TW379332B

TW379332B - Load-free glass composition and thick film paste composition comprising the same

Info

Publication number: TW379332B
Application number: TW83105823A
Authority: TW
Inventors: Alan Frederick Carroll; Kenneth Warren Hang
Original assignee: Du Pont
Priority date: 1994-06-27
Filing date: 1994-06-27
Publication date: 2000-01-11

Description

經濟部中央標準局負工消費合作社印製 A7 _；_B7 五、發明説明（1 ) 太發明的相關領域 «» 本發明是有關經加熱過的窗子的應用上-比如汽車後玻璃窗除霧線（b a c k 1 i g h t d e f 〇 g g e r )，的厚膜膏組成物，尤其是和使用無鉛玻璃原料（frit)作黏合劑的這類組成物有關。本發明背景眘料傳統用以混合玻璃原料（其同時存在有低熔融、適當的膨脹性和耐用性，並可提升所需求濕滴特性）的方法包括使用硼矽酸鉛（比如那些在美國專利號碼3，2 5 8， 350、2，642，633 和 3，404，〇27 中說明的）或硼矽酸鋅系統（比如那些在美國專利號碼 3 ，873 ，330 和 3 ，25 8 ，350 中說明的）。然而，這些硼矽酸鉛系統中的主要成份是具有高毒性的氧化鉛。這個有毒的氧化鉛在處理時必須小心處理以避免攝入或吸入。爲增加這些以鉛爲主系統的耐用性而加入矽以防止鉛成份的酸性浸濾，但此舉使軟化溫度提高。然而，具有低熔融性、適當膨張性和耐用性且可提供良好濕潤性的無毒、無鉛玻璃原料系統在此技藝領域中尙未發現。一些鹼性硼矽玻璃有適度的低熔融性和存在有良好的濕潤性，但卻不耐用，並且它們具有非常高的膨脹性。其他的鹼性硼矽玻璃，比如那些商標名爲派萊克斯（Printed by the Central Standards Bureau, Ministry of Economic Affairs, Consumer Cooperatives A7 _; _B7 V. Description of the invention (1) Relevant fields of the invention «» The present invention relates to the application of heated windows-such as the defogging line of automobile rear glass windows (Back 1 ightdef ogger), thick film paste composition, especially related to this type of composition using lead-free glass raw material (frit) as a binder. BACKGROUND OF THE INVENTION Conventional methods for mixing glass raw materials (which also have low melting, proper swelling and durability, and can improve the required wet-drop characteristics) include the use of lead borosilicate (such as those in the US patent Nos. 3, 2 5 8, 350, 2,642, 633, and 3,404, 027) or zinc borosilicate systems (such as those in US Patent Nos. 3,873,330 and 3,25 8,350) As explained). However, the main component in these lead borosilicate systems is lead oxide, which is highly toxic. This toxic lead oxide must be handled with care to avoid ingestion or inhalation. To increase the durability of these lead-based systems, silicon was added to prevent acidic leaching of lead components, but this increased the softening temperature. However, a non-toxic, lead-free glass raw material system that has low melting properties, proper expansion and durability, and provides good wetting properties has not been found in this technical field. Some alkaline borosilicate glasses have moderately low melting and good wetting properties, but they are not durable, and they have very high swelling properties. Other alkaline borosilicate glass, such as those under the trade name Plexex (

Py rex’ 康寧玻璃廠（Corning Glass Works))及奇美克斯（Kima.x，歐文—伊利諾公司（〇wens_iiiin〇is,inc. 私紙張尺度適用中國國家標準（CNS > A4規格（210X297公釐 (請先閲讀背面之注意事項再填寫本頁)Py rex 'Corning Glass Works and Kima.x, Irvine-Illinois (〇wens_iiiin〇is, inc.) Private paper standards are applicable to Chinese national standards (CNS > A4 specifications (210X297) (Please read the notes on the back before filling this page)

、1T 4 A7 B7 五、發明説明（2 ) ))者，是耐用且低膨脹性的玻璃，但它們爲高熔融性。然而，這類硼矽酸鹽摻合物的混合或使用並不會生成具有所需求低熔融性、適度膨脹性和適度耐用性的玻璃原料。像美國專利3，1 1 3，8 7 8說明的硼矽酸鋅可提供適度的耐用性和適度的膨脹性；然而，這類系統不會生成令人滿意的低熔融玻璃原料》鹼性磷酸鹽玻璃或砷-硒-碲 -銻玻璃可提供適度的低熔融性，但它們的耐用性很差以致在中等溫度時即會溶解於水。雖然鹼性磷酸氟玻璃的耐用性有顯著改善，這些低熔融玻璃的潤濕性很差。經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 由 Francel 在美國 4，5 5 4，.2' 5 8 和Rei_nherz 在美國4，8 9 2，8 4 7中說明之以S i 0 2 — B i 20 3 - B2〇 3化學爲主的耐化學品、無鉛玻璃原料被用作裝飾性琺瑯和釉彩。Fracel建議的S i 〇2-B i203 — B2〇3組成物含有2 9-3 8重量％的已i 02、4 8-57 重量i203、3-8 重量％的8203、約 2 — 8重量％的鹼金屬氧化物和最高9重量％的鹼土族氧化物。Reinherz另外建議的S i 02_B i 203_B203玻璃原料混合物含有25-35重量％的3 i 02、25-45 重量％的8 i2〇.3、10-25重量％的8203，並加入 4—19重量％的鹼金屬氧化物和0. 3—8重量％的 Z r 02+T i 02來改質。這些玻璃組成物和先前發明所用黏合劑不同的地方在先前技術的組成物含有顯著較高的矽含量和較低的鉍氧化物含量，因此無法提供高度充填導體組成物所需的良好濕潤性和流動性的適當組合。本紙張尺度通用中國國家標準（CNS ) A4規格（210X297公釐）經濟部中央標準局員工消費合作社印製 A7 ' ____B7_ 五、發明説明（3 )1T 4 A7 B7 5. Invention description (2))) are durable and low-expansion glass, but they are highly meltable. However, the mixing or use of such borosilicate blends does not produce glass raw materials with the required low melting, moderate swelling, and moderate durability. Zinc borosilicate as described in U.S. Patent 3, 1 1 3, 8 7 8 provides moderate durability and moderate swelling; however, such systems do not produce satisfactory low-melt glass raw materials. Salt glass or arsenic-selenium-tellurium-antimony glass can provide moderately low melting, but they have poor durability so that they dissolve in water at moderate temperatures. Although the durability of alkaline fluorophosphate glass has improved significantly, the wettability of these low-melting glasses is poor. Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) by Francel in the United States 4, 5 5 4, .2 '5 8 and Rei_nherz in the United States 4, 8 9 2, 8 4 The chemical-resistant, lead-free glass raw materials mainly based on S i 0 2 — B i 20 3-B 2 03 chemistry described in 7 are used as decorative enamels and glazes. Fracel's S i 02-B i203 — B203 composition contains 2 9-3 8% by weight of i 02, 4 8-57% by weight i203, 3-8% by weight 8203, and about 2-8% by weight Of alkali metal oxides and up to 9% by weight of alkaline earth oxides. Reinherz also suggested that S i 02_B i 203_B203 glass raw material mixture contains 25-35 wt% of 3 i 02, 25-45 wt% of 8 i20.3, 10-25 wt% of 8203, and 4-19 wt% is added. Alkali metal oxide and 0.3-8% by weight of Z r 02 + T i 02 to modify. These glass compositions differ from the adhesives used in previous inventions in that the compositions of the prior art contain significantly higher silicon content and lower bismuth oxide content, and therefore cannot provide the good wetting and The right combination of liquidity. The paper size is in accordance with the Chinese National Standard (CNS) A4 (210X297 mm). Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 '____B7_ V. Description of the invention (3)

