201215577 六、發明說明： 【發明所屬之技術領域】 [0001] 本揭示的產品及方法概略有關強化玻璃片，並且特別有 關對於撓曲應力和衝擊損傷展現出高阻抗性的玻璃片。 【先前技術】 [0002] 運用於包含行動電話、PDA、桌上型/膝上型/筆記型電腦 以及LCD和電漿電視在内之消費性電子裝置的覆蓋玻璃片 在現今具有高度需求。這種可由此等裝置之設計者、生 產者與終端使用者所高度評價之薄片的效能屬性包含低 r% 厚度、高表面強度和防刮痕性，以及對於撓曲應力和衝 擊損傷的高阻抗度。 [0003] 用以評估覆蓋玻璃片對衝擊損傷，像是破裂或粉碎，之 阻抗度的普遍接受方法包含標準化的撓曲（彎折）應力以 及球落（衝擊）測試。球落測試的要求相當高，並且，若 未對玻璃品質施行緊密控制，則可在甚至單一商業覆蓋 玻璃片品線上顯現出廣泛範圍的衝擊損傷阻抗度。因此 ，緊密分佈的球落失敗效能結果是與在較高球落高度處 的破損阻抗度一樣重要。 [0004] 球落測試雖廣泛運用於系統及元件層級測試兩者上，然 會對球落效能造成影響的玻璃屬性實頗為複雜。例如在 一般情況下是可預期並觀察到在較高的球落高度處，及/ 或減少的覆蓋玻璃片厚度或薄片強度，失敗率會增加， 然對於具有常見製造來源、名目厚度和等同彎折強度之 玻璃片在單一球落高度處的失敗率變異度一直是主要課 題所在。 100100423 表單編號A0101 第3頁/共29頁 1003229699-0 201215577 [0005] [0006] [0007] [0008] 效的坡續· 折斷強Γ 仍可能生產出在經設計以評估玻璃 A之f折模數的撓曲測試裡展現廣泛強度變異性 /片。例如，對經預處理以改善損傷阻抗度之名目 會2樣本所進行的雙減或環上賴㈣度測試可能 1廣泛變異的撓曲強度結果。 【發明内容】 根據本揭示，可經由提供經顯著改善之雙軸式撓曲強度 及衝擊損傷阻抗度的玻璃表面化學處理來解決薄型玻璃 片中之表面強度變化度的問題。因此，併人該等經處理 玻璃之薄型覆蓋片的消費性電子裝i，尤其是含有運用 於LCD及電漿電視顯示螢幕之大面積覆蓋片，然亦延伸至 手持式電子裝置，可對於因使用上可能遭遇到之衝擊和 撓曲應力所致生的破損展現出大幅提升且更為—致的阻 抗度。 從而，在第一特點裡，本揭示提供一種具有衝擊損傷阻 抗性的玻璃片，此者含有至少一經調適並經化學姑刻的 表面，而且展現出至少120cm的標準化128§球落失敗高 度。為提供此項效月b ’《玄玻璃片併入具有至少8微乎.'W产 的表面壓縮層以及至少200MPa的表面壓應力值。 尤其，本揭示的具體實施例提供一種含有至少—經化學 餘刻、壓應力表面的薄型抗損傷石夕酸銘玻璃片，其中在 該表面處之壓應力的值為至少400MPa並且該表面壓縮層 (DOL)的深度為至少15微米。 [0009] 100100423 在又進一步具體實施例裡，本揭示提供一種含有 表單煸號A0101 第4頁/共29頁 至少一 1003229699-0 201215577 經化學細、壓應力表面的薄型抗損傷驗金財酸紹玻 璃片’其中在該表面處之愿應力的值為至少400MPa並且 該表面壓縮層（d〇l)的深度為至少3〇微米。 [0010] 該經化學_表面可為經酸性蚀刻表面 。在球落測試裡 ’可發現到具有這#特徵的薄型酸性射j驗金屬石夕酸紹 玻璃片展現出至少I40cm，或甚至少^化讯，的標準化球 落失敗高度，而觀察到在3〇〇cm範圍内的失敗高度是在較 高的表面壓縮值和壓縮層深度處。 〇 [0011] 為本揭示之目的’薄型玻璃片為具有不超過2mm厚度的玻 璃片。鹼金屬矽酸鋁玻璃片是指由主要（不超過總重量的 50%)含有二氧化矽與氧化鋁之玻璃所組成的玻璃片，其 中含有足夠的可交換鹼金屬以藉由在低於該玻璃之應變 點的溫度下進行離子交換強化處理（化學調適）藉以發展 出超過500MPa的表面壓應力。 [0012] ο 本案所揭示之抗損傷玻璃片的特別重要具體實施例含有 具備不超過1. 5mm，或甚1. 0mm ’之均勻厚度的驗金屬發 酸鋁玻璃片。對於該等具體實施例而言，該薄片表面通 常將包含具有至少約30微米’或甚至少約40微米’之覆 層深度（DOL)的表面壓縮層，而在該表面壓縮層内之薄片 表面處的壓應力值為至少約5〇〇MPa ’或甚至少約6〇〇MPa 〇 在又另一特點裡，本揭示提供一種含有強化玻璃覆蓋薄 片的視訊顯示裝置，其中該玻璃覆蓋薄片具有在〇. 2-2mm 之範圍内的厚度、鹼金屬矽酸鋁玻璃組成份，以及至少 100100423 表單編號A0101 第5頁/共29頁 1003229699-0 [0013] 201215577 一併入有經化學姓刻表面的表面壓縮層。本揭納入多項 具體實施例，其中該表面壓縮層併入酸性蝕刻表面並且 具有至少30微米的深度以及至少500MPa的表面應力值。 同時本揭示亦納入多項具體實施例，其中併入該酸性蝕 刻表面的表面壓縮層係經供置於該玻璃覆蓋片的至少後 侧或非曝出表面上。 [0014] 在又另一特點裡，本揭示提供一種製作強化玻璃片的方 法，包含下列步驟，即（i)令該玻璃片的至少一表面承受 於調適處理以在其上發展成壓縮表面層，以及（ii)令該 玻璃片的至少一表面接觸於一化學蝕刻介質，像是酸性 蝕刻介質，以自其去除略微厚度的玻璃表面層。在本揭 示的特別具體實施例裡，令該玻璃片之至少一表面接觸 的步驟係針對有效於自該薄片去除不超過4微米之表面玻 璃，或甚不超過2微米之表面玻璃，的時間和溫度下。 [0015] 多項具體實施例係經特別地納入在本揭方法之範疇内， 其中該玻璃片擁有鹼金屬矽酸鋁組成份，並且其中該待 予調適且蝕刻的玻璃片係經預選定以具有至少一大致不 含超過約2微米之深度的表面瑕疵之表面。就以鹼金屬矽 酸鋁玻璃起始薄片的情況而言，該調適處理可為自包含 熱調適和化學調適之群組中所選定，並且該蝕刻介質可 為含有流體化合物的水性介質。 【實施方式】 [0016] 根據本揭示所提供之方法及產品雖可廣泛地運用於各種 產品及產品製造程序，然該等可應用在製造用於併入消 費性電子裝置之顯示器的覆蓋玻璃片而獲致特定優點。 100100423 表單編號A0101 第6頁/共29頁 1003229699-0 201215577 [0017] ❹ [0018] Ο [0019] 從而彳特&地參照於此等覆蓋玻璃以陳述後文中所呈 現之该等產。。及方法的特定範例和具體實施例，即使本 揭方法及產品_途實非侷限於此。 、'曼離子乂換強化之⑦酸銘玻璃可運用於廣泛消費性電子 裝置的各式顯$覆蓋玻填應用項目，其中對於表面損傷 會要求而度的表面強度和阻抗度。㈣些目前的離子交 換強化玻璃）ί對於衝擊損傷及/或撓錢力失敗僅能顯現 出有限’或至少非所樂見之變異性’的阻抗度。而隨著 '肖費性電子裝置的數量及種類增多並且此等裝置的使用 %境變得更為不利’此項課題會特別重要。 藉由較南且較為—致標準化的球落測試結果所顯示，既 已發現化學調適（離子交換）處理且連同於玻璃覆蓋片之 簡單酸性處理的合併運用可顯著地改善薄型矽酸鋁玻螭 片的衝擊損傷阻抗度，為本案說明之目的，該標準化球 落測試為其中具有標準大小和重量的球體，亦即具有直 徑31.75mm及重量128公克的不鏽鋼球體，自遞增高度處 重複地墜落在具有5〇x5〇mm外部維度的方形玻璃片樣本上 ，直到該玻璃片樣本出現破損為止。 用以改善薄型調適玻璃片之表面完工作業的傳統機械完 工程序在一些情況下確能改善球落衝擊阻抗度。然並無 單一機械方式足能對各種玻璃組成份及/或各種玻璃形狀 施予一致的有效結果。同時亦無機械完工處理能夠降低 對於玻璃衝擊阻抗度或撓曲強度上之瑕疵形狀以及缺陷 大小與形狀的隨機化效應。利用包含令玻璃片之其一或 兩者表面接觸於酸性玻璃蝕刻介質的化學表面處理具有 100100423 表單編號A0101 第7頁/共29頁 1003229699-0 201215577 [0020] [0021] [0022] 相當高的靈活度，隨可調整配用於多數玻璃，並且能夠 便即地施用於平面與複雜的覆蓋玻璃片幾何性兩者。此 外，既已發現，即使在具有低表面瑕疵發生度的玻璃裡 ，尤其是包含傳統上被視為在製造過程中或在後製造處 理過知中大致上並不會引生表面瑕症的上汲或下汲（即如 熔融汲拉）玻璃片，如此確可有效於降低強度變異性。 具有微型厚度（厚度2mm)之玻璃覆蓋片的球落效能可 展現特別高值的變化度，可觀察到衝擊損傷阻抗度的巨 大差異，即使是在一給定處理批項中具有平滑熔融表面 的下汲薄片裡亦同。例如，針對一組給定測試條件，在 單一汲拉薄片批項裡該球落失敗高度的範圍可自低如 20cm至超過120cm ’即高達六倍的變異度。 即如這些結果所示，改善薄型玻璃覆蓋片的衝擊損傷阻 抗度將要求提升該失敗高度分佈曲線的低末端，並且降 低該等結果的整體變化度。若母體中含有對衝擊破損展 現出無法令人接受之低度阻抗度的成員，則在該產品母 體之平均球落失敗高度方面的改善結果實具微小價值。 本揭化學表面處理方法特別有效於提供在針對任何特定 的經處理樣本群組所收集之整體衝擊強度結果展幅上的 顯著改善結果，而不致無可接受地降低化學調適處理的 強化效應。 當相較於單獨經由化學調適處理的玻璃時，包含化學調 適（離子交換處理步驟）及酸性蝕刻步驟兩者的本揭方法 具體實施例可在衝擊阻抗度方面提供—致的顯著改善結 果。該酸性處理步驟被視為提供該表面的化學拋光處理 100100423 表單編號A0101 第8頁/共29頁 1003229699-0 201215577 [0023] Ο [0024] Ο 100100423 而可改變表面瑕疵的大小及/或幾何性，此等大小及形狀 變數在球落效能上被視為扮演重要角色，然對於該表面 的一般拓樸而言僅具低微效應。一般說來，可為本揭之 目的運用有效於去除不超過約4微米表面玻璃，或在一些 具體實施例裡為不超過2微米，或甚不超過1微米，的酸 性钱刻處理。 然基於至少兩項理由應避免自經化學調適玻璃片上醆性 去除超過前述厚度的表面玻璃。首先，過度去除會減少 該表面壓縮層的厚度以及由該覆層所提供的表面應力值 兩者。兩者效應對於該玻璃的衝擊和撓曲損傷阻抗度而 言皆為不利。其次，過度地蝕刻該玻璃表面可能會使得 該玻璃裡的表面光霧度值提高至令人生厭的層級。對於 消費性電子顯示應用項目來說，在該顯示器的玻璃覆蓋 片内是無法容允視覺可感見的表面光霧。 可運用各種不同化學物、濃度和處理時間以達到所選定 的球落衝擊測試效能值。適於進行該酸性處理步驟之化 學物的範例可包括含有至少一自如下群組所選定之活性 玻璃蝕刻化合物的含氟水性處理介質，即HF、HF與HCL、 ΗΝΟ。及H SO 、氟化氫銨、氟化氫鈉以及其他之一或更多 者的組合。即如一特定範例，在水中含有5 vol.%之HF (48%)和5 vol. %2H2S〇4(98%)的水性酸性溶液將能利 用短達一分鐘時段的處理時間以顯著地改善具有 〇. 5-1. 5mm厚度範園之經離子交換強化鹼金屬矽酸鋁玻 璃片的球落效能。 利用先前利用化學（離子交換）調適處理所強化的没拉薄 第9頁/共29頁 表單編號A0101 1003229699-0 [0025] 201215577 片，可獲得藉由HF/H2S〇r&成之酸性蝕刻介質的最佳結 果。而無論在進行酸性蚀刻之前或之後皆未承受於離子 交換強化或熱調適的玻璃則可能需要不同的餘刻介質組 合’俾於球落測試結果方面得到顯著的改善結果。 [0026] [0027] [0028] 100100423 若能密切掌握含H F溶液内之H F以及所溶解玻壤組成物的 濃度，則將能有助於保持適當地控制由該含HF溶液之蝕 刻所去除的破璃層厚度。定期地更換整個姓刻浴液以恢 復可接受的蝕刻率雖有效於此項目的’然浴液更換的價 格昂貴，同時有效地處理且置放所移除蚀刻溶液的成本 極高。 根據本揭示，茲提供一種用以連續地復新含有過度量值 之溶解玻璃或不足濃度之HF的HF蚀刻浴液之方法。根據 該方法，可自含有已知濃度之溶解玻璃組成份和HF的浴 液，其中HF濃度低於一預定最小值及/或該溶解玻璃的質 量高於一預定最大值，去除一定容積的浴液。然後以等 同容積的含HF溶液來替代該所去除容積，而該含肝溶液 中含有具備足以將該浴液之HF濃度回復成至少該預定最 小HF濃度之濃度的HF。在典型的具體實施例裡，忒替代 溶液亦將大致不含溶解玻璃組成份。 本揭方法步驟可按步階方式或是按大致連續方式所實作 ，即如待予運用之特定玻璃片完工計畫中所註述者。然 若以步階方式所實作，則該等去除及替換步驟係依照足 以將該HF濃度維持在該預定最小值之處或其上，並且將 該溶解玻璃組成份的質量維持在該預定最大值之處或其 下，的頻率所進行。該等最小和最大溶解破璃值係自 1003229699-0 表單編號A0101 第10頁/共29頁 201215577 經發現為無可接受轉㈣祕之麵表祕解率的值 所預疋可對遠冷液中在任何選定時間處的HF和溶解玻 璃濃度進行測量，或者給定轉_條件、溶解玻璃組 成刀、及所予處理破璃片之表面積的知識俾對其等進行 計算。 [0029] Ο [0030] Ο 從對於«可獲之域理薄片料行的球落測試 、-果料顯見Μ述方法在改善薄型汲拉驗金屬石夕酸铭 玻璃片之衝擊損傷阻抗度方面的有效性。附圖中的圖【及 2即分別地敘述提供對於兩項此等商用玻璃薄片，亦即201215577 VI. Description of the Invention: [Technical Field of the Invention] [0001] The products and methods of the present disclosure are generally related to a tempered glass sheet, and particularly to a glass sheet exhibiting high resistance to flexural stress and impact damage. [Prior Art] [0002] Covering glass sheets for consumer electronic devices including mobile phones, PDAs, desktop/laptop/notebook computers, and LCD and plasma televisions are highly demanded today. The performance attributes of such sheets that can be highly evaluated by designers, producers, and end users of such devices include low r% thickness, high surface strength and scratch resistance, and high impedance to flexural stress and impact damage. degree. [0003] A generally accepted method for assessing the degree of impedance of a cover glass sheet against impact damage, such as cracking or comminution, includes standardized flexural (bending) stress and ball drop (shock) testing. The ball drop test requirements are quite high and, without tight control of the glass quality, a wide range of impact damage resistance can be exhibited on even a single commercial cover glass product line. Therefore, the tightly distributed ball fall failure performance is as important as the damage resistance at higher ball drop heights. [0004] Although the ball drop test is widely used in both system and component level testing, the glass properties that affect the ball drop performance are quite complicated. For example, in general, it is expected and observed at higher ball drop heights, and/or reduced cover glass thickness or sheet strength, the failure rate will increase, but for common manufacturing sources, nominal thicknesses, and equivalent bends. The failure rate variability of a piece of glass with a folding strength at a single ball drop height has been the main issue. 