1276617 玖、發明說明： 【發明所為之技術領域】 本發明係有關平面顯示器（以下稱「」）基板用破璃及 FPD基板#划有關作為利用電漿顯示器面板(以下稱 jPDP」）或場發射面板（以下稱「咖」）等之放電之咖之 前面板及背面板而使用之FpD基板用玻璃及FPD基板。 【先前技術】 近年來，作為大型平面電視，pDp、FED、液晶顯示器等 卿之開發急速進展。其中，酿及卿係利用將電場施加 於内部電極間時所產生之放電之顯示裝置。 PDP係猎由在封閉於面板内部之低壓之稀有氣體中放 電’由稀有氣體使紫外線產i，激發特定螢光體，使可視 光線產生而顯示文字或圖形等之圖像之方式。又，FED係 面板内部維持高真空，制於此高真空中施加電場所產生 之電子束激發螢光體’使可視光線產生之方式之顯示裝置。 以下，說明有關PDP之製造方法之一例。 、先支同面基板用玻璃上，以絲網印刷法等形成銀（Ag) 斤、成 址兒極，於位址電極上，以特定間隔形成介電 體玻璃所組成之可视光反射層及玻璃製之間隔壁。在由此 等1隔土所夹著之各玄間内，藉由分別配 而形成勞光體層，以約赋燒成勞光體層，除：：二 體糊中之樹脂成分等。 、k成螢光體層後，於背面基板用玻璃之周圍，塗佈用於 封m基板用破璃及前面基板用玻璃之低融點玻璃粉 89823 1276617 (Glass Fr:t) ’並為了除去玻璃粉之樹脂成分，以約3，c進 行煅燒。 其後，將形成顯示電極、介電體玻璃層及保護層之前面 基板用玻璃及背面基板用破璃相對配置，以便經由間隔壁， 使顯示電極及位址電極正交’以約600t燒成，藉由低融點 破璃粉封著周圍。而且’在約加熱至300t之狀態下，將面 板間隙之大氣減壓排氣，減壓排氣後，藉由填充放電氣體 而完成PDP。 作為PDP基板用玻璃，廣泛使用軟化點高，並且熱膨服 係數大之玻璃。此種PDP基板用玻璃一般係主表面之平坦 性：玻璃組成之均質性優異，並且藉由生產性高之浮式法 生屋。浮式玻璃在生產過程暴露於氫氣氛中，故玻璃表面 形成厚度數心之還原層，據知，此還原層存在來自炼融錫 之錫離子（以下稱為「Sn2+」。 不在以汙式法形成之PDP基板用玻璃之主表面，經由透明 電極’塗佈作4電極之Ag糊後，若重複數次熱處理工序， ♦離（、下稱+」）將擴散於透明電極内，並到達玻璃 表面W破璃中心鹼離子（特別是鈉離子（以下稱「Na +」） 之間產切子交換。而且，Ag+侵入玻璃中，侵入之Ag+藉 由存在万、還原層之Sn2 +還原，產生金屬~之膠體。其結果， 產生由於金屬Ag之膠體，基板用玻璃著色成黃色（以下稱「黃 變」）之問題。 — 又I〜電極形成部，Ag+亦擴散於其周邊部，與前述 同^ jc ’ _ 皆由 S η 2 +、翠 ， 遂原而產生金屬Ag之膠體，基板用玻璃黃 89823 1276617 變之情況亦多，產生顯示性能受損之故障。 因此，將含鹼玻璃作為PDP基板用玻璃使用之情況，至 今提案各種抑制基板用玻璃黃變之方法。 於特開平丨0-255669號公報，揭示—種FpD基板用玻璃’ 其係藉由將浮式法所製造之基板用玻璃之主表面研磨，除 去產生於主表面之還原性異質層者。 據以往所知，以浮式法形成之基板用玻璃在前述之成型 過私中，由於暴路於氫氣氛中，故與錫（Sn)槽相接之面（底 面）及與氣氛側相接之面（頂面）均於基板用玻璃之主表面產 生厚度數/zm之還原層，於此還原層形成Sn2+之擴散層。 又，Sn2+之擴散層具有還原性，之擴散層將玻璃中之 鐵還原，其結果，底面著色成藍色之現象（Bl〇〇m ••起霜）亦 同樣為人所知。故，將存在於基板用玻璃之主表面之Sn2+ 擴散層研磨除去係熟悉此技藝之人士可容易進行之技術。 然而’將基板用玻璃之全數研磨之對策，為極大之成本上 升要因’故並不實際。 又’於特開平10-334813號公報，揭示一種電漿顯示器裝 置’其係前面基板用玻璃所含有之Fe2〇3之量未滿2〇〇〇 ppm，金屬電極以Ag形成者。 通常’於浮式法成型之平板破璃，從玻璃原料混入之雜 貝位準之Fe2〇3量為1 5 00 ppm程度，故即使將該玻璃作為ρρρ 基板用玻璃使用之情況，亦無法抑制由於前述金屬Ag之膠 體所造成之黃變，無法稱為實際之解決方法。 又’於特開200 1-2 13634號公報，揭示一種顯示器基板用 89823 1276617 =式破璃，其係將U2〇、Na2〇及κ2〇之合計含有量為7 5〜2〇 莫耳％、入丨2〇;之含有量為15莫耳％以上、Ba〇之含有量為〇 〜3.5莫耳％之矽酸鹽破璃，藉由浮式法成型為板狀之平板 破璃，並含有選自F、Cb Br及I所組成之群之1種以上者。 通常，於浮式法成型之平板玻璃，從玻璃原料混入之雜 貝位準之氯為0.01重量％程度，然而，F-*C1•等硬鹼與軟酸 足Ag+之優先結合力弱，幾乎無法獲得著色抑制效果。又， 右使用或Γ等軟鹼，由於與Ag+優先結合，故可期待著色 抑制效果，然而，兩者在工業上均不存在適當之原料，或 成本亦高，故並不實際。 又’於特開2000-226233號公報，揭示一種平面顯示器基 板用浮式玻璃，其係Na^O、K：2〇及Li20之合計含有量為5重 量〇/。以上、在20°C之比重為2.7以下之浮式玻璃，由銀處理 ⑸之浮式玻璃在波長4 1 0 nm之透過率Tref，及銀處理後之 洋式玻璃在波長410 nm之透過率T，根據A=-l〇gl〇(T/Tre:〇 所算出之吸光度A在0·08以下者。在此，所謂前述銀處理， 其係在浮式玻璃表面中，於浮式槽内未與熔融錫接觸側（頂 面）之表面，塗佈含有銀粒子、有機溶劑及樹脂之Ag糊，在 大氣中以5 8 0。(：、1小時燒成，於該浮式玻璃之表面形成厚 度在1 〇以m以上、銀含有量在95重量％以上之膜，藉由硝 酉义將前述膜由該浮式玻璃之表面除去之處理。 然而，前述特開2000-226233號公報中，只不過敘述「破 璃中錫之浸透量少者，發色較少，儘量以錫含有量少之破 璃為苴」之習知事實，及評估由金屬Ag之膠體所造成之黃 89823 1276617 變之方法，並未到達根本之解決手段。 有鑑於上述先前技術之問顳 ,^ π 心门〜點，本發明之目的在於提供 一種可抑制由金屬Ag之膠體所泮士、、廿以 ， 6〜也所乂成乏黃變之FPD基板用玻 璃及F P D基板。 【發明内容】 為了達成上述目的，根據本發明之第—態樣，提供一種 FPD基板用玻璃’其係含有以重量％表示之未滿6%之％〇, 具有未滿560〜580t之軟化點、在5〇〜35〇t：之溫度範圍内 之80〜95 X 1 0 7/ C之平均熱膨脹係數、2 7 χ 1〇3Kg/m3以下 之搶度’並且具有0.60以下之光學鹼度者。 於本發明之第一態樣，以重量％表示之Κ2〇/ν^〇之值宜 在2以上。 於本發明之第一態樣，宜含有以重量％表示，換算成Q2 〜2.5°/。之Zr〇2i氧化锆，及換算成0·01〜o.5❶/()未滿之Fe203 之全氧化鐵（T-Fe2〇3)。 於本發明之第一態樣，基礎破璃組成以重量％表示，宜 由： 55 〜70%之 Si02 ; 〇·2〜5%之 Al2〇3 ; 〇〜15%之 MgO ; 2〜15%之Ca〇； ^ 〇〜15%之Sr〇； l〇〜30%iMg〇+Ca〇+Sr〇+Ba〇； 〇〜5%之 Li20 ; 89823 -10- 1276617 〇〜6%之Na2〇； 〇〜15%之K2〇； 5 〜25% 之 Na20+ Κ2〇； 挺异成0·2〜2.5%之ZrO?t氧化錯. 換算成(Μ〜〇.5%未滿之Fee;之全氧化鐵（T_Fe2〇3)，及； 0〜5%之B2〇3所組成。 於本發明之第一態樣，作為基礎玻璃組成’宜實質上不 含有BaO。 為了達成上述目的，根據本發明之第二態樣，提供一種 FPD基板，其係使用本發明之第—態樣之卿基板用玻璃 者。 【實施方式】 以下，詳細說明本發明之實施型態。