Dumesni等人在美國2，9 4 2，9 9 2建議使用5 一 5 0%鹼金屬鉍一硼矽酸鹽玻璃原料和9 5 %至5 0% 三氧化二鉍的組合來作銀粒子的黏合劑，以形對高 T i 〇2介電容器本體有良好黏著性的可焊接複合物。這些玻璃原料混合物主要含有2至10重量％的鹼金屬氧化物，9至3 2重量％的已i 〇2、3 5至7 5重量％的_ B i2〇3、5至1 5重量％的82〇3，和0至3 5重量％的鎘氧化物。Dumesnil强調，對要得到商業上有用之黏合劑系統的玻璃原料而言，鹼金屬氧化物是很重要的。在先前技術說明的硼矽酸鉍玻璃原料中，需使用鹼金屬氧化物作改質劑（modifier)，而本發明可焊接導體的所需求效能標準是由經C a Ο、Ζ η Ο、和A 1 2〇3改質之較佳硼矽酸鉍玻璃原料混合物的優良濕潤性得到的。基於要從許多種含有玻璃原料的產品中減少或去除鉛及鎘的一貫努力，本發明的無鉛玻璃原料已顯示可用聆加熱玻璃應用的導電材料配方中，包括汽車後擋風玻璃的除霧線。除了供作先前技術中以鉛爲主玻璃原料之另一種化學選擇外，經加熱窗戶導體組成物的玻璃原料成份必須存在有幾個重要的性質，比如 1 )提供適當的基質黏度和濕潤性，以便灼燒時能在導體和玻璃基質間形成結合； 2 )在灼燒期間提供適當的金屬粉末黏度和濕潤性，以使粉末燒結形成存在有優良焊接可濕潤性的緊密導體： 3 )使在導體組成物與玻璃基質間的殘餘應力達到最本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐）_ 6 - 請先閱讀背面之注意事項'本頁) -裝· 訂 A7 B7 五、發明説明（4 ) 小，因此可使複合物結構對溫度循環的靈敏度減少。 (請先間讀背面之注意事項再填寫本頁) 本發明經加熱窗導體組成物不使用以鉛爲主的玻璃原料作黏合劑即達到所有上述優點。較佳的無鉛玻璃原料成份的組成物業已獲得證實，此外，它們還可在含水醋酸中提供改良之耐化學品性。另外，無鉛玻璃原料混合物成份的優良濕潤特性使它很適合來和另外存在有無鉛化學現象的耐用玻璃原料混合物-包括那些濕潤性較差者，摻合在 —來生成存在有優良效能和廣泛處理範圍的導體組成物。使用這些玻璃原料的導體組成物可在寬廣的灼燒溫度範圍內加以處理，並可一致地得到可接受的黏著性並提高對醋酸耐用性。本發明槪要就第一點來看，本發明是針對適用來在硬質基質上形成具導電性圖案的可網版印花的厚膜育組成物，它包含：經濟部中央標準局員工消費合作社印製 (a )無鉛玻璃組成物的精細切割粒子，其軟化點 l〇g(r?)在 400 — 650 °C 時=7. 6，其 1 〇g (?7)比黏度範圍從500°C的2至700°C的5 之間，並且主要由6 5 — 9 5重量％的8 i203、2 — 15重量％的31〇2、0. 1-9重量％的82〇3、〇 —5重量％的八12〇3、0-5重量％CaO、和0 — 20重量％的211 ◦所組成；和 (b)具導電性的粒子；所有的（a)和（b)都分布在（c)有機媒質中。本紙張尺度適用中國國家標準（CNS ) A4規格（210X2.97公釐） A7 ____ B7_ 五、發明説明（5 ) 第二點，本發明是針對在硬質基質上-比如汽車後玻璃窗，即後除霧線窗-含有無鉛玻璃組成物之可焊接導電膏狀物的應用。還有一點，本發明是針對無鉛玻璃組成物。本發明詳細說明製造廠商使用具導電性的除霧線配方來形成永久黏附在硬質基質上的電路格線，它可在電壓源供給能量時產生熱。用於經加熱窗戶電路導體材料所需的特定物理及化學功能包括導電度、良好的可焊接性、對玻璃和裝飾性琺瑯的黏著性、耐化學品性和在包括溫度和濕度等變化環境條件下的信賴度》應甩在汽車後玻璃窗除霧線領域的，還另外需要有吸引人的美容外觀特性，這對消費者而言是很重要的。一般來講，適用於經加熱窗子應用的導體組成物包括無機黏合劑和分布在有機媒質中之導電金屬粉末的精細切割粒子。經濟部中央標準局員工消費合作社印製 A . 無機黏合劑配方中的一個主要成份是無機玻璃原料的精細切割粒子。玻璃原料必須是用來黏結燒結的金屬粉末，如此在灼燒時玻璃原料的軟化點和黏度，以及其對金屬粉末和基質的濕潤特性就很重要了。玻璃原料混合物的粒子大小不是非常重要，適用於本發明之玻璃原料的平均粒子大小通常在約0.5至4. 5微米，較宜在約1至約3微米。黏合本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 8 - A7 B7 五、發明説明（6 ) 劑的量通常佔導體組成物（不包括有機媒質）約1至2 0 重量％，較宜爲約1至1 0重量％，更適宜爲約1至6重量％。一般將液體對固體表面的濕潤定義爲液一固介面間：'：的接觸角和液面在接觸點的正切（tangent)。接觸角越小，則存在有越好的濕涅性，和要使一定固體表面積完全濕潤所需的玻璃也較少。玻璃原料或玻璃原料混合物形成之用於經加熱窗戶應用上的厚膜導體所需求的灼燒溫度較宜爲5 8 0 — 6 8 0°C之間。對單一玻璃原料之表成 log (7?)的玻璃黏度，或玻璃原料混合物的容積計算 .平均1 〇g (7?)在680 °C時要小於4。此處的玻璃黏度單位爲泊（poise)。線性重量平均黏度，可大約在特定溫度（比如6 8 0 °C )時將個別產物之參考1 〇 g ( ?? )的個別玻璃原料成份的1 〇g (?7)比黏度和配方中全部玻璃原料的容積分率總和起來計算得之。經濟部中央標準局員工消費合作社印製要使厚膜導體和基質間的應力最小化則要視其熱膨脹性、個別的彈性模數和相對厚度而定。汽車玻璃的熱膨脹系數（TCE)約爲9x10 _e/ °C。和玻璃相較，銀金屬-導體組成物中較高的主要成份，有較高的T C E ( 1 7 . 5 X 1 〇 -.e/ °C )，但也具有比玻璃低很多的模數。爲了善用具有比玻璃低的彈性模數的金屬之優點，希望導體配方中使用實際上最低的玻璃黏合劑量，因此可使連結介面間的應力達到最小。存在有優良濕潤性的玻璃黏合劑使配方人員在維持優良的可焊接性和黏著性之餘，使所需的黏合劑量減到最少。本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 9 - A7 B7 五、發明説明（7 ) 用於經加熱汽車窗戶的先前技術導體是以含鉛的玻璃原料爲主。爲符合目前對毒性和環境考量而將鉛由玻璃組成物中拿掉，則限制了要在同時符合濕潤性、熱膨脹性、美觀（cosmetic)和效能的需求，而又要有適當低軟化及流動性的選擇。本發明有關一系列以B i 2 0 3、A 1 2 ◦ 3 、S i 〇2、CaO、ZnO、和B2〇3等成份爲主之玻璃未預期的傑出效能，它們全部都符合低毒性的要求。請先閱讀背面之注意事項2 裝 B . 具導電性功能的材料像金、銀、鉑、鈀、或其混合物的金屬粒子可用於本發明。金屬粉末或片狀粉末（flake)的粒子大小就本身而言並未受到技術有效性觀點的狹隘限制。然而，粒子大小的確影響到金屬的燒結特性，較大的粒子會比小粒子以較慢的速率來燒結。如技術上所熟知的，不同大小之粉末或片狀粉末的混合物可在灼燒時用來配合（tailor)導體配方的燒結特性。然而，金屬粒子的大小必須適合所應用的方法一通常是網版印花。因此金屬粒子的大小不可大於 20微半，並較宜不大於1〇微米。最小的粒子大小通常是約0 . 1微米。適用於汽車後玻璃窗除霧線之導體組成物的金靥較宜爲銀。大於1. 0微米之銀粒子可提供育狀物有較大的著色能力。因此，本發明組成物較宜含有5 0重量％之大於 1. 〇微米的銀粒子。銀通常是靥於高純度（9 9+%) 。然而在考量到圖案的電子需求也可使用較不純的材料。本紙張尺度適用中國國家標準（CMS ) A4規格（210 X 297公釐X 1 〇 - 訂經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（8 ) 組合物中銀的量通常在5 0 — 9 0重量％ —以膏爲基準（比如包括液態有機媒質），在灼燒後爲60—99重量％ 9 C 有機媒質經濟部中夬標準局員工消費合作社印袋 (請先聞讀背面之注意事項再填寫本頁) 具有電子功能材料的精細切割粒子和無機黏合劑通常是分布在有機媒質中來形成半液體的膏狀物，它可以所需求電路圖案來印花。有機媒質可以是任何適合的鈍態液體，以非含水鈍態液體較適宜，它可對固體和基質提供適當的濕潤性，在膏狀物中有相當穩定的分布，在可接受的網版使用期限下有良好的印花效能，乾燥薄膜的強度足以耐得住粗暴的處理，和良好的灼燒性質。可使用各式有機液體的任何一種，且在增稠劑、安定劑和/或其他常用添加劑存在與否都可使用。可使用之有機媒質的例子有醇類、這類醇類的酯類-包括醋酸酯和丙酸酯；萜烯（terpene )-比如松油、萜品醇等等；及樹脂溶液-前述樹脂比如聚甲基丙烯酸酯、聚乙烯吡咯烷酮、或乙基纖維素，前述樹脂係於如松.油和二甘醇-醋酸酯的丁醚之溶劑中。媒質中也可含有揮發性液體使印花至基質後可迅速的固定。有機媒質通常佔膏狀物5 — 50重量％。在此使用的較佳有機媒質是以包含乙基纖維素在萜品醇中（比值爲1: 9 )的增稠劑的組合，並結合以商標名爲丁基卡必醇（Carbitol)醋酸酯銷售之乙二醇醋酸酯的丁醚。具導電性音狀組成物可方便在三滾輪的碾磨機中製本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A7 B7 五、發明説明（9 ) 備。這些組成物的黏度較宜約爲30-1 OOP a · S — 在2 5 °C於一個Brookfield HBT黏度計中使用5號旋子（ (請先閲讀背面之注意事項再填寫本頁) spindle)以1 0 r pm來量測。所用增稠劑的量是以最終需求的配方黏度來決定，後者則是由系統的印刷需求來決定。經濟部中央標準局員工消費合作社印製可在燒結時促成較佳導體微結構形成的燒結抑制劑（ inhibitor )可選擇性地使用於本發明，當存在時，通常是在進行碾磨之前納入膏狀物。最多可加入1 %的燒結抑制劑來在灼燒循環中延滯金屬稠密祀速率，只要導體組成物的效能未被降解即可。在金屬粒子表面的精細分布耐火氧化物是用來抑制燒結，並可由將氧化物添加劑分布於有機媒質中，或較宜將可在灼燒時在原處分解形成精細分布之耐火氧化物的金屬樹脂酸鹽加入。導電金屬的較佳燒結抑制劑爲鍺（Rh)和釕（Ru)的氧化物，和那些以鍺和以釕爲主的化合物，它們在進行灼燒條件時會變化成金屬氧化物》這類材料可以是爲粒子形式，或是可溶解於有機媒質中的有機金屬化合物形式》以R u爲主之材料的例子包括Ru金屬，Ru02，以Ru爲主的燒綠石（Pyr-ochlore )化合物—比如釘酸船祕*和釘酸祕銅’ R u樹脂酸鹽及其混合物。適當的含有R h的材料包括R h金屬、Rh02、Rh2〇3，Rh樹脂酸鹽及其混合物。使用於本發明之特別適宜燒結添加劑材料爲R u 02’釕酸鉍銅和R h樹脂酸鹽。然而要知道的是.抑制劑也可呈導電金屬粒子上的塗膜形式存在。這類塗膜可藉將導電金靥粒本紙張尺度適用中國國家標準（〇奶）八4规格（210父297公釐）_12 A7 ___ 五、發明説明（10) (請先閱讀背面之注意事項再填寫本頁) 子分布在燒結抑制劑之金屬的樹脂酸鹽溶液中，從懸浮液中將大部份的液體移走’然後使粒子乾燥來形成氧化物塗膜。另一種選擇則是’如美國5，126，9 15所說明的可將耐火性金屬氧化物的薄層塗覆在精細切割的金屬粉末上，以便在玻璃原料組成物將耐火性氧化物溶解之前抑制金屬粉末的過早燒結。技術熟練人士所熟知之另外的選擇性成份包括表面活性劑、增稠劑和調節膏狀物流變性的流變性的流量劑（flow agent );在不使電阻率、可焊接性或黏著性降解下最多可加入5重量％的色料來增進顏色；著色劑包括那些Eust ice在美國4，446，059 中所建議的；玻璃原料和/或金屬氧化物，可在灼燒時將銀氧化成氧化銀而擴散至緊鄰的窗戶玻璃，接著沉澱成引入注意、可由玻璃目視的著色點（stain)。測試步驟 1.熱膨脹/介電變形點經濟部中央標準局員工消費合作社印製在一個工具鋼模中以雙向來壓製玻璃原料以製備矩形樣品棒。然後在足以使條棒完全實心化（densify )的溫度將該經壓製的樣品灼燒。將冷卻過的樣品置於An ter 1 1 2 1型膨脹計（An ter實驗室公司，匹茲堡，賓州）中’並以溫度爲函數量測熱膨脹表現，最高溫度測至樣品變形的溫度-即在樣品膨脹達最大而開始收縮（因爲玻璃流動）的溫度。該膨脹變形溫度大約相當於1og(7) 的玻璃黏度爲13至14時。本紙張尺度適用t國國家標準（CNS ) A4規格（210X297公釐） 13 - A7 B7 五、發明説明（η) 2 .玻璃黏度個別玻璃原料成份的黏度測定方法可藉著在整體玻璃樣品上使用平行板方法來進行》康寧C E L S實驗室服務中心（康寧，N Y )有提供收費量測》在此情形的黏度量測所牽涉到的平行板方法是原先由 G . J . Dienes和H.F. KlemmCJ.Appl. Phys·， 1 7 ( 6 )，第458頁，1946)提出。在該方法，於應力下將一丸狀的玻璃樣品置於兩塊平行的板子中間且與玻璃接觸。從頭到尾玻璃樣品會完全充滿陶瓷壓印滾輪（platen )之間的空間。壓印滾輪彼此接近的速率是在緩慢加熱和將樣品負載上去期間量測。黏度是以下列方程式計算Dumesni et al. In the United States 2,9 4, 2, 9 9 2 suggested the use of a combination of 5-50% alkali metal bismuth-borosilicate glass raw materials and 95-50% bismuth trioxide for silver particles. Adhesive, a solderable compound with good adhesion to the body of high T i 〇2 dielectric capacitors. These glass raw material mixtures mainly contain 2 to 10% by weight of alkali metal oxides, 9 to 32% by weight of i 02, 35 to 75% by weight of _B i203, 5 to 15% by weight 82.03, and 0 to 35% by weight of cadmium oxide. Dumesnil emphasized that alkali metal oxides are important for obtaining glass raw materials for commercially useful binder systems. In the bismuth borosilicate glass raw materials described in the prior art, it is necessary to use an alkali metal oxide as a modifier, and the required performance standard of the solderable conductor of the present invention is determined by C a 0, Z η 0, and A 1 2 03 modified better bismuth borosilicate glass raw material mixture is obtained by the excellent wetting property. Based on consistent efforts to reduce or remove lead and cadmium from many glass-containing products, the lead-free glass raw materials of the present invention have been shown to be useful in formulating conductive materials for heated glass applications, including defogging lines for automotive rear windshields. . In addition to being used as another chemical alternative for the lead-based glass raw material in the prior art, the glass raw material composition of the heated window conductor composition must have several important properties, such as 1) providing proper matrix viscosity and wettability, In order to form a bond between the conductor and the glass substrate during burning; 2) Provide proper viscosity and wettability of the metal powder during burning, so that the powder is sintered to form a compact conductor with excellent solder wettability: 3) Residual stress between the conductor composition and the glass substrate reaches the maximum paper size Applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) _ 6-Please read the precautions on the back first 'on this page)-Binding and ordering A7 B7 V. Invention description (4) is small, so the sensitivity of the composite structure to temperature cycling can be reduced. (Please read the precautions on the back before filling out this page.) The heated window conductor composition of the present invention achieves all the above advantages without using lead-based glass materials as the binder. The composition properties of the preferred lead-free glass raw material components have been proven. In addition, they provide improved chemical resistance in aqueous acetic acid. In addition, the excellent wetting characteristics of the ingredients of the lead-free glass raw material mixture make it very suitable to mix with other durable glass raw materials with lead-free chemical phenomenon-including those with poor wettability, blended in-to produce excellent performance and wide processing range. Conductor composition. Conductor compositions using these glass raw materials can be processed over a wide range of firing temperatures, and consistently achieve acceptable adhesion and improved durability to acetic acid. In view of the first point, the present invention is directed to a thick-film printable composition suitable for forming a screen-printable screen with a conductive pattern on a hard substrate. The composition includes: (A) Fine cut particles of lead-free glass composition, with a softening point of 10 g (r?) At 400-650 ° C = 7.6, and a specific viscosity of 10 g (? 7) ranging from 500 ° C Between 2 and 700 ° C, and mainly composed of 6 5-95% by weight of 8 i203, 2-15% by weight of 3102, 0.1-9% by weight of 8203, 0-5 It consists of 80% by weight of 0203, 0-5% by weight of CaO, and 0-20% by weight of 211; and (b) conductive particles; all of (a) and (b) are distributed in ( c) in organic media. This paper size applies the Chinese National Standard (CNS) A4 specification (210X2.97 mm) A7 ____ B7_ V. Description of the invention (5) The second point is that the invention is directed to a hard substrate-such as the rear glass window of a car, that is, the rear Defogging window-Application of solderable conductive paste containing lead-free glass composition. In addition, the present invention is directed to a lead-free glass composition. The invention is described in detail. Manufacturers use conductive defogging formulations to form circuit grids that are permanently adhered to a rigid substrate, which generates heat when a voltage source supplies energy. Specific physical and chemical functions required for heated window circuit conductor materials include electrical conductivity, good solderability, adhesion to glass and decorative enamel, chemical resistance, and changing environmental conditions including temperature and humidity "Under Reliability" should be thrown in the field of automobile rear glass window defogging lines, and it also needs attractive cosmetic appearance characteristics, which is very important for consumers. In general, conductor compositions suitable for heated window applications include inorganic binders and finely cut particles of conductive metal powder distributed in an organic medium. