1270895 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關感光性導電糊料及使用其形成之導電體 圖型’特別是，有關適於作爲由煅燒照像平版技術所形成 圖型塗膜之導電體材料之感光性糊料。 【先前技術】 向來，相關於電漿顯示面板（PDP )或CCD感應器， 影像感應器等的零件，無鹼玻璃或其他各種玻璃基板上之 電極係由蒸鍍法所形成。 但是，此蒸鍍法爲收容於真空容器內之電極形成材料 以金的蒸鍍膜形成，不僅裝置大金額高，還有材料的進出 麻煩，抽真空費時等作業性差的缺點。 對此作爲其他方法之於基板上形成導電體之圖型層， 係混合金屬粉末之非感光性有機粘劑糊料材料，例如乾燥 型或熱硬化型之導電糊料，以網版印刷等的印刷技術於基 板上圖型化之方法。 但’使用之相關印刷技術之圖型化方法，以低成本且 作業良好之安定工業化形成具1 〇 〇 # m以下線幅之導電體 圖型有困難。 因此最近有提案’利用使用感光性導電糊料之照相平 版技術之導電體圖型形成法（參閱日本特開平10_269848 號公報）。 一方面，由於於玻璃基板形成電極時，必要性爲在玻 • 4 - 1270895 (2) 璃不變形的620 °C以下煅燒，與使用以更高溫（8〇〇〜900 °C )煅燒形成之陶瓷基板導電體比較，其導電性有偏低的 問題。 【發明內容】 (發明所欲解決之課題） 所以，本發明係祈使解決向來技術擔負的上述課題。 其主要目的係提供同時具優高精密圖型的形成性及於620 °C以下溫度之煅燒性之感光性導電糊料。 又，本發明的其他目的爲提供以62(TC以下溫度锻燒 亦具優導電性之導電體圖型。 (課題解決手段） 本發明者爲實現上述目的經深入硏究結果，發現作m 用於感光性導電糊料之導電粉末，以使用低結晶度之銀粉 末之感光性導電糊料，不必經複雜的步驟，可容易得到同 時具優導電性與高精密圖型形成性的導電體圖型，而完成 本發明。 即，本發明之感光性導電糊料，係含（A )低結晶度 的銀粉末、（B)有機粘劑、（C)光聚合性單體、（〇)光聚 合引發劑之糊料，上述低結晶度的銀粉末（A)爲X光繞 射圖之 Ag( 111)面燒射峰之所不半寬値爲0.15。以上者 爲其特徵。 又，本發明之導電體圖型，係使用如上述之感光性導 -5- 1270895 (3) 電糊料所形成之煅燒物圖型爲其特徵。 又，此導電體圖型，係於基材上塗覆本發明之感光性 導電糊料，經乾燥形成乾燥塗膜，其次曝光、顯影後，得 到感光性糊料之乾燥塗膜圖型，理想爲以48〇〜620°C理 想的溫度煅燒將粘劑脫除有機分。 (發明之實施型態） 爲能於6 2 0 °C以下煅燒溫度得到優導電性，導電粉末 必要特別選擇。一般，於空氣環繞下煅燒時，可不受氧化 的影響進行煅燒。使用貴金屬之中比較價廉的銀粉末。 又，爲能於620 °C以下煅燒溫度得到導電性，導電粉 的锻燒性必要提昇，其手段係使用極小粒子徑的導電粉末 的方法或平片狀的導電粉末的方法。確實依該方法，可於 62 0 °C以下的煅燒溫度得到優導電性。但是該方法爲感光 个生糊料時，反而，光的穿透性變差，難於形成高精密之導 電圖型。 因而本發明者爲不妨礙圖型形成時光的穿透性，煅燒 #得到優導電性的手段，著眼於銀粉末之結晶度，實施深 Λ的硏究。其結果，發現低結晶度銀粉末，即由使用X 線解析圖型所示之 Ag ( 1 1 1 )面繞射峰之半寬値爲0 · 1 5。 以上粉末，銀粉末之粒子徑無需微細化即可提昇煅燒性。 如果依本發明的感光性導電糊料，可於620 °C以下低 溫充分煅燒，提供具有優導電性之高精密導電體圖型。 以下說明有關本發明之感光性導電糊料。 -6- 1270895 (4) 構成本發明感光性導電糊料之低結晶度銀粉末（A ) 係爲賦與糊料導電性者，使用X線解析圖型所示之 Ag ( 】】1)面繞射峰之半寬値爲0·15°以上粉末，理想之示値爲 以上者。此半寬値低於〇·15。之銀粉末，銀粉末之結 晶度高，粒子間由於容易引起燒結，6 2 0 °C以下的烟燒溫 度其電阻不降低故不理想。又，該半寬値以1.〇。以下者爲 理想。半寬値超過1 · 〇。時銀粉的結晶度低，由於粒子間不 會進行結合，線條會有產生波紋或扭曲之不規則不理想。 此銀粉末（A)，一般係使用原子法或化學還原法等的 方法製造。原子法係熔融之銀以氣體、水等之流體噴霧得 到銀粉末的方法，容易得到球形的粒子，量產性優。化學 還原法係使用水溶性銀鹽與還原劑化學反應得到銀粉末的 方法’具體的如使用硝酸銀爲水溶性銀鹽，還元劑使用荷 性鹼或銨鹽、肼等的鹼性基析出金屬銀，其次得到之銀淤 ^水洗、乾燥得到銀粉末的方法。 上述銀粉末（A )可使用球狀、平片狀、松林石狀等 種種形狀，考慮光特性或分散性以使用球狀爲理想。 又，此使用之銀粉末（A )以1 0,000倍電子顯微鏡（ SEM)觀察時，10個隨機銀粉末之平均粒徑以o.i〜5// m ’理想爲〇·4〜2.0 // m大小者爲理想。此平均粒徑低於 〇 · 1 // m時，光的穿透性變差難以描繪高精密的圖型，一 方面’平均粒徑超過5 m時，難以得到直線性的線邊沿 故不理想。又，使用以微軌道法測定之平均粒徑爲0.5〜 3 · 5 " m大小者爲理想。 -7- 1270895 (5) 又，此使用之銀粉末（A)之比面積爲0.01〜2.0 m2 / g，理想爲0 · 1〜1 .0 m2 / g者爲理想，此比面積低於 0.01 m2 / g時，保存時容易產生沈積，一方面比面積大 於2 · 0 m2 / g時，吸油量變大，有損糊料之流動性不理 想。 此銀粉末（A )之配合量，相對於1 00質量份感光性 導電糊料，以5 0〜90質量份爲適當。導電性粉末之配合 量低於上述範圍時，由該糊料所得之導電體圖型不能得到 充分的導電性，一方面，超過上述範圍時，與基材的密合 性變差不理想。 其次，成本發明之感光性導電糊料之有機粘劑（Β ) ，係賦與煅燒前各成分之結合材料，或組成物之光硬化性 或顯影性之機能者。 此有機粘劑（Β )可使用具羧基之樹脂，具體的如其 本身含有具有乙烯性不飽和雙鍵之羧基感光性樹脂及含有 不具乙烯性不飽和雙鍵羧基之樹脂之任一者。可適切使用 的樹脂（低聚物及聚合物之任一者均可）可列舉如以下所 示者。 (1)由（a)不飽和羧酸與（b)具有不飽和雙鍵之化 合物共聚合所得之含羧基樹脂 (2 )由（a )不飽和羧酸與（b )具有不飽和雙鍵之化 合物共聚合物以乙烯性不飽和基側枝加成而得之含羧基樹 脂 (3) (c)環氧基與具有不飽和雙鍵之化合物與（l3) 1270895 (6) 具有不飽和雙鍵化合物之共聚合物，以（a )不飽和羧酸 反應’所生成之羥基以（d )多價酸酐反應所得之含羧基 感光性樹脂 (4) ( e )具有不飽和雙鍵之酸酐與（b )具有不飽和 雙鍵化合物之共聚合物以（f )具有羥基之化合物反應所 得之含羧基樹脂 (5) (e)具有不飽和雙鍵之酸酐與（b)具有不飽和 雙鍵化合物之共聚合物以（g )具有羥基及不飽和雙鍵之 化合物反應所得之含羧基感光性樹脂 (6) ( h )多官能環氧化合物與（h )不飽和單羧酸反 應，所生成之2級羥基以（i )多價酸酐反應之含羧基感 光性樹脂 (7) (b)具有不飽和雙鍵之化合物與環氧丙基（甲基 )丙烯酸酯之共聚物之環氧基，以（j) 1分子中具有羧基 ，不持有乙烯性不飽和鍵之有機酸反應，所生成之2級羥 基以（d )多價酸酐反應所得之含羧基樹脂 (8) ( k )含羧基聚合物以（d )多價酸酐反應所得之 含羧基樹脂 (9) ( k )含羧基聚合物以（d )多價酸酐反應所得之 含羧基樹脂以（c)環氧基與具有不飽和雙鍵之化合物反 應所得之含羧基感光性樹脂 此等之含羧基感光性樹脂與含羧基樹脂，可單獨或混 合使用，任一情形其合計量爲組成物全體之5〜5 0質量％ 之比例配合爲理想。此等樹脂之配合量低於上述範圍時， -9 - 1270895 (7) 形成之塗膜中上述之樹脂分佈容易不均勻’難以得到充分 的光硬化性及光硬化度，依選擇之曝光、顯影圖型化有困 難。一方面，超過上述範圍時，煅燒時之圖型容易產生扭 曲或線幅收縮，不理想。 又，上述含羧基感光性樹脂及含羧基樹脂’其重量平 均分子量爲1，〇〇〇〜1〇〇5〇〇〇。理想爲5,000〜70,000’及 酸價爲30〜250 mg KOH / g，且，使用含羧基感光性樹 脂時，其雙鍵當量爲350〜2,000’理想爲400〜1，500者 爲適宜。 上述樹脂之分子量低於1，〇〇〇時，顯影時之皮膜之 密合性有不良影響，一方面，超過100，〇〇〇時，容易產生 顯影不良，不理想。又，酸價低於30 mg KOH / g時，對 鹼性水溶液之溶解性不充分，容易產生顯影不良，一方面 ，超過25 0 mg KOH / g時皮膜之密合性惡化或光硬化部 (曝光部）產生溶解，不理想。更且，含羧基感光性樹脂 時，感光性樹脂之雙鍵當量低於3 5 0時，煅燒時容易殘 留殘渣，一方面，超過2,000時，顯影之作業容許度狹小 ，又光硬化時需要高曝光量，不理想。 構成本發明之感光性導電性糊料之光聚合性單體（C) ’係爲賦與促進組成物之光硬化性及提昇顯影性而使用此 光聚合性單體（C )可列舉如2-羧基乙基丙烯酸酯、2-羧 基丙基丙烯酸酯、二乙二醇二丙烯酸酯、三乙二醇二丙烯 酸酯、聚乙二醇二丙烯酸酯、聚氨基甲酸二丙烯酸酯、二 羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇 -10- 1270895 (8) 四丙烯酸酯、三羥甲基丙烷環氧乙烷變性三丙烯酸酯 羥甲基丙烷環氧丙烷變性三丙烯酸酯、二季戊四醇五 酸酯、二季戊四醇六丙烯酸酯及對應上述丙烯酸之各 丙烯酸酯；鄰苯二甲酸、己二酸、馬來酸、甲叉丁二 偏苯三酸、對苯二甲酸等的多價酸及羧基烷基（甲基 烯酸酯及單、二、三或其上之聚酯等，並無特別限定 又此等可單獨或二種以上組合使用。此等光聚合性單 ，亦以1分子中具有2個以上之丙烯醯基或甲基丙烯 之多官能單體爲理想。 該光聚合性單體之配合量，每100質量份上述有 劑以20〜1〇〇質量份爲適當。光聚合性單體之配合 於上述範圍時，組成物難於得到充分的光硬化性，一 ，大量超過上述範圍時，表層部之光硬化比皮膜之深 ，容易產生硬化差異。 構成本發明之感光性導電性糊料之光聚合引發齊 )’係爲引發光反應之成分，主要爲吸收紫外線產生 基’上述光聚合引發劑（D )之具體例可列舉如偶苯 偶苯因甲醚、偶苯因乙醚、偶苯因異丁醚等的偶苯因 苯因烷基醚類；苯乙酮、2，2·二甲氧基-2 -苯基苯乙 2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮等的苯 類；2 -甲基-1 -[-(甲硫基）苯基]-2 -嗎啉代丙酮-1、 基-2-二甲基胺基-1-(4-嗎啉代苯基）· 丁酮等的胺 乙酮類；2-甲基蒽醌、2-乙基蒽醌、2-t-丁基蒽醌、 蒽酿等的蒽g昆類；2，4 -二甲硫基咕噸酮、2，4 -二乙硫 丙烯 甲基 酸' )丙 者， 體中 醯基 機粘 量低 方面 部快 (D 自由 因、 及偶 酮、 乙酮 2 ·爷 基苯 1 -氯 基咕 -11 - 1270895 (9) 噸酮、2-氯咕噸酮、異丙硫基咕噸酮、2,4-二乙硫基咕囉 酮等的硫基咕噸酮I類；乙苯酮二甲基酮縮醇、卡基二甲基 醒縮醇等的酮縮醇，一本甲酮等一苯甲酮類；或咕噸酮類 ;(2,6-二甲氧基偶苯因）-2,4,4-戊基氧化膦，雙（2,4,6-三 甲基偶苯因）-苯基氧化膦、2,4,6-三甲基偶苯因二苯基氧 化膦、乙基-2，4，6 -三甲基偶苯因苯基氧化膦等氧化膦類； 各種過氧化物類等，並無特別的限定，又，此等可單獨或 二種以上組合使用。 