢幕)，具有氟終 端基的外部塗膜，賦予蓋板玻璃某種程度的疏水性和疏油 f·生（即雙疏[·生)，使玻璃表面被水和油的濕潤減到最少。（雙 疏物質的傾向是缺乏油和水）。塗膜的產品具有玻璃壓縮 ' 表面D0L賦予的抗到痕，磨損，和其他損傷的特性，此外還有 氟終止基提供的抗指印，抗污痕的特性，減少油從手指到破 _ 璃的傳輸(指印)，進一步使油/指印容易用布擦拭移除。本 發明提供厚度至少約〇. 3mm的鹼金屬鋁矽酸鹽玻璃製品，表 • 面壓縮應力至少約200MPa，表面壓縮層的深度大約20-70 • 以111，和具有雙疏性吸附氟根基的表面層。 吸收氟主表面層藉由玻璃終端〇H基之氫與氟為主基元 例如含氟單體交換以形成具有終端氟化基。例如非限制性 ，交換能夠依據下列反應進行： 5 200948734 氟碳化物以及更優先地為G-CiO烷基全氟聚醚;n為1_3範 圍之整數；以及X為可水解基，其與玻璃終端〇H基交換。優 先地，X為異於氟之鹵素或烷氧機(_〇R)，其中尺為丨_6個碳原 子線性或分支之碳氫化合物，例如非限制性之_ch3, c2jj5， CIKCH3)2碳氫化合物。在一些實施例中n=2或3,優先地為3 。優先地鹵素為氣。優先地烷氧梦烷為三曱氧基發烷 RFSi(OMe)3。能夠使用於實施本發明中全氟碳化物基元包 含(RFhSiCI，RF-C(0)-C1，RF-C(0)-NH2,以及其他全氟碳 化物基元，其具有終端基可與玻璃氫氧基(〇H)作交換。在 此所謂π全氟碳化物"以及"氟碳化物"係指在此所說明碳氫 • 化合物基實質上全部C-H鍵轉換為C-F鍵。 . 在另一個實施例中吸收氟為主的表面層是由氟終止分 子鏈的組合單層所構成。在更進一步實施例中，吸收氟為 φ 主的表面層是由薄的氟聚合塗膜所構成。在最後一個實施 範例中，吸收氟為主的表面層是由具有附著到粉塵顆粒突 出的碳氟基的二氧化矽粉塵顆粒所構成。 本發明更進一步的實施例是關於由透明，防損害，有抗 反射層的化學堅韌保護的蓋板玻璃所構成的產品，舉例但 不是限制性之抗反射Si〇2或F_Si〇2(氟塗料二氧化矽或熔 融一氧化矽)層，並且更進一步具有氟終端基的外部塗膜， 賦予蓋板玻璃某種程度的疏水性和疏油性（即雙疏性)，使 玻璃表面被水和油的濕潤減到最少。也施加最外層如這裡 200948734 描述的雙疏性材料，賦予抗反射製品抗磨損的特性。雙疏 性枯科塗屏葯1品真有放瑜妁塵縮表蚕胃藏^^氣 磨損，和其他損傷的特性，此外還有氟終端基提供的抗指印’ 抗污痕的特性，減少油從手指到玻璃的傳輸(指印），進一步 使油/指印容易用布擦拭移除。抗反射塗膜可能比基礎化 學強化玻璃有較低的抗磨損/刮痕特性。以雙疏性材料塗 - 上抗反射塗膜化學強化玻璃可提供抗反射塗膜玻璃抗磨損 0 特性，因而使抗反射塗膜玻璃再得到主要玻璃的效能，而仍 然可提供抗反射塗膜玻璃抗指印抗污痕的特性。在最佳 的實施例中，抗反射塗膜的外層（最外層）含Si〇2層，例如F_ Si〇2,溶融·一氧化梦或二氧化梦。 除此之外，蟓金屬鋁矽酸鹽玻璃製品可進一步包括紋 理或圖樣的薄膜表面，位在主要玻璃和氟為主的表面塗膜 • 之間°紋理可能是來自於包括其組合的酸/鹼餘刻產生以 RMS粗糖度為單位範圍在5〇nm到5/zM(5000 nm)的粗縫度。 φ 在近表面的粗糙玻璃成份最好富含Si〇2。粗糙度的測量技 術可以使用原子力顯微術(AFM)和掃瞄白光干涉量測法（ . SWLI)。或者，紋理也可能是來自於微影術或使用沉積結構 ，而且也同樣在近表面的粗糙玻璃成份最好富含Si〇2。在 紋理層形成後，接著以這裡描述的含氟材料塗膜紋理層和 任何無紋理主要玻璃，形成有紋理含氟材料塗膜的製品。 本發明其他特性及優點揭示於下列祝明，以及部份可 由說明清楚瞭解，或藉由實施下列說明以及申請專利範圍 以及附圖而明瞭。 200948734 【實施方式】 在以下的說明中，同樣的參考編號表示顯示在所有圖 中的相關零件。應該也要瞭解，除非另外標示，像是"頂端" ^底部” ”向外"，”向内"等這些詞都是因為方便說明而不 是做為限制詞。此外，當一個群組被描述成包含至少一個 群組的元素和其組合時，應該要知道群組可包含數個這些 - 重複的元素’不是個別地就是互相組合。同樣的，當一個群 ❹組被描述成是由至少-個群_元素和其組合所構成應該 要知道群組可以是由數個這些重複的元素所構成，不是個 別地就是互相組合。"主要玻璃，，一詞是指任何驗金屬_ 石夕酸鹽玻璃，在這種玻璃適合用來在以任何材料譬如可用 來抗油潰或污痕的抗反射塗膜，及/或全氟碳化物材料作離 子父換或塗膜之前形成保護性蓋板玻璃。如這裡使用的" Si〇2塗膜”一詞是指Si〇2塗膜或F-Si〇2塗膜，或組合的· /F-Si〇2塗膜。在這裡描述的所有實施例，全氟碳化物鍵結 〇 部分或含全氟碳化物鍵結部分(如同層或塗膜)，藉由共價 鍵鍵結到玻璃，化學強化玻璃，或化學強化以及&〇2(或 ^ Sl〇2)塗膜玻璃表面。這裡使用的"雙疏性"一詞是指施加 到表面的材料是對於表面具有疏水性和疏油性。 參考圖1，人們了解所顯示的作為說明本發明特定實施 例之用途以及並不預期限制本發明。 -般而言，所顯示的是有加強抗損害和雙疏性特性的透 明保護性蓋板玻璃，因而可提供抗到痕表面顯示最小的指 印附著以及容易去除指印。 200948734 圖1特麵示厚度至少〇· 3mm的銘秒酸鹽玻璃製品1〇〇 表面壓縮應方至少·ΜΡη的表面壓_朗層 106。表面壓縮層1〇4的厚度大約20一7〇仰，通常是藉由以 下描述的離子交換處理而達成。除了表面壓縮層1〇4和無 離子交換中間層破璃部份1〇6之外，製品⑽具有雙疏性吸收 氟主要表面層102 〇 - 雙疏性吸收氟主要表面層或塗膜可以任何方式達成可 ❺，自下列群組:（1 )-〇Η基終端的活性表面部位和氟為主的 單體父換;（2)氟終端分子鍵的組合單層；（3)薄的氟聚合物 塗膜，（4)處理先刚的一氧化發粉塵顆粒，以得到氟終端基 。可藉由浸潰，蒸氣塗膜，喷霧，使用滾筒或其他合適的方 法施加塗膜至表面。浸潰或喷霧是較好的方式。施加塗膜 . 之後，在含有40-95%濕氣的空氣中以25-1501範圍的溫度， • 最好是4〇_l〇〇°C固化1-4小時的時間。這裡的範例施加二 塗膜是"50/50固化"，這意味著在含有50%濕氣的空氣中，以 ❹ 50°c固化2小時。在固化之後，以溶劑浸濕試樣以去除任何 未結合的塗膜，使用前在空氣中晾乾。 現在參考圖2,顯示的是鋁矽酸鹽玻璃製品1Q0的另一 實施例。在這個實施例中，玻璃製品1〇〇包括圖丨實施例的 所有特徵，包括表面壓縮應力層104,無離子交換中間層玻 璃部份106,和雙疏性吸收氟主要的表面層1〇2 ^此外，這個實 施例包括位在吸收氟主要表面層1 〇2 (以粗黑色畫線表示） 和表面壓縮應力層104之間的紋理或圖樣表面1〇8。在一項 實施例中，紋理或圖樣層是藉著飯刻或微影術由壓縮層形 9 200948734 成。在另一實施例中，紋理或圖樣層是藉著顆粒塗膜鍵仕 任何沒有紋理或圖樣的壓縮層。 圖2所示的紋理或圖樣表面增加到主要破璃，或在基礎 玻璃上形成。這種紋理或圖樣表面的施加可以任何熟悉此 項技術的人已知的方式達成。增加紋理/圖樣表面到基礎 - 玻璃，或在主要玻璃上形成紋理/圖樣表面的選擇方式包括 暴 聚合物或無機材料的電旋轉，沉積無機薄膜順序性 顆粒塗膜，或任何其他此項技術紋理或圖樣化破璃表面的 方式。玻璃製產生的紋理或圖樣化表面顯示出增加的表面 積，而仍維持所需的透明程度。以這裡描述的雙疏性塗膜塗 抹紋理表面。 氟表面處理/層和提升的表面粗糙度會一起造成玻璃 •製品濕潤特性的提高。因此，玻璃製品會顯示最少的指印 附著，用一點點抹擦就可輕易移除指印。 〇 在此所揭示雙疏性玻璃物品呈現出下列提昇特性優於 市場可利用保護性覆蓋玻璃解決方案。 、 , 指印黏附。氟處理（因而是氟終端）表面比-0H終端基 的表面較少極性，也因而可導致顆粒和液體之間最少的氫 (即Van der Waals)結合。因此對於和指印有關的指印油 污和碎屑可大幅減少這種結合和附著直接造成最小化從 手指到玻璃表面油污和碎屑的傳輸。 清理及清潔度。指印的移除通常是在乾燥或濕潤的條 件下以布擦拭表面來執行。這些布是可再用的因此可能 200948734 包含會刮傷表面的塵土和顆粒。產品的氟表面使指印的移 除更為容昜厂而且可最小化污痕和賊咐量後者更可進 一步減少造成表面傷害事件的次數和頻率導致立即或延遲 的玻璃產品破裂。雖然盡量減少指印油污附著，並增加以 乾布擦拭可移除油潰的程度，但任何擦拔引起的表面磨損 會產生到痕，造成表面的傷害及/或導致最後保護性玻璃蓋 - 板的失敗。這裡所描述玻璃的高硬度（比同類玻璃還高）和 ❹ 高壓縮表面IX)L(40-60微米深，比同類玻璃還深)一起保護， 防止重複擦拭造成的損傷。只要壓縮表面D0L深於擦拭期 間或其他處理模式引起的損害，就可消除這種失敗。 刮損抵抗性。實施抗刮痕的測試是所用的玻璃製品是 半面以雙疏性材料塗膜，另一半面未塗膦。這項測試是砂紙 刮痕測試，使用往復模損工具使砂紙（15〇粒度)通過兩種表 面以使這兩種塗膜或未塗膜的表面受到同等的磨損。然後 測量製品兩邊區域的模糊度，模糊度是根據擴散光線對所 _ 有擴散光線和傳輸光線的總和來測量光學的清晰度。結果 顯示雙疏性塗膜的模糊度減少到80%，也就是因磨損造成破璃 . 光學可見的損害。這種結果顯示雙疏性塗膜大幅增加了抗到 性。 Η 除了抗刮性之外，雙疏性塗膜也減少摩擦係數。明確地 說，相反於兩個物品都不移動的靜態摩擦^，在玻璃製品 的整個塗膜上測量滑動或動態摩擦係數，這裡製品的半 面是以雙疏性材料塗膜，另一半面則未塗膜。測試的結果顯 示未塗膜玻璃的βκ=0·25,而塗膜玻璃的#κ=〇·05,因此指 200948734 出了由於雙疏性塗膜的關係減少了 80%的動態摩擦。當有人 涵 •画琴-厂以 及當玻璃被置放在攜帶盒内時，這種摩擦的減少也會降低 玻璃表面的傷害。這種優良的效能特性也使得觸控螢幕的 應用產品更容易使用。 以下提供有關適合用在立即實施例的特定鹼金屬鋁矽 - 酸鹽玻璃的額外資訊。玻璃的液相黏滯係數至少130千泊 。如這裡使用的，"液相黏滯係數"是指熔態玻璃在液相溫 ® 度下的黏滯係數，這裡液相溫度是指晶體首先從融化溫度 冷卻呈現為熔態玻璃的溫度，或晶體隨著溫度從室溫增加 到融化的溫度。玻璃組成份以莫耳百分比表示包含:64%$ Si〇2^68%; 12%^Na2〇^ 16%;8%^Al2〇3^ 12%; 0%^B2〇3^ 3%;2%SK2〇S5%;4%蕊Mg〇S6%;以及 〇%sca〇$5%，其中識 —SiQ2+B2〇3+CaO S 69%; Na2〇+K2〇+B2〇3+MgO+CaO+SrO> 10%; 5% ^ MgO+CaO+SrO ^ 8%; (Na2〇+B2〇3) ^ A l2〇3 ^ 2%; 2% S Na2〇-A12〇3 S 6/^;以及 4% S (Na2〇+K2〇) S A12〇3 S10%。 鹼金屬鋁矽酸鹽玻璃的最大單一成份是Si〇2,形成玻 ‘ 璃的基質以範圍從約_莫耳比以上到包含約68%莫耳比的 濃度呈現在本發明的玻璃。Si〇2可充當為黏滯係數提升劑 有助於塑型並賦予玻璃化學持久性。高於上述範圍的濃度 會過高地提升融化溫度，而在範圍以下的濃度則會破壞玻 璃持久性。此外，較低的Si〇2濃度可能導致玻璃内的液相 溫度增加，有較高的K2〇或較高的Mg〇漢度。 當呈現的濃度範圍從約8%莫耳比以上到包含約12%莫 12 200948734 耳比時，Α12〇3會提升黏滞係數。當ai2〇3黏滞係數高於這 梱範簡高，太 尚而無法維持連續的向下抽拉過程。為了防止這點，本發 明玻璃的驗金脣氧化金屬（譬如Na20, K20)總濃度遠超過總 Α1ζ〇3含量。驗金屬氧化金屬可以幫忙達到較低的液相溫 度，較低的融化溫度。如這裡使用的，”融化黏滯係數"一詞 是指對應200泊玻璃黏滯係數的溫度。在鈉的例子中，使用 ^ Na〇2可成功進行離子交換。為了可以有足夠的離子交換以 產生真正提升的玻璃強度，可提供範圍從約12%莫耳比以上 到包含約16%莫耳比濃度的Na〇2。然而，假使玻璃是由這裡 所描述範圍以外的Na〇2，Al2〇3和Si〇2組成，黏滞係數就會 太高而不適合融化。因而必須有其他成分以確保好的融化 和形成效能。假定那些成分存在，在Na〇2和a12〇3之間濃度 範圍的差異在從約2%莫耳比以上到包含約6%莫耳比（即2% 莫耳比S NazO-A 12〇3S 6%莫耳比）時，就可得到適合的融化 ^ 溫度。 ❿ 可包括氧化钟(Μ)以得到較低的液相溫度。然而，甚 , 至比Na〇2更會減少玻璃黏滯係數。因此，Na〇2和κ20濃度總 和以及Alz〇3濃度之間的總差異範圍應該在約4%莫耳比以 上到包含約10%莫耳比（即4%莫耳比S(Na2〇+K2〇)-Al2〇3$ 10%莫耳比）。 B2O3可充當做助熔劑，亦即添加以降低融化溫度的成 分。即使增加小量的B2〇3,也可急劇降低同等玻璃的融化 溫度達100°C。然而如前面提及的，加入鈉可使得離子交換 13 200948734 成功，在相當低Na〇2含量和高Al2〇3含量的情況最好可添加 祕7码娜成能夠願的玻璃—I ，連結Na2〇及M)3總濃度使得(Na2〇+K2〇)-Al2〇3S2%莫耳 比。因而，在一項實施例中，Si〇2，B2〇3以及CaO總濃度在 66%莫耳比至高達以及包含69%莫耳比（即66%莫耳比$ si〇2 +B2〇3+Ca〇S69%莫耳比）。The component of H can be down to a sheet. The glass melting temperature is less than 165 (TC liquidus viscosity coefficient is at least 130 kilopoise and in one embodiment greater than ^250 kilopoise. Glass can be ion exchanged at relatively low temperatures and depths of at least 3 〇em. The composition of the group is expressed as a percentage of moles including Si〇2^68%; 12%^Na2〇^16°/〇; 8%^Al2〇3^12%; 0°/〇^B2〇3^ 30/〇; %SK2〇S5%; 4%SMg〇S6%; and 0%SCaOS5%, of which 66% 'Si〇2+B2〇3+CaO $69%; Na2〇+K2〇+B2〇3+MgO+CaO+SrO&gt 10%; 5% ^ MgO+CaO+SrO ^ 8%; (Na2〇+B2〇3) ^ ΑΙ2Ο3 ^ 2%; 2% SNa2〇-Al2〇3$6%; and 4% S(Na2〇+K2 〇)SAl2〇3$10%. 3 200948734 Mingshixi acid glass can be used as an anti-damage cover glass in electronic products. The completion of the construction of the building is to be formed by the 祀_chain: _-sub-exchange (10) To form a compressive surface layer to avoid mechanical damage such as smooth wear, thus providing damage-resistant properties. The treatment is carried out by changing the depth of the exchange between the __ and the temperature control and providing the Wei depth layer (10) L) on the surface of the glass, if the damage caused by the surface is deeper during the use of the product. Prevent rupture. The advantage of this new product is that the 'ion exchange process acid exchanges the exchanges to a greater depth layer than the same type of glass, thus greatly reducing damage and avoiding damage. However, there are several important issues with regard to the use of such applications as seesaw glass for media/electronic devices, such metallurgical glass (and all similar cover glass products). The first important issue is the inability to transfer and difficult to remove the oil and oil that is meant to leave Hp on the surface. Difficulties in removing oil and grease are important in touchscreen applications because fingerprints are applied repeatedly to the cover glass surface when the device is in use. Fingerprints and stains from other sources can be displayed on the screen, especially when the background is dark or black-background when the device is not in use. This creates optical interference problems because fingerprints/stains can affect image quality (reducing its display capabilities) and cause customers to feel negative about the device. The oils and greases included in the fingerprints may be dust, cosmetics and emulsions. The first important issue is the glare that may come from surface reflections. The glare comes from the reflection of the light and is not perpendicular to the operator's field of view. The presence of glare causes the user to tilt the device and continue to adjust the screen angle for a better view of 200948734. It is annoying to the user to constantly change the angle of view. In addition, the tilt of the surface of the 'Yufei anti-reflective coating film will make the fingerprint invalid due to strong light, and any surface including anti-reflection (AR) will make the fingerprint more obvious. Therefore, anti-fingerprint or easy-to-clean coatings are highly desirable against reflective surfaces. Although some of the existing industrial coatings provide some degree of protection, 'improving the oil/water wetting behavior and greatly reducing the fingerprint adhesion, but this film has not been successfully used in touch screen applications. Chemically strong glass. [Explanation] An embodiment of the present invention relates to a cover glass (also referred to as a cover or a cover screen) protected by a transparent anti-damage chemical firmer, an outer coating film having a fluorine terminal group, and a cover The plate glass is somewhat hydrophobic and oleophobic (ie, double-skinned), which minimizes the wetting of the glass surface by water and oil. (The tendency to double substances is the lack of oil and water). The film-coated product has the characteristics of resistance to marks, abrasion, and other damage imparted by the glass D'L surface. In addition, the anti-marking and anti-staining properties provided by the fluorine terminating group reduce the transmission of oil from the finger to the broken glass. (fingerprint), further make the oil/fingerprint easy to wipe and remove with a cloth. The present invention provides an alkali metal aluminosilicate glass article having a thickness of at least about 〇3 mm, having a surface compressive stress of at least about 200 MPa, a surface compression layer having a depth of about 20-70, • 111, and a double-lubricating fluorophore. Surface layer. The fluorine-absorbing main surface layer is exchanged with fluorine as a main component by a glass terminal 〇H group, such as fluorine-containing monomer, to form a terminal fluorinated group. For example and without limitation, the exchange can be carried out according to the following reactions: 5 200948734 fluorocarbons and more preferably G-CiO alkyl perfluoropolyethers; n is an integer in the range 1 to 3; and X is a hydrolysable group, which is associated with a glass terminal 〇H-based exchange. Preferentially, X is a fluorine-free halogen or alkoxy machine (_〇R), wherein the ruler is a linear or branched hydrocarbon of 丨_6 carbon atoms, such as, without limitation, _ch3, c2jj5, CIKCH3)2 Hydrocarbons. In some embodiments n = 2 or 3, preferably 3 . Preferably, the halogen is gas. Preferentially, the alkoxy oxane is a trimethoxy oxane RFSi(OMe)3. The perfluorocarbide element that can be used in the practice of the invention comprises (RFhSiCI, RF-C(0)-C1, RF-C(0)-NH2, and other perfluorocarbonate motifs, which have a terminal group The glass hydroxy group (〇H) is exchanged. Here, π-perfluorocarbons " &fluorocarbons" means that substantially all CH bonds of the hydrocarbon groups are converted to CF bonds. In another embodiment, the fluorine-absorbing surface layer is composed of a combined monolayer of fluorine-terminated molecular chains. In still further embodiments, the surface layer that absorbs fluorine as φ is a thin fluoropolymer coating film. In the last embodiment, the fluorine-absorbing surface layer is composed of cerium oxide dust particles having a fluorocarbon group attached to the dust particles. Further embodiments of the present invention relate to transparency, a product consisting of a cover glass having a chemically tough protective layer of an antireflection layer, for example but not limited to a layer of antireflective Si〇2 or F_Si〇2 (fluorine coating ceria or molten niobium oxide), and Further, an external coating film having a fluorine terminal group, The cover glass is somewhat hydrophobic and oleophobic (ie, double-strength), minimizing the wetting of the glass surface by water and oil. The outermost layer is also applied as described in 200948734 to impart anti-reflection. The anti-wear properties of the product. The double-skinned smear-coated drug 1 has the characteristics of the gas-staining, the gas-staining, the gas-staining, and other damage characteristics, in addition to the anti-fingerprint anti-staining provided by the fluorine terminal. The characteristic is to reduce the transfer of oil from the finger to the glass (fingerprint), further making the oil/fingerprint easy to wipe and remove. The anti-reflective coating may have lower anti-wear/scratch characteristics than the basic chemically strengthened glass. Sparse Material Coating - Anti-Reflective Coating Chemically tempered glass provides anti-wear coating glass anti-wear 0 characteristics, thus making the anti-reflective coating glass get the main glass performance, while still providing anti-reflective coating glass anti-fingerprint Anti-staining characteristics. In a preferred embodiment, the outer layer (outermost layer) of the anti-reflective coating film contains a layer of Si〇2, such as F_Si〇2, a dream of melting, a dream of oxidation or a dream of oxidizing. Bismuth metal aluminic acid The salt glass article may further comprise a textured or patterned film surface located between the main glass and the fluorine-based surface coating. • The texture may be