TW200401757A - Glass and method for production of glass - Google Patents
Glass and method for production of glass Download PDFInfo
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- TW200401757A TW200401757A TW92115737A TW92115737A TW200401757A TW 200401757 A TW200401757 A TW 200401757A TW 92115737 A TW92115737 A TW 92115737A TW 92115737 A TW92115737 A TW 92115737A TW 200401757 A TW200401757 A TW 200401757A
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
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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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
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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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Abstract
Description
200401757 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關矽酸鹽玻璃及矽酸鹽玻璃之製造方法。 【先前技術】 窗戶玻璃、平面控制盤顯示用玻璃基板等玻璃板、玻 璃瓶、玻璃杯、螢光燈玻璃管等各種用途中,以質量百分 率代表之Si〇2換算含40%以上之Si玻璃(以下稱矽酸 鹽玻璃。)被廣泛使用之。 此等用途所使用之矽酸鹽玻璃中,除滿足化學性耐久 性等特性面要求之外,被要求滿足各用途中不存在大泡沬 之問題點、或即使存在亦僅爲個數之容許個數以下者。 爲滿足有關此泡沬之要求,通常,矽酸鹽玻璃之原料 爲含有爲了由溶解原料後取得熔融玻璃去除氣泡之澄淸劑 者。 做爲此澄淸劑者公知者如:As203、Sb2〇3等氧化物 系澄淸劑、Na2S〇4、K2S〇4、CaS〇4、BaS04、等硫酸鹽系 澄淸劑、NaCl等者。 有關泡沫之上記要求依其用途而異,一般對於平面控 制盤顯示用玻璃基板,特別是薄膜晶體管驅動彩色液晶顯 示器(TFT - LCD)、電激發光顯示器(EL)、電漿顯示 器(PDP )、電漿補助液晶顯示器(PALC )、場致發射顯 示器(FED )等用玻璃基板之上記要求屬最爲嚴格者。亦 即,TFT - LCD用玻璃基板等平面控制盤顯示用玻璃基板 (2) (2)200401757 中被要求即使爲尺寸數1 0 // m之小泡沬亦減少爲宜。 TFT- LCD用玻璃基板中使用實質上未含鹼金屬氧化 物之矽酸鹽玻璃(以下稱無鹼玻璃),做爲該澄淸劑者使 用 As2S03、Sb203或硫酸鹽。又,無鹼玻璃中,NaCl爲 不宜使用者。200401757 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to silicate glass and a method for manufacturing silicate glass. [Prior art] In various applications such as glass, window glass, glass substrate for flat control panel display, glass bottles, glass cups, fluorescent glass tubes, etc., Si glass containing 40% or more of Si glass is represented by mass percentage. (Hereinafter referred to as silicate glass.) It is widely used. Among the silicate glass used in these applications, in addition to meeting the requirements for characteristic surfaces such as chemical durability, it is required to meet the problem of no large foam in each application, or allow only a few if it exists. Less than the number. In order to meet the requirements for this foam, usually, the raw material of silicate glass is a clearing agent containing a molten glass to remove bubbles from the molten glass obtained by dissolving the raw material. Known as such tinctures are oxide-based tinctures such as As203, Sb2O3, Na2S04, K2S04, CaS04, BaS04, and other sulfate-based tinctures, NaCl and the like. The requirements on the foam note vary depending on its application. Generally, glass substrates for flat panel display, especially thin film transistor-driven color liquid crystal displays (TFT-LCD), electroluminescent displays (EL), plasma displays (PDP), Plasma subsidized liquid crystal displays (PALC), field emission displays (FED), and other glass substrates are the most stringent requirements. In other words, glass substrates for flat control panel displays such as TFT-LCD glass substrates (2) (2) 200401757 are required to reduce the number of small bubbles even if the size is 1 0 // m. As the glass substrate for TFT-LCD, silicate glass (hereinafter referred to as alkali-free glass) which does not substantially contain an alkali metal oxide is used. As the tincture agent, As2S03, Sb203, or sulfate is used. Also, in alkali-free glass, NaCl is not suitable for users.
As2S03及Sb203,特別是As2S03係由熔融玻璃去除 氣泡者爲極佳之澄淸劑者,惟,其對於環境負荷極大,因 此被要求控制其之使用。 另外,硫酸鹽相較於As203對於環境之負荷明顯減少 ,因此,其爲極佳之澄淸劑者。惟,無鹼玻璃中其鹽基性 度低,S042 —之溶解度亦低,其結果硫酸鹽中由熔融玻璃 去除氣泡面相較於As203爲較爲劣化之問題產生。 本發明係提供一種可解決該課題,亦即製造未含 As203、Sb203之一方,氣泡數少之矽酸鹽玻璃及矽酸鹽 玻璃的方法爲目的者。 【發明內容】 本發明係提供一種以Fe離子比例代表玻璃之還原度 ’該Fe2 + /(Fe2 + + Fe3+)相當於0.61以上還原度之玻璃者 〇 又,溶解原料後,於質量百分率顯示下,以Si02換 算下含40%以上之Si玻璃的製造方法,其特徵係提供一 種原料爲含有錢鹽(除硫酸銨及硝酸銨)之玻璃製造方法 者(本發明之方法A)。 -5 - 200401757As2S03 and Sb203, especially As2S03, are those which are excellent as tinctures by removing bubbles from molten glass. However, they are extremely burdensome to the environment and are therefore required to control their use. In addition, compared with As203, the sulfate has a significantly reduced environmental load, so it is an excellent tincture. However, alkali-free glass has low alkalinity, and the solubility of S042- is also low. As a result, the removal of the bubble surface from molten glass in sulfate is more problematic than that of As203. The present invention aims to provide a method that can solve this problem, that is, a method for manufacturing silicate glass and silicate glass that do not contain one of As203 and Sb203 and have a small number of bubbles. [Summary of the invention] The present invention provides a reduction ratio of glass represented by the proportion of Fe ions. The Fe2 + / (Fe2 + + Fe3 +) is equivalent to a glass with a reduction degree of 0.61 or more. After the raw materials are dissolved, the mass percentage is displayed. The manufacturing method of Si glass containing more than 40% in terms of SiO2 is characterized by providing a glass manufacturing method whose raw material is money salt (except ammonium sulfate and ammonium nitrate) (Method A of the present invention). -5-200401757
又’溶解原料後,於質量百分率顯示下,以S i Ο 2換 算下含40%以上Si玻璃之製造方法,其特徵係提供一種 於溶解原料後取熔融玻璃中供與銨鹽(除硫酸銨及硝酸銨 )之玻璃的製造方法者(本發明之方法B)。 另外’本發明玻璃係藉由熔融法被製造者。After dissolving the raw materials, the method of manufacturing Si glass containing more than 40% of Si glass in terms of Si0 2 conversion is shown in the mass percentage display. It is characterized by providing an ammonium salt (excluding ammonium sulfate in molten glass after dissolving the raw materials). And ammonium nitrate) for glass (method B of the present invention). In addition, the glass of the present invention is produced by a melting method.
本發明者針對各種物質進行檢測可做爲無鹼玻璃澄淸 劑之結果發現’氯化銨係由熔融玻璃去除氣泡者爲極佳之 澄淸劑者,進而完成本發明。通常無鹼玻璃等之矽酸鹽玻 璃係使原料加熱至1 000 °C以上後,溶解之後做成熔融玻 璃後進行冷卻後被製造者。又,冷卻時,必要時被成型呈 所期待之形狀。 氯化銨由該熔融玻璃去除氣泡之作用(以下稱此作用 爲澄淸作用)係如下被考量者。The present inventors have tested various substances and can use them as alkali-free glass clarifiers. As a result, they found that those who remove bubbles from molten glass are excellent clarifiers, and have completed the present invention. Generally, silicate glass such as alkali-free glass is made by heating the raw material to 1 000 ° C or more, dissolving it into a molten glass, and then cooling it. In addition, it is molded into a desired shape when necessary during cooling. The role of ammonium chloride in removing bubbles from the molten glass (hereinafter referred to as the "clearing effect") is considered as follows.
亦即,該原料中氯化銨於3 3 7.8 t下進行昇華者, 因此,1000 °C以上之原料溶解時,瞬間解離氨氣(NH3 )與氯化氫氣(HC1 )。 氨氣係於1000 °C以上高溫下分解氮氣(NO與氫氣 (H2 ) 〇 2NH3— N2 + 3H2 。 氮氣對於熔融玻璃之溶解度雖低,卻有發泡反應,因 此,熔解玻璃氣泡中可期待做爲氣體擴散流入後促進該氣 泡變大浮出脫泡之效果。 另外,氫氣其部份暫時溶解於熔融玻璃後,於數分鐘 至數小時後可期待氣化之。爲此氫氣係使由玻璃呈發泡氣 -6 - κ i.' .ii (4) 200401757 體,促進熔融玻璃中之氣泡浮出脫泡。本發明者係藉由拉 曼分光分析後檢出於原料中添加氯化銨之玻璃(特別是無 鹼玻璃)於溶解初期產生大量氫氣泡。 又,該氫氣產生後熔融玻璃呈還原性,考量氧化物系 澄淸劑與硫酸鹽系澄淸劑中對比澄淸作用後,亦可促進熔 融玻璃降溫過程中由含有氧氣之氣泡往熔融玻璃中擴散氧 氣者。That is, the ammonium chloride in the raw material is sublimated at 3 3 7.8 t. Therefore, when the raw material above 1000 ° C is dissolved, ammonia gas (NH3) and hydrogen chloride (HC1) are dissociated instantaneously. Ammonia decomposes nitrogen (NO and hydrogen (H2) 〇2NH3-N2 + 3H2) at a high temperature above 1000 ° C. Although nitrogen has a low solubility in molten glass, it has a foaming reaction, so it can be expected to melt in glass bubbles The effect is to promote the expansion of the gas bubbles after the gas diffuses into the gas. The hydrogen gas is temporarily dissolved in the molten glass, and it can be expected to evaporate in a few minutes to several hours. To this end, the hydrogen gas is made from glass It is a foaming gas-6-κ i. '.Ii (4) 200401757, which promotes the bubble out and defoaming in the molten glass. The inventor detected the addition of ammonium chloride to the raw material after Raman spectroscopic analysis Glass (especially alkali-free glass) generates a large amount of hydrogen bubbles at the initial stage of dissolution. In addition, after the hydrogen is generated, the molten glass is reducing. Considering the contrasting effect between oxide-based clearing agents and sulfate-based clearing agents, It can also promote the diffusion of oxygen from the bubbles containing oxygen into the molten glass during the cooling of the molten glass.
另外,分解氯化銨所產生之氯化氫氣雖非主要反應者 ,惟,具次反應之效果者。氯化氫氣係於1 0 0 0 °c以上高 溫下解離呈質子(H+)與氯離子(cr )、部份溶於熔融 玻璃中。 HC1— H + + C1— 。 質子於熔融玻璃中無法安定存在,與氫氧基反應後呈 水(H2〇)。 H + + OH_ H2O 。In addition, although the hydrogen chloride produced by the decomposition of ammonium chloride is not the main responder, it has the effect of secondary reactions. Hydrogen chloride dissociates as protons (H +) and chloride ions (cr) at high temperatures above 1000 ° C, and is partially dissolved in molten glass. HC1— H + + C1—. Protons cannot be stably present in molten glass, and they react with hydroxyl groups to form water (H2O). H + + OH_ H2O.
