TWI252844B - Glasses for display panels - Google Patents
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- TWI252844B TWI252844B TW92136886A TW92136886A TWI252844B TW I252844 B TWI252844 B TW I252844B TW 92136886 A TW92136886 A TW 92136886A TW 92136886 A TW92136886 A TW 92136886A TW I252844 B TWI252844 B TW I252844B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
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Abstract
Description
1252844 五、發明說明（1) 【發明所屬之技術領域】 本發明係有關一種硼鋁矽酸鹽玻璃配方，尤指一種可 用於生產平面顯示器玻璃基板，特別是用於液晶顯示器（ L C D )玻璃基板之玻璃。 【先前技術】1252844 V. INSTRUCTION DESCRIPTION (1) Technical Field of the Invention The present invention relates to a boroaluminosilicate glass formulation, and more particularly to a glass substrate for producing a flat display, particularly for a liquid crystal display (LCD) glass substrate. Glass. [Prior Art]
按，顯示器可謂電腦部件中最重要的輸出設備，它的 作用就是將主機發出的電信號經一系列處理後轉換成光信 號，最終將文字、圖形顯示出來。顯示器按其工作原理來 分，比較常見的是：陰極射線之管顯示器（CRT)和液晶顯示 器（LCD)，此外還有等離子體顯示器（PDP)、真空螢光顯示 器（VFD)等，然而，等離子體顯示器（PDP)、真空螢光顯示 器（VF D )是新一代顯示器的代表，但是由於技術未臻成熟 ，因此尚未普及。Press, the display can be described as the most important output device in the computer component. Its function is to convert the electrical signal sent by the host into a light signal after a series of processing, and finally display the text and graphics. The display is divided according to its working principle. Commonly used are: cathode ray tube display (CRT) and liquid crystal display (LCD), in addition to plasma display (PDP), vacuum fluorescent display (VFD), etc., however, plasma A body display (PDP) and a vacuum fluorescent display (VF D) are representative of a new generation of displays, but they have not yet become popular due to their maturity.
又，顯示器依據製造材料和技術的不同可分為陰極射 線管顯示器（CRT )、等離子顯示器（PDP )、發光二極管 顯示器（L E D )、場致發光顯示器（E L D )、液晶顯示器（ LCD )、電致變色顯示器（ECD )和電泳顯示器（EPID )等 類型。其中彩色CRT (Cathode Ray Tube，陰極射線管） 顯示器又分為蔭罩式CRT和電壓穿透式CRT。蔭罩式CRT顯 示器就是我們最常見的顯示器，利用電子槍與螢光屏之間 有一用以形成栅孔或栅條的金屬隱罩板而得名。雖然隱罩 式CRT顯示器比較耗電而且體積大，但價格相對便宜、使 用壽命較長，而且顯示效果也不錯。Moreover, the display can be classified into a cathode ray tube display (CRT), a plasma display (PDP), a light emitting diode display (LED), an electroluminescence display (ELD), a liquid crystal display (LCD), and an electrolysis according to different materials and technologies. Types such as color change display (ECD) and electrophoretic display (EPID). The color CRT (Cathode Ray Tube) display is further divided into a shadow mask type CRT and a voltage penetrating type CRT. The shadow mask CRT display is our most common display, and it is named after a metal cover plate for forming a gate hole or a grid bar between the electron gun and the fluorescent screen. Although the cover-type CRT display is relatively power-hungry and bulky, it is relatively inexpensive, has a long service life, and has a good display effect.
第6頁 1252844_ 五、發明說明（2) 雖然陰極射線管顯示器的綜合性能不錯，但是它仍有 一些與生倶來的缺點，如體積龐大、耗電量大、輻射較強 、容易受磁化等。然，上述這些缺點是由陰極射線管顯示 器的工作原理造成的，不可能從根本上予以改變，只能進 行後續的修補改進或在問題發生後再另行解決，為了解決 上述種種缺陷，便發展出平面顯示器。 所謂的平面顯示器是泛指非映像管（CRT )式的其他 顯示器，但就產品技術差異而言，它包含有電漿顯示器（ PDP )、液晶顯示器（LCD )、有機電激發光顯示器（OLED )、真空螢光顯示器（VFD )、場效發射顯示器（FED )及 微型顯示器（M i c r 〇 D i s p 1 a y )等多種類型。液晶顯示器 包含下述優點： 1 ·結構和產品體積 傳統顯示器由於使用CRT，必須透過電子搶發射電子 束到螢幕，因而顯像管的管頸不能做得很短，當螢幕增大 時也必然增大整個顯示器的體積。TFT液晶顯示器透過顯 示屏上的電極控制液晶分子狀態來達到顯示目的，即使螢 幕加大，它的體積也不會成正比的增加（只增加尺寸而不 增加厚度，可以讓使用者更節省空間），而且在重量上比 相同顯示面積的傳統顯示器要輕得多。同時TFT液晶顯示 器由於功耗只在於電極和驅動的積體電路上，因而耗電量 比傳統顯示器也要小得多。 2 ·幅射和電磁波干擾 傳統顯示器由於採用電子搶發射電子束，在打到螢幕Page 6 1252844_ V. Description of the invention (2) Although the comprehensive performance of the cathode ray tube display is good, it still has some disadvantages such as large size, large power consumption, strong radiation, and easy magnetization. . However, these shortcomings are caused by the working principle of the cathode ray tube display, and it is impossible to fundamentally change it. Only subsequent repairs can be made or solved after the problem occurs. In order to solve the above various defects, it is developed. Flat panel display. The so-called flat panel display refers to other displays of the non-image tube (CRT) type, but in terms of product technology differences, it includes a plasma display (PDP), a liquid crystal display (LCD), and an organic electroluminescent display (OLED). Various types such as vacuum fluorescent display (VFD), field emission display (FED) and micro display (M ic 〇D isp 1 ay ). The liquid crystal display has the following advantages: 1. Structure and product volume. Due to the use of the CRT, the electron beam must be emitted to the screen through the electrons, so that the neck of the picture tube cannot be made very short, and the entire screen must be increased when the screen is enlarged. The size of the display. The TFT liquid crystal display controls the state of the liquid crystal molecules through the electrodes on the display screen to achieve the display purpose. Even if the screen is enlarged, its volume will not increase proportionally (only increase the size without increasing the thickness, which can save the user more space) And it is much lighter than conventional displays with the same display area. At the same time, the TFT liquid crystal display consumes only a small amount of power compared to the conventional display because the power consumption is only on the integrated circuit of the electrode and the driving. 2 · Radiation and electromagnetic interference The traditional display uses the electronic robbing electron beam to hit the screen.
1252844 五、發明說明（3) 上後會產生幅射，儘管現有產品在技術上有很大的提高， 把幅射損害降到最小，但不可能根除。在這一點上，T F T 液晶顯示器具有先天的優勢，它根本沒有幅射可言。至於 電磁波的干擾’ T F T液晶顯不器只有來自驅動電路的少置 電磁波，只要將外殼嚴格密封即可排除電磁波外泄，而傳 統顯示器為了散熱，不得不將外殼鑽上散熱孔，所以電磁 波干擾就不可避免了 。所以液晶顯示器有稱為冷顯示器或 環保顯示器。 3 ·平面直角和解析度 T F T液晶顯示器一開始就使用純平面的玻璃板，其平 面直角的顯示效果比傳統顯示器看起來好得多。不過在解 析度上，T F T液晶顯示器理論上可提供更高的解析度，但 實際顯示效果卻差得多，因為它存在一個最佳解析度的問 題。而傳統顯示器在較好顯示卡的支持下可以達到完美的 顯示效果。 4. 附設 現在很多液晶顯示器都内建了 USB Hub介面，隨著平 面式音箱等的問世，液晶顯示器内置音箱或麥克風也會成 為主流，種種附設使液晶顯示器有更大的選擇空間。 液晶顯示器（LCD)比之傳統的CRT顯示器，有著圖像不 失真、無閃爍、無輻射、輕、薄等利於健康和環保的優點 ，使其較傳統顯示器具有更好的發展空間。 液晶顯示器是以液晶材料為基本元件，由於液晶是介 於固態和液態之間，不但具有固態晶體光學特性，又具有1252844 V. INSTRUCTIONS (3) Radiation will occur afterwards, although the existing products are greatly improved in technology, minimizing radiation damage, but it is impossible to eradicate. At this point, the T F T liquid crystal display has an innate advantage, and it has no radiation at all. As for the interference of electromagnetic waves, the TFT liquid crystal display has only a small amount of electromagnetic waves from the driving circuit. As long as the outer casing is tightly sealed, the electromagnetic wave can be excluded. However, in order to dissipate heat, the conventional display has to be drilled with a heat dissipation hole, so electromagnetic interference is caused. Inevitably. Therefore, liquid crystal displays are called cold displays or environmentally friendly displays. 3 · Plane Right Angle and Resolution The T F T liquid crystal display uses a flat glass plate from the beginning, and its flat right angle display looks much better than a conventional display. However, in terms of resolution, the TF LCD can theoretically provide higher resolution, but the actual display is much worse because it has an optimal resolution problem. The traditional display can achieve perfect display with the support of a better display card. 4. Attached Many LCD monitors now have a built-in USB Hub interface. With the advent of flat-panel speakers, the built-in speakers or microphones of LCD monitors will become mainstream, and various options will make LCD monitors have more choices. Compared with traditional CRT monitors, liquid crystal displays (LCDs) have the advantages of undisturbed images, no flicker, no radiation, light and thin, which are beneficial to health and environmental protection, making them have better development space than traditional displays. The liquid crystal display is based on a liquid crystal material. Since the liquid crystal is between a solid state and a liquid state, it has not only solid crystal optical characteristics but also
