TW201207089A - Ink for etching electroconductive polymer and patterning method of electroconductive polymer - Google Patents

Ink for etching electroconductive polymer and patterning method of electroconductive polymer Download PDF

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TW201207089A
TW201207089A TW100112147A TW100112147A TW201207089A TW 201207089 A TW201207089 A TW 201207089A TW 100112147 A TW100112147 A TW 100112147A TW 100112147 A TW100112147 A TW 100112147A TW 201207089 A TW201207089 A TW 201207089A
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conductive polymer
ink
etching
film
patterning
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TW100112147A
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TWI500739B (en
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Yasuo Nishimura
Takashi Ihara
Hiromu Taguchi
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Toagosei Co Ltd
Tsurumi Soda Kk
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/02—Polyamines
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
    • H10K71/236—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers using printing techniques, e.g. applying the etch liquid using an ink jet printer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/72—Derivatisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Weting (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

An object of the present invention is to provide an ink for etching electroconductive polymer and a patterning method of electroconductive polymer using the said ink for etching electroconductive polymer, in which the ink has good etching ability to the electroconductive polymer and the precision of the obtained pattern is high. The ink for etching electroconductive polymer of the present invention is characterized by comprising an etching agent for electroconductive polymer, a thickener and aqueous medium. Further, the patterning method of electroconductive polymer of the present invention is a patterning method using the said ink for etching electroconductive polymer.

Description

201207089 六、發明說明： 【發明所屬之技術領域】 本發明係關於導電性高分子蝕刻用印墨及導電性高分 子之圖案化方法。 【先前技術】 現今’雖主要使用包含銦之ITO(氧化銦錫）做爲透明導 電膜’但由於In係可開採蘊藏量爲3千噸之稀有元素，亦 有快則約在2011年至2013年間耗盡可開採蘊藏量之預 測’故正硏究不使用In之ITO的替代材料。導電性高分子 之導電率已顯著地提升’導電性高分子有希望做爲IT〇之 替代材料。 該導電性高分子具有導電性、光之透射性、發光性、 成膜後亦有彈性之特徴，已硏究用於透明導電膜、電解電 容器、抗靜電劑、電池、及有機EL元件等之應用，且一部 份正被實用化。 藉由使用相較於電解電容器的電解液之導電性高且安 定性亦高之導電性高分子，可製作能改善頻率特性之耐熱 性亦優異的電解電容器。 由於藉由在高分子薄膜之表面上使導電性高分子成爲 薄膜以保持透明性同時防止靜電，可使用該者做爲使用便 利性佳的抗靜電薄膜或抗靜電容器。 使用導電性高分子做爲2次電池之正極，可被用於鋰 聚苯胺電池或鋰離子高分子電池等。 201207089 具有在發光層使用導電性高分子之高分子有機.EL顯 示器’且在基板上無玻璃而使用塑膠，藉此可製作具彈性 之顯示器。又’亦可使用導電性高分子於電洞輸送層。包 含高分子有機EL顯示器之有機EL顯示器，由於是自發光 之顯示器，故視角廣、容易薄型化、色彩之再現性優異。 又，由於是以電洞與電子之再結合所致之發光，故應答速 度快。由於有機EL顯示器具有該等優異之特徴，係具有未 來潛力之顯示器。 又，正硏究可使用導電性高分子以製作二極體或電晶 體等之電子元件、性能之提升。藉由使用導電性高分子以 取代鉑做爲色素增感型太陽能電池之二氧化鈦之相對電 極’正硏究目標爲較現爲主流之利用矽的太陽能電池便宜 之太陽能電池的開發。 如此之導電性高分子係對於未來的電子産業有益之材 料’而導電性高分子之圖案化方法係在使用導電性高分子 時爲重要之技術。 使導電性高分子圖案化的方法方面，例如使用包含導 電性材料液體材料之方法係記載於專利文獻1及2。 在專利文獻1中，揭示一種磁磚（tile)狀元件用配線形 成方法，其係當將至少具有電極同時具有磁磚形狀之磁磚 狀元件，連接於至少具有電極之基板以形成迴路裝置時， 在形成使該磁磚狀元件的電極與該基板的電極電連接之電 氣配線時，所使用之磁磚狀元件用配線形成方法，其中在 201207089 前述基板及磁磚狀元件中至少一者的表面上形成前述電氣 配線的範圍之配線範圍的至少一部份中，藉由以噴墨噴嘴 (ink jet nozzle)或分注器（dispenser)印刷包含導電性材料 之液體材料。 又，並未揭示關於用於藉由蝕刻進行圖案化所必須之 方法或印墨組成物等。 又，在專利文獻2中，記載著應用含有1〇至5000m g/m2 的導電性高分子之層於支撐載體上以製作導電性層；及使 用選自由 CIO·、BrO·、Mn04_、Cr2072·，S2082-及 H2〇2 所 組成之群組之氧化劑的印刷溶液，以於前述層上印刷電極 圖案之方法。 又’蝕刻氧化物膜的方法方面，舉例爲記載於專利文 獻2之方法。 在專利文獻3中，揭示做爲氯化鐵（111)或氯化鐵（III) 六水和物之用於氧化物表面蝕刻之組成物的蝕刻成分之使 用。 [先前技術文獻] [專利文獻1]特開2005-109435號公報 [專利文獻2]特開2001-35276號公報 [專利文獻3]特表2〇〇8_547232號公報 【發明內容】 [發明欲解決之課題] 然而’以記載於專利文獻i之方法，因導電性高分子 201207089 難溶於溶劑，而有印墨之調製困難、噴嘴容易堵塞等問題。 又，以記載於專利文獻2之方法，則有所得之圖案的 精確度差的問題。 再者’在專利文獻3中，雖記載使用分注器（dispenser) 或絲網（screen)以印刷包含氯化鐵化合物之水性糊於ιτο 等氧化膜，.並藉由蝕刻除去氧化膜以進行圖案化之方法， 但未揭示適合於導電性高分子蝕刻用印墨之印墨組成或特 性。 本發明之目的爲提供對於導電性高分子具有優異之蝕 刻能力、所得之圖案的精確度高之導電性高分子蝕刻用印 墨；及使用前述導電性高分子蝕刻用印墨的導電性高分子 之圖案化方法。 [解決課題之手段] 本發明者等爲了克服在上述習知技術中之問題點而專 心一意硏究的結果，發現藉由以下之&lt;1&gt;、&lt;8&gt;、&lt;12&gt;至&lt;15&gt; 或&lt;2 0&gt;可達成上述課題，進而完成本發明。於以下同時記 載其爲較佳的實施樣態之&lt;2&gt;至&lt;7&gt;、&lt;9&gt;至&lt;11&gt;、及&lt;16&gt; 至 &lt;19&gt;及 &lt;21&gt;至 &lt;23&gt;。 &lt;1&gt;—種導電性高分子蝕刻用印墨，其特徵爲包含導電 性高分子用蝕刻劑、增稠劑、及水性媒介； &lt;2&gt;如記載於上述&lt;1&gt;之導電性高分子蝕刻用印墨，其 中前述導電性高分子用鈾刻劑爲選自由（NH4)2Ce(N03)6、 Ce(S04)2、（NH4)4Ce(S04)4、亞硝醯氯、溴酸化合物、氯酸 201207089 化合物、過錳酸化合物、6價鉻化合物、及次氯酸鹽所組 成之群組之化合物； &lt;3&gt;如記載於上述&lt;1&gt;或&lt;2&gt;之導電性高分子蝕刻用印 墨，其中前述導電性高分子用蝕刻劑爲選自由 (NH4)2Ce(N03)6、Ce(S04)2、（NH4)4Ce(S04)4、過錳酸化合 物、及次氯酸鹽所組成之群組之化合物； &lt;4&gt;如記載於上述&lt;1&gt;至&lt;3&gt;中任一項之導電性高分子 蝕刻用印墨，其中前述增稠劑爲選自由矽石粒子、礬土粒 子、矽石粒子與礬土粒子之混合物、及界面活性劑所組成 之群組之增稠劑； &lt;5&gt;如記載於上述&lt;1&gt;至&lt;4&gt;中任一項之導電性高分子 蝕刻用印墨，其中前述增稠劑爲選自由矽石粒子、礬土粒 子、及矽石粒子與礬土粒子之混合物所組成之群組之增稠 劑； &lt;6&gt;如記載於上述&lt;1&gt;至&lt;4&gt;中任一項之導電性高分子 蝕刻用印墨，其中前述增稠劑爲界面活性劑； &lt;7&gt;如記載於上述&lt;1&gt;至&lt;6&gt;中任一項之導電性高分子 蝕刻用印墨，其中前述水性媒介爲水； &lt;8&gt; —種導電性高分子之圖案化之方法，其特徵爲包含 形成導電性高分子薄膜於基材上之成膜步驟、在除去前述 膜上之導電性高分子的範圍中塗敷記載於上述&lt;1&gt;至&lt;7&gt;中 任一項之導電性高分子蝕刻用印墨之印刷步驟、藉由前述 導電性高分子蝕刻用印墨以蝕刻前述除去範圍之導電性高 201207089 分子之触刻步驟'以及從基板上除去殘存之導電性高分子 蝕刻用印墨及導電性高分子之蝕刻殘渣之除去步驟； &lt;9&gt;如記載於上述&lt;8&gt;之導電性高分子之圖案化之方 法’其中則述導電性闻分子爲選自由聚乙炔類、聚對伸苯 類、聚對伸苯基伸乙烯類、聚伸苯類'聚伸噻吩伸乙烯類、 聚蒹類、聚并苯類、聚苯胺類、聚吡咯類、及聚噻吩類所 組成之群組之導電性高分子； &lt;10&gt;如記載於上述&lt;8&gt;或&lt;9&gt;之導電性高分子之圖案 化之方法’其中前述導電性高分子爲聚苯胺類、聚吡咯類 或聚噻吩類； &lt;11&gt;如載於上述&lt;8&gt;至&lt;10&gt;中任一項之導電性高分 子之圖案化之方法’其中前述導電性高分子爲聚（3，4_乙烯 二氧噻吩）。 &lt;12&gt; —種導電性高分子蝕刻用印墨，其特徵爲包含 (&gt;1114)2〇6(1^03)6或 Ce(S04)2、與增稠劑、水性媒介； &lt;13&gt;—種導電性高分子蝕刻用印墨，其特徵爲包含次 氯酸鹽 '增稠劑、及水性媒介； &lt; 1 4 &gt; —種導電性高分子蝕刻用印墨，其特徵爲包含過 錳酸化合物、增稠劑、及水性媒介； &lt;15&gt; —種導電性高分子蝕刻用印墨，其特徵爲包含 (NH4)4Ce(S04)4、增稠劑、及水性媒介： &lt;16&gt;如記載於上述&lt;12&gt;至&lt;15&gt;中任—項之導電性高 分子鈾刻用印墨，其中前述增稠劑爲選自由矽石粒子、礬 201207089 土粒子、矽石粒子與礬土粒子之混合物、及界面活性劑所 組成之群組之增稠劑； &lt;17&gt;如記載於上述&lt;12&gt;至&lt;16&gt;中任一項之導電性高 分子蝕刻用印墨，其中前述增稠劑爲矽石粒子、礬土粒子、 及矽石粒子與礬土粒子之混合物所組成之群組之增稠劑； &lt;18&gt;如記載於上述&lt;12&gt;至&lt;16&gt;中任一項之導電性高 分子蝕刻用印墨，其中前述增稠劑爲界面活性劑； &lt;19&gt;如記載於上述&lt;12&gt;至&lt;18&gt;中任一項之導電性高 分子蝕刻用印墨，其中前述水性媒介爲水； &lt;2〇&gt;—種導電性高分子之圖案化方法，其特徵爲包含 形成導電性高分子薄膜於基材上之成膜步驟、在除去前述 膜之導電性高分子的範圍中塗敷記載於上述&lt;12&gt;至&lt;19&gt;中 任一項之導電性高分子蝕刻用印墨之印刷步驟、藉由前述 導電性高分子蝕刻用印墨蝕刻前述除去之範圍的導電性高 分子之蝕刻步驟、及從基板上除去殘存導電性高分子蝕刻 用印墨及導電性高分子之蝕刻殘渣之除去步驟； &lt;2 1 &gt;如記載於上述&lt;2 0&gt;之導電性高分子之圖案化方 法’其中前述導電性高分子爲選自由聚乙炔類、聚對伸苯 類、聚對伸苯基伸乙烯類、聚伸苯類、聚伸噻吩伸乙烯類、 聚弗類、聚并苯類、聚苯胺類、聚吡咯類、及聚噻吩類所 組成之群組之導電性高分子； &lt;22&gt;如記載於上述&lt;2〇&gt;或&lt;21&gt;之導電性高分子之圖 案化方法，其中前述導電性高分子爲聚苯胺類、聚吡咯類、 -10- 201207089 或聚噻吩類； &lt;23&gt;如記載於上述&lt;20&gt;至&lt;22&gt;中任一項之導電性高 分子之圖案化方法，其中前述導電性高分子爲聚（3,4-乙烯 二氧噻吩）。 [發明效果] 根據本發明，可提供對於導電性高分子具有優異之餓 刻能力、所得圖案的精確度高之導電性高分子蝕刻用印 墨；及使用前述導電性高分子蝕刻用印墨的導電性高分子 之圖案化方法。 【實施方式】 [實施發明之形態] 以下’詳細説明本發明。還有，「％」若無特別明確說 明則表示限定爲「重量％」。 (導電性高分子蝕刻用印墨） 本發明之導電性高分子蝕刻用印墨（以下，簡稱爲「本 發明之印墨」。），其特徵爲包含導電性高分子用蝕刻劑' 增稠劑、及水性媒介。 本發明之導電性高分子蝕刻用印墨係可藉由與導電性 高分子接觸’蝕刻該接觸部分的導電性高分子。即，以所 希望之形狀將本發明之導電性高分子蝕刻用印墨塗敷於導 電性高分子上’藉由蝕刻，可將導電性高分子圖案化成爲 所希望之形狀。 習知之導電性高分子之圖案化方法方面，雖然已知有 -11 - 201207089 使用光阻劑膜之方法，但藉由使用本發明之導電性高分子 蝕刻用印墨’而不使用光阻劑膜，可簡便地進行導電性高 分子之圖案化。 又’本發明較佳之第一方面，舉出爲包含 (NH4)2Ce(NO〇6或Ce(S04)2、增稠劑、與水性媒介之導電 性高分子蝕刻用印墨。 本發明較佳之第二方面，舉出爲以包含次氯酸鹽、增 稠劑、及水性媒介爲特徴之導電性高分子蝕刻用印墨。 本發明較佳之第三方面，舉出爲以包含過錳酸化合 物、增稠劑、及水性媒介爲特徴之導電性高分子蝕刻用印 墨。 本發明較佳之第四方面，舉出爲以包含 (NH4)4Ce(S04)4、增稠劑、及水性媒介爲特徴之導電性高分 子蝕刻用印墨。 又’本發明之導電性高分子蝕刻用印墨的黏度，從安定 性或所得圖案之精確度的觀點來看，使用B型黏度計並以 6rpm(25°C)測定時所得之黏度，較佳爲50至100,000mPa· s， 更佳爲 200 至 50,000mPa· s，特佳爲 5QO 至 20,000mPa· s。 又，使用B型黏度計並以60rpm(2 5°C )測定時所得之黏度，較 佳爲 10 至 20,000mPa· s，更佳爲 40 至 10,000mPa· s，特佳 爲 4 0 至 4，0 0 〇 m P a · s。 又’搖變減黏度（thixotropic index)(TI値）較佳爲2至 20，更佳爲3至15。 -12- 201207089 還有’本發明中之印墨的黏度係在藉由攪拌印墨形成 均勻狀態後，所測定之値。 本發明之導電性高分子蝕刻用印墨中之黏度的測定方 法方面，雖無特別限制，但較佳爲藉由旋轉式黏度計進行 測定。具體而言，可較佳地舉例說明藉由B型黏度計進行 測定之方法。還有，所謂B型黏度計爲旋轉黏度計之1種， 係在測定試料（印墨）中以固定速度旋轉内筒，測定該内筒 本身所承受之力的黏度計。又，B型黏度計稱爲布氏黏度 If (Brookfield viscometer) ° 還有，所謂搖變減黏度（thixotropic index)(TI値）爲2 種不同之旋轉速度（剪切速度）中所顯現之黏度比，在JIS K 688 3 - 1 : 2008中，係在變化旋轉速度爲1 : 10所測定之各 種黏度比之定義。 搖變減黏度（thixotropic index)(TI値）係藉由前述黏度 之測定方法測定在6rpm(25〇C )下之黏度&lt;5 6、及在60rpm(25 t )下之黏度5 6t)，以求出（5 6/ (5 6Q所計算出來。 在通常之影像印刷用之印墨中，除了用於防止擴散或 散亂而調高黏度，同時提高印墨附著於或通過平版時的流 動性之外，緩緩地將印刷後之印墨表面勻塗平整，並且爲 了使印墨表面具有光澤而進行黏度之調整。然而，由於在 使用本發明之蝕刻用印墨時不需要蝕刻印墨表面之光澤或 審美性，在以藉由蝕刻所得之圖案的切割優劣爲第一指標 進行探索時，除了上述較佳之黏度及TI値之外，發現若使 •13- 201207089 用施加剪應力（s h e a r)後之黏度的恢復速度在一定範圍之印 墨時’可實現特別精細之圖案。 施加剪應力後之黏度的恢復速度係以例如與TI値之 測定同樣的方法，在藉由旋轉黏度計以高旋轉（高剪應力 (high shear))下之測定後，在放置短的固定時間後可藉由進 行以低旋轉之黏度測定所決定。其原理爲印墨受高剪應力 之剪切而破壞構造，變成低黏度後，直到再次構築構造而 黏度上升的時間長度，隨印墨系統（蝕刻劑等）與增稠劑之 組合而異，該結果爲本發明者等發現造成精密之圖案的最 佳組合。 &lt;導電性高分子用蝕刻劑&gt; 本發明之導電性高分子蝕刻用印墨包含導電性高分子 用蝕刻劑。 可用於本發明之導電性高分子用蝕刻劑方面，若爲可 蝕刻導電性高分子之化合物則無特別限制，較佳爲可蝕刻 導電性高分子之氧化劑。 又，可用於本發明之導電性高分子用蝕刻劑方面，從 蝕刻性的觀點來看，較佳爲選自由（NH4)2Ce(N03)6、 Ce(S04)2、（NH4)4Ce(S04)4、亞硝醯氯、溴酸化合物、氯酸 化合物、過錳酸化合物、6價鉻化合物、及次氯酸鹽所組 成之群組之化合物，更佳爲選自由（NH4)2Ce(N03)6、 Ce(S04)2、（NH4)4Ce(S04)4、過錳酸化合物、及次氯酸鹽所 組成之群組之化合物。彼等之中，從蝕刻性的觀點來看， -14- 201207089 特佳爲選自由（NH4)2Ce(N03)6 、 Ce(S〇4)2 、及 (Ν Η 4 ) 4 C e ( S Ο 4 ) 4所組成之群組之化合物，從成本及泛用性 的觀點來看，特佳爲次氯酸鹽。 可適當地使用（NH4)2Ce(N〇3)6做爲前述導電性高分子 用蝕刻劑。 當使用（NH4)2Ce(N〇3)6於本發明之印墨時，從蝕刻性 的觀點來看，本發明之印墨中的（NH4)2Ce(N03)6含量，相 對於除去增稠劑重量之印墨全體重量，較佳爲0.5 %以上， 更佳爲1.0%以上，又，從同時提升濃度與處理速度或溶解 度的觀點來看，以70%以下爲佳，較佳爲40%以下，更佳 爲2.0至3 0 %，特佳爲5.0至1 5 % » 在使用（NH4)2Ce(N03)6的本發明之印墨中，爲了防止 印墨中之四價铈化合物的分解，較佳爲使用安定劑。 前述安定劑方面較佳爲HN03或HC104。 若使用ΗΝ03做爲前述安定劑時，該濃度爲相對於除 去增稠劑重量之印墨全體重量，以大於0 . 1 %爲佳，又以7 0 % 以下爲佳，較佳爲1 ·〇至60%，更佳爲5至50%，最佳爲 1 〇 至 2 0 %。 又，當使用HC104做爲前述安定劑時，該濃度爲相對 於除去增稠劑重量之印墨全體重量，以0.1 %以上爲佳，又 以60%以下爲佳，較佳爲1 ·〇至50%，更佳爲5至40%。 在使用（NH4)2Ce(N03)6於本發明之印墨時，若安定劑 爲上述範圍之濃度時則提升蝕刻液之安定性。 -15- 201207089 還有’由於硫酸會使包含（NH4)2Ce(N〇3)6之印墨混 濁，不利做爲安定劑。 可適宜使用C e ( S Ο 4 ) 2做爲前述導電性高分子用蝕刻 劑。 在使用Ce(S〇4)2於本發明之印墨時，本發明的印墨中 之Ce(S〇4h含量’從蝕刻性的觀點來看，相對於除去增稠 劑重量之印墨全體重量’較佳爲0 _ 5 %以上，更佳爲1.0% 以上’又’從同時提升濃度與處理速度或溶解度的觀點來 看，以3 0 %以下爲佳’較佳爲2 0 %以下，更佳爲2.0至2 5 %， 特佳爲5至1 5 %。 在使用Ce(S04)2的本發明之印墨中，爲了防止印墨中 的四價鈽化合物之分解，較佳爲使用安定劑。 前述安定劑方面，較佳爲 hno3或H2S04，更佳爲 hno3。 若使用hno3做爲前述安定劑時，該濃度爲相對於除 去增稠劑重量之印墨全體重量，以大於0.1 %爲佳，又以70% 以下爲佳，較佳爲1.0至60%，更佳爲5.0至50%。 又，若使用H2S〇4做爲前述安定劑時、該濃度以大於 0.1 %爲佳，又以40%以下爲佳，較佳爲1.0至30% ’更佳 爲 5.0 至 2 0 %。 在使用Ce(S04)2於本發明之印墨時，若安定劑爲上述 範圍之濃度時則可防止印墨的蝕刻能力之降低° 可適宜地使用（NH4)4Ce(S04)4做爲前述導電性高分子 -16 - 201207089 用蝕刻劑。 在使用（NH4)4Ce(S04)4 於本發明之印墨時， (NH4)4Ce(S04)4之含量從蝕刻性的觀點來看，相對於除去 增稠劑重量之印墨全體重量，以大於0.5%爲佳，較佳爲 1 ·〇%以上，又，從同時提升濃度與處理速度或溶解度的觀 點來看，以30%以下爲佳，較佳爲25%以下，更佳爲：1.〇 至2 5 %，特佳爲5至1 5 % » 在使用（NH4)4Ce(S04)4的本發明之印墨中，爲了防止 印墨中的四價鈽化合物之分解，較佳爲使用安定劑。 前述安定劑較佳爲H2S〇4。若使用H2S〇4做爲前述安 定劑時，該濃度係以1.0%以上爲佳，又以40 %以下爲佳’ 較佳爲2.0至30% ，更佳爲3至20%。若H2S〇4爲上述範 圍之濃度時，可防止印墨蝕的蝕刻能力之降低。 還有，由於硝酸會使含有（NH4)4Ce(S04)4之本發明印 墨變混濁，不利做爲安定劑。 可適宜地使用亞硝醯氯做爲前述導電性高分子用蝕刻 劑》 亞硝醯氯係以如下式般地混合鹽酸與硝酸而同時與活 性氯一起產生。 HN〇3 + 3HC1 — NOC1 + Cl2 + 2H2〇 若本發明之印墨含有亞硝醯氯時’除了亞硝酿氯之 外，較佳爲進一步含有鹽酸及硝酸，更佳爲相對於除去增 稠劑重量之印墨全體重量，含有5 %以上鹽酸、含有20%以 -17- 201207089 上硝酸、（鹽酸濃度+ 〇·5 lx硝酸濃度）之値爲35%以下、而 且（鹽酸濃度+ 0 · 5 X硝酸濃度）之値爲3 0 %以上。 若使用亞硝醯氯於本發明之印墨時，硝酸之濃度相對 於除去增稠劑重量之印墨全體重量，以20%以上爲佳，較 佳爲2 5至5 0 %，更佳爲3 0至4 0 %。 又，若使用亞硝醯氯於本發明之印墨時，鹽酸之濃度 相對於除去增稠劑重量之印墨全體重量，較佳爲5%以上， 更佳爲滿足以（鹽酸濃度+ 0.5 lx硝酸濃度）所表示之算式値 爲35 %以下、而且以（鹽酸濃度+ 0.：5Χ硝酸濃度）所表示之算 式値爲30%以上之關係的濃度。 可適宜地使用溴酸化合物或氯酸化合物做爲前述導電 性高分子用蝕刻劑。 溴酸化合物及氯酸化合物係藉由與酸組合使用而可提 高蝕刻能力。 前述溴酸化合物較佳爲溴酸之鹼金屬鹽，更佳爲鈉鹽 或鉀鹽。 若使用溴酸化合物於本發明之印墨時，溴酸化合物之 濃度相對於除去增稠劑重量之印墨全體重量，以3至40% 爲佳，較佳爲5至35%，更佳爲1 0至30%。 與溴酸化合物倂用之無機酸方面，可舉例爲磷酸、硝 酸及硫酸，而較佳爲硝酸及硫酸。所倂用之無機酸濃度相 對於除去增稠劑重量之印墨全體重量，較佳爲4至30%， 更佳爲1 〇至2 5 %。 -18- 201207089 前述氯酸化合物較佳爲氯酸之鹼金屬鹽，更佳爲鈉鹽 或鉀鹽。 若使用氯酸化合物於本發明之印墨時，氯酸化合物之 濃度相對於除去增稠劑重量之印墨全體重量，較佳爲6至 4 0 % ，更佳爲1 0至3 5 %。 與氯酸化合物倂用之無機酸方面，較佳爲鹵化氫，可 舉例有鹽酸及溴化氫酸’較佳爲鹽酸。所倂用之無機酸濃 度相對於除去增稠劑重量之印墨全體重量，較佳爲7至 3 0 %，更佳爲1 0至2 5 %。 可適宜地使用過錳酸化合物做爲前述導電性高分子用 蝕刻劑。 前述過錳酸化合物較佳爲鹼金屬鹽，更佳爲鈉鹽或鉀 鹽。 若使用過錳酸化合物於本發明之印墨時，過錳酸化合 物之濃度相對於除去增稠劑重量之印墨全體重量，以0.001 至20%爲佳，較佳爲0.01至10%，更佳爲0」至5%。 過錳酸化合物係因對軛離子之影響而使印墨成爲鹼 性，亦可加酸以調整印墨之pH。 在過錳酸化合物中所倂用之酸方面，舉例爲有機酸或 無機酸，在本發明中較佳爲無機酸。在本發明中，有機酸 方面，可舉例爲甲酸、乙酸及丙酸等，較佳爲乙酸。無機 酸方面’可舉例爲磷酸、硝酸及硫酸，較佳爲硝酸及硫酸， 更佳爲硫酸。與過錳酸化合物倂用的酸之濃度相對於除去 -19- 201207089 增稠劑重量之印墨全體重量，較佳爲1至5 0 %，更 至 25%。 可適宜地使用6價鉻化合物做爲前述導電性高 蝕刻劑。 在6價鉻化合物中，有氧化鉻、鉻酸化合物與 化合物，鉻酸化合物方面可舉例爲鹼金屬鹽者，二 合物方面亦可舉例爲鹼金屬鹽者，彼等鹼金屬鹽方 爲鈉鹽或鉀鹽。 前述6價鉻化合物方面，氧化鉻或二鉻酸化合 酸化合物爲佳，更佳爲氧化鉻。 若使用6價鉻化合物於本發明之印墨時，6價 物之使用濃度相對於除去增稠劑重量之印墨全體重 3至3 0 %爲佳，較佳爲5至2 5 %，更佳爲1 0至2 0 % 較佳爲在6價鉻化合物中倂用無機酸，該無 面，可舉例爲磷酸、硝酸及硫酸，較佳爲硝酸及硫 佳爲硫酸。與6價鉻化合物倂用之無機酸的濃度相 去增稠劑重量之印墨全體重量，較佳爲1至5 0%， 5 至 25%。 可適宜地使用次氯酸鹽做爲前述導電性高分子 劑。 次氯酸鹽大多爲在氫氧化鹼金屬或氫氧化鹼土 中吸收氯所製造的情況，在該情況下，因未反應之 鹸金屬或氫氧化鹼土族金屬之影響而使該水溶液顯 佳爲5 分子用 二鉻酸 鉻酸化 面較佳 物較鉻 鉻化合 量，以 〇 機酸方 酸，更 對於除 更佳爲 用蝕刻 族金屬 氫氧化 示強鹼 -20- 201207089 性。 爲了調整本發明之印墨的pH，亦可倂用酸。所倂用之 酸方面係可使用無機酸及有機酸之任一者。具體而言，可 較佳地舉例爲鹽酸、硫酸、硝酸、磷酸、乙酸、檸檬酸等， 彼等之中更佳爲硫酸或硝酸。 若使用次氯酸鹽於本發明之印墨時，本發明之印墨的 pH並無特別限制，雖可隨所使用之基材或導電性高分子膜 之材質來選擇，但從抑制氯氣的產生或蝕刻性的觀點來 看，以pH爲4至13爲佳，較佳爲6至12.5，更佳爲7至 12，最佳爲7至11。本發明之印墨的PH測定係可使用市 售之pH計來測定。 若使用次氯酸於本發明之印墨時，次氯酸之有效氯濃 度相對於除去增稠劑重量之印墨全體重量，以0.0 6 %以上 爲佳’較佳爲0.1 %以上，更佳爲0.2 %以上，又以3 %以下 爲佳’較佳爲2%以下’更佳爲1 %以下。若有效氯濃度爲 該範圍内時則可效率佳地進行導電性高分子之蝕刻。 在本發明中，次氯酸之有效氯濃度係由以Na2S03之滴 定法進行測定。即’採取^克的所測定之試料，加入離子 交換水而成爲250ml。取出部份l〇ml之該試料液，加入i〇ml 之碘化鉀爲1 0 %之水溶液。然後，加入1 0 m 1之乙酸（1 : 2 ) 而使pH爲酸性’以0. 1當量濃度硫代硫酸鈉水溶液滴定（爲 了於滴定途中容易判定終點，亦可加入可溶性澱粉。）。由 0.1當量濃度的Na2S03之滴定量及試料採取量w與以下算 -21- 201207089 式求出有效氯濃度。 