合倂此2反應後,結果氯化氫氣體於熔融玻璃中呈氯 離子溶入之同時由熔融玻璃釋出水。 HC1 + OH- -> cr +H2O 。 該水擴散流入存在於熔融玻璃之微小氣泡後,增大該 氣泡後促進浮出脫泡者。又,使用含有氯化銨之原料後所 製造之矽酸鹽玻璃之/3 - OH小於使用未含氯化銨之原料 所製造之矽酸鹽玻璃,此乃其內含有如上述水相關之促進 浮出脫泡之機序所致者。 除氯化銨之外,氟化銨、溴化銨、碘化銨等鹵化銨鹽 200401757After combining these two reactions, as a result, hydrogen chloride gas was dissolved in the molten glass as chloride ions and water was released from the molten glass. HC1 + OH--> cr + H2O. When the water diffuses and flows into the minute bubbles existing in the molten glass, the bubbles are enlarged to promote the emergence of deaerators. In addition, the / 3-OH of the silicate glass produced by using the raw material containing ammonium chloride is smaller than that of the silicate glass manufactured by using the raw material containing no ammonium chloride. Appears due to the sequence of defoaming. In addition to ammonium chloride, ammonium halide salts such as ammonium fluoride, ammonium bromide, and ammonium iodide 200401757
中亦與氯化銨同法進行反應,因此,可有效做爲澄淸劑者 玻璃構成化合物之銨鹽亦爲有效之澄淸劑者。做爲此 鹽之例者如:四硼酸銨四水合物等硼酸銨鹽。藉由銨基所 產生之氫’進行玻璃之澄淸反應後,殘餘部份以不混入除 玻璃構成成份之硼酸與分解於水之玻璃中構成成份以外之 元素者宜。It also reacts with ammonium chloride in the same way, so it can be effectively used as a clear tincture. The ammonium salt of the glass constituent compound is also a valid clear tincture. Examples of such salts are ammonium borate salts such as ammonium tetraborate tetrahydrate. After the glass clarification reaction with hydrogen generated by the ammonium group, it is preferable that the remainder is not mixed with elements other than boric acid, which is a constituent of glass, and constituents, which are decomposed in water.
有機酸銨鹽亦出現明顯之澄淸效果者。做爲此銨鹽之 例者有:醋酸銨 '甲酸銨、碳酸銨、檸檬酸三銨、檸檬酸 氫二銨、檸檬酸二氫銨、延胡索酸銨、馬來酸銨、草酸銨 、琥珀酸銨、酒石酸氫銨、乳酸銨等。有機酸銨鹽藉由高 溫氧化反應後所有反應物呈氣體成份,最後固體成份未殘 留於玻璃中,因此,爲理想之澄淸劑。The organic acid ammonium salt also shows obvious clearing effect. Examples of such ammonium salts are: ammonium acetate 'ammonium formate, ammonium carbonate, triammonium citrate, diammonium citrate, diammonium citrate, ammonium fumarate, ammonium maleate, ammonium oxalate, ammonium succinate , Ammonium hydrogen tartrate, ammonium lactate, etc. The organic acid ammonium salt is a gaseous component after the high temperature oxidation reaction, and finally the solid component is not left in the glass, so it is an ideal tincture.
做爲該澄淸劑者使用氯化銨、氟化銨、溴化銨或碘化 銨之鹵化銨鹽時,藉由測定溶存於玻璃之Cl、F、Br、I 後,可確定係使用做爲澄淸劑之該鹵化銨鹽者。 另外,硝酸銨、硫酸銨等未出現充份之澄淸效果。此 係硝酸根、硫酸根爲做爲氧化劑作用者,銨基所產生之氫 阻礙了澄淸反應。 因此,做爲本發明澄淸劑者,以硫酸銨及硝酸銨之外 的銨鹽者宜。 【實施方式】 〔發明實施之形態〕 .8 - (6) 200401757 以下,以質量百分率代表玻璃組成,又,Si 02換算之 Si含量稱爲Si02含量或Si02者。 本發明玻璃爲矽酸鹽玻璃,用於前示例之各種用途中 。典型之Si02含量爲40%以上,80%以下者。 本發明玻璃之玻璃轉移溫度(T g )爲5 0 0 °C以上, 較佳者爲8 00 °C以下者。變形點用於窗戶玻璃等之鹼石 灰二氧化矽玻璃時,典型者爲500 °C以上,用於TFT — LCD用玻璃基板等之無鹼玻璃時,爲64〇 。(:以上,特別 以6 60 °C以上、720 t以下爲宜,又,用於PDP用基板 之高變形點玻璃時’爲5 7 0 °C以上,6 5 0 °C以下者宜。 本發明玻璃之熱膨脹係數(JIS R3102 ( 1995年)爲 基準所測定之値)用於TFT - LCD用基板之無鹼玻璃時, 典型者爲25〜5〇χΐ〇 - 71: - 1 (測定溫度範圍50〜350 °C者 )’用於pdp用基板之高變形點玻璃時典型者爲 7 5〜90 X 1 0 — 7 °C _ 1 (測定溫度範圍50〜3 5 0 °C )者。 本發明玻璃係含有1個以上選自典型之Al、B、Mg 、€&、31*、:8&及211所成群中之元素、八1203 0~350/〇、 B2〇3 0 〜25〇/〇 、MgO + CaO + SrO + BaO + ZnO 0^50% 者,When using ammonium chloride, ammonium fluoride, ammonium bromide or ammonium iodide as the clear tincture agent, it can be determined that it is used by measuring Cl, F, Br, and I dissolved in glass It is the ammonium halide salt of the tincture. In addition, ammonium nitrate, ammonium sulfate, and the like did not exhibit a sufficient clearing effect. The nitrate and sulfate groups act as oxidants, and the hydrogen produced by the ammonium group hinders the clarification reaction. Therefore, as the tincture of the present invention, ammonium sulfate and ammonium salts other than ammonium nitrate are preferred. [Embodiment] [The embodiment of the invention] .8-(6) Below 200401757, the glass composition is represented by mass percentage, and the Si content in terms of Si 02 is referred to as the Si02 content or Si02. The glass of the present invention is a silicate glass, which is used in various applications as previously exemplified. Typical Si02 content is above 40% and below 80%. The glass transition temperature (T g) of the glass of the present invention is above 500 ° C, and preferably below 800 ° C. Deformation point is typically 500 ° C or higher for alkali lime ash silica glass such as window glass, or 64 ° for alkali-free glass such as TFT-LCD glass substrates. (: Above, especially above 60 ° C to 720t is preferred, and when used for PDP substrates with high deformation point glass, it is above 570 ° C and below 650 ° C. Coefficient of thermal expansion of the invention glass (measured based on JIS R3102 (1995) as a reference) When used in alkali-free glass for TFT-LCD substrates, typically 25 to 50 × 70- 71:-1 (measurement temperature range 50 ~ 350 ° C) 'High deformation point glass for pdp substrate is typically 7 5 ~ 90 X 1 0 — 7 ° C _ 1 (measurement temperature range 50 ~ 3 5 0 ° C). The invention glass contains one or more elements selected from the group consisting of typical Al, B, Mg, € &, 31 *,: 8 & and 211, eight 1203 0 ~ 350 / 〇, B2 0 3 0 ~ 25 〇 / 〇, MgO + CaO + SrO + BaO + ZnO 0 ^ 50%,
Al203 + B203 + Mg0 + Ca0 + Sr0 + Ba0 + Zn0 爲 19 〜59%者。較 佳者 MgO、Ca〇、SrO、BaO 及 ZnO 分別爲 0〜30%, MgO + CaO + SrO + Ba〇 + Zn〇 爲 i% 以上者。又,例如:Γ Al2〇3 0〜35%」其Α12〇3雖不需要,惟亦可含35%爲止。 以本發明玻璃做爲TFT — LCD用基板使用時,典型者 ,質量百分率含有 (7) 200401757Al203 + B203 + Mg0 + Ca0 + Sr0 + Ba0 + Zn0 is 19 to 59%. The better MgO, Ca0, SrO, BaO and ZnO are 0 ~ 30%, and MgO + CaO + SrO + Ba〇 + ZnO are i% or more. Also, for example: Γ Al2 03 0 ~ 35% "Although A12 03 is not required, it may be contained up to 35%. When the glass of the present invention is used as a substrate for a TFT-LCD, typically, the mass percentage contains (7) 200401757
Si02 45〜70% 、Si02 45 ~ 70% 、
Al2〇3 5 〜25%、 B2〇3 1 〜20%、 M g Ο 0 〜1 5 %、 C a Ο 0 〜1 5 %、Al2〇3 5 to 25%, B2〇3 1 to 20%, M g 〇 0 to 15%, C a 〇 0 to 15%,
SrO 0〜1 5 %、 B a Ο 0 〜2 0 %SrO 0 ~ 1 5%, B a 〇 0 ~ 2 0%
又如:「M g Ο 0〜1 0 %」、Μ g 〇雖未必需者,惟,亦 可含10%爲止者。 s i Ο 2爲必須成份者,當超出7 0 %時,則玻璃溶解性將 降低,且易反玻璃化。較佳者爲68 %以下,更佳者爲67% 以下。當不足45%則比重增加,變形點降低,熱膨脹係數 增加、耐藥性降低。理想者爲51%以上,更佳者爲57%以 上。Another example: "M g 〇 0 ~ 10%", MG g 〇 Although not necessary, but can also contain up to 10%. s i 〇 2 is an essential component. When it exceeds 70%, the solubility of glass will decrease and it will easily devitrify. It is preferably 68% or less, and more preferably 67% or less. When it is less than 45%, the specific gravity increases, the deformation point decreases, the thermal expansion coefficient increases, and the drug resistance decreases. The ideal is 51% or more, and the more preferable is 57% or more.
Al2〇3可抑制玻璃之分相,且,提高變形點之必須成 份者。超出25 %時,則易反玻璃化,降低耐藥性。理想者 爲22%以下,更佳者爲19%以下。當不足5%時,則玻璃 易分相,且降低變形點。較佳者爲1 0%以上,更佳者爲 14%以上。 B 2 〇3比重小,提高玻璃之溶解性,不易反玻璃化之 必須成份者。當超出2 0 %時則降低變形點,降低耐藥性’ 或玻璃溶解時明顯揮散,增加玻璃之不均質性。理想者爲 1 6 %以下,更佳者爲丨2 %以下。當不足1 %時,則比重增 加’降低玻璃溶解性,且易反玻璃化。以3 %以上者宜, -10 - 200401757Al2O3 can suppress the phase separation of glass, and it is necessary to increase the deformation point. When it exceeds 25%, it is easy to devitrify and reduce the resistance. Ideally, it is 22% or less, and more preferably 19% or less. When it is less than 5%, the glass is liable to phase separation, and the deformation point is reduced. It is more preferably 10% or more, and more preferably 14% or more. B 2 〇3 small specific gravity, improve the solubility of glass, it is difficult to devitrify the necessary components. When it exceeds 20%, the deformation point is reduced, the chemical resistance is reduced, or the glass is significantly dispersed when dissolved, increasing the heterogeneity of the glass. The ideal is 16% or less, and the more preferable is 2% or less. When it is less than 1%, the specific gravity is increased, and the solubility of the glass is lowered, and the glass is easily devitrified. More than 3%, -10-200401757
更佳者爲6%以上。 M g 0雖未必須要者,惟’係爲比重小可提昇玻璃溶 解性之成份者。超出1 〇 %則易使玻璃分相’呈反玻璃化、 或降低耐藥性。較佳者爲7%以下,更佳者爲5%以下。含 有MgO時,以含1%以上者宜。特別是爲維持溶解性與降 低比重下,以含1 %以上者爲宜。The better is more than 6%. Although M g 0 is not necessary, it is a component having a small specific gravity and improving the solubility of glass. If it exceeds 10%, the glass phase separation 'is likely to devitrify or reduce the resistance. It is preferably 7% or less, and more preferably 5% or less. When MgO is contained, it should be contained at 1% or more. In particular, in order to maintain solubility and reduce specific gravity, it is preferable to contain more than 1%.