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A. Inorganic Adhesive A major ingredient in the formula is the finely cut particles of inorganic glass raw materials. The glass raw material must be used to bond the sintered metal powder, so the softening point and viscosity of the glass raw material and the wetting characteristics of the metal powder and the matrix are very important during burning. The particle size of the glass raw material mixture is not very important, and the average particle size of the glass raw material suitable for use in the present invention is usually about 0.5 to 4.5 microns, and more preferably about 1 to about 3 microns. The size of this paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) (please read the precautions on the back before filling this page) 8-A7 B7 V. Description of the invention (6) The amount of the agent usually accounts for the conductor composition (Excluding organic medium) about 1 to 20% by weight, more preferably about 1 to 10% by weight, and more preferably about 1 to 6% by weight. Wetting of a solid surface by a liquid is generally defined as the contact angle between the liquid-solid interface: ': and the tangent of the liquid surface at the contact point. The smaller the contact angle, the better the wetness and the less glass required to completely wet a certain solid surface area. The igniting temperature required for thick glass conductors made of glass raw materials or glass raw material mixtures for heated window applications is preferably between 580 and 680 ° C. Calculate the glass viscosity of log (7?) For a single glass raw material, or the volume of the glass raw material mixture. The average 10g (7?) Is less than 4 at 680 ° C. The unit of glass viscosity here is poise. Linear weight average viscosity, about 10g (? 7) specific viscosity and all in the formula can be referenced to 10g (??) of the individual glass raw materials at a specific temperature (such as 680 ° C) The volume fractions of the glass raw materials are calculated together. Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs To minimize the stress between the thick film conductor and the substrate depends on its thermal expansion properties, individual elastic modulus and relative thickness. The thermal expansion coefficient (TCE) of automotive glass is approximately 9x10 _e / ° C. Compared with glass, silver metal-conductor composition has a higher main component, higher T C E (17.5 X 1 0 -.e / ° C), but also has a much lower modulus than glass. In order to make the best use of metals with a lower modulus of elasticity than glass, it is desirable to use the practically lowest glass bonding amount in the conductor formulation, so that the stress between the connection interfaces can be minimized. The presence of glass adhesives with excellent wettability allows formulators to maintain excellent weldability and adhesion while minimizing the amount of adhesive required. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the notes on the back before filling out this page) 9-A7 B7 V. Description of the invention (7) Previous technology for heated car windows The conductor is mainly glass material containing lead. The removal of lead from glass compositions in order to comply with current toxicity and environmental considerations limits the need to meet the requirements of wettability, thermal expansion, aesthetics, and performance at the same time, while having a suitably low softening and flow Sexual choice. The present invention relates to a series of glass based on B i 2 0 3, A 1 2 ◦ 3, Si 02, CaO, ZnO, and B2O3, all of which have outstanding unexpected performance. All of them meet the requirements of low toxicity. Claim. Please read the Note 2 on the back side first. B. Materials with conductive functions. Metal particles such as gold, silver, platinum, palladium, or mixtures thereof can be used in the present invention. The particle size of metal powders or flakes is not itself narrowly limited by the point of view of technical effectiveness. However, the particle size does affect the sintering characteristics of the metal, and larger particles sinter at a slower rate than smaller particles. As is well known in the art, mixtures of powders or flakes of different sizes can be used to tailor the sintering characteristics of conductor formulations during firing. However, the size of the metal particles must be suitable for the method to be applied. One is usually screen printing. Therefore, the size of the metal particles should not be more than 20 micrometers, and more preferably not more than 10 micrometers. The smallest particle size is usually about 0.1 microns. The gold tin which is suitable for the conductor composition of the defog line of the rear glass window of the automobile is more preferably silver. Silver particles larger than 1.0 micron can provide a greater coloring ability for the brooder. Therefore, the composition of the present invention preferably contains 50% by weight of silver particles larger than 1.0 micron. Silver is usually of high purity (99 +%). However, in consideration of the electronic requirements of the pattern, less pure materials can also be used. This paper size is applicable to Chinese National Standard (CMS) A4 (210 X 297 mm X 1 0-Ordered by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs and printed by A7 B7. V. Description of the invention (8) The amount of silver in the composition is usually within 5 0 — 9 0% by weight — based on paste (for example, including liquid organic media), 60-99% by weight after burning 9 C Organic Consumers Bureau of the Ministry of Economic Affairs, China Standards Bureau Consumer Consumption Printing Bag (Please read the back first (Please note before filling out this page) Fine-cut particles and inorganic binders with electronic functional materials are usually distributed in organic media to form a semi-liquid paste, which can be printed with the required circuit pattern. Organic media can be any Suitable passive liquid, non-aqueous passive liquid is more suitable. It can provide proper wetting to solids and substrates, has a fairly stable distribution in the paste, and has good performance under acceptable screen life. Printing efficiency, the strength of the dry film is enough to withstand rough processing, and good burning properties. Any of a variety of organic liquids can be used, and in thickeners, Tackifiers and / or other commonly used additives can be used with or without. Examples of organic media that can be used are alcohols, esters of such alcohols-including acetates and propionates; terpene-such as pine Oil, terpineol, etc .; and resin solutions-the aforementioned resins such as polymethacrylate, polyvinylpyrrolidone, or ethyl cellulose, the aforementioned resins are based on butyl ether such as pine oil and diethylene glycol-acetate Solvents. The medium may also contain volatile liquids, which can be quickly fixed after printing to the substrate. Organic media usually accounts for 5-50% by weight of the paste. The preferred organic media used here is containing ethyl cellulose in A combination of thickeners in terpineol (ratio of 1: 9) combined with butyl ether of ethylene glycol acetate sold under the trade name Carbitol Acetate. Conductive tone The composition can be easily produced in a three-roller mill. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of the invention (9). The viscosity of these compositions is preferably about 30 -1 OOP a · S — at 2 5 ° C in a Bro The okfield HBT viscometer uses a No. 5 spindle ((Please read the precautions on the back before filling this page) spindle) to measure at 10 r pm. The amount of thickener used is determined by the final required formula viscosity, The latter is determined by the printing requirements of the system. The Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs prints a sintering inhibitor that can promote the formation of better conductor microstructures during sintering and can be selectively used in the present invention. In general, the paste is incorporated before milling. A sintering inhibitor of up to 1% can be added to delay the metal dense rate during the firing cycle, as long as the effectiveness of the conductor composition is not degraded. The finely distributed refractory oxide on the surface of the metal particles is used to suppress sintering, and the oxide additive can be distributed in the organic medium, or it is more suitable to dissolve in situ during firing to form a finely distributed refractory oxide. The acid salt was added. The preferred sintering inhibitors for conductive metals are germanium (Rh) and ruthenium (Ru) oxides, and those compounds mainly composed of germanium and ruthenium, which change to metal oxides when subjected to burning conditions. " The material can be in the form of particles, or in the form of an organometallic compound that can be dissolved in an organic medium. Examples of Ru-based materials include Ru metal, Ru02, and Ru-based pyrochlore (Pyr-ochlore) compounds -Such as Naphthenate Shipper * and Naphthenate Copper 'R u resinate and mixtures thereof. Suitable Rh-containing materials include Rh metals, Rh02, Rh203, Rh resinates, and mixtures thereof. Particularly suitable sintering additive materials for use in the present invention are Ru 02 'bismuth ruthenate copper and Rh resinate. It is to be understood, however, that the inhibitor may also be in the form of a coating film on conductive metal particles. This type of coating can be made by applying the conductive gold particles to the Chinese paper standard (〇奶) 8 4 specifications (210 father 297 mm) _12 A7 ___ V. Description of the invention (10) (Please read the precautions on the back first Fill in this page again) The particles are distributed in the resinate solution of the metal of the sintering inhibitor, most of the liquid is removed from the suspension ', and then the particles are dried to form an oxide coating film. Another option is' could apply a thin layer of refractory metal oxide to finely cut metal powder as described in U.S. 5,126,9 15 so that the refractory oxide can be dissolved before the glass raw material composition dissolves the refractory oxide. Suppresses premature sintering of metal powder. Other optional ingredients well known to those skilled in the art include surfactants, thickeners, and flow agents that adjust the flow properties of the paste; without degrading resistivity, weldability, or adhesion Colorants can be added up to 5% by weight to enhance color; colorants include those suggested by Eust ice in US 4,446,059; glass raw materials and / or metal oxides that can oxidize silver to oxidize when burned The silver diffuses into the adjacent window glass and then precipitates into stains that attract attention and can be seen by the glass. Test Procedure 1. Thermal Expansion / Dielectric Deformation Point Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Press the glass material in two directions in a tool steel mold to prepare rectangular sample rods. The pressed sample was then burned at a temperature sufficient to fully densify the rod. The cooled sample was placed in an Anter 1 1 2 1 dilatometer (An ter Laboratories, Pittsburgh, Pennsylvania) and the thermal expansion performance was measured as a function of temperature. The highest temperature was the temperature at which the sample deformed-ie The temperature at which the sample expands to its maximum and begins to shrink (because of glass flow). This swelling deformation temperature is approximately equivalent to 1og (7) when the viscosity of the glass is 13 to 14. This paper size is applicable to the national standard (CNS) A4 specification (210X297 mm) 13-A7 B7 V. Description of the invention (η) 2. The method for measuring the viscosity of individual glass raw materials can be used on the whole glass sample The parallel plate method is used. "The Corning CELS Laboratory Service Center (Corning, NY) provides a charge measurement." The parallel plate method involved in the viscosity measurement in this case was originally by G. J. Dienes and HF KlemmCJ. Phys., 17 (6), p. 458, 1946). In this method, a pill-shaped glass sample is placed between two parallel plates under contact with the glass under stress. From beginning to end the glass sample will completely fill the space between the ceramic platen. The rate at which the embossing rollers approach each other is measured during slow heating and loading of the sample. Viscosity is calculated by the following equation