100100423 Form No. A0101 Page 3 / Total 29 Page 1003229699-0 201215577 [0005] [0006] [0007] [0008] Effective Slope · Breaking Strong 仍 It is still possible to produce a f-module designed to evaluate glass A A number of flexural tests show extensive intensity variability/slices. For example, a double-decimation or a ring-up (four-degree) test on a sample that has been pretreated to improve damage resistance may result in a widely variable flexural strength result. SUMMARY OF THE INVENTION According to the present disclosure, the problem of the degree of change in surface strength in a thin glass sheet can be solved by providing a glass surface chemical treatment that significantly improves the biaxial flexural strength and impact damage resistance. Therefore, the consumer electronic devices of the thin cover sheets of the treated glass, especially the large-area cover sheets for LCD and plasma television display screens, also extend to handheld electronic devices. The damage caused by the impact and flexural stress that may be encountered in use exhibits a substantial increase and a higher degree of impedance. Thus, in a first feature, the present disclosure provides a glass sheet having impact damage resistance that contains at least one adapted and chemically engraved surface and exhibits a standardized 128 § ball failure failure height of at least 120 cm. To provide this effect b', the sinus glass sheet incorporates a surface compression layer having a yield of at least 8 micrometers, and a surface compressive stress value of at least 200 MPa. In particular, a specific embodiment of the present disclosure provides a thin, damage-resistant, sulphuric acid glass sheet containing at least a chemically-reduced, compressively stressed surface, wherein the value of the compressive stress at the surface is at least 400 MPa and the surface compressive layer (DOL) has a depth of at least 15 microns. [0009] 100100423 In still further embodiments, the present disclosure provides a thin, damage-resistant gold test containing a form nickname A0101, page 4 of 29, at least one 1003229699-0 201215577, a chemically fine, compressively stressed surface. The glass sheet 'where the value of the desired stress at the surface is at least 400 MPa and the depth of the surface compression layer (d〇l) is at least 3 μm. [0010] The chemically-surface may be an acid etched surface. In the ball drop test, it can be found that the thin-type acid shot with the feature of this #-metallurgical glass shows at least I40cm, or at least the normalized ball fall failure height, while observed at 3 The failure height in the range of 〇〇cm is at a higher surface compression value and compression layer depth. 〇 [0011] For the purposes of this disclosure, a thin glass sheet is a glass sheet having a thickness of no more than 2 mm. An alkali metal silicate glass flake refers to a glass flake composed of a main (not more than 50% by weight) glass containing ceria and alumina, which contains sufficient exchangeable alkali metal to be lower than An ion exchange strengthening treatment (chemical conditioning) is carried out at the temperature of the strain point of the glass to develop a surface compressive stress exceeding 500 MPa. [0012] The particularly important embodiment of the damage-resistant glass sheet disclosed in the present invention comprises a metal aluminosilicate glass sheet having a uniform thickness of not more than 1.5 mm, or even 1.0 mm. For such specific embodiments, the surface of the sheet will typically comprise a surface compression layer having a coating depth (DOL) of at least about 30 microns 'or at least about 40 microns', and the surface of the sheet within the surface compression layer The compressive stress value is at least about 5 MPa MPa' or at least about 6 MPa MPa. In yet another feature, the present disclosure provides a video display device comprising a tempered glass cover sheet, wherein the glass cover sheet has 〇. Thickness in the range of 2-2mm, alkali metal silicate glass composition, and at least 100100423 Form No. A0101 Page 5 / Total 29 Page 1003229699-0 [0013] 201215577 One incorporates a chemically surnamed surface Surface compression layer. The present disclosure incorporates a number of specific embodiments wherein the surface compressive layer incorporates an acidic etched surface and has a depth of at least 30 microns and a surface stress value of at least 500 MPa. Also disclosed herein is a plurality of embodiments in which a surface compressive layer incorporating the acidic etch surface is applied to at least the back side or non-exposed surface of the glass cover sheet. [0014] In yet another feature, the present disclosure provides a method of making a tempered glass sheet comprising the steps of (i) subjecting at least one surface of the glass sheet to an adaptation treatment to develop a compressed surface layer thereon And (ii) contacting at least one surface of the glass sheet with a chemically etched medium, such as an acidic etch medium, to remove a slight thickness of the surface layer of glass therefrom. In a particular embodiment of the present disclosure, the step of contacting at least one surface of the glass sheet is directed to a time effective for removing surface glass of no more than 4 microns from the sheet, or surface glass of no more than 2 microns. At temperature. [0015] A number of specific embodiments are specifically incorporated within the scope of the present method, wherein the glass sheet possesses an alkali metal ruthenate component, and wherein the glass sheet to be adapted and etched is preselected to have At least one surface of the surface flaw substantially free of depths greater than about 2 microns. In the case of an alkali metal silicate glass starting sheet, the conditioning treatment can be selected from the group consisting of thermal conditioning and chemical conditioning, and the etching medium can be an aqueous medium containing a fluid compound. [Embodiment] [0016] The methods and products provided in accordance with the present disclosure are widely applicable to various product and product manufacturing processes, and are applicable to the manufacture of cover glass for use in incorporating a display for consumer electronic devices. And to achieve specific advantages. 