CaO非爲必須者,惟,可提高玻璃溶解性,不易反玻 璃化,可含有1 5 %以內者。超出1 5 %時將增加比重,熱膨 脹係數變大,反而易呈反玻璃化。理想者爲12%以下,更 佳者爲8%以下。含CaO時,以含2%以上者宜。較佳者 爲4%以上。CaO is not essential, but it can improve the solubility of glass, it is not easy to devitrify, and it can contain less than 15%. If it exceeds 15%, the specific gravity will increase, and the thermal expansion coefficient will increase, but it will tend to be devitrified. Ideally, it is 12% or less, and more preferably 8% or less. When CaO is contained, it is preferred to contain 2% or more. It is more preferably 4% or more.
SrO非爲必須者,惟,可抑制玻璃分相,不易反玻璃 化,可含有15%以內者。超出15%時,將增加比重,熱膨 脹係數變大,反而易呈反玻璃化。理想者爲12%以下,更 佳者爲10°/。以下。含有SrO時,以含0.5 %以上者宜。更 佳者爲3%以上。SrO is not necessary, but it can suppress glass phase separation and is not easy to devitrify, and it can contain less than 15%. When it exceeds 15%, the specific gravity will increase, and the thermal expansion coefficient will increase, but it will tend to be devitrified. Ideally, it is 12% or less, and more preferably 10 ° /. the following. When SrO is contained, it is preferable to contain 0.5% or more. More preferably, it is 3% or more.
BaO非爲必須者,惟,可抑制玻璃之分相,不易反玻 璃化,因此可含有20%以內者。超出20%時,比重將增加 ,且,熱膨脹係數變大。理想者爲10%以下,更佳者爲 1 %以下。特別是注重輕量化時,以不含者宜。特別理想 之組成者爲BaO is not essential. However, it can suppress the phase separation of glass and is not easy to reverse vitrification, so it can contain less than 20%. When it exceeds 20%, the specific gravity will increase and the coefficient of thermal expansion will increase. Ideal is 10% or less, and more preferably 1% or less. Especially when weight reduction is important, it is better not to include. Particularly ideal is composed of
Si02 5 1 ~68%、 A12 〇3 10〜22%、 B2O3Si02 5 1 ~ 68%, A12 〇3 10 ~ 22%, B2O3
6 〜1 6 %、 .11 . (9) 2004017576 to 16%, .11. (9) 200401757
MgO 1 〜7%、 CaO 2〜12%、 SrO 0 · 5 〜1 0 %、 BaO 0〜1 % 者。 以本發明玻璃做爲PDP用基板使用時,典型例,於 質量百分率下,含有MgO 1 to 7%, CaO 2 to 12%, SrO 0 · 5 to 10%, and BaO 0 to 1%. When the glass of the present invention is used as a substrate for a PDP, a typical example includes
Si02 50〜75%、 Al2〇3 0 〜1 5 %、 B 2 0 3 0 〜1 0 %、 r2o 6〜24% ( R 係指 Li、Na、K 者)、 R,0 1 2 〜2 7 % ( R ’ 係指 Mg、C a、Sr、B a 者) Zr〇2 0 〜1 0 % 者。又,R2O 含量爲Li20 + Na20 + K20之總量者。另外, R’O之含量爲 MgO + CaO + SrO + BaO 之總量。Li20 爲 0 〜3% 、Na20 爲 1 〜7%、K2〇 爲 3 〜20%、MgO 爲 0.5 〜7°/。、CaO 爲0.5〜12%、81*0爲0〜10%者、83〇爲0〜10%者宜。 理想者以含有Si02 50 ~ 75%, Al2〇3 0 ~ 15%, B 2 0 3 0 ~ 10%, r2o 6 ~ 24% (R means Li, Na, K), R, 0 1 2 ~ 2 7 % (R 'means Mg, Ca, Sr, Ba) Zr〇2 0 to 10%. The content of R2O is the total amount of Li20 + Na20 + K20. The content of R'O is the total amount of MgO + CaO + SrO + BaO. Li20 is 0 to 3%, Na20 is 1 to 7%, K2O is 3 to 20%, and MgO is 0.5 to 7 ° /. , CaO is 0.5 to 12%, 81 * 0 is 0 to 10%, 83% is 0 to 10%. Ideal
Si02 5 0〜70%、 AI2O3 1 〜1 4 %、 B 2 〇 3 0〜3%、 R2〇 8 〜24% ( R 意指 Li、Na、K 者)、 R-0 12 〜25%(R’意指 Mg、Ca、Sr、Ba 者) Zr〇2 0〜6 % -12 - (10) (10)200401757 者。又,R20含量爲Li20 + Na20 + K20之總量者。另外, R’〇之含量爲MgO + CaO + SrO + BaO之總量。Li20爲0〜3% 、Na20 爲 1 〜7%、K20 爲 3 〜20%、MgO 爲 0.5 〜7%、CaO 爲0.5〜12%、SrO爲0〜10%者、BaO爲0〜10%者宜。 更佳者爲含有Si02 5 0 to 70%, AI2O3 1 to 14%, B 2 〇3 0 to 3%, R2 08 to 24% (R means Li, Na, K), R-0 12 to 25% (R 'Means Mg, Ca, Sr, Ba) Zr〇2 0 ~ 6% -12-(10) (10) 200401757. The content of R20 is the total amount of Li20 + Na20 + K20. The content of R'0 is the total amount of MgO + CaO + SrO + BaO. 0 to 3% for Li20, 1 to 7% for Na20, 3 to 20% for K20, 0.5 to 7% for MgO, 0.5 to 12% for CaO, 0 to 10% for SrO, and 0 to 10% for BaO should. Better to contain
Si〇2 50〜65 %、Si〇2 50 ~ 65%,
Al2〇3 2〜12%、 B 2 Ο 3 0 〜1 %、 R2〇 8〜1 6% ( R 意指 Li、Na、K 者)、 R'〇 13 〜24%(R’意指 Mg、Ca、Sr、Ba 者)Al2〇3 2 ~ 12%, B 2 〇3 0 ~ 1%, R2〇8 ~ 1 6% (R means Li, Na, K), R'〇13 ~ 24% (R 'means Mg, Ca, Sr, Ba)
Zr〇2 0〜5% 者。又,R2〇之含量爲Li20 + Na20 + K20之總量者。另外 ,R’〇 含量爲 MgO + CaO + SrO + BaO 之總量。Li20 爲 0 〜2% ' Na20 爲 2〜6°/〇、K20 爲 5〜14%、MgO 爲 1 〜6%、Ca〇爲 1〜9%、SrO爲〇〜6%者、BaO爲0〜3%者宜。 又’本發明玻璃中,Zn非常必須成份者,惟,可含 有5 %以內者。 本發明玻璃即使未含As203或Sb203,仍含有NH4 +者 ’亦即,具有藉由銨基產生H2等氣體成份之浮出效果, 可減少其內部氣泡之特點,惟,因此,務必提高還原度。 玻璃之還原度通常使用Fe2 +之含量與Fe3 +之含量後, 以r = Fe2 + / ( Fe2 + + Fe3+)代表之,本發明玻璃中爲0.61以 上者。當不足0.61時,則恐增加氣泡。理想者爲0.8以上 ’更佳者爲0.9以上,特別以〇 · 9 5以上爲最佳。 -13 - (11) (11)200401757 本發明玻璃爲可測定r ’以Fe離子做爲指標時,Fe 爲必須含有成份者。Fe ( Fe2 +與Fe3 +之總量)之Fe2〇3換 算含量務必爲0.0015%以上者。Fe之Fe2Ch換算含量不足 0.0 0 1 5 %時,貝!J r之測定不易。爲更易於1·之測定,其F e 之Fe2Ch換算含量爲0.01%以上者宜。又’ Fe之?02〇3換 算含量其典型例爲〇. 3 %以下者。顯示器用玻璃以0 · 2 %以 下者宜。超出0.2 %則將著色呈藍色’做爲顯示器用玻璃 爲不理想者。理想者爲0.1 %以下,更佳者爲〇.〇5 %以下。 本發明玻璃之還原度亦可使用Fe離子以外之指標進 行測定。如:以ESR (電子旋轉共振分析)進行分析做爲 微量不純物存在之Ti3 +離子後,可預測Fe離子之狀態。 又,玻璃再熔融係藉由玻璃電位測定亦可有效測定氧活量 〇 光波長400〜700nm爲可視光領域者,具此範圍內吸收 之玻璃不適於做爲顯示器用玻璃基板者。代表可視光光線 波長於 CRT規格(日本電子工業會顯像管用玻璃特性規 格「EIAJ ED— 2138A」)中以 546nm代表之。本發明玻 璃適於基板狀之玻璃,基板厚度爲 0.7mm時,波長 546nm中光透射率爲85%以上(特別爲90%以上)者宜。 基板厚度非爲〇.7nim之玻璃基板中,測定透射率及反射 率後,換算成〇.7mm後可進行許定之。 波長300nm附近之紫外線透射率藉由吸收Fe3 +後將 降低係公知者。本發明玻璃其前述之Γ極高,因此易於提 昇紫外線透射率。本發明玻璃其基板厚度爲0.7mm時, ** 14 - (12) 200401757 波長3 00nm中紫外線透射率爲60%以上者宜,較佳者爲 77%以上。本發明中,含Fe之量以Fe2〇3換算下爲0.2 %以 下者則澄淸效果良好,且該透射率亦可爲80%以上者。 使用銨鹽製造本發明玻璃時,所取得玻璃中含微量 NH/。 本發明玻璃含NH/者如以下被檢測之。 (1 )粉碎玻璃後於鉑皿上精秤1 g量。Zr〇2 0 ~ 5%. The content of R20 is the total amount of Li20 + Na20 + K20. In addition, the content of R'〇 is the total amount of MgO + CaO + SrO + BaO. Li20 is 0 to 2% 'Na20 is 2 to 6 ° / 〇, K20 is 5 to 14%, MgO is 1 to 6%, Cao is 1 to 9%, SrO is 0 to 6%, BaO is 0 to 3% is appropriate. In addition, in the glass of the present invention, Zn is an essential component, but it may be contained within 5%. Even if the glass of the present invention does not contain As203 or Sb203, it still contains NH4 +, that is, it has the characteristics of floating out of gas components such as H2 by the ammonium group, which can reduce its internal bubbles. . The reduction degree of glass is usually expressed by the content of Fe2 + and Fe3 +, and is represented by r = Fe2 ++ ((Fe2 ++ Fe3 +)), which is 0.61 or more in the glass of the present invention. When it is less than 0.61, bubbles may increase. It is preferably 0.8 or more ', more preferably 0.9 or more, and particularly preferably 0.95 or more. -13-(11) (11) 200401757 When the glass of the present invention can measure r 'using Fe ion as an index, Fe is a component which must contain a component. The Fe2O3 conversion content of Fe (total amount of Fe2 + and Fe3 +) must be 0.0015% or more. When the Fe2Ch conversion content of Fe is less than 0.0 0 15%, shellfish! Determination of J r is not easy. For easier measurement of 1 ·, the Fe2Ch conversion content of Fe is preferably 0.01% or more. What ’s Fe? A typical example of the conversion content of 02〇3 is 0.3% or less. The glass for the display should be less than 0.2%. If it exceeds 0.2%, the coloration of blue is not desirable as a glass for a display. It is preferably 0.1% or less, and more preferably 0.05% or less. The degree of reduction of the glass of the present invention can also be measured using indexes other than Fe ions. For example, the state of Fe ions can be predicted after analyzing Ti3 + ions as trace impurities by ESR (electron rotation resonance analysis). In addition, glass remelting can also effectively measure oxygen activity by glass potential measurement. ○ Light wavelengths of 400 to 700 nm are in the visible light field. Glass with absorption within this range is not suitable for glass substrates for displays. Represents the wavelength of visible light in the CRT standard (Japanese Electronic Industry Association glass characteristics specification "EIAJ ED-2138A") represented by 546nm. The glass of the present invention is suitable for substrate-like glass. When the substrate thickness is 0.7 mm, the light transmittance at a wavelength of 546 nm is preferably 85% or more (especially 90% or more). For glass substrates with a substrate thickness other than 0.7 nm, the transmittance and reflectance can be measured and converted to 0.7 mm. It is known that the ultraviolet transmittance near a wavelength of 300 nm will decrease after absorbing Fe3 +. The glass of the present invention is extremely high in the aforementioned Γ, and therefore it is easy to increase the ultraviolet transmittance. When the thickness of the substrate of the glass of the present invention is 0.7 mm, ** 14-(12) 200401757 at a wavelength of 300 nm is preferably 60% or more, and more preferably 77% or more. In the present invention, if the Fe content is 0.2% or less in terms of Fe2O3, the clarification effect is good, and the transmittance may be 80% or more. When the glass of the present invention is produced using an ammonium salt, the obtained glass contains a trace amount of NH /. The glass of the present invention containing NH / is tested as follows. (1) After crushing the glass, weigh 1 g on a platinum dish.