1276617 发明 发明 发明 发明 发明 发明 766 766 766 766 766 766 766 766 766 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面 平面A FpD substrate glass and an FPD substrate used for a front panel and a back panel of a discharge coffee such as a panel (hereinafter referred to as "coffee"). [Prior Art] In recent years, as a large-scale flat-panel TV, the development of pDp, FED, and liquid crystal display has progressed rapidly. Among them, the brewing and cultivating system is a display device that uses a discharge generated when an electric field is applied between internal electrodes. PDP hunting is performed by discharging a low-pressure rare gas enclosed in a panel to generate ultraviolet light from a rare gas, exciting a specific phosphor, and generating visible light to display an image of a character or a figure. Further, a high vacuum is maintained inside the FED panel, and a display device in which an electron beam generated by an electric field is excited by a high-vacuum to generate visible light is generated. Hereinafter, an example of a method of manufacturing a PDP will be described. On the glass for the same substrate, the silver (Ag) jin, the site electrode is formed by screen printing, and the visible light reflecting layer composed of the dielectric glass is formed on the address electrode at a specific interval. And the partition wall made of glass. In each of the stiles sandwiched by the ones of the soils, a mortar layer is formed by each of the partitions, and the burnt layer is formed by firing, and the resin component in the two-part paste is removed. After k is formed into a phosphor layer, a low-melting glass powder 89823 1276617 (Glass Fr:t) ' for sealing the glass for the substrate and the glass for the front substrate is applied around the glass for the back substrate and in order to remove the glass. The resin component of the powder is calcined at about 3, c. Thereafter, the display electrode, the dielectric glass layer, and the protective layer are placed on the front substrate glass and the rear substrate are arranged to face each other so that the display electrode and the address electrode are orthogonally formed by the partition wall at about 600 ft. , sealed by a low melting point broken glass. Further, in a state of heating to about 300 t, the atmosphere in the panel gap is depressurized and exhausted, and after decompressing and decompressing, the PDP is completed by filling the discharge gas. As the glass for a PDP substrate, a glass having a high softening point and a large thermal expansion coefficient is widely used. The glass for such a PDP substrate is generally flatness of the main surface: the glass composition is excellent in homogeneity, and is produced by a highly productive floating method. The floating glass is exposed to a hydrogen atmosphere during the production process, so that a reduction layer of a plurality of cores is formed on the surface of the glass. It is known that the reduction layer has tin ions derived from smelting tin (hereinafter referred to as "Sn2+". After forming the main surface of the glass for the PDP substrate, the Ag paste is applied as a 4-electrode through the transparent electrode, and if the heat treatment step is repeated several times, ♦ (hereinafter referred to as +) will diffuse into the transparent electrode and reach the glass. On the surface of the glass, the alkali ions (especially sodium ions (hereinafter referred to as "Na +") are exchanged between the seeds. Moreover, Ag+ invades the glass, and the invading Ag+ is reduced by the existence of 10,000 and the reduction layer of Sn2 + to produce metal. As a result, a colloid of metal Ag is generated, and the glass for the substrate is colored yellow (hereinafter referred to as "yellow"). - I to the electrode forming portion, and Ag+ is also diffused to the peripheral portion thereof. ^ jc ' _ All of them are made of S η 2 +, Cui, and 遂, which produce a colloid of metal Ag. The substrate is also changed with glass yellow 89823 1276617, which causes a failure in display performance. Therefore, the alkali glass is used as the PDP. base In the case of using glass, various methods for suppressing glass