1252844 五、發明說明（4) 液態流動特性，所以已經可以說是一個中間相。而要了解 液晶的所產生的光電效應，液晶的黏性和彈性從流體力學 的觀點來看，可說是一個具有排列性質的液體，依照作用 力量不同的方向，應該有不同的效果。此外，液晶除了有 黏性的反應外，還具有彈性的反應，它們都是對於外加的 力量，呈現了方向性的效果。也因此光線射入液晶物質中 ，必然會按照液晶分子的排列方式行進，產生了自然的偏 轉現像。至於液晶分子中的電子結構，都具備著很強的電 子共輛運動能力，所以當液晶分子受到外加電場的作用， 便很容易的被極化產生感應偶極性（i n d u c e d d i ρ ο 1 a r )，這也是液晶分子之間互相作用力量的來源。 一般電子產品中所用的液晶顯示器，就是利用液晶的 光電效應，藉由外部的電壓控制，再透過液晶分子的折射 特性，以及對光線的旋轉能力來獲得亮暗情況（或著稱為 可視光學的對比），進而達到顯像的目的。 液晶顯示器，英文通稱為LCD (Liquid Crystal D i sp 1 ay )，是屬於平面顯示器的一種，是依靠外部光源 照明的平面顯示裝置，主要由二片玻璃基板及液晶等構成 ，依驅動方式來分類可分為靜態驅動（S t a t i c )、單純矩 陣驅動（Simple Matrix)以及主動矩陣驅動（Active Matrix )三種。其中，單純矩陣型又可分為扭轉式向列型 (Twisted Nematic ;TN)、超扭轉式向列型（Super Twisted Nematic ; S T N )及其他單純矩陣驅動液晶顯示器 ;而主動矩陣型大致可區分為薄膜式電晶體型（Th i η1252844 V. INSTRUCTIONS (4) Liquid flow characteristics, so it can be said to be a mesophase. To understand the photoelectric effect produced by the liquid crystal, the viscosity and elasticity of the liquid crystal can be said to be a liquid having an alignment property from the viewpoint of fluid mechanics, and should have different effects depending on the direction of the action force. In addition, in addition to the viscous reaction of the liquid crystal, the liquid crystal also has an elastic reaction, and they all exert a directional effect on the applied force. Therefore, light is incident on the liquid crystal material, and it is inevitably traveled in accordance with the arrangement of the liquid crystal molecules, resulting in a natural deflection phenomenon. As for the electronic structure in the liquid crystal molecules, they all have a strong ability to move electrons together, so when the liquid crystal molecules are subjected to an applied electric field, they are easily polarized to produce an induced dipole (induceddi ρ ο 1 ar ). It is also a source of interaction between liquid crystal molecules. The liquid crystal display used in general electronic products utilizes the photoelectric effect of the liquid crystal, and the brightness and darkness of the liquid crystal molecules are controlled by external voltage control, and the ability to rotate the light to obtain a bright and dark condition (or a contrast of visible optics). ), and then achieve the purpose of imaging. Liquid crystal display, commonly known as LCD (Liquid Crystal D i sp 1 ay), is a type of flat panel display. It is a flat display device that relies on external light source illumination. It is mainly composed of two glass substrates and liquid crystals. It can be divided into static drive (S tatic ), simple matrix drive (Simple Matrix) and active matrix drive (Active Matrix ). Among them, the simple matrix type can be divided into Twisted Nematic (TN), Super Twisted Nematic (STN) and other simple matrix driven liquid crystal displays; and the active matrix type can be roughly divided into Thin film transistor type (Th i η
第9頁 1252844_ 五、發明說明（5)Page 9 1252844_ V. Description of invention (5)
Film Transistor ;TFT)及二端子二極體型（Metal/ Insulator/Metal ;MIM)二種方式。 目前在市場上常見的LCD有超扭轉向列型（STN)及薄 膜電晶體型（T F T ) ’其中s τ N型屬於單純矩陣定址方式， 而TFT型屬於主動矩陣定址方式，由於顯示效果比STN型更 好，尤為市場上的主流。TFT型又常被分為非晶矽型（ a - Si)及更先進的多晶石夕型（P〇ly~Si) 二種構型。 L C D用的玻璃基板配合上述技術進程 '，而有種種組成 、製造方式及特性上的區別。S T N型一般使用鹼石灰玻璃 ，T F T型則使用無鹼硼鋁矽酸鹽破璃。Film Transistor; TFT) and two-terminal diode type (Metal/Insulator/Metal; MIM). At present, LCDs commonly used in the market have super twisted nematic (STN) and thin film transistor type (TFT) 'where s τ N type belongs to simple matrix addressing mode, and TFT type belongs to active matrix addressing mode, because display effect is better than STN The type is better, especially the mainstream in the market. The TFT type is often divided into two types: amorphous 矽 (a - Si) and more advanced polycrystalline 夕 (P〇ly~Si). The glass substrate for L C D cooperates with the above-mentioned technical process, and has various compositions, manufacturing methods, and characteristics. S T N type generally uses soda lime glass, while T F T type uses alkali-free boroalumino silicate powder.
於美國專利第5，811,361號、第5，851，939號、第6，32 9, 310號等提到了作為TFT型LCD用之基板玻璃所必須具備 下述的基本物理特性： 1、 為了減少基板玻璃在T F T製程溫度下，因熱脹冷縮造成 的熱震破壞，玻璃的熱膨脹係數必須夠低，一般需低 於40 X 1 0-7/ 〇C。 2、 應減少基板玻璃在TFT製程溫度下，因再熱緻密化引起 的體積收縮和尺寸不安定性。具體要求是玻璃的應變 點溫度應高於6 5 0 °C。 3、 為了因應大尺寸基板玻璃輕量化的要求，玻璃的密度 必須夠低，一般需低於2 · 6 ( g / c m3 )。U.S. Patent Nos. 5,811,361, 5,851,939, 6,32,310, etc. mention that the following basic physical characteristics must be possessed as a substrate glass for a TFT type LCD: 1. To reduce At the TFT process temperature, the thermal shock of the glass due to thermal expansion and contraction, the thermal expansion coefficient of the glass must be low enough, generally less than 40 X 1 0-7 / 〇C. 2. The volume shrinkage and dimensional instability caused by reheat densification of the substrate glass at the TFT process temperature should be reduced. The specific requirement is that the strain point temperature of the glass should be higher than 650 °C. 3. In order to meet the requirements of lightweighting large-size substrate glass, the density of glass must be low enough, generally less than 2 · 6 ( g / c m3 ).
因此，為了生產符合上述基本需求的基板玻璃，現今 常以熔融溢流法及浮式法等成型方式製造基板玻璃。然而 ，由於成型方式的需求，更衍生出對基板玻璃特性的進一Therefore, in order to produce a substrate glass that meets the above basic requirements, a substrate glass is often produced by a melt overflow method or a floating method. However, due to the demand for molding methods, the characteristics of the glass of the substrate are further derived.
第10頁 1252844 五、發明說明（6) 步要求如下： 1、 基板玻璃之液相溫度必須夠低，以免在成型過程中失 透或析晶，影響到玻璃的外觀品質。液相溫度一般需 低於 1 2 0 0 °C。 2、 基板玻璃的氣泡含量必須減少，以免在T F T製程中造成 斷路等缺陷，或影響到玻璃的外觀品質。一般需要每 公斤基板玻璃中泡徑在0 . 5〜1 . 0 m m内的氣泡數目少於2 0 個。 隨著多晶矽型（poly-Si ) TFT-LCD等次世代製程或產 品需求的擴大，且為了因應ρ ο 1 y - S i製程更高的精密度， 對基板玻璃基本物理特性的要求，除了上述已經提及的部 分之外，更進一步衍生出以下的要求： 1、 熱膨脹係數繼續降低，一般需低於34 X 1 0_7/ °C，除了 減少熱震破壞，更希望與矽質驅動元件接近，以便曰 後驅動元件電路直接製作在基板上（chip-on-glass ) 時，減少玻璃和矽質間因熱膨脹係數失配引起的電路 破壞。 2、 poly-Si TFT製程中，光學微影的精密度提升，電路線 徑變窄，因此應變點溫度應再提高，最好高於6 6 5 °C ， 以減少因再熱緻密化引起的體積收縮和尺寸不安定性 ，減輕曝光顯影過程中的對焦失準現象。 3、 為了因應第五世代以上（llOOmmx 1250mm)玻璃基板的 製造、搬運等的要求，玻璃基板需儘可能輕量化，因 此，玻璃的密度需降低，一般需低於2 · 4 ( g / c m3 )。Page 10 1252844 V. INSTRUCTIONS (6) The steps are as follows: 1. The liquidus temperature of the substrate glass must be low enough to avoid devitrification or crystallization during the molding process, which affects the appearance quality of the glass. The liquidus temperature is generally lower than 1 2 0 0 °C. 2. The bubble content of the substrate glass must be reduced to avoid defects such as open circuit in the T F T process or affect the appearance quality of the glass. Generally, it is required that the number of bubbles in the cell diameter of 0. 5~1 . 0 m m per kg of substrate glass is less than 20 pieces. With the expansion of next-generation processes or product requirements such as poly-Si TFT-LCDs, and in order to respond to the higher precision of the ρ ο 1 y - S i process, the basic physical properties of the substrate glass are required to be In addition to the parts already mentioned, the following requirements are further derived: 1. The coefficient of thermal expansion continues to decrease, generally lower than 34 X 1 0_7/ °C, in addition to reducing thermal shock damage, it is more desirable to be close to the enamel drive element. In order to make the rear drive element circuit directly on the chip-on-glass, the circuit damage caused by the thermal expansion coefficient mismatch between the glass and the tantalum is reduced. 2. In the poly-Si TFT process, the precision of the optical lithography is improved, and the circuit diameter is narrowed. Therefore, the strain point temperature should be further increased, preferably higher than 6 6 5 °C, to reduce the reheating densification. Volume shrinkage and dimensional instability prevent loss of focus during exposure and development. 3. In order to meet the requirements for the manufacture and handling of glass substrates of the fifth generation or higher (llOOmmx 1250mm), the glass substrate needs to be as lightweight as possible. Therefore, the density of the glass needs to be reduced, generally less than 2 · 4 ( g / c m3 ).