(2 )以少量離子交換水濕潤該12玻璃粉。 (3 )於離子交換水所濕潤之玻璃粉中加入1 〇 W之 HF (濃度:29mol/l)及 5 ^之 H2S〇4(濃度.9mol/l) ’ 於砂浴上進行加熱分解。 (4 )冷卻後,再度添加5 m£ HF (濃度·· 29mol/l ) ’ 於砂浴上進行加熱分解之。加熱持續至硫酸白煙浮出液體 呈糖漿狀爲止。(2) Wet the 12 glass powder with a small amount of ion-exchanged water. (3) Add 10 W of HF (concentration: 29 mol / l) and 5 ^ of H2S〇4 (concentration. 9 mol / l) 'to the glass frit moistened with ion-exchanged water, and perform thermal decomposition on a sand bath. (4) After cooling, add 5 m £ HF (concentration · 29mol / l) 'on the sand bath to decompose it by heating. Heating was continued until the white smoke from the sulfuric acid fumes appeared to be syrupy.
(5 )冷卻後,藉由離子交換水於基耶達蒸餾用燒瓶 中洗出殘渣及分解液。此時,溶液容量爲300m£。 (6 )置入沸騰石於該燒瓶中’將此燒瓶設於基耶達 蒸餾裝置。 (7)於基耶達蒸餾裝置之接受器量筒中置入50 2之 H2S〇4 (濃度:25mmol/l )。通過注入漏斗後,添加40 2 Na〇H水溶液(濃度:Wg/1 )於燒瓶內。 (8 )該燒瓶經加熱後’進行蒸態。 (9 )餾出約140 後’停止蒸飽’以離子交換水進 行200 m£餾出液定容之。 -15 - (13) 200401757 (10)以離子層析法進行檢出餾出液中之NH4+。 本發明中,其玻璃中NH/含量爲0.000 1 %以上被定量 時稱設玻璃爲含有NH/者。(5) After cooling, the residue and the decomposed solution were washed out in a flask for Chieda distillation with ion-exchanged water. At this time, the solution capacity was 300 m £. (6) Put zeolite in the flask 'and set the flask in a Kieda distillation apparatus. (7) Put 50 2 of H2S04 (concentration: 25 mmol / l) in the measuring cylinder of the receiver of the Kieda distillation apparatus. After passing through the funnel, a 40 2 NaOH aqueous solution (concentration: Wg / 1) was added to the flask. (8) The flask is heated to a vaporized state. (9) After distilling about 140, 'stop steaming' and dilute the distillate with ion-exchanged water for 200 m. -15-(13) 200401757 (10) NH4 + in distillate was detected by ion chromatography. In the present invention, when the content of NH / in the glass is 0.0001% or more, the glass is said to contain NH /.
又’基耶達蒸態裝置係使用]IS K 0 1 0 2 「工場排水試 驗方法」(1993年)之『42·銨離子(NH4+)』所示者。 又,蒸餾順序係相同於JIS K01 02之「42」所規定之銨離 子分析法,及其『44·有機體氮』所規定之有機體氮之分 析方法爲基準進行者。 本發明者係做爲離子層析裝置爲使用Dionex公司製 者。做爲預柱體、分離柱體者分別使用Dionex公司製之 Ion — Pak CG14 Ion- Pak CS14。 做爲抑制因子裝置者係使用自動抑制因子(再利用型 )。做爲檢出器者係使用電氣傳導度計。 使用甲磺酸(濃度:10mm〇l/l )做爲溶離液、溶離液 流量爲 1 . 0 m£ / m i η。Also used in the “Kiyada Steamed Device” is shown in "42 · Ammonium Ion (NH4 +)" in IS K 0 1 0 2 "Workshop Drainage Test Method" (1993). The distillation sequence is based on the ammonium ion analysis method specified in "42" of JIS K01 02 and the organic nitrogen analysis method specified in "44 · Organic Nitrogen". The inventors used Dionex Corporation as the ion chromatography device. As the pre-column and the separation column, Ion-Pak CG14 Ion-Pak CS14 manufactured by Dionex was used. As the suppressor device, an automatic suppressor (recycling type) is used. As the detector, an electrical conductivity meter is used. Methanesulfonic acid (concentration: 10 mm0 / l) was used as the eluent, and the flow rate of the eluent was 1.0 m £ / m i η.
本發明玻璃中ΝΗ4 +含量爲0.0001〜〇·〇ι%者宜,特別 以0.0004%以上爲更佳。最佳者爲〇.0〇〇4〜〇 〇〇1〇/。。 本發明玻璃含有1種以上選自Cl、F、Br及I所成群 中之兀素時,其典型之含量爲〇.〇3〜1°/〇者宜,特別以 0.0 5〜1 %爲更佳。當該含量超出1 %時,使本發明玻璃用於 TFT - LCD玻璃基板時,恐有降低變形點或耐藥性。該 含量以0.5%以下者宜,澄淸效果明顯條件下,以〇 〇5%以 上者宜,0.08%以上爲更佳者。 本發明玻璃未含S、或即使含S其S03換算含量亦僅 -16 - (14) 200401757 爲0.005%以下者宜。S03換算含量若超出0.005 %則玻璃 還原度將變小無法有效取得澄淸作用,或,藉由S03之再 沸騰後恐有增加氣泡之產生。或S含量即使爲微量,藉由 S與Fe2 +或與Fe3 +共存後產生琥珀著色,恐無法做爲平面 控制顯示器用玻璃基板之使用。爲防止著色,理想之S03 換算含量爲0.002%以下者宜,更佳者爲0.0005%。It is preferable that the content of ΝΗ4 + in the glass of the present invention is 0.0001 to 0.00%, and more preferably 0.0004% or more. The best is from 0.0004 to 0.00001. . When the glass of the present invention contains more than one element selected from the group consisting of Cl, F, Br, and I, its typical content is preferably from 0.03 to 1 ° / 〇, particularly 0.0 5 to 1%. Better. When the content exceeds 1%, when the glass of the present invention is used in a TFT-LCD glass substrate, there is a fear of reducing the deformation point or chemical resistance. The content is preferably less than 0.5%, and under the condition that the clearing effect is obvious, the content is more than 0.005%, and more than 0.08% is more preferable. The glass of the present invention does not contain S, or even if it contains S, its S03 conversion content is only -16-(14) 200401757 is preferably 0.005% or less. If the conversion content of S03 exceeds 0.005%, the reduction degree of the glass will be reduced and the clearing effect will not be obtained effectively. Or, the re-boiling of S03 may increase the generation of bubbles. Or even if the content of S is small, the coexistence of S with Fe2 + or Fe3 + produces amber coloration, and it may not be used as a glass substrate for a flat control display. In order to prevent coloring, the ideal conversion content of S03 is 0.002% or less, more preferably 0.0005%.
本發明玻璃均未含As及Bb、或即使含As或Sb其 AhO3換算含量與Sb203換算含量之合計亦以0.1%以下者 宜。更佳者爲0 · 0 1 %以下。 本發明玻璃未含Sn、或即使含有Sn其Sn02換算含 量亦僅爲0 · 0 2 y。以下者宜。當超出〇 . 〇 2 %時,藉由氯化銨 等之玻璃還原度恐變小、或Sn存在於金屬膠質之玻璃後 ’使玻璃著色 '恐不易做爲平面控制顯示器用玻璃基板之 使用。 本發明玻璃以未含Ti、V、Nb、Mo、Ce等氧化物者None of the glasses of the present invention contains As and Bb, or even if As or Sb is contained, the total content of the AhO3 conversion content and the Sb203 conversion content is preferably 0.1% or less. More preferably, it is less than or equal to 0.1%. The glass of the present invention does not contain Sn, or even if it contains Sn, its Sn02 conversion content is only 0 · 0 2 y. The following are appropriate. When it exceeds 0.02%, the reduction degree of glass such as ammonium chloride may become small, or Sn may be present in the colloidal glass, and the glass may be colored, and it may not be easily used as a glass substrate for a flat control display. The glass of the present invention does not contain oxides such as Ti, V, Nb, Mo, Ce, etc.
