[go: up one dir, main page]

TW201100487A - Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition - Google Patents

Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition Download PDF

Info

Publication number
TW201100487A
TW201100487A TW099105071A TW99105071A TW201100487A TW 201100487 A TW201100487 A TW 201100487A TW 099105071 A TW099105071 A TW 099105071A TW 99105071 A TW99105071 A TW 99105071A TW 201100487 A TW201100487 A TW 201100487A
Authority
TW
Taiwan
Prior art keywords
meth
acrylate
group
conductive polymer
polymer composition
Prior art date
Application number
TW099105071A
Other languages
Chinese (zh)
Other versions
TWI595038B (en
Inventor
Fumiaki Kobayashi
Shuji Okamoto
Hikaru Meguro
Original Assignee
Soken Chemical & Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Soken Chemical & Engineering Co Ltd filed Critical Soken Chemical & Engineering Co Ltd
Publication of TW201100487A publication Critical patent/TW201100487A/en
Application granted granted Critical
Publication of TWI595038B publication Critical patent/TWI595038B/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H01M14/005—Photoelectrochemical storage cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
    • 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
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
    • 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
    • C08G2261/79—Post-treatment doping
    • C08G2261/794—Post-treatment doping with polymeric dopants

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Power Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Hybrid Cells (AREA)
  • Conductive Materials (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Disclosed is a composite conductive polymer composition which is obtained by doping a p-conjugated polymer that contains, as a monomer constituting component, a compound which is optionally substituted with an alkyl group and selected from among aniline, thiophene and pyrrole, with a polymer compound that is composed of 20-50 mol% of a monomer having a sulfonic acid group and a polymerizable vinyl group, 20-50 mol% of a monomer having an aromatic group or an alicyclic group and a polymerizable vinyl group, and 30-60 mol% of an alkyl (meth)acrylate. Also disclosed are a method for producing the composite conductive polymer composition, and a solution which is obtained by dissolving the composition in an aromatic solvent and/or an ester solvent.

Description

201100487 六、發明說明： 【發明所屬之技術領域】 本發明係關於複合導電性高分子組成 ’含有該組成物之溶液及該組成物之用途 關於爲了將溶劑可溶性賦予至以苯胺、噻 香系、雜環系化合物作爲單體構成成分之 ，而摻雜高分子化合物之複合導電性高分 Ο 造方法，含有該組成物之溶液，以及對色 電氣用電極或防帶電膜等之運用。 【先前技術】 對π共軛系高分子賦予高導電性者， 進行摻雜。然而，原先π共軛較發達之高 鏈的平面性高，而成爲由7Γ鍵的親和力所 間的結晶性（堆疊性）較高之構造。且藉 U 雜後的π共軛系高分子，更由於其平面性 形成的親和力高，使堆疊性更形顯著。因 分子之溶解（依據熱或溶劑）與電傳導度 之課題。 因此，係有人提出將烷基或烷氧基等 高分子的側鏈之高分子（專利文獻1 )， 電傳導度提高至可充分地稱爲導電體之1 • m以下，必須進行摻雜。當進行此摻雜 導電性高分子的平面性發達與7Γ共軛親和 物’其製造方法 ’詳細而言，係 吩、吡咯等之芳 π共軛系高分子 子組成物，其製 素增感型太陽能 必須藉由摻雜劑 分子，其高分子 形成之高分子鏈 由摻雜劑進行摻 以及由7Γ共飯所 此，π共軛系高 的並存，爲困難 導入至7Γ共軛系 但實際上爲了將 〇的負5次方s 時，其結果會因 性的發達，而導 -5- 201100487 致無法獲得充分的溶劑可溶性之問題。 當考量到導電性高分子的運用時，就取汲容易度來看 ，較佳是可藉由溶劑來溶解或是藉由熱來熔融，且在成型 成膜後可製得具有充分的電傳導度之自支撐膜或自支撐形 成體，以往，當使用此等導電性聚合物時，係進行藉由電 解聚合或蒸氣暴露將聚合物膜直接形成於欲賦予導電性之 基體上之成膜，或是進行浸漬於氧化劑與導電性聚合物前 驅物單體溶液後再加熱等之薄膜聚合，然後再對所得之聚 合物膜進行摻雜等處理。 然而，此時在電解聚合中，基體必須爲半導體或導電 體，且亦要求對電解液之耐腐蝕性，所以可使用之基體乃 受到限制。此外，在依據直接蒸氣所進行之薄膜聚合中， 必須使氧化劑均質地存在於成爲聚合場所之薄膜，就成膜 控制的方面來看並不充分，且在此等手法所用之聚合物電 容器用途中，爲了增大表面積而形成細微的凹凸，因而難 以充分地將導電性聚合物形成於均質的表面上。 因此，係嘗試將導電性聚合物溶解於有機溶劑，而提 出有幾項實現此之手段。專利文獻2中，係揭示一種使用 無機高鐵鹽類及氧化劑將3,4_二取代噻吩進行聚合之聚（ 3，4-二取代噻吩）的製造方法，此外，專利文獻3中，係 主要具有含有重複噻吩單位之聚合物T、以及至 少1個其他聚陰離子聚合物p之水分散性粉末。然而，專 W 2 Μ 2的方法，爲製得粉末體之手法或是直接在對象被 胃11$面進行氧化聚合之方法，在本手法中所得之聚合物 -6- 201100487 無法溶解於溶劑或水等，此外，專利文獻3者，亦僅爲水 分散性良好之分散體，並非是分子可溶於有機溶劑者。 此外，關於更直接之溶劑奈米分散化的手段已進行各 種探討，專利文獻4中，係揭示一種將本質上不可溶於溶 劑之聚苯胺進行粉碎至奈米尺寸等級使其微粒化，並將相 對於聚苯胺及溶劑之親和性高的SDS (十二烷基苯磺酸） 或PTS (對甲苯磺酸）等之磺酸陰離子乳化劑用作爲分散 〇 劑，並在溶劑中進行共分散，來提供奈米等級的微分散體 溶液，但其實質上並非可溶於溶劑，所以塗佈膜的表面呈 凹凸，且無法構成僅爲聚苯胺之自支撐膜（亦稱爲均質膜 ，係意味著單獨不會產生針孔等而膜化者），所以若未與 黏結劑組合，則無法在塗佈後膜化。 再者，專利文獻5中，係揭示有：具有分子量爲 2,000~500,000之範圍的分子量，且在聚苯乙烯磺酸的聚 陰離子的存在下進行氧化化學聚合之聚噻吩；以及分子量 Ο 爲2,000~500,000，並將來自聚苯乙烯磺酸的聚陰離子含 有於水或水與水混合性有機溶劑的混合溶劑中而成之聚噻 吩的溶液。 此專利文獻，係提出藉由在聚苯乙烯磺酸（PSS)與 氧化劑的共存下之氧化聚合’來製造出可溶解或分散於水 或醇類溶劑之聚（二氧乙烯噻吩）（PED0T)的製法，然 而，在此所得之pedot/pss雖分散於水’但並未完全溶 解，仍難以抑制部分P ED Ο τ之間的堆疊，溶解導電性聚 合物之能力仍不足。 201100487 此外’專利文獻6中，係揭示一種在疏水性大之陰離 子性界面活性劑的存在下，在含有有機酸或無機酸之溶劑 中’將苯胺或苯胺衍生物進行氧化聚合並使其析出，經單 離、精製後’以不與水混合之有機溶劑來萃取而形成有機 溶液者。 然而’此專利文獻中所用之乳化劑爲低分子磺酸系， 雖在聚合前將苯胺進行鹽酸氯化，然後藉由磺酸系乳化劑 進行苯胺鹽取代，但實際上難以引發充分的鹽交換，此外 ’藉由本專利文獻的合成法所得之聚苯胺，實際上不溶解 於溶劑’而具有僅能獲得微分散狀態的溶劑分散液之問題 。此外’由於使用相對於苯胺而言爲等量莫耳以上的磺酸 系乳化劑，所以殘留有50%以上之實質被摻雜之乳化劑以 外的乳化劑，使用時必須去除此等乳化劑，因而具有洗淨 步驟較繁瑣之問題。再者，低分子乳化劑中，非常難以將 相對於溶劑的溶解賦予效果以及聚苯胺堆疊的抑制效果， 導入作爲1分子的設計中，即使是暫時溶解於溶劑之聚苯 胺的狀態，亦有立即產生堆疊（PANI的結晶化）所造成 之微凝聚的問題。 再者，專利文獻7中，係揭示一種將（A )具有磺酸 官能基與自由基聚合性官能基之單體及（B)由苯胺或其 衍生物所構成之單體溶解於水或有機溶劑而成之溶液進行 乳化，將來自（A)的單體之磺酸結構導入至（B)的單 體後，在聚合起始劑的下列共存下將（A )及（B )的單 體進行聚合，來製作出（B )的聚合物與（A )的聚合物 -8 - 201100487 互相纏繞之狀態的導電性聚合物。 然而’此專利文獻的方法中，由於將過硫酸銨鹽用作 爲水系氧化劑兼自由基起始劑，所以實際上難以形成如本 說明書所述之理想的乙烯系聚合物與聚苯胺的相互網目狀 結構。因此，此專利文獻方法中，實際上存在許多不含 PANI之乙烯聚合物’反而是在pani中存在許多未納入 於乙烯聚合物之摻雜單體’而有成爲極不均一且不安定之 〇 化合物的問題。 此外，例如在專利文獻8中，係揭示一種溶解於實質 上未與水混合之有機溶劑之（a )經質子化之取代或未經 取代的聚苯胺複合體以及（b)含有具有酚性羥基之化合 物的導電性聚苯胺組成物。 然而’此專利文獻中’由於在溶劑/水/單體/乳化劑的 聚合場所中使用水溶性氧化劑來進行聚苯胺的合成，所以 其本質上是水溶性苯胺單體一邊進行聚合，一邊介於乳化 ^ 劑分散於甲苯之系統下成爲聚苯胺，實質上除了甲苯以外 ’無法溶解於可稍微溶解於水之溶劑中。此外，本專利文 獻之發明中，實際使用之二異辛基硫化琥珀酸鈉（AOT ) 中，由於無法充分抑制聚苯胺的堆疊，所以需與酚類（甲 酚）等倂用。此在說明書中的記載雖不充分，但其爲非專 利文獻1所記載之技術，係揭示有藉由聚苯胺覆膜中之施 體強度的調整，使酚性化合物的親和性變得顯著，而有用 於提升聚苯胺覆膜的導電性。此可考量爲，藉由將如酚類 般之相對於甲苯的溶解性良好且對聚苯胺的相溶性良好之 -9 - 201100487 非揮發性添加劑予以混合，不僅可提升乾燥塗膜的導電性 ，並且酚類可抑制可溶於甲苯中之聚苯胺彼此的堆疊，當 不具此等添加劑時，係如AOT般，在立體阻礙性下之聚 苯胺的結晶性控制中無法達到充分可溶性的安定化，此情 形在本發明者們的追蹤試驗中亦被確認。 另一方面，關於使用導電性聚合物組成物之用途，有 色素增感型太陽能電池用對極及防帶電膜。專利文獻10 中，係揭示一種在設有透明導電層之塑膠膜上設置導電性 高分子層而成之色素增感型太陽能電池的對極。 然而，此專利文獻中，雖然是塗佈含有導電性高分子 之分散液，並去除溶劑來形成導電性高分子層，但導電性 高分子爲微粒子的分散膜，所以相對於透明導電層之密著 性差，而須預先進行電漿處理等以提高透明導電層的表面 能量。此外，此專利文獻的實施例中，係記載有將聚苯乙 烯磺酸用作爲分散劑者，但此時存在有未投入導電性高分 子的摻雜之閒置的磺酸，使溶劑成爲水溶液，所以當塗佈 於膜基板上時，溶劑與膜基板表面之選擇性變得極大，容 易產生由導電性高分子塗膜的不均一性所起因之針孔，且 由於殘存的磺酸基使塗膜的極性提高，導致相對於在電解 質溶液中一般所用之乙腈或離子性液體等之耐久性惡化， 容易產生塗膜的剝離，並且以此等爲原因，而產生透明導 電膜被電解液中的碘所腐蝕之問題，就作爲對極的長期安 定性而言乃存在著問題，用來取代白金對極者仍不充分。 此外，專利文獻1 1中，係揭示一種將含有聚噻吩系 -10- 201100487 化合物、酸性聚合物及糖醇之防帶電材料塗佈於熱可塑性 樹脂膜上之防帶電膜。 然而，此專利文獻中，由於需將糖醇用作爲防帶電材 料的必要成分，雖然所得之防帶電膜的透明性及防帶電性 良好，但其僅使用聚苯乙烯磺酸等之酸性聚合物作爲對聚 噻吩系化合物之摻雜劑，所以防帶電膜會隨時間經過而吸 濕’而具有密著性及防帶電性降低之問題。 Ο [先前技術文獻] [專利文獻] [專利文獻1]日本特表2002-539287 [專利文獻2]日本特開平01_313521 [專利文獻3]日本特表2004-514753 [專利文獻4]日本特表2007-518859 [專利文獻5]日本特許第2636968 [專利文獻Μ日本特開2008-169255 ❹ [專利文獻7]日本特開2007-314606 [專利文獻8]日本W02005/052058 [專利文獻9]日本特開2〇〇〇_344823 [專利文獻10]日本特開2006-155907 [專利文獻11]日本特開2008-179809 [非專利文獻 1]Y. Ca〇 et al. / Synthetic Metals 69 (1 9 95 ) 1 8 7- 1 90 【發明內容】 -11 - 201100487 (發明所欲解決之課題） 因此’本發明之課題係提供一種對溶劑的溶解性佳， 且可成爲自支撐膜，亦即單獨不會產生針孔等之均質膜或 成形體之導電性高分子組成物及其製造方法等。 (用以解決課題之手段） 本發明者們係爲了解決上述課題，對前述先前技術進 行追蹤探討，結果明確地掌握到下列諸等要素對於從導電 性聚合物的合成至精製、以及對溶劑的再溶解乃爲必要之 事實，亦即，<1>在π共軛系高分子的聚合場所中，必 須使用充分的電解質溶劑，並安定且均一地賦予可使氧化 進行之陰離子場所，<2>必須控制聚合成長中之冗共軛 系高分子的堆疊性並賦予安定的單體供給，<3>積極地 進行對此等聚合成長場所中的7Ζ：共軛系聚合物之摻雜，< 4 >在此等摻雜的過程中，可使水等從初期聚合場所的電 解質溶劑中析出，<5>聚合後的π共軛系高分子可藉由 某種立體性分子阻礙來抑制主鏈骨架的堆疊，<6>此等 立體阻礙性因子本身不具有結晶性，且可藉由溶劑或熱等 予以熔融。 因此，本發明者們係更進一步地進行探討，結果發現 ’當將使特定單體進行共聚合之高分子化合物用作爲；Γ共 軛系高分子的聚合時之添加劑，除了具有可將作爲乳化劑 的聚合場所形成爲均一狀態之功能外，並且可發揮作爲摻 雜劑之功能，且由於對π共軛系高分子具有適度的立體阻 -12- 201100487 礙性，所以可製得對特定溶劑具有較佳的可溶性之複合導 電性高分子組成物。此外，本發明者們係發現到可將前述 複合導電性高分子組成物運用在色素增感型太陽能電池用 對極及防帶電膜等，因而完成本發明。 亦即，本發明是一種複合導電性高分子組成物，其係 將藉由使下列成分（a-l )〜（a-3 )進行聚合所製得之高 分子化合物（A )，摻雜於以選自下列式（I ) ~ ( III )的 〇 化合物作爲單體構成成分之7Γ共軛系高分子（沒）而成； (a-1)具有磺酸基與聚合性乙烯基之單體：2 50 mol% ； (a-2)具有芳香族基或脂環族基與聚合性乙烯基之 單體：20~50 mol% ; (a-3 )(甲基）丙烯酸烷酯：30-60 mol% ; 【化3】201100487 VI. OBJECT OF THE INVENTION: TECHNICAL FIELD The present invention relates to a composite conductive polymer composition 'a solution containing the composition and a use of the composition, in order to impart solvent solubility to aniline, thiocene, A method of a composite conductive high-scoring method in which a heterocyclic compound is used as a monomer component, and a polymer compound is doped, and a solution containing the composition, an electrode for color electricity, an antistatic film, and the like are used. [Prior Art] When a high conductivity is imparted to a π-conjugated polymer, doping is performed. However, the high-chain which is more developed in the original π-conjugate has a higher planarity, and has a higher crystallinity (stackability) between the affinity of the 7-inch bond. Further, the U-doped π-conjugated polymer has a higher affinity for planarity, and the stacking property is more remarkable. Due to the dissolution of molecules (based on heat or solvent) and electrical conductivity. Therefore, it has been proposed to increase the electrical conductivity of a polymer having a side chain of a polymer such as an alkyl group or an alkoxy group (Patent Document 1) to a level which is sufficiently less than 1 m of the conductor, and it is necessary to dope. When the planarity of the doped conductive polymer is developed and the 7-inch conjugated affinity product 'manufacturing method' is detailed, the aromatic π-conjugated polymer composition such as pheno- or pyrrole is sensitized to the nucleus. The type of solar energy must be doped with a dopant molecule, the polymer chain formed by the polymer is doped with a dopant, and the π-conjugated system is coexisting, and the conjugated system is difficult to introduce into the 7-inch conjugated system. In order to reduce the negative 5th power s of 〇, the result will be developed due to the fact that the guide -5 - 201100487 will not be able to obtain sufficient solvent solubility. When considering the use of a conductive polymer, it is preferable to use a solvent to dissolve or melt by heat, and to obtain sufficient electrical conduction after forming a film. A self-supporting film or a self-supporting formed body. Conventionally, when such a conductive polymer is used, a film formed by directly forming a polymer film on a substrate to be imparted with conductivity by electrolytic polymerization or vapor exposure is performed. Alternatively, the film is immersed in an oxidizing agent and a conductive polymer precursor monomer solution, followed by heating, and the like, and then the obtained polymer film is doped or the like. However, at this time, in the electrolytic polymerization, the substrate must be a semiconductor or a conductor, and corrosion resistance to the electrolyte is also required, so that the substrate which can be used is limited. Further, in the film polymerization by direct vapor, it is necessary to uniformly present the oxidizing agent in the film to be a polymerization site, which is insufficient in terms of film formation control, and is used in the polymer capacitor application used in such a method. In order to form a fine unevenness in order to increase the surface area, it is difficult to sufficiently form the conductive polymer on a homogeneous surface. Therefore, attempts have been made to dissolve the conductive polymer in an organic solvent, and several means for achieving this have been proposed. Patent Document 2 discloses a method for producing poly(3,4-disubstituted thiophene) which polymerizes 3,4-disubstituted thiophene using an inorganic high-iron salt and an oxidizing agent, and further, Patent Document 3 mainly has A water-dispersible powder containing a polymer T of a repeating thiophene unit and at least one other polyanionic polymer p. However, the method of W 2 Μ 2 is a method of preparing a powder body or a method of oxidative polymerization of a body directly on the surface of the stomach. The polymer obtained in the present method is not dissolved in a solvent or In addition, in Patent Document 3, it is only a dispersion having good water dispersibility, and it is not a molecule which is soluble in an organic solvent. Further, various means for more direct solvent nano-dispersion have been discussed. In Patent Document 4, it is disclosed that a polyaniline which is substantially insoluble in a solvent is pulverized to a nanometer size to be micronized, and A sulfonic acid anionic emulsifier such as SDS (dodecylbenzenesulfonic acid) or PTS (p-toluenesulfonic acid) having high affinity for polyaniline and a solvent is used as a dispersing agent and is co-dispersed in a solvent. To provide a nano-scale microdispersion solution, but it is not substantially soluble in a solvent, so the surface of the coated film is uneven, and it cannot constitute a self-supporting film of polyaniline (also called a homogeneous film, which means If it is not formed by pinholes or the like, it is not formed, and if it is not combined with a binder, it cannot be film-formed after application. Further, Patent Document 5 discloses a polythiophene having a molecular weight of a molecular weight of 2,000 to 500,000 and an oxidative chemical polymerization in the presence of a polyanion of polystyrenesulfonic acid; and a molecular weight of 2,000 Å. 500,000, and a polyanion derived from polystyrenesulfonic acid is contained in a mixed solvent of water or a mixed organic solvent of water and water to form a solution of polythiophene. This patent document proposes to produce poly(dioxyethylene thiophene) (PED0T) which can be dissolved or dispersed in water or an alcohol solvent by oxidative polymerization in the coexistence of polystyrenesulfonic acid (PSS) and an oxidizing agent. However, the pedot/pss obtained here are dispersed in water 'but not completely dissolved, and it is still difficult to suppress the stacking between portions of P ED Ο τ, and the ability to dissolve the conductive polymer is still insufficient. 201100487 In addition, in Patent Document 6, it is disclosed that an aniline or an aniline derivative is oxidatively polymerized and precipitated in a solvent containing an organic acid or an inorganic acid in the presence of a highly hydrophobic anionic surfactant. After being separated and refined, it is extracted by an organic solvent which is not mixed with water to form an organic solution. However, the emulsifier used in this patent document is a low molecular sulfonic acid system. Although aniline is chlorinated by hydrochloric acid before polymerization and then substituted with an aniline salt by a sulfonic acid emulsifier, it is practically difficult to initiate sufficient salt exchange. Further, 'the polyaniline obtained by the synthesis method of this patent document does not actually dissolve in the solvent' and has a problem that only a solvent dispersion liquid in a slightly dispersed state can be obtained. In addition, since a sulfonic acid-based emulsifier having an equivalent amount or more with respect to aniline is used, 50% or more of an emulsifier other than the substantially doped emulsifier remains, and these emulsifiers must be removed during use. Therefore, there is a problem that the washing step is cumbersome. Further, in the low-molecular emulsifier, it is very difficult to impart an effect of dissolving the solvent with respect to the solvent and the effect of suppressing the polyaniline stack, and it is introduced into the design of one molecule, even in the state of polyaniline which is temporarily dissolved in the solvent. The problem of microcoagulation caused by stacking (crystallization of PANI) occurs. Further, Patent Document 7 discloses a method in which (A) a monomer having a sulfonic acid functional group and a radical polymerizable functional group and (B) a monomer composed of aniline or a derivative thereof are dissolved in water or organic. The solution obtained by the solvent is emulsified, and after introducing the sulfonic acid structure of the monomer of (A) into the monomer of (B), the monomers of (A) and (B) are coexisted in the following coexistence of the polymerization initiator. Polymerization was carried out to produce a conductive polymer in a state in which the polymer of (B) and the polymer of (A) -8 - 201100487 were intertwined. However, in the method of this patent document, since ammonium persulfate is used as a water-based oxidizing agent and a radical initiator, it is practically difficult to form a mutual mesh of a desired ethylene-based polymer and polyaniline as described in the present specification. structure. Therefore, in this patent document method, there are actually many ethylene polymers which do not contain PANI. Instead, there are many doping monomers which are not incorporated in the ethylene polymer in the pani, and they become extremely uneven and unstable. The problem with the compound. Further, for example, in Patent Document 8, it is disclosed that (a) a protonated substituted or unsubstituted polyaniline complex dissolved in an organic solvent which is not substantially mixed with water, and (b) contains a phenolic hydroxyl group. A conductive polyaniline composition of the compound. However, in this patent document, since the synthesis of polyaniline is carried out using a water-soluble oxidizing agent in a polymerization site of a solvent/water/monomer/emulsifier, it is essentially a water-soluble aniline monomer which is polymerized while being interposed. The emulsifier is dispersed in a system of toluene to form polyaniline, which is substantially insoluble in a solvent which is slightly soluble in water except for toluene. Further, in the invention of the present patent application, in the actual use of sodium diisooctylsulfosuccinate (AOT), since the stacking of polyaniline cannot be sufficiently suppressed, it is required to be used together with a phenol (cresol). Although the description in the specification is not sufficient, the technique described in Non-Patent Document 1 discloses that the affinity of the phenolic compound is remarkable by adjusting the body strength in the polyaniline film. It is used to enhance the conductivity of the polyaniline film. This can be considered to improve the conductivity of the dried coating film by mixing non-volatile additives such as phenols which have good solubility with respect to toluene and good compatibility with polyaniline. Further, the phenols can inhibit the stacking of polyanilines which are soluble in toluene. When such additives are not present, such as AOT, the solubility of the polyaniline under steric hindrance cannot be sufficiently stabilized. This situation was also confirmed in the inventors' follow-up test. On the other hand, regarding the use of the conductive polymer composition, there are a counter electrode and an antistatic film for a dye-sensitized solar cell. Patent Document 10 discloses a counter electrode of a dye-sensitized solar cell in which a conductive polymer layer is provided on a plastic film provided with a transparent conductive layer. However, in this patent document, although a dispersion containing a conductive polymer is applied and a solvent is removed to form a conductive polymer layer, the conductive polymer is a dispersed film of fine particles, so that it is dense with respect to the transparent conductive layer. Poorness is required, and plasma treatment or the like is required in advance to increase the surface energy of the transparent conductive layer. Further, in the examples of the patent documents, polystyrene sulfonic acid is used as a dispersing agent, but in this case, there is a sulfonic acid which is not doped into the doping of the conductive polymer, and the solvent is made into an aqueous solution. Therefore, when applied to a film substrate, the selectivity of the solvent and the surface of the film substrate becomes extremely large, and pinholes caused by the unevenness of the conductive polymer coating film are likely to occur, and the residual sulfonic acid group is coated. When the polarity of the film is increased, the durability of the acetonitrile or the ionic liquid or the like which is generally used in the electrolyte solution is deteriorated, and peeling of the coating film is liable to occur, and for this reason, the transparent conductive film is generated in the electrolyte. The problem of iodine corrosion is a problem with regard to the long-term stability of the pole. The replacement of platinum is still insufficient for the extreme. Further, Patent Document 1 discloses an antistatic film in which an antistatic material containing a polythiophene-10-10,00487 compound, an acidic polymer, and a sugar alcohol is applied onto a thermoplastic resin film. However, in this patent document, since sugar alcohol is required as an essential component of an antistatic material, although the obtained antistatic film has good transparency and antistatic property, it uses only an acidic polymer such as polystyrenesulfonic acid. As a dopant for the polythiophene-based compound, the antistatic film absorbs moisture over time and has a problem of poor adhesion and antistatic property. [Prior Art Document] [Patent Document 1] [Patent Document 1] Japanese Patent Application Publication No. 2002-539287 [Patent Document 2] Japanese Patent Laid-Open No. Hei 01-313521 [Patent Document 3] Japanese Patent Application No. 2004-514753 [Patent Document 4] Japanese Special Table 2007 [Patent Document 5] Japanese Patent No. 2636968 [Patent Document No. JP-A-2008-169255] [Patent Document 7] JP-A-2007-314606 [Patent Document 8] Japan W02005/052058 [Patent Document 9] 2〇〇〇_344823 [Patent Document 10] JP-A-2006-155907 [Patent Document 11] JP-A-2008-179809 [Non-Patent Document 1] Y. Ca〇et al. / Synthetic Metals 69 (1 9 95 ) 1 8 7- 1 90 [Description of Invention] -11 - 201100487 (Problems to be Solved by the Invention) Therefore, the subject of the present invention is to provide a solvent which is excellent in solubility and can be a self-supporting film, that is, it does not stand alone. A conductive polymer composition which produces a homogenous film or a molded body such as a pinhole, a method for producing the same, and the like. (Means for Solving the Problems) The inventors of the present invention have studied the above-described prior art in order to solve the above problems, and as a result, have clearly grasped the following elements for the synthesis from the conductive polymer to the purification, and to the solvent. Re-dissolution is a necessary fact, that is, <1> In the polymerization site of the π-conjugated polymer, it is necessary to use a sufficient electrolyte solvent, and to stably and uniformly impart an anion site capable of undergoing oxidation, <2> It is necessary to control the stacking property of the redundant conjugated polymer during polymerization growth and to supply a stable monomer supply, <3> actively carry out the doping of the conjugated polymer in the polymerization growth site. , < 4 > In the process of doping, water or the like can be precipitated from the electrolyte solvent in the initial polymerization site, and <5> the π-conjugated polymer after polymerization can be formed by a stereoscopic molecule Blocking to suppress the stacking of the main chain skeleton, <6> These steric hindrance factors themselves have no crystallinity and can be melted by a solvent or heat. Therefore, the inventors of the present invention conducted further investigations and found that 'when a polymer compound which copolymerizes a specific monomer is used as an additive in the polymerization of a fluorene-conjugated polymer, in addition to having an emulsification The polymerization site of the agent is formed into a function of a uniform state, and functions as a dopant, and since the π-conjugated polymer has a moderate steric hindrance-12-201100487, a specific solvent can be obtained. A composite conductive polymer composition having a preferred solubility. In addition, the present inventors have found that the composite conductive polymer composition can be applied to a counter electrode and an antistatic film for a dye-sensitized solar cell, and the like. That is, the present invention is a composite conductive polymer composition which is prepared by doping the polymer compound (A) obtained by polymerizing the following components (al) to (a-3). A ruthenium compound of the following formula (I) to (III) is used as a monomeric constituent 7 conjugated polymer (not); (a-1) a monomer having a sulfonic acid group and a polymerizable vinyl group: 2 50 mol%; (a-2) monomer having an aromatic group or an alicyclic group and a polymerizable vinyl group: 20 to 50 mol%; (a-3) alkyl (meth)acrylate: 30-60 mol % ; 【化3】