100100423 Form No. A0101 Page 6 of 29 1003229699-0 201215577 [0017] Ο [0019] Thus, the cover glass is referred to herein to state such products as hereinafter. . Specific examples and specific embodiments of the method, even if the method and product _ are not limited thereto. , 'Mannium ion exchange enhanced 7 acid glass can be applied to a wide range of consumer electronic devices for a variety of significant coverage of glass filling applications, which will require surface strength and impedance for surface damage. (4) Some current ion exchange tempered glass) ί can only exhibit limited or at least unpleasant variability for impact damage and/or scratching force failure. This issue is particularly important as the number and variety of electronic devices increase and the use of such devices becomes more unfavorable. As a result of the more southerly and more standardized ball drop test results, it has been found that the chemical adaptation (ion exchange) treatment combined with the simple acid treatment of the glass cover sheet can significantly improve the thin aluminum silicate glass crucible. The impact damage resistance of the sheet is the purpose of the description of the present invention. The standardized ball drop test is a sphere having a standard size and weight therein, that is, a stainless steel sphere having a diameter of 31.75 mm and a weight of 128 grams, repeatedly falling from the incremental height. On a square piece of glass with a 5 〇 x 5 〇 mm outer dimension until the glass piece sample is damaged. The traditional mechanical finishing procedure used to improve the surface finish of thin-adjusted glass sheets does improve ball drop impact resistance in some cases. However, there is no single mechanical means that provides consistently effective results for various glass components and/or various glass shapes. At the same time, no mechanical finishing treatment can reduce the randomization effect on the shape of the glass impact resistance or flexural strength and the size and shape of the defect. A chemical surface treatment comprising contacting one or both surfaces of the glass sheet with an acid glass etch medium has a 100100423 form number A0101 page 7 / page 29 1003229699-0 201215577 [0020] [0022] quite high Flexibility, adaptable to most glass, and can be applied instantly to both planar and complex cover glass geometry. In addition, it has been found that even in glass having a low surface flaw, especially including those which are conventionally considered to be substantially non-inducing surface defects during manufacturing or post-production processing. It is indeed effective to reduce the intensity variability by rubbing or snagging (ie, melting the glass). The ball drop performance of a glass cover sheet having a micro thickness (thickness of 2 mm) can exhibit a particularly high degree of variation, and a large difference in impact damage resistance can be observed, even in a given treatment batch having a smooth molten surface. The same is true in the lower jaw. For example, for a given set of test conditions, the height of the ball fall failure in a single pull sheet batch may range from as low as 20 cm to over 120 cm', i.e., up to six times the variability. That is, as shown by these results, improving the impact damage resistance of the thin glass cover sheet will require an increase in the low end of the failure height profile and a reduction in the overall variation of the results. If the parent contains a member exhibiting an unacceptably low resistance to impact damage, the improvement in the average ball failure height of the parent of the product is of little value. The chemical surface treatment method is particularly effective in providing significant improvements in the overall impact strength results exhibited for any particular group of treated samples without unacceptably reducing the enhancement effect of the chemical conditioning treatment. The present embodiment, which includes both chemical conditioning (ion exchange processing steps) and acidic etching steps, provides a significant improvement in impact resistance as compared to glass that is chemically treated separately. The acid treatment step is considered to provide the chemical polishing treatment of the surface 100100423 Form No. A0101 Page 8 / 29 pages 1003229699-0 201215577 [0023] Ο [0024] Ο 100100423 to change the size and/or geometry of the surface flaw These size and shape variables are considered to play an important role in ball drop performance, but have only a low micro effect for the general topology of the surface. In general, it is possible for the purposes of the present disclosure to utilize an acidity treatment effective to remove surface glass of no more than about 4 microns, or, in some embodiments, no more than 2 microns, or even less than 1 micron. For at least two reasons, it is desirable to avoid the removal of surface glass from the chemically tempered glass sheet by more than the aforementioned thickness. First, excessive removal reduces both the thickness of the surface compression layer and the surface stress values provided by the coating. Both effects are detrimental to the impact and deflection resistance of the glass. Second, excessive etching of the glass surface may increase the surface haze value in the glass to an unpleasant level. For consumer electronic display applications, visually sensible surface haze is not acceptable within the glass cover of the display. A variety of different chemicals, concentrations, and processing times can be utilized to achieve selected ball fall impact test performance values. An example of a chemical suitable for carrying out the acidic treatment step can include a fluorine-containing aqueous treatment medium comprising at least one active glass etching compound selected from the group consisting of HF, HF and HCL, hydrazine. And a combination of H SO , ammonium hydrogen fluoride, sodium hydrogen fluoride, and one or more others. That is, as a specific example, an aqueous acidic solution containing 5 vol.% HF (48%) and 5 vol. %2H2S〇4 (98%) in water will be able to significantly improve with a treatment time of as little as one minute. 〇. 5-1. 