又，此等光聚合引發劑（D )於糊料中之配合比例， 每1〇〇質量份上述有機粘劑（B)以1〜3〇質量份爲適 當’理想爲5〜2 0質量份。低於上述範圍時，糊料難於 得到充分的光硬化性，一方面，大量超過上述範圍時，產 生光穿透障礙，底部難於得到光硬化性。 又’本發明感光性導電糊料，爲提高對玻璃基板的密 合性，煅燒膜的強度爲目的可配合低融點玻璃粉末。 上低融點玻璃粉末，以使用鉛系、鉍系、磷系、鋰系 等玻璃轉移點（Tg)爲300〜500 °C，軟化點（Ts)爲400 〜600°C之低融點玻璃粉末爲理想。Tg低於3 00 °C、Ts低 於40 0 °C時，比脫除粘劑更低的溫度產生熔融容易將有機 粘劑包藏，殘存之有機粘劑容易產生氣泡不理想。一方面 ’ T g超過5 0 0 t：、T s超過6 0 0 t：時，6 2 0。(：以下的煅燒條 件對基板的密合性不充分，不理想。 又’由解像性的觀點，低融點玻璃粉末，其粒徑以 1 0 // m以下者爲理想，結晶性或非結晶性之任一者均可。 -12- 1270895 (10) 該低融點玻璃粉末於糊料中之配合比例，以1 00 份本發明之銀粉末（A )以1〜3 0質量份爲理想，更 爲2〜1 5質量份。此低融點玻璃粉末之配合比例低 質量份時，不能充分得到對基板的密合性，一方面， 3 〇質量份時，導電性變低不理想。又，要求深光硬 度時，依必要可使用引發可視範圍自由基聚合之 Specialy Chemicals 公司製 IRUGA CURE 7 84 等的鈦 光聚合引發劑，白染料等之硬化助劑組合。 依必要，爲確保本發明感光導電糊料之保存安定 可配合磷酸、磷酸酯、含羧酸化合物等的酸性化合物 矽氧烷系、丙烯基系等的消泡•調整劑，爲調整流動 搖溶性賦與劑，爲提高皮膜的密合性之矽烷偶合劑等 他添加劑。依必要，爲防止導電性金屬粉的氧化之公 用之抗氧化劑，爲提高保存時熱安定性之熱聚合抑止 有關煅燒時與基板結合之金屬氧化物，矽氧化物、硼 物，低融點玻璃等微粒子。 又，爲調整煅燒收縮目的，可添加氧化矽、氧化 氧化鋁、氧化鈦等的無機粉末，有機金屬化合物，金 機酸鹽，金屬烷氧化物等。 又，爲調整色調之目的，可添加1種或2種類 Fe、Co、CU、Cr、Μη、Al、RU、Ni 爲主成分之含金 化物或複合金屬氧化物所成的黑色顏料，四氧化三 C03 〇4 )，氧化釕、鑭複合氧化物等的黑色材料。 本發明感光性導電糊料，係如上述之必要成分以 質量 理想 於1 超過 化深 Ciba 烴系 性， ，聚 性之 的其 知慣 劑， 氧化 鉍、 屬有 以上 屬氧 鈷（ 所定 -13- 1270895 (11) 比例之任意成分配合，以三輥輪或混合器等混練機均勻分 散而得。 如此所得之本發明感光導電糊料，經如以下之步驟於 基板上形成導電體圖型。 (1)首先’本發明感光性導電糊料，係由網版印刷法 、棒塗覆器等適宜的塗覆方法，塗覆於基材，例如電漿顯 示面板（P D P )面基板等的玻璃基板，其次爲得到指觸乾 燥性，以熱風循環式乾燥爐或紅外線乾燥爐等，於6 0〜 1 2 0 °C乾燥5〜4 0分鐘，蒸發溶劑，得到不沾手塗膜。 此處之基材，非特別限定者，例如可使用玻璃基板、 陶瓷基板等耐熱性基板。 又，糊料可預先成膜爲薄膜狀，此時將薄膜層合於基 板即可。 (2 )其次，基材上形成之乾燥塗膜以圖型曝光後顯影 〇 曝光步驟，係使用具曝光圖型之負片，以接觸曝光或 非接觸曝光均可。曝光用光源，使用鹵素燈、高壓水銀燈 、雷射光、金屬高熾燈、黑光燈、無極電燈等。曝光量以 50 〜l〇〇〇mJ/cm2 爲理想。 顯影步驟使用噴霧法、浸漬法。顯影液如氫氧化鈉、 氫氧化鉀、碳酸鈉、碳酸鉀、矽酸鈉等的金屬鹼性水溶液 ，或單乙醇胺、二乙醇胺、三乙醇胺等的胺基水溶液，特 別以1 . 5質量％以下濃度的稀鹼性水溶液爲合適，組成物 中之含羧基樹脂之羧基皂化，除去未硬化部份（未曝光部 -14 - 1270895 (12) 份）即可，不限定於如上述之顯影液。又，顯影後爲脫除 不要之顯影液，以進行水洗或酸中和爲理想。 (3 )煅燒由此所得之感光性導電糊料之圖型，糊料中 所含之有機分以脫粘劑方法，形成所定導電體圖型。 【實施方式】 以下以實施例爲基準具體的說明本發明，本發明不限 定於以下實施例，以下「份」如無特別指明時爲質量份。 有機粘劑、使用銀粉末及低融點玻璃粉末，配合含此 等之後述各成分以所定的組成比，以攪拌機攪拌後，再以 三輥輪機練合進行糊料化。製作成感光性導電糊料（組成 物例1)。 又，對該組成物例1，除了銀粉末變更如表1所示以 外’同樣製作成相關之感光性導電糊料組成物例2 (銀粉 末B)及比較組成物例1 (銀粉末C )。 (有機粘劑） 備有溫度計、攪拌機、滴定漏斗及迴流冷卻器之燒瓶 投入〇·87 :0.13莫耳比的甲基甲基丙烯酸酯及甲基丙 烯酸，以二丙二醇單甲基醚作爲溶劑，以偶氮二丁基晛作 爲催化劑，於氮氣環境下，以8 0 °C攪拌2〜6小時，得到 樹脂溶液。此樹脂溶液中之有機粘劑（共聚合樹脂）之重 量平均分子量爲105000，酸價爲74mgKOH/g。 又，所得之有機粘劑之重量平均分子量，係以日本島 -15- 1270895 (13) 津製作所栗浦L c - 6 A D及日本昭和電工製玻璃柱S h o d e x (登記商標）KF- 8 04、KF- 803、KF-8 02與三輥輪連接之 高速色譜儀測定。 (銀粉末） 具有如表1所示半寬値、平均粒徑及比表面積係使用 銀粉末A、B、及C。又，半寬値係使用X線分析裝置（ 曰本理學製，RINT- 1 500 )之銀粉末之X線繞射圖相關 Ag ( 1 1 1 )面脊峰之半寬値，不過粒徑係由SEM觀察隨機 1 〇個銀粉末之平均粒徑。 其製法如下所述。1270895 (1) 玖 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光A photosensitive paste of a conductive material of a coating film. [Prior Art] Conventionally, a part related to a plasma display panel (PDP), a CCD sensor, an image sensor, or the like, an alkali-free glass or an electrode on various other glass substrates is formed by a vapor deposition method. However, this vapor deposition method is formed by depositing an electrode forming material in a vacuum container with a gold vapor-deposited film, which is not only a large amount of equipment, but also has troubles in that material is introduced and discharged, and workability such as vacuuming is time-consuming. In this regard, as another method, a pattern layer for forming a conductor on a substrate is a non-photosensitive organic binder paste material mixed with a metal powder, such as a dry or thermosetting conductive paste, for screen printing or the like. A method of patterning a printing technique on a substrate. However, the patterning method of the related printing technology used has difficulty in forming a conductor pattern having a line width of 1 〇 〇 # m at a low cost and a good operation. Therefore, there has recently been proposed a method of forming a conductor pattern using a photolithography technique using a photosensitive conductive paste (refer to Japanese Laid-Open Patent Publication No. Hei 10-269848). On the one hand, since the electrode is formed on the glass substrate, the necessity is to be calcined at 620 ° C which is not deformed by glass, and is formed by calcination at a higher temperature (8 〇〇 to 900 ° C). Compared with the ceramic substrate conductor, the conductivity is low. SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) Therefore, the present invention has been made to solve the above problems of the prior art. The main purpose of the invention is to provide a photosensitive conductive paste which is excellent in both high-precision pattern formation and calcinability at temperatures below 620 °C. Further, another object of the present invention is to provide a conductor pattern having an excellent conductivity at a temperature of TC or lower. (Problem for solving the problem) The present inventors have found in order to achieve the above object. In the conductive powder of the photosensitive conductive paste, a photosensitive conductive paste using a low crystallinity silver powder