201247808 六、發明說明： 【發明所屬之技術領域】 本發明有關導電性膏及使用其之導電電路之製造方法 【先前技術】 近幾年來，於多功能擺帶式終端機等之使用觸控面板 之電子裝置中，已使用於例如PET等之薄膜上形成ιτο( 銦錫氧化物）電極之ΙΤΟ薄膜。 此種ΙΤΟ薄膜係藉由於薄膜上形成ΙΤΟ層，使電極部 分殘留而予以鈾刻去除（蝕刻掉）而形成。接著，於露出之 薄膜上及ΙΤΟ層上使用將Ag等之導電性粉末分散於有機 黏合劑中之導電性膏而形成導電電路。 於使用如此薄膜等之耐熱性低的裝置中可低溫燒成之 導電性膏已有多種提案（例如參考專利文獻1等）。然而， 關於I TO薄膜上之導電電路，對於薄膜及I TO層之密著性 並不充分，而有產生剝離等缺陷之問題，於蝕刻掉的部分 尤爲顯著。 另一方面，於電子裝置中之高精細導電電路之形成， 一般係使用於有機黏合劑等中利用使用感光性樹脂等之感 光性導電性膏之光微影術。然而，光微影術係藉由去除材 料而形成導電電路之減法製程，所用之導電性膏的使用效 率低、步驟複雜，於濕式製程中需要較大設備。 相對於此，作爲於特定部位附加材料之加法製程之凹 -5- 201247808 版印刷、凹版平版印刷等之印刷法受到矚目。例如依據凹 版平版印刷，藉由對凹版供給導電性钲，將其例如依序轉 印至聚矽氧製的外包部（blanket)、基材，可形成導電電路 〇 * 於此種印刷法中，由於係透過版將導電性讶轉印至基 材上，因此對於所用之導電性订要求良好的轉印性。尤其 於凹版平版印刷，由於係將導電性眘自凹版透過外包部轉 印至基材上，故有必要於各步驟確實轉印導電性臂，於連 續印刷中，要求有自外包部朝基材之轉印率爲1 00%或抑 制轉印於基材上之印刷物之形狀不良等之印刷適性優異之 订。 且，於利用印刷法於耐熱性低的裝置中形成導電電路 時，不僅要求订的良好印刷適性，亦要求於利用低溫燒成 所形成之導電電路中之良好電特性。然而，有難以獲得同 時滿足該等之订之問題。 [先前技術文獻] [專利文獻1 ]特開2 0 0 4 - 3 5 5 9 3 3號公報 【發明內容】 [發明欲解決之課題] 本發明係爲解決該等課題而開發者，第一目的係提供 與I TO薄膜之密著性優異、且於利用低溫製程形成之導電 電路中可獲得良好導電性之導電性贷，第二目的係提供除 了上述特性以外亦具有於凹版平版印刷中之優異印刷適性 -6- 201247808 之導電性膏。 [用以解決課題之手段] 本實施形態之一樣態之導電性膏之特徵爲含有胺基甲 酸酯樹脂、導電粉末及有機溶劑。藉由此種構成，使與 ITO薄膜之密著性優異、且於利用低溫製程形成之導電電 路中可獲得良好導電性。 又，本實施形態之導電性膏中，較好胺基甲酸酯樹脂 包含有羧基之胺基甲酸酯樹脂。 藉由此種構成，可提高胺基甲酸酯之凝集力，更提高 與ITO薄膜之密著性。 又，本實施形態之導電性膏之特徵爲更含有於至少1 分子中包含2個以上縮水甘油基之環氧樹脂作爲交聯劑。 藉由此種構成，可於導電電路形成中形成3次元網眼 鏈，而提高所得導電電路之耐溶劑性、密著性。 又，本實施形態之導電電路之形成方法之特徵爲在 ITO薄膜上，形成由上述導電性膏所成形之圖型的塗膜， 且以80〜200°C以該塗膜乾燥或硬化。 藉由此種構成，可獲得與ITO薄膜之密著性優異、所 形成之導電電路中之良好導電性。 且，本實施形態之一樣態中之導電性膏之特徵爲上述 有機溶劑含有30〜90質量％之在760mmHg之沸點爲240 〜3 3 0 °C之高沸點溶劑。藉由此種構成，除了上述特性以 外，亦可獲得在凹版平版印刷中之印刷物之直行性、線寬 201247808 再現性等之優異印刷適性。 又’本實施形態之導電電路之形成方法之特徵爲將上 述導電性订塡充於版上，將被塡充之上述導電性订進行一 次轉印至膠印滾筒（blanket cylinder)表面，將以被一次轉 印之前述導電性膏二次轉印至基材表面，以80〜200 °C使 被二次轉印之上述導電性钌乾燥或硬化。 於藉由此種構成形成之導電電路，具有良好導電性， 同時由於具有良好直行性、線寬再現性，故可獲得具有高 信賴性、導電特性之電子裝置。 又，本實施形態之電子裝置之特徵爲具備ITO薄膜、 與形成於上述ITO薄膜上之含有胺基甲酸酯樹脂及導電粉 末之導電電路。 藉由此種構成，導電電路與ITO薄膜之密著性優異， 具有良好導電性，故可獲得具有高信賴性、導電特性之電 子裝置。 [發明效果] 依據本發明，可提供可獲得與ITO薄膜之密著性優異 、藉低溫製程形成之導電電路之良好導電性之導電性订。 又，除了上述特性以外，亦可獲得在凹版平版印刷中之印 刷物之直行性、線寬再現性等之優異印刷適性》 【實施方式】 本發明之發明人等鑒於上述課題進行積極檢討之結果 -8- 201247808 ，發現藉由含有胺基甲酸酯樹脂、導電粉末及有機溶劑作 爲導電性膏，可獲得與ITO薄膜之密著性優異、藉低溫製 程形成之導電電路之良好導電性，進而發現藉由於上述有 機溶劑中含有30〜90質量％之在760mmHg之沸點爲240 〜3 3 0 °C之高沸點溶劑，除了上述特性以外，亦可獲得在 凹版平版印刷中之朝基板等之被轉印體之轉印性、轉印後 之印刷物之直行性、線寬再現性等之優異印刷適性，因而 完成本發明。 以下，針對本實施形態之導電性膏加以說明》 本實施形態之導電性膏爲由含有胺基甲酸酯樹脂、導 電粉末及有機溶劑者。 本實施形態之導電性膏中胺基甲酸酯樹脂，係作爲對 膏賦予良好印刷適性、殘存於該硬化物（導電電路）中而賦 予密著性或耐彎曲性、硬度等物性之黏合劑樹脂而使用者 。作爲此種胺基甲酸酯樹脂，若爲可對導電性膏賦予印刷 適性者，即無特別限制，舉例有例如含羧基之胺基甲酸酯 樹脂、含酚性羥基之胺基甲酸酯樹脂、含胺基之胺基甲酸 酯樹脂等。 其中，尤其以含羧基之胺基甲酸酯樹脂較佳。係使用 例如使聚異氰酸酯（a)、雙酚A型環氧烷加成物二醇（b)、 聚碳酸酯多元醇（c)及二羥甲基烷酸（d)反應而形成之具有 胺基甲酸酯鍵且含有藉由二羥甲基烷酸（d)而導入之羧基者 。於反應之際，亦可添加單羥基化合物（e)作爲反應終止劑 (末端封端劑）。 201247808 該種胺基甲酸酯樹脂可藉由使例如聚異氰酸酯（a)、雙 酚A型環氧烷加成物二醇（b)、聚碳酸酯多元醇（c)、二羥 甲基烷酸（d)及作爲反應終止劑（末端封端劑）發揮功能之單 羥基化合物（e)—起混合並反應，或使聚異氰酸酯（a)、雙 酚A型環氧烷加成物二醇（b)、聚碳酸酯多元醇（c)及二羥 甲基烷酸（d)反應，接著與單羥基化合物（e)反應而獲得》 該反應係藉由在室溫〜1 〇〇 °C攪拌、混合以無觸媒進行， 但未提高反應速度，較好加熱至70〜100°C。 作爲聚異氛酸酯（a)，具體舉例有例如2,4-甲苯二異氛 酸酯、2，6-甲苯二異氰酸酯、異佛爾酮二異氰酸酯、六亞 鉀基二異氛酸酯、二苯基甲烷二異氛酸酯、（鄰-、間-或 對·）二甲苯二異氰酸酯、（鄰-、間·或對-)氫化二甲苯二異 氛酸酯、亞甲基雙（環己基異氛酸酯）、三甲基六亞甲基二 異氰酸酯、環己烷-1，3-二亞甲基二異氛酸酯、環己烷-丨，4-二亞甲基二異氛酸酯、1，5-萘二異氰酸酯等之二異氛酸酯 。該等聚異氛酸酯可使用1種或組合2種以上使用。 該等中，較好爲甲苯二異氰酸酯、三甲基六亞甲基二 異甄酸酯。使用該等二異氛酸酯時，可獲得焊接耐熱性優 異之硬化物。 至於雙酚A型環氧烷加成物二元醇（b)，舉例有雙酚 A之環氧乙烷加成物、環氧丙烷加成物、環氧丁烷加成物 等，但該等中以雙酚A之環氧丙烷加成物較佳. 接著’作爲聚碳酸酯多元醇（c)，較好爲聚碳酸酯二元 醇。至於聚碳酸酯二元醇舉例有含有源自1種或2種以上 -10- 201247808 之直鏈狀脂肪族二元醇之重複單位作爲構成單位之聚碳酸 酯二元醇、含有源自1種或2種以上之脂環式二元醇之重 複單位作爲構成單位之聚碳酸酯二元醇、或含有源自該兩 者之二元醇之重複單位作爲構成單位之聚碳酸酯二元醇。 該等聚碳酸酯二元醇可藉由使直鏈狀脂肪族或脂環式二元 醇與例如碳酸酯之酯交換反應或藉由與碳醯氯反應等而製 造。 至於含有源自直鏈狀脂肪族二元醇之重複單位作爲構 成單位之聚碳酸酯二元醇，具體舉例有例如自1，6-己烷二 醇衍生之聚碳酸酯二元醇、自1，5-戊二醇及1,6-己二醇衍 生之聚碳酸酯二元醇、自1，4-丁二醇及1，6-己二醇衍生之 聚碳酸酯二元醇、自3-甲基-1，5-戊烷二醇及1,6-己烷二醇 衍生之聚碳酸酯二元醇》 至於含有源自脂環式二元醇之重複單位作爲構成單位 之聚碳酸酯二元醇具體舉例有例如自1,4-環己烷二甲醇衍 生之聚碳酸酯二元醇。 至於含有源自直鏈脂肪族二元醇及脂環式二元醇兩者 之重複單位作爲構成單位之聚碳酸酯二元醇具體舉例有例 如自1,6-己烷二醇及1，4-環己烷二己醇衍生之聚碳酸酯二 元醇。 含有源自直鏈狀脂肪族二元醇之重複單位作爲構成單 位之聚碳酸酯二元醇有低翹曲性或可撓性優異之傾向。且 含有源自脂環式二元醇之重複單位作爲構成單位之聚碳酸 酯二元醇有結晶性高、耐鍍錫性、焊接耐熱性優異之傾向 -11 - 201247808 。由以上觀點而言，可組合使用該等聚碳酸酯二 種以上，或亦可使用含有源自直鏈脂肪族二元醇 二元醇兩者之重複單位作爲構成單位之聚碳酸酯 就平衡良好地展現低翹曲性或可撓性、焊接耐熱 錫性而言，較好使用直鏈脂肪族二元醇及脂環式 共聚合比例以質量比計爲3: 7〜7: 3之聚碳酸 e 聚碳酸酯二元醇較好爲數平均分子量200〜 ，但於聚碳酸酯二元醇含有源自直鏈狀脂肪族二 環式二元醇之重複單位作爲構成單位，且直鏈脂 醇及脂環式二元醇之共聚合比例以質量比計爲3 : 時，較好爲數平均分子量爲400〜2,000者。 二羥甲基烷酸（d)爲具有羧基之二羥基脂肪族 體舉例有例如二羥甲基丙酸、二羥甲基丁酸等。 二羥甲基烷酸，可容易地於胺基甲酸酯樹脂中導」 至於單羥基化合物（e)係作爲聚胺基甲酸酯之 劑者，只要於分子中具有1個羥基之化合物即可 脂肪族醇、單羥基單（甲基）丙烯酸酯化合物等。 至於脂肪族醇，具體舉例有例如甲醇、乙醇 異丁醇等，至於單羥基單（甲基）丙烯酸酯化合物 例有例如丙烯酸2-羥基乙酯等。 含有羧基之胺基甲酸酯樹脂之重量平均分子 〜1 00,000。含有羧基之胺基甲酸酯樹脂之重量: 量未達5 00時，會有損及硬化膜之伸長度、可撓 元醇之2 及脂環式 二元醇。 性或耐鍍 二元醇之 酯二元醇 5,000 者 元醇與脂 肪族二元 7〜7 : 3 羧酸，具 藉由使用 \羧基。 末端封端 ，舉例有 、丙醇、 ，具體舉 量爲5 0 0 平均分子 性以及強 -12- 201247808 度之情況，另一方面超過1 0 0,000時會有變硬而使可撓性 降低之虞。更好爲 4,000〜50,000，又更好爲 6,000〜 3 0,0 00。又，本說明書中之重量平均分子量爲以凝膠滲透 層析儀測定並經聚苯乙烯換算之値》 含羧基之胺基甲酸酯樹脂之酸價較好在 5〜150 mgKOH/g之範圍。酸價未達5mgKOH/g時，膏之凝集力降 低、於印刷時容易引起轉移不良。另一方面，酸價超過 150mgKOH/g時，膏的黏度變得過高、必須調配多量之交 聯劑等，而難以賦予印刷適性。更好爲10〜100mgKOH/g 。樹脂酸價係依據JIS K5407測定之値。 且作爲彌補印刷性之目的，亦可含有胺基甲酸酯樹脂 以外之有機黏合劑。具體舉例有例如聚酯樹脂、胺基甲酸 酯改質之聚酯樹脂、環氧基改質之聚酯樹脂、丙烯酸改質 之聚酯樹脂等之各種改質聚酯樹脂、氯乙烯·乙酸乙烯酯 共聚物、環氧樹脂、酚樹脂、丙烯酸樹脂、聚乙烯縮丁醛 樹脂、聚醯胺醯亞安、聚醯亞胺、聚醯胺、硝基纖維素、 纖維素·乙酸酯· 丁酸酯（CAB)、纖維素·乙酸酯·丙酸 酯（CAP)等之改質纖維素類等。 其中，由其較好爲至少1分子內含有2個以上羧基之 含有羧基之樹脂。該種含有羧基之樹脂具體舉例有如下所 列舉之樹脂，但不限定於該等。 (1)藉由使（甲基）丙烯酸等之不飽和羧酸與其以外之具 有不飽和鍵之化合物之1種以上共聚合而得之含有羧基之 樹脂。 -13- 201247808 (2) 藉由於（甲基）丙烯酸等之不飽和羧酸與其以外之具 有不飽和鍵之化合物之1種以上共聚物中’加成丁基縮水 甘油醚、苯基縮水甘油醚等之單官能環氧化合物而得之含 有羧基之樹脂。 (3) 使（甲基）丙烯酸縮水甘油酯或（甲基）丙烯酸3,4-環 氧基環己基甲酯等之含有環氧基及不飽和雙鍵之化合物及 其以外之具有不飽和雙鍵之化合物之共聚物，與丙酸等之 飽和羧酸反應而生成之二級羥基，再與多元酸酐反應而得 之含有羧基之樹脂。 (4) 使馬來酸酐等之具有不飽和鍵脂酸酐及其以外之具 有不飽和鍵之化合物之共聚物，與丁醇等之具有羥基之化 合物反應而得之含有羧基之樹脂。 (5) 使多官能環氧化合物與飽和單羧酸反應而生成之羥 基再與不飽和多元酸酐反應而得之含有羧基之樹脂。 (6) 使聚乙烯醇衍生物等之含有羥基之聚合物與飽和或 不飽和多元酸酐反應而得之含羥基及羧基之樹脂。 (7) 對於使多官能環氧化合物、飽和單羧酸、1分子中 具有至少1個醇性羥基及與環氧基反應之醇性羥基以外之 1個反應性基之化合物之反應生成物，反應飽和或不飽和 多元酸酐而得之含有羧基之樹脂。 (8) 使於1分子中具有至少2個氧雜環丁烷之多官能氧 雜環丁烷化合物與飽和單羧酸反應所得之改質氧雜環丁烷 樹脂中之一級羥基再與飽和或不飽和多元酸酐反應而得之 含有羧基之樹脂。 -14- 201247808 (9)使多官能環氧樹脂與飽和單羧酸反應後，與多元酸 酐反應而得之含有羧基之樹脂上，再與分子中具有1個環 氧乙烷環之化合物反應而得之含有羧基之樹脂。 該等中，尤其較好使用（1)、（2)及（3)之含有羧基之樹 脂。該等可任意調整分子量、玻璃轉移點等，而可適當控 制膏之印刷適性之調整、對於基材之密著性。 且，該種含有羧基之樹脂之酸價，較好爲40〜200 mgKOH/g。含有羧基之樹脂酸價未達40mgKOH/g時，膏 之凝集力降低而容易引起印刷時之轉移不良。另一方面， 超過200mgKOH/g時，膏的黏度變過高、必須調配多量交 聯劑，而難以賦予印刷適性。更好爲45〜150mgKOH/g。 胺基甲酸酯樹脂以外之有機黏合劑之調配量，宜在不 損及對於ITO薄膜之密著性之範圍內添加》胺基甲酸酯樹 脂以外之有機黏合劑之調配比例較好於有機黏合劑中之5 0 質量％以下。調配量若超過50質量％，則ITO薄膜與基材 之密著性降低而不佳。且於凹版平版印刷，印刷物之線寬 會產生混亂，且損及膏之特性，而較不佳。更好爲30質 量％以下。 本實施形態之導電性膏中之導電粉末爲對所形成之導 電電路賦予導電性者，具體可舉例爲例如Ag、Au、Pt、 Pd、Ni、Cu ' A1 ' Sn、Pb、Zn、Fe、Ir、Os、Rh、W、 Mo、Ru 等。 該等導電性粉末不限於以單體形態使用者，亦可爲該 等之任意合金或以該等任意者作爲芯或被覆層之多層體。 -15- 201247808 再者，亦可使用氧化錫（Sn〇2)、氧化銦（Ιη203)、ITO(銦錫 氧化物）等之氧化物。 至於其形狀，可使用球狀、薄片狀、樹枝狀等之各種 形狀者，但若特別考慮印刷適性或分散性，則較好使用球 狀者爲主體。 該等導電粉末，以導電性膏之不揮發成分（於乾燥步 驟不自贷中揮發而殘存於膜中之成分）爲基準，較好爲85 〜95質量％。若未達85質量％，則難以獲得充分之導電性 ，若超過95質量％，則難以獲得充分之印刷適性，或難以 維持導電電路之形狀。更好爲90〜94質量％。 .導電粉末粒徑使用球狀導電粉末時，使用電子顯微鏡 (SEM)以1 0,000倍觀察隨機10個導電粉末之平均粒徑較 好爲0.1〜5μηι。平均粒徑未達Ο.ΐμπι時，難以引起導電 粉末彼此之接觸而使導電性降低。另一方面，平均粒徑超 過5 μιη時，難以獲得印刷時之線邊緣之直行性。更好爲 0 · 4 〜2 μηι。 又，較好使用由粒度分佈測定裝置（MICRO TRAC)測 定之平均粒徑爲0.5〜3.5μηι之大小者。 又，使用薄片狀導電粉末時，使用電子顯微鏡（SEM) 以1 0,000倍觀察隨機10個導電粉末之平均粒徑較好爲 0.1〜ΙΟμιη。平均粒徑未達Ο.ΐμπι時，難以引起導電粉末 彼此之接觸而使導電性降低。另一方面，平均粒徑超過 1 0 μιη時，難以獲得印刷時之線邊緣之直行性。更好爲〇.4 〜5 μ m。 -16- 201247808 又，較好使用由粒度分佈測定裝置（MICRO TRAC)測 定之平均粒徑爲〇.5〜之大小者。 作爲該等導電粉末較好爲銀粉末，該情況下’銀粉末 之比表面積較好爲0.01〜2m2/g。比表面積未達0.01m2/g 時，於保存時容易引起沉降，另一方面，比表面積超過 2m2/g時，吸油量變大而損及膏之流動性。更好爲〇·5〜 1 · 5 m2/g。 本實施形態之導電性膏中之有機溶劑爲用以賦予良好 印刷適性所用者。至於該種有機溶劑，爲不與胺基甲酸酯 樹脂產生化學反應而可溶解者，尤其爲了防止凹版平版印 刷等之印刷過成之膏的乾燥，並保有轉印性，導電性膏中 所含之有機溶劑中有必要含有在760mmHg下之沸點爲240 〜33 0°C之範圍的高沸點溶劑。 高沸點溶劑在760mmHg下之沸點若低於24CTC，則印 刷時之膠印滚筒轉印步驟（off mode)-圖型轉印步驟（set mode)中轉印於膠印滾筒之膏容易乾燥，於固定步驟無法 轉印至基材。另一方面，若高於3 3 0 °C，則於上述印刷步 驟之乾燥雖可受抑制，但印刷後之乾燥步驟中於印刷物中 容易殘存溶劑，而引起電阻値上升、密著性降低等之缺陷 。更好爲240〜300°C。 又’導電性膏中所含之有機溶劑中之高沸點溶劑之比 例較好爲3 0〜9 0質量％。高沸點溶劑之比例少於3 〇質量 %時’難以獲得印刷物係以比版尺寸更細地印刷之良好印 刷物。另一方面’若多於90質量％ ’則容易於印刷物中產 -17- 201247808 生滲出’仍然無法獲得良好印刷物。更好爲3〇〜⑽質量％ 之比例。 —° 至於此種高沸點溶劑，舉例有二戊基苯（沸點：26〇〜 HOC )、二戊基苯（沸點：3〇〇〜32(Γ(：)、正·十二院醇⑽ 點.255〜259°C)、二乙二醇（沸點：245 〇c)'二乙二醇單 丁醚乙酸酯（沸點：247t ) '二乙二醇二丁醚（沸點· 255 t： )—乙—醇單乙酸酯（沸點：25〇艺）、三乙二醇（沸點： 276C)、二乙—醇單甲基醚（沸點：249。〇）、三乙二醇單乙 醚（沸點：2 5 6。〇 )、三乙二醇單丁醚（沸點：271 t )、四乙 一醇（沸點：3 2 7 °C )、四乙二醇單丁醚（沸點：3 〇 4 〇c )、三 丙一醒（沸點：267 °C)、三丙二醇單甲醚（沸點：243 °C)、 ’，-二甲基-1,3-戊二醇單異丁酸酯（沸點：25 3 eC)等。又 ’作爲石油系烴類’亦舉例有新日本石油公司製之AF溶 劑4號（沸點：240〜265 °C )、5號（沸點：275〜306°C )、6 號（沸點：296〜317 °C)、7號（沸點：259〜282 °C)及〇號 溶劑H(沸點：245〜265 t)等，依據需要亦可含有該等之 2種以上。該等中，較好使用三乙二醇衍生物或三丙二醇 衍生物。 