5mm thickness Fan Park ion-exchange enhanced alkali metal silicate glass flakes ball drop performance. The acid etching medium formed by HF/H2S〇r& can be obtained by using the chemically (ion exchange) conditioning treatment to enhance the etched film by the HF/H2S〇r& The best result. A glass that does not undergo ion exchange strengthening or thermal conditioning before or after an acid etch may require a different combination of residual media to achieve significant improvements in ball drop test results. [0028] 100100423 If the concentration of HF in the HF-containing solution and the dissolved glassy soil composition can be closely monitored, it will help to maintain proper control of the removal of the HF-containing solution. The thickness of the broken layer. Regular replacement of the entire bath of the surname to restore acceptable etch rates is effective in the cost of replacing the bath of the project, while the cost of effectively treating and placing the removed etching solution is extremely high. In accordance with the present disclosure, a method for continuously refreshing an HF etching bath containing an excessive amount of dissolved glass or an insufficient concentration of HF is provided. According to the method, a bath containing a known concentration of dissolved glass composition and HF may be used, wherein the HF concentration is below a predetermined minimum and/or the mass of the dissolved glass is above a predetermined maximum to remove a volume of bath liquid. The removed volume is then replaced by an HF containing solution of equal volume, and the liver containing solution contains HF having a concentration sufficient to restore the HF concentration of the bath to at least the predetermined minimum HF concentration. In a typical embodiment, the ruthenium replacement solution will also be substantially free of dissolved glass components. The method steps can be implemented in a stepwise manner or in a substantially continuous manner, i.e., as noted in the particular glass sheet completion plan to be utilized. However, if implemented in a stepwise manner, the removing and replacing steps are performed in accordance with or sufficient to maintain the HF concentration at or above the predetermined minimum, and maintain the quality of the dissolved glass component at the predetermined maximum. The value is performed at or below the frequency. The minimum and maximum dissolved glass values are from 1003229699-0 Form No. A0101 Page 10 / Total 29 pages 201215577 It is found that there is no acceptable transfer (4) The secret surface of the secret rate is expected to be far from the cold liquid The HF and dissolved glass concentrations are measured at any selected time, or given the knowledge of the surface conditions, the dissolved glass composition knives, and the surface area of the treated granules. [0029] Ο From the ball drop test for the available sheet material, and the method of sifting the fruit to improve the impact damage resistance of the thin metal sheet Effectiveness. The figures [ and 2 in the drawings are separately provided for two such commercial glass sheets, that is,
Corning Code 2318玻璃和c〇rning c〇de 2317玻璃 ’之球落測試資料的條狀圖。 該等球落測試是洲前料標準化球落職程序所進行 。不鏽鋼球體係自遞增高度墜落在方形（5〇1111^5〇111111)玻 璃片樣本上，直到出現樣本衝擊失敗為止。所有經測試 樣本在測試之前皆先承受㈣的傳_子交換調適處理 ，同時該等樣本中的所選定者亦於球落測試之前都事先 經由在水中含有5 vol.%iHF (48%)和5v〇1%之 H2S〇4(989〇的水性溶液之調適表面蝕刻所處理。該等經 酸性蝕刻或處理（T)的樣本是以條棒樣式區分於未經處理 (NT)的樣本，即如各個圖式的”鍵值（Key)”中所示者 。所有的酸性蝕刻處理都進行一段有效於令前述蝕刻溶 液能夠自該等Corning Code 2318及Corning Code 2317玻璃片表面上去除一層在厚度上不超過約2微米之玻 璃的處理時間間距。 [0031] 100100423 兩個經編號集組之樣本（—經處理（τ)樣本以及 表單編號Α0101 第Π頁/共29頁 一相伴隨 1003229699-0 201215577 的未經處理（NT)樣本）各者在衝擊失敗處所觸抵的球落高 度（失敗尚度）是由各圖之垂直轴上的條棒高度（in/cm) 所顯示，除對於l80cm條棒高度外，圖2中的一項例外， 此者表不在該球落高度處的存活而非失敗。該等樣本集 合係於圖式的水平軸上加以編號，且該等集合為依照遞 增處理樣本失敗高度的次序所任意排置。在本項測試系 列裡，不會對存活於l80cin球落的樣本在更高的球落高度 處進行測試。 [0032] 圖1中顯示對於厚度〇.7mm之Corning Code 2318玻璃片 樣本的代表性球落測試結果，而圖2則顯示對於厚度 1.3则1之Corning Code 2317玻璃片樣本的代表性球落 測試結果。可明顯看出，對於兩者玻璃以及在兩者薄片 厚度處，該等經處理薄片在衝擊損傷阻抗度上優於該等 未經處理薄片的顯著提高，即使是在其中該等未經處理 薄片展現相對低度的衝擊損傷阻抗度之情況下亦然。 [0033] 透過利用本揭方法所確保的球落效能改善結果，這代表 須對於顯示器覆蓋玻璃應用提供適當的衝擊損傷阻抗度 ，即使是在該球落高度範圍之較低末端處失敗的樣本裡 亦同。不過，運用雙轴式撓曲強度測試方法以進一步評 估強化薄片效能則顯現出平均撓曲強度值雖有所提升， 然個別的薄片強度仍維持非所樂見地多變◊因此，部份 的薄片會具有足夠低的撓曲強度值而呈現出在未來使用 上產生無可接受之覆蓋薄片失敗的風險。 [0034] 100100423 圖3為顯示對於兩個薄型玻璃片樣本系列之雙轴式撓曲強 度測試結果的圖式。這些資料是表示來自對於具有矽酸 1003229699-0 表單編號A0101 第12頁/共29頁 201215577Bar graph of Corning Code 2318 glass and c〇rning c〇de 2317 glass 'ball drop test data. These ball drop tests are carried out by the pre-season standardization ball drop-off procedure. The stainless steel ball system falls on the square (5〇1111^5〇111111) glass piece sample from the incremental height until the sample impact fails. All tested samples were subjected to the (4) pass-to-sub-exchange adaptation process prior to testing, and the selected ones of the samples were also previously subjected to 5 vol.% iHF (48%) in water before ball drop test. 5v 〇 1% of H2S 〇 4 (adapted surface etching of an aqueous solution of 989 Å. The samples that are acid etched or treated (T) are separated into untreated (NT) samples by bar pattern, ie As shown in the "Key" of each figure, all acidic etching processes are performed for a period of time to enable the etching solution to remove a layer from the surface of the Corning Code 2318 and Corning Code 2317 glass sheets. Processing time interval of no more than about 2 micrometers of glass. [0031] 100100423 Two sampled grouped samples (-processed (τ) sample and form number Α0101 page/total 29 pages with one phase 1003229699-0 The untreated (NT) sample of 201215577) The height of the ball (the failure degree) that each person touched at the impact failure point is indicated by the bar height (in/cm) on the vertical axis of each figure, except for l80cm. Outside the bar height, in Figure 2 An exception, this table does not survive or not fail at the height of the ball. The sample sets are numbered on the horizontal axis of the graph, and the sets are in any order in the order of increasing the failure height of the sample. In this test series, samples that survive the l80cin ball drop are not tested at higher ball drop heights. [0032] Figure 1 shows a Corning Code 2318 glass piece sample with a thickness of 〇.7 mm. Representative ball drop test results, while Figure 2 shows representative ball drop test results for a Corning Code 2317 glass piece sample with a thickness of 1.3. It is apparent that for both glasses and at both sheet thicknesses, Equally treated sheets have a significant improvement in impact damage resistance over such untreated sheets, even in the case where the untreated sheets exhibit relatively low impact damage resistance. [0033] By using the method of the present invention to ensure improved ball drop performance, this represents the need to provide appropriate impact damage resistance for display overlay glass applications, even at the ball drop height. The same is true for samples that fail at the lower end of the circumference. However, using the biaxial flexural strength test method to further evaluate the performance of the strengthened sheet shows that although the average flexural strength value is improved, the individual sheet strength is maintained. Undesirably variable, therefore, some of the sheets will have a sufficiently low flexural strength value to present a risk of failure to produce an unacceptable cover sheet in future use. [0034] 100100423 Figure 3 shows for two A diagram of the results of the biaxial flexural strength test for a thin glass sample series. The information is expressed from the pair for the tannins 1003229699-0 Form No. A0101 Page 12 of 29 201215577