can easily obtain a conductor pattern having excellent conductivity and high-precision pattern formation without complicated steps. The photosensitive conductive paste of the present invention contains (A) a low crystallinity silver powder, (B) an organic binder, (C) a photopolymerizable monomer, and (〇) light. In the paste of the polymerization initiator, the low crystallinity silver powder (A) is a non-half width of the Ag (111) plane burning peak of the X-ray diffraction pattern of 0.15. Further, the present invention is characterized. The electrical conductor pattern is characterized by the use of the calcined image pattern formed by the photosensitive conductive material of the above-mentioned photosensitive conductive material, which is formed by the electroconductive paste, and is coated on the substrate. The photosensitive conductive paste of the invention is dried to form a dry coating film, followed by exposure After development, a dry coating film pattern of the photosensitive paste is obtained, and it is desirable to remove the organic component by calcining at a desired temperature of 48 〇 to 620 ° C. (Inventive mode) It is capable of 6 2 0 ° The calcination temperature below C gives excellent conductivity, and the conductive powder must be specially selected. Generally, when calcined under air, it can be calcined without being affected by oxidation. The cheaper silver powder is used among precious metals. The calcination temperature below C gives conductivity, and the calcinability of the conductive powder is required to be improved, and the method is a method of using a conductive powder having a very small particle diameter or a method of using a sheet-like conductive powder. According to the method, it can be used at 60 ° C. The following calcination temperature gives excellent conductivity. However, when the method is to expose a raw paste, on the contrary, the light transmittance is deteriorated, and it is difficult to form a high-precision conductive pattern. Therefore, the inventors do not hinder the formation of the pattern. Penetration, calcination # is a means of obtaining excellent conductivity, focusing on the crystallinity of the silver powder, and carrying out a squat study. As a result, it was found that the low crystallinity silver powder was obtained by using the X-ray analysis pattern. The half width 値 of the diffraction peak of the Ag (1 1 1 ) surface is 0 · 15 . The above powder, the particle diameter of the silver powder can be improved without refining. If the photosensitive conductive paste according to the present invention is used, It is sufficiently calcined at a low temperature of 620 ° C or lower to provide a high-precision conductor pattern having excellent conductivity. The photosensitive conductive paste of the present invention will be described below. -6- 1270895 (4) constituting the photosensitive conductive paste of the present invention The low crystallinity silver powder (A) is one in which the conductivity of the paste is imparted, and the Ag (Fig. 1) of the X-ray analysis pattern is used, and the half-width of the surface diffraction peak is 0·15° or more. The 半 is the above. The half-width 値 is lower than 〇·15. The silver powder has a high crystallinity, and the particles are easily sintered. The sinter temperature below 60 ° C does not decrease the resistance. ideal. Also, the half width is 1. The following are ideal. Half width 値 more than 1 · 〇. When the crystallinity of the silver powder is low, the irregularities of the lines may be corrugated or distorted because the particles do not combine. This silver powder (A) is usually produced by a method such as atomic method or chemical reduction method. In the atomic method, the molten silver is sprayed with a fluid such as a gas or water to obtain a silver powder, and spherical particles are easily obtained, and the mass productivity is excellent. The chemical reduction method uses a method in which a water-soluble silver salt is chemically reacted with a reducing agent to obtain a silver powder. Specifically, silver nitrate is used as a water-soluble silver salt, and a reducing agent is used to precipitate a metallic silver using a basic base such as a base or an ammonium salt or a hydrazine. Then, the obtained silver silt is washed with water and dried to obtain a silver powder. The silver powder (A) may have various shapes such as a spherical shape, a flat sheet shape, and a pine forest shape, and it is preferable to use a spherical shape in consideration of light characteristics or dispersibility. Further, when the silver powder (A) used was observed by a 10,000-fold electron microscope (SEM), the average particle diameter of 10 random silver powders was oi~5//m' ideally 〇4 to 2.0 // m. It is ideal. When the average particle diameter is less than 〇·1 // m, it is difficult to