V -(2h3Mg)//(3^ra4(dh/d 請先閱讀之注事V-(2h3Mg) // (3 ^ ra4 (dh / d Please read the notes before reading

ί 訂其中經濟部中央標隼局員工消費合作社印製 η h Μ g 黏度（泊）壓印滾輪間的距離（公尺）質量（公斤）重力加速度（9. 8 0米/秒壓印板半徑（米） t —時間（秒）所用樣品通常製成直徑6 mm和厚1 m_m_。在末端具有平坦經碾壓表面之直徑6 · 3 5 mm和長4 一 7 mm的本紙張尺度適用中國國家標準（€阳）八4規格(_210父297公釐） -14 - A7 B7 經濟部中央揉準局貝工消費合作社印製 .一 a 9 五、發明説明（12 ) 陶瓷棒可用作玻璃樣品的接觸壓印滾輪。在不會限制垂直移動下，使用一個外部金屬夾子來支撑條棒。將樣品*** 在爐子裡的兩個壓印滾輪中間，同時可改變溫度和負重以量測對變形速率的效應。然而，這個技術的有效量測範圍在5 — 10的1 〇g (77)，由該量測衍生出來的數據可用指數曲線以外插得到較高或較低的値。可根據H.E.Hagy (』.及!11.〇61'.5〇(：.,46(2),第9 3頁，1 9 6 3 )說明的束臀曲方法（Beam Bending Method)，在淬火和應變點一即log(7)分別=13. 5和14. 5，時在5- 1 0 °C範圍內來驗證量測結果。也可使用旋轉圓筒方法來確定黏度外插値1 og (?/) = 3或較低値。根據 ASTM纖維拉長方法C 3 3 8 — 5 7得到的纖維軟化溫度相當於log (π)=7. 6。 3 ·粒子大小，表面積和輕敲密度（tap density) 使用配備有Leeds及Northrup公司（聖匹兹堡， F L )製造之先進電腦控制儀的Microtrac® 7 9 9 8型粒子大小分析儀來量測粒子大小。表面積在Micrometries Flowsorb 11-2300氣體吸附設備上利用B E T方法來量測。在氣體吸附測量之前，於通乾燥N2流下，將樣品加熱至高溫一定時間以使材料適合量測下以使脫氣（使用Desorb 2 3 0 0 A元件）。粉末的表觀容積是在輕敲粉末使其緊密後以置筒量測。輕敲密度（T D )'的計算是將粉末的表觀.容積除以其相對應的重量。本紙張尺度適用中國國家榣準（CNS ) A4規格（210X 297公釐]L 15 - "ί Order which is printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs η h Μ g Viscosity (poise) Distance between embossing rollers (meters) Mass (kg) (M) t — time (seconds) The samples used are usually made with a diameter of 6 mm and a thickness of 1 m_m_. The diameter of the flat rolled surface at the end is 6 · 3 5 mm and the length of 4-7 mm is suitable for the country of China. Standard (€ yang) 8 4 specifications (_210 father 297 mm) -14-A7 B7 Printed by the Central Government Bureau of the Ministry of Economic Affairs, Printed by the Shellfish Consumer Cooperative. 1a 9 V. Invention Description (12) Ceramic rods can be used as glass samples The contact embossing roller. Without limiting the vertical movement, use an external metal clip to support the bar. Insert the sample between the two embossing rollers in the furnace, while changing the temperature and load to measure the rate of deformation However, the effective measurement range of this technique is 10-10 g (77) from 5 to 10, and the data derived from this measurement can be extrapolated to obtain higher or lower radon from the exponential curve. According to HEHagy (』. And! 11.〇61'.5〇 ( ., 46 (2), page 93, 1 9 6 3) Beam Bending Method, log (7) = 13.5 and 14.5 after quenching and strain point, respectively, The measurement results are verified in the range of 5 to 10 ° C. The rotating cylinder method can also be used to determine the viscosity extrapolation 値 1 og (? /) = 3 or lower 値. According to ASTM fiber elongation method C 3 The softening temperature of the fiber obtained from 3 8 — 5 7 is equivalent to log (π) = 7.6. 3. Particle size, surface area and tap density are manufactured by Leeds and Northrup (St. Pittsburgh, FL). Advanced computer-controlled Microtrac® 7 9 9 8 particle size analyzer to measure particle size. Surface area was measured using the BET method on a Micrometries Flowsorb 11-2300 gas adsorption device. Before gas adsorption measurement, dry the N2 in Tongtong Flow down, heat the sample to high temperature for a certain period of time to make the material suitable for measurement to degas (using a Desorb 2 3 0 0 A element). The apparent volume of the powder is measured by tapping the powder to make it compact. The tap density (TD) 'is calculated by dividing the apparent apparent volume of the powder by its corresponding Weight. This paper size applies to China National Standard (CNS) A4 (210X 297mm) L 15-"