[0035] [0036] 〇 鋁玻璃組成份及l.0mm薄片 結果。料強相試包含令各縣衫^2=的 力至支撐位於1英吋直徑圓環上之各樣：曲〜、 備内的破損點處，同時利用居中於該底d: 叶直徑的圓環以將雙轴式撓曲應力施加於該頂部表面 圖3中的水平轴表示在該等樣本各者之破損點處所施用的 失敗負載S，按力度公斤（kgi)為單位，而垂私則表示 這兩個群組各者中之樣本的百分比失敗機率P (%)。 這兩個系_結果落在沿兩條*同的最佳擬配趨勢線曲 線上，圖式中予以標註為A&B。曲線A上的資料是關於並 未承受於補充性表面處理的離子交換強化玻璃樣本，而 曲線B上的資料則是有關根據本揭示承受於補充性酸性蝕 刻強化處理的離子交換強化玻璃樣本。 圖3内的資料呈現出確可根據本揭方法經由樣本的酸性蝕 刻強化處理以獲得平均撓曲強度的顯著提高。因此，對 於具有選定組成份及厚度的玻璃片而言，經酸性姓刻樣 本（B)可測得超過840kgf的平均失敗負載，然樣本（A)則 測得294kgf的平均失敗負載《不過，曲線B亦表明，對於 該等酸性蝕刻樣本，在低於400kgf處的失敗負載仍存在 有顯著的失敗機率（即如大於5%)。因此玻璃片調適和補 充性酸性蝕刻強化處理的組合並無法在所有情況下都能 產獲先進資訊顯示裝置商業應用上所需要的一致性高度 撓曲強度。 [0037] 為識別前述低撓曲強度樣本點中之破裂起源所進行的失 敗分析是朝向於具有相當深度的駐留表面瑕疵成為這些 100100423 表單編號A0101 第13頁/共29頁 1003229699-0 201215577 破裂的來源。即如在薄片製造過程中所引入者，這些瑕 疵並無法藉由在運用於電子資訊顯示器之經化學調適破 璃片中所能容忍的有限度表面蝕刻予以有效地消除。 [0038] 基於這些分析，結論為經薄型調適及酸性蝕刻玻璃片的 撓曲強度會整體性地因起始玻璃片的表面品質受到顯著 地影響’尤其是包含任何在進行處理前即已出現在該薄 片上之表面瑕庇的大小與空間分佈。這項薄片失敗來源 並無法從球落衝擊測試即隨能顯見，理由是在球落衝擊 下所應變的薄片表面積實遠小於在雙轴式或四點式彎折 測試過程中所應變者。 [0039] 圖4說明在未經處理玻璃片之破裂強度的模數上顯示表面 瑕疵深度之所算得效應的曲線，此圖是以傳統的四點彎 折來測量該強度。表面瑕疵深度D是在水平軸上以微米（ 微米）為單位，而所算得的破裂應力模數（MOR)則是在垂 直軸上以百萬帕斯卡（MPa)所表示。即如圖4中的破損應 力曲線所展現’玻璃破裂強度模數會隨著瑕疵深度增加 快速地降減’而在0.5-3微米深度範圍内的瑕疵深度觀察 到最大降幅。 [0040] 故而為確保根據本揭方法承受於化學調適及酸性蝕刻處 理之薄型破璃片内的一致性高強度，在進行處理之前先 選定大致無含超過2微米深度之表面瑕疵的薄片以行處理 之預先步驟實有其重要性。此等薄片可一致地提供高撓 曲強度，即使是其中經設計以僅自該經調適薄片上去除 最小表面厚度的蝕刻處理為必要亦同。 100100423 表單編號A0101 第14頁/共29頁 1003229699-0 201215577 [0041] [0042] Ο[0036] 〇 Alumina glass composition and 1.0 mm sheet results. The material strength phase test includes the force of each county shirt to support the various diameters on the 1 inch diameter ring: the break point in the bend ~, and the circle at the bottom d: the diameter of the leaf The ring applies a biaxial flexural stress to the top surface. The horizontal axis in Figure 3 represents the failure load S applied at the break point of each of the samples, in kilograms (kgi), while Indicates the percentage failure probability P (%) of the samples in each of the two groups. The results of these two systems are on the best fit trend line along the two *, which is labeled A&B. The data on curve A is for ion exchange strengthened glass samples that are not subjected to replenishing surface treatment, while the data on curve B is for ion exchange strengthened glass samples subjected to complementary acid etching enhancement treatment according to the present disclosure. The data in Figure 3 presents a significant increase in the average flexural strength that can be obtained by acid etching enhancement of the sample according to the method of the present invention. Therefore, for a glass piece with a selected composition and thickness, an average failure load of more than 840 kgf can be measured by the acid surname sample (B), while the sample (A) measures an average failure load of 294 kgf. However, the curve B also indicates that for such acidic etch samples, there is still a significant probability of failure (i.e., greater than 5%) at failure loads below 400 kgf. Therefore, the combination of glass sheet adaptation and complementary acid etch enhancement does not, in all cases, yield the consistent high degree of flexural strength required for commercial applications of advanced information display devices. [0037] The failure analysis performed to identify the origin of the fracture in the aforementioned low flexural strength sample points is toward a dwelling surface having a considerable depth 瑕疵 become these 100100423 Form No. A0101 Page 13 / Total 29 Page 1003229699-0 201215577 source. That is, as introduced in the sheet manufacturing process, these defects cannot be effectively eliminated by the limited surface etching that can be tolerated in chemically-adapted glass sheets used in electronic information displays. [0038] Based on these analyses, it is concluded that the flexural strength of the thin-adapted and acid-etched glass sheets is significantly affected by the surface quality of the starting glass sheets as a whole, especially including any that has appeared before processing. The size and spatial distribution of the surface on the sheet. The source of this sheet failure was not able to be seen from the ball drop test, as the surface area of the strained sheet under the impact of the ball drop was much smaller than that of the two-axis or four-point bending test. [0039] FIG. 4 illustrates a graph showing the effect of the calculated surface depth on the modulus of the burst strength of the untreated glass sheet, which is measured by a conventional four-point bend. The surface defect depth D is in micrometers (micrometers) on the horizontal axis, and the calculated fracture stress modulus (MOR) is expressed in megapascals (MPa) on the vertical axis. That is, as shown by the broken stress curve in Fig. 4, the glass rupture strength modulus rapidly decreases as the enthalpy depth increases, while the maximum radiance is observed at the enthalpy depth in the range of 0.5-3 micrometers. [0040] Therefore, in order to ensure the uniform high strength in the thin glass sheet subjected to the chemical adjustment and the acid etching treatment according to the method of the present invention, a sheet having a surface flaw of not more than 2 micrometers in depth is selected before the treatment. The pre-steps of processing are of great importance. These sheets can consistently provide high flexural strength, even if etching is designed to remove only the minimum surface thickness from the adapted sheet. 100100423 Form No. A0101 Page 14 of 29 1003229699-0 201215577 [0041] [0042] Ο
[0043] 而足能提供無含深度超過2微米之表面瑕疵的玻璃片表面 之方法則並非關鍵。利用機械性前完工（透過研磨和拋光 處理），或是利用具備既經審慎保護不受後製造處理損傷 之、熔融構成表面的薄片’的各種強度篩濾處理皆能提供 擁有無含大型表面瑕疲之必要條件的玻璃。然通常會提 供較高層級的強度強化作業，其中可將本揭方法施用於 具有溶融汲_拉表面的玻璃片β 對於牽涉到具有觸控螢幕功能性及/或要求最小可實用覆 蓋玻璃厚度之視訊顯示器的視訊顯示器覆蓋片應用項目 而言’會需要高保持的（後蝕刻）壓縮表面應力以及高保 持的壓縮層深度兩者。適用於此等應用項目的具體實施 例包含具有鹼金屬矽酸鋁組成份而厚度不超過lmin，或者 在一些具體實施例裡為厚度不超過0. 7mm或甚厚度不超過 0. 55mm，並在製造後根據本揭示加以處理的熔融汲拉破 璃片。對於該等應用項目擁有所述組成份和厚度的令人 滿意地強化玻璃覆蓋片在表面蝕刻處理之後可保持具有 至少30μιη深度，或甚40wm深度，的壓縮表面層，該表面 層提供至少500MPa，或甚650MPa，的尖峰壓應力值。 為提供具備此等性質之組合的薄型鹼金屬矽酸鋁玻璃覆 蓋片，會要求進行有限時段長度的薄片表面蝕刻處理。 尤其，令該玻璃片之表面接觸於蝕刻介質的步驟會進行 一段不超過能夠有效於去除2μπι表面玻璃，或在一些具體 實施例裡為不超過能夠有效於去除Ιμπι表面玻璃，的時間 。在任何情況下為限制玻璃去除所必要的實際蝕刻時間 將是依據該蝕刻介質的組成份和溫度以及所予處理之溶 100100423 表單編號Α0101 第15頁/共29頁 1003229699-0 201215577 液和玻璃的組成份而定，然有效於自一選定玻璃片之表 面上去除不超過1或2μιη玻璃的處理確可依照例行實驗方 式所隨即決定。 [0044] 一種用以確保玻璃片強度與表面壓縮層深度能夠適用於 薄型覆蓋或觸控螢幕應用項目的替代性方法是涉及到， 當進行蝕刻處理時，追蹤表面壓應力值的降低程度。然 後限制蝕刻時間，藉此對由該蝕刻處理所必要地產生的 表面壓縮層降減加以限制。從而，在一些具體實施例裡 ，令強化鹼金屬矽酸鋁玻璃片之表面接觸於蝕刻介質的 步驟會進行不超過有效於將該玻璃片表面内之壓應力值 降低3%的時間之時段長度。再度地，適合於達到該結果 的時段長度將是依據該蝕刻介質的組成份和溫度以及該 玻璃片的組成份而定，然可隨能藉由例行實驗方式所決 定。 [0045] 即如前述，用以處理該經調適玻璃片之表面的特定蝕刻 程序並非關鍵，而是依據所運用的特定蝕刻介質以及該 覆蓋玻璃應用項目的特定要求而定。