draw a high-precision pattern when the light transmittance is deteriorated. On the other hand, when the average particle diameter exceeds 5 m, it is difficult to obtain a linear line edge, which is not preferable. . Further, it is preferable to use an average particle diameter of 0.5 to 3 · 5 " m measured by the micro-track method. -7- 1270895 (5) Further, the silver powder (A) used herein has a specific area of 0.01 to 2.0 m 2 /g, and is preferably 0 · 1 to 1.0 m 2 / g, which is ideally smaller than 0.01. When m2 / g, deposition is easy to occur during storage. On the other hand, when the area is larger than 2 · 0 m 2 / g, the oil absorption is large, and the fluidity of the damaged paste is not ideal. The amount of the silver powder (A) is preferably from 50 to 90 parts by mass based on 100 parts by mass of the photosensitive conductive paste. When the amount of the conductive powder is less than the above range, the conductivity pattern obtained from the paste cannot provide sufficient conductivity. On the other hand, when it exceeds the above range, the adhesion to the substrate is deteriorated. Next, the organic binder (Β) of the photosensitive conductive paste of the present invention is a function of imparting photohardenability or developability of a bonding material of each component before calcination. The organic binder (Β) may be a resin having a carboxyl group, and specifically, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond and a resin having a carboxyl group having no ethylenically unsaturated double bond. The resin (any of the oligomer and the polymer) which can be suitably used can be enumerated as follows. (1) a carboxyl group-containing resin (2) obtained by copolymerizing (a) an unsaturated carboxylic acid with (b) a compound having an unsaturated double bond, wherein (a) an unsaturated carboxylic acid and (b) have an unsaturated double bond a compound-containing copolymer obtained by addition of an ethylenically unsaturated group to a carboxyl group-containing resin (3) (c) an epoxy group and a compound having an unsaturated double bond and (l3) 1270895 (6) having an unsaturated double bond compound a co-polymer, a carboxyl group-containing photosensitive resin (4) (e) obtained by reacting (a) a hydroxyl group formed by the reaction of (a) an unsaturated carboxylic acid with (d) a polyvalent acid anhydride, has an unsaturated double bond anhydride and (b) a copolymer having a unsaturated double bond compound (b) a carboxyl group-containing resin obtained by reacting a compound having a hydroxyl group (5) (e) an acid anhydride having an unsaturated double bond and (b) a compound having an unsaturated double bond The polymer is obtained by reacting (g) a carboxyl group-containing photosensitive resin (6) (h) a polyfunctional epoxy compound obtained by reacting a compound having a hydroxyl group and an unsaturated double bond with (h) an unsaturated monocarboxylic acid, and generating a grade 2 a carboxyl group-containing photosensitive resin (7) having a hydroxyl group reacted with (i) a polyvalent acid anhydride (b) having an unsaturated double The epoxy group of the copolymer of the compound and the epoxy propyl (meth) acrylate is reacted with an organic acid having a carboxyl group in 1 molecule and not holding an ethylenically unsaturated bond, and the resulting 2-stage hydroxyl group (d) a carboxyl group-containing resin obtained by reacting a polyvalent acid anhydride (8) (k) a carboxyl group-containing polymer obtained by reacting (d) a polyvalent acid anhydride with a carboxyl group-containing resin (9) (k) a carboxyl group-containing polymer (d) The carboxyl group-containing resin obtained by the reaction of the polyvalent acid anhydride is a carboxyl group-containing photosensitive resin obtained by reacting (c) an epoxy group with a compound having an unsaturated double bond, and the carboxyl group-containing photosensitive resin and the carboxyl group-containing resin may be used singly or in combination. In either case, the total amount is preferably 5 to 50% by mass of the entire composition. When the amount of the resin is less than the above range, the above-mentioned resin distribution in the coating film formed by -9 - 1270895 (7) is easily uneven. It is difficult to obtain sufficient photocurability and light hardening degree, and exposure and development are selected depending on the selection. Drawing is difficult. On the other hand, when it exceeds the above range, the pattern at the time of calcination tends to cause twisting or shrinkage of the wire web, which is not preferable. Further, the carboxyl group-containing photosensitive resin and the carboxyl group-containing resin have a weight average molecular weight of 1, 〇〇〇1 to 1〇〇5〇〇〇. It is preferably 5,000 to 70,000' and an acid value of 30 to 250 mg KOH / g, and when a