第11頁 1252844 五、發明說明（7) 由於液晶顯示器需求日漸殷切，然，用於顯示器之基 板玻璃仍具有上述種種如：玻璃的熱膨脹係數需低於4 Ο X 1 0_7/ °C、玻璃的應變點溫度應高於6 5 0 °C、玻璃的密度必 須低於2. 6 (g/cm3 )、液相溫度需低於1 2 0 0 °C、每公斤基 板玻璃中泡徑在0 . 5〜1 . 0 m m内的氣泡數目少於2 0個等物理 特性需克服。因此本發明人遂竭其心智研究克服，進而研 發出一種顯示器用基板玻璃之組成，藉由特定比例之氧化 矽（Si02)、氧化鋁（Al2〇3)、氧化硼（B2 03 )、氧化鎂（MgO)、 氧化4弓（C a 0 )、氧化錄（S r 0 )、氧化鋇（B a 0 )、氧化鋅（Ζ η 0 ) 、氧化锆（Zr02)、氧化砷（As2 03 )、氧化銻（Sb2 03 )、氧化錫 (S η 02)、氧化鈽（C e 02)，能因應平面顯示器基板玻璃之種 種需求，且符合更嚴苛物理特性的要求如：熱膨脹係數低 於34 X 1 0_7/ °C、應變點溫度高於6 6 5 °C、玻璃的密度低於 2.4 (g/cm3)等。 【發明内容】 由是，本發明的主要目的，即在設計一種可用於顯示 器玻璃基板之玻璃，藉由特定比例之氧化矽（S i 02)、氧化 鋁（Al2〇3)、氧化硼（B2〇3)、氧化鎂（MgO)、氧化鈣（CaO)、 氧化認（S r 0 )、氧化鎖（B a 0 )、氧化鋅（Ζ η 0 )、氧化錯（Z r 0 2 )、氧化珅（As2 03 )、氧化銻（Sb2 03 )、氧化錫（Sn02)、氧化 鈽（C e 02)，達到符合平面顯示器基板玻璃之種種需求。 為達上述目的，本發明是這樣實現的：一種可用於顯 示器玻璃基板之玻璃，該玻璃之組成成份為重量百分比Page 11 1252844 V. Invention Description (7) Due to the increasing demand for liquid crystal displays, the substrate glass used for displays still has the above-mentioned various types such as: the thermal expansion coefficient of glass needs to be lower than 4 Ο X 1 0_7/ °C, glass The strain point temperature should be higher than 650 °C, the density of the glass must be lower than 2.6 (g/cm3), the liquidus temperature should be lower than 1 2 0 0 °C, and the bubble diameter per kilogram of substrate glass is 0. Physical properties such as less than 20 bubbles in 5 to 1. 0 mm need to be overcome. Therefore, the inventors have exhausted their mental research to overcome, and have developed a composition of a substrate glass for display by a specific ratio of cerium oxide (SiO 2 ), aluminum oxide (Al 2 〇 3 ), boron oxide (B 2 03 ), magnesium oxide. (MgO), oxidized 4 bow (C a 0 ), oxidized record (S r 0 ), yttrium oxide (B a 0 ), zinc oxide (Ζ η 0 ), zirconia (Zr02), arsenic oxide (As2 03 ), Cerium oxide (Sb2 03 ), tin oxide (S η 02), and cerium oxide (C e 02) can meet the requirements of flat panel display glass and meet the requirements of more stringent physical properties such as: thermal expansion coefficient less than 34 X 1 0_7/ °C, the strain point temperature is higher than 6 6 5 °C, and the density of the glass is lower than 2.4 (g/cm3). SUMMARY OF THE INVENTION Therefore, the main object of the present invention is to design a glass which can be used for a display glass substrate by a specific ratio of cerium oxide (S i 02), aluminum oxide (Al 2 〇 3), boron oxide (B2). 〇3), magnesium oxide (MgO), calcium oxide (CaO), oxidized (S r 0 ), oxidized lock (B a 0 ), zinc oxide (Ζ η 0 ), oxidized error (Z r 0 2 ), oxidation珅 (As2 03 ), yttrium oxide (Sb2 03 ), tin oxide (Sn02), yttrium oxide (C e 02), to meet the various needs of flat panel display glass. To achieve the above object, the present invention is achieved by a glass which can be used for a glass substrate of a display, the composition of which is a weight percentage
1252844_ 五、發明說明（8) 5 6 · 0 %至6 4 . 0 %之氧化矽、1 4 . 0 %至1 9 · 0 %之氧化鋁、7 · 5 %至 1 4 . 0 %之氧化硼、0 . 0 %至4 · 0 %之氧化鎂、3 · 0 %至1 0 · 0 %之氧 化鈣、0 . 0 %至6 . 0 %之氧化勰、0 . 0 %至1 0 · 0 %之氧化鋇、 0 · 0 %至1 . 0 %之氧化鋅、0 . 0 %至1 · 0 %之氧化锆、0 · 0 %至2 · 0 % 之氧化砷、0 . 0 %至1 . 0 %之氧化銻、0 · 0 %至1 . 0 %之氧化錫、 0 . 0 %至1 . 0 %之氧化鈽；且其中氧化矽與氧化鋁的總和超過 7 1 . 0 %，氧化鋁與氧化硼的比例介於1 . 0與2 . 1之間，氧化 鎂、氧化鈣之總和介於3 . 0 %至1 0 . 0%之間，氧化勰、氧化 鋇之總和介於0 . 0 %至1 3 . 0 %之間，氧化砷與氧化銻、氧化 錫、氧化鈽之總和介於0 . 3 %至2 . 0 %之間；藉由特定之比例 可使所生產之玻璃更符合平面顯示器基板玻璃之種種需求 〇 為使 貴審查委員瞭解本發明之目的、特徵及功效， 茲藉由下述具體之實施例，對本發明做一詳細說明，說明 如后 ： 本發明之顯示器用基板玻璃之組成，其組成成分之重 量百分比如下： (1 )重量百分比5 6 · 0 %至6 4 · 0 %之氧化矽（S i 02); (2) 重量百分比14. 0%至19· 0%之氧化鋁（A 1 2 03 ); (3) 重量百分比7· 5%至14· 0%之氧化硼（B2〇3); (4) 重量百分比0·0%至4.0%之氧化鎂（MgO); (5) 重量百分比3· 0°/。至10· 0%之氧化鈣（CaO); (6) 重量百分比0·0%至6.0%之氧化錄（SrO); (7) 重量百分比0. 0%至10· 0%之氧化鋇（BaO);1252844_ V. INSTRUCTIONS (8) 5 6 · 0 % to 6 4 . 0 % of cerium oxide, 14.0% to 1 9 · 0 % of alumina, 7.5 % to 14. 0% of oxidation Boron, 0. 0% to 4 · 0% of magnesium oxide, 3 · 0% to 1 0 · 0% of calcium oxide, 0. 0% to 6.0% of cerium oxide, 0. 0% to 1 0 · 0% yttrium oxide, 0. 0% to 1.0% zinc oxide, 0. 0% to 1 · 0% zirconia, 0. 0% to 2 · 0% arsenic oxide, 0. 0% to 1.0% yttrium oxide, 0. 0% to 1.0% tin oxide, 0. 0% to 1.0% cerium oxide; and wherein the total of cerium oxide and aluminum oxide exceeds 71.0%, The ratio of alumina to boron oxide is between 1.0 and 2.1, and the sum of magnesium oxide and calcium oxide is between 3.0% and 10.0%, and the sum of yttrium oxide and yttrium oxide is between Between 0% and 13.0%, the sum of arsenic oxide and antimony oxide, tin oxide and antimony oxide is between 0.3% and 2.0%; it can be produced by a specific ratio. The glass is more in line with the various requirements of the flat display substrate glass, so that the reviewers can understand the purpose, features and effects of the present invention. The embodiment of the present invention will be described in detail with reference to the following: The composition of the substrate glass for a display of the present invention, the weight percentage of its constituent components is as follows: (1) Weight percentage 5 6 · 0 % to 6 4 · 0 %矽 矽 S S S S S 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 (B2〇3); (4) Magnesium oxide (MgO) in a weight percentage of 0·0% to 4.0%; (5) Weight percentage 3·0°/. To 10% 0% calcium oxide (CaO); (6) 0. 0% to 6.0% by weight of oxidation record (SrO); (7) Weight percent 0. 0% to 10·0% of barium oxide (BaO );
1252844 五、發明說明（9) (8 )重量百分比0 · 0 %至1 · 0 %之氧化鋅（Ζ η 0 ); (9 )重量百分比0 . 0 %至1 . 0 %之氧化鍅（Z r 02); (10)重量百分比0· 0%至2· 0%之氧化砷（As2 03 ); (1 1 )重量百分比0· 0%至1 · 0%之氧化銻（Sb2 03 ); (1 2 )重量百分比0 · 0 %至1 · 0 %之氧化錫（S η 02); (1 3 )重量百分比0 · 0 %至1 . 0 %之氧化铈（C e 02);1252844 V. INSTRUCTIONS (9) (8) Weight percent 0 · 0 % to 1 · 0% of zinc oxide (Ζ η 0 ); (9) Weight percent 0. 0 % to 1.0% of cerium oxide (Z r 02); (10) Weight percent 0·0% to 2.0% of arsenic oxide (As2 03 ); (1 1 ) Weight percent 0·0% to 1 · 0% of cerium oxide (Sb2 03 ); 1 2 ) weight percentage 0 · 0 % to 1 · 0% of tin oxide (S η 02); (1 3 ) weight percentage 0 · 0 % to 1.0% of cerium oxide (C e 02);
其中氧化矽與氧化鋁的總和超過7 1 . 0 %，氧化鋁與氧 化硼的比例介於1 . 0與2 . 1之間，氧化鎂、氧化鈣之總和介 於3 . 0 %至1 0 . 0%之間，氧化勰、氧化鋇之總和介於0 . 0 %至 1 3. 0 %之間，氧化砷與氧化銻、氧化錫、氧化鈽之總和介 於0 · 3 %至2 . 0 %之間。The sum of cerium oxide and aluminum oxide is more than 7.1%, and the ratio of alumina to boron oxide is between 1.0 and 2.1, and the sum of magnesium oxide and calcium oxide is between 3.0% and 1 0. Between 0%, the sum of yttrium oxide and yttrium oxide is between 0. 0% and 1.3%, and the sum of arsenic oxide and lanthanum oxide, tin oxide and lanthanum oxide is between 0. 3 % and 2 . Between 0%.
由上述本發明所揭露之玻璃組成，當僅具有TFT-LCD 玻璃基板所需的基本物理特性時，其組成成份之重量百分 比分別為5 6 . 0 %至6 0 · 0 %之氧化矽，1 4 · 0 %至1 8 · 0 %之氧化 鋁，7 . 5 %至1 4 . 0 %之氧化硼，0 . 0 %至2 · 0 °/〇之氧化鎂，3 . 0 % 至7 . 0 %之氧化鈣，1 · 0 %至6 · 0 %之氧化勰，2 . 0 %至1 0 · 0 %之 氧化鋇，0 · 0 %至1 . 0 %之氧化鋅，0 . 0 %至1 . 0 %之氧化锆，0 · 0 %至2 · 0 %之氧化砷 ，0 · 0 %至1 · 0 %之氧化銻，0 . 0 %至1 · 0 % 之氧化錫，0 . 0 %至1 . 0 %之氧化鈽，且其中氧化矽與氧化鋁 的總和超過7 1 . 0 %，氧化鋁與氧化硼的比例介於1 . 0與2 . 1 之間，氧化鎂、氧化鈣之總和介於3 . 0 %至7 . 0 %之間，氧化 锶、氧化鋇之總和介於4 . 0 %至1 3 . 0%之間，氧化砷與氧化 銻、氧化錫、氧化鈽之總和介於0 . 3 %至2 . 0 %之間。該等組 成之玻璃，其熱膨脹係數低於40 X 1 0-7/ t ( 30〜4 0 0 °C )，The composition of the glass disclosed in the above invention, when having only the basic physical properties required for the TFT-LCD glass substrate, the weight percentage of its constituent components is 56.0% to 60% of cerium oxide, respectively. 4 · 0 % to 1 8 · 0 % of alumina, 7.5 % to 14. 0% of boron oxide, 0. 0% to 2 · 0 ° / 〇 of magnesium oxide, 3.0% to 7. 0 % of calcium oxide, 1 · 0 % to 6 · 0 % of cerium oxide, 2.0% to 1 0 · 0 % of cerium oxide, 0 · 0 % to 1.0% of zinc oxide, 0. 0 % To 1.0% zirconia, 0. 0% to 2 · 0% arsenic oxide, 0. 0% to 1 · 0% yttrium oxide, 0. 0% to 1 · 0% tin oxide, 0. 0%至1. 0% of yttrium oxide, and wherein the total of yttrium oxide and alumina exceeds 71.0%, the ratio of alumina to boron oxide is between 1.0 and 2.1, magnesium oxide, oxidation The sum of calcium is between 3.0% and 7.0%, and the total of yttrium oxide and yttrium oxide is between 4.0% and 13.00%, arsenic oxide and lanthanum oxide, tin oxide, lanthanum oxide. The sum is between 0.3% and 2.0%. The glass of the composition has a coefficient of thermal expansion lower than 40 X 1 0-7/t (30 to 400 ° C).