derived from the acid/base residue including its combination in RMS crude sugar content. Roughness in the range of 5〇nm to 5/zM (5000 nm). φ The rough glass component on the near surface is preferably rich in Si〇2. The roughness measurement technique can use atomic force microscopy (AFM) and sweep. Aiming at white light interference measurement (.SWLI). Alternatively, the texture may be from lithography or using a deposited structure, and the rough glass component also on the near surface is preferably rich in Si〇2. After the texture layer is formed Next, an article of textured fluorine-containing material coating is formed using the fluorine-containing material coating texture layer and any untextured primary glass described herein. Other features and advantages of the invention will be apparent from the description and appended claims. [Embodiment] In the following description, the same reference numerals denote related parts shown in all the drawings. It should also be understood, unless otherwise indicated, such as "top"^bottom" "outward", "inward", etc. These words are used for convenience rather than as restrictive words. Also, when a group When a group is described as containing at least one group of elements and combinations thereof, it should be known that the group can contain several of these - the repeated elements 'are not individually or in combination with each other. Similarly, when a group is described as being It consists of at least a group_element and its combination. It should be known that a group can be composed of several such repeated elements, not individually or in combination with each other. "Main glass, the term refers to any metal. A silicate glass that is suitable for use in the protection of an antireflective coating, and/or a perfluorocarbon material, which can be used to resist oil or stains, and/or a perfluorocarbon material. Cover glass. The term "Si〇2 coating film" as used herein refers to a Si〇2 coating film or an F-Si〇2 coating film, or a combined /F-Si〇2 coating film. In all of the embodiments described herein, the perfluorocarbon bonded ruthenium moiety or the perfluorocarbon-bonded moiety (like a layer or coating) is bonded to glass, chemically strengthened glass, or chemically strengthened by covalent bonds. And &〇2 (or ^ Sl〇2) coated glass surface. The term "double sparsity" as used herein means that the material applied to the surface is hydrophobic and oleophobic to the surface. With reference to Figure 1, it is to be understood that the invention has been shown as illustrative of specific embodiments of the invention and is not intended to limit the invention. In general, it is shown that the transparent protective cover glass has enhanced damage resistance and double hydrophobicity properties, thereby providing minimal fingerprint adhesion to the trace surface and easy removal of fingerprints. 200948734 Figure 1 shows the surface of the chrono-salt glass product with a thickness of at least 〇·3mm. 〇〇 Surface compression at least ΜΡη surface pressure _ 朗 layer 106. The surface compression layer 1 〇 4 has a thickness of about 20 to 7 and is usually achieved by ion exchange treatment as described below. In addition to the surface compression layer 1〇4 and the non-ion exchange intermediate layer glass portion 1〇6, the article (10) has a double-strength absorption fluorine main surface layer 102 〇- double-strength absorption fluorine main surface layer or coating film can be any The method can be achieved from the following groups: (1) - the active surface part of the thiol terminal and the fluorine-based monomer replacement; (2) the combined monolayer of the fluorine terminal molecular bond; (3) the thin fluorine The polymer coating film, (4) treating the first oxidized dust particles to obtain a fluorine terminal group. The coating film can be applied to the surface by dipping, vapor coating, spraying, using a roller or other suitable method. Dipping or spraying is a better way. The coating film is applied. Thereafter, it is cured in air containing 40-95% moisture at a temperature in the range of 25-1501, preferably at 4 〇 10 ° C for 1-4 hours. The example here applies a two-coat film of "50/50 cure", which means curing in 空气50°c for 2 hours in air containing 50% moisture. After curing, the sample was wetted with a solvent to remove any unbound film, and air-dried before use. Referring now to Figure 2, there is shown another embodiment of an aluminosilicate glass article 1Q0. In this embodiment, the glazing 1 〇〇 includes all of the features of the embodiment, including the surface compressive stress layer 104, the ion-free intermediate layer glass portion 106, and the double-phobic absorbing fluorine main surface layer 〇2 Further, this embodiment includes a texture or pattern surface 1 〇 8 between the main surface layer 1 〇 2 (indicated by a thick black line) and the surface compressive stress layer 104. In one embodiment, the texture or pattern layer is formed by compression layering 9 200948734 by meal or lithography. In another embodiment, the texture or pattern layer is any layer of compression that is not textured or patterned by the particle coating. The texture or pattern surface shown in Figure 2 is added to the primary fringe or formed on the base glass. Application of such texture or pattern surface can be accomplished in any manner known to those skilled in the art. Increasing the texture/pattern surface to the base - glass, or forming a texture/pattern surface on the primary glass, includes electrical rotation of the polymer or inorganic material, deposition of an inorganic film sequential particle coating, or any other technical texture Or pattern the way the glass surface is broken. The textured or patterned surface produced by the glass exhibits an increased surface area while still maintaining the desired degree of transparency. The textured surface is applied with the double hydrophobic coating described herein. The fluorine surface treatment/layer and the elevated surface roughness together will result in an increase in the wetting properties of the glass. As a result, glassware shows minimal fingerprint adhesion and fingerprints can be easily removed with a little wiping.双 The disclosed double-leaf glass article exhibits the following lifting characteristics over the marketable protective cover glass solution. , , Fingerprint adhesion. The fluorine treated (and thus fluorine terminated) surface is less polar than the surface of the -OH terminal group and can therefore result in the combination of minimal hydrogen (i.e., Van der Waals) between the particles and the liquid. Therefore, fingerprints and debris associated with fingerprints can be greatly reduced. This combination and attachment directly minimizes the transfer of oil and debris from the fingers to the glass surface. Cleaning and cleanliness. Fingerprint removal is typically performed by wiping the surface with a cloth under dry or wet conditions. These cloths are reusable so it is possible that 200948734 contains dust and particles that can scratch the surface. The fluorinated surface of the product allows fingerprint removal to be more tolerant and minimizes smudges and thieves. The latter further reduces the number and frequency of surface damage events leading to immediate or delayed breakage of the glass product. While minimizing the adhesion of fingerprint oil and increasing the extent of removable oil squeegee with a dry cloth, any surface abrasion caused by scratching can cause marks, cause surface damage and/or lead to failure of the last protective glass cover-board. . The high hardness (higher than comparable glass) and ❹ high compression surface IX) L (40-60 microns deep, deeper than comparable glass) described here are protected together to prevent damage from repeated wiping. This failure can be eliminated as long as the compression surface D0L is deeper than the damage caused by wiping or other processing modes. Scratch resistance. The anti-scratch test was carried out in that the glass article used was coated with a double-sided material and the other half was not coated with phosphine. This test is a sandpaper scratch test using a reciprocating die loss tool to pass sandpaper (15 Å particle size) through both surfaces to impart equal wear to both coated or uncoated surfaces. The ambiguity of the two sides of the article is then measured, and the ambiguity is measured by the sum of the diffused ray and the transmitted ray. The results show that the ambiguity of the double-repellent coating is reduced to 80%, that is, the glass is broken due to abrasion. Optically visible damage. This result shows that the double-repellent coating film greatly increases the resistance.双 In addition to scratch resistance, the double-repellent coating also reduces the coefficient of friction. Specifically, contrary to the static friction that does not move the two articles, the sliding or dynamic coefficient of friction is measured over the entire coating of the glass article, where the half of the article is coated with a double hydrophobic material and the other half is not. Coating film. The results of the test showed that β κ = 0.25 of the uncoated glass, while #κ = 〇·05 of the coated glass, therefore, referred to 200948734, which reduced the dynamic friction by 80% due to the relationship of the double-repellent coating film. This reduction in friction also reduces the damage on the glass surface when someone hangs • the piano-factory and when the glass is placed in the carrying case. This excellent performance also makes touch screen applications easier to use. Additional information regarding the particular alkali metal aluminosilicate glass suitable for use in the immediate examples is provided below. The glass has a liquid phase viscosity coefficient of at least 130 kpoise. As used herein, "liquid phase viscosity coefficient" refers to the viscosity coefficient of molten glass at liquidus temperature, where liquidus temperature refers to the temperature at which the crystal first cools from the melting temperature to the molten glass. , or the crystal increases with temperature from room temperature to the temperature of melting. The glass composition is expressed as a percentage of moles: 64% $ Si〇 2^68%; 12%^Na2〇^ 16%; 8%^Al2〇3^ 12%; 0%^B2〇3^ 3%; %SK2〇S5%; 4% core Mg〇S6%; and 〇%sca〇$5%, where ——SiQ2+B2〇3+CaO S 69%; Na2〇+K2〇+B2〇3+MgO+CaO+ SrO>10%; 5% ^ MgO+CaO+SrO ^ 8%; (Na2〇+B2〇3) ^ A l2〇3 ^ 2%; 2% S Na2〇-A12〇3 S 6/^; % S (Na2〇+K2〇) S A12〇3 S10%. The largest single component of the alkali aluminosilicate glass is Si 〇 2, and the matrix forming the glass is present in the glass of the present invention at a concentration ranging from about _ molar ratio to about 68% molar ratio. Si〇2 acts as a viscosity coefficient enhancer to help shape and impart chemical durability to the glass. Concentrations above the above range will raise the melting temperature too high, while concentrations below the range will destroy the glass durability. In addition, lower Si〇2 concentrations may result in an increase in liquidus temperature within the glass, with a higher K2〇 or higher Mg〇. When the concentration ranged from about 8% molar ratio to about 12% Mo 12 200948734 ear ratio, Α12〇3 will increase the viscosity coefficient. When the ai2〇3 viscosity coefficient is higher than this, it is too high to maintain a continuous downward drawing process. In order to prevent this, the total concentration of gold-plated metal oxides (such as Na20, K20) of the glass of the present invention far exceeds the total Α1ζ〇3 content. Metal oxide metal can help achieve lower liquidus temperatures and lower melting temperatures. As used herein, the term "melting viscous coefficient" refers to the temperature corresponding to the viscosity coefficient of 200 poise glass. In the case of sodium, ion exchange can be successfully carried out using ^ Na〇2. In order to have sufficient ion exchange To produce a truly enhanced glass strength, it is possible to provide Na〇2 ranging from about 12% molar ratio to a concentration of about 16% molar ratio. However, if the glass is outside the range described herein, Na2, Al2 〇3 and Si〇2, the viscosity coefficient is too high to be melted. Therefore, other components must be used to ensure good melting and formation efficiency. Assuming that those components exist, the concentration range between Na〇2 and a12〇3 A suitable melting temperature is obtained when the difference is from about 2% molar ratio to about 6% molar ratio (i.e., 2% molar ratio S NazO-A 12 〇 3S 6% molar ratio). ❿ may include an oxidation clock (Μ) to obtain a lower liquidus temperature. However, even more than Na〇2 will reduce the glass viscosity coefficient. Therefore, the sum of Na〇2 and κ20 concentrations and the concentration of Alz〇3 The total difference should range from about 4% Mo ratio to about 10% Mo (ie 4% Mo Er S (Na2〇+K2〇)-Al2〇3$ 10% Mo Er). B2O3 can act as a fluxing agent, ie a component added to lower the melting temperature. Even if a small amount of B2 is added 〇3, can also drastically reduce the melting temperature of the same glass up to 100 ° C. However, as mentioned earlier, the addition of sodium can make ion exchange 13 200948734 successful, in the case of relatively low Na 〇 2 content and high Al 2 〇 3 content It is preferable to add a glass-I, which is capable of binding, to a total concentration of Na2〇 and M)3 such that (Na2〇+K2〇)-Al2〇3S2% molar ratio. Thus, in one embodiment, The total concentration of Si〇2, B2〇3 and CaO is between 66% molar ratio and up to 69% molar ratio (ie 66% molar ratio $si〇2 + B2〇3+Ca〇S69% molar ratio) .