(請先閲讀背面之注意事項V -裝— A本頁) 訂 Λ A7 B7_______ 五、發明説明（13 ) 4 .電阻使用惠普（Hewlett Packard) 3 4 7 8.A (電錶）來量測經灼燒之銀導體絲的電阻。導體厚度是使用Dektak 3 0 3 0表面剖面計（profilometer)的量測。薄片電阻 (單位爲歐姆/方形（ohms per square))的計算是將電阻除以印花圖案上的方形數目。該方形數目爲4 8 6 mm/0.76mm=640方形。 5 .黏著性 , 令7 0/2 7/3Pb/Sn/Ag焊錫合金流回到一在3/16英时厚玻璃底質上的經灼燒銀導體上以將銅夾子焊上。使用丨nstron A2-14 0型張力試驗儀來量測夾子對銀的黏著性。黏著度較宜大於4 0磅。在將熔焊過的測試結構曝露於8 5 °C / 8 5 %RH環境中一週後量測老化的黏著性。經濟部中央標準局員工消費合作社印製 6.在基質上灼燒之導體育狀物的耐酸性將灼燒過的導體樣品置於含有約5 0 0m 1之4%醋酸溶液的瓶中，如此一半的電路圖案會浸漬在溶液中，另外一半則仍留在液面上的空氣中。在曝露1分鐘後，將樣品移出，以去離子水流沖洗並用紙巾擦乾。在模擬日光的高强度光源照射下，以目視來觀察樣品，要注意有浸潰於酸中的樣品區域相對未浸潰樣品區域的銀點顏色（經由玻本紙張尺度適用中國國家標準（CNS)A4規格（210Χ297公釐）_ 16 - 五、發明説明（w) 璃基質來目視電鍍圖案）是否有任何差異。根據以下標準來評分： 5 =沒有差異（具耐酸性） 3 =中等差異 1 =大差異（強烈對比）再將樣品前次浸漬於酸溶液相同一半的電路圖案浸漬於酸溶液中另外4分鐘。然後將樣品移開，以去離子水沖洗、乾燥和使用刮刀來刮表面以作耐酸性測試。刮的動作是從未浸漬到酸液之樣品區域中蘭始，並持續至已浸漬到醋酸溶液中的區域。耐酸性是由目視兩個區域之間的刮痕結果差異，並根據以下標準來評估：等級5 =無差異（耐酸的） 3=中等差異（刮痕變大） 1=大差異（材料很輕易移走）實施例1 經濟部中央標準局員工消費合作社印製 {請先聞讀背面之注意事項再填寫本頁) 製備一系列玻璃組成物並加以試測以說明本發明，如表1所示。用來製備玻璃批的原料爲鉍氧化物，B i 2〇3 ，銘氧化物’ A 1 2〇3，鲜氧化物，Ζ Π〇，玻璃（·yitr'* eous)矽，S i 02;和硼酐，B2〇3。稱重批原料，混合後置入白金合金坩堝（crucible)。將含有批混合物坩渦***控制在1 1 0 0°C的髙溫爐中。玻璃在3 〇分鐘的溶融後進行淬火（quench)。玻璃是在具有窄空隙（1〇本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ A7 ______B7__；_ 五、發明説明（is) —2 5m i 1)的同向（contra)旋轉金屬滾輪間進行淬火。然後在球磨機中，於水中將玻璃原料片碾磨成平均粒子大小約爲3微米》在經由美國標準1 〇〇網眼網版來從碾磨機中將碾磨過的玻璃原料淤漿釋出，玻璃原料粉末在 1 5 0 C供箱乾燥。對樣品D和E進行另外的Swec.o碼磨以得到平均粒子大小約爲1微米的玻璃原料。對經碾磨的玻璃粉末測試安定性（沒有相分離或結晶）。對各個玻璃進行熱膨脹性質測試》 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製本紙張尺度適用中國國家標隼（CNS ) ΑΛ規格（210X297公釐） ~ 18 - 五、發明説明（！6) 表1 A B C D E Βι·2〇3 75.1 wt% 75.1 wt% 73.0 wt% 72.46 wt% 69.81 wt% Al2〇3 0.9 wt% 1.8 wt% 2.0 wt% 2.02 wt% 2.13 wt% CaO 2.5 wt% 1.0 wt% 0,5 wt% 0.5 wt% 0.53 wt% ZnO 10.0 Wt% 10.0 wt% 10.0 wt% 10.32 wt% 12.03 wt% Si02 10.0 wt% 10.0 wt% 7.0 wt% 6.75 wt% 7.11 wt% b2〇3 1.5 wt% 2.1 wt% 7.5 wt% 7.95 wt% 8.38 wt% 膨脹變形點 478〇C 471 °C 450〇C 453〇C 452〇C 7^£@稀0卩(1/0)><106 10.04 10.48 11.7 10.5 8.4 TCE@RT-400*C(1/C)x106 f.U tit 經濟部中央標準局員工消費合作社印製(Please read the precautions on the back V-mount — A page first) Order Λ A7 B7_______ V. Description of the invention (13) 4. The resistance is measured by Hewlett Packard 3 4 7 8.A (electric meter) Resistance of burnt silver conductor wire. Conductor thickness is measured using a Dektak 3 0 3 0 profilometer. The sheet resistance (in ohms per square) is calculated by dividing the resistance by the number of squares on the printed pattern. The number of squares is 4 8 6 mm / 0.76mm = 640 squares. 5. Adhesiveness, allowing 7 0/2 7 / 3Pb / Sn / Ag solder alloy to flow back to a burnt silver conductor on a 3/16 inch thick glass substrate to solder the copper clip. Use the nstron A2-14 0 tensile tester to measure the adhesiveness of the clip to silver. The adhesion is preferably greater than 40 pounds. Measure the aged adhesion after exposing the welded test structure to 85 ° C / 85% RH for one week. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 6. Acid resistance of the conductors burned on the substrate Place the burned conductor samples in a bottle containing a 4% acetic acid solution of about 500m 1 Half of the circuit pattern is immersed in the solution, and the other half remains in the air on the surface. After 1 minute of exposure, the sample was removed, rinsed with a stream of deionized water and wiped dry with a paper towel. Observe the sample visually under the illumination of a high-intensity light source that simulates daylight. Pay attention to the silver dot color of the sample area immersed in the acid relative to the non-impregnated sample area (the Chinese national standard (CNS) applies to the paper size) A4 specification (210 × 297mm) _ 16-V. Description of the invention (w) Whether there is any difference in the electroplating pattern on the glass substrate). Scoring according to the following criteria: 5 = no difference (with acid resistance) 3 = medium difference 1 = large difference (strong contrast) The sample was immersed in the same half of the circuit pattern of the acid solution for another 4 minutes. The sample was then removed, rinsed with deionized water, dried and scraped with a spatula for acid resistance testing. The scraping action starts from the area of the sample that has never been immersed in the acid solution, and continues to the area that has been immersed in the acetic acid solution. Acid resistance is determined by visually examining the difference in scratch results between the two areas, and is evaluated according to the following criteria: Level 5 = No difference (acid-resistant) 3 = Medium difference (scratch becomes larger) 1 = Large difference (material is easy (Removed) Example 1 Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs {Please read the notes on the back before filling out this page) A series of glass compositions were prepared and tested to illustrate the invention, as shown in Table 1. . The raw materials used to prepare the glass batch are bismuth oxide, B i 2 0 3, Ming oxide 'A 1 2 0 3, fresh oxide, Z Π〇, glass (· yitr' * eous) silicon, S i 02; And boric anhydride, B203. The batch of raw materials were weighed and mixed into a platinum crucible. The crucible containing the batch mixture was inserted into an autoclave furnace controlled at 110 ° C. The glass was quenched after 30 minutes of melting. The glass is in the same direction with a narrow gap (10 paper sizes applicable to Chinese National Standards (CNS) A4 specifications (210X297 mm) _ A7 ______B7__; _ 5. Description of the invention (is)-2 5m i 1) Quenching between rotating metal rollers. Then, in a ball mill, the glass raw material sheet was milled in water to an average particle size of about 3 microns. The milled glass raw material slurry was released from the mill through a US standard 100 mesh screen. The glass raw material powder was dried in a box at 150 ° C. Samples D and E were subjected to additional Swec.o yard milling to obtain glass raw materials having an average particle size of about 1 micron. The milled glass powder was tested for stability (no phase separation or crystallization). Test the thermal expansion properties of each glass "(Please read the precautions on the back before filling this page) Printed on the paper by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The paper size applies to the Chinese National Standard (CNS) ΑΛ size (210X297 mm) ~ 18-V. Description of the invention (! 6) Table 1 ABCDE Βι · 203 75.1 wt% 75.1 wt% 73.0 wt% 72.46 wt% 69.81 wt% Al2〇3 0.9 wt% 1.8 wt% 2.0 wt% 2.02 wt% 2.13 wt % CaO 2.5 wt% 1.0 wt% 0.5 wt% 0.5 wt% 0.53 wt% ZnO 10.0 Wt% 10.0 wt% 10.0 wt% 10.32 wt% 12.03 wt% Si02 10.0 wt% 10.0 wt% 7.0 wt% 6.75 wt% 7.11 wt % b2〇3 1.5 wt% 2.1 wt% 7.5 wt% 7.95 wt% 8.38 wt% Expansive deformation point 478 ° C 471 ° C 450 ° C 453 ° C 452 ° C 7 ^ £ @ 稀 0 卩 (1/0) > < 106 10.04 10.48 11.7 10.5 8.4 TCE @ RT-400 * C (1 / C) x106 fU tit Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐> _ 19 _ 經濟部中央榡準局貝工消費合作杜印製 A7 _____B7_ 五、發明説明（17〉市售無鉛鹼性磷酸氟玻璃原料Pemco 2 J 5 7 (Miles公司，巴爾地摩（Baltimore) ，MD )具有約3 8 0 °C的膨脹變形點，和一個在室溫及變形點間爲2 1 p pm /°C 的熱膨脹係數（TC E )。該玻璃原料是使用流體化床噴射磨子來碾磨，其中使玻璃粒子彼此相撞以降低尺寸大小，然後收集在旋風器（cyclone)中。所得經噴射碾磨之玻璃原料（標識成CF# 1 )的平均粒子大小約爲3微米 0 實施例2 玻璃耐用性的決定是將完全緊密的玻璃曝露於4 %醋酸中達1 5分鐘來量測其重量損失（表2 )。玻璃珠的製備是在可完全緊密化的溫度下使Q. 2至0. 4克的玻璃原料進行燒結。以鉛爲主之玻璃原料的耐用性會隨著鉛含量下降而獲得改善。LF# 1是一個硼矽鎘鉛玻璃原料， L F# 2是一個硼矽鉍鉛原料，而L F# 3是一個硼矽鋅鉛。由於本發明玻璃的低矽含量，它的耐用性出人意料之外〇 - 表2 玻璃 C D E LF#1 LF#2 LF#3 CF#1 %重量損失 0.42 0.35 0.13 22.88 8.88 0.33 0.00 本紙張尺度適用中國國家標準（CNS } A4規格（210 X 297公釐）_ 2(3 (請先間讀背面之注意事項本頁) 裝. 訂 A7 B7 五、發明説明（is) 實施例3 由玻璃E和C F # 1得到的玻璃黏度數據呈現在。使用這些黏度數據，可決定相當於10、7· 6、 4之log (7?)的溫度（表4)。根據這些數據，一個軟化點（1 〇 g ( ;? ) = 7 . 6 )低於 5 2 5 °C 1 〇 g ( π )之比黏度少於5的玻璃黏合劑以得到適玻璃流，以便在6 10至6 6 0°C的灼燒溫度中可增體的緊密化。對具有熱處理窗戶在5 8 0至6 8 0 °C 體而言，在6 1 0 °C的處理溫度時臨界黏度上下限在 log(J?)=2 和 4 之間。表3 識別 L〇g(黏度〉獅實 400 c 50CTC 600°C 650〇C 700。。玻癘E 8.7 4.0 2.9 2.2 CF#1 12.7 3.9 1.6 1.1 0.8 表4 識別酿(。⑽黏度 10 7.6 6 4 玻璃Ε 484 516 545 601 ' cm_ 418 440 460 498 經濟部中央標準局β;工消費合作社印製 3 和要和的導導良 3 瞽，螯售 (請先間讀背面之注意事項再填寫本頁) 然後將玻璃原料形成適用作經加熱窗戶除霧線應用中的銀導體組成物。在包括玻璃原料，銀粉，和燒結抑制劑（如果存在的話）的導體配方中混入乙基織維素在萜品醇中的有機媒質以使粉末濕潤，然後以壓碾方式使之分散。如有本紙張尺度適用中國國家標準（CNS)M規格（210x297公釐） 21 - A7 ______B7___ 五、發明説明（19) 需要，將育狀物調整至適當的印刷黏度。以下實施例之導體組成物所用銀粉的特性列在表5中。表5 {請先閲讀背面之注意事項再填寫本頁) 銀粉特性樣品形態 SA(m2/g) TD(g/ec) S1 不規則 0.2 至 0.4 1.5 至 3_0 S2 不規則 1.8 至 2.2 1.8 至 2.1 S3 片狀 0.6至 0.9 4.0 至 6.0 S4 球狀 0.5 至 0.7 4.0 至 5.0 以下製程是用來製備少量的導體測試電路以供下列實施例評估： 1.使用傳統網版一通常是1 5 6 — 1 9 5網眼聚酯類，將以溶劑爲主或UV可固化型的裝飾性琺瑯資狀物網版印花在平坦玻璃基質上。 2 .端視琺瑯種類而定，使印花琺瑯在1 5 0 °C乾燥 1 5分鐘或在1 . 2 J/cm2下進行UV固化。 3 .使用傳統網版一通常是1 9 5網眼，將銀的膏狀物網版印花在平坦玻璃基質的空氣一面或錫面，或印花在未灼燒的琺瑯上。其他像1 5 6和2 3 0的網眼也可獲得經濟部中央標隼局員工消費合作社印製同樣成功。 4.在一個帶式（be 1 t)爐組中將銀灼燒，或對銀和琺瑯一起灼燒來達到5 8 0至6 8 0 °C的最高玻璃表面溫度，並在5 0 0°C以下保持5分鐘。特定導體組成物的應用會隨其操作範圍增加而增加一即隨其灼燒窗的寬度變大而增加，灼燒窗定義爲得到可接受黏附性效能的變化灼燒溫度。希望玻璃基質和琺瑯的黏本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐）_ 2.2 _ A7 B7 五、發明説明（20 ) 附度要超過4 0 磅。部份組成物經證實適用於需要耐醋酸配體導· 銀的主爲料原璃玻1 ο 單的以現明呈說所 3 8 1 和至 7 4 、。例 6 中施表用實如應’ 的方 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製本紙張尺度適用中國國家標準（CNS ) A4規格（2丨OX2.?7公釐） 23 - A7 B7 經濟部中央標準局員工消費合作社印製五、發明説〖明（21 ) 表6 \ 實施例 4 5 6~~ 1 玻璃原料成份 LF#1 (%) 4.0 成份玻璃原料C (%) 4.0 成份玻璃原料D (%) 4.0 銀銀I 70.0 銀I 70.0 銀1 70.0 性質最高灼燒SSCC) 610 620 630 660 610 620 630 660 610 620 630 630 玻堪黏附性(lb) 57.5 54.5 52.0 54.0 47.5 49:0 71.5 67.8 49.3 59.0 68.0 82.3 琺瑯黏附性〇b) 67.0 66.3 61.0 43.8 65.5 64.0 35.5 26.0 73.0 73.0 50.5 24.0 会璃老化黏附性⑽ 57.3 66.5 57.3 灼mm度_ 12.3 12.4 .12.1 11.6 12.2 12.5 11.8 12.3 12.8 12.9 12.8 12.3 電阻(mil/sq) 4.2 4.2 4.1 4.0 4.4 4.3 4.3 4.2 4.1 4.1 4.1 4.0 比電阻(μΩ-cm) 5.1 5.2 5.0 4.6 5.4 5.4 5.1 5.1 5.2 5.3 5.2 4.9 耐酸性評比 5=優良在酸中1分鐘在酸中5分鐘 2 2 3 表6(接縝）實施例 7 8 玻璃原料成份 LF#1 (%) 4.0 成份玻璃原料C . (%) 4.0 銀銀I 70.0 銀1 84.0 性質最高灼燒舰(·<:) 610 620 630 660 610 620 630 660 玻璃黏附性(lb) 51.8 75.7 88.5 59.5 50.5 52.5 66.8 49.0 琺瑯黏附性(lb) 64.5 68.5 55.3 30.7 86.3 96.0 93.3 97.3 ( i i 玻璃老化黏附性(ib) 66.3 55.0 灼燒厚度_ 12.9 13.0 12.8 12.3 23.3 23.3 22.7 21.6 電阻(mQ/sq) 4.2 4.1 4.1 4.0 1.7 1.7 1.7 1.6 比電阻(μΩ-cm) 5.3 5.4 5.3 4.9 4.0 3.9 3.8 3.5 耐酸性評比 5=優良 1=差在酸中份鐘在酸中5分鐘 2 5 本紙張尺度適用中國國家標準（CNS)A4規格（21〇><29*7公釐> -24 - A7 -------B7___^_ 五、發明説明（22) 實施例4至7 (表6)使用4重量％平均粒子大小在 2. 5至3_ 0微米的玻璃原料和重量百分比的銀1 ’其中銀是4 8%粗粉末（S 1 )和2 2次微米粉末（ 5 2 )的摻合物。如表6所說明的’實施例4使用傳統的硼矽鉛玻璃原料’而實施例5、6和7則分別使用玻璃C 、D 和 E。實施例4說明以單一傳統硼矽酸玻璃原料爲主之用於經加熱汽車窗戶的傳統導體組成物的廣泛灼燒窗戶（ L F # 1 )。以本發明無鉛之玻璃廪料爲主的實施例5、 6和7也顯示類似的結果。和傳統硼矽酸鉛玻璃原料相比 (實施例4)，含有玻璃原料E的實施例7可產生可比擬或較高黏附結果。由各個情形可注意到，在琺瑯的黏附性在最高灼燒溫度（6 6 0 °C)會稍微降解。實施例4至7 的耐酸性是在低至平均的範圍內。和含有相同玻璃原料的實施例6相比*實施例8 (表經濟部中央標隼局員工消費合作社印裝 (請先閲讀背面之注意事項再填寫本頁) 6 )說明增加玻璃原料中銀含量的效應。實施例8含有8 4 %的銀I，其中銀是66%粗粉末（S1)和18%次微米粉末（S 2 )的摻合物。除了減少薄片電阻（sheet resistance)外，實施例8顯示類似的玻璃黏著性，除了在6 6 0 °C時；在琺瑯的較高黏附性；在琺班的較寬廣灼燒窗戶；和增加的耐酸性》本紙張尺度適用中國國家樣準（CNS ) A4規格（21〇Χ297公釐） 25 - Α7 Β7 五、發明説明（23〉表.This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) _ 19 _ Printed A7 by Shellfish Consumer Cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs _____B7_ V. Description of the invention (17) Commercially available lead-free alkaline Fluorophosphate glass raw material Pemco 2 J 5 7 (Miles, Baltimore, MD) has an expansion deformation point of about 3 0 0 ° C, and a temperature of 2 1 p pm / ° between room temperature and the deformation point. Thermal expansion coefficient (TC E) of C. The glass raw material is ground using a fluidized bed jet mill, in which glass particles are collided with each other to reduce the size, and then collected in a cyclone. The resulting jet mill is The average particle size of the ground glass material (labeled CF # 1) is about 3 microns. Example 2 The durability of the glass was determined by exposing the completely tight glass to 4% acetic acid for 15 minutes to measure its weight loss. (Table 2). Glass beads are prepared by sintering Q. 2 to 0.4 grams of glass raw materials at a temperature that can be fully compacted. The durability of lead-based glass raw materials will decrease as the lead content decreases. Improved. LF # 1 is a borosilicate cadmium lead glass Raw material, LF # 2 is a borosilicate bismuth lead material, and LF # 3 is a borosilicate zinc lead. Due to the low silicon content of the glass of the present invention, its durability is unexpected. 0-Table 2 Glass CDE LF # 1 LF # 2 LF # 3 CF # 1% weight loss 0.42 0.35 0.13 22.88 8.88 0.33 0.00 This paper size applies to Chinese national standards (CNS) A4 size (210 X 297 mm) _ 2 (3 (Please read the precautions on the back first) This page) Binding. Order A7 B7 V. Description of the invention (is) Example 3 The glass viscosity data obtained from glass E and CF # 1 are presented. Using these viscosity data, it can be determined that the equivalent of 10, 7, 6, 4 log (7?) temperature (Table 4). Based on these data, a softening point (10 g (;?) = 7.6) is less than 5 2 5 ° C and the specific viscosity of 10 g (π) is less than 5 glass adhesive to obtain a suitable glass flow, so that the compaction can be increased at a burning temperature of 6 10 to 6 60 ° C. For the body with a heat treated window at 5 8 0 to 6 8 0 ° C At the processing temperature of 6 1 0 ° C, the upper and lower limits of the critical viscosity are between log (J?) = 2 and 4. Table 3 Identification of L0g (viscosity> Lions 400 c 50CTC 600 ° C 650〇 C 700 ... Glass E 8.7 4.0 2.9 2.2 CF # 1 12.7 3.9 1.6 1.1 0.8 Table 4 Identification ⑽Viscosity 10 7.6 6 4 Glass E 484 516 545 601 'cm_ 418 440 460 498 Central Standards Bureau of the Ministry of Economic Affairs β; Printed by the Industrial and Commercial Cooperatives 3 and Guided by Guihe 3 瞽, chelated (please read the Note for refilling this page) The glass material is then formed into a silver conductor composition suitable for use in heated window defogging applications. An organic medium of ethyl oryzanol in terpineol is mixed in a conductive formulation including glass raw materials, silver powder, and sintering inhibitor (if present) to wet the powder and then dispersed by crushing. If this paper size applies the Chinese National Standard (CNS) M specification (210x297 mm) 21-A7 ______B7___ V. Description of the invention (19) If necessary, adjust the broth to a proper printing viscosity. The characteristics of the silver powder used in the conductor composition of the following examples are shown in Table 5. Table 5 (Please read the notes on the back before filling this page) Silver powder characteristics Sample form SA (m2 / g) TD (g / ec) S1 Irregular 0.2 to 0.4 1.5 to 3_0 S2 Irregular 1.8 to 2.2 1.8 to 2.1 S3 Sheet 0.6 to 0.9 4.0 to 6.0 S4 Spherical 0.5 to 0.7 4.0 to 5.0 The following process is used to prepare a small number of conductor test circuits for evaluation by the following examples: 1. Using traditional screens-usually 1 5 6 — 1 9 5 Mesh polyesters. Solvent-based or UV-curable decorative enamel materials are screen-printed on a flat glass substrate. 2. Depending on the type of enamel, the printed enamel is dried at 150 ° C for 15 minutes or UV-cured at 1.2 J / cm2. 3. Using a traditional screen, usually 195 mesh, print the silver paste screen on the air side or tin side of a flat glass substrate, or on unburned enamel. Other meshes like 156 and 230 can also be printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. 4. Burn the silver in a belt furnace (be 1 t), or burn the silver and enamel together to reach a maximum glass surface temperature of 5800 to 6800 ° C at 500 ° Hold below C for 5 minutes. The application of a particular conductor composition increases as its operating range increases, ie as the width of its burning window becomes larger. The burning window is defined as the change in burning temperature to achieve acceptable adhesive performance. It is hoped that the adhesion of the glass substrate and enamel will be in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) _ 2.2 _ A7 B7 V. Description of the invention (20) The degree of attachment shall exceed 40 pounds. Some of the compositions have been proven to be suitable for use with acetic acid-resistant ligands and silver. The main ingredients are glass 1 ο single, as shown in the present statement 3 8 1 and 7 4. The application method in Example 6 should be as it should be (please read the precautions on the back before filling this page). The paper size printed by the Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specifications (2 丨OX2.?7mm) 23-A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Inventory [21] Table 6 \ Example 4 5 6 ~~ 1 Glass raw material composition LF # 1 (%) 4.0 Composition glass raw material C (%) 4.0 Composition glass raw material D (%) 4.0 Silver Silver I 70.0 Silver I 70.0 Silver 1 70.0 Highest burning SSCC) 610 620 630 660 610 620 630 660 610 620 630 630 lb) 57.5 54.5 52.0 54.0 47.5 49: 0 71.5 67.8 49.3 59.0 68.0 82.3 enamel adhesion 〇b) 67.0 66.3 61.0 43.8 65.5 64.0 35.5 26.0 73.0 73.0 50.5 24.0 will ageing adhesive ⑽ 57.3 66.5 57.3 burn mm_ 12.3 12.4. 12.1 11.6 12.2 12.5 11.8 12.3 12.8 12.9 12.8 12.3 Resistance (mil / sq) 4.2 4.2 4.1 4.0 4.4 4.3 4.3 4.2 4.1 4.1 4.1 4.0 Specific resistance (μΩ-cm) 5.1 5.2 5.0 4.6 5.4 5.4 5.1 5.1 5.2 5.3 5.2 4.9 Acid resistance rating 5 = Excellent 1 minute in acid 5 minutes in acid 2 2 3 Table 6 (continued) Example 7 8 Glass raw material composition LF # 1 (%) 4.0 Ingredient glass raw material C. (%) 4.0 Silver Silver I 70.0 Silver 1 84.0 Properties Highest Burner (< :) 610 620 630 660 610 620 630 660 Glass adhesion (lb) 51.8 75.7 88.5 59.5 50.5 52.5 66.8 49.0 Enamel adhesion (lb) 64.5 68.5 55.3 30.7 86.3 96.0 93.3 97.3 (ii Glass aging Adhesion (ib) 66.3 55.0 Burning thickness_ 12.9 13.0 12.8 12.3 23.3 23.3 22.7 21.6 Resistance (mQ / sq) 4.2 4.1 4.1 4.0 1.7 1.7 1.7 1.6 Specific resistance (μΩ-cm) 5.3 5.4 5.3 4.9 4.0 3.9 3.8 3.5 Acid resistance Rating 5 = Excellent 1 = Poor in acid, 5 minutes in acid 2 5 This paper size applies Chinese National Standard (CNS) A4 specification (21〇 > < 29 * 7mm > -24-A7- ------ B7 ___ ^ _ V. Description of the invention (22) Examples 4 to 7 (Table 6) use 4% by weight of glass raw materials with an average particle size of 2.5 to 3_0 microns and weight percent of silver 1 ' Among them, silver is a blend of 48% coarse powder (S 1) and 22 times micron powder (5 2). As shown in Table 6, 'Example 4 uses conventional borosilicate lead glass raw materials' and Examples 5, 6 and 7 use glasses C, D and E, respectively. Example 4 illustrates a widely burned window (L F # 1) based on a single conventional borosilicate glass raw material for a conventional conductor composition for a heated automobile window. Examples 5, 6 and 7 based on the lead-free glass frit of the present invention also showed similar results. Compared with the conventional lead borosilicate glass raw material (Example 4), Example 7 containing glass raw material E can produce comparable or higher adhesion results. It can be noticed from each case that the adhesion to enamel is slightly degraded at the highest burning temperature (660 ° C). The acid resistance of Examples 4 to 7 is in a range from low to average. Compared with Example 6 containing the same glass raw material * Example 8 (printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) 6) effect. Example 8 contains 84% of silver I, where silver is a blend of 66% coarse powder (S1) and 18% submicron powder (S2). In addition to reducing sheet resistance, Example 8 shows similar glass adhesion except at 60 ° C; higher adhesion in enamel; wider burning window in enamel; and increased "Acid resistance" This paper size applies to China National Standard (CNS) A4 specification (21〇 × 297 mm) 25-Α7 Β7 V. Description of the invention (23> Table.