第14頁 1252844 五、發明說明（ίο) 應變點溫度高於6 5 0 °C，密度低於2. 6 (g/cm3 )，液相溫度 低於1 2 0 0 °C ，每公斤基板玻璃中泡徑在0 . 5〜1 . 0 m m内的氣 泡數目少於2 0個，滿足T F T - L C D玻璃基板所需之基本物理 特性。 以下將--說明上述該等組成限制的原因。 氧化矽係為玻璃網路形成之主體，其較佳之含量為 5 6 . 0 %至6 0 . 0 %。若氧化矽含量少於5 6 · 0 %，則所製作出之 玻璃熱膨脹係數太高，且玻璃將容易失透，然，若氧化矽 含量多於6 0 . 0 %，將導致玻璃之熔解溫度太高，則很難以 一般熔解爐製造，且所製成之玻璃也容易失透。Page 14 1252844 V. Description of invention (ίο) The strain point temperature is higher than 65 ° C, the density is lower than 2.6 (g/cm3), the liquidus temperature is lower than 1 2 0 0 °C, and the substrate glass per kg The number of bubbles in the medium bubble diameter is less than 20 in 0. 5~1. 0 mm, which satisfies the basic physical properties required for the TFT-LCD glass substrate. The following will explain the reasons for the above-mentioned composition restrictions. The cerium oxide is the main body of the glass network, and the preferred content thereof is 56.0% to 60.0%. If the content of cerium oxide is less than 5 6 · 0%, the coefficient of thermal expansion of the glass produced is too high, and the glass will be easily devitrified. However, if the content of cerium oxide is more than 0.000%, the melting temperature of the glass will be caused. Too high, it is difficult to manufacture in a general melting furnace, and the glass produced is also easily devitrified.
氧化铭係用以提高玻璃結構之強度，而較佳之含量係 在1 4 . 0 %至1 8 , 0 %間。若氧化鋁含量少於1 4 . 0 %，玻璃將容 易失透，也容易受到外界水氣或化學試劑之侵蝕，然，若 氧化鋁含量多於1 8. 0 %，亦將導致玻璃之熔解溫度太高， 而不利於以一般熔解爐製造。 由此，氧化石夕和氧化紹共同為構成玻璃網路結構的主 體，其較佳總和應超過7 1 . 0 %，若氧化矽與氧化鋁的總和 少於7 1 . 0 %，則玻璃結構將不夠安定，容易失透，也容易 受到外界水氣或化學試劑之侵蝕。Oxidation is used to increase the strength of the glass structure, and the preferred content is between 14.0% and 18%. If the alumina content is less than 14.0%, the glass will be easily devitrified and easily eroded by external moisture or chemical agents. However, if the alumina content is more than 18.0%, it will also cause the glass to melt. The temperature is too high, which is not conducive to the manufacture of a general melting furnace. Thus, the combination of oxidized oxide and oxidized oxidized is the main body constituting the glass network structure, and the preferred sum thereof should exceed 7.1%. If the total of cerium oxide and aluminum oxide is less than 7.1%, the glass structure It will not be stable enough, easily devitrified, and easily eroded by external moisture or chemical agents.
氧化硼係作為助熔劑使用，主要用以降低熔製玻璃時 玻璃膏之黏度，較佳之含量為7 . 5 %至1 4 . 0 %。若氧化硼含 量少於7. 5 %，則其助熔劑效果即無法充分發揮，然，若氧 化硼含量多於14.0%，由於氧化的揮發，不易製成均質 的玻璃。The boron oxide is used as a fluxing agent, and is mainly used for reducing the viscosity of the glass paste when the glass is melted, and the content is preferably 7.5 % to 14.5%. If the boron oxide content is less than 7.5 %, the effect of the flux is not sufficiently exhibited. However, if the boron oxide content is more than 14.0%, it is difficult to form a homogeneous glass due to the volatilization of oxidation.
第15頁 1252844 五、發明說明（11) 由於氧化鋁和氧化硼對玻璃黏度和熔解溫度都有極大 影響，因此其比例範圍應有限制。氧化鋁與氧化硼的較佳 比例介於1 . 0與2 . 1之間，若比例低於1 . 0，玻璃膏之黏度 太低，玻璃基板將不易成型。若比例高於2 . 1 ，玻璃膏之 黏度太高，不利於以一般熔解爐製造。 氧化鎂係用以降低熔製玻璃時玻璃膏之黏度，以減少 其中之氣泡或不純物之含量，及調整玻璃成型性，其較佳 之含量係介於0. 0%至2. 0%間，若氧化鎂含量多於2. 0%，則 玻璃將容易失透。Page 15 1252844 V. INSTRUCTIONS (11) Since alumina and boron oxide have a great influence on glass viscosity and melting temperature, the ratio range should be limited. The preferred ratio of alumina to boron oxide is between 1.0 and 2.1. If the ratio is less than 1.0, the viscosity of the glass paste is too low, and the glass substrate will not be easily formed. If the ratio is higher than 2.1, the viscosity of the glass paste is too high, which is not conducive to the manufacture of a general melting furnace. 0%之间。 If the content is between 0. 0% to 2. 0%, if the content is between 0. 0% to 2. 0%, if the content of the glass is less than 0. 0% to 2. 0%, if When the content of magnesium oxide is more than 2.0%, the glass will be easily devitrified.
氧化鈣之作用係為促進玻璃之熔解，及調整玻璃成型 性，其較佳含量係介於3 . 0 %至7 . 0 %間。若氧化妈含量少於 3. 0 %，將無法有效降低玻璃之黏度，而若氧化#5含量多於 7. 0 % 5玻璃將容易失透’且熱膨服係數會大幅提南’不利 於後續製程之應用。 由此，氧化鎮與氧化#5之作用係作為助溶劑，及調整 玻璃成型性。氧化鎭與氧化舞之較佳之總含量係介於3. 0 % 至7 . 0 %間，若總含量少於3 . 0 %，將無法發揮促進玻璃熔解 之效果，若總含量多於7.0%，將導致玻璃失透和成型不良 ，且熱膨脹係數會太高。The effect of the calcium oxide is to promote the melting of the glass and to adjust the glass formability, and the preferred content thereof is between 3.0% and 7.0%. If the content of the oxidized mother is less than 3.0%, the viscosity of the glass will not be effectively reduced, and if the content of oxidizing #5 is more than 7. 0%, the glass will be easily devitrified and the coefficient of thermal expansion will be greatly increased. Application of subsequent processes. Thus, the action of Oxidation Town and Oxidation #5 serves as a co-solvent and adjusts the moldability of the glass. The preferred total content of cerium oxide and oxidized dance is between 3.0% and 7.0%. If the total content is less than 3.0%, the effect of promoting glass melting will not be exerted. If the total content is more than 7.0% Will cause the glass to be devitrified and poorly formed, and the coefficient of thermal expansion will be too high.
氧化勰之作用係作為助熔劑以及防止玻璃失透，其較 佳含量係在1 . 0 %至6 . 0 %間。若氧化勰含量少於1 . 0 %，將無 法發揮助熔劑之效果，且玻璃將容易失透，若氧化勰含量 多於6 . 0 %，玻璃密度會太高，不利於產品之應用。 氧化鋇之作用與氧化勰相似，其較佳之含量為2 . 0 %至The cerium oxide acts as a fluxing agent and prevents devitrification of the glass, and the preferred content is between 1.0% and 6.0%. If the cerium oxide content is less than 1.0%, the effect of the flux will not be exerted, and the glass will be easily devitrified. If the cerium oxide content is more than 6.0%, the glass density will be too high, which is not suitable for the application of the product. The effect of cerium oxide is similar to that of cerium oxide, and its preferred content is 2.0% to
第16頁 1252844 五、發明說明（12) 1 0 . 0 %，若氧化鋇含量少於2 . 0 %，將無法發揮助熔劑之效 果，且玻璃將容易失透，然，若氧化鋇含量多於1 0 . 0 %， 玻璃密度會太高，且應變點會大幅降低。 由於氧化锶與氧化鋇之作用係作為助熔劑，及防止玻 璃失透，其較佳之總含量係介於4 . 0 %至1 3 . 0 %間，若總含 量少於4 . 0 %，將無法發揮促進玻璃熔解之效果，且玻璃將 容易失透，而若總含量多於1 3 . 0 %，將導致玻璃密度會太 高。 氧化鋅亦係用以促進玻璃之熔解，其較佳含量為0. 0 % 至1 . 0 %，若氧化鋅含量多於1 . 0 %，玻璃將容易失透。 氧化锆亦係用以降低玻璃之黏度，以促進玻璃之熔解 作用，其較佳之含量係介於0 . 0 %至1 . 0 %，若氧化锆含量多 於1 . 0 %，玻璃將容易失透。 由於氧化砷、氧化銻、氧化錫與氧化鈽的作用是玻璃 熔解時的澄清劑或除泡劑，其較佳之總含量為0 . 3 %至2 . 0 % 。若總含量少於0 . 3 %，其澄清劑或除泡劑效果即無法充分 發揮，若總含量多於2 . 0 %，將導致玻璃變黃或發黑，影響 透光度。 氧化砷較佳之含量係在〇 . 〇 %至2 . 〇 %間，若氧化砷含量 多於2 . 0 %，則將導致玻璃發黑。Page 16 1252844 V. Description of invention (12) 1 0. 0 %, if the content of cerium oxide is less than 2.0%, the effect of the flux will not be exerted, and the glass will be easily devitrified, however, if the content of cerium oxide is high, At 100.0%, the glass density will be too high and the strain point will be greatly reduced. Since the action of cerium oxide and cerium oxide acts as a fluxing agent and prevents devitrification of the glass, the preferred total content is between 4.0% and 13.0%, and if the total content is less than 4.0%, The effect of promoting glass melting cannot be exerted, and the glass will be easily devitrified, and if the total content is more than 13.0%, the glass density will be too high. Zinc oxide is also used to promote the melting of glass. The preferred content is from 0. 0% to 1.0%. If the zinc oxide content is more than 1.0%, the glass will be easily devitrified. Zirconium oxide is also used to reduce the viscosity of the glass to promote the melting of the glass. The preferred content is from 0. 0% to 1.0%. If the zirconia content is more than 1.0%, the glass will be easily lost. through. Since the arsenic oxide, cerium oxide, tin oxide and cerium oxide act as a clarifying agent or a defoaming agent in the glass melting, the total content thereof is preferably 0.3% to 2.0%. If the total content is less than 0.3%, the effect of the clarifier or defoaming agent cannot be fully exerted. If the total content is more than 2.0%, the glass will turn yellow or black, which will affect the transmittance. The preferred content of arsenic oxide is between 〇% and .%, and if the arsenic oxide content is more than 2.0%, the glass will be blackened.
氧化銻較佳之含量係在0 . 0 %至1 . 0 %間，若氧化銻含量 多於1 . 0 %，也將導致玻璃發黑。 氧化錫較佳之含量係在0 . 0 %至1 . 0 %間，若氧化錫含量 多於1 . 0 %，將導致玻璃失透。The preferred content of cerium oxide is between 0.0% and 1.0%, and if the cerium oxide content is more than 1.0%, the glass will also be blackened. The preferred content of tin oxide is between 0% and 1.0%, and if the tin oxide content is more than 1.0%, the glass will be devitrified.