0.003546x(Na2SO3 之滴定量:ml) 250201207089 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for patterning a conductive polymer etching ink and a conductive polymer. [Prior Art] Today, although ITO (Indium Tin Oxide) containing indium is mainly used as a transparent conductive film, but because the In system can extract rare elements of 3,000 tons, it is also about 2011 to 2013. The prediction of the depletion of recoverable reserves during the year is an alternative material that does not use In's ITO. The conductivity of conductive polymers has been significantly improved. Conductive polymers are promising as an alternative to IT. The conductive polymer has properties such as conductivity, light transmittance, luminescence, and elasticity after film formation, and has been used for a transparent conductive film, an electrolytic capacitor, an antistatic agent, a battery, and an organic EL device. Application, and some are being put into practical use. By using a conductive polymer having high conductivity and high stability as compared with an electrolytic solution of an electrolytic capacitor, an electrolytic capacitor excellent in heat resistance which can improve frequency characteristics can be produced. Since the conductive polymer is made into a film on the surface of the polymer film to maintain transparency and prevent static electricity, it can be used as an antistatic film or an antistatic container which is excellent in convenience. The conductive polymer is used as a positive electrode of a secondary battery, and can be used for a lithium polyaniline battery or a lithium ion polymer battery. 201207089 A polymer organic EL display having a conductive polymer in a light-emitting layer and using a plastic without a glass on a substrate can produce a flexible display. Further, a conductive polymer may be used in the hole transport layer. Since the organic EL display including the polymer organic EL display is a self-luminous display, the viewing angle is wide, the thickness is easy to be thin, and the color reproducibility is excellent. Moreover, since the light is emitted by the recombination of the hole and the electron, the response speed is fast. Since the organic EL display has such excellent characteristics, it is a display having a potential for the future. Further, it is possible to use a conductive polymer to produce an electronic component such as a diode or an electric crystal, and to improve the performance. The use of a conductive polymer to replace platinum as a relative electrode of titanium dioxide for a dye-sensitized solar cell is aimed at the development of a solar cell which is cheaper than the currently used solar cell. Such a conductive polymer is a material that is beneficial to the future electronics industry, and a patterning method of a conductive polymer is an important technique when a conductive polymer is used. For the method of patterning a conductive polymer, for example, a method of using a liquid material containing a conductive material is described in Patent Documents 1 and 2. Patent Document 1 discloses a method of forming a tile-like component wiring by connecting a tile-shaped component having at least an electrode and a tile shape to a substrate having at least an electrode to form a circuit device. In the method of forming a wiring for a tile-shaped component to be used for electrically connecting an electrode of the tile-shaped element to an electrode of the substrate, wherein at least one of the substrate and the tile-shaped component is used in 201207089 In at least a portion of the wiring range in which the range of the electric wiring is formed on the surface, the liquid material containing the conductive material is printed by an ink jet nozzle or a dispenser. Further, a method or an ink composition or the like which is necessary for patterning by etching is not disclosed. Further, Patent Document 2 describes the use of a layer containing a conductive polymer of 1 〇 to 5000 m g/m 2 on a support carrier to prepare a conductive layer; and the use of a layer selected from CIO·, BrO·, Mn04_, Cr2072· a printing solution of an oxidizing agent of the group consisting of S2082- and H2〇2 for printing an electrode pattern on the layer. Further, the method of etching the oxide film is exemplified by the method described in Patent Document 2. In Patent Document 3, the use of an etching component as a composition for etching an oxide surface of iron chloride (111) or iron(III) chloride hexahydrate is disclosed. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2001-35276 (Patent Document 3) JP-A-2001-35276 (Patent Document 3) However, in the method described in Patent Document i, since the conductive polymer 201207089 is hardly soluble in a solvent, there is a problem that the ink is difficult to be modulated and the nozzle is easily clogged. Further, according to the method described in Patent Document 2, there is a problem that the accuracy of the obtained pattern is poor. In addition, in Patent Document 3, it is described that a dispenser or a screen is used to print an aqueous paste containing an iron chloride compound on an oxide film such as ιτο, and the oxide film is removed by etching. The method of patterning, but does not disclose the ink composition or characteristics suitable for the ink for conductive polymer etching. An object of the present invention is to provide an electroconductive polymer etching ink having excellent etching ability for a conductive polymer and having high precision of a obtained pattern, and a pattern of a conductive polymer using the electroconductive polymer etching ink Method. [Means for Solving the Problems] The inventors of the present invention have found that the results of the above-mentioned conventional techniques are focused on the results of the above-mentioned prior art, and it is found that the following <1>, &lt;8&gt;, &lt;12&gt; to &lt; 1515 or <2 0&gt; can achieve the above problems, and further complete the present invention. The following <2> to &lt;7&gt;, &lt;9&gt; to &lt;11&gt;, and &lt;16&gt; to &lt;19&gt; and &lt;21&gt; to &lt;21&gt;;23&gt;.&lt;1&gt; - An ink for conductive polymer etching, comprising an etchant for a conductive polymer, a thickener, and an aqueous medium; &lt;2&gt; as described in the above &lt;1&gt; The ink for molecular etching, wherein the uranium engraving agent for the conductive polymer is selected from the group consisting of (NH4)2Ce(N03)6, Ce(S04)2, (NH4)4Ce(S04)4, nitrous oxide chloride, and bromic acid compound a compound of a group consisting of a compound of chloric acid 201207089, a permanganate compound, a hexavalent chromium compound, and a hypochlorite; &lt;3&gt; as described in the above &lt;1&gt; or &lt;2&gt; The ink for molecular etching, wherein the etchant for conductive polymer is selected from the group consisting of (NH4)2Ce(N03)6, Ce(S04)2, (NH4)4Ce(S04)4, permanganic acid compound, and hypochlorous acid The ink for conductive polymer etching according to any one of the above-mentioned items, wherein the thickener is selected from the group consisting of vermiculite particles. , a mixture of alumina particles, a mixture of vermiculite particles and alumina particles, and a thickening agent composed of a surfactant; &lt;5&gt; The ink for conductive polymer etching according to any one of the above-mentioned items, wherein the thickener is selected from the group consisting of vermiculite particles, alumina particles, and vermiculite particles and alumina particles. The ink for conductive polymer etching according to any one of the above-mentioned <1> to <4>, wherein the thickener is a surfactant. The ink for conductive polymer etching according to any one of the above-mentioned <1> to <6> wherein the aqueous medium is water; &lt;8&gt; The method of forming a film comprising a step of forming a conductive polymer film on a substrate and coating the conductive polymer on the film is described in the above &lt;1&gt; to &lt;7&gt; In the printing step of the conductive polymer etching ink, the conductive ink etching ink is used to etch the above-mentioned removal range of the high conductivity 201207089 molecular contact step 'and the residual conductivity is removed from the substrate Ink and guide for polymer etching <9> The method for patterning the conductive polymer according to the above <8>, wherein the conductive olefin is selected from the group consisting of polyacetylene and poly-strand a group consisting of benzenes, poly-p-phenylene-extended ethylene, poly-extended benzenes, polythiophene-extended ethylene, polyfluorenes, polyacenes, polyanilines, polypyrroles, and polythiophenes The method of patterning the conductive polymer according to the above <8> or <9>, wherein the conductive polymer is polyaniline, polypyrrole or polythiophene. The method of patterning a conductive polymer according to any one of the above items <8> to <10> wherein the conductive polymer is poly(3,4-ethylene dioxygen). Thiophene). &lt;12&gt; — A conductive polymer etching ink comprising (&gt; 1114) 2〇6(1^03)6 or Ce(S04)2, a thickener, and an aqueous medium; &lt;13&gt; An ink for conductive polymer etching characterized by comprising a hypochlorite' thickener and an aqueous medium; &lt;1 4 &gt; A conductive polymer etching ink characterized by containing permanganese An acid compound, a thickener, and an aqueous medium; &lt;15&gt; A conductive polymer etching ink comprising (NH4)4Ce(S04)4, a thickener, and an aqueous medium: &lt;16&gt; The conductive polymer uranium engraving ink according to any one of the above-mentioned items, wherein the thickener is selected from the group consisting of vermiculite particles, 矾201207089 soil particles, vermiculite particles and alumina The ink for conductive polymer etching according to any one of the above-mentioned items <12> to <16>, wherein the foregoing is a thickening agent for a group of the particles, and a mixture of the surfactants; The thickener is a group of vermiculite particles, alumina particles, and a mixture of vermiculite particles and alumina particles. The ink for conductive polymer etching according to any one of the above-mentioned <12> to <16> wherein the thickener is a surfactant; &lt;19&gt; The ink for conductive polymer etching according to any one of the above-mentioned, wherein the aqueous medium is water; and the method for patterning a conductive polymer is characterized by comprising The conductive polymer etching described in any one of the above items <12> to <19> is applied to a film forming step of forming a conductive polymer film on a substrate, and a range in which the conductive polymer of the film is removed. The etching step of the ink, the etching step of etching the conductive polymer in the range removed by the conductive ink etching ink, and the etching of the conductive ink etching ink and the conductive polymer removed from the substrate The step of removing the residue; wherein the conductive polymer is selected from the group consisting of polyacetylenes, polyparaphenylenes, and polycondensates, wherein the conductive polymer is described in the above-mentioned &lt;20&gt; Phenylene extension a conductive polymer of a group consisting of a olefin, a polyphenylene, a polythiophene, an anthracene, a polyacene, a polyaniline, a polypyrrole, and a polythiophene; &lt;22&gt; The method for patterning a conductive polymer according to the above <2> or <21>, wherein the conductive polymer is polyaniline, polypyrrole, -10-201207089 or polythiophene; The method for patterning a conductive polymer according to any one of the above-mentioned items, wherein the conductive polymer is poly(3,4-ethylenedioxythiophene). [Effect of the Invention] According to the present invention, it is possible to provide an electroconductive polymer etching ink which has excellent hunting ability for a conductive polymer and has high precision of a obtained pattern, and conductivity of the electroconductive polymer etching ink. A method of patterning a polymer. [Embodiment] [Embodiment of the Invention] Hereinafter, the present invention will be described in detail. Also, "%" is limited to "% by weight" unless otherwise specified. (Ink for Conductive Polymer Etching) The ink for conductive polymer etching of the present invention (hereinafter, simply referred to as "the ink of the present invention") is characterized in that it contains an etchant for a conductive polymer as a thickener. And aqueous media. In the ink for conductive polymer etching of the present invention, the conductive polymer in the contact portion can be etched by contact with the conductive polymer. That is, the conductive polymer etching ink of the present invention is applied to the conductive polymer in a desired shape. By etching, the conductive polymer can be