yellowing of a substrate have been proposed. Japanese Laid-Open Patent Publication No. 0-255669 discloses a glass for a substrate for FpD substrate. The surface of the main surface is polished to remove the reducing heterogeneous layer which is generated on the main surface. It is known that the glass for the substrate formed by the floating method is formed in the above-mentioned manner, and the tunnel is in a hydrogen atmosphere, so that it is tinned. A surface on which the (Sn) groove is in contact with each other (bottom surface) and a surface (top surface) that is in contact with the atmosphere side are each formed on the main surface of the glass for substrate to have a thickness of /zm, and the reduced layer forms a diffusion layer of Sn2+. Further, the diffusion layer of Sn2+ has a reducing property, and the diffusion layer reduces the iron in the glass, and as a result, the phenomenon that the bottom surface is colored blue (Bl〇〇m •• blooming) is also known. The Sn2+ diffusion layer which is present on the main surface of the glass for the substrate can be easily removed by a person skilled in the art. However, it is not practical to measure the total amount of the glass for the substrate.Japanese Patent Publication No. Hei 10-334813 discloses a plasma display device in which the amount of Fe 2 〇 3 contained in the glass for the front substrate is less than 2 〇〇〇 ppm, and the metal electrode is formed of Ag. In the case of the flat-plate glass which is formed by the method, the amount of Fe2〇3 which is mixed from the glass raw material is about 1 500 ppm. Therefore, even if the glass is used as a glass for the ρρρ substrate, the above-mentioned metal Ag cannot be suppressed. The yellowing caused by the colloid can not be called the actual solution. In Japanese Patent Publication No. 200 1-2 13634, a display substrate is used for 89823 1276617 = type of glass, which is U2〇, Na2〇 and The total content of κ2〇 is 7 5~2〇mol%, 丨2〇; the content is 15% by mole or more, and the content of Ba〇 is 〇~3.5mol% of bismuth phosphate. It is formed into a plate-shaped flat glass by a floating method, and contains one or more selected from the group consisting of F, Cb Br, and I. Usually, in the flat glass formed by the floating method, the chlorine level of the mixed shell from the glass raw material is about 0.01% by weight, however, the preferential binding force of the hard base such as F-*C1• and the soft acid foot Ag+ is weak, almost Color suppression is not available. Further, since the right base or a soft base such as hydrazine is preferentially bonded to Ag+, a coloring suppressing effect can be expected. However, neither of them has industrially suitable raw materials, or the cost is high, which is not practical. Japanese Laid-Open Patent Publication No. 2000-226233 discloses a floating glass for a flat-panel display substrate, which has a total content of Na^O, K:2〇, and Li20 of 5 〇/. Above, the floating glass having a specific gravity of 2.7 or less at 20 ° C, the transmittance T90 of the floating glass of silver (5) at a wavelength of 40 nm, and the transmittance of the western glass of the silver after treatment of a wavelength of 410 nm According to A=-l〇gl〇 (T/Tre: 吸 the calculated absorbance A is below 0·08. Here, the silver treatment described above is in the surface of the floating glass, not in the floating tank. On the surface of the contact side (top surface) of the molten tin, an Ag paste containing silver particles, an organic solvent, and a resin is applied, and it is baked at 850 in the air (:, 1 hour, and formed on the surface of the floating glass). A film having a thickness of 1 m or more and a silver content of 95% by weight or more, wherein