201001444 六、發明說明： 【發明所屬之技術領域】 本發明關於一種配置於例如觸摸面板之前面使用，對於重複之筆輸入 具有良好書寫耐久性之透明導電性膜片以及配備該透明導電性膜片之觸 摸面板0 [先前技術] 於透明塑料膜片上形成透明且具有導電性之化合物薄膜的透明導電性 膜片，因其具備導電性，故而被廣泛用於電氣、電子領域，例如液晶顯 示器、EL顯示器等平板顯示器或觸摸面板之透明電極等。作爲該透明導 電性膜片，於聚對苯二甲酸乙二醇酯（PET)、三醋酸纖維素（TAC)等 透明膜片之至少一面上，採用真空蒸鍍法、濺鍍法、離子電鍍法等乾式 製程，設置氧化錫（Sn〇2)、氧化銦（InCb )與氧化錫之混合燒結體（ITO ) 或氧化鋅（ZnO)等製造而成者爲衆所周知。 利用輸入筆在顯示器上書寫文字之輸入操作具有紙上書寫之相同感 覺，利用此優點，近年來移動資訊終端、電子手冊及多媒體機器等得到 迅速普及，利用範圍大幅擴大。由於利用之普及，因此要求導電性膜片 具有利用筆輸入文字之功能。與此相隨，在導電性膜片之耐久性方面， 亦要求其導電性不會因筆之輸入而產生劣化。然而，當透明導電性膜片 用於觸摸面板時，介隔襯墊相對之一對導電性薄膜在筆輸入所產生之壓 力下緊密接觸，因此存在導電性薄膜產生裂縫、發生剝離，造成電阻增 大或斷線等問題。201001444 6. Technical Field of the Invention The present invention relates to a transparent conductive film which is disposed in front of, for example, a touch panel, has good writing durability for repeated pen input, and is provided with the transparent conductive film. Touch panel 0 [Prior Art] A transparent conductive film which forms a transparent and conductive compound film on a transparent plastic film is widely used in electrical and electronic fields, such as liquid crystal displays, because of its electrical conductivity. A flat panel display such as an EL display or a transparent electrode of a touch panel. As the transparent conductive film, vacuum deposition, sputtering, or ion plating is applied to at least one surface of a transparent film such as polyethylene terephthalate (PET) or cellulose triacetate (TAC). A dry process such as a method is known, and it is known to provide a sintered body (ITO) of tin oxide (Sn〇2), indium oxide (InCb), and tin oxide, or zinc oxide (ZnO). The input operation of writing text on the display by the stylus has the same feeling of writing on paper. With this advantage, mobile information terminals, electronic manuals, and multimedia devices have been rapidly popularized in recent years, and the scope of use has been greatly expanded. Due to the popularity of use, it is required that the conductive film has a function of inputting characters using a pen. Along with this, in terms of durability of the conductive film, it is also required that the conductivity does not deteriorate due to the input of the pen. However, when the transparent conductive film is used for a touch panel, the spacer film is in close contact with the conductive film under the pressure generated by the pen input, so that the conductive film is cracked and peeled off, resulting in an increase in resistance. Big or broken issues.
因此，爲緩和觸控筆之應力，坊間銷售之透明導電膜片採用硬化層/PET 4 201001444 膜片黏著劑層/PET層/夾膜層/透明導電性薄膜之疊層構造。使用此透明 導電性膜片時，柔軟之黏著劑層可緩和筆輸入時之應力，書寫耐久性(筆 輸入耐久性）得以提高，然其存在膜片構造非常複雜，製造方法亦很複 雜，故成本高昂之缺點。 因此，有提出一種透明導電性膜片，其在以構造更加簡單之硬化型樹 脂作爲主要構造成分之硬化物層上，層疊硬度爲0.4〜0.8GPa之透明導 電性薄膜而形成透明導電性膜片（例如參考專利文獻1) 〇此透明導電性 膜片之目的在於提高將其用於觸摸面板時筆的滑動耐久性。另外，還提 出一種將動態硬度爲0.005〜2之緩衝層設置於透明塑料膜片層與透明導 電性薄膜層之間的透明導電性膜片（例如參考專利文獻2)〇此透明導電 性膜片之目的在於改良將其用於觸摸面板時筆的輸入耐久性。 此外，還提出一種透明導電體，其於透明基體上具有以有機導電性組 成物形成之透明導電膜（例如參考專利文獻3)。此透明導電體具有對應 環境變化之高度可靠性，長時間使用也不會造成阻抗劣化，壽命長。 [專利文獻1]日本專利特開2002-163932號公報（第2頁、第3頁、第9 頁及第10頁） [專利文獻2]日本專利特開平11-34206號公報（第2頁、第7頁及第8 頁） [專利文獻3]日本專利特開2005-146259號公報（第2頁及第4頁） 【發明內容】 / 八 【发明所欲解决之课题】 然而，於專利文獻1所述之透明導電性膜片中，透明導電性薄膜之硬 度規定爲0.4〜0.8GPa，雖對透明導電性薄膜之脆性有所抑制，針對筆滑 5 201001444 動時之磨耗劣化的耐久性得以提高，但透明導電性薄膜之厚度極薄，例 如22〜27nm (專利文獻1之實施例）。因此，僅依靠該透明導電性薄膜 難以在使用中完成對筆滑動所產生之應力進行緩和的作用，硬化物層及 透明導電性薄膜上會產生損傷或裂縫，並不耐用。 此外，專利文獻2所述之透明導電性膜片則只是將緩衝層之硬度指 定，然僅憑藉硬度之調整無法消除長期使用中筆輸入所產生的凹進（凹 陷），其存在會留下凹進痕跡、書寫耐久性惡化且外觀變差之缺點。此外， 專利文獻3所述之透明導電體存在以下問題，透明導電膜本身係由有機 導電性組成物形成，耐久性差，並且該透明導電膜直接形成於透明基體 上，故對於筆輸入所產生之應力，其應力緩和作用並不充分，使用中透 明導電膜會發生剝離。 因此，本發明之目的在於提供一種針對例如觸摸面板之筆輸入可抑制 有機導電層損傷或裂縫之發生、可提高書寫耐久性之導電性膜片以及具 備該導電性膜片之觸摸面板。 【解决课题之手段】 本發明第1發明所述之透明導電性膜片係於透明基材上設置軟質樹脂 層，並於該軟質樹脂層上層叠基於導電性高分子之有機導電層而構成， 上述軟質樹脂層於溫度20°C ’相對濕度50%之環境下，利用超顯微硬度 測試裝置測得之馬氏硬度爲〇_1〜7〇N/nm2，且具有自我修復性。 第2發明所述之透明導電性膜片於第1發明中，上述軟質樹脂層係於 透明基材上塗佈硬化性組成物，並使其硬化而形成，上述硬化性組成物 包含10〜90重量％之下列化學式（1)、（2)或（3)所示之重複單位。 6 201001444 -0—〔(CB)厂0〕k— · · · (1) 式中，j=2〜4，k=2〜30。 -〇- (C- (CHZ) ,-〇) ° ---(2) 式中，1=3〜12，m=l 〜15。 —(CH2) p— . · · (3) 式中，p=10〜24。 第3發明所述之透明導電性膜片於第2發明中，上述硬化性組成物係 含有氨酯改質（甲基）丙烯酸酯之活丨生能量線硬化性組成物。 第4發明所述之透明導電性膜片於第1至第3任一項所述之發明中， 形成上述有機導電層之有機導·丨生问分子係聚嚷吩、聚卩必咯·、聚苯胺或 聚喹喔啉。 第5發明所述之觸摸面板係於其前面配置第1至4中任一項所述之一 對透明導電讎片而構成，上述一對透明導電性膜片之有機導電層方向 相對。 【发明功效】 使用本發明，可發揮以下效果。 於第1發明所述之透明導電性膜片中’透明基材與有機導電層之間設 有馬氏硬度爲0.1〜70N/mm2之軟質樹脂層。因此，即使輸入筆等重複滑 動，亦可藉由該軟質樹脂層分散力道，有機導電層上不易發生裂縫、剝 離之現象。此外，軟質樹脂層具有自我修復性，因此輸入筆滑動所造成 之凹進（凹陷）得以恢復，外觀不良之發生得以抑制。再者，導電層係 具有柔軟性之有機導電層，因此可抑制裂縫之產生，提高耐久性。因此， 可抑制例如觸摸面板上由於筆輸入所造成之有機導電層的損傷以及裂縫 201001444 之產生，可以提高書寫耐久性。 於第2發明所述之透明導電性膜片中，軟質樹脂層係於透明基材上塗 佈硬化性組成物，並使其硬化而形成，上述硬化性組成物包含10〜9〇重 量％之上述化學式（1)、（2)或（3)所示之重複單位。此等重複單位可 提高軟質樹脂層之柔軟性與自我修復性。因此，於第1發明功效之基礎 上，可進而抑制有機導電層損傷、裂縫之產生，亦可進一步抑制外觀不 良。 第3發明所述之透明導電性膜片中，上述硬化性組成物係含有氨酯改 質（甲基）丙烯酸酯之活性能量線硬化性組成物。因此，於第2發明功 效之基礎上，可提高軟質樹脂層之彈力性，提高恢復性，並可實現迅速 硬化’發揮透明導電性膜片之連續生産性。 第4發明所述之透明導電性膜片中，形成有機導電層之有機導電性高 分子係聚噻吩、聚秘咯、聚苯胺或聚喹喔啉。因此，在第1至第3中任 一項所述之發明功效的基礎上，可進而提高透明導電性膜片之光學特性 以及導電性。 第5發明所述之觸摸面板係於其前面配置上述一對透明導電性膜片構 成，上述一對透明導電性膜片之有機導電層相對。因此，即使由於筆輸 入時在觸摸面板之透明基材表面重複滑動，亦可抑制有機導電層之損傷 或裂縫產生，可提供書寫耐久性良好之觸摸面板。 【實施方式】 以下，具體説明被認爲是本發明之最佳形態的實施方式。 本實施方式之透明導電性膜片係於透明基材上設置軟質樹脂層，並於 該軟質樹脂層上層疊基於導電性高分子之有機導電層而構成。軟質樹脂 層於溫度20°C、相對濕度5〇%之環境^，利用超顯微硬度測試裝置測得 201001444 之馬氏硬度爲0.1〜70N/mm2，且具有自我修復性。該一對透明導電性膜 片例如以彼等之有機導電層方向相對之方式配置於觸摸面板之前面，以 此形成觸摸面板。另，觸摸面板係指藉由手指或專用筆觸摸畫面，從而 執行計算機操作之裝置。 具體而言，如圖1所示，構成觸摸面板10之透明導電性膜片11係於 透明基材12上設置軟質樹脂層13 ’並於其上層叠有機導電層14而_$ 〇 另，圖1係模式性表示觸摸面板之截面圖’各層之厚度、有機導電層 14之間之間隔等均以誇張之手法描繪。此外，觸摸面板1〇係由雙面膠 帶（襯墊）15將2片透明導電性膜片11之周圍貼合構成，該2片透明導 電性膜片11之有機導電層14相對。然後，使用觸摸面板輸入筆I6在^ 摸面板10前面側（圖1之上側）之透明基材12上從左往右（圖1中自 實線向二點虛線）滑動，以此進行輸入操作。此時’透明導電性膜片11 於透明基材12與有機導電層14之間設有上述軟質樹脂層13 ,因此可抑 制因觸摸面板輸入筆16在透明謝12上輸入而造成有機導電層Μ損 傷、裂縫產生，可提高書寫耐久性（尖端按壓耐久性）。 於上述透明基材12之與軟質樹脂層13相反的面上，層叠有未圖示之 硬化層、防眩層以及具有自我修復性之軟質樹脂層，可在硬化層上 比其折射率低之低折射率層形成減反射層，或可在上述防眩層上層叠比 其折射率低之低折射率層形成減反射防眩層。此時，藉由硬化層’胃^ 大表面之強度，而防眩層可使表面具有防眩1生，能夠抑制反射，具有自 我修復性之軟質樹脂層可提高用筆輸入時表面之書寫手感。此外’藉由 設有低折射率層之減反射層，可有效抑制表面之反光現象，藉由設有低 折射率層之減反射防眩層，可使表面具有防眩性，抑制反射’ 防眩層表面上之反光現象。 9 201001444 以下，按照順序説明透明導電性膜片11之各項構成要素。 [透明基材12] 透明基材12可使用透明樹脂膜片、透明刪旨板、透明玻璃板等，無特 別限制。形成透明基材12之樹脂材料具體可列舉聚（甲基）丙烯系樹脂、 聚（甲基）丙烯腈系棚旨、聚苯乙烯系樹脂、聚颯系樹脂、聚醚砜系樹 脂、聚醚系棚旨、聚甲基戊烯系樹脂、三醋酸纖維素（TAC)系樹脂、 聚對苯二甲酸乙二醇酯（PET)系樹脂、聚氨酯系樹脂、再生纖維素系 樹脂、二乙醯纖維素系樹脂、醋酸纖維素系棚旨、聚酯系樹脂、丙烯腈 一丁二烯一苯二烯三元共聚物系樹脂、聚碳酸酯系樹脂、聚醚酮系樹脂、 聚氯乙烯系樹脂、聚偏氯乙烯系樹脂、聚乙烯醇系樹脂、聚乙烯系樹脂、 聚丙烯系樹脂、聚醯胺（尼龍）系樹脂、聚亚醯胺系樹脂、降冰片烯系 棚旨等。其中，由通用性及用途實績等觀點考量，較好的是聚（甲基） 丙烯系樹脂、聚苯乙烯系樹脂、三醋酸纖維素系樹脂、聚對苯二甲酸乙 二醇酯系樹脂及聚碳酸酯系树脂。設置偏光層作爲功能層時，通常使用 三醋酸纖維素系樹脂。 透明基材12之厚度通常爲10〜5000/zm，較好的是25〜1000/zm，更 好的是35〜500//m。當此厚度比10/zm薄時，在形成透明導電性膜片 11之作業等中其作業性變差，透明基材12之強度亦有降低之傾向。另 一方面，當厚度比5000/zm厚時，將透明導電性膜片11用於觸摸面板 10時，必須加大筆輸入之力道，非所期望者。 [軟質樹脂層13] 以下，針對軟質棚旨層13進行説明。此軟質棚旨層13於溫度2(TC、 相對濕度50%之環境下，利用超顯微硬度測試裝置測得之馬氏硬度爲0.1 〜70N/mm2，且具有自我修復性。此處，所謂自我修復性是指一旦產生凹 201001444 進（凹陷），該凹進（凹陷）之痕跡會隨時間消失並回到原來形狀（恢復） 之性質。軟質樹脂層13之厚度較好的是5〜100，更好的是10〜80 /zm。當其厚度低於.5/zm時’則軟質樹脂層13之柔軟性不足，自我修 復性及書寫耐久性變差。而另一方面，當厚度超過100"in時，軟質樹 脂層13則過厚，將其用於觸摸面板10時，必須加大筆輸入之力道，非 所期望者。 軟質樹脂層13係於透明基材12上塗佈用於形成軟質樹脂層之硬化性 組成物使其硬化形成，硬化性組成物之黏度過高等情形下，則塗佈經過 稀釋溶劑稀釋之硬化性組成物（液體）’然後除去溶劑再使其硬化後形 成。用於形成軟質樹脂層之硬化性組成物的硬化塗膜（$欠質樹脂層13) 之上述馬氏硬度爲0.1〜70N/_2 ’較好的是〇.1〜65N/mm2，更好的是0.5 〜10N/mm2。馬氏硬度係根據將維氏硬度塊壓入膜片表面時之測試負重與 壓入表面積所計算得出的塗膜硬度，係物體表面硬度之指標。當該馬氏 硬度低於0.1N/mm2時，顯不過軟且過於凹進之傾向，耐久性低。另一方 面，超過70N/mm2時，顯示過硬且難以凹進之傾向，無法吸收施加之力 量。 用於形成軟質樹脂層之硬化性組成物中，包含紫外線硬化性或熱硬化 性之不飽和丙稀樹脂組成物、氨醋改質（甲基）丙稀酸酯等不飽和聚氨 酯樹脂組成物、不飽和聚酯樹脂組成物、聚醯胺樹脂組成物、熱硬化型 之矽系、三聚氰胺系及環氧系之樹脂組成物等。 進一步具體而言，可例舉含有多官能聚合性化合物之樹脂組成物、含 有氨酯改質（甲基）丙烯酸酯之樹脂組成物、以及含有矽系、三聚氰胺 系或環氧系之多官能聚合性化合物之樹脂組成物等，上述多官能聚合1 生 化合物至少含有2個多價乙醇與（甲基）丙烯酸之酯化物等的（甲基） 11 201001444 丙烯醯基。其中’由耐久性及操作便利性之觀點考量，以可利用紫外線、 電子線或加熱方式硬化之多價乙醇與（甲基）丙稀酸之酯化物、或氨醋 改質（甲基）丙烯酸酯等含（甲基）丙烯醯基之化合物爲主要成分的樹 脂組成物較佳。進而，由操作性及連續生産性之觀點考量’具有紫外線 硬化性、電子線硬化性等活性能量線硬化性之樹脂更好。用於形成軟質 樹脂層之硬化性組成物通常含有50重量％以上此等含（甲基）丙烯醯基 之活性能量線硬化性樹脂，較好的是含有60重量％以上。 上述多價乙醇可例舉乙一醇、聚乙—醇' 丙二醇（propylene glycol)、 聚丙二醇、丙二醇（propanediol)、丁二醇、戊二醇、己二醇、新戊二醇、 2-乙基-1,3-己二醇、2,2’-硫代乙二醇、1，4環己二甲醇等2價乙醇；三經 甲基丙院、丙三醇、異戊四醇、三丙二醇、二季戊四醇、雙三經甲基丙 烷等三價以上之乙醇。 上述氨酯改質（甲基）丙烯酸酯可藉由一個分子中含有複數個異氰酸 酯基之有機異氰酸酯與具有氫氧基之（甲基）丙稀酸衍生物進行有氨酯 化反應獲得。至於一個分子中含有複數個異氰酸酯基之有機異氰酸酯， 可歹！J舉二異氰酸己二酯或異佛爾酮二異氰酸酯、甲苯二異氰酸酯、萘二 異氰酸酯、二苯基甲烷二異氰酸、二甲苯二異氰酸酯、二環己基甲烷二 異氰酸酯等一個分子中含有兩個異氰酸酯基之有機異氰酸酯，以及將此 等有機異氰酸酯進行異氰尿酸酯改質、附加物改質、縮二脲改質後一個 分子中含有三個異氰酸酯基之有機異氰酸酯等。 至於具有氫氧基之（甲基）丙烯酸衍生物，可例舉（甲基）丙烯酸2-羥乙酯、（甲基）丙烯酸2-羥丙酯、（甲基）丙烯酸聚己內酯改質經卞酯 等。其中，如（甲基）丙烯酸聚己內酯改質經卞酯等具有長鏈部分之化 合物的彈性高，具有自我修復性，故較好。 201001444 此外，可在氨酯改質（甲基）丙烯酸酯之構成成分中使用聚己内酯二 元醇或聚四甲基二醇等具有複數個氫氧基之寡聚物、十三烷醇、肉豆蔻 醇、鯨蠟醇、十八烷醇、二十二醇、聚氧乙烯單硬脂酸酯、聚氧乙烯鯨 蠟基醚、聚氧乙烯硬脂基醚、單硬脂酸甘油酯等具有長鏈烷基乙醇，使 得軟質樹脂層13具有良好之恢復性，可實現適度之表面光滑性。這些成 分可單獨使用，亦可同時使用兩種以上。此外，爲取得優良之凹進感以 及適當之恢復性，較好的是上述多價乙醇或氨酯改質（甲基）丙烯酸酯 等上述各種樹脂中適度含有長鏈部分。 至於長鏈部分，可列舉含有以下列化學式（1 )、（ 2 )或（3 )所示之重 複單位之鍵等。 —〇—〔(CH2)厂〇〕k— ...(1) 式中，j=2〜4，k=2〜30。 -〇-（jj5- (ch2) ° …（2) 式中 ’ 1=3〜12，m=l〜15。 —(CH2) P— ... (3) 式中，p=10〜24。 化學式（1)之情形下，重複單位k較好的是2〜30個鏈，更好的是2 〜20個鏈。化學式（1)之重複單位中，碳素數j較好的是2〜4個。化 學式（2)之情形下，111較好的是1〜15個鏈，更好的是1〜10個鏈。化 學式（2)之重複單位中，碳素數1較好的是3〜12個，更好的是3〜8 個。化學式（3)之情形下，碳素數p較好的是10〜24個，更好的是12 〜20個 較好的是，此等長鏈部分之重複單位於硬化性組成物中含有10〜90重 13 201001444 量％，更好的是含有25〜85重量％，含有30〜80重量％尤佳。該含有量 少於10重量％時，軟質樹脂層13之彈性升高，難以具備自我修復性。 而另一方面，當高於90重量％時，軟質樹脂層13存在強度不足之傾向’ 透明導電性膜片11之耐久性降低，非所期望者。 如上所述，硬化性組成物若係含有氨酯改質（甲基）丙烯酸酯之活性 能量線硬化性組成物，便可提高軟質樹脂層13之彈性，增強其恢復性， 並可使硬化迅速完成，因此可提高透明導電性膜片11之連續生産性。在 此情形下，依據常規方法向硬化性組成物添加光聚合起始劑，並藉由照 射活性能量線進行硬化性組成物之硬化。繼而，氨酯改質（甲基）丙烯 酸酯若經過聚己內酯改質或異氰尿酸酯改質’便可提高軟質樹脂層13之 恢復性，增強自我修復性。 (密著性提高成分） 此外，爲改善透明基材12與軟質樹脂層13之間以及軟質樹脂層13與 有機導電層14之間之密著性，較好的是硬化性組成物中含有1種或2種 以上具有羧基與氫氧基中至少一者之化合物。具有竣基與氫氧基中至少 一者之化合物並無限定，具體而言可列舉羥基琥珀酸、水楊酸、乳醯乳 酸、2-羥基丁酸等同時具有氫氧基以及羧基之化合物、或者（甲基）丙 烯酸、反丁烯二酸、馬來酸、衣康酸、檸康酸、鄰苯二甲酸單甲基丙烯 酸羥乙酯等同時具有不飽和結合以及羧基之化合物、以及將這些單體共 聚合之共聚合體、烯丙醇、甲基丙烯醇、乙烯醇、油醇、丙烯酸-2-羥丙 酯等同時具有不飽和結合以及氫氧基之化合物、以及將這些單體共聚合 之共聚合體等。此種化合物之含有量在硬化性組成物中較好的是〇.〇1〜 30重量％，更好的是0.1〜15重量％。此等化合物之含有量少於0.01重量 %時，軟質樹脂層13對於透明基材12之密著性不夠充分，多於30重量 14 201001444 %時，軟質樹脂層13之自我修復性降低，非所期望者。 (反應性稀釋劑） 進而，硬化性組成物還可以同時使用具有一個不飽和結合之化合物， 作爲提高軟質樹脂層13之強度、韌性等物性的反應性稀釋劑。此反應性 稀釋劑只要係與形成軟質樹脂層13之上述成分具有良好相溶彳生之單體 即可，並無特別限制。至於反應性稀釋劑，可例舉（甲基）丙烯酸乙酯、 (甲基）丙烯酸2—乙基己酯、丙烯酸月桂基酯、苯乙烯、甲基苯乙烯、 N-乙稀基吡咯烷酮、二甲基丙烯醯胺等。這些單體可單獨使用，亦可兩 種以上同時使用。 (稀釋溶媒） 爲調整硬化性組成物之粘度，可使用稀釋溶媒。稀釋溶媒只要是非聚 合性物質即可，無特別限制，例如可使用甲苯、二甲苯、乙酸乙酯、乙 酸丁酯、甲氧基乙醇醚、乙氧基乙醇醚、乙基乙二醇醋酸酯、異丙醇、 甲基乙基酮、丙二醇單甲醚、3-甲氧丁醇等。這些稀釋溶媒可單獨使用， 亦可兩種以上同時使用。其含有量取決於硬化性組成物之組成，但通常 爲硬化性組成物之〇.1〜8〇重量％ 〇 (表面調節劑） 爲提高硬化組成物之塗工性’較好的是於硬化性組成物中添加表面 調節劑。該表面調節劑較好的是聚砂氧院系化合物或丙烯系聚合物等。 聚矽氧烷系化合物較好的是直鏈狀或分支狀之聚二取代基矽氧烷系化合 物，亦可爲含有聚矽氧烷基之共聚合體。聚二取代基矽氧烷之代表例爲 聚二甲基矽氧烷。進而，主鏈或側鏈可具有乙烯基或（甲基）丙烯醯基 等反應性基。該甲基之部分乃至全部可由其他有機基置換（該甲基被置 換之位置可爲末端亦可爲鏈內）。 15 201001444 此種其他有機基可例舉甲基之外之烷基'芳基、環烷基以及聚氧化伸 烷基鏈或聚酯鏈等具有重複單位之鏈等。進而，此等有機基可具有氫氧 基、胺基、環氧基、醯基、醯氧基、羧基等其他官能基。上述具有重複 單位之鏈可例舉聚氧乙烯鏈、聚氧丙嫌鏈、聚四氫呋喃鏈、聚（氧乙嫌 丙烯）鏈等聚氧化伸烷基鏈，或聚己內酯鏈、聚癸二酸亞乙基酯鏈、聚 乙二醇己二酸等聚酯鏈。此等鏈之末端可爲氫氧基或羧基，亦可爲（甲 基）丙烯醯基或乙烯基’其末端可由有機基封閉。例如，可用烷基醚化、 烷基酯化等方式進行封閉。此外，該鏈通常係通過二甲基或三甲基等烷 基與矽原子結合，並不僅限於此。 具體而言，表面調節劑中，作爲包含聚醚改質聚二甲基矽氧烷之市售 產品，較好的是 “ BYK-306 ” 、“ BYK-330 ” “ BYK-341” 、 “ BYK-344 ” 、“ BYK-307 ”、“ BYK-333 ” （畢克化學生產）、 “VXL4930” （維諾華樹脂公司（Vianova Resins)生產）等。此外，作 爲包含丙烯系聚合物之市售品，較好的是“BYK-356” ' “BYK-359”、 “BYK-361” 、“BYK-352 ” 、“BYK-354 ” 、“BYK-355 ” 、 “BYK-358”、“BYK-380”、“ΒΥΚ-381”、“BYK-390” （畢克化學 生產）等。進而，作爲含有聚矽氧烷基之共聚合體，較好的是由含有聚 矽氧烷基之化合物與其他聚合體形成的含有聚矽氧烷基之接枝共聚合 體，或是由含有聚矽氧烷基之化合物與其他聚合體形成的含有聚矽氧烷 基之接枝共聚合體鏈段A與由其他聚合體形成之不含有聚矽氧烷基之聚 合體鏈段B形成的AB塊狀共聚合體，或是由含有聚矽氧烷基之化合物 鏈段A與由其他聚合體形成之不含有聚矽氧烷基之聚合體鏈段B形成之 AB塊狀共聚物。上述共聚合體之市售品可列舉MODIPER FS700、 MODIPERFS710、MODIPERFS720、MODIPERFS730旧本油脂株式會社 16 201001444 生產傳。 表面調節劑於硬化性組成物中的含有量通常爲0.01〜10重量％，較好 的是0.01〜5重量％。該含有量超過10重量％時，有機導電層14與軟質 樹脂層13之間的密著性會降低。而另一方面，如果低於0.01重量％，軟 質樹脂層13則無法取得足夠之表面平滑性。硬化性組成物由上述含有 (甲基）丙烯醯基之化合物、至少具有竣基與氫氧基中至少一者之化合 物、反應性稀釋劑、表面調節劑、稀釋溶媒、以及後述之其他化合物等 配合調製而成。調製時，用於調配之器械及調配步驟等依常法進行，無 特別限制。 軟質樹脂層13既可爲單層，亦可形成爲複數層。形成軟質樹脂層13 之樹脂之具體例可歹—NATOCO株式會社生產之紫外線（UV)硬化性 的特殊改質丙烯酸胺酯塗料“UV自我愈合性透明涂料”等。 (光聚合起始劑） 光聚合起始劑用於將紫外線、電子線等活性能量線照射在上述活性能 量線硬化性樹脂上，使聚合開始，可使用公知之化合物。該光聚合起始 劑可例舉二苯甲酮類、苯乙酮類、α-戊基肟酯、米氏苯甲酸苄酯、一硫 化四甲β火蘭姆、塞噸酮類等。具體而言，可列舉1-羥基環己基苯基酮、 2-經基-2-甲基-1-苯基丙院-1-嗣、2-甲基-1-[4-(甲硫基）苯基]-2-吗琳基丙 烷-1-酮、1-[4-(2-羥乙氧基）苯基)-2-羥基-2-甲基-1-丙烷-1.、安息香、 2,2-二甲氧基_1，2_二苯基乙院-1-酮、二苯甲酮、[4-(甲基苯硫基）苯基〕 苯基甲酮、4-經基二苯甲酮、4-苯基二苯甲酮、3，3’，4，4’ -四（t-丁 院基幾基）二苯甲酮、2-氯噻噸酮、2,4-二乙基噻噸酮、α-戊基聘酯、 米氏苯甲酸苄酯、一硫化四甲基秋蘭姆等。 光聚合起始劑之含有量相對於活性能量線硬化性樹脂1〇〇重量部，較 17 201001444 好的是αοι〜2〇重量部，1〜10重量部更好。此含有量低於o.oi重量部 時，由硬化性組成物獲得之硬化物（被膜）難以完全硬化，硬化不充分， 因此非所期望者。