至於上述高沸點溶劑以外之有機溶劑，舉例有例如甲 本、二甲苯、乙酸乙酯、乙酸丁酯、甲醇、乙醇、異丙醇 、異丁醇、1· 丁醇、二丙酮醇、二乙二醇、乙二醇單丁醚 、—乙二醇單丁酸乙酸酯、三乙二醇單甲醚、丙二醇單甲 醜、两二醇單乙醚、丙二醇單甲醚乙酸酯、三丙二醇單甲 酸、碎品醇、甲基乙基酮、卡必醇、卡必醇乙酸酯、丁基 -18- 201247808 卡必醇等。該等可以單體使用或可混合2種以上使用。 本實施形態之導電性膏之黏度，尤其使用於凹版平版 印刷時，爲獲得良好印刷適性，以錐板形黏度計之測定値 (25°C)較好爲50〜lOOOdPa. s。黏度未達50 dPa. s時， 導電性膏中之有機溶劑比例過多，使轉印性降低而成爲難 以良好印刷。另一方面，黏度超過lOOOdPa · s時，難以 塡充於凹版中，且於刮板之錄寫性惡化，容易產生污染（ 膏對非畫線部之附著）。更好爲100〜650dPa. s。又，亦 可於印刷時適當稀釋。 且，該種導電性膏之顯示動態黏著性的黏性（tack)値 較好爲5〜3 5。黏性値未達5時，有印刷時之轉移性差而 使印刷品質惡化之情況。另一方面，黏性値超過3 5時， 容易引起印刷時被印刷物之投梭（picking)(被印刷物之破 損）或堵塞（被印刷物堵塞於印刷機中）。更好爲1 0〜3 0。 又，黏性値係使用旋轉黏性計（rotary tack meter)( —般名 :Incometer)，於30°C、400轉之條件下測定之値。 又’本實施形態之導電性膏中，爲了形成3次元網目 鏈構造，提高所形成之導電電路之耐溶劑性、密著性，較 好進而含有交聯劑。 作爲交聯劑，只要不使印刷適性劣化而可與胺基甲酸 酯反應、交聯即可。作爲此種交聯劑，只要爲藉由加熱可 硬化之樹脂則無特別限制，但舉例有例如環氧樹脂、酚樹 脂、三聚氰胺樹脂、醇酸樹脂、聚酯樹脂、丙烯酸樹脂、 聚醯亞胺樹脂以及該等之改質樹脂。該等可單獨使用或組 -19- 201247808 合2種以上使用。此外，舉例有分子中至少具有2個氧雜 環丁烷基之氧雜環丁烷化合物等。 該等交聯劑中，較好包含至少於1分子中含有2個以 上縮水甘油基之環氧樹脂。至於該種環氧樹脂，舉例有例 如雙酚A型、氫化雙酚A型 '雙酚F型、雙酚S型、酚 酚醛清漆型、甲酚酚醛清漆型、雙酚A之酚醛清漆型、聯 酚型、聯二甲酚型、三酚甲烷型、N -縮水甘油型、N -縮水 甘油型之環氧樹脂、脂環式環氧樹脂等之公知環氧樹脂， 但並非特別限定於該等，且該等可單獨使用或組合2種以 上使用。其中，藉由使用環氧當量（含有1克當量之環氧 基的樹脂克數）爲1〇〇〜3 00之範圍的環氧樹脂，則可少量 添加而效率良好地交聯故而較佳。 該等環氧樹脂之調配率|每胺基甲酸酯樹脂1〇〇質量 份宜爲1〜100質量份，較好爲5〜40質量份。 且，該等以外，亦可調配爲了促進胺基甲酸酯樹脂與 交聯劑之反應之胺化合物、咪唑衍生物等之硬化觸媒、或 在不損及印刷適性之範圍內，調配金屬分散劑、觸變性賦 予劑、消泡劑、勻化劑、可塑劑、抗氧化劑、金屬惰性化 劑、偶合劑或塡充劑等之添加劑。 使用此種導電性讶，如下述般形成導電電路。 首先，於ITO薄膜上，形成由導電性裔所成形之圖型 的塗膜。此時，作爲印刷方法，爲網版印刷、平版印刷、 凹版平版印刷等，並無特別限制。 如此於ITO薄膜上形成之塗膜，在60〜120°c乾燥1 -20- 201247808 〜60分鐘後，在100〜250°C低溫燒成1〜60分鐘，藉此 使塗膜硬化，形成導電電路。 如此，藉由形成導電電路，ITO薄膜中之ITO蝕刻掉 部分與ITO層兩者之密著性優異，可獲得良好之導電性。 因此，藉由將此種導電電路使用於多功能攜帶式終端機等 之電子裝置的觸控面板等，可獲得高的信賴性或導電特性 〇 又，如上述，於導電性膏中所含之有機溶劑中含有在 760mmHg下之沸點爲240〜3 3 0 °C範圍之高沸點溶劑時， 於凹版平版印刷中可獲得良好印刷適性。使用含有該種高 沸點溶劑之導電性膏，如下述般於基材上形成電路。 圖1顯示凹版平版印刷之槪略圖。 如圖1所示，以於凹版11中成爲所需圖型形狀之方 式所形成之凹部11a中，塡充導電性膏12。隨後，轉印於 中間轉印體的矽氧膠印滾筒1 3上（一次轉印）》將轉印於矽 氧膠印滾筒13上之導電性膏再轉印於載置於階差14上之 基材15上（二次轉印），藉此形成塗膜16。 此處使用之基材可使用印刷配線板、玻璃基板，此外 可使用樹脂薄膜等之軟性基板。又，所用之凹版係對於由 銅、42合金、玻璃等所構成之滾筒或平版表面，施以照相 製版或雷射雕刻等進行製版。依據須要，施以電暈電鍍處 理或DLC (似鑽石碳）處理，亦可提高凹版之耐久性。 由上述印刷而於基材上形成之塗膜16在80〜200°C乾 燥1〜60分鐘或硬化，而形成導電電路。 -21 - 201247808 [實施例] 以下關於本實施形態顯示實施例及比較例加以具體說 明，但本發明並非限於該等實施例者。又，下述中’ 「％ 」若未特別指明則全部爲質量基準’且重量平均分子量係 使用凝膠擔體液體層析儀（HLC-8120 GPC，TOSOH公司製） 與聚苯乙烯換算之値所求得者。 [有機黏合劑樹脂之合成] (合成例1) 於具備搅拌裝置、溫度計、冷凝器之反應容器中，饋 入288g(0.36mol)之作爲多元醇成分之由1，5 -戊二醇及 1,6-己二醇衍生之聚碳酸酯多元醇（旭化成化學公司製， T5 65 0J -數平均分子fl 800)、45g(0.09mol)之雙酚A型環 氧丙烷加成物二元醇（ADEKA公司製，BPX33，數平均分 子量5 00)、81.4g(0.55mol)之作爲二羥甲基烷酸之二羥甲 基丁酸、11.8g(0.16mol)之作爲分子量調節劑（反應終止劑） 之正丁醇、及25 0g之作爲溶劑之卡必醇乙酸酯（DAICEL 化學工業公司製），在60 °C使所有原料溶解。 邊搅拌多元醇成分，邊以滴加漏斗，滴加作爲聚異氛 酸酯之三甲基六亞甲基二異氰酸酯200.9g(1.08mol)。滴加 結束後，邊在80°C攪拌邊繼續反應，以紅外線吸收光譜確 認異氰酸酯基之吸收光譜（2280cm·1)消失時，作爲反應結 束。以使固體成分成爲60%之方式添加卡必醇乙酸酯，獲 -22- 201247808 得胺基甲酸酯樹脂溶液（漆料1)。 所得聚胺基甲酸酯樹脂之重量平均分子量爲1 83 00， 固體成份之酸價爲50.3mgKOH/g。 (合成例2) 於具備攪拌裝置、溫度計、冷凝器之反應容器中，饋 入360g(0.45mol)之作爲多元醇成分之由1，5 -戊二醇及 1，6 -己二醇衍生之聚碳酸酯多元醇（旭化成化學公司製， T5650J，數平均分子量800)、81.4g(0.55mol)之作爲二羥 甲基烷酸之二羥甲基丁酸、11.8g(0.16mol)之作爲分子量 調節劑（反應終止劑）之正丁醇、及2 5 0 g之作爲溶劑之卡必 醇乙酸酯（DAICEL化學工業公司製），在60。(3使所有原料 溶解。 邊攪拌多元醇成分’邊以滴加漏斗，滴加作爲聚異氰 酸酯之三甲基六亞甲基二異氰酸酯200.9g(1.08mol)。滴加 結束後’邊在8 0 °C攪拌邊繼續反應，以紅外線吸收光譜確 認異氰酸酯基之吸收光譜（2280cm·1)消失時，作爲反應結 束。以使固體成分成爲60wt %之方式添加卡必醇乙酸酯， 獲得胺基甲酸酯樹脂溶液（漆料2)。 所得聚胺基甲酸醋樹脂之重量平均分子量爲21200, 固體成份之酸價爲48.0mgKOH/g。 (合成例3) 於具備溫度計、攪拌機、滴加漏斗及迴流冷卻器之燒 -23- 201247808 瓶，以0.80: 0.20之莫耳比饋入甲基丙烯酸甲酯及丙烯酸 ，加入作爲溶劑之三丙二醇單甲醚、作爲觸媒之偶氮雙異 丁腈，在氮氣環境下於80°C攪拌6小時，獲得不揮發成分 爲40重量％之丙烯酸樹脂溶液（漆料3)。 所得樹脂之數平均分子量爲15000，重量平均分子量 約爲40000，固體成份之酸價爲97mgKOH/g。 (合成例4) 於具備揽拌裝置、溫度計、滴加漏斗冷凝器之反應容 器中，以0.80: 0.20之莫耳比饋入甲基丙烯酸甲酯及丙烯 酸’加入作爲溶劑之三乙二醇單丁醚（沸點：27 1 °C )、作爲 觸媒之偶氮雙異丁腈，在氮氣環境下於8 0。(：攪拌6小時， 獲得不揮發成分爲4 0 wt%之丙烯酸樹脂溶液（漆料4)。所 得樹脂之數平均分子量爲15000，重量平均分子量約爲 40000，酸價爲 97mgKOH/g。 (合成例5) 除了將三乙二醇單丁醚替代爲二乙二醇單乙醚乙酸酯 以外，與合成例4相同之方法獲得不揮發成分爲40 wt %之 丙烯酸樹脂溶液（漆料5)。所得樹脂之數平均分子量爲 15000’重量平均分子量約爲42000，酸價爲98mgK〇H/g [ITO密著性評價] -24- 201247808 (導電性膏之製作） 以表1所示之調配比例（質量比）調配各成分，以三根 輥硏磨機混練，獲得實施例1〜3、比較例1、2之導電性 膏。又，將膏的黏度調整爲150dPa· s。 [表1] 項目 實施例 比較例 2 3 1 2 有機黏合 劑樹脂 漆料1 167 漆料2 167 150 漆料3 25 250 250 導電粉末 銀粉·1 1870 1870 1870 1820 2290 有機溶劑 二乙二醇單乙 醚乙酸酯 100 100 100 100 100 交聯劑 jER828*2 18 18 18 15 JER1001 *3 45 硬化觸媒 Curezol 2E4MZ*4 2 2 2 2 2 *1 :球狀銀粉(平均粒徑：0.8ym，比表面積：1.0m2/g) *2 : jER828(三菱化學公司製，環氧當量=190g/eq) *3 : jERlOOl(三菱化學公司製，環氧當量=500g/eq) M : Curezol 2E4MZ(四國化成工業公司製） <比電阻値之測定> 以網版印刷形成線寬1 mm、長度40cm之測試圖型，使 用熱風循環式乾燥爐，在120t進行30分鐘之加熱處理。 所得導電電路之電阻値係使用 Tester(Milliohm Hi-TeSter3 540, HIOKI公司製）測定，自導電電路之膜厚算出比 電阻値。 -25- 201247808 [表2] 項目 a施例 比較例 1 2 3 1 2 比電阻値[Ω· cm] 8.0E-05 6.8E-05 7.0E-05 9.5E-05 7.1E-05 <密著性評價> (試驗用基材之製作） 於ITO層之一部分經蝕刻掉之ITO薄膜（帝人化成公 司製）上，使用200網目之網版，形成實施例1〜3、比較 例1、2之導電性订之圖型。接著，於120°C烘箱中進行 30分鐘加熱處理，製作於ITO薄膜上形成導電電路之試 驗用薄膜》 (初期密著評價） 於所得試驗用薄膜上，以1mm之間隔，形成10塊X 10塊之合計100塊網眼之交叉切割，進行賽璐分膠帶剝離 。接著，以目視評價ITO及ITO蝕刻掉之部份之塗膜剝落 程度。評價基準如下》 〇：完全未剝離者。 △: 一部分產生剝離者。 X :產生50%以上之剝離者。 (高溫高濕處理後之密著評價） 將所得基板放入85°C -85%RH之高溫高濕槽中，進行 96小時處理後，於所得試驗用薄膜上，以1 mm之間隔， -26- 201247808 形成10塊Χίο塊之合計100塊網眼之交叉切割，進行賽璐 分膠帶剝離。接著，以目視評價ΙΤΟ及ΙΤΟ蝕刻掉之部份 之塗膜剝落程度。評價基準如下。 〇：完全未剝離者。 △: 一部分產生剝離者。 X :產生50%以上之剝離者。 [表3] 項目 基材 實施例 比較例 1 2 3 1 2 初期密著 ITO 〇 〇 〇 X X ITO工蝕刻掉 〇 〇 〇 Δ 〇 高溫高濕處理後 ITO 〇 〇 〇 X X ITO工蝕刻掉 〇 〇 〇 X 〇 如表2、3所示可知，藉由使用本實施形態之胺基甲 酸酯樹脂作爲有機黏合劑，可獲得導電電路之良好導電性 ，同時導電電路之對ΙΤΟ層及ΙΤΟ蝕刻掉部份之密著性獲 得提高。 [印刷適性評價] (導電性膏之製作） 以表4所示之調配比例（質量比）調配各成分，以三根 輥硏磨機混練，獲得實施例4〜7、比較例3〜5之導電性 膏。又，將膏的黏度調整爲150dPa.s。且黏性値在10〜 2 5 (3 0 °C，6 0秒之値）之間。 -27- 201247808 [表4] 項目 m m 比較例 4 5 6 7 3 4 5 有機黏合 劑樹脂 漆料1 167 167 漆料2 167 167 150 漆料4 25 250 漆料5 250 導電粉末 銀粉*1 1870 1870 1870 1870 1820 2290 1870 有機溶劑 二乙二醇單乙醚乙 酸酯(沸點=217〇C) 50 50 20 100 100 三乙二醇單丁醚 (沸點=2·71°〇 50 50 80 125 100 交聯劑 jER828*2 18 18 18 18 15 18 jERIOOl*3 45 硬化觸媒 Curezol 2E4MZ.4 2 2 2 2 2 2 2 [備註] 參考表1之備註 實施例4〜7及比較例3〜5之導電性贷中所含之有機 溶劑中之高沸點溶劑之比例示於表5。 [表5] 溶劑比例[%] m m 比較例 4 5 6 7 3 4 5 高沸點溶劑 30 30 48 70 100 0 0 其他溶劑 70 70 52 30 0 100 100 (藉簡易凹版印刷之印刷適性評價） 將所得之各導電性订，使用鋼製刮刀，塡充於形成有 線/間隔=70/3 0μη!，版深：ΙΟμιη之條紋圖型之玻璃凹版之 凹部中。 -28- 201247808 接著，將該玻璃凹版抵接於由橡膠硬度30°之矽氧橡 膠所構成之膠印滾筒上，將塡充於凹部之導電性膏轉印至 膠印滾筒表面（膠印滾筒轉印步驟，一次轉印）。將導電性 膏轉印於膠印滾筒表面30秒後，將膠印滾筒表面之導電 性膏轉印至厚1.8mm之鈉鈣玻璃表面上（圖型轉印步驟， 二次轉印）。針對如此獲得之印刷物進行以下評價。 (印刷適性1 :直行性評價） 以光學顯微鏡觀察轉印有各導電性膏之玻璃基板，評 價印刷物之直行性。評價基準如下。評價結果示於表6。 〇：直行性良好。 △:稍欠缺直行性。 X :顯著欠缺直行性，有斷線。 (印刷適性2 :線寬再現性之評價） 以光學顯微鏡觀察轉印有導電性膏之玻璃基板，評價 印刷物之線寬。評價基準如下。評價結果示於表6。 〇：線寬與玻璃凹版相同，或誤差相對於版尺寸爲± 10%以內。 △:線寬誤差相對於版尺寸爲超過±10%且±30%以內。 x :線寬誤差相對於版尺寸爲超過±3 0%。 (印刷適性3 :於膠印上放置60秒後之轉印性評價） 膠印滾筒轉印步驟（一次轉印）後，於60秒後進行圖型 -29 - 201247808 轉印步驟（二次轉印），以目視評價於膠印滾筒表面是否殘 留有導電性订。評價基準如下。評價結果示於表6。 〇：於膠印滾筒表面未殘留導電性订（1 〇〇%轉印）。 △:於膠印滾筒表面一部分上殘留導電性脊。 X:於膠印滾筒表面全面上殘留導電性膏。 (比電阻値之測定） 印刷線寬1mm '長度40cm之測試圖型，使用熱風循 環式乾燥爐，在1 2 0 °C進行3 0分鐘之加熱處理。所得印刷 物之電阻値係使用 Tester(Milliohm Hi-Tester3540，HIOKI 公司製）測定，自印刷物之膜厚算出比電阻値。 [表6] 項目 m m 比較例 4 5 6 7 3 4 5 印刷適性1 ο ο ο ο Δ Δ 無法評價 印刷適性2 ο ο ο ο Δ X 無法評價 印刷適性3 ο ο ο ο ο X 無法評價 比®阻値[Q· cm] 8.0Ε-05 6.8Ε-05 7.0Ε-05 7.2Ε-05 9.5Ε-05 7.1 巳 05 1.1Ε-04 如表6所示，可知使用本實施形態之導電性膏之實施 例4〜7中，任一經印刷之導電電路之線寬再現性、直行 性優異，且自膠印滾筒轉印步驟至圖型轉印步驟之時間即 使較長，订亦保有轉印性。 作爲使用本實施形態之導電性眘之印刷物圖像之一例 ，於圖2中顯示實施例7之印刷物（導電電路）之光學顯微 鏡照片。如圖2所示，可知線寬之再現性，相對於版尺寸 -30- 201247808 70μιη，印刷物（導電電路）之線寬爲64〜67μηι(誤差：-8.6% 〜-4.3%)，關於直行性亦爲良好。 另一方面，不含本實施形態之胺基甲酸酯樹脂之比較 例3可知，自膠印滾筒轉印步驟至圖型轉印步驟之時間即 使較長時雖亦保有轉印性，但所得印刷物缺乏線寬再現性 、直行性。且於不含本實施形態之胺基甲酸酯樹脂及高沸 點溶劑之比較例4，可知膏在膠印上長時間放置時會乾燥 而損及轉印性。且於不含有本實施形態之高沸點溶劑之比 較例5，可知膏在膠印上乾燥而無法進行印刷之評價。 圖3中顯示使用比較例3之導電性眘之印刷物（導電 電路）之光學顯微鏡照片。如圖3所示，可知線寬之再現 性，相對於版尺寸70μιη，印刷物（導電電路）之線寬爲58 〜62μπι(誤差：-17.1%〜-11·4%)，關於直行性，亦可知印 刷物會產生起伏，稍欠缺直行性。 【圖式簡單說明】 圖1爲顯示本實施形態之第二形態之凹版平版印刷之 步驟的圖。 圖2爲實施例7之印刷物之光學顯微鏡照片。 圖3爲比較例3之印刷物之光學顯微鏡照片。 