j727 tft lcd free sample

In this Arduino touch screen tutorial we will learn how to use TFT LCD Touch Screen with Arduino. You can watch the following video or read the written tutorial below.

As an example I am using a 3.2” TFT Touch Screen in a combination with a TFT LCD Arduino Mega Shield. We need a shield because the TFT Touch screen works at 3.3V and the Arduino Mega outputs are 5 V. For the first example I have the HC-SR04 ultrasonic sensor, then for the second example an RGB LED with three resistors and a push button for the game example. Also I had to make a custom made pin header like this, by soldering pin headers and bend on of them so I could insert them in between the Arduino Board and the TFT Shield.

Here’s the circuit schematic. We will use the GND pin, the digital pins from 8 to 13, as well as the pin number 14. As the 5V pins are already used by the TFT Screen I will use the pin number 13 as VCC, by setting it right away high in the setup section of code.

I will use the UTFT and URTouch libraries made by Henning Karlsen. Here I would like to say thanks to him for the incredible work he has done. The libraries enable really easy use of the TFT Screens, and they work with many different TFT screens sizes, shields and controllers. You can download these libraries from his website, RinkyDinkElectronics.com and also find a lot of demo examples and detailed documentation of how to use them.

After we include the libraries we need to create UTFT and URTouch objects. The parameters of these objects depends on the model of the TFT Screen and Shield and these details can be also found in the documentation of the libraries.

So now I will explain how we can make the home screen of the program. With the setBackColor() function we need to set the background color of the text, black one in our case. Then we need to set the color to white, set the big font and using the print() function, we will print the string “Arduino TFT Tutorial” at the center of the screen and 10 pixels  down the Y – Axis of the screen. Next we will set the color to red and draw the red line below the text. After that we need to set the color back to white, and print the two other strings, “by HowToMechatronics.com” using the small font and “Select Example” using the big font.

555715 五、 發明說明 ( ) 發 明 背 景 本 發 明 係 關 於 一 種 無驗 玻璃，其合適用來形成平面 顯 示 器 用 之 顯 示 器 玻 璃 板 .基材，諸如液晶顯示器（LCD )及 電 致 發 光 (EL)顯 示 器 用 於圖 像傳感器之玻璃板，諸如電 荷 耦 合 裝 置 (CCD )及接觸式圖像傳感器（C I S )、太陽能電池 及 其 類 似 物 0 本 發 明 亦 關 於使 用該無鹼玻璃之玻璃板。 巨 >八 刖 平 面 顯 示 器 正廣 泛地使用著，諸如LCD及EL 顯 示 器 〇 特 別 地 諸 如 丨有主動型陣列薄膜電晶管LCD (TFT- LCD)之 電 子 裝 置 其 厚度 薄及耗電量低因此可使用在 不 同 的 應 用 上 例 如 ， 可 使用 在汽車導航系統和數位照相 機 取 景 器 且 最 近 亦 使 用 在個 人電腦監視器及TV上。至 於平 面 顯 示 器 的 顯 示 器 基 材， 則廣泛地使用玻璃板。 TFT- LCD 面 板 製 造 者嘗 試藉由在由玻璃製造者所形 成 的 玻 璃 板 上 (空白板） 提 供數 個裝置，再將該玻璃板切割 成各 白 分 離 的 裝 置 以 作 爲 產物 來改善產率及減低成本。在 最 近 的 應 用 中 諸 如 個 人 電腦 之監視器及TV，則需要其自 身 爲 大 尺 寸 的 裝 置 〇 爲 了 獲得 數個如此大尺寸之裝置，已 需 要 具 有 大 面 積 的玻 璃 板 ，例 如，尺寸1 000x 1 200毫米。 另 一 方 面 行 動 裝 置（諸如行動電話及筆記型個人電腦） 則 需 要 重 量 輕 以 便 可由 使用者方便且容易地攜帶。 因 此 亦 需 要 重 量 輕 的 玻 璃板 。爲了減輕玻璃板的重量， 減 低 厚 度 爲 一 種 有 效 的 方 法。 目前’ TFT-LCD所使用的玻 璃 板 其典型的 厚 度 非 常 地 薄， 如約0 . 7毫米。 -3- 555715 五、 發明說明 ( 2 ) 但 是 具 有 此 大 尺 寸 及厚 度薄的玻 璃 板則會 因 其重 量 而 具 有 大 的 垂 度 〇 此 會 在 接下 來的製造 製 程中造 成 嚴重 的 問 題 〇 在玻 璃 製 造 者 中 先 形成 此型式的 玻 璃板， 然 後將 其 接 受 不 同 的 步 驟 諸 如 切 割、 退火、測 試 及淨化 〇 在這 步 驟 中 會 將 玻 璃 板 從 具 有多 層架子的 匣 子中載 入 及載 出 〇 詳 細 地 說 即 在 匣 子 的 內部 表面二邊 上 (在左及右邊上） 或 在 內 部 表 面 的 三 邊 上 (在左’ ‘右及背面邊上）設 有架子 〇 而 玻 璃 板則 水 平 地 保持 在 由支 持在架子 上 的二相 反 邊或 三 邊 之 位 置 上 〇 如 上 所 述 大尺 寸及厚度 薄 的玻璃 板 具有 較 大 的 垂 度 0 因 此 y 當 玻 璃 板放 到匣子的 架 子上時 有部 分 的 玻 璃 板 經 常 會 與 匣 子 接 觸或 有些玻璃 板 會斷裂 〇 另一 方 面 ， 當 將 玻 璃 板從 匣 子 的 架子 取出時， 玻 璃板會 因 猛烈 地 震 動 而 變 成 不 穩 定 〇 在 顯 示器 製造者中 同樣地 會 使用 類 似 的 匣 子 因 而 會 發 生 類 似的問 題。 因 其 重 里 而 產 生 的 玻 璃板 垂度會以 與 玻璃或 形 成玻 璃 板 的 玻 璃 材料 之 密 度 成 正 比， 而與楊式 模 數成反 比 的方 式改 變 〇 因 此 爲 了 抑 制 玻 璃板 :的垂度必 、需增加由楊式模數/ 密 度 之 比 率 所 提 供 的 比 模數 。爲此這 的，玻 璃 必需 具 有 高 的 楊 式 模 數 和 低 的 密 度。 甚至在相 同 的比模 數 下， 玻 璃 具 有 較 低的 密 度 (即， ，每單位體積相對地輕）而 允許玻 璃 板 可 在 相 同 重 量 下 增 加 厚 度。 玻璃板的 垂 度以與 厚 度的 平 方 成 反 比 的 方 式改 變 0 因 此， 此增加玻 -4- 璃 板厚度 可 非常 有 效 555715555715 V. Description of the invention () Background of the invention The present invention relates to a non-inspection glass, which is suitable for forming a display glass plate for a flat display. A substrate such as a liquid crystal display (LCD) and an electroluminescence (EL) display is used for Glass plates of image sensors, such as charge-coupled devices (CCD) and contact image sensors (CIS), solar cells and the like. The present invention also relates to glass plates using the alkali-free glass. Giant > Hachiman flat-panel displays are widely used, such as LCD and EL displays. In particular, electronic devices such as active-array thin-film transistor LCDs (TFT-LCD) have thin thicknesses and low power consumption. It is used in different applications, for example, in car navigation systems and digital camera viewfinders, and more recently in personal computer monitors and TVs. As for the display substrate of a flat display, a glass plate is widely used. TFT-LCD panel makers try to improve yield and reduce yield by providing several devices on a glass plate (blank plate) formed by a glass maker, and cutting the glass plate into separate devices as products. cost. In recent applications, such as personal computer monitors and TVs, they need to be large-sized devices themselves. In order to obtain several such large-sized devices, glass plates with large areas have been required, for example, sizes 1 000x 1 200 Mm. On the other hand, mobile devices (such as mobile phones and notebook personal computers) need to be lightweight and portable by users. Therefore, a light-weight glass plate is also required. In order to reduce the weight of the glass plate, reducing the thickness is an effective method. The typical thickness of the glass plate currently used for TFT-LCDs is very thin, such as about 0.7 mm. -3- 555715 V. Description of the invention (2) However, a glass plate with this large size and thin thickness will have a large sag due to its weight. This will cause serious problems in the subsequent manufacturing process. In glass Manufacturers first form this type of glass plate and then subject it to various steps such as cutting, annealing, testing and cleaning. In this step, the glass plate is loaded and carried out from a box with multiple shelves. Detailed That is to say, there are shelves on the two sides of the inner surface of the box (on the left and right sides) or on the three sides of the inner surface (on the left and right sides and the back side). The glass plate is held horizontally by the support. On two opposite sides or three sides of the shelf. As mentioned above, the large and thin glass plates have a large sag 0. Therefore, when the glass plates are placed on the shelf of the box, some of the glass plates are often meeting The box touches or some glass plates break. On the other hand, when the glass plate is taken out of the box"s shelf, the glass plate becomes unstable due to violent vibration. Similar boxes are used in the display maker, and this happens. Similar question. The sag of the glass plate due to its weight will change in proportion to the density of the glass or the glass material forming the glass plate, and inversely proportional to the Young"s modulus. Therefore, in order to suppress the glass plate, the sag must be increased Specific modulus provided by the Young"s modulus / density ratio. For this purpose, glass must have a high Young"s modulus and a low density. Even at the same specific modulus, glass has a lower density (ie, relatively light per unit volume) and allows the glass plate to be thickened at the same weight. The sag of the glass sheet is changed in an inversely proportional manner to the thickness square. Therefore, increasing the thickness of the glass sheet can be very effective.

