550598 五、 發明說明 ( 1 ) [ 發 明所 屬 技 術 領 域】 本 發明 係 關 於 一 種在透明 塑 膠基材上依序積層硬化 物 層 和 透 明導 電 性 薄 膜 之透明導 電 性膜、及其製造方法、 或 透 明 導 電性 薄 片 以 及使用此 等 之觸控面板，特別是關 於 一 種 使 用在 筆 輸 入 用 之觸控面 板 時具有優良之筆滑動耐 久 性 之 透 明導 電 性 膜 及其製造 方 法、或透明導電性薄片 及使 用 此 等之 觸 控 面 板 〇 [ 習 用技 術 ] 在 透明 塑 膠 膜 基 材上積層 —. 透明且阻抗小的薄膜之 透 明 導 電 性膜 係 已 廣 泛地使用 在 利用其導電性之用途， 例 如 ， 液 晶顯 示 器 % 或 電氣照明 (EL)顯示器等之平面顯示 器 y 或 觸 控面板 之 透 明 電極等電 氣 、電子領域之用途上了 〇 近年來 由 於 攜 帶式資訊 終 端機、或附有觸控面板 之 筆 言己 型 個人 電 腦 等 之 普及化， 進 而要求具有筆滑動耐久 性在 向 來之上 的 優 良 觸 控面板。 因 而， 期 望 一 種 當以筆在 觸 控面板上輸入之際，固 定 電 極 側 之透 明 導 電 性 薄膜，與可 動電極（膜電極）側之透 明 導 電 性 薄膜 間 彼 此 接 觸之時， 在 筆荷重之透明導電性薄 膜 上 不 會產 生 裂 縫 Λ 剝離等之 破 壞，且具有優良之筆滑 動 耐 久 性之透 明 導 電 性 膜。 然 而， 向 來 之 透 明導電性I 膜/ 係具有如下之課題。 在特開 平 2 -66809號公報 上 揭示一種透明導電性膜 其 係 在 厚度 爲 1 20 微 米以下之 透 3 - 明塑膠膜基材上，使形 成 550598 五、 發明說明 ( 2 : ) 透 明 導 電 性 薄 膜 並 以黏合劑層 貼合 — 其他之透明基 體 所 形 成 0 但 是 使 用 在下 述 之筆滑動耐 久性 試 驗中所記載之 聚 縮 醛 樹 脂 製 之 筆 以 5 .0 N之荷重進行 20 萬次之直線滑 動 試 後 在 透 明 導 電 性 薄膜上產生 剝離 其對於筆輸入 力 之 耐 久 性不 夠 充 分 〇 因 此之故，由 於該 剝 離部分之白化 以 致 使 用在 附 有 觸 控 面 板之顯示器 上利 用 時，將會有顯 示 品 質 變 差 之 問 題 〇 又 例如 ， 特 開 昭 60-13171 1 號公 報 、特開昭6 1 - 79647 號 公 報 特 開 昭 61 - 1 783809號公報， •特開平2 - 1 94943 號 公 報 特 開 平 2 - 276630號公報 、特丨 炉 8-64034 號 公 報 等 也 曾 提 議 在 透 明 塑 膠膜基材上 ，設 置 使有機矽化合 物 因 加 氣 分 解 所 生 成 之 底 層，進一步 積層 結 晶質之透明導 電 性 薄 膜 之 透 明 導 電 性 膜 〇 然 而 5 此 等 透 明 導 電性膜係非 常地 脆 弱，使用在下 述 之 筆 滑 動 耐久性 試 驗 中 所記載之聚: 縮醛: 樹, 脂製之筆，以 5 · 0N 之 荷 重 進 行 20 萬 次 之直線滑動 試驗 後 ，在透明導電 性 薄 膜 上 產 生 裂 縫 〇 也 就 是 說 > 本 發 明 之目的，乃 有鑑 於 上述之向來的 問 題 點 5 而 提 供 一 種 在 觸 控面板使用 之際 具 有優異的筆滑 動 耐 久 性 j 特別 是 使 用 聚 縮醛樹脂製 之筆 7 以5 . 0N之荷 重 進 行 20 萬 次 之 直 線 滑 動試驗後， 透明 導 電性薄膜也不 產 生 破 壞 之 透 明 導 電 性 膜 及製造方法 -4 - ;或 透 明導電性薄片 及使 550598 五、發明說明（3 ) 用此等之觸控面板。 【發明揭示】 本發明即是有鑑於上述之狀況，而提供一種爲解決上述 課題之一種透明導電性膜及製造方法；或透明導電性薄片 及使用此等之觸控面板；詳如下述。 意即，本發明透明導電性膜中之第1發明係一種透明導 電性膜，其係一種在透明塑膠基材上，依序積層以硬化型 樹脂做爲主要構成成分之硬化物層，和以金屬氧化物爲主 要構成成分之透明導電性膜，其中前述透明導電性膜之透 明導電性薄膜面的均方平均面粗糙度（Rms )，在廣領域係 爲 4奈米〜20奈米，而在窄領域係爲0.35奈米〜2奈米。 此處，該廣領域乃指爲算出Rms而利用原子間力顯微鏡予 以評價之範圍係在10微米xlO微米區域之意；又，該窄 領域係在1微米X 1微米區域之意。 又，本發明透明導電性膜中之第2發明係一種透明導電 性膜，其係一種在透明塑膠基材上，依序積層以硬化型樹 月旨做爲主要構成成分之硬化物層，以及以金屬氧化物爲主 要構成成分之透明導電性薄膜，其特徵在於：在前述透明 導電性薄膜中，係具有5個/微米2以上1 000個/微米2以 下範圍之由粒徑在5奈米以上1 00奈米以下的金屬氧化物 構成的結晶粒子所形成。 更且，在本發明中關於透明導電性膜之製造方法的發明 ，其係一種在透明塑膠基材上，依序積層以硬化型樹脂做 550598 五、省蒼明說明（5 ) ，並賦與耐葯品性。 更且，做爲前述硬化型樹脂之主要構成成分之硬化物層 ，係進一步含有對硬化物樹脂具非相溶性之高分子樹脂； 而且藉由將前述非相溶性高分子樹脂予以分散成粒子狀， 而使得在硬化物層表面上基於微粒子狀的非相溶性樹脂而 形成微細凸起部，並賦與在其上所積層之透明導電性薄膜 也形成同樣的微細凸起部。 由於在本發明中之硬化物層因形成凸起部，而使得在透 明導電層之廣領域中的表面粗糙度增加。又且，使得透明 導電層本身之窄領域中的表面粗糙度增加。因此，將使得 因聚縮醛筆之荷重而使透明導電性薄膜與玻璃接觸時之真 接觸面積減少，進而改善玻璃面與透明導電性薄膜面之滑 動特性。由此結果，將可使得筆滑動耐久性向上提高。 在本文中，該廣領域乃指在10微米X 10微米區域之 意；而該窄領域係指在1微米X 1微米區域之意。具體的 評價方法，係如以下所述。爲了得到良好的筆滑動耐久性 ，則前述透明導電性膜的均方平均面粗糙度（Rms )，在廣 領域必須爲4〜20奈米，較宜是5. 5〜15奈米。當在廣領域 之均方平均面粗糙度（Rm s )係不足4奈米的平滑表面時， 貝[J透明導電性薄膜與玻璃接觸時之接觸面積將會變大，結 果使得滑動耐久性變差。另一方面，在廣領域中之均方平 均面粗糙度（Rms)超過20奈米時，將使在凸起部之應力集 中化，以致凸起部因不耐筆滑動試驗而被部壞’結果’使 550598 五、發明說明（6) 得筆滑動耐久性惡化。 又，在窄領域必須爲0.35〜2奈米，較宜是0.45〜1.5奈 米。當在窄領域之均方平均面粗糙度（Rms)係不足0.35奈 米的平滑表面時，則透明導電性薄膜與玻璃接觸時之接觸 面積將會變大，結果使得滑動耐久性變差。另一方面，在 窄領域中之均方平均面粗糙度（Rms)超過2奈米時，將使 在凸起部之應力集中化，以致凸起部因不耐筆滑動試驗而 被部壞，結果，使得筆滑動耐久性惡化。而在窄領域必須 爲0.35奈米〜2奈米； 另外，本發明之其他的透明導電性膜，其係具有在透明 塑膠基材上，依序積層以硬化型樹脂做爲主要構成成分之 硬化物層，以及以金屬氧化物爲主要構成成分之透明導電 性薄膜之構成，而且係由特定數量之在透明導電性薄膜中 之金屬氧化物構成的結晶粒子所形成，以使透明導電性薄 膜之膜質變硬，於筆滑動試驗時，使透明導電性薄膜難以 劣化。因此結果，而可以使得筆滑動耐久性向上提高。 爲了得到良好的筆滑動耐久性，在透明導電性薄膜中， 乃必須是具有5個/微米2以上1 000個/微米2以下範圍之 由粒徑在5奈米以上1 00奈米以下的金屬氧化物構成的結 晶粒子所形成。前述結晶粒子的個數，其下限較宜是1 0 個/微米2，其上限較宜是800個/微米2。 又，前述硬化物層較宜是含有對硬化物樹脂具非相溶性 之高分子樹脂；而且較宜是前述非相溶性高分子樹脂爲分 550598 五、 發明說明 C 7) 散 成 粒 子 狀 〇 因此，在硬化物 層 表面面基於微粒子 狀的 非 丰巨 溶 樹 脂 而 形 成微細凸起部。 此 結果，於其上所積 層 之 透 明 導 電 性 薄 膜 表面上也賦與膜 厚 度同樣已經薄化之 微 細 突 起 〇 藉 由 該 微 細突起，而使得 因 聚縮醛筆施力之荷 重 而使 透 明 導 電 性 薄 膜與玻璃接觸時 之 真接觸面積減少， 進 而 改 善 玻 璃 面 與 透 明導電性薄膜面 之 滑動特性。由此結 果 y 將 可 使 得 筆 滑 動 耐久性向上提高 〇 當 透 明 導 電 性薄膜中金屬氧 化 物構成的結晶粒子 ， 其 直 徑 不 足 5 奈米時，就將會有使 得 透明導電性薄膜之 膜 質 難 以 變 硬 以 致 筆滑動耐久性不 夠 充分。另一方面， 當 結 晶 企丄 子 之 直 徑 超 過100奈米時， 則 透明導電性薄膜將 變 得 脆 弱 〇 又 5 當 上、r · 刖 述 結晶粒子之個數 不‘ 足5個/微米2之情 況下 就 將 會 有使 得 透明導電性薄膜 之 膜質難以變硬，以 致 筆 滑 動 耐久性 不 夠 充分。更且，當 由 金屬氧化物所成之 結 晶 ik丄 子 個 數 超 過 1 000個/微米2時 ’ 則透明導電性薄膜 將 變 得 脆 弱 〇 在本 發 明 中 所使用的透明塑 膠 膜基材，係將有機 高 分 子 予 以 熔 融 押 出 、或者是以溶液 押 出，並視情況需要 地在 長 軸 方 向 及 /或寬度方向實施拉1 ί申 、冷卻、熱固化等 做 法 〇 可 用 來 當 做 有 機高分子者，舉 例 來說，例如，係有 聚 乙 烯 、 聚 丙 烯 > 聚 對酞酸乙二酯、 聚 :伸乙基-2，6 -萘酸 酯 聚 對 酞 酸 丙 酯 、耐綸6、耐綸 -9 4、 耐綸6 6、耐綸1 2 聚 醯 550598 五、發明說明（8) 亞胺、聚醯胺醯亞胺、聚醚楓、多醚醚酮、聚碳酸酯、多 芳化樹脂、纖維素丙酸酯、聚氯化乙烯、聚氯化亞乙烯、 聚乙烯醇、聚醚醯亞胺、聚伸苯基硫化物、聚伸苯基氧化 物、聚苯乙烯、反式立構聚苯乙烯、正萡烯系聚合物等。 此等有機高分子中，較適當者爲聚對酞酸乙二酯、聚對 敗酸丙二酯、聚伸乙基-2, 6 -萘酸酯、反式立構聚苯乙烯 、正萡烯系聚合物、聚碳酸酯、多芳化樹脂等。又，此等 有機高分子，也可以和少量其他的有機聚合物之單聚物一 起共聚合，與其他的有機高分子摻混也可以。 在本發明中所使用的透明塑膠膜基材之厚度，較宜是在 超過100微米而在300參以下之範圍，以其上限値在260 微米，而下限値在70微米特佳。當透明塑膠膜基材之厚 度在1 0微米以下時，其機械強度不足，特別是對於在觸 控面板上使用時之筆施力，其變變形將會有變大之傾向， 而耐久性也容易變得不充分。另一方面，當厚度超過300 微米時，在使用觸控面板時，爲使膜變形，則必須使筆荷 重變大。因此之故，必然使透明導電性薄膜之荷重也變大 ，以致對透明導電性薄膜之耐久性觀點不佳。 在本發明中所使用的透明塑膠膜基材，在不損及本發明 目的之範圍內，也可以對前述之膜施予電暈放電處理、輝 光放電處理、火焰處理、紫外線照射處理、電子線照射處 理、臭氧處理等之表面活化處理。 又’在本發明中所使用的硬化型樹脂，並沒有特別地限 -10- 550598 五、發明說明（9) 定爲藉由加熱紫外線照射、電子線照射等之施加能量而使 硬化之樹脂’舉例來說，例如，其可以是聚矽氧樹脂、丙 烯酸酯樹脂、甲基丙烯酸酯樹脂、環氧樹脂、蜜胺樹脂、 聚酯樹脂、聚胺基甲酸酯樹脂等。依照生產性之觀點來看 ，較宜是以紫外線硬化型樹脂做爲主成分者。 可做爲此種紫外線硬化型樹脂者，例如，多元醇之丙烯 酸或甲基丙烯酸酯等這樣之多官能性丙烯酸酯樹脂、多元 醇及丙烯酸或甲基丙烯酸之羥基烷基酯等所合成之多官能 性聚胺基甲酸酯丙烯酸酯樹脂等。視情況需要地，此種多 官能性樹脂中之單官能性單聚物，例如，其可以是添加乙 烯丙酮、甲基甲基丙烯酸酯、苯乙烯等使共聚合而成。 又，爲了使透明導電性薄膜和硬化物層間之附著力增加 ’則對硬化物層進行表面處理係爲有效的。具體的方法， 可使用輝光或電暈放電之照射放電處理法以增加羰基、羧 酸基、氫氧基之方法，使用以酸或鹼處理之化學葯品處理 法以使胺基、氫氧基、羰基等之極性基增加之方法等。 紫外線硬化型樹脂通常會添加光聚合起始劑來使用。可 當做光聚合起始劑者，其並沒有特別地限定，可以使用公 知的吸收紫外線而產生自由基之化合物。此種光聚合起始 齊Ιί，舉例來說，例如，可以使用各種苯偶因類、苯酮類、 笮基酚類等。光聚合起始劑之添加量，對100質量份之紫 外線硬化型樹脂通常是1〜5質量份較佳。 再者，在本發明中所使用的硬化物層，關於該主要構成 -11- 550598 五、發明說明（1 o) 成分之紫外線硬化型樹脂，較宜是倂用對硬化型樹脂爲非 相溶之高分子樹脂。少量倂用對基體之硬化型樹脂爲非相 ί谷之樹脂’將引起硬化型樹脂中之相分離而使粒子狀之非 相溶樹脂分散。在硬化物層表面上，由於該等非相溶樹脂 之分散粒子引起所形成之凹凸，而得以在高透明導電性薄 膜面上賦與凹凸，以致可將廣領域中之表面粗糙度控制在 適當的範圍內。因此之故，可改善在筆施力時玻璃與透明 導電性薄膜面間之滑動特性。如此結果，將可提高筆滑動 耐久性。 當硬化型樹脂係爲紫外線硬化型樹脂之情況下，可做爲 多^相溶樹脂者，例如，可以是聚酯樹脂、聚烯烴樹脂、聚 苯乙烯樹脂、聚醯胺樹脂等。 前述聚酯樹脂之重量平均分子量，較宜是5000〜50000 之高分子量。前述之平均分子量的下限値，特佳是爲 8 0 000;而上限値特佳是爲3〇〇〇〇 〇當聚醋樹月旨之重量平均 分子量不足5 000時，則將有使在聚酯樹脂之硬化物層中 適當大小之粒子難以分散之傾向。另一方面，當聚酯樹脂 之重量平均分子量超5 00 00時，則較宜是在調整成塗布液 時不會降低對溶劑之溶解性者。 前述高分子量之聚酯樹脂可以是以二元醇和二元羯酸^ 合所得到的非結晶性之飽和聚酯樹脂，也可以是使溶解在 與上述紫外線硬化型樹脂共同之溶媒中者。 可做爲前述之二元醇者，舉例來說，例如，可以是& = -12- 550598 五、發明說明（11) 醇、丙二醇、1，3 - 丁 二醇、1，4 - 丁 二醇、1，6 -己二醇、二 乙二醇、新戊二醇、1，4 -環己二甲醇、羥化雙酚A等。 可做爲前述之二元羰酸者，舉例來說，例如，可以是異 醜酸、酞酸、己二酸、酞酸酐、四氫酞酸酐、六氫酞酸酐 "等。 更且，在不會對溶媒之溶解性變得不充分之範圍內，也 可以使之與如三羥甲基丙烷、或季戊四醇等之三元以上的 醇類，以及如三苯六甲酸酐、焦三苯六甲酸酐等三元以上 之羰酸一起共聚合。 在本發明中，當做爲硬化物層之主要構成成分的硬化型 樹脂係使用紫外線硬化型樹脂，而做爲對硬化物樹脂具非 相溶性之高分子樹脂係使用高分子量之聚酯樹脂的情況下 ’其配合比例，相對於100質量份之紫外線硬化型樹脂計 ，較宜是具有〇 .丨〜20質量份之聚酯樹脂。前述聚酯樹 月旨配合比之上限更宜是1 0質量份，特別合宜的是5質量 份。又，前述聚酯樹脂配合比之下限更宜是〇 . 2質量份， 特別合宜的是0 . 5質量份。 當前述聚酯樹脂配合比，相對於1 〇〇質量份之紫外線硬 化型樹脂計，不足〇 . 1質量份時，在硬化物層表面上所形 成的凸起會變小，以致凸起有減少的傾向。因此之故，在 廣領域中之均方平均面粗糙度，將會容易地變成不足4.0 奈米’而使得難以發現對筆滑動耐久性具有改良之效果。 另一方面，當前述聚酯樹脂配合比，相對於丨00質量份之 -13- 550598 五、發明說明（12) 紫外線硬化型樹脂計，超出20.0質量份時，在廣領域中 之均方平均面粗糙度，將會容易地變成超出20.0奈米， 而使得硬化物層之強度變差，對容易使耐葯品性惡化。 更且，由於聚酯樹脂之折射率與紫外線硬化型樹脂有差 異，當相對於1 00質量份之紫外線硬化型樹脂計，聚酯樹 月旨爲超出2 0 . 0質量份時，將使得硬化物層之霧値上昇， 以致透明性有惡化之傾向。相反的，積極地利用因該高分 子量聚酯樹脂之分散粒子而使透明變差之現象，將可以提 高霧値而做爲具有防眩功能之防眩膜使用。 前述紫外線硬化型樹脂、光聚合起始劑及高分子之聚酯 樹脂，係分別地使溶解在共同的溶劑中而調製成塗布液。 所使用的溶劑並沒有特別地限定，舉例來說，例如，可以 使用乙二醇、異丙二醇等之醇系溶劑，乙酸乙酯、乙酸丁 酯等之酯系溶劑，二丁醚、乙二醇單乙醚等之醚系溶劑， 甲基異丁酮、環己酮等之酮系溶劑，甲苯、二甲苯、松香 水等之芳香族羥系溶劑等，此等係可以單獨使用，或者混 合使用也可以。 塗布液中之樹脂成分的濃度，可依照塗布方法、考慮黏 度等而適切地選擇。例如，在塗布液中紫外線硬化型樹脂 、光聚合起始劑、及高分子量聚酯樹脂之總量所佔有的比 例，通常爲2 0〜8 0質量％。又，在該塗布液中，視情況 需要地添加其他公知的添加劑，例如，聚矽氧系整平劑等 也可以。 -14- 550598 五、發明說明（13) 在本發明中，所調製的塗布液係可塗布在透明塑膠基材 上。塗布方法並沒有特別地限定，例如，可使用條柱塗布 法、溝槽塗布法、反復塗布法等向來已知的方法。 塗布用之塗布液，係可藉由以下之乾燥步驟中蒸發除去 溶劑。在該步驟中，將使得於塗布液中均一溶解之高分子 量的聚酯之微粒子，予以析出在紫外線硬化型樹脂中。在 使塗膜乾燥之後，藉由紫外線照射塑膠膜，使紫外線硬化 型樹脂交聯、硬化而形成硬化物層。在該硬化步驟中，高 分子量之聚酯樹脂的微粒子，將在硬塗布層中被固定化， 同時在硬化物層之表面上形成凸起。依照該凸起之高度及 個數’將可以控制在廣領域中之均方平均面粗縫度。 又，硬化物層之厚度較宜是在0.1〜15微米之範圍。 硬化物層厚度之下限値較宜是0.5微米，特佳是1微米。 又，硬化物層厚度之上限値較宜是10微米，特佳是8微 米。當硬化物層厚度不足0 · 1微米時，將難以充分地形成 凸起。另一方面，當超出1 5微米時，依照生產性之觀點 來看，其乃不適宜。 做爲在本發明中所用的透明導電性薄膜，雖然並沒有特 SQ地限定爲具有透明及導電性之材料，但舉例來說，宜是 女口氧化銦、氧化錫、氧化鋅、銦-錫複合氧化物、錫-銻複 合氧化物、鉢·銘複合氧化物、麵-鉢複合氧化物、銀及銀 合金、銅及銅合金、金等之單層或2層以上之積層構造物 。在彼等之中’依照環境安定性及反復加工性之觀點來看550598 V. Description of the invention (1) [Technical field of the invention] The present invention relates to a transparent conductive film in which a hardened material layer and a transparent conductive film are sequentially laminated on a transparent plastic substrate, and a method for manufacturing the same, or transparent conductive Sheet, and a touch panel using the same, in particular, a transparent conductive film having excellent pen sliding durability when used in a touch panel for pen input and a manufacturing method thereof, or a transparent conductive sheet and use of the same Etc. Touch panel 〇 [Conventional technology] Laminated on a transparent plastic film substrate—. Transparent and low-impedance thin transparent conductive films have been widely used in applications that use their conductivity, for example, liquid crystal displays% or Flat-panel displays such as electric lighting (EL) displays, or transparent electrodes for touch panels are used in the electrical and electronic fields. In recent years, due to portable information terminals or touch panels, The popularization of personal computers and the like has demanded a superior touch control panel with a pen sliding durability that has always been superior. Therefore, when a pen is used for inputting on a touch panel, a transparent conductive film on the fixed electrode side and a transparent conductive film on the movable electrode (film electrode) side are in contact with each other, and the transparent conductive load on the pen is desired. A transparent conductive film that does not cause cracks Λ or peeling on the flexible film and has excellent pen sliding durability. However, the conventional transparent conductive I film / system has the following problems. Japanese Unexamined Patent Publication No. 2-66809 discloses a transparent conductive film which is formed on a transparent 3-film plastic substrate having a thickness of 1 20 micrometers or less to form 550598. 5. Description of the Invention (2 :) Transparent conductive film Adhesive layer bonding-formed by other transparent substrates 0. However, using a pen made of polyacetal resin described in the following sliding durability test, 200,000 linear slides were performed at a load of 5.0 N. After the test, peeling occurred on the transparent conductive film, and its durability against pen input force was insufficient. Therefore, due to the whitening of the peeled part, the display quality will be displayed when it is used on a display with a touch panel. The problem of deterioration. For another example, Japanese Patent Application Laid-Open No. 60-13171 1 and Japanese Patent Application Laid-Open No. 6 1-79647, Japanese Patent Application No. 61- 1 783809, and Japanese Patent Application Laid-Open No. 2-1 94943 Japanese Patent Application Laid-Open No. 2- Gazette No. 276630, Special furnace No. 8-64034 Newspapers have also suggested that a transparent conductive film be provided on the transparent plastic film substrate with a bottom layer formed by decomposing organic silicon compounds and further laminated with a crystalline transparent conductive film. However, 5 such transparent conductive films It is very fragile and uses the poly described in the sliding durability test of the following pens: acetal: tree, fat pen, 200,000 times of linear sliding test under a load of 5.0N, transparent conductivity Cracks occur in the film. That is, the object of the present invention is to provide excellent pen sliding durability when using a touch panel in view of the above-mentioned conventional problem point 5, especially using a polyacetal resin. Pen 7 made after 200,000 times of linear sliding test with a load of 5.0N, the transparent conductive film does not cause damage to the transparent conductive film and its manufacturing method -4-; or transparent conductive sheet and 550598 Invention description 3) the use of such a touch panel. [Disclosure of the Invention] In view of the above situation, the present invention provides a transparent conductive film and a manufacturing method for solving the above-mentioned problems; or a transparent conductive sheet and a touch panel using the same; details are as follows. That is to say, the first invention of the transparent conductive film of the present invention is a transparent conductive film, which is a hardened material layer in which a hardening resin is used as a main constituent layer on a transparent plastic substrate, and The transparent conductive film whose main constituent is a metal oxide, wherein the mean square average surface roughness (Rms) of the transparent conductive film surface of the transparent conductive film is 4 nm to 20 nm in a wide area, and In the narrow range, it ranges from 0.35nm to 2nm. Here, the wide field means that the range evaluated by an interatomic force microscope in order to calculate Rms is in the range of 10 micrometers by 10 micrometers; and the narrow field is in the range of 1 micrometer by 1 micrometer. In addition, the second invention of the transparent conductive film of the present invention is a transparent conductive film, which is a hardened layer on a transparent plastic substrate in which a hardened tree moon is the main component, and The transparent conductive thin film using metal oxide as a main component is characterized in that the transparent conductive thin film has a particle size of 5 nanometers in a range of 5 particles / micron 2 or more and 1 000 particles / micron 2 or less. It is formed by crystal particles composed of a metal oxide of 100 nm or less. In addition, in the present invention, the invention of a method for manufacturing a transparent conductive film is a method in which a hardened resin is laminated on a transparent plastic substrate in order to make 550598. 5. Cangming province (5), and Chemical resistance. Furthermore, the hardened material layer, which is the main constituent of the hardened resin, further contains a polymer resin that is incompatible with the hardened resin; and the non-compatible polymer resin is dispersed into particles. As a result, fine protrusions are formed on the surface of the hardened layer based on the particulate incompatible resin, and the same transparent protrusions are formed on the transparent conductive film laminated thereon. Since the hardened material layer in the present invention is formed with raised portions, the surface roughness in a wide area of the transparent conductive layer is increased. Moreover, the surface roughness in a narrow area of the transparent conductive layer itself is increased. Therefore, due to the load of the polyacetal pen, the true contact area when the transparent conductive film is in contact with the glass is reduced, and the sliding characteristics of the glass surface and the transparent conductive film surface are improved. As a result, the pen sliding durability can be improved upward. In this context, the wide field refers to a region of 10 micrometers by 10 microns; and the narrow field refers to a region of 1 micrometer by 1 micrometer. The specific evaluation method is as follows. In order to obtain good pen sliding durability, the mean square average surface roughness (Rms) of the aforementioned transparent conductive film must be 4 to 20 nm in a wide area, and more preferably 5. 