在其中強化處理可 為限制在僅視訊顯示器覆蓋片之後側表面，亦即待予設 置在或靠近於一選定視訊顯示裝置之顯示表面上的薄片 表面，的情況下，該蝕刻介質可藉由滚塗、刷佈、喷灑 等等便利地施用。另一方面，在其中該玻璃覆蓋片之兩 侧皆予處理的情況下，沾浸方式可為最具經濟性的程序 〇 [0046] 展現出特需之強度與光學性質組合，像是光霧度、表面 澤度和耀光抑制，的強化玻璃覆蓋片在其中該覆蓋片係 100100423 表單編號Α0101 第16頁/共29頁 1003229699-0 201215577 [0047] Ο [0048][0043] The method of providing a glass sheet surface free of surface flaws having a depth of more than 2 microns is not critical. The use of mechanical pre-completion (through grinding and polishing), or the use of various strength screening processes that have been carefully protected from post-manufacturing damage and melted the surface of the sheet can provide a large surface without 含Glass that is necessary for fatigue. However, higher levels of strength intensification work are generally provided, wherein the present method can be applied to a glass sheet having a molten 汲-pull surface for the purpose of having touch screen functionality and/or requiring a minimum practical cover glass thickness. Video display covers for video displays, 'will require high retention (post-etch) compression surface stress and high retention compression layer depth. 5毫米的范围内的范围内的范围内。 The specific embodiment of the application of the present invention comprising a composition of the alkali metal ruthenate having a thickness of not more than 1min, or in some embodiments, the thickness is not more than 0. 7mm or the thickness does not exceed 0. 55mm, and The molten crucible treated in accordance with the present disclosure after manufacture is pulled through the glass. A satisfactory tempered glass cover sheet having said composition and thickness for such applications maintains a compressed surface layer having a depth of at least 30 μm, or a depth of 40 wm after surface etching, the surface layer providing at least 500 MPa, Or a peak pressure stress value of 650 MPa. In order to provide a thin alkali metal silicate glass cover sheet having a combination of such properties, a sheet surface etching treatment for a limited period of time is required. In particular, the step of contacting the surface of the glass sheet with the etching medium may be carried out for a period of time which is not more effective than removal of the 2 μm surface glass or, in some embodiments, no more than the effective removal of the Ιμπι surface glass. In any case, the actual etching time necessary to limit the removal of the glass will be based on the composition and temperature of the etching medium and the solution being processed. 100100423 Form No. 1010101 Page 15 of 29 pages 1003229699-0 201215577 Liquid and glass Depending on the composition of the composition, the treatment effective to remove no more than 1 or 2 μm of glass from the surface of a selected glass sheet can be determined in accordance with routine experimental methods. [0044] An alternative method to ensure that the strength of the glass sheet and the depth of the surface compression layer can be adapted for thin overlay or touch screen applications involves tracking the degree of reduction in surface compressive stress values as the etching process is performed. The etching time is then limited, thereby limiting the reduction of the surface compression layer that is necessarily produced by the etching process. Thus, in some embodiments, the step of contacting the surface of the strengthened alkali metal silicate glass sheet with the etching medium is performed for a period of time not exceeding a period effective to reduce the compressive stress value in the surface of the glass sheet by 3%. . Again, the length of the period suitable for achieving this result will depend on the composition and temperature of the etch medium and the composition of the glass sheet, although it can be determined by routine experimentation. [0045] As mentioned above, the particular etching process used to process the surface of the conditioned glass sheet is not critical, but is dependent upon the particular etch medium employed and the particular requirements of the overlay glass application. In the case where the strengthening treatment can be limited to the rear side surface of only the video display cover sheet, that is, the surface of the sheet to be placed on or near the display surface of a selected video display device, the etching medium can be rolled by Applying, brushing, spraying, etc. are conveniently applied. On the other hand, in the case where both sides of the glass cover sheet are treated, the dipping method can be the most economical process [0046] exhibiting a combination of special strength and optical properties, such as haze. , reinforced glass cover sheet with surface finish and glare suppression, wherein the cover sheet is 100100423. Form No. 1010101 Page 16 of 29 pages 1003229699-0 201215577 [0048] Ο [0048]
100100423 為以併入在經設計於高解析度视訊顯示器之裝置内的情 況下可為必要。生產運用在這些先進應用項目之覆蓋玻 璃會對於可供運用的強化程序進一步要求多項限制條件 〇 適用於高解析度視訊應用項目之強化玻璃覆蓋片的所揭 方法具體實施例概略包含下列步驟，即選定具有鹼金屬 矽酸鋁組成份的玻璃片，其厚度不超過約1. 〇mm ;然後令 該玻璃片的至少一表面接觸於包含具有，相較於出現在 該玻璃内之至少一鹼金屬離子成份，更大離子直徑之鹼 金屬離子來源的離子交換強化介質。令該表面接觸於該 離子交換強化介質的步驟係按下列方式進行，即（i)在低 於該玻璃之應變點的溫度下進行，以及（i i )進行一段足 可展成具有超過40Mm深度之壓應力層以及超過65〇MPa之 尖峰壓應力值的時間。 ‘ 在離子交換強化處理之後，令該玻璃片的至少一表面接 觸於包含其中具有氟質化合物之酸性溶液的蝕刻介質。 根據特定具體實施例，令以接觸於該蝕刻介質的步驟會 在一溫度下進行一段時間，使得（i)不會自該薄片表面去 除超過2μπι厚度的表面玻璃；（ii)在該薄片表面上保持至 少650MPa的玻璃壓應力；（iii)該玻璃片保持較該玻璃 片之初始透光度和表面澤度值相差分別不超過1%的最終 透光度和表面澤度值；以及（iv)該玻璃片保持不超過 0. 1%的最終光霧度值。 底下表1說明對於薄型驗金屬㈣銘玻璃片樣本所收集的 光學資料，這些樣本中包含_些具有未經餘刻表面，而 第17頁/共29頁 表單編號A0101 1003229699-0 [0049] 201215577 一些則是具有前述之經酸性氟質溶液所蝕刻以自該等薄 片上去除微小表面玻璃量值的表面。在表1中的”類型” A樣本-為具有在進行處理前先藉由研磨及拋光所完工之表 面的玻璃片樣本’而”類型” B樣本則為具有未經修改或 如同汲拉表面之相同尺寸和形狀的汲拉薄片樣本。 [0050] 表1内所說明的透光值包含對應於自已知光源穿過該等薄 片樣本之兩者表面所傳透的可見光百分比數值。根據 ASTM D1 003方法所決定之光霧值係自—已知光源而在穿 過該薄片兩者表面的過程中經由該光線之廣角散射所損 失光線的百分比測量值。根據ASTM D523方法所決定之 澤度值為來自各薄片之兩者表面的合併光線全反射，而 對於這些特定樣本總共超過100%。自表1資料確能顯見本 揭用以改善樣本強度而不致顯著地影響該等玻璃片之光 學性質的表面蝕刻處理之有效度。 [0051] 能夠產生符合所要求強度性質之薄片玻璃的本揭強化方 法具體實施例對於處理在該薄片之至少一表面上併入抗 耀光表面層的薄型驗金屬石夕酸鋁玻璃片可提供特定優點 。此款薄片的生產作業通常在令該玻璃之表面接觸於離 子交換強化介質的步驟前會先包含一項額外步驟，即對 該玻璃片的至少一表面進行處理俾於其上提供抗耀光表 面層。用以提供抗耀光表面並且相容於本揭強化方法的 步驟包含足可在該玻璃片上構成無機性、鹼金屬離子可 穿透、光線散射性之表面或表面層的任何已知方法。本 揭覆蓋 [〇〇52] 薄片強化方法之特顯優點在於可用以強化併有此等抗耀 1003229699-0 100100423 表單編號A0101 第18頁/共29頁 201215577 光表面的鹼金屬矽酸鋁玻璃片而不須無可接受地修改該 等表面的抗耀光特徵。 [0053] Ο [0054]100100423 may be necessary to incorporate into a device designed for high resolution video displays. The production of cover glass for use in these advanced applications will further require a number of restrictions on the available enhancement procedures. The disclosed method for reinforced glass cover sheets for high resolution video applications includes the following steps: a glass sheet having a composition of an alkali metal ruthenate having a thickness of not more than about 1. 