當總鹼金屬氧化金屬濃度超過Al2〇3時，任何玻璃内呈 現的鹼土氧化物主要是充作助熔劑。MgO是最有效的助熔 劑’然而在鈉鋁矽酸鹽玻璃中較低的Mg〇濃度，容易形成矽 酸鎮石（Mg2Si〇4)，因而導致玻璃的液相溫度隨著鎂含量急 速提升。在較高的MgO含量，玻璃的融化溫度是正好在連續When the total alkali metal oxidized metal concentration exceeds Al2 〇 3, any alkaline earth oxide present in the glass is mainly used as a flux. MgO is the most effective flux. However, the lower Mg 〇 concentration in sodium aluminosilicate glass tends to form strontium ballast (Mg2Si〇4), which causes the liquidus temperature of the glass to increase rapidly with the magnesium content. At higher MgO content, the melting temperature of the glass is just in the continuous

製造所需的限制内。然而，液相溫度可能太高，因而液相黏 滞係數可能太低，而無法與向下抽拉處理例如熔融抽拉處 理相容。然而，添加至少一種B203和Ca〇可急劇降低這些富 含％〇成分的液相溫度。的確，我們可能需要一些含量β晶 ，CaO或兩者，以得到和熔融處理相容的液相溫度尤其是具 有尚鈉’低IG0,和高Al2〇3濃度的玻璃。我們希望氧化鳃 (SrO)也對於和Ca0 一樣的高_玻璃的液相溫度有同樣的 影響。在—項實施例中，驗土金屬氧化物濃度因而比％0濃 度本身更寬廣，使得5%#耳比$触+⑽莫耳比。 鋇也是-種驗土金屬，添加小量的氧化鋇_)，或其他鹼 土^氧化_代物可藉著去敎富含驗切糾以產生較 質的=線溫度。然而，鋇被認為是—種危險或有毒的物 質。因此，可^少2%料比含量魄侧添加到這裡描 200948734 述的玻璃，不具傷害性的影響或甚至溫和改善液相線溫度， 通常都維持很低的犯^貝-含量Χχ減少玻璃的環1竟因 此，在一項實施例中，玻璃是真正不含鋇。 除了以上描述的元素，也可添加其他元素和化合物，以 消除或減少玻璃内的缺陷。本發明破璃在約15〇〇t和膨 C之間顯不2GG千泊相當高的轉係數。這是工業融化處 '理中使用的典型黏滯係數，在有些例子可能需要在這種溫 度下融化以得到較低含量氣體夾雜物的玻璃。為了幫助消 除氣體夾雜物，添加化學澄清劑可能是有用的。這種化學 澄清劑以氣體充滿早期階段的氣泡，因而增加整個融體上 升的速度。典型澄清劑包括非限繼之氧化珅，録，錫和鈽 ;金屬齒化物（氟化物，氣化物和溴化物）;金屬硫化物等。 氧化砷是特別有效的澄清劑，因為其再熔化階段很晚才釋 出氧氣。然而砷和銻一般被認為是有害物質。 據此，在一項實施例中玻璃是真正沒有砷和錄，包含 ❹這些元素氧化物的至少約0.05%重量比。因此，在特定應用 上最好是避免使用石申和録，而是以譬如錫鹵化物或硫化物 的無毒成份替代以產生澄清效果。在本梦财，錫(IV)氧 化物(Sn〇2)和錫（iv)氧化物的組合和卣化物作為澄清劑特 別有用。 這裡描述的玻璃是可向下抽拉的;也K是說，玻璃是可 利用向下抽拉方法，譬如但不限定是熟悉玻璃製造技術的 人已知的向下抽拉和隙縫抽拉方法形成玻璃片。這種向 下抽拉處理可用在離子交換平板式玻璃的大賴製造上。 15 200948734 熔融抽拉處理過程制的抽拉槽有—俩道用以接收 熔融玻璃祕。通道_在通道兩邊沿著通道的長度，在 頂端是開放式的。當通道充滿溶融材料熔融玻璃會溢流 到堰外。由於地心引力，熔融玻璃會向下流到抽拉槽的外 表面。這齡表面向下延伸並向触，在抽域下方連結 成一個邊。這兩個流動玻璃表面在這個邊連結起來，溶融 並形成:片流動玻璃。熔融抽拉方法提供的優點是由於兩 _ 4玻璃薄膜流經通道熔融在一起所產生玻璃片的外表面 不會和設備的任何部分接觸。因此，表面的性質不會受這 種接觸的影響。 隙縫抽拉方法和熔融抽拉方法是不同的。這裡提供溶 融原料玻璃到抽拉槽。抽拉槽底部有開放式隙縫，有延伸 隙縫長度㈣嘴。缝玻雜雌縫/喷嘴，向下抽拉成連 續的玻璃流，經由那裡到退火區。和熔融抽拉處理比較起 來’隙縫抽拉處理可提供㈣的玻璃片，因為只有-片玻璃 拉，而不是雜融向下抽拉處理，是由兩片玻璃 為了和向下抽拉處理相容，這裡描述的驗金 屬銘魏鹽玻璃有相當高的液相線黏滯係數。在 例中，液相黏滞係數是至少130千泊(kpoise)，而在另 她例中’液相黏滯係數是至少250千泊。 在項實知例中，這裡描述的驗金屬鋁石夕酸鹽玻 f正不含鐘。如這裡使用的，”真正不含鐘"是指二二 驗金屬細㈣玻翻處理步驟綱，鐘不是故意加^ 玻璃或玻填原料。應該要瞭解，驗金屬__破 16 200948734 金屬鋁矽酸鹽玻璃製品是真正不含鋰可能由於污染才包 含小量¥益。示含減少蘇子-交直n少 補充鹽供應，其為化學強化玻璃所需求的。此外，由於不含 鋰，玻璃可和連續單元(cu)融化技術相容，譬如上述的向下 抽拉處理和這裡使用的材料，後者包括熔融鍅土和鋁土防 火材料，和錯·土和銘土隔離管。 在一項實施例中，玻璃是藉著離子交換而化學地強化 0 。如這裡使用的，"離子交換”一詞是指玻璃藉由熟悉玻璃 製造技術的人已知的離子交換處理來強化。這種離子交換 處理包括非限制性地比玻璃表面較大離子半徑的離子的加 熱溶液，處理加熱的鹼金屬鋁矽酸鹽玻璃，因而以較大離子 取代較小離子。例如，鉀離子可取代玻璃内的鈉離子。或 者，其他具有較大原子半徑的鹼性金屬離子譬如铷和铯可 取代玻璃内較小的鹼性金屬離子。同樣地，其他鹼性金屬 鹽譬如非限制性之硫化物，鹵化物等其他可用在離子交換 Q 處理的材料。在一項實施例中，向下抽拉玻璃是藉著將其 置放在包含KN〇3的溶融鹽浴一段既定的時間以達到離子交 . 換以進行化學強化。在一項實施例中，熔融鹽浴的溫度是 約430 C，而既定的一段時間是約8小時。藉著離子交換的 化學強化可以在大片玻璃上執行，接著再切割（切成薄片， 鋸開或其他處理）成特定應用適合的大小，或是在預先切割 成適合大小的玻璃上執行化學強化。 向下抽拉處理所產生的表面是相當原始的。因為玻璃 表面的強度是由表面缺陷的量和大小所控制最少接觸的 17 200948734 原始表面有較高的域賊。當這種高強度玻璃被化學強 化後，產至两強度 離子交換的化學強化或锻鍊也可增加玻璃因處理而形成缺 陷的抵抗性。據此，在一項實施例中向下抽拉鹼金屬鋁矽 酸鹽玻璃的彎曲偏斜，就300^^400^玻璃片而言是小於 約0.5mm。在另一實施例中彎曲偏斜是小於約〇 3腿。 表面壓縮應力是指玻璃表面層所含的鹼金屬離子被具 φ 有較大離子半徑的離子取代的化學強化期間所導致的應力 。在一項實施例中，鉀離子取代所描述的玻璃表面層内的 鈉離子。玻璃的表面壓縮應力至少約2〇〇MPa。在一項實施 範例中，表面壓縮應力至少約6〇〇MPa。離子交換提供鹼金 屬铭矽酸鹽玻璃的壓縮應力層深度至少約2〇//ιη。在一項 實施例中，離子交換提供的壓縮應力層範圍約3〇_8〇 “ m。 較小離子在一溫度下被較大離子取代在整個導致應力 變化的玻璃表面產生離子分佈，在低於該溫度下玻璃網狀 ❹ 結構變得寬鬆。進入的較大離子會在玻琿表面產生壓應力Within the limits required for manufacturing. However, the liquidus temperature may be too high, and thus the liquid phase viscosity coefficient may be too low to be compatible with a downward draw process such as melt draw. However, the addition of at least one of B203 and Ca〇 drastically reduces the liquidus temperature of these % cerium-rich components. Indeed, we may need some levels of beta crystal, CaO or both to obtain a liquid phase temperature compatible with the melt treatment, especially glass having a concentration of still sodium 'low IG0, and high Al2〇3. We hope that strontium oxide (SrO) will have the same effect on the liquidus temperature of the same high glass as Ca0. In the embodiment, the soil metal oxide concentration is thus broader than the %0 concentration itself, such that 5%# ear is greater than $touch + (10) molar ratio.钡 is also a kind of soil test metal, adding a small amount of yttrium oxide _), or other alkaline soil oxidized _ substitutes can be enriched by deuteration to produce a better = line temperature. However, cockroaches are considered to be dangerous or toxic substances. Therefore, it is possible to add 2% of the material content to the side of the glass described in 200948734, which has no harmful effects or even mildly improves the liquidus temperature, and generally maintains a very low incidence of 贝--- Thus, in one embodiment, the glass is truly free of bismuth. In addition to the elements described above, other elements and compounds may be added to eliminate or reduce defects in the glass. The glass of the present invention exhibits a relatively high coefficient of rotation between about 15 〇〇t and swell C. This is the typical viscosity coefficient used in industrial melting, and in some cases it may be desirable to melt at this temperature to obtain a lower content of gas inclusions. To help eliminate gas inclusions, it may be useful to add a chemical clarifying agent. This chemical clarifying agent fills the bubbles in the early stages with a gas, thereby increasing the rate at which the entire melt rises. Typical fining agents include non-limiting cerium oxide, lanthanum, tin and antimony; metal dentates (fluoride, vapor and bromide); metal sulfides and the like. Arsenic oxide is a particularly effective clarifying agent because it releases oxygen very late in the remelting phase. However, arsenic and antimony are generally considered to be harmful substances. Accordingly, in one embodiment the glass is truly free of arsenic and contains at least about 0.05% by weight of the oxide of these elements. Therefore, it is best to avoid using Shishen and recorded in specific applications, but instead use a non-toxic component such as tin halide or sulfide to produce a clarifying effect. In this dream, the combination of tin (IV) oxide (Sn〇2) and tin (iv) oxide and telluride are particularly useful as fining agents. The glass described herein is drawable downwards; also K is said to be a downward draw method, such as but not limited to those known to those skilled in the art of glass making, down draw and slit draw methods. A glass piece is formed. This downward drawing process can be used in the manufacture of ion exchange flat glass. 15 200948734 The draw trough made by the melt drawing process has two channels for receiving molten glass. The channel _ is along the length of the channel on both sides of the channel and is open at the top. When the channel is filled with molten material, the molten glass will overflow to the outside of the crucible. Due to gravity, the molten glass flows down to the outer surface of the drawing groove. The aged surface extends downwards and is in contact with each other and joins an edge below the pumping area. The two flowing glass surfaces are joined at this side, melted and formed: a sheet of flowing glass. The melt drawing method provides the advantage that the outer surface of the glass sheet produced by the melting of the two - 4 glass film through the channels does not come into contact with any part of the apparatus. Therefore, the nature of the surface is not affected by this contact. The slit drawing method and the melt drawing method are different. Here, the raw material glass is supplied to the drawing tank. There is an open slot at the bottom of the draw slot and a length of the extended slot (4). Sewing the female seam/nozzle and drawing it down into a continuous stream of glass through which it passes to the annealing zone. Compared with the melt drawing process, the 'slot extraction process can provide (4) the glass piece, because only the piece of glass is pulled, instead of the heterozygous downward drawing process, it is compatible with the two pieces of glass for the downward drawing process. The metallurgical Wei salt glass described here has a fairly high liquidus viscosity coefficient. In the example, the liquid phase viscosity coefficient is at least 130 kpoise, while in other cases the liquid phase viscosity coefficient is at least 250 kpoise. In the case of the actual example, the metal aluminosilicate f described herein does not contain a clock. As used here, "the real does not contain the clock" refers to the second and second metal fine (four) glass turning process steps, the clock is not intentionally added ^ glass or glass filling materials. Should understand, metal inspection __ broken 16 200948734 metal aluminum The bismuth silicate glass product is truly lithium-free. It may contain a small amount of smear due to pollution. It contains a small amount of supplemental salt supply, which is required for chemically strengthened glass. In addition, because it does not contain lithium, glass It is compatible with continuous unit (cu) melting techniques such as the pull-down process described above and the materials used here, the latter including fused alumina and alumina fireproof materials, and the wrong soil and Ming soil isolation tubes. In the examples, the glass is chemically strengthened by ion exchange. As used herein, the term "ion exchange" means that the glass is strengthened by ion exchange treatment known to those skilled in the art of glass making. This ion exchange treatment involves heating a solution of ions having a larger ionic radius than the surface of the glass, without limitation, treating the heated alkali metal aluminosilicate glass, thereby replacing the smaller ions with larger ions. For example, potassium ions can replace sodium ions in the glass. Alternatively, other basic metal ions such as ruthenium and osmium having a larger atomic radius may replace the smaller basic metal ions in the glass. Similarly, other basic metal salts such as non-limiting sulfides, halides, and the like, which may be used in ion exchange Q treatment. In one embodiment, the glass is pulled down by placing it in a bath of molten salt containing KN〇3 for a predetermined period of time to achieve ion exchange for chemical strengthening. In one embodiment, the temperature of the molten salt bath is about 430 C, and the predetermined period of time is about 8 hours. Chemical strengthening by ion exchange can be performed on large pieces of glass, followed by cutting (cutting, sawing or other processing) to a suitable size for a particular application, or performing chemical strengthening on pre-cut to a suitable size of glass. The surface produced by the downward draw process is quite primitive. Because the strength of the glass surface is controlled by the amount and size of surface defects, the minimum contact is observed. 17 200948734 The original surface has a higher domain thief. When such high-strength glass is chemically strengthened, chemical strengthening or forging of the two-strength ion exchange can also increase the resistance of the glass to defects due to treatment. Accordingly, in one embodiment, the downward deflection of the alkali metal aluminosilicate glass is less than about 0.5 mm in the case of a 300 ^ ^ 400 glass piece. In another embodiment the bending deflection is less than about 〇 3 legs. The surface compressive stress refers to the stress caused by the chemical strengthening of the alkali metal ions contained in the surface layer of the glass by the substitution of ions having a larger ionic radius. In one embodiment, potassium ions replace the sodium ions in the surface layer of the glass described. The surface compressive stress of the glass is at least about 2 MPa. In one embodiment, the surface compressive stress is at least about 6 MPa. Ion exchange provides alkali metal silicate glass having a compressive stress layer depth of at least about 2 Å//ιη. In one embodiment, the ion exchange provides a compressive stress layer in the range of about 3 〇 8 〇 "m. Smaller ions are replaced by larger ions at one temperature to produce an ion distribution throughout the surface of the glass that causes stress changes, at low At this temperature, the glass mesh structure becomes loose. The larger ions entering will generate compressive stress on the surface of the glass.