patterned into a desired shape. In the conventional method for patterning a conductive polymer, although a method of using a photoresist film of -11 - 201207089 is known, the use of the conductive polymer etching ink of the present invention does not use a photoresist film. The patterning of the conductive polymer can be easily performed. Further, the first aspect of the present invention is preferably an ink for etching a conductive polymer comprising (NH4)2Ce (NO〇6 or Ce(S04)2, a thickener, and an aqueous medium. In the second aspect, a conductive polymer etching ink containing a hypochlorite, a thickener, and an aqueous medium is used. The third aspect of the present invention is preferably a permanganate compound. The thickener and the aqueous medium are special inks for etching conductive polymers. The fourth preferred aspect of the present invention is characterized in that it is characterized by containing (NH4)4Ce(S04)4, a thickener, and an aqueous medium. Ink for inkjet etching. The viscosity of the ink for etching a conductive polymer of the present invention is measured by a B-type viscometer and measured at 6 rpm (25 ° C) from the viewpoint of stability or accuracy of the obtained pattern. The viscosity obtained at the time is preferably from 50 to 100,000 mPa·s, more preferably from 200 to 50,000 mPa·s, particularly preferably from 5 QO to 20,000 mPa·s. Further, a B-type viscometer is used at 60 rpm (25 ° C) The viscosity obtained at the time of measurement is preferably from 10 to 20,000 mPa·s, more preferably from 40 to 10,000 mPa·s, particularly preferably 40 to 4,0 0 〇m P a · s. Further, the 'thixotropic index' (TI値) is preferably 2 to 20, more preferably 3 to 15. -12-201207089 Further, the viscosity of the ink of the present invention is measured by agitating the ink to form a uniform state. In the method for measuring the viscosity in the ink for conductive polymer etching of the present invention, Although it is not particularly limited, it is preferably measured by a rotary viscometer. Specifically, a method of measuring by a B-type viscometer can be preferably exemplified. Further, the so-called B-type viscometer is a rotational viscosity. One type is a viscometer that rotates the inner cylinder at a fixed speed in the measurement sample (ink) and measures the force of the inner cylinder itself. Further, the B-type viscometer is called Brookfield viscometer. ° Also, the so-called thixotropic index (TI値) is the viscosity ratio exhibited in two different rotation speeds (shear speeds). In JIS K 688 3 - 1 : 2008, the system is changing. The rotation speed is defined by the various viscosity ratios measured by 1:10. The thixotropic index (TI値) is determined by measuring the viscosity at 6 rpm (25 ° C) &lt;56, and the viscosity at 60 rpm (25 t) 5 6 t) by the above-mentioned viscosity measurement method. (5 6/ (5 6Q calculated. In the usual ink for printing, in addition to preventing the diffusion or scattering, increase the viscosity, while improving the fluidity of the ink attached to or through the lithography The surface of the printed ink is smoothly flattened, and the viscosity is adjusted in order to make the surface of the ink glossy. However, since it is not necessary to etch the gloss or aesthetics of the ink surface when using the etching ink of the present invention, when the cutting quality of the pattern obtained by etching is the first index, in addition to the above preferred viscosity and TI In addition to 値, it was found that a particularly fine pattern can be achieved if •13-201207089 is used to apply a shear stress after the shear rate is restored to a certain range. The recovery rate of the viscosity after applying the shear stress is, for example, the same as the measurement of TI値, after being measured by a rotary viscometer under high rotation (high shear), after being placed for a short fixed time. This can be determined by performing a viscosity measurement with low rotation. The principle is that the ink is damaged by the shearing of the high shear stress, and the length of time until the viscosity is increased until the structure is low again, depending on the combination of the ink system (etching agent, etc.) and the thickener, This result is an optimum combination of the patterns which the inventors found to cause precision. &lt; Etching Agent for Conductive Polymer&gt; The conductive polymer etching ink of the present invention contains an etchant for a conductive polymer. The etchant for a conductive polymer of the present invention is not particularly limited as long as it is a compound capable of etching a conductive polymer, and is preferably an oxidant capable of etching a conductive polymer. Further, the etchant for a conductive polymer of the present invention is preferably selected from the group consisting of (NH4)2Ce(N03)6, Ce(S04)2, (NH4)4Ce (S04). a compound of the group consisting of nitrous oxide chlorine, a bromic acid compound, a chloric acid compound, a permanganic acid compound, a hexavalent chromium compound, and a hypochlorite, more preferably selected from the group consisting of (NH4)2Ce (N03) 6. A compound of the group consisting of Ce(S04)2, (NH4)4Ce(S04)4, permanganic acid compound, and hypochlorite. Among them, from the viewpoint of etchability, -14-201207089 is particularly selected from (NH4)2Ce(N03)6, Ce(S〇4)2, and (ΝΝ4) 4 C e (S化合物 4) The compound of the group consisting of 4 is particularly preferred as hypochlorite from the viewpoint of cost and versatility. (NH4)2Ce(N〇3)6 can be suitably used as the etchant for the above-mentioned conductive polymer. When (NH4)2Ce(N〇3)6 is used in the ink of the present invention, the (NH4)2Ce(N03)6 content in the ink of the present invention is thickened relative to the removal from the viewpoint of etchability. The total weight of the ink of the agent is preferably 0.5% or more, more preferably 1.0% or more, and further preferably 70% or less, preferably 40%, from the viewpoint of simultaneously increasing the concentration and the treatment speed or solubility. More preferably, it is 2.0 to 30%, particularly preferably 5.0 to 15%. » In the ink of the present invention using (NH4)2Ce(N03)6, in order to prevent decomposition of the tetravalent europium compound in the ink Preferably, a stabilizer is used. The stabilizer is preferably HN03 or HC104. When ΗΝ03 is used as the stabilizer, the concentration is preferably greater than 0.1%, more preferably 70% or less, and most preferably 1%, based on the total weight of the ink to which the weight of the thickener is removed. Up to 60%, more preferably 5 to 50%, and most preferably 1 to 20%. Further, when HC104 is used as the stabilizer, the concentration is preferably 0.1% or more, more preferably 60% or less, and most preferably 1% to the total weight of the ink for removing the thickener. 50%, more preferably 5 to 40%. When (NH4)2Ce(N03)6 is used in the ink of the present invention, if the stabilizer is in the above range, the stability of the etching solution is enhanced. -15- 201207089 Also, due to sulfuric acid, the ink containing (NH4)2Ce(N〇3)6 is turbid, which is disadvantageous as a stabilizer. C e (S Ο 4 ) 2 can be suitably used as the etchant for the conductive polymer. When Ce (S〇4) 2 is used in the ink of the present invention, Ce (S〇4h content ' in the ink of the present invention is from the viewpoint of etchability with respect to the entire ink in which the weight of the thickener is removed The weight ' is preferably 0 _ 5 % or more, more preferably 1.0% or more 'and' from the viewpoint of simultaneously increasing the concentration and the treatment speed or solubility, preferably 30% or less, preferably 20% or less. More preferably, it is from 2.0 to 25%, particularly preferably from 5 to 15%. In the ink of the present invention using Ce(S04)2, in order to prevent decomposition of the tetravalent europium compound in the ink, it is preferably used. The stabilizer is preferably hno3 or H2S04, more preferably hno3. If hno3 is used as the stabilizer, the concentration is greater than 0.1% relative to the total weight of the ink from which the thickener is removed. Preferably, it is preferably 70% or less, preferably 1.0 to 60%, more preferably 5.0 to 50%. Further, when H2S〇4 is used as the stabilizer, the concentration is preferably more than 0.1%. Further preferably 40% or less, more preferably 1.0 to 30%', more preferably 5.0 to 20%. When using Ce(S04)2 in the ink of the present invention, if the stabilizer is the above When the concentration is in the range, the etching ability of the ink can be prevented from being lowered. (NH4)4Ce(S04)4 can be suitably used as the etchant for the above-mentioned conductive polymer-16 - 201207089. In the use of (NH4)4Ce (S04 4 In the ink of the present invention, the content of (NH4)4Ce(S04)4 is preferably more than 0.5%, more preferably from 0.5% by weight, based on the total weight of the ink from which the thickener is removed. It is more than 1% by weight, and more preferably 30% or less, more preferably 25% or less, and more preferably: 1. 〇 to 25%, from the viewpoint of simultaneously increasing the concentration and the treatment speed or solubility. Preferably, in the ink of the present invention using (NH4)4Ce(S04)4, in order to prevent decomposition of the tetravalent cerium compound in the ink, it is preferred to use a stabilizer. Preferably, H2S〇4. If H2S〇4 is used as the stabilizer, the concentration is preferably 1.0% or more, and preferably 40% or less, preferably 2.0 to 30%, more preferably 3 to 20. %. If H2S〇4 is at the concentration of the above range, the etching resistance of the ink etch can be prevented from being lowered. Also, since the nitric acid causes the invention containing (NH4)4Ce(S04)4 The ink becomes turbid, which is disadvantageous as a stabilizer. Nitrogen oxychloride can be suitably used as the etchant for the conductive polymer. Nitrous oxychloride is mixed with hydrochloric acid and nitric acid at the same time as the active chlorine. HN〇3 + 3HC1 — NOC1 + Cl2 + 2H2〇 If the ink of the present invention contains nitrosyl chloride, it is preferably further contained with hydrochloric acid and nitric acid, in addition to nitrous chloride. The total weight of the ink of the thickener is 5% or more of hydrochloric acid, 20% of -9-201207089 of nitric acid, (hydrochloric acid concentration + 〇·5 lx nitric acid concentration), the enthalpy is 35% or less, and (hydrochloric acid concentration + 0 · 5 X nitric acid concentration) is more than 30%. When nitrous cerium chloride is used in the ink of the present invention, the concentration of nitric acid is preferably 20% or more, more preferably 25 to 50,000%, more preferably 25% to 50%, based on the total weight of the ink from which the thickener is removed. 3 0 to 40%. Further, when nitrous cerium chloride is used in the ink of the present invention, the concentration of hydrochloric acid is preferably 5% or more with respect to the total weight of the ink from which the thickener is removed, and more preferably satisfies (hydrochloric acid concentration + 0.5 lx). The concentration represented by the nitric acid concentration is 35% or less, and the concentration expressed by the formula (hydrochloric acid concentration + 0::5 nitric acid concentration) is 30% or more. A bromic acid compound or a chloric acid compound can be suitably used as the etchant for the above conductive polymer. The bromic acid compound and the chloric acid compound can be improved in etching ability by being used in combination with an acid. The aforementioned bromic acid compound is preferably an alkali metal salt of bromic acid, more preferably a sodium salt or a potassium salt. When a bromic acid compound is used in the ink of the present invention, the concentration of the bromic acid compound is preferably from 3 to 40%, more preferably from 5 to 35%, more preferably from 5 to 35%, based on the total weight of the ink from which the thickener is removed. 