【主要元件符號說明】 1 1 :凹版 1 1 a :凹部 -31 - 201247808 1 2 :導電性膏 1 3 :矽氧膠印滾筒 1 4 :階差 1 5 :基材 16 :塗膜 -32201247808 VI. TECHNOLOGICAL FIELD OF THE INVENTION [Technical Field] The present invention relates to a conductive paste and a method of manufacturing a conductive circuit using the same. [Prior Art] In recent years, a touch panel has been used in a multi-functional band-type terminal or the like. In the electronic device, a tantalum film in which an ITO (indium tin oxide) electrode is formed on a film such as PET has been used. Such a ruthenium film is formed by forming a ruthenium layer on a film and leaving the electrode portion to be removed and etched away (etched away). Next, a conductive paste in which a conductive powder such as Ag is dispersed in an organic binder is used on the exposed film and the ruthenium layer to form a conductive circuit. A conductive paste which can be fired at a low temperature in a device having low heat resistance such as a film has been proposed (for example, refer to Patent Document 1, etc.). However, regarding the conductive circuit on the I TO film, the adhesion to the film and the I TO layer is not sufficient, and there is a problem that defects such as peeling occur, and the portion which is etched is particularly remarkable. On the other hand, the formation of a high-precision conductive circuit in an electronic device is generally used for photolithography using a photosensitive conductive paste such as a photosensitive resin in an organic binder or the like. However, photolithography is a subtractive process for forming conductive circuits by removing materials. The conductive paste used has low efficiency and complicated steps, and requires large equipment in the wet process. On the other hand, the printing method of the printing process, gravure lithography, and the like, which is a process for adding a material to a specific portion, has been attracting attention. For example, according to gravure lithography, a conductive circuit can be formed by sequentially supplying a conductive crucible to a gravure, for example, by sequentially transferring it to a blanket or substrate made of polyfluorene oxide. Since the conductivity is transferred to the substrate through the plate, a good transfer property is required for the conductivity to be used. Especially in gravure lithography, since the conductivity is carefully transferred from the gravure through the outer cover to the substrate, it is necessary to transfer the conductive arm at each step. In continuous printing, it is required to face the substrate from the outer cover. The transfer rate is 100%, or the printability of the printed matter transferred onto the substrate is suppressed, and the printing suitability is excellent. Further, when a conductive circuit is formed in a device having low heat resistance by a printing method, not only good printing suitability but also good electrical characteristics in a conductive circuit formed by low-temperature firing are required. However, it is difficult to obtain the problem of satisfying the order at the same time. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2000- 3 5 5 9 3 3 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The present invention has been developed to solve these problems, and is the first The objective is to provide an electrically conductive loan which is excellent in adhesion to an I TO film and which can obtain good conductivity in a conductive circuit formed by a low temperature process, and a second object is to provide in addition to the above characteristics in gravure lithography. Excellent printability -6- 201247808 conductive paste. [Means for Solving the Problem] The conductive paste of the same embodiment is characterized by containing a urethane resin, a conductive powder, and an organic solvent. According to this configuration, excellent conductivity can be obtained by using a conductive circuit which is excellent in adhesion to an ITO thin film and formed by a low-temperature process. Further, in the conductive paste of the present embodiment, the urethane resin preferably contains a carboxyl group urethane resin. According to this configuration, the cohesive force of the urethane can be enhanced, and the adhesion to the ITO film can be further improved. Further, the conductive paste of the present embodiment is characterized in that an epoxy resin containing two or more glycidyl groups in at least one molecule is further contained as a crosslinking agent. According to this configuration, the three-dimensional mesh chain can be formed in the formation of the conductive circuit, and the solvent resistance and adhesion of the obtained conductive circuit can be improved. Further, in the method for forming a conductive circuit according to the present embodiment, a coating film formed of the conductive paste is formed on the ITO film, and the coating film is dried or cured at 80 to 200 °C. According to this configuration, it is possible to obtain excellent adhesion to the ITO film and good conductivity in the formed conductive circuit. Further, the conductive paste in the same state of the present embodiment is characterized in that the organic solvent contains 30 to 90% by mass of a high boiling point solvent having a boiling point of 760 mmHg of 240 to 3300 °C. According to this configuration, in addition to the above characteristics, excellent printability such as straightness of the printed matter in the lithographic printing, line width 201247808 reproducibility, and the like can be obtained. Further, the method for forming a conductive circuit according to the present embodiment is characterized in that the conductive material is filled on a plate, and the charged conductive material is primarily transferred onto a surface of a blanket cylinder to be The conductive paste of the primary transfer is secondarily transferred onto the surface of the substrate, and the conductive enthalpy which is secondarily transferred is dried or hardened at 80 to 200 °C. The conductive circuit formed by such a structure has good conductivity, and since it has good straightness and line width reproducibility, an electronic device having high reliability and electrical conductivity can be obtained. Further, the electronic device of the present embodiment is characterized by comprising an ITO film and a conductive circuit containing a urethane resin and a conductive powder formed on the ITO film. According to this configuration, the conductive circuit is excellent in adhesion to the ITO film and has good conductivity, so that an electronic device having high reliability and electrical conductivity can be obtained. [Effect of the Invention] According to the present invention, it is possible to provide a conductive material which is excellent in adhesion to an ITO film and which is excellent in electrical conductivity of a conductive circuit formed by a low-temperature process. In addition, in addition to the above-described characteristics, it is possible to obtain excellent printability such as straightness and line width reproducibility of the printed matter in gravure lithography. [Embodiment] The inventors of the present invention conducted a positive review based on the above-mentioned problems - 8-201247808, it was found that by containing a urethane resin, a conductive powder, and an organic solvent as a conductive paste, it is possible to obtain a good electrical conductivity of a conductive circuit formed by a low-temperature process, which is excellent in adhesion to an ITO film, and further found. In the above organic solvent, 30 to 90% by mass of a high boiling point solvent having a boiling point of 760 mmHg of 240 to 3300 ° C is contained, and in addition to the above characteristics, the substrate or the like can be obtained in gravure lithography. The present invention has been accomplished by excellent printability such as transferability of a print, straightness of a printed matter after transfer, and line width reproducibility. Hereinafter, the conductive paste of the present embodiment will be described. The conductive paste of the present embodiment is composed of a urethane resin, a conductive powder, and an organic solvent. The urethane resin in the conductive paste of the present embodiment is an adhesive which imparts good printability to the paste and remains in the cured product (conductive circuit) to impart physical properties such as adhesion, bending resistance, and hardness. Resin and user. The urethane resin is not particularly limited as long as it imparts printability to the conductive paste, and examples thereof include a carboxyl group-containing urethane resin and a phenolic hydroxyl group-containing urethane. Resin, amino group-containing urethane resin, and the like. Among them, a carboxyl group-containing urethane resin is particularly preferable. For example, an amine formed by reacting a polyisocyanate (a), a bisphenol A type alkylene oxide adduct diol (b), a polycarbonate polyol (c), and a dimethylol alkanoic acid (d) A urethane bond and a carboxyl group introduced by dimethylol alkanoic acid (d). At the time of the reaction, a monohydroxy compound (e) may also be added as a reaction terminator (end capping agent). 