(CS)，在玻璃中央產生張力（CT)。壓應力與中央張力關係 • 如下：CS=CT X (t-2DOL)/DOL 不含鋰的玻璃厚度至少約0.3mm，表面壓縮應力至少約 200MPa，表面壓縮層的深度至少約30 。在·—項實施例中 ，壓縮應力至少約600MPa，壓縮層的深度至少約4〇ym，而不 含鋰的玻璃厚度範圍從約0· 7mm到約1.1咖。 在一項實施例中，不含鐘破璃包含:64% ^ Si〇2$ 68%; 12%^Na2〇^16%;8%^Al2〇3^12%；〇%^B2〇3^3%;2%^K2〇 200948734 $5%;4%SMg〇S6%;以及 〇%$CaOS5%，其中 66%$ Si〇2+ Β2〇3+(^σ ^Bg%]Na^jfK2〇;B2〇3：f晒;------(CS), tension (CT) is generated in the center of the glass. Relationship between compressive stress and central tension • As follows: CS=CT X (t-2DOL)/DOL Lithium-free glass has a thickness of at least about 0.3 mm, a surface compressive stress of at least about 200 MPa, and a surface compression layer depth of at least about 30 Å. In the embodiment, the compressive stress is at least about 600 MPa, the depth of the compressed layer is at least about 4 〇 ym, and the thickness of the glass containing no lithium ranges from about 0.7 mm to about 1.1 Å. In one embodiment, the bell-free glass comprises: 64% ^ Si〇2$ 68%; 12%^Na2〇^16%; 8%^Al2〇3^12%; 〇%^B2〇3^ 3%; 2%^K2〇200948734 $5%; 4%SMg〇S6%; and 〇%$CaOS5%, of which 66%$Si〇2+ Β2〇3+(^σ^Bg%]Na^jfK2〇; B2〇3:f drying;------

MgO+CaO+SrO S 8%; (Na2〇+B2〇3) S A12〇3 g 2%; 2% S Na2〇-MgO+CaO+SrO S 8%; (Na2〇+B2〇3) S A12〇3 g 2%; 2% S Na2〇-