10 to 30%. The inorganic acid to be used in combination with the bromic acid compound may, for example, be phosphoric acid, nitric acid or sulfuric acid, and is preferably nitric acid and sulfuric acid. The concentration of the inorganic acid to be used is preferably from 4 to 30%, more preferably from 1 to 25 %, based on the total weight of the ink from which the weight of the thickener is removed. -18- 201207089 The aforementioned chloric acid compound is preferably an alkali metal salt of chloric acid, more preferably a sodium salt or a potassium salt. When a chloric acid compound is used in the ink of the present invention, the concentration of the chloric acid compound is preferably from 6 to 40%, more preferably from 10 to 35 %, based on the total weight of the ink from which the weight of the thickener is removed. The inorganic acid to be used in combination with the chloric acid compound is preferably a hydrogen halide, and hydrochloric acid and hydrogen bromide are exemplified as hydrochloric acid. The inorganic acid concentration to be used is preferably from 7 to 30%, more preferably from 10 to 25 %, based on the total weight of the ink from which the weight of the thickener is removed. A permanganic acid compound can be suitably used as the etchant for the above-mentioned conductive polymer. The above permanganic acid compound is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt. When the permanganic acid compound is used in the ink of the present invention, the concentration of the permanganic acid compound is preferably 0.001 to 20%, preferably 0.01 to 10%, based on the total weight of the ink from which the thickener is removed. Good is 0" to 5%. The permanganic acid compound causes the ink to be alkaline due to the influence of the yoke ion, and an acid may be added to adjust the pH of the ink. The acid to be used in the permanganic acid compound is exemplified by an organic acid or an inorganic acid, and in the present invention, a mineral acid is preferred. In the present invention, examples of the organic acid include formic acid, acetic acid, propionic acid and the like, and acetic acid is preferred. The inorganic acid aspect can be exemplified by phosphoric acid, nitric acid and sulfuric acid, preferably nitric acid and sulfuric acid, more preferably sulfuric acid. The concentration of the acid used for the permanganic acid compound is preferably from 1 to 50%, more preferably 25%, based on the total weight of the ink from which the weight of the thickener of -19 to 201207089 is removed. A hexavalent chromium compound can be suitably used as the above-mentioned highly conductive etchant. Among the hexavalent chromium compounds, there are chromium oxide, a chromic acid compound and a compound, and the chromic acid compound may be exemplified by an alkali metal salt, and the compound may also be exemplified by an alkali metal salt, and the alkali metal salt is sodium. Salt or potassium salt. In the case of the above hexavalent chromium compound, a chromium oxide or a dichromate acid compound is preferred, and more preferably chromium oxide. When a hexavalent chromium compound is used in the ink of the present invention, the hexavalent content is preferably used in an amount of from 3 to 30,000%, preferably from 5 to 5%, based on the total weight of the ink from which the thickener is removed. Preferably, it is from 10 to 20%. The inorganic acid is preferably used in the hexavalent chromium compound. The noodle is exemplified by phosphoric acid, nitric acid and sulfuric acid, and preferably nitric acid and sulfur are sulfuric acid. The total weight of the ink of the weight of the thickener relative to the concentration of the inorganic acid used for the hexavalent chromium compound is preferably from 1 to 50%, from 5 to 25%. Hypochlorite can be suitably used as the above-mentioned conductive polymer. Most of the hypochlorite is produced by absorbing chlorine in an alkali metal hydroxide or an alkaline earth hydroxide. In this case, the aqueous solution is preferably 5 due to the influence of the unreacted base metal or the alkali metal hydroxide. The chromic chromic acid surface of the molecule is more chromic than the chromium chrome, and the acid squaric acid is used as the sulphuric acid, and more preferably the etched metal oxyhydroxide is used as the strong base -20-201207089. In order to adjust the pH of the ink of the present invention, an acid may also be used. Any of inorganic acids and organic acids can be used for the acid used. Specifically, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, citric acid or the like can be preferably exemplified, and among them, sulfuric acid or nitric acid is more preferable. When the hypochlorite is used in the ink of the present invention, the pH of the ink of the present invention is not particularly limited, and may be selected depending on the material of the substrate or the conductive polymer film to be used, but the chlorine gas is suppressed. From the viewpoint of production or etching property, the pH is preferably 4 to 13, preferably 6 to 12.5, more preferably 7 to 12, most preferably 7 to 11. The pH measurement of the ink of the present invention can be measured using a commercially available pH meter. When hypochlorous acid is used in the ink of the present invention, the effective chlorine concentration of hypochlorous acid is preferably 0.06% or more with respect to the total weight of the ink from which the thickener is removed, preferably 0.1% or more, more preferably It is preferably 0.2% or more, and more preferably 3% or less, preferably 2% or less, more preferably 1% or less. When the effective chlorine concentration is within this range, the conductive polymer can be efficiently etched. In the present invention, the effective chlorine concentration of hypochlorous acid is determined by titration with Na2S03. Namely, the sample to be measured was taken in an amount of 250 g. A portion of the sample solution was taken out, and i.ml. of potassium iodide was added as an aqueous solution of 10%. Then, 10 0 1 of acetic acid (1:2) was added to make the pH acidic. The solution was titrated with an aqueous solution of sodium thiosulfate of 0.1 equivalent (in order to easily determine the end point during the titration, soluble starch may also be added). The effective chlorine concentration was determined from the titer of 0.1 equivalent of Na2S03 and the amount of sample taken and the following formula -21 - 201207089. 0.003546x (Dose of Na2SO3: ml) 250

有效氯濃度(°/〇)=___χ/χ_ xlOO W 10 還有’/(因子（factor))係表示0.1之規定濃度的Na2S03 之修正係數、即修正實際所使用之Na2S03A溶液與o.i當 量濃度的Na2S03水溶液之差的係數。 &lt;增稠劑&gt; 本發明之導電性高分子蝕刻用印墨包含增稠劑。 可用於本發明之增稠劑方面，從印墨之安定性及與導 電性高分子用蝕刻劑之非反應性的觀點來看，較佳爲無機 粒子、及/或界面活性劑。 無機粒子之材質方面，可舉例爲矽石、礬土、氧化鈦、 氧化鍩、氧化鍺、氧化铈、氧化鋅、碳化矽、滑石、雲母、 及高嶺石等。 無機粒子之形狀方面，並無特別限制，可舉出爲球狀、 板狀 '針狀、纖維狀、不定形狀等，但較佳爲球狀。 無機粒子之平均一次粒徑方面，以3nm至l/zm爲佳， 較佳爲3至500nm，更佳爲3至lOOnm。 增稠劑方面，從成本或印墨之安定性的觀點來看，較 佳爲界面活性劑。 界面活性劑方面，可使用陰離子界面活性劑、陽離子 界面活性劑、兩性界面活性劑、非離子性界面活性劑。 陰離子界面活性劑方面，舉出爲脂肪酸鹽、烷基苯磺 -22- 201207089 酸鹽、單烷基硫酸鹽。兩性界面活性劑方面舉出有氧化烷 基胺、甜菜鹼（b e ta in e)化合物。非離子性界面活性劑方面 舉出有聚氧乙烯烷基醚。 彼等之中，界面活性劑方面較佳爲單烷基硫酸鹽、或 氧化烷基胺，更佳爲單烷基硫酸鹽。 單烷基硫酸鹽方面，舉出較佳爲十二基硫酸鹽、十四 基硫酸鹽，舉出更佳爲十二基硫酸鹽。 又，若使用單烷基硫酸鹽時，爲了使單烷基硫酸鹽存 在酸成分並提升溶解度，較佳爲與酸性成分一起使用。酸 性成分係可適宜地選擇無機酸、有機酸中任一者、且不受 蝕刻劑不良影響者。 單烷基硫酸鹽的較佳之添加量方面，相對於印墨之全 體重量’以3至40重量％爲佳，較佳爲7至35重量％，更 佳爲9至35重量％，最佳爲9至2 5重量％。 單烷基硫酸鹽方面，特佳爲在本發明之印墨含有選自 由（NH4)2Ce(N03)6、Ce(S04)2、及（NH4)4Ce(S04)4 所組成之 群組之化合物時所含有。 氧化烷基胺方面，舉例爲氧化十二醯基醯胺丙基二甲 基胺、氧化十六醯基醯胺基丙基二甲基胺、氧化十八醯基 醯胺丙基二甲基胺、氧化椰油醯基醯胺丙基二甲基胺、氧 化油酿基醯胺丙基二甲基胺、氧化硬化牛脂烷醯基醯胺丙 基二甲基胺、氧化椰子油二甲基胺、氧化椰子油二乙基胺、 椰子油、氧化椰子油甲基乙基胺、氧化N,N_二甲基-N_烷基 -23- 201207089 胺等。 氧化烷基胺方面，特佳爲在本發明之印墨含有次氯酸 時所含有。 增稠劑方面，從成本或印墨之安定性、與導電性高分 子用蝕刻劑之非反應性、圖案精確度的觀點來看，較佳爲 無機粒子。 無機粒子方面，較佳爲金屬氧化物粒子，更佳爲氧化 矽（矽石）粒子、氧化鈦粒子、氧化铈粒子、氧化鋁（礬土） 粒子、氧化鋅粒子、氧化錫粒子、或彼等之複合氧化物粒 子、及混合物。 彼等之中，更佳爲矽石粒子及/或礬土粒子，矽石粒子 與礬土粒子之混合物係因施加上述之剪切應力後之黏度的 恢復速度高之觀點而爲特佳。 又，在使用（NH4)2Ce(N03)6、Ce(S04)2、及 / 或 (NH4)4Ce(S04)4做爲導電性高分子用蝕刻劑時，從成本或 與導電性高分子用蝕刻劑之非反應性的觀點來看，特佳爲 矽石粒子，在使用次氯酸鹽時，從與導電性高分子用蝕刻 劑之非反應性的觀點來看，特佳爲矽石粒子與礬土粒子之 混合物。 本發明之印墨中的增稠劑之含量雖可隨所希望之黏度 而適宜地調整，但相對於印墨之全體重量，以0.5至50重 量％爲佳，較佳爲1至20重量％，更佳爲5至1 0重量％。 &lt;水性媒介&gt; -24- 201207089 本發明之導電性高分子蝕刻用印墨包含水性媒介。 可用於本發明之水性媒介若爲對蝕刻處理無影響之媒 介，則無特別之限制，但較佳爲水》 本發明之印墨較佳爲含有25重量％以上之水性媒介， 更佳爲含有50重量％以上。 又，如前述，在本發明之導電性高分子蝕刻用印墨中， 亦可包含酸。 又，本發明之導電性高分子蝕刻用印墨較佳爲水性印 墨。 &lt;導電性高分子&gt; 本發明之導電性高分子蝕刻用印墨對於導電性高分子 具有優異之蝕刻能力。 導電性高分子係π電子移動而顯示導電性。眾多報告 該等導電性高分子。 可用於本發明之導電性高分子方面，舉例爲聚苯胺、 聚噻吩、聚吡咯、聚伸苯、聚蕗、聚聯噻吩、聚異噻吩、 聚（3,4-乙烯二氧噻吩）、聚異噻茚、聚異萘并噻吩、聚乙炔' 聚二乙炔、聚對伸苯基伸乙烯、聚并苯、聚噻唑、聚乙烯 伸乙烯、聚對伸苯、聚十二基噻吩、聚伸苯基伸乙烯、聚 伸噻吩伸乙烯、聚硫化伸苯等或彼等之衍生物。彼等之中， 較佳爲聚苯胺類、聚毗咯類、或聚噻吩類，更佳爲聚耻略 類、或聚噻吩類’最佳爲導電度 '在空氣中之安定性及耐 熱性優異之聚（3,4 -乙烯二氧噻吩）》 -25- 201207089 又’可用於本發明之導電性高分子較佳爲不溶水性之 導電性高分子。 又’以使用導電性高分子時發現較高導電度爲目的， 可倂用稱爲摻雜物（dopant)之慘雜劑。可用於前述導電性高 分子之摻雜物方面，可使用熟知之摻雜物，隨導電性高分 子之種類’可舉例爲鹵素類（溴、碘、氯等）、路易斯酸 (BF3、PF5等）、質子酸（hno3、H2S04等）、過渡金屬鹵化 物（FeCl3、M〇Cl5等）、鹼金屬（Li、Na等）、有機物質（胺酸、 核酸、界面活性劑、色素、烷基銨離子、氯醌（chi or aniU、 四氰乙烯（TCNE)、7,7,8,8-四氰對醌二甲烷（TCNQ)等）等。 亦可爲於導電性高分子本身具有摻雜效果之自身摻雜型導 電性高分子。又，若使用聚噻吩時，較佳爲使用聚苯乙烯 磺酸做爲摻雜物。 可用於本發明之導電性高分子的導電率若在顯示導電 性之値的範圍則無特別限制，以1(Γ6至104S/cm爲佳，較 佳爲1〇·5'5至103S/cm，更佳爲10_5至5xl〇2S/cm。在本發 明中所使用之導電性高分子的導電率爲上述範圍時，在連 接部分之圖案化等之中則較佳。 又，可用於本發明之導電性高分子，較佳爲在其使用 時於可見光範圍之透射率高者。還有，透射率在波長5 5 0 nm 係以60至98%爲佳，較佳爲70至95%，更佳爲80至93%。 導電性高分子本身之透過率爲上述範圍時，可適用於顯視 器等之用途。 -26- 201207089 其中，在本發明中，所謂可見光範圍爲400至700n:m。 還有，透過率之測定係可藉由分光光度計測定。 市售有各種的導電性高分子。由Panipol公司製造之 以「Panipol」商品名所市售之聚苯胺，爲以機能性磺酸所 摻雜之有機溶劑可溶型聚苯胺。由Ormecon公司所製造之 以「Ormecon」之以商品名所市售之聚苯胺，爲使用有機酸 於摻雜物之溶劑分散型聚苯胺。由拜耳（Bayer)公司所製造 之以「Baytron」商品名所市售之聚（3,4-乙烯二氧噻吩}係 以聚苯乙烯磺酸做爲摻雜物。在其他方面，亦可在本發明 中使用由阿基里斯（Achilles)(股）公司所製造之商品名「ST Poly j之聚吡咯、由東洋紡織（股）公司所製造之商品名 「PETMAX」之磺化聚苯胺、由九愛（Maruai)(股）公司所製 造之商.品名「SCS-NEO」之聚苯胺。 亦可使用記載於專利流通支援圖表之平成1 3年度化 學6「有機導電性高分子」做爲專利流通促進事業之導電 性高分子。 (導電性高分子之圖案化方法） 本發明之導電性高分子的圖案化方法（以下，亦簡稱爲 「本發明之圖案化方法」。）’爲使用本發明之導電性高分 子蝕刻用印墨所進行之方法。 可藉由使本發明之導電性高分子蝕刻用印墨接觸導電 性高分子，蝕刻該接觸部分。 藉由本發明之導電性高分子之圖案化方法所飽刻之導 -27- 201207089 電性闻分子的形狀’並無特別限制，雖可爲任意之形狀， 但較佳爲膜狀。 又’本發明之導電性高分子之圖案化方法，較佳爲包 含於基材上形成導電性高分子膜之成膜步驟、在除去前述 膜上之導電性高分子的範圍中塗敷本發明之導電性高分子 飽刻用印墨之印刷步驟'藉由前述導電性高分子鈾刻用印 墨蝕刻前述所除去之範圍的導電性高分子之纟φ刻步驟、以 及從基板除去所殘存之導電性高分子蝕刻用印墨及導電性 高分子之蝕刻殘渣之除去步驟。 &lt;成膜步驟&gt; 本發明之導電性高分子之圖案化方法較佳爲包含在基 材上形成導電性高分子膜之成膜步驟。 基材方面並無特別限制，可隨使用用途來選擇，具體 而言’舉例爲玻璃、石英、聚酯（例如聚對苯二甲酸乙二酯 (PET)、聚萘二甲酸乙二酯等）、聚烯烴（例如聚乙烯、聚丙 烯、聚苯乙烯等）、聚醯亞胺、聚丙烯酸酯、甲基丙烯酸酯 等。 前述成膜步驟中之導電性高分子膜之厚度方面，並無 特別限制，雖可爲所希望之厚度，但以lnm至100“111爲 佳，較佳爲2nm至1/zm，更佳爲5至500nm。 前述成膜步驟中之導電性高分子方面，可適用前述者。 前述成膜步驟中之於基材上形成導電性高分子膜之方 法方面，並無特別限制，可藉由熟知之方法形成。具體而 -28- 201207089 言，可舉例爲將導電性高分子之溶液旋轉塗布或浸漬塗布 於基材上並乾燥的方法等。 在基材與導電性高分子膜之間，必要時亦可具有其他 層。又，在前述印刷步驟之前、在導電性高分子膜上，必 要時亦可形成其他層。 形成於基材上之導電性高分子膜可爲相同的膜，亦可 爲一部分已藉由本發明之圖案化方法或其他方法進行圖案 化之膜。 &lt;印刷步驟&gt; 本發明之導電性高分子之圖案化方法，較隹爲包含在 除去於前述膜上之導電性高分子的範圍中塗敷本發明之導 電性高分子蝕刻用印墨之印刷步驟。 在除去導電性高分子之範圍中塗敷本發明之導電性高 分子蝕刻用印墨之方法方面，可舉例爲孔版印刷、凸版印 刷、凹版印刷、及平版印刷等。彼等之中，從在蝕刻中可 容易地調整充分之印墨量的觀點來看，以孔版印刷爲佳， 較佳爲絲網印刷、模板（s t e n c i 1)印刷、及襯墊（p a d)印刷， 更佳爲絲網印刷。 塗敷前述印刷步驟中之本發明的印墨量方面，並無待 別限制，可隨印墨之組成、導電性高分子之材質或膜厚、 進行蝕刻之時間或溫度、進行蝕刻之深度等而適宜地選擇。 又，塗敷前述印刷步驟中之本發明的印墨量，可平均 前述膜之面積塗敷固定的量，必要時亦可相對於其他部分 -29- 201207089 之印墨量增減一部分之印墨量。 又，除去前述膜上之導電性高分子之範圍的形狀並無 特別限制，可爲針對需要的形狀。又，本發明之導電性高 分子的圖案化方法，可適用於例如奈米級至厘米級之線寬 的蝕刻、可適用於微米級至毫米級之線寬的軸刻。 &lt;蝕刻步驟&gt; 本發明之導電性高分子的圖案化方法，較佳爲包含藉 由前述導電性高分子蝕刻用印墨蝕刻前述除去之範圍的導 電性高分子之蝕刻步驟。 在前述蝕刻步驟中，由於在前述導電性高分子膜之 內，蝕刻本發明之導電性高分子蝕刻用印墨接觸的部分， 可經過於前述印刷步驟後、前述所除去之範圍的蝕刻中所 需要之時間。 前述蝕刻步驟中之經過時間（蝕刻時間）並無特別限 制，可隨印墨之組成、導電性高分子之材質或膜厚、進行 蝕刻之溫度、進行蝕刻之深度等而適宜地選擇。 前述蝕刻步驟中之蝕刻時的溫度方面並無特別限制， 可於例如常溫（10至30°C )下進行。又，爲了蝕刻速度之調 整等，亦可加熱或冷卻蝕刻氣體環境及/或具有導電性高分 子膜之基材。 又’在蝕刻步驟中，前述除去之範圍的除去，必要時 可爲貫穿薄膜之完全地蝕刻之樣態，亦可爲未貫穿薄膜之 僅蝕刻前述除去範圍之一部分之樣態。 -30- 201207089 又，在前述蝕刻步驟中，可靜置具有前述導電性高分 子膜之基材，亦可在運輸等對蝕刻無大影響的範圍內移動 具有前述導電性高分子膜之基材。 &lt;除去步驟&gt; 本發明之導電性高分子之圖案化方法，較佳爲包含從 基板上除去所殘存之導電性高分子蝕刻用印墨及導電性高 分子之蝕刻殘渣之除去步驟。 前述導電性高分子之蝕刻殘渣方面，舉例爲藉由本發 明之印墨的導電性高分子之分解物、或因蝕刻所產生之導 電性高分子之細微粉末等。 又，在前述除去步驟中，當然不僅除去殘存之導電性 高分子蝕刻用印墨及導電性高分子之蝕刻殘渣，亦可除去 不需要之蝕刻殘渣。 在前述除去步驟中，從簡便性或成本的觀點來看，較 佳爲藉由水洗除去殘存之導電性高分子蝕刻用印墨及導電 性高分子之蝕刻殘渣。 前述水洗中所使用之水量方面，只要爲對於前述除去 充分的量即可。 水洗方法方面並無特別限制，可較佳地舉例爲藉由流 水洗淨具有已圖案化的導電性高分子之基材之方法、或將 具有已圖案化的導電性高分子膜之基材浸漬於水中之方 法。 又，若在前述除去步驟中進行水洗時，本發明之導電 -31 - 201207089 性高分子之圖案化方法，較佳爲在前述除去步驟之後，包 含乾燥已圖案化的導電性高分子膜之步驟。 前述乾燥方法方面並無特別限制，可使用以熱之乾 燥、風乾、以溫空氣之乾燥等熟知之方法。 又，本發明之導電性高分子之圖案化方法，在前述步 驟以外，必要時亦可包含其他步驟。 例如，在進行本發明之導電性高分子的圖案化方法之 後、或進行之前，可爲藉由本發明以外之其他圖案化方法 進行圖案化，又亦可進行2次以上本發明之導電性高分子 的圖案化方法。 又，在本發明之導電性高分子的圖案化方法中，必要 時使用2種以上本發明之導電性高分子蝕刻用印墨。 本發明之導電性高分子鈾刻用印墨、及本發明之導電 性高分子的圖案化方法，可適用於使用於電解電容器、電 池、觸控面板、液晶面板、及有機EL元件等之導電性高分 子的蝕刻。 因此，可期待在所謂代表高分子有機EL顯示器之顯示 器的顯示畫素部分之導電性高分子及周邊迴路與導電性高 分子之連接部分的圖案化、觸控面扳的檢測部分之導電性 高分子及周邊迴路與導電性高分子之連接部分之圖案化、 與電容器製造時府著於不需要部分之導電性高分子的除去 等之蝕刻之必要用途中’促進導電性高分子之利用。 [實施例] -32- 201207089 以下，雖利用實施例以說明本發明，但不以彼等實施 例限制本發明。還有，所謂以下記載中之「份」，若無特別 說明，則表示爲「重量份」。 [實施例1] 混合5 0份的有效氯濃度爲1 3 %之次氯酸鈉與9 5 0份的 水，製作1，〇〇〇份的有效氯濃度爲〇·65 %之次氯酸鈉溶液。 以在該次氯酸鈉溶液中加入 82 份的日本氣膠 (AEROSIL)(股）製之氣膠（AEROSIL)COK84(矽石粒子與礬 土粒子之5 : 1混合物、平均一次粒徑：約12nm)並攪拌而 均勻地分散，得到1，〇 8 2份的蝕刻印墨。另外在A4尺寸之 聚對苯二甲酸乙二酯（PET)板的表面上，製作聚噻吩系導電 性高分子（H· C·史塔克（H_ C. Starck)(股）製 CLEVIOS PH 5 00)之薄膜（厚度約爲5〇nm)與4.0cm見方之PET製絲網 版。在手刷之印刷機上裝置薄膜與絲網版，置入適量的先 前所製作之蝕刻印墨並進行絲網印刷。印刷結束3 0秒後， 以大量水洗除薄膜上之蝕刻印墨並乾燥，完全溶解或剝離 蝕刻印墨附著部分之薄膜，完成依照絲網圖案之導電性高 分子的圖案化。 [實施例2] 混合50份的有效氯濃度爲13%之次氯酸鈉與9 5 0份的 水，製作1，〇〇〇份的有效氯濃度爲0.65 %之次氯鈉溶液。以 在該次氯酸鈉溶液中緩緩加入600份的0.062重量％之硫酸 同時攪拌，最後加入400份的水並混合，製作2,000份的 -33- 201207089 有效氯濃度爲〇 · 3 2 5 %之次氯酸鈉溶液°以在該次氯酸鈉溶 液中加入 180份的日本氣膠（AEROSIL)(股）製之氣膠 (AEROSIL)COK84並攪拌而均勻地分散，得到2,180份的 蝕刻印墨。另外在A4尺寸之聚對苯二甲酸乙二酯（PET)板 的表面上，製作聚噻吩系導電性高分子（H· C·史塔克（H. C. Starck)(股）製 CLEVIOS PH 500)之薄膜（厚度約爲 50nm) 與4.0cm見方之PET製絲網版。在手刷之印刷機上裝置薄 膜與絲網版，置入適量的先前所製作之蝕刻印墨並進行絲 網印刷。印刷結束3 0秒後，以大量水洗除薄膜上之鈾刻印 墨並乾燥，完全溶解或剝離蝕刻印墨附著部分之薄膜，完 成依照絲網圖案之導電性高分子的圖案化。 [實施例3] 在5 0份的有效氯濃度爲1 3 %之次氯酸鈉中混合1 · 5份 的48重量％之氫氧化鈉水溶液與948.5份的水，製作1，0 00 份的有效氯濃度爲0.65%之次氯鈉溶液。以在該次氯酸鈉 溶液中加入 65份的日本氣膠（AEROSIL)(股）製之氣膠 (AEROSIL) COK84並攪拌而均句地分散，得到1，065份的 蝕刻印墨。另外在A4尺寸之聚對苯二甲酸乙二酯（PET)板 的表面，製作聚噻吩系導電性高分子（H· C·史塔克（H.C. Starck)(股）製CLEVIOS PH 500)之薄膜（厚度約爲50nm)與 4.0cm見方之PET製絲網版。在手刷之印刷機上裝置薄膜 與絲網版，置入適量的先前所製作之蝕刻印墨並進行絲網 印刷。印刷結束3 0秒後，以大量水洗除薄膜上之蝕刻印墨 -34- 201207089 並乾燥，完全溶解或剝離蝕刻印墨附著部分之薄膜，完成 依照絲網圖案之導電性高分子的圖案化。 [實施例4] 將具有聚吡咯系導電性高分子之薄膜的板材（阿基里 斯（Achilles)(股）公司製 ST真空成形用板材（膜厚約爲 10 Onm))切割成任意之大小，使用另外準備之4.0cm見方之 PET製絲網版，在手刷之印刷機上裝置薄膜與絲網版，置 入適量的於實施例1所製作之蝕刻印墨並進行絲網印刷。 印刷結束3 0秒後，以大量水洗除薄膜上之蝕刻印墨並乾 燥，完全溶解或剝離蝕刻印墨附著部分之薄膜，完成依照 絲網圖案之導電性高分子的圖案化。 [實施例5 ] 將具有聚吡咯系導電性高分子之薄膜的板材（阿基里 斯（Achilles)(股）公司製ST真空成形用板材）切割成任意之 大小，使用另外準備之4.0 cm見方之PET製絲網版，在手 刷之印刷機上裝置薄膜與絲網版，置入適量的於實施例2 所製作之蝕刻印墨並進行絲網印刷。印刷結束3 0秒後’以 大量水洗除薄膜上之蝕刻印墨並乾燥，完全溶解或剝離蝕 刻印墨附著部分之薄膜，完成依照絲網圖案之導電性高分 子的圖案化。 [實施例6] 將具有聚吡咯系導電性高分子之薄膜的板材（阿基里 斯（Achilles)(股）公司製ST真空成形用板材）切割成任意之 -35- 201207089 大小，使用另外準備之4.0 cm見方之PET製絲網版，在手 刷之印刷機上裝置薄膜與絲網版，置入適量的於實施例3 所製作之蝕刻印墨並進行絲網印刷。印刷結束3 0秒後，以 大量水洗除薄膜上之蝕刻印墨並乾燥，完全溶解或剝離蝕 刻印墨附著部分之薄膜，完成依照絲網圖案之導電性高分 子的圖案化。 [實施例7] 混合水與硝酸銨亞鈽（Cerric Ammonium Nitrate)及濃 硝.酸，製作1，〇〇〇份的硝酸銨亞铈濃度爲1 〇% ·硝酸濃度 爲1 5 %之蝕刻液。以在該蝕刻液中加入8 0份的日本氣膠 (AEROSIL)(股）製之氣膠（AEROSIL) 130(矽石粒子、卒均一 次粒徑：約16nm)攪拌並均勻地分散，得到1，080份的蝕刻 印墨。另外在A4尺寸之聚對苯二甲酸乙二酯（PET)板的表 面上，製作聚噻吩系導電性高分子（H· C·史塔克（H. C. Starck)(股）製CLEVIOS PH 500)之薄膜（厚度約爲50nm)與 4.0cm見方之PET製絲網版。在手刷之印刷機上裝置薄膜 與絲網版，置入適量的先前所製作之蝕刻印墨並進行絲網 印刷。印刷結束3 0秒後，以大量水洗除薄膜上之蝕刻印墨 並乾燥，完全溶解或剝離蝕刻印墨附著部分之薄膜，完成 依照絲網圖案之導電性高分子的圖案化。 [實施例8] 混合水與硫酸亞鈽及濃硫酸，製作1，〇〇〇份的硫酸亞 姉濃度爲5% ·硫酸濃度爲1 5%之蝕刻液。在該蝕刻液中加 -36- 201207089 Λ 90份的日本氣膠（AEROSIL)(股）製之氣膠（AEROSIL) 1 3 0攪拌並均勻地分散，得到1，090份之蝕刻印墨。另外在 A4尺寸之聚對苯二甲酸乙二酯（PET)板的表面上，製作聚 噻吩系導電性高分子（H · C ·史塔克（H. C. Starck)(股）製 CLEVIOS PH 5 00)之薄膜（厚度約爲50nm)與4.0cm見方之 PET製絲網版。在手刷之印刷機上裝置薄膜與絲網版，置 入適量的先前所製作之蝕刻印墨並進行絲網印刷。印刷結 束3 0秒後，以大量水洗除薄膜上之蝕刻印墨並乾燥，完全 溶解或剝離蝕刻印墨附著部分之薄膜，完成依照絲網圖案 之導電性高分子的圖案化。 [實施例9 ] 混合水與硫酸銨亞鈽及濃硫酸，製作1,000份的硫酸 銨亞铈濃度爲1 〇% ·硫酸濃度爲1 5%之蝕刻液。在該蝕刻 液中加入 90份的日本氣膠（AEROSIL)(股）製之氣膠 (AEROSIL) 130攪拌並均勻地分散，得到1，〇90份的鈾刻印 墨。另外在A4尺寸之聚對苯二甲酸乙二酯（PET)板的表面 上，製作聚噻吩系導電性高分子（H· C·史塔克（H. C. Starck)(股）製CLEVIOS PH 5 00)之薄膜（厚度約爲50nm)與 4.0cm見方之PET製絲網版。在手刷之印刷機上裝置薄膜 與絲網版，置入適量的先前所製作之蝕刻印墨並進行絲網 印刷。印刷結束3 0秒後，以大量水洗除薄膜上之蝕刻印墨 並乾燥，完全溶解或剝離蝕刻印墨附著部分之薄膜，完成 依照絲網圖案之導電性高分子的圖案化。 -37- 201207089 [實施例l〇] 將具有聚吡咯系導電性高分子之薄膜的板材（阿基里 斯（Achilles)(股）公司製ST真空成形用板材）切割成任意之 大小，使用另外準備之4.0cm見方之PET製絲網版，在手 刷之印刷機上裝置薄膜與絲網版，置入適量的於實施例7 所製作之蝕刻印墨並進行絲網印刷。印刷結束3 0秒後，以 大量水洗除薄膜上之蝕刻印墨並乾燥，完全溶解或剝離蝕 刻印墨附著部分之薄膜，完成依照絲網圖案之導電性高分 子的圖案化。 [實施例11 ] 將具有聚吡咯系導電性高分子之薄膜的板材（阿基里 斯（Achilles)(股）公司製ST真空成形用板材）切割成任意之 大小，使用另外準備之4.0cm見方之PET製絲網版，在手 刷之印刷機上裝置薄膜與絲網版，置入適量的於實施例8 所製作之蝕刻印墨並進行絲網印刷。印刷結束3 0秒後，以 大量水洗除薄膜上之蝕刻印墨並乾燥，完全溶解或剝離蝕 刻印墨附著部分之薄膜，完成依照絲網圖案之導電性高分 子的圖案化。 [實施例12] 將具有聚吡咯系導電性高分子之薄膜的板材（阿基里 斯（Achilles)(股）公司製ST真空成形用板材）切割成任意之 大小’使用另外準備之4.0cm見方之PET製絲網版，在手 刷之印刷機上裝置薄膜與絲網版，置入適量的於實施例9 -38- 201207089 所製作之蝕刻印墨並進行絲網印刷。印刷結束3 0秒後，以 大量水洗除薄膜上之蝕刻印墨並乾燥，完全溶解或剝離飩 刻印墨附著部分之薄膜，完成依照絲網圖案之導電性高分 子的圖案化。 [比較例1 ] 混合5 〇份的有效氯濃度爲1 3 %之次氯酸鈉與9 5 0份的 水，製作1，〇〇〇份的有效氯濃度爲0.65%之次氯酸鈉溶液。 以在該次氯酸鈉溶液中加入 45 份的日本氣膠 (AEROSIL)(股）製之氣膠（AEROSIL) COK84攪拌並均勻地 分散，得到1,045份之蝕刻印墨。另外在Α4尺寸之聚對苯 二甲酸乙二酯（PET)板的表面上，製作聚噻吩系導電性高分 子（H· C·史塔克（H. C. Starck)(股）製 CLEVIOS PH 500) 之薄膜（厚度約爲50nm)與4.0cm見方之PET製絲網版。在 手刷之印刷機上裝置薄膜與絲網版，置入適量的先前所製 作之蝕刻印墨並進行絲網印刷。印刷結束3 0秒後，以大量 水洗除薄膜上之蝕刻印墨並乾燥，完全溶解或剝離蝕刻印 墨附著部分之薄膜，完成導電性高分子之圖案化。然而， 由於印墨之黏度低，故一部份從絲網圖案突出，所完成的 圖案之精確度低。 [實施例13] 混合水與硝酸銨亞铈及濃硝酸，製作1，000份的硝酸 銨亞铈濃度爲10% ·硝酸濃度爲15%之蝕刻液。以在該蝕 刻液中加入2〇〇份的日本氣膠（AEROSIL)(股）製之氣膠 -39- 201207089 (A E R O S I L) 1 3 0攪拌並均勻地分散，得至[J 1，2 0 0份的蝕刻印 墨。另外在A4尺寸之聚對苯二甲酸乙二酯（PET)板的表面 上，製作聚噻吩系導電性高分子（H· C·史塔克（H. C. Starck)(股）製 CLEVIOS PH 500)之薄膜與 4_0cm 見方之 PET 製絲網版。在手刷之印刷機上裝置薄膜與絲網版，置入適 量的先前所製作之蝕刻印墨並進行絲網印刷。印刷結束3 0 秒後，以大量水洗除薄膜上之蝕刻印墨並乾燥，完全溶解 或剝離蝕刻印墨附著部分之薄膜，完成導電性高分子的圖 案化。然而，由於印墨之黏度高，故絲網之印墨穿透差， 與實施例7至9相比，所完成的圖案之精確度，雖爲實用 上無問題之程度，但是稍差。 [實施例14] 將對於 1,000份的硝酸錢’亞铈（Cerric Ammonium Nitrate)爲1 0 % ·硝酸爲1 5 %之溶液，加入8 1份的氣膠 (AERO SIL·) 130，調製導電性高分子蝕刻用印墨時之黏度與 TI値顯示於以下之表1。 還有，在黏度之測定中，使用（股）東京計器製型式 BM(B 型黏度計），依照 JISK 7117-1: 1999,測定於 6rpm(25 °C )下之測定値及於60rPm(25°C )下之測定値、以及由彼等 計算出TI値。 [表1] 氣膠(AEROSIL) 130之添加量(份） 以6rpm所測定 之黏度(mPa · s) 以60rpm所測定 之黏度(mPa · s) ΤΙ値 81 13,900 2,600 5.3 -40- 201207089 分別使用於上述所作製之導電性高分子触刻用印墨， 與實施例7或實施例1 0同樣地，進行聚噻吩系導電性高分 子或聚吡咯系導電性高分子之蝕刻時，得到依照絲網圖案 的導電性高分子之圖案化。 [實施例1 5 ] 將對於1,000份的有效氯濃度爲0.65%之次氯酸鈉溶 液，添加73份的氣膠（AEROSIL) COK84 ’調製導電性高分 子蝕刻用印墨時之黏度與TI値顯示於以下之表2。還有， 黏度之測定係以與實施例1 4相同之方法進行。 [表2] 氣膠(AEROSIL) COK84之添加量(份） 以6rpm所測定 之黏度(mPa · s) 以60rpm所測定 之黏度(mPa· s) τι値 73 9,800 900 10.9 分別使用於上述所作製之導電性高分子蝕刻用印墨， 與實施例1或實施例4同樣地，進行聚噻吩系導電性高分 子或聚吡咯系.導電性高分子之蝕刻時，得到依照絲網圖案 的導電性高分子之圖案化。 [實施例1 6 ]The effective chlorine concentration (°/〇)=___χ/χ_ xlOO W 10 and '/(factor)) indicates the correction coefficient of Na2S03 at a specified concentration of 0.1, that is, the correction of the actually used Na2S03A solution and oi equivalent concentration. The coefficient of the difference between the Na2S03 aqueous solution. &lt;Thickener&gt; The conductive polymer etching ink of the present invention contains a thickener. The thickener to be used in the present invention is preferably inorganic particles and/or a surfactant from the viewpoint of the stability of the ink and the non-reactivity with the etchant for the conductive polymer. Examples of the material of the inorganic particles include vermiculite, alumina, titania, cerium oxide, cerium oxide, cerium oxide, zinc oxide, cerium carbide, talc, mica, and kaolinite. The shape of the inorganic particles is not particularly limited, and examples thereof include a spherical shape, a plate shape, a needle shape, a fiber shape, and an indefinite shape, but are preferably spherical. The average primary particle diameter of the inorganic particles is preferably from 3 nm to 1/zm, more preferably from 3 to 500 nm, still more preferably from 3 to 100 nm. In terms of the thickener, it is preferably a surfactant from the viewpoint of cost or ink stability. As the surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant can be used. The anionic surfactant is exemplified by a fatty acid salt, an alkylbenzenesulfon-22-201207089 acid salt, and a monoalkyl sulfate. The amphoteric surfactant is exemplified by an alkylene oxide or a betaine (b e ta in e) compound. As the nonionic surfactant, polyoxyethylene alkyl ether is exemplified. Among them, the surfactant is preferably a monoalkyl sulfate or an alkylamine oxide, more preferably a monoalkyl sulfate. As the monoalkyl sulfate, preferred is a dodecyl sulfate or a tetradecyl sulfate, and more preferably a dodecyl sulfate. Further, when a monoalkyl sulfate is used, it is preferably used together with an acidic component in order to impart an acid component to the monoalkyl sulfate and improve the solubility. The acid component can be suitably selected from any one of an inorganic acid and an organic acid, and is not affected by an etchant. The preferred addition amount of the monoalkyl sulfate is preferably from 3 to 40% by weight, preferably from 7 to 35% by weight, more preferably from 9 to 35% by weight, based on the total weight of the ink. 9 to 25 wt%. In terms of monoalkyl sulfate, it is particularly preferred that the ink of the present invention contains a compound selected from the group consisting of (NH4)2Ce(N03)6, Ce(S04)2, and (NH4)4Ce(S04)4. Contained at the time. Examples of the alkylene oxide are oxidized dodecyl guanamine dimethylamine, hexadecanol guanidinopropyl dimethylamine, octadecyl decyl propyl dimethylamine , oxidized coconut oil decyl hydrazinyl dimethylamine, oxidized oil decyl propylamine dimethylamine, oxidatively hardened tallow alkyl decyl propylamine dimethylamine, oxidized coconut oil dimethylamine , oxidized coconut oil diethylamine, coconut oil, oxidized coconut oil methyl ethylamine, oxidized N, N-dimethyl-N-alkyl-23- 201207089 amine, and the like. The alkylamine is particularly preferably contained in the ink of the present invention containing hypochlorous acid. The thickener is preferably inorganic particles from the viewpoints of cost or ink stability, non-reactivity with an electroconductive high molecular etchant, and pattern accuracy. The inorganic particles are preferably metal oxide particles, more preferably cerium oxide (antimonite) particles, titanium oxide particles, cerium oxide particles, alumina (alumina) particles, zinc oxide particles, tin oxide particles, or the like. Composite oxide particles, and mixtures thereof. Among them, it is more preferable that the vermiculite particles and/or the alumina particles are mixed, and the mixture of the vermiculite particles and the alumina particles is particularly preferable from the viewpoint that the viscosity of the above-mentioned shear stress is high. Further, when (NH4)2Ce(N03)6, Ce(S04)2, and/or (NH4)4Ce(S04)4 are used as the etchant for the conductive polymer, the cost or the conductive polymer is used. From the viewpoint of the non-reactivity of the etchant, it is particularly preferred that the vermiculite particles have a non-reactive property with an etchant for a conductive polymer when using hypochlorite, and particularly preferably a vermiculite particle. Mixture with alumina particles. The content of the thickener in the ink of the present invention may be suitably adjusted depending on the desired viscosity, but is preferably 0.5 to 50% by weight, preferably 1 to 20% by weight based on the total weight of the ink. More preferably, it is 5 to 10% by weight. &lt;Aqueous medium&gt; -24- 201207089 The ink for conductive polymer etching of the present invention contains an aqueous medium. The aqueous medium which can be used in the present invention is not particularly limited as long as it does not affect the etching treatment, but is preferably water. The ink of the present invention preferably contains 25% by weight or more of an aqueous medium, more preferably contains 50% by weight or more. Further, as described above, the conductive polymer etching ink of the present invention may contain an acid. Further, the ink for conductive polymer etching of the present invention is preferably an aqueous ink. &lt;Electrically Conductive Polymer&gt; The conductive polymer etching ink of the present invention has excellent etching ability for a conductive polymer. The conductive polymer is π-electron moving and exhibits conductivity. Many reports of these conductive polymers. Examples of the conductive polymer which can be used in the present invention are polyaniline, polythiophene, polypyrrole, polyphenylene, polyfluorene, polythiophene, polyisothiophene, poly(3,4-ethylenedioxythiophene), poly Isothiazide, polyisophthalazinthiophene, polyacetylene 'polydiacetylene, polyparaphenylene stretched ethylene, polyacene, polythiazole, polyethylene extended ethylene, polyparaphenylene, polydodecylthiophene, polyphenylene Base extension ethylene, polythiophene ethylene, polysulfide benzene, etc. or derivatives thereof. Among them, preferred are polyaniline, polypyrrole, or polythiophene, more preferably polydisperse, or polythiophene 'best conductivity' in air stability and heat resistance. Excellent poly(3,4-ethylenedioxythiophene) -25- 201207089 Further, the conductive polymer which can be used in the present invention is preferably a water-insoluble conductive polymer. Further, for the purpose of using a conductive polymer to find a high conductivity, a dopant called a dopant can be used. As the dopant of the conductive polymer, a well-known dopant can be used, and the type of the conductive polymer can be exemplified by halogen (bromine, iodine, chlorine, etc.), Lewis acid (BF3, PF5, etc.). ), protonic acid (hno3, H2S04, etc.), transition metal halides (FeCl3, M〇Cl5, etc.), alkali metals (Li, Na, etc.), organic substances (amine acids, nucleic acids, surfactants, pigments, alkylammonium) Ions, chloranil (chi or aniU, tetracyanoethylene (TCNE), 7,7,8,8-tetracyanoquinone dimethane (TCNQ), etc.) may also have a doping effect on the conductive polymer itself. Further, when polythiophene is used, polystyrene sulfonic acid is preferably used as a dopant. The conductivity of the conductive polymer which can be used in the present invention exhibits conductivity. The range of the crucible is not particularly limited, and is preferably 1 (Γ6 to 104 S/cm, preferably 1〇·5'5 to 103 S/cm, more preferably 10_5 to 5x1〇2 S/cm. In the present invention When the conductivity of the conductive polymer to be used is in the above range, it is preferable to pattern the connection portion or the like. The conductive polymer of the present invention preferably has a high transmittance in the visible light range when used. Further, the transmittance is preferably 60 to 98%, preferably 70 to 70 nm. 95%, more preferably 80 to 93%. When the transmittance of the conductive polymer itself is in the above range, it can be suitably used for a display device or the like. -26- 