carboxyl group-containing photosensitive resin is used, a double bond equivalent of 350 to 2,000' is preferably 400 to 1,500. When the molecular weight of the above resin is less than 1, the adhesion of the film at the time of development is adversely affected. On the other hand, when it exceeds 100, it tends to cause development failure, which is not preferable. Further, when the acid value is less than 30 mg KOH / g, the solubility in the alkaline aqueous solution is insufficient, and development failure is liable to occur. On the other hand, when the content exceeds 25 mg KOH / g, the adhesion of the film is deteriorated or the photohardened portion is deteriorated ( The exposure unit) is dissolved, which is not preferable. Further, in the case of the carboxyl group-containing photosensitive resin, when the double bond equivalent of the photosensitive resin is less than 5,000, the residue is likely to remain during firing, and on the other hand, when it exceeds 2,000, the work permittivity for development is narrow, and high light curing is required. The amount of exposure is not ideal. The photopolymerizable monomer (C) which constitutes the photosensitive conductive paste of the present invention is used to impart photocurability and enhance developability of the composition, and the photopolymerizable monomer (C) is used, for example, -carboxyethyl acrylate, 2-carboxypropyl acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polyurethane diacrylate, dimethylol Propane triacrylate, pentaerythritol triacrylate, pentaerythritol-10- 1270895 (8) tetraacrylate, trimethylolpropane ethylene oxide modified triacrylate hydroxymethylpropane propylene oxide modified triacrylate, dipentaerythritol Acid ester, dipentaerythritol hexaacrylate and acrylate corresponding to the above acrylic acid; polyvalent acid and carboxyl group of phthalic acid, adipic acid, maleic acid, methylidene trimellitic acid, terephthalic acid, etc. The alkyl group (methic acid ester and the polyesters of the mono-, di-, or tri- or the above-mentioned polyesters are not particularly limited, and these may be used alone or in combination of two or more. These photopolymerizable monomers are also in one molecule. Has more than 2 kinds of acrylonitrile The amount of the photopolymerizable monomer is preferably 20 to 1 part by mass per 100 parts by mass of the above-mentioned organic compound. The photopolymerizable monomer is blended in the above range. In the case of the composition, it is difficult to obtain sufficient photocurability. When the amount exceeds the above range, the photohardening of the surface layer portion is deeper than that of the film, and the difference in hardening is likely to occur. The photopolymerization initiation of the photosensitive conductive paste constituting the present invention ' is a component which initiates a photoreaction, and is mainly a absorbing ultraviolet ray generating group'. The specific example of the photopolymerization initiator (D) may, for example, be styrene-butadiene-methyl ether, acetoin-ethyl ether or acetoin-isobutyl ether. Ethylene benzoin alkyl ethers; acetophenone, 2,2. dimethoxy-2-phenylphenethyl 2,2-diethoxy-2-phenylacetophenone, 1, Benzene such as 1-dichloroacetophenone; 2-methyl-1 -[-(methylthio)phenyl]-2-morpholinoacetone-1, benzyl-2-dimethylamino-1 -(4-morpholinophenyl)-butanone and other amine ketones; 2-methyl hydrazine, 2-ethyl hydrazine, 2-t-butyl hydrazine, broth, etc. Class; 2,4-dimethylthioxanthone , 2,4-diethylthiopropene methyl acid'), the body of the bismuth-based machine has a low viscosity and is fast (D-free, and even ketone, ethyl ketone 2 · yl benzene 1 - chloro hydrazine - 11 - 1270895 (9) Sulfur-based xanthone class I, such as ketone, 2-chloroxanthone, isopropylthioxanthone, 2,4-diethylthioxanone; ethyl benzophenone a ketal of a ketal, a ketone dimethyl ketal, a benzophenone such as a ketone; or a xanthone; (2,6-dimethoxy azoene)- 2,4,4-pentylphosphine oxide, bis(2,4,6-trimethylphenylene)-phenylphosphine oxide, 2,4,6-trimethylphenylene diphenylphosphine oxide, The phosphine oxides such as ethyl-2,4,6-trimethylphenylene phenylphosphine oxide; various peroxides and the like are not particularly limited, and these may be used alone or in combination of two or more. Further, the blending ratio of the photopolymerization initiator (D) in the paste is suitably from 1 to 3 parts by mass per 1 part by mass of the organic binder (B), preferably from 5 to 20 parts by mass. . When the amount is less than the above range, it is difficult to obtain sufficient photocurability of the paste. On the other hand, when the amount exceeds the above range, a light penetrating barrier is caused, and it is difficult to obtain photocurability at the bottom. Further, the photosensitive conductive paste of the present invention can be blended with a low-melting