5 to 15 nm. When the average surface roughness (Rm s) in a wide area is less than 4 nanometers on a smooth surface, the contact area between the transparent conductive film and glass will increase, resulting in sliding durability. difference. On the other hand, when the mean square roughness (Rms) in a wide area exceeds 20 nanometers, the stress on the convex portion will be concentrated, so that the convex portion is damaged by the pen sliding test. Result 'makes 550598 5. Invention description (6) The pen sliding durability is deteriorated. In a narrow area, the thickness must be 0.35 to 2 nm, preferably 0.45 to 1.5 nm. When the mean square average surface roughness (Rms) in a narrow area is less than 0.35 nm, the contact area between the transparent conductive film and the glass will increase, resulting in poor sliding durability. On the other hand, when the mean square average surface roughness (Rms) in a narrow area exceeds 2 nm, the stress on the convex portion will be concentrated, so that the convex portion is damaged by the pen sliding resistance test. As a result, the pen sliding durability is deteriorated. In a narrow area, it must be 0.35 nm to 2 nm. In addition, the other transparent conductive film of the present invention has a hardening resin as a main component in order to be hardened on a transparent plastic substrate. The material layer, and the transparent conductive film mainly composed of metal oxides, and is formed by a specific number of crystalline particles of metal oxides in the transparent conductive film to make the transparent conductive film The film became hard, and it was difficult to make the transparent conductive film deteriorate during the pen sliding test. As a result, the pen sliding durability can be improved upward. In order to obtain good pen sliding durability, the transparent conductive film must be a metal having a particle size of 5 nanometers or more and 100 nanometers or less in a range of 5 particles / micron 2 or more and 1,000 particles / micron 2 or less. Formed by crystalline particles made of oxide. The lower limit of the number of the crystal particles is preferably 10 particles / micron 2, and the upper limit thereof is more preferably 800 particles / micron 2. The hardened material layer preferably contains a polymer resin that is non-compatible with the hardened resin. The non-compatible polymer resin is more preferably 550598. 5. Description of the invention C 7) The particles are dispersed into particles. The fine convex portion is formed on the surface of the hardened material layer based on a fine particle-like non-rich solvent. As a result, the surface of the transparent conductive film laminated thereon is also provided with fine protrusions that have also been thinned in film thickness. The fine protrusions make transparent conductive due to the load of the polyacetal pen. The true contact area of the film when it contacts the glass is reduced, thereby improving the sliding characteristics between the glass surface and the transparent conductive film surface. As a result, y will increase the sliding durability of the pen. When the crystal particles made of metal oxide in the transparent conductive film have a diameter of less than 5 nm, it will make it difficult to harden the film quality of the transparent conductive film. As a result, the pen sliding durability is insufficient. On the other hand, when the diameter of the crystal grains exceeds 100 nanometers, the transparent conductive film becomes fragile. At the same time, the number of crystal particles is not more than 5 per micron. In some cases, it will be difficult to harden the film quality of the transparent conductive film, so that the pen sliding durability is insufficient. In addition, when the number of crystalline ions made of metal oxide exceeds 1 000 pieces / micron 2 ', the transparent conductive film becomes weak. The transparent plastic film substrate used in the present invention is The organic polymer is extruded or melted, or it is extruded as a solution, and if necessary, it can be pulled, cooled, and cured in the long axis direction and / or width direction. It can be used as an organic polymer, for example For example, there are polyethylene, polypropylene > polyethylene terephthalate, poly: ethylene-2,6-naphthalate, polypropyl terephthalate, nylon 6, nylon-9 4. Nylon 6 6. Nylon 1 2 Polyfluorene 550598 5. Description of the invention (8) Imine, polyamidamine, imine, polyether maple, polyetheretherketone, polycarbonate, polyaromatic resin, fiber Plain propionate, polyvinyl chloride, polyvinyl chloride, polyvinyl alcohol, polyetherimide, polyphenylene sulfide, polyphenylene oxide, polystyrene, trans stereopolybenzene Ethylene and n-pinene polymerization Wait. Of these organic polymers, more suitable are polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthoate, trans stereopolystyrene, n-fluorene Ethylene polymers, polycarbonates, polyaromatic resins, etc. These organic polymers may be copolymerized with a small amount of a single polymer of other organic polymers, or may be blended with other organic polymers. The thickness of the transparent plastic film substrate used in the present invention is preferably in the range of more than 100 micrometers and less than 300 parameters, and the upper limit thereof is preferably 260 micrometers, and the lower limit thereof is particularly preferably 70 micrometers. When the thickness of the transparent plastic film substrate is less than 10 micrometers, its mechanical strength is insufficient, especially for the pen force applied on the touch panel, its deformation will tend to increase, and the durability will also increase. It is easy to become insufficient. On the other hand, when the thickness exceeds 300 micrometers, the pen load must be increased in order to deform the film when using a touch panel. Therefore, the load of the transparent conductive film is necessarily increased, so that the viewpoint of durability of the transparent conductive film is not good. The transparent plastic film substrate used in the present invention may be subjected to a corona discharge treatment, a glow discharge treatment, a flame treatment, an ultraviolet irradiation treatment, an electron beam, to the extent that the purpose of the present invention is not impaired. Surface activation treatments such as irradiation treatment and ozone treatment. Also, 'the curable resin used in the present invention is not particularly limited to -10- 550598. 5. Description of the Invention (9) The resin is set to be hardened by applying energy such as heating by ultraviolet irradiation or electron beam irradiation.' For example, it may be a silicone resin, an acrylate resin, a methacrylate resin, an epoxy resin, a melamine resin, a polyester resin, a polyurethane resin, or the like. From the viewpoint of productivity, it is more preferable to use ultraviolet curing resin as the main component. As the UV-curable resin, for example, polyfunctional acrylic resins such as polyacrylic acid and methacrylic acid esters, polyhydric alcohols and hydroxyalkyl esters of acrylic acid or methacrylic acid, etc. Functional polyurethane acrylate resin and the like. If necessary, the monofunctional monopolymer in such a polyfunctional resin may be copolymerized by adding ethylene acetone, methyl methacrylate, styrene, or the like. In order to increase the adhesion between the transparent conductive film and the cured layer, it is effective to perform a surface treatment on the cured layer. Specific methods include glow discharge or corona discharge irradiation treatment methods to increase carbonyl groups, carboxylic acid groups, and hydroxyl groups, and acid or base chemical treatment methods to make amine groups, hydroxyl groups, A method for adding a polar group such as a carbonyl group. The ultraviolet-curable resin is usually used by adding a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and a known compound that absorbs ultraviolet rays and generates radicals can be used. Such photopolymerization is initiated, for example, for example, various benzoin, benzophenone, and fluorenylphenol can be used. The addition amount of the photopolymerization initiator is usually 1 to 5 parts by mass based on 100 parts by mass of the ultraviolet curing resin. Furthermore, regarding the main structure of the hardened material layer used in the present invention, -11-550598 V. Description of the invention (1 o) UV-curable resin of the component is preferably non-compatible with the hardened resin Polymer resin. A small amount of non-phase hardening resin used for the substrate is a non-phase resin, which will cause phase separation in the hardening resin and disperse the particulate incompatible resin. On the surface of the hardened material layer, the unevenness caused by the dispersed particles of these immiscible resins can provide unevenness on the surface of the highly transparent conductive film, so that the surface roughness in a wide range can be controlled appropriately. In the range. Therefore, it is possible to improve the sliding characteristics between the glass and the surface of the transparent conductive film when a force is applied from the pen. As a result, the sliding durability of the pen can be improved. When the curable resin is an ultraviolet curable resin, it can be used as a multi-compatible resin. For example, it can be a polyester resin, a polyolefin resin, a polystyrene resin, or a polyamide resin. The weight average molecular weight of the aforementioned polyester resin is preferably a high molecular weight of 5,000 to 50,000. The lower limit of the aforementioned average molecular weight, particularly preferred, is 8,000; and the upper limit, particularly preferred, is 30,000. When the weight average molecular weight of the polyester is less than 5,000, there will be Particles of a suitable size in the hardened layer of the ester resin tend to be difficult to disperse. On the other hand, when the weight average molecular weight of the polyester resin is more than 5,000, it is more preferable to adjust it to a coating solution without lowering the solubility to the solvent. The high-molecular-weight polyester resin may be a non-crystalline saturated polyester resin obtained by combining a diol and a dicarboxylic acid, or may be dissolved in a solvent common to the ultraviolet curable resin. It can be used as the aforementioned dihydric alcohol. For example, for example, it can be & = -12-550598. 5. Description of the invention (11) Alcohol, propylene glycol, 1,3-butanediol, 1,4-butane Alcohols, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, hydroxylated bisphenol A, and the like. As the aforementioned binary carbonyl acid, for example, it may be isougic acid, phthalic acid, adipic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride ", and the like. Furthermore, as long as the solubility in the solvent does not become insufficient, it can also be used with trihydric or higher alcohols such as trimethylolpropane or pentaerythritol, as well as, for example, trimellitic anhydride and coke. Copolymerization of tricarboxylic acid with tribasic acid or more. In the present invention, when the hardening type resin used as the main constituent of the hardened material layer is an ultraviolet hardening type resin, and the high molecular weight polyester resin is used as the polymer resin having no compatibility with the hardened material resin, The proportion below is more preferably 0.1 to 20 parts by mass of the polyester resin relative to 100 parts by mass of the ultraviolet curing resin. The upper limit of the aforementioned blend ratio of the polyester tree is more preferably 10 parts by mass, and particularly preferably 5 parts by mass. The lower limit of the blending ratio of the polyester resin is more preferably 0.2 parts by mass, and particularly preferably 0.5 part by mass. When the aforementioned blend ratio of the polyester resin is less than 0.1 part by mass relative to 100 parts by mass of the ultraviolet curable resin, the protrusions formed on the surface of the hardened layer will become smaller, so that the protrusions are reduced. Propensity. For this reason, the mean square average surface roughness in a wide area will easily become less than 4.0 nm ', making it difficult to find an effect of improving the sliding durability of the pen. On the other hand, when the blend ratio of the aforementioned polyester resin is -13- 550598 relative to 00 parts by mass. V. Description of the invention (12) Ultraviolet curable resin meter exceeds 20.0 parts by mass. The surface roughness will easily exceed 20.0 nanometers, and the strength of the hardened layer will be deteriorated, which will easily deteriorate the chemical resistance. Furthermore, because the refractive index of polyester resins is different from that of UV-curable resins, when the polyester tree is intended to exceed 20.0 parts by mass relative to 100 parts by mass of UV-curable resins, it will harden. The fog of the material layer rises, so that the transparency tends to deteriorate. On the contrary, the phenomenon of poor transparency due to the dispersed particles of the high-molecular-weight polyester resin is actively used, and it can be used as an anti-glare film having an anti-glare function by increasing fogging. The ultraviolet curable resin, the photopolymerization initiator, and the polymer polyester resin are each dissolved in a common solvent to prepare a coating solution. The solvent to be used is not particularly limited. For example, for example, alcohol solvents such as ethylene glycol and isopropyl glycol, ester solvents such as ethyl acetate and butyl acetate, dibutyl ether and ethylene glycol can be used. Ether-based solvents such as monoethyl ether, ketone-based solvents such as methyl isobutyl ketone and cyclohexanone, aromatic hydroxy-based solvents such as toluene, xylene, and pine perfume, etc. These systems can be used alone or in combination. can. The concentration of the resin component in the coating liquid can be appropriately selected in accordance with the coating method and the viscosity. For example, the proportion of the total amount of the ultraviolet curing resin, the photopolymerization initiator, and the high molecular weight polyester resin in the coating liquid is usually 20 to 80% by mass. In addition, other known additives may be added to the coating liquid as needed, for example, a silicone leveling agent or the like. -14- 550598 V. Description of the invention (13) In the present invention, the prepared coating solution can be coated on a transparent plastic substrate. The coating method is not particularly limited, and for example, a conventionally known method such as a pillar coating method, a groove coating method, and a repeated coating method can be used. The coating liquid for coating can be removed by evaporation in the following drying step. In this step, fine particles of a polyester having a high molecular weight which are uniformly dissolved in the coating solution are deposited in the ultraviolet curable resin. After the coating film is dried, the plastic film is irradiated with ultraviolet rays to crosslink and cure the ultraviolet curable resin to form a cured material layer. In this hardening step, fine particles of the high-molecular-weight polyester resin are fixed in the hard coating layer, and protrusions are formed on the surface of the hardened layer. According to the height and the number of the protrusions', the mean square average surface roughness in a wide area can be controlled. The thickness of the hardened material layer is preferably in the range of 0.1 to 15 microns. The lower limit of the thickness of the hardened layer is preferably 0.5 micrometers, particularly preferably 1 micrometer. The upper limit 厚度 of the thickness of the hardened material layer is preferably 10 m, and particularly preferably 8 m. When the thickness of the hardened material layer is less than 0.1 m, it is difficult to sufficiently form protrusions. On the other hand, when it exceeds 15 micrometers, it is not suitable from the viewpoint of productivity. As the transparent conductive film used in the present invention, although it is not specifically limited to materials having transparency and conductivity, it is preferably, for example, indium oxide, tin oxide, zinc oxide, and indium-tin. Single-layered or multi-layered structures of composite oxides, tin-antimony composite oxides, bowl-ming composite oxides, face-bowl composite oxides, silver and silver alloys, copper and copper alloys, and gold. Among them ’from the viewpoint of environmental stability and repetitive processability.