另一方面，當超過20重量部時，雖可充分完成硬化’ 但並無更多效果，因此用量過多而無用，造成浪費。 (軟質樹脂層13之調製） 將以上用於形成軟質樹脂層之硬化性組成物塗佈於透明基材12上之 後，藉由照射活性能量線使其硬化，從而取得在透明基材12上形成有軟 質樹脂層13之膜片。將用於形成軟質樹脂層之硬化性組成物塗佈於透明 基材12上之方法有滾筒塗佈法、自旋式塗佈法、浸漬塗佈法、刷毛塗佈 法、噴霧塗佈法、線棒塗佈法、刀式塗佈法、擠壓式塗佈法、凹版印刷 塗佈法、淋幕塗佈法、反向塗佈法、吻合塗佈法、刮刀式塗佈法等，所 有公知之方法均可採用。塗佈時，爲提高密著性，可預先在透明基材12 之表面實施電暈放電處理等前處理。 用於照射活性能量線之活性能量線源例如可使用高壓水銀燈、鹵素 燈、氙氣燈、氮氣雷射、電子線加速裝置、放射性元素等線源等。至於 活性能量線之照射量，以紫外線波長365nm之積算光量爲例，較好的是 50〜5000mJ/cm2。照射量低於50mJ/cm2時，用於形成軟質樹脂層之硬化 性組成物的硬化不充分，非所期望者。另一方面’超過5000mJ/cm2時， 活性能量線硬化性樹脂存在著色傾向，非所期望者。 [有機導電層14] 上述有機導電層14與以往之無機導電層相比，柔軟性與彈性均更高， 因此可在長期使用中緩和輸入筆滑動所造成之應力。用於形成此有機導 電層14之有機導電性高分子只要是具有透明性及導電性之有機導電性 材料即可，並無特別限制。較好的有機導電性高分子具體有聚噻吩、聚 18 201001444 秘略'聚苯胺或聚嗤喔啉。其中，較好的是導電性及光學特性良好之聚 噻吩及聚苯胺’更好的是聚噻吩。在軟質樹脂層13上形成此有機導電層 14可採用常法進行。有機導電層14之厚度通常爲1〇〇〜2〇〇nm。 [其他層] 此外，如上所述，透明基材12之與形成有軟質樹脂層13之面相反的 面上，可設置硬化層，在該硬化層上層疊折射率比硬化層低的低折射率 層，形成減反射層。或者，在上述硬化層上設置防眩層，在該防眩層上 設置折射率比防眩層低的低折射率層，形成減反射防眩層。 形成硬化層可爲透明導電性膜片11賦予充分之表面強度，可提高耐久 性。硬化層之厚度較好的是1〜20//m。該厚度低於i 時，透明導電 性膜片11難以獲得充分之表面強度。另〜方面，當厚度超過2〇_時， 會造成透明導電性膜片11耐彎曲性降低等問題。 形成硬化層之材料並無特別限定，可例舉單官能（甲基）丙稀酸酯、 多官能（甲基）丙烯酸酯以及四乙氧基矽烷等反應 物。其中，從兼顧生產性及硬度之觀點考量，包含紫外線硬化性多官能 (甲基）丙烯酸酯之組成物的聚合硬化物尤佳。此 多官能（甲基）丙烯酸酯之組成物無特別限制。_D， 上公知之紫外線硬化性多官能（甲基）丙烯酸酯混合者、坊間作爲紫外 線硬化性硬化層材料而銷售者、或者其他在不損害硬化性之範圍內，進 而添加其他成分者。 形成減反射層後，可對表面反光現象作有效抑制。上述低折射率層之 折射率比硬化層低’可使其表面具有防止反射功能。至於形成低折射率 層之材料，可例舉紫外線硬化型丙烯樹脂等樹脂系材料、在樹脂中分^ 膠體氧化砂等無機微粒子所形成之混合材料、四乙氧基砂院或欽酸四乙 19 201001444 酯等使用金屬烷醇鹽等之溶膠-凝膠系材料等。尤其，眾所周知具有氟原 子之化合物具有低折射率，具體可列舉側鏈中具有全氟烷基之聚合性單 體，例如聚合甲基（丙烯酸）含氟烷基酯而形成之聚合體、聚合氟烷基 苯乙烯而形成的聚合體等。進而，有效降低折射率之方法可列舉在作爲 黏合劑之含有氟原子的化合物中添加中空氧化矽微粒子之方法。 低折射率層之厚度無特別限制，可視光波長之1/4 (約10〇nm)時，其 干擾效果可減少表面反射，提高透過率，較爲理想。此外，從獲得較佳 之防止反射效果的觀點考量，低折射率層之折射率係越低越好，但過低 時，反射光會著色，非所期望。因此，考慮到防止反射和防止著色，該 低折射率層之折射率較好的是在1.30〜1.50，尤其著重於防止反射效果 時，1.30〜1.45更佳。 形成防眩層時，表面可具有防眩性，可抑制反射。此種防眩層例如可 藉由使含有活性能量線硬化性樹脂及透光性微粒子之用於形成防眩層之 組成物硬化而形成。上述活性能量線硬化性樹脂之構成成分中必須含有 聚合性成分，亦可根據需要含有其他成分。該聚合性成分可從單官能單 體、多官能單體、含有乙烯基或（甲基）丙烯醯基之寡聚物、以及含有 (甲基）丙烯醯基之聚合體中選擇1種或2種以上使用。 上述透光性微粒子可例舉無機質之微粒子或樹脂微粒子(塑料球珠）， 從透明性以及方便調節與硬化層之折射率差的觀點考量，較好的是樹脂 微粒子。形成該樹脂微粒子之材料可列舉氯乙烯樹脂、（甲基）丙稀樹月旨 (折射率1.49)、聚苯乙烯樹脂（折射率1.54)、三聚氰胺樹脂（折射率 1.57)、聚乙烯樹脂、聚碳酸酯樹脂、苯丙共聚合樹脂等。此等樹脂中含 有交聯樹脂。苯丙共聚合樹脂中，可藉由改變兩單體之共聚合比例來任 意調節折射率。 20 201001444 至於所使用之其他成分，還有光分解型或熱分解型聚合起始劑、不含 乙烯基或（甲基）丙烯醯基之寡聚物（以下稱非聚合性寡聚物）、不含乙 烯基或（甲基）丙烯醯基之聚合體（以下稱非聚合性聚合體）、金屬氧化 物、界面活性劑、稀釋溶劑、光增感劑、穩定劑、紫外線吸收劑、紅外 線吸收劑、防止氧化劑等。使用此等成分形成之防眩層較好的是厚度在 0.1〜50/zm範圍內。 形成有具有自我修複性之軟質樹脂層時，當輸入筆在該軟質樹脂層表 面滑動時，可提高筆輸入之書寫手感。此種軟質樹脂層較好的是使用形 成上述軟質樹脂層之成分，厚度在10〜1〇〇/m範圍內。 設置防眩層，並在該防眩層上形成具有折射率低於防眩層折射率之低 折射率層的減反射防眩層時，表面可具有防眩性，可抑制反射，進而有 效抑制防眩層表面上之反光現象。該低折射率層之折射率比防眩層低， 其表面具有防止反射功能。至於形成低折射率層之材料，可例舉紫外線 硬化性丙烯樹脂等画旨系材料、在棚旨中分散膠體氧化矽等無機微粒子 所形成之混合材料、四乙氧基矽烷或鈦酸四乙酯等使用金屬烷醇鹽等之 溶膠-凝膠系材料等。尤其，眾所周知具有氟原子之化合物具有低折射 率，具體可列舉側鏈中具有全氟烷基之聚合性單體’例如可例舉聚合（甲 基）丙烯酸含氟烷基酯而形成之聚合體、聚合氟烷基苯乙烯而形成的聚 合體等。進而’有效降低折射率之方法亦可列舉將含有氟原子之化合物 作爲黏合劑，並添加中空氧化矽微粒子之方法。 低折射率層之厚度無特別限制，可視光線波長之1/4 (約loonm)時， 其干擾效果可減少表面反射，提高透過率，較爲理想。此外，從獲得較 佳之防止反射效果的觀點考量，低折射率層之折射率係越低越好，但過 低時，反射光會著色，非所期望。因此，考慮到防止反射和防止著色， 21 201001444 該低折射率層之折射率較好的是在ΠΟ〜1.50 ’尤其著重於防止反射效果 時，1.30〜1.45更佳。 [實施方式之作用及功效] •本實施方式所述之透明導電性膜片11中，透明基材12與有機導 電層14之間設有馬氏硬度爲0.7〜70N/mm2之軟質樹脂層13。因此，即 使觸摸面板輸入筆16在透明基材12上重複滑動，亦可藉由該軟質樹脂 層13分散力道，因此有機導電層14上不易發生裂縫或剝離之現象。並 且，軟質樹脂層13具有自我修複性，因此可使凹進復原，抑制外觀不良 之產生。再者，導電層係具有柔軟性之有機導電層14，因此可抑制裂縫 之產生’提高耐久性。因此，可抑制例如觸摸面板1〇上由於筆輸入所造 成之有機導電層14的損傷、裂縫之產生，可以提高書寫耐久性。 •軟質樹脂層13係於透明基材12上塗佈硬化性組成物，並使其硬 化而形成，上述硬化性/組成物包含10〜90重量％，更好的是包含30〜80 重量％之上述化學式（1 )、（2)或（3)所示之重複單位。該等重複單位 可提高軟質樹脂層13之柔軟倾自我修複性，進一步抑制有機導電層 14之損傷、裂縫之產生以及外觀不良。 • _h述硬化性組成物若##有氨酯改質（甲基）丙烯酸酯之活性能 量線硬化性組成物’便可提高軟質樹月旨層13之彈性，增強其恢復性，並 可使硬化迅速完成，因此可提高透明導電性膜片11之連續生産性。 •形成有機導電層14之有機導電性高分子爲聚噻吩、聚·咯、聚苯 胺或聚喹喔啉，藉此可進一步提高透明導電性膜片11之光學特性及導電 性。 .觸摸面板1〇係於其前面配置上述一對透明導電性膜片11構成， 上述一對透明導電性膜片11之有機導電層14方向相對。因此，即使由 22 201001444 於觸摸面板輸入筆16在觸摸面板10之透明基材12表面重複滑動’亦可 抑制有機導電層14之損傷、裂縫產生，可提供書寫耐久性良好之觸摸面 板10。 [實施例] 以下，舉製造例、實施例以及比較例進一步具體說明上述實施方式’ 但本發明並非由此等實施例之範圍限定。各例中之馬氏硬度、霧度値、 全光線透過率、表面阻抗率以及書寫耐久性係採用下述方法測量。此外， 各例中之部代表的是重量部。 (1) 馬氏硬度 於作爲透明基材12之PET膜片上，以乾燥膜厚30/zm之厚度塗佈用 於形成軟質樹脂層之硬化性組成物並使其硬化形成軟質樹脂層13，利用 超顯微硬度測試裝置[株式會社Fischer Instruments生產，Fischer Scope H-100]測量所形成之軟質樹脂層13的馬氏硬度（N/mm2)。測量條件爲溫 度20°C，相對濕度50%，最大負重2mN，第一懦變：5秒，第二蠕變：5 秒。 (2) 霧度値， 使用日本電飾工業株式會社生產之NDH-2000，測量透明導電性膜片 11光學特[生之霧度値（％)。 (3) 全光線透過率 使用日本電飾工業株式會社生產之NDH-2000，測量透明導電性膜片 11光學特性之全光線透過率（％)。 ⑷表面阻抗率 使用三菱化學株式會社生產之Loresta GP (4探針探頭），測量透明導 電性膜片11之表面阻抗率（Ω/Ε])。 23 201001444 (5)書寫耐久性 如圖1所示，使用2片透明導電性膜片11，用厚度爲30//m之雙面膠 帶15將其粘合，使有機導電層14方向相對，然後配置於玻璃之上。接 著，使用聚縮醛樹脂製之觸摸面板輸入筆16 (尖端部：φ 0.8mm )，以負 重2.5N (250gf)、速度lOOmm/sec、10萬次往返之條件，在透明導電性膜 片11之有機導電層形成面的相反面，在向內側方向與雙面膠15相距2mm 之位置進行滑動（圖1中從實線至兩點虛線之位置）。針對如此進行之透 明導電性膜片11之書寫耐久性測試結果，如下進行了三等級之評價。. ◎:利用光學顯微鏡觀察（倍率：280倍），有機導電層14完全未見剝 離、裂縫及損傷。 〇：目視觀察未見，但利用光學顯微鏡觀察（倍率：280倍）發現有 機導電層14之剝離、裂縫或損傷。 △:目視可見有機導電層14之剝離、裂縫或損傷，其面積在觸摸面板 輸入筆16滑動部位（面積）之1/5以下。 X :目視可見有機導電層14之剝離、裂縫或損傷，其面積在觸摸面板 輸入筆16滑動部位（面積）之1/5以上。 [製造例1-1，用於形成軟質樹脂層之硬化性塗液CF-1)之調製] 將由二異氰酸己二酯[三井武田化學株式會社生產，商品名稱： ΤΑΚΕΝΑΤΕ 700]2·1部、及聚己內酯改質羥基乙酯[Daicel化学工業株式會 社生產，商品名稱：PLACCEL FA10L，聚己內酯單位之重複數量=10]97.9 部構成之丙烯酸胺酯90部、鄰苯二甲酸單甲基丙烯酸經乙酯[東亞合成 株式會社生產’商品名稱：Μ-5400]6·8部、1-羥基環己基苯基丙酮3部、 表面調節劑[畢克化學生產，商品名稱“ΒΥΚ-381” ]0.2部以及甲基乙基 酮100部混合’調製用於形成軟質樹脂層之硬化性塗液（F-1)。 24 201001444 此用於形成軟質樹脂層之硬化性塗液中含有上述化學式（2)所示之重 複單位（其中1=5，m=l〇) 80重量％。 [製造例1-2，用於形成軟質樹脂層之硬化性塗液（F_2)之調製] 將由二異氰酸己二酯之異氰尿酸酯改質丙烯酸胺酯[三井武田化學株 式會社生產，商品名稱：TAKENATE D-170]20.5部、及聚己內酯改質羥 基乙酯[Daicel化学工業株式會社生產，商品名稱：PLACCEL FA5，聚己 內酯單位之重複數量=5]79.5部構成之丙烯酸胺酯90部、丙烯酸-2-羥丙 酯[大阪有機化學工業株式會社生產，商品名稱：HPA]6.8部、1-經基環 f 己基苯基丙酮3部、表面調節劑(畢克化學生產，商品名稱“ΒΥΚ·38Γ ) 0.2部以及甲基乙基酮1〇〇部混合，調製用於形成軟質棚旨層之硬化性塗 液（F-2)〇 此用於形成軟質樹脂層之硬化性塗液中含有上述化學式（2)所示之重 複單位（其中1=5，m=5) 57雷量％。 [製造例1-3，用於形成軟質樹脂層之硬化性塗液（F-3)之調製] 將由二異氰酸己二酯之異氰尿酸酯改質型[三井武田化學株式會社生 產，商品名稱：TAKENATE 170N]34部、及聚己內酯改質經基乙酯[Daicel i 化学工業株式會社生產，商品名稱：PLACCEL FA2，聚己內酯單位之重 複數量=2]66.〇部構成之丙烯酸胺酯90部、鄰苯二甲酸單甲基丙烯酸羥 乙酯[東亞合成株式會社生產，商品名稱：M-5400]6.8部、1-羥基環己基 苯基丙酮3部、表面調節劑[畢克化學生產，商品名稱“ΒΥΚ-38Γ ) 0.2 部以及甲基乙基酮1〇〇部混合，調製用於形成軟質樹脂層之硬化性塗液 (F-3)。 此用於形成軟質樹脂層之硬化性塗液中含有上述化學式（2)所示之重 複單位（其中1=5，m=2) 40重量％。 25 201001444 [製造例1-4，用於形成軟質樹脂層之硬化性塗液（F-4)之調製] 將由二異氰酸己二酯之異氰尿酸酯改質型[三井武田化學株式會社生 產，商品名稱：ΤΑΚΕΝΑΤΕ 170N]34部、及聚己內酯改質羥基乙酯[Daicel 化学工業株式會社生產，商品名稱：PLACCELFA2，聚己內酯單位之重 複數量=2]66.0部構成之丙烯酸胺酯85部、鄰苯二甲酸單甲基丙烯酸羥 乙酯凍亞合成株式會社生產，商品名稱：M-5400]6.8部、雙季戊四醇六 丙烯酸酯旧本化藥株式會社生產、KAYARAD、商品名稱:DPHA]5.0部、 1-羥基環己基苯基丙酮3部、表面調節劑[畢克化學生產，商品名稱 : “ΒΥΚ-38Γ ) 0.2部以及甲基乙基酮100部混合，調製用於形成軟質樹 脂層之硬化性塗液（F-4)。 此用於形成軟質樹脂層之硬化性塗液中含有上述化學式（2)所示之重 複單位（其中1=5，m=2) 37重量％。 [製造例2-1，有機導電性組成物（EC-1)之調製] 以聚(3,4-二氧乙基塞吩)與聚磺酸作爲主要成分，在含有矽烷耦合劑而 形成之水分散溶媒導電性塗料旧本AGFA Gevaert株式會社生產，商品名 稱：Orgacon S-300 ]100部中分別添加乙二醇[和光純藥株式會社生產]5 部、乙二醇二縮水甘油醚(Nagasechemtex公司生產，EX-810)0.3部，以及 3-甘油基丙基三乙基矽烷氧[信越化學工業株式會社生產]0.3部作爲上述 含有烷氧基之化合物，混合攪拌一小時，直至各成分達到均勻，調製出 有機導電性組成物（EC-l)〇 [製造例2-2，有機導電性組成物（EC-2)之調製] 在含有聚(3,4-二氧乙基塞吩)0.5部與聚磺酸0.8部而形成之水分散體 (BaytronP : Bayer AG公司生產）100部中分別添加N-甲基吡咯烷酮[和 光純藥株式會社生產]5部、乙二醇二縮水甘油醚(Nagasechemtex公司生 26 201001444 產，EX-810)0.3部’以及3-甘油基丙基三乙基矽烷氧[信越化學工業株式 會社生產]0.3部作爲上述含有烷氧基之化合物，混合攪拌一小時，直至 各成分達到均勻，調製出有機導電性組成物（EC-2)。 [製造例2-3，有機導電性組成物（EC-3)之調製] 在含有吡咯0.4部、聚磺酸1_5部而形成之水分散體100部中添加過硫 酸銨1部、硫酸鐡0.5部’調製出摻雜聚磺酸之聚卩必咯液。在獲得之摻 雜聚磺酸之聚秘咯液中添加咪唑2部，混合攪拌1小時，直至各成分達 到均勻，調製出有機導電性組成物（EC-3)。 [製造例3，硬化層用塗液（HC)之調製] 將二異戊四醇六丙烯酸酯70部、1,6-双(3-丙烯醯氧基-2-羥基丙氧基) 己烷30部、光聚合起始劑[Ciba-Geigy株式會社生產之IRUGACURE184]4 部以及異丙醇100部混合，調製出硬化層用塗液（HC) 〇 [製造例4，高折射率層用塗液（H)之調製] 將平均粒徑爲0.07"m之ITO微粒子85部、季戊四醇三丙烯酸酯15 部、光聚合起始劑旧本化藥株式會社生產之KAYACURE BMS]5部及丁 醇900部混合，調製出高折射率層用塗液⑻。 [製造例5-1，低折射率用塗液（L-1)] 將 1，1〇-二丙烯醯氧基-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-十六氟癸 70 部、雙季 戊四醇六丙烯酸酯10部、矽膠微粒子分散液旧產化學株式會社生產之 XBA-ST]60部以及光聚合起始劑旧本化藥株式會社生產之KAYACURE BMS]5部混合，調製出低折射率用塗液（L-1) ° [製造例6-1，防眩層用塗液（AG-1)] 將丙烯酸胺酯[大日本油墨化學工業株式會社生產’ GRANDIC PC6-6150F，含光聚合起始劑]50部及甲基異丁基酮（MIBK) 83.4部混合’ 27 201001444 調製黏合劑，在該黏合劑中混合交聯丙烯樹脂之微粒子[綜硏化學株式會 社生產，MX-500，粒徑一致之單分散微粒子，平均粒徑5/zm]17部作爲 透光性微粒子，調製出防眩層用塗液（AG-1)。 [製造例6-2 ,防眩層用塗液（AG-2)] 將6官能丙烯酸胺酯[日本合成化學工業株式會社生產，紫光 UV-7600B]80部、聚甲基丙烯酸甲酯（PMMA :分子量40xl03) 10部、交 聯聚苯乙烯珠[綜硏化學株式會社生產，SX-130H，平均粒徑1.3//m]10 部、1-羥基環己基苯基酮2部以及甲基異丁基酮150部混合，調製出防 眩層用塗液（AG-2)。 (實施例1) 使用厚度爲188 之聚對苯二甲酸乙二醇酯（PET)膜片[東洋紡株 式會社生產之A4300]作爲透明基材12。於PET膜片一側之面上，利用塗 佈棒使用於形成軟質樹脂層之硬化性塗液（F-1)成膜，並使乾讎厚大 約爲30 ，然後以400mJ/cm2之能量照射紫外線使其硬化，形成軟質樹 脂層13。接著’於講欠質樹脂層13上，利用塗佈棒使導電性組成物EC-1 形成被膜，並使乾燥膜厚大約爲150nm，然後於室溫下放置1分鐘，於 150°C之溫度下乾燥1分鐘，層疊有機導電層14，製作出透明導電性膜片 1卜 (實施例2) 使用厚度爲188#m之聚對苯二甲酸乙二醇酯（pet)膜片[東洋紡株 式會社生產之A4300]作爲透明基材12。於該透明基材12之一側的面上， 利用塗佈棒塗佈硬化層用塗液HC，並使乾燥膜厚爲5，然後在氮氣 環境下以400mJ/cm2之能量照射紫外線使其硬化，形成硬化層。接著，於 PET膜片另一側之面上，利用塗佈棒使用於形成軟胃_^旨胃^ 28 201001444 液F-2成膜，並使乾燥膜厚大約爲3〇//m，然後以4QQmJ/em2之能量照射 紫外線使其硬化，形成軟質樹脂層13。進而，在該軟質樹脂層丨3上， 利用塗佈棒使導電性組成物ECM成膜，並使乾燥膜厚大約爲15〇nm，然 後在室溫下放置1分鐘，在BOX：之溫度下乾燥1分鐘，層疊有機導電層 14，製作出透明導電性膜片n 〇 (實施例3) 實施例3係於實施例2中，將用於形成軟質樹脂層之硬化性塗液F-2 以用於形成軟質樹脂層之硬化性塗液F-3取代，除此之外與實施例2實 施相同之處理，製作出透明導電性膜片11 〇 (實施例4) 實施例4係於實施例2中，將用於形成軟質樹脂層之硬化性塗液F-2 以用於形成軟質樹脂層之硬化性塗液F-4取代，除此之外與實施例2實 施相同之處理，製作出透明導電性膜片11 〇 (實施例5) 實施例5係於實施例2中，將導電性組成物EC-1以EC-2取代，除此 之外與實施例2實施相同之處理，製作出透明導電性膜片11。 (實施例6) 使用厚度爲188μιη之聚對苯二甲酸乙二醇酯（PET)膜片[東洋紡株 式會社生產之A4300]作爲透明基材12。於該透明基材12上，利用塗佈 棒塗佈硬化層用塗液HC，並使乾燥膜厚爲5 //m，然後以4〇〇mJ/cm2之能 量照射紫外線使其硬化，形成硬化層。然後’在硬化層上’利用旋轉塗 佈機按順序塗佈高折射率用塗液H以及低折射率用塗液L·1 ’使其乾燥， 並使其光學膜厚分別爲110〜125nm，然後在氮氣環境下，以.400mJ/cm2 之輸出照射紫外線使其硬化，於PET膜片之一側的面上形成減反射層。 29 201001444 接著，於PET膜片另一側之面上，利用塗佈棒使用於形成軟質觀旨層 之硬化性塗液F-2成膜，並使乾燥膜厚大約爲10/zm，然後以400mJ/cm2 之能量照射紫外線使其硬化，形成軟質樹脂層13 〇接著，於該軟質樹脂 層13上，利用塗佈棒使導電性組成物EC-1形成被膜，並使乾燥膜厚大 約爲150nm，然後於室溫下放置1分鐘，於150°C之溫度下乾燥1分鐘， 層疊有機導電層14，製作出透明導電性膜片11。其結果，與實施例2相 比，全光線透過率爲88.9%，反射率爲4.5%，視認性得到改善。 (實施例7) 使用厚度爲188/zm之聚對苯二甲酸乙二醇酯（PET)膜片[東洋紡株 式會社生產之A4300]作爲透明基材12 〇於該透明基材12上，利用塗佈 棒塗佈防眩層用塗液AG-1，使其乾燥膜厚爲ό/zm，並於氮氣環境下以 250m；i/cm2之輸出照射紫外線使其硬化，在PET膜片之另一側的面上形成 具有凹凸部之防眩層。接著，於PET膜片一側之面上，利用塗佈棒使用 於形成軟質樹脂層之硬化性塗液F-1成膜，並使乾燥膜厚大約爲45 " m， 然後以400mJ7cm2之能量照射紫外線使其硬化，形成軟質樹脂層13。接 著，於該軟質樹脂層13上，利用塗佈棒使導電性組成物EC-1形成被膜， 並使乾燥膜厚大約爲150nm，然後於室濫下放置1分鐘，於150°C之溫度 下乾燥1分鐘，層疊有機導電層14，製作出透明導電性膜片11。其結果， 與實施例2相比，反光性及指紋視認性提高，視認性得到改善。 (實施例8) 實施例8係於實施例7中，將防眩層用塗液AG-1以AG-2取代，將導 電性組成物EC-1以EC-3取代，除此之外與實施例7實施相同之處理， 製作出透明導電性膜片11。其結果，與實施例2相比，反光性及指紋視 認性提高，視認性得到改善。 30 201001444 (實施例9) 實施例9係於實施例7中，在防眩層上，使用旋轉塗佈機塗佈低折射 率用塗液L-1，使其乾燥，並使其光學膜厚分別爲li〇〜i25nm，然後在 氮氣環境下，以4〇〇mJ/cm2之輸出照射紫外線使其硬化，除此之外與實施 例7實施相同之處理，製作出透明導電性膜片11。其結果，與實施例2 相比，全光線透過率爲88 9%，反射率爲43%，反光性提高，視認性得 到改善。 (實施例10) 實施例10係於實施例7中，以用於形成軟質樹脂層之硬化性塗液ΪΜ 取代防眩層用塗液AG-1進行塗佈，使乾燥膜厚大約爲30/zm，以 250mJ/cm之輸出照射紫外線使其硬化，除此之外與實施例4實施相同之 胃S 透明導電性膜片11。其結果，與實施例2相比，動摩擦係 數爲0.24 ’書寫手感得以提高。 (比較例1) ittmi 1係於實施例2中，將用於形成軟質樹脂層之塗液F4以硬化 層用塗液HC取代，除此之外與實施例2實施相同之處理，製作出透明 導電性膜片11。 (比較例2) 比較例2不是在軟質樹脂層13上，而是於PET膜片一側之面上，利用 滾筒塗佈機直接層疊導電性組成物EC_1，使乾燥膜厚爲大約MOnm，然 後在室溫下放置1分鐘，在15〇°C溫度下乾燥1分鐘，由此製作出透明導 電性膜片11。 針對以上實施例1〜10以及比較例1及2之透明導電性膜片11，對軟 質樹脂層13之膜厚 '透明導電性膜片11之馬氏硬度、霧度値、全光線 31 201001444 透過率、表面阻抗率以及書寫耐久性進行了測定’測定結果如表丨所示 【表1】 實施例 —~~ 1 2 3 4 5 6 7 8 9~~ 10 1 2 軟質樹脂 層 膜厚_) 30 30 30 30 30 10 45 30 30— 30 30 馬氏硬度 (N/mm2) 1.0 3.8 14.7 65.0 3.8 3.8 3.8 3.8 3.8 3.8 184 85 霧度値(%) 0.1 0.1 0.1 0.1 0.1 0.1 5.8 7.8 4.2 0.1 0.1 0.1 全光線透過率(％) 87.6 87.5 87.7 87.5 87.5 88.9 87.0 87.1 88.9 87.1 87.4 87 5 表面阻抗率(ΩΟ 740 755 730 765 880 750 730 990 740 740 735 745 書寫耐久性 ◎ ◎ 〇 Δ ◎ ◎ ◎ ◎ ◎ ◎ X X 一 如表1所示，實施例1〜10中，軟質樹脂層13之馬氏硬度爲1.0〜65.0. 因此，實施例卜10之透明導電性膜片11具有提高書寫耐久性之作用， 可見使用透明導電性膜片11之觸摸面板10具有良好之書寫耐久性。此 外，如實施例2〜10所示，在PET膜片之與有機導電層14相反的面上， 藉由形成硬化層、減反射層、防眩層、軟質樹脂層等功能層，可使其具 有防止反射功能、防眩彳生功能、書寫手感提高等功能。 另一方面，比較例1及2中，軟質樹脂層13之馬氏硬度在本發明之範 圍之外，因此在書寫耐久性評估中發現有機導電層14剝離，結果表明其 不適於作爲透明導電性膜片11使用。 另，上述實施方式在實施中可作以下變更。 •上述透明基材12、硬化層、低折射率層等中可添加紫外線吸收劑、 紅外線吸收劑、近紅外線吸收劑等。此時，可使其具有紫外線吸收效果、 紅外線吸收效果、近紅外線吸收效果等。 .於形成上述硬化層之組成物中’可添加具有羧基、胺基等之單體， 32 201001444 提高硬化層相對於透明基材12之密著性。 •於上述透明基材12與軟質樹脂層13之間、透明基材12與硬化層 之間等設置接著層，可提高密著性并減少干擾斑。 •上述觸摸面板10可用於例如銀行ATM、自動販賣機、移動資訊 終端、複印機、傳真機、汽車導航儀等設備。 以下說明由上述實施方式所掌握之技術思想。 〇如專利申請範圍3或4所述之透明導電性膜片，其中，上述氨酯 改質（甲基）丙烯酸酯係經過聚己內酯改質或異氰尿酸酯改質者。採用 此種方式構成時，則在專利申請範圍3或4之發明功效的基礎上’可提 高軟質樹脂層之恢復性，提高自我修複性。 〇如專利申請範圍2至4中任一項所述之透明導電性膜片，其中， 上述硬化性組成物含有至少具有羧基與氫氧基其中一者之化合物。此 時，在專利申請範圍2至4中任一項之發明功效的基礎上，可改善透明 基材與軟質樹脂層之間以及軟質樹脂層與有機導電層14之間之密著性。 〇如專利申請範圍2至4中任一項所述之透明導電性膜片，其中， 上述硬化性組成物含有反應性稀釋劑，該反應性稀釋劑包含具有一個不 飽和結合之化合物。此時，在專利申請範圍2至4中任一項之發明功效 的基礎上，可提高軟質樹脂層之強度'韌性等物性。 〇如專利申請範圍2至4中任一項所述之透明導電性膜片，其中， 上述硬化性組成物含有表面調節劑，該表面調節劑包含丙烯系聚合物或 聚矽氧烷系化合物。此時，在專利申請範圍2至4中任一項之發明功效 的基礎上，可改善硬化性組成物之流動性，提高其塗工性。 〇如專利申請範圍1至4中任一項所述之透明導電性膜片，其中， 於上述透明基材之與軟質樹脂層相反側的面上設置硬化層、防眩層以及 33 201001444 具有自我修複性之軟質樹脂層，並於上述硬化層上設置比硬化層折射率 低之低折射率層形成減反射層，或在上述防眩層上設置比防眩層折射率 低之低折射率層形成減反射防眩層。