201207089 In the present invention, the visible light range is 400. The measurement of the transmittance is measured by a spectrophotometer. Various conductive polymers are commercially available. Polyaniline manufactured by Panipol under the trade name "Panipol" is used. An organic solvent-soluble polyaniline doped with a functional sulfonic acid. A polyaniline commercially available from Ormecon under the trade name "Ormecon" is a solvent-dispersed polyaniline using an organic acid in a dopant. The poly(3,4-ethylenedioxythiophene) commercially available from Bayer under the trade name "Baytron" is made of polystyrene sulfonic acid as a dopant. In other respects, Used by Achilles Inc. in the present invention The sulfonated polyaniline of the product name "PET Poly" manufactured by Toyo Textile Co., Ltd., manufactured by Toyo Textile Co., Ltd., and the trade name of the product manufactured by Maruai Co., Ltd. Polyaniline of "SCS-NEO". It is also possible to use the conductive organic polymer "organic conductive polymer" described in the patent distribution support chart as a conductive polymer for the patent distribution promotion business. Patterning method) The patterning method of the conductive polymer of the present invention (hereinafter also referred to simply as "the patterning method of the present invention"). ) is a method performed by using the ink for conductive high molecular etching of the present invention. The contact portion can be etched by bringing the conductive polymer etching ink of the present invention into contact with the conductive polymer. The shape of the electrically conductive polymer is not particularly limited, and may be any shape, but is preferably in the form of a film. Further, the method of patterning the conductive polymer of the present invention is preferably a film forming step of forming a conductive polymer film on a substrate, and coating the present invention in a range in which the conductive polymer on the film is removed. The printing step of the conductive polymer saturating ink is etched by the conductive polymer uranium engraving ink to etch the conductive polymer in the range removed, and the conductive property remaining from the substrate is high. A step of removing the etching residue of the ink for molecular etching and the conductive polymer. &lt;Film Forming Step&gt; The patterning method of the conductive polymer of the present invention is preferably a film forming step of forming a conductive polymer film on a substrate. The substrate is not particularly limited and may be selected depending on the intended use, and specific examples are glass, quartz, polyester (for example, polyethylene terephthalate (PET), polyethylene naphthalate, etc.) , polyolefin (for example, polyethylene, polypropylene, polystyrene, etc.), polyimide, polyacrylate, methacrylate, and the like. The thickness of the conductive polymer film in the film formation step is not particularly limited, and may be a desired thickness, but is preferably from 1 nm to 100 "111, preferably from 2 nm to 1/zm, more preferably 5 to 500 nm. The above-mentioned method of forming a conductive polymer film on the substrate in the film formation step is not particularly limited, and can be known by a known method. In particular, -28-201207089 is a method in which a solution of a conductive polymer is spin-coated or immersed on a substrate and dried, etc. It is necessary to form a substrate and a conductive polymer film. In addition, other layers may be formed on the conductive polymer film before the printing step. The conductive polymer film formed on the substrate may be the same film. A film which has been patterned by the patterning method of the present invention or another method. <Printing step> The patterning method of the conductive polymer of the present invention is more preferably included in the conductivity removed from the film. high The printing step of applying the conductive polymer etching ink of the present invention in the range of the molecule. The method of applying the conductive polymer etching ink of the present invention in the range of removing the conductive polymer may be, for example, stencil printing or letterpress printing. Printing, gravure printing, lithography, etc. Among them, stencil printing is preferred from the viewpoint of easily adjusting the amount of sufficient ink during etching, preferably screen printing, template (stenci 1 Printing, and pad printing, more preferably screen printing. The amount of ink of the present invention in the printing step is not limited, and may follow the composition of the ink and the conductive polymer. The material or film thickness, the etching time or temperature, the depth of etching, and the like are appropriately selected. Further, by applying the ink amount of the present invention in the printing step, the area of the film can be averaged and fixed. If necessary, it is also possible to increase or decrease the amount of ink relative to the ink amount of other parts -29-201207089. Further, the shape of the range of the conductive polymer on the film is not particularly limited. The limitation can be a shape suitable for the desired shape. Further, the patterning method of the conductive polymer of the present invention can be applied to, for example, a line width of a nanometer to a centimeter, and a line width applicable to a micrometer to a millimeter. &lt;Etching Step&gt; The patterning method of the conductive polymer of the present invention preferably includes an etching step of etching the conductive polymer in the range removed by the conductive polymer etching ink. In the etching step, the portion in contact with the conductive polymer etching ink of the present invention is etched in the conductive polymer film, and is required to be subjected to etching after the printing step and the range removed. The elapsed time (etching time) in the etching step is not particularly limited, and may be appropriately selected depending on the composition of the ink, the material or film thickness of the conductive polymer, the temperature at which etching is performed, the depth of etching, and the like. . The temperature at the time of etching in the etching step is not particularly limited and can be carried out, for example, at normal temperature (10 to 30 ° C). Further, in order to adjust the etching rate or the like, the etching gas atmosphere and/or the substrate having the conductive high molecular film may be heated or cooled. Further, in the etching step, the removal of the range of the removal may be a state in which the film is completely etched through the film, or a portion in which the film is not etched through the film. -30-201207089 Further, in the etching step, the substrate having the conductive polymer film may be left to stand, and the substrate having the conductive polymer film may be moved within a range that does not greatly affect etching by transportation or the like. . &lt;Removal Step&gt; The patterning method of the conductive polymer of the present invention preferably includes a removal step of removing the remaining conductive polymer etching ink and the conductive residue from the substrate. The etching residue of the conductive polymer is exemplified by a decomposition product of the conductive polymer of the ink of the present invention or a fine powder of a conductive polymer produced by etching. Further, in the removal step, of course, not only the remaining etching residue of the conductive polymer etching ink and the conductive polymer but also the unnecessary etching residue can be removed. In the removal step, it is preferable to remove the remaining conductive polymer etching ink and the conductive residue of the conductive polymer by water washing from the viewpoint of simplicity and cost. The amount of water used in the water washing may be a sufficient amount for the above removal. The washing method is not particularly limited, and a method of washing a substrate having a patterned conductive polymer by running water or impregnating a substrate having a patterned conductive polymer film is preferably exemplified. The method in the water. Further, when the water washing is carried out in the removing step, the patterning method of the conductive-31 - 201207089 polymer of the present invention is preferably a step of drying the patterned conductive polymer film after the removing step. . The drying method is not particularly limited, and a well-known method such as drying with heat, drying with air, drying with warm air, or the like can be used. Further, the patterning method of the conductive polymer of the present invention may include other steps as necessary in addition to the above steps. For example, after performing the patterning method of the conductive polymer of the present invention or before, the patterning may be performed by a patterning method other than the present invention, or the conductive polymer of the present invention may be carried out twice or more. The patterning method. Further, in the method of patterning a conductive polymer of the present invention, two or more kinds of inks for conductive polymer etching of the present invention are used as necessary. The conductive polymer uranium engraving ink of the present invention and the patterning method of the conductive polymer of the present invention are applicable to conductivity used in electrolytic capacitors, batteries, touch panels, liquid crystal panels, and organic EL elements. Polymer etching. Therefore, it is expected that the conductive polymer of the display pixel portion of the display of the polymer organic EL display and the connection portion between the peripheral circuit and the conductive polymer are patterned, and the detection portion of the touch panel is highly conductive. The use of a conductive polymer is promoted in the necessary applications of the etching of the connection between the molecule and the peripheral circuit and the conductive polymer, and the etching of the conductive polymer in the capacitor manufacturing process. [Examples] -32-201207089 The following examples are given to illustrate the invention, but the invention is not limited by the examples. In addition, the "part" in the following description means "parts by weight" unless otherwise specified. [Example 1] 50 parts of sodium hypochlorite having an effective chlorine concentration of 13% and 950 parts of water were mixed to prepare a sodium hypochlorite solution having an effective chlorine concentration of 〇·65 %. To the sodium hypochlorite solution, 82 parts of AEROSIL (AEROSIL) COK84 (5:1 mixture of vermiculite particles and alumina particles, average primary particle size: about 12 nm) was added. The mixture was uniformly dispersed by stirring to obtain 1, 2 parts of an etched ink. Further, a polythiophene-based conductive polymer (H_C. Starck) CLEVIOS PH 5 was produced on the surface of an A4 size polyethylene terephthalate (PET) board. 