200811075 九、發明說明 【發明所屬之技術領域】 本發明爲有關一種於透明之玻璃板表面形成凹凸，而 不容易由玻璃板表面辨識反射像之防眩玻璃，及其製造方 法。 【先前技術】 φ 液晶顯示器（LCD )，於設置於薄型電視、觸控式面 板之顯示面板、平板電腦時，除可將文字、圖案等以輸入 筆等數據輸入裝置進行手寫輸入等方式以外，也可作爲輸 入内容可顯示於顯示面板等顯示裝置（筆輸入裝置）所使 用之顯示面板等用途。 而於前述顯示面板中，爲防止螢光燈等照明器或背景 之反射等所造成之無法觀察到顯示內容，且提高顯示之辨 識性等目的，多要求顯示面具有防眩性等機能。 # 具有防眩性機能之玻璃板，目前多採用將玻璃板之表 面以氫氟酸等進行蝕刻處理，而於玻璃板之表面設置適當 „ 之凹凸形狀等方法。專利文獻1中，則揭示一種由經飩刻 . 處理所得之具有防眩性之玻璃板的表面將凹凸轉印於樹脂 薄膜之表面，以製造具有防眩性之樹脂薄膜等內容。 又’玻璃基板表面貼附有0.05〜0.5# m之凹凸形狀 的樹脂薄膜之物品，亦揭示於專利文獻2中。 又，專利文獻3則揭示一種使用溶膠凝膠法形成5〜 1 0 // m之凸狀形狀，而具有防眩性機能之物品。 200811075 〔專利文獻1〕特開2005-3 3 1 90 1號公報 〔專利文獻2〕特開2000- 1 1 1 7 1 3號公報 〔專利文獻3〕特開2003- 1 86004號公報 【發明內容】 依蝕刻處理之方法，除製法上爲高價位，且必須對蝕 刻處理所使用之氫氟酸等廢液進行處理以外，還有需控制 凹凸形狀之大小等問題。 又，形成有凹凸之樹脂薄膜，或經溶膠凝膠法所得之 散亂反射膜，其耐磨耗性不佳，且附著污穢時不易進行洗 浄，故極需一種具有耐磨耗性及易洗浄性之表面。 本發明即以提供一種具有優良耐磨耗性及易洗浄性， 且可以低費用下製造之防眩性玻璃及其製造方法爲目的。 本發明之防眩性玻璃，爲表面形成有凹凸之防眩玻璃 ，其特徵爲，具有由玻璃板表面所形成之鋁金屬膜與玻璃 板中之氧化矽成分反應所生成之表面凹凸。 又，本發明之前述防眩玻璃的製造方法，其特徵爲， 包含使玻璃板之表面形成鋁金屬膜之步驟，與對成膜後之 玻璃板進行加熱處理之步驟所形成者。 又，本發明之防眩玻璃的製造方法爲，於前述防眩玻 璃之製造方法中，其特徵爲加熱處理之溫度爲600〜1000 t之防眩性玻璃的製造方法。 本發明之防眩玻璃，可提供液晶顯示或電漿顯示等平 板面板顯示器之前面板，特別是顯示面可使用筆輸入之液 -5- 200811075 晶表示器之前面板所使用之玻璃板、建 用之玻璃板、櫥窗之玻璃板等，除提高 供一種具有優良表面硬度、容易洗浄， 生產之優良量產性的廉價防眩玻璃。 本發明之防眩性玻璃，爲於玻璃板 再以鋁金屬膜對製膜之玻璃板進行加熱 玻璃板中所含之Si〇2成分與鋁金 而產生反應，而於玻璃板形成表面凹凸 使用之玻璃板，其與鋁金屬反應之 45wt%以上，較佳爲 50wt%以上之含矽 使用鹼石灰（Soda lime)矽酸鹽玻璃、 矽酸鹽玻璃、鋇硼矽酸玻璃、石英玻璃 特別是本發明所使用之玻璃板，於 品質時，以使用浮動（float)法所製得 動法所製得之玻璃板，除透明玻璃以外 青銅等著色玻璃、吸收紅外線或紫外線 玻璃所製造之浮動法之玻璃板皆可使用 所使用之玻璃基板的厚度，可依防 以選擇，一般以具有0.1〜10.0mm厚度 顯示裝置之前面，以使用具有〇.1 的玻璃板爲佳，於櫥窗等傢倶、建築物 之厚度爲2〜10mm之範圍，其可配合 面積，而使用適當厚度之玻璃板。 又，鋁金屬膜成膜於玻璃板之方法 築物之展示區所使 辨識性以外，亦提 且可廉價地大面積 上製造鋁金屬膜， 處理而得。 屬，推測經由加熱 ，因此，本發明所 Si〇2成分以含有 酸鹽玻璃，例如以 硼矽酸鹽玻璃、鋁 等玻璃板爲佳。 考慮價格或表面之 之玻璃板爲佳。浮 ，其他例如綠色、 之玻璃等，任一種 〇 眩性玻璃之用途予 之玻璃板爲佳。 〜2mm範圍之板厚 之展示區等所使用 所使用之玻璃板的 ，例如可使用濺鍍 -6- 200811075 或離子植入等物理蒸鍍（PVD)，或熱、電漿或光CVD等 化學蒸鍍（CVD )等乾式製膜法，特別是考慮生產性等觀 點時’以灑鑛蒸鑛法爲佳。 製膜所使用之鋁金屬膜厚度，爲得到可產生防眩性之 表面凹凸形狀等目的，以成膜爲具有膜厚1 〇nm以上者爲 佳。 爲形成具有大凹凸形狀時，以鋁金屬膜成膜爲較厚者 H 爲佳，但膜厚越厚時，須提高加熱溫度，或必須增長加熱 時間等，故所形成之膜厚度以1 〇 μπι以下爲佳。凹凸過大 時，會增大穿透光之散亂性，而於透視性上會發生問題， 故鋁金屬膜之成膜厚度，更佳爲Ιμιη以下，最佳爲500nm 以下。 鋁金屬膜製膜於玻璃板之表面後，該玻璃板之加熱處 理以於600°C以上，以較該玻璃板之軟化溫度高出300°C之 溫度下進行爲佳。 Φ 加熱處理而形成於玻璃板之表面的微細表面凹凸，爲 由玻璃基板成分與鋁金屬之反應所形成者，其可由改變鋁 ^ 金屬膜之膜厚、加熱處理之溫度或時間等，而改變表面凹 凸之形狀。 熱處理溫度於未達60(TC時，則玻璃基板成分與鋁金 屬不容易進行反應，而無法製得達所期待之微細表面凹凸 之形狀。又，遠超過玻璃板軟化點之溫度，例如鹼石灰（ Soda lime)玻璃，於超過1 000°C時，即使玻璃基板成分 與鋁金屬反應而形成表面凹凸，但因溫度所造成之玻璃基 -7- 200811075 板的軟化變形，將無法維持該表面凹凸之形狀。 因此，玻璃板爲驗石灰（Soda lime)玻璃時，熱處理 溫度以於650〜950 °C之範圍內進行爲佳。更佳爲700〜 900 〇C。 又，熱處理時間，依該熱處理之溫度及必要之表面凹 凸形狀而決定，就生產性之觀點而言，以200分以內爲佳 〇 熱處理時之氛圍，只要爲大氣、惰性氣體或還原氛圍 中則無任何問題，但就生產性或費用等觀點而言，特佳爲 於大氣氛圍中進行。 本發明之防眩製玻璃的表面凹凸，爲依JIS B 0601 -2001所得之算術表面粗度Ra爲0.1〜0.5 μηι之範圍，又， 可形成平均間距（凹凸周期）Sm爲50〜100 μπι範圍之具 有較佳防眩性能之物品。 【實施方式】 以下，將列舉實施例及比較例對本發明作詳細之説明 ，但本發明並不僅限定於下述內容。 防眩性玻璃之製作 使用厚度2.3mm之浮動法所製得之鹼石灰矽酸鹽玻璃 之玻璃板，該玻璃板之表面使用濺鍍法製膜10Onm之鋁金 屬薄膜。製膜後，對該玻璃板依表1所示溫度與時間進行 加熱處理，以製作實施例1至3之防眩玻璃。又，依實施 -8 - 200811075 例之相同內容，成膜爲鋁金屬之薄膜，使用該玻璃板，製 作比較例1與2。 〔表1〕 實施例1 實施例2 實施例3 比較例1 比較例2 熱處理 溫度(。〇 825 850 800 550 1050 條件 時間(分） 90 30 90 90 30 將實施例之防眩玻璃與比較例，依下述所示方法，對 表面凹凸進行評估。得表2所示評估結果。 1. 表面粗度與平均間距之測定 依JIS B 060 1 -200 1爲基準之方法，使用小坂硏究所 製觸針式表面掃描計（SURFC ORDER ET4 000 A )測定其算 術表面粗度Ra與平均間距Srn。 • 2. 60°鏡面光澤度 . 