the film is removed from the surface of the floating glass by niobium. However, in the above-mentioned Japanese Patent Publication No. 2000-226233, It is only a description of the fact that "the amount of tin in the broken glass is less, the color is less, and the glass with less tin content is used as a flaw", and the evaluation of the yellow 89823 1276617 caused by the colloid of metal Ag The method has not reached the fundamental solution. In view of the above-mentioned prior art questions, ^ π heart In order to achieve the above, it is an object of the present invention to provide a FPD substrate glass and an FPD substrate which are capable of suppressing the yellowing of the colloid of the metal Ag, and the ruthenium. OBJECTS According to the first aspect of the present invention, there is provided a glass for an FPD substrate which comprises less than 6% by weight of 5% by weight %, and has a softening point of less than 560 to 580 tons at 5 〇 to 35 〇. t: the average thermal expansion coefficient of 80 to 95 X 1 0 7/C in the temperature range, the gravitation degree of 2 7 χ 1 〇 3 Kg/m 3 or less and having an optical alkalinity of 0.60 or less. In the aspect, the value of Κ 2 〇 / ν 〇 expressed in % by weight is preferably 2 or more. In the first aspect of the present invention, it is preferable to contain Zr 〇 2i oxidation expressed by weight % in terms of Q 2 〜 2.5 ° /. Zirconium, and total iron oxide (T-Fe2〇3) of Fe203 which is not converted to 0·01~o.5❶/(). In the first aspect of the present invention, the basic glass composition is expressed by weight%, preferably From: 55 to 70% of SiO2; 〇·2 to 5% of Al2〇3; 〇~15% of MgO; 2 to 15% of Ca〇; ^ 〇~15% of Sr〇; l〇~30 %iMg〇+Ca〇+Sr〇+Ba〇; 〇~5% of Li20; 89823 -10- 1276617 〇~6% of Na2〇; 〇~15% of K2〇; 5~25% of Na20+ Κ2〇; It is quite different from 0. 2 to 2.5% of ZrO?t oxidation. It is converted into (Μ~〇.5% underfilled Fee; total iron oxide (T_Fe2〇3), and; 0~5% of B2〇3) Composed of. In the first aspect of the invention, it is preferable that the composition of the base glass is substantially free of BaO. In order to achieve the above object, according to a second aspect of the present invention, there is provided an FPD substrate which is a glass for a substrate for use in the first aspect of the invention. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail.
於本發明之會施项能士 F -也土 ^、又tPD基板用玻璃，Ν~〇具有使玻 璃之溶解性提升’降低溶解貞荷而使生產性提升之作用。 又，Na20係使熱膨脹係數變大，降低化學耐久性、電性絕 緣性。並且’著眼於由於金屬岣之膠體所造成之黃變時， 推測Nas〇對於黃變造成甚大之影響。 若思考Ag離子侵入玻璃中之情況，推測其係首先電子被 奪取=成為Ag+ ’以與破璃中之驗離子產生離子交換之形 式ί又入玻璃者。尤其是玻璃中之Na +係擴散速度快，在 與Ag+之離子交換中，擔任支配性之角色。因此，為了抑 制Ag+侵入破璃，心2〇必須未滿6%〇 據知’侵入破璃中之Ag+本身無法造成發色，藉由在玻 89823 1276617 璃中被提供電子’形成金屬Ag(Agn)後，凝聚而形成膠體， 產生黃變。 於玻璃中將電子提供給Ag+之對象為Snh或鐵離子（Feh ) 等’發明者等發現減低玻璃本身之電子提供性，有抑制 Ag+發色之效果。 玻璃之光學鹼度（Optical Basicity)係作為表示玻璃之電子 才疋供性之標準之一而為人所知。關於表示各元素之酸鹼之 係數，有各種說法，各種數值亦被提倡，然而，並非針對 全部元素求出。因此，採用與PauHng(鮑林）之電負度 (Electr〇negativity^關，即使是係數不明之元素亦能以較 佳精度推定之Duffy及ingram之鹼度緩和係數（BasichyIn the present invention, the energy of the F-soil and the tPD substrate is used, and the Ν~〇 has the effect of improving the solubility of the glass, reducing the dissolution charge and improving the productivity. Further, the Na20 system has a large thermal expansion coefficient and reduces chemical durability and electrical insulation. And 'focusing on the yellowing caused by the colloid of the metal ruthenium, it is speculated that Nas 造成 has a great influence on the yellowing. If you think about the intrusion of Ag ions into the glass, it is presumed that the electrons are first captured = become Ag+' in the form of ion exchange with the ions in the glass. In particular, the Na + system in glass has a high diffusion rate and plays a dominant role in ion exchange with