00) film (thickness about 5 〇 nm) and 4.0 cm square PET screen version. The film and the screen plate were placed on a hand-printed printing machine, and an appropriate amount of the previously produced etching ink was placed and screen printed. After the end of printing for 30 seconds, the etched ink on the film was washed with a large amount of water and dried to completely dissolve or peel off the film of the ink-attached portion, thereby completing the patterning of the conductive high molecular weight according to the screen pattern. [Example 2] 50 parts of sodium hypochlorite having an effective chlorine concentration of 13% and 950 parts of water were mixed to prepare a sodium hypochlorite solution having an effective chlorine concentration of 0.65%. To the sodium hypochlorite solution, 600 parts of 0.062% by weight of sulfuric acid was gradually added while stirring, and finally 400 parts of water was added and mixed to prepare 2,000 parts of -33-201207089 sodium chloride solution having an effective chlorine concentration of 〇·3 2 5 %. °Into the sodium hypochlorite solution, 180 parts of AEROSIL COK 84 (AEROSIL) COK 84 was added and stirred to uniformly disperse to obtain 2,180 parts of an etched ink. Further, on the surface of an A4-size polyethylene terephthalate (PET) plate, a polythiophene-based conductive polymer (CLEVIOS PH 500 manufactured by HC Starck Co., Ltd.) was produced. A film (thickness of about 50 nm) and a 4.0 cm square PET screen. A thin film and a screen plate were placed on the hand-printing press, and an appropriate amount of the previously produced etching ink was placed and screen printed. After 30 seconds from the end of printing, the uranium engraved ink on the film was washed with a large amount of water and dried to completely dissolve or peel off the film of the etched ink adhering portion, thereby completing the patterning of the conductive polymer according to the screen pattern. [Example 3] 1 part of a 48% by weight aqueous sodium hydroxide solution and 948.5 parts of water were mixed with 50 parts of sodium hypochlorite having an effective chlorine concentration of 13% to prepare an effective chlorine concentration of 1,00 parts. It is a 0.65% sodium hypochlorite solution. To the sodium hypochlorite solution, 65 parts of AEROSIL COK84 manufactured by AEROSIL Co., Ltd. was added and stirred to uniformly disperse, to obtain 1,065 parts of an etched ink. Further, a film of a polythiophene-based conductive polymer (CLEVIOS PH 500 manufactured by HC Starck Co., Ltd.) was produced on the surface of an A4-size polyethylene terephthalate (PET) plate. (thickness of about 50 nm) and a 4.0 cm square PET screen plate. A film and a screen plate were placed on a hand-printed press, and an appropriate amount of previously produced etched ink was placed and screen printed. After 30 seconds from the end of printing, the etched ink -34 - 201207089 on the film was washed with a large amount of water and dried to completely dissolve or peel off the film of the ink-attached portion, thereby completing the patterning of the conductive polymer according to the screen pattern. [Example 4] A sheet material (a sheet for vacuum forming of ST (a film thickness of about 10 Onm) manufactured by Achilles Co., Ltd.) having a film of a polypyrrole-based conductive polymer was cut into an arbitrary size. Using a separately prepared 4.0 cm square PET screen plate, a film and a screen plate were placed on a hand-printing press, and an appropriate amount of the etched ink prepared in Example 1 was placed and screen-printed. After 30 seconds from the end of printing, the etched ink on the film was washed with a large amount of water and dried to completely dissolve or peel off the film of the ink-attached portion, thereby completing the patterning of the conductive polymer in accordance with the screen pattern. [Example 5] A sheet material (a sheet for vacuum forming of ST made by Achilles Co., Ltd.) having a film of a polypyrrole-based conductive polymer was cut into an arbitrary size, and a separately prepared 4.0 cm square was used. A PET screen plate was used to mount a film and a screen plate on a hand-printing press, and an appropriate amount of the etched ink produced in Example 2 was placed and screen-printed. After 30 seconds from the end of printing, the etched ink on the film was washed with a large amount of water and dried to completely dissolve or peel off the film which etched the ink-attached portion, thereby completing the patterning of the conductive high-mole according to the screen pattern. [Example 6] A sheet material (a sheet for vacuum forming of ST made by Achilles Co., Ltd.) having a film of a polypyrrole-based conductive polymer was cut into an arbitrary size of -35 to 201207089, and prepared separately. A 4.0 cm square PET screen plate was used to mount a film and a screen plate on a hand-printing press, and an appropriate amount of the etched ink produced in Example 3 was placed and screen printed. After the end of printing for 30 seconds, the etched ink on the film was washed with a large amount of water and dried to completely dissolve or peel off the film which etched the ink-attached portion, thereby completing the patterning of the conductive high molecular weight according to the screen pattern. [Example 7] Mixed water and ammonium nitrate (Cerric Ammonium Nitrate) and concentrated nitric acid were used to prepare 1, an ammonium nitrate having a concentration of 1% by weight of cerium nitrate and a concentration of 15% of an etchant having a nitric acid concentration of 15%. . 80 parts of AEROSIL 130 (aragonite particles, primary particle size: about 16 nm) prepared by adding AEROSIL (stock) to the etching solution was stirred and uniformly dispersed to obtain 1 , 080 parts of etched ink. Further, on the surface of an A4-size polyethylene terephthalate (PET) plate, a polythiophene-based conductive polymer (CLEVIOS PH 500 manufactured by HC Starck Co., Ltd.) was produced. A film (thickness of about 50 nm) and a 4.0 cm square PET screen plate. A film and a screen plate were placed on a hand-printed press, and an appropriate amount of previously produced etched ink was placed and screen printed. After 30 seconds from the end of printing, the etched ink on the film was washed with a large amount of water and dried to completely dissolve or peel off the film of the ink-attached portion, thereby completing the patterning of the conductive polymer according to the screen pattern. [Example 8] A mixed solution of hydrazine sulfate and concentrated sulfuric acid was used to prepare an etchant having a hydrazine sulfate concentration of 5% and a sulfuric acid concentration of 1 5%. In the etching solution, -36-201207089 Λ 90 parts of AEROSIL AEROSIL 1300 was stirred and uniformly dispersed to obtain 1,090 parts of an etched ink. Further, on the surface of an A4 size polyethylene terephthalate (PET) board, a polythiophene-based conductive polymer (H.C., HC Starck Co., Ltd., CLEVIOS PH 5 00) was produced. The film (thickness about 50 nm) and the 4.0 cm square PET screen plate. A film and a screen plate were placed on a hand-printed press, and an appropriate amount of previously fabricated etched ink was placed and screen printed. After the printing was completed for 30 seconds, the etched ink on the film was washed with a large amount of water and dried to completely dissolve or peel off the film of the ink-attached portion, thereby completing the patterning of the conductive polymer according to the screen pattern. [Example 9] An aqueous solution of ammonium sulfite and concentrated sulfuric acid was mixed with water to prepare 1,000 parts of an etchant having an ammonium sulfite concentration of 1% by weight and a sulfuric acid concentration of 15%. 90 parts of AEROSIL 130 (AEROSIL) 130 was added to the etching solution to stir and uniformly disperse to obtain 1, 90 parts of uranium engraved ink. Further, a polythiophene-based conductive polymer (CLEVIOS PH 5 00 manufactured by HC Starck Co., Ltd.) was produced on the surface of an A4-size polyethylene terephthalate (PET) plate. The film (thickness about 50 nm) and the 4.0 cm square PET screen plate. A film and a screen plate were placed on a hand-printed press, and an appropriate amount of previously produced etched ink was placed and screen printed. After 30 seconds from the end of printing, the etched ink on the film was washed with a large amount of water and dried to completely dissolve or peel off the film of the ink-attached portion, thereby completing the patterning of the conductive polymer according to the screen pattern. -37-201207089 [Example l] A sheet material (a sheet for vacuum forming of ST made by Achilles Co., Ltd.) having a film of a polypyrrole-based conductive polymer was cut into an arbitrary size and prepared separately. A 4.0 cm square PET screen plate was used to mount a film and a screen plate on a hand-printing press, and an appropriate amount of the etched ink produced in Example 7 was placed and screen printed. After the end of printing for 30 seconds, the etched ink on the film was washed with a large amount of water and dried to completely dissolve or peel off the film which etched the ink-attached portion, thereby completing the patterning of the conductive high molecular weight according to the screen pattern. [Example 11] A sheet material (a sheet for vacuum forming of ST made by Achilles Co., Ltd.) having a film of a polypyrrole-based conductive polymer was cut into an arbitrary size, and a separately prepared 4.0 cm square was used. A PET screen plate was used to mount a film and a screen plate on a hand-printing press, and an appropriate amount of the etched ink produced in Example 8 was placed and screen-printed. After the end of printing for 30 seconds, the etched ink on the film was washed with a large amount of water and dried to completely dissolve or peel off the film which etched the ink-attached portion, thereby completing the patterning of the conductive high molecular weight according to the screen pattern. [Example 12] A sheet material (a sheet for vacuum forming of ST made by Achilles Co., Ltd.) having a film of a polypyrrole-based conductive polymer was cut into an arbitrary size, and a separately prepared 4.0 cm square was used. A PET screen plate was used to mount a film and a screen plate on a hand-printing press, and an appropriate amount of the etched ink produced in Example 9-38-201207089 was placed and screen-printed. After 30 seconds from the end of printing, the etched ink on the film was washed with a large amount of water and dried to completely dissolve or peel off the film of the ink-attached portion, thereby completing the patterning of the conductive high-mole according to the screen pattern. [Comparative Example 1] A mixture of 5 parts of sodium hypochlorite having an effective chlorine concentration of 13% and 950 parts of water was mixed to prepare a sodium hypochlorite solution having an effective chlorine concentration of 0.65%. To the sodium hypochlorite solution, 45 parts of AEROSIL COK84 (AAROSIL) COK84 was stirred and uniformly dispersed to obtain 1,045 parts of an etched ink. Further, on the surface of a polyethylene terephthalate (PET) plate having a size of 4, a polythiophene-based conductive polymer (CLEVIOS PH 500 manufactured by HC Starck Co., Ltd.) was produced. A film (thickness of about 50 nm) and a 4.0 cm square PET screen plate. A film and a screen plate were placed on a hand-printed press, and an appropriate amount of previously prepared etched ink was placed and screen printed. After 30 seconds from the end of printing, the etched ink on the film was washed with a large amount of water and dried to completely dissolve or peel off the film of the adhered portion of the ink to complete the patterning of the conductive polymer. However, since the viscosity of the ink is low, a part of the ink is protruded from the screen pattern, and the accuracy of the finished pattern is low. [Example 13] An aqueous solution of ammonium nitrate and concentrated nitric acid was mixed to prepare 1,000 parts of an etching solution having an ammonium nitrate concentration of 10% and a nitric acid concentration of 15%. To the etchant, 2 parts of a gas gel of AEROSIL (shared) was added and stirred and uniformly dispersed to obtain [J 1,2 0 0 Parts of the etched ink. Further, on the surface of an A4-size polyethylene terephthalate (PET) plate, a polythiophene-based conductive polymer (CLEVIOS PH 500 manufactured by HC Starck Co., Ltd.) was produced. Film and 4_0cm square PET screen version. A film and a screen plate were placed on a hand-printed press, and an appropriate amount of previously fabricated etched ink was placed and screen printed. After 30 seconds from the end of printing, the etched ink on the film was washed with a large amount of water and dried to completely dissolve or peel off the film of the adhered portion of the ink to complete the patterning of the conductive polymer. However, since the ink has a high viscosity, the ink penetration of the screen is poor. Compared with Examples 7 to 9, the accuracy of the finished pattern is practically problem-free, but it is slightly inferior. [Example 14] For 1,000 parts of a solution of "Cerric Ammonium Nitrate" of 10% nitric acid and 15% of nitric acid, 81 parts of a gas gel (AERO SIL.) 130 was added to prepare conductivity. The viscosity at the time of ink printing for polymer etching and TI 値 are shown in Table 1 below. In addition, in the measurement of the viscosity, the measurement was performed at 6 rpm (25 ° C) and at 60 rPm (25 Å) according to JIS K 7117-1: 1999 using a KK (B type viscometer). The measurement under °C) and the calculation of TI値 by them. [Table 1] Aerogel (AEROSIL) 130 Addition amount (parts) Viscosity measured at 6 rpm (mPa · s) Viscosity measured at 60 rpm (mPa · s) ΤΙ値81 13,900 2,600 5.3 -40- 201207089 Used separately In the case of etching the polythiophene-based conductive polymer or the polypyrrole-based conductive polymer in the same manner as in the example 7 or the embodiment 10, the ink for the conductive polymer of the conductive polymer produced in the above manner is obtained in accordance with the screen. Patterning of the patterned conductive polymer. [Example 1 5] For 1,000 parts of sodium hypochlorite solution having an effective chlorine concentration of 0.65%, 73 parts of a gas gel (AEROSIL) COK84' was added to prepare a conductive polymer etching ink, and the viscosity and TI 値 are shown below. Table 2. Further, the measurement of the viscosity was carried out in the same manner as in Example 14. [Table 2] Aerogel (AEROSIL) COK84 addition amount (parts) Viscosity measured at 6 rpm (mPa · s) Viscosity measured at 60 rpm (mPa·s) τι値73 9,800 900 10.9 Used in the above-mentioned system In the same manner as in the first or fourth embodiment, when the polythiophene-based conductive polymer or the polypyrrole-based conductive polymer is etched, the conductive ink having a high conductivity in accordance with the screen pattern is obtained. The patterning of molecules. [Example 1 6 ]