依JIS Z 874卜1 997爲基準之方法，使用日本電色製[Technical Field] The present invention relates to an anti-glare glass which forms irregularities on a surface of a transparent glass plate and which does not easily recognize a reflection image from the surface of the glass plate, and a manufacturing method thereof. [Prior Art] When a φ liquid crystal display (LCD) is installed on a display panel of a thin TV or a touch panel, or a tablet computer, in addition to text input, input, etc., such as input pens, etc. The input content can also be displayed on a display panel used by a display device (pen input device) such as a display panel. In the display panel, in order to prevent the display content from being observed by a illuminator such as a fluorescent lamp or a reflection of a background, and to improve the visibility of display, the display surface is required to have an anti-glare property or the like. #玻璃板 with anti-glare function, at present, the surface of the glass plate is etched with hydrofluoric acid or the like, and a method such as a concave-convex shape is provided on the surface of the glass plate. Patent Document 1 discloses a method. The surface of the glass plate having anti-glare property obtained by the etching process is transferred onto the surface of the resin film to produce a resin film having anti-glare property, etc. Further, the surface of the glass substrate is attached with 0.05 to 0.5. The article of the resin film of the irregular shape of #m is also disclosed in Patent Document 2. Further, Patent Document 3 discloses a convex shape of 5 to 10 // m by the sol-gel method, and has anti-glare property. Japanese Patent Publication No. 2005-3075 [Patent Document 1] JP-A-2005-3 3 1 90 1 (Patent Document 2) JP-A-2000- 1 1 1 7 1 3 (Patent Document 3) Special Opening 2003- 1 86004 SUMMARY OF THE INVENTION According to the etching treatment method, in addition to the high-priced method, it is necessary to treat a waste liquid such as hydrofluoric acid used in the etching treatment, and it is also necessary to control the size of the uneven shape and the like. Have The convex resin film or the scattered reflection film obtained by the sol-gel method has poor abrasion resistance and is difficult to be cleaned when it is contaminated, so that a surface having abrasion resistance and easy-washing property is highly desired. The present invention aims to provide an anti-glare glass which is excellent in abrasion resistance and easy to clean, and which can be manufactured at a low cost, and a method for producing the same. The anti-glare glass of the present invention has an anti-glare surface formed thereon. The glare glass has a surface unevenness which is formed by reacting an aluminum metal film formed on the surface of the glass plate with a cerium oxide component in the glass plate. The method for producing the anti-glare glass of the present invention is characterized in that The method includes the steps of forming an aluminum metal film on the surface of the glass sheet, and the step of heat-treating the glass sheet after the film formation. The method for producing the anti-glare glass of the present invention is the manufacture of the anti-glare glass. In the method, the method for producing an anti-glare glass having a heat treatment temperature of 600 to 1000 t. The anti-glare glass of the present invention can provide a flat surface such as a liquid crystal display or a plasma display. The front panel of the display, especially the display surface, can use the pen input liquid-5-200811075. The glass plate used for the front panel of the crystal display, the glass plate for the construction, the glass