五、 發明說明 ( 3 ) 地 抑 制 垂 度 〇 低 密 度 玻 璃 亦 可有 效 地 減 低玻 璃 板 的 重 量 〇 因 此 玻 璃 密 度 較 佳 地 儘 可能地低 〇 通 常 地 Μ j\\\ 鹼 玻 璃 型 式包含一 相 當 大 量鹼 土 金 屬 氧 化 物 〇 爲 了 降 低玻 璃 密 度 有 效 的是 減 低 驗 土金 屬 氧 化 物 的 含 量 〇 但 是 驗 土 金 屬 氧 化 物 爲一 種 可 加 強玻 璃 的 可 熔 性 之 成 分 若 減 低 其 含 量 則 會 減 少其 可 熔 性 。玻 璃 的 可 熔 性 減 少則 會 導 致 容 易 發 生 內 部 缺 陷， 諸 如 種 子及 結 石 〇 於玻 璃 中 存在 的 種 子 及 結 石 爲 用 做 顯示 器 之 玻 璃板 的 嚴 重 缺 陷 J 因 爲 其 會 防 止 光 穿 透 0 爲 了 抑制 此 內 部缺 陷 1 玻 璃 必 需 在 局 溫 下 熔 化 --- 段 長 時 間 〇 但 是 在 高 溫 下 熔 化 會 增 加玻 璃 熔 爐 的負 載 量 〇 例 如 9 使用 作 爲 爐 材料 的 耐 火 材料 (諸如氧化鋁或氧化锆） 當 溫 度 較 高 時 會 受 到 更 猛 烈 的 侵 蝕。 在此 事 件中 爐 的 壽 口卩 會 縮 短 〇 此 外 ， 可 在 局 溫 使 用 的器 具 及 設 備亦 有 所 限 制 且 成 本 相 當 高 〇 再 者 爲 了 將 爐 :內溫 L度 :連繪地保持在局溫（ 如 與 可 在 低 溫 熔 化 的 玻 璃 比 較 :)，， 則； 宜 /、 經 營費 較 局 〇 因 此 1 局 溫 熔 化 對 玻 璃 製 造 來 說 非 常不 利 〇 故 ，想 要 提 供 — 種 可 在低 溫 熔 化的 Μ 驗 玻 璃 〇 至 於 另 一 個 重 要 的 需 求 爲 ，此 型 式 的 玻璃 板 必 需 具 有 抗 熱 衝 擊 性 〇 在玻 璃 板 的 終 面 ，即 使 在 進 行切 面 時亦 會 顯 現 出 顯 微 的 瑕 疵 及 裂 痕 〇 在 熱 抗張 應 力 凝 結至 該 些 瑕 疵及 裂 痕 的 情 況 中 玻 璃 板 可 能 會 斷裂 〇 玻 璃 板的 破 損 會 減 低 生 產 線 的 操 作 速 率 〇 此外 在 破損 •5- 後 散 亂 的細 玻 璃 顆 ik丄 ψΐί 會 黏 555715 五、 發明說明（4) 附 至 另 一 個玻璃板上，而造成在上面形成的電子 電 路線 中 斷 或 圖 形 誤差的情形。 最 近 的 TFT-LCD發展不僅定位在較寬且重量較 輕 的螢 幕 而 且 亦在其性能的改良，諸如較高的淸晰度、 較 商速 的 反 應 性 及 較高的孔徑比。最近，爲了改善LCD的 性能和 減 低 其 重 量 之目的，已積極地在發展多晶矽TFT-LCD ( p-Si • TFT- LCD) 。現在的P-Si · TFT-LCD需要溫度非常; 筒1 (如 800 °C 或 更 局 )之製造製程。此一高製造製程溫度僅 可 單獨 地 使 用 在 二 氧化矽玻璃板上。但是，由於最近的發 展 ，製 造 製 程 溫 度 已降低到400至600°C的程度。因此， 已 將無 驗 玻 璃 板 引 入p-Si · TFT-LCD的製造中，如於目前 已 大量 製 造 的 非 晶 矽 TFT-LCD(a-Si · TFT-LCD)—般。 如 與 a -Si · TFT-LCD的製造製程比較，P-Si · • TFT-LCD 之 製 造 製 程包括更多的熱處理步驟。玻璃板重覆 地 接受 快 速 加 熱 及 快速冷卻，如此在玻璃板上的熱衝擊較 大 。如 上 所 述 玻 璃板的尺寸會增加。因此，玻璃板易受 溫 度分 佈 的 影 響 〇 此外，在玻璃板終面處所發生的顯微瑕 疵 及裂 痕 之 發 生 機 率高。此意謂著玻璃板在加熱處理步驟 時 斷裂 的 機 率 筒 〇 最基本且最有效地解決上述所提及的問 題 之方 法 爲 減 低在 熱膨脹時所產生的熱應力差異。爲此目 的 ，需 要 具 有 低 熱 膨脹係數的玻璃。若在玻璃與薄膜電晶體（TFT) 材料 間 的 熱膨脹差異增加，則玻璃板將會變形。 因 此， 此 玻 璃 所 需 要具有的熱膨脹係數需接近TFT材料（ -6- 約 30- 555715 五、發明說明（5) 3 3 X 1 (Γ7 / °C )，諸如 p - S i。 p-Si · TFT-LCD的製造製程溫度最近已降低到如上所述 ，但是其與a-Si · TFT-LCD的製造製程溫度比較起來尙非 常高。若玻璃板具有低的耐熱性，則當將玻璃板曝露至在 p-Si · TFT-LCD製造製程期間的400至60(TC高溫時，其 會發生尺寸上的縮小（所謂的熱收縮）。熱收縮可能會造成 TFT的圖素間距誤差而產生顯示器缺陷。若玻璃板具有較 低的耐熱性，則玻璃板會變形和翹曲。再者，圖案誤差可 能會因玻璃板在液晶製造步驟（諸如薄膜沈積步驟）時的熱 收縮而產生。鑑於上述，此玻璃需要優良的耐熱性。 在TFT-LCD的玻璃板表面上，會沉積透明的導電薄膜、 絕緣薄膜、半導體薄膜、金屬薄膜及其類似物，再利用光 微影光刻程序來鈾刻（光蝕刻）而形成不同的電路及圖案。 在薄膜沈積步驟及光蝕刻步驟中，玻璃板會接受不同種類 的加熱處理及化學處理。 因此，若玻璃包含驗金屬氧化物（N a 2 Ο、K 2 0、L i 2 0 )，則 鹼金屬離子會在加熱處理期間擴散至沉積的半導體材料中 而惡化薄膜特徵。此外，此玻璃需要實質上不包含鹼金屬 氧化物且具有抗化性，如此不會由光鈾刻步驟中所使用的 不同化學物質（諸如酸類及強鹼類）造成惡化。 大體而言，TFT陣列製程包括重覆的薄膜沈積步驟、光 阻圖案形成步驟、蝕刻步驟及光阻移除步驟。可使用多種 化學溶液來製得蝕刻劑，例如，可使用磷酸溶液來蝕刻以 555715 五、發明說明（6) A1-或Mo-爲基底的薄膜；可使用王水（HC1+HN〇3)溶液來蝕 刻IT0薄膜；緩衝的氫氟酸（BHF)溶液則可用於SlNx或 S i 02膜薄上。爲了節省成本，蝕刻劑並不會在單一次使用 後拋棄，而是會透過液體循環系統再循環。 若玻璃板具有低的抗化性，則玻璃板會在蝕刻步驟中與 蝕刻劑反應而產生反應產物，此些產物會堵塞或塞滿液體 循環系統中的過濾器。此外，不均勻的蝕刻會使玻璃產生 白色霧狀表面。再者，蝕刻劑的組分改變會使得蝕刻速率 不穩定。因此，可能會發生多種問題。特別地，諸如BHF 的氫氟酸溶液會猛烈地侵蝕玻璃板，因此，會趨向於發生 上述提及的問題。此外，玻璃板特別地需要優良的抗BHF 性。 至於玻璃板的抗化性，重要的是其不僅只可有小的侵蝕 而且亦需在外觀上不會造成改變。特別地，玻璃板僅會由 化學溶液小小地侵蝕是非常重要的，尤其是此性能可防止 在蝕刻步驟期間因其反應產物而污染化學溶液及阻塞過濾 器。對透光度很重要的顯示器基材來說，不可缺少的特徵 爲在玻璃外觀上不可由化學處理而造成任何改變，諸如白 色霧狀或粗糙。侵蝕及外觀的改變之評估結果不需相符合 ，特別是關於抗BHF性。例如，具有相同侵蝕度的那些玻 璃可或可不在化學處理後造成外觀改變’完全依其組成物 而定。 同時，TFT-LCD用之玻璃板主要地利用下拉法或漂浮法 555715 五、發明說明（7 ) 形成。下拉方法包括狹縫下拉法及擠出下拉法。在考慮到 成本的減低，則下拉法較優良，因爲以此方法形成的玻璃 板不需要拋光。但是，在利用下拉法形成玻璃板的情況中 ’玻璃會趨向於失透明。因此，玻璃必需具有優良的抗失 透明性。 目前，商業上可購得的TFT-LCD用之玻璃板有，由康寧 公司（Corning Incorporated)製造的1737玻璃及由日本 電玻璃有限公司（Nippon Electric Glass Co. ， Ltd.)製 造的0A-10玻璃等等。這些玻璃具有約6 50 °C的應變點， 因此具優良的耐熱性。但是，每種玻璃都具有高的熱膨脹 係數和密度。因此，若將其使用作爲P-Si · TFT-LCD的玻 璃板，則其抗熱衝擊性不足。此外，這些玻璃皆很重，此 會使得其難以增加尺寸和減低厚度。 發明槪述= 因此，本發明之目標爲提供一種無鹼玻璃，其合適於製 造用做顯示器基材及其類似物的玻璃板。 本發明的另一個目標爲提供一種利用上述提及之無鹼玻 璃所製造的玻璃板。 本發明另一個目標爲提供一種包含上述提及之玻璃板的 液晶顯示器。 根據本發明已提供一種無鹼玻璃’其實質上的組成爲（ 質量百分比）58 - 70%Si02、10-19%A12〇3、6·5-15%Β2〇3、0-2%MgO 、 3-12%CaO 、 0.1-5%BaO 、 0-4%Sr〇、0.1- 555715 五、發明說明（8) 6%(Ba〇+Sr〇）、0-5%ZnO、 5-15% (MgO+Ca〇+Ba〇+SrO+Zn〇） 、0-5%-ZrO2、0-5%Τι02 及 〇-5%P205，其實質上無包含鹼 金屬氧化物且具有密度2.45克/立方公分或更少，在30 至3 80°C間的溫度範圍中之平均熱膨脹係數爲25χ 10_7/°C -36x1(T7/°C及應變點不低於640°C。 根據本發明，亦已提供一種由一無鹼玻璃形成的玻璃板 ，其實質上由 58-70%Si02、 l〇-19%Al2〇3、 6.5-15%B203、 0-2%MgO、3-12%CaO、0.1-5%BaO、0-4%SrO、0.1-6%(Ba〇+Sr〇）、0-5%ZnO、 5-15% (MgO+CaO+BaO+SrO+ZnO) 、0-5%Zr02、0-5%Ti02 及 〇-5%P205 組成（質量百分比），其 實質上無包含鹼金屬氧化物且具有密度2.45克/立方公分 或更少，在30至3 80°C間之溫度範圍中的平均熱膨脹係數 爲 25><10_7/t -36xl0_7/t：及應變點不低於 640°C。 根據本發明，亦已提供一種包含一由無鹼玻璃所形成的 玻璃板之液晶顯示器，該無鹼玻璃實質上之組成爲（質量 百分比）5 8 - 70%Si02、10-19%A12〇3、6.5-15%B203、0-2%Mg〇 、3-12%Ca〇、0.1-5%BaO 、 0-4%SrO 、 0.1-6%(Ba〇+SrO)、 0-5%ZnO、5-15%(Mg〇 + CaO + Ba〇 + SrO + Zn〇）、0-5%Zr〇2、0-5%ΤΊ02及〇-5%P205，其實質上無包含鹼金屬氧化物且具有 密度2.45克/立方公分或更少，在30至3 80 °C間之溫度範 圍中的平均熱膨脹係數爲25 Μ 0_7/°C -36 xlO·7/°C及應變點 不低於640°C。 較佳具體實施例之描沭： -10- 555715 五、發明說明（9) 根據本發明之具體實施例的無鹼玻璃，其實質上無包含 鹼金屬氧化物且其基本組成爲（質量百分比）58 - 70%Si02、 10-19%Al2〇3、6.5-15%B2〇3、0-2%MgO、3-12%CaO、0.1-5%BaO 、 0-4%Sr〇、0·卜6%(Ba〇+SrO) 、 0-5%ZnO 、 5-15% (Mg〇+CaO+BaO+Sr〇+ZnO) 、 0-5%Zr02 、 0-5%Ti〇2 及 0- 5%P2 0 5。上述提及的組成物乃考慮到無鹼玻璃的應變點、 密度、熱膨脹係數、抗化性、比模數、可熔性及模鍛性而 決定。如此獲得的無鹼玻璃具有密度2.45克/立方公分或 較少，在30至380°C間之溫度範圍中的平均熱膨脹係數爲 25xl(T7/1 -36xl0_7/°C及應變點不低於640°C。因此，該 無鹼玻璃可提供優良的抗熱衝擊性、無翹曲（因爲熱膨脹 係數接近TFT材料）、輕的重量、減低的垂度及小的熱收 縮。 較佳地，密度不高於2 . 40克/立方公分。平均熱膨脹係 數較佳地在28xl(T7/°C至35M(T7/°C之範圍間。應變點較 佳地不低於6 5 0 °C，更佳地不低於6 6 0 °C。 在上述提及的無鹼玻璃中，其液線溫度不高於1150°C， 較佳地不高於113(TC，更佳地不高於110(TC。在液線溫 度處的黏度不低於105 4dPa · s，較佳地不低於106 ()dPa · s。因此，玻璃板可利用下拉法將無鹼玻璃形成板狀而獲 得，其無失透明且可因省略拋光步驟而減低製造成本。 當該無鹼玻璃於80°C的10%HC1水溶液中處理24小時後 ，其侵蝕不大於10微米。當該無鹼玻璃於80°C的10%HC1 -11- 555715 五、發明說明（1〇) 水溶液中處理3小時後，由視覺觀察確定在表面上並無白 色霧狀或粗糙。當該無鹼玻璃在20°C的130 BHF溶液中處 理30分鐘後，其侵蝕度不大於〇 . 8微米。當該無鹼玻璃 在20°C的63 BHF溶液中處理30分鐘後，利用視覺觀察確 定在表面上並無白色霧狀或粗糙。因此，該無鹼玻璃具有 優良的抗化性。 該比模數不小於 27.5GPa/(克·公分·3)，較佳地爲 29. OGPa/(克·公分_3)。因此，可減低該玻璃板在形成後 之垂度。因爲該玻璃在黏度102‘5dPa · s處的熔融溫度不 高於1 650t，故其可熔性優良。 上述提及的玻璃板具有低密度及高比模數。因此，即使 將該玻璃板的厚度減低至0.6毫米或更少（例如，0 . 5毫米 或更少）時，如與現存的玻璃板比較其垂度亦較小。因此 可防止將該玻璃板從匣子的架子中放入及取出時的斷裂。 因此，該玻璃板可合適地使用作爲顯示器基材。 其次，將描述爲何會將上述提及的無鹼玻璃之每種成分 的含量決定爲如上述所詳細指明之理由。 上述提及的無鹼玻璃包含5 8 - 70%Si02。若其含量少於 5 8%，則抗化性（特別是抗酸性）會降低且難以獲得低密度 。另一方面，若其含量多於70%，則其高溫度黏度會增加 而會降低其可熔性，因而容易在玻璃中造成失透明結石（ 白矽石）的缺陷。Si02的含量較佳地不小於60%(更佳地不 小於62%)及不大於68%(更佳地不大於66%)。 -12- 555715 五、發明說明（11) A 1 203的含量爲10-19% \若其含量少於10%則難以獲得 不低於640°C的應變點。A 1 2 03可提供改善玻璃的楊式模數 而增加比模數。若A 12〇3的含量少於1 〇%則楊式模數會減 少。另一方面，若其含量多於1 9%時，則液線溫度會變高 以至於會降低抗失透明性。A 1 203的含量較佳地不小於 12%(更佳地不小於14.5%)及不大於18.0%。 在上述提及之無鹼玻璃中，富鋁紅柱石或鈣長石會趨向 於與白矽石一起沉積而成爲失透明結晶。