訂實施例 9 10 11 12 成份 (%) 成份 (%) 成份 (%) 成份 (%) 玻璃原料E 4.0 玻璃原料E 4.0 玻璃原料E 4.0 玻璃原料E 8.0 銀II 74.5 銀II 74.5 銀II 74.5 銀II 74.5 Rh樹脂酸st 0.2 Rh榭脂酸靂 0.4 Rh ^啦敌通 0.2 Ί -性質挪灼燒酿(*c) 580 640 670 580 640 670 580 640 670 580 640 670 -對玻璃黏附性(lb) 110.0 112.8 141.3 137.3 133.5 134.5 142.0 139.3 157.8 120.8 143.3 138.5 對聰黏附性(lb) 85.5 10.3 0 42.5 120.3 17.8 40.3 135.8 71.0 44.8 25.0 4.0 灼度(μπι) 11.4 10.0 9.9 14.0 12.7 11.7 15.6 14.2 12.6 16.0 14.1 13.7 電阻(mQ/sq) .8 2.5 2.4 4.0 3.4 3.1 5.1 4.2 3.7 3.2 2.8 2.5 比電阻(μΩ-cm) 3.2 2.5 2.4 5.5 4.3 3.6 7.9 6.0 4.7 5.1 3.9 3.4 耐離評比 5=優良仁差在酸中1分鐘 2 5 1 4.5 1 4.5 3.5 5 在酸中5分鐘 1 4 1 3.5 1 3.5 1 5 經濟部中央標準局員工消費合作社印製實施例9至1 2 (表7)說明其中玻璃原料的平均粒子大小在約1微米的單一玻璃原料成份。實施例9至12 所用的銀，銀II，是5 4. 3%銀片（S3)和20%次微米粉末（S2)的組合，它比實施例4至8所用的銀I 要更容易燒結，如比較實施例9 ( 7 4 . 5%銀II)和實施例5 (70%銀I)及實施例8 (84%銀）的比電阻 (resistivity).可看出。實施例9、10及1 1 (表7)說明加入購自Order example 9 10 11 12 Ingredient (%) Ingredient (%) Ingredient (%) Ingredient (%) Glass material E 4.0 Glass material E 4.0 Glass material E 4.0 Glass material E 8.0 Silver II 74.5 Silver II 74.5 Silver II 74.5 Silver II 74.5 Rh resin acid 0.2 Rh resin fatty acid 0.4 Rh ^ Laditong 0.2 Ί-properties of burning (* c) 580 640 670 580 640 670 580 640 670 580 640 670-adhesion to glass (lb) 110.0 112.8 141.3 137.3 133.5 134.5 142.0 139.3 157.8 120.8 143.3 138.5 Adhesion to Satoshi (lb) 85.5 10.3 0 42.5 120.3 17.8 40.3 135.8 71.0 44.8 25.0 4.0 Ignition (μπι) 11.4 10.0 9.9 14.0 12.7 11.7 15.6 14.2 12.6 16.0 14.1 13.7 Resistance (mQ / sq) .8 2.5 2.4 4.0 3.4 3.1 5.1 4.2 3.7 3.2 2.8 2.5 Specific resistance (μΩ-cm) 3.2 2.5 2.4 5.5 4.3 3.6 7.9 6.0 4.7 5.1 3.9 3.4 Isolation resistance ratio 5 = Excellent kernel difference in acid for 1 minute 2 5 1 4.5 1 4.5 3.5 5 5 minutes in acid 1 4 1 3.5 1 3.5 1 5 Examples 9 to 1 2 (Table 7) printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs show that the average particle size of the glass raw material is between Single component glass material 1 micron. The silver used in Examples 9 to 12, Silver II, is a combination of 54.3% silver flakes (S3) and 20% submicron powder (S2), which is easier to sinter than the silver I used in Examples 4 to 8. It can be seen, for example, that the specific resistances of Example 9 (7.4.5% silver II) and Example 5 (70% silver I) and Example 8 (84% silver) are compared. Examples 9, 10 and 1 1 (Table 7) illustrate the addition of