-15- 550598 五、發明說明C 14) ，較宜是使用銦-錫複合氧化物、或錫-銻複合氧化物。 透明導電性薄膜之膜厚較宜是在4〜800奈米之範圍 ，特佳是在5〜500奈米。當透明導電性薄膜之厚度不足 4奈米之情況，將難以形成連續薄膜，以致有難以顯示良 好導電性之傾向。另一方面，當厚度比800厚時，則透明 性容易變差。 在本發明中所使用之透明導電性薄膜之成膜方法，已知 係有真空蒸鍍法、濺鍍法、CVD法、離子鍍上法、噴霧法 等，必要時可以視膜厚需要，而適當地選擇前述方法。 例如，在濺鍍法之情況下，係可以使用一利用氧化物標 靶之一般性濺鍍法、或者是使用該利用金屬標靶之反應性 濺鍍法等。此時，倂用導入氧、氮等做爲反應性氣體，添 力口臭氧，利用電漿照射、離子輔助等手段也可以。又，在 不損及本發明目的之範圍內，在基板上施加直流、交流、 高頻率等偏壓也可以。 依照本發明，而使得由在透明導電性薄膜中之金屬氧化 物所構成之結晶粒子個數變多，以致透明導電性薄膜之膜 質會變硬，而使得在筆滑動試驗時難以削去該透明導電性 薄膜之表面，進而達成提高筆滑動耐久性。 在本發明之透明導電膜中，爲了使透明導電性薄膜之窄 領域上的均方平均面粗糙度爲0 . 3〜2奈米，或者使得由 在透明導電性薄膜中之金屬氧化物所構成、而直徑爲5奈 米以上1 00奈米以下之結晶粒子的個數增加，則在透明導 -16- 550598 五、發明說明（15) 電性薄膜成膜之際，使用以下二個方法係爲有效的。 (1 )提高膜基板之溫度。 (2)除去在成膜氛圍氣中之水分及有機物等。 爲了適度地提高透明導電性薄膜之表面粗糙度’或者爲 了增加由在透明導電性薄膜中之金屬氧化物所構成之結晶 粒子的個數，最爲重要的1點係爲提高該做爲基板之膜的 溫度。在此，於透明導電性薄膜成膜之時，爲了使蒸鍍粒 子堆積時之基板（膜）表面上產生遷移，則令比較大的複合 氧化物（例如，ΙΤ0)粒子形成在最表面上。此一結果，將 使在ΙΤ0粒子間界面上之溝深予以深化，並可以適度地提 高表面粗糙度。 例如，利用捲曲取集式裝置，以濺鍍法使在膜之透明導 電性薄膜上成膜的情況下，使膜背面（透明導電性薄膜形 成膜之相反面）接觸經提高溫度之輥，將可以提高做爲基 板之膜的溫度。 在做爲基板之透明塑膠膜上成膜透明導電性薄膜之際， 其溫度較宜是10〜150°C。當成膜時之溫度超過150°c時， 該塑膠膜表面將變得柔軟，以致於真空室行動時，該塑膠 膜將容易地產生傷害。又，當溫度不足1 〇 °C時，則難以得 至α由金屬氧化物所形成之結晶粒子個數多的導電性薄膜。 就輥溫度之控制而言，較佳是在輥內設置水道，並使調 整溫度用之熱介質於該水道中流動。用來做爲該熱介質者 ，並沒有特別地限定，但較適宜的是水或油、乙二醇、丙 -1 7 --15-550598 V. Description of the invention C 14), it is more preferable to use an indium-tin composite oxide or a tin-antimony composite oxide. The thickness of the transparent conductive film is preferably in the range of 4 to 800 nm, and particularly preferably in the range of 5 to 500 nm. When the thickness of the transparent conductive film is less than 4 nm, it is difficult to form a continuous film, so that it tends to be difficult to show good conductivity. On the other hand, when the thickness is thicker than 800, the transparency tends to deteriorate. The film-forming method of the transparent conductive film used in the present invention is known to be a vacuum evaporation method, a sputtering method, a CVD method, an ion plating method, a spray method, etc., and if necessary, depending on the thickness of the film, The foregoing method is appropriately selected. For example, in the case of a sputtering method, a general sputtering method using an oxide target or a reactive sputtering method using a metal target can be used. At this time, it is possible to use oxygen, nitrogen, etc. as reactive gases, add ozone, and use plasma irradiation and ion assist. Further, as long as the object of the present invention is not impaired, a bias voltage such as DC, AC, or high frequency may be applied to the substrate. According to the present invention, the number of crystal particles composed of the metal oxide in the transparent conductive film is increased, so that the film quality of the transparent conductive film is hardened, which makes it difficult to remove the transparency during the pen sliding test. The surface of the conductive film improves the sliding durability of the pen. In the transparent conductive film of the present invention, in order to make the mean square average surface roughness in a narrow area of the transparent conductive film 0.3 to 2 nm, or to make up a metal oxide in the transparent conductive film When the number of crystalline particles with a diameter of 5 nanometers or more and 100 nanometers or less increases, the transparent guide -16-550598 V. Description of the invention (15) When forming an electrical thin film, the following two methods are used: For effective. (1) Increase the temperature of the film substrate. (2) Remove the moisture and organic matter in the film-forming atmosphere. In order to moderately improve the surface roughness of the transparent conductive film 'or to increase the number of crystal particles composed of metal oxides in the transparent conductive film, the most important point is to improve the substrate thickness. The temperature of the membrane. Here, when the transparent conductive film is formed, in order to cause migration on the surface of the substrate (film) when the deposited particles are deposited, relatively large composite oxide (for example, ITO) particles are formed on the outermost surface. As a result, the depth of the grooves at the interface between the ITO particles will be deepened, and the surface roughness can be improved moderately. For example, when a film is formed on a transparent conductive thin film by a sputtering method using a roll-collecting device, the back surface of the film (the opposite surface of the transparent conductive thin film forming film) is brought into contact with a temperature-increasing roller, The temperature of the film used as the substrate can be increased. When forming a transparent conductive film on a transparent plastic film as a substrate, the temperature is preferably 10 to 150 ° C. When the film formation temperature exceeds 150 ° c, the surface of the plastic film will become soft, so that when the vacuum chamber moves, the plastic film will easily cause injury. When the temperature is less than 10 ° C, it is difficult to obtain a conductive thin film having a large number of crystalline particles made of a metal oxide. In terms of controlling the temperature of the roller, it is preferable to set a water channel in the roller and make the heat medium for temperature adjustment flow in the water channel. Those used as the heat medium are not particularly limited, but more suitable are water or oil, ethylene glycol, and propylene.
550598 五、發明說明（16) 二醇等之單體及其混合物。 又，爲了得到由金屬氧化物所形成之結晶粒子個數多的 導電性薄膜，則除報在成膜氣氛圍氣體中之水及有機物等 不純物質也是重要的事情。 例如，於濺鍍法中成膜之情況下，在進行濺鍍之前，將 經排氣使真空室內之壓力到達0 . 000 1 Pa之真空度後，將 A r等之惰性氣體、以及氧等之反應性氣體導入真空室中， 以 0.01〜10 Pa之壓力使發生放電，以進行濺鍍較佳。又 ’在蒸鍍法，CVD法等之其他的方法中，也是同樣的做法 〇 雖然可藉由濺鍍法等之真空程序，將透明導電性薄膜予 以成膜在此種做法所形成的硬化物層上，但是在硬化物層 及/或塑膠膜中所含有的揮發成分的時候，就會對直空程 序造成不良的影響。 當在硬化物層及/或塑膠膜中所含有的揮發成分的時候 ’例如’在膜基板巨以濺鍍法使形成銦-錫詹合氧化物薄 月莫之情況下，由被濺鍍之銦原子與硬化物層而來之揮發氣 體’將會在氣相中衝突，而使得銦原子降低。結果，造成 ^&硬化物層上所形成的由在透明導電性薄膜中之金屬氧化 物所構成的結晶粒子個數變低。又且，會使得在硬化物層 h所形的透明導電性薄膜之均方平均面粗糙度降低。 當使用此種由金屬氧化物所構成的結晶粒子個數少、或 者表面平滑而均方平均面粗糙度（Rm s )低的透明導電性薄 -18- 550598 五、發明說明（17) 膜所積層之透明導電膜，予以積層透明導電性薄膜之透明 導電膜的觸控面板時，當以5 . ON之荷重進行20萬次之直 線滑動試驗後，該透明導電性薄膜較宜是不產生磨耗劣化 者。 舉例來說，例如，在硬化物層中所存在之揮發成分，係 爲不會使得在前述硬化物層之塗布工程中用的塗布液之溶 劑或紫外線產生硬化反應、殘留的光聚合起始劑及其副產 物。 爲了減少前述之揮發成分，則在藉由紫外線照射進行交 聯反應後，而實施加熱處理較爲適當。此時，加熱處理溫 度之範圍較宜是100〜2 00°C。當不足100°C時，則減少揮發 成分之效果容易變得不充分；當溫度超過200t時，則將 有難以保持膜的平面性之傾向。 又，使膜真空曝露在進行濺鍍等之真空室中，係爲一用 以減少揮發成分之有效手段。 此時之真空度，較宜是在1000 Pa以下，更宜是在100 Pa以下。當以比1〇〇 pa高之壓力實施時，除去揮發成分 之效果將會不夠充分。 又’真空曝露時間，較宜是1分鐘〜1〇〇分鐘。當真空曝 露時間不足1分鐘時，則除去揮發成分之效果將不夠充分 。另一方面，當時間超過1 〇 〇分鐘時，由於生產性會顯著 地降低，因而不適合於工業利用。 然而’在硬化型樹脂中不倂用非相溶之高分子樹脂的情550598 V. Description of the invention (16) Monomers such as diols and mixtures thereof. In addition, in order to obtain a conductive thin film having a large number of crystalline particles formed of a metal oxide, it is also important to remove impurities such as water and organic substances in the atmosphere of the film-forming gas. For example, in the case of forming a film in a sputtering method, before the sputtering is performed, the pressure in the vacuum chamber is exhausted to reach a vacuum of 0.00 1 Pa, and then an inert gas such as Ar and oxygen are used. The reactive gas is introduced into a vacuum chamber, and a discharge is performed at a pressure of 0.01 to 10 Pa to perform sputtering. It is also the same method in other methods such as a vapor deposition method and a CVD method. Although a transparent conductive thin film can be formed by a vacuum process such as a sputtering method, a hardened material formed by such a method Layer, but when the volatile components contained in the hardened material layer and / or plastic film, it will adversely affect the direct air program. When the volatile components contained in the hardened material layer and / or the plastic film are 'for example', when the indium-tin oxide oxide is formed by the sputtering method on the film substrate, the The indium atom and the volatile gas from the hardened layer will collide in the gas phase, which will reduce the indium atom. As a result, the number of crystal particles formed of the metal oxide in the transparent conductive film formed on the hardened layer becomes low. In addition, the mean square average surface roughness of the transparent conductive film formed in the cured material layer h is reduced. When using this kind of metal oxide, the number of crystal particles is small, or the surface is smooth and the mean square roughness (Rm s) is low, the transparent conductivity is thin -18- 550598 V. Description of the invention (17) When a laminated transparent conductive film is used for a touch panel with a transparent conductive film laminated with a transparent conductive film, when the linear sliding test is performed 200,000 times with a load of 5. ON, the transparent conductive film is preferably non-wearing. Degraded. For example, for example, the volatile component present in the hardened material layer is a photopolymerization initiator that does not cause a hardening reaction or residual photopolymerization in the solvent or ultraviolet rays of the coating liquid used in the coating process of the hardened material layer. And its by-products. In order to reduce the above-mentioned volatile components, it is appropriate to perform a heat treatment after performing a crosslinking reaction by ultraviolet irradiation. In this case, the range of the heat treatment temperature is preferably 100 to 200 ° C. When the temperature is lower than 100 ° C, the effect of reducing volatile components tends to be insufficient; when the temperature exceeds 200t, it tends to be difficult to maintain the flatness of the film. Furthermore, exposing the film to a vacuum chamber for performing sputtering or the like is an effective means for reducing volatile components. The degree of vacuum at this time is preferably 1000 Pa or less, and more preferably 100 Pa or less. When the pressure is higher than 100 pa, the effect of removing volatile components is insufficient. The vacuum exposure time is preferably 1 minute to 100 minutes. When the vacuum exposure time is less than 1 minute, the effect of removing volatile components will be insufficient. On the other hand, when the time exceeds 1000 minutes, productivity is significantly reduced, and therefore it is not suitable for industrial use. However, the use of non-compatible polymer resins is not a problem in hardening resins.