宜。此等氧化物於還原玻璃中釋出氧,因此,恐藉由氯化 鞍後縮小還原度、或呈金屬離子使玻璃著色、恐不易用於 平面控制顯示器用玻璃基板。 本發明玻璃以未含Se、Cu、Pb、Ni、Cd、Mn、Ge、 Cs等者宜。此等元素呈金屬膠質後存在於玻璃中,使玻 璃著色’恐不易做爲平面控制顯示器用玻璃基板之使用。 本發明玻璃於質量百分率代表下,爲含有以Si〇2換 算呈40%Si〇2之玻璃者,含Nh4 +或c卜未含S (或即使 含S亦以質量百分率代表下其s〇3換算含量僅〇.005 %以 -17 - (15) (15)200401757 下),均未含As及Sb (或即使含As或Sb以質量百分率 代表下,其As2 03換算含量與Sb203換算含量總計亦僅爲 0.1 %以下),更且,未含Sn’ (或即使含Sn以質量百分 率代表下其Sn02換算含量亦僅爲〇·〇2%以下)之玻璃者 〇 其中又以Si之Si〇2換算含量以質量百分率代表下爲 80°/。以下者宜。NH4 +以質量%代表下爲 0.000 1〜0.01%者宜 ,特別以0.0 0 0 4〜0.0 0 1 %含有者爲最佳。1種以上選自C1 、F、Br及I群中之元素以質量%代表下以〇.〇3〜1°/。者宜 ,特別是含0.05〜1%之C1者爲最佳。should. These oxides release oxygen in the reduced glass. Therefore, the degree of reduction may be reduced after the saddle chloride, or the glass may be colored with metal ions, and it may not be easily used in a glass substrate for a flat control display. The glass of the present invention is preferably one that does not contain Se, Cu, Pb, Ni, Cd, Mn, Ge, Cs, and the like. These elements are present in the glass after being in the form of a metal colloid, so that the glass may not be used as a glass substrate for a flat control display. The glass of the present invention is represented by mass percentage, which is a glass containing 40% Si0 2 in terms of Si0 2, containing Nh4 + or c, but not containing S (or even if S is contained, it is represented by mass%.) The conversion content is only 0.005% to -17-(15) (15) 200401757 or less, and neither As nor Sb is included (or even if As or Sb is included, represented by mass percentage, the total As2 03 conversion content and Sb203 conversion content total It is only 0.1% or less), and it does not contain Sn '(or even if it contains Sn in terms of mass percentage, its content of Sn02 conversion is only 0.02% or less). Among them, Si is Si. 2Converted content is 80 ° / under the mass percentage. The following are appropriate. NH4 + is preferably 0.000 1 to 0.01% in terms of mass%, especially 0.04 to 0.01 0% is the best. One or more kinds of elements selected from the group consisting of C1, F, Br, and I are represented by mass% and represented by 0.03 to 1 ° /. It is preferred, especially C1 containing 0.05 ~ 1% is the best.
又,含有1種以上選自 Al、B、Mg、Ca、Sr、Ba& Z群中之元素,下記氧化物換算之質量%代表含量爲 Al2〇3 : 0〜35%、B2〇3 ·· 0〜25%、MgO + CaO + SrO + BaO + ZnO ·· 0 〜50 % 者,Al203 + B203 + Mg0 + Ca0 + Sr0 + Ba0 + Zn0 爲 1 9〜5 9 %者宜。 又,該玻璃爲 Si02: 45 〜70%、Al2〇3: 5 〜25%、,B2〇3 :1 〜20%、MgO : 0 〜10%、CaO : 0 〜15%、SrO : 0 〜15%、 BaO : 〇〜20% 者、或 Si02 : 50〜75%、AI2O3 : 〇〜15%、 B2〇3: 0〜10%、R20 : 6 〜24 % (R 代表 Li、Na、K ) 、ΙΓ〇 :12 〜27%〔R·代表 Mg、Ca、Sr、Ba) 、Zr〇:0〜10% 者宜 ο 更且’使NH/爲含有o.oooi〜o.oi%、及Cl爲含有 0.05〜1 %之該玻璃者宜。 本發明玻璃係藉由本發明方法A、方法B所製造之。 •18- (16) 200401757 針對本發明方法A進行說明。 進行加熱爲取得目標組成之矽酸鹽玻璃所調合之原半斗 後溶解做成熔融玻璃。該熔融玻璃進行脫泡、均質化等之 後進行後冷卻。熔融玻璃之均質化亦可藉由攪拌促進之。 又,一般於冷卻當中使板玻璃等進行成型。 該原料,通常由矽砂等所成者,亦可含有屑玻璃(碎 玻璃)者。In addition, it contains one or more elements selected from the group consisting of Al, B, Mg, Ca, Sr, and Ba & Z group, and the representative mass percentage of the following oxide conversion is Al203: 0 to 35%, and B203. 0 to 25%, MgO + CaO + SrO + BaO + ZnO · 0 to 50%, Al203 + B203 + Mg0 + Ca0 + Sr0 + Ba0 + Zn0 is preferably 19 to 59%. The glass is Si02: 45 to 70%, Al203 to 5 to 25%, B203 to 1 to 20%, MgO: 0 to 10%, CaO: 0 to 15%, and SrO: 0 to 15 %, BaO: 0 to 20%, or Si02: 50 to 75%, AI2O3: 0 to 15%, B2O3: 0 to 10%, R20: 6 to 24% (R stands for Li, Na, K), ΙΓ〇: 12 to 27% [R · stands for Mg, Ca, Sr, Ba), Zr0: 0 to 10%. Ο 'and NH / to contain o.oooi ~ o.oi%, and Cl is Contains 0.05 ~ 1% of the glass is appropriate. The glass of the present invention is produced by the methods A and B of the present invention. • 18- (16) 200401757 The method A of the present invention will be described. It is heated to obtain the original half hopper blended with the silicate glass of the target composition, and then dissolved into molten glass. This molten glass is degassed, homogenized, and the like, and then post-cooled. The homogenization of the molten glass can also be promoted by stirring. In addition, plate glass and the like are generally formed while cooling. This raw material is usually made of silica sand or the like, and may also contain cullet (broken glass).
該溶解係將原料置於適當之坩堝,亦可置於該坩堝維 持於高溫之電爐等爐內進行之,亦可將原料連續性投入高 溫爲1 5 00〜1 6 00 °C下維持之玻璃熔融鋈中進行之。 本發明方法A係使用如上述極佳澄淸劑之該銨鹽, 如含有氯化銨之原料。The dissolution is carried out by placing the raw materials in a suitable crucible, or in an electric furnace such as an electric furnace maintained at a high temperature by the crucible. The raw materials can also be continuously put into glass maintained at a high temperature of 1 500 ~ 1 600 ° C. It is carried out in molten tincture. The method A of the present invention uses the ammonium salt of the excellent elixirs described above, such as a raw material containing ammonium chloride.
原料中含氯化銨之比例以1 〇〇份之溶解該原料取得之 玻璃質量時爲0.1〜10份者宜,亦即,氯化銨針對每100 份溶解原料取得玻璃質量以相當於0.1〜1 0份之量加入玻 璃原料者宜。若不足0.1份則恐有縮小氯化銨之澄淸作用 。更佳者爲0.2份以上。玻璃維持於熔融狀態之時間長時 ,該含有比例以〇. 3份以上者宜,更佳者爲1 · 〇份以上。 又,該含有比例超過10份時,恐出現溶解時產生氨氣、 氯化氫氣、氯氣或其他氣體的大量產生之虞。更佳者爲3 份以下者。 又,溶解後取得玻璃中爲含NH/、C1者,惟,極爲 微量者,因此,計算對於氯化銨添加原料之量時’使該含 ΝΗΓ、C1之玻璃質量做爲1〇〇份進行計算者亦無妨。 -19 - (17) 200401757 原料未含硫酸鹽、或即使含硫酸鹽其含有比例之合計 以1 〇 〇份溶解該原料後取得玻璃質量時亦僅爲0 · 01份以 下者’亦即’ 1 0 0份溶解原料後取得玻璃之質量時,於玻 璃原料中添加0 · 0 1份以下之硫酸鹽者宜。若超出0 · 0 1份 時’恐降低氯化銨之澄淸作用。或出現琥珀著色無法做爲 顯示器用玻璃基板之使用。The proportion of ammonium chloride in the raw material is preferably 0.1 to 10 parts when the mass of the glass obtained by dissolving the raw material is 100 parts. That is, ammonium chloride is equivalent to 0.1 to 100 parts per 100 parts of the dissolved raw material. It is advisable to add 10 parts of glass raw materials. If it is less than 0.1 parts, it may reduce the clearing effect of ammonium chloride. More preferred is 0.2 or more. When the glass is maintained in a molten state for a long time, the content ratio is preferably 0.3 parts or more, and more preferably 1.0 part or more. When the content ratio exceeds 10 parts, there is a possibility that a large amount of ammonia gas, hydrogen chloride gas, chlorine gas, or other gas may be generated during dissolution. The better is 3 or less. In addition, after dissolving, the glass containing NH / and C1 was obtained, but the amount was extremely small. Therefore, when calculating the amount of the raw material added to ammonium chloride, 'the mass of the glass containing ΝΓΓ and C1 was performed as 100 parts. It does not matter to the calculator. -19-(17) 200401757 The raw material does not contain sulphate, or even if the total content of sulphate is contained in the raw material, it is only 0. 01 or less when obtaining the glass quality after dissolving the raw material in 100 parts. When the mass of the glass is obtained after 0 parts of the raw materials are dissolved, it is preferable to add less than 0.1 parts of sulfate to the glass raw materials. If it exceeds 0 · 0 1 part, it may reduce the clearing effect of ammonium chloride. Or it may not be used as a glass substrate for displays.
又’以微量硫酸鹽做爲澄淸劑使用時,於溶解後取得 玻璃中含有源於硫酸鹽之S Ο 3等,惟,極爲微量,因此, 計算對於硫酸鹽之添加原料量時,使含s 0 3等玻璃之質量 做成100份進行計算亦無妨。 以下As、Sb、Sn02亦相同。亦即,使用微量As、Sb 、Sn02等時,溶解後取得玻璃中含有as、Sb、Sn02等, 惟’極其微量,因此,計算對於As、Sb、Sn〇2等添加原 料量時’將含As、Sb、Sn02等玻璃質量做爲100份進行 計算亦可。Also, when using a small amount of sulfate as a clarifying agent, the glass containing S 0 3 derived from sulfate is obtained after the dissolution, but it is extremely small. Therefore, when calculating the amount of raw materials for sulfate, It is not necessary to calculate 100 parts of glass such as s 0 3. The same applies to the following As, Sb, and Sn02. That is, when using a small amount of As, Sb, Sn02, etc., the glass containing as, Sb, Sn02, etc. is obtained after dissolving, but the amount is extremely small. Therefore, when calculating the amount of raw materials for As, Sb, Sn02, etc., it will contain As, Sb, Sn02 and other glass masses can be calculated as 100 parts.