富鋁紅柱石或鈣長 石的沈積程度大大地受了除MgO外的鹼土金屬氧化物之總 莫耳數和 A12〇3莫耳數之莫耳比率，g卩， (Ca0 + Ba0 + Sr0)/Al 203的影響。若該莫耳比率不大於〇.8 則不適合，因爲此會趨向於增加失透明性且減少模鍛性。 另一方面，莫耳比率不小於1 . 5亦不適合，因爲此會增加 密度。更佳地，此莫耳比率在0 . 9至1 . 2之範圍間。 Beg爲一種用作爲熔化劑之成分，其可減低黏度並改善 可熔性。若B203的含量小於6 . 5%，則其作爲熔化劑的效 應會不足且抗BHF性會降低。若含量大於1 5%，則玻璃的 應變點會降低以至於會減少其耐熱性。此外，抗酸性會降 低。再者，會因楊式模數降低而減低比模數。B20 3的含量 較佳地不小於7%(更佳地不小於8.6%)且不大於14%(更佳 地不大於12%)。 Mg〇之提供可減低高溫黏度並改善玻璃的可熔性而沒有 降低應變點。在鹼土金屬的氧化物類當中，MgO在減低密 555715 五、發明說明（12) 度上最有效。但是，若MgO的含量較多時，則液線溫度會 提昇以至於抗失透明性會降低。此外，MgO會與BHF反應 而產生一反應產物，其會附著至位於玻璃板表面上之裝置 ，或其會黏附至玻璃板上。所以玻璃板會變模糊。因此， 必需限制其含量。M g 0的含量爲0 - 2 %，較佳地爲0 - 1 %，更 佳地爲0-0.5%。再者，想要的是實質上不包含Mg〇。 如MgO般，CaO可提供減低高溫黏度和可明顯地改善玻 璃的可熔性而沒有降低應變點。CaO的含量爲3 - 1 2%。通 常地，此型式的無鹼玻璃幾乎不熔化。爲了以低成本供應 大量高品質的玻璃板，重要的是改善其可熔性。減低S i〇2 的含量可最有效地改善可熔性。但是，減低Si02含量是不 利的，因爲其抗酸性會極度地降低且玻璃的密度和熱膨脹 係數會增加。因此，爲了改善可熔性可包含3%或更多的 Ca〇° 若CaO的含量少於3%，則必需增加BaO及SrO的含量以 便使（Ca0 + Ba0 + Sr0)/Al 203的莫耳比率落在0.8至1.5的 範圍之間。但是，高的BaO及S 1*0含量是不利的，因爲此 會相當大地增加密度。另一方面，多於12%的CaO亦不利 ，因爲玻璃的抗BHF性會降低。在此情況中，玻璃板表面 容易受侵蝕且其反應產物會黏附至玻璃板表面，以至於玻 璃變模糊。此外，熱膨脹係數會變得過高。想要的CaO含 量爲不小於4%(更佳地不小於5%)及不大於10%(更佳地不 大於9 % )。 -14- 555715 五、發明說明（13) Ba〇及SfO每種皆爲一種可改善玻璃的抗化性及抗失透 明性之成分。但是，高含量的BaO及S 1*0會增加玻璃的密 度及熱膨脹係數。因此，BaO及SrO的含量必需各別地限 制在0. 1-5%及0-4%。在減低BaO及S rO的含量以達成低 密度之目的的情況中，若BaO及S 1*0的含量極度地不均衡 時則改善抗BHF性的效應會減少。因此，想要的是所包含 的 BaO 及 SrO 可滿足：（Ba0 + Sr0)/Ba0=l.l-I0(較佳地， 1 . 2 - 5 )(以質量比）。想要的BaO含量爲不小於0 . 3%(更佳 地不小於0 . 5%)及不大於2%(更佳地不大於1%)。SrO的含 量較佳地爲0 . 1 - 2 . 7%，更較佳地爲0 . 3 - 1 . 5%。 BaO及SrO每種爲一種具有可特別地改善抗BHF性特徵 之成分。因此，爲了改善抗BHF性，這些成分的總含量需 要爲0.1%或更多（較佳地爲0.3%或更多，更佳地爲0.5%或 更多）。但是，若BaO及SrO的含量過多，則密度和熱膨 脹係數會如上述所提及般增加。因此，總含量必需抑制在 6%或較少。在上述提及的範圍中，考慮到改良抗BHF性， 則BaO及S rO的總含量想要儘可能地大。另一方面，若考 慮到減低密度及熱膨脹係數，則總含量想要儘可能地小。 ZnO爲一種可改善玻璃板的抗BHF性及可熔性之成分。 但是，高含量的ΖηΟ並不適宜，因爲如此玻璃會趨向於失 透明、降低應變點及增加密度。因此，ZnO的含量爲0-5% ，較佳地不大於3%，更佳地不大於0.9%及最佳地不大於 0.5%。 -15- 555715 五、發明說明（14) 藉由包含MgO、CaO、BaO、SrO及ZnO成分的混合物， 該玻璃的液線溫度會明顯地降低而且幾乎不會產生失透明 結石。因此，可改善玻璃的可熔性及模鍛性。但是，若 MgO、CaO、BaO、SrO及ZnO的總含量小於5%，則作爲熔 化劑的效應並不足所以可熔性會降低。此外，若熱膨脹係 數降低的過多則會無法與TFT材料相符。另一方面，總含 量多於1 5%亦不適宜，因爲密度會增加所以無法達成減低 玻璃板重量。此外，比模數會減少。MgO、CaO、BaO、Sr〇 及ZnO的總含量較佳地爲5-12%，更佳地爲5-10%。 Z f02爲一種可改善玻璃的抗化性（特別是抗酸性）及增加 楊式模數之成分。但是，含量多於5 %亦不適宜，因爲液線 溫度會提昇且會趨向於產生锆石的失透明結石。Z r02的含 量較佳地爲0 - 3%，更佳地爲0 - 1 %。 Ti〇2爲一種可改善玻璃的抗化性（特別是抗酸性）及減低 高溫黏度以改善可熔性之成分。但是，高含量使用對作爲 顯示器的玻璃板來說並不適宜，因爲玻璃會呈色而使透明 度減低。因此，T i 02的含量必需限制至〇 - 5%，較佳地0 -3%，更佳地0 - 1%。 P2〇5爲一種可改善玻璃的抗失透明性之組分。但是，高 含量亦不適宜，因爲會在玻璃中造成相分離及不透明，且 抗酸性會明顯地惡化。因此，P205的含量必需限制在0 - 5% ，較佳地0 - 3%，更佳地0 - 1%。 除了上述提及的成分之外，可包含最高約5%的Y 203、 -16- 555715 五、發明說明（15) Nb2D3及La 203。可提供這些成分以便獲得高應變點及高楊 式模數。但是，高含量並不適宜，因爲密度會增加。 再者，就不降低玻璃特徵而言，可包括最高5%的澄淸劑 ，諸如 As203、Sb203、Sb205、F2、Cl2、S03、C 或金屬粉末 (A1或Si)。亦可包括最高5%的Ce02、Sn02或Fe 203作爲 澄淸劑。 在無鹼玻璃熔融的情況中，可使用可於高溫下做爲澄淸 劑的A s 203。但是，最近則考慮不適宜使用會增加環境負 荷的化學物質，諸如As 203。如As 203般，Sn02具有於高溫 澄淸的能力而可非常有效地用於熔融的無鹼玻璃中作爲澄 淸劑。但是，高含量的3!1〇2會使玻璃失透明。因此，含量 需限制爲5%或更少，較佳地爲2%或更少。 C 1具有促進無鹼玻璃熔融的效應。藉由加入C1玻璃可 在低溫下熔化。因此，可使澄淸劑更有效地操作。再者， 其可降低熔化玻璃的成本並可延長生產設備的壽命。但是 ，過多的C1含量會降低玻璃的應變點。因此，想要的含 量限制在3%或更少。至於含C 1成分的原始材料，則可使 用由鹼土金屬氧化物製得之氯化物（例如氯化鋇）或諸如氯 化鋁之材料。 至於可使用於上述提及的無鹼玻璃之澄淸劑，Sb 203或 Sb 205亦有效。但是，因爲該無鹼玻璃具有高熔化溫度， Sb 203或Sb 205作爲澄淸劑的效應比As 203小。因此，在使 用Sb 203或Sb205的情況中，則想要增加諸如C1的含量或 -17- 555715 五、發明說明（16) 與之結合的成分來促進可熔性，而使熔化溫度降低。但是 ，若Sb 203或Sb 205的含量大於5%，則密度會增加。因此 ，其含量較佳地限制在2%或更少，更佳地1 . 5%或更少。 在不使用A s 203作爲澄淸劑的情況中，在〇 . 5 - 3 . 0%的含 量下較佳地包括至少一種選自於Sb 203、Sb 205、Sn02及C1 的物質。特別地，最佳地包含0.05-2.0%(Sb 20 3 + Sb 20 5 )、 0 . 01 · 1 .0%Sn02及 0 · 005 - 1 ·0%C1。 現在，將詳細地描述相關的特定實例。 在表1 - 1 7中，樣品案號1 - 46爲上述提及的無鹼玻璃之 特定實例。樣品案號47 - 49則爲比較例。樣品案號49爲 由康寧公司製造的1 737玻璃。V. Description of the invention (3) Suppression of low-density glass can also effectively reduce the weight of the glass plate. Therefore, the glass density is preferably as low as possible. Generally, the type of alkali glass contains a considerable amount. Alkaline earth metal oxides. In order to reduce the density of the glass, it is effective to reduce the content of the soil test metal oxides. However, the soil test metal oxides are a component that can strengthen the solubility of the glass. If the content is reduced, the solubility will be reduced. Decrease in the meltability of the glass will lead to the occurrence of internal defects, such as seeds and stones. Seeds and stones present in the glass are serious defects of the glass plate used as a display J because it will prevent light from penetrating. 0 In order to suppress this internal Defect 1 The glass must be melted at local temperature-for a long time. However, melting at high temperature will increase the load of the glass furnace. For example 9 Use refractory materials (such as alumina or zirconia) as furnace materials. When the temperature is higher Will be more severely eroded. In this event, the life span of the furnace will be shortened. In addition, the equipment and equipment that can be used at the local temperature are also limited and the cost is quite high. Furthermore, in order to keep the furnace: the internal temperature, the degree of temperature, and the continuous temperature at the local temperature (If it is compared with glass that can be melted at low temperature :), then; It should be /, the operating cost is more bureaucratic. Therefore, melting at 1 bureau temperature is very unfavorable to glass manufacturing. Therefore, I want to provide-a kind of M that can be melted at low temperature As for glass inspection, another important requirement is that this type of glass plate must be resistant to thermal shock. On the final surface of the glass plate, microscopic flaws and cracks will appear even when the surface is cut. In the case of stress condensing to these flaws and cracks, the glass plate may break. The damage of the glass plate will reduce the operating speed of the production line. In addition, the scattered thin glass particles after the breakage • 5 will stick 555715 (4) The invention description (4) is attached to another glass plate, which causes a broken or graphic error in the electronic circuit formed above. The recent development of TFT-LCD is not only positioned in a wider and lighter screen, but also in its performance improvements, such as higher clarity, faster response, and higher aperture ratio. Recently, polycrystalline silicon