如此構成時，在專利申請範圍1至 4中任一項之發明功效的基礎上，可藉由硬化層，增大表面之強度，防 眩層可使表面具有防眩性，能夠抑制反射，而具有自我修復性之軟質樹 脂層可提高用筆輸入時表面之書寫手感。此外，藉由設有低折射率層之 減反射層，可有效抑制表面之反光現象，藉由設有低折射率層之減反射 防眩層，可使表面具有防眩性，抑制反射，進而抑制防眩層表面上之反 光現象。 【圖式簡單說明】 圖1係模式性顯示具備實施方式中透明導電性膜片之觸摸面板的截面 圖。 【主要元件符號說明】 10…觸摸面板 11···透明導電性膜片 12…透明基材 13…軟質樹脂層 14…有機導電層 34Therefore, in order to alleviate the stress of the stylus, the transparent conductive film sold in the market has a laminated structure of a hardened layer/PET 4 201001444 film adhesive layer/PET layer/sandwich layer/transparent conductive film. When the transparent conductive film is used, the soft adhesive layer can alleviate the stress at the time of pen input, and the writing durability (pen input durability) can be improved, but the film structure is very complicated and the manufacturing method is complicated. The disadvantage of high cost. Therefore, there has been proposed a transparent conductive film which has a laminated hardness of 0 on a cured layer having a more structurally simple hardened resin as a main structural component. 4~0. A transparent conductive film of 8 GPa is formed to form a transparent conductive film (for example, refer to Patent Document 1). The purpose of the transparent conductive film is to improve the sliding durability of the pen when it is used for a touch panel. In addition, a dynamic hardness of 0 is also proposed. The buffer layer of 005 to 2 is provided in a transparent conductive film between the transparent plastic film layer and the transparent conductive film layer (for example, refer to Patent Document 2). The purpose of the transparent conductive film is to improve the use thereof for touch. The input durability of the pen when the panel is used. Further, a transparent electric conductor having a transparent conductive film formed of an organic conductive composition on a transparent substrate has been proposed (for example, refer to Patent Document 3). This transparent conductor has high reliability corresponding to environmental changes, and does not cause impedance deterioration and long life for long-term use. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2002-163932 (page 2, page 3, page 9 and page 10) [Patent Document 2] Japanese Patent Laid-Open No. Hei 11-34206 (page 2, [Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-146259 (pages 2 and 4) [Summary of the Invention] / VIII [Problems to be Solved by the Invention] However, in the patent literature 1 in the transparent conductive film, the hardness of the transparent conductive film is specified as 0. 4~0. 8GPa, although the brittleness of the transparent conductive film is suppressed, the durability against the deterioration of the wear of the pen slip 5 201001444 is improved, but the thickness of the transparent conductive film is extremely thin, for example, 22 to 27 nm (the implementation of Patent Document 1) example). Therefore, it is difficult to alleviate the stress generated by the sliding of the pen in use by the transparent conductive film alone, and damage or cracks may occur on the cured layer and the transparent conductive film, and it is not durable. Further, the transparent conductive film described in Patent Document 2 only specifies the hardness of the buffer layer, but the adjustment of the hardness alone cannot eliminate the recess (depression) caused by the pen input in long-term use, and the existence thereof may be concave. The disadvantages of the deterioration of the writing, the deterioration of the writing, and the deterioration of the appearance. Further, the transparent electric conductor described in Patent Document 3 has the following problem, the transparent conductive film itself is formed of an organic conductive composition, and the durability is poor, and the transparent conductive film is directly formed on the transparent substrate, so that the pen input is generated. Stress, its stress relaxation effect is not sufficient, and peeling occurs in the transparent conductive film during use. Accordingly, it is an object of the present invention to provide a conductive film which can suppress the occurrence of damage or cracks in the organic conductive layer, and which can improve writing durability, for example, and a touch panel having the conductive film. [Means for Solving the Problem] The transparent conductive film according to the first aspect of the present invention is characterized in that a soft resin layer is provided on a transparent substrate, and an organic conductive layer based on a conductive polymer is laminated on the soft resin layer. The soft resin layer has a Martens hardness of 〇_1 to 7〇N/nm2 measured by an ultra-micro hardness tester under an environment of a temperature of 20 ° C and a relative humidity of 50%, and is self-healing. In the transparent conductive film according to the first aspect of the invention, the soft resin layer is formed by applying a curable composition to a transparent substrate and curing the composition, and the curable composition comprises 10 to 90. % by weight of the repeating unit represented by the following chemical formula (1), (2) or (3). 6 201001444 -0—[(CB)厂0]k— · · · (1) where j=2~4, k=2~30. -〇- (C-(CHZ) , -〇) ° ---(2) where 1=3~12, m=l~15. —(CH2) p— . · · (3) where p = 10~24. According to a second aspect of the invention, in the second aspect of the invention, the curable composition contains a urethane-modified (meth) acrylate active energy ray-curable composition. The transparent conductive film according to any one of the first to third aspects of the present invention, wherein the organic conductive layer of the organic conductive layer is formed by a polybenzazole or a polybenzazole. Polyaniline or polyquinoxaline. The touch panel according to the fifth aspect of the present invention is characterized in that the transparent conductive sheet is formed by one of the first to fourth aspects, and the organic conductive layers of the pair of transparent conductive films are opposed to each other. [Effect of the Invention] According to the present invention, the following effects can be exhibited. In the transparent conductive film according to the first aspect of the invention, a Martens hardness of 0 is provided between the transparent substrate and the organic conductive layer. A soft resin layer of 1 to 70 N/mm2. Therefore, even if the input pen or the like is repeatedly slid, the phenomenon of cracking and peeling of the organic conductive layer is less likely to occur by the dispersion of the soft resin layer. Further, since the soft resin layer is self-healing, the recess (depression) caused by the sliding of the input pen is restored, and the occurrence of poor appearance is suppressed. Further, since the conductive layer is a flexible organic conductive layer, the occurrence of cracks can be suppressed and the durability can be improved. Therefore, it is possible to suppress the damage of the organic conductive layer caused by the pen input on the touch panel and the generation of the crack 201001444, for example, and the writing durability can be improved. In the transparent conductive film according to the second aspect of the invention, the soft resin layer is formed by applying a curable composition to a transparent substrate and curing the composition, and the curable composition contains 10 to 9% by weight. The repeating unit represented by the above chemical formula (1), (2) or (3). These repeating units increase the softness and self-healing properties of the soft resin layer. Therefore, in addition to the effects of the first invention, the damage of the organic conductive layer and the occurrence of cracks can be further suppressed, and the appearance can be further suppressed. In the transparent conductive film according to the third aspect of the invention, the curable composition contains an active energy ray-curable composition of a urethane-modified (meth) acrylate. Therefore, in addition to the effects of the second invention, the elasticity of the soft resin layer can be improved, the recovery property can be improved, and rapid hardening can be achieved, and the continuous productivity of the transparent conductive film can be exhibited. In the transparent conductive film according to the fourth aspect of the invention, the organic conductive high molecular polythiophene, polypyrrole, polyaniline or polyquinoxaline having an organic conductive layer is formed. Therefore, in addition to the effects of the invention described in any one of the first to third aspects, the optical characteristics and conductivity of the transparent conductive film can be further improved. In the touch panel according to the fifth aspect of the invention, the pair of transparent conductive films are disposed on the front surface of the touch panel, and the organic conductive layers of the pair of transparent conductive films are opposed to each other. Therefore, even if the surface of the transparent substrate of the touch panel is repeatedly slid during the pen input, damage or cracking of the organic conductive layer can be suppressed, and a touch panel excellent in writing durability can be provided. [Embodiment] Hereinafter, an embodiment considered to be the best mode of the present invention will be specifically described. In the transparent conductive film of the present embodiment, a soft resin layer is provided on a transparent substrate, and an organic conductive layer based on a conductive polymer is laminated on the soft resin layer. The soft resin layer is in an environment of a temperature of 20 ° C and a relative humidity of 5%, and the hardness of the 201001444 is 0. 1~70N/mm2 and self-healing. The pair of transparent conductive films are disposed on the front surface of the touch panel, for example, with their organic conductive layers facing each other, thereby forming a touch panel. In addition, a touch panel refers to a device that performs a computer operation by touching a screen with a finger or a dedicated pen. Specifically, as shown in FIG. 1 , the transparent conductive film 11 constituting the touch panel 10 is provided with a soft resin layer 13 ′ on the transparent substrate 12 and the organic conductive layer 14 is laminated thereon. The 1 series schematically shows a cross-sectional view of the touch panel, 'the thickness of each layer, the interval between the organic conductive layers 14, and the like, all drawn in an exaggerated manner. Further, the touch panel 1 is formed by laminating the periphery of two transparent conductive films 11 by a double-sided tape (pad) 15, and the organic conductive layers 14 of the two transparent conductive films 11 are opposed to each other. Then, using the touch panel input pen I6, the transparent substrate 12 on the front side (the upper side of FIG. 1) of the touch panel 10 is slid from left to right (from the solid line to the two-dotted dotted line in FIG. 1), thereby performing an input operation. . At this time, the transparent conductive film 11 is provided with the soft resin layer 13 between the transparent substrate 12 and the organic conductive layer 14, so that the organic conductive layer can be suppressed from being input by the touch panel input pen 16 on the transparent electrode 12 Damage and crack generation can improve writing durability (tip press durability). On the surface of the transparent substrate 12 opposite to the soft resin layer 13, a hardened layer (not shown), an antiglare layer, and a self-healing soft resin layer are laminated, and the refractive index is lower than that of the hardened layer. The low refractive index layer forms an antireflection layer, or a low refractive index layer having a lower refractive index may be laminated on the antiglare layer to form an antireflection antiglare layer. At this time, by the strength of the hardened layer 'stomach' large surface, the anti-glare layer can make the surface anti-glare, and can suppress reflection, and the self-healing soft resin layer can improve the writing feel of the surface when inputting with a pen. . In addition, by providing an anti-reflection layer with a low refractive index layer, the surface reflection phenomenon can be effectively suppressed. By providing an anti-reflection layer with a low refractive index layer, the surface can be made to have anti-glare property and suppress reflection. Reflective phenomenon on the surface of the glare layer. 