1252844 五、發明說明（13) 氧化鈽較佳之含量係在0 . 0 %至1 . 0 %間，若氧化鈽含量 多於1 . 0 %，將使玻璃變黃，影響透光度。 藉由本發明所揭露的玻璃組成，具有如多晶矽型 (p〇ly-Si ) TFT-LCD等次世代製程或產品所需求的TFT-L C D玻璃基板特性時，其組成成份之重量百分比分別為6 0 . 0 %至6 4 · 0 %之氧化矽、1 5 · 0 %至1 9 . 0 %之氧化鋁、9 · 5 %至1 3 · 0 %之氧化硼、0 · 0 %至4 . 0 %之氧化鎂、3 . 0 %至1 0 . 0 %之氧化 鈣、0 . 0 %至3 , 0 %之氧化鋰、（K 0 %至2 · 0 %之氧化鋇、（K 0 %至1252844 V. INSTRUCTIONS (13) The preferred content of cerium oxide is between 0.0% and 1.0%. If the cerium oxide content is more than 1.0%, the glass will be yellowed and the transmittance will be affected. By the composition of the glass disclosed in the present invention, when the characteristics of the TFT-L CD glass substrate required for a next-generation process or product such as a polycrystalline germanium (p〇ly-Si) TFT-LCD, the weight percentage of the constituent components is 6 0 . 0 % to 6 4 · 0 % of cerium oxide, 1 5 · 0 % to 19.9% of alumina, 9 · 5 % to 1 3 · 0 % of boron oxide, 0 · 0 % to 4. 0% magnesium oxide, 3.0% to 10.0% calcium oxide, 0. 0% to 3, 0% lithium oxide, (K 0% to 2 0% yttrium oxide, (K 0 %) to
1 · 0 %之氧化鋅、0 · 0 %至1 . 0 %之氧化锆、0 · 0 %至2 . 0 %之氧化 砷、（K 0 %至1 . 0 %之氧化銻、0 . 0 %至1 · 0 %之氧化錫、0· 0 %至 1 . 0 %之氧化鈽、其中氧化矽與氧化鋁的總和超過7 6 . 0 %， 氧化铭與氧化的比例介於1 . 3與1. 8之間，氧化錢、氧化 鈣之總和介於5 . 0 %至1 0 . 0 %之間，氧化锶、氧化鋇之總和 介於0 . 0 %至4 . 5 %之間，氧化砷與氧化銻、氧化錫、氧化鈽 之總和介於0. 3%至2. 0%之間。該等組成的玻璃，其熱膨脹 係數低於34\10—7/°0：(30〜4 0 0 °(：)，應變點溫度高於665 °C，密度低於2 · 4 ( g / c m3 )，液相溫度低於1 2 0 0 °C，每公 斤基板玻璃中泡徑在0 . 5〜1 . 0 m in内的氣泡數目少於2 0個， 滿足如多晶矽型（ρ ο 1 y - S i ) T F T - LC D等次世代製程或產品 所需求的TFT-LCD玻璃基板特性。 以下將--說明上述該等組成限制的原因。1 · 0 % of zinc oxide, 0 · 0 % to 1.0% of zirconium oxide, 0 · 0 % to 2.0% of arsenic oxide, (K 0 % to 1.0% of cerium oxide, 0. 0 %至1·0% of tin oxide, 0. 0% to 1.0% of cerium oxide, wherein the total of cerium oxide and aluminum oxide exceeds 76. 0%, the ratio of oxidation to oxidation is between 1.3 and Between 8., the sum of oxidized money and calcium oxide is between 5.0% and 10.0%, and the total of yttrium oxide and yttrium oxide is between 0.02% and 4.5%. The sum of arsenic and antimony oxide, tin oxide and antimony oxide is between 0.3% and 2.0%. The glass of the composition has a thermal expansion coefficient lower than 34\10-7/°0: (30~4) 0 0 °(:), the strain point temperature is higher than 665 °C, the density is lower than 2 · 4 ( g / c m3 ), the liquidus temperature is lower than 1 2 0 0 °C, and the bubble diameter per kg of substrate glass is 0. The number of bubbles in 5 to 1. 0 m in is less than 20, satisfying the characteristics of TFT-LCD glass substrates required for next-generation processes or products such as polycrystalline ( (ρ ο 1 y - S i ) TFT - LC D The following will explain the reasons for the above-mentioned composition restrictions.
由於氧化石夕係玻璃網路形成之主體，其較佳之含量為 6 0 . 0 %至6 4 . 0 %。若氧化矽含量少於6 0 · 0 %，所製作出之玻 璃熱膨脹係數太高，且玻璃將容易失透。若氧化矽含量多The content of the oxidized stone-glass network is preferably from 0.001% to 6.4%. If the cerium oxide content is less than 60 %, the thermal expansion coefficient of the glass produced is too high, and the glass will be easily devitrified. If the content of cerium oxide is high
第18頁 1252844 五、發明說明（14) 於6 4 . 0 %，則將導致玻璃之熔解溫度太高，致其很難以一 般熔解爐製造，且所製成之玻璃也容易失透。 氧化鋁係用以提高玻璃結構之強度，較佳之含量係在 1 5 . 0 %至1 9 . 0 %間。若氧化鋁含量少於1 5 . 0 %，玻璃將容易 失透，也容易受到外界水氣或化學試劑之侵蝕，然，若氧 化銘含量多於1 9 . 0 %，亦將導致玻璃之熔解溫度太高，而 不利於以一般熔解爐製造。Page 18 1252844 V. Inventive Note (14) At 64. 0%, the melting temperature of the glass will be too high, making it difficult to manufacture in a general melting furnace, and the glass produced will be easily devitrified. The alumina is used to increase the strength of the glass structure, and the content is preferably between 10.5% and 19.9%. If the alumina content is less than 15.0%, the glass will be easily devitrified, and it will be easily corroded by external moisture or chemical agents. However, if the content of oxidation is more than 19.9%, it will also cause melting of the glass. The temperature is too high to be produced in a general melting furnace.
由於氧化矽和氧化鋁係為共同構成玻璃網路結構的主 體，其較佳總和應超過7 6 . 0 %，若氧化矽與氧化鋁的總和 少於7 6 . 0 %，玻璃結構將不夠安定，容易失透，也容易受 到外界水氣或化學試劑之侵蝕。 氧化硼之作用係作為助熔劑，主要係用以降低熔製玻 璃時玻璃膏之黏度，其較佳之含量為9. 5%至13.0%，若氧 化含量少於9 . 5 %，其助溶劑效果即無法充分發揮，若氧 化硼含量多於1 3. 0 %，由於氧化硼的揮發，不易製成均質 的玻璃。 而氧化鋁和氧化硼對玻璃黏度和熔解溫度都有極大影 響，因此其比例範圍應有限制。氧化铭與氧化棚的較佳比 例介於1 . 3與1 . 8之間，若比例低於1 . 3，玻璃膏之黏度太 低，玻璃基板將不易成型。若比例高於1 . 8，玻璃膏之黏 度太高，不利於以一般熔解爐製造。Since yttrium oxide and alumina are the main bodies of the glass network structure, the preferred sum should exceed 76. 0%. If the total of yttrium oxide and alumina is less than 76. 0%, the glass structure will not be stable enough. It is easy to devitrify and is easily eroded by external moisture or chemical agents. The role of boron oxide is mainly used as a flux to reduce the viscosity of the glass paste when the glass is melted. The preferred content is 9.5% to 13.0%. If the oxidation content is less than 9.5 %, the solvent effect is improved. That is, it cannot be fully utilized. If the boron oxide content is more than 1.3%, it is difficult to form a homogeneous glass due to the volatilization of boron oxide. Alumina and boron oxide have a great influence on the viscosity and melting temperature of the glass, so the ratio range should be limited. The preferred ratio of oxidation to oxidation shed is between 1.3 and 1.8. If the ratio is less than 1.3, the viscosity of the glass paste is too low, and the glass substrate will not be easily formed. If the ratio is higher than 1.8, the viscosity of the glass paste is too high, which is not conducive to the manufacture of a general melting furnace.
氧化鎂係用以降低炼製玻璃時玻璃膏之黏度，以減少 其中之氣泡或不純物之含量，及調整玻璃成型性。其較佳 之含量係介於0. 0%至4. 0%間，但若氧化鎂含量多於4. 0%，Magnesium oxide is used to reduce the viscosity of the glass paste when refining glass, to reduce the content of bubbles or impurities therein, and to adjust the glass formability. 0%, if the content of magnesium oxide is more than 4.0%,
第19頁 1252844 五、發明說明（15) 玻璃將容易失透。 氧化鈣之作用亦係促進玻璃之熔解，及調整玻璃成型 性。其較佳含量係介於3 . 0 %至1 0 . 0%間，若氧化鈣含量少 於3 . 0 %，將無法有效降低玻璃之黏度，若氧化鈣含量多於 1 0 . 0 %，玻璃將容易失透，且熱膨脹係數會大幅提高，不 利於後續製程之應用。 氧化鎂與氧化鈣之作用係作為助熔劑，及調整玻璃成 型性。氧化鎮與氧化I弓之較佳之總含量係介於5.0%至 1 0 . 0 %間，若總含量少於5 . 0 %，將無法發揮促進玻璃熔解 之效果，若總含量多於1 0 . 0 %，將導致玻璃失透和成型不 良，且熱膨脹係數會太高。 氧化锶之作用在作為助熔劑，及防止玻璃失透，其較 佳含量係在0. 0%至3. 0%間，若氧化勰含量多於3. 0%，玻璃 密度會太高，不利於產品之應用。 氧化鋇之作用與氧化勰相似，其較佳之含量為0. 0 %至 2 . 0 %，若氧化鋇含量多於2 . 0 %，玻璃密度會太高，且應變 點會大幅降低。 氧化勰與氧化鋇之作用係作為助熔劑，及防止玻璃失 透。其較佳之總含量係介於0%至4. 5%間，若總含量多於4. 5 %，將導致玻璃密度會太高。 氧化鋅亦係用以促進玻璃之溶解，其較佳含量為0. 0 % 至1 . 0 %，若氧化鋅含量多於1 . 0 %，玻璃將容易失透。 氧化錯亦係用以降低玻璃之黏度，以促進玻璃之熔解作用 ，其較佳之含量係介於0. 0%至1 . 0%，若氧化鍅含量多於1 .Page 19 1252844 V. INSTRUCTIONS (15) The glass will be easily devitrified. The role of calcium oxide is also to promote the melting of the glass and to adjust the glass formability. The preferred content is between 3.0% and 10.0%. If the calcium oxide content is less than 3.0%, the viscosity of the glass will not be effectively reduced. If the calcium oxide content is more than 10.0%, The glass will be easily devitrified and the coefficient of thermal expansion will be greatly increased, which is not conducive to the application of subsequent processes. The action of magnesium oxide and calcium oxide acts as a fluxing agent and adjusts the formability of the glass. The preferred total content of the oxidized town and the oxidized I bow is between 5.0% and 1.0%, and if the total content is less than 5.0%, the effect of promoting glass melting cannot be exerted, if the total content is more than 10 0 % will cause devitrification and poor molding of the glass, and the coefficient of thermal expansion will be too high. The glass content is too high, which is unfavorable, if the content of cerium oxide is more than 3.0%, if the content of cerium oxide is more than 3.0%, the content of cerium oxide is too high. For product applications. The effect of cerium oxide is similar to that of cerium oxide. The preferred content is from 0. 0% to 2.0%. If the cerium oxide content is more than 2.0%, the glass density will be too high and the strain point will be greatly reduced. The action of cerium oxide and cerium oxide acts as a flux and prevents glass from devitrifying. The preferred total content is between 0% and 4.5%, and if the total content is more than 4.5%, the glass density will be too high. Zinc oxide is also used to promote the dissolution of glass. The preferred content is from 0. 0% to 1.0%. If the content of zinc oxide is more than 1.0%, the glass will be easily devitrified. Oxidation is also used to reduce the viscosity of the glass, in order to promote the melting of the glass, the preferred content is between 0. 0% to 1.0%, if the content of cerium oxide is more than 1.