Ry (各式中，Ri至R7表示氫原子或碳數1至12的烷基） 〇 此外’本發明是一種複合導電性高分子組成物的製造 方法，其特徵爲：係將藉由使下列成分（a-Ι )〜（a-3 ) -13- 201100487 進行聚合所製得之高分子化合物（A)、與選自前述式（I )~( III)的化合物共存於電解性基質溶劑中，並使用氧 化劑進行化學氧化聚合； (a-1)具有磺酸基與聚合性乙烯基之單體：20~ 50 mol% ; (a-2)具有芳香族基或脂環族基與聚合性乙烯基之 單體：20〜50 mol%; (a - 3 )(甲基）丙餘酸院酯：30〜60 mol%。 再者，本發明是一種複合導電性高分子組成物溶液， 其係在選自甲苯、苯及二甲苯的芳香族系溶劑及/或選自 乙酸乙酯、乙酸丙酯、乙酸丁酯的酯系溶劑中，於溶解狀 態下含有0.1〜10質量％之前述複合導電性高分子組成物而 成。 此外’本發明是一種色素增感型太陽能電池用對極， 其係使用前述複合導電性高分子組成物而成。 再者’本發明是一種防帶電膜，其係使用前述複合導 電性高分子組成物而成。 發明之效果： 在本發明之高分子化合物的存在下，藉由氧化劑的作 用進行聚合所得之複合導電性高分子組成物，可安定地溶 解於甲苯等之芳香族溶劑或乙酸乙酯等之酯系溶劑中。 因此’藉由將在芳香族溶劑中溶解有此複合導電性高 分子組成物之溶液’塗佈於需賦予導電性之部位並將此乾 -14 - 201100487 燥’可簡單地製得導電性覆膜。 【實施方式】 本發明中所用之高分子化合物（A )，可依循 法，在聚合起始劑的存在下，將成分（a-1)之具 基與聚合性乙烯基之單體、成分（a-2)之具有芳 或脂環族基與聚合性乙烯基之單體及成分（a-3) Π ^ 基）丙烯酸烷酯進行聚合而製造出。 成分（a-1)之具有磺酸基與聚合性乙烯基之 爲具有苯乙烯磺酸基或磺乙基等的磺酸基之單體， 有苯乙烯磺酸或苯乙烯磺酸鈉、苯乙烯磺酸鉀、苯 酸鈣等之苯乙烯磺酸鹽、（甲基）丙烯酸2-磺乙 甲基）丙烯酸2-磺乙酯鈉鹽、（甲基）丙烯酸2-鉀鹽、（甲基）丙烯酸2-磺乙酯鈣鹽等之（甲基 酸2-磺乙酯鹽。 ^ 此外，成分（a-2 )之具有芳香族或脂環族基 性乙烯基之單體的例子，有（甲基）丙烯酸苯甲酯 基）丙烯酸苯氧基乙酯、（甲基）丙烯酸乙基2_ 甲酸甲酯、（甲基）丙烯酸乙基2-鄰苯二甲酸乙 甲基）丙烯酸環己酯、（甲基）丙烯酸二環戊酯、 )丙烯酸二環戊烯氧基乙酯、（甲基）丙烯酸異莰 甲基）丙烯酸三級丁基環己酯、（甲基）丙烯酸環 (甲基）丙烯酸嗎啉酯、苯乙烯、二甲基苯乙烯、 )丙烯酸萘酯、乙烯基萘、乙烯基正乙基咔唑、乙 一般方 有磺酸 香族基 之（甲 單體， 此例子 乙烯磺 酯或（ 磺乙酯 )丙烯 與聚合 、（甲 鄰苯二 酯、（ (甲基 酯、（ 己酯、 (甲基 烯基芴 -15- 201100487 等。 再者，成分（a-3)之（甲基）丙烯酸烷酯的具體例 ，有（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基 )丙烯酸正丙酯、（甲基）丙烯酸異丙酯、（甲基）丙烯 酸正丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸異丙 酯、（甲基）丙烯酸三級丁酯、（甲基）丙烯酸2-乙基 己酯、（甲基）丙烯酸異辛酯、（甲基）丙烯酸十二烷酯 及（甲基）丙烯酸十八烷酯等。 本發明中所用之高分子化合物（A)的製造時，單體 (a-Ι )、單體（a-2 )及單體（a-3 )的莫耳比爲重要。亦 即，此係由於本發明之高分子化合物，可藉由將芳香族或 脂環族基所形成之疏水性與磺酸基所形成之親水性予以適 當地均衡，對導電性高分子化合物形成作用而能夠將其溶 解於溶劑中之故。 用以製造本發明之高分子化合物（A)之成分（a-i) 的調配量，爲2 0 ~ 5 0 m ο 1 %，較佳爲2 5 ~ 4 0 m ο 1 %。此外， 成分（a-2)的調配量爲20~50mol%，較佳爲30-45 mol% 。再者，成分（a-3 )的調配量爲30〜60 mol%，較佳爲 35 〜50 mol% 〇 本發明之高分子化合物中，亦可含有上述單體（a-1 )、（a-2 )及（a-3 )以外的聚合性成分。此聚合性成分 的例子’有（甲基）丙烯酸2 -羥乙酯、（甲基）丙烯酸 3- 羥丙酯、（甲基）丙烯酸2-羥丁酯、（甲基）丙烯酸 4- 羥丁酯、（甲基）丙烯酸甲氧基乙酯、（甲基）丙烯酸 -16- 201100487 丁氧基乙酯、（甲基）丙烯酸聚乙二醇酯、（甲基）丙烯 酸甲氧基聚乙二醇酯、（甲基）丙烯酸、（甲基）丙烯酸 乙醯乙醯氧基乙酯、（甲基）丙烯酸四氫呋喃酯、（甲基 )丙烯酸N，N_二甲基胺乙酯、乙烯基吡啶等，調配時的 調配量爲〇~20 mol%。 上述成分（a-Ι) 、成分（a-2)、成分（a-3)及因應 必要所加入之聚合性成分的聚合反應，可藉由一般所知的 〇 方法來進行。例如可在將此等各成分混合後，將聚合起始 劑添加於此’並藉由加熱、光照射等來開始聚合而製造出 〇 製造上述高分子化合物（A)所能夠採用之聚合法， 只要可在成分（a-2)不會從單體混合物中分離之狀態下 實施的方法，則無特別限定，例如可採用溶液聚合法、塊 狀（總體）聚合法、析出聚合法等。 此外，聚合反應中所用之聚合起始劑，只要可溶解於 〇 上述各成分或反應時所用之溶劑者，則無特別限定。此聚 合起始劑的例子，有過氧化苯甲醯（BPO)等之油溶性過 氧化物系熱聚合起始劑、偶氮雙異丁腈（AIBN )等之油 溶性偶氮系熱聚合起始劑、偶氮雙氰基纈草酸（ACVA ) 等之水溶性偶氮系熱.聚合起始劑等。此外，當溶液聚合時 溶劑中的水比例較多時，亦可使用過硫酸銨或過硫酸鉀等 之水溶性過氧化物系熱聚合起始劑、過氧化氫水等。再者 ，亦可與鐵莘或胺類等氧化還原劑的組合使用。 此等聚合起始劑的使用範圍，可在相對於上述化合物 -17- 201100487 1莫耳而言爲0.001〜〇· 1莫耳的範圍內任意地使用，亦可 運用總括投入、滴入投入、逐次投入的任一方法。此外， 在塊狀聚合或使用少量（相對於單體而言爲5 0wt%以下） 溶劑之溶液聚合時’亦有依據硫醇與金屬芳香類來進行聚 合之方法（專利文獻9)。 此外，上述聚合反應中所用之溶劑，例如有甲醇、乙 醇、異丙醇、丁醇等之醇系溶劑；丙酮、丁酮、甲基異丁 酮等之酮系溶劑；甲基溶纖劑、乙基溶纖劑、丙二醇甲醚 、丙二醇乙醚等之二醇系溶劑；乳酸甲酯、乳酸乙酯等之 乳酸系溶劑等。 再者’聚合時除了聚合起始劑之外，亦可倂用連鎖轉 移劑’當欲調整分子量時可適當地使用。能夠使用之連鎖 轉移劑，只要可溶解於上述單體或溶劑者，則可使用任意 化合物’例如可適當地使用十二烷基硫醇或庚基硫醇等之 烷基硫醇；锍基丙酸（BMPA )般之具有極性基的水溶性 硫醇；α苯乙烯二聚物（ASD )等之油性自由基抑制劑等 〇 此外，此聚合反應，係以在所使用之溶劑（總體聚合 時除外）的沸點以下進行者爲佳，例如65°C〜80°C者爲佳 。惟進行總體聚合或進行依據硫醇與金屬芳香類所進行之 專利文獻9般的聚合時，係以在25°C ~80°C進行者爲佳。 如此製得之聚合物，可因應必要進行精製來構成高分 子化合物（A)。此精製方法的例子，有使用己烷等之油 性不良溶劑，來去除油性低分子雜質及殘存單體、低分子 -18- 201100487 雜質後，再藉由乙腈、甲醇、乙醇、丙酮等之水性不良溶 劑進行聚合物析出等，以去除水系雜質、殘存物之方法。 進行此精製之較佳理由，是由於高分子化合物（A) 作爲摻雜劑被導入至導電性高分子組成物中作用爲堆疊抑 制劑及溶劑可溶劑，使其以外的聚合起始劑殘留物、單體 、低聚物、不均一組成物等殘存成爲聚合後的殘存物，而 產生導電性高分子組成物的功能降低之問題，因而須予以 〇 去除之故。此外，進行此精製後之結果，係不會如專利文 獻7般之使不均一的自由基聚合物混合存在，而能夠顯現 出均一導電性高分子組成物的組成與高分子化合物（A ) 的組成同質地相溶之可溶狀態。 以上製得之高分子化合物（A )，其經GPC換算之重 量平均分子量較佳爲3,000〜1 00,000。當重量平均分子量 未達3,000時，其作爲高分子化合物之功能不足。相反的 ，當超過10萬時，對導電性聚合物合成時的聚合場所（ 〇酸性水溶液）之溶解性可能不足，此外，使高分子化合物 本身的溶劑溶解性變差，可能對導電性聚合物的可溶化性 產生顯著的不良影響。 本發明之複合導電性高分子組成物，係使用上述製得 之高分子化合物（A )並以下列方式製造出。亦即，將上 述高分子化合物（A)溶解於電解性基質溶劑中，接著將 成爲π共軛系高分子（A )的原料之前述式（I)至式（ III )所表示的化合物添加於此溶液中，然後再藉由氧化 劑將此進行氧化，藉此，可製得高分子化合物（A )被摻 -19- 201100487 雜於以前述式（I )至式（III )所表示的化合物作爲單體 構成成分之7Γ共軛系高分子（)之複合導電性高分子組 成物。 原料的化合物中’式（I)所表示之化合物，爲取代 基是氫原子或烷基之苯胺。此化合物的具體例，有苯胺、 鄰甲苯胺、間甲苯胺、3,5 -二甲基苯胺、2,3 -二甲基苯胺 、2,5-二甲基苯胺、2,6-二甲基苯胺、2-乙基苯胺、3-乙 基苯胺、2_異丙基苯胺、3 -異丙基苯胺、2 -甲基-6-乙基苯 胺、2-正丙基苯胺、2_甲基_5_異丙基苯胺、2_ 丁基苯胺、 3 -丁基苯胺、5,6,7,8 -四氫-1-萘基苯胺、2,6-二乙基苯胺 等。 此外，式（II)所表示之化合物，爲取代基是氫原子 或烷基之噻吩。該具體例有噻吩、3 -甲基噻吩、3 -乙基噻 吩、3-丙基噻吩、3-丁基噻吩、3-戊基噻吩、3-己基噻吩 、3-庚基噻吩、3-正辛基噻吩等。 再者’式（III )所表示之化合物，爲取代基是氫原 子或烷基之吡咯，該具體例有吡咯、3 -甲基吡咯、3 -庚基 肶咯、3-正辛基吡咯等。 藉由本發明之方法來製造複合導電性高分子組成物之 具體方法的一例，有首先將作爲電解性基質溶劑的離子交 換水，因應必要構成爲酸性後，將前述製得之高分子化合 物（A)添加於此，接著將原料之式（I)至式（in)的 化合物的1種或2種以上添加於此，然後再添加氧化劑進 行氧化聚合之方法。由於高分子化合物（A)對離子交換 -20 - 201100487 水之溶解性的不同，亦可適當地倂用丙酮、丁酮等之嗣系 溶劑；甲醇、乙醇、異丙醇等之醇系溶劑；乙腈等之親水 性高的有機溶劑。 上述反應中’爲了將電解性基質溶劑構成爲酸性所用 之酸性物質，例如有鹽酸、硫酸、過氯酸、過碘酸、氯化 鐵（Π)、硫酸鐵（II)等，其量相對於式（I )〜式（III )的化合物1 mol而言可爲0.5〜3.0 mol。 〇 此外，反應中所用之氧化劑，亦須因應形成複合導電 性高分子組成物之芳香族化合物（單體）之氧化還原電位 的不同來適當地調整’可使用過氧二硫酸銨、過氧二硫酸 鉀、過氧二硫酸鈉、氯化鐵（III)、硫酸鐵（Ιπ)、四 氟硼酸鐵（III)、六氟磷酸鐵（III)、硫酸銅（u)、氯 化銅（II)、四氟硼酸銅（II)、六氟磷酸銅（π)等。 此外’反應中之闻分子化合物（Α)與化合物（I)至 (III )的比例，雖與最終所得之複合導電性高分子組成 〇 物的性質相依，而無法單純地決定，但較佳範圍的例子， 例如以高分子化合物（Α)中之磺酸基的數目與所用之化 合物（I)至（III)之莫耳比計，有下列所示者。 亦即，相對於選自式（I) ~(111)的化合物1莫耳而 言，係以該化合物中之磺酸基的莫耳比成爲〇.2~1.5的量 使闻分子化合物（Α)共存。 再者，氧化劑的用量，一般相對於化合物（I )至（ III) 1莫耳而言爲使用1.5〜2·5莫耳（1價換算），但因 系內的氧化度（酸性度）之不同，相對於單體1莫耳而言 -21 - 201100487 爲1莫耳以下，有時亦可充分地聚合。 此外，用以製得複合導電性高分子組成物之聚合反應 的溫度，其氧化反應後的發熱量或氫去除容易度係因化合 物（I)至（III)之種類的不同而不同，所以較佳溫度範 圍亦有所不同。 一般而言，當運用化合物（I)時，較佳爲4(TC以下 ，運用化合物（II )時，較佳爲9(TC以下，運用化合物（ ΠΙ)時，較佳爲20°C以下。 再者，當欲將複合導電性高分子組成物進行高分子量 化時，只需將反應溫度相對地降低，將反應時間相對地增 長即可，欲進行低分子量化時，只需與此相反。 如此製得之聚合物，可因應必要更進行洗淨等之後， 再構成爲目的物的複合導電性高分子組成物。此組成物， 如後述般，可在無法溶解以往的導電性高分子組成物之甲 苯等芳香族溶劑及乙酸乙酯等酯系溶劑中，安定地溶解。 如此製得之本發明的複合導電性高分子組成物之運用 方法的例子’有在均質狀態下將此溶解於芳香族溶劑及酯 系溶劑中之複合導電性高分子組成物溶液。複合導電性高 分子組成物溶液’可將此塗佈於需形成導電性覆膜之部分 上，接著藉由乾燥等手段，使該組成物中的芳香族溶劑揮 發，而在目的部分上形成均一的導電性覆膜。 調製上述複合導電性高分子組成物溶液時，較佳係以 成爲0.1-10質量％的程度，將複合導電性高分子組成物溶 解於甲苯、苯及二甲苯等之芳香族系溶劑及/或乙酸乙酯 -22- 201100487 、乙酸丙酯、乙酸丁酯等之酯系溶劑中。 此外，上述複合導電性高分子組成物溶液中，以提升 溶液的安定性及塗膜狀態下的導電性者爲目的，更可添加 苯甲醇、酚、間甲酚、鄰甲酚、2-萘烷醇、卜萘烷醇、癒 創木酚、2,6-二甲基酚等之具有羥基之芳香族化合物。此 等具有羥基之芳香族化合物，相對於複合導電性高分子組 成物溶液的溶劑100重量份而言，較佳係添加0.01〜45重 Ο 量份。 此外，上述複合導電性髙分子組成物溶液中，以提升 作爲防帶電塗料之自支撐膜的導電性及太陽能電池用對極 料之觸媒性能者爲目的，更可含有銅、銀、鋁、鉑等之金 屬；氧化鈦、氧化銦錫、摻雜氟之氧化錫、氧化鋁、二氧 化矽等之金屬氧化物；導電性聚合物組成物、碳奈米管（ CNT )、富勒烯、碳黑等之碳粉末、或是分散體作爲塡充 材成分。此等粉末或分散體，相對於複合導電性高分子組 ® 成物溶液的固形份1 〇〇重量份而言，較佳係添加固形份 0 · 0 1〜5 0重量份。 再者’上述複合導電性高分子組成物可使用在色素增 感型太陽能電池用對極。此色素增感型太陽能電池用對極 ’當要求透明性時，可將上述複合導電性高分子組成物層 合於透明基板的單面上’或是將透光性電極配置在透明基 板一方的面上’並將上述複合導電性高分子組成物層合於 該透光性電極而形成。此外’當未要求透明性時，可藉由 層合於金屬箔等來形成。此複合導電性高分子組成物的厚 -23- 201100487 度，一般爲0.01〜ΙΟΟμιη，較佳爲0.1〜50μιη的範 本發明之色素增感型之上述所用的透明基板 透光率一般爲50%以上，較佳爲8〇%以上之膜或 透明基板的例子’有玻璃等之無機透明基板、聚 酸乙二酯（PET)、聚碳酸酯（PC)、聚苯硫化 颯、聚酯颯、聚（甲基）丙烯酸烷酯、聚萘二甲 (PEN)、聚醚楓（PES)、聚環烯烴等之高分 板等。此外’金屬箔例如有金、鉑、銀、錫、銅 鏽鋼、鎳等之金屬箔。 此等透明基板的厚度，爲無機透明基板時 2〇0〜7〇ΟΟμιη的範圍內，爲高分子透明基板時 2 0~4 000μιη，較佳爲20〜2000μιη的範圍內。爲金 時，爲 0.1μηι~1000μηι，較佳爲 1μιη~500μιη 的範 範圍內的厚度之高分子透明基板及金屬箔基板， 性賦予至所得之色素增感太陽能電池。 此外，上述透明基板一方的面上，可因應必 透光性電極。在此所用之透光性電極，例如有膜 金屬電極、網目狀導電性金屬電極等。 上述膜狀導電性金屬電極，係將氧化錫、摻 化銦（ΙΤΟ )、摻雜氟之氧化鋁（FTO )等形成 。此膜狀導電性金屬電極，可藉由蒸鍍或濺鍍等 、：[TO、FTO等形成於透明基板的表面。此膜狀 屬電極的厚度，一般爲0.0卜Ιμηι，較佳爲0.01-範圍內。 圍內。 ，可使用 板。此般 對苯二甲 合物、聚 酸二乙酯 子透明基 、銘、不 ，一般爲 ，一般爲 屬箔基板 圍內。此 可將可撓 要而配置 狀導電性 雜錫之氧 爲膜狀者 將氧化錫 導電性金 -0 · 5 μιη 的 -24- 201100487 另一方面’網目狀導電性金屬電極，係將銅、鎳、鋁 等之導電性金屬形成爲網目狀者。具體而言，網目狀導電 性金屬電極’係使用銅、鎳、鋁等之導電性金屬，並例如 藉由微影技術，以成爲線寬一般爲10〜70μιη，較佳爲 10〜20μιη，間距寬度一般爲50〜300μπι，較佳爲50〜200μηι 之網目的方式進行蝕刻而形成。此時網目狀導電性金屬電 極之導線的厚度，係與所用之導電性金屬的厚度大致相同 0 ，一般爲8~150μιη，較佳爲8~15μιη的範圍內。此網目狀 導電性金屬電極，可使用黏著劑等來貼著於透明基板的表 面。 製造上述色素增感型太陽能電池用對極時，將複合導 電性高分子組成物層合於上述透明基板的單面上或是配置 在透明基板一方的面之透光性電極上之方法，例如有進行 1次或複數次下列操作者，亦即將上述複合導電性高分子 組成物溶液塗佈於上述透明基板的單面上或是配置在透明 〇基板一方的面之透光性電極上，並去除溶液中的溶劑。 上述複合導電性高分子組成物溶液的塗佈，可運用浸 漬塗佈機、微棒塗佈機、輥塗佈機、刮刀塗佈機、壓模塗 佈機、凹版塗佈機等之一般所知的塗佈機。 此外，溶劑的去除，可運用依據靜置所進行之自然乾 燥、在熱風·紅外線的加熱條件下之強制乾燥等方法。 上述色素增感型太陽能電池用對極，由於其所用之上 述複合導電性高分子組成物可溶於有機溶劑，與以往藉由 水性媒體使複合導電性高分子組成物分散之分散液相比’ -25- 201100487 其塗佈步驟容易進行，生產性較佳。此外，亦可抑制由酸 性水溶液所起因之對極製作階段中的金屬腐鈾劣化。 此外，上述色素增感型太陽能電池用對極，其所用之 上述複合導電性高分子組成物，係採用在特定範圍內將上 述成分（a-l)、成分（a-2)及成分（a-3)進行共聚合所 製得之高分子化合物（A)，藉此可使相對於上述透明基 板或透光性電極或金屬箔之密著性變佳，所以能夠長時間 使用。 再者，上述色素增感型太陽能電池用對極，其所用之 上述複合導電性高分子組成物，係採用在特定範圍內將上 述成分（a-l)、成分（a-2)及成分（a-3)進行共聚合所 製得之酸性度經抑制的高分子化合物（A)，藉此可使透 光性電極（導電性金屬）不易被腐蝕，並提升相對於電解 液之耐久性，所以能夠長時間使用。 此外，上述色素增感型太陽能電池用對極，相對於以 往用作爲對電解液具有耐氧化性之電極的價昂的鉑電極， 複合導電性高分子膜可作用爲均一的耐氧化性膜而爲各種 金屬所使用，所以可廉價地提供。 此外，使用上述複合導電性高分子組成物而成之防帶 電膜，由於上述複合導電性高分子組成物可進行塗佈·乾 燥而單獨成爲自支撐膜，所以可加工成低電阻的防帶電膜 。此外，當因應必要使複合導電性高分子組成物與熱可塑 性樹脂及/或熱硬化性樹脂混合存在時，例如可藉由（1 ) 使用τ模具等，將藉由擠出機或擠壓機等進行熔融捏合者 -26- 201100487 進行成膜之方法，（2)將上述複合導 溶液塗佈於熱可塑性樹脂、熱硬化性樹 的單面或雙面上，並去除溶液中的溶劑 之方法而製得。 上述防帶電膜中所用之熱可塑性樹 、聚氯乙烯、聚偏二氯乙烯、聚苯乙烯 聚四氟乙烯、聚丙烯腈丁二烯苯乙烯、 〇聚甲基丙烯酸、聚丙烯酸、飽和聚酯、 、聚改質苯醚、聚苯硫化合物、聚颯、 聚合物、聚醚醚酮、聚醯胺醯亞胺等， 性樹脂的聚合物合金或熱可塑性彈性體 本發明之上述防帶電膜中所用之熱 有聚酚、聚環氧、不飽和聚酯、聚胺基 、聚脲、矽氧烷樹脂、三聚氰胺樹脂、 等。 ® 此外，上述防帶電膜，藉由使用在 成分（a-Ι)、成分（a-2)及成分（a-3 得之高分子化合物（A)，可形成在各 件下的性能不均一較少，且具有高透射 [實施例] 接著舉出實施例來更詳細地說明本 不受此等實施例所限制。本實施例中之 値’係藉由下列方法所測定。 電性高分子組成物 脂、及玻璃製之膜 來形成防帶電膜等 脂，例如有聚烯烴 、聚乙酸乙烯酯、 聚丙烯腈苯乙烯、 聚醯胺、聚碳酸酯 聚丙烯酸酯、液晶 亦含有此等熱可塑 〇 硬化性樹脂，例如 甲酸酯、聚醯亞胺 氟樹脂、醇酸樹脂 特定範圍內將上述 )進行共聚合所製 種高濕低濕環境條 性之防帶電膜。 發明，但本發明並 分子量與表面電阻 -27- 201100487 <分子量> 藉由下列條件下的GPC來測定。 裝置名稱·· HLC-8120 ( Tosoh公司製） 管柱：GF-1G7B + GF-510HQ ( Asahipak :註冊商標、 昭和電工公司製） 基準物質：聚苯乙烯及聚苯乙烯磺酸鈉 樣本濃度·· 1 .〇mg/ml 溶離液：50毫莫耳氯化鋰水溶液/CH3CN = 60/40wt 流量：0.6ml/min 管柱溫度：30°C 檢測器：UV254nm <表面電阻値> 使用 DIA Instruments公司製之低電阻率計Loresta GP、PSP型式的探針，藉由四端子四探針法來測定。 實施例1 (1 )高分子化合物（2-NaSEMA/BzMA/2-EHMA = 30/ 40/30 ) 量取甲基丙烯酸2-磺乙酯鈉鹽（2-NaSEMA) 50g、 甲基丙烯酸苯甲酯（BzMA ) 55g、甲基丙烯酸2-乙基己 酯（2-EHA) 47g、水150g及異丙醇300g，投入至燒瓶內 。升溫至回流溫度後，添加偶氮雙異丁腈（AIBN ) 0.7g -28- 201100487 以進行聚合。在回流的狀態下進行18小時的反應。 (2) 高分子化合物的精製 將己烷5 0 0 g添加於上述（1 )中所得之聚合物溶液後 ，藉由分液萃取來去除油層的雜質。於1小時之間將lkg 的甲醇滴入至分液後的水層來析出固形份，並過濾固形份 。於減壓下、l〇〇°C下將所得之固形物進行24小時的乾燥 Ο 後，以搗缽進行粉碎而製得高分子化合物的粉體（α -1 ) 。藉由GPC來測定所得之聚合物，其結果爲Mw = 38,000 〇 (3) 高分子化合物的再溶解 將上述（2)中所得之高分子化合物16. lg、離子交換 水200g及35%鹽酸水溶液6g量取至燒瓶，在60°C下進 行加熱攪拌，而製得均一的高分子化合物水溶液。 ❹ (4 )聚苯胺聚合 在冷卻上述（3 )中所得之高分子化合物水溶液後， 量秤出苯胺4.65g並加入至此。將此混合物進行攪拌及溶 解後，成爲均一的乳化液。另外量取水30g、過氧二硫酸 銨1 〇g並混合，在0°C下於2小時之間將此混合物滴入至 裝有此乳化液之燒瓶中。滴入結束後，返回室溫（25 °C ) 並進行48小時的攪拌。 -29- 201100487 (5) 聚苯胺精製 將反應結束後的聚合溶液進行過濾，使所得的結晶於 水中進行再分散並進行洗淨，並再次進行過濾。取出重複 進行4次前述洗淨所得之含水的固形物，於減壓下、40 °C 下進行96小時的乾燥，而製得聚苯胺乾燥物（複合導電 性高分子組成物）（Θ -1 )。測定複合導電性高分子組成 物的揮發份，其結果爲揮發份2%以下。 (6) 聚苯胺溶解 量秤出前述（5 )中所得之複合導電性高分子組成物 5g、甲苯47g及乙酸乙酯48g並放入燒瓶內，將此進行攪 拌及溶解，而製得複合導電性高分子組成物溶液。 (7 )塗膜評估Ry (wherein, Ri to R7 represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms) 〇 In addition, the present invention is a method for producing a composite conductive polymer composition, which is characterized in that Component (a-Ι)~(a-3) -13- 201100487 The polymer compound (A) obtained by the polymerization and the compound selected from the above formulas (I) to (III) are coexisted in an electrolytic matrix solvent. And using an oxidizing agent for chemical oxidative polymerization; (a-1) a monomer having a sulfonic acid group and a polymerizable vinyl group: 20 to 50 mol%; (a-2) having an aromatic group or an alicyclic group and polymerizability Vinyl monomer: 20~50 mol%; (a-3) (methyl)propionic acid ester: 30~60 mol%. Furthermore, the present invention is a composite conductive polymer composition solution which is an aromatic solvent selected from the group consisting of toluene, benzene and xylene and/or an ester selected from the group consisting of ethyl acetate, propyl acetate and butyl acetate. In the solvent, 0.1 to 10% by mass of the composite conductive polymer composition is contained in a dissolved state. Further, the present invention relates to a counter electrode for a dye-sensitized solar cell, which is obtained by using the above composite conductive polymer composition. Further, the present invention is an antistatic film which is obtained by using the above composite conductive polymer composition. Advantageous Effects of the Invention The composite conductive polymer composition obtained by the polymerization of an oxidizing agent in the presence of the polymer compound of the present invention can be stably dissolved in an aromatic solvent such as toluene or an ester of ethyl acetate or the like. In the solvent. Therefore, a conductive coating can be simply prepared by applying a solution in which the composite conductive polymer composition is dissolved in an aromatic solvent to a portion to which conductivity is to be imparted and drying the dry-14 - 201100487 membrane. [Embodiment] The polymer compound (A) used in the present invention can be subjected to a monomer and a component of the component (a-1) and a polymerizable vinyl group in the presence of a polymerization initiator according to the method. A-2) A monomer having an aromatic or alicyclic group and a polymerizable vinyl group and a component (a-3) methacrylate alkyl acrylate are produced by polymerization. a monomer having a sulfonic acid group and a polymerizable vinyl group as a sulfonic acid group having a styrenesulfonic acid group or a sulfoethyl group, and a styrene sulfonic acid or sodium styrene sulfonate, benzene. Styrene sulfonate such as potassium vinyl sulfonate or calcium benzoate, 2-sulfoethyl sodium 2-sulfoethyl (meth) acrylate, 2-potassium (meth) acrylate, (methyl) (2-sulfonyl acrylate, calcium salt, etc. (methyl 2-sulfoethyl salt) ^ In addition, the component (a-2) has an aromatic or alicyclic vinyl monomer. Phenylethyl (meth) acrylate) phenoxyethyl acrylate, methyl 2-(methyl) acrylate, cyclohexyl (ethyl) 2-ethyl phthalate , dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl acrylate, tert-butylcyclohexyl (meth)acrylate, methacrylate, (methyl) acrylate (methyl) acrylate ) morpholinyl acrylate, styrene, dimethyl styrene, naphthyl acrylate, vinyl naphthalene, vinyl n-ethyl oxazole, general sulfonic acid Group-based (a monomer, this example vinyl sulfonate or ( sulfoethyl) propylene with polymerization, (methyl phthalate, ((methyl ester, (hexyl ester, (methyl alkenyl -15 - 201100487 Further, specific examples of the alkyl (meth)acrylate of the component (a-3) include methyl (meth)acrylate, ethyl (meth)acrylate, and n-propyl (meth)acrylate. Isopropyl methacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, isopropyl (meth) acrylate, tertiary butyl (meth) acrylate, (meth) acrylate 2-ethylhexyl ester, isooctyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, etc. Production of polymer compound (A) used in the present invention The molar ratio of the monomer (a-Ι), the monomer (a-2), and the monomer (a-3) is important. That is, the polymer compound of the present invention can be aromatic The hydrophobicity formed by the group or the alicyclic group and the hydrophilicity formed by the sulfonic acid group are appropriately balanced to the conductive polymer compound The amount of the component (ai) used to produce the polymer compound (A) of the present invention is from 20 to 50 m ο 1 %, preferably 2 5 . ~ 4 0 m ο 1 %. Further, the compounding amount of the component (a-2) is 20 to 50 mol%, preferably 30 to 45 mol%. Further, the compounding amount of the component (a-3) is 30 to 60. Mol%, preferably 35 to 50 mol% The polymer compound of the present invention may contain a polymerizable component other than the above monomers (a-1), (a-2) and (a-3). Examples of the polymerizable component are 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. , (meth)acrylic acid methoxyethyl ester, (meth)acrylic acid-16- 201100487 butoxyethyl ester, (meth)acrylic acid polyethylene glycol ester, (meth)acrylic acid methoxy polyethylene glycol Ester, (meth)acrylic acid, ethoxylated ethyl (meth) acrylate, tetrahydrofuran (meth) acrylate, N, N dimethyl amine ethyl (meth) acrylate, vinyl pyridine, etc. , The blending amount during blending is 〇~20 mol%. The polymerization of the above components (a-Ι), component (a-2), component (a-3), and the polymerizable component added as necessary can be carried out by a generally known method. For example, after the components are mixed, a polymerization initiator is added thereto, and polymerization is started by heating, light irradiation, or the like to produce a polymerization method which can be used to produce the polymer compound (A). The method to be carried out in a state where the component (a-2) is not separated from the monomer mixture is not particularly limited, and for example, a solution polymerization method, a bulk (overall) polymerization method, a precipitation polymerization method, or the like can be employed. Further, the polymerization initiator used in the polymerization reaction is not particularly limited as long as it can be dissolved in the above respective components or the solvent used in the reaction. Examples of the polymerization initiator include oil-soluble peroxide-based thermal polymerization initiators such as benzamidine peroxide (BPO), and oil-soluble azo-based thermal polymerizations such as azobisisobutyronitrile (AIBN). A water-soluble azo-based heat polymerization initiator such as a starter or azobiscyanoshikimic acid (ACVA). Further, when the proportion of water in the solvent at the time of solution polymerization is large, a water-soluble peroxide-based thermal polymerization initiator such as ammonium persulfate or potassium persulfate or hydrogen peroxide water may be used. Further, it may be used in combination with a redox agent such as iron or an amine. The range of use of such a polymerization initiator may be arbitrarily used within a range of 0.001 to 〇 1 mol with respect to the above-mentioned compound -17-201100487 1 mol, and it is also possible to use the total input, the drip input, Any method of successive inputs. Further, in the case of bulk polymerization or solution polymerization using a small amount of a solvent (50% by weight or less relative to a monomer), there is also a method of polymerizing a thiol and a metal aryl group (Patent Document 9). Further, the solvent used in the polymerization reaction may, for example, be an alcohol solvent such as methanol, ethanol, isopropanol or butanol; a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; methyl cellosolve; A glycol solvent such as ethyl cellosolve, propylene glycol methyl ether or propylene glycol ethyl ether; a lactic acid solvent such as methyl lactate or ethyl lactate. Further, in the polymerization, in addition to the polymerization initiator, a chain transfer agent can be used. When the molecular weight is to be adjusted, it can be suitably used. As the chain transfer agent which can be used, any compound can be used as long as it can be dissolved in the above monomer or solvent. For example, an alkylthiol such as dodecyl mercaptan or heptyl mercaptan can be suitably used; a water-soluble thiol having a polar group like an acid (BMPA); an oily radical inhibitor such as an α styrene dimer (ASD); and the like, in addition, the polymerization is carried out in a solvent (in general polymerization) It is preferable to carry out the boiling point below the boiling point, for example, it is preferably 65 ° C to 80 ° C. However, it is preferred to carry out the polymerization at a temperature of from 25 ° C to 80 ° C when the polymerization is carried out in the same manner as in the case of the polymerization of the thiol and the metal aryl. The polymer thus obtained can be purified as necessary to constitute the polymer compound (A). An example of the purification method is to use an oily poor solvent such as hexane to remove oily low molecular impurities and residual monomers, low molecular weight -18-201100487 impurities, and then poorly hydrated by acetonitrile, methanol, ethanol, acetone or the like. A method in which a solvent is subjected to polymer precipitation or the like to remove water-based impurities and residues. The reason why the purification is carried out is that the polymer compound (A) is introduced as a dopant into the conductive polymer composition to act as a stack inhibitor and a solvent solvent, and other polymerization initiator residues are added. The monomer, the oligomer, the heterogeneous composition, and the like remain as a residue after the polymerization, and the function of the conductive polymer composition is lowered, so that it must be removed. Further, as a result of the purification, the heterogeneous radical polymer is not mixed as in Patent Document 7, and the composition of the uniform conductive polymer composition and the polymer compound (A) can be exhibited. A soluble state that is homogeneously compatible. The polymer compound (A) obtained above preferably has a GPC-equivalent weight average molecular weight of 3,000 to 10,000,000. When the weight average molecular weight is less than 3,000, its function as a polymer compound is insufficient. On the other hand, when it exceeds 100,000, the solubility in the polymerization site (aqueous acidic solution) at the time of synthesis of the conductive polymer may be insufficient, and the solvent solubility of the polymer compound itself may be deteriorated, possibly to the conductive polymer. The solubilization produces significant adverse effects. The composite conductive polymer composition of the present invention is produced by the following method using the polymer compound (A) obtained above. In other words, the polymer compound (A) is dissolved in an electrolytic matrix solvent, and then the compound represented by the above formula (I) to formula (III) which is a raw material of the π-conjugated polymer (A) is added to the compound. This solution is then oxidized by an oxidizing agent, whereby the polymer compound (A) is obtained by mixing the compound represented by the above formula (I) to formula (III) with -19-201100487 as a compound A composite conductive polymer composition of a 7-inch conjugated polymer () having a monomer component. In the compound of the starting material, the compound represented by the formula (I) is an aniline wherein the substituent is a hydrogen atom or an alkyl group. Specific examples of the compound include aniline, o-toluidine, m-toluidine, 3,5-dimethylaniline, 2,3-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethyl Aniline, 2-ethylaniline, 3-ethylaniline, 2-isopropylacetamide, 3-isopropylaniline, 2-methyl-6-ethylaniline, 2-n-propylaniline, 2-sheet 5-1-5 isopropylaniline, 2-butylaniline, 3-butylaniline, 5,6,7,8-tetrahydro-1-naphthylaniline, 2,6-diethylaniline, and the like. Further, the compound represented by the formula (II) is a thiophene whose substituent is a hydrogen atom or an alkyl group. Specific examples are thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-pentylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-positive Octylthiophene and the like. Further, the compound represented by the formula (III) is a pyrrole whose substituent is a hydrogen atom or an alkyl group, and specific examples thereof include pyrrole, 3-methylpyrrole, 3-heptylpyrrole, 3-n-octylpyrrole, and the like. . An example of a specific method for producing a composite conductive polymer composition by the method of the present invention is to firstly obtain an ion-exchanged water as an electrolytic matrix solvent, and if necessary, acidification, and then obtain the polymer compound (A) obtained as described above. In addition, one or two or more kinds of the compounds of the formula (I) to the formula (in) of the starting materials are added thereto, and then an oxidizing agent is further added to carry out oxidative polymerization. Depending on the solubility of the polymer compound (A) in the ion exchange-20 - 201100487 water, an oxime solvent such as acetone or methyl ketone or an alcohol solvent such as methanol, ethanol or isopropanol may be suitably used; An organic solvent having high hydrophilicity such as acetonitrile. In the above reaction, 'the acidic substance used to make the electrolytic matrix solvent acidic, for example, hydrochloric acid, sulfuric acid, perchloric acid, periodic acid, iron chloride (iron), iron (II) sulfate, etc. The compound of the formula (I) to the formula (III) may be 0.5 to 3.0 mol in terms of 1 mol. In addition, the oxidizing agent used in the reaction must be appropriately adjusted depending on the oxidation-reduction potential of the aromatic compound (monomer) forming the composite conductive polymer composition. 'Using ammonium peroxodisulfate and peroxydialdehyde can be used. Potassium sulphate, sodium peroxodisulfate, iron (III) chloride, iron sulphate (Ιπ), iron (III) tetrafluoroborate, iron (III) hexafluorophosphate, copper (u) sulfate, copper (II) chloride , copper (II) tetrafluoroborate, copper hexafluorophosphate (π) and the like. Further, the ratio of the molecular compound (Α) to the compound (I) to (III) in the reaction may not be simply determined depending on the nature of the finally obtained composite conductive polymer composition, but a preferred range. For example, the number of sulfonic acid groups in the polymer compound (Α) and the molar ratio of the compounds (I) to (III) used are as follows. That is, relative to the compound 1 selected from the formula (I) to (111), the molar ratio of the sulfonic acid group in the compound is 〇. 2 to 1.5 to give a molecular compound (Α )coexist. Further, the amount of the oxidizing agent is generally 1.5 to 2.5 moles per mole of the compound (I) to (III) 1 mole (in terms of monovalent conversion), but the degree of oxidation (acidity) in the system is It is different from the monomer 1 mol to 21 - 201100487, which is 1 mol or less, and may be sufficiently polymerized. Further, the temperature at which the polymerization reaction of the composite conductive polymer composition is carried out is such that the calorific value after the oxidation reaction or the ease of hydrogen removal differs depending on the type of the compounds (I) to (III). The temperature range is also different. In general, when the compound (I) is used, it is preferably 4 (TC or less, and when the compound (II) is used, it is preferably 9 (TC or less, and when the compound (?) is used, it is preferably 20 ° C or lower. In addition, when the composite conductive polymer composition is to be subjected to high molecular weight, the reaction temperature may be relatively lowered, and the reaction time may be relatively increased. When the molecular weight is to be reduced, the reverse is required. The polymer obtained in this manner can be used as a composite conductive polymer composition of the object after being washed, etc., and the composition can be dissolved in the conventional conductive polymer composition as will be described later. An aromatic solvent such as toluene or an ester solvent such as ethyl acetate is dissolved in an ester solvent. The example of the method for using the composite conductive polymer composition of the present invention obtained in this way is dissolved in a homogeneous state. a solution of a composite conductive polymer composition in an aromatic solvent and an ester solvent. The composite conductive polymer composition solution can be applied to a portion where a conductive film is to be formed, followed by drying And a method of volatilizing the aromatic solvent in the composition to form a uniform conductive film on the target portion. When the solution of the composite conductive polymer composition is prepared, it is preferably 0.1 to 10% by mass. To the extent, the composite conductive polymer composition is dissolved in an aromatic solvent such as toluene, benzene or xylene, and/or an ester solvent such as ethyl acetate-22-201100487, propyl acetate or butyl acetate. In the above composite conductive polymer composition solution, benzyl alcohol, phenol, m-cresol, o-cresol, 2-decalin may be added for the purpose of improving the stability of the solution and the conductivity in the coating state. An aromatic compound having a hydroxyl group such as an alcohol, a naphthyl alcohol, a guaiacol or a 2,6-dimethylphenol, etc. The aromatic compound having a hydroxyl group, a solvent relative to the solution of the composite conductive polymer composition 100 parts by weight is preferably added in an amount of 0.01 to 45 parts by weight. Further, in the above composite conductive ruthenium molecular composition solution, the conductivity of the self-supporting film as an antistatic paint and the counter electrode for a solar cell are improved. For the purpose of the catalyst performance of the material, it may further contain metals such as copper, silver, aluminum, platinum, etc.; metal oxides of titanium oxide, indium tin oxide, fluorine-doped tin oxide, aluminum oxide, cerium oxide, etc.; a polymer powder, a carbon powder such as a carbon nanotube (CNT), fullerene or carbon black, or a dispersion as a ruthenium filler component. These powders or dispersions are relative to a composite conductive polymer. The solid content of the group solution is preferably 0. 0 1 to 50 parts by weight of the solid portion. Further, the above composite conductive polymer composition can be used in the dye-sensitized type. The solar cell uses a counter electrode. When the transparency of the dye-sensitized solar cell is required, the composite conductive polymer composition may be laminated on one surface of the transparent substrate or the translucent electrode may be used. The composite conductive polymer composition is disposed on one surface of the transparent substrate and is laminated on the light-transmitting electrode. Further, when transparency is not required, it can be formed by laminating a metal foil or the like. The composite conductive polymer composition has a thickness of -23 to 201100487 degrees, generally 0.01 to ΙΟΟμηη, preferably 0.1 to 50 μm. The dye-sensitized type of the above-mentioned transparent substrate generally has a light transmittance of 50% or more. An example of a film or a transparent substrate of preferably 8% or more 'inorganic transparent substrate having glass or the like, polyethylene terephthalate (PET), polycarbonate (PC), polyphenyl sulfonium sulfide, polyester ruthenium, poly High-grade plates such as alkyl (meth)acrylate, polynaphthalene (PEN), polyether maple (PES), and polycycloolefin. Further, the metal foil is, for example, a metal foil such as gold, platinum, silver, tin, copper rust steel or nickel. The thickness of the transparent substrate is in the range of 2 〇 0 to 7 〇ΟΟ μηη in the case of the inorganic transparent substrate, and is in the range of 20 to 4 000 μm, preferably 20 to 2000 μm in the case of the polymer transparent substrate. In the case of gold, the polymer transparent substrate and the metal foil substrate having a thickness in the range of 0.1 μm to 1000 μm, preferably in the range of 1 μm to 500 μm, are imparted to the obtained dye-sensitized solar cell. Further, on one surface of the transparent substrate, a translucent electrode may be required. The translucent electrode used herein includes, for example, a film metal electrode, a mesh-like conductive metal electrode, or the like. The film-shaped conductive metal electrode is formed of tin oxide, indium doped (yttrium), fluorine-doped alumina (FTO) or the like. The film-shaped conductive metal electrode can be formed on the surface of the transparent substrate by vapor deposition, sputtering, or the like: [TO, FTO, or the like. The thickness of the membranous electrode is generally 0.0 Ιμηι, preferably 0.01 Å. Inside. , the board can be used. Such a para-phenylene phthalate, a polyethylene glycol transparent group, inscriptions, no, generally, generally belong to the foil substrate. This can be used to make the oxygen of the conductive tin which is configurable and has a film shape. The tin oxide conductive gold -5 - 5 μιη -24-201100487 On the other hand, the mesh-like conductive metal electrode is made of copper, A conductive metal such as nickel or aluminum is formed into a mesh shape. Specifically, the mesh-shaped conductive metal electrode 'uses a conductive metal such as copper, nickel or aluminum, and is, for example, by a lithography technique, has a line width of generally 10 to 70 μm, preferably 10 to 20 μm, and a pitch. It is formed by etching in a manner of a width of 50 to 300 μm, preferably 50 to 200 μm. The thickness of the wire of the mesh-like conductive metal electrode at this time is substantially the same as the thickness of the conductive metal used, and is generally in the range of 8 to 150 μm, preferably 8 to 15 μm. The mesh-shaped conductive metal electrode can be attached to the surface of the transparent substrate by using an adhesive or the like. When the counter electrode for a dye-sensitized solar cell is produced, a method in which a composite conductive polymer composition is laminated on one surface of the transparent substrate or a translucent electrode disposed on one surface of a transparent substrate, for example, The above-mentioned composite conductive polymer composition solution is applied to one surface of the transparent substrate or to a light-transmitting electrode disposed on one surface of the transparent germanium substrate, and the following operations are performed one or more times; Remove the solvent from the solution. For the application of the solution of the composite conductive polymer composition, a general application such as a dip coater, a micro bar coater, a roll coater, a knife coater, a die coater, or a gravure coater can be used. Known coating machine. Further, the removal of the solvent can be carried out by natural drying according to standing, forced drying under heating by hot air or infrared rays. In the counter electrode for the dye-sensitized solar cell, the composite conductive polymer composition used in the above is soluble in an organic solvent, and is compared with a dispersion in which a composite conductive polymer composition is dispersed by an aqueous medium. -25- 201100487 The coating step is easy to carry out and the productivity is good. Further, deterioration of the metal uranium in the counter production stage caused by the aqueous acid solution can be suppressed. Further, in the above-mentioned composite conductive polymer composition for the dye-sensitized solar cell, the above-mentioned component (al), component (a-2) and component (a-3) are used in a specific range. When the polymer compound (A) obtained by the copolymerization is obtained, the adhesion to the transparent substrate or the translucent electrode or the metal foil can be improved, so that it can be used for a long period of time. In the above-mentioned composite conductive polymer composition for the dye-sensitized solar cell, the above-mentioned component (al), component (a-2) and component (a-) are used in a specific range. 3) The polymer compound (A) having a suppressed acidity obtained by copolymerization can prevent the light-transmitting electrode (conductive metal) from being corroded and improve the durability against the electrolytic solution. Use for a long time. In addition, the counter electrode of the dye-sensitized solar cell can be used as a uniform oxidation-resistant film by using a platinum electrode which is conventionally used as an electrode having oxidation resistance to an electrolytic solution. It is used for various metals, so it can be provided at low cost. Further, the antistatic film obtained by using the above composite conductive polymer composition can be processed into a low-resistance antistatic film because the composite conductive polymer composition can be applied and dried to form a self-supporting film. . Further, when the composite conductive polymer composition is mixed with the thermoplastic resin and/or the thermosetting resin as necessary, for example, (1) a τ mold or the like can be used, and the extruder or the extruder can be used. The method of performing film formation by melt-kneading, -26-201100487, and (2) the method of applying the above-mentioned composite lead solution to one side or both sides of a thermoplastic resin or a thermosetting tree, and removing the solvent in the solution And made. Thermoplastic tree used in the above antistatic film, polyvinyl chloride, polyvinylidene chloride, polystyrene polytetrafluoroethylene, polyacrylonitrile butadiene styrene, fluorene polymethacrylic acid, polyacrylic acid, saturated polyester , poly-modified phenyl ether, polyphenylene sulfide compound, polyfluorene, polymer, polyetheretherketone, polyamidoximine, etc., polymer alloy of thermoplastic resin or thermoplastic elastomer, the above antistatic film of the present invention The heat used in the present invention is polyphenol, polyepoxy, unsaturated polyester, polyamine, polyurea, decane resin, melamine resin, and the like. In addition, the antistatic film described above can be formed into a non-uniform performance under the respective components by using the component (a-Ι), the component (a-2), and the component (a-3). Less, and high transmission [Embodiment] Next, the embodiment will be described in more detail to be not limited by the embodiments. The 値' in this embodiment is determined by the following method. The composition of the fat and the film made of glass to form a grease such as an antistatic film, such as polyolefin, polyvinyl acetate, polyacrylonitrile styrene, polyamine, polycarbonate polyacrylate, liquid crystal also contains such heat A plastic, sturdy and hardenable resin, for example, a formic acid ester, a polyimide, a fluororesin, or an alkyd resin, which is obtained by copolymerizing the above-mentioned) in a high-humidity and low-humidity environment. Invention, but the present invention and molecular weight and surface resistance -27-201100487 <Molecular weight> were determined by GPC under the following conditions. Device name · HLC-8120 (manufactured by Tosoh Corporation) Pipe column: GF-1G7B + GF-510HQ (Asahipak: registered trademark, manufactured by Showa Denko Co., Ltd.) Reference material: Sample concentration of polystyrene and sodium polystyrene sulfonate·· 1. 〇mg/ml Dissolution: 50 mM aqueous solution of lithium chloride/CH3CN = 60/40wt Flow rate: 0.6ml/min Column temperature: 30°C Detector: UV254nm <Surface resistance 値> Using DIA Instruments The company's low resistivity meter Loresta GP, PSP type probe is measured by four-terminal four-probe method. Example 1 (1) Polymer compound (2-NaSEMA/BzMA/2-EHMA = 30/40/30) Amount of 2-sulfoethyl methacrylate sodium salt (2-NaSEMA) 50 g, benzoyl methacrylate 55 g of ester (BzMA), 47 g of 2-ethylhexyl methacrylate (2-EHA), 150 g of water, and 300 g of isopropyl alcohol were placed in a flask. After heating to reflux temperature, azobisisobutyronitrile (AIBN) 0.7 g -28-201100487 was added to carry out polymerization. The reaction was carried out for 18 hours under reflux. (2) Purification of polymer compound After adding 500 kg of hexane to the polymer solution obtained in the above (1), impurities in the oil layer were removed by liquid separation extraction. LTg of methanol was dropped into the water layer after separation for 1 hour to precipitate a solid fraction, and the solid fraction was filtered. The obtained solid matter was dried under reduced pressure at 10 ° C for 24 hours, and then pulverized with hydrazine to obtain a powder (α -1 ) of a polymer compound. The obtained polymer was measured by GPC, and the result was Mw = 38,000 〇 (3) Re-dissolution of the polymer compound 16. The polymer compound obtained in the above (2) was 16. g, ion-exchanged water 200 g, and 35% hydrochloric acid aqueous solution. 6 g of the flask was weighed and heated and stirred at 60 ° C to obtain a uniform aqueous polymer compound solution. (4) Polyaniline polymerization After cooling the aqueous solution of the polymer compound obtained in the above (3), 4.65 g of aniline was weighed and added thereto. After the mixture was stirred and dissolved, it became a uniform emulsion. Further, 30 g of water and 1 〇g of ammonium peroxodisulfate were weighed and mixed, and the mixture was dropped into a flask containing the emulsion at 0 ° C for 2 hours. After the completion of the dropwise addition, the mixture was returned to room temperature (25 ° C) and stirred for 48 hours. -29-201100487 (5) Polyaniline purification The polymerization solution after completion of the reaction was filtered, and the obtained crystals were redispersed in water, washed, and filtered again. The aqueous solid matter obtained by the above-described washing was washed four times, and dried under reduced pressure at 40 ° C for 96 hours to obtain a dried polyaniline (composite conductive polymer composition) (Θ -1) ). The volatile matter of the composite conductive polymer composition was measured, and as a result, the volatile matter was 2% or less. (6) The amount of the polyaniline dissolved was 5 g of the composite conductive polymer composition obtained in the above (5), 47 g of toluene, and 48 g of ethyl acetate, and placed in a flask, and stirred and dissolved to obtain a composite conductive material. A solution of a polymer composition. (7) Coating evaluation