混合水與過錳酸鉀及濃硫酸，製作1,000份的過錳酸 鉀濃度爲1 . 5 % ·硫酸濃度爲5 %之蝕刻液。以在該蝕刻液 中加入175份的日本氣膠（AEROSIL)(股）製之氣膠130(矽 石粒子、平均一次粒徑：約1 6nm)攪拌並均勻地分散，得 到1，175份之蝕刻印墨。另外在A4尺寸之聚對苯二甲酸乙 二酯（PET)板的表面上，製作聚噻吩系導電性高分子（H· C -41 - 201207089 •史塔克（H. C. Starck)(股）製 CLEVIOS PH 500)之薄膜（厚 度約爲50n m)與4.0 cm見方之PET製絲網版。在手刷之印 刷機上裝置薄膜與絲網版，置入適量的先前所製作之蝕刻 印墨並進行絲網印刷。印刷結束3 0秒後，以大量水洗除薄 膜上之蝕刻印墨並乾燥，完全溶解或剝離蝕刻印墨附著部 分之薄膜，完成依照絲網圖案之導電性高分子的圖案化。 [實施例17] 將具有聚吡咯系導電性高分子之薄膜的板材（阿基里 斯（Achilles)(股）公司製ST真空成形用板材）切割成任意之 大小，使用另外準備之4.0cm見方之PET製絲網版，在手 刷之印刷機上裝置薄膜與絲網版，置入適量的於實施例1 6 所製作之蝕刻印墨並進行絲網印刷。印刷結束3 0秒後，以 大量水洗除薄膜上之蝕刻印墨並乾燥，完全溶解或剝離蝕 刻印墨附著部分之薄膜，完成依照絲網圖案之導電性高分 子的圖案化。 [實施例18] 混合水與硝酸銨亞鈽及濃硝酸，製作1，〇〇〇份的硝酸 銨亞鈽濃度爲5.5 % ·硝酸濃度爲5.5 %之蝕刻液。在該蝕刻 液中加入250份的和光純藥工業（股）製之十二烷基硫酸鈉 (和光一級）攪拌並均勻地分散，得到1，250份的蝕刻印墨。 另外在A4尺寸之聚對苯二甲酸乙二酯（PET)板的表面上， 製作聚噻吩系導電性高分子（H · C ·史塔克（H. C.The mixed water and potassium permanganate and concentrated sulfuric acid were used to prepare 1,000 parts of an etching solution having a potassium permanganate concentration of 1.5% and a sulfuric acid concentration of 5%. To the etching solution, 175 parts of a gas gel 130 (aragonite particle, average primary particle diameter: about 16 nm) made of AEROSIL (available) was stirred and uniformly dispersed to obtain 1,175 parts. Etching the ink. Further, a polythiophene-based conductive polymer was produced on the surface of an A4-size polyethylene terephthalate (PET) plate (H·C -41 - 201207089 • HC Starck Co., Ltd.) PH 500) film (thickness of about 50n) and 4.0 cm square of PET screen version. The film and screen are mounted on a hand-printed printer, and an appropriate amount of previously produced etched ink is placed and screen printed. After 30 seconds from the end of printing, the etched ink on the film was washed with a large amount of water and dried to completely dissolve or peel off the film of the etched ink adhering portion, thereby completing the patterning of the conductive polymer according to the screen pattern. [Example 17] A sheet material (a sheet for vacuum forming of ST made by Achilles Co., Ltd.) having a film of a polypyrrole-based conductive polymer was cut into an arbitrary size, and a separately prepared 4.0 cm square was used. A PET screen plate was used to mount a film and a screen plate on a hand-printing press, and an appropriate amount of the etched ink produced in Example 16 was placed and screen printed. After the end of printing for 30 seconds, the etched ink on the film was washed with a large amount of water and dried to completely dissolve or peel off the film which etched the ink-attached portion, thereby completing the patterning of the conductive high molecular weight according to the screen pattern. [Example 18] An aqueous solution of ammonium cerium nitrate and concentrated nitric acid was mixed to prepare an etchant having a cerium ammonium nitrate concentration of 5.5% and a nitric acid concentration of 5.5%. To the etching solution, 250 parts of sodium lauryl sulfate (and light first stage) manufactured by Wako Pure Chemical Industries Co., Ltd. was added and stirred, and uniformly dispersed to obtain 1,250 parts of an etched ink. On the surface of an A4 size polyethylene terephthalate (PET) board, a polythiophene-based conductive polymer (H.C. Stark (H. C.) was produced.

Starck)(股）製CLEVIOS PH 500)之薄膜（厚度約爲50nm)與 -42 - 201207089 4.0cm見方之PET製絲網版。在手刷之印刷機上裝置已形 成薄膜的PET板與絲網版，置入適量的先前所製作之蝕刻 印墨並進行絲網印刷。印刷結束3 0秒後，以大量水洗除薄 膜上之蝕刻印墨並乾燥，完全溶解或剝離飩刻印墨附著部 分之薄膜，完成依照絲網圖案之導電性高分子的圖案化》 [實施例1 9 ] 除了十二烷基硫酸鈉之添加量爲1 00份以外，進行與 實施例1 8相同之操作時，完全溶解或剝離蝕刻印墨附著部 分之薄膜，完成依照絲網圖案之導電性高分子的圖案化。 使用（股）東京計器製型式BM(B型黏度計），依照JIS K： 7 1 1 7- 1 : 1 999測定於6rpm(25°C )下之測定値及於60rpm(25 °C )下之測定値、以及由彼等計算出ΤΙ値。結果示於以下 之表3。 [表3] 十二烷基硫酸鈉 之添加量(份） 以6rpm所測定 之黏度(mPa · s) 以60rpm所測定 之黏度(mPa · s) ΤΙ値 100 85,000 9,400 9.0 [實施例2 0 ] 除了十二烷基硫酸鈉之添加量爲5 00份以外，進行與 實施例1 8相同之操作時，完全溶解或剝離蝕刻印墨附著部 分之薄膜，完成依照絲網圖案之導電性高分子的圖案化。 [實施例21] , 除了加入十四烷基硫酸鈉以取代十二烷基硫酸鈉以 外’進行與實施例1 8相同之操作時，完全溶解或剝離蝕刻 -43- 201207089 印墨附著部分之薄膜，完成依照絲網圖案之導電性高分子 的圖案化。 [實施例22] 除了十二烷基硫酸鈉之添加量爲3 0份以外，進行與實 施例1 8相同之操作時，蝕刻印墨亦擴散至絲網圖案以外之 部分，所完成之圖案較實施例18差。 &lt;由所完成之圖案的顯微鏡之觀察&gt; 將絲網印刷之版預製成線與間隙爲1 〇 〇 β m、2 0 0 // m、 400 μ m者。使用前述實施例及比較例之導電性高分子蝕刻 用印墨並進行絲網印刷，以顯微鏡進行觀察所完成之圖 案。結果示於下述表4.。 [表4] 導電性高分子蝕刻用印墨 觀察結果 實施例1 可完全地圖案化至l〇〇Vm 實施例7 可完全地圖案化至1〇〇//m 比較例1 即使在400//m由於印墨溢出而有線部份之斷線 實施例13 雖可完全地圖案化至100//m，印墨之溢出差且 圖案之終端部分不是完美的直線而直線性差 實施例19 可完全地圖案化至l〇〇//m 實施例22 由於在200//m印墨溢出而有線部份之斷線 【圖式簡單說明】 姐。 【主要元件符號說明】 姐。 /\\\ -44-Starck) (Stock) CLEVIOS PH 500) film (thickness about 50nm) and -42 - 201207089 4.0cm square PET screen version. A film-formed PET plate and screen plate were placed on a hand-printed press, and an appropriate amount of previously fabricated etched ink was placed and screen printed. After 30 seconds from the end of printing, the etched ink on the film is washed with a large amount of water and dried to completely dissolve or peel off the film of the ink-imprinted portion of the ink to complete the patterning of the conductive polymer according to the screen pattern. [Example 1 9] When the same operation as in Example 18 was carried out except that the amount of sodium lauryl sulfate added was 100 parts, the film of the ink-attached portion was completely dissolved or peeled off, and the conductivity according to the screen pattern was high. The patterning of molecules. Measured at 6 rpm (25 ° C) and measured at 60 rpm (25 ° C) according to JIS K: 7 1 1 7- 1 : 1 999 using a Tokyo Stock Exchange BM (B type viscometer) The measurement is performed, and the enthalpy is calculated from them. The results are shown in Table 3 below. [Table 3] Addition amount of sodium lauryl sulfate (parts) Viscosity measured at 6 rpm (mPa · s) Viscosity measured at 60 rpm (mPa · s) ΤΙ値 100 85,000 9,400 9.0 [Example 2 0 ] When the same operation as in Example 18 was carried out except that the amount of sodium lauryl sulfate added was 500 parts, the film of the ink-attached portion was completely dissolved or peeled off, and the conductive polymer according to the screen pattern was completed. Patterned. [Example 21], except that sodium tetradecyl sulfate was added in place of sodium lauryl sulfate, when the same operation as in Example 18 was carried out, the film of the ink-attached portion was completely dissolved or peeled off-43-201207089 The patterning of the conductive polymer according to the screen pattern is completed. [Example 22] Except that the addition amount of sodium lauryl sulfate was 30 parts, when the same operation as in Example 18 was carried out, the etching ink was also diffused to a portion other than the screen pattern, and the pattern was completed. Example 18 is poor. &lt;Observation of Microscope from Finished Pattern&gt; The screen-printed plate was prefabricated into a line and a gap of 1 〇 〇 β m, 2 0 0 // m, and 400 μm. Using the ink for electroconductive polymer etching of the above-described examples and comparative examples, screen printing was carried out, and the pattern obtained by observation with a microscope was used. The results are shown in Table 4. below. [Table 4] Ink observation results for conductive polymer etching Example 1 Can be completely patterned to 10 Vm. Example 7 can be completely patterned to 1 〇〇 / / m Comparative Example 1 Even at 400 / / m Since the ink portion overflows and the wire portion is broken, the embodiment 13 can be completely patterned to 100//m, the ink overflow is poor and the terminal portion of the pattern is not a perfect straight line and the linearity is poor. Embodiment 19 can be completely patterned. Turn to l〇〇//m Example 22 The wire is broken due to overflow of 200//m ink [Simple description] Sister. [Main component symbol description] Sister. /\\\ -44-

Claims (1)

201207089 七、申請專利範圍： 1 · 一種導電性高分子蝕刻用印墨，其特徵爲包含導電性高 分子用蝕刻劑、 增稠劑、及 水性媒介。 2 .如申請專利範圍第1項之導電性高分子蝕刻用印墨，其 中該導電性高分子用蝕刻劑爲選自由（NH4)2Ce(N03)6、 Ce(S04)2、（NH4)4Ce(S04)4、亞硝醢氯、溴酸化合物、 氯酸化合物、過錳酸化合物、6價鉻化合物、及次氯酸 鹽所組成之群組之化合物。 3 ·如申請專利範圍第1項之導電性高分子蝕刻用印墨，其 中該導電性高分子用蝕刻劑爲選自由（NH4)2Ce(N03)6、 Ce(S04)2、（NH4)4Ce(S04)4、.過錳酸化合物、及次氯酸 鹽所組成之群組之化合物。 4·如申請專利範圍第1項之導電性高分子蝕刻用印墨，其 中該增稠劑爲選自由矽石粒子、礬土粒子、矽石粒子和 礬土粒子之混合物、及界面活性劑所組成之群組之增稠 劑。 5 ·如申請專利範圍第1項之導電性高分子蝕刻用印墨，其 中該增稠劑爲選自由矽石粒子、礬土粒子、及矽石粒子 和礬土粒子之混合物所組成之群組之增稠劑。 6.如申請專利範圍第丨項之導電性高分子蝕刻用印墨，其 中該增稠劑爲界面活性劑。 7 .如申請專利範圍第1項之導電性高分子蝕刻用印墨，其 -45- 201207089 中該水性媒介爲水。 8·—種導電性高分子之圖案化方法，其特徵爲包含 形成導電性高分子之薄膜於基材上之成膜步驟、 在除去於該膜上之導電性高分子的範圍中塗敷如申請 專利範圍第1至7項中任一項所記載之導電性高分孑貪虫 刻用印墨之印刷步驟、 藉由該導電性高分子蝕刻用印墨蝕刻該所除去之範圍 的導電性高分子之蝕刻步驟、以及 從基板上除去所殘存之導電性高分子蝕刻用印墨及導 電性高分子之蝕刻殘渣之除去步驟。 9.如申請專利範圍第8項之導電性高分子之圖案化方法’ 其中該導電性高分子爲選自由聚乙炔類、聚對伸苯類、 聚對伸苯基伸乙烯類、聚伸苯類、聚伸噻吩伸乙烯類、 聚苐類、聚并苯類、聚苯胺類、聚吡咯類、及聚噻吩類 所組成之群組之導電性高分子。 1 〇 ·如申請專利範圍第8項之導電性高分子之圖案化方法， 其中該導電性高分子爲聚苯胺類、聚吡咯類、或聚噻吩 類。 1 1 .如申請專利範圍第7項之導電性高分子之圖案化方法， 其中該導電性高分子爲聚（3,4_乙烯二氧噻吩）。 -46 - 201207089 四、指定代表圖： ’ （一）本案指定代表圖為：無。 (二）本代表圖之元件符號簡單說明： 4fff 〇 /iw 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：201207089 VII. Patent application scope: 1 · An ink for conductive polymer etching, which is characterized by comprising an electroconductive high-molecular etchant, a thickener, and an aqueous medium. 2. The ink for conductive polymer etching according to the first aspect of the invention, wherein the etchant for the conductive polymer is selected from the group consisting of (NH4)2Ce(N03)6, Ce(S04)2, (NH4)4Ce( S04) 4. A compound of the group consisting of nitrous oxide, a bromic acid compound, a chloric acid compound, a permanganic acid compound, a hexavalent chromium compound, and a hypochlorite. 3. The ink for conductive polymer etching according to claim 1, wherein the conductive polymer etchant is selected from the group consisting of (NH4)2Ce(N03)6, Ce(S04)2, (NH4)4Ce( S04) 4. A compound of the group consisting of permanganic acid compounds and hypochlorite. 4. The ink for conductive polymer etching according to claim 1, wherein the thickener is selected from the group consisting of vermiculite particles, alumina particles, a mixture of vermiculite particles and alumina particles, and a surfactant. a group of thickeners. 5. The ink for conductive polymer etching according to claim 1, wherein the thickener is selected from the group consisting of vermiculite particles, alumina particles, and a mixture of vermiculite particles and alumina particles. Thickener. 6. The ink for conductive polymer etching according to claim </RTI> wherein the thickener is a surfactant. 7. The ink for conductive polymer etching according to item 1 of the patent application, wherein the aqueous medium is water in -45-201207089. 8. A method for patterning a conductive polymer, which comprises a film forming step of forming a film of a conductive polymer on a substrate, and coating in a range of a conductive polymer removed on the film. The printing step of the electroconductive high-scoring ink-printing ink according to any one of the first to seventh aspects of the invention, wherein the conductive polymer having the removed range is etched by the conductive polymer etching ink The etching step and the step of removing the remaining etching residue of the conductive polymer etching ink and the conductive polymer from the substrate. 9. The method for patterning a conductive polymer according to claim 8 wherein the conductive polymer is selected from the group consisting of polyacetylenes, polyparaphenylenes, polyparaphenylenes, and benzenes. A conductive polymer of a group of polythiophene-extended ethylene, polyfluorene, polyacene, polyaniline, polypyrrole, and polythiophene. 1 〇 A method for patterning a conductive polymer according to the eighth aspect of the patent application, wherein the conductive polymer is polyaniline, polypyrrole or polythiophene. The method of patterning a conductive polymer according to claim 7, wherein the conductive polymer is poly(3,4-ethylenedioxythiophene). -46 - 201207089 IV. Designated representative map: ’ (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 4fff 〇 /iw 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
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