TFT-LCD (p-Si • TFT-LCD) has been actively developed for the purpose of improving the performance and reducing the weight of LCDs. The current P-Si · TFT-LCD requires very high temperature; the manufacturing process of tube 1 (such as 800 ° C or more). This high manufacturing process temperature can only be used on silica glass plates alone. However, due to recent developments, manufacturing process temperatures have been reduced to 400 to 600 ° C. Therefore, glassless panels have been introduced into the manufacture of p-Si · TFT-LCDs, just like amorphous silicon TFT-LCDs (a-Si · TFT-LCDs), which have been mass-produced at present. Compared with the manufacturing process of a-Si · TFT-LCD, the manufacturing process of P-Si · • TFT-LCD includes more heat treatment steps. The glass plate repeatedly receives rapid heating and rapid cooling, so the thermal shock on the glass plate is greater. The size of the glass plate described above will increase. Therefore, the glass plate is susceptible to the temperature distribution. In addition, micro-defects and cracks occurring at the glass plate"s final surface are more likely to occur. This means that the glass plate is likely to break during the heat treatment step. The most basic and effective way to solve the above mentioned problems is to reduce the difference in thermal stress generated during thermal expansion. For this purpose, glass with a low coefficient of thermal expansion is required. If the difference in thermal expansion between glass and thin-film transistor (TFT) materials increases, the glass sheet will deform. Therefore, the thermal expansion coefficient of this glass needs to be close to the TFT material (-6- about 30-555715) V. Description of the invention (5) 3 3 X 1 (Γ7 / ° C), such as p-S i. P-Si · The manufacturing process temperature of TFT-LCD has recently been reduced to the above, but it is very high compared with the manufacturing process temperature of a-Si · TFT-LCD. If the glass plate has low heat resistance, the glass plate should be exposed Up to 400 to 60 during the p-Si · TFT-LCD manufacturing process (at high temperature TC, it will shrink in size (so-called thermal shrinkage). Thermal shrinkage may cause TFT pixel pitch errors and display defects If the glass plate has low heat resistance, the glass plate may be deformed and warped. Furthermore, pattern errors may be caused by thermal contraction of the glass plate during a liquid crystal manufacturing step such as a thin film deposition step. In view of the above, This glass needs excellent heat resistance. On the surface of the TFT-LCD glass plate, transparent conductive films, insulating films, semiconductor films, metal films, and the like are deposited, and then lithography is used to etch uranium ( Photo-etching ) To form different circuits and patterns. In the thin film deposition step and photo-etching step, the glass plate will be subjected to different types of heat treatment and chemical treatment. Therefore, if the glass contains metal oxide (N a 2 0, K 2 0 , L i 2 0), the alkali metal ions will diffuse into the deposited semiconductor material during the heat treatment and deteriorate the thin film characteristics. In addition, the glass needs to contain substantially no alkali metal oxides and be resistant, so it will not Deterioration is caused by different chemicals (such as acids and strong bases) used in the photo-uranium etch step. Generally speaking, the TFT array process includes repeated thin film deposition steps, photoresist pattern formation steps, etching steps and photoresist shifts. In addition, a variety of chemical solutions can be used to prepare the etchant. For example, a phosphoric acid solution can be used to etch a film based on 555715 V. Invention Description (6) A1- or Mo-; aqua regia (HC1 + HN. 3) Solution to etch IT0 film; buffered hydrofluoric acid (BHF) solution can be used on SlNx or Si 02 film. In order to save costs, the etchant will not be discarded after a single use Instead, it will be recirculated through the liquid circulation system. If the glass plate has low resistance, the glass plate will react with the etchant during the etching step to produce reaction products, which will block or fill the liquid circulation system. Filter. In addition, uneven etching can cause a white hazy surface on the glass. Furthermore, changes in the composition of the etchant can make the etching rate unstable. Therefore, various problems may occur. In particular, hydrofluoride such as BHF The acid solution erodes the glass plate violently, and therefore, the problems mentioned above tend to occur. In addition, the glass plate particularly requires excellent BHF resistance. As for the resistance of the glass sheet, it is important that it not only has a small amount of erosion but also does not cause a change in appearance. In particular, it is very important that the glass plate is only slightly attacked by the chemical solution, especially this property prevents the chemical solution from being contaminated by the reaction products during the etching step and the filter is blocked. An indispensable feature for display substrates where transmittance is important is that the appearance of the glass must not be altered by any chemical treatment, such as white haze or roughness. Evaluation of erosion and appearance changes need not be consistent, especially with regard to BHF resistance. For example, those glasses having the same degree of erosion may or may not cause a change in appearance after chemical treatment "depending entirely on their composition. At the same time, the glass plate for TFT-LCD is mainly formed by the pull-down method or the float method 555715 V. Description of the invention (7). The pull-down method includes a slit pull-down method and an extrusion pull-down method. In consideration of cost reduction, the down-draw method is superior because the glass plate formed by this method does not need to be polished. However, in the case where a glass plate is formed by the down-draw method, the glass tends to be