-19- 550598 五、發明說明（19) 透明導電性薄膜，也可以在成膜後，以加熱、紫外線照射 等手段來提供能量。在此種提供能量之手醺中，較適當者 是在氧氛圍氣下進行加熱處理。 加熱處理溫度較宜是在150〜200 °C之範圍。當溫度不滿 1 5 0 °C時，貝(]改善膜品質之效果不夠充分，另一方面，當 溫度超過200 °C時，則難以維持膜之平面性，更且，在透 明導電性薄膜中由金屬氧化物所構成的結晶粒之個數會變 得非常高，而變成易脆的透明導電性薄膜。 又，加熱處理時間較適當之範圍係爲0.2〜6 0分鐘。當 不滿0.2分鐘，即使是以220°C之高溫來進行加熱處理， 對於改善膜品質之效果也會不夠充分，因而不佳。另一方 面，加熱處理時間超過60分鐘時，則不適於工業上使用 〇 又，進行加熱處理之氛圍氣體，較宜是預先排氣使真空 室內之壓力到達0 . 2 Pa以下後，並於充滿氧氣之空間中 進行。此時之壓力，較宜是在大氣壓以下。 又，爲了進一步提高此時觸控面板之最外層（筆施力面） 之耐擦傷性，則較宜是在透明塑膠膜之透明導電性薄膜所 形成的表面之相對面（此時觸控面板之最外層（筆施力面）） 上，設置一硬被覆層。前述之硬被覆層之硬度，較宜是在 2 Η鉛筆硬度以上。當硬度不足2H時，則該透明導電膜之 硬被覆層的耐擦傷性特點將不充分。 前述硬被覆層之厚度，較宜是0.5〜10微米。當厚度不 -21 - 550598 五、發明說明（2〇) 足 0.5微米時，則耐擦傷性易變得不充分，而比1 0微米 厚的情況下，就生產性之觀點來看，係爲不好的。 可用在前述硬被覆層之硬化型樹脂組成物，較宜是具有 丙燃酸酯之官能基的樹脂，舉例來說，例如，分子量比較 低的聚酯樹脂、聚醚樹脂、丙烯酸樹酯、環氧樹脂聚胺基 甲酸酯、聚硫醇聚烯樹脂、多元醇等之多官能性化合物、 (甲基）丙烯酸酯等之寡聚物或預聚合物等。 又，可做爲反應性烯釋劑者，舉例來說，例如，使用含 有比較多量之乙基（甲基）丙烯酸酯、乙基已基（甲基）丙烯 酸酯、乙烯、甲基苯乙烯、N -乙烯吡咯烷酮等之單官能單 聚物，以及多官能單聚物，例如，三甲醇基丙烷三（甲基） 芮烯酸酯、己烷二醇（甲基）丙烯酸酯、三丙二醇二（甲基） 芮烯酸酯、、二乙二醇二（甲基）丙烯酸酯、、季戊四醇三 (甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、1，6 -己 燒二醇二（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯等 〇 在本發明中，較宜是混合有胺基甲酸酯丙烯酸酯之寡聚 物、二季戊四醇六（甲基）丙烯酸酯之單聚物等。 又’可做爲用於前述硬被覆層上之硬化型樹脂組成物， 以使用聚酯丙烯酸酯和聚胺基甲酸酯丙烯酸酯之混合物特 另!1合適。 聚酯丙烯酸酯之被覆膜係適合於做爲非常硬之硬被覆層 。然而’單獨爲聚酯丙烯酸酯之被覆膜，致具有耐衝擊性 -22 - 550598 五、發明說明（21) 低而變得易脆之問題。 因此，爲了賦與被覆膜耐衝擊性及柔軟性，較宜是倂用 聚胺基甲酸酯丙烯酸酯。也就是說，藉由倂用聚胺基甲酸 酯丙烯酸酯，一方面可維持做爲硬被覆層的被覆膜之硬化 ，一方面也賦與所謂的耐衝擊性和柔軟性等之機能。 兩者之配合比例，相對於1 00質量份之聚酯丙烯酸酯計 ，該聚胺基甲酸酯丙烯酸酯較宜是在30質量份以下。當 聚胺基甲酸酯丙烯酸酯之配合比例係超過30質量份時， 則被覆膜將過於柔軟，而具有使得耐衝擊性變得不充分之 傾向。 硬化前述硬化型樹脂組成物之方法，係可以使用一般之 硬化方法，意即是藉由加熱、電子線或紫外線照射而使硬 化之方法。例如，在電子線硬化之情況下，較宜是使用由 光控制型、反曲線型、共振變壓型、絕緣芯變壓器型直線 型、負阻管型、高頻率型等各種電子線加速器所放出之具 有 50~1000 keV能量的電子線，更宜是使用具有；[〇〇〜300 k e V能量的電子線。又’在紫外線硬化之情況下，係可以 手Q用由超高壓水銀燈、高壓水銀燈、低壓水銀燈、碳電弧 、氙電弧、氫化金屬燈等光線所發出之紫外線。 更且，在電離放射線硬化之情形下，較宜是在前述硬化 型樹脂組成物中含有光聚合起始劑或光增感劑。可做爲光 聚合起始劑者，舉例來說’例如是乙醯酣類、苯甲醯酹類 米烯勒苄基苯酸酯、α -澱粉肟酯、四甲基酪胺單硫化物 -23 - 550598 五、發明說明（22) 、噻噸酮類等。又，可做爲光增感劑者，較宜是η - 丁胺、 三乙胺、三- η-丁基亞楓等。 爲了使硬被覆層賦與防眩性，而於硬化型樹脂中分散 CaC03或Si02等之無機粒子，或於硬被覆層之表面使形成 凹凸形狀等，係爲有效之手段。例如，爲使形成凹凸，可 於塗布含有硬化型樹脂組成物之塗布液步驟後，積層在袠 面具有凸形狀的賦形膜，經由照射在該賦形膜上之紫外線 而使硬化型樹脂硬化後，僅剝離該賦形膜而得。 就前述賦形膜而言，係可以使用具有離形性之聚對苯二 甲酸乙二酯（以下，簡稱爲PET)等之基材膜上設置所期望 的凸形狀之物，或者是使用在PET等基材膜上形成細小凸 部之物。前述可部之形成，例如係可在使用由無機粒子和 黏合劑樹脂所構成的樹脂組成物之基材膜上，藉由實施塗 布工程而得。 可做爲前述黏合劑樹脂者，例如，可以使用以聚異氰酸 酯交聯之丙烯酸基多醇；而無機粒子則係可使用0&(：03或 S i02等。又，也可以使用在製造PET時混練3丨02等無機粒 子之霧面型PET。 在紫外線硬化型樹脂之被覆膜上積層此種賦形膜之後， 照射紫外線而使被覆膜硬化之情況下，於該PET賦形膜做 爲基材膜時，由於該膜會吸收紫外線之短波長側，因而具 有紫外線硬化型樹脂之硬化不足等所謂的缺點。從而，在 紫外線硬化型樹脂之被覆膜上有必要使用具全光線透過率 -24- 550598 五、發明說明（23) 皮在20%以上之賦形膜。 又，爲了在觸控面板上使用時使可見光線之透過率進一 步：t曾加，則較宜是在硬被覆層上施予低反射處理。此種低 反射處理，較宜是積層單層或2層以上之具有和硬被覆層 之折射率相異的折射率之材料。 在單層構造之情況下，較宜是使用具有比硬被覆層小之 折射率的材料。又，在2層以上之多層構造的情形下，該 與硬被覆層相鄰接之層，較宜是使用比硬被覆層小之折射 率的材料；其上方之層更宜是選擇具有比硬被覆層小之折 身寸率的材料。做爲構成此種低反射處理之材料，不論是有 機材料或無機材料只要能滿足上述折射率關係即可，並沒 有特別地限定。例如，較宜是使用CaF2、MgF2、NaAlF4、 SI 〇2、ThF4、 Zr〇2、Nd2〇3、 Sn〇2、Ti〇2、Ce〇2、 ZnS 、 ln203 等之介電體。 此種低射處理係爲濺鍍法、CVD法、離子鍍上法等乾式 塗布法，但以凹刻方式、反復方式、模鑄方式等溼式塗布 程序也可以。 更且’此種低反射處理層之積層前，較宜是對硬被覆層 實施電暈放電處理、塑膠處理、濺鍍處理、電子線照射處 H '紫外線照射處理、電漿處理、易接著處理等公知的表 面處理，來做爲前處理。 使用本發明之透明導電性膜，藉由透過黏著劑與不形成 透明導電性薄膜來積層透明樹脂薄片，因而可得到用於觸 -25 - 550598 五、發明說明（24) 控面板之固定電極的透明導電性積層樹脂薄片。也就是說 ，藉由將觸控面板之固定電極之基板變更爲透明樹脂薄片 ，因而可以製造出質量輕、而且難以破壞之觸控面板。 前述黏合劑係爲一種具有透明性之物，並沒有特別地限 定，例如，以丙烯酸系黏著劑、聚矽氧系黏著劑、橡膠系 黏著劑等較適當。此等黏著劑之厚度並沒有特別地限定， 通常理想上係設定在1〜1 00微米之範圍。當黏著劑之厚度 不足1微米的情形下，將難以得到實用上毫無問題之黏著 性；當厚度超過1 00微米時，依照生產性之觀點來看，其 係不佳。 此種透過黏著劑貼合之透明樹脂薄片，爲了成爲使用時 會g賦與和玻璃同樣等級的機械強度之物，則厚度之範圍較 宜是0.05〜5毫米。當前述透明樹脂薄片之厚度不足 0.05毫米時，其機械強度較玻璃爲差。另一方面，當厚度 超過5毫米的情況下，因爲過於厚而不適合使用於觸控面 板上。又’該透明樹脂之材質，係可以使用與前述透明塑 膠薄膜同樣之物。 第27圖所示者，係爲使用本發明之透明導電性膜的觸 控面板例。此處，具有透明導電性薄膜之一對面板，其觸 控面板係透過隔離物而使透明導電性薄膜以相對之方向配 置而成；另一側之面板上係具有使用本發明透明導電性膜 之物。 此種觸控面板當以筆輸入文字時，由筆而來之壓力，將 -26- 550598 五、發明說明（25) 使得對向間之透明導電性薄膜彼此接觸，而成爲電氣0N 之狀態，而可以檢測出在觸控面板上筆之位置。藉由此種 連續並且正確地檢測筆位置，因而得以由筆之軌跡而辨認 出文字。此時，筆接觸側之可動電極係使用本發明之透明 導電性膜時，因爲使得筆滑動耐久性變爲優良，以致可以 做成長期安定之觸控面板。 又，可做爲使用本發明之透明導電性膜及透明導電性薄 片而得，但不使用玻璃基板之塑膠製的觸控面板，其斷面 圖係如第2 8圖所示。此種塑膠製之觸控面板，由於係不 使用玻璃的原故，因而質量係非常的輕，而且可比較耐衝 擊而不破裂。 【圖式之簡說明】 第1圖所示者，係爲說明實施例1中觸控面板之出力形 狀的說明圖。 第2圖所示者，係爲說明實施例2中觸控面板之出力形 狀的說明圖。 第3圖所示者，係爲說明實施例3中觸控面板之出力形 狀的說明圖。 第4圖所示者，係爲說明實施例4中觸控面板之出力形 狀的說明圖。 第5圖所示者，係爲說明實施例5中觸控面板之出力形 狀的說明圖。 第6圖所示者，係爲說明實施例6中觸控面板之出力形 -27 - 550598 五、發明說明（26) 狀的說明圖。 第7圖所示者，係爲說明實施例7中觸控面板之出力形 狀的說明圖。 第8圖所示者，係爲說明實施例8中觸控面板之出力形 狀的說明圖。 第9圖所示者，係爲說明實施例9中觸控面板之出力形 狀的說明圖。 第10圖所示者，係爲說明實施例10中觸控面板之出力 形狀的說明圖。 第11圖所示者，係爲說明比較例1中觸控面板之出力 形狀的說明圖。 弟11圖所不者’係爲說明比較例2中觸控面板之出力 形狀的說明圖。 第1 2圖所示者，係爲說明比較例3中觸控面板之出力 形狀的說明圖。 弟13圖所不者’係爲說明比較例4中觸控面板之出力 形狀的說明圖。 第14圖所示者，係爲說明實施例10中觸控面板之出力 形狀的說明圖。 第1 5圖所示者，係爲說明實施例1 1中觸控面板之出力 形狀的說明圖。 第1 6圖所示者，係爲說明實施例1 2中觸控面板之出力 形狀的說明圖。-19- 550598 5. Description of the invention (19) The transparent conductive film can also be supplied with energy by heating, ultraviolet irradiation, etc. after film formation. In this energy supply device, it is more appropriate to perform heat treatment in an oxygen atmosphere. The heat treatment temperature is preferably in the range of 150 to 200 ° C. When the temperature is less than 150 ° C, the effect of improving the film quality is insufficient. On the other hand, when the temperature exceeds 200 ° C, it is difficult to maintain the planarity of the film. Moreover, in a transparent conductive film The number of crystal grains made of metal oxides becomes very high, and becomes a brittle transparent conductive film. In addition, a more suitable range of heat treatment time is 0.2 to 60 minutes. When less than 0.2 minutes, Even if the heat treatment is performed at a high temperature of 220 ° C, the effect of improving the film quality is not sufficient, so it is not good. On the other hand, if the heat treatment time exceeds 60 minutes, it is not suitable for industrial use. The atmosphere gas for heat treatment is preferably exhausted in advance to make the pressure in the vacuum chamber below 0.2 Pa, and then carried out in a space filled with oxygen. The pressure at this time is preferably below atmospheric pressure. Also, in order to further To improve the scratch resistance of the outermost layer of the touch panel (the force applied to the pen at this time), it is better to be on the opposite side of the surface formed by the transparent conductive film of the transparent plastic film (at this time the touch panel A hard coating layer is provided on the outermost layer (strength surface of the pen). The hardness of the aforementioned hard coating layer is preferably above 2 硬度 pencil hardness. When the hardness is less than 2H, the hard coating layer of the transparent conductive film The abrasion resistance characteristics will be insufficient. The thickness of the aforementioned hard coating layer is preferably 0.5 to 10 microns. When the thickness is not -21-550598 V. Description of the Invention (20) When the abrasion resistance is 0.5 microns, the abrasion resistance is likely to change. It is not sufficient, and when it is thicker than 10 micrometers, it is not good from the viewpoint of productivity. The hardening resin composition that can be used for the aforementioned hard coating layer is preferably one having a propionate. Functional group resins, for example, polyfunctional polyester resins, polyether resins, acrylic resins, epoxy polyurethanes, polythiol resins, polyols, etc. Oligomers, prepolymers, etc. of chemical compounds, (meth) acrylates, etc. In addition, those that can be used as a reactive diluent, for example, use a relatively large amount of ethyl (meth) acrylic acid Ester, ethylhexyl (meth) acrylate, Monofunctional monopolymers of ethylene, methylstyrene, N-vinylpyrrolidone, etc., as well as polyfunctional monopolymers, for example, trimethylolpropane tri (methyl) arenoate, hexanediol (methyl) Acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 6-Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. In the present invention, an oligomer, Monomer of pentaerythritol hexa (meth) acrylate, etc. It can also be used as a hardening resin composition for the aforementioned hard coating layer to use a mixture of polyester acrylate and polyurethane acrylate Special! 1 suitable. The polyester acrylate coating is suitable as a very hard hard coating. However, ’is a coating film of polyester acrylate alone, which has impact resistance. -22-550598 Fifth, the description of the invention (21) is low and becomes brittle. Therefore, in order to impart impact resistance and flexibility to the coating film, it is preferable to use polyurethane acrylate. That is, by using polyurethane acrylate, on the one hand, the hardening of the coating film as a hard coating layer can be maintained, and on the other hand, functions such as impact resistance and softness can be imparted. The mixing ratio of the two is preferably 30 parts by mass or less based on 100 parts by mass of the polyester acrylate. When the blending ratio of the polyurethane acrylate is more than 30 parts by mass, the coating film will be too soft and tend to make the impact resistance insufficient. The method of hardening the aforementioned hardening resin composition is a general hardening method, that is, a method of hardening by heating, electron beam, or ultraviolet radiation. For example, when the electron wire is hardened, it is more suitable to use a variety of electron wire accelerators, such as light control type, anti-curve type, resonance transformer type, insulated core transformer type linear type, negative resistance tube type, high frequency type, etc. It is more suitable to use an electron wire having an energy of 50 to 1000 keV, and an electron wire having an energy of [〇〇 ~ 300 ke V. In the case of ultraviolet curing, it is possible to use ultraviolet rays emitted from light such as ultra-high-pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, xenon arcs, and hydrogenated metal lamps. Furthermore, when the ionizing radiation is hardened, it is preferable to include a photopolymerization initiator or a photosensitizer in the hardening resin composition. Examples of photopolymerization initiators include, for example, acetamidine, benzamidine, milene benzyl benzoate, α-starch oxime ester, and tetramethyltyramine monosulfide— 23-550598 V. Description of the invention (22), thioxanthone, etc. In addition, as a photosensitizer, η-butylamine, triethylamine, tri-η-butylsulfenylamine, etc. are more preferable. In order to impart anti-glare properties to the hard coating layer, it is effective to disperse inorganic particles such as CaC03 or SiO2 in a hardening resin, or to form an uneven shape on the surface of the hard coating layer. For example, in order to form unevenness, after the step of applying a coating solution containing a curable resin composition, a shaping film having a convex shape on the faint surface may be laminated, and the curing resin may be hardened by ultraviolet rays irradiated onto the shaping film. Then, only this shaping | molding film was peeled. The aforementioned shaped film can be a substrate film having a release property, such as polyethylene terephthalate (hereinafter, referred to as PET), with a desired convex shape, or can be used in A substance that forms fine protrusions on a substrate film such as PET. The formation of the aforementioned parts can be obtained, for example, by performing a coating process on a substrate film using a resin composition composed of inorganic particles and a binder resin. As the aforementioned binder resin, for example, an acrylic polyol crosslinked with polyisocyanate can be used; and for inorganic particles, 0 & (: 03 or Si02) can be used. It can also be used in the production of PET The matte type PET of inorganic particles such as 3 and 02 is kneaded. After the forming film is laminated on the coating film of the ultraviolet curable resin, and the coating film is hardened by irradiating ultraviolet rays, the PET forming film is made. In the case of a base film, since the film absorbs short-wavelength side of ultraviolet rays, it has so-called shortcomings such as insufficient curing of ultraviolet curable resins. Therefore, it is necessary to use a full light transmission on the coating film of ultraviolet curable resin Rate -24-550598 V. Description of the invention (23) Shaped film with skin over 20%. In addition, in order to make visible light transmittance further when used on touch panels: t has been added, it is more suitable for hard A low-reflective treatment is applied to the coating layer. This low-reflective treatment is preferably a laminated single layer or two or more layers having a refractive index different from that of the hard coating layer. In the case of a single-layer structure, It is better to make Use a material with a lower refractive index than that of the hard coating layer. In the case of a multilayer structure with two or more layers, it is preferable to use a layer with a lower refractive index than that of the hard coating layer. The material above it is more suitable to choose a material with a smaller inflection ratio than that of the hard coating. As a material constituting such a low reflection treatment, whether it is an organic material or an inorganic material, as long as it can satisfy the above refractive index relationship Yes, it is not particularly limited. For example, it is preferable to use CaF2, MgF2, NaAlF4, SI 〇2, ThF4, Zr〇2, Nd203, Sn〇2, Ti02, Ce02, ZnS, ln203, etc. This low-emission treatment is a dry coating method such as a sputtering method, a CVD method, or an ion plating method, but a wet coating process such as a gravure method, a repetitive method, and a die casting method is also possible. 'Before laminating such a low-reflective treatment layer, it is better to perform corona discharge treatment, plastic treatment, sputtering treatment, and electron beam irradiation on the hard coating layer. Surface treatment for pre-treatment. Using the transparent conductive film of the present invention, the transparent resin sheet is laminated through the adhesive and the transparent conductive film is not formed, so that a fixed electrode for contacting -25-550598 can be obtained. Transparent conductive laminated resin sheet. In other words, by changing the substrate of the fixed electrode of the touch panel to a transparent resin sheet, a touch panel that is light in weight and difficult to break can be manufactured. The aforementioned adhesive is a kind of The transparent material is not particularly limited. For example, acrylic adhesives, polysiloxane adhesives, rubber adhesives, etc. are suitable. The thickness of these adhesives is not particularly limited, and is usually ideally Set it in the range of 1 to 100 microns. When the thickness of the adhesive is less than 1 micron, it is difficult to obtain practically non-problematic adhesion; when the thickness is more than 100 micron, it is not good from the viewpoint of productivity. In order to make the transparent resin sheet adhered through the adhesive with the same level of mechanical strength as glass, the thickness is preferably in the range of 0.05 to 5 mm. When the thickness of the transparent resin sheet is less than 0.05 mm, its mechanical strength is inferior to that of glass. On the other hand, when the thickness exceeds 5 mm, it is too thick to be suitable for use on a touch panel. The material of the transparent resin is the same as that of the transparent plastic film. Figure 27 shows an example of a touch panel using the transparent conductive film of the present invention. Here, a pair of panels having a transparent conductive film, and the touch panel is configured by placing the transparent conductive films in opposite directions through a spacer; the other side of the panel is provided with the transparent conductive film using the present invention Thing. When this type of touch panel is used to input text with a pen, the pressure from the pen will bring -26-550598 to V. Description of Invention (25) The transparent conductive films between the opposite sides will be in contact with each other, and become an electrical 0N state. The position of the pen on the touch panel can be detected. By detecting the position of the pen continuously and correctly, the text can be recognized by the track of the pen. At this time, when the transparent conductive film of the present invention is used as the movable electrode on the pen contact side, the sliding durability of the pen is made excellent, so that a long-term stable touch panel can be made. In addition, it can be obtained by using the transparent conductive film and the transparent conductive sheet of the present invention, but without using a glass substrate for a plastic touch panel. The sectional view is shown in FIG. 28. This kind of plastic touch panel, because it does not use glass, is very light in weight, and it is relatively resistant to impact without breaking. [Brief description of the drawings] The one shown in FIG. 1 is an explanatory diagram illustrating the output shape of the touch panel in the first embodiment. The figure shown in FIG. 2 is an explanatory diagram illustrating the output shape of the touch panel in the second embodiment. FIG. 3 is an explanatory diagram illustrating the output shape of the touch panel in the third embodiment. The figure shown in FIG. 4 is an explanatory diagram illustrating the output shape of the touch panel in the fourth embodiment. FIG. 5 is an explanatory diagram illustrating the output shape of the touch panel in the fifth embodiment. The one shown in FIG. 6 is an explanatory diagram for explaining the output shape of the touch panel in Embodiment 6. -27-550598 V. Description of Invention (26). FIG. 7 is an explanatory diagram illustrating the output shape of the touch panel in the seventh embodiment. The figure shown in FIG. 8 is an explanatory diagram illustrating the output shape of the touch panel in the eighth embodiment. The figure shown in FIG. 9 is an explanatory diagram illustrating the output shape of the touch panel in the ninth embodiment. The figure shown in FIG. 10 is an explanatory diagram illustrating the output shape of the touch panel in the tenth embodiment. The figure shown in FIG. 11 is an explanatory diagram illustrating the output shape of the touch panel in Comparative Example 1. What is not shown in Fig. 11 is an explanatory diagram illustrating the output shape of the touch panel in Comparative Example 2. Figures 12 and 12 are explanatory diagrams illustrating the output shape of the touch panel in Comparative Example 3. What is not shown in FIG. 13 is an explanatory diagram illustrating the output shape of the touch panel in Comparative Example 4. The figure shown in FIG. 14 is an explanatory diagram illustrating the output shape of the touch panel in the tenth embodiment. The figures shown in FIG. 15 are explanatory diagrams for explaining the output shape of the touch panel in Embodiment 11. The figures shown in FIG. 16 are explanatory diagrams for explaining the output shape of the touch panel in Embodiment 12.