〇mm; and then contacting at least one surface of the glass sheet with at least one alkali metal present in the glass Ionic component, an ion exchange strengthening medium derived from an alkali metal ion of a larger ion diameter. The step of contacting the surface with the ion exchange strengthening medium is carried out in the following manner (i) at a temperature below the strain point of the glass, and (ii) performing a length sufficient to have a depth of more than 40 Mm. The time of the compressive stress layer and the peak compressive stress value exceeding 65 MPa. After the ion exchange strengthening treatment, at least one surface of the glass sheet is brought into contact with an etching medium containing an acidic solution having a fluorine compound therein. According to a particular embodiment, the step of contacting the etching medium is carried out at a temperature for a period of time such that (i) no surface glass is removed from the surface of the sheet by more than 2 μm; (ii) on the surface of the sheet Maintaining a compressive stress of the glass of at least 650 MPa; (iii) maintaining a final transmittance and a surface image value of not less than 1% of the initial transmittance and the surface dimension of the glass sheet, respectively; and (iv) The final haze value of the glass piece is not more than 0.1%. The following table 1 shows the optical data collected for the thin metal test (4) glass samples, which contain _ some have no residual surface, and page 17 / 29 page form number A0101 1003229699-0 [0049] 201215577 Some are surfaces having the aforementioned acid fluorinated solution etched to remove the amount of minute surface glass from the sheets. The "type" A sample in Table 1 - is a glass piece sample having a surface that has been finished by grinding and polishing prior to processing, and the "type" B sample is unmodified or has a pull-like surface. A sample of a pull-up sheet of the same size and shape. [0050] The light transmission values illustrated in Table 1 include the percentage of visible light that is transmitted through the surface of both of the wafer samples from known light sources. The haze value determined according to the ASTM D1 003 method is a measure of the percentage of light lost by wide-angle scattering of the light during the passage through the surface of the sheet from a known source. The Zeta value determined according to the ASTM D523 method is the total reflection of the combined light from both surfaces of each of the sheets, and for these particular samples exceeds 100% in total. The data from Table 1 does show the effectiveness of the surface etching process used to improve the sample strength without significantly affecting the optical properties of the glass sheets. [0051] The present invention is capable of producing a sheet glass conforming to the desired strength properties. A specific embodiment is provided for treating a thin metallized aluminate glass sheet incorporating an anti-glare surface layer on at least one surface of the sheet. Specific advantages. The production of the sheet usually involves an additional step of contacting the surface of the glass with the ion exchange strengthening medium, i.e., treating at least one surface of the sheet to provide a glare resistant surface. Floor. The step of providing a glare resistant surface and compatible with the present intensive method comprises any known method of forming an inorganic, alkali metal ion permeable, light diffusing surface or surface layer on the glass sheet. Coverage [〇〇52] The special advantage of the sheet strengthening method is that it can be used to strengthen and have such resistance. 1003229699-0 100100423 Form No. A0101 Page 18 / 29 Page 201215577 Alkali Metal Aluminate Glass Sheet It is not necessary to modify the anti-glare characteristics of the surfaces unacceptably. [0053] 005 [0054]
[0055] 本揭方法的進一步具體實施例包含其中該玻璃片在進行 強化處理前先經預處理以減少其上之表面瑕疵的數目及/ 或大小者。此等具體實施例的特定範例包含該等在令該 玻璃之至少一表面接觸於離子交換介質的步驟前先含有 一項額外步驟者，即令該玻璃的至少一表面接觸於—蝕 刻介質以自其去除表面玻璃。適用於此項預處理之蝕刻 "質包含能夠用以自該等玻璃片去除薄型表面層的相同 含氟溶液，然後再進行離子交換處理。 圖5為顯示對於三個承受於不同離子交換及表面蝕刻處理 組合的薄型玻璃片樣本系列之雙轴式撓曲強度測試結果 的圖式。34些資料是表示來自對於具有矽酸鋁玻璃組成 份及1. 0mm薄片厚度之玻璃片樣本進行測試的結果。該等 強化測試包含令各個樣本承受於環上環撓曲應力，隨後 進行用以產生前述圖3所示之資料的程序。圖6中的水平 軸表示在該等樣本各者之破損點處所施用的撓曲應力負 載S，按力度公斤（kgf)為單位，而垂直軸則表示這三個 群組各者中之樣本的百分比失敗機率p (%)。 這二個樣本系列的結果概略落在沿三條不同的趨勢線上 ’圖式中予以標註為A、B及C。由方形資料點且概如趨勢 線A (A樣本）所表示的資料是關於並未藉氟質溶液以承受 於預先或補充性表面姓刻處理的離子交換強化玻璃樣本 ，而由圓形資料點且概如趨勢線B (B樣本）所表示的資料 是關於具有相同組成份及幾何性而經循序地承受於離子 表單編號A0101 100100423 第19頁/共29頁 1003229699-0 201215577 父換強化處理然後藉如前所述之酸性氟質溶液的表面蝕 刻處理之樣本。最後，概由趨勢線c (c樣本）所表示的該 專一角形資料點為有關循序地承受於藉酸性氟質溶液之， 預先表面蝕刻然後如同該等八及8樣本之離子交換強化處 理，並且最後承受於藉酸性氟質溶液之第二表面蝕刻處 理的薄片樣本，其中此溶液與處理該等6樣本所使用的溶 液相同。 [0056] 即如圖5中之資料所反映者，該等承受於預先與最終蝕刻 處理兩者的C樣本展現出至少等同於由曲線B所表示之B樣 本的撓曲強度，並且在該圖式的最小強度範圍裡比起曲 線A及B之樣本者具有顯著較高的強度。因此，曲線[樣本 展現出位於約651kgf破損處的平均失敗負載，而曲線A及 曲線B樣本則分別地展現出位在258kgf和569kgf破損處 的平均失敗負載。 [0057] 自令該薄型石夕酸_紹玻璃片承受於化學姓刻隨後進行調適 處理之步驟所獲得的進一步益處為顯著地改善因出現在 薄片邊緣處之邊緣瑕疵所致生的撓曲破損之薄片阻抗度 。這些瑕疵可為例如在薄片切割的處理過程中引生。 [0058] 圖6顯示有關兩組承受於4點彎折應力至破損點之薄型玻 璃片樣本的失敗機率資料。相比於產獲表示玻璃片表面 品質和強度之結果的球落及環上環測試環境，4點彎折資 料為薄片邊緣強度的測量值，亦即任何出現在玻璃片樣 本上之邊緣瑕疲的弱化效應。 [0059] 圖6中所點繪之資料表示獲自於具有44mm乘60mm大小之 100100423 表單編號A0101 第20頁/共29頁 1003229699-0 201215577 薄型薄片玻璃樣本的彎折測試結果。圖6之趨勢線A所表 示的資料點為對於經調適、未錄狀樣本群組的失敗 機率值p (在該圖的垂直輪上按百分比所表示），而由趨 勢線B所表示的資料點為對於承受於紐㈣隨後為調適 處理之樣本敎的數值。_處理是依前文所述之酸性 氟質溶液組成份與方式所進行。於該«本各者之失敗 點處所針的應力值S為該圖的水平轴上依百萬帕斯卡 (MPa)所表示。 [0060] 自該資料可顯見圖6中R ~ (經酸性蝕刻）樣本在彎折強度上 所展現的改。結果’該等A樣本展現約㈣阶a的平均失敗 應力並且該等B樣本展現約728μρ&的平均失敗應力。即使 是藉由蝕刻處理所去降 ^ 除' 的破璃量值為微小（約2um)而限制 薄片強度之邊緣贼具有15_3_範圍破為事實，然仍能 獲致這些改善結果。 [0061][0055] A further embodiment of the present method includes wherein the glass sheet is pretreated prior to the strengthening treatment to reduce the number and/or size of surface imperfections thereon. Specific examples of such specific embodiments include that the step of contacting at least one surface of the glass prior to contacting the ion exchange medium comprises contacting the at least one surface of the glass with an etch medium Remove the surface glass. The etching suitable for this pretreatment includes the same fluorine-containing solution that can be used to remove the thin surface layer from the glass sheets, followed by ion exchange treatment. Figure 5 is a graph showing the results of a biaxial flexural strength test for three thin glass piece sample series subjected to different ion exchange and surface etching treatment combinations. 