9 201001444 Hereinafter, each constituent element of the transparent conductive film 11 will be described in order. [Transparent Substrate 12] The transparent substrate 12 may be a transparent resin film, a transparent plate, a transparent glass plate or the like, and is not particularly limited. Specific examples of the resin material forming the transparent substrate 12 include a poly(meth)acrylic resin, a poly(meth)acrylonitrile-based resin, a polystyrene resin, a polyfluorene-based resin, a polyether sulfone resin, and a polyether. Department of cloison, polymethylpentene resin, cellulose triacetate (TAC) resin, polyethylene terephthalate (PET) resin, polyurethane resin, regenerated cellulose resin, diethyl hydrazine Cellulose resin, cellulose acetate system, polyester resin, acrylonitrile-butadiene-benzenediene terpolymer resin, polycarbonate resin, polyether ketone resin, polyvinyl chloride A resin, a polyvinylidene chloride-based resin, a polyvinyl alcohol-based resin, a polyethylene-based resin, a polypropylene-based resin, a polyamide (nylon)-based resin, a polyamidide-based resin, and a norbornene-based lining. Among them, poly(methyl) propylene resin, polystyrene resin, cellulose triacetate resin, polyethylene terephthalate resin, and the like are preferable from the viewpoints of versatility and use. Polycarbonate resin. When a polarizing layer is provided as a functional layer, a cellulose triacetate resin is usually used. The thickness of the transparent substrate 12 is usually from 10 to 5,000 / zm, preferably from 25 to 1,000 / zm, more preferably from 35 to 500 / / m. When the thickness is less than 10/zm, the workability is deteriorated in the operation of forming the transparent conductive film 11, and the strength of the transparent substrate 12 tends to be lowered. On the other hand, when the thickness is more than 5000/zm, when the transparent conductive film 11 is used for the touch panel 10, it is necessary to increase the force of the pen input, which is not desirable. [Soft Resin Layer 13] Hereinafter, the soft chamber layer 13 will be described. The soft slab layer 13 has a Martens hardness of 0 in an environment of temperature 2 (TC, relative humidity of 50%, using an ultra-micro hardness tester). 1 ~ 70N / mm2, and self-healing. Here, the self-healing property refers to the property that the concave (depression) trace disappears with time and returns to the original shape (recovery) once the concave 201001444 is formed. The thickness of the soft resin layer 13 is preferably from 5 to 100, more preferably from 10 to 80 /zm. When its thickness is lower than. When the thickness is 5/zm, the softness of the soft resin layer 13 is insufficient, and the self-repairability and writing durability are deteriorated. On the other hand, when the thickness exceeds 100 "in, the soft resin layer 13 is too thick, and when it is used for the touch panel 10, it is necessary to increase the force of the pen input, which is not desirable. The soft resin layer 13 is formed by applying a curable composition for forming a soft resin layer to the transparent substrate 12 to be hardened, and when the viscosity of the curable composition is too high, the coating is diluted with a dilution solvent to form a hardenability. The composition (liquid) is then formed by removing the solvent and hardening it. The above-mentioned Martens hardness of the hardened coating film ($under resin layer 13) for forming the curable composition of the soft resin layer is 0. 1~70N/_2 ’ is better. 1~65N/mm2, more preferably 0. 5 ~ 10N/mm2. The Martens hardness is the hardness of the coating film calculated from the test load and the pressed surface area when the Vickers hardness block is pressed into the surface of the diaphragm, and is the index of the surface hardness of the object. When the Martens hardness is less than 0. At 1 N/mm2, the tendency is not too soft and too concave, and the durability is low. On the other hand, when it exceeds 70 N/mm2, it tends to be too hard and it is difficult to be recessed, and the applied force cannot be absorbed. The curable composition for forming the soft resin layer contains an ultraviolet curable or thermosetting unsaturated acryl resin composition, an unsaturated urethane resin composition such as ammonia vinegar modified (meth) acrylate, An unsaturated polyester resin composition, a polyamide resin composition, a thermosetting type lanthanide, a melamine-based, and an epoxy-based resin composition. More specifically, a resin composition containing a polyfunctional polymerizable compound, a resin composition containing a urethane-modified (meth) acrylate, and a polyfunctional polymerization containing a lanthanoid, melamine-based or epoxy-based polymer may, for example, be mentioned. The polyfunctional polymer compound of the above-mentioned compound contains at least two (meth) 11 201001444 acrylonitrile groups such as an ester of (meth)acrylic acid and the like. Among them, from the viewpoint of durability and ease of operation, polyvalent ethanol and (meth)acrylic acid esterified, or ammoniated modified (meth)acrylic acid which can be hardened by ultraviolet rays, electron wires or heating methods A resin composition containing a (meth)acrylonitrile group-containing compound such as an ester as a main component is preferred. Further, from the viewpoints of workability and continuous productivity, it is preferable to use a resin having active energy ray curability such as ultraviolet curability and electron beam curability. The curable composition for forming the soft resin layer usually contains 50% by weight or more of such an active energy ray-curable resin containing a (meth) acrylonitrile group, and preferably contains 60% by weight or more. The above polyvalent ethanol may, for example, be an ethyl alcohol, a polyethylene glycol, a propylene glycol, a polypropylene glycol, a propanediol, a butanediol, a pentanediol, a hexanediol, a neopentyl glycol, or a 2-ethyl group. -1,3-hexanediol, 2,2'-thioethylene glycol, 1,4 cyclohexanedimethanol and other divalent ethanol; three by methyl propylamine, glycerol, pentaerythritol, tripropylene glycol , dipentaerythritol, di-trimethylpropane and other trivalent or higher ethanol. The urethane-modified (meth) acrylate can be obtained by urethanizing an organic isocyanate having a plurality of isocyanate groups in a molecule with a (meth)acrylic acid derivative having a hydroxyl group. As for an organic isocyanate containing a plurality of isocyanate groups in a molecule, it is awkward! J contains diisocyanate or isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, dicyclohexylmethane diisocyanate, etc. Two isocyanate-based organic isocyanates, and organic isocyanates in which the organic isocyanates are modified with isocyanurate, the additives are modified, and the diurea is modified to have three isocyanate groups in one molecule. As the (meth)acrylic acid derivative having a hydroxyl group, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and polycaprolactone (meth)acrylate may be exemplified. Mercapto ester and the like. Among them, a compound having a long-chain moiety such as a modified polymer of (meth)acrylic acid polycaprolactone is preferred because it has high elasticity and self-healing property. 201001444 Further, an oligomer having a plurality of hydroxyl groups such as polycaprolactone diol or polytetramethyl diol, or a tridecyl alcohol can be used as a constituent of the urethane-modified (meth) acrylate. , myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, polyoxyethylene monostearate, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, glyceryl monostearate The long-chain alkyl alcohol has a good recovery property, and a moderate surface smoothness can be achieved. These components may be used singly or in combination of two or more. Further, in order to obtain an excellent concave feeling and appropriate restorability, it is preferred that the above various resins such as polyvalent ethanol or urethane modified (meth) acrylate contain a moderately long-chain portion. As the long-chain moiety, a bond or the like containing a repeating unit represented by the following chemical formula (1), (2) or (3) can be cited. —〇—[(CH2)厂〇]k— . . . (1) where j=2 to 4 and k=2 to 30. -〇-(jj5- (ch2) ° (2) where ’ 1=3~12, m=l~15. —(CH2) P— . . . (3) where p = 10~24. In the case of the chemical formula (1), the repeating unit k is preferably 2 to 30 chains, more preferably 2 to 20 chains. In the repeating unit of the chemical formula (1), the number of carbons j is preferably from 2 to 4. In the case of the chemical formula (2), 111 is preferably from 1 to 15 chains, more preferably from 1 to 10 chains. In the repeating unit of the chemical formula (2), the number of carbon atoms is preferably from 3 to 12, more preferably from 3 to 8. In the case of the chemical formula (3), the carbon number p is preferably from 10 to 24, more preferably from 12 to 20, and preferably, the repeating unit of the long-chain portion contains 10 in the curable composition. ~90 weight 13 201001444 % by volume, more preferably 25 to 85% by weight, particularly preferably 30 to 80% by weight. When the content is less than 10% by weight, the elasticity of the soft resin layer 13 is increased, and it is difficult to provide self-healing property. On the other hand, when it is more than 90% by weight, the soft resin layer 13 tends to have insufficient strength. The durability of the transparent conductive film 11 is lowered, which is not desirable. As described above, when the curable composition contains the active energy ray-curable composition of the urethane-modified (meth) acrylate, the elasticity of the soft resin layer 13 can be improved, the recovery property can be enhanced, and the hardening can be made rapid. This is completed, so that the continuous productivity of the transparent conductive film 11 can be improved. In this case, a photopolymerization initiator is added to the curable composition according to a conventional method, and hardening of the curable composition is carried out by irradiating the active energy ray. Then, if the urethane-modified (meth) acrylate is modified by polycaprolactone or modified by isocyanurate, the recovery property of the soft resin layer 13 can be improved, and self-healing property can be enhanced. (Adhesion improving component) Further, in order to improve the adhesion between the transparent substrate 12 and the soft resin layer 13 and between the soft resin layer 13 and the organic conductive layer 14, it is preferred that the curable composition contains 1 One or two or more compounds having at least one of a carboxyl group and a hydroxyl group. The compound having at least one of a mercapto group and a hydroxyl group is not limited, and specific examples thereof include a compound having a hydroxyl group and a carboxyl group such as hydroxysuccinic acid, salicylic acid, chylolactic acid, and 2-hydroxybutyric acid. Or a compound having both an unsaturated bond and a carboxyl group, such as (meth)acrylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, hydroxyethyl methacrylate, and the like Monomer copolymerized copolymer, allyl alcohol, methacrylol, vinyl alcohol, oleyl alcohol, 2-hydroxypropyl acrylate, etc., which have both unsaturated bonding and hydroxyl groups, and copolymerization of these monomers a copolymer or the like. The content of such a compound is preferably in the hardenable composition. 