opaque. Therefore, glass must have excellent anti-opacity properties. Currently, commercially available glass plates for TFT-LCDs include 1737 glass manufactured by Corning Incorporated and 0A-10 manufactured by Nippon Electric Glass Co., Ltd. Glass and so on. These glasses have a strain point of approximately 6 50 ° C and therefore have excellent heat resistance. However, each glass has a high coefficient of thermal expansion and density. Therefore, if it is used as a glass plate of P-Si.TFT-LCD, its thermal shock resistance is insufficient. In addition, these glasses are heavy, which makes it difficult to increase the size and reduce the thickness. Summary of the Invention = Therefore, an object of the present invention is to provide an alkali-free glass suitable for manufacturing a glass plate used as a display substrate and the like. Another object of the present invention is to provide a glass plate manufactured using the alkali-free glass mentioned above. Another object of the present invention is to provide a liquid crystal display including the above-mentioned glass plate. According to the present invention, an alkali-free glass has been provided whose substantial composition is (mass percentage) 58-70% SiO2, 10-19% A1203, 6.5-15% B202, 0-2% MgO, 3-12% CaO, 0.1-5% BaO, 0-4% Sr0, 0.1-555715 V. Description of the invention (8) 6% (Ba〇 + Sr〇), 0-5% ZnO, 5-15% ( MgO + Ca〇 + Ba〇 + SrO + Zn〇), 0-5% -ZrO2, 0-5% T02, and 0-5% P205, which are substantially free of alkali metal oxides and have a density of 2.45 g / cm3 Or less, the average thermal expansion coefficient in the temperature range of 30 to 3 80 ° C is 25 × 10_7 / ° C -36x1 (T7 / ° C and the strain point is not less than 640 ° C. According to the present invention, it is also provided A glass plate formed of an alkali-free glass, which is substantially composed of 58-70% SiO2, 10-19% Al203, 6.5-15% B203, 0-2% MgO, 3-12% CaO, 0.1- 5% BaO, 0-4% SrO, 0.1-6% (Ba〇 + Sr〇), 0-5% ZnO, 5-15% (MgO + CaO + BaO + SrO + ZnO), 0-5% Zr02, 0-5% Ti02 and 0-5% P205 composition (mass percentage), which is substantially free of alkali metal oxides and has a density of 2.45 g / cm3 or less, in a temperature range of 30 to 3 80 ° C Average thermal expansion The coefficient is 25 > < 10_7 / t -36xl0_7 / t: and the strain point is not lower than 640 ° C. According to the present invention, a liquid crystal display including a glass plate formed of an alkali-free glass has also been provided. The composition of glass is (mass percentage) 5 8-70% SiO2, 10-19% A1203, 6.5-15% B203, 0-2% Mg〇, 3-12% Ca〇, 0.1-5% BaO , 0-4% SrO, 0.1-6% (Ba〇 + SrO), 0-5% ZnO, 5-15% (Mg〇 + CaO + Ba〇 + SrO + Zn〇), 0-5% Zr〇2 , 0-5% T02, and 0-5% P205, which are substantially free of alkali metal oxides and have a density of 2.45 g / cm3 or less, and average thermal expansion coefficients in a temperature range of 30 to 3 80 ° C 25 Μ 0_7 / ° C -36 x 10 · 7 / ° C and the strain point is not less than 640 ° C. Description of the preferred embodiment: -10- 555715 V. Description of the invention (9) According to the specifics of the present invention The alkali-free glass of the embodiment is substantially free of alkali metal oxides and its basic composition is (mass percentage) 58-70% SiO2, 10-19% Al203, 6.5-15% B203, 0-2 % MgO, 3-12% CaO, 0.1-5% BaO, 0-4% Sr0, 0 · 6% (Ba0 + SrO), 0-5% ZnO, 5-15% (Mg〇 + CaO + BaO + Sr〇 + ZnO), 0-5% Zr02, 0-5% TiO2, and 0-5% P205. The composition mentioned above is determined in consideration of the strain point, density, thermal expansion coefficient, chemical resistance, specific modulus, meltability, and forgeability of alkali-free glass. The alkali-free glass thus obtained has a density of 2.45 g / cm3 or less, and an average thermal expansion coefficient in a temperature range of 30 to 380 ° C is 25xl (T7 / 1 -36xl0_7 / ° C and a strain point of not less than 640 ° C. Therefore, the alkali-free glass can provide excellent thermal shock resistance, no warpage (because the thermal expansion coefficient is close to that of a TFT material), light weight, reduced sag, and small thermal shrinkage. Preferably, the density is not Higher than 2. 40 g / cm3. The average thermal expansion coefficient is preferably in the range of 28xl (T7 / ° C to 35M (T7 / ° C). The strain point is preferably not less than 650 ° C, more preferably The ground temperature is not lower than 6 60 ° C. In the alkali-free glass mentioned above, its liquidus temperature is not higher than 1150 ° C, preferably not higher than 113 (TC, more preferably not higher than 110 (TC) The viscosity at the liquidus temperature is not less than 105 4dPa · s, preferably not less than 106 () dPa · s. Therefore, the glass plate can be obtained by forming the alkali-free glass into a plate shape by the down-draw method without loss. Transparent and can reduce the manufacturing cost by omitting the polishing step. When the alkali-free glass is treated in a 10% HC1 aqueous solution at 80 ° C for 24 hours, its erosion is not greater than 10 micrometers. When the alkali-free glass is treated at 80 ° C in 10% HC1 -11- 555715 V. Description of the invention (10) After being treated for 3 hours in an aqueous solution, it is confirmed by visual observation that there is no white mist or roughness on the surface. After the alkali-free glass is treated in a 130 BHF solution at 20 ° C for 30 minutes, its erosion degree is not greater than 0.8 microns. When the alkali-free glass is treated in a 63 BHF solution at 20 ° C for 30 minutes, it is determined by visual observation There is no white haze or roughness on the surface. Therefore, the alkali-free glass has excellent chemical resistance. The specific modulus is not less than 27.5GPa / (g · cm · 3), preferably 29. OGPa / ( G · cm_3). Therefore, the sag of the glass sheet after formation can be reduced. Because the melting temperature of the glass at a viscosity of 102"5dPa · s is not higher than 1 650t, its meltability is excellent. The glass sheet has a low density and a high specific modulus. Therefore, even when the thickness of the glass sheet is