-28 - 550598 五、發明說明C 27) 第1 7圖所元者，係爲說明實施例1 3中觸控面板之出力 形狀的說明圖。 第1 8圖所示者，係爲說明實施例1 4中觸控面板之出力 形狀的說明圖。 第1 9圖所示者，係爲說明實施例1 5中觸控面板之出力 形狀的說明圖。 第20圖所示者，係爲說明實施例1 6中觸控面板之出力 形狀的說明圖。 第21圖所示者，係爲說明實施例1 7中觸控面板之出力 形狀的說明圖。 第22圖所示者，係爲說明實施例16中觸控面板之出力 形狀的說明圖。 第23圖所元者，係爲說明實施例17中觸控面板之出力 形狀的說明圖。 第24圖所示者，係爲說明比較例5中觸控面板之出力 形狀的說明圖。 第25圖所示者，係爲說明比較例6中觸控面板之出力 形狀的說明圖。 第26圖所示者，係爲說明比較例7中觸控面板之出力 形狀的說明圖。 第27圖所示者，係爲說明使用本發明透明導電膜之觸 控面板的說明圖。 第28圖所示者，係爲說明使用本發明透明導電膜、但-28-550598 V. Description of the invention C 27) The elements shown in Fig. 17 are explanatory diagrams for explaining the output shape of the touch panel in the embodiment 13. The figures shown in FIG. 18 are explanatory diagrams for explaining the output shape of the touch panel in the fourteenth embodiment. The figures shown in FIG. 19 are explanatory diagrams for explaining the output shape of the touch panel in Embodiment 15. The figure shown in FIG. 20 is an explanatory diagram for explaining the output shape of the touch panel in the sixteenth embodiment. The diagram shown in FIG. 21 is an explanatory diagram for explaining the output shape of the touch panel in the seventeenth embodiment. The diagram shown in FIG. 22 is an explanatory diagram illustrating the output shape of the touch panel in the sixteenth embodiment. FIG. 23 is an explanatory diagram illustrating the output shape of the touch panel in the seventeenth embodiment. The diagram shown in FIG. 24 is an explanatory diagram illustrating the output shape of the touch panel in Comparative Example 5. The diagram shown in FIG. 25 is an explanatory diagram illustrating the output shape of the touch panel in Comparative Example 6. The diagram shown in FIG. 26 is an explanatory diagram illustrating the output shape of the touch panel in Comparative Example 7. Fig. 27 is an explanatory diagram illustrating a touch panel using the transparent conductive film of the present invention. The one shown in FIG. 28 is for explaining the use of the transparent conductive film of the present invention, but
-29 - 550598 五、發明說明（28) 不使用玻璃基板之觸控面板的說明圖。 [ 元件符 號 對 眧 J V \N 表 ] 1 滑 動 試 驗 部 2 觸 控 面 板出 力 形狀 10 透 明 導 電 膜 11 透 明 塑 膠 薄 膜 基材 12 硬 化物 層 13 透 明 導 電 性 薄 膜 14 硬 被 覆 層 20 珠 子 30 玻 璃 板 40 透 明 導 電 性 薄 片 41 黏 著 劑 42 透 明 樹 脂 薄 片 【實施例】 以下，利用實施例來進一步詳細地說明本發明，但本發 明並沒有特別地限定於實施例中之物而已。又，透明導電 膜之性能及結晶化程度之測定，觸控面板之筆滑動耐久性 試驗，係依照下述方法而測定之。 〇)均方平均面粗糙度 藉由使用掃描式探針顯微鏡（精工儀器公司製， SPI 3800 /SPA300 )之原子間力顯微鏡（AFM)來評量。掃描器 係使用FS - 2 0。懸臂係使用聚矽氧製之s I - DF 2 0。同時使 -30 - 550598 五、發明說明（29) 用一般可由精工儀器公司購得之物。觀察模式係以DFM模 式來進行。觀察時所用的懸臂，因探針污染降低解析度而 不能使用時，通常就使用新品。又，爲了防止在觀察時期 中之磨耗劣化，則在不犧牲解析度之範圍內，可以在有限 度地縮小探針負荷之條件下來進行。 妨礙解析度，而速度不能太大。觀察後藉由附隨的軟體 補正傾斜之數據；之後，以附隨之軟體來進行均方平均面 粗糙度之評量。計算出均方平均面粗糙度（Rms)，以評量 無規則的AFM像1 0點以上之平均値。 窄領域中之均方平均面粗糙度（Rms)之評量，係藉由前 述AFM以解析度256像素X 256像素來進行1微米 X 1 微米面積之觀察。掃描速度係在0.5Hz以下進行，但不得 妨礙解析度，而速度不能太大。觀察後藉由附隨的軟體補 正傾斜之數據；之後，以附隨之軟體來進行均方平均面粗 糙度之評量。計算出均方平均面粗糙度（Rms)，以評量無 規則的AFM像1 0點以上之平均値。 然而，成爲評量對象之AFM像經補正傾斜後之面中的最 大高低差不足12.5奈米之物、以及在12.5奈米以上之物 ，則在評量對象之外。此處，因硬化型樹脂而引發導電層 之凹凸、突起之處理，係不包括在窄領域均方平均面粗糙 度之評量對象之內。如果係在包括之情形下，則因硬化型 樹脂所導入的廣領域之應評量的面粗糙度，當不得包括在 窄領域評量之面粗糙度之中。-29-550598 V. Description of the invention (28) Illustration of touch panel without glass substrate. [Component symbol JV \ N table] 1 Slide test part 2 Touch panel output shape 10 Transparent conductive film 11 Transparent plastic film substrate 12 Hardened layer 13 Transparent conductive film 14 Hard coating 20 Bead 30 Glass plate 40 Transparent Conductive sheet 41 Adhesive 42 Transparent resin sheet [Example] Hereinafter, the present invention will be described in more detail using examples, but the present invention is not particularly limited to those in the examples. The measurement of the performance and crystallization degree of the transparent conductive film and the pen sliding durability test of the touch panel were measured in accordance with the following methods. 〇) Mean square average surface roughness was measured by an interatomic force microscope (AFM) using a scanning probe microscope (manufactured by Seiko Instruments Inc., SPI 3800 / SPA300). The scanner uses FS-2 0. The cantilever system uses s I-DF 2 0 made of polysiloxane. At the same time, use -30-550598. V. Description of the invention (29) Use something generally available from Seiko Instruments. The observation mode is performed in DFM mode. When the cantilever used for observation cannot be used because the probe contamination reduces the resolution, a new product is usually used. In addition, in order to prevent abrasion deterioration during the observation period, it can be performed under a condition that the load of the probe is reduced to a limited extent without sacrificing the resolution. Obstructs resolution, but not too fast. After the observation, the tilting data was corrected by the accompanying software; after that, the mean square roughness was evaluated with the accompanying software. The mean square average surface roughness (Rms) was calculated to evaluate the average 値 of the random AFM image above 10 points. The measurement of the mean square average surface roughness (Rms) in a narrow area is based on the observation of 1 micrometer by 1 micrometer by using the aforementioned AFM with a resolution of 256 pixels by 256 pixels. The scanning speed is performed below 0.5Hz, but the resolution must not be hindered, and the speed must not be too large. After the observation, the tilted data was corrected by the accompanying software; after that, the mean square roughness of the mean square was evaluated with the accompanying software. The mean square average surface roughness (Rms) was calculated, and the average 値 of 10 points or more of the irregular AFM image was evaluated. However, the AFM image that is the subject of evaluation is corrected for tilted faces with a maximum height difference of less than 12.5 nanometers and objects with a maximum elevation difference of 12.5 nanometers or less. Here, the treatment of irregularities and protrusions of the conductive layer caused by the hardening resin is not included in the evaluation of the mean square roughness of the narrow area. If it is included, the surface roughness that should be evaluated in a wide area introduced by the hardening resin should not be included in the surface roughness that is evaluated in a narrow area.
-31 - 550598 五、發明說明（3〇) ⑵由金屬氧化物所構成之結晶粒子的直徑及個數 將透明導電膜試樣片切割成300微米X 300微米之正方 形，並使透明導電性薄膜難以送出至超微切片機之試料承 斗般地固定。接著，儘最大可能之程度，相對於透明導電 性薄膜之極銳角地來設置刀，以得到具有1微米X 1微 米以上的目標觀察部位之切片，設定切削厚度設定爲70 奈米。 在此切片之透明導電性薄膜表面側上，而且損傷不顯著 的部位中，確保1微米X 1微米之觀察視野，使用穿透式 電子顯微鏡（JEOL公司製、JEM-2010)，加速電壓爲 20 0 kV，於明亮視野以5萬倍之觀察倍率來進行照相攝影 。在視野內電子密度高的領域，計算所觀察到的直徑5奈 米以上1 00奈米以下之單獨粒子的結晶粒子，並以1 0領 域中之平均粒子數來做爲由金屬氧化物所構成之結晶粒子 的個數（個/微米2)。 ⑶光線透過率及霧値 根據JIS-K7105，使用日本電色工業（股）公司製_心 1 0 0 1DP，來測定光線透過率及霧値。 (4) 表面電阻率 根據II S - K7 1 94，以4端子法來測定之。測定機係使用 三菱油化（股）公司製羅測試AMCP-T400。 (5) 筆滑動耐久性試驗 使用聚縮醛樹脂製之筆（前端形狀：0 . 8毫米R )，以 -32 - 550598 五、發明說明（31) 5· ON之荷重，對觸控面板進行20萬次（來回10萬次）之直 線滑動試驗。此時滑動距離爲3 0奈米，而滑動速度爲60 毫米/秒。在該滑動耐久性試驗後，首先，以目視觀察該 滑動部之白化現象。進一步，以5.0N之筆荷重於上述滑 動部筆記一 2 0毫米之記號〇印記，正確讀出數値以評量 之。測定以5 ·0Ν之筆荷重壓在滑動部時之0N電阻（可動 電極（薄膜電極）和固定電極間接時之電阻値）。 (6)透明導電性薄膜脆性之評量 在上述觸控面板之筆滑動耐久性試驗，使用掃描式探針 電子顯微鏡（精工儀器公司製，SPI 3 800/SPA300 )之原子間 力顯微鏡AFM，來觀察評量相對於筆之滑動部和記號〇印 筆記部分之反面的透明導電性薄膜之表面上100微米2(1 微米X 1微米）之範圍，解析度爲5 1 2像素X 5 1 2像素。掃 描速度係在0 . 5Hz以下進行，若不妨礙解析度的話，則速 度不固定。觀察後藉由附隨的軟體補正傾斜之數據；之後 ，以附隨之軟體來進行表面形狀之評量。掃描器係使用 FS -20。懸臂係使用聚矽氧製之SI-DF20。同時使用一般可 由精工儀器公司購得之物。觀察模式係以DFM模式來進行 。觀察時所用的懸臂，因探針污染降低解析度而不能使用 時，通常就使用新品。又，爲了防止在觀察時期中之磨耗 劣化，則在不犧牲解析度之範圍內，可以在有限度地縮小 探針負荷之條件下來進行。 ⑺附著力測定 -33 - 550598 五、發明說明（32) 使用聚酯係黏著劑，於厚度爲75微米聚對酞酸乙二酯 上積層厚度爲40微米之離子單體膜，而製做成附著力測 定用之積層體。使該附著力測定用積層體之離子單體膜面 、與透明導電膜之透明導電性薄膜面相對向，以13〇°C而 熱密封之。利用1 80度剝離法，將此積層體之附著力測定 用積層體、與透明導電膜予以剝離，將此剝離力當作附著 力。此時之剝離速度爲1〇〇〇毫米/分鐘。 (實施例1 ) 相對於100質量份之含有光聚合起始劑之丙烯酸系樹脂 (大日精化工業公司製，精化物EXF · 0 U )，摻混3質量份 之共聚合聚酯樹脂（東洋紡績公司製，拜龍200，重量平均 分子量爲1 80 00 )，依照使固形分濃度爲50質量％，而加入 甲苯/MEK(質量比爲8 : 2)之溶劑之混合物溶媒，均勻地攪 拌使溶解而調製成塗布液。 於兩面上具有易接著層之雙軸配向透明PET膜（東洋紡 績公司製，A4 340，厚度爲188微米）上，塗布上述所調製 的塗布液，使成爲厚度爲5微米之塗膜。於180 °C下進行 乾燥1分鐘後，利用紫外線照射裝置（艾格拉弗庫斯公司 製，UB-042 - 5 AM-W型）之紫外線來照射（光量：3〇〇毫焦耳 /公分2 )，使塗膜硬化。接著，以1 8 〇 °C施予加熱處理1分 鐘，以進行揮發成分之降低。 又，使積層此種硬化物層之雙軸配向透明PET膜真空曝 露，於真空室中反復地進行捲曲處理。此時，使濺鍍前之 -34 - 550598 五、發明說明（33) 壓力爲0.000 7 Pa，以含有5質量％氧化錫之氧化銦（三井 金屬礦業公司製’密度爲7.1克/公分3)做爲標靶，施加 2W /公分2之DC電力。又，以流速爲HO seem流通Ar氣 體，以流速爲10 seem流通〇2氣體，於〇.4Pa之氣氛圍下 ，利用磁性賤鍍法而使成膜。但是，因爲通常之DC不能 防止電弧放電，而使用日本伊奴阿斯製RPG- 1〇〇，以 5 0 kHz週期而施加5微米幅度之脈衝。再者，於中心輥爲 5 0 °C下，來進行濺鍍。 又，一邊以濺鍍程序測定器（伯東公司製，SPM200 )時常 觀測氛圍氣體之氧氣分壓，一邊依照使銦-錫複合氧化物 薄膜中之氧化度爲一定之狀態，來回饋氧氣氣體之流量計 和DC電源。根據以上之做法，使堆積成厚度爲22奈米之 由銦-錫複合氧化物所構成的透明導電性薄膜。 <觸控面板之製作> 使用此種透明導電膜來做爲面板之一面，面板另一面則 使用在玻璃基板上以電漿CVD法，由厚度爲20奈米之銦-錫複合氧化物薄膜（氧化錫含有量：1〇質量％)所成的透明 導電性薄膜（日本曹達公司製’ S500)。使此2枚面板之透 明導電性薄膜成相對方向，透過直徑爲30微米之環氧樹 月旨珠而製做出經配置的觸控面板。 (實施例2 ) 將以由聚酯丙條酸酯和聚胺基甲酸酯丙嫌酸酯之混合物 所形成的紫外線硬化樹脂（大曰精化工業公司製’ EXG)來 -35 - 550598 五、發明說明（34) 做爲在實施例1中之由雙軸配向透明PET膜基材/硬化物 層所成積層體的在硬化物層相反面上之硬質被覆層樹脂， 藉由凹版印刷法而塗布、使溶劑乾燥，乾燥後之膜厚度爲 5微米。之後，以1〇公尺/分鐘之速度通過160W之紫外線 照射裝置，使硬化成紫外線硬化型樹脂，而形成硬質被覆 層。接著，以180°C施予加熱處理1分鐘，以進行揮發成 分之降低。 和實施例1同樣地做法，使在此種硬質被覆層/雙軸配 向透明PET膜基材/硬化物層所成積層體的硬化物層上， 成膜一銦-錫複合氧化物薄膜。進一步，使用此種透明導 電膜，和實施例1同樣地做法而製做出觸控面板。 (實施例3 ) 將以由聚酯丙烯酸酯和聚胺基甲酸酯丙烯酸酯之混合物 所形成的紫外線硬化樹脂（大日精化工業公司製，EXG)來 做爲在實施例1中之由雙軸配向透明PET膜基材/硬化物 層所成積層體的在硬化物層相反面上之硬質被覆層樹脂， 藉由凹版印刷法而塗布、使溶劑乾燥，乾燥後之膜厚度爲 5微米。之後，使表面與霧面紫外線硬化型樹脂之形成微 細凸形狀之PET膜的霧面賦形膜（東麗公司製，X)接著而 積層。此種霧面賦形膜之表面形狀之平均面粗糙度係爲 〇· 40微米，波峰之平均間隔爲1 60微米，最大表面粗糙度 爲25微米。 以1 0公尺/分鐘之速度通過1 60W之紫外線照射裝置，-31-550598 V. Description of the invention (3〇) 的 The diameter and number of crystalline particles made of metal oxide. Cut the transparent conductive film sample piece into a square of 300 micrometers by 300 micrometers, and make the transparent conductive film. Samples that are difficult to send to the microtome are fixed like a bucket. Next, as far as possible, set the knife at an extremely acute angle with respect to the transparent conductive film to obtain a slice having a target observation site of 1 micrometer by 1 micrometer or more, and set the cutting thickness to 70 nanometers. On the surface of the transparent conductive film of this slice, and in the area where the damage is not significant, a 1 micron by 1 micron observation field is ensured. A transmission electron microscope (JEOL Corporation, JEM-2010) is used, and the acceleration voltage is 20 At 0 kV, photography is performed at a bright field of view with an observation magnification of 50,000 times. In the field of high electron density in the visual field, calculate the observed crystalline particles of individual particles with a diameter of 5 nm to 100 nm, and use the average number of particles in the 10 field as the metal oxide. The number of crystalline particles (number / micron 2). (3) Light transmittance and haze According to JIS-K7105, the light transmittance and haze were measured using Nippon Denshoku Kogyo Co., Ltd._1 0 0 1DP. (4) Surface resistivity According to II S-K7 1 94, it was measured by the 4-terminal method. The measuring system was tested by Mitsubishi Petrochemical Co., Ltd. Roch Test AMCP-T400. (5) Pen sliding durability test Using a polyacetal resin pen (tip shape: 0.8 mm R), -32-550598 V. Description of the invention (31) 5 · ON load on the touch panel 200,000 times (100,000 round trips) linear sliding test. At this time, the sliding distance is 30 nm and the sliding speed is 60 mm / sec. After the sliding durability test, first, the whitening phenomenon of the sliding portion was visually observed. Further, a 5.0mm pen load was applied to the above-mentioned sliding part note-mark 20mm mark 0, and the number was correctly read for evaluation. Measure the 0N resistance (resistance when the movable electrode (thin film electrode) and fixed electrode are indirect) when the sliding part is pressed with a pen load of 5.0N. (6) Evaluation of the brittleness of the transparent conductive film In the pen sliding durability test of the above touch panel, a scanning probe electron microscope (manufactured by Seiko Instruments Inc., SPI 3 800 / SPA300) was used to measure the atomic force microscope AFM. Observe the range of 100 micron 2 (1 micron x 1 micron) on the surface of the transparent conductive film on the opposite side of the pen's sliding part and the mark. The resolution is 5 1 2 pixels X 5 1 2 pixels. . The scanning speed is performed below 0.5 Hz, and the speed is not fixed unless the resolution is hindered. After the observation, the tilt data was corrected by the accompanying software; after that, the surface shape was evaluated by the accompanying software. The scanner uses FS-20. The cantilever system uses SI-DF20 made of polysiloxane. Also use what is generally available from Seiko Instruments. The observation mode is performed in DFM mode. When the cantilever used for observation cannot be used because the probe contamination reduces the resolution, a new product is usually used. In addition, in order to prevent the deterioration of the wear during the observation period, it can be performed under a condition that the load of the probe is reduced to a limited extent without sacrificing the resolution. ⑺ Adhesion measurement -33-550598 V. Description of the invention (32) A polyester adhesive is used, and an ionic monomer film with a thickness of 40 microns is laminated on a polyethylene terephthalate with a thickness of 75 microns. Laminate for adhesion measurement. The surface of the ionic monomer film of the laminated body for adhesion measurement and the surface of the transparent conductive film of the transparent conductive film faced each other, and were heat-sealed at 13 ° C. The laminated body for measuring the adhesion of the laminated body was peeled from the transparent conductive film by a 180 degree peeling method, and this peeling force was regarded as the adhesive force. The peeling speed at this time was 1,000 mm / min. (Example 1) 3 parts by mass of a copolymerized polyester resin (Toyo) was blended with 100 parts by mass of an acrylic resin containing a photopolymerization initiator (manufactured by Daiichi Seika Chemical Co., Ltd., EXF · 0 U). Made by Textile Corporation, Bailong 200, with a weight average molecular weight of 1 80 00), a solid solvent concentration of 50% by mass is added, and a toluene / MEK (mass ratio of 8: 2) solvent mixture solvent is added and stirred uniformly. Dissolve to prepare a coating solution. A biaxially oriented transparent PET film (manufactured by Toyobo Co., Ltd., A4 340, with a thickness of 188 micrometers) having an easy-to-adhesive layer was applied on both sides to prepare a coating film having a thickness of 5 micrometers. After drying at 180 ° C for 1 minute, the light was irradiated with ultraviolet rays from an ultraviolet irradiation device (manufactured by Agrafocus, UB-042-5 AM-W type) (light amount: 300 mJ / cm 2) To harden the coating. Then, heat treatment was performed at 180 ° C for 1 minute to reduce the volatile components. The biaxially oriented transparent PET film laminated with such a hardened material layer was vacuum-exposed, and the curling process was repeatedly performed in a vacuum chamber. At this time, make -34-550598 before sputtering. 