Ag+. Therefore, in order to suppress the intrusion of Ag+ into the glass, the heart 2〇 must be less than 6%. It is known that Ag+ itself intrusion into the glass does not cause color development. By providing electrons in the glass 89823 1276617, the formation of metal Ag (Agn) After that, it agglomerates to form a colloid, which causes yellowing. The inventors who supplied electrons to Ag+ in the glass were Snh or iron ions (Feh), etc. The inventors found that the electron supply of the glass itself was reduced, and the effect of suppressing Ag+ color development was observed. The optical basicity of glass is known as one of the standards for the electron supply of glass. There are various expressions regarding the coefficient of acid and alkali of each element, and various values are also advocated. However, it is not determined for all elements. Therefore, using the electrical negative degree with PauHng (Electr〇negativity^, even the element with unknown coefficients can estimate the alkalinity mitigation coefficient of Duffy and ingram with better precision (Basichy)
Moderating parameter)?^ ，由次式⑴求出各玻璃組成之光 學驗度。 光學鹼度=Σ (配位於m之全氧數）/( r m X破璃中之全氧 數） i ···式（1) m:玻璃所含有之陽離子種類 7 m :陽離子m之鹼度緩和係數 發明者等在幾種破璃組成之光學鹼度與由金屬Ag之膠體 斤k成之貝史之間發現相關，並得知若將光學驗度之值設 足在〇·60以下’尤其是〇·57〜〇.60之範圍内，可改善金屬Ag 之膠體所造成之黃變。 以下’說明各組成範圍之限定理由。 與則述相同，ΚζΟ使玻璃之溶解性提升，降低溶解 負荷而使生產性提升。又，雖比Ν^〇之效果小，仍使熱膨 89823 1276617 脹係數又纟，降低化學耐久性、電性絕緣性。然而，若著 眼於金屬膠體所造成之黃變，可推測Re之舉動與Na2〇 大幅不同。 鉀離子（以下稱「κ+」）與Na+同樣’助於與Ag+之離子 交換，然而，相較於Na+，κ+之擴散速度非常小，故妨礙 Ag+到達玻璃深部形成擴散層。並且，一旦離開玻璃外之κ +會妨礙Na+與Ag+之離子交換’故可抑制Ag+侵入玻璃之 速度，抑制擴散。故，以重量％表示’ K2〇/Na2〇之比在2以 上為佳，尤其是設定在6〜14之範圍内為佳。 鹼土類金屬氧化物之R0(R為選自Ca、Mg、Sr、以之1種 以上）用於提高破璃之軟化點，使玻璃之耐久性提升，同時 調整成型時之失透溫度、黏度。又，降低黏度之效果亦大， 故可適量含有。然而，若Mg0之含有量超過15%，失透溫度 上升。CaO之含有量未滿2。/。或超過15%，或Sr〇之含有量超 過15%時’失透溫度亦同樣上升。Moderating parameter)?^, the optical spectroscopy of each glass composition is obtained from the following formula (1). Optical alkalinity = Σ (with the total oxygen number in m) / (the total oxygen number in rm X broken glass) i ··· Formula (1) m: The cationic species contained in the glass 7 m : the alkalinity of the cation m The inventor of the relaxation coefficient found that the optical alkalinity of several kinds of broken glass composition is related to the history of the colloid of the metal Ag, and it is known that if the value of the optical verification is set below 〇·60 or less' In particular, in the range of 〇·57~〇.60, the yellowing caused by the colloid of the metal Ag can be improved. The following 'describes the reasons for limiting the scope of each component. As described above, the solubility of the glass is improved, and the dissolution load is lowered to improve productivity. Moreover, although the effect of the Ν^〇 is small, the thermal expansion 89823 1276617 is further reduced, and the chemical durability and electrical insulation are lowered. However, if you look at the yellowing caused by the metal colloid, it is speculated that the action of Re is significantly different from that of Na2〇. Potassium ions (hereinafter referred to as "κ+") are the same as Na+ to facilitate ion exchange with Ag+. However, compared with Na+, the diffusion speed of κ+ is very small, so that Ag+ is prevented from reaching the deep portion of the glass to form a diffusion layer. Further, when κ + leaving the glass interferes with the ion exchange between Na + and Ag + , the rate at which Ag + invades the glass can be suppressed, and the diffusion can be suppressed. Therefore, the ratio of 'K2〇/Na2〇' expressed in % by weight is preferably 2 or more, and particularly preferably set in the range of 6 to 14. R0 (R is selected from Ca, Mg, Sr, or more than one type) of the alkaline earth metal oxide is used to increase the softening point of the glass to improve the durability of the glass, and to adjust the devitrification temperature and viscosity at the time of molding. . Moreover, the effect of lowering the viscosity is also large, so it can be contained in an appropriate amount. However, if the content of Mg0 exceeds 15%, the devitrification temperature rises. The content of CaO is less than 2. /. When the content exceeds 15%, or the content of Sr〇 exceeds 15%, the devitrification temperature also increases.