201247808 The urethane resin can be obtained by, for example, polyisocyanate (a), bisphenol A type alkylene oxide adduct diol (b), polycarbonate polyol (c), dimethylol The acid (d) and the monohydroxy compound (e) functioning as a reaction terminator (end capping agent) are mixed and reacted, or the polyisocyanate (a), bisphenol A type alkylene oxide adduct glycol (b) a reaction of a polycarbonate polyol (c) and a dimethylol alkanoic acid (d), followed by reaction with a monohydroxy compound (e). The reaction is carried out at room temperature to 1 〇〇 ° C. Stirring and mixing are carried out without a catalyst, but the reaction rate is not increased, and it is preferably heated to 70 to 100 °C. Specific examples of the polyisocyanate (a) include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, and hexa-potassium diisocyanate. Diphenylmethane diisocyanate, (o-, m- or p-) xylene diisocyanate, (o-, m- or p-) hydrogenated xylene diisocyanate, methylene double (ring Hexyl isocyanate), trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-oxime, 4-dimethylene diisopoly a diisocyanate such as an acid ester or a 1,5-naphthalene diisocyanate. These polyisocyanurates may be used alone or in combination of two or more. Among these, toluene diisocyanate and trimethylhexamethylene diisocyanate are preferred. When these diisocyanates are used, a cured product excellent in solder heat resistance can be obtained. As the bisphenol A type alkylene oxide adduct diol (b), an ethylene oxide adduct of bisphenol A, a propylene oxide adduct, a butylene oxide adduct, etc. are exemplified, but Preferably, the propylene oxide adduct of bisphenol A is preferred. Next, 'as the polycarbonate polyol (c), preferably a polycarbonate diol. The polycarbonate diol is exemplified by a polycarbonate diol containing a repeating unit derived from one or two or more kinds of linear aliphatic diols of -10-201247808 as a constituent unit, and one containing one kind Or a repeating unit of two or more kinds of alicyclic diols as a constituent unit of a polycarbonate diol or a repeating unit containing a diol derived from the two as a constituent unit of a polycarbonate diol. These polycarbonate diols can be produced by transesterification of a linear aliphatic or alicyclic diol with, for example, a carbonate or by reaction with carbon ruthenium chloride or the like. As the polycarbonate diol having a repeating unit derived from a linear aliphatic diol as a constituent unit, specifically, for example, a polycarbonate diol derived from 1,6-hexanediol, from 1 , 5-pentanediol and 1,6-hexanediol-derived polycarbonate diol, polycarbonate diol derived from 1,4-butanediol and 1,6-hexanediol, from 3 -Methyl-1,5-pentanediol and 1,6-hexanediol-derived polycarbonate diol" As for the polycarbonate containing a repeating unit derived from an alicyclic diol as a constituent unit The diol is specifically exemplified by, for example, a polycarbonate diol derived from 1,4-cyclohexanedimethanol. As the polycarbonate diol having a repeating unit derived from both a linear aliphatic diol and an alicyclic diol as a constituent unit, specifically, for example, 1,6-hexanediol and 1,4 are exemplified. a cyclohexanedihexyl alcohol-derived polycarbonate diol. The polycarbonate diol containing a repeating unit derived from a linear aliphatic diol as a constituent unit tends to have low warpage or flexibility. Further, the polycarbonate diol containing a repeating unit derived from an alicyclic diol as a constituent unit tends to have high crystallinity, tin-resistance, and solder heat resistance -11 - 201247808. From the above viewpoints, two or more kinds of these polycarbonates may be used in combination, or a polycarbonate containing a repeating unit derived from both of linear aliphatic diols as a constituent unit may be used in a well-balanced manner. In terms of low warpage or flexibility, solder heat resistance, it is preferred to use a linear aliphatic diol and an alicyclic copolymerization ratio of 3: 7 to 7: 3 by mass ratio. e The polycarbonate diol preferably has a number average molecular weight of 200 Å, but the polycarbonate diol contains a repeating unit derived from a linear aliphatic bicyclic diol as a constituent unit, and the linear aliphatic alcohol When the copolymerization ratio of the alicyclic diol is 3:by mass ratio, it is preferably a number average molecular weight of 400 to 2,000. The dimethylol alkanoic acid (d) is a dihydroxy aliphatic group having a carboxyl group, and examples thereof include, for example, dimethylolpropionic acid, dimethylolbutanoic acid, and the like. The dimethylol alkanoic acid can be easily introduced into the urethane resin. As for the monohydroxy compound (e) as a polyurethane, as long as it has a hydroxyl group in the molecule, An aliphatic alcohol, a monohydroxy mono(meth)acrylate compound, or the like. As the aliphatic alcohol, for example, methanol, ethanol isobutanol or the like is exemplified, and as the monohydroxy mono(meth)acrylate compound, for example, 2-hydroxyethyl acrylate or the like is exemplified. The weight average molecular weight of the carboxyl group-containing urethane resin is ~1 00,000. Weight of carboxyl group-containing urethane resin: When the amount is less than 500, the elongation of the cured film, the flexible alcohol 2, and the alicyclic diol are impaired. Or a plated diol ester diol 5,000 Alkene and aliphatic binary 7~7: 3 Carboxylic acid, by using \carboxyl. The end capping is exemplified by propanol, and the specific molecular weight is 500% average molecular strength and strong -12-201247808 degrees. On the other hand, when it exceeds 100,000, it will become hard and the flexibility will be lowered. Hey. More preferably 4,000 to 50,000, and even more preferably 6,000 to 3,0,00. Further, the weight average molecular weight in the present specification is determined by a gel permeation chromatograph and converted to polystyrene. The acid value of the carboxyl group-containing urethane resin is preferably in the range of 5 to 150 mgKOH/g. . When the acid value is less than 5 mgKOH/g, the cohesive force of the paste is lowered, and the transfer failure is likely to occur at the time of printing. On the other hand, when the acid value exceeds 150 mgKOH/g, the viscosity of the paste becomes too high, and a large amount of a crosslinking agent or the like must be formulated, and it is difficult to impart printability. More preferably, it is 10 to 100 mgKOH/g. The resin acid value is determined in accordance with JIS K5407. Further, as a material for compensating the printability, an organic binder other than the urethane resin may be contained. Specific examples include various modified polyester resins such as polyester resin, urethane-modified polyester resin, epoxy-modified polyester resin, and acrylic modified polyester resin, and vinyl chloride acetate. Vinyl ester copolymer, epoxy resin, phenol resin, acrylic resin, polyvinyl butyral resin, polyamidoxime, polyimine, polyamine, nitrocellulose, cellulose acetate Modified cellulose such as butyrate (CAB), cellulose, acetate, propionate (CAP), etc. Among these, a carboxyl group-containing resin containing at least one carboxyl group in at least one molecule is preferred. The resin containing a carboxyl group is specifically exemplified by the following resins, but is not limited thereto. (1) A resin containing a carboxyl group obtained by copolymerizing one or more kinds of unsaturated carboxylic acids such as (meth)acrylic acid with a compound having an unsaturated bond. -13- 201247808 (2) Addition of butyl