原料均未含As及Sb、或即使含As或Sb其As203換 算含有比例及Sb203換算含有比例之合計爲100份該溶解 原料後取得玻璃質量之0. 1份以下者,亦即,As203換算 含有比例與Sb203換算含有比例之合計當100份溶解原料 取得之玻璃質量時於玻璃原料中添加相當於0 · 1份以下之 量者宜。 原料未含Sn02、或即使含Sn02其含有比例之合計亦 僅爲100份溶解該原料取得玻璃質量之〇.〇3份以下者, 亦即,Sn〇2於玻璃原料中添加100份溶解原料取得玻璃 -20 - (18) 200401757 質量之0· 03份以下量者,特別以0·02份以下爲更佳。超 出〇·〇2份時,特別是超出〇.〇3份則將減少氨化銨之澄淸 作用。 原料亦可含氟化物、氯化銨以外之氯化物。如:使氯 化銨倂用氯化緦水合物(S r C 12 · 6 Η 2〇)或氯化鋇水合物 (BaCh · 2Η2〇)後,可保持一定之還原度下增加玻璃中 之C1含量。None of the raw materials contain As and Sb, or even if As or Sb is included, the total As203 conversion ratio and Sb203 conversion ratio are 100 parts. After the dissolved raw materials, 0.1 or less of glass quality is obtained, that is, As203 conversion contains When the total content of the ratio and the conversion ratio of Sb203 is 100 parts of the glass obtained by dissolving the raw material, it is advisable to add an amount equal to or less than 0.1 part to the glass raw material. The raw material does not contain Sn02, or even if it contains Sn02, the total content of the raw material is only 100 parts. Dissolving the raw material to obtain the glass mass of less than 0.03 parts, that is, Sn02 is added to the glass raw material to obtain 100 parts of the dissolved raw material. Glass-20-(18) 200401757 Mass of 0.03 parts or less, especially 0.002 parts or less is more preferred. Exceeding 0.002 parts, especially exceeding 0.03 parts will reduce the clearing effect of ammonium ammonium. The raw materials may contain fluorides and chlorides other than ammonium chloride. For example, after using ammonium chloride and rhenium chloride hydrate (S r C 12 · 6 Η 20) or barium chloride hydrate (BaCh · 2 Η 20), C1 in the glass can be increased while maintaining a certain degree of reduction. content.
本發明玻璃可利用以下本發明方法Α製造之。亦即, 以一般所使用之本發明玻璃各成份原料做成目標組成調合 後製作原料,連續性投入最高溫度爲1 500〜160〇 °c之玻 璃熔融鋈中溶解後做成熔融玻璃。另外,該原料中添加適 量之氯化錢。 熔融玻璃於其後維持1 200〜1 500 t進行脫泡、或藉 由減壓脫泡技術進行脫泡之。The glass of the present invention can be produced by the following method A of the present invention. That is, the raw materials of each component of the glass of the present invention are used to prepare the target composition, and the raw materials are prepared. The molten glass is prepared by continuously dissolving it in a glass melting tin with a maximum temperature of 1500 to 160 ° C. In addition, an appropriate amount of chlorinated chloride is added to this raw material. The molten glass is then degassed for 1 200 to 1 500 t, or degassed by a degassing technique under reduced pressure.
被脫泡之熔融玻璃呈板玻璃被成型之。成型方法如: 浮動法、熔融法、裂口下拉法等示例。板玻璃冷卻切斷後 ,做成TFT - LCD用玻璃基板,PDP用玻璃基板。 以下針對本發明方法B進行說明。 本發明方法中藉由含氯化銨於原料後,於熔融玻璃中 含NH4+ ’亦即,計算產生h2氣體,其他氣體,惟,本發 明方法B中直接供與氯化銨於熔融玻璃後,計算於該熔融 玻璃中含ΝΗΓ者,亦即,以產生H2氣體,其他氣體爲其 特徵者。做爲直接供與氯化銨與熔融玻璃中之方法者如: 噴霧熔融玻璃粉末於該熔融玻璃表面之方法例者。 -21 - (19) 200401757 又’本發明方法B中,亦等同針對本發明方法a之 硫酸鹽及Sn02之說明者。 本發明方法B亦可與本發明方法a組合後使用之。 錯由本發明方法A,方法B後,即使未使用A s 2 Ο 3、 Sb2〇3等氧化物系澄淸劑、硫酸鹽系澄淸劑,仍可製造氣 泡數少之無鹼玻璃。 〔實施例〕The defoamed molten glass is formed as sheet glass. Examples of molding methods are: floating method, melting method, rip-down method, etc. After the plate glass is cooled and cut, glass substrates for TFT-LCD and glass substrates for PDP are produced. The method B of the present invention will be described below. In the method of the present invention, after the ammonium chloride is contained in the raw material, NH4 + is contained in the molten glass, that is, the H2 gas and other gases are calculated to be generated. It is calculated that those containing N 含 Γ in the molten glass, that is, those in which H 2 gas is generated and other gases are characteristic. As a method of directly supplying ammonium chloride and molten glass, for example, a method of spraying molten glass powder on the surface of the molten glass is exemplified. -21-(19) 200401757 Also in the method B of the present invention, it is also equivalent to the description of sulfate and Sn02 in the method a of the present invention. The method B of the present invention can also be used in combination with the method a of the present invention. By mistake, the method A and method B of the present invention can produce alkali-free glass with a small number of bubbles even without using oxide-based clearing agents such as As 2 0 3 and Sb203, and sulfate-based clearing agents. [Example]
表1之Si02〜Fe203係本發明實施例中取得玻璃之 Si〇2〜BaO成份總量做成100時之各成份質量比例者,又 ’錢鹽/氯化物〜S03代表對於玻璃原料之添加量等。另外 ’本實施例中所使用玻璃原料中之組成與表 1之 Si02〜Fe2 03之組成幾乎相同者(b2〇3於溶解中約爲1/3 被揮散之)。表2代表本實施例中玻璃之特性。Si02 ~ Fe203 in Table 1 are those obtained when the total amount of Si02 ~ BaO components of the glass in the examples of the present invention is made to 100, and the amount of glass salt / chloride ~ S03 represents the amount of glass raw material added. Wait. In addition, the composition of the glass raw material used in this example is almost the same as the composition of Si02 to Fe2 03 in Table 1 (b203 is dissolved in about 1/3 during dissolution). Table 2 represents the characteristics of the glass in this example.
表1之Si02〜Ba〇欄之總計做成100,進行調合實質 上未含質量比例所示組成硫酸鹽之工業原料後,製作 250g含氧化鈦、銨鹽(氯化銨)、氯化物(氯化緦水合 物)或硫酸鹽(硫酸鈣)於此中之原料。又,氧化鐵、氯 化物或硫酸鹽含量係以表中前記Si02〜Ba〇總計做爲100 之質量比例下分別代表Fe之Fe2〇3換算含量、C1含量、 SO:、含量者。氯化銨之C1含量換算量進行投入。又’以玻 璃質量做成1 00份時原料中含銨鹽比例與表1銨鹽質量比 例之値實質上爲相同者。表中「一」代表「未含有者」、 「未」代表「未測定」。 -22- (20) 200401757 另外,本發明實施例中Ti、V、Nb、Mo、Ce之氧化 物實質上未含者。又,Se、Cu、Pb、Ni、Cd、Μη、Ge、The total of the columns Si02 ~ Ba0 in Table 1 is 100, and after blending industrial raw materials which do not contain sulfates with the composition shown in the mass ratio, 250 g of titanium oxide, ammonium salt (ammonium chloride), and chloride (chlorine) are prepared. Sulfonium hydrate) or sulfate (calcium sulfate) as the raw material. In addition, the content of iron oxide, chloride, or sulfate represents the Fe2O3 conversion content, C1 content, SO :, content of Fe in the mass ratio of Si02 ~ Ba0 in the preceding table as 100, respectively. The amount of C1 content conversion of ammonium chloride was input. In addition, when the glass mass is made into 100 parts, the ratio of the ammonium salt in the raw material to that in Table 1 is substantially the same. In the table, "one" means "not included" and "not" means "not determined". -22- (20) 200401757 In addition, the oxides of Ti, V, Nb, Mo, and Ce are not substantially contained in the examples of the present invention. Also, Se, Cu, Pb, Ni, Cd, Mη, Ge,
Cs爲實質上未含者。 於鉑坩鍋中置入設2 5 0g原料,利用電爐於大氣氣氛 下,例1〜3、5〜7中於1 600 °C,例4中於1 5 5 0 °C下, 分別保持1小時,溶解後做成熔融玻璃。將此熔融玻璃於 碳板流出後固化之後進行漸冷之。Cs is essentially not included. Place 250 grams of raw materials in a platinum crucible, and use an electric furnace in the atmosphere, at 1 600 ° C in Examples 1 ~ 3, 5 ~ 7, and at 1 50 ° C in Example 4, respectively. Hours, melted into molten glass. This molten glass was solidified after flowing out of the carbon plate, and then gradually cooled.
測定所取得玻璃之r、溶存NH/量(單位:1 0 — 4% ) 、溶存C1量(單位:%) 、/3 — OH (單位:mm— D 、氣 泡數(單位:個/cm3 )。又,針對例4〜7未測定溶存NH/ 量。 r:藉由聯二吡啶吸光光度法進行定量玻璃中之Fe2 + ’以ICP發光分光分析法定量總Fe離子、亦即Fe2 + + Fe3 + 後求取之。又,例6之r並未測定,被推算爲〇. 6 〇。The r of the glass obtained, the amount of dissolved NH / (unit: 10-4%), the amount of dissolved C1 (unit:%), / 3-OH (unit: mm-D, the number of bubbles (unit: unit / cm3)) In addition, the dissolved NH / amount was not determined for Examples 4 to 7. r: Quantitative determination of Fe2 + in glass by bipyridine absorption spectrometry Quantitative analysis of total Fe ions, ie, Fe2 + + Fe3 by ICP emission spectrophotometry. +。 It is obtained after +. Moreover, r of Example 6 has not been measured and is estimated to be 0.6 〇.
ί谷存C 1里·粉碎玻璃後藉由營光X線法進行測定之 。又針對例5未進行測定之。 Β — Ο Η ··測定紅外線透射率,以3 5 7 0 c m — 1之透射率 除以4000c — 1之透射率後求取之。又,針對例5、6未進 行測定之。 氣泡數:將玻璃切斷、硏磨後,做成厚度2mm之玻 璃板,於實體顯微鏡下,數約1 0 // m以上之氣泡數,以 玻璃板體積除後求取之。本評定中,進行評定丨小時溶解 保持後玻璃中之氣泡。氣泡數以1 〇〇〇個/cm3以下者宜, 更佳者爲5 00個/cm3以下。 -23- (21) 200401757 藉由延長溶解時間後,氣泡數急劇減少。本評定中氣 泡數爲2000個/cm3以下時,相同條件下6小時溶解後氣 泡數爲1個/cm3以下。本評定中,氣泡爲1〇〇個/cm3以 下時’ 6小時溶解後氣泡數可減至實質爲零之氣泡數。本 評定中’氣泡數爲5 00個/cm3以下時,於多數連續溶解鋈 進行展開時,亦可減至實質上爲零之氣泡數。另外,浮動 法中溶解時間通常爲6小時以上。ί Gucun C 1 li · After the glass was crushed, it was measured by the Yingguang X-ray method. It was not measured for Example 5. Β — 〇 Η • Measure the infrared transmittance and calculate it by dividing the transmittance of 3 5 7 0 c m — 1 by the transmittance of 4000c — 1. In addition, the measurements were not performed for Examples 5 and 6. Number of bubbles: After cutting and honing the glass, make a glass plate with a thickness of 2mm. Under a solid microscope, count the number of bubbles above about 10 // m, and divide it by the volume of the glass plate. In this evaluation, the evaluation is performed. Hours of dissolution and retention of bubbles in the glass. The number of air bubbles is preferably 1,000 or less / cm3, and more preferably 500 or less / cm3. -23- (21) 200401757 By increasing the dissolution time, the number of bubbles decreased sharply. In this evaluation, when the number of air bubbles is 2,000 / cm3 or less, the number of air bubbles after being dissolved for 6 hours under the same conditions is 1 or less / cm3. In this evaluation, when the number of bubbles is 100 or less / cm3, the number of bubbles after 6 hours of dissolution can be reduced to a substantially zero number of bubbles. In this evaluation, when the number of bubbles is 5,000 or less / cm3, the number of bubbles can be reduced to substantially zero when a large number of continuous dissolutions are carried out. The dissolution time in the floating method is usually 6 hours or more.