Ba離子（Ba2—)相較於其他鹼土類金屬離子，鹼度緩和係 數r小，故具有增大光學鹼度之作用。又，若添加以〇,玻 璃密度上升。故，為了使玻璃密度在27以下，實質上不含 有BaO為佳。 在工業上，BaO係作為其他鹼土類金屬原料中之雜質而 導入。於本發明中，「實質上不含有Ba〇」係指〇.2%以了 之含有量。Compared with other alkaline earth metal ions, Ba ion (Ba2—) has a small alkalinity relaxation coefficient r, so it has an effect of increasing optical alkalinity. Further, if 〇 is added, the glass density increases. Therefore, in order to make the glass density 27 or less, it is preferable that BaO is not substantially contained. Industrially, BaO is introduced as an impurity in other alkaline earth metal materials. In the present invention, "substantially free of Ba" means a content of 2% or less.
Zr〇2具有使軟化點變大’使玻璃之耐久性提升之作用。 Zr〇2之含有量宜在〇.2%以上。Zr離子（Zr4+)相較於其他網孔 89823 -13- 1276617 形成離子’絵度緩和信齡y 系数r較小，故具有增大光學鹼度之 作用。並且，Zr〇）之本右旦A 4 0有里且在2 · 5 %以下，否則玻璃之失 透溫度變高，超過成型溫度。 換算成Fe2〇3之全氧仆讲 王乳化鐵（T-Fe2〇3)之含有量若在0.5%以 上’由基板會黃變的觀勢爽I ^ 娜^木看，供法忽視Fe2 +所造成之Ag +還原作用，故不適宜。Zr〇2 has the effect of increasing the softening point to improve the durability of the glass. The content of Zr〇2 is preferably 〇. 2% or more. The Zr ion (Zr4+) has a smaller ion y coefficient than the other meshes 89823 -13 - 1276617, and has a smaller optical y coefficient r, so it has the effect of increasing the optical alkalinity. Moreover, Zr〇) has a temperature of less than 2 · 5 %, otherwise the glass devitrification temperature becomes higher and exceeds the molding temperature. If the content of the oxidized iron (T-Fe2〇3) converted to Fe2〇3 is 0.5% or more, the substrate will be yellowed and the surface will be yellow. I ^ Na ^mu, the supply neglects Fe2 + The resulting Ag + reduction is not suitable.
SiOJ—氧化旬為形成玻璃之架構之主成分。仙2之含有 量若未滿55%，坡璃之耐久性下降，若超過7〇%，則難二容 解破璃。SiOJ—Oxidation is the main component of the framework for forming glass. If the content of Xian 2 is less than 55%, the durability of the glass is reduced. If it exceeds 7〇%, it is difficult to dissolve the glass.
Al2〇3係使玻璃之耐久性提升之成分，然而，含有量若超 過5%，將難以溶解坡璃。Α1〗〇3之適宜範圍為〇·2〜。 Β2〇3係為了提升坡璃之耐久性，或亦作為溶解助劑而使 用之成刀。Β2〇3之含有量若超過5%，由於揮發等，將產生 成型時之不便，故上限為5%。 、本發明之組成範圍之玻璃宜採用浮式法製造，通常，澄 清劑係使用鹼金屬或鹼土類金屬之硫酸鹽。此時，殘留: 破璃中之s〇3之量之範圍宜在〇」〜〇」％。 本發明之基板用玻璃之組成物係5〇〜35〇〇c之溫度範圍内 之平均熱膨脹係數在8〇〜95X1 Ο-Vt：之範圍，故可抑制起 因於熱應力之基板用玻璃之裂缝或破裂。平均熱膨脹係數 若未滿8〇xi〇-Vt或超過95χ1〇·νι，則難以使周邊材料與 平均為㈣服係數整合。 本發明之基板用玻璃之組成物可藉由將欲成為目標組成 而调合之原料供給至熔融爐，進行玻璃化，藉由浮式法等 89823 -14- 1276617 成·^為特疋厚度之透明平板玻璃而製造。 1下’舉例具體之實施例’說明本發明之實施型態。 (貫施例） ★表1所7^足組成所組成之破璃原料供給至標準之玻璃熔 π 、、而t解，藉由浮式法成型為板狀，製作本實施例之破 璃4料。針對此玻璃試料，測定軟化點、平均熱膨脹係數、 么度、光學驗度及銀處理前後之吸光度變化量。軟化點、 平均熱恥脹係數、被度之測定係以一般所習知之方法進行。 又，銀處理前後之吸光度變化量之測定係按照先前所述之 特開2000-226233號公報所記載之方法。 89823 15 - 1276^17 --- (wt%2—-— 實施例 比較例1 比較例2 Si〇7_^—— 61.90 71.75 58.1 ΑΐηΟχ^.一-- 3.16 1.81 6.65 Na2〇_-- 1.97 13.45 4.17 〆-^ K2〇^-—— 10.21 0.84 6.56 Mg〇_^- 6.93 3.99 1.96 Ca〇^^- 3.56 7.88 4.94 Sr〇____ 11.97 0.00 6.97 〆-〆 BaO____ 0.16 0.00 7.92 〆-〆 Ti〇2_^—— 0.020 0.000 0 ZrCV^-- 0.380 0.000 2.68 ¥en〇x^—— 0.094 0.016 0.103 S〇3^—-^— 0.180 0.193 0.11 --------- 軟化§__ 576 509 575 - ---- 熱膨脹—— 84 86 85 密度 2.64 2.49 2.78 ---- 光學鹼度 〆----- 0.58380298 0.57818547 0.6096982 如表1所示，本實施例之玻璃試料具有576°C之軟化點、84 xl(r7rC之熱膨脹係數及2.64X1 〇3 Kg/m3之密度。故，本實 施例之玻璃試料具有高軟化點，故其係作為FPD用基板使一用 ’熱收縮小，而且具有大的熱膨脹係數及低密度之優異 特十生、士、 〈玻璃。並且，光學鹼度抑制在0.60以下，故抑制由 的823 -16- 1276617 金屬Ag之膠體所造成之黃變之效果亦優異。 (比較例1、2) :匕較例1為典型之鹼石灰矽玻璃，為本發明之範圍外之玻 璃、且成根據此組成之玻璃之熱膨脹係數為86 χ 1〇-7/。