1252844__ 五、發明說明（16) 0 %，玻璃將容易失透。 氧化神、氧化録、氧化錫與氧化錦的作用是玻璃溶解 時的澄清劑或除泡劑，其較佳之總含量為0 . 3 %至2 . 0 %，若 總含量少於0 . 3 %，其澄清劑或除泡劑效果即無法充分發揮 ，若總含量多於2 . 0 %，將導致玻璃變黃或發黑，影響透光 度。 氧化砷較佳之含量係在〇 . 〇 %至2 . 0 %間，若氧化砷含量 多於2. 0%，將導致玻璃發黑。 氧化銻較佳之含量係在0 . 0 %至1 . 0 %間，若氧化銻含量 多於1 . 0 %，也將導致玻璃發黑。 氧化錫較佳之含量係在0 . 0 %至1 . 0 %間，若氧化錫含量 多於1 . 0 %，將導致玻璃失透。 氧化鈽較佳之含量係在0. 0 %至1 . 0 %間，若氧化鈽含量 多於1 . 0 %，將使玻璃變黃，影響透光度。 本發明係先將上述之組成物，均句混合後，將混合原 料導入一玻璃熔解槽，待此混合原料熔解成玻璃膏後，將 其溫度降低至成型所需之溫度範圍，予以成型，製作出預 定厚度之玻璃基板，再將玻璃基板徐緩冷卻，即可切割加 工成液晶顯不用之玻璃基板成品。 【實施方式】 於下列之表一、表二（例1至例1 0 )中顯示出根據本 發明所製成玻璃樣品的組成及特性，此亦即本發明的實施 例。而表一係依據本發明所揭露的玻璃組成範圍，對應於1252844__ V. Description of invention (16) 0 %, the glass will be easily devitrified. Oxidation, oxidation, tin oxide and oxidized bromine is a clarifying agent or a defoaming agent when the glass is dissolved, preferably having a total content of 0.3% to 2.0%, if the total content is less than 0.3% The effect of the clarifying agent or defoaming agent cannot be fully exerted. If the total content is more than 2.0%, the glass will turn yellow or black, which will affect the transmittance. The arsenic oxide content is preferably between 〇% and 2.0%, and if the arsenic oxide content is more than 2.0%, the glass will be blackened. The preferred content of cerium oxide is between 0.0% and 1.0%, and if the cerium oxide content is more than 1.0%, the glass will also be blackened. The preferred content of tin oxide is between 0% and 1.0%, and if the tin oxide content is more than 1.0%, the glass will be devitrified. The preferred content of cerium oxide is between 0. 0% and 1.0%, and if the cerium oxide content is more than 1.0%, the glass will be yellowed and the transmittance will be affected. The invention firstly mixes the above-mentioned composition, and then mixes the mixed raw materials into a glass melting tank. After the mixed raw material is melted into a glass paste, the temperature is lowered to a temperature range required for molding, and is formed. The glass substrate of a predetermined thickness is released, and then the glass substrate is slowly cooled, and the glass substrate can be cut into a finished glass substrate. [Embodiment] The composition and characteristics of the glass sample produced according to the present invention are shown in Tables 1 and 2 (Examples 1 to 10) below, which is an embodiment of the present invention. Table 1 is a range of glass composition according to the present invention, corresponding to
1252844 五、發明說明（17) ^ ίTFT LCD玻璃基板所需之基本物理特性务一 r $，电明戶斤揭露的玻璃級成範圍，對應於尚且。表係依 i (P〇ly-Si ) TFT-LCD等次世代製程或连。口，、有如夕晶矽 MD玻璃基板特子人—世代衣私或產品所需求之TFT_ 示不同於本發明所制^ /\二、表四（例11至例16)中顯 明的比較例】Π成樣…成及特性，亦即本發 照組。 /、中表二係表一的對照組，表四係表二的i 用之各‘成H : : f 2 : σ:、，均係以如下方法製造：使 加以均勻i a : 1β:用原料’依所對應之重量百分ί 内溶至8 7 一再以1 6 0 0〜1 6 5 0 °C之溫度，並在白金掛禍 時，以促進；U中之=白金授拌棒授拌 4屬模板中冷卻成型為板狀…寺，針；貧倒 4:*分別得到熱膨脹係數玻，表品進 對應攔位i寺特性值，亚分別表列於下列之表-至表四： 价1Γ其中，檢測本發明各玻璃樣品之各特性值眸 .^ . 依下歹m進行檢測： } Μ值4 ’主要係 (1 >熱膨服係數（單位：丨0—ν它）之檢測：係表日”、， 枓:式驗協會(American S0Clety for Testin=d國材 標準以下曰簡稱AlTM)所訂定之編號E 2 2 8 -95檢測 教、，曰 钱械推桿式熱膨脹儀及氧化紹為參考標準，力 :坡Ϊ樣品之伸長量，溫度範圍自室溫；到玻璃。 甲長’甚至因軟化而收縮為止之溫度，升溫速率為1252844 V. INSTRUCTIONS (17) ^ The basic physical characteristics required for the ί TFT LCD glass substrate are r $, and the glass-level range revealed by the electrician is corresponding to the standard. The watch is based on next-generation processes such as i (P〇ly-Si) TFT-LCD. The mouth, which is similar to the TFTs of the MD glass substrate, the TFTs required by the generations of clothing or products, are different from the comparative examples shown in the invention by ^ / \ 2, Table 4 (Examples 11 to 16). Π Π ... ... 成 成 成 成 成 成 成 成 成 成 成 成/, the middle table of the second table of the control group, Table 4 of the second table of the use of each of the 'H: : f 2 : σ:,, are made by the following method: to make uniform ia: 1β: raw materials 'According to the weight percentage corresponding to ί internally dissolved to 8 7 and then at a temperature of 1 6 0 0~1 6 5 0 °C, and in the case of Platinum, to promote; U in the = Platinum 4 kinds of templates in the cooling form into a plate shape... Temple, needle; lean down 4: * respectively to obtain the thermal expansion coefficient of glass, the table into the corresponding barrier i temple characteristic values, sub-listed in the following table - to the table four: price 1), detecting the characteristic values of each glass sample of the present invention 眸.^. Detected according to the lower 歹m: } Μ value 4 'main line (1 > thermal expansion coefficient (unit: 丨0-ν it) detection : "Day of the table",, 枓: Test No. E 2 2 8 -95, which is set by the American Society for Testing and Testing (American S0Clety for Testin=d National Standards, hereinafter referred to as AlTM). Oxidation is the reference standard, force: the elongation of the sloping sample, the temperature range from room temperature; to the glass. The length of the nail length even shrinks due to softening, the heating rate for
第22頁 1252844 五、發明說明（18) 每分鐘3 °C。熱膨脹係數由3 0至4 0 0 °C之玻璃伸長量計算 得到。 (2 )應變點（單位：°c )之檢測：係參照A s T M c 5 9 8 - 9 3， 加熱並量測玻璃樣品之變形率與溫度之關係，以特定變 形率所對應之溫度作為應變點。 (3)岔度（單位：g/cm3 )之檢測：係參照ASTM C729_75， ==2—公克重不含氣泡之塊狀玻璃，以玻璃樣品在比重 /夜中洋沉之情形量測其密度。Page 22 1252844 V. INSTRUCTIONS (18) 3 °C per minute. The coefficient of thermal expansion is calculated from the glass elongation of 30 to 400 °C. (2) Detection of strain point (unit: °c): Refer to A s TM c 5 9 8 - 9 3, heat and measure the relationship between the deformation rate of the glass sample and the temperature, and take the temperature corresponding to the specific deformation rate as Strain point. (3) Detection of twist (unit: g/cm3): Refer to ASTM C729_75, ==2—gram-weight glass without bubbles, and measure the density of the glass sample in the case of specific gravity/night sinking.