reduced to 0.6 mm or less (for example, 0.5 mm or less), it is compared with the existing glass sheet. The sag is also small. Therefore, it is possible to prevent the glass plate from being put in and out of the box shelf. Therefore, the glass plate can be suitably used as a display substrate. Next, the reason why the content of each component of the alkali-free glass mentioned above is determined as the reason specified in detail above will be described. Alkali-free glass contains 5 8-70% SiO2. If the content is less than 5 8%, the chemical resistance (especially acid resistance) will be reduced and low density will be difficult to obtain. On the other hand, if the content is more than 70%, Then its high temperature viscosity will increase and its meltability will be reduced, so it is easy to cause the defects of opaque stones (white silica) in the glass. The content of SiO2 is preferably not less than 60% (more preferably not less than 62%) and not more than 68% (more preferably not more than 66%). -12- 555715 V. Description of the invention (11) The content of A 1 203 is 10-19% \ If the content is less than 10%, it is difficult to obtain a strain point of not less than 640 ° C. A 1 2 03 can improve the Young"s modulus of glass and increase the specific modulus. If the content of A 12〇3 is less than 10%, the Young"s modulus will decrease. On the other hand, if the content is more than 19%, the liquidus temperature becomes so high that devitrification resistance is reduced. The content of A 1 203 is preferably not less than 12% (more preferably not less than 14.5%) and not more than 18.0%. In the alkali-free glass mentioned above, mullite or anorthite tends to deposit together with wollastonite and become opaque crystals. The degree of deposition of mullite or anorthite is greatly influenced by the molar ratio of the total molar number of alkaline earth metal oxides other than MgO to the molar number of A1203 molar number, g 卩, (Ca0 + Ba0 + Sr0) / Influence of Al 203. It is not suitable if the Mohr ratio is not more than 0.8, because this tends to increase the opacity and reduce the forgeability. On the other hand, a Mohr ratio of not less than 1.5 is not suitable because it increases the density. More preferably, this Mohr ratio is in the range of 0.9 to 1.2. Beg is a component used as a melting agent, which reduces viscosity and improves meltability. If the content of B203 is less than 6.5%, its effect as a melting agent will be insufficient and the BHF resistance will be reduced. If the content is more than 15%, the strain point of the glass is reduced so that its heat resistance is reduced. In addition, acid resistance is reduced. Furthermore, the specific modulus is reduced due to a decrease in the Young"s modulus. The content of B20 3 is preferably not less than 7% (more preferably not less than 8.6%) and not more than 14% (more preferably not more than 12%). MgO provides lowering of high temperature viscosity and improved glass meltability without lowering the strain point. Among the oxides of alkaline earth metals, MgO is most effective in reducing the density. However, if the content of MgO is large, the liquidus temperature will increase and the resistance to devitrification will decrease. In addition, MgO will react with BHF to produce a reaction product, which will adhere to the device on the surface of the glass plate, or it will adhere to the glass plate. Therefore, the glass plate becomes blurred. Therefore, it is necessary to limit its content. The content of M g 0 is 0 to 2%, preferably 0 to 1%, and more preferably 0 to 0.5%. Furthermore, it is desirable that Mg0 is not substantially contained. Like MgO, CaO provides reduced viscosity at high temperatures and can significantly improve the meltability of the glass without reducing the strain point. The content of CaO is 3-12%. Generally, this type of alkali-free glass hardly melts. In order to supply a large number of high-quality glass plates at a low cost, it is important to improve their meltability. Reducing the Si02 content can most effectively improve the meltability. However, reducing the content of SiO2 is disadvantageous because its acid resistance will be extremely reduced and the density and thermal expansion coefficient of glass will increase. Therefore, in order to improve the meltability, 3% or more Ca may be included. If the content of CaO is less than 3%, it is necessary to increase the content of BaO and SrO in order to make (Ca0 + Ba0 + Sr0) / Al 203 Mol The ratio falls in the range of 0.8 to 1.5. However, high BaO and S 1 * 0 contents are disadvantageous because this increases the density considerably. On the other hand, more than 12% of CaO is also disadvantageous because the BHF resistance of the glass is reduced. In this case, the surface of the glass plate is easily eroded and the reaction products thereof adhere to the surface of the glass plate, so that the glass becomes blurred. In addition, the thermal expansion coefficient may become too high. The desired CaO content is not less than 4% (more preferably not less than 5%) and not more than 10% (more preferably not more than 9%). -14- 555715 V. Description of the invention (13) Each of Ba0 and SfO is a component that can improve the chemical resistance and devitrification resistance of glass. However, high contents of BaO and S 1 * 0 increase the density and thermal expansion coefficient of glass. Therefore, the contents of BaO and SrO must be individually limited to 0.1-5% and 0-4%. In the case where the content of BaO and S rO is reduced to achieve a low density, if the content of BaO and S 1 * 0 is extremely uneven, the effect of improving BHF resistance is reduced. Therefore, what is desired is that the contained BaO and SrO can satisfy: (Ba0 + Sr0) / Ba0 = 1.1-I0 (preferably, 1.2-5) (in terms of mass ratio). The desired BaO content is not less than 0.3% (more preferably not less than 0.5%) and not more than 2% (more preferably not more than 1%). The content of SrO is preferably from 0.1 to 2.7%, and more preferably from 0.3 to 1.5%. BaO and