Engelhard公司（東內華克（East Newark) ，N J )之姥樹脂酸鹽#8866的燒結抑制劑可減少使用無鉛玻璃原料組成物之灼燒導體的密度，可由這系列組成物的導電度增加看出：實施例9 (無抑制劑），實施例1 0 ( 0 . 2 本紙張尺度適用中國國家標準（CNS ) Μ規格（210X297公釐）_ 26 A7 B7 五、發明説明（24) %鍺樹脂酸鹽）和實施例11 (〇· 4%鍺樹脂酸鹽）》實施例9 (無抑制劑）在6 4 Οΐ和6 7 0 °C灼燒時其對琺瑯的導體黏附性很差，然而加入燒結抑制劑後，對琺瑯的黏附性卻可大幅獲得改進，於是使導體組成物的灼燒窗變大。在實施例2將玻璃原料E的量增加至8. 0%可增加耐酸性，但也損失了一些對琺瑯的黏附性（與實施例1 0 的4 · 0 %量相比）。表 8 .實施例 13 14(帶有鉛） 15 性質成份 CF#1 銀II Rh mmm (%) 2.5 74.5 0.2 成份 LF#2 · LF#3 CF#1 銀Η Rh -樹脂酸鹽.. (%) 2.0 1.0 0.5 74.5 0.2 成份玻璃原料e CF#1 銀II Rh樹脂哮鹽丨 (%) 2.5 0.5 74.5 0.2 最高灼燒MCC} 580 640 670 580 640 670 580 640 670 對玻班黏附性(lb) 0.3 55.8 62.5 77.5 >100 >100 99.0 >100 >100 對联郎黏附性⑽ 5Ω.8 98.5 夕100 70.5 >100 96.0 87.3 >100 >55.0 灼度(μίπ) 16.6 13.1 :13.1 13.4 14.3 13.5 13.1 12.1 10.7 電阻(πίΩ/sq) 4.9 4.0 4.2 Γ 4.2 2,9 2.6 4.3 3.5 3.5 比電阻(μΩ-cm) 8.2 5.3 5.4 5.6 4.2 3.5 5.6 4.2 3.7 耐離評比 5=優良 1b差在酸中1分鐘在酸中5分鐘 5 1 5 1 5 2 5 5 3 2 5 5 經濟部中央標準局貝工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁).. 本紙張尺度適用中國國家標準（CNS )A4規格（210x297公釐）-27 -Engelhard's (East Newark, NJ) sintering inhibitor # 8866 can reduce the density of burnt conductors using lead-free glass raw material compositions. Out: Example 9 (without inhibitor), Example 10 (0.2) This paper size applies Chinese National Standard (CNS) M specification (210X297 mm) _ 26 A7 B7 V. Description of the invention (24)% germanium resin Acid salt) and Example 11 (0.4% germanium resinate) "Example 9 (without inhibitor) at 6 4 0ΐ and 6 70 ° C, its adhesion to the enamel conductor was poor, however, After the sintering inhibitor is added, the adhesion to the enamel can be greatly improved, so that the burning window of the conductor composition becomes larger. Increasing the amount of glass raw material E to 8.0% in Example 2 can increase acid resistance, but also lost some adhesion to enamel (compared to the 4.0% amount in Example 10). Table 8. Example 13 14 (with lead) 15 Properties CF # 1 Silver II Rh mmm (%) 2.5 74.5 0.2 Composition LF # 2 · LF # 3 CF # 1 Silver tincture Rh-resinate. (% ) 2.0 1.0 0.5 74.5 0.2 Ingredient glass raw material e CF # 1 Silver II Rh resin whizzing salt 丨 (%) 2.5 0.5 74.5 0.2 Maximum burning MCC} 580 640 670 580 640 670 580 640 670 Adhesion to glass (lb) 0.3 55.8 62.5 77.5 > 100 > 100 99.0 > 100 > 100 couplet Lang adhesiveness 5Ω. 8 98.5 eve 100 70.5 > 100 96.0 87.3 > 100 > 55.0 Ignition (μίπ) 16.6 13.1: 13.1 13.4 14.3 13.5 13.1 12.1 10.7 Resistance (πίΩ / sq) 4.9 4.0 4.2 Γ 4.2 2,9 2.6 4.3 3.5 3.5 Specific resistance (μΩ-cm) 8.2 5.3 5.4 5.6 4.2 3.5 5.6 4.2 3.7 Resistance to separation rating 5 = excellent 1b worse than acid 1 minute in acid 5 minutes 5 1 5 1 5 2 5 5 3 2 5 5 Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page): This paper size is applicable to China National Standard (CNS) A4 Specification (210x297 mm) -27-

五、發明説明（25) Ε施例 16 17 18 性筲 •成份 (%) 成份 (%) 成份 (%) 玻璃原料Ε. 2.5 玻瑶原料E 2.5 玻堪原料E 8.0 CF#1 1.0 CF#1 1.0 CF#r 1.0 銀II 75.0 S4 74.0 銀II 74.5 Rh祕酸强 0.2 Rh樹脂豉斑 0.2 Rh崎辞ar 0.2 ft®灼燒罐.〇 580 640 670 580 640 670 580 640 670 99.5 99.8 89.8 124,0 158.3 133.5 .131.0 109.0 110.0 對_*6附性仲） 84.3 98.5 >100 100.7 113.0 141.5 80.0 63.5 30.3 酿厚度(_ 13.7 11.3 10.1 14 13.7 1Z2 16.7 14.8 13,7 聯且(ωΩ/sq) 3.8 3.4 3.3 5..6 4.0 '3.7 3.4 2.9 2.7 比電阻(μΠ-cm) 5.2 3.9 3.3 8.3 5.5 4.5 5.6 4.2 3.2 酎酸性評比 5=優良，差碰中1分鏟 4.5 5 5 5 5 5 在酸中5^3·鐘 ♦ - · . · *3.5 *5 .». 2 5 4.5 5 {請先閲讀背面之注意事项再填寫本頁) 經濟部中央標準局貝工消費合作社印製實施例1 3 (表8)使用對市售Pemco 2 J 5 7 ( Miles公司，巴爾地摩’ MD )進行噴射碾磨而得到屯％粒子大小約爲3微米的無鉛鹸性磷酸氟玻璃原料C F #工。即令該玻璃有約3 8 0 °C的低膨脹變形點（與玻璃原料 E的4 5 2 °C相比），但其不佳的濕潤性使它在低灼燒溫度（5 8 0 °C)時導體對玻璃的黏附性無法令人接受。實施例14至18 (表8)說明使用玻璃原料摻合物來得到對寬廣處理玻璃的所需求效能。這些導體組成物使用銀II -爲銀片與次微米銀的摻合物’或球狀銀（S 4 ) 及鍺樹脂酸鹽來作燒結抑制劑。實施例1 4說明用於經加熱汽車窗戶的極佳市售帶有鉛的導體組成物，除了 C F # 1 —鹼性磷酸氟玻璃原料，外，它還含有一個由兩個以鉛爲主的玻璃原料，一個標記本紙張尺度適用中國國家標準（CNS)A4規格（ 210X297公釐）^ 28 A7 B7 S?S332 i、發明説明（26) Γ請先間讀背面之注意事項再填寫本頁) 爲L F # 2的硼矽酸鉍鉛組成物和一個標記爲L F # 3的硼矽酸鋅鉛組成物構成的摻合物。和只含有單一玻璃原料的實施例4相比，使用實施例1 4的多重玻璃原料可獲得在耐醋酸性及處理範圍上的改進。寳施例1 5至1 8 (表8 )說明平均粒子大小爲1微米的無鉛組成物E與C F # 1 -經噴射碾磨的市售鹼性磷酸氟玻璃原料，的摻合物。和含有單一玻璃原料的導體實施例相比（實施例10、12和13)，實施例15至 1 7的無鉛玻璃摻合提供加強的性寶。實施例1 5、1 6 和1 8變化玻璃原料組成物的數量。實施例1 7說明球狀銀（S 4 )的使用。實施例1 7使用以聚乙烯吡咯烷酮和二甘醇醋酸酯之丁醚爲主的水可清淨有機載體。實施例5 、16和17說明對玻璃和琺瑯產生優良黏附性的廣泛處理範圍，以及改良之耐酸性。這些無鉛組成物超過目前最佳之鉛爲主導體（實施例14)的效能。經濟部中央標準局員工消費合作社印聚無鉛玻璃原料在厚膜導體上的實際應用已獲得評估，並可觀察到與帶有P b之膏狀物有堪比擬的效能。本發明的最佳效能是由結合兩個或以上的玻璃原料，選用適當的銀粉和使用R h樹脂酸鹽的組合來作膏狀物的成份。本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -29 -V. Description of the invention (25) Ε Example 16 17 18 Sex 筲 • Ingredients (%) Ingredients (%) Ingredients (%) Glass raw materials E. 2.5 Bo Yao materials E 2.5 Bo Kan materials E 8.0 CF # 1 1.0 CF # 1 1.0 CF # r 1.0 Silver II 75.0 S4 74.0 Silver II 74.5 Rh Mysteric Acid 0.2 Rh Resin Spots 0.2 Rh Zircon 0.2 ft® Burning Pot. 0 580 640 670 580 640 670 580 640 670 99.5 99.8 89.8 124,0 158.3 133.5 .131.0 109.0 110.0 pair _ * 6 secondary secondary) 84.3 98.5 > 100 100.7 113.0 141.5 80.0 63.5 30.3 thickness (_ 13.7 11.3 10.1 14 13.7 1Z2 16.7 14.8 13,7 joint and (ωΩ / sq) 3.8 3.4 3.3 5..6 4.0 '3.7 3.4 2.9 2.7 Specific resistance (μΠ-cm) 5.2 3.9 3.3 8.3 5.5 4.5 5.6 4.2 3.2 酎 Acid rating 5 = excellent, 1 point in the difference 4.5 5 5 5 5 5 in acid 5 ^ 3 · 钟 ♦-·. · * 3.5 * 5. ». 2 5 4.5 5 {Please read the notes on the back before filling out this page) Example 1 printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Table 8 ) A commercially available Pemco 2 J 5 7 (Miles, Baltimore's MD) was used to perform jet milling to obtain a %% particle size of about 3 microns without Jian phosphatase fluoride glass material C F # ENGINEERING. That is, the glass has a low expansion deformation point of about 3 0 0 ° C (compared with 4 5 2 ° C of glass raw material E), but its poor wettability makes it at low burning temperature (5 8 0 ° C ), The adhesion of the conductor to the glass is unacceptable. Examples 14 to 18 (Table 8) illustrate the use of glass raw material blends to obtain the required performance for broad-processed glass. These conductor compositions use silver II-a blend of silver flakes and submicron silver 'or spherical silver (S 4) and germanate resinate as sintering inhibitors. Example 14 illustrates an excellent commercially available lead-containing conductor composition for a heated car window. In addition to CF # 1-a basic fluorophosphate glass raw material, it also contains one lead-based Glass material, one mark This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) ^ 28 A7 B7 S? S332 i. Description of the invention (26) Please read the precautions on the back before filling this page) Blend consisting of bismuth lead borosilicate composition LF # 2 and a zinc lead borosilicate composition labeled LF # 3. Compared with Example 4 containing only a single glass raw material, the use of the multiple glass raw materials of Example 14 can achieve improvements in acetic acid resistance and processing range. Proximity Examples 15 to 18 (Table 8) illustrate a blend of lead-free composition E and C F # 1-jet milled commercially available basic phosphoric acid fluoroglass raw materials having an average particle size of 1 µm. The lead-free glass blends of Examples 15 to 17 provide enhanced properties compared to conductor examples containing a single glass raw material (Examples 10, 12 and 13). Examples 15, 16 and 18 varied the amount of the glass raw material composition. Example 17 illustrates the use of spherical silver (S 4). Example 17 A water-cleanable organic vehicle based on polyvinylpyrrolidone and butyl ether of diethylene glycol acetate was used. Examples 5, 16 and 17 illustrate a wide range of processing which gives excellent adhesion to glass and enamel, and improved acid resistance. These lead-free compositions exceed the performance of the currently best lead-based conductor (Example 14). The Ministry of Economic Affairs Central Standard Bureau employee consumer cooperative printed poly lead-free glass raw material has been evaluated for its practical application in thick film conductors, and it has been observed that it has comparable performance to pastes with Pb. The best performance of the present invention is to combine two or more glass raw materials, select a suitable silver powder and use a combination of Rh resinate as ingredients of the paste. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -29-