透射率:針對例〗〜3玻璃切斷玻璃硏磨後,做成厚度 0.7mm之板玻璃,選取氣泡未存在部份進行測定分光透射 率。測定係利用日立製U - 3 5 0 0形自記分光光度計,求 出546nm與300nm之透射率(%)。 比重、熱膨脹係數與玻璃轉移溫度(Tg )、變形點、 楊氏率、耐HC1性係與實施例3〜5同組成同原料構成之 5 00g 玻璃於鉗坩鍋中,1 600 °C下進行溶解 6小時,製 作完全由玻璃去除氣泡之玻璃試料後,進行測定之。Transmittance: For example: ~ 3 After cutting the glass and honing the glass, a plate glass having a thickness of 0.7 mm is made, and the non-existing part of the bubble is selected to measure the spectral transmittance. The measurement was performed using a U-3500-type self-recording spectrophotometer manufactured by Hitachi to determine transmittances (%) at 546 nm and 300 nm. The specific gravity, coefficient of thermal expansion and glass transition temperature (Tg), deformation point, Young's rate, and HC1 resistance are 5,000 g of glass with the same composition and the same raw materials as in Examples 3 to 5 in a crucible at 1 600 ° C. After dissolving for 6 hours, a glass sample having bubbles completely removed from the glass was prepared, and then measured.
比重:藉由阿基米德法進行測定之。 熱膨脹係數與Tg :藉由指示熱膨脹計(TMA )進行 測定熱膨脹係數(1 7 °C _ 1 (測定溫度範圍5 0〜3 5 0 °C ) )。由熱膨脹曲線之變曲點溫度進行讀取Tg ( t )。 變形點:藉由纖維伸長法(nS R3103— 2 2001年)進 行測定變形點(°C )。 楊氏率:製作厚度 10mm之玻璃(50mmx50mmx10mm )後,藉由超音波脈衝法進行測定楊氏率(GPa )。 耐HC1性··於濃度〇」莫耳/1之鹽酸中,90 °C下浸 -24 - (22) 200401757 漬20小時,由玻璃表面積與浸漬之玻璃質量變化求取單 位面積之質量減少。 該取得玻璃中Si02〜Fe2〇3之含量其Si〇2〜BaO以外成 份之質量比例極爲微量,因此,等同於由表lSi02〜Fe2〇3 之値所算取者。 針對例3之玻璃之玻璃中不純物,亦即,表中所載之 外的元素,藉由誘導結合電漿質量分析計(ICP - MS ;Specific gravity: It is measured by Archimedes' method. Coefficient of thermal expansion and Tg: The coefficient of thermal expansion (17 ° C _ 1 (measurement temperature range: 50 to 350 ° C)) was measured by the indicated thermal expansion meter (TMA). Read Tg (t) from the temperature of the inflection point of the thermal expansion curve. Deformation point: The deformation point (° C) was measured by the fiber elongation method (nS R3103-2 2001). Young's rate: After making glass (50mmx50mmx10mm) with a thickness of 10mm, the Young's rate (GPa) was measured by the ultrasonic pulse method. Resistance to HC1 ·· Immersion at 90 ° C / 1 hydrochloric acid at 90 ° C -24-(22) 200401757 After 20 hours of immersion, the mass reduction per unit area is obtained from the change in the surface area of the glass and the quality of the impregnated glass. The content of Si02 ~ Fe203 in the obtained glass is extremely small in terms of the mass ratio of components other than Si02 ~ BaO. Therefore, it is equivalent to the one calculated from Table 1 Si02 ~ Fe203. For the impurities in the glass of the glass of Example 3, that is, the elements other than those listed in the table, were induced by a plasma mass spectrometer (ICP-MS;
A g 1 i e n t公司製7 5 0 0 s )進行定性分析。針對I c P - M S所檢 出元素中定量性之元素藉由標準添加法進行定量分析。其 結果,最高濃度之不純物元素Τι爲45ppm,接著Pb爲 1.5ppm、Ni爲l.lppm者,此外之不純物元素均爲不足 1 ppm者,被判定爲實質上未含有者。As、Sb、Sn均爲可 定量極限以下者。針對S〇3藉由螢光X線法進行定量分析 後爲 8ppm ( 0.0008% )者。 又,例7之玻璃溶存SCh量爲0.001 %者。Ag 1 i Ent Co., Ltd. 7500 s) for qualitative analysis. Quantitative analysis of the quantitative elements detected by I c P-M S was performed by the standard addition method. As a result, those having the highest concentration of impurity element Tm of 45 ppm, followed by Pb of 1.5 ppm, and Ni of 1.1 ppm, and those whose impurities were all less than 1 ppm were judged to be substantially free. As, Sb, and Sn are all below the quantifiable limit. Quantitative analysis of S03 by fluorescent X-ray method was 8 ppm (0.0008%). The amount of dissolved SCh in glass of Example 7 was 0.001%.
例1〜5爲本發明方法A之實施例、例6、7爲比較例 者。例1〜5之原料中,做爲澄淸劑者爲含氯化銨者,S〇3 爲實質上未含有者。另外,As及Sb亦爲實質上未含者。 玻璃中含NH/及C1兩者。 例1〜5之玻璃適於TFT - LCD用玻璃基板。 例1〜3之結果證明/3 - OH增加玻璃中溶存C1之量亦 同時減少之。此係原料中含氯化銨比例增加之同時由熔融 玻璃所釋出之H2〇亦增加所致者。 又,原料中含氯化銨比例增加之同時r亦增大,且’ -25 - (23) 200401757 氣泡數減少之。Examples 1 to 5 are examples of the method A of the present invention, and examples 6 and 7 are comparative examples. Among the raw materials of Examples 1 to 5, those containing clarifying agents were those containing ammonium chloride, and those of S03 were substantially not contained. In addition, As and Sb are also substantially not included. The glass contains both NH / and C1. The glasses of Examples 1 to 5 are suitable for TFT-LCD glass substrates. The results of Examples 1 to 3 proved that the amount of C1 dissolved in the glass increased as / 3 -OH decreased. The increase in the proportion of ammonium chloride in the raw materials and the increase in H2O released from the molten glass at the same time. In addition, as the proportion of ammonium chloride in the raw material increases, r also increases, and the number of bubbles is reduced as ′ -25-(23) 200401757.
本發明中澄淸效果依玻璃組成而定,一般,無鹼玻璃 中其鹼土類金屬氧化物(Mg〇、Ca〇、Sr〇、Ba〇)總量愈 少之組成,以更少澄淸劑添加量可取得明顯之澄淸效果。 此係本發明藉由氫氣作用取得澄淸者,因此,玻璃中氧活 量少之組成,亦即,該鹼土類金屬氧化物總量少之組成其 澄淸效果爲極明顯者。例1〜3之玻璃換算成莫耳%後,爲 含有1 1. 7 %之鹼土類金屬氧化物者,惟,例4爲1 4.5 %, 例5爲12.3 %者,特別是例3與例4之氣泡數不同係此影 響所致者。鹼土類金屬之含量爲20%以下者宜,特別以 15 %以下爲較佳,更以12%以下爲最佳者。The clarifying effect in the present invention depends on the composition of the glass. Generally, the composition of the alkali earth metal oxide (Mg0, Ca0, Sr0, Ba〇) in the alkali-free glass has a smaller total amount, and a less clarifying agent. Adding amount can achieve a clear effect. This is because the present invention obtains clear water by the action of hydrogen. Therefore, the composition with a small amount of oxygen activity in the glass, that is, the composition with a small total amount of alkaline earth metal oxides has a clear effect. The glass of Examples 1 to 3 is converted to Mohr%, and it contains 11.7% of alkaline earth metal oxides. However, Example 4 is 14.5%, Example 5 is 12.3%, especially Examples 3 and 1. The difference in the number of bubbles in 4 is due to this effect. The content of alkaline earth metals is preferably less than 20%, particularly preferably less than 15%, and more preferably less than 12%.
(24)200401757 表1 例 1 2 3 4 5 6 7 Si02 64 64 64 60 58.9 64 64 Al2〇3 17 17 17 17.3 16.1 17 17 B 2 0 3 8 8 8 8 8.6 8 8 MgO 1.4 1.4 1 .4 3 . 1 0.8 1.4 1 .4 CaO 6.2 6.2 6.2 3.6 4.3 6.2 6.2 SrO 3.4 3.4 3.4 7.9 1 .9 3.4 3.4 BaO 0 0 0 0. 1 9.4 0 0 F e 2 〇 3 0.07 0.07 0.07 0.07 0.02 0.07 0.07 銨鹽/氯 化物 NH4C1 Ν Η 4 C 1 nh4ci nh4ci nh4ci nh4ci SrCl2 · 6H20 銨鹽 添加量 0.75 1.06 1.5 1 1.5 1 0.98 0.75 — nh4 + 0.25 0.36 0.5 1 0.5 1 0.33 0.25 未 Cl 0.5 0.7 1 1 0.65 0.5 1 硫酸鹽 — 一 — — 一 C a S 0 4 一 S〇3 未 未 未 未 未 0.2 未 -27 - (25) 200401757 表2 例 1 2 3 4 5 6 7 Γ 0.80 0.97 0.99 0.97 未 未 0.6 溶存nh4 + 4 6 8 未 未 未 未 溶存Cl 0.12 0.15 0.2 0.3 未 0.1 0.18 溶存S〇3 未 未 0.0008 未 未 未 0.001 β -OH 0.27 0.25 0.22 0.24 未 未 ,0.28 泡數 1000 200 20 500 300 2000 3 400 透射率(546nm) 9 1.3 90.8 90.4 未 未 未 未 透射率(3 00nm) 63.4 77.7 87.9 未 未 未 未 比重 未 未 2.42 2.50 2.54 未 未 熱膨脹係數 未 未 33 38 39 未 未 Tg 未 未 742 728 726 未 未 變形點 未 未 690 670 670 未 未 楊氏率 未 未 75 76 70 未 未. 耐HC1性 未 未 0.06 0.13 0.08 未 未(24) 200401757 Table 1 Example 1 2 3 4 5 6 7 Si02 64 64 64 60 58.9 64 64 Al2〇3 17 17 17 17.3 16.1 17 17 B 2 0 3 8 8 8 8 8.6 8 8 MgO 1.4 1.4 1. 4 3 .1 0.8 1.4 1 .4 CaO 6.2 6.2 6.2 3.6 4.3 6.2 6.2 SrO 3.4 3.4 3.4 7.9 1 .9 3.4 3.4 BaO 0 0 0 0. 1 9.4 0 0 F e 2 〇3 0.07 0.07 0.07 0.07 0.02 0.07 0.07 Ammonium salt / Chloride NH4C1 Ν Η 4 C 1 nh4ci nh4ci nh4ci nh4ci SrCl2 · 6H20 Ammonium salt addition 0.75 1.06 1.5 1 1.5 1 0.98 0.75 — nh4 + 0.25 0.36 0.5 1 0.5 1 0.33 0.25 not Cl 0.5 0.7 1 1 0.65 0.5 1 sulfate — One — — One Ca S 0 4 One S〇3 Not yet Not yet 0.2 Not yet 27-(25) 200401757 Table 2 Example 1 2 3 4 5 6 7 Γ 0.80 0.97 0.99 0.97 Not dissolved 0.6 nh4 + 4 6 8 Not yet undissolved Cl 0.12 0.15 0.2 0.3 Not 0.1 0.18 Soluble S〇3 Not 0.0008 Not yet 0.001 β-OH 0.27 0.25 0.22 0.24 Not yet, 0.28 Number of bubbles 1000 200 20 500 300 2000 3 400 Transmission (546nm ) 9 1.3 90.8 90.4 Transmission rate (300 nm) 63.4 77.7 87.9 Specific gravity 2.42 2.50 2.5 4 Coefficient of Thermal Expansion Co. 33 38 39 Co. Tg Co. 742 728 726 Co. Deformation Point Co. 690 670 670 Co. Young's Rate Co. 75 76 70 Co. HC1 Resistance Co. 0.06 0.13 0.08 Co.