將上述（6 )中所得之複合導電性高分子組成物溶液 塗佈於玻璃基板上，在90°C下將此進行乾燥，而製得綠 色的均一塗膜（7-1)。此塗膜的表面電阻値爲60kQ/D 比較例1 (1 )比較高分子化合物（2-NaSEMA/BzMA/2-EHMA =30/10/60) 量取 2-NaSEMA50g、BzMA13.8g、2-EHA94g、離子 交換水150g及異丙醇3 00g，投入至燒瓶內。升溫至回流 -30- 201100487 溫度後，添加AIBN0.7g以進行聚合。在回流的狀態下進 行1 8小時的反應。 (2) 高分子化合物的精製 將己烷約500g添加於上述（1 )中所得之聚合物溶液 後，藉由分液萃取來去除油層的雜質。於1小時之間將 1 kg的甲醇滴入至分液後的水層來析出固形份，並過濾固 〇 形份。於減壓下、1 〇〇°C下將所得之固形物進行24小時的 乾燥後，以搗缽進行粉碎而製得高分子化合物（α -6)的 粉體。藉由GPC來測定所得之聚合物的分子量，其結果 爲 Mw = 35,000。 (3) 高分子化合物的再溶解 將上述高分子化合物16.7g、離子交換水200g及3 5% 鹽酸水溶液6g量取至燒瓶，在60 °C下進行加熱攪拌，而 〇製得均一的高分子化合物水溶液。 (4 )聚苯胺聚合 在冷卻上述（3 )中所得之高分子化合物水溶液後， 量秤出苯胺4.6 5g並加入至此。將此混合物進行攪拌及溶 解後’成爲均一的乳化液。另外量取離子交換水3 0 g、過 氧二硫酸銨1 〇g並混合，在0°C下於2小時之間將此混合 物滴入至裝有此乳化液之燒瓶中。滴入結束後，返回室溫 (25°C )並進行30小時的攪拌。 -31 - 201100487 (5 )聚苯胺精製 將反應結束後的聚合溶液進行過濾’使所得的結晶於 水中進行再分散並進行洗淨，並再次進行過濾。取出重複 進行4次前述洗淨所得之含水的固形物，於減壓下、4 0 °C 下進行96小時的乾燥，而製得聚苯胺乾燥物（阼較導電 性高分子組成物）（Θ -7 )。測定比較導電性高分子組成 物的揮發份，其結果爲揮發份2%以下。 (6) 聚苯胺溶解 量秤出前述（5 )中所得之比較導電性高分子組成物 5g、甲苯47g及乙酸乙酯48 g並放入燒瓶內，將此進行攪 拌卻無法溶解，而製得產生一部分沉澱物之比較導電性高 分子組成物的微分散溶液。The solution of the composite conductive polymer composition obtained in the above (6) was applied onto a glass substrate, and dried at 90 ° C to obtain a green uniform coating film (7-1). The surface resistance 値 of this coating film was 60 kQ/D. Comparative Example 1 (1) Comparative polymer compound (2-NaSEMA/BzMA/2-EHMA = 30/10/60) Measured by 2-NaSEMA 50g, BzMA13.8g, 2- EHA 94g, 150 g of ion-exchanged water, and 300 g of isopropyl alcohol were placed in a flask. After heating to reflux -30-201100487 temperature, AIBN 0.7g was added to carry out the polymerization. The reaction was carried out for 18 hours under reflux. (2) Purification of polymer compound After adding about 500 g of hexane to the polymer solution obtained in the above (1), the impurities in the oil layer were removed by liquid separation extraction. 1 kg of methanol was dropped into the water layer after separation for 1 hour to precipitate a solid portion, and the solid portion was filtered. The obtained solid matter was dried under reduced pressure at 1 °C for 24 hours, and then pulverized with hydrazine to obtain a powder of a polymer compound (?-6). The molecular weight of the obtained polymer was measured by GPC, and as a result, Mw = 35,000. (3) Redissolution of polymer compound 16.7 g of the above polymer compound, 200 g of ion-exchanged water, and 6 g of a 35% hydrochloric acid aqueous solution were weighed into a flask, and heated and stirred at 60 ° C to obtain a uniform polymer. An aqueous solution of the compound. (4) Polyaniline polymerization After cooling the aqueous solution of the polymer compound obtained in the above (3), 4.6 g of aniline was weighed and added thereto. After the mixture was stirred and dissolved, it became a uniform emulsion. Further, 30 g of ion-exchanged water and 1 〇g of ammonium peroxodisulfate were weighed and mixed, and the mixture was dropped into a flask containing the emulsion at 0 °C for 2 hours. After the completion of the dropwise addition, the mixture was returned to room temperature (25 ° C) and stirred for 30 hours. -31 - 201100487 (5) Polyaniline purification The polymerization solution after completion of the reaction was filtered. The obtained crystals were redispersed in water, washed, and filtered again. The aqueous solid matter obtained by the above-described washing was washed four times, and dried under reduced pressure at 40 ° C for 96 hours to obtain a dried polyaniline (a conductive polymer composition). -7). The volatile content of the conductive polymer composition was measured and found to be 2% or less of the volatile matter. (6) The amount of polyaniline dissolved: 5 g of the comparative conductive polymer composition obtained in the above (5), 47 g of toluene, and 48 g of ethyl acetate were placed in a flask, and the mixture was stirred but not dissolved. A finely dispersed solution of a comparative conductive polymer composition which produces a part of the precipitate.