〇， 雖在,發明之範圍内，但軟化點為5〇9°C，密度為2 49 χι〇3 Κ#’兩者均低於本發明之範圍。又，比較例2為現在市 面上流通之典型PDp基板用玻璃之玻璃組成。比較例〕之光 子鹼度超過〇·6〇，可知抑制由金屬Ag之膠體所造成之黃變 足效果不佳。又，密度亦高達2.78，在本發明之範圍外。 並且，關於銀處理後之銀之分佈，比較實施例與比較例工、 2。其結果，相較於比較例丨及2，實施例之助於發色之銀分 佈層之厚度薄。由此可知，實施例之基板用玻璃係抑制金 屬Ag之膠體在玻璃中擴散而黃變。 產業上之利用可能性 如以上詳述’根據本發明之]PPD基板用玻璃，含有以重 f /〇表示之未滿6%之Na2 0，具有未滿5 6 0〜5 8 0 °C之軟化點、 在50〜3 50°C之溫度範圍内之80〜95 X 10-7/t之熱膨脹係 數、2.7 X 1〇3 Kg/m3以下之密度，並且具有0.60以下之光學 鹼度’故於基板用玻璃上塗佈Ag糊，進行燒成並形成電極 之情況，可有效抑制金屬Ag之膠體擴散於基板用玻璃而黃 變’獲得熱收縮變小，而且化學耐久性優異之FPD基板用j皮 璃。 又，根據本發明之FPD基板用玻璃，基礎玻璃組成以重 量％表示，係由：55〜70%之Si02、0.2〜5%之A1203、0〜15% 89823 -17- 1276617 之MgO、2〜15%之CaO、0〜15%之Sr〇、10〜30%之Mg〇 + CaO+ Sr0 + Ba〇、0 〜5%之 Li2〇、0 〜6%之 Na2〇、0 〜15% 之匕20、5〜25%之Na20 + K20、換算成0.2〜2.5%之Zr〇2i 氧化锆、換算成0.1〜0.5%未滿之Fe203之全氧化鐵（T-Fe203) 及0〜5%之B203所組成，故耐熱衝擊性、耐裂性及成型性優 異，並且軟化點高，熱收縮性小，故可作為FPD基板使用。 又’根據本發明之FPD基板用玻璃，作為基礎玻璃組成， 實質上不含有B a〇，故可將玻璃密度抑制在2.7以下。 又’根據本發明之FPD基板，使用本發明之FPD基板用玻 璃’故熱收縮率變小，而且化學耐久性亦優異，故適於作 為PDP或FED等之FPD用途之玻璃基板。 89823Al2〇3 is a component which improves the durability of the glass. However, if the content exceeds 5%, it is difficult to dissolve the glass.适宜1〗 〇3 The appropriate range is 〇·2~. Β2〇3 is a knife used to improve the durability of the slab or as a dissolution aid. When the content of Β2〇3 exceeds 5%, the volatilization or the like causes inconvenience in molding, so the upper limit is 5%. The glass of the composition range of the present invention is preferably produced by a floating method. Usually, the clarifying agent is a sulfate of an alkali metal or an alkaline earth metal. At this time, the residue: the amount of s〇3 in the broken glass should be in the range of 〇"~〇"%. The glass composition of the substrate of the present invention has an average thermal expansion coefficient in the range of 5 〇 to 35 〇〇 c in the range of 8 〇 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 Or rupture. If the average coefficient of thermal expansion is less than 8〇xi〇-Vt or exceeds 95χ1〇·νι, it is difficult to integrate the surrounding material with the average (four) service factor. The composition for glass for a substrate of the present invention can be made vitrified by supplying a raw material to be a target composition to a melting furnace, and is made into a thickness by a floating method or the like 89823 - 14 - 1276617. Manufactured from transparent flat glass. The following is a description of the embodiments of the present invention. (Examples) ★ The glass material composed of the composition of Table 7 is supplied to the standard glass melting π, and the solution is t, and is formed into a plate shape by a floating method to produce the broken glass of the present embodiment. material. For this glass sample, the softening point, the average thermal expansion coefficient, the degree of the degree, the optical degree of the measurement, and the amount of change in the absorbance before and after the silver treatment were measured. The determination of the softening point, the average thermal swell coefficient, and the degree of the degree are carried out by a generally known method. Further, the amount of change in absorbance before and after the silver treatment is measured by the method described in JP-A-2000-226233. 89823 15 - 1276^17 --- (wt%2—-- Example Comparative Example 1 Comparative Example 2 Si〇7_^—— 61.90 71.75 58.1 ΑΐηΟχ^.