(4ί二璃度（單位：°C)之檢測：係根據ASTM 描择@1 ’將小於8 5 〇μ m之玻璃屑放入白金耻中，番仏 又爐24小時後，以顯微鏡測量玻璃 ’置於 其/文相溫度而得。 舆之π曰曰情形，判定 (5 )氣泡產生數（單位：個/公斤）：將板狀# + 、ϋ力土 Μ 卞叙狀坡墙挺Tt 光後，在顯微鏡下觀察其内部氣泡數，▲樣nu研磨 八5〜1 · 〇 mm内的氣泡數目，再以玻璃樣品/算泡徑在 么斤坡螭的氣泡數。而表一、表二、表二I換算為每 產生數斟應欄位中，凡以〇標記者 一-及表四之氣泡 品，廿 ^ 〜衣不言女λ 屬於不佳的情況。 • 其氣泡產生數在1 0個/公斤以下，屬於Λ、、、且成之樣 ’凡以厶標記者，表示該組成之樣品，复I良好的情況 〜_5Μ固/公斤之間，屬於中等的情況：產生數在 不為纟且成之樣品，其氣泡產生數在5 〇 榡記者， 不佳的情況。 公斤以上，(4 ί chromaticity (unit: °C) detection: according to ASTM description @1 'put less than 8 5 〇μ m glass shards into the platinum shame, Panyu and furnace for 24 hours, measuring the glass with a microscope 'Placed at its / text temperature. 舆 π 曰曰 situation, judge (5) number of bubble generation (unit: one / kg): the plate shape # +, ϋ力土Μ 卞 坡 坡 坡 坡 坡 坡 坡 坡 坡 坡 坡Under the microscope, observe the number of bubbles inside the microscope, ▲ sample nu grind the number of bubbles in the 55~1 · 〇mm, and then use the glass sample / calculate the bubble diameter in the number of bubbles in the 斤 螭 。 。, and Table 1, Table 2, Table 2 I is converted into the number of fields in each of the number of fields, and the number of bubbles in the first and the fourth table is 不^ 〜 衣 不 female λ is not good. • The number of bubbles generated is 10 Less than one kilogram, belonging to the sample of Λ, 、, and 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 In the case of a sample, the number of bubbles generated is 5 〇榡 reporter, poor condition. More than kilograms,
第23頁 1252844 五、發明說明（19)Page 23 1252844 V. Description of invention (19)
表· 以下紺成爲重量百分比（Wt%) 實施例 例1 例2 例3 例4 例5 氧化矽(Si〇2) 58.3 56.9 58.7 57.5 59.1 氧化祖ΙΑ) 17.2 16.2 15.7 18.1 16.4 _氧化硼(B2〇3)_ 10.5 9.8 8.5 11.2 10.8 氯化錯⑽〇） 0.4 0.7 1.1 0.6 〇 _氯化鈣㈣)_ 4.5 3.6 4.1 5.9 6.1 氧化麵0) 2.7 4.6 3.2 1.3 2.4 氯化鋇(BaO) 5.1 6.6 7.1 4.2 3.4 氧化鋅(ZnO) 0.3 0 0.6 0.2 0.4 氧化鍇(Zr〇2) 0.5 0.5 0.4 0 0.2 氧化砷(AS2〇3) 0.4 0.3 0.3 0.8 0.6 氧化銻(Sb2〇3) 0.1 0.3 0 0.2 0.3 氧化鍚(Sn〇2) 0 0.2 〇 0 0.2 氧化鋪（Ce〇2) 0 0.3 0.3 0 0.1 氯化矽+氧化鋁(Si〇2 +Α12〇3) 75.5 73.1 74.4 75.6 75.5 氧化纖化硼（ALOV&a) 1.64 1.65 1.85 1.62 1.52 氧化饌+氧化弼 (MgO + CaO) 4.9 4.3 5.2 6.5 6.1 氧化緦+氧化鋇 (SrO + BaO) 7.8 11.2 10.3 5.5 5.8 氧化砷+氧化銻+氧化鍚+氧化姉 (As2〇3+Sb2〇3+Sn〇2+Ce〇2) 0.5 1.1 0.6 1 1.2 熱膨脹係數（xKT7/°C3(M0Q°C) 37.9 37.1 38.5 39.6 39.2 _應戀占rc)_ 659 653 660 664 662 _密度( g/cm3)_ 2.54 2.57 2.58 2.53 2.53 玻璃液相溫度 1120 1100 1100 1180 1160 _氣泡產生動_ 0 0 0 0 0 ill· 第24頁 1252844 五、發明說明（20) 表一^ 以下組成爲雷量酉分比（wt% ) 實施例 例6 例7 例8 例9 例1〇 氧化矽(Si〇2) 62.5 60.8 63.1 62.9 61.6 氧化絕(AI2 Ch) 17.1 16.3 15.4 15.9 18.1 氧化硼(B2〇3) 9.8 10.5 10.2 10.8 10.3 1.2 〇 0.2 2.2 0.6 氣化銳Ca〇） 4.2 9.1 8.2 6.5 5.1 氧化緦βΓ〇） 1.6 1.3 0.8 0.3 1.9 氧化鋇(Ba〇） 1.1 0.2 0.4 0.3 0.5 氧化鋅βη〇） 0.6 0 0.3 0.1 0.4 氧化·Γ〇2) 0.5 0.5 0 0.2 0.3 氣化砷(AS2〇3) 0.7 0.5 0.3 0.6 0.2 氧化銻伽〇3) 0.3 0.5 0.7 0.2 0.8 氧化錫(Sn〇2) 0.2 0 0.4 0 0.1 氧化鋪（Ce〇2) 0.2 0.3 〇 0 0.1 氧化矽+氧化鋁(Si〇2 +Α12〇3) 79.6 77.1 78.5 78.8 79.7 氧化絕/氧化硼（Aka/B^a) 1.74 1.55 1.51 1.47 1.76 氧化鎂+氧化鈣 (MgO + CaO) 5.4 9.1 8.4 8.7 5.7 氧化緦+氧化鋦 (SrO + BaO) 2.7 1.5 1.2 0.6 2.4 氧化砷+氧化銻+氧化鍚+氧化_ (As2〇3+Sb2〇3+Sn〇2+Ce〇2) 1.4 1.3 1.4 0.8 1.2 熟膨脹係數（xlOYC ) i 30〜4〇0oC ) 32.7 33.8 33.4 33.8 32.9 應戀點rc) 675 671 673 671 676 密度（2/cm3) 2.38 2.36 2.35 2.32 2.38 玻璃液相溫度C°C) 1140 1160 1170 1180 1140 氣泡達生勳 0 0 0 0 0 iill 1252844 五、發明說明（21) 表三Table· The following 绀 is a weight percentage (Wt%) Example 1 Example 2 Example 3 Example 4 Example 5 Cerium oxide (Si〇2) 58.3 56.9 58.7 57.5 59.1 Oxidation of ancestors) 17.2 16.2 15.7 18.1 16.4 _Boron oxide (B2〇 3) _ 10.5 9.8 8.5 11.2 10.8 Chlorination error (10) 〇) 0.4 0.7 1.1 0.6 〇 _ calcium chloride (4)) _ 4.5 3.6 4.1 5.9 6.1 Oxidation surface 0) 2.7 4.6 3.2 1.3 2.4 Barium chloride (BaO) 5.1 6.6 7.1 4.2 3.4 Zinc Oxide (ZnO) 0.3 0 0.6 0.2 0.4 Antimony oxide (Zr〇2) 0.5 0.5 0.4 0 0.2 Arsenic oxide (AS2〇3) 0.4 0.3 0.3 0.8 0.6 Antimony oxide (Sb2〇3) 0.1 0.3 0 0.2 0.3 Antimony oxide ( Sn〇2) 0 0.2 〇0 0.2 Oxidation shop (Ce〇2) 0 0.3 0.3 0 0.1 Barium chloride + alumina (Si〇2 +Α12〇3) 75.5 73.1 74.4 75.6 75.5 Oxidized boron oxide (ALOV&a) 1.64 1.65 1.85 1.62 1.52 Antimony oxide + antimony oxide (MgO + CaO) 4.9 4.3 5.2 6.5 6.1 Cerium oxide + antimony oxide (SrO + BaO) 7.8 11.2 10.3 5.5 5.8 Arsenic oxide + antimony oxide + antimony oxide + antimony oxide (As2〇3 +Sb2〇3+Sn〇2+Ce〇2) 0.5 1.1 0.6 1 1.2 Thermal expansion coefficient (xKT7/°C3(M0Q°C) 37.9 37.1 38.5 39.6 39.2 _ should be occupied rc)_ 659 653 660 664 662 _ dense ( g/cm3)_ 2.54 2.57 2.58 2.53 2.53 Glass liquid temperature 1120 1100 1100 1180 1160 _ Bubble generation _ 0 0 0 0 ill · Page 24 1252844 V. Description of invention (20) Table 1 ^ The following composition is Ray Quantitative split ratio (wt%) Example 6 Example 7 Example 8 Example 9 Example 1 〇 〇 (Si〇2) 62.5 60.8 63.1 62.9 61.6 Oxidation (AI2 Ch) 17.1 16.3 15.4 15.9 18.1 Boron oxide (B2〇3) ) 9.8 10.5 10.2 10.8 10.3 1.2 〇0.2 2.2 0.6 Gasified sharp Ca〇) 4.2 9.1 8.2 6.5 5.1 缌 Γ〇 Γ〇 1.6 1.6 1.6 1.3 1.3 0.3 1.9 钡 钡 〇 〇 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.3 0.1 0.4 Oxidation·Γ〇2) 0.5 0.5 0 0.2 0.3 Gasified arsenic (AS2〇3) 0.7 0.5 0.3 0.6 0.2 Strontium oxide 3) 0.3 0.5 0.7 0.2 0.8 Tin oxide (Sn〇2) 0.2 0 0.4 0 0.1 Oxidation shop (Ce〇2) 0.2 0.3 〇0 0.1 yttrium oxide + alumina (Si〇2 + Α12〇3) 79.6 77.1 78.5 78.8 79.7 Oxidation/boron oxide (Aka/B^a) 1.74 1.55 1.51 1.47 1.76 Magnesium oxide + Calcium Oxide (MgO + CaO) 5.4 9.1 8.4 8.7 5.7 Strontium Oxide + Strontium Oxide (SrO + BaO) 2.7 1.5 1.2 0.6 2.4 Arsenic Oxide + Antimony Oxide + Oxidation + Oxidation _ (As2〇3+Sb2〇3+Sn〇2+Ce〇2) 1.4 1.3 1.4 0.8 1.2 Mature expansion coefficient (xlOYC) i 30~4〇0oC ) 32.7 33.8 33.4 33.8 32.9 Love point rc) 675 671 673 671 676 Density (2/cm3) 2.38 2.36 2.35 2.32 2.38 Glass liquid temperature C°C) 1140 1160 1170 1180 1140 Bubble Dashengx 0 0 0 0 0 iill 1252844 V. Description of invention (21) Table 3
以下紐成爲重量酉分比（wt%) 例 例11 例12 例13 氧化矽(Si〇2) 57.4 59.2 58.5 氧化鋁(Al2〇3) 17.1 18.6 16.5 氧化硼(b2〇3) 10.6 11.5 9.5 氧化籍触0) 0.6 1.4 1.2 氧化鈣(CaO) 7.6 5.3 4 氧化緦(ao) 1.8 0.6 3.1 氧化鋇(BaO) 3.8 1.7 6.6 氧化鈴(ZnO) 0 0.3 0.2 氧化鍇(Zr〇2) 0.2 0 0.3 氧化砷(As2〇4 0.3 0.6 0.1 氧化銻(Sb2〇3) 0.6 0.6 〇 氧化—(Sn〇2) 〇 0 0 氧化鋪（Ce〇2) 0 0.2 0 氧化矽+氧化鋁(Si〇2 +AI2O3) 74.5 77.8 75 氧化絕/氧化硼CAl2Ch/B2〇3) 1.61 1.62 1.74 氧化鎂+氧化鈣 (MgO + CaO) 8.2 6.7 5.2 氧化緦+氧化鋇 (SrO + BaO) 5.6 2.3 9.7 氧化碑+氧化鍊+氧化鎮+氧化鋪 (As2〇3+Sb2〇3+Sn〇2+Ce〇2) 0.9 1.4 0.1 熱膨脹係數（xl(T7/°C ) ( 3Q〜40〇°C ) 41.2 39.6 38.7 應戀點rc) 655 660 660 密度（吮m3) 2.54 2.51 2.58 玻璃液相溫度（°C) 1130 1220 1120 氣泡產生動 0 0 XThe following New Zealand is the weight fraction (wt%). Example 11 Example 12 Example 13 Cerium oxide (Si〇2) 57.4 59.2 58.5 Alumina (Al2〇3) 17.1 18.6 16.5 Boron oxide (b2〇3) 10.6 11.5 9.5 Oxidation Touch 0) 0.6 1.4 1.2 Calcium Oxide (CaO) 7.6 5.3 4 Antimony Oxide (ao) 1.8 0.6 3.1 Antimony Oxide (BaO) 3.8 1.7 6.6 Oxidized Ring (ZnO) 0 0.3 0.2 Antimony Oxide (Zr〇2) 0.2 0 0.3 Arsenic Oxide (As2〇4 0.3 0.6 0.1 yttrium oxide (Sb2〇3) 0.6 0.6 〇 ——(Sn〇2) 〇0 0 铺 铺 (Ce〇2) 0 0.2 0 矽 矽 + alumina (Si〇2 + AI2O3) 74.5 77.8 75 Oxidation/Boron Oxide CAl2Ch/B2〇3) 1.61 1.62 1.74 Magnesium Oxide + Calcium Oxide (MgO + CaO) 8.2 6.7 5.2 Cerium Oxide + Strontium Oxide (SrO + BaO) 5.6 2.3 9.7 Oxidation Monument + Oxidation Chain + Oxidation Town + Oxidation shop (As2〇3+Sb2〇3+Sn〇2+Ce〇2) 0.9 1.4 0.1 Thermal expansion coefficient (xl(T7/°C) (3Q~40〇°C) 41.2 39.6 38.7 Love point rc) 655 660 660 Density (吮m3) 2.54 2.51 2.58 Glass liquid temperature (°C) 1130 1220 1120 Bubble generation 0 0 X
_丨11 第26頁 1252844 五、發明說明（22) 表四_丨11 Page 26 1252844 V. Description of invention (22) Table 4