(7) 塗膜評估 U 以200網目過濾器將上述（6 )中所得之比較導電性 高分子組成物的微分散溶液進行過濾，將濾液塗佈於玻璃 基板上並進行乾燥，雖然製得作爲微粒子膜的均一膜（ r -7)，但該膜卻是以手指擦拭表面時會產生脫落之膜質 ’無法成爲如實施例1中所製得之均一的自支撐塗膜，其 表面電阻値爲1ΜΩ /□。 實施例2〜5及比較例2〜4 -32- 201100487 藉由實施例1之（1)及（2)所示的方法，以 a Is列第 1表所示之組成調製出高分子化合物α -2至α -5。此外， 藉由比較例1之（1 )及（2 )所示的方法’以第1表所示 之組成調製出比較高分子化合物α -7至α 。包含實施例 1及比較例1中所得者，各高分子化合物的分子量以及對 水之溶解性，係於第1表中顯示。(7) Coating evaluation U The fine dispersion solution of the comparative conductive polymer composition obtained in the above (6) was filtered by a 200 mesh filter, and the filtrate was applied onto a glass substrate and dried, although it was obtained as a uniform film of the microparticle film (r-7), but the film is a film which is peeled off when the surface is wiped with a finger. It cannot be a uniform self-supporting film prepared as in Example 1, and its surface resistance is 1 Μ Ω / □. Examples 2 to 5 and Comparative Examples 2 to 4 - 32 - 201100487 By the methods shown in (1) and (2) of Example 1, the polymer compound α was prepared by the composition shown in Table 1 of the a Is column. -2 to α -5. Further, the comparative polymer compounds α -7 to α were prepared by the method shown in the first table by the method ' (1) and (2) of Comparative Example 1. The molecular weight of each of the polymer compounds and the solubility in water, as shown in the first table, are shown in the first and the comparative examples.