〇1~ 30% by weight, more preferably 0. 1 to 15% by weight. The content of these compounds is less than 0. When the amount is 0.01% by weight, the adhesion of the soft resin layer 13 to the transparent substrate 12 is insufficient, and when it is more than 30% by weight of 14 201001444%, the self-healing property of the soft resin layer 13 is lowered, which is not desirable. (Reactive diluent) Further, as the curable composition, a compound having one unsaturated bond can be used at the same time as a reactive diluent for improving the physical properties such as strength and toughness of the soft resin layer 13. The reactive diluent is not particularly limited as long as it has a monomer which is excellent in compatibility with the above-mentioned components forming the soft resin layer 13. As the reactive diluent, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl acrylate, styrene, methylstyrene, N-ethlylpyrrolidone, and the like may be mentioned. Methyl acrylamide and the like. These monomers may be used singly or in combination of two or more. (Diluted Solvent) To adjust the viscosity of the curable composition, a dilute solvent can be used. The diluent solvent is not particularly limited as long as it is a non-polymerizable substance, and for example, toluene, xylene, ethyl acetate, butyl acetate, methoxyethanol ether, ethoxyethanol ether, ethyl glycol acetate, or the like can be used. Isopropyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether, 3-methoxybutanol, and the like. These diluted solvents may be used singly or in combination of two or more. Its content depends on the composition of the hardenable composition, but is usually the sclerosing composition. 1 to 8 重量% by weight 表面 (surface conditioner) To improve the coating workability of the hardened composition, it is preferred to add a surface conditioner to the curable composition. The surface conditioner is preferably a polyxide system compound or a propylene polymer. The polyoxyalkylene-based compound is preferably a linear or branched polydisubstituted fluorene-based compound, or may be a polyfluorenated alkyl group-containing copolymer. A representative example of the polydisubstituted oxirane is polydimethyl siloxane. Further, the main chain or the side chain may have a reactive group such as a vinyl group or a (meth) acrylonitrile group. Some or all of the methyl group may be replaced by other organic groups (the position at which the methyl group is exchanged may be the end or the chain). 15 201001444 Such another organic group may, for example, be an alkyl group having an alkyl group other than a methyl group, an alkyl group, a polyalkylene oxide chain or a polyester chain, or the like having a repeating unit. Further, these organic groups may have other functional groups such as a hydroxide group, an amine group, an epoxy group, a decyl group, a decyloxy group, and a carboxyl group. The above chain having a repeating unit may, for example, be a polyoxyethylene chain, a polyoxypropylene chain, a polytetrahydrofuran chain, a poly(oxyethylene) chain, or a polyoxyalkylene chain, or a polycaprolactone chain or a polyfluorene chain. A polyester chain such as an acid ethylene ester chain or polyethylene glycol adipate. The ends of these chains may be a hydroxyl group or a carboxyl group, or may be a (meth)propenyl group or a vinyl group, the ends of which may be blocked by an organic group. For example, blocking can be carried out by alkyl etherification, alkyl esterification, or the like. Further, the chain is usually bonded to a ruthenium atom through an alkyl group such as dimethyl or trimethyl, and is not limited thereto. Specifically, among the surface conditioners, as a commercially available product containing a polyether-modified polydimethyl siloxane, "BYK-306", "BYK-330", "BYK-341", and "BYK" are preferred. -344 ”, “BYK-307”, “BYK-333” (produced by BYK Chemicals), “VXL4930” (produced by Vianova Resins), etc. Further, as a commercial product containing a propylene-based polymer, "BYK-356" '"BYK-359", "BYK-361", "BYK-352", "BYK-354", "BYK- are preferred. 355 ”, “BYK-358”, “BYK-380”, “ΒΥΚ-381”, “BYK-390” (produced by BYK Chemical). Further, as the copolymer containing a polyoxyalkylene group, a polyoxyalkylene group-containing graft copolymer formed of a compound containing a polyoxyalkylene group and another polymer or a polyfluorene-containing polymer is preferably used. The polyoxyalkylene group-containing graft copolymer segment A formed of an oxyalkyl group and another polymer forms an AB block formed of a polymer chain segment B formed of another polymer and containing no polyoxyalkylene group. A copolymer, or an AB block copolymer formed of a compound segment A containing a polyoxyalkylene group and a polymer segment B formed of a different polymer and having no polyoxyalkylene group. Commercial products of the above-mentioned copolymer are exemplified by MODIPER FS700, MODIPERFS 710, MODIPERFS 720, and MODIPERFS 730. The content of the surface conditioner in the curable composition is usually 0. 01 to 10% by weight, preferably 0. 01 to 5 wt%. When the content exceeds 10% by weight, the adhesion between the organic conductive layer 14 and the soft resin layer 13 is lowered. On the other hand, if it is below 0. 01% by weight, the soft resin layer 13 could not obtain sufficient surface smoothness. The curable composition is composed of a compound containing a (meth) acrylonitrile group, a compound having at least one of a mercapto group and a hydroxyl group, a reactive diluent, a surface conditioner, a diluent solvent, and other compounds described later. Combined with modulation. When modulating, the instruments used for blending and the mixing steps are performed according to the usual method, and are not particularly limited. The soft resin layer 13 may be a single layer or a plurality of layers. Specific examples of the resin forming the soft resin layer 13 include a UV-curable special modified urethane amide paint "UV self-healing transparent paint" manufactured by NATOCO Co., Ltd., and the like. (Photopolymerization initiator) The photopolymerization initiator is used to irradiate an active energy ray such as an ultraviolet ray or an electron beam onto the above active energy ray-curable resin to start polymerization, and a known compound can be used. The photopolymerization initiator may, for example, be a benzophenone, an acetophenone, an α-amyl decyl ester, a benzyl benzoate benzoate, a monosulfide tetramethyl flammamine or a ketoxime. Specific examples thereof include 1-hydroxycyclohexyl phenyl ketone, 2- mercapto-2-methyl-1-phenylpropan-1-ol, 2-methyl-1-[4-(methylthio) Phenyl]-2-morphinylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propane-1. Benzoin, 2,2-dimethoxy-1,2-diphenylphenan-1-one, benzophenone, [4-(methylphenylthio)phenyl]phenyl ketone, 4 - benzophenone, 4-phenylbenzophenone, 3,3',4,4'-tetrakis(t-butylene) benzophenone, 2-chlorothioxanthone, 2 , 4-diethylthioxanthone, α-pentyl lactate, benzyl m-benzoate, tetramethylthiuram monosulfide, and the like. The content of the photopolymerization initiator is preferably from 1 to 10% by weight, more preferably from 1 to 10 parts by weight, based on the weight of the active energy ray-curable resin. This content is lower than o. In the oi weight portion, the cured product (film) obtained from the curable composition is less likely to be completely cured, and the hardening is insufficient, which is not desirable. On the other hand, when it exceeds 20 parts by weight, the hardening can be sufficiently completed, but there is no more effect, so the amount is too large to be useless, resulting in waste. (Preparation of Soft Resin Layer 13) After the above-mentioned curable composition for forming a soft resin layer is applied onto the transparent substrate 12, it is cured by irradiation with an active energy ray to form a transparent substrate 12. There is a diaphragm of the soft resin layer 13. The method for applying the curable composition for forming the soft resin layer to the transparent substrate 12 includes a roll coating method, a spin coating method, a dip coating method, a brush coating method, a spray coating method, and the like. Wire bar coating method, knife coating method, extrusion coating method, gravure coating method, curtain coating method, reverse coating method, conformation coating method, blade coating method, etc., all Well-known methods can be used. At the time of coating, in order to improve the adhesion, a pretreatment such as a corona discharge treatment may be performed on the surface of the transparent substrate 12 in advance. As the active energy ray source for illuminating the active energy ray, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a nitrogen gas laser, an electron beam accelerator, a radioactive element or the like can be used. As for the amount of irradiation of the active energy ray, the amount of light calculated by the ultraviolet ray wavelength of 365 nm is exemplified, and preferably 50 to 5000 mJ/cm 2 . When the irradiation amount is less than 50 mJ/cm2, the curing of the curable composition for forming the soft resin layer is insufficient, which is not desirable. On the other hand, when it exceeds 5000 mJ/cm2, the active energy ray-curable resin tends to be colored, which is not desirable. [Organic Conductive Layer 14] The organic conductive layer 14 has higher flexibility and elasticity than the conventional inorganic conductive layer, so that the stress caused by the sliding of the stylus can be alleviated during long-term use. The organic conductive polymer for forming the organic conductive layer 14 is not particularly limited as long as it is an organic conductive material having transparency and conductivity. Preferred organic conductive polymers are specifically polythiophene, poly 18 201001444 secret 'polyaniline or polyporphyrin. Among them, polythiophene and polyaniline, which are excellent in conductivity and optical properties, are more preferably polythiophenes. The formation of the organic conductive layer 14 on the soft resin layer 13 can be carried out by a usual method. The thickness of the organic conductive layer 14 is usually 1 〇〇 to 2 〇〇 nm. [Other Layers] Further, as described above, a surface of the transparent substrate 12 opposite to the surface on which the soft resin layer 13 is formed may be provided with a hardened layer on which a low refractive index lower than that of the hardened layer is laminated. The layer forms an anti-reflection layer. Alternatively, an antiglare layer is provided on the hardened layer, and a low refractive index layer having a lower refractive index than the antiglare layer is provided on the antiglare layer to form an antireflection layer. Forming the hardened layer can impart sufficient surface strength to the transparent conductive film 11, and can improve durability. The thickness of the hardened layer is preferably from 1 to 20/m. When the thickness is less than i, the transparent conductive film 11 is difficult to obtain sufficient surface strength. On the other hand, when the thickness exceeds 2 Å, problems such as deterioration of bending resistance of the transparent conductive film 11 are caused. The material for forming the hardened layer is not particularly limited, and examples thereof include a reactant such as a monofunctional (meth) acrylate, a polyfunctional (meth) acrylate, and a tetraethoxy decane. Among them, a polymer cured product containing a composition of an ultraviolet curable polyfunctional (meth) acrylate is particularly preferable from the viewpoint of achieving both productivity and hardness. The composition of the polyfunctional (meth) acrylate is not particularly limited. _D, a known ultraviolet curable polyfunctional (meth) acrylate blender, sold as an ultraviolet curable hardenable layer material, or other components which do not impair the hardenability, and further add other components. After the anti-reflection layer is formed, the surface reflection phenomenon can be effectively suppressed. The low refractive index layer has a lower refractive index than the hardened layer, and has a surface anti-reflection function. The material for forming the low refractive index layer may, for example, be a resin material such as an ultraviolet curable acrylic resin, a mixed material formed of inorganic fine particles such as colloidal oxide sand in the resin, or a tetraethoxy sand or tetrahedron tetraacetate. 