34 These data are the results from tests conducted on glass flake samples having a composition of aluminosilicate glass and a thickness of 1.0 mm. These intensive tests involve subjecting each sample to the ring ring flexural stress and subsequently performing the procedure for generating the data shown in Figure 3 above. The horizontal axis in Figure 6 represents the flexural stress load S applied at the break point of each of the samples, in kilograms (kgf), while the vertical axis represents the sample in each of the three groups. Percentage failure probability p (%). The results of these two sample series are outlined in the three different trend lines, which are labeled A, B and C. The data represented by the square data points and as the trend line A (A sample) is about the ion exchange strengthened glass sample that has not been subjected to the pre- or complementary surface surname treatment by the fluorinated solution, but by the circular data point. And the data represented by trend line B (B sample) is about having the same composition and geometry and being sequentially subjected to ion form number A0101 100100423 Page 19 / 29 pages 1003229699-0 201215577 Parent transformation enhancement process then A sample of the surface etching treatment of the acidic fluorochemical solution as described above. Finally, the specific angular data point represented by the trend line c (c sample) is sequentially subjected to the acid fluorinated solution, pre-surface etching and then ion exchange strengthening treatment of the eight and eight samples, and Finally, it is subjected to a second surface etching treatment of the sheet sample by the acidic fluorinated solution, wherein the solution is the same as the solution used to treat the six samples. [0056] That is, as reflected in the data in FIG. 5, the C samples subjected to both the pre- and final etching processes exhibit a flexural strength at least equivalent to the B sample represented by the curve B, and in the figure The minimum intensity range of the formula has a significantly higher intensity than the samples of curves A and B. Therefore, the curve [sample exhibits an average failure load at approximately 651 kgf break, while curve A and curve B samples exhibit an average failure load at 258 kgf and 569 kgf break, respectively. [0057] A further benefit obtained by the step of subjecting the thin-type oxalic acid _ s glass sheet to the chemical surrogate followed by the conditioning treatment is to significantly improve the flexural damage caused by the edge 出现 occurring at the edge of the sheet. Sheet resistance. These defects can be induced, for example, during the processing of sheet cutting. [0058] FIG. 6 shows the failure probability data for two sets of thin glass sheets subjected to a 4-point bending stress to a break point. The 4-point bending data is a measure of the edge strength of the sheet, that is, any edge that appears on the edge of the glass sheet, compared to the ball drop and ring-ring test environment that yields the surface quality and strength of the glass sheet. Weakening effect. [0059] The data plotted in FIG. 6 indicates the results of the bending test obtained from a sample having a size of 44 mm by 60 mm, 100100423, form number A0101, page 20/29, and 1003229699-0 201215577 thin sheet glass samples. The data points represented by trend line A in Figure 6 are the probability of failure probability p (indicated by the percentage on the vertical wheel of the figure) for the adapted, unrecorded sample group, and the data represented by trend line B. The point is the value for the sample that is subjected to the New Zealand (4) and subsequent adaptations. The treatment is carried out according to the composition and manner of the acidic fluorochemical solution described above. The stress value S of the needle at the point of failure of the individual is expressed in megapascals (MPa) on the horizontal axis of the graph. [0060] From this data, it can be seen that the R ~ (acid etched) sample exhibits a change in bending strength. Results 'These A samples exhibited an average failure stress of about (four)th order a and the B samples exhibited an average failure stress of about 728 μρ & Even if the amount of broken glass by the etching process is small (about 2 um) and the edge thief who limits the strength of the sheet has a 15_3_ range, the improvement results can still be obtained. [0061]
#之衝擊損傷阻抗玻璃覆蓋薄片的 圖7顯示併有根據本揭 即如圖7的側視截面略圖 視訊顯示裝置之略圖戴面說明。 所示’該視訊輪裝置1Q含有視簡㈤12，此者藉由 選擇I·生雜著層14接合於衝耗傷阻鎌金射酸銘玻 ^ 16 °在®7的具體實施例裡，至少該覆蓋薄片 中面朝Λ視A顯不器之作用顯示表面⑶的後侧表面16a 為併有表轉縮層的經酸性㈣表面。在減的具想實 施例裡〜後側表面i 6a是在至少侧胸的表面壓應力 下，並且該表面壓縮層具有至少15⑽的深度。 100100423 *然本揭所述之玻璃產品、視訊顯示器及玻璃處理方 法的特定具體實施例僅為說明之目的所呈現，並且就以 表單編號A0101 第21頁/共29頁 1003229699-0 [0062] 201215577 [0063] 歸屬於後栽申請專利範 '方法或其等之等同項 限制或侷束。 [0064] [0065] 圍之範疇而言，無意對該等產。 目的設計、用途或實作方式如以 【圖式簡單說明】 '复文中將參照隨附圖式以進一步描述本示 法，其中： 度。。及方 圖2為顯㈣於第二組_片樣本之標準化球落失 的第二圖式； 敗資料 [0066] 圖3為顯示對於兩組玻璃片樣本之標準化雙轴式撓曲 資料的圖式； 強度 [0067] 圖4為，對於具有瑕疫表面之玻璃樣本’點繪出坡續持曲 強度相對於瑕疵深度的圖式； [0068] 圖5為顯示對於三組強化玻璃片樣本之標準化雙軸式 強度資料的圖式； [0069] 圖6為顯示對於兩組強化玻璃片樣本之4點彎折撓曲強度 資料的圖式；以及 [0070] 圖7為併入一強化玻璃覆蓋片之視訊顯示裝置的側视載面 略圖。 【主要元件符號說明】 視訊顯示裝置1 〇;視訊顯示器12;黏著層14;覆蓋薄片 16;顯示表面12a;後侧表面16a ° 100100423 表單編號A0101 第22頁/共29頁 1003229699-0 [0071]Fig. 7 shows a schematic view of the video display device according to the present invention. The video wheel device 1Q is shown to contain a simple (five) 12, which is joined to the wear and tear sputum by the selection of the I-heterogeneous layer 14 in a specific embodiment of the ®7 The rear side surface 16a of the cover sheet facing the squint A display is shown to have an acidic (four) surface having a surface-reducing layer. In the subtractive embodiment, the back side surface i 6a is at a surface compressive stress of at least the side chest, and the surface compressive layer has a depth of at least 15 (10). 100100423 * Certain specific embodiments of the glass products, video displays, and glass processing methods described herein are presented for illustrative purposes only, and are in the form number A0101 page 21 / page 29 1003229699-0 [0062] 201215577 [0063] The equivalent of the post-application patent application method or its equivalent restrictions or constraints. [0065] In the context of the scope, there is no intention to produce such products. The purpose of the design, use or implementation of the method is as follows: [Simple description of the drawing] The text will be further described with reference to the accompanying drawings, where: . Figure 2 is a second diagram showing the normalized ball loss of the second set of _ slice samples; the data of the failure [0066] Figure 3 is a diagram showing the normalized biaxial deflection data for the two sets of glass samples. [0067] Figure 4 is a graph depicting the slope strength versus the depth of the enamel for a glass sample with a plaque surface; [0068] Figure 5 is a graph showing samples for three sets of tempered glass A drawing of standardized biaxial strength data; [0069] FIG. 6 is a diagram showing data of 4-point bending flexural strength for two sets of tempered glass sheets; and [0070] FIG. 7 is incorporated into a tempered glass cover A side view of the video display device of the film. [Description of main component symbols] Video display device 1; video display 12; adhesive layer 14; cover sheet 16; display surface 12a; rear side surface 16a ° 100100423 Form No. A0101 Page 22 of 29 1003229699-0 [0071]