plate for the window, etc., in addition to improving the surface hardness, The anti-glare glass of the present invention is excellent in mass production and production of the anti-glare glass. The anti-glare glass of the present invention is obtained by heating the glass plate of the glass film with the aluminum metal film and heating the glass plate. a glass plate which is reacted with aluminum gold to form a surface unevenness on a glass plate, and which is used in an amount of 45 wt% or more, preferably 50 wt% or more, which is reacted with aluminum metal, using soda lime silicate glass, A bismuth silicate glass, a bismuth borosilicate glass, a quartz glass, in particular, a glass plate used in the present invention, in the case of quality, a glass plate obtained by a moving method using a float method, except for a transparent glass. The thickness of the glass substrate used for the colored glass such as bronze or the floating glass which absorbs infrared or ultraviolet glass can be selected according to the defense, generally with 0.1. 10.0mm thickness of the display device in front of, to a glass plate having a 〇.1 preferably at windows and other home Ju, a thickness of a building 2~10mm the range which can be used with the area, and a glass plate of suitable thickness. Further, in addition to the visibility of the aluminum metal film formed on the glass plate, the display area of the structure can be obtained by processing the aluminum metal film on a large area at low cost. The genus is presumed to be heated. Therefore, the Si 2 component of the present invention preferably contains a glass frit, for example, a glass plate such as borosilicate glass or aluminum. It is preferable to consider the price or the surface of the glass plate. Floating, other glass such as green, glass, etc., is preferably used for any glass glare glass. For the glass plate used in the display area of the thickness range of ~2 mm, for example, physical vapor deposition (PVD) such as sputtering -6-200811075 or ion implantation, or chemistry such as thermal, plasma or photo CVD can be used. A dry film forming method such as vapor deposition (CVD) is preferable in terms of productivity, etc. The thickness of the aluminum metal film used for film formation is preferably such that the film thickness is 1 〇 nm or more for the purpose of obtaining a surface unevenness shape capable of producing an anti-glare property. In order to form a large uneven shape, it is preferable to form a thick film of aluminum metal film, but the thicker the film thickness, the heating temperature must be increased, or the heating time must be increased, so that the film thickness is 1 〇. Below μπι is preferred. When the unevenness is too large, the scattering of the transmitted light is increased, and there is a problem in the transparency. Therefore, the film thickness of the aluminum metal film is more preferably Ιμηη or less, and most preferably 500 nm or less. After the aluminum metal film is formed on the surface of the glass plate, the heat treatment of the glass plate is preferably performed at a temperature of 600 ° C or more and a temperature higher than a softening temperature of the glass plate by 300 ° C. Φ The fine surface irregularities formed on the surface of the glass sheet by heat treatment are formed by the reaction of the