Claims

曰經濟部中央標準局員工消費合作社印製第831〇5823號專利申請案奶青專利範園修正本(88年2月备年月申請專利範圍 C用在硬貝基貝上形成導電性圖案的可網版印衣厚膜L且成物，E包含（a)—種玻璃組成物的精細切割粒子；（b)導電性的粒子；所有的⑷與㈨都分布在⑷有機媒質中；⑷適需要之一種燒結抑制劑；及（e)通需要之一種鹼性磷酸氟玻璃；其改良部分在於該玻璃組成物是一種無錯玻璃組成物，且在4〇0-65(rc時其軟化點㈣㈠）為7 6，並 — (Ο比黏度範圍從5oo^U7〇cr(^^n 亚且王要由65 -7 8重量％的^丨2〇3，5_i3重量％的 m W重量“B2〇3，0.8_3 〇重量％的 Al2〇3，0.3-3.0重量％的。〇，和 9_15 重量％的 Ζ η 0所組成。 2· ”請專利範圍第丨項的膏狀组成物，其中灼燒溫度疋在5 8 0 - 6 8 0 °C之間。 3. 如申請專利範圍第β的膏狀組成物，其中… 比黏度是在5 〇〇 t：的2至6 8 0 °C的4之間。 4. :::請專利範園第w的膏狀组成物，其中該燒結抑制劑係選自銜，錄的氧化物及其混合物和其前質。如：請專利範圍第β的膏狀組成物，其中具導電性的粒子為銀片’銀粉或其混合物。 a7請專利範圍第1項的膏狀组成物1中玻璃組成 s_王要由6 8 - 7 5重量％的叫〇…-13重量％的 2 ’ Η重量％的〜〇3，。13·。重量％的 L：\EXT\4N\4i：010CL.D〇aWCK ^ 本紙張尺舰财®國家標準（cli7^ii7^~x297公釐)--— (請先閱讀背面之注意事項再填寫本頁)That is, the revised version of the patent application No. 831058523 printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Amended in February 88). The scope of patent application C is used to form a conductive pattern on a hard shell base. Screen printable clothing has a thick film L and a product, E contains (a) finely cut particles of a glass composition; (b) conductive particles; all of the rhenium and rhenium are distributed in the rhenium organic medium; A sintering inhibitor is needed; and (e) A basic fluorophosphate glass is needed; part of the improvement is that the glass composition is an error-free glass composition, and its softening point is at 400-65 (rc ㈣㈠) is 7 6 and — (0 specific viscosity ranges from 5oo ^ U7〇cr (^^ n Ya and Wang should be 65-7 8% by weight ^ 丨 2〇3, 5_i3% by weight mW weight "B2 〇3, 0.8_3 0% by weight of Al203, 0.3-3.0% by weight. 〇, and 9-15% by weight of Z η 0. 2. "Please apply the paste composition of the scope of the patent, wherein The firing temperature is between 5 8 0-6 8 0 ° C. 3. For example, the paste-like composition in the scope of patent application β, where ... The degree is between 500 °: 2 and 680 ° C of 4. 4. ::: Please apply for the patented paste composition of the wth paragraph, wherein the sintering inhibitor is selected from the title, recorded Oxides and mixtures and precursors thereof. For example, the paste composition in the patent scope β, where the conductive particles are silver flakes or silver powder or a mixture thereof. A7 The paste composition in the patent scope 1 1 medium glass composition s_Wang is composed of 6 8-7 5 wt% called 0 ...- 13 wt% 2 'Η wt% ~ 〇3, ... 13. wt% L: \ EXT \ 4N \ 4i ： 010CL.D〇aWCK ^ This paper ruler “Jiancai®” National Standard (cli7 ^ ii7 ^ ~ x297mm) --- (Please read the precautions on the back before filling this page)

r 曰經濟部中央標準局員工消費合作社印製第831〇5823號專利申請案奶青專利範園修正本(88年2月备年月申請專利範圍 C用在硬貝基貝上形成導電性圖案的可網版印衣厚膜L且成物，E包含（a)—種玻璃組成物的精細切割粒子；（b)導電性的粒子；所有的⑷與㈨都分布在⑷有機媒質中；⑷適需要之一種燒結抑制劑；及（e)通需要之一種鹼性磷酸氟玻璃；其改良部分在於該玻璃組成物是一種無錯玻璃組成物，且在4〇0-65(rc時其軟化點㈣㈠）為7 6，並 — (Ο比黏度範圍從5oo^U7〇cr(^^n 亚且王要由65 -7 8重量％的^丨2〇3，5_i3重量％的 m W重量“B2〇3，0.8_3 〇重量％的 Al2〇3，0.3-3.0重量％的。〇，和 9_15 重量％的 Ζ η 0所組成。 2· ”請專利範圍第丨項的膏狀组成物，其中灼燒溫度疋在5 8 0 - 6 8 0 °C之間。 3. 如申請專利範圍第β的膏狀組成物，其中… 比黏度是在5 〇〇 t：的2至6 8 0 °C的4之間。 4. :::請專利範園第w的膏狀组成物，其中該燒結抑制劑係選自銜，錄的氧化物及其混合物和其前質。如：請專利範圍第β的膏狀組成物，其中具導電性的粒子為銀片’銀粉或其混合物。 a7請專利範圍第1項的膏狀组成物1中玻璃組成 s_王要由6 8 - 7 5重量％的叫〇…-13重量％的 2 ’ Η重量％的〜〇3，。13·。重量％的 L：\EXT\4N\4i：010CL.D〇aWCK ^ 本紙張尺舰财®國家標準（cli7^ii7^~x297公釐)--— (請先閱讀背面之注意事項再填寫本頁)r: The revised version of the patent application No. 831058223 printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Amended in February 88). The scope of patent application C is used to form a conductive pattern on a hard shell The screen-printable clothing has a thick film L and a product, E contains (a) finely cut particles of a glass composition; (b) conductive particles; all of the rhenium and rhenium are distributed in the ⑷ organic medium; ⑷ A sintering inhibitor suitable for the need; and (e) A basic phosphoric acid fluoroglass generally needed; the improvement part is that the glass composition is an error-free glass composition and softens at 400-65 (rc at rc) The point ㈣㈠) is 7 6 and — (0 specific viscosity ranges from 5oo ^ U7〇cr (^^ n) and the king shall be 65 -8 8% by weight of ^ 丨 2〇3, 5_i3% by weight of mW weight " B203, 0.8-3 wt% Al203, 0.3-3.0 wt%. 0, and 9-15 wt% Z η 0. 2. "Please apply the paste composition of the scope of the patent, wherein The ignition temperature is between 5 8 0 and 6 8 0 ° C. 3. For example, the paste-like composition in the scope of patent application β, where ... Viscosity is between 500t: 2 and 4 at 680 ° C. 4. ::: Please apply for the patented paste-like composition of Article W, in which the sintering inhibitor is selected from Oxides and mixtures and precursors thereof. For example, the paste composition in the patent scope β, where the conductive particles are silver flakes or silver powder or a mixture thereof. A7 The paste composition in the patent scope 1 1 medium glass composition s_Wang is composed of 6 8-7 5 wt% called 0 ...- 13 wt% 2 'Η wt% ~ 〇3, ... 13. wt% L: \ EXT \ 4N \ 4i ： 010CL.D〇aWCK ^ This paper ruler “Jiancai®” National Standard (cli7 ^ ii7 ^ ~ x297mm) --- (Please read the precautions on the back before filling this page)

r 申請專利範園r Patent application park

經濟部中央標準局員工消費合作社印製 Al2〇3 ’ 0·3_3 重量％的〇〇，和 Ζη〇所组成。里！ /的 7. 如申請專利範園第 4組成物，其巾每個破璃〇g(??)比黏度或是所有破璃的容積計算平均 1 0 g ( ?7 )是在5 0 〇 °C的2至6 8 〇的4之間。 8. 如申请專利範圍第4項的鲁抑知士十,、 ◎貞的“大组成物，其中燒結抑制对1J疋錄樹脂酸鹽。 9·如申請專利範園第丨項的膏狀組成物質含有一個光學透明物質。 ία如申請專利範園第9項的膏狀組成物在於該導電性圖案層中。 11. 如申凊專利範圍第9項的膏狀組成物質為汽車後破璃。 12, 如申請專利範圍第9項的膏狀组成物物主要由6 8 - 75重量％的Bi2〇3，5_13重量％的 5 1〇2，5-9重量％的22〇3’_.,〇.8-3,.〇...重量％的. AI2O3，0.3-3重量％的CaO，和9-15重量％的 -Z η Ο所組成。 lvX —種無錯玻璃组成物，其在4 0 0 - 6 5 0 °C的軟化點 1〇g(W)為7,6 ’其’l〇g(7/)比黏度範圍從500 °C的2 至7〇〇 t：的5之間，並且主要由65-78重量％的 Bi2〇3 ’ 5-13 重量％的5102，1-9重量％的8203，〇.8-3.〇重量％的人12〇3，0.3-3.〇重量％的〇&0，其中該硬質基其中有5法瑯存其中該硬質基其中玻璃組成請先閲讀背 Si 意事項再填寫本頁訂 L.\E>CI\4S\4S6\6CL.DOC\WCK -2- 本紙張尺度家辟ϋ) A4· (21QX297；^7 經濟部中央標準局員工消費合作社印製 A8 Βδ » q C8 ： u. ^ D8 六、申請專利範圍和9 - 1 5重量％的Z η 0所组成。 14如申請專利範圍第1 3項之玻璃組成物，其主要由6 8 -75重量％的8丨203，5-13重量％的8丨02，5-9重量 %的：6203，0.8-3.0重量％的八1203，0.3-3重量％的CaO，和9-15重量％的211〇所組成。 L:\E\Tv4RUS616CL. DOCWVCK 本紙張尺度適用中國國家榇準（CNS ) A4規格（210X297公釐） (請先閱請背面之汰意事項再填寫本頁)Printed by Al2O3'0 · 3_3% by weight of 〇〇 and Znη〇 by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. in! 7. For the fourth composition of the patent application Fanyuan, the average viscosity of each broken glass is 0g (??) or the volume of all broken glass is calculated as an average of 10 g (? 7) at 50 ° C is between 2 and 6 8 0. 8. For example, Lu Yizhi Shi, who applied for the scope of patent application No. 4, ◎ Zhen's "large composition, in which sintering inhibits 1J recorded resinate. 9. Such as the paste composition of the patent application Fanyuan The substance contains an optically transparent substance. Αα The paste-like composition of item 9 in the patent application park is in the conductive pattern layer. 11. The paste-like composition of item 9 in the patent application scope is automobile rear glass. 12, such as the application of the patent scope of the 9th paste composition is mainly composed of 6 8-75% by weight of Bi203, 5-13% by weight of 5102, 5-9% by weight of 2203'_., 〇.8-3, .〇 ... wt%. AI2O3, 0.3-3wt% CaO, and 9-15wt% -Z η Ο. LvX — a kind of error-free glass composition, which 4 0 0-6 5 0 ° C softening point 10 g (W) is 7,6 'its '10 g (7 /) specific viscosity ranging from 500 ° C 2 to 700 t: 5 of 5 And mainly composed of 65-78% by weight of Bi203, 5-13% by weight of 5102, 1-9% by weight of 8203, 0.8-3.0% by weight of people 120.3, 0.3-3. 〇wt% 〇 & 0, wherein the hard base has 5 methods, and the For the hard glass composition, please read the Si content first and then fill in this page to order L. \ E > CI \ 4S \ 4S6 \ 6CL.DOC \ WCK -2- Home Paper Size) A4 · (21QX297; ^ 7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A8 Βδ »q C8: u. ^ D8 VI. Patent application scope and 9-15% by weight of Z η 0. 14 Such as the glass of patent application scope No. 13 Composition, which mainly consists of 6 8-75% by weight 8 丨 203, 5-13% by weight 8 丨 02, 5-9% by weight: 6203, 0.8-3.0% by weight eight 1203, 0.3-3% by weight It is composed of CaO and 9-15% by weight of 211. L: \ E \ Tv4RUS616CL. DOCWVCK This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) (please read the description on the back first) (Fill in this page again)