19 201001444 A sol-gel material such as a metal alkoxide or the like is used as the ester. In particular, it is known that a compound having a fluorine atom has a low refractive index, and specific examples thereof include a polymerizable monomer having a perfluoroalkyl group in a side chain, for example, a polymer formed by polymerizing a methyl (acrylic acid) fluorine-containing alkyl ester, and a polymerized fluorine. A polymer formed by alkylstyrene or the like. Further, a method for effectively lowering the refractive index includes a method of adding hollow cerium oxide microparticles to a fluorine atom-containing compound as a binder. The thickness of the low refractive index layer is not particularly limited, and when the visible light wavelength is 1/4 (about 10 Å), the interference effect can reduce surface reflection and improve transmittance. Further, from the viewpoint of obtaining a preferable antireflection effect, the refractive index of the low refractive index layer is preferably as low as possible, but when it is too low, the reflected light is colored, which is not desirable. Therefore, in view of preventing reflection and preventing coloration, the refractive index of the low refractive index layer is preferably 1. 30~1. 50, especially when focusing on preventing reflection effects, 1. 30~1. 45 is better. When the antiglare layer is formed, the surface can have anti-glare properties and can suppress reflection. Such an antiglare layer can be formed, for example, by curing a composition for forming an antiglare layer containing an active energy ray-curable resin and translucent fine particles. The constituent component of the active energy ray-curable resin must contain a polymerizable component, and may contain other components as needed. The polymerizable component may be one or two selected from the group consisting of a monofunctional monomer, a polyfunctional monomer, an oligomer containing a vinyl group or a (meth)acryl fluorenyl group, and a polymer containing a (meth) acrylonitrile group. More than one kind. The light-transmitting fine particles may, for example, be inorganic fine particles or resin fine particles (plastic beads), and are preferably resin fine particles from the viewpoints of transparency and ease of adjustment of the difference in refractive index from the hardened layer. Examples of the material for forming the fine resin particles include a vinyl chloride resin and a (meth) acryl tree (refractive index of 1. 49), polystyrene resin (refractive index 1. 54), melamine resin (refractive index 1. 57), a polyethylene resin, a polycarbonate resin, a styrene-acrylic copolymer resin, and the like. These resins contain a crosslinked resin. In the styrene-acrylic copolymer resin, the refractive index can be arbitrarily adjusted by changing the copolymerization ratio of the two monomers. 20 201001444 As for other components used, there are photodegradable or thermally decomposable polymerization initiators, oligomers containing no vinyl or (meth) acrylonitrile groups (hereinafter referred to as non-polymerizable oligomers), a polymer containing no vinyl or (meth)acrylonitrile group (hereinafter referred to as a non-polymerizable polymer), a metal oxide, a surfactant, a diluent solvent, a photosensitizer, a stabilizer, an ultraviolet absorber, and an infrared absorption Agent, anti-oxidant, etc. The antiglare layer formed using these components preferably has a thickness of 0. 1 to 50/zm range. When a self-healing soft resin layer is formed, when the stylus slides on the surface of the soft resin layer, the writing feel of the pen input can be improved. It is preferable to use a component which forms the above-mentioned soft resin layer in such a soft resin layer, and has a thickness in the range of 10 to 1 Å/m. When an anti-glare layer is provided and an anti-reflection layer having a low refractive index layer having a refractive index lower than that of the anti-glare layer is formed on the anti-glare layer, the surface can have anti-glare property, can suppress reflection, and thus effectively suppress Reflective phenomenon on the surface of the anti-glare layer. The low refractive index layer has a lower refractive index than the antiglare layer and has a surface anti-reflection function. The material for forming the low refractive index layer may, for example, be a mixed material such as an ultraviolet curable acryl resin, a mixed material obtained by dispersing inorganic fine particles such as colloidal cerium oxide, or tetraethoxy decane or tetrabasic titanate. As the ester or the like, a sol-gel material such as a metal alkoxide or the like is used. In particular, it is known that a compound having a fluorine atom has a low refractive index, and specifically, a polymerizable monomer having a perfluoroalkyl group in a side chain, for example, a polymer formed by polymerizing a fluorine-containing alkyl (meth)acrylate is exemplified. A polymer formed by polymerizing a fluoroalkylstyrene or the like. Further, a method of effectively lowering the refractive index may be a method of adding a compound containing a fluorine atom as a binder and adding hollow cerium oxide microparticles. The thickness of the low refractive index layer is not particularly limited, and when the visible light wavelength is 1/4 (about loonm), the interference effect can reduce surface reflection and improve transmittance. Further, from the viewpoint of obtaining a better antireflection effect, the refractive index of the low refractive index layer is preferably as low as possible, but when it is too low, the reflected light is colored, which is not desirable. Therefore, considering the prevention of reflection and prevention of coloring, 21 201001444 the refractive index of the low refractive index layer is better at ΠΟ~1. 50 ’ especially focused on preventing reflections, 1. 30~1. 45 is better. [Effects and Effects of Embodiments] In the transparent conductive film sheet 11 of the present embodiment, a Martens hardness of 0 is provided between the transparent substrate 12 and the organic conductive layer 14. A soft resin layer 13 of 7 to 70 N/mm 2 . Therefore, even if the touch panel input pen 16 is repeatedly slid on the transparent substrate 12, the soft resin layer 13 can be dispersed, so that the organic conductive layer 14 is less likely to be cracked or peeled off. Further, since the soft resin layer 13 is self-healing, it is possible to restore the recess and suppress the occurrence of poor appearance. Further, since the conductive layer has the flexible organic conductive layer 14, the occurrence of cracks can be suppressed, and the durability can be improved. Therefore, it is possible to suppress the damage of the organic conductive layer 14 caused by the pen input on the touch panel 1 and the occurrence of cracks, and the writing durability can be improved. The soft resin layer 13 is formed by applying a curable composition to the transparent substrate 12 and curing it, and the curability/composition includes 10 to 90% by weight, more preferably 30 to 80% by weight. The repeating unit shown by the above chemical formula (1), (2) or (3). These repeating units can improve the softness and self-healing property of the soft resin layer 13, and further suppress the damage of the organic conductive layer 14, the generation of cracks, and the appearance defects. • _h describes the hardening composition, if ## has a urethane-modified (meth) acrylate active energy ray-curable composition', it can improve the elasticity of the soft tree layer 13, enhance its recovery, and can The hardening is completed quickly, so that the continuous productivity of the transparent conductive film 11 can be improved. The organic conductive polymer forming the organic conductive layer 14 is polythiophene, polystyrene, polyaniline or polyquinoxaline, whereby the optical properties and conductivity of the transparent conductive film 11 can be further improved. . The touch panel 1A is configured by arranging the pair of transparent conductive films 11 on the front surface thereof, and the organic conductive layers 14 of the pair of transparent conductive films 11 are opposed to each other. Therefore, even if the touch panel input pen 16 is repeatedly slid on the surface of the transparent substrate 12 of the touch panel 10 by 22 201001444, damage or cracking of the organic conductive layer 14 can be suppressed, and the touch panel 10 excellent in writing durability can be provided. [Examples] Hereinafter, the above-described embodiments will be specifically described by way of Production Examples, Examples and Comparative Examples. However, the present invention is not limited by the scope of the examples. The Martens hardness, haze 値, total light transmittance, surface resistivity, and writing durability in each of the examples were measured by the following methods. In addition, the parts in each case represent the weight portion. (1) Martens hardness is applied to a PET film as the transparent substrate 12 by applying a curable composition for forming a soft resin layer to a thickness of 30/zm, and hardening it to form a soft resin layer 13, The Martens hardness (N/mm 2 ) of the formed soft resin layer 13 was measured using an ultra micro hardness tester [manufactured by Fischer Instruments, Inc., Fischer Scope H-100]. The measurement conditions were a temperature of 20 ° C, a relative humidity of 50%, a maximum load of 2 mN, a first enthalpy change: 5 seconds, and a second creep: 5 seconds. (2) Haze 値, using NDH-2000 manufactured by Nippon Denshi Kogyo Co., Ltd., to measure the transparent conductive film 11 optical special [haze haze (%). (3) Total light transmittance The total light transmittance (%) of the optical characteristics of the transparent conductive film 11 was measured using NDH-2000 manufactured by Nippon Denshi Kogyo Co., Ltd. (4) Surface resistivity The surface resistivity (Ω/Ε) of the transparent conductive film 11 was measured using a Loresta GP (4 probe probe) manufactured by Mitsubishi Chemical Corporation. 23 201001444 (5) Writing durability As shown in Fig. 1, two transparent conductive films 11 are used, and they are bonded by a double-sided tape 15 having a thickness of 30/m, so that the organic conductive layers 14 are opposed to each other, and then Disposed on the glass. Next, a touch panel input pen 16 made of polyacetal resin was used (tip portion: φ 0. 