glycidyl ether or phenyl glycidyl ether by one or more copolymers of an unsaturated carboxylic acid such as (meth)acrylic acid and a compound having an unsaturated bond A resin containing a carboxyl group derived from a monofunctional epoxy compound. (3) A compound containing an epoxy group and an unsaturated double bond such as glycidyl (meth)acrylate or 3,4-epoxycyclohexyl (meth)acrylate, and the like having an unsaturated double A copolymer of a bond compound, a secondary hydroxyl group formed by reacting a saturated carboxylic acid such as propionic acid, and a polyvalent acid anhydride to obtain a carboxyl group-containing resin. (4) A resin containing a carboxyl group obtained by reacting a copolymer such as maleic anhydride or the like having an unsaturated bond fatty acid anhydride and a compound having an unsaturated bond with a compound having a hydroxyl group such as butanol. (5) A resin containing a carboxyl group obtained by reacting a hydroxyl group formed by reacting a polyfunctional epoxy compound with a saturated monocarboxylic acid and then reacting with an unsaturated polybasic acid anhydride. (6) A resin containing a hydroxyl group and a carboxyl group obtained by reacting a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative with a saturated or unsaturated polybasic acid anhydride. (7) a reaction product of a compound having a polyfunctional epoxy compound, a saturated monocarboxylic acid, and a reactive group having at least one alcoholic hydroxyl group and an alcoholic hydroxyl group reactive with an epoxy group in one molecule, A resin containing a carboxyl group obtained by reacting a saturated or unsaturated polybasic acid anhydride. (8) a first-order hydroxyl group in a modified oxetane resin obtained by reacting a polyfunctional oxetane compound having at least two oxetane groups in one molecule with a saturated monocarboxylic acid, and then saturated or A resin containing a carboxyl group obtained by reacting an unsaturated polybasic acid anhydride. -14- 201247808 (9) After reacting a polyfunctional epoxy resin with a saturated monocarboxylic acid, a resin containing a carboxyl group obtained by reacting with a polybasic acid anhydride is reacted with a compound having one oxirane ring in the molecule. A resin containing a carboxyl group. Among these, the carboxyl group-containing resin of (1), (2) and (3) is particularly preferably used. These can be arbitrarily adjusted in molecular weight, glass transition point, etc., and the adjustment of the printability of the paste and the adhesion to the substrate can be appropriately controlled. Further, the acid value of the carboxyl group-containing resin is preferably from 40 to 200 mgKOH/g. When the acid value of the resin having a carboxyl group is less than 40 mgKOH/g, the cohesive force of the paste is lowered to cause a poor transfer at the time of printing. On the other hand, when it exceeds 200 mgKOH/g, the viscosity of the paste becomes too high, and a large amount of crosslinking agent must be formulated, and it is difficult to impart printability. More preferably 45 to 150 mgKOH/g. The blending amount of the organic binder other than the urethane resin should preferably be added to the organic binder other than the urethane resin in a range that does not impair the adhesion to the ITO film. 50% by mass or less of the binder. When the amount is more than 50% by mass, the adhesion between the ITO film and the substrate is not preferable. In gravure lithography, the line width of the printed matter is confusing and detrimental to the characteristics of the paste, which is less preferred. More preferably 30 mass% or less. The conductive powder in the conductive paste of the present embodiment is one in which conductivity is imparted to the formed conductive circuit, and specific examples thereof include Ag, Au, Pt, Pd, Ni, Cu 'A1 'Sn, Pb, Zn, Fe, and the like. Ir, Os, Rh, W, Mo, Ru, etc. The conductive powder is not limited to being used as a monomer, and any of these alloys or a multilayer of the core or the coating layer may be used. -15- 201247808 Further, an oxide such as tin oxide (Sn〇2), indium oxide (?n203), or ITO (indium tin oxide) may be used. As for the shape, various shapes such as a spherical shape, a flake shape, and a dendritic shape can be used. However, if the printing suitability or dispersibility is particularly considered, it is preferable to use a spherical shape as a main body. These conductive powders are preferably from 85 to 95% by mass based on the nonvolatile components of the conductive paste (components which remain in the film during volatilization in the drying step). If it is less than 85 mass%, it is difficult to obtain sufficient conductivity, and if it exceeds 95 mass%, it is difficult to obtain sufficient printability, or it is difficult to maintain the shape of the conductive circuit. More preferably 90 to 94% by mass. When the spherical conductive powder is used as the conductive powder particle diameter, the average particle diameter of the random 10 conductive powders is preferably 0.1 to 5 μm by using an electron microscope (SEM) at 10,000 times. When the average particle diameter is less than Ομπι, it is difficult to cause the conductive powders to contact each other to lower the conductivity. On the other hand, when the average particle diameter exceeds 5 μm, it is difficult to obtain the straightness of the line edge at the time of printing. More preferably 0 · 4 〜 2 μηι. Further, it is preferred to use an average particle diameter of 0.5 to 3.5 μηι as measured by a particle size distribution measuring apparatus (MICRO TRAC). Further, when a sheet-like conductive powder is used, the average particle diameter of the random 10 conductive powders observed by an electron microscope (SEM) at 10,000 times is preferably 0.1 to ΙΟμιη. When the average particle diameter is less than Ο.μπι, it is difficult to cause the conductive powders to contact each other to lower the conductivity. On the other hand, when the average particle diameter exceeds 10 μm, it is difficult to obtain the straightness of the line edge at the time of printing. More preferably 〇.4 〜5 μ m. Further, it is preferable to use an average particle diameter of 〇.5 to be measured by a particle size distribution measuring device (MICRO TRAC). The conductive powder is preferably a silver powder. In this case, the specific surface area of the silver powder is preferably 0.01 to 2 m2/g. When the specific surface area is less than 0.01 m2/g, sedimentation is likely to occur during storage. On the other hand, when the specific surface area exceeds 2 m2/g, the oil absorption amount is increased to impair the fluidity of the paste. More preferably 〇·5~ 1 · 5 m2/g. The organic solvent in the conductive paste of the present embodiment is used to impart good printability. As for the organic solvent, it is soluble in a chemical reaction without urethane resin, in particular, in order to prevent drying of a paste which has been printed by gravure printing, and to retain transferability, in a conductive paste. It is necessary to contain a high boiling point solvent having a boiling point of 240 to 33 ° C at 760 mmHg in the organic solvent. If the boiling point of the high boiling point solvent at 760 mmHg is lower than 24 CTC, the offset transfer mode in the offset mode of the printing-printing process in the set mode is easy to dry, in the fixing step. Unable to transfer to substrate. On the other hand, when the temperature is higher than 340 ° C, the drying in the printing step can be suppressed. However, in the drying step after printing, the solvent is likely to remain in the printing, and the resistance enthalpy rises and the adhesion is lowered. Defects. Better for 240~300 °C. Further, the ratio of the high boiling point solvent in the organic solvent contained in the conductive paste is preferably from 30 to 90% by mass. When the ratio of the high boiling point solvent is less than 3 〇 mass %, it is difficult to obtain a good printed matter in which the printed matter is printed finer than the plate size. On the other hand, if it is more than 90% by mass, it is easy to produce in the printing material -17-201247808, and it is still impossible to obtain a good printed matter. More preferably, the ratio is 3 〇 ~ (10)% by mass. —° As such a high boiling point solvent, there are exemplified dipentylbenzene (boiling point: 26 〇 to HOC) and dipentylbenzene (boiling point: 3 〇〇 32 32 (Γ), 正· 12 院 (10) points .255~259°C), diethylene glycol (boiling point: 245 〇c) 'diethylene glycol monobutyl ether acetate (boiling point: 247t) 'diethylene glycol dibutyl ether (boiling point · 255 t: ) - Ethyl alcohol monoacetate (boiling point: 25 〇 art), triethylene glycol (boiling point: 276C), diethyl alcohol monomethyl ether (boiling point: 249. 