-33- 201100487 1-33- 201100487 1

If) 〇if 5 〇if £ 〇isils 〇(蠢—T5 〇 SI1S 〇siigflff v (囊*崖震K-rf) XSIls 〇 I 1111¾ Z3IV(s) i ils— VHm—tsVSHovsNg sscdMVW3snlN_fs oooricn i*s£οοοκε 0000-寸οοσοοε 卜.0 5 5 5 5 w A寸 【寸巴 9·寸8οει Ζ,寸οει ζ.寸οε】 δ寸 -- 寸·寸ε 【0寸】 Si 000-ε 000-寸 000°寸 000-ε ·0 5 5 0 -9】 8·Ι0Ι-ει ·寸S 【§】 寸6 o2L lr><Ns to[2J 寸·6rn 【OS】 9_S9If) 〇if 5 〇if £ 〇isils 〇 (stupid - T5 〇SI1S 〇siigflff v (sacred sacred K-rf) XSIls 〇I 11113⁄4 Z3IV(s) i ils— VHm—tsVSHovsNg sscdMVW3snlN_fs oooricn i*s£οοοκε 0000-inch οοσοοε 卜.0 5 5 5 5 w A inch [inch bar 9 · inch 8οει Ζ, inch οει ζ. inchοε] δ inch --- inch · inch ε [0 inch] Si 000-ε 000-inch 000 ° inch 000-ε ·0 5 5 0 -9] 8·Ι0Ι-ει · inch S [§] inch 6 o2L lr><Ns to[2J inch·6rn [OS] 9_S9

15-., I 8>9 -- 9·Ιε I 【oil 8-115-., I 8>9 -- 9·Ιε I [oil 8-1

•π I 【01】 tooiJon 【SI 17_οοεοει os 【ς寸】 iLοε】os•π I [01] tooiJon [SI 17_οοεοει os [ς inch] iLοε] os