8mm), with a weight of 2. The condition of 5N (250 gf), speed of 100 mm/sec, and 100,000 round trips is performed on the opposite side of the surface of the organic conductive layer forming surface of the transparent conductive film 11, and is slid at a position 2 mm apart from the double-sided tape 15 in the inward direction ( In Figure 1, the position from the solid line to the two-dot dotted line). The results of the writing durability test of the transparent conductive film 11 thus performed were evaluated in three levels as follows. . ◎: Observed by an optical microscope (magnification: 280 times), the organic conductive layer 14 was completely free from peeling, cracks, and damage. 〇: No visual observation was observed, but peeling, cracking or damage of the organic conductive layer 14 was observed by observation with an optical microscope (magnification: 280 times). △: Peeling, cracking or damage of the organic conductive layer 14 was visually observed, and the area thereof was 1/5 or less of the sliding portion (area) of the touch panel input pen 16. X: The peeling, cracking or damage of the organic conductive layer 14 was visually observed, and the area thereof was 1/5 or more of the sliding portion (area) of the touch panel input pen 16. [Preparation of the production example 1-1, the curable coating liquid CF-1 for forming a soft resin layer] will be produced from hexane diisocyanate [Mitsui Takeda Chemical Co., Ltd., trade name: ΤΑΚΕΝΑΤΕ 700] 2·1 And polycaprolactone modified hydroxyethyl ester [produced by Daicel Chemical Industry Co., Ltd., trade name: PLACCEL FA10L, repeat number of polycaprolactone units = 10] 97. 90 parts of urethane amide, 9 parts of phthalic acid monomethacrylic acid [East Synthetic Co., Ltd. product name: Μ-5400] 6.8 parts, 1-hydroxycyclohexyl phenyl ketone 3 parts , Surface Conditioner [BI Ke Chemical Production, trade name "ΒΥΚ-381"] 0. Two parts and 100 parts of methyl ethyl ketone were mixed to prepare a curable coating liquid (F-1) for forming a soft resin layer. 24 201001444 This hardening coating liquid for forming a soft resin layer contains 80% by weight of the repeating unit (where 1 = 5, m = 1 〇) shown in the above chemical formula (2). [Manufacturing Example 1-2, Preparation of Curable Coating Liquid (F_2) for Forming Soft Resin Layer] Isocyanurate Modified with Dihexyl Hexyl Dicarboxylate Modified Amino Acid Amine [Mitsui Takeda Chemical Co., Ltd. , product name: TAKENATE D-170] 20. 5, and polycaprolactone modified hydroxyethyl ester [produced by Daicel Chemical Industry Co., Ltd., trade name: PLACCEL FA5, repeat number of polycaprolactone units = 5] 79. Nine parts of acetaminophen and 5-hydroxypropyl acrylate (produced by Osaka Organic Chemical Industry Co., Ltd., trade name: HPA). 8 parts, 1-passyl ring, cyclohexyl phenylacetone, 3 parts, surface conditioner (produced by BYK Chemical, trade name "ΒΥΚ·38Γ" 0. The two parts and the methyl ethyl ketone 1 混合 are mixed to prepare a curable coating liquid (F-2) for forming a soft lining layer, and the sclerosing coating liquid for forming the soft resin layer contains the above chemical formula ( 2) Repeating units shown (where 1 = 5, m = 5) 57% of the amount. [Preparation Example 1-3, Preparation of Curable Coating Liquid (F-3) for Forming Soft Resin Layer] Isocyanurate Modified by Dihexyl Hexaisoate [Mitsui Takeda Chemical Co., Ltd. , trade name: TAKENATE 170N] 34, and polycaprolactone modified trans-ethyl ester [Daicel i Chemical Industry Co., Ltd., trade name: PLACCEL FA2, polycaprolactone unit repeat number = 2] 66. 90 parts of urethane amide and hydroxyethyl methacrylate methacrylate (manufactured by Toagosei Co., Ltd., trade name: M-5400) 6. 8 parts, 1-hydroxycyclohexyl phenylacetone 3, surface conditioner [Manufactured by BYK Chemical, trade name "ΒΥΚ-38Γ" 0. The two parts and the methyl ethyl ketone 1 are mixed to prepare a curable coating liquid (F-3) for forming a soft resin layer. The curable coating liquid for forming the soft resin layer contains 40% by weight of the repeating unit (where 1 = 5, m = 2) represented by the above chemical formula (2). 25 201001444 [Preparation Example 1-4, Preparation of Curable Coating Liquid (F-4) for Forming Soft Resin Layer] Isocyanurate Modified by Dihexyl Diisocyanate [Mitsui Takeda Chemical Co., Ltd. Produced by the club, the product name: ΤΑΚΕΝΑΤΕ 170N] 34, and polycaprolactone modified hydroxyethyl ester [Daicel Chemical Industry Co., Ltd., trade name: PLACCELFA2, repeat number of polycaprolactone units = 2] 66. 85 parts of acetaminophen composed of 0 parts, hydroxyethyl methacrylate hydroxyethyl methacrylate freeze-synthesis company, trade name: M-5400] 6. 8 parts, dipentaerythritol hexaacrylate, manufactured by Kodak Chemical Co., Ltd., KAYARAD, trade name: DPHA] 5. Part 0, 1-hydroxycyclohexylphenylacetone 3, surface conditioner [BI Ke Chemical Production, trade name: "ΒΥΚ-38Γ" 0. The two parts and 100 parts of methyl ethyl ketone were mixed to prepare a curable coating liquid (F-4) for forming a soft resin layer. The curable coating liquid for forming the soft resin layer contained 37% by weight of the repeating unit (where 1 = 5, m = 2) represented by the above chemical formula (2). [Production Example 2-1, Preparation of Organic Conductive Composition (EC-1)] Poly(3,4-dioxyethylphene) and polysulfonic acid were used as main components, and a decane coupling agent was formed. Water-dispersible solvent-conducting paint, manufactured by AGFA Gevaert Co., Ltd., trade name: Orgacon S-300] Addition of ethylene glycol [manufactured by Wako Pure Chemical Co., Ltd.], part 5, ethylene glycol diglycidyl ether (Nagasechemtex) Company production, EX-810) 0. 3 parts, and 3-glyceryl propyl triethyl decyloxy [manufactured by Shin-Etsu Chemical Co., Ltd.] 0. Three parts of the above-mentioned alkoxy group-containing compound were mixed and stirred for one hour until the components were homogeneous, and the organic conductive composition (EC-1) was prepared. [Production Example 2-2, Organic Conductive Composition (EC-) 2) Modulation] Containing poly(3,4-dioxyethyl phene) 0. 5 parts with polysulfonic acid 0. N-methylpyrrolidone [manufactured by Wako Pure Chemical Co., Ltd.] and ethylene glycol diglycidyl ether (Nagasechemtex Co., Ltd. 26 201001444) were added to 100 parts of the water dispersion (BaytronP: Bayer AG). Production, EX-810) 0. 3 parts and 3-glyceryl propyl triethyl decyloxy [manufactured by Shin-Etsu Chemical Industry Co., Ltd.] 0. Three of the above-mentioned alkoxy-containing compounds were mixed and stirred for one hour until the components were homogeneous, and an organic conductive composition (EC-2) was prepared. [Production Example 2-3, Preparation of Organic Conductive Composition (EC-3)] Containing pyrrole 0. Adding 4 parts of ammonium persulfate and bismuth sulfate to the 100 parts of the aqueous dispersion formed by 4 parts and 1 to 5 parts of polysulfonic acid. The 5 parts were prepared by polycondensation of polysulfonic acid. Two parts of imidazole were added to the obtained polysulfonic acid-doped poly-pyrolyte, and the mixture was stirred for 1 hour until the components were homogeneous to prepare an organic conductive composition (EC-3). [Production Example 3, Preparation of Coating Liquid (HC) for Hardened Layer] 70 parts of diisopentyl alcohol hexaacrylate, 1,6-bis(3-propenyloxy-2-hydroxypropoxy)hexane 30 parts, a photopolymerization initiator [IRUGACURE 184 by Ciba-Geigy Co., Ltd.] and 100 parts of isopropyl alcohol were mixed to prepare a coating liquid (HC) for a hardened layer. [Production Example 4, Coating for High Refractive Index Layer Preparation of liquid (H)] The average particle size is 0. 07"m ITO granules 85, pentaerythritol triacrylate 15 parts, photopolymerization initiator, KAYACURE BMS, manufactured by Kodak Chemical Co., Ltd., 5 parts and 900 parts of butanol, and prepared a coating liquid for high refractive index layer (8). [Production Example 5-1, coating liquid for low refractive index (L-1)] 1,1 〇-dipropylene fluorenyl-2,2,3,3,4,4,5,5,6,6 , 7,7,8,8,9,9-hexadecafluoroindole 70, dipentaerythritol hexaacrylate 10, silicone particle dispersion XBA-ST] 60 parts and photopolymerization start Mixing 5 parts of KAYACURE BMS, manufactured by Kodak Chemical Co., Ltd., to prepare a coating liquid for low refractive index (L-1) ° [Production Example 6-1, Coating solution for anti-glare layer (AG-1)] Ammonium acrylate [Production of GRANDIC PC6-6150F, photopolymerization initiator] and 50 parts of methyl isobutyl ketone (MIBK) produced by Dainippon Ink & Chemicals Co., Ltd. 4 parts mixed ' 27 201001444 modulating the binder, and mixing the propylene resin microparticles in the binder [manufactured by Kyoritsu Chemical Co., Ltd., MX-500, monodisperse microparticles of uniform particle size, average particle size 5/zm] 17 As a light-transmitting fine particle, the coating liquid (AG-1) for an anti-glare layer was prepared. [Production Example 6-2, Coating Liquid for Anti-Glare Layer (AG-2)] 80-functional urethane amide ester (produced by Nippon Synthetic Chemical Co., Ltd., Violet UV-7600B), polymethyl methacrylate (PMMA) :Molecular weight 40xl03) 10 parts, cross-linked polystyrene beads [manufactured by Kyoritsu Chemical Co., Ltd., SX-130H, average particle size 1. 3//m] 10 parts, 2 parts of 1-hydroxycyclohexyl phenyl ketone, and 150 parts of methyl isobutyl ketone were mixed, and the coating liquid (AG-2) for anti-glare layers was prepared. (Example 1) A polyethylene terephthalate (PET) film having a thickness of 188 (A4300 manufactured by Toyobo Co., Ltd.) was used as the transparent substrate 12. On the side of the PET film, a coating bar is used to form a film of the curable coating liquid (F-1) for forming a soft resin layer, and the dry thickness is about 30, and then irradiated with an energy of 400 mJ/cm 2 . The ultraviolet rays harden to form the soft resin layer 13. Then, on the under-refining resin layer 13, the conductive composition EC-1 was formed into a film by a coating bar, and the dried film thickness was about 150 nm, and then left at room temperature for 1 minute at a temperature of 150 ° C. After drying for 1 minute, the organic conductive layer 14 was laminated to prepare a transparent conductive film 1 (Example 2) A polyethylene terephthalate (pet) film having a thickness of 188 #m was used [Toyobo Co., Ltd. The produced A4300] is used as the transparent substrate 12. On the surface on one side of the transparent substrate 12, the coating liquid HC for a hardened layer was applied by a coating bar to have a dry film thickness of 5, and then irradiated with ultraviolet rays at a rate of 400 mJ/cm 2 in a nitrogen atmosphere to be hardened. Forming a hardened layer. Next, on the other side of the PET film, a coating rod is used to form a soft stomach, and a dry film thickness of about 3 〇//m is formed. The ultraviolet ray is irradiated with ultraviolet light at 4QQmJ/em2 to form a soft resin layer 13. Further, on the soft resin layer 3, the conductive composition ECM was formed into a film by a coating bar, and the dried film thickness was about 15 〇 nm, and then left at room temperature for 1 minute at a temperature of BOX: After drying for 1 minute, the organic conductive layer 14 was laminated to prepare a transparent conductive film n 〇 (Example 3). Example 3 is the same as Example 2, and the curable coating liquid F-2 for forming a soft resin layer was used. The same procedure as in Example 2 was carried out except that the curable coating liquid F-3 for forming the soft resin layer was replaced, and a transparent conductive film 11 was produced (Example 4). Example 4 is based on Examples. In the second embodiment, the