5. Description of the Invention (33) The pressure is 0.007 Pa, and indium oxide containing 5% by mass of tin oxide (Mitsui Metal Mining Corporation's density is 7.1 g / cm 3). As a target, a DC power of 2W / cm 2 was applied. An Ar gas was flowed at a flow rate of HO seem, and a 0 2 gas was flowed at a flow rate of 10 seem. Under a gas atmosphere of 0.4 Pa, a film was formed by a magnetic base plating method. However, because ordinary DCs cannot prevent arcing, a pulse of 5 micron width is applied at a 50 kHz period using RPG-100 manufactured by Inuas, Japan. Furthermore, sputtering was performed at a center roll of 50 ° C. In addition, while constantly measuring the partial pressure of oxygen in the atmosphere with a sputtering program measuring device (SPM200 manufactured by Bodong Co., Ltd.), the flow rate of the oxygen gas is fed back in accordance with the constant oxidation degree in the indium-tin composite oxide film. Meter and DC power. As described above, a 22 nm-thick transparent conductive film made of an indium-tin composite oxide was deposited. < Production of touch panel > This transparent conductive film is used as one side of the panel, and the other side of the panel is formed by plasma CVD on a glass substrate, and the thickness of the indium-tin composite oxide is 20 nm. Transparent conductive thin film ('S500 manufactured by Soda Co., Ltd.) made of a thin film (tin oxide content: 10% by mass). The transparent conductive films of the two panels were oriented in opposite directions, and a configured touch panel was made through an epoxy tree moon bead with a diameter of 30 micrometers. (Example 2) A UV-curable resin ("EXG" manufactured by Daiichi SEIKA Kogyo Co., Ltd.) formed from a mixture of polyester propionate and polyurethane propionate was -35-550598. Explanation of the invention (34) As a hard coating resin on the opposite side of the hardened material layer of the laminated body formed of the biaxially oriented transparent PET film substrate / hardened material layer in Example 1, the gravure printing method was used. After coating and drying the solvent, the thickness of the film after drying was 5 micrometers. After that, it was passed through a 160W ultraviolet irradiation device at a speed of 10 meters / minute to be cured into an ultraviolet curing resin to form a hard coating layer. Next, heat treatment was performed at 180 ° C for 1 minute to reduce the volatile components. In the same manner as in Example 1, an indium-tin composite oxide thin film was formed on the hardened layer of the laminated body formed of such a hard coating layer / biaxially oriented transparent PET film substrate / hardened layer. Furthermore, a touch panel was fabricated using this transparent conductive film in the same manner as in Example 1. (Example 3) A UV-curable resin (EXG) manufactured by Daiichi Seika Chemical Industry Co., Ltd., which is a mixture of a polyester acrylate and a polyurethane acrylate, was used as The hard coating resin on the opposite side of the hardened material layer of the laminated body formed of the axis-oriented transparent PET film substrate / hardened material layer was coated by a gravure printing method and the solvent was dried. The thickness of the dried film was 5 micrometers. Thereafter, a matte surface-forming film (X-manufactured by Toray Co., Ltd.) of a PET film having a fine convex shape formed on the surface and the matte ultraviolet curable resin was laminated. The average surface roughness of the surface shape of such a matte shaped film is 40 μm, the average interval of wave peaks is 160 μm, and the maximum surface roughness is 25 μm. Passing through a 60W ultraviolet irradiation device at a speed of 10 meters / minute,
-36- 550598 五、發明說明（35) 使硬化成紫外線硬化型樹脂，而形成硬質被覆層。接著， 以1 80°C施予加熱處理1分鐘，以進行揮發成分之降低。 和實施例1同樣地做法，使在此種防眩性硬質被覆層/ 雙軸配向透明PET膜基材/硬化物層所成積層體的硬化物 層上，成膜一銦-錫複合氧化物薄膜。進一步，使用此種 透明導電膜，和實施例1同樣地做法而製做出觸控面板。 (實施例4 ) 和實施例3同樣地做法，由防眩性硬質被覆層/雙軸配 向透明PET膜基材/硬化物層/透明導電性薄膜所製做成之 積層體。接著，使在此種防眩性硬質被覆層依序積層ΤΊ〇2 薄膜層（折射率：2.30，膜厚度爲15奈米）、Si 02薄膜層（ 折射率：1 .46，膜厚度爲29奈米）、Ti02薄膜層（折射率 :2.30，膜厚度爲29奈米）、Si 02薄膜層（折射率：1.46 ，膜厚度爲87奈米）使形成反射處理層。就Ti02薄膜層之 形成而言，使用鈦標靶，利用直流磁性賤鍍法，真空度爲 0 . 27 Pa，以流速爲5000 seem流通Ar氣體，以流速爲 80 seem流通02氣體。又，以設有基板背面上之0°C冷卻 輥，將透明塑膠膜予以冷卻。此時所供給的電力爲7 · 8W/ 公分2，動率爲23奈米•公尺/分鐘。 就Si 02薄膜層之形成而言，使用矽標靶’利用直流磁性 賤鍍法，真空度爲0 . 27 Pa，以流速爲5000 s c cm流通Ar 氣體，以流速爲80 seem流通〇2氣體。又’以設有基板背 面上之冷卻輥，將透明塑膠膜予以冷卻。此時所供給 -37 - 550598 五、發明說明（36) 的電力爲7.8W/公分2 ’動率爲23奈米•公尺/分鐘。更且 ，使用此種透明導電膜來做爲另一面之面板’以和實施例 1同樣地做法而製做成觸控面板。 (實施例5 ) 和實施例1同樣地做法所製做的透明導電膜，透過丙烯 酸系黏著劑而貼附在厚度爲1 . 〇毫米之聚碳酸酯製之薄片 上，以製做成一透明導電性積層薄片。使用此種透明導電 性積層薄片來做爲固定電極，使用實施例2透明導電膜之 可動電極，以和實施例1同樣地做法而製做成觸控面板。 (實施例6) 除了爲使雙軸配向透明PET膜真空曝露，於真空室中反 復地進行捲曲處理時中心輥之溫度，以及濺鍍I TO時中心 輥之溫度差爲20t以外，和實施例1同樣地做法而製做成 透明導電膜。更且，使用此種透明導電性積層薄片，以和 實施例1同樣地做法而製做成觸控面板。 (實施例7 ) 除了於真空室中反復地進行捲曲處理時中心輥之溫度， 以及濺鍍IT0時壓力爲〇.〇〇〇7Pa，曝露時間爲30分鐘， 而於真空室中反復地進行捲曲處理時中心輥之溫度爲5〇C ’以及濺鍍I TO時中心輥之溫度爲60°C以外，和實施例1 同樣地做法而製做成透明導電膜。更且，使用此種透明導 電性積層薄片，以和實施例1同樣地做法而製做成觸控面 板。 -38 - 550598 五、發明說明（37) (比較例1 ) 除了省略該以18(TC加熱處理1分鐘及真空曝露處理10 分鐘以減低揮發成分之程序以外，和實施例1同樣地做法 而製做成透明導電膜。更且，使用此種透明導電性積層薄 片，以和實施例1同樣地做法而製做成觸控面板。 (比較例2) 除了形成硬化物層用之塗液中不添加共聚合聚酯樹脂以 外，和實施例1同樣地做法而製做成透明導電膜。更且， 使用此種透明導電性積層薄片，以和實施例1同樣地做法 而製做成觸控面板。 (比較例3 ) 在實施例1中，除了在形成硬化物層用之塗液中，添加 相對於1 00質量份之含有光聚合起始劑的丙烯酸系樹脂計 ，爲30質量份之共聚合聚酯樹脂以外，和實施例1同樣 地做法而製攸成透明導電膜。更且，使用此種透明導電性 積層薄片，以和實施例1同樣地做法而製做成觸控面板。 (t匕較例4 ) 製做和實艇例1同樣之透明導電膜，除了以20 0 °C之烘 爐加熱5分鐘以外，和實施例1同樣地做法而製做成透明 導電膜。更i，使用此種透明導電性積層薄片，以和實施 例J 1同樣地攸法而製做成觸控面板。 將在實施例1〜9和比較例1〜4中所得到的透明導電膜及 觸控面板之fP量結果，示於表1中。-36- 550598 V. Description of the invention (35) The hard coating layer is formed by curing into a UV-curable resin. Next, heat treatment was performed at 1 80 ° C. for 1 minute to reduce the volatile components. In the same manner as in Example 1, an indium-tin composite oxide was formed on the hardened layer of the multilayer body formed of such an anti-glare hard coating layer / biaxially oriented transparent PET film substrate / hardened layer. film. Further, a touch panel was fabricated using this transparent conductive film in the same manner as in Example 1. (Example 4) A laminated body made of an anti-glare hard coating layer / biaxially oriented transparent PET film substrate / cured material layer / transparent conductive film in the same manner as in Example 3. Next, a thin film layer (refractive index: 2.30, film thickness of 15 nm) and a Si 02 film layer (refractive index: 1.46, film thickness of 29) were sequentially laminated on the anti-glare hard coating layer. Nanometer), Ti02 thin film layer (refractive index: 2.30, film thickness of 29 nanometers), Si 02 thin film layer (refractive index: 1.46, film thickness of 87 nanometers) to form a reflection treatment layer. As for the formation of the Ti02 thin film layer, a titanium target was used, a direct current magnetic base plating method was used, and the vacuum degree was 0.27 Pa. Ar gas was flowed at a flow rate of 5000 seem, and 02 gas was flowed at a flow rate of 80 seem. The transparent plastic film was cooled by a 0 ° C cooling roller provided on the back surface of the substrate. The power supplied at this time was 7.8 W / cm2 and the momentum was 23 nanometers / meter / minute. As for the formation of the Si 02 thin film layer, a silicon target was used to utilize a direct current magnetic base plating method with a vacuum degree of 0.27 Pa, Ar gas was flowed at a flow rate of 5000 s c cm, and O 2 gas was flowed at a flow rate of 80 seem. Also, a transparent plastic film is cooled by a cooling roller provided on the back surface of the substrate. -37-550598 supplied at this time V. The electric power of invention description (36) is 7.8W / cm 2 ′ Momentum is 23nm • m / min. Furthermore, a touch panel is manufactured in the same manner as in Example 1 by using such a transparent conductive film as a panel on the other side. (Example 5) A transparent conductive film prepared in the same manner as in Example 1 was attached to a sheet made of polycarbonate having a thickness of 1.0 mm through an acrylic adhesive to make it transparent. Conductive laminated sheet. The transparent conductive laminated sheet was used as a fixed electrode, and the movable electrode of the transparent conductive film of Example 2 was used to manufacture a touch panel in the same manner as in Example 1. (Example 6) Except for the vacuum exposure of the biaxially oriented transparent PET film, the temperature of the center roller during repeated crimping treatment in a vacuum chamber, and the temperature difference of the center roller during sputtering I TO was 20t, and the example 1 In the same manner, a transparent conductive film is produced. Furthermore, a touch panel was manufactured in the same manner as in Example 1 by using such a transparent conductive laminated sheet. (Example 7) Except for the temperature of the center roll when the crimping process was repeatedly performed in a vacuum chamber, and the pressure during sputtering IT0 was 0.007 Pa, the exposure time was 30 minutes, and the crimping was repeatedly performed in a vacuum chamber. The temperature of the center roll during processing was 50 ° C. and the temperature of the center roll during sputtering I TO was other than 60 ° C. In the same manner as in Example 1, a transparent conductive film was prepared. Furthermore, a touch panel was produced in the same manner as in Example 1 using such a transparent conductive laminated sheet. -38-550598 V. Description of the invention (37) (Comparative Example 1) The procedure is the same as that of Example 1 except that the procedure of reducing the volatile components by 18 (TC heating treatment for 1 minute and vacuum exposure treatment for 10 minutes) is omitted. A transparent conductive film was made. Furthermore, a touch panel was manufactured in the same manner as in Example 1 using such a transparent conductive laminated sheet. (Comparative Example 2) A transparent conductive film was prepared in the same manner as in Example 1 except that the copolymerized polyester resin was added. Furthermore, a touch panel was manufactured in the same manner as in Example 1 by using such a transparent conductive laminated sheet. (Comparative Example 3) In Example 1, a total of 30 parts by mass was added to 100 parts by mass of an acrylic resin containing a photopolymerization initiator, in addition to the coating solution for forming a cured material layer. Except for the polymerized polyester resin, a transparent conductive film was prepared in the same manner as in Example 1. Furthermore, a touch panel was manufactured in the same manner as in Example 1 by using such a transparent conductive laminated sheet. t dagger comparison example 4) making and The transparent conductive film similar to Example 1 was prepared in the same manner as in Example 1 except that it was heated in an oven at 200 ° C for 5 minutes. Furthermore, using this transparent conductive laminated sheet, A touch panel was manufactured in the same manner as in Example J 1. The results of the fP amount of the transparent conductive film and the touch panel obtained in Examples 1 to 9 and Comparative Examples 1 to 4 are shown in the table. 1 in.