SrO are each a component having characteristics that can particularly improve the resistance to BHF. Therefore, in order to improve the resistance to BHF, the total content of these ingredients needs to be 0.1% or more (preferably 0.3% or more, more preferably 0.5% or more). However, if the content of BaO and SrO is too large, the density and the coefficient of thermal expansion will increase as mentioned above. Therefore, the total content must be suppressed to 6% or less. In the above-mentioned range, considering the improvement of BHF resistance, the total content of BaO and S rO is desired to be as large as possible. On the other hand, considering the reduction in density and the coefficient of thermal expansion, the total content should be as small as possible. ZnO is a component that can improve the BHF resistance and the meltability of glass plates. However, high levels of ZnO are not suitable because glass tends to lose transparency, reduce strain points, and increase density. Therefore, the content of ZnO is 0-5%, preferably not more than 3%, more preferably not more than 0.9%, and most preferably not more than 0.5%. -15- 555715 V. Description of the invention (14) By using a mixture containing MgO, CaO, BaO, SrO, and ZnO components, the liquidus temperature of the glass will be significantly lowered and almost no opaque stones will be produced. Therefore, it is possible to improve the meltability and the forgeability of the glass. However, if the total content of MgO, CaO, BaO, SrO, and ZnO is less than 5%, the effect as a melting agent is insufficient, and the meltability is reduced. In addition, if the thermal expansion coefficient is reduced too much, it may not be compatible with the TFT material. On the other hand, it is not appropriate to have a total content of more than 15%, because it is impossible to reduce the weight of the glass because the density will increase. In addition, the specific modulus is reduced. The total content of MgO, CaO, BaO, Sr0 and ZnO is preferably 5-12%, more preferably 5-10%. Z f02 is a component that can improve the resistance of glass (especially acid resistance) and increase the Young"s modulus. However, more than 5% is not suitable because the liquidus temperature will increase and it will tend to produce opaque stones of zircon. The content of Z r02 is preferably 0 to 3%, and more preferably 0 to 1%. Ti〇2 is a component that can improve the resistance of glass (especially acid resistance) and reduce the viscosity at high temperature to improve the meltability. However, the high content is not suitable for the glass plate of the display, because the glass will color and reduce the transparency. Therefore, the content of T i 02 must be limited to 0-5%, preferably 0-3%, more preferably 0-1%. P205 is a component that can improve the devitrification resistance of glass. However, high contents are not suitable because they cause phase separation and opacity in the glass, and the acid resistance is significantly deteriorated. Therefore, the content of P205 must be limited to 0-5%, preferably 0-3%, and more preferably 0-1%. In addition to the ingredients mentioned above, it may contain up to about 5% of Y 203, -16-555715, 5. Description of the invention (15) Nb2D3 and La 203. These components can be provided for high strain points and high Young"s modulus. However, high levels are not suitable because the density will increase. Furthermore, as long as the glass characteristics are not degraded, a clearing agent such as As203, Sb203, Sb205, F2, Cl2, S03, C or metal powder (A1 or Si) may be included. Ce02, Sn02 or Fe 203 can also be included as clearing agents up to 5%. In the case of alkali-free glass melting, As 203 which can be used as a clearing agent at high temperatures can be used. However, recently, it has been considered inappropriate to use chemicals that increase environmental load, such as As 203. Like As 203, Sn02 has the ability to clarify at high temperatures and can be used very effectively as a clarifying agent in molten alkali-free glass. However, a high content of 3.10 2 makes the glass opaque. Therefore, the content needs to be limited to 5% or less, preferably 2% or less. C 1 has the effect of promoting the melting of alkali-free glass. It can be melted at low temperature by adding C1 glass. Therefore, the tincture can be handled more efficiently. Furthermore, it can reduce the cost of melting glass and extend the life of production equipment. However, excessive C1 content reduces the strain point of the glass. Therefore, the desired content is limited to 3% or less. As the starting material containing the C 1 component, a chloride (for example, barium chloride) made of an alkaline earth metal oxide or a material such as aluminum chloride can be used. As for the clarifying agent which can be used in the alkali-free glass mentioned above, Sb 203 or Sb 205 is also effective. However, because the alkali-free glass has a high melting temperature, Sb 203 or Sb 205 has a smaller effect as a clearing agent than As 203. Therefore, in the case of using Sb 203 or Sb205, it is desired to increase the content such as C1 or -17-555715 V. Invention Description (16) The components combined with it to promote meltability and reduce the melting temperature. However, if the content of Sb 203 or Sb 205 is more than 5%, the density will increase. Therefore, its content is preferably limited to 2% or less, and more preferably 1.5% or less. In the case where As 203 is not used as a clarifying agent, it is preferable to include at least one substance selected from the group consisting of Sb 203, Sb 205, Sn02, and C1 at a content of 0.5 to 3.0%. In particular, it is optimal to contain 0.05-2.0% (Sb 20 3 + Sb 20 5), 0.01 to 1.0% Sn02, and 0 to 005 to 1.0% C1. Now, specific related examples will be described in detail. In Tables 1 to 17, sample case numbers 1 to 46 are specific examples of the alkali-free glass mentioned above. Sample case numbers 47-49 are comparative examples. Sample case number 49 is 1 737 glass manufactured by Corning Corporation.