〇), triethylene glycol monoethyl ether (boiling point) : 2 5 6. 〇), triethylene glycol monobutyl ether (boiling point: 271 t), tetraethyl alcohol (boiling point: 3 2 7 ° C), tetraethylene glycol monobutyl ether (boiling point: 3 〇 4 〇 c ), three propylene and one awake (boiling point: 267 ° C), tripropylene glycol monomethyl ether (boiling point: 243 ° C), ',-dimethyl-1,3-pentanediol monoisobutyrate (boiling point: 25 3 eC), etc. Also, 'as a petroleum-based hydrocarbon', there is an AF solvent No. 4 (boiling point: 240 to 265 ° C), No. 5 (boiling point: 275 to 306 ° C), No. 6 manufactured by Nippon Oil Corporation. (boiling point: 296~317 °C), No. 7 (boiling point: 259~282 °C) and nickname solvent H ( Two or more kinds of these may be contained as needed, and it is preferable to use a triethylene glycol derivative or a tripropylene glycol derivative in the above, etc. As for the organic solvent other than the above-mentioned high-boiling solvent, Examples include, for example, methyl, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropanol, isobutanol, butanol, diacetone alcohol, diethylene glycol, ethylene glycol monobutyl ether, - ethylene glycol monobutyrate acetate, triethylene glycol monomethyl ether, propylene glycol monomethyl ugly, diglycol monoethyl ether, propylene glycol monomethyl ether acetate, tripropylene glycol monocarboxylic acid, broken alcohol, methyl ethyl Ketone, carbitol, carbitol acetate, butyl-18-201247808 carbitol, etc. These may be used alone or in combination of two or more. The viscosity of the conductive paste of the present embodiment is particularly When used in gravure lithography, in order to obtain good printability, the measurement of the cone-shaped viscometer (25 ° C) is preferably 50 to 100 dPa·s. When the viscosity is less than 50 dPa·s, the conductive paste is used. When the ratio of the organic solvent is too large, the transfer property is lowered and it becomes difficult to print well. When the viscosity exceeds 1000dPa·s, it is difficult to fill the gravure, and the recording property of the squeegee is deteriorated, which is likely to cause contamination (the adhesion of the paste to the non-line portion). It is preferably 100 to 650 dPa.s. It can be appropriately diluted at the time of printing. Moreover, the tackiness of the conductive paste exhibiting dynamic adhesiveness is preferably from 5 to 35. When the viscosity is less than 5, the transferability during printing is poor. On the other hand, when the viscosity is more than 35, it is likely to cause picking (damage of the printed matter) or clogging of the printed matter at the time of printing (the printed matter is clogged in the printing machine). Better for 1 0~3 0. Further, the viscous enthalpy was measured at 30 ° C and 400 rpm using a rotary tack meter (General name: Incometer). Further, in the conductive paste of the present embodiment, in order to form a three-dimensional mesh chain structure, the solvent resistance and adhesion of the formed conductive circuit are improved, and a crosslinking agent is preferably contained. The crosslinking agent may be reacted and crosslinked with the urethane without deteriorating the printability. The crosslinking agent is not particularly limited as long as it is a resin which can be hardened by heating, but examples thereof include an epoxy resin, a phenol resin, a melamine resin, an alkyd resin, a polyester resin, an acrylic resin, and a polyimine. Resins and these modified resins. These can be used alone or in groups -19- 201247808 in combination of two or more. Further, an oxetane compound having at least two oxacyclobutane groups in the molecule, and the like are exemplified. Among these crosslinking agents, an epoxy resin containing at least two glycidyl groups in at least one molecule is preferably contained. As such an epoxy resin, for example, a bisphenol A type, a hydrogenated bisphenol A type 'bisphenol F type, a bisphenol S type, a phenol novolak type, a cresol novolac type, a bisphenol A novolak type, a known epoxy resin such as a biphenol type, a bisphenol type, a trisphenol methane type, an N-glycidyl type, an N-glycidyl type epoxy resin, or an alicyclic epoxy resin, but is not particularly limited thereto. And the like, and these may be used alone or in combination of two or more. Among them, an epoxy resin having an epoxy equivalent (containing 1 gram equivalent of the epoxy group of the resin) in an amount of from 1 Å to 30,000 is preferred because it can be added in a small amount and efficiently crosslinked. The blending ratio of the epoxy resins is preferably from 1 to 100 parts by mass, preferably from 5 to 40 parts by mass per 1 part by mass of the urethane resin. Further, in addition to these, a curing catalyst such as an amine compound or an imidazole derivative for promoting the reaction between the urethane resin and the crosslinking agent may be blended, or the metal dispersion may be formulated within a range not impairing the printability. Additives such as a thixotrope imparting agent, an antifoaming agent, a leveling agent, a plasticizer, an antioxidant, a metal inerting agent, a coupling agent or a chelating agent. Using such conductivity, a conductive circuit is formed as follows. First, a coating film of a pattern formed by a conductive man is formed on an ITO film. At this time, as the printing method, screen printing, lithography, gravure lithography, and the like are not particularly limited. The coating film formed on the ITO film is dried at 60 to 120 ° C for 1 -20 to 201247808 to 60 minutes, and then fired at a low temperature of 100 to 250 ° C for 1 to 60 minutes, thereby hardening the coating film to form a conductive film. Circuit. Thus, by forming the conductive circuit, the adhesion between the ITO etched portion and the ITO layer in the ITO thin film is excellent, and good electrical conductivity can be obtained. Therefore, by using such a conductive circuit for a touch panel or the like of an electronic device such as a multi-functional portable terminal device, high reliability or conductivity characteristics can be obtained, as described above, in the conductive paste. When the organic solvent contains a high boiling point solvent having a boiling point of 240 to 3300 ° C at 760 mmHg, good printability can be obtained in gravure lithography. Using a conductive paste containing such a high boiling point solvent, an electric circuit is formed on the substrate as follows. Figure 1 shows a schematic of gravure lithography. As shown in Fig. 1, the conductive paste 12 is filled in the concave portion 11a formed in the concave pattern 11 to have a desired pattern shape. Subsequently, the conductive paste transferred onto the xenon offset printing cylinder 13 is transferred to the base placed on the step 14 on the xenon offset printing cylinder 13 (primary transfer) transferred to the intermediate transfer body. On the material 15 (secondary transfer), the coating film 16 is thereby formed. A printed wiring board or a glass substrate can be used as the substrate used here, and a flexible substrate such as a resin film can be used. Further, the intaglio plate used is plated by