Al2〇3$6%;以及 4%S(Na2〇+K2〇)SAl2〇3$l〇%，以及液相 線黏滞係數至少為13〇千泊。在一項實施例中，液相線黏 滯係數至少為250千泊。 化學強化抗反射雙疏性玻璃： _ 本發明的另一實施例是關於由透明，防損害，化學強化 保護的蓋板玻璃所構成的產品以抗反射Si〇2或F_Si〇2(二 氧化砍，熔融二氧化石夕或氟塗料二氧化带）來塗覆，並且更 進一步具有氟終端基的外部塗膜賦予蓋板玻璃某種程度的 疏水性和疏油性（即雙疏性)，使玻璃表面被水和油的濕潤 減到最少。此外，藉著施加雙疏性材料塗膜到抗反射塗膜，化 學強化的玻璃可改善抗刮痕，磨損，和其他損傷的特性，此 外還有在雙疏性塗膜中的氟終端基所提供抗指印，抗污痕的 ❹ 特性，減少油從手指到玻璃的傳輸(指印），進一步使油/指 印谷易用布擦拭移除。在此所使用所謂"Si〇2塗膜”係指 . Si〇2或F_Si〇2塗膜或複合Si〇2/F-Si〇2塗膜。 抗反射和抗磨損的Si〇2或F-Si〇2袁膜最好在離子交換 之前或之後放在主要玻璃上。在最佳實施例中，F_Si〇2塗 層是放在已經離子交換的主要玻璃上，而且是在任何用來 改善來自指印的油潰或污痕移除的全敦碳化物置放之前。 全氟碳化物可用來減少玻璃表面的表面能量，這是由於氟 終端表面鍵的低極性。很重要的是，全氟碳化物有很好的 200948734 持久性，可保護使用的設備維持夠久的時間一般至少兩 ~~ . —-------------- —------ -----. —__-—_ ....._ ________ I ·*Γ " -----* I ......--- 也可使用各種附加的化學方法將全氟碳化物或含全氟 碳化物的材料塗覆到玻璃表面。然而，藉著離子交換(例如 在基礎玻璃内，K離子替換％及/或Li離子）化學強化的玻璃 表面富K離子，限制了 Si-ΟΗ活性表面部位的數目，而且抑制 • 共價鍵鍵結全氟碳化物或含全氟碳化物部分體到離子交換 0 玻璃的表面。塗覆Si〇2或F-Si〇2塗膜的新產物是加強的& 終端部位，呈現在Si〇2或F-Si〇2塗膜化學強化的玻璃上，相 反於沒有含鹼離子交換表面塗膜的化學強化玻璃。於是， 化學強化的玻璃表面上的Si〇2或F-Si〇2塗膜，加強了全氟 碳化物或含全氟碳化物部分體的鍵結，而且增加了共價鏈 結全氟碳化物或含全氟碳化物部分體的表面密度。最外層 的氟化物質產生蓋板玻璃"抗指印"或"易清潔”的特性，不 會因化學強化而減損玻璃強度。除此之外，Si〇2或F-Si〇2 ❹ 塗膜本身或和另一層Si〇2或F-Si〇2以及其他氧化金屬薄膜 (可能依序是Si〇2及/或F-Si〇2及/或”其他氧化金屬”的多 > 塗膜)結合，可以作為一種抗反射塗膜。這種11其他氧化金 屬"的例子包括Hf〇2, Ti〇2, Zr〇2, Y2〇3, Gd2〇3,以及此項技 術中已知的其他氧化金屬可用來作為抗反射塗膜。此外， 可使用MgFz作為抗反射層，也可施加到化學強化玻璃。接 下來可施加含全氟碳化物部分體到抗反射塗膜◊產生的塗 層，化學強化玻璃有提升的抗損害，抗反#，和雙疏性特性因 而可提供顯示來自反射光和指印最小光學干擾的抗刮表面 20 200948734 。由於抗反射塗臈，手握顯示裝備，高壓縮表面D0L塗膜玻 璃的特性X雙疏性和抗反射兼異，-這是使用冥他-爾贿的 裝置所沒有的。 圖3顯示的鹼金屬鋁矽酸鹽玻璃製品1〇〇，具有離子交 換所形成的表面壓縮層1Q4,其壓縮強度至少2QQMPa，非離 子父換的中間部份106,抗反射塗膜11〇，和雙疏性氣主要表面 層102。表面壓縮層104的厚度大約2〇_7〇仰。除了抗反射 魏110和雙疏性氟主要表面層102以外的玻璃製品，其厚度 至少約0· 3mm，包含在離子交換層1 和中間層1 〇6。 抗反射塗膜110是由至少一層所構成，厚度範圍是2〇_ 70"m。當抗反射塗膜是由二層或以上所構成時抗反射塗 層的總居度也疋在l〇~7〇vm範圍。氟主要雙疏性層其厚度 範圍是卜10nm，最好是^咖的範圍。在一項實施例中雙 疏塗膜的厚度範圍是1-2ηπ^當使用單一的抗反射層時，使 用的塗膜材料Si〇z或F-Si〇2。當使用多層的抗反射塗臈時 Φ ，最接近層1〇4的是氧化金屬層，選自於Hf〇2，Ti〇2，Zr〇2， Y2O3, Gd2〇3群組，以及此項技術中已知的其他氧化金屬可 用來作為抗反射塗膜，而頂端層則是Si〇2或F-Si〇2。當抗 反射塗膜是三層或以上時，最頂層是&〇2或1?_&〇2,而在 Si〇2或F-Si〇2層之間的抗反射塗膜，和層1〇4可以是任何 順序的前述抗反射塗膜材料，雖然在最佳實施例中第一層 是氧化金屬層。例如，三層的塗膜可以是玻璃_Y2〇3_Ti〇2 -SiO。 化學強化，抗反射，雙疏性特性的玻璃在目前業界所用的 21 200948734 蓋板玻璃具有下列的優點。 1.在以Ϋΐ；雙疏S特性部分蘧4S之前「塗覆瓦瓦S塗膜 到主要玻璃，用來讓光學干擾無視於反射，因而消除強光。 抗反射塗膜的功能是多樣性的，其效能包括控制光學干擾 的角度（或可見度)，因而藉由結構化多層塗膜提升此效果 ，提供"秘密"效果的選擇。 φAl2〇3$6%; and 4% S(Na2〇+K2〇)SAl2〇3$l〇%, and a liquidus viscosity coefficient of at least 13〇10 poise. In one embodiment, the liquidus viscosity coefficient is at least 250 kilopoise. Chemically Enhanced Anti-Reflective Double-Skinning Glass: _ Another embodiment of the present invention relates to a product consisting of a cover glass that is protected by transparency, damage prevention, and chemical strengthening with anti-reflection Si〇2 or F_Si〇2 (secondary oxidation , coated with molten sulphur dioxide or a fluorine coating dioxide strip, and an external coating film further having a fluorine terminal group imparts a certain degree of hydrophobicity and oleophobicity (ie, sparsity) to the cover glass, making the glass The surface is minimized by the wetting of water and oil. In addition, chemically strengthened glass improves the scratch resistance, abrasion, and other damage characteristics by applying a double-phobic material to the anti-reflective coating film, in addition to the fluorine terminal group in the double-phobic coating film. Provides anti-fingerprint, anti-staining properties, reduces the transfer of oil from the finger to the glass (fingerprint), and further removes the oil/fingerprint from the cloth. The so-called "Si〇2 coating film" as used herein means a Si〇2 or F_Si〇2 coating film or a composite Si〇2/F-Si〇2 coating film. Anti-reflective and anti-wearing Si〇2 or F The -Si〇2 film is preferably placed on the main glass before or after ion exchange. In the preferred embodiment, the F_Si〇2 coating is placed on the main glass that has been ion exchanged and is used to improve Pre-carbon carbides from the fingerprints of oily or stain removal are removed. Perfluorocarbons can be used to reduce the surface energy of the glass surface due to the low polarity of the fluorine terminal surface bonds. It is important that the perfluorocarbons Have a good 200948734 persistence, can protect the equipment used for a long time, usually at least two ~ ~. ---------------------------- ---- -. —__-__ ....._ ________ I ·*Γ " -----* I ......--- Various additional chemical methods can also be used to treat perfluorocarbons or The perfluorocarbon-containing material is applied to the glass surface. However, by ion exchange (for example, in the base glass, K ion replacement % and / or Li ions) chemically strengthened glass surface rich in K ions, limiting Si-ΟΗ The number of active surface sites, and inhibits • covalent bonding of perfluorocarbons or perfluorocarbon-containing fractions to the surface of ion-exchanged 0. New products coated with Si〇2 or F-Si〇2 coatings It is a reinforced & terminal part that appears on a chemically strengthened glass of Si〇2 or F-Si〇2 coating, as opposed to a chemically strengthened glass that does not contain an alkali ion exchange surface coating. Thus, on a chemically strengthened glass surface The Si〇2 or F-Si〇2 coating enhances the bonding of perfluorocarbons or perfluorocarbon-containing moieties and increases the covalent chain of perfluorocarbons or perfluorocarbon-containing moieties. The surface density. The outermost layer of fluorinated material produces the cover glass "anti-fingerprint" or "easy to clean" properties that do not detract from the strength of the glass due to chemical strengthening. In addition, the Si〇2 or F-Si〇2 涂 coating film itself or another layer of Si〇2 or F-Si〇2 and other oxidized metal films (possibly Si〇2 and/or F-Si in order) The combination of 〇2 and/or "other oxidized metal" > coating film can be used as an anti-reflective coating film. Examples of such 11 other oxidized metal " include Hf 〇 2, Ti 〇 2, Zr 〇 2, Y 2 〇 3, Gd 2 〇 3, and other oxidized metals known in the art can be used as the antireflective coating film. Further, MgFz may be used as the antireflection layer or may be applied to the chemically strengthened glass. Next, a coating containing the perfluorocarbon partial body to the anti-reflective coating film can be applied, and the chemically strengthened glass has improved damage resistance, anti-anti-#, and double-sparing characteristics, thereby providing display with minimum reflection from reflected light and fingerprints. Optically resistant scratch-resistant surface 20 200948734. Due to the anti-reflective coating and the hand-held display equipment, the characteristics of the high-compression surface D0L coated glass are different between X-sexuality and anti-reflection, which is not available in the device using the He-Bai bribe. Fig. 3 shows an alkali metal aluminosilicate glass product having a surface compression layer 1Q4 formed by ion exchange, a compressive strength of at least 2QQMPa, a non-ionic parent-exchanged intermediate portion 106, and an anti-reflective coating film 11〇. And a double-phobic gas main surface layer 102. The thickness of the surface compression layer 104 is approximately 2 〇 7 〇. A glass article other than the antireflective Wei 110 and the double hydrophobic fluorine main surface layer 102 has a thickness of at least about 0.3 mm and is contained in the ion exchange layer 1 and the intermediate layer 1 〇6. The anti-reflective coating film 110 is composed of at least one layer and has a thickness in the range of 2 〇 70 " m. When the antireflection coating film is composed of two or more layers, the total residence resistance of the antireflection coating layer is also in the range of l〇~7〇vm. The main double-phobic layer of fluorine has a thickness range of 10 nm, preferably a range of coffee. In one embodiment, the thickness of the double-coating film is 1-2 η π ^ when a single anti-reflective layer is used, the coating material Si〇z or F-Si 〇 2 is used. When using multi-layer anti-reflective coating Φ, the layer closest to layer 1〇4 is an oxidized metal layer selected from the group of Hf〇2, Ti〇2, Zr〇2, Y2O3, Gd2〇3, and this technology. Other oxidized metals known in the art can be used as the antireflection coating film, and the top layer is Si〇2 or F-Si〇2. When the antireflection coating film is three or more layers, the topmost layer is &〇2 or 1?_&〇2, and the antireflective coating film between the Si〇2 or F-Si〇2 layers, and layer 1 The crucible 4 may be any of the foregoing antireflective coating materials, although in the preferred embodiment the first layer is an oxidized metal layer. For example, the three-layer coating film may be glass _Y2〇3_Ti〇2-SiO. Chemically strengthened, anti-reflective, and double-strength glass is currently used in the industry. 21 200948734 Cover glass has the following advantages. 1. Before applying the 双; double-sparing S characteristic part 蘧4S, “coating the tile S to the main glass, so that the optical interference is ignored, thus eliminating the glare. The function of the anti-reflective coating is diverse. Its performance includes controlling the angle (or visibility) of the optical interference, thus enhancing this effect by structuring the multilayer coating to provide a choice of "secret" effects.

2. 在以含氟雙疏性特性部分體處理之後，產生的表面是非 極性的，最小化外部顆粒及油污和處理玻璃表面之間的氫 (也就是凡得瓦爾）鍵。產生的表面有很低的表面能量和低 摩擦差係數。置放含_分體作為最錄膜献果和效能 對於抗反射塗膜和表面有好處，因為消除強光意味著任何 清晰可見的指印變的只是光學干擾來源可以被拭去。 3. 指印的雜通常是在乾燥或测的餅下，以布擦拭 表面來執行。這些布是可再用的，因此可能包含會刮傷表 面的塵土和顆粒。氟表面使指印的移除更為容易，而且可 最小化污痕和減少造成表面傷害事件的次數和頻 玻璃破裂的立即或早發性失敗。 ，導致 4.也可改善玻璃的抗雛。化學強化的高硬度和其高壓 f表面D0L(例如3G-8G_深)，可以避免損傷，以及因 二拭產生傷害所造摘纽。抗刮痕_量可使用半面以 試料塗膜，另—半面未塗膜的玻璃製品。執行到痕測 ，方式如上所述。錢在製品兩邊_舰域 細槪辑犧先線的 J量先予的清晰度。測試的結果顯示未塗膜破璃 22 200948734 /zfO. 25,而塗膜玻璃的βκ=0. 〇5,因此指出了由於雙疏性塗 層的關係，減少了 80%的動態摩擦。也測量動態摩擦係數 //κ。我們發現塗膜的面比未塗膜的面減少8〇%的摩擦。 藉由酸處理表面活性化： 在本發明更進一步的實施例中，化學強化玻璃的表面 在施加雙疏性塗膜前，先以酸處理活化表面。如前面描述的， 依據本發明，原始的抽拉玻璃利用比抽拉玻璃的陽離子還 ^ 大的陽離子，藉著離子交換到至少30 "m的深度以進行化學 強化。例如，抽拉玻璃的Na或Li離子可以K離子交換。這種 交換如以上所述會賦予玻璃壓縮強度。然而，化學強化玻 璃的表面含富鉀離子被認為會限制雙疏性塗膜共價鍵結的Si -OH活性表面部位，因而防止譬如（RF)2SiCi2或 (RF)3SiCl，或其他塗膜材料的雙疏性材料鍵結到玻璃表面。 我們也發現離子交換玻璃在施加雙疏性塗膜前，先執行酸處 理可加強雙疏性塗膜的黏著性，並增進玻璃的可濕性和可擦 我 械性。 ❹ 執行酸處理可使被化學交換到玻璃的離子可移除到選 定的深度，這種深度使化學強化玻璃的機械性效能（譬如強 度，抗刮痕，抗撞擊傷害，）不會受影響。例如，如這裡所說 明的執行Na或Li離子和K離子進行離子交換,使得交換可完 成到至少約2〇βιη的深度，最好是範圍30-8〇em的深度。執 行酸處理使得只有接近離子交換玻璃表面的K離子被移除， 一般是在<50nm的深度。 酸處理可移除交換離子(K離子交換主要玻璃内的Na及 23 200948734 /或Li離子）到範圍5-15nm的深度。例如，〇 3mm厚的玻璃以 ’ 运中利ST藤罕祚為Li 的離子沉浸一段足夠的時間後，執行離子交換到5〇#m的深 度，以K離子取代Na及/或Li離子。透過一邊的厚度觀看產 生的範例玻璃，有50nm離子交換層的厚度和2〇〇 無交換 層夾在兩個離子交換層之間。接著進行酸處理以使交換 的Κ離子移除到l〇nm的深度，這個深度不會影響玻璃的機械 办 性效此。在執行.酸處理後，透過其厚度從一面到另一面觀 看，有第一 0. Olem無K層，第一 49.9；izm K交換層，200//m無 交換中間層，第二49.9/zm K交換層，和第二〇.〇iem#K層 。或者，可以保護層覆蓋離子交換層的一邊，再進行酸處 理，使K離子只從一邊移除。在移除κ離子之後，移除κ離子 那邊以雙疏性材料塗覆，或是先以雙疏性材料塗覆再塗上抗反 ' 射塗膜。處理玻璃的酸通常是強酸，舉例但不作為限制，是 硫酸(腿)4)，氯化氫酸(HC1)，高氣酸(HCIOO,頌酸⑽〇3) ❹ 和此項技術已知的強酸。其他可使用的酸有磷酸(H3P(W， 醋酸(CHaCOOH)，和全氟醋酸(CFaCOOH)。 圖4是顯示以雙疏性材料塗膜玻璃表面的一般處理流程， 包括酸處理步驟，如果想要的話也可以檢查和測試雙疏性塗 層的完整性和持久性。一般而言，進行酸處理是使用〇. 3一 〇· 5莫耳硫酸溶液在室溫下（大約18_3〇〇c的範圍）放置 分鐘的時間。 表1顯示取自業界，以氟矽烷塗覆本公司 編號1317玻璃的執行效能資料，如這裡辨明的經過或未經 24 200948734 酸處理。以水和皮脂腺油（用來代替真正的指印油）來測得 接觸角m兩種的接觸角度在酸處理候是增況it但 是使用往復的磨損測試機器的負載，經過1〇,〇〇〇 次來回擦拭，我們發現塗膜的持久性並沒有受酸處理的影 響。經過酸處理或未經酸處理玻璃表面的持久性，塗上皮 脂腺油後，使用機械摩擦裝備，以1. 5psi和60Hz可承受 10000次摩擦擦拭。摩擦是使用木棉纖維。摩擦後，接觸角 . 度僅有些微或沒有改變。 ® 表1 預先塗覆數據 無酸處理 酸處理 初始模糊度(％) 0.00 0.00 初始接觸角 水=93.4 ± 1.3° 皮脂油=72.0 ±2.8。 水=109.2 ± 5.4。 皮脂油=81.2 ±0.9。 後-10K模糊度 0.00 0.00 後-10K接觸角(與水） 水=91.2 ± 1.7。 皮脂油=72.0 ±2.8。 - 水=104.6 ± 1.7。 劍旨油=80.4 ± 1,9〇 1.玻璃爲Coming編號1317商用玻璃塗覆氟矽烷 2_酸處理爲浸漬於在〜21。(：下0.367M H2S04 10分鐘 3.皮脂油亦稱爲指印油 圖5A顯示的是擦拭效能以減少模糊度，並因而增進塗 ® 層玻璃對未塗膜玻璃的光學清晰度。首先這兩種表面顯示 可忽視的模糊度(<0. 03%，未顯示出）。塗上指印油後(〇次 擦拭)，塗膜或未塗膜表面的模糊度差不多一樣(分別約為 " 3· 8%和4%)。然而，在擦拭後，塗膜玻璃比未塗膜玻璃顯示 快速的復原光學清晰度(減少模糊度）。在第6次擦拭後，塗 層玻璃顯示完全的復原（箭頭162顯示未測出模糊度)，而未 塗覆玻璃仍然顯示約為〇· 5%模糊度(箭頭160)。圖5B是圖 5A玻璃在經過第6次擦拭後的照片。玻璃藉著左邊的鉗子 25 200948734 (未編號）固定在背景上方。在圖5B中，編號160表示未塗膜 蘇著膜的面，以屬號版的嫌务痛每面。' 圖5C疋使用150粒度砂紙通過整個表面磨損玻璃的照片。 在圖5C中，編號16〇表示未塗膜面因砂紙的磨損，而塗膜的 面162則沒有顯示磨損而仍維持清晰。編號164顯示兩面的 分隔，而玻璃藉著左邊的鉗子（未編號）固定在背景上方。2. After partial treatment with a fluorine-containing double hydrophobic property, the resulting surface is non-polar, minimizing the hydrogen (ie, van der Waals) bond between the outer particles and the oil surface and the treated glass surface. The resulting surface has a very low surface energy and a low coefficient of friction. The inclusion of _separators as the most film-seeking fruit and performance is good for anti-reflective coatings and surfaces, because eliminating glare means that any clearly visible fingerprints can only be wiped off by sources of optical interference. 3. Fingerprints are usually carried out under a dry or measured cake and wiped with a cloth. These cloths are reusable and may contain dust and particles that can scratch the surface. The fluorine surface makes fingerprint removal easier, minimizes stains and reduces the number of surface damage events and immediate or early failure of the glass break. , resulting in 4. Can also improve the anti-feeding of the glass. The high hardness of the chemical strengthening and its high pressure f surface D0L (for example, 3G-8G_depth) can avoid damage and the damage caused by the second wipe. The anti-scratch _ amount can be half-faced with a sample coating, and the other half is an uncoated glass. Execute to the trace, as described above. The money is on both sides of the product _ the ship's fineness. The results of the test showed that uncoated glass 22 200948734 /zfO. 25, while the coated glass had a βκ=0. 〇5, thus indicating that the dynamic friction was reduced by 80% due to the relationship of the double-disseminated coating. The dynamic friction coefficient //κ is also measured. We found that the surface of the film was reduced by 8% compared to the uncoated side. Surface activation by acid treatment: In a further embodiment of the invention, the surface of the chemically strengthened glass is first treated with an acid to activate the surface prior to application of the amphiphobic film. As previously described, in accordance with the present invention, the original drawn glass utilizes a cation that is larger than the cation of the drawn glass, by ion exchange to a depth of at least 30 " m for chemical strengthening. For example, the Na or Li ions of the drawn glass can be exchanged for K ions. This exchange imparts compressive strength to the glass as described above. However, the surface of the chemically strengthened glass containing potassium-rich ions is believed to limit the Si-OH active surface sites covalently bonded to the double-phobic coating, thus preventing (RF) 2SiCi2 or (RF) 3SiCl, or other coating materials. The double hydrophobic material is bonded to the glass surface. We have also found that the acid treatment of the ion-exchanged glass prior to the application of the double-repellent coating enhances the adhesion of the double-repellent coating and enhances the wettability and erasability of the glass. ❹ Performing an acid treatment removes ions that are chemically exchanged into the glass to a selected depth that does not affect the mechanical properties of the chemically strengthened glass (such as strength, scratch resistance, and impact damage). For example, performing ion exchange of Na or Li ions and K ions as described herein allows the exchange to be completed to a depth of at least about 2 〇 βιη, preferably a depth ranging from 30 to 8 〇em. The acid treatment is performed such that only K ions near the surface of the ion exchange glass are removed, typically at a depth of < 50 nm. The acid treatment removes the exchanged ions (Na and 23 200948734 / or Li ions in the main ion glass of K ion exchange) to a depth in the range of 5-15 nm. For example, 〇 3 mm thick glass is immersed in ions of 运 利 ST 藤 祚 for a sufficient period of time to perform ion exchange to a depth of 5 〇 #m, replacing Na and/or Li ions with K ions. The sample glass produced was observed through the thickness of one side, with a thickness of 50 nm ion exchange layer and a 2 〇〇 non-exchange layer sandwiched between the two ion exchange layers. An acid treatment is then carried out to remove the exchanged cerium ions to a depth of l 〇 nm, which does not affect the mechanical properties of the glass. After performing the acid treatment, the first 0. Olem has no K layer, the first 49.9; the izm K exchange layer, the 200//m non-exchange intermediate layer, the second 49.9/zm through its thickness from one side to the other side. K exchange layer, and second 〇.〇iem#K layer. Alternatively, the protective layer may cover one side of the ion exchange layer and then acid treated to remove the K ions from only one side. After the κ ions are removed, the κ ions are removed and coated with a double-phobic material, or coated with a double-phobic material and then coated with an anti-reflective coating. The acid which treats the glass is usually a strong acid, exemplified by, but not limited to, sulfuric acid (leg) 4), hydrogen chloride acid (HC1), high gas acid (HCIOO, decanoic acid (10) 〇 3) ❹ and a strong acid known in the art. Other acids that can be used are phosphoric acid (H3P (W, acetic acid (CHaCOOH), and perfluoroacetic acid (CFaCOOH). Figure 4 is a general treatment process showing the surface of a glass coated with a double-phobic material, including an acid treatment step, if desired If necessary, the integrity and durability of the double-repellent coating can also be checked and tested. In general, the acid treatment is carried out using a 〇.3 〇·5 molar sulfuric acid solution at room temperature (approximately 18_3〇〇c Scope) Placement of minutes. Table 1 shows the performance data of the company's No. 1317 glass coated with fluorohalane from the industry, as identified here with or without acid treatment of 24 200948734. Water and sebaceous gland oil (used Instead of the real fingerprint oil), the contact angles of the contact angles m are measured. In the acid treatment, the load is increased. However, the load of the reciprocating wear test machine is used. After 1 〇, rubbing back and forth, we find the coating film. Persistence is not affected by acid treatment. The surface of the acid treated or untreated glass surface is coated with sebaceous gland oil and mechanical friction equipment is used. It can withstand 10,000 rubs at 1.5 psi and 60 Hz. Wipe. The friction is the use of kapok fiber. After rubbing, the contact angle is only slightly or not changed. ® Table 1 Pre-coating data Acid-free treatment Acid treatment Initial ambiguity (%) 0.00 0.00 Initial contact angle water = 93.4 ± 1.3 ° Sebum oil = 72.0 ± 2.8. Water = 109.2 ± 5.4 Sebum oil = 81.2 ± 0.9. After -10K ambiguity 0.00 0.00 After -10K contact angle (with water) Water = 91.2 ± 1.7 Sebum oil = 72.0 ± 2.8. - Water = 104.6 ± 1.7. Sword oil = 80.4 ± 1,9 〇 1. Glass for Coming No. 1317 Commercial glass coated fluorodecane 2 - acid treated to be immersed in ~ 21. (: 0.367M H2S04 10 minutes 3 Sebum oil, also known as fingerprint oil Figure 5A shows the wiping performance to reduce blur and thus enhance the optical clarity of the coated glass to uncoated glass. First, the two surfaces show negligible ambiguity (< 0. 03%, not shown. After applying the fingerprint oil (wipe wipe), the ambiguity of the coated or uncoated surface is about the same (about 3.8% and 4%, respectively). After wiping, the coated glass shows a faster recovery optical clarity than the uncoated glass (reduced mode) Degree) After the 6th wipe, the coated glass showed complete recovery (arrow 162 shows no ambiguity), while uncoated glass still showed approximately 〇·5% ambiguity (arrow 160). Figure 5B It is a photograph of the glass of Fig. 5A after the sixth wiping. The glass is fixed on the background by the pliers 25 200948734 (not numbered) on the left side. In Fig. 5B, reference numeral 160 denotes a surface on which the film is not coated, and the face of the genus is painful on each side. Figure 5C is a photograph of a worn glass passing through the entire surface using 150 grit sandpaper. In Fig. 5C, the numeral 16A indicates that the uncoated surface is worn by the sandpaper, and the surface 162 of the coating film does not show wear and remains clear. Reference numeral 164 shows the separation on both sides, and the glass is fixed above the background by the left pliers (unnumbered).