-27- 555715 五、發明說明（26) 表10 樣品案號28 樣品案號29 樣品案號30 質量％ 莫耳％ 質量％ 莫耳％ 質量％ 莫耳％ Si〇2 63.3 69.7 63.1 69.5 63.1 69.4 A 12〇3 16.1 10.4 16.3 10.6 16.1 10.4 B 2〇 3 10.3 9.8 10.3 9.8 10.3 9.7 Mg〇 - - - - - - Ca〇 7.6 9.0 7.6 9.0 7.8 9.2 Sr〇 1.0 0.6 1.0 0.6 0.5 0.3 BaO 0.5 0.2 0.5 0.2 0.5 0.2 ZnO - - - - 0.5 0.4 P2〇5 - - - - - - AS2〇3 - - - - - - Sn〇2 0.1 <0.05 0.1 <0.05 0.1 <0.05 Sb2〇3 1.0 0.2 1.0 0.2 1.0 0.2 Zr〇2 0.1 0.1 0.1 0.1 0.1 0.1 Cl - - - - - - (Ba〇+Sr〇）/Ba〇 3 3 2 密度（克/立方公分） 2.388 2.389 2.392 熱膨脹係數 [30-380〇C ]( X 10"7/°C ) 33 33 33 溫度（°C ) 應變點 673 674 671 退火點 731 732 728 軟化點 989 990 984 於黏度1〇4 ϋ 1344 1342 1334 103 0 1516 1514 1504 102 5 1629 1626 1615 楊式模數（Gpa) 69 69 69 比模數（Gpa/(克•公分_3)) 28.9 29.0 28.8 侵蝕如爲抗BHF性（微米） 0.6 0.6 0.5 外觀評估 〇 〇 〇 侵蝕如爲抗HCI性（微米） 4.5 4.5 4.5 外觀評估 〇 〇 〇 液線溫度（°C ) 1103 1104 1091 液線黏度（dPa · s) 10 6.1 10 6.3 10 6.2 -28- 555715 五、發明說明（27) 表1 1 樣品案號31 樣品案號32 樣品案號33 質量％ 莫耳％ 質量％ 莫耳％ 質量％ 莫耳％ Si〇2 63.4 69.6 62.9 69.2 63.8 69.9 A 1 2〇3 15.8 10.2 16.3 10.6 15.8 10.2 B2〇3 10.3 9.7 10.3 9.8 10.3 9.7 Mg〇 - - - - — - Ca〇 7.8 9.2 7.8 9.2 7.9 9.3 Sr〇 0.5 0.3 0.5 0.3 0.5 0.3 Ba〇 0.5 0.2 0.5 0.2 0.5 0.2 Zn〇 0.5 0.4 0.5 0.4 - - P2〇5 - - - - - - AS2〇3 - - - - - - Sn〇2 0.1 <0.05 0.1 <0.05 0.1 <0.05 Sb203 1.0 0.2 1.0 0.2 1.0 0.2 Zr02 0.1 0.1 0.1 0.1 0.1 0.1 Cl - - - - - - (BaO+SrO)/BaO 2 2 2 密度（克/立方公分） 2.390 2.393 2.381 熱膨脹係數 [30-380〇C ]( xi〇-7/t ) 33 33 33 溫度（°C ) 應變點 670 672 671 退火點 726 726 730 軟化點 983 984 988 於黏度104ϋ 1336 1332 1349 ΙΟ30 1507 1501 1523 102·5 1620 1611 1638 楊式模數（Gpa) 68 69 69 比模數（Gpa/(克•公分·3)) 28 .7 28.9 28.8 侵蝕如爲抗BHF性（微米） 0.5 0.5 0.6 外觀評估 〇 〇 〇 侵蝕如爲抗HCI性（微米） 4.5 4.5 4.5 外觀評估 〇 〇 〇 液線溫度（°C ) 1088 1112 1063 液線黏度（dPa · s) 10 6.2 10" 6.0 10" 6.6 -29- 555715 五、發明說明（28) 表12 樣品案號34 樣品案號35 樣品案號36 質量％ 莫耳％ 質量％ 莫耳％ 質量％ 莫耳％ Si〇2 63.5 69.7 63.3 69.6 63.2 69.5 A 1 2 〇 3 16.1 10.4 16.3 10.6 15.9 10.3 ^2〇3 10.3 9.7 10.3 9.7 10.4 9.9 Mg〇 - - - - - - Ca〇 7.9 9.3 7.9 9.3 7.6 9.0 Sr〇 0.5 0.3 0.5 0.3 1.0 0.7 Ba〇 0.5 0.2 0.5 0.2 0.5 0.2 Zn〇 - - - - - - P2O5 - - - - - - as2o3 - - - - 0.7 0.2 Sn02 0.1 <0.05 0.1 <0.05 - - S b 2〇 3 1.0 0.2 1.0 0.2 0.5 0.1 Zr〇2 0.1 0.1 0.1 0.1 0.1 0.1 Cl - - - - 0.1 0.2 (BaO+SrO)/BaO 2 2 3 密度（克/立方公分） 2.382 2.384 2.382 熱膨脹係數 [30-380〇C ]( ΧΙΟ·7"。） 33 33 33 溫度（°C ) 應變點 673 674 676 退火點 731 732 735 軟化點 989 990 987 於黏度104ϋ 1346 1345 1324 103 0 1519 1516 1498 1〇2·5 1633 1630 1612 楊式模數（Gpa) 69 69 70 比模數（Gpa/(克•公分·3)) 29.0 29.0 29.4 侵蝕如爲抗BHF性（微米） 0.6 0.6 0.6 外觀評估 〇 〇 〇 侵蝕如爲抗HCI性（微米） 4.5 4.5 2. 1 外觀評估 〇 〇 〇 液線溫度（°C ) 1082 1090 1105 液線黏度（dPa · s) 10丨 6.4 10( 5.3 10" 6.0 -30- 555715 五、發明說明（29) 表13 樣品案號37 樣品案號38 樣品案號39 質量％ 莫耳％ 質量％ 莫耳％ 質量％ 莫耳％ Si〇2 63.3 69.5 63.1 69.5 63.0 69.4 A 12〇3 15.9 10.3 15.9 10.3 15.9 10.3 B2〇3 10.4 9.9 10.4 9.9 10.4 9.9 MgO - - - - - - Ca〇 7.6 9.0 7.6 9.0 7.6 9.0 Sr〇 1.0 0.7 0.5 0.3 0.5 0.3 Ba〇 0.5 0.2 1.2 0.5 1.2 0.5 Zn〇 - - - - - - P2〇5 - - - - - - A S 2〇 3 S n02 0.1 <0.05 0.1 <0.05 0.7 0.2 Sb203 1.0 0.2 1.0 0.2 0.5 0.1 Zr02 0.1 0.1 0.1 0.1 0.1 0.1 Cl 0.1 0.2 0.1 0.2 0.1 0.2 (BaO+SrO)/BaO 3 1.4 1.4 密度（克/立方公分） 2.387 2.388 2.384 熱膨脹係數 [30-380°C](Xl〇-7/°C) 33 33 33 溫度fc) 應變點 676 671 672 退火點 732 729 729 軟化點 987 989 989 於黏度1〇4·ϋ 1327 1348 1342 1〇3.0 1501 1525 1516 102 5 1612 1639 1628 楊式模數（Gpa) 71 69 69 比模數（Gpa/(克•公分_3)) 29.7 28 • 7 28.8 侵蝕如爲抗BHF性（微米） 0.6 0.6 0.6 外觀評估 〇 〇 〇 侵蝕如爲抗HCI性（微米） 2.3 2. 1 2.2 外觀評估 〇 〇 〇 液線溫度（°C ) 1101 1099 1101 液線黏度（dPa · s) 101 5.1 10( 3.2 10" 5.1 -31 - 555715 五、發明說明（30) 表14 樣品案號40 樣品案號41 樣品案號42 質量％ 莫耳％ 質量％ 莫耳％ 質量％ 莫耳％ Si〇2 61.2 68.6 60.2 68.0 61.1 68.9 A 1 2 〇 3 15.8 10.5 15.8 10.5 15.8 10.5 B20 3 11.8 11.4 11.8 11.5 10.9 10.6 Mg〇 - - - - - - Ca〇 5.9 7.1 5.9 7.1 5.9 7.1 Sr〇 1.0 0.6 1.0 0.7 1.0 0.7 Ba〇 3.0 1.3 3.0 1.3 3.0 1.3 ZnO - - - - - - P2〇5 - - 1.0 0.5 1.0 0.5 AS2〇3 - - - - - - Sn02 - - - - - - Sb2〇3 1.0 0.2 1.0 0.2 1.0 0.2 Zr02 0.3 0.2 0.3 0.2 0.3 0.2 Cl - - - - - - (Ba〇+Sr〇）/Ba〇 1.3 1.3 1.3 密度（克/立方公分） 2.403 2.401 2.405 熱膨脹係數 [30-380〇C ]( X10"7/°C ) 32 32 32 溫度（°C ) 應變點 659 654 663 退火點 718 713 722 軟化點 977 974 986 於黏度1〇4° 1326 1320 1337 ίο3·0 1512 1512 1514 102·5 1630 1602 1636 楊式模數（Gpa) 68 68 68 比模數（Gpa/(克•公分_3)) 28.3 28.3 28 .3 侵蝕如爲抗BHF性（微米） 0.4 0.4 0.4 外觀評估 〇 〇 〇 侵蝕如爲抗HCI性（微米） 4.5 4.6 2.6 外觀評估 〇 〇 〇 液線溫度（°C ) 1150 1141 1128 液線黏度（dPa · s) 10: 5.5 10: ).5 10: 5.8 -32- 555715 五、發明說明（w) 表15 樣品案號43 樣品案號44 樣品案號45 質量％ 莫耳％ 質量％ 莫耳％ 質量％ 莫耳％ Si〇2 62.1 69.5