photolithography or laser engraving on a drum or lithographic surface composed of copper, a 42 alloy, glass or the like. Corona plating treatment or DLC (diamond-like carbon) treatment can be applied as needed to improve the durability of the intaglio. The coating film 16 formed on the substrate by the above printing is dried at 80 to 200 ° C for 1 to 60 minutes or hardened to form a conductive circuit. -21 - 201247808 [Embodiment] Hereinafter, the embodiment and the comparative example will be specifically described in the present embodiment, but the present invention is not limited to the embodiments. In addition, in the following, '%' is the mass standard unless otherwise specified, and the weight average molecular weight is calculated by using a gel-support liquid chromatograph (HLC-8120 GPC, manufactured by TOSOH Co., Ltd.) and polystyrene. The person sought. [Synthesis of Organic Binder Resin] (Synthesis Example 1) In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, 288 g (0.36 mol) of 1,5-pentanediol and 1 as a polyol component were fed. , 6-hexanediol-derived polycarbonate polyol (manufactured by Asahi Kasei Chemicals Co., Ltd., T5 65 0J - number average molecule fl 800), 45 g (0.09 mol) of bisphenol A type propylene oxide adduct diol ( ADEKA, BPX33, number average molecular weight 500), 81.4g (0.55mol) of dimethylol butyric acid as dimethylol alkanoic acid, 11.8g (0.16mol) as a molecular weight regulator (reaction terminator) N-butanol and 25 g of carbitol acetate (manufactured by DAICEL Chemical Industry Co., Ltd.) as a solvent, and all the raw materials were dissolved at 60 °C. While stirring the polyol component, 200.9 g (1.08 mol) of trimethylhexamethylene diisocyanate as a polyisocyanate was added dropwise as a polyisoester. After the completion of the dropwise addition, the reaction was continued while stirring at 80 ° C, and when the absorption spectrum of the isocyanate group (2280 cm·1) was confirmed by the infrared absorption spectrum, the reaction was terminated. Carbitol acetate was added in such a manner that the solid content became 60%, and a urethane resin solution (lacquer 1) of -22-201247808 was obtained. The obtained polyurethane resin had a weight average molecular weight of 1,380, and the solid content had an acid value of 50.3 mgKOH/g. (Synthesis Example 2) In a reaction vessel equipped with a stirring device, a thermometer, and a condenser, 360 g (0.45 mol) of a polyol component derived from 1,5-pentanediol and 1,6-hexanediol was fed. Polycarbonate polyol (manufactured by Asahi Kasei Chemicals Co., Ltd., T5650J, number average molecular weight 800), 81.4 g (0.55 mol) of dimethylolbutanoic acid as dimethylol alkanoic acid, 11.8 g (0.16 mol) as molecular weight The n-butanol of the regulator (reaction terminator) and the carbitol acetate (manufactured by DAICEL Chemical Industry Co., Ltd.) as a solvent of 250 g were at 60. (3) Dissolve all the raw materials. While stirring the polyol component, add 200.9 g (1.08 mol) of trimethylhexamethylene diisocyanate as a polyisocyanate dropwise to the funnel. The reaction was continued while stirring, and the absorption spectrum of the isocyanate group (2280 cm·1) disappeared by the infrared absorption spectrum, and the reaction was completed. The carbitol acetate was added so that the solid content became 60% by weight to obtain an amine group. The ester resin solution (paint 2). The obtained polyaminocarbamic acid resin has a weight average molecular weight of 2,1200 and a solid content of 48.0 mgKOH/g. (Synthesis Example 3) A thermometer, a stirrer, a dropping funnel and The -23-201247808 bottle of the reflux cooler was fed with methyl methacrylate and acrylic acid at a molar ratio of 0.80: 0.20, and tripropylene glycol monomethyl ether as a solvent and azobisisobutyronitrile as a catalyst were added. The mixture was stirred at 80 ° C for 6 hours under a nitrogen atmosphere to obtain an acrylic resin solution (paint 3) having a nonvolatile content of 40% by weight. The obtained resin had a number average molecular weight of 15,000 and a weight average molecular weight of about 40,000, solid. The acid value of the component was 97 mgKOH/g. (Synthesis Example 4) In a reaction vessel equipped with a mixing device, a thermometer, and a dropping funnel condenser, methyl methacrylate and acrylic acid were fed at a molar ratio of 0.80: 0.20. Adding triethylene glycol monobutyl ether as a solvent (boiling point: 27 1 ° C), azobisisobutyronitrile as a catalyst, under nitrogen atmosphere at 80. (: stirring for 6 hours, obtaining a nonvolatile content 40% by weight of an acrylic resin solution (lacquer 4). The obtained resin had a number average molecular weight of 15,000, a weight average molecular weight of about 40,000, and an acid value of 97 mgKOH/g. (Synthesis Example 5) In addition to triethylene glycol monobutyl An acrylic resin solution (lacquer 5) having a nonvolatile content of 40 wt% was obtained in the same manner as in Synthesis Example 4 except that the ether was replaced by diethylene glycol monoethyl ether acetate. The number average molecular weight of the obtained resin was 15000' weight average. The molecular weight is about 42,000, and the acid value is 98 mg K 〇 H / g [Evaluation of ITO adhesion] -24 - 201247808 (Production of conductive paste) The components are blended in the proportion (mass ratio) shown in Table 1, and three rolls are used. The honing machine was kneaded, and Examples 1 to 3 and Comparative Examples 1 and 2 were obtained. Conductive paste. Further, the viscosity of the paste was adjusted to 150 dPa·s. [Table 1] Item Example Comparative Example 2 3 1 2 Organic binder resin paint 1 167 Paint 2 167 150 Paint 3 25 250 250 Conductive powder Silver powder 1 1870 1870 1870 1820 2290 Organic solvent diethylene glycol monoethyl ether acetate 100 100 100 100 100 Crosslinking agent jER828*2 18 18 18 15 JER1001 *3 45 Hardening catalyst Curezol 2E4MZ*4 2 2 2 2 2 *1 : Spherical silver powder (average particle diameter: 0.8 μm, specific surface area: 1.0 m 2 /g) *2 : jER828 (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent = 190 g/eq) *3 : jERlOOl (manufactured by Mitsubishi Chemical Corporation, Epoxy equivalent = 500g/eq) M : Curezol 2E4MZ (manufactured by Shikoku Chemical Industry Co., Ltd.) <Measurement of specific resistance & A test pattern having a line width of 1 mm and a length of 40 cm was formed by screen printing, and heat-treated in a hot air circulation type drying oven at 120 t for 30 minutes. The electric resistance of the obtained conductive circuit was measured using a Tester (Milliohm Hi-TeSter 3 540, manufactured by HIOKI Co., Ltd.), and the specific resistance 値 was calculated from the film thickness of the conductive circuit. -25- 201247808 [Table 2] Item a Example Comparative example 1 2 3 1 2 Specific resistance 値 [Ω· cm] 8.0E-05 6.8E-05 7.0E-05 9.5E-05 7.1E-05 <Adhesiveness Evaluation> (Preparation of Test Substrate) On the ITO film (manufactured by Teijin Chemicals Co., Ltd.) which was etched away from one part of the ITO layer, a mesh of 200 mesh was used to form Examples 1 to 3, and comparison was made. The conductivity type of the examples 1 and 2. Subsequently, heat treatment was carried out in an oven at 120 ° C for 30 minutes to prepare a test film for forming a conductive circuit on an ITO film (initial adhesion evaluation). On the obtained test film, 10 X 10 were formed at intervals of 1 mm. The total of 100 pieces of mesh cross-cutting is carried out, and the celluloid is peeled off. Next, the degree of peeling of the coating film of the portion etched by ITO and ITO was visually evaluated. The evaluation criteria are as follows: 〇: Those who have not been stripped at all. △: A part of the peeler is produced. X: Produces more than 50% of the stripper. (Evaluation of adhesion after high-temperature and high-humidity treatment) The obtained substrate was placed in a high-temperature and high-humidity bath of 85 ° C - 85% RH, and after 96 hours of treatment, on the obtained test film, at intervals of 1 mm, - 26- 201247808 Forms a total of 100 pieces of Χίο block of 100 mesh cross-cuts, and performs celluloid separation. Next, the degree of peeling of the coating film of the etched portion of the crucible and the crucible was visually evaluated. The evaluation criteria are as follows. 