glass substrate component with aluminum metal, which may be changed by changing the film thickness of the aluminum metal film, the temperature or time of heat treatment, and the like. The shape of the surface relief. When the heat treatment temperature is less than 60 (TC), the glass substrate component does not easily react with the aluminum metal, and the shape of the desired fine surface irregularities cannot be obtained. Further, the temperature far beyond the softening point of the glass sheet, such as soda lime (Soda lime) glass, when it exceeds 1 000 °C, even if the glass substrate component reacts with aluminum metal to form surface irregularities, the surface of the glass base-7-200811075 is softened and deformed due to temperature. Therefore, when the glass plate is Soda lime glass, the heat treatment temperature is preferably in the range of 650 to 950 ° C. More preferably, it is 700 to 900 〇 C. Further, the heat treatment time depends on the heat treatment. The temperature and the necessary surface unevenness are determined. From the viewpoint of productivity, the atmosphere at the time of heat treatment is preferably within 200 minutes, and there is no problem in the atmosphere, inert gas or reducing atmosphere, but productivity. In view of the cost, etc., it is particularly preferable to carry out the atmosphere in an atmosphere. The surface unevenness of the anti-glare glass of the present invention is an arithmetic surface roughness R obtained in accordance with JIS B 0601-2001. a is in the range of 0.1 to 0.5 μm, and an article having an average anti-glare property in the range of 50 to 100 μm in average pitch (concavity and convexity) Sm can be formed. [Embodiment] Hereinafter, examples and comparative examples will be described. The invention will be described in detail, but the present invention is not limited to the following. The production of the anti-glare glass is a glass plate of soda lime silicate glass obtained by a floating method having a thickness of 2.3 mm, and the surface of the glass plate is used. 10 nanometers of aluminum metal film was formed by sputtering method. After film formation, the glass plate was heat-treated according to the temperature and time shown in Table 1 to prepare the anti-glare glasses of Examples 1 to 3. Further, according to the implementation -8 - 200811075 In the same manner, a film of aluminum metal was formed, and Comparative Examples 1 and 2 were produced using the glass plate. [Table 1] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Heat treatment temperature (. 850 800 550 1050 Condition time (minutes) 90 30 90 90 30 Using the anti-glare glass of the example and a comparative example, the surface unevenness was evaluated by the method shown below. The evaluation results shown in Table 2 were obtained. Degree and level The measurement of the average pitch is based on JIS B 060 1 -200 1 and the arithmetic surface roughness Ra and the average spacing Srn are measured using a stylus surface scanner (SURFC ORDER ET4 000 A) manufactured by Xiaoyan Research Institute. 60° specular gloss. Based on JIS Z 874 1 997, using Japanese electric color