-39 - 550598 五、發明說明（38) 依照表1之結果，在實施例1〜9中所得到的透明導電膜 及觸控面板，該透明導電性薄膜之廣領域及窄領域中之均 方平均面粗糖度（Rms) ’係均滿足本發明所規定之要件。 因此，使用此種透明導電膜之觸控面板，於使用聚縮醛樹 脂製之筆（前端形狀：0 · 8毫米R )，以5 . ON之荷重進行 2 0萬次之直線滑動試驗後，在透明導電性薄膜上沒有白化 現象，0N電阻也無異常。又，也可正確地確認出所輸入記 號〇印。 另一方面，在比較例1〜4中所記載的透明導電膜及觸 控面板，該透明導電性薄膜之廣領域及窄領域中之均方平 均面粗糙度（Rms )，係均不能滿足本發明所規定之要件。 因此，使用此種透明導電膜之觸控面板，於使用聚縮醛樹 月旨製之筆（前端形狀：0.8毫米R)，以5.0N之荷重進行 2〇萬次之直線滑動試驗後，在透明導電性薄膜上會生成白 化，0N電阻也發生異常。又，無法正確地確認出所輸入記 號〇印。 此外，在比較例3中所記載的透明導電膜之光透過率減 低，霧値也變高，因而無法得到實用上充分的光學特性。 又，使用在比較例3中所記載的透明導電膜之觸控面板， 於使用聚縮醛樹脂製之筆（前端形狀：0 . 8毫米 R )，以 5 · ON之荷重進行20萬次之直線滑動試驗後，在透明導電 性薄膜上會生成白化，不僅ON電阻也發生異常，而且無 法正確地確認出所輸入記號◦印，所以不能達成實用而充-39-550598 5. Explanation of the invention (38) According to the results in Table 1, the transparent conductive film and the touch panel obtained in Examples 1 to 9, the mean square in a wide field and a narrow field of the transparent conductive film. The average surface sugar content (Rms) 'all meets the requirements specified in the present invention. Therefore, a touch panel using such a transparent conductive film was subjected to a linear sliding test of 200,000 times using a pen made of polyacetal resin (front end shape: 0.8 mm R) with a load of 5. ON. There is no whitening phenomenon on the transparent conductive film, and there is no abnormality in the 0N resistance. It is also possible to correctly confirm the entered mark 〇. On the other hand, in the transparent conductive film and the touch panel described in Comparative Examples 1 to 4, the mean square average surface roughness (Rms) of the transparent conductive film in a wide area and a narrow area did not satisfy this requirement. Elements required by the invention. Therefore, a touch panel using such a transparent conductive film was subjected to a linear sliding test of 200,000 times under a load of 5.0 N using a pen made of polyacetal tree (tip shape: 0.8 mm R). Whitening occurs on the transparent conductive film, and abnormality occurs in the 0N resistance. In addition, the entered mark 0 cannot be confirmed correctly. In addition, the transparent conductive film described in Comparative Example 3 had a reduced light transmittance and high haze, so that practically sufficient optical characteristics could not be obtained. In addition, the touch panel using the transparent conductive film described in Comparative Example 3 was subjected to a stroke of 200,000 times using a pen made of polyacetal resin (tip shape: 0.8 mm R) with a load of 5 · ON. After the linear sliding test, whitening is generated on the transparent conductive film. Not only the ON resistance is abnormal, but also the input mark cannot be accurately confirmed. Therefore, it cannot be practical and sufficient.
-40 - 550598 五、發明說明C 39) 分的性能。 均方平均面粗 糙度（奈米） 光透 霧値 表面電 附著力 筆滑動耐久性 過率 (%) 阻率 (N/15毫米） 滑動部 初期ON 試驗後 廣領域 窄領域 (%) (Ω/Π) 分白化 電阻 ON電阻 (kQ) (kQ) 實施例1 8.2 0.8 88.1 1.2 250 1.5 無 2.0 2.0 實施例2 17.2 0.9 87.9 1.7 250 1.5 Μ 2.0 2.0 實施例3 5.2 0.8 88.3 0.8 250 1.5 並 2.0 2.0 實施例4 8.2 0.8 88.5 5.9 250 1.5 2.0 2.0 實施例5 8.2 0.8 87.3 5.9 250 1.5 Μ 2.0 2.0 實施例6 8.2 0.8 89.8 1.5 250 1.5 並 2.0 2.0 實施例7 8.2 0.8 88.1 1.7 250 1.5 Μ 2.0 2.0 實施例8 8.1 0.4 88.5 0.8 250 1.5 姐 >N 2.0 2.2 實施例9 8.3 1.6 88.1 0.9 250 1.5 無 2.0 2.0 上匕較例1 8.0 0.2 88.5 1.2 250 1.5 有 2.0 >1000 tt：較例2 2.2 0.7 88.8 1.2 250 1.4 有 2.0 >1000 比^較例3 25.5 0.8 83.6 15.2 250 1.5 有 2.0 2.0 tb較例4 8.2 2.5 88.1 1.2 250 1.5 有 2.0 2.0 (實施例1 0 ) 相對於100質量份之含有光聚合起始劑之丙烯酸系樹脂 (大日精化工業公司製，精化物EXF-01J)，依照使固形分 鎢度爲50質量％，而加入甲苯/MEK(質量比爲8 : 2)之做爲 -41 - 550598 五、發明說明（40 ) 溶劑的混合物溶媒，均勻地攪拌使溶解而調製成塗布液。 於兩面上具有易接著層之雙軸配向透明PET膜（東洋紡 績公司製，A4 340，厚度爲188微米）上，塗布上述所調製 的塗布液，使成爲厚度爲5微米之塗膜。於180°C下進行 乾燥1分鐘後，利用紫外線照射裝置（艾格拉弗庫斯公司 製，UB- 042 - 5AM-W型）之紫外線來照射（光量：300毫焦耳 /公分2)，使塗膜硬化。接著，以iSOt：施予加熱處理1分 鐘，以進行揮發成分之降低。 又，使積層此種硬化物層之雙軸配向透明PET膜真空曝 露，於真空室中反復地進行捲曲處理。此時，使濺鍍前之 壓力爲0.002Pa，曝露時間爲20分鐘。又，中心輥之溫度 爲 40°C。 接著，在硬化物層上形成由銦-錫複合氧化物所構成的 透明導電性薄膜。此時，濺鍍前之壓力爲0.0001 Pa，以含 有5質量％氧化錫之氧化銦（三井金屬礦業公司製，密度爲 7 · 1克/公分3 )做爲標IE，施加2W /公分2之DC電力。又 ，以流速爲130 seem流通Ar氣體，以流速爲10 seem流 通〇2氣體，於0.4Pa之氣氛圍下，利用磁性賤鍍法而使成 膜。但是，因爲通常之DC不能防止電弧放電，而使用日 本伊奴阿斯製RPG-100，以50kHz週期而施加5微米幅度 之脈衝。再者，於中心輥爲50°C下，來進行濺鍍。 又，一邊以濺鍍程序測定器（伯東公司製，SPM200 )時常 觀測氛圍氣體之氧氣分壓，一邊依照使銦-錫複合氧化物 -42 - 550598 五、發明說明（41) 薄膜中之氧化度爲一定之狀態，來回饋氧氣氣體之流量計 和DC電源。根據以上之做法，使堆積成厚度爲22奈米之 由銦-錫複合氧化物所構成的透明導電性薄膜。 <觸控面板之製作〉 使用此種透明導電膜來做爲面板之一面，面板另一面則 使用在玻璃基板上以電漿CVD法，由厚度爲20奈米之銦-錫複合氧化物薄膜（氧化錫含有量：1 〇質量所成的透明 導電性薄膜（日本曹達公司製，S500 )。使此2枚面板之透 明導電性薄膜成相對方向，透過直徑爲30微米之環氧樹 月旨珠而製做出經配置的觸控面板。 (實施例11 ) 相對於1 0 0質量份之含有光聚合起始劑之丙烯酸系樹脂 (大日精化工業公司製，精化物EXF - 0 1 J )，摻混3質量份 之共聚合聚酯樹脂（東洋紡績公司製，拜龍200，重量平均 分子量爲1 8000 )，依照使固形分濃度爲50質量％，而加入 甲苯/MEK(質量比爲8 : 2)之溶劑之混合物溶媒，均勻地攪 伴使溶解而調製成塗布液。 在實施例1 0中除了使用上述塗布液來做爲硬化物層形 成用之塗覆液以外，和實施例1 〇同樣地做法而製成透明 導電膜。進一步，使用此種透明導電膜，和實施例1同樣 也做法而製做出觸控面板。 (實施例1 2 ) 將由聚酯丙烯酸酯和聚胺基甲酸酯丙烯酸酯之混合物所 -43- 550598 五、發明說明（42) 开夕成的紫外線硬化樹脂（大日精化工業公司製，EXG)來做 爲在貫施例1〇中之由雙軸配向透明PET膜基材/硬化物層 所成積層體的在硬化物層相反面上之硬質被覆層樹脂，藉 由E1版印刷法而塗布、使溶劑乾燥，乾燥後之膜厚度爲5 微米。之後’以1〇公尺/分鐘之速度通過l6〇W之紫外線 照射裝置’使硬化成紫外線硬化型樹脂，而形成硬質被覆 層。接著’以180°C施予加熱處理1分鐘，以進行揮發成 分之降低。 和實施例1 〇同樣地做法，使在此種硬質被覆層/雙軸配 向I透明PET膜基材/硬化物層所成積層體的硬化物層上， 成膜一銦-錫複合氧化物薄膜。進一步，使用此種透明導 電膜’和實施例1 〇同樣地做法而製做出觸控面板。 (實施例1 3 ) 將由聚酯丙烯酸酯和聚胺基甲酸酯丙烯酸酯之混合物所 形成的紫外線硬化樹脂（大日精化工業公司製，EXG)來做 爲在實施例10中之由雙軸配向透明PET膜基材/硬化物層 所成積層體的在硬化物層相反面上之硬質被覆層樹脂，藉 由凹版印刷法而塗布、使溶劑乾燥，乾燥後之膜厚度爲5 微米。之後，使表面與霧面紫外線硬化型樹脂之形成微細 凸形狀之PET膜的霧面賦形膜（東麗公司製，X)接著而積 層。此種霧面賦形膜之表面形狀之平均面粗糙度係爲0.40 微米，波峰之平均間隔爲160微米，最大表面粗糙度爲25 微米。 -44 - 550598 五、發明說明（43) 以10公尺/分鐘之速度通過160W之紫外線照射裝置， 使硬化成紫外線硬化型樹脂，而形成硬質被覆層。接著， 以1 8Qt施予加熱處理1分鐘，以進行揮發成分之降低。 和實施例1 0同樣地做法，使在此種防眩性硬質被覆層/ 雙軸配向透明PET膜基材/硬化物層所成積層體的硬化物 層上，成膜一銦-錫複合氧化物薄膜。進一步，使用此種 透明導電膜，和實施例1 0同樣地做法而製做出觸控面板 〇 (實施例14) 和實施例1 3同樣地做法，由防眩性硬質被覆層/雙軸配 向透明PET膜基材/硬化物層/透明導電性薄膜所製做成之 積層體。接著，使在此種防眩性硬質被覆層依序積層Ti02 薄膜層（折射率：2.30，膜厚度爲15奈米）、Si02薄膜層（ 折射率：1.46，膜厚度爲29奈米）、Ti02薄膜層（折射率 :2.30，膜厚度爲29奈米）、Si 02薄膜層（折射率：1.46 ，膜厚度爲87奈米）使形成反射處理層。就了丨02薄膜層之 形成而言，使用鈦標靶，利用直流磁性賤鍍法，真空度爲 0 . 27 Pa，以流速爲5000 seem流通Ar氣體，以流速爲80 seem流通02氣體。又，以設有基板背面上之〇°C冷卻輥， 將透明塑膠膜予以冷卻。此時所供給的電力爲7 · 8 W /公分 2，動率爲23奈米•公尺/分鐘。 就S i 02薄膜層之形成而言’使用矽標靶，利用直流磁性 賤鍍法，真空度爲〇·27 Pa ’以流速爲5000 seem流通Αί α - 550598 五、發明說明（44) 氣體，以流速爲80 seem流通02氣體。又，以設有基板背 面上之0 °C冷卻輥，將透明塑膠膜予以冷卻。此時所供給 的電力爲7.8W/公分2，動率爲23奈米•公尺/分鐘。更且 ，使用此種透明導電膜來做爲另一面之面板’以和實施例 1 0同樣地做法而製做成觸控面板。 (實施例1 5 ) 和實施例1 0同樣地做法所製做的透明導電膜，透過丙 燏酸系黏著劑而貼附在厚度爲1 . 0毫米之聚碳酸酯製之薄 片上，以製做成一透明導電性積層薄片。使用此種透明導 電性積層薄片來做爲固定電極，使用實施例1 3透明導電 膜之可動電極，以和實施例1 0同樣地做法而製做成觸控 面板。 (實施例1 6 ) 除了爲使雙軸配向透明PET膜真空曝露，於真空室中反 復地進行捲曲處理時中心輥之溫度，以及濺鍍ITO時中心 車毘之溫度差爲20°C以外，和實施例10同樣地做法而製做 成透明導電膜。更且，使用此種透明導電性積層薄片，以 手口實施例1 0同樣地做法而製做成觸控面板。 (實施例1 7 ) 除了於真空室中反復地進行捲曲處理時中心輥之溫度， 以及濺鍍ITO時壓力爲0.0007Pa，曝露時間爲30分鐘， 而於真空室中反復地進行捲曲處理時中心輥之溫度爲5(TC ，以及濺鍍I TO時中心輥之溫度爲60t以外，和實施例 -46- 550598 五、發明說明（45) 1〇同樣地做法而製做成透明導電膜。更且’使用此種透明 導電性積層薄片，以和實施例1 〇同樣地做法而製做成觸 控面板。 (實施例1 8 ) 除了於真空室中反復地捲曲時倂用紅外線加熱器以外， 禾口實施例1 7同樣地做法而製做成透明導電膜。此時加熱 器之輸入電力爲40 0W/公尺2·分鐘。更且，使用此種透明 導電性積層薄片，以和實施例1 〇同樣地做法而製做成觸 控面板。 (實施例1 9 ) 除了將達lOOOPa之氧氣氣體導入經減壓至O.lPa之真 空室的氛圍氣中，以160°C進行加熱處理2分鐘以外，和 實施例11同樣地做法而製做成透明導電膜。更且，使用 此種透明導電性積層薄片，以和實施例11同樣地做法而 製做成觸控面板。 (比較例5 ) 除了省略該以180°C加熱處理1分鐘及真空曝露處理10 分鐘以減低揮發成分之程序以外，和實施例1 0同樣地做 法而製做成透明導電膜。更且，使用此種透明導電性積層 薄片，以和實施例1 0同樣地做法而製做成觸控面板。 (t匕較例6 ) 除了形成硬化物層用之塗液中不添加共聚合聚酯樹脂以 夕^ ’和實施例1 0同樣地做法而製做成透明導電膜。更且 -47- 550598 五、發明說明（46) ，使用此種透明導電性積層薄片，以和實施例1 〇同樣地 做祛而製做成觸控面板。 (t匕較例7 ) 製做和實施例10同樣之透明導電膜，除了以200t之烘 爐加熱5分鐘以外，和實施例1 0同樣地做法而製做成透 明導電膜。更且，使用此種透明導電性積層薄片，以和實 施例10同樣地做法而製做成觸控面板。 將在實施例1〇〜1 7和比較例5〜7中所得到的透明導 電膜及觸控面板之評量結果，示於表2中。 依照表2之結果，使用滿足本發明範圍之在實施例10〜 1 7中所得到的透明導電膜或透明導電性薄片之觸控面板， 於使用聚縮醛樹脂製之筆（前端形狀：0.8毫米R )，以 5 . ON之荷重進行20萬次之直線滑動試驗後，並沒有生成 白化現象，ON電阻也無異常。又，也可正確地確認出所輸 入記號〇印。更且，在原子間力顯微鏡上之滑動部及記號 〇印筆記部分之評量，也無異常發生。 另一方面，在透明導電性薄膜中並不存在由金屬氧化物 所構成之結晶粒子，使用比較例5及6中所記載的透明導 電膜之觸控面板，於使用聚縮醛樹脂製之筆（前端形狀： 0 · 8毫米R)，以5.0N之荷重進行20萬次之直線滑動試 驗後，在透明導電性薄膜上會生成白化，ON電阻也發生異 常。又，無法正確地確認出所輸入記號〇印。更且，在原 子間力顯微鏡上之滑動部及記號〇印筆記部分之評量，也 -48- 550598 五、發明說明（47) 可觀察到裂痕發生。 此外，在透明導電性薄膜中之由金屬氧化物所構成的結 晶粒子個數超出本發明之上限時，使用比較例7中所記載 的透明導電膜之觸控面板，於使用聚縮醛樹脂製之筆（前 端形狀：0.8毫米R)，以5.0N之荷重進行20萬次之直 線滑動試驗後，在透明導電性薄膜上會生成白化，0N電阻 也發生異常。又，無法正確地確認出所輸入記號〇印，因 而無法滿足實用上之充分的性能。更且，在原子間力顯微 鏡上之滑動部及記號〇印筆記部分之評量，在滑動部上可 觀察到裂痕發生，在記號〇印筆記部分也可觀察到裂痕發 生° -49 - 550598 五、發明說明（48) 表2 結晶粒子·數 (個/微米2) 光透 霧値 表面電阻率 附著力 筆滑動耐久性 過率 (%) (Ω/ϋ) (Ν/15毫米） 滑動部 初期0N 試驗後 (%) 分白化 電阻 0N電阻 (kQ) (kQ) 實施例10 400 88.3 0.8 250 1.5 無 2.0 2.2 實施例11 400 88.1 1.2 250 1.5 無 2.0 2.0 實施例12 400 88.5 1.5 250 1.5 Μ •Μ、、 2.0 2.2 實施例13 400 87.3 5.9 250 1.5 4nr 無 2.0 2.2 實施例14 400 89.8 5.9 250 1.5 無 2.0 2.2 實施例15 400 88.1 1.7 250 1.5 姐 2.0 2.2 實施例16 200 S8.5 0.8 250 1.5 無 2.0 2.6 實施例17 800 88.1 0.9 250 1.5 4nL 無 2.0 2.1 實施例18 880 88.2 0.9 250 1.5 無 2.0 2.1 實施例19 850 88.5 1.2 260 1.5 無 2.0 2.0 比較例5 0 88.5 1.2 250 1.5 有 2.0 >1000 比較例6 0 88.8 1.2 250 1.4 有 2.0 >1000 比較例7 1400 88.1 1.2 250 1.5 4cpi 2.0 2.0 【發明效果】 本發明之透明導電性膜，其係一種在透明塑膠基材上’ 依序積層以硬化型樹脂做爲主要構成成分之硬化物層’以 及以金屬氧化物爲主要構成成分之透明導電性薄膜’前述 透明導電性膜之透明導電性薄膜面係具有特定之均方平均 面粗糙度，或者其係由特定數量之在透明導電性薄膜中之 -50- 550598 五、發明說明（49) 特定粒徑的金屬氧化物構成的結晶粒子所形成；因而，當 以筆施壓在用筆輸入之使用前述透明導電性膜的觸控面板 時，既不會使對向之透明導電性薄膜彼此間相接觸、也不 會產生剝離、裂痕等而具有高度優良之筆滑動耐久性，而 且具有優良的位置檢測精度及顯示品質。從而，適合於使 用來做爲以筆輸入之觸控面板。 -51 --40-550598 V. Description of invention C 39) points. Mean square average surface roughness (nanometer) Light-transmitting haze surface Electro-adhesive pen Sliding endurance rate (%) Resistivity (N / 15 mm) Wide area narrow area (%) (Ω) after initial ON test of the sliding part / Π) Whitening resistance ON resistance (kQ) (kQ) Example 1 8.2 0.8 88.1 1.2 250 1.5 No 2.0 2.0 Example 2 17.2 0.9 87.9 1.7 250 1.5 M 2.0 2.0 Example 3 5.2 0.8 88.3 0.8 250 1.5 and 2.0 2.0 Example 4 8.2 0.8 88.5 5.9 250 1.5 2.0 2.0 Example 5 8.2 0.8 87.3 5.9 250 1.5 M 2.0 2.0 Example 6 8.2 0.8 89.8 1.5 250 1.5 and 2.0 2.0 Example 7 8.2 0.8 88.1 1.7 250 1.5 M 2.0 2.0 Example 8 8.1 0.4 88.5 0.8 250 1.5 sister > N 2.0 2.2 Example 9 8.3 1.6 88.1 0.9 250 1.5 No 2.0 2.0 Comparative example 1 8.0 0.2 88.5 1.2 250 1.5 Yes 2.0 > 1000 tt: Comparative example 2 2.2 0.7 88.8 1.2 250 1.4 with 2.0 > 1000 ratio ^ Comparative Example 3 25.5 0.8 83.6 15.2 250 1.5 Yes 2.0 2.0 tb Comparative Example 4 8.2 2.5 88.1 1.2 250 1.5 Yes 2.0 2.0 (Example 10) Contains 100 parts by mass of photopolymerization initiation Agent of acrylic resin (Dainichi Chemical Industry Made by the company, refined compound EXF-01J), and the toluene / MEK (mass ratio 8: 2) is added as -41-550598 in accordance with the solid tungsten content of 50% by mass. 5. Description of the invention (40) The mixture solvent is uniformly stirred and dissolved to prepare a coating solution. A biaxially oriented transparent PET film (manufactured by Toyobo Co., Ltd., A4 340, with a thickness of 188 micrometers) having an easy-to-adhesive layer was applied on both sides to prepare a coating film having a thickness of 5 micrometers. After drying at 180 ° C for 1 minute, the coating was irradiated with ultraviolet rays (light quantity: 300 millijoules / cm 2) using an ultraviolet irradiation device (manufactured by Agrafocus, UB-042-5AM-W). The film is hardened. Next, iSOt: heat treatment was performed for 1 minute to reduce the volatile components. The biaxially oriented transparent PET film laminated with such a hardened material layer was vacuum-exposed, and the curling process was repeatedly performed in a vacuum chamber. At this time, the pressure before sputtering was 0.002 Pa, and the exposure time was 20 minutes. The temperature of the center roll was 40 ° C. Next, a transparent conductive film made of an indium-tin composite oxide is formed on the hardened layer. At this time, the pressure before sputtering was 0.0001 Pa. Indium oxide containing 5% by mass of tin oxide (manufactured by Mitsui Metals Mining Corporation, density: 7.1 g / cm3) was used as the standard IE, and 2W / cm2 was applied. DC power. Further, Ar gas was flowed at a seeming flow rate of 130, and O2 gas was flowed at a seeming flow rate of 10, and the film was formed by a magnetic base plating method under a gas atmosphere of 0.4 Pa. However, because ordinary DCs cannot prevent arcing, a pulse of 5 micron width is applied at a 50 kHz period using a Japanese RPG-100 made by Inuas. In addition, sputtering was performed at a center roll of 50 ° C. In addition, while constantly measuring the partial pressure of oxygen in the atmosphere with a sputtering program measuring device (SPM200 manufactured by Bodong Co., Ltd.), the indium-tin composite oxide-42-550598 was used in accordance with the description of the invention (41) The degree of oxidation in the film For a certain state, the flow meter and DC power supply of oxygen gas are fed back and forth. As described above, a 22 nm-thick transparent conductive film made of an indium-tin composite oxide was deposited. < Production of touch panel> This transparent conductive film is used as one side of the panel, and the other side of the panel is formed by a plasma CVD method on a glass substrate with an indium-tin composite oxide film with a thickness of 20 nm (Tin oxide content: 10 mass transparent conductive film (manufactured by Soda Co., Ltd., S500). The transparent conductive films of the two panels are oriented in opposite directions, and an epoxy tree with a diameter of 30 micrometers is transmitted. (Embodiment 11) A 100% by mass acrylic resin containing a photopolymerization initiator (manufactured by Daiichi Seika Chemical