point glass powder for the purpose of improving the adhesion to a glass substrate and for the strength of the fired film. Low-melting point glass powder, using lead-, lanthanide, phosphorus-based, lithium-based glass transition points (Tg) of 300~500 °C, softening point (Ts) of 400 ~ 600 °C low melting point glass Powder is ideal. When the Tg is lower than 30,000 ° C and the Ts is lower than 40 ° C, the lower temperature than the debonding agent causes melting, and the organic binder is easily occluded, and the residual organic binder is liable to generate bubbles. On the one hand, 'T g exceeds 50,000 t:, T s exceeds 605 t: when, 6 2 0. (The following calcination conditions are insufficient for adhesion to the substrate, which is not preferable. From the viewpoint of resolution, the low-melting-point glass powder preferably has a particle diameter of 10 // m or less, crystallinity or Any one of non-crystalline. -12- 1270895 (10) The mixing ratio of the low-melting point glass powder in the paste is 1 to 30 parts by mass of 100 parts of the silver powder (A) of the present invention. It is more preferably 2 to 15 parts by mass. When the mixing ratio of the low melting point glass powder is low in mass, the adhesion to the substrate cannot be sufficiently obtained. On the other hand, when the mass is 3 parts by mass, the conductivity is lowered. In addition, when deep-light hardness is required, a titanium photopolymerization initiator such as IRUGA CURE 7 84 manufactured by Specialy Chemicals Co., Ltd., which is a free radical polymerization in the visible range, and a combination of a hardening aid such as a white dye may be used as necessary. In order to ensure the preservation stability of the photosensitive conductive paste of the present invention, an anti-foaming agent such as an acidic compound such as a phosphoric acid phosphate, a phosphate ester or a carboxylic acid-containing compound, or a propylene-based defoaming agent can be added to adjust the flow-shake agent. In order to improve the adhesion of the film a coupling agent and other additives. If necessary, a common antioxidant for preventing oxidation of the conductive metal powder, a thermal polymerization for improving the thermal stability during storage, suppressing metal oxides associated with the substrate during calcination, niobium oxide, boron In addition, an inorganic powder such as cerium oxide, oxidized alumina or titanium oxide, an organometallic compound, a metallocate or a metal alkoxide may be added for the purpose of adjusting the calcination shrinkage. For the purpose of adjusting the color tone, a black pigment or a composite metal oxide containing one or two types of Fe, Co, CU, Cr, Μη, Al, RU, and Ni as a main component may be added, and the oxidized three C03 may be added. 〇4), a black material such as cerium oxide or cerium composite oxide. The photosensitive conductive paste of the present invention is an essential component such as the above-mentioned essential component, preferably having a mass exceeding 1 to a depth of Ciba hydrocarbon system, and a polyacrylic acid, a cerium oxide, and a genus of the above-mentioned oxy-cobalt. - 1270895 (11) The optional components of the ratio are uniformly dispersed by a kneader such as a three-roller or a mixer. The thus obtained photosensitive conductive paste of the present invention is formed into a conductor pattern on the substrate by the following procedure. (1) First, the photosensitive conductive paste of the present invention is applied to a substrate such as a plasma display panel (PDP) surface substrate by a suitable coating method such as a screen printing method or a bar coater. The substrate, followed by the dryness of the touch, is dried in a hot air circulating drying oven or an infrared drying oven at 60 to 120 ° C for 5 to 40 minutes, and the solvent is evaporated to obtain a non-stick coating film. The substrate is not particularly limited, and for example, a heat-resistant substrate such as a glass substrate or a ceramic substrate can be used. Further, the paste can be formed into a film in advance, and in this case, the film can be laminated on the substrate. (2) Next, the base is used. Dry coating formed on the material After the pattern exposure and development 〇 exposure step, the negative film with exposure pattern is used for contact exposure or non-contact exposure. Light source for exposure, using halogen lamp, high pressure mercury lamp, laser light, metal incandescent lamp, black lamp, stepless Electric light, etc. The exposure is preferably 50 to l〇〇〇mJ/cm2. The development step uses a spray method or a dipping method. The developing solution is a metal such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium citrate. An aqueous alkaline solution, or an aqueous solution of an amine base such as monoethanolamine, diethanolamine or triethanolamine, particularly preferably a dilute alkaline aqueous solution having a concentration of 1.5% by mass or less, wherein the carboxyl group of the carboxyl group-containing resin in the composition is saponified to remove unhardened The portion (unexposed portion - 14 - 270895 (12) parts) is not limited to the developer as described above, and it is preferable to remove the unnecessary developer after development to perform water washing or acid neutralization. 