-- •I 寸 -I】 SZ 【0-OS *卜瞰粼義：NpqIV gleIfI3«K)-CN趦裝M«fr: vhh-cn 餵03酹經载 M«ffi-: VWHU 餾氍^Mwffi-: VWNPQ TEf 趦ig^K]擗：ssKlK 顬^觀KIfiCN趑装 MSEl·: VWH3N-<N 撇 lH-桕^张T黯 21¾¾¾¾¾:鹦gte昍踣 'a 寸丨53 « z,d 1-¾ 6-¾ 'r> L—ό 9丨« (i(i -34- 201100487 實施例6~10及比較例5〜10 使用實施例2至5中所得之局分子化合物〇；-2至α-5 ’藉由實施例1之（3)及（4)所示的方法，以第2表之 組成調製出複合導電性高分子組成物；8 -2〜yS -6 (惟在/3 -4的調製中，高分子化合物的再溶解時，係使用離子交換 水100g及25°C飽和食鹽水l〇〇g來取代離子交換水200g )。此外，使用比較例2至4中所得之比較高分子化合物 Ο α -7至α -9，藉由比較例1之（1)及（2)所示的方法， 以第2表之組成調製出比較導電性高分子組成物卢-8~冷-13。第2表中，包含實施例1及比較例1中所得者，係顯 示出各導電性聚合物的單體組成、所用之高分子化合物的 種類及量、所用之鹽酸量、所用之氧化劑及其量以及反應 條件（反應溫度及反應時間）。 ❹ -35- 201100487 99 50 60 註2) 1 50 i 48 50 〇〇〇*/>〇〇〇 i〇 v〇 »n 反應溫度 ΓΟ 0 1 | 80 註2) 0 -5 0 〇〇〇〇§〇〇 氧化劑種類 及量（g) APS 註 1) 10 FeCl3 16.5 iFe2 (S04) 3 ! 50 APS 1 10 , FeCl3 1 16.5 APS 10 APS 10 APS 10 APS 10 FeCl3 16.5 FeCl3 16.5 APS 10 APS I 10 ! 35%鹽酸量 (g) VO v〇 v〇 v〇 so v〇 so v〇 \〇 v〇 2 乳化劑種類 及量（g) a-1 16.1 1 a'2 1 8.8 1 a-3 22.2 a-4 29.9 a-5 24 a-2 15.5 a-6 16.7 a-7 19.3 a-8 19.9 a-6 33.3 a-6 13.3 a-9 5.15 1 a-9 ! 20.6 b〇 噻吩 Ill'll 1 1 1 1 5 1 1 <π 搂 淞 1 1 1 1 ^ 1 m 1 i 1 ^ 1 1 1 cn 將 4.65 4.65 4.65 4.65 4.65 4.65 4.65 — 4.65 4.65 ! 導電性高分子 化合物 — CN CO 寸 Ό 1 1 1 1 1 1 0¾ 0¾ 0¾ CQ_ CQ^ (¾. β-Ί /3-8 /3-9 /3-10 ；S-11 /5-12 /3-13 。iiMstsIrisH-poln^flT'Y^efproMp-ascswJl^m^aii 。趨氍攆11嘁頰flmiIDKSdV (Iffl -36- 201100487 實施例1 1 ~ 1 5及比較例1 1〜1 6 使用實施例1及6~1 0中所得之複合導電性高分子組 成物/S-l~yS-6，依據實施例1之（6)及（7)所示的方 法，溶解於種種芳香族系溶劑及/或酯系溶劑後進行乾燥 ，而形成r -2〜r -6之複合導電性高分子組成物覆膜。此 外，對於比較例1及5~1 0中所得之比較導電性高分子組 成物，亦同樣地溶解於種種芳香族系溶劑及/或酯系溶劑 Ο 後進行乾燥，以嘗試進行覆膜的形成（T -8〜r -13)。第 3表係分別顯示各導電性高分子組成物對溶劑之溶解狀態 ，以及使用其所製作之乾燥覆膜的狀態及其表面電阻値。 表中，亦一同顯示實施例1及比較例1中所得之覆膜，以 及使用水作爲溶劑時之覆膜（r -17 )。 〇 -37- 201100487 we撕】 表(¾値 60k 40k 150k 210k 60k 80k 1M 1.2M 600k 1M 20M< 20M< 20M< 3M 乾燥塗膜的狀態 /~N ItrjV /"N s i鲣鲣s s ¢3 S ¢3 ¢3 ¢3 ¢3 〇i〇alo|oio|〇S & ^ *m -m «πι in 1 T 1 1 1 1 恶 j]p 现：S1 ^ ^ \s_^ *+λ 'W Μ Μ « S 03^ B2Q 〇 ¢3 ¢3 ¢3 ^ ^ 2 χ|χ|χ|χ|^1^1φ ir ir i 士 _ 隹 _ •+Λ 4-\ ·+Λ ·+\ v-x If Iv If ___^ ___, 對溶劑之溶解狀態 /^N /^N /^N 邀毖毖邀裳毖 键黎键键键铤 〇s〇s〇s〇s〇s〇s 111111 驭驭逝钽迓近 >w/ Sw^ V-X V—^ /—V xSxSxSxSxixixS〇| K- if }f K- K- K- κ-υτ v_> \^/ \^/ 1 s-x 溶劑的種類及量（g) 餾 题 氍餵 K)避 NJ Μ K) 氍夺θα氍2擀…氍^趦豸 擗N3擀 浒浒 B- ffi- W E- 餾 觀餵 题 M 餾 N3 ΚΙ N3iT)梢 m 經S K) 牌K]擀擀 H~ El· E~ 士_ S驟 Prg? » — CN c〇 寸 ^ 。 C-〇〇〇n2^^^^ '^'ι〇'»Τϊ tin ινΊ iir» ii〇 ii〇 11 Sis pr nt 1—< CN m 寸们 ^ 1 1 1 > 1 1 * 1 ' 1 1 1 1 1 -38- 201100487 從該結果中可得知’使用本發明之高分子化合物（ α-l至α -5)將芳香族化合物進行氧化所得之複合導電性 高分子組成物，均可溶解於芳香族系溶劑及酯系溶劑’並 且使此等溶劑揮發後所得之覆膜，其導電性高。 相對於此，使用與本發明之高分子化合物的組成爲不 同之高分子化合物所得之比較導電性高分子組成物’相對 於芳香族系溶劑或酯系溶劑不具溶解性，使用此所調製之 〇 覆膜，幾乎不具有導電性。 實施例16〜實施例22及比較例12~比較例14 將日本國際公開號碼WO/2 009/0 13 94 2的實施例1中 所用之對向電極（開口銅網目電極）及對向電極基板（厚 度80μιη的PET膜），取代爲以使乾燥後的厚度成爲5μιη 之方式，使用刮刀將實施例1 ~4中所調製之複合導電性高 分子組成物溶液或比較例2中所調製之導電性高分子組成 Ο 物溶液塗佈於SUS箔、ITO PEN膜、玻璃基板、ΙΤΟ玻璃 基板或FTO玻璃基板上而成者，而製造出色素增感型太 陽能電池元件。 使用山下電裝公司製的Solar Simulator YSS-80A，對 所得之色素增感型太陽能電池元件進行評估。對1 cm2的 單元面積的元件調查其在AMI .5 ( 1 sun ; 1 00mW/cm2 ) 的照射下之I-V特性，藉此來評估單元的短路電流、開放 電壓、全因子及發電效率。第4表係顯示該結果。 -39- 201100487 [第4表] 對向電極及 對向電極基板 短路 電流 (Jsc/mA) 開放電壓 (Voc/v) 全因子 (FF) 發電 效率 (Eff%) 實施例 16 ITO玻璃基板+實施例1之 複合導電性高分子組成物 8.8 0.80 46 3.2 實施例 17 ITO玻璃基板+實施例2之 複合導電性高分子組成物 8.7 0.81 48 3.4 實施例 18 SUS箔+實施例3之複合導 電性高分子組成物 7.3 0.79 40 2.3 實施例 19 ITO玻璃基板+實施例4之 複合導電性高分子組成物 6.8 0.77 40 2.1 實施例 20 FTO玻璃基板+實施例1之 複合導電性高分子組成物 9.2 0.80 48 3.5 實施例 21 ITOPEN膜+實施例1之複 合導電性高分子組成物 8.9 0.81 49 3.6 實施例 22 玻璃基板+實施例1之複合 導電性高分子組成物 1.2 0.52 59 0.37 比較例 12 ITO玻璃基板+比較例2之 複合導電性高分子組成物 1.5 0.58 6 0.05 比較例 13 ITO玻璃基板 1.3 0.56 7 0.05 比較例 14 FTO玻璃基板 1.3 0.56 7 0.05 從上述結果中可得知，使用本發明之複合導電性高分 子組成物所成之色素增感型太陽能電池元件，係顯示出高 光電轉換效率。 實施例2 3 ~實施例2 4及比較例1 5 ~比較例1 6 將實施例1〜2中所調製之複合導電性高分子組成物溶 -40- 201100487 液或比較例2中所調製之導電性高分子組成物溶液，分別 再次將固形份調整至 2.5%，藉由旋轉塗佈法，在 4000rpm-15sec的條件下，將此塗佈於厚度ΙΟΟΟμπι的玻 璃基板及ΙΟΟμηι的PET膜基板，以熱風乾燥機來去除溶 劑，而製作出形成有防帶電層之防帶電膜。藉由觸針型表 面形狀測定器（Dektak 6M ; ULVAC公司製）進行測定， 其結果爲防帶電層的厚度均約爲25nm。 〇 對於所得之防帶電膜，在下列條件下靜置後，進行表 面電阻値的評估。第5表係顯示該評估結果。 條件（1 ) : 23°C、50%RH 下靜置 192hr 條件（2) : 40°C、80%RH 下靜置 168hr [第5表] 玻璃基板 PET膜基板 條件⑴ 條件⑵ 條件⑴ 條件（2) 防帶電膜 上：膜的狀態 上：膜的狀態 上：膜的狀態 上：膜的狀態 下：表面電阻 下：表面電阻 下：表面電阻 下：表面電阻 (Ω/口） (Ω/口） (Ω/Π) (Ω/口） 實施例 實施例1之複合導 〇 〇 〇 〇 23 電性高分子組成物 1.0x10® 2.2x10s 4.3x10s 4.2x10s 實施例 實施例2之複合導 〇 〇 〇 〇 24 電性高分子組成物 9.1xl07 9.9χ107 5.2x10s 6.3xl09 比較例 比較例5之導電性 X X X X 15 高分子組成物 >1.00xl015 >1.00χ1015 M.OOxlO15 >1.00xl015 比較例 比較例14之將導電 〇 X 〇 X 16 性高分子組成物溶 3_2xl09 由於吸濕而無 6.5xl09 由於吸濕而無 解於水者 法測定 法測定 從上述結果中可得知’本發明之防帶電膜，即使在高 -41 - 201100487 溫多濕的環境中使用，亦充分顯示出防帶電特性。 產業上之可利用性： 本發明之複合導電性高分子組成物，係將以疏水性強 的芳香環或脂環族爲主成分之高分子化合物（A)用作爲 摻雜劑’因此可安定地溶解於甲苯等之芳香族溶劑或乙酸 乙酯等之酯系溶劑中。 此外，在透明狀態下將如此製得之複合導電性高分子 組成物溶解於芳香族溶劑或酯系溶劑中之導電性高分子形 成組成物溶液，可簡單地將導電性覆膜形成於要求導電性 之部分，所以在電子零件等之領域中，能夠極有利地使用 〇 再者，使用本發明之複合導電性高分子組成物的色素 增感型太陽能電氣用電極或防帶電膜，係具有較佳性能。 -42--- • I inch - I] SZ [0-OS * 卜观粼: NpqIV gleIfI3«K)-CN armored M«fr: vhh-cn Feed 03酹 by M«ffi-: VWHU Distillation ^Mwffi -: VWNPQ TEf 趦ig^K]擗:ssKlK 顬^View KIfiCN趑MSEl·: VWH3N-<N 撇lH-桕^张T黯213⁄43⁄43⁄43⁄43⁄4: Parrot gte昍踣'a inch丨53 « z,d 1 -3⁄4 6-3⁄4 'r> L-ό 9丨« (i(i -34-201100487 Examples 6 to 10 and Comparative Examples 5 to 10 using the molecular compound obtained in Examples 2 to 5; -2 to Α-5 ', by the method shown in (3) and (4) of Example 1, the composite conductive polymer composition was prepared in the composition of the second table; 8 -2 to yS -6 (only at /3) In the preparation of -4, when re-dissolving the polymer compound, 100 g of ion-exchanged water and 100 g of saturated brine of 25 ° C were used instead of ion-exchanged water (200 g). Further, the results obtained in Comparative Examples 2 to 4 were used. The comparative polymer compound Ο α -7 to α -9 was prepared by the method shown in (1) and (2) of Comparative Example 1, and the comparative conductive polymer composition was prepared in the composition of the second table. Cold-13. In the second table, the results obtained in Example 1 and Comparative Example 1 show that each conductive polymerization The monomer composition, the type and amount of the polymer compound used, the amount of hydrochloric acid used, the amount of the oxidizing agent used, and the reaction conditions (reaction temperature and reaction time). ❹ -35- 201100487 99 50 60 Note 2) 1 50 i 48 50 〇〇〇*/>〇〇〇i〇v〇»n Reaction temperatureΓΟ 0 1 | 80 Note 2) 0 -5 0 〇〇〇〇§〇〇 Type and amount of oxidizing agent (g) APS Note 1 10 FeCl3 16.5 iFe2 (S04) 3 ! 50 APS 1 10 , FeCl3 1 16.5 APS 10 APS 10 APS 10 APS 10 FeCl3 16.5 FeCl3 16.5 APS 10 APS I 10 ! 35% hydrochloric acid (g) VO v〇v〇v〇 So v〇so v〇\〇v〇2 Emulsifier type and amount (g) a-1 16.1 1 a'2 1 8.8 1 a-3 22.2 a-4 29.9 a-5 24 a-2 15.5 a-6 16.7 A-7 19.3 a-8 19.9 a-6 33.3 a-6 13.3 a-9 5.15 1 a-9 ! 20.6 b〇thiophene Ill'll 1 1 1 1 5 1 1 <π 搂淞1 1 1 1 ^ 1 m 1 i 1 ^ 1 1 1 cn will be 4.65 4.65 4.65 4.65 4.65 4.65 4.65 — 4.65 4.65 ! Conductive polymer compound - CN CO inch Ό 1 1 1 1 1 1 03⁄4 03⁄4 03⁄4 CQ_ CQ^ (3⁄4. β-Ί / 3-8 /3-9 /3-10; S-11 /5-12 /3-13. iiMstsIrisH-poln^flT'Y^efproMp-ascswJl^m^aii.氍撵11嘁 cheek flmiIDKSdV (Iffl -36- 201100487 Example 1 1 to 15 and Comparative Example 1 1 to 1 6 The composite conductive polymer composition obtained in Example 1 and 6 to 10 /Sl~ yS-6 is dissolved in various aromatic solvents and/or ester solvents according to the methods shown in (6) and (7) of Example 1, and dried to form a composite conductive material of r -2 to r -6 . The conductive polymer composition obtained in Comparative Examples 1 and 5 to 10 is similarly dissolved in various aromatic solvents and/or ester solvents, and then dried. In order to attempt to form a film (T -8 to r -13), the third table shows the state of dissolution of each conductive polymer composition with respect to a solvent, and the state of the dried film produced using the same Surface resistance 値 In the table, the film obtained in Example 1 and Comparative Example 1 and the film (r -17 ) when water is used as a solvent are also shown together. 〇-37- 201100487 we tear] Table (3⁄4値60k 40k 150k 210k 60k 80k 1M 1.2M 600k 1M 20M<20M<20M<3M Dry Coating Film Status /~N ItrjV /"N Si鲣鲣ss ¢3 S ¢3 ¢3 ¢3 ¢3 〇i〇alo|oio|〇S & ^ *m -m «πι in 1 T 1 1 1 1 恶j]p Now: S1 ^ ^ \ S_^ *+λ 'W Μ Μ « S 03^ B2Q 〇¢3 ¢3 ¢3 ^ ^ 2 χ|χ|χ|χ|^1^1φ ir ir i 士_隹_ •+Λ 4-\ +Λ ·+\ vx If Iv If ___^ ___, the dissolution state of the solvent /^N /^N /^N Invite to invite the 毖 毖 key Li key 铤〇s〇s〇s〇s〇s〇s 111111驭驭 钽迓 &>w/ Sw^ VX V—^ /—V xSxSxSxSxixixS〇| K- if }f K- K- K- κ-υτ v_> \^/ \^/ 1 sx Solvent type and Quantity (g) Distillation problem 氍 Feed K) Avoid NJ Μ K) Capture θα氍2擀...氍^趦豸擗N3擀浒浒B- ffi- W E- Distillation feed M distillation N3 ΚΙ N3iT) By SK) K] 擀擀 H~ El· E~ _ _ S Prg? » — CN c〇 inch ^. C-〇〇〇n2^^^^ '^'ι〇'»Τϊ tin ινΊ iir» ii〇ii〇11 Sis pr nt 1—< CN m inch^^ 1 1 1 > 1 1 * 1 ' 1 1 1 1 1 -38- 201100487 From the results, it is known that the composite conductive polymer composition obtained by oxidizing an aromatic compound using the polymer compound (α-l to α -5) of the present invention can be used. The film obtained by dissolving in an aromatic solvent and an ester solvent and volatilizing these solvents has high conductivity. On the other hand, the comparative conductive polymer composition 'which is obtained by using a polymer compound having a composition different from that of the polymer compound of the present invention has no solubility with respect to an aromatic solvent or an ester solvent, and is prepared by using the same. The film is almost non-conductive. Example 16 to Example 22 and Comparative Example 12 to Comparative Example 14 The counter electrode (open copper mesh electrode) and the counter electrode substrate used in Example 1 of Japanese International Publication No. WO/2 009/0 13 94 2 (The PET film having a thickness of 80 μm) was replaced with a solution of the composite conductive polymer composition prepared in Examples 1 to 4 or the conductive layer prepared in Comparative Example 2 by using a doctor blade so as to have a thickness of 5 μm after drying. The polymer composition is applied to a SUS foil, an ITO PEN film, a glass substrate, a bismuth glass substrate or an FTO glass substrate to produce a dye-sensitized solar cell element. The obtained dye-sensitized solar cell element was evaluated using Solar Simulator YSS-80A manufactured by Yamashita Denso Co., Ltd. The I-V characteristics of the unit area of 1 cm2 were investigated under the illumination of AMI .5 (1 sun; 1 00 mW/cm 2 ), thereby evaluating the short-circuit current, open voltage, full factor, and power generation efficiency of the unit. The fourth table shows the result. -39- 201100487 [Table 4] Short-circuit current (Jsc/mA) of the counter electrode and the counter electrode substrate Open voltage (Voc/v) Full factor (FF) Power generation efficiency (Eff%) Example 16 ITO glass substrate + implementation Composite conductive polymer composition of Example 1 8.8 0.80 46 3.2 Example 17 ITO glass substrate + composite conductive polymer composition of Example 2 8.7 0.81 48 3.4 Example 18 SUS foil + Example 3 has high composite conductivity Molecular Composition 7.3 0.79 40 2.3 Example 19 ITO Glass Substrate + Composite Conductive Polymer Composition of Example 4 6.8 0.77 40 2.1 Example 20 FTO Glass Substrate + Composite Conductive Polymer Composition of Example 1 9.2 0.80 48 3.5 Example 21 ITOPEN film + composite conductive polymer composition of Example 1 8.9 0.81 49 3.6 Example 22 Glass substrate + composite conductive polymer composition of Example 1 1.2 0.52 59 0.37 Comparative Example 12 ITO glass substrate + Composite conductive polymer composition of Comparative Example 2 1.5 0.58 6 0.05 Comparative Example 13 ITO glass substrate 1.3 0.56 7 0.05 Comparative Example 14 FTO glass substrate 1.3 0.56 7 0.05 From the above results, it was found that The dye-sensitized solar cell element formed by using the composite conductive polymer composition of the present invention exhibits high photoelectric conversion efficiency. Example 2 3 - Example 2 4 and Comparative Example 1 5 - Comparative Example 1 6 The composite conductive polymer composition prepared in Examples 1 to 2 was dissolved in -40 to 201100487 or prepared in Comparative Example 2. The conductive polymer composition solution was again adjusted to 2.5% by solid solution, and applied to a glass substrate having a thickness of ΙΟΟΟμπι and a PET film substrate of ΙΟΟμηι by a spin coating method at 4000 rpm to 15 sec. The solvent was removed by a hot air dryer to produce an antistatic film formed with an antistatic layer. The measurement was carried out by a stylus type surface shape measuring device (Dektak 6M; manufactured by ULVAC Co., Ltd.), and as a result, the thickness of the antistatic layer was about 25 nm. 〇 For the obtained antistatic film, the surface resistance 値 was evaluated after standing under the following conditions. The fifth table shows the results of this evaluation. Condition (1) : 192 hr at 23 ° C, 50% RH. Condition (2) : 168 hr at 40 ° C, 80% RH [Table 5] Glass substrate PET film substrate conditions (1) Conditions (2) Conditions (1) Conditions ( 2) Anti-charged film: Film state: Film state: Film state: Film state: Surface resistance: Surface resistance: Surface resistance: Surface resistance (Ω/mouth) (Ω/Π) (Ω/□) Example of the composite guide of Example 1 23 Electrical polymer composition 1.0x10® 2.2x10s 4.3x10s 4.2x10s Example Example 2 composite guide 〇24 Electrical polymer composition 9.1xl07 9.9χ107 5.2x10s 6.3xl09 Comparative Example Conductivity of Comparative Example 5 XXXX 15 Polymer composition >1.00xl015 >1.00χ1015 M.OOxlO15 >1.00xl015 Comparative Example Comparative Example 14 The conductive 〇X 〇X 16 polymer composition is dissolved in 3_2xl09 due to moisture absorption without 6.5xl09. The moisture absorption is not solved by the method of water measurement. From the above results, the antistatic film of the present invention can be known. Even in high-41 - 201100487 warm and humid environment It also fully shows the anti-charge characteristics. Industrial Applicability: The composite conductive polymer composition of the present invention is a polymer compound (A) having a highly hydrophobic aromatic ring or an alicyclic group as a main component, and thus can be stabilized. The solution is dissolved in an aromatic solvent such as toluene or an ester solvent such as ethyl acetate. Further, the conductive polymer having the composite conductive polymer composition thus obtained is dissolved in an aromatic solvent or an ester solvent to form a composition solution, and the conductive film can be easily formed to be electrically conductive. In the field of electronic components and the like, the dye-sensitized solar electric electrode or the antistatic film using the composite conductive polymer composition of the present invention can be used extremely advantageously. Good performance. -42-

Claims (1)