表3之Si02〜Fe2 03係使本發明實施例中取得玻璃之 Si02〜BaO成份總量做成100時各成份之質量比例者’又 ,銨鹽〜NH/代表對於玻璃原料之添加量等。另外’本實 施例所使用玻璃原料中組成與表3之Si02〜Fe2〇3組成幾乎 相同(B2Ch於溶解中約揮散1/3 )。表4代表本實施例中 玻璃之特性等。 表3之Si02〜Ba〇攔之總計係以100之質量比例所示 .28 - (26) 200401757 組成、進行調合實質上未含硫酸鹽之工業原料,於此中製 作含有氧化鐵、銨鹽(溴化銨、碘化銨、四硼酸銨四水合 物,檸檬酸氫二銨、或硫酸銨)之25 0g原料。銨鹽係使 該Si〇2〜Ba〇總計做成100質量比例後,投入0.25份量之 含NH/量者。 又,使玻璃質量做成1 00時之原料中含銨鹽比例與表 3之銨鹽質量比例之値實質上爲相同者。The SiO2 ~ Fe203 in Table 3 are those obtained when the total SiO2 ~ BaO components of the glass obtained in the embodiment of the present invention are made to 100, and the ammonium salt ~ NH / represents the amount of glass raw materials added. In addition, the composition of the glass raw material used in this example is almost the same as that of SiO2 to Fe203 in Table 3 (B2Ch is about 1/3 in the dissolution during dissolution). Table 4 shows the characteristics and the like of the glass in this example. The total of Si02 ~ Ba0 in Table 3 is shown in a mass ratio of 100. 28-(26) 200401757 Composition and blending of industrial raw materials that do not contain sulfates, in which iron oxides and ammonium salts ( 250 g of ammonium bromide, ammonium iodide, ammonium tetraborate tetrahydrate, diammonium hydrogen citrate, or ammonium sulfate). The ammonium salt was made into a total mass ratio of 100 to SiO 2 to Ba 0, and NH / amount was added in an amount of 0.25 parts. In addition, the ratio of the ammonium salt content in the raw material when the glass mass is 100 is substantially the same as that in Table 3.
於鉗坩鍋中置入該250g原料,利用電爐於大氣氣氛 中,1 600 °C下保持1小時,溶解後做成熔融玻璃。此熔 融玻璃於碳板流出後固化進行漸次冷卻。與表1同法計測 取得之玻璃氣泡數。 該取得玻璃中Si〇2〜Fe2〇3含量其Si〇2〜BaO以外成份 之質量比例極爲微量,因此,等同由表3 Si02〜FeCh之値 所算出者。The 250 g of the raw material was placed in a crucible of a forceps, and the molten glass was prepared by dissolving the raw material in an electric furnace at 1 600 ° C for 1 hour. This fused glass is solidified and cooled gradually after the carbon plate flows out. Measure the number of glass bubbles obtained in the same way as in Table 1. The content of Si02 ~ Fe2O3 in the obtained glass is extremely small, and the mass ratio of components other than Si02 ~ BaO is equivalent to that calculated from Table 3 Si02 ~ FeCh.
-29 - (27) 200401757 表3 例 8 9 10 11 12 Si02 64 64 64 64 64 Al2〇3 17 17 17 17 17 B 2 〇 3 8 8 8 8 8 MgO 1 .4 1.4 1 .4 1 .4 1 .4 CaO 6.2 6.2 6.2 6.2 6.2 SrO 3.4 3.4 3.4 3.4 3.4 BaO 0 0 0 0 0 F e 2 〇 3 0.03 0.03 0.03 0.03 0.03 銨鹽 NH4Br nh4i (NH4)2B4〇7 • 4H20 (nh4)2hc6h5o7 (nh4)2so4 銨鹽 添加量 1.3 8 2.04 1.86 1.59 0.93 nh4 + 0.25 0.25 0.25 0.25 0.25 表4 例 8 9 10 11 12 r 0.86 0.83 0.79 0.83 0.45 氣泡數 300 100 80 600 4000 表 5、表 6代表 PDP用玻璃基板之實施例。表 5 Si02〜Fe2 03係本發明實施例取得玻璃Si02〜K20成份總量 做成100時各成份之質量比例者,又,銨鹽〜ΝΗ,代表對 .30 - (28) 200401757 於玻璃原料之添加量等。另外,本實施例中所使用玻璃原 料中組成與表5之Si02〜Fe203組成幾乎爲相同者(B2〇3 於溶解中的揮散1 / 3 )。表6代表本實施例中玻璃之特性 等。實施方法與表1、表3爲相同者。 又’將玻璃質量做成1 00份時原料中含銨鹽之比例與 表5銨鹽之質量比例値實質上爲相同者。-29-(27) 200401757 Table 3 Example 8 9 10 11 12 Si02 64 64 64 64 64 Al2〇3 17 17 17 17 17 B 2 0 3 8 8 8 8 8 MgO 1.4 .1.4 1.4 .1.4 1 .4 1 .4 CaO 6.2 6.2 6.2 6.2 6.2 SrO 3.4 3.4 3.4 3.4 3.4 BaO 0 0 0 0 0 F e 2 〇3 0.03 0.03 0.03 0.03 0.03 0.03 Ammonium salt NH4Br nh4i (NH4) 2B4〇7 • 4H20 (nh4) 2hc6h5o7 (nh4) 2so4 Ammonium salt addition amount 1.3 8 2.04 1.86 1.59 0.93 nh4 + 0.25 0.25 0.25 0.25 0.25 Table 4 Example 8 9 10 11 12 r 0.86 0.83 0.79 0.83 0.45 Number of bubbles 300 100 80 600 4000 Tables 5 and 6 represent the implementation of glass substrates for PDP example. Table 5 Si02 ~ Fe2 03 are examples of the present invention when the total mass ratio of each component when glass Si02 ~ K20 components are made to 100, and ammonium salt ~ ΝΗ, representing the ratio of 30. (28) 200401757 to glass raw materials. Add amount and so on. In addition, the composition of the glass raw material used in this example is almost the same as the composition of Si02 to Fe203 in Table 5 (B203 is 1/3 of the volatilization in dissolution). Table 6 shows the characteristics and the like of the glass in this example. The implementation methods are the same as those in Tables 1 and 3. In addition, when the mass of the glass is made to 100 parts, the ratio of the ammonium salt in the raw material and the mass ratio of the ammonium salt in Table 5 are substantially the same.
該取得玻璃中Si02〜Fe203之含量其Si02〜K20以外成 份之質量比例極爲微量,因此,等同於表5之Si02〜 Fe2〇3之値。 另外,表6之r與溶存NH/未進行測定,而r被推斷 爲〇·96〜0.99,溶存NH /爲5x10— 4 %以上者。The content of Si02 to Fe203 in the obtained glass is extremely small in terms of the mass ratio of components other than Si02 to K20, and is therefore equivalent to that of Si02 to Fe203 in Table 5. In addition, r and the dissolved NH / in Table 6 were not measured, and r was estimated to be 0.96-0.99, and the dissolved NH / was 5 × 10-4% or more.
-31 - (29)200401757 表5 例 13 Si02 57.8 Al2〇3 6.9 B 2 0 3 0 MgO 2.0 CaO 5.0 SrO 7.0 BaO 8.0 Zr02 3.0 Li2〇 0 Na2〇 4.3 K2〇 6.0 Fe2〇3 0.10 銨鹽 (nh4)2hc6h5o7 銨鹽添加量 3.19 nh4 + 0.15 (30) 200401757 表6 例 13 r 未 溶存nh4 + 未 β -OH 未 泡數 50 透射率(546nm) 未 透射率(3 00nm) 未 比重 2.77 熱膨脹係數 83 Tg 620 變形點 570 楊氏率 76 耐HC1性 <0.0 1-31-(29) 200401757 Table 5 Example 13 Si02 57.8 Al2〇3 6.9 B 2 0 3 0 MgO 2.0 CaO 5.0 SrO 7.0 BaO 8.0 Zr02 3.0 Li2〇0 Na2〇4.3 K2〇6.0 Fe2〇3 0.10 Ammonium salt (nh4) 2hc6h5o7 Addition of ammonium salt 3.19 nh4 + 0.15 (30) 200401757 Table 6 Example 13 r Undissolved nh4 + Unβ-OH Unbubble number 50 Transmission (546nm) Untransmittance (3 00nm) Unspecific gravity 2.77 Thermal expansion coefficient 83 Tg 620 Deformation point 570 Young's rate 76 HC1 resistance < 0.0 1
〔產業上可利用性〕 本發明未含As2〇3及Sb2〇3’更未含S〇3時,仍可取 得氣泡少之玻璃。此玻璃可適用於顯示器用玻璃基板(特 別是TFT - LCD用玻璃基板)。 又,溶解未含As203及Sb2〇3之原料後可取得氣泡少 之玻璃。特別是適於TFT - LCD用玻璃基板所使用之無鹼 玻璃之製造。 -33 -[Industrial Applicability] When the present invention does not contain As203 and Sb203, and S03 is not contained, a glass with few bubbles can be obtained. This glass is suitable for glass substrates for displays (especially glass substrates for TFT-LCD). Further, a glass having few bubbles can be obtained by dissolving raw materials not containing As203 and Sb203. It is especially suitable for the production of alkali-free glass for TFT-LCD glass substrates. -33-
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JP5867953B2 (en) * | 2008-06-27 | 2016-02-24 | 日本電気硝子株式会社 | Tempered glass and tempered glass |
TWI494286B (en) * | 2009-03-19 | 2015-08-01 | Nippon Electric Glass Co | Alkali-free glass |
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KR101528396B1 (en) * | 2011-07-01 | 2015-06-11 | 아반스트레이트 가부시키가이샤 | Glass substrate for flat pannel display |
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