〇: Those who have not been stripped at all. △: A part of the peeler is produced. X: Produces more than 50% of the stripper. [Table 3] Project substrate Example Comparative Example 1 2 3 1 2 Initially adhered to ITO 〇〇〇 XX ITO worker etched 〇〇〇Δ 〇 ITO 〇〇〇 XX ITO etched after high temperature and high humidity treatment X 〇 As shown in Tables 2 and 3, it can be seen that by using the urethane resin of the present embodiment as an organic binder, good conductivity of the conductive circuit can be obtained, and the opposite layer of the conductive circuit and the etched portion of the ruthenium The confidentiality of the shares is improved. [Printing suitability evaluation] (Production of conductive paste) Each component was blended at a mixing ratio (mass ratio) shown in Table 4, and kneaded by three roller honing machines to obtain conductive materials of Examples 4 to 7 and Comparative Examples 3 to 5. Sexual cream. Also, the viscosity of the paste was adjusted to 150 dPa.s. And the viscosity is between 10 and 2 5 (30 ° C, 60 seconds). -27- 201247808 [Table 4] Item mm Comparative Example 4 5 6 7 3 4 5 Organic Adhesive Resin Paint 1 167 167 Paint 2 167 167 150 Paint 4 25 250 Paint 5 250 Conductive Powder Silver Powder *1 1870 1870 1870 1870 1820 2290 1870 Organic solvent diethylene glycol monoethyl ether acetate (boiling point = 217 〇 C) 50 50 20 100 100 triethylene glycol monobutyl ether (boiling point = 2.71 ° 〇 50 50 80 125 100 cross-linking Agent jER828*2 18 18 18 18 15 18 jERIOOl*3 45 Hardening catalyst Curezol 2E4MZ.4 2 2 2 2 2 2 2 [Remarks] Refer to Table 1 for the conductivity of Examples 4 to 7 and Comparative Examples 3 to 5. The ratio of the high boiling point solvent in the organic solvent contained in the loan is shown in Table 5. [Table 5] Solvent ratio [%] mm Comparative Example 4 5 6 7 3 4 5 High boiling point solvent 30 30 48 70 100 0 0 Other solvent 70 70 52 30 0 100 100 (Evaluation of printability by simple gravure printing) The obtained conductivity is set by using a steel scraper to form a stripe of wire/space = 70/3 0μη!, plate depth: ΙΟμιη In the recess of the glass intaglio of the pattern. -28- 201247808 Next, the glass intaglio plate is abutted The conductive paste filled in the concave portion is transferred to the surface of the offset cylinder by a conductive roller composed of a rubber rubber having a rubber hardness of 30° (printing roller transfer step, primary transfer). Transfer of the conductive paste to the conductive paste After 30 seconds on the surface of the blanket cylinder, the conductive paste on the surface of the blanket cylinder was transferred onto the surface of a soda lime glass having a thickness of 1.8 mm (pattern transfer step, secondary transfer). The following evaluation was performed on the thus obtained printed matter. Printability 1 : Straightness evaluation) The glass substrate on which each conductive paste was transferred was observed with an optical microscope, and the straightness of the printed matter was evaluated. The evaluation criteria are as follows. The evaluation results are shown in Table 6. 〇: Good straightness. △: Slightly lacking Straightness X: Significant lack of straightness and disconnection. (Printability 2: Evaluation of line width reproducibility) The glass substrate to which the conductive paste was transferred was observed with an optical microscope, and the line width of the printed matter was evaluated. The evaluation results are shown in Table 6. 〇: The line width is the same as the glass intaglio, or the error is within ±10% with respect to the plate size. △: The line width error is more than ±10% and within ±30% with respect to the plate size. x : The line width error is more than ±30% with respect to the plate size. (Printability 3: Transferability evaluation after 60 seconds on the offset printing) After the offset printing step (primary transfer), after 60 seconds Perform a transfer step (secondary transfer) of Figure -29 - 201247808 to visually evaluate whether or not a conductive bond remains on the surface of the blanket cylinder. The evaluation criteria are as follows. The evaluation results are shown in Table 6. 〇: No conductive bond (1 〇〇% transfer) remains on the surface of the blanket cylinder. △: A conductive ridge remains on a part of the surface of the blanket cylinder. X: A conductive paste remains on the entire surface of the blanket cylinder. (Measurement of specific resistance 値) A test pattern having a printing line width of 1 mm and a length of 40 cm was heat-treated at 120 ° C for 30 minutes using a hot air circulating drying oven. The electric resistance of the obtained printed matter was measured using a Tester (Milliohm Hi-Tester 3540, manufactured by HIOKI Co., Ltd.), and the specific resistance 算出 was calculated from the film thickness of the printed matter. [Table 6] Item mm Comparative Example 4 5 6 7 3 4 5 Printability 1 ο ο ο ο Δ Δ Cannot evaluate printability 2 ο ο ο ο Δ X Cannot evaluate printability 3 ο ο ο ο ο X Cannot evaluate ratio® Resistance [Q·cm] 8.0Ε-05 6.8Ε-05 7.0Ε-05 7.2Ε-05 9.5Ε-05 7.1 巳05 1.1Ε-04 As shown in Table 6, it is known that the conductive paste of the present embodiment is used. In Examples 4 to 7, any printed conductive circuit was excellent in line width reproducibility and straightness, and the transfer was retained even if the time from the offset cylinder transfer step to the pattern transfer step was long. An optical micrograph of the printed matter (conductive circuit) of the seventh embodiment is shown in Fig. 2 as an example of the image of the conductive printed matter of the present embodiment. As shown in Fig. 2, the reproducibility of the line width is known, and the line width of the printed matter (conductive circuit) is 64 to 67 μm (error: -8.6% to -4.3%) with respect to the plate size -30 - 201247808 70 μm, regarding the straightness. Also good. On the other hand, in Comparative Example 3 which does not contain the urethane resin of the present embodiment, it is understood that the transfer property is retained even when the time from the transfer cylinder transfer step to the pattern transfer step is long, but the obtained printed matter is obtained. Lack of line width reproducibility and straightness. Further, in Comparative Example 4 which did not contain the urethane resin of the present embodiment and the high boiling point solvent, it was found that the paste was dried when it was left for a long time on the offset printing, and the transfer property was impaired. Further, in Comparative Example 5 which did not contain the high boiling point solvent of the present embodiment, it was found that the paste was dried on the offset printing and the printing could not be evaluated. Fig. 3 shows an optical micrograph of a conductive print (conductive circuit) using Comparative Example 3. As shown in FIG. 3, it can be seen that the line width is reproducible, and the line width of the printed matter (conductive circuit) is 58 to 62 μm (error: -17.1% to -11. 4%) with respect to the plate size of 70 μm, and regarding the straightness, It can be seen that the printed matter will be undulating and slightly lacking in straightness. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a procedure of gravure lithography according to a second embodiment of the present embodiment. Fig. 2 is an optical micrograph of the printed matter of Example 7. 3 is an optical micrograph of a printed matter of Comparative Example 3. [Description of main component symbols] 1 1 : Gravure 1 1 a : Recessed part -31 - 201247808 1 2 : Conductive paste 1 3 : Oxygen blanket printing roller 1 4 : Step difference 1 5 : Substrate 16 : Coating film -32