3) calcining the pattern of the photosensitive conductive paste thus obtained, and the organic component contained in the paste is formed into a predetermined conductor pattern by a debonding agent method. [Embodiment] The following is based on the examples. BEST MODE FOR CARRYING OUT THE INVENTION The present invention is not limited to the following examples, and the following "parts" are parts by mass unless otherwise specified. Organic binders, silver powders, and low-melting glass powders, and the ingredients described later After the mixture was stirred by a stirrer at a predetermined composition ratio, the mixture was further pulverized by a three-roll mill to prepare a photosensitive conductive paste (composition example 1). Further, in addition to the silver powder, the composition example 1 was changed. As shown in Table 1, the photosensitive composite paste composition example 2 (silver powder B) and the comparative composition example 1 (silver powder C) were prepared in the same manner. (Organic adhesive) A thermometer, a stirrer, and a titration were prepared. The flask of the funnel and reflux cooler was charged with 〇87:0.13 molar ratio of methyl methacrylate and methacrylic acid, dipropylene glycol monomethyl ether as solvent, azodibutyl hydrazine as catalyst, and nitrogen gas. Under the environment, the mixture was stirred at 80 ° C for 2 to 6 hours to obtain a resin solution. The organic binder (copolymer resin) in this resin solution had a weight average molecular weight of 105,000 and an acid value of 74 mgKOH/g. In addition, the weight average molecular weight of the obtained organic binder is based on the Japanese island -15- 1270895 (13) Tsugaru Rupee L c - 6 AD and the Japanese Showa Denko glass column Shodex (registered trademark) KF-804, KF-803, KF-8 02 and high-speed chromatograph connected to three-roller. (Silver powder) Silver powders A, B, and C were used as shown in Table 1 for the half-width, average particle diameter, and specific surface area. In addition, the X-ray diffraction pattern of the silver powder of the X-ray analysis apparatus (RINT-1500) is half-width of the Ag (1 1 1 ) surface ridge, but the particle size is The average particle size of 1 silver powder was observed by SEM. Its production method is as follows.
銀粉末A 5 L 20 g / L之硝酸銀水溶液作爲銀離子，加入 3 5 0 mL工業用氨，得到銀的胺絡溶液。加入純水5 L稀 釋，加入作爲還原劑32 mL之80 %肼溶液，隨即加 0.43 g油酸。水洗如此所得之銀淤漿，乾燥得到銀粉末 A 〇Silver powder A 5 L 20 g / L silver nitrate aqueous solution was used as silver ion, and 350 mL of industrial ammonia was added to obtain a silver amine solution. Add 5 L of pure water to dilute, add 32 mL of a solution of 80% hydrazine as a reducing agent, and then add 0.43 g of oleic acid. The silver slurry thus obtained is washed with water and dried to obtain a silver powder A 〇
銀粉末B 5 L 20 g / L之硝酸銀水溶液作爲銀離子，加入40 mL之1〇〇 g / L度之氫氧化鈉調節pH，加入450 mL工業 用氨，得到銀的胺絡溶液。加入純水5 L稀釋，加入還元 劑工業用馬林5 00 mL，隨即加0.43 g油酸。水洗如此所 -16- (14) 1270895 得之銀漿，乾燥得到銀粉末B。Silver powder B 5 L 20 g / L silver nitrate aqueous solution was used as silver ion, 40 mL of 1 〇〇 g / L sodium hydroxide was added to adjust the pH, and 450 mL of industrial ammonia was added to obtain a silver amine solution. Add 5 L of pure water to dilute, add 5 00 mL of the refinery industrial Marlin, and then add 0.43 g of oleic acid. Wash the silver paste so that it is -16- (14) 1270895 and dry to obtain silver powder B.
銀粉末C 純水3 3 0 0 g攪拌邊添加硝酸銀水溶液（相當於3 8 g 銀），氨水溶液（相當於3 4 g氨），攪拌15分鐘後，添加 5 g硝酸銨、硬脂酸鈉溶液5 0 mL (硬脂酸鈉添加比率： 500 ppm / Ag)，其後，於240秒內同時各自以100 mL / 分）之速度添加過氧化氫水溶液（3.3 mol / L )及氫氧化 鈉水溶液（〇·8 mol / L)。水洗如此所得之銀漿，乾燥得 到銀粉末C。 表1 半寬値（°) 平均粒徑 比表面積 (// m ) (m2 / g) 銀粉末A 0.446 1 1 .1 0.45 銀粉末B 0.2480 1.2 0.43 銀粉末C 0.1354 1.2 0.42Silver powder C pure water 3 3 0 0 g, add silver nitrate aqueous solution (equivalent to 3 8 g silver), ammonia solution (equivalent to 34 g ammonia), stir for 15 minutes, add 5 g ammonium nitrate, sodium stearate Solution 50 mL (sodium stearate addition ratio: 500 ppm / Ag), then add hydrogen peroxide solution (3.3 mol / L) and sodium hydroxide at a rate of 100 mL / min in 240 seconds Aqueous solution (〇·8 mol / L). The silver paste thus obtained was washed with water and dried to obtain a silver powder C. Table 1 Semi-wide 値 (°) Average particle size Specific surface area (// m ) (m2 / g) Silver powder A 0.446 1 1 .1 0.45 Silver powder B 0.2480 1.2 0.43 Silver powder C 0.1354 1.2 0.42