圖6顯示使用塗膜玻璃或未塗膜玻璃，以ι5〇粒度砂紙 磨損所產生的模糊度（清晰度的損耗）。一半的玻璃試樣塗 上雙疏性材料塗膜，並且50/50固化（50/50=5(rc加上5〇%溼 氣兩小時，然後清洗以移除未結合的塗膜)，而另一半則未 塗覆。接著磨損整個試樣的塗覆或未塗覆表面。資料分別 顯示未塗覆表面約為9· 8%模糊度，而塗覆表面約為1.76%模 糊度。因而表示塗覆可比未塗覆的表面減少75%因刮痕傷 害而產生的模糊度。圖6偶數編號210-226的意義如表格3 所示。 ❹ 表3 物質 接觸角 —-丨丨 _______ 滑動角 水 十六院， 115° 9° 65° 1。 皮脂油 73° ----- 3° 二，7顯示塗膜和未塗膜表面的動態摩擦係數/a。摩擦 ，試疋使用平板上的球和藍寶^球滑動接觸，觀的速度 是20mm/s’以〇. 2到15· 4克漸增的負載經過2. 〇麵距離。 料顯不使用塗齡比未麵玻璃〉6賴減少…Figure 6 shows the blur (loss of sharpness) produced by the abrasion of the ι5〇 grain sandpaper using coated or uncoated glass. Half of the glass samples were coated with a double-strength material and cured at 50/50 (50/50=5 (rc plus 5〇% moisture for two hours, then washed to remove unbound film), and The other half was uncoated. The coated or uncoated surface of the entire sample was then worn. The data showed an uncoated surface of about 9.8% ambiguity, respectively, while the coated surface was about 1.76% ambiguity. The coating can reduce the ambiguity caused by scratch damage by 75% compared to the uncoated surface. The meaning of the even number 210-226 in Figure 6 is shown in Table 3. ❹ Table 3 Material Contact Angle—丨丨_______ Sliding Angle Water Sixteen, 115° 9° 65° 1. Sebum oil 73° ----- 3° 2, 7 shows the dynamic friction coefficient of the coated and uncoated surfaces / a. Friction, test using the plate The ball and the sapphire ^ ball slide contact, the speed of the view is 20mm / s ' 〇. 2 to 15 · 4 grams of increasing load after 2. 〇 surface distance. The material is not used to paint the age than the surface of the glass > 6 Lai cut back…

圖8的圖表是—半赠處理，另-半未經酸處理玻璃試 26 200948734 樣的圖表。在酸處理後，沖洗玻璃並以電漿處理，接著以雙 疏材料塗膜《Γ表面，在塗膜1Γ化⑽T5(TIRtJ17iTX指 印油處理。在第〇次擦拭的資料顯示未塗膜和塗膜表面的 模糊度分別是17%和14%。一次擦拭分別減少未塗膜和塗膜 表面的模糊度約為1· 3%和1%。兩次擦拭減少未塗膜表面的 模糊度約為0.2%，而塗膜表面是〇%。這些結果顯示在以雙 疏性材料塗膜之前先以酸處理，可大幅改善擦拭效能，我們 相彳s這種改善是由於雙疏性塗膜增加了到玻璃表面的黏著 ® 性。The chart in Figure 8 is a semi-baked, another-semi-untreated glass test 26 200948734. After the acid treatment, the glass was rinsed and treated with a plasma, and then the film was coated with a double-sparse material, and the surface of the coating was applied to the coating film (10) T5 (TIRtJ17iTX fingerprint printing oil treatment. The data of the second cleaning showed uncoated film and coating film. The ambiguity of the surface was 17% and 14%, respectively. One wipe reduced the opacity of the uncoated and coated surfaces by about 3% and 1%, respectively. The two wipes reduced the ambiguity of the uncoated surface by about 0.2. %, and the surface of the coating film is 〇%. These results show that the acid treatment before the coating of the double-phobic material can greatly improve the wiping performance, and our improvement is due to the increase of the double-repellent coating film. Adhesion® properties on the glass surface.

這裡描述的塗膜蓋板有一個流體物質置放其上小於 10度的滑動角度。表2顯示如這裡描迷的全氟碳化物玻璃 表面’針對水，十六烧，和皮脂油的接觸角度和滑動角度。 接觸角度在115度和65度之間變化，依據材質而定^滑動 角度安排在1度和9度之間，依據材質而定。The film cover described herein has a fluid material that is placed at a sliding angle of less than 10 degrees. Table 2 shows the contact angle and sliding angle of the perfluorocarbon glass surface as described herein for water, hexagram, and sebum oil. The contact angle varies between 115 and 65 degrees, depending on the material. The sliding angle is between 1 and 9 degrees, depending on the material.

機器加工或其他修飾零件 212 利用高pH清潔劑超音波清理零件Machined or other modified parts 212 Ultrasonic cleaning parts with high pH cleaner