鏡面光澤度測定機（Σ 80 COLOR MEASURING SYSTEM VGS )，於玻璃基板之裏面塗佈黒色塗料以進行抗反射處 理後，測定樣品中心點之6〇°鏡面光澤度。 3. 膜硬度之評估 依JIS K 5400- 1 990爲基準，評估其是否有因鉛筆芯 9 - 200811075 硬度所造成之損傷。又，以不會產生損傷之最硬鉛筆芯爲 鉛筆硬度，6H以上爲優（〇）、5H以上爲可（△)。 4.易洗浄性之評估 於使污穢之灰塵或指紋等有機污染有意地附著後，再 依（1)使用濕巾輕輕擦拭（5重複）-> (2)使用濕巾強 力擦拭（1 0重複）—（3 )使用硬海綿強力擦拭（100重 複）-(4 )使用鐵棉圈硏磨（lmin ) θ ( 5 )使用二氧化 鈽硏磨（2min)之順序洗淨表面，以將污穢完全去除之作 業程度定義易洗浄性，本發明之形成表面凹凸之面的評估 ，以可將有機物之污穢去除之情形爲優（〇），其他則爲 可（△)。 〔表2〕 評估項目 實施例1 實施例2 實施例3 比較例1 比較例2 表面粗度叹㈣ 0.15 0.38 0.37 0.08 0.01 平均間距Sm(//m) 59 87 85 無法測量 無法測量 60。鏡面光澤度 79 81 57 114 91 凹凸面之膜硬度 0(9H) 〇(9H) 0(9H) 〇(9H) 〇(9H) 易洗淨性 〇 〇 〇 〇 〇 就實施例及比較例之形成表面凹凸之面，測定其表面 粗度與平均間距、60°鏡面光澤度、膜硬度及易洗浄性之 評估結果係如表2所示。 比較例1與2因熱處理條件並不適當，故其算術平均 粗度Ra與平均間距Sm極小，即表面凹凸之凹凸極小， -10- 200811075 其結果當爲不具有有效防眩性機能之物，而難以作爲LCD 顯示元件用之防眩性玻璃基板使用。 又，實施例1〜3所得之防眩性玻璃，因可適當地依 熱處理條件進行處理，故算術平均粗度Ra與平均間距Sm 爲可發揮防眩性之適當數値。又，60°鏡面光澤度亦爲良 好，而顯示出優良之防眩性能。 又，因具有膜硬度、易洗浄性等良好性能，故極適合 作爲筆輸入裝置等LCD顯示元件用之防眩性玻璃使用。A specular gloss measuring machine (Σ 80 COLOR MEASURING SYSTEM VGS) was used to apply a ochre coating on the inside of a glass substrate for anti-reflection treatment, and then measured the specular gloss of 6 〇 ° at the center of the sample. 3. Evaluation of film hardness Based on JIS K 5400-1 990, it was evaluated whether it was damaged by the hardness of pencil lead 9 - 200811075. Further, the hardest pencil core which does not cause damage is pencil hardness, and 6H or more is excellent (〇), and 5H or more is (△). 4. Evaluation of easy-to-cleanness After intentionally attaching organic pollution such as dust or fingerprints, (1) Wipe gently with a wet wipe (5 repetitions)-> (2) Wipe strongly with a wet wipe (1) 0 repeat)—(3) Use a hard sponge to wipe strongly (100 repeats)-(4) Use iron wool ring honing (lmin) θ ( 5 ) Wash the surface with a cerium oxide mill (2 min) in order to The degree of operation in which the contamination is completely removed defines the washability, and the evaluation of the surface on which the surface is uneven in the present invention is evaluated so that the contamination of the organic matter can be removed (y), and the others are (?). [Table 2] Evaluation item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Surface roughness (4) 0.15 0.38 0.37 0.08 0.01 Average pitch Sm (//m) 59 87 85 Cannot be measured Cannot measure 60. Specular gloss 79 81 57 114 91 Film hardness of uneven surface 0 (9H) 〇(9H) 0(9H) 〇(9H) 〇(9H) Easy-cleaning 〇〇〇〇〇Formation of examples and comparative examples Table 2 shows the evaluation results of the surface roughness and the average pitch, 60° specular gloss, film hardness and easy-washing. In Comparative Examples 1 and 2, since the heat treatment conditions are not appropriate, the arithmetic mean roughness Ra and the average pitch Sm are extremely small, that is, the unevenness of the surface unevenness is extremely small, and -10-200811075, as a result, does not have an effective anti-glare function, It is difficult to use as an anti-glare glass substrate for an LCD display element. Further, since the anti-glare glass obtained in Examples 1 to 3 can be appropriately treated under heat treatment conditions, the arithmetic mean roughness Ra and the average pitch Sm are appropriate numbers which can exhibit anti-glare properties. In addition, the 60° specular gloss is also good, showing excellent anti-glare properties. Further, since it has excellent properties such as film hardness and easy-cleanability, it is suitably used as an anti-glare glass for an LCD display element such as a pen input device.
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