201100487 七、申請專利範圍： ι—種複合導電性高分子組成物，其係將藉由使下列 成分（a-l )〜（a_3 )進行聚合所製得之高分子化合物（A )’摻雜於以選自下列式（I ) ~ ( III )的化合物作爲單體 構成成分之7Γ共軛系高分子（点）而成； (a-Ι)具有磺酸基與聚合性乙烯基之單體：20~50 mol% ； 〇 (a_2)具有芳香族基或脂環族基與聚合性乙烯基之 單體：20〜50 mol%; (a-3 )(甲基）丙烯酸烷酯：30〜60 mol% ;201100487 VII. Patent application scope: ι-type composite conductive polymer composition, which is obtained by polymerizing the polymer compound (A) obtained by polymerizing the following components (al) to (a-3) a compound selected from the following formulas (I) to (III) as a monomeric constituent 7Γ conjugated polymer (dot); (a-Ι) a monomer having a sulfonic acid group and a polymerizable vinyl group: 20 ~50 mol% ; 〇(a_2) monomer having an aromatic group or an alicyclic group and a polymerizable vinyl group: 20 to 50 mol%; (a-3) alkyl (meth) acrylate: 30 to 60 mol % ; (I) ⑽ (UD (各式中’ Ri至R7表示氫原子或碳數1至12的烷基）。 2 ·如申請專利範圍第1項之複合導電性高分子組成物 ，其中成分（a-Ι)之具有磺酸基與聚合性乙烯基之單體 ，係選自由苯乙烯磺酸鈉、苯乙烯磺酸、（甲基）丙烯酸 2-磺乙酯鈉鹽及（甲基）丙烯酸2-磺乙酯所成群者。 3.如申請專利範圍第1或2項之複合導電性高分子組 成物，其中成分（a-2)之具有芳香族基或脂環族基與聚 -43- 201100487 合性乙烯基之單體，係選自由（甲基）丙烯酸苯甲酯、（ 甲基）丙烯酸苯氧基乙酯、鄰苯二甲酸2-(甲基）丙烯醯 氧基乙酯、六氫鄰苯二甲酸2-(甲基）丙烯醯氧基乙酯、 (甲基）丙烯酸苯甲酸新戊二醇酯、（甲基）丙烯酸2-羥 基-3-苯氧基丙酯、（甲基）丙烯酸羥乙基化鄰酚酯、（甲 基）丙烯酸鄰苯基酚縮水甘油醚酯、（甲基）丙烯酸環己 酯、（甲基）丙烯酸異莰酯、（甲基）丙烯酸二環戊酯、 (甲基）丙烯酸三級丁基環己酯、（甲基）丙烯酸二環戊 烯酯、（甲基）丙烯酸二環戊烯氧基乙酯、（甲基）丙烯 酸四氫呋喃酯、乙烯基吡啶及（甲基）丙烯醯基嗎啉所成 群者。 4. 如申請專利範圍第1至3項中任一項之複合導電性 高分子組成物，其中成分（a-3)之（甲基）丙烯酸烷酯 ，係選自由（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、 (甲基）丙烯酸正丙酯、（甲基）丙烯酸異丙酯、（甲基 )丙烯酸正丁酯、（甲基）丙烯酸異丁酯、（甲基）丙嫌 酸異丙酯、（甲基）丙烯酸三級丁酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸異辛酯、（甲基）丙烯酸十二 烷酯及（甲基）丙烯酸十八烷酯所成群者。 5. —種複合導電性高分子組成物的製造方法，其特徵 爲· 係將藉由使下列成分（a-1 ) ~ ( a-3 )進行聚合所製得 之高分子化合物（A )、與選自下列式（I )〜（ΙΠ )的化 合物共存於電解性基質溶劑中，並使用氧化劑進行化學氧 -44- 201100487 化聚合； (a-l)具有磺酸基與聚合性乙烯基之單體：20~50 mol%; (a-2)具有芳香族基或脂環族基與聚合性乙烯基之 單體：20〜50 mol% ; (a - 3 )(甲基）丙稀酸院醋：30~60mol%;(I) (10) (UD (wherein, Ri to R7 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms). 2) The composite conductive polymer composition of the first aspect of the patent application, wherein the component (a) - Ι) a monomer having a sulfonic acid group and a polymerizable vinyl group selected from the group consisting of sodium styrene sulfonate, styrene sulfonic acid, sodium 2-sulfonate (meth) acrylate, and (meth) acrylate 2 A composite conductive polymer composition according to claim 1 or 2, wherein the component (a-2) has an aromatic group or an alicyclic group and poly-43 - 201100487 A monomer of a conjugated vinyl group selected from the group consisting of benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-(methyl) propylene methoxyethyl phthalate, 2-(methyl)propenyloxyethyl hexahydrophthalate, neopentyl glycol benzoate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ( Methyl) hydroxyethylated o-phenolate, o-phenylphenol glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Isodecyl ester, dicyclopentanyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate a mixture of an ester, a tetrahydrofuran (meth) acrylate, a vinyl pyridine, and a (meth) acryloyl morpholine. 4. A composite conductive polymer composition according to any one of claims 1 to 3. And an alkyl (meth)acrylate of the component (a-3) selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (methyl) Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isopropyl (meth)propionate, butyl (meth)acrylate, (meth)acrylic acid 2 a group of -ethylhexyl ester, isooctyl (meth)acrylate, dodecyl (meth)acrylate, and octadecyl (meth)acrylate. 5. Composite conductive polymer composition The manufacturing method is characterized in that it is produced by polymerizing the following components (a-1) to (a-3) The polymer compound (A) is coexisted with a compound selected from the following formulas (I) to (ΙΠ) in an electrolytic matrix solvent, and is subjected to chemical oxygen-44-201100487 polymerization using an oxidizing agent; (al) having a sulfonic acid group Monomer with a polymerizable vinyl group: 20 to 50 mol%; (a-2) a monomer having an aromatic group or an alicyclic group and a polymerizable vinyl group: 20 to 50 mol%; (a - 3 ) ( Methyl) acrylic acid vinegar: 30~60mol%; R7 (各式中，1至、表示氫原子或碳數1至12的烷基）。 6.如申請專利範圍第5項之複合導電性高分子組成物 Ο 的製造方法，其中成分（a-Ι)之具有磺酸基與聚合性乙 烯基之單體，係選自由苯乙烯磺酸鈉、苯乙烯磺酸、（甲 基）丙烯酸2_磺乙酯鈉鹽及（甲基）丙烯酸2-磺乙酯所成 群者。 7 .如申請專利範圍第5或6項之複合導電性高分子組 成物的製造方法，其中成分（a-2)之具有芳香族基或脂 環族基與聚合性乙烯基之單體，（甲基）丙烯酸單體，係 選自由（甲基）丙烯酸苯甲酯、（甲基）丙烯酸苯氧基乙 酯、鄰苯二甲酸2-(甲基）丙烯醯氧基乙酯、六氫鄰苯二 -45- 201100487 甲酸2-(甲基）丙烯醯氧基乙酯、（甲基）丙烯酸苯甲酸 新戊二醇酯、（甲基）丙烯酸2-羥基-3-苯氧基丙酯、（ 甲基）丙烯酸羥乙基化鄰酚酯、（甲基）丙烯酸鄰苯基酚 縮水甘油醚酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸 異莰酯、（甲基）丙烯酸二環戊酯、（甲基）丙烯酸三級 丁基環己酯、（甲基）丙嫌酸二環戊燦酯、（甲基）丙嫌 酸二環戊烯氧基乙酯、（甲基）丙烯酸四氫呋喃酯、乙烯 基吡啶及（甲基）丙烯醯基嗎啉所成群者。 8.如申請專利範圍第5至7項中任一項之複合導電性 高分子組成物的製造方法，其中成分（a-3)之（甲基） 丙烯酸烷酯，係選自由（甲基）丙烯酸甲酯、（甲基）丙 烯酸乙酯、（甲基）丙烯酸正丙酯、（甲基）丙烯酸異丙 酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯、（ 甲基）丙烯酸異丙酯、（甲基）丙烯酸三級丁酯' (甲基 )丙烯酸2 -乙基己酯、（甲基）丙烯酸異辛酯、（甲基） 两烯酸十二烷酯及（甲基）丙烯酸十八烷酯所成群者。 9 ·如申請專利範圍第5至8項中任一項之複合導電性 高分子組成物的製造方法，其中相對於選自式（I )〜（111 )的化合物1莫耳而言，係以該磺酸基莫耳比成爲 〇·2〜I·5之方式使高分子化合物（a)共存。 10.如申請專利範圍第5至9項中任一項之複合導電 性高分子組成物的製造方法，其中氧化劑係選自由過氧二 硫酸銨、過氧二硫酸鉀、過氧二硫酸鈉、氯化鐵（III)、 硫酸鐵（III)、四氟硼酸鐵（ΠΙ)、六氟磷酸鐵（ΙΠ) -46- 201100487 、硫酸銅（II)、氯化銅（II)、四氟硼酸銅（II)、六 氟磷酸銅（II)及氧二硫酸銨所成群的氧化劑。 11. 如申請專利範圍第5至10項中任一項之複合導電 性高分子組成物的製造方法，其中電解性基質溶劑爲離子 交換水。 12. 如申請專利範圍第5至π項中任一項之複合導電 性高分子組成物的製造方法，其中相對於1 mol之選自式 Ο ( I) ~ ( III)的化合物而言，係加入0.5〜3.0 mol之選自 鹽酸、硫酸、過氯酸、過碘酸、氯化鐵（II)及硫酸鐵（ π)的酸性成分來進行化學氧化聚合。 1 3 · —種複合導電性高分子組成物溶液，其係在選自 甲苯、苯及二甲苯的芳香族系溶劑及/或選自乙酸乙酯、 乙酸丙酯、乙酸丁酯的酯系溶劑中，於溶解狀態下含有 0.1〜10質量％之申請專利範圍第1至4項中任一項之複合 導電性高分子組成物而成。 β 1 4 · —種複合導電性高分子組成物溶液，其中相對於 申請專利範圍第1 3項之複合導電性高分子組成物溶液的 溶劑1 0 0重量份而言，係混合0.0 1〜4 5重量份之具有羥基 之芳香族化合物而成。 1 5 .如申請專利範圍第1 4項之複合導電性高分子組成 物溶液，其中具有羥基之芳香族化合物，係選自由苯甲醇 、酚、間甲酚、鄰甲酚、2-萘烷醇、1-萘烷醇、癒創木酚 及2，6-二甲基酚所成群的化合物。 1 6 .如申請專利範圍第1 3至1 5項中任一項之複合導 -47- 201100487 電性高分子組成物溶液，其係更含有金屬、氧化金屬、導 電性聚合物組成物、碳粉末或分散體。 17.—種色素增感型太陽能電池用對極，其係使用申 請專利範圍第1至4項中任一項之複合導電性高分子組成 物而成。 1 8 . —種防帶電膜，其係使用申請專利範圍第1至4 項中任一項之複合導電性高分子組成物而成。 -48- 201100487 四、指定代表囷·· (一） 本案指定代表圖為：無 (二） 本代表圊之元件符號簡單說明：無R7 (in the formula, 1 to represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms). 6. The method for producing a composite conductive polymer composition according to claim 5, wherein the monomer having a sulfonic acid group and a polymerizable vinyl group of the component (a-fluorene) is selected from the group consisting of styrene sulfonic acid. A group of sodium, styrenesulfonic acid, sodium 2-sulfonate (meth)acrylate and 2-sulfoethyl (meth)acrylate. 7. The method for producing a composite conductive polymer composition according to claim 5 or 6, wherein the component (a-2) has an aromatic group or a monomer having an alicyclic group and a polymerizable vinyl group, ( a methyl)acrylic monomer selected from the group consisting of benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-(methyl)propenyloxyethyl phthalate, hexahydroortho Benzene-45- 201100487 2-(methyl)propenyloxyethyl formate, neopentyl glycol benzoate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, (Methyl) hydroxyethylated o-phenolate, o-phenylphenol glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid Dicyclopentyl ester, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)propanoic acid, dicyclopentenyloxyethyl (meth)propanoic acid, (methyl) A group of tetrahydrofurfuryl acrylate, vinyl pyridine, and (meth) acryloyl morpholine. The method for producing a composite conductive polymer composition according to any one of claims 5 to 7, wherein the alkyl (meth)acrylate of the component (a-3) is selected from (meth) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (A Isopropyl acrylate, tertiary butyl (meth)acrylate '2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, dodecyl (meth) oleate Groups of octadecyl (meth)acrylate. The method for producing a composite conductive polymer composition according to any one of claims 5 to 8, wherein the compound 1 is selected from the formula (I) to (111) The polymer compound (a) coexists in such a manner that the sulfonic acid molar ratio becomes 〇·2 to I·5. The method for producing a composite conductive polymer composition according to any one of claims 5 to 9, wherein the oxidizing agent is selected from the group consisting of ammonium peroxodisulfate, potassium peroxydisulfate, and sodium peroxodisulfate. Ferric chloride (III), iron (III) sulfate, iron tetrafluoroborate (strontium), iron hexafluorophosphate (ΙΠ) -46- 201100487, copper (II) sulfate, copper (II) chloride, copper tetrafluoroborate (II) An oxidizing agent in which copper (II) hexafluorophosphate and ammonium oxydisulfate are grouped. The method for producing a composite conductive polymer composition according to any one of claims 5 to 10, wherein the electrolytic matrix solvent is ion-exchanged water. 12. The method for producing a composite conductive polymer composition according to any one of claims 5 to 3, wherein, relative to 1 mol of the compound selected from the group consisting of the formulae (I) to (III), Chemical oxidation polymerization is carried out by adding 0.5 to 3.0 mol of an acidic component selected from the group consisting of hydrochloric acid, sulfuric acid, perchloric acid, periodic acid, iron (II) chloride, and iron sulfate (π). 1 3 - a composite conductive polymer composition solution selected from an aromatic solvent selected from the group consisting of toluene, benzene, and xylene, and/or an ester solvent selected from the group consisting of ethyl acetate, propyl acetate, and butyl acetate In the dissolved state, the composite conductive polymer composition of any one of the first to fourth aspects of the patent application is contained in an amount of 0.1 to 10% by mass. β 1 4 · a composite conductive polymer composition solution in which 0.01 1 to 4 parts are mixed with respect to 100 parts by weight of the solvent of the solution of the composite conductive polymer composition of claim 13 5 parts by weight of an aromatic compound having a hydroxyl group. 1 5 . The composite conductive polymer composition solution according to claim 14 , wherein the aromatic compound having a hydroxyl group is selected from the group consisting of benzyl alcohol, phenol, m-cresol, o-cresol, 2-naphthyl alcohol a compound in the group of 1-naphthyl alcohol, guaiacol and 2,6-dimethylphenol. 16. A composite conductive-47-201100487 electrical polymer composition solution according to any one of claims 1 to 5, which further comprises a metal, an oxidized metal, a conductive polymer composition, carbon Powder or dispersion. 17. A counter electrode for a dye-sensitized solar cell, which is obtained by using the composite conductive polymer composition according to any one of claims 1 to 4. An antistatic film obtained by using the composite conductive polymer composition according to any one of claims 1 to 4. -48- 201100487 IV. Designated representative 囷·· (1) The representative representative of the case is: None (2) The symbolic symbol of the representative 简单 is simple: None -3- 201100487 五 本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無-3- 201100487 V If the case has a chemical formula, please reveal the chemical formula that best shows the characteristics of the invention: none -4--4-
TW099105071A 2009-02-17 2010-02-22 Composite conductive polymer composition, method for producing the same, solution containing the composition, and use of the composition TWI595038B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2009033646 2009-02-17

Publications (2)

Publication Number Publication Date
TW201100487A true TW201100487A (en) 2011-01-01
TWI595038B TWI595038B (en) 2017-08-11

Family

ID=42633931

Family Applications (1)

Application Number Title Priority Date Filing Date
TW099105071A TWI595038B (en) 2009-02-17 2010-02-22 Composite conductive polymer composition, method for producing the same, solution containing the composition, and use of the composition

Country Status (3)

Country Link
JP (1) JP5869880B2 (en)
TW (1) TWI595038B (en)
WO (1) WO2010095651A1 (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010095652A1 (en) * 2009-02-17 2010-08-26 綜研化学株式会社 Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition
WO2010095649A1 (en) 2009-02-17 2010-08-26 綜研化学株式会社 Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition
KR101295763B1 (en) * 2009-02-17 2013-08-12 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition
US9460860B2 (en) 2011-09-06 2016-10-04 Tayca Corporation Dispersion of electrically conductive polymer, and electrically conductive polymer and use thereof
JP5919095B2 (en) * 2012-05-31 2016-05-18 信越ポリマー株式会社 Conductive polymer paint and conductive coating film
KR101927240B1 (en) * 2016-09-09 2018-12-10 롯데케미칼 주식회사 Preparation method of highly dispersed conductive polymer nanocomposite by solution blending
CN118280737A (en) 2018-08-10 2024-07-02 京瓷Avx元器件公司 Solid electrolytic capacitor comprising polyaniline
JP7442502B2 (en) 2018-08-10 2024-03-04 キョーセラ・エイブイエックス・コンポーネンツ・コーポレーション Solid electrolytic capacitors containing intrinsically conductive polymers
WO2020033820A1 (en) 2018-08-10 2020-02-13 Avx Corporation Solid electrolytic capacitor formed from conductive polymer particles
WO2020123577A1 (en) 2018-12-11 2020-06-18 Avx Corporation Solid electrolytic capacitor containing an intrinsically conductive polymer
CN114521278A (en) 2019-09-18 2022-05-20 京瓷Avx元器件公司 Solid electrolytic capacitor for use at high voltage
KR102709339B1 (en) 2019-12-10 2024-09-25 교세라 에이브이엑스 컴포넌츠 코포레이션 Solid electrolytic capacitors comprising pre-coated and inherently conductive polymers
WO2021119088A1 (en) 2019-12-10 2021-06-17 Avx Corporation Tantalum capacitor with increased stability
US11631548B2 (en) 2020-06-08 2023-04-18 KYOCERA AVX Components Corporation Solid electrolytic capacitor containing a moisture barrier
CN115286730B (en) * 2022-08-16 2023-05-26 乳源东阳光氟树脂有限公司 Vinylidene fluoride copolymer and preparation method and application thereof

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6469621A (en) * 1987-09-10 1989-03-15 Fuji Photo Film Co Ltd Preparation of conductive polymer emulsion
JP3078100B2 (en) * 1992-03-18 2000-08-21 日本カーリット株式会社 Water-dispersible polyaniline composition and method for producing the same
US7112368B2 (en) * 2001-11-06 2006-09-26 E. I. Du Pont De Nemours And Company Poly(dioxythiophene)/poly(acrylamidoalkyslufonic acid) complexes
JP2004307722A (en) * 2003-04-09 2004-11-04 Nippon Shokubai Co Ltd Emulsion-type electrically conductive polymer composition and manufacturing method thereof
WO2005052058A1 (en) * 2003-11-28 2005-06-09 Idemitsu Kosan Co., Ltd. Conductive polyaniline composition, process for producing the same, and molded object thereof
JP4647292B2 (en) * 2004-11-25 2011-03-09 帝人デュポンフィルム株式会社 Counter electrode of dye-sensitized solar cell and dye-sensitized solar cell using the same
US7582403B2 (en) * 2006-07-17 2009-09-01 E. I. Du Pont De Nemours And Company Metal compositions, thermal imaging donors and patterned multilayer compositions derived therefrom
KR100810682B1 (en) * 2006-11-08 2008-03-07 제일모직주식회사 Conductive polymer, conductive polymer copolymer composition, conductive polymer copolymer composition film, and organic photoelectric device using the same
JP2008169255A (en) * 2007-01-09 2008-07-24 Noriyuki Kuramoto Highly conductive polyaniline having excellent solubility and method for producing the same
WO2010095649A1 (en) * 2009-02-17 2010-08-26 綜研化学株式会社 Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition
WO2010095650A1 (en) * 2009-02-17 2010-08-26 綜研化学株式会社 Complex conductive polymer composition, manufacturing method thereof, solution containing said composition, and applications for said composition
KR101295763B1 (en) * 2009-02-17 2013-08-12 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition
WO2010095652A1 (en) * 2009-02-17 2010-08-26 綜研化学株式会社 Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition

Also Published As

Publication number Publication date
JPWO2010095651A1 (en) 2012-08-30
JP5869880B2 (en) 2016-02-24
TWI595038B (en) 2017-08-11
WO2010095651A1 (en) 2010-08-26

Similar Documents

Publication Publication Date Title
TW201100487A (en) Composite conductive polymer composition, method for producing same, solution containing the composition, and use of the composition
TWI448520B (en) A composite conductive polymer composition, a method for producing the same, a solution containing the composition, and use of the composition
TWI595036B (en) Composite conductive polymer composition, method for producing the same, solution containing the composition, and use of the composition
TWI448500B (en) A composite conductive polymer composition, a method for producing the same, a solution containing the composition, and use of the composition
JP5869881B2 (en) Composite conductive polymer solution and method for producing the same
Ouyang et al. Imaging the phase separation between PEDOT and polyelectrolytes during processing of highly conductive PEDOT: PSS films
CN103328541B (en) Polyaniline composite, method for producing same, and composition
TWI711657B (en) Manufacturing method of polyaniline composite composition and polyaniline composite composition
JP6266241B2 (en) Conductive polymer composition and method for producing the same
TW201229191A (en) Conductive adhesive composition, electronic device and manufacturing method for electronic device
JP6417452B2 (en) Conductive polymer and method for producing the same
JP5731974B2 (en) Conductive composition