利用氟碳化物塗膜Utilizing fluorocarbon coating

27 200948734 背侧保護： 間也提供本發明玻璃製品背面（或裝置元件面）的保護。背 面保護是確保如這裡所描述具有雙疏性，化學強化的玻璃 蓋板面的另一面不會被使用者接觸到。既然玻璃背面不會 被接觸到，但鄰近蓋板玻璃使用的元件，因而不需要塗膜。 * 背面保護可藉著使用"膠帶或薄膜"或是塗覆到玻璃的，，紙/ 無黏性薄膜"。"膠帶或薄膜"的處理是使用薄片材料，在雙 疏性塗膜處理期間可避免溶解，而且在醇類（曱醇，乙醇，異 丙醇等）或酿I類（丙嗣，曱基乙基丙酮和類似的丙酮溶劑）中 是可移除的。丙烯酸黏性薄片是範例的材料，可用來作為 薄膜，並用來在浸泡或熱蒸發技術期間保護一個面，可以抗 雙疏塗膜，但這種黏性層是可溶於丙酮的。 聚酿亞胺，聚酯，聚乙稀和聚乙烯對萃二曱酸酯(ΡΕτ) 都是膠帶/薄膜背面材料的範例中可以和丙烯酸黏劑或改 & 善的丙烯酸黏劑耦合塗覆到玻璃背面。膠帶/薄膜在一面 上有粘性，可在施加雙疏性塗膜到玻璃製品的正面或使用 面之後，將膠帶移除。膠帶/薄膜最好是玎以印模切割並使 用疊合機在玻璃表面製成薄板。在背面保護玻璃製品塗覆 雙疏性塗膜之後，就可剝下膠帶。在移除膠帶後就可使用 適當的溶劑移除黏膠殘渣，而且不會影響到雙疏性塗膜。 一般而言，塗膜是不溶於和移除黏膠殘渣相同溶劑的。 也可使用紙/無黏性薄臈作為背面保護。例如，可在將 零件浸泡在包含雙疏性塗膜的池中之前，在兩個製品間壓 28 200948734 進乾或溼的紙。使用紙作為背面保護時較佳的方式是先 放紙(最好是以不包含雙疏性材料的液體浸濕)在表面上， 再放玻璃製品在紙的頂端。然後施加乾淨的或在溶劑中的 雙疏性塗膜到製品的暴露表面。使用濕紙可防止雙疏性塗 層在玻璃和紙之間通過。 本發明也提供包含至少—部分蓋缺翻的移動式電 子裝置。這種移動式電子裝置包括，但不限制是移動式傳 Q 輸裝置，譬如個人資料秘書，手機，傳呼器，手錶，收音機，膝 上型或筆記型電腦等。如這裡使用的，"蓋板"是指覆蓋顯 示器的玻璃片或視窗至少一部分的蓋板是透明的，好讓使 用者可看到顯示畫面。蓋板可以抗震動，破裂刮痕，而且 在具有絲面強度’硬度，和抗刮€子裝置的應帛上是很需 要的。在一項實施例中，蓋板是觸摸感控的。圖丨顯示的是 手機蓋板的侧面示意圖。手機的蓋板1〇〇包含這裡描述的& 向下抽拉鹼金屬鋁矽酸鹽玻璃和化學強化玻璃。手機的蓋 ❹板100可用作顯示視窗，而且是抗刮痕的。蓋板1〇〇是由任 何這裡描述的玻璃所形成。玻璃片是向下抽拉然後切割 - 成蓋板所需的形狀和大小。在一項實施例中，玻璃片是如 這裡描述藉由離子交換強化的。在一項實施例令，切割的 玻璃片和蓋板厚度範圍是從約〇· 3mm到約3mra。在另一實施 例中，玻璃片和蓋板的厚度範圍是從約〇. 3臟到約h 5mm。27 200948734 Backside protection: The back side of the glassware of the invention (or the surface of the device component) is also protected. The backside protection is to ensure that the other side of the chemically strengthened glass cover surface as described herein is not accessible to the user. Since the back side of the glass is not touched, it is adjacent to the components used in the cover glass, so no film is required. * Back protection can be achieved by using "tape or film" or coated to glass, paper/non-adhesive film". "tape or film" is treated with a sheet material that avoids dissolution during the treatment of the double-disseminated film, and is in the form of alcohols (sterols, ethanol, isopropanol, etc.) or in the class I (B, 嗣, 曱Removable in ethyl ethyl acetonate and similar acetone solvents). Acrylic adhesive sheets are exemplary materials that can be used as a film and are used to protect a face during soaking or thermal evaporation techniques. They are resistant to double-coating films, but the adhesive layer is soluble in acetone. Polyaniline, polyester, polyethylene and polyethylene are the two examples of tape/film backing materials that can be coupled with acrylic adhesives or modified acrylic adhesives. To the back of the glass. The tape/film is tacky on one side and can be removed after application of the double hydrophobic coating to the front side or side of the glass article. Preferably, the tape/film is cut by a die and a laminate is used to form a sheet on the surface of the glass. After the back protective glass article is coated with the double-repellent coating, the tape can be peeled off. After removing the tape, the appropriate solvent can be used to remove the adhesive residue without affecting the double-repellent coating. In general, the coating film is insoluble in and removes the same solvent as the adhesive residue. Paper/non-adhesive tweezers can also be used as back protection. For example, dry or wet paper may be applied between two articles before immersing the part in a cell containing a double-disseminated film. The preferred way to use paper as the backside protection is to first release the paper (preferably wetted with a liquid that does not contain a double hydrophobic material) on the surface and then place the glass article on top of the paper. A clean or double hydrophobic coating in the solvent is then applied to the exposed surface of the article. The use of wet paper prevents the double hydrophobic coating from passing between the glass and the paper. The present invention also provides a mobile electronic device that includes at least a portion of the cover that is missing. Such mobile electronic devices include, but are not limited to, mobile Q-transmission devices such as personal data secretary, cell phones, pagers, watches, radios, knee-top or notebook computers. As used herein, "cover" means that the cover of at least a portion of the glass or window covering the display is transparent so that the user can see the display. The cover plate is resistant to vibration, rupture scratches, and is highly desirable in terms of the strength of the matte strength and the resistance of the device. In one embodiment, the cover is touch sensitive. Figure 丨 shows the side view of the phone cover. The cover plate 1 of the mobile phone contains the & draw down alkali metal aluminosilicate glass and chemically strengthened glass as described herein. The cover of the mobile phone 100 can be used as a display window and is scratch resistant. The cover 1 is formed from any of the glasses described herein. The glass piece is pulled down and then cut - into the desired shape and size of the cover. In one embodiment, the glass flakes are strengthened by ion exchange as described herein. In one embodiment, the cut glass sheets and cover sheets range in thickness from about 〇 3 mm to about 3 mra. In another embodiment, the thickness of the glass sheet and cover sheet ranges from about 0.3 to about 5 mm.

然後蓋板是以粘膠或其他此項技術已知的方法來連結移動 式電子裝置的主體。 W 本發明也提供裝置的蓋板，譬如但不作限制是以上描 29 200948734 述的移動^電子裝置，以及非電子式手錶等等。蓋板是由 任荷道裡以上福述葯疲璃所形成hm 在本發明各種實施例的玻璃也可用在非手握裝置，譬如自 動收銀機，和互動觸摸軟體所用的電腦顯示銀幕。 雖然典型的實施例是用來作為說明的目的，但先前的 描述不應該視為是本發明範嘴的限制。據此，熟悉此項都 '可進行各種修改，調整或選擇，只要不違背本發明的範脅 0 和精神。 【圖式簡單說明】 圖1為依據驗金屬鋁矽酸鹽玻璃物品一項實施例之示 及顯示出物品，其中-層雙疏性全氟碳化物或含有 全氣碳化物基元共價地鍵結至化學強化玻璃之表面。 圖2為依據第二實施例化學強化驗金屬鋁矽酸鹽玻璃 物。口以及顯示出物品其中存在紋理或圖案化表面以及雙 疏性層共價地鍵結至包含紋理面積化學強化玻璃的表面。 泛圖3為依據本發明額外實施例鹼金屬鋁矽酸鹽玻璃以 及顯不出物品，其中至少一層抗反射性材料位於化學強化 _ 及-層雙疏性塗膜層共價地鍵結至抗反射塗膜 的表面。 圖4為示意圖，其顯示出一般處理流程以塗覆雙疏性塗膜 處理破璃表面。 、 圖5A顯不出掃除效能以減少模糊度以及因而改善塗膜 玻璃與非塗膜破續之光學清澈。 圖5β顯示出在指印油已塗覆及擦淨後圖5A中所表示之 30 200948734 覆蓋玻璃，左侧為未塗覆以及右側為塗覆。 圖顧无岀在;利用5矿粒度砂戴研磨以及擦淨後覆蓋 玻璃，左侧為未塗覆以及右侧為塗覆。 圖6顯示出用塗覆玻璃以及未塗覆玻璃藉由15〇粒度 砂紙研磨產生之模糊度。 圖7顯示出塗膜及無塗膜玻璃表面動磨擦业效果。 - 圖8為條狀圖，其顯示出玻璃試樣一半利用酸處理一半 未用酸處理之結果，兩者均塗覆雙疏性塗膜。 Ό 【主要元件符號說明】 玻璃製品（手機蓋板）謂；雙疏性氣主要表面層 1〇2;表面壓縮應力層1G4;中間層1G6;紋理或圖樣表 面108;抗反射塗膜no。 31The cover is then joined to the body of the mobile electronic device by glue or other means known in the art. W The present invention also provides a cover for the device, such as, but not limited to, the mobile electronic device described above, and the non-electronic wristwatch and the like. The cover is formed by any of the above-described smudges of the above-mentioned remedies. The glass of various embodiments of the present invention can also be used in non-hand grip devices such as automatic cash registers, and computer display screens for interactive touch software. While the exemplary embodiments are intended to be illustrative, the foregoing description should not be considered as limiting. Accordingly, the familiarity with this item can be variously modified, adjusted or selected as long as it does not violate the scope and spirit of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram showing and showing an article according to an embodiment of a metal aluminosilicate glass article in which a layer of bismuth perfluorocarbon or a gas-containing carbide element is covalently Bonded to the surface of the chemically strengthened glass. Fig. 2 is a view showing a chemically strengthened metal aluminosilicate glass according to a second embodiment. The mouth and the article are shown to have a textured or patterned surface and the amphiphilic layer is covalently bonded to the surface comprising the textured area chemically strengthened glass. FIG. 3 is an illustration of an alkali metal aluminosilicate glass according to an additional embodiment of the present invention, wherein at least one antireflective material is covalently bonded to the chemically strengthened _ and - layer double hydrophobic coating layer. Reflect the surface of the film. Figure 4 is a schematic diagram showing the general treatment procedure for treating a broken glass surface with a double hydrophobic coating. Figure 5A shows the sweeping performance to reduce blur and thus improve the optical clarity of the coated glass and non-coated film. Figure 5β shows the 30 200948734 cover glass shown in Figure 5A after the fingerprint oil has been applied and wiped, with the left side uncoated and the right side coated. The picture is innocent; the surface is covered with a 5 grit sand and rubbed, and the left side is uncoated and the right side is coated. Figure 6 shows the ambiguity produced by grinding with 15 Å grit sandpaper using coated glass and uncoated glass. Figure 7 shows the effect of the dynamic rubbing of the coated film and the uncoated glass surface. - Figure 8 is a bar graph showing the results of half of the glass sample treated with acid and half of the unused acid, both coated with a double-repellent coating. Ό [Main component symbol description] Glass product (mobile phone cover); double sparse gas main surface layer 1〇2; surface compressive stress layer 1G4; intermediate layer 1G6; texture or pattern surface 108; anti-reflective coating film no. 31

Claims (1)