same treatment as in the second embodiment was carried out except that the curable coating liquid F-2 for forming the soft resin layer was replaced with the curable coating liquid F-4 for forming the soft resin layer. Transparent conductive film 11 实施 (Example 5) Example 5 was produced in the same manner as in Example 2 except that the conductive composition EC-1 was replaced with EC-2. The transparent conductive film 11 is formed. (Example 6) A polyethylene terephthalate (PET) film (A4300 manufactured by Toyobo Co., Ltd.) having a thickness of 188 μm was used as the transparent substrate 12. On the transparent substrate 12, the coating liquid HC for a hardened layer is applied by a coating bar to have a dry film thickness of 5 //m, and then irradiated with ultraviolet rays at an energy of 4 〇〇mJ/cm 2 to form a hardening. Floor. Then, the coating liquid H for high refractive index and the coating liquid L·1' for low refractive index are sequentially applied to the 'hardened layer' by a spin coater to have an optical film thickness of 110 to 125 nm, respectively. Then in a nitrogen atmosphere, to The output of 400 mJ/cm2 was irradiated with ultraviolet rays to be hardened, and an antireflection layer was formed on the surface on one side of the PET film. 29 201001444 Next, on the other side of the PET film, a coating bar is used to form a film of the curable coating liquid F-2 which forms a soft layer, and the dried film thickness is about 10/zm, and then The energy of 400 mJ/cm 2 is irradiated with ultraviolet rays to be hardened to form a soft resin layer 13 . Then, on the soft resin layer 13 , the conductive composition EC-1 is formed into a film by a coating bar, and the dried film thickness is about 150 nm. Then, it was allowed to stand at room temperature for 1 minute, and dried at 150 ° C for 1 minute to laminate the organic conductive layer 14 to produce a transparent conductive film 11. As a result, compared with Example 2, the total light transmittance was 88. 9%, the reflectivity is 4. 5%, visibility improved. (Example 7) A polyethylene terephthalate (PET) film having a thickness of 188/zm (A4300 manufactured by Toyobo Co., Ltd.) was used as a transparent substrate 12 on the transparent substrate 12, and coated with The coating bar is coated with the coating liquid AG-1 for the anti-glare layer to have a dry film thickness of ό/zm, and is irradiated with ultraviolet rays at a output of 250 m; i/cm 2 in a nitrogen atmosphere to be hardened, and the other is in the PET film. An anti-glare layer having irregularities is formed on the side surface. Next, on the side of the PET film side, a coating bar is used to form a film of the curable coating liquid F-1 for forming a soft resin layer, and the dry film thickness is about 45 " m, and then the energy is 400 mJ 7 cm 2 . The soft resin layer 13 is formed by irradiation with ultraviolet rays. Next, on the soft resin layer 13, the conductive composition EC-1 was formed into a film by a coating bar, and the dried film thickness was about 150 nm, and then left in the chamber for 1 minute at a temperature of 150 ° C. After drying for 1 minute, the organic conductive layer 14 was laminated to form a transparent conductive film 11. As a result, as compared with Example 2, the light reflectivity and the fingerprint visibility were improved, and the visibility was improved. (Example 8) In Example 8, in Example 7, the coating liquid AG-1 for antiglare layer was replaced by AG-2, and the conductive composition EC-1 was replaced by EC-3, and In the same manner as in the seventh embodiment, the transparent conductive film 11 was produced. As a result, as compared with Example 2, the light reflectivity and the fingerprint visibility were improved, and the visibility was improved. 30 201001444 (Example 9) In Example 7, in Example 7, the coating liquid L-1 for low refractive index was applied onto an antiglare layer by a spin coater, dried, and optically thick. The transparent conductive film 11 was produced in the same manner as in Example 7 except that the ultraviolet rays were irradiated with ultraviolet light at a temperature of 4 〇〇 mJ/cm 2 and hardened in a nitrogen atmosphere. As a result, compared with Example 2, the total light transmittance was 88 9%, the reflectance was 43%, the light reflectivity was improved, and the visibility was improved. (Example 10) Example 10 was applied in Example 7 with a curable coating liquid for forming a soft resin layer instead of the anti-glare layer coating liquid AG-1 to have a dry film thickness of about 30/ The gastric S transparent conductive film 11 which was the same as that of Example 4 except that zm was irradiated with ultraviolet rays at an output of 250 mJ/cm. As a result, compared with Example 2, the dynamic friction coefficient was 0. 24 ‘writing feel is improved. (Comparative Example 1) Ittmi 1 was produced in the same manner as in Example 2 except that the coating liquid F4 for forming the soft resin layer was replaced with the coating liquid HC for the hard layer. Conductive diaphragm 11. (Comparative Example 2) In Comparative Example 2, the conductive composition EC_1 was directly laminated on the surface of the PET film sheet by the roll coater so as not to be on the soft resin layer 13, so that the dried film thickness was about MO nm, and then The mixture was allowed to stand at room temperature for 1 minute and dried at 15 ° C for 1 minute to prepare a transparent conductive film 11. With respect to the transparent conductive film sheets 11 of the above Examples 1 to 10 and Comparative Examples 1 and 2, the film thickness of the soft resin layer 13 was such that the Martens hardness, the haze 値, and the total ray 31 201001444 of the transparent conductive film 11 were transmitted. Rate, surface resistivity, and writing durability were measured. The measurement results are shown in Table 1. [Example 1] Example -~~ 1 2 3 4 5 6 7 8 9~~ 10 1 2 Soft resin layer film thickness _) 30 30 30 30 30 10 45 30 30— 30 30 Martens hardness (N/mm2) 1. 0 3. 8 14. 7 65. 0 3. 8 3. 8 3. 8 3. 8 3. 8 3. 8 184 85 Haze 値 (%) 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 5. 8 7. 8 4. 2 0. 1 0. 1 0. 1 total light transmittance (%) 87. 6 87. 5 87. 7 87. 5 87. 5 88. 9 87. 0 87. 1 88. 9 87. 1 87. 4 87 5 Surface resistivity (ΩΟ 740 755 730 765 880 750 730 990 740 740 735 745 Writing durability ◎ ◎ 〇 Δ ◎ ◎ ◎ ◎ ◎ ◎ XX As shown in Table 1, in Examples 1 to 10, soft resin Layer 13 has a Martens hardness of 1. 0~65. 0. Therefore, the transparent conductive film 11 of the embodiment 10 has an effect of improving writing durability, and it can be seen that the touch panel 10 using the transparent conductive film 11 has good writing durability. Further, as shown in Examples 2 to 10, on the surface of the PET film opposite to the organic conductive layer 14, a functional layer such as a hardened layer, an antireflection layer, an antiglare layer, or a soft resin layer can be formed. It has functions such as anti-reflection function, anti-glare effect, and improved writing feel. On the other hand, in Comparative Examples 1 and 2, the Martens hardness of the soft resin layer 13 was outside the range of the present invention, and therefore the organic conductive layer 14 was found to be peeled off in the evaluation of writing durability, and it was found to be unsuitable as transparent conductivity. The diaphragm 11 is used. Further, the above embodiment can be modified as follows in the implementation. An ultraviolet absorber, an infrared absorber, a near-infrared absorber, or the like may be added to the transparent substrate 12, the cured layer, the low refractive index layer, or the like. In this case, it is possible to have an ultraviolet absorbing effect, an infrared absorbing effect, a near infrared absorbing effect, and the like. . A monomer having a carboxyl group, an amine group or the like may be added to the composition forming the hardened layer, and 32 201001444 enhances the adhesion of the hardened layer to the transparent substrate 12. • An adhesive layer is provided between the transparent substrate 12 and the soft resin layer 13 and between the transparent substrate 12 and the cured layer to improve adhesion and reduce interference spots. • The touch panel 10 described above can be used in devices such as bank ATMs, vending machines, mobile information terminals, copiers, facsimile machines, car navigation systems, and the like. The technical idea grasped by the above embodiment will be described below. The transparent conductive film according to claim 3 or 4, wherein the urethane-modified (meth) acrylate is modified by polycaprolactone or modified by isocyanurate. When constructed in this manner, the recovery of the soft resin layer can be improved and the self-healing property can be improved based on the effects of the invention of Patent Application No. 3 or 4. The transparent conductive film according to any one of claims 2 to 4, wherein the curable composition contains a compound having at least one of a carboxyl group and a hydroxyl group. In this case, the adhesion between the transparent substrate and the soft resin layer and between the soft resin layer and the organic conductive layer 14 can be improved on the basis of the effects of the invention of any one of the patent applications 2 to 4. The transparent conductive film according to any one of claims 2 to 4, wherein the curable composition contains a reactive diluent comprising a compound having one unsaturated bond. At this time, in addition to the effects of the invention of any one of Patent Application Nos. 2 to 4, physical properties such as strength and toughness of the soft resin layer can be improved. The transparent conductive film according to any one of claims 2 to 4, wherein the curable composition contains a surface conditioner containing a propylene polymer or a polyoxyalkylene compound. At this time, on the basis of the effects of the invention of any one of Patent Application Nos. 2 to 4, the fluidity of the curable composition can be improved and the workability can be improved. The transparent conductive film according to any one of claims 1 to 4, wherein a hardened layer, an anti-glare layer, and 33 are provided on a surface of the transparent substrate opposite to the soft resin layer; a repairable soft resin layer, wherein a low refractive index layer having a lower refractive index than the hardened layer is formed on the hardened layer to form an antireflection layer, or a low refractive index layer having a lower refractive index than the antiglare layer is disposed on the antiglare layer An anti-reflection anti-glare layer is formed. In such a configuration, on the basis of the effects of the invention of any one of the patent applications 1 to 4, the strength of the surface can be increased by the hardened layer, and the antiglare layer can make the surface have anti-glare property and can suppress reflection. The self-healing soft resin layer improves the writing feel of the surface when pen input. In addition, by providing an anti-reflection layer with a low refractive index layer, the surface reflection phenomenon can be effectively suppressed, and the anti-glare layer provided with the low refractive index layer can provide an anti-glare property and suppress reflection. Suppresses the reflection on the surface of the anti-glare layer. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically showing a touch panel including a transparent conductive film in an embodiment. [Description of main component symbols] 10...Touch panel 11···Transparent conductive film 12...Transparent substrate 13...Soft resin layer 14...Organic conductive layer 34