一-- 3.16 1.81 6.65 Na2〇_-- 1.97 13.45 4.17 〆-^ K2〇^-—— 10.21 0.84 6.56 Mg〇_^- 6.93 3.99 1.96 Ca〇^^- 3.56 7.88 4.94 Sr〇____ 11.97 0.00 6.97 〆-〆BaO____ 0.16 0.00 7.92 〆-〆Ti〇2_^— — 0.020 0.000 0 ZrCV^-- 0.380 0.000 2.68 ¥en〇x^—— 0.094 0.016 0.103 S〇3^—-^— 0.180 0.193 0.11 --------- Softening §__ 576 509 575 - -- -- Thermal expansion - 84 86 85 Density 2.64 2.49 2.78 ---- Optical alkalinity 〆----- 0.58380298 0.57818547 0.6096982 As shown in Table 1, the glass sample of this example has a softening point of 576 ° C, 84 x l (The thermal expansion coefficient of r7rC and the density of 2.64X1 〇3 Kg/m3. Therefore, the glass sample of the present embodiment has a high softening point, so it is used as a substrate for FPD to have a small heat shrinkage and a large thermal expansion coefficient. And the low density of the excellent special ten, Shi, <glass. Moreover, the optical alkalinity is suppressed below 0.60, so the inhibition of the 823 -16-1276617 metal A The effect of yellowing caused by the gel of g is also excellent. (Comparative Examples 1 and 2): 匕 Comparative Example 1 is a typical soda lime bismuth glass, which is a glass outside the scope of the present invention and is made into a glass according to this composition. The coefficient of thermal expansion is 86 χ 1〇-7/. 〇, although within the scope of the invention, the softening point is 5〇9 ° C, and the density is 2 49 χι〇3 Κ#' both are lower than the scope of the present invention. Further, Comparative Example 2 is a glass composition of a glass for a typical PDp substrate which is currently on the market. The photon alkalinity of the comparative example is more than 〇·6〇, and it is understood that the effect of suppressing the yellowing caused by the colloid of the metal Ag is not good. Further, the density is also as high as 2.78, which is outside the scope of the present invention. Further, regarding the distribution of silver after silver treatment, comparative examples and comparative examples, 2, the results are compared with the comparative examples and 2, the examples It is understood that the thickness of the silver distribution layer of the coloring is thin, and it is understood that the glass for the substrate of the embodiment suppresses the diffusion of the colloid of the metal Ag in the glass and yellowing. The industrial use possibility is as described above. Inventive] Glass for PPD substrate, containing less than 6% expressed by weight f / 〇 Na2 0, having a softening point of less than 5 6 0 to 5 80 ° C, a thermal expansion coefficient of 80 to 95 X 10-7/t in a temperature range of 50 to 3 50 ° C, 2.7 X 1 〇 3 Kg /m3 or less density, and having an optical alkalinity of 0.60 or less. Therefore, when an Ag paste is applied onto a glass for a substrate and fired to form an electrode, the colloid of the metal Ag can be effectively prevented from diffusing on the glass for the substrate and yellowing. 'J glass for FPD substrates with low heat shrinkage and excellent chemical durability. Further, according to the glass for FPD board of the present invention, the base glass composition is expressed by weight %, which is: 55 to 70% of SiO 2 , 0.2 to 5% of A 1203, 0 to 15% of 89823 -17 to 1276617 of MgO, 2~ 15% CaO, 0~15% Sr〇, 10~30% Mg〇+ CaO+ Sr0 + Ba〇, 0~5% Li2〇, 0~6% Na2〇, 0~15%匕20 5 to 25% of Na20 + K20, converted to 0.2 to 2.5% of Zr〇2i zirconia, converted to 0.1 to 0.5% of Fe203 total iron oxide (T-Fe203) and 0 to 5% of B203 Since it has a composition, it is excellent in thermal shock resistance, crack resistance, and moldability, and has a high softening point and a small heat shrinkability, so it can be used as an FPD substrate. Further, the glass for an FPD substrate according to the present invention has a composition of a base glass and does not substantially contain B a , so that the glass density can be suppressed to 2.7 or less. In the FPD substrate of the present invention, the glass for FPD substrate of the present invention has a small heat shrinkage rate and excellent chemical durability. Therefore, it is suitable as a glass substrate for FPD applications such as PDP or FED. 89823