200948734 七、申請專利範圍： 1. 一種驗奎屬鋁矽酸鹽玻璃製品，包含長度寬度和厚度至 少為0· 3mm的主要鹼金屬鋁矽酸鹽玻璃，表面壓應力至少為 200MPa，表面壓力層的深度大約2〇_8〇jtzm，和具有雙疏性氟 主要表面層化學地黏接到玻璃製品表面以形成含塗膜玻璃 製品，以及 - 其中流體物質放置於其上面時，此含塗膜玻璃製品的滑 動角度為小於10度。 0 , 2. 依據申請專利範圍第丨項之鹼金屬鋁矽酸鹽玻璃製品其 中黏接氟為主表面層選自於下列群組： (1) 矽石-0Η基終端的活性表面部位其與氟為主單體交 換； (2) 氟終端分子鍵的組合單層； • (3)薄的氟聚合物塗膜； (4) 一身又为子式為(RF)nSiX4ii之發化合物，其中即為全 ❹氟碳化物基元，X選自於包含雜以及絲，n為卜3範 圍之整數；以及 (5) 具有先前導出或處理之矽石粉塵顆粒以得到氟铢端 基。 、、 3. 依據申請專利範圍第1項之鹼金屬鋁矽酸鹽破璃製品，其 中玻璃物品更進一步包含紋理或圖案化表面層於主要玻璃、 以及雙疏性氟為主表面層之間，該雙疏性氟為主表面層黏 接至紋理或圖案化表面層以及任何無紋理或無圖案化主要 玻璃表面；以及 32 200948734 其中，紋理表面具有粗糙度在5〇nm至5微米範圍内。 4. 依請專利範圍第1項之鹼金屬鋁矽酸鹽玻ϋ品，其 中壓應力至少為600MPa，表面壓力層深度至少為40微米，以 及厚度在0. 7mm至1.1mm範圍内。 5. 依據申請專利範圍第1項之鹼金屬鋁矽酸鹽玻璃製品，其 中玻璃以莫耳百分比表示包含： 64%^Si〇2^68%; 12%^Na2〇^16%; 8%^Al2〇3^12%; 0%^Β2〇3^3ο/〇; 20/0^Κ20^5°/0； 4%SMgOS6%;以及 0°/〇^CaO^5%, 其中 66%^ Si〇2+B2〇3+CaO ^69%; Na2〇+K2〇+B2〇3+MgO+CaO+SrO> 10%; 5%^Mg0+Ca0+Sr0^8%; (Na2〇+B2〇3) ^ Al2〇3^2%; 20/〇SNa2〇-Al2〇66%;以及 4%S(Na2〇+K2〇)gAh〇3S10%，以及 其中玻璃液相線黏滯係數至少為130千泊。 6. 依據申請專利範圍第1項之鹼金屬鋁矽酸鹽玻璃製品，其 中玻璃具有抗反射塗膜在其上面以及抗反射塗膜選自於包 含石夕石，熔融碎石，掺雜F熔融夕石，Hf〇2, Ti〇2, Zr〇2, Y2〇3， 33 200948734 以及Gd2〇3之群組。 7· —種亩驗查屬鋁矽酸鹽玻璃所構成之鹼金屬鋁矽酸鹽破 璃物品，其具有長度，寬度以及厚度至少為0. 3mm，表面壓應 力至少為200MPa，表面壓力層深度在20-70微米範圍内，以 及具有雙疏性氟為主表面層化學性地黏接至玻璃物品之表 面； 其中玻璃表面使用酸處理至深度<50nm於塗覆氟為主表 Q 面層至玻璃表面之前；以及 其中在塗覆氟為主表面層後，由水，十六烧，和皮脂油的 群組選取出流體之滑動角度為小於10度。 8.依據申請專利範圍第7項之鹼金屬鋁矽酸鹽玻璃物品其 中黏接氟為主表面層主要為分子式⑽)nSiX“之化合物， 其中RF為G-G2烷基全氟碳化物，n為1_3範圍之整數；以及 X為可水解基，其與玻璃終端〇H基交換，以及氟為主表面層 厚度在l-l〇nm範圍内。 © 9.依據申請專利範圍第7項之鹼金屬鋁矽酸鹽玻璃物品，其 中X選自於包含異於氟之自素或烧氧機之群組，其" ' 為I-6個碳原子線性或分支之碳氫化合物。 10. 依據申請專利範圍第7項之鹼金屬鋁矽酸鹽玻璃物品其 中壓應力至少為600MPa，在處理之前表面壓力層深度至少為 40微米，以及玻璃物品之厚度在〇· 7刪至1· 1咖範圍内。 11. 依據申請專利範圍第7項之驗金屬鋁矽酸鹽玻璃物品其 中玻璃包含： 64%^Si〇2^68%; 34 200948734 12°/〇^Na2〇^16%; '8%ΊΑΐ2〇3^ΐ2%;~........... 一一— —------------- 0%^Β2〇3^3%; 2%^Κ2〇^5%; 4%SMg0S6%;以及 0%^Ca0^5%, - 其中 66%^ Si〇2+B2〇3+CaO ^69%; ® Na2〇+K2〇+B2〇3+MgO+CaO+SrO> 10°/〇; 5%^Mg0+Ca0+Sr0^8%; (Na2〇+B2〇3 ) ^ A12〇3 ^ 2%; 2% S Na2〇-A 12〇3 S 6%;以及 (Na2〇+K2〇) SAl2〇3$ 10%，以及 其中玻璃液相線黏滯係數至少為130千泊。 12. —種鹼金屬鋁矽酸鹽玻璃物品，該物品包含 @ 玻璃基板，其具有長度，寬度以及厚度至少為0. 3mm，表面 壓應力至少為200MPa，表面壓力層具有深度正數值在20-70 微米之間； 抗反射塗膜在玻璃一個表面上；以及 雙疏性氟為主表面層化學性地黏接至抗反射塗膜之表面； 其中玻璃包含： 64%^Si〇2^68%; 12%^Na2〇^16%; 8%^Al2〇3^12%; 35 200948734 0%^B2〇3^3%; 4%SMg0$6%;以及 0%^Ca0^5°/〇, 其中 66%^ Si〇2+B2〇3+CaO ^69%; Na2〇+K2〇+B2〇3+MgO+CaO+SrO> 10%; 5°/〇^MgO+CaO+Sr0^8%; (Na2〇+B2〇3 ) ^ A12〇3 ^ 2%; 2%SNa2〇-A12(X6%;以及 4%S(Na2〇+K2〇)SAl2〇3S10%，以及 其中玻璃液相線黏滯係數至少為130千泊。 13·依據申請專利簏圍第12項之鹼金屬鋁矽酸鹽玻璃物品 其中抗反射塗膜選自於包含矽石，熔融石夕石，摻雜F之熔融 矽石以及MgF2之群組；以及 其中抗反射塗膜之厚度在10—60微米範圍内。 14. 依據申請專利範圍第12項之鹼金屬鋁矽酸鹽玻璃物品， 其中抗反射塗膜選自於包含Hf〇2, Zr〇2,桃以及Gd2〇3之 群組，以及抗反射塗膜之厚度在1〇_6〇微米範圍内。 15. 依據申請專利範圍第12項之鹼金屬鋁矽酸鹽玻璃物品， 其中黏接氟為主表面層主要分子式為(RF)nSiX4_n：^化合 物，其中RF為G-C22烷基全氟碳化物，η為1-3範圍之整數; 以及X為可水解基，其能夠與玻璃終端〇Η基交換。 16. 依據申請專利範圍第12項之驗金屬鋁矽酸鹽玻璃物品， 36 200948734 其中X選自於包含異於氟之鹵素及烷氧機(一〇R)之群組，其 申R爲1-6插碳原芋線性或分支之被氫化奋场。—— 17. 依據申睛專利範圍第12項之驗金屬紹珍酸鹽玻璃製品 其中壓應力至少為600MPa，表面壓力層深度至少為微米 以及厚度在〇. 7mm至1. linm範圍内。 18. —種製造含塗膜鹼金屬鋁矽酸鹽玻璃物品之方法，該玻 , 璃物品具有抗指邱以及抗污痕特性，該方法包含下列步驟： m &供具有長度，寬度以及厚度之驗金屬銘梦酸鹽玻璃基 板； 化學性地強化玻璃基板之表面至深度在2〇_8〇微米範圍 内； ， 機械加工或修飾玻璃表面； 超音波地清理玻璃表面； 附加上，使用強酸溶液酸洗玻璃之至少一個表面. 使用〇2等離子清洗玻璃之至少一個表面； ❹ _雙級塗難錢理之朗表喊抗反絲面. 在經選擇溫度以及經選擇濕度下固化疏性塗膜歷時經選 擇之時間；以及 檢視含塗膜鹼金屬鋁矽酸鹽玻璃物品。 19. 依據申請專利範圍第18項之方法，其中利用抗反射塗膜 塗覆玻璃係指抗反射塗膜材料選自於包含梦石，溶融石夕石以 及摻雜F之熔融矽石的群組。 2〇·依據申請專利範圍第18項之方法其中利用抗反射塗膜 塗覆玻璃係指抗反射塗膜材料選自於包含眺，Zr〇2, γ晶 37 200948734 以及Gd2〇3之群組。 21:WTO^範娜调线良其中麵酿麵塗 覆玻璃係指疏性塗膜分子式為⑽乂犯“，其中RF為 c22烧基全氟碳化物，n為卜3範圍之整數;以及χ為可水解基 ，其能夠與玻璃終端0Η基交換；以及 其中X選自於群組包含異於氟之齒素或烧氧機(_〇R)，其 . 中R為丨-6個碳原子線性或分支之碳氫化合物。 0 〇 38200948734 VII. Scope of application: 1. A quinonic aluminosilicate glass product comprising a major alkali metal aluminosilicate glass having a length and a thickness of at least 0.3 mm, a surface compressive stress of at least 200 MPa, and a surface pressure layer. a depth of about 2 〇 〇 8 〇 jtzm, and a primary surface layer having a double hydrophobic fluorine chemically bonded to the surface of the glazing to form a coated glass article, and - wherein the fluid material is placed thereon, the coating film The sliding angle of the glass article is less than 10 degrees. 0, 2. The alkali metal aluminosilicate glass product according to the scope of the patent application section wherein the fluorine-based surface layer is selected from the group consisting of: (1) the active surface portion of the vermiculite-methyl group terminal Fluorine-based monomer exchange; (2) a combination of fluorine-terminated molecular bonds; (3) a thin fluoropolymer coating; (4) a compound of the formula (RF)nSiX4ii, which is As a ruthenium fluorocarbonate element, X is selected from the group consisting of hetero and silk, n is an integer in the range of 3; and (5) has previously derived or treated vermiculite dust particles to give a fluorene end group. 3. The alkali metal aluminosilicate glass-breaking article according to item 1 of the patent application scope, wherein the glass article further comprises a textured or patterned surface layer between the main glass and the double-phobic fluorine-based surface layer, The double hydrophobic fluorine-based surface layer is bonded to the textured or patterned surface layer and any untextured or unpatterned primary glass surface; and 32 200948734 wherein the textured surface has a roughness in the range of 5 Å to 5 microns. The range of the surface pressure layer is at least 40 μm, and the thickness is in the range of 0.7 mm to 1.1 mm, and the thickness of the surface pressure layer is at least 40 μm. 5. The alkali metal aluminosilicate glass article according to item 1 of the patent application scope, wherein the glass is expressed in terms of percentage of moles: 64%^Si〇2^68%; 12%^Na2〇^16%; 8%^ Al2〇3^12%; 0%^Β2〇3^3ο/〇; 20/0^Κ20^5°/0; 4%SMgOS6%; and 0°/〇^CaO^5%, of which 66%^ Si 〇2+B2〇3+CaO ^69%; Na2〇+K2〇+B2〇3+MgO+CaO+SrO>10%;5%^Mg0+Ca0+Sr0^8%; (Na2〇+B2〇3 ) ^ Al2〇3^2%; 20/〇SNa2〇-Al2〇66%; and 4%S(Na2〇+K2〇)gAh〇3S10%, and wherein the glass liquidus viscosity coefficient is at least 130 kbo . 6. The alkali metal aluminosilicate glass article according to claim 1, wherein the glass has an antireflection coating film thereon and the antireflection coating film is selected from the group consisting of a stone stone, a molten gravel, and a doped F melt. Xi Shi, Hf〇2, Ti〇2, Zr〇2, Y2〇3, 33 200948734 and Gd2〇3 group. 7 毫米 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 In the range of 20-70 microns, and with a double-phobic fluorine-based surface layer chemically bonded to the surface of the glass article; wherein the glass surface is treated with acid to a depth of <50 nm in the coated fluorine-based surface Q-layer Before the surface of the glass; and after coating the fluorine-based surface layer, the sliding angle of the fluid is selected to be less than 10 degrees from the group of water, hexagram, and sebum oil. 8. The alkali metal aluminosilicate glass article according to the scope of claim 7 wherein the fluorine-based surface layer is mainly a compound of the formula (10)) nSiX, wherein RF is a G-G2 alkyl perfluorocarbon, n An integer of the range 1_3; and X is a hydrolyzable group which is exchanged with a glass terminal 〇H group, and a fluorine-based surface layer thickness is in the range of 11 〇 nm. © 9. Alkali metal aluminum according to claim 7 a bismuth silicate glass article, wherein X is selected from the group consisting of a fluorine-free auto- or oxygen-burning machine, and the " 'is a linear or branched hydrocarbon of 1 to 6 carbon atoms. The alkali metal aluminosilicate glass article of item 7 has a compressive stress of at least 600 MPa, a surface pressure layer depth of at least 40 μm before treatment, and a thickness of the glass article in the range of 〇·7 to 1.1. 11. According to the scope of the patent application, the metal aluminosilicate glass article comprises: 64%^Si〇2^68%; 34 200948734 12°/〇^Na2〇^16%; '8%ΊΑΐ2〇 3^ΐ2%;~........... One-one--------------- 0%^Β2〇3^3%; 2%^Κ2〇^ 5 %; 4%SMg0S6%; and 0%^Ca0^5%, - where 66%^ Si〇2+B2〇3+CaO ^69%; ® Na2〇+K2〇+B2〇3+MgO+CaO+SrO&gt 10°/〇; 5%^Mg0+Ca0+Sr0^8%; (Na2〇+B2〇3) ^ A12〇3 ^ 2%; 2% S Na2〇-A 12〇3 S 6%; Na2〇+K2〇) SAl2〇3$ 10%, and wherein the glass liquidus viscosity coefficient is at least 130 kP. 12. Alkaloid metal aluminosilicate glass article, the article comprises @玻璃 substrate, which has The length, the width and the thickness are at least 0.3 mm, the surface compressive stress is at least 200 MPa, the surface pressure layer has a positive depth value of between 20 and 70 μm; the antireflective coating film is on one surface of the glass; and the double hydrophobic fluorine is dominant The surface layer is chemically bonded to the surface of the anti-reflective coating film; wherein the glass comprises: 64%^Si〇2^68%; 12%^Na2〇^16%; 8%^Al2〇3^12%; 35 200948734 0%^B2〇3^3%; 4%SMg0$6%; and 0%^Ca0^5°/〇, where 66%^ Si〇2+B2〇3+CaO ^69%; Na2〇+K2〇+ B2〇3+MgO+CaO+SrO>10%;5°/〇^MgO+CaO+Sr0^8%; (Na2〇+B2〇3) ^ A12〇3 ^ 2%; 2%SNa2〇-A12( X6%; and 4% S (Na2〇+K2〇)SAl2〇3S10%, And wherein the glass liquidus viscosity coefficient is at least 130 kpoise. 13. The alkali metal aluminosilicate glass article according to claim 12, wherein the antireflection coating film is selected from the group consisting of vermiculite, molten stone, doped F-fused vermiculite, and MgF2; The thickness of the antireflection coating film is in the range of 10 to 60 μm. 14. The alkali metal aluminosilicate glass article according to claim 12, wherein the antireflection coating film is selected from the group consisting of Hf〇2, Zr〇2, peach and Gd2〇3, and an antireflection coating film The thickness is in the range of 1 〇 6 〇 micrometers. 15. The alkali metal aluminosilicate glass article according to claim 12, wherein the main surface of the bonded fluorine is (RF)nSiX4_n: compound, wherein RF is G-C22 alkyl perfluorocarbon. , η is an integer in the range of 1-3; and X is a hydrolyzable group which is capable of being exchanged with a glass terminal sulfhydryl group. 16. Aluminium silicate glass article according to item 12 of the patent application, 36 200948734 wherein X is selected from the group consisting of halogen-free halogen and alkoxygen machine (one 〇R), the R is 1 The -6-inserted carbon is linear or branched and hydrogenated. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 18. A method of making a coated metal alkali aluminosilicate glass article having resistance to scratch and stain resistance, the method comprising the steps of: m & having length, width and thickness A metallurgical glass substrate; chemically tempering the surface of the glass substrate to a depth of 2 〇 8 μm; mechanically or modifying the glass surface; ultrasonically cleaning the glass surface; additionally, using a strong acid solution Pickling at least one surface of the glass. Use 〇2 plasma to clean at least one surface of the glass; ❹ _ double-stage coating difficult to remedy anti-reverse surface. Curing the coating at selected temperature and selected humidity The time selected over the time; and the inspection of the glass containing the alkali metal aluminosilicate. 19. The method according to claim 18, wherein the anti-reflective coating film is coated with an anti-reflective coating film, and the anti-reflective coating film material is selected from the group consisting of a dream stone, a molten stone, and a molten vermiculite doped with F. . 2. The method according to claim 18, wherein the anti-reflective coating film is used to coat the glass, and the anti-reflective coating material is selected from the group consisting of ruthenium, Zr〇2, γ crystals 37 200948734 and Gd2〇3. 21: WTO^范娜调线良中面面面面coated glass refers to the hydrophobic coating film formula (10)乂", where RF is c22 alkyl-based perfluorocarbon, n is an integer of the range of 3; a hydrolyzable group capable of exchanging with a glass terminal oxime; and wherein X is selected from the group consisting of a fluorine-free dentate or an oxygen burner (_〇R), wherein R is 丨-6 carbon atoms Linear or branched hydrocarbons. 0 〇38
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US9617639B2 (en) 2013-03-18 2017-04-11 Apple Inc. Surface-tensioned sapphire plate
US9718249B2 (en) 2012-11-16 2017-08-01 Apple Inc. Laminated aluminum oxide cover component
TWI663138B (en) * 2014-05-20 2019-06-21 美商康寧公司 Scratch resistant glass and method of making
TWI676608B (en) * 2014-09-12 2019-11-11 德商首德公司 Method for producing coated anti-fingerprint type chemically strengthened glass substrate and glass substrate produced thereby
TWI678350B (en) * 2014-09-12 2019-12-01 德商首德公司 Coated glass substrate or glass-ceramic substrate with stable multifunctional surface characteristics, and manufacturing method and application thereof
US11269374B2 (en) 2019-09-11 2022-03-08 Apple Inc. Electronic device with a cover assembly having an adhesion layer
US11548810B2 (en) 2017-09-14 2023-01-10 Corning Incorporated Textured glass-based articles with scratch resistance and methods of making the same

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI504921B (en) * 2012-09-21 2015-10-21 Apple Inc Oleophobic coating on sapphire
US9718249B2 (en) 2012-11-16 2017-08-01 Apple Inc. Laminated aluminum oxide cover component
US9617639B2 (en) 2013-03-18 2017-04-11 Apple Inc. Surface-tensioned sapphire plate
TWI663138B (en) * 2014-05-20 2019-06-21 美商康寧公司 Scratch resistant glass and method of making
TWI699342B (en) * 2014-05-20 2020-07-21 美商康寧公司 Scratch resistant glass and method of making
TWI676608B (en) * 2014-09-12 2019-11-11 德商首德公司 Method for producing coated anti-fingerprint type chemically strengthened glass substrate and glass substrate produced thereby
TWI678350B (en) * 2014-09-12 2019-12-01 德商首德公司 Coated glass substrate or glass-ceramic substrate with stable multifunctional surface characteristics, and manufacturing method and application thereof
US11548810B2 (en) 2017-09-14 2023-01-10 Corning Incorporated Textured glass-based articles with scratch resistance and methods of making the same
US11269374B2 (en) 2019-09-11 2022-03-08 Apple Inc. Electronic device with a cover assembly having an adhesion layer

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