以下細.成爲雷量酉分比（wt%) 比較例 例14 例15 例16 氧化矽(Si〇2) 61.2 61 61.9 氧化絕(AI2O3) 15.5 15.7 16.7 氧化硼(B2〇3) 10.1 9.8 11.5 氧化鎂(MgO) 0.5 0.9 0.5 氧化鈣(CaO) 10.5 5.5 6.2 氧化緦(SrO) 0.6 3.1 1.3 氧化鋇收0) 0.9 2.9 1.1 氧化鋅(ZnO) 0.3 0 0.4 氧化齡〇2) 0.2 0.1 0.4 氧化砷(AS2〇3) 〇 0.5 0 氧化銻(Sb2〇3) 0 0.5 0 氧化鍚(Sn〇2) 〇 0 〇 氧化鋪（Ce〇2) 0.2 0 0 氧化矽+氧化鋁(Si〇2 +Α12〇3) 76.1 76.7 78.6 氧化醜化硼Cai2〇伽3) 1.53 1.60 1.45 氧化鎂+氧化鈣 (MgO + CaO) 11 6.4 6.7 氧化緦+氧化鋇 (SrO + BaO) 1.5 6 2.4 氧化碑+氧化鍊+氧化鎮+氧化_ (As2 〇3+Sb2 〇3+Sn O2+Ce O2) 0.2 1 〇 熟膨脹係數（xl(T/°C ) ( 30〜4(D°C ) 36.1 33.5 33.4 應麵點（〇C) 669 670 667 密度（2/cm3) 2.36 2.49 2.38 玻璃液相溫度rc) 1180 1160 1180 氣泡產生動 △ 0 XThe following details are the ratio of the amount of sag (wt%). Comparative Example 14 Example 15 Example 16 Cerium oxide (Si〇2) 61.2 61 61.9 Oxidation (AI2O3) 15.5 15.7 16.7 Boron oxide (B2〇3) 10.1 9.8 11.5 Oxidation Magnesium (MgO) 0.5 0.9 0.5 Calcium Oxide (CaO) 10.5 5.5 6.2 Strontium Oxide (SrO) 0.6 3.1 1.3 Oxidation of Oxide 0) 0.9 2.9 1.1 Zinc Oxide (ZnO) 0.3 0 0.4 Oxidation Age 2) 0.2 0.1 0.4 Arsenic Oxide ( AS2〇3) 〇0.5 0 yttrium oxide (Sb2〇3) 0 0.5 0 yttrium oxide (Sn〇2) 〇0 〇 〇 铺 (Ce〇2) 0.2 0 0 yttrium oxide + alumina (Si〇2 +Α12〇3 76.1 76.7 78.6 Oxidized Ugly Boiled Cai2 Sangha 3) 1.53 1.60 1.45 Magnesium Oxide + Calcium Oxide (MgO + CaO) 11 6.4 6.7 Oxide Oxide + Strontium Oxide (SrO + BaO) 1.5 6 2.4 Oxidation Monument + Oxidation Chain + Oxidation Town + Oxidation _ (As2 〇3+Sb2 〇3+Sn O2+Ce O2) 0.2 1 膨胀Expansion coefficient of expansion (xl(T/°C) (30~4(D°C) 36.1 33.5 33.4 Face point (〇C) 669 670 667 Density (2/cm3) 2.36 2.49 2.38 Glass liquid temperature rc) 1180 1160 1180 Bubble generation △ 0 X
由表一所示實施例1至實施例5中之各檢測數據，可清 楚觀察出，當僅需要具有TFT-LCD玻璃基板所需的基本物 理特性時，依據本發明所揭露的玻璃組成範圍所製成之玻From the respective test data in the first embodiment to the fifth embodiment shown in Table 1, it can be clearly observed that the glass composition range according to the present invention is disclosed when only the basic physical properties required for the TFT-LCD glass substrate are required. Made of glass
第27頁 12528^44 _ 五、發明說明（23) 璃’其熱膨脹係數於界於溫度3 0〜4 0 0 °C時均低於4 Ο X 1 〇~?/ °C ，應變點溫度均高於6 5 0 t，密度均低於2.6 (g/cm3)， 玻璃液相溫度均低於1 2 0 0 〇C，每公斤基板玻璃中泡徑在〇 5〜1 · Omm内的氣泡數目均少於20個，均滿足TFT-LCD玻璃基 板所需的基本物理特性。而表二所示實施例6至實施例;[〇 中之各檢測數據，亦可清楚觀察出，當需要具有如多晶石夕 型（poly-Si ) TFT-LCD專次世代製程或產品所需求的Tp丁〜 LCD玻璃基板特性時，依據本發明所揭露的另一玻璃組成 範圍所製成之玻璃，其熱膨脹係數於界於溫度3 〇〜4 〇 〇 〇c時 均低於34 X 1 0_7/ °C ’應變點溫度均高於6 6 5。〇，密度均低 於2. 4 (g/cm3 )，玻璃液相溫度均低於12〇〇，每公斤基 板玻璃中泡徑在0 · 5〜1 · 0 mm内的氣泡數目均少於2 〇個，^ 均滿足如多晶矽型（poly-Si ) TFT-LCD等次世代製程或產 品所需求的T F T - L C D玻璃基板特性。 而表三、表四中，則列示了其它不同於本發明之組成 成份所施作之比較例1 1至比較例丨6。表三之比較例丨丨至比 較例1 3，係表一的對照組。表四之比較例1 4至比較例1 6， 係表二的對照組。由表三所示之各檢測數據中，可清楚顯 示’比較例1 1之熱膨脹係數偏高，比較例丨2之玻璃液相溫 度偏高，比較例1 3之玻璃氣泡產生數過高，均不能滿足 TFT-LCD玻璃基板所需的基本物理特性。另，由表四所示 之各檢測數據中’亦可清楚顯示，比較例丨4之熱膨脹係數 偏高，比較例15之玻璃密度偏高，比較例16之玻璃氣泡產 生數過高，亦不能滿足如多晶矽型（p〇1y-Si ) TFT — LC])等Page 27 12528^44 _ V. Description of invention (23) The thermal expansion coefficient of the glass is lower than 4 Ο X 1 〇~?/ °C at a temperature of 30 to 400 °C, and the temperature at the strain point is Above 65 k t, the density is lower than 2.6 (g/cm3), the liquidus temperature of the glass is lower than 1 2 0 0 〇C, and the number of bubbles in the cell diameter of 公斤5~1 · Omm per kg of substrate glass All of them are less than 20, which satisfy the basic physical characteristics required for the TFT-LCD glass substrate. And the embodiment 6 to the embodiment shown in Table 2; [the detection data in the 〇, can also clearly observe that when it is required to have a poly-Si TFT-LCD special generation process or product When the Tp Ding~ LCD glass substrate characteristic is required, the glass made according to another glass composition range disclosed by the present invention has a thermal expansion coefficient lower than 34 X 1 at a temperature of 3 〇 4 4 〇〇〇 c. 0_7/ °C 'The strain point temperature is higher than 6 6 5 . 〇, the density is less than 2.4 (g / cm3), the liquidus temperature of the glass is less than 12 〇〇, the number of bubbles in the bubble diameter of 0 · 5~1 · 0 mm per kilogram of substrate glass are less than 2 Each of them meets the TFT-LCD glass substrate characteristics required for next-generation processes or products such as poly-Si TFT-LCD. Further, in Tables 3 and 4, Comparative Examples 1 to 6 which are different from the components of the present invention are shown. The comparative examples in Table 3 are compared to Comparative Example 1 3, which is the control group of Table 1. Comparative Example 1 to Comparative Example 1 in Table 4 are the control groups of Table 2. From the respective test data shown in Table 3, it can be clearly shown that the thermal expansion coefficient of Comparative Example 1 1 is relatively high, and the glass liquidus temperature of Comparative Example 偏 2 is too high, and the number of glass bubbles generated in Comparative Example 13 is too high, The basic physical characteristics required for a TFT-LCD glass substrate cannot be satisfied. In addition, it can be clearly seen from the respective detection data shown in Table 4 that the thermal expansion coefficient of Comparative Example 4 is relatively high, and the glass density of Comparative Example 15 is high, and the number of glass bubbles generated in Comparative Example 16 is too high, and Satisfy such as polycrystalline germanium (p〇1y-Si) TFT — LC])
第28頁 1252844 五、發明說明（24) 次世代製程或產品所需求的TFT-LCD玻璃基板特性。 承前所述，本發明較習用之玻璃基板創新，除可達到 一般TFT-LCD玻璃基板所需要之基本特性外，更可達到前 述之多晶石夕型（poly-Si )TFT-LCD之玻璃基板所需要之諸 多特性，極具新穎性與進步性，符合發明專利之法定要件 ，爰依法提出發明專利申請。Page 28 1252844 V. INSTRUCTIONS (24) Characteristics of TFT-LCD glass substrates required for next-generation processes or products. As described above, the glass substrate innovation of the present invention can achieve the above-mentioned polycrystalline silicon-type (poly-Si) TFT-LCD glass substrate in addition to the basic characteristics required for a general TFT-LCD glass substrate. Many of the characteristics required are extremely novel and progressive, comply with the statutory requirements of the invention patent, and file an invention patent application according to law.
雖本發明以一較佳實施例揭露如上，但並非用以限定 本發明實施之範圍，任何熟習此項技藝者，在不脫離本發 明之精神與範圍内，當可做些許的更動與潤飾，及凡依本 發明所作的均等變化與修飾，應以本發明之申請專利範圍 所涵蓋，其界定應已申請專利範圍為準。The present invention has been described above with reference to a preferred embodiment, and is not intended to limit the scope of the invention, and may be modified and modified without departing from the spirit and scope of the invention. The equivalent changes and modifications made in accordance with the present invention should be covered by the scope of the patent application of the present invention, and the definition should be based on the scope of the patent application.
第29頁 1252844 圖式簡單說明Page 29 1252844 Schematic description
第30頁Page 30
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104276754A (en) * | 2013-08-27 | 2015-01-14 | 东旭集团有限公司 | Silicate glass substrate for flat-panel display |
| CN109650723A (en) * | 2019-03-01 | 2019-04-19 | 陕西科技大学 | A kind of the alkali-free high alumina Pyrex and preparation method of high rigidity |
| US11168018B2 (en) | 2013-08-15 | 2021-11-09 | Corning Incorporated | Aluminoborosilicate glass substantially free of alkali oxides |
| USRE49307E1 (en) | 2013-08-15 | 2022-11-22 | Corning Incorporated | Alkali-doped and alkali-free boroaluminosilicate glass |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11168018B2 (en) | 2013-08-15 | 2021-11-09 | Corning Incorporated | Aluminoborosilicate glass substantially free of alkali oxides |
| USRE49307E1 (en) | 2013-08-15 | 2022-11-22 | Corning Incorporated | Alkali-doped and alkali-free boroaluminosilicate glass |
| CN104276754A (en) * | 2013-08-27 | 2015-01-14 | 东旭集团有限公司 | Silicate glass substrate for flat-panel display |
| CN109650723A (en) * | 2019-03-01 | 2019-04-19 | 陕西科技大学 | A kind of the alkali-free high alumina Pyrex and preparation method of high rigidity |
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