(低融點玻璃粉末） 低融點玻璃粉末，係粉碎成分組成爲Bi2〇3 : 49%、 B 2 0 3 : 1 4%' Ζ η Ο ： 14%、S i 0 2 : 6 %、B a 0 : 17%，熱膨脹 係數a 3gg=85 X 1 0 /°C，玻璃轉移溫度460°C之低融點 玻璃，平均粒徑爲1 · 6 // m。 -17- 1270895 (15) (組成物例1) 1 0 0 · 0 份 4 5 · 0 份 1 〇 · 〇 份 1.0份 90.0 份 5 5 0.0 份 2 5 · 0 份 2.0份 1·〇份(Low-melting point glass powder) Low-melting point glass powder, the composition of the pulverized component is Bi2〇3: 49%, B 2 0 3 : 1 4%' Ζ η Ο : 14%, S i 0 2 : 6 %, B a 0 : 17%, thermal expansion coefficient a 3gg=85 X 1 0 /°C, low melting point glass with a glass transition temperature of 460 ° C, and an average particle diameter of 1 · 6 // m. -17- 1270895 (15) (Composition example 1) 1 0 0 · 0 parts 4 5 · 0 parts 1 〇 · 〇 Parts 1.0 parts 90.0 parts 5 5 0.0 parts 2 5 · 0 parts 2.0 parts 1·〇份
有機粘劑A 三羥甲基丙烷三丙烯酸酯 2-苄基-2-2二甲基胺基-1-(4-嗎啉代苯基）· 丁酮-1 2,4-二乙硫基咕噸酮 二丙二醇單甲基醚 銀粉 A 玻璃粉末 磷酸酯 消泡劑（BYK-354:日本 BIKKU-CHEMI • JAPAN 製） 如此所得之組成物例1，2，比較組成物例1之各感 光性導電糊料評價其解像性、比電阻、密合性、煅燒收縮 。其評價方法如以下所述。 製作試驗片： 玻璃基板上，以180 mesh之聚酯網版全面塗覆評價 用之各感光性導電糊料，其次，以90 °C熱風循環式乾燥 爐乾燥20分鐘形成指觸感乾燥性良好之塗膜。續之，使 用金屬高熾燈爲光源，介以負片圖型膜，使乾燥塗膜上之 積分光量爲3 00 mJ / cm2進行圖型曝光後，使用液溫30 °C之0.5質量％ Na2C03水溶液進行顯影，水洗。由此形 -18- 1270895 (16) 成塗膜圖型之基板，於空氣環境下以5C/分昇溫至55〇C ，以5 7 0 °C煅燒30°C，製作成形成導電體圖型之試驗片。 (解像性）： 評價依上述製作之試驗片之最細的線寬。 (比電阻）： 依上述方法製成4 mm xlO cm具圖型之試驗片’測 定圖型之電阻及厚度’計算比電阻。 (密合性）： 依上述方法製作之試驗片，進行膠帶剝落試驗’評價 圖型有否剝落。評價基準如下。 〇：圖型無剝落 X :圖型有剝落 (煅燒收縮率（寬、厚））： 依上述方法形成之導電體圖型，膜幅1 0 0 β m之線條 測定顯影後及顯像後之線幅、膜厚，計算收縮率（％)。 其評價結果如表2所示。 1270895 (17) 表2 實施例 組成物 組成物 比較組成 例1 例2 物例1 解像性 β m 10 10 10 比電阻 2.2 2.3 3.9 xl (Γ5 Ω · cm 密合性 〇 〇 〇 煅燒收縮率（幅）％ 16 17 17 煅燒收縮率（厚）％ 71 72 62Organic Adhesive A Trimethylolpropane Triacrylate 2-Benzyl-2-2dimethylamino-1-(4-morpholinophenyl)· Butanone-1 2,4-Diethylthio Xanthone Dipropylene Glycol Monomethyl Ether Silver Powder A Glass Powder Phosphate Defoamer (BYK-354: Japan BIKKU-CHEMI • JAPAN) Compositions 1 and 2 thus obtained were compared for each photosensitive property of Composition Example 1. The conductive paste was evaluated for its resolution, specific resistance, adhesion, and calcination shrinkage. The evaluation method is as follows. Preparation of test piece: On the glass substrate, each of the photosensitive conductive pastes for evaluation was completely coated with a polyester mesh of 180 mesh, and secondly, dried in a hot air circulating drying oven at 90 ° C for 20 minutes to form a good touch dryness. Coating film. Continued, using a metal incandescent lamp as the light source, with a negative film pattern, the integrated light amount on the dried coating film is 300 mJ / cm2 for pattern exposure, and then developing with a 0.5% by mass Na2C03 aqueous solution at a liquid temperature of 30 °C. , washed. Thus, the substrate of the coating pattern of -18- 1270895 (16) is heated to 55 〇C at 5 C/min in an air atmosphere, and calcined at 30 ° C at 570 ° C to form a conductor pattern. Test piece. (Resolving property): The thinnest line width of the test piece prepared as described above was evaluated. (Specific resistance): A test piece of 4 mm x lO cm pattern was prepared by the above method. [Resistance and thickness of the measured pattern] The specific resistance was calculated. (Adhesiveness): The test piece prepared by the above method was subjected to a tape peeling test to evaluate whether the pattern was peeled off. The evaluation criteria are as follows. 〇: The pattern has no peeling X: The pattern has peeling (calcination shrinkage (width, thickness)): The pattern of the conductor formed by the above method, the line of the film width of 100 μm is measured after development and after development. The line width and film thickness were calculated and the shrinkage ratio (%) was calculated. The evaluation results are shown in Table 2. 1270895 (17) Table 2 Example composition composition comparison composition example 1 Example 2 Example 1 Resolving property β m 10 10 10 Specific resistance 2.2 2.3 3.9 xl (Γ5 Ω · cm Adhesion 〇〇〇 calcination shrinkage ratio ( Amplitude)% 16 17 17 Calcination shrinkage (thickness)% 71 72 62
由此表所示結果可清楚，依本發明感光性導電糊料， 確認可容易形成導電性及解像性均優之導電體圖型。 (發明的功效） 如以上所說明，依本發明可提供高精密圖型之成形性 及620°C以下溫度之煅燒性均優之感光性導電糊料。其結 果’由於可在620 °C以下溫度煅燒，可不必經複雜的步驟 可容易形成導電性及解像性均優之導電體圖型。 -20-As is apparent from the results shown in the table, it was confirmed that the photosensitive conductive paste of the present invention can easily form a conductor pattern having excellent conductivity and resolution. (Effect of the Invention) As described above, according to the present invention, it is possible to provide a photosensitive conductive paste which is excellent in formability of a high-precision pattern and calcinability at a temperature of 620 ° C or lower. As a result, since it can be calcined at a temperature of 620 ° C or lower, it is possible to easily form a conductor pattern having excellent conductivity and resolution without complicated steps. -20-