Co., Ltd., EXF-0 1 J) ), 3 parts by mass of a copolymerized polyester resin (made by Toyobo Corporation, Bailong 200, with a weight average molecular weight of 1 8000), and toluene / MEK (mass ratio of 50% by mass) 8: 2) A mixture of solvents and solvents was uniformly stirred and dissolved to prepare a coating liquid. In Example 10, the above coating liquid was used as a coating liquid for forming a hardened layer, and the embodiment 1 〇 It is made in the same way The transparent conductive film is used. Further, a touch panel is made by using this transparent conductive film in the same manner as in Example 1. (Example 1 2) A mixture of polyester acrylate and polyurethane acrylate will be used. -43- 550598 V. Description of the invention (42) Kai-sei ’s UV-curable resin (Dainichi Seika Chemical Co., Ltd., EXG) is used as the biaxially oriented transparent PET film substrate in Example 10 / The hard coating resin of the laminated body formed on the hardened layer on the opposite side of the hardened layer was applied by the E1 printing method, and the solvent was dried. The thickness of the dried film was 5 microns. After that, the thickness was 10 meters. A speed of 1 / minute was cured by a UV irradiation device of 160W to form a hard coating layer. Then, a heat treatment was performed at 180 ° C for 1 minute to reduce the volatile components. And Examples 1〇 In the same manner, an indium-tin composite oxide thin film is formed on the hardened layer of the laminated body formed of such a hard coating layer / biaxially oriented I transparent PET film substrate / hardened layer. Further, Using this transparent conductive film 'A touch panel was produced in the same manner as in Example 10. (Example 1 3) A UV-curable resin (Dainichi Chemical Industry Co., Ltd.) formed from a mixture of polyester acrylate and polyurethane acrylate EXG) was used as the hard coating resin on the opposite side of the hardened material layer of the laminated body formed of the biaxially oriented transparent PET film substrate / hardened material layer in Example 10 by the gravure printing method. After coating and drying the solvent, the thickness of the dried film was 5 micrometers. Then, a matte shaped film (made by Toray Co., Ltd.) of a PET film having a fine convex shape was formed on the surface and the matte ultraviolet curable resin. And lamination. The average surface roughness of the surface shape of this matte shaped film is 0.40 microns, the average interval of the wave peaks is 160 microns, and the maximum surface roughness is 25 microns. -44-550598 5. Description of the invention (43) Passing through a 160W ultraviolet irradiation device at a speed of 10 meters / minute, it is cured into an ultraviolet curing resin to form a hard coating layer. Next, heat treatment was performed at 18 Qt for 1 minute to reduce the volatile components. In the same manner as in Example 10, an indium-tin composite oxide was formed on the hardened layer of the multilayer body formed of such an anti-glare hard coating layer / biaxially oriented transparent PET film substrate / hardened layer.物 Film. Furthermore, using such a transparent conductive film, a touch panel was fabricated in the same manner as in Example 10 (Example 14) and in the same manner as in Example 13 with an anti-glare hard coating layer / biaxial alignment Laminated body made of transparent PET film substrate / cured material layer / transparent conductive film. Next, a Ti02 thin film layer (refractive index: 2.30, film thickness of 15 nm), a Si02 thin film layer (refractive index: 1.46, film thickness of 29 nm), and Ti02 were sequentially laminated on the anti-glare hard coating layer. A thin film layer (refractive index: 2.30, film thickness of 29 nanometers) and a Si 02 thin film layer (refractive index: 1.46, film thickness of 87 nanometers) make a reflection treatment layer. In terms of the formation of the 02 thin film layer, a titanium target was used, and a direct current magnetic base plating method was used, with a vacuum of 0.27 Pa. Ar gas was flowed at a flow rate of 5000 seem, and 02 gas was flowed at a flow rate of 80 seem. The transparent plastic film was cooled with a 0 ° C cooling roller provided on the back surface of the substrate. The power supplied at this time was 7.8 W / cm 2 and the momentum was 23 nm · m / min. Regarding the formation of the Si 02 thin film layer, 'using a silicon target, using a DC magnetic base plating method, and a vacuum degree of 0.27 Pa', flowing at a flow rate of 5000 seem Αί α-550598 5. Description of the invention (44) Gas, 02 gas flows at a flow rate of 80 seem. The transparent plastic film was cooled by a 0 ° C cooling roller provided on the back surface of the substrate. The power supplied at this time was 7.8 W / cm2 and the momentum was 23 nanometers / meter / minute. Furthermore, using such a transparent conductive film as a panel on the other side, a touch panel is manufactured in the same manner as in Example 10. (Example 15) A transparent conductive film prepared in the same manner as in Example 10 was attached to a polycarbonate sheet having a thickness of 1.0 mm through a propionic acid-based adhesive to produce Make a transparent conductive laminated sheet. The transparent conductive laminated sheet was used as a fixed electrode, and the movable electrode of the transparent conductive film of Example 13 was used to make a touch panel in the same manner as in Example 10. (Example 16) Except for the vacuum exposure of the biaxially oriented transparent PET film, the temperature of the center roll when the crimping process was repeatedly performed in a vacuum chamber, and the temperature difference between the center car adjacent to the ITO during sputtering was 20 ° C. A transparent conductive film was produced in the same manner as in Example 10. Furthermore, using such a transparent conductive laminated sheet, a touch panel was fabricated in the same manner as in Example 10 of the hand mouth. (Example 17) Except for the temperature of the center roll when the crimping process was repeatedly performed in a vacuum chamber, and the pressure was 0.0007 Pa when the ITO was sputtered, and the exposure time was 30 minutes, the center was repeatedly performed when the crimping process was performed in a vacuum chamber. The temperature of the roll was 5 ° C, and the temperature of the center roll was 60t when sputtering I TO, and the transparent conductive film was made in the same manner as in Example-46-550598 V. Invention Description (45) 10. In addition, a touch panel was manufactured in the same manner as in Example 10 using such a transparent conductive laminate sheet. (Example 18) Except for using an infrared heater when repeatedly rolled in a vacuum chamber, Hekou Example 17 was made in the same way as a transparent conductive film. At this time, the input power of the heater was 40 0 W / meter 2 · min. Furthermore, the transparent conductive laminated sheet was used in the same manner as in the embodiment. 10. The touch panel was made in the same way. (Example 19) Except that oxygen gas up to 100 OPa was introduced into the atmosphere of a vacuum chamber decompressed to 0.1 Pa, heat treatment was performed at 160 ° C. 2 Except for minutes, the same procedure as in Example 11 A transparent conductive film was prepared. Furthermore, a touch panel was manufactured in the same manner as in Example 11 using this transparent conductive laminated sheet. (Comparative Example 5) Except that the heat treatment at 180 ° C was omitted. Except for the procedures of 1 minute and vacuum exposure treatment for 10 minutes to reduce volatile components, a transparent conductive film was prepared in the same manner as in Example 10. Furthermore, using such a transparent conductive laminated sheet was the same as in Example 10. The touch panel was made in the same way. (T6 Comparative Example 6) It was made in the same manner as in Example 10 except that the copolymerized polyester resin was not added to the coating liquid for forming the hardened layer. Into a transparent conductive film. Moreover, -47- 550598 V. Description of the invention (46), using this transparent conductive laminated sheet, a touch panel was fabricated in the same manner as in Example 10. (tagger) Example 7) A transparent conductive film similar to that in Example 10 was prepared, except that it was heated in a 200 t oven for 5 minutes, and a transparent conductive film was prepared in the same manner as in Example 10. Moreover, such a transparent conductive film was used. Sexually laminated sheet in the same manner as in Example 10 The touch panel was manufactured by the method. The evaluation results of the transparent conductive film and the touch panel obtained in Examples 10 to 17 and Comparative Examples 5 to 7 are shown in Table 2. According to Table 2 As a result, a touch panel of the transparent conductive film or transparent conductive sheet obtained in Examples 10 to 17 that satisfies the scope of the present invention was used, and a pen made of polyacetal resin (front end shape: 0.8 mm R) was used. After 200,000 times of linear sliding test with a load of 5. ON, no whitening phenomenon was generated, and the ON resistance was not abnormal. Moreover, the input mark 〇 was confirmed correctly. Furthermore, on an atomic force microscope There was no abnormality in the evaluation of the sliding part and the mark 印. On the other hand, there are no crystal particles made of metal oxides in the transparent conductive film. The touch panel using the transparent conductive film described in Comparative Examples 5 and 6 is a pen made of polyacetal resin. (Front end shape: 0 · 8 mm R) After a linear sliding test of 200,000 times under a load of 5.0 N, whitening was generated on the transparent conductive film, and ON resistance was abnormal. In addition, the entered mark 0 cannot be confirmed correctly. In addition, the evaluation of the sliding part and the mark 0 on the interatomic force microscope is also -48- 550598 V. Description of the invention (47) The occurrence of cracks can be observed. In addition, when the number of crystal particles made of a metal oxide in the transparent conductive film exceeds the upper limit of the present invention, the touch panel using the transparent conductive film described in Comparative Example 7 is made of polyacetal resin. After the pen (tip shape: 0.8 mm R) was subjected to a linear sliding test of 200,000 times under a load of 5.0 N, whitening occurred on the transparent conductive film, and an abnormality of the 0 N resistance also occurred. In addition, the input mark 印 cannot be accurately recognized, so that it cannot satisfy the practically sufficient performance. In addition, in the evaluation of the sliding part and the mark 0 on the interatomic force microscope, cracks can be observed on the sliding part, and the cracks can also be observed on the mark 0. ° -49-550598 5 、 Explanation of the invention (48) Table 2 Crystal particles · Number (pieces / micron 2) Light-transmitting haze Surface resistivity Adhesion pen Sliding durability Over-ratio (%) (Ω / ϋ) (N / 15 mm) Initial stage of the sliding part 0N test (%) Whitening resistance 0N resistance (kQ) (kQ) Example 10 400 88.3 0.8 250 1.5 No 2.0 2.2 Example 11 400 88.1 1.2 250 1.5 No 2.0 2.0 Example 12 400 88.5 1.5 250 1.5 Μ • Μ 2.0 2.0 Example 13 400 87.3 5.9 250 1.5 4nr No 2.0 2.2 Example 14 400 89.8 5.9 250 1.5 No 2.0 2.2 Example 15 400 88.1 1.7 250 1.5 2.0 2.0 Example 16 200 S8.5 0.8 250 1.5 No 2.0 2.6 Example 17 800 88.1 0.9 250 1.5 4nL without 2.0 2.1 Example 18 880 88.2 0.9 250 1.5 Without 2.0 2.1 Example 19 850 88.5 1.2 260 1.5 Without 2.0 2.0 Comparative Example 5 0 88.5 1.2 250 1.5 With 2.0 > 1000 Comparative Example 6 0 88.8 1.2 250 1.4 Yes 2.0 > 1000 Comparative Example 7 1400 88.1 1.2 250 1.5 4cpi 2.0 2.0 [Effect of the invention] The transparent conductive film of the present invention is a kind of “sequentially laminated on a transparent plastic substrate with hardened resin as the main constituent component” The hardened material layer 'and the transparent conductive film containing metal oxide as a main constituent' The transparent conductive film surface of the aforementioned transparent conductive film has a specific mean square average surface roughness, or it is formed by a specific amount -50 to 550598 in transparent conductive films V. Description of the invention (49) It is formed by crystalline particles made of metal oxide with a specific particle size; therefore, when pressure is applied with a pen, the transparent conductive film When a touch panel is used, the transparent conductive films facing each other do not come into contact with each other, and no peeling, cracks, or the like are generated. The pen has excellent pen sliding durability, and has excellent position detection accuracy and display quality. Therefore, it is suitable for use as a touch panel for pen input. -51-