TW201041964A - 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

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Publication number
TW201041964A
TW201041964A TW099105072A TW99105072A TW201041964A TW 201041964 A TW201041964 A TW 201041964A TW 099105072 A TW099105072 A TW 099105072A TW 99105072 A TW99105072 A TW 99105072A TW 201041964 A TW201041964 A TW 201041964A
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Taiwan
Prior art keywords
meth
acrylate
group
conductive polymer
polymer composition
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TW099105072A
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Chinese (zh)
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TWI593733B (en
Inventor
Fumiaki Kobayashi
Shuji Okamoto
Hikaru Meguro
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Soken Chemical & Engineering Co Ltd
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Publication of TW201041964A publication Critical patent/TW201041964A/en
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Publication of TWI593733B publication Critical patent/TWI593733B/en

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    • 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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • 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

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Compositions Of Macromolecular Compounds (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)
  • Photovoltaic Devices (AREA)
  • Hybrid Cells (AREA)

Abstract

Disclosed is a composite conductive polymer composition which is obtained by doping a p-conjugated polymer (ss) that contains, as a monomer constituting component, a compound which is selected from among (I) an aniline compound that has a hydrogen atom or an alkyl group as a substituent, (II) a thiophene compound that has a hydrogen atom or an alkyl group as a substituent, and (III) a pyrrole compound that has a hydrogen atom or an alkyl group as a substituent, with a polymer compound (A) that is composed of (a-1) a monomer having a sulfonic acid group and a polymerizable vinyl group, (a-2) a polar monomer having a hydrophilic group and a polymerizable vinyl group, and (a-3) a monomer having an aromatic group or an alicyclic group and a polymerizable vinyl group.

Description

201041964 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物、其製造方法 、含有該組成物之溶液、及該組成物之用途，更詳細爲係 關於欲使對於將苯胺、噻吩、吡咯等芳香族系、雜環系化 合物作爲單體構成成分之π共軛系高分子賦予溶劑可溶性 時，於摻合高分子化合物·之複合導電性高分子組成物、其 製造方法、含有該組成物之溶液、及該組成物的色素增感 型太陽電氣用電極或防帶電薄膜等之利用。 【先前技術】 π共軛系高分子中賦予高導電性時，必須藉由摻雜物 之摻合。然而，原先π共軛即發達的高分子，成爲高分子 鏈之平面性高，藉由π鍵的親和力之高分子鏈間的結晶性 (重疊性）高之結構。而且藉由摻雜物，經摻合的π共軛 系高分子的平面性及藉由π共軛之親和力會進一步提高， 使得重疊性更爲顯著。因此，兼具π共軛系高分子的溶解 (經熱或經溶劑）與電傳導度成爲困難的課題。 其中，於π共軛系高分子之側鏈導入烷基或烷氧基等 的高分子已被提案（專利文獻1)，實際上欲提高至所謂 充分導電體的1 〇 _5之S · m以下的電傳導度時必須進行摻 合。而進行該摻合之結果爲，藉由導電性高分子之平面性 發達與π共軛親和性之發達，會有無法得到充分溶劑可溶 性之問題。 -4 - 201041964 若考慮到導電性高分子之利用時，由處理容易度來看 ，藉由溶劑之溶解、或藉由熱之熔融成爲可能，且可望得 到成型成膜後具有充分電傳導度的自立膜或自立形成體， 過去使用這些導電性聚合物時，在欲賦予直接導電性的基 體上藉由電解聚合或蒸氣暴露、氧化劑與導電性聚合物前 驅物單體溶液浸漬後加熱等進行薄膜聚合，其後進行摻合 等處理。 〇 然而此時，在電解聚合時基體必須爲半導體或導電體 ，又亦欲求得對電解液之耐腐蝕性，可使用的基體受到限 制。又，在藉由直接蒸氣之薄膜聚合中，成爲聚合場所的 薄膜上必須使氧化劑成均質地存在，在成膜控制的層面上 來看並非充分，又在這些手法所使用的聚合物冷凝器用途 中，欲擴大表面積時形成微細凹凸，對充分均質之表面的 導電性聚合物之形成係爲困難。 因此，嘗試將導電性聚合物溶解於有機溶劑，該手段 〇 已被提案出幾項。專利文獻2中揭示將3,4 -二取代噻吩使 用無機高鐵鹽類及氧化劑使其聚合的聚（3,4 -二取代噻吩 )之製造方法，又專利文獻3中揭示具有主要具有重複噻 吩單位之聚合物T及至少1個其他聚陰離子聚合物p之水 分散性粉末。然而’專利文獻2的方法係爲以得到粉末物 之方法或直接在對象被覆體表面進行氧化聚合的方法，不 可能將以該方法所得之聚合物溶解於溶劑或水等，又專利 文獻3所揭示者亦僅爲水分散性良好的分散體，對於有機 溶劑並非爲分子可溶性者。 -5- 201041964 又，作爲更直接之溶劑奈米分散化的方法，雖有各種 方法經檢討，專利文獻4中揭示將以本質上不可溶解於溶 劑的聚苯胺，使其粉碎微粉化至奈米尺寸水準，對於聚苯 胺及溶劑的親和性高的SDS (十二烷基苯磺酸）或PTS( 對甲苯磺酸）等磺酸陰離子乳化劑作爲分散劑使用下，共 同分散於溶劑中，在奈米水準下的微分散體溶液之提供， 實質上並非可溶解於溶劑，故塗敷膜的表面成爲凸凹狀， 又不能成爲僅爲聚苯胺的自立膜（亦稱爲均質膜。表示單 獨下不會產生針孔等的膜化者），若未與膠黏劑等組合下 進行塗佈時，不可能使其膜化。 且又專利文獻5中揭示對於疏水性較大的陰離子性界 面活性劑之存在下，將苯胺、或苯胺衍生物在含有有機酸 或無機酸之溶劑中進行氧化聚合，並進行析出、分離、純 化後’以不與水混合的有機溶劑進行萃取，形成有機溶液 〇 該專利文獻所使用之乳化劑爲低分子磺酸系，於聚合 前將苯胺進行鹽酸氯化，其後藉由磺酸系乳化劑進行苯胺 鹽取代，但實際上難以進行充分的鹽交換，又藉由本專利 文獻之合成法所得的聚苯胺於實際上不能溶解於溶劑中， 有著僅得到微分散狀態之溶劑分散液的問題。且，因增大 所使用的界面活性劑的疏水性，故所得之聚苯胺未顯示對 於氫鍵性強的醇或酮類之極性溶劑之溶解或安定的微分散 ’對於這些極性溶劑類會促進聚苯胺之結晶性。 又，且專利文獻6中揭示將（A)具有磺酸官能基與 -6 - 201041964 自由基聚合性官能基之單體及（B)由苯胺或其衍生物所 成之單體溶解於水或有機溶劑的溶液進行乳化，於（B ) 的單體中導入來自（A)的單體之磺酸結構後，將聚合啓 始劑於下述共存下聚合（A)及（B)之單體，製作出締合 (B)之聚合物與（A)之聚合物狀態的導電性聚合物之方 法。 然而’該專利文獻之方法中’作爲水系氧化劑兼自由 〇 基啓始劑使用過硫酸銨鹽時，實際上難成爲如本說明書所 記載的理想乙烯基系聚合物與聚苯胺之相互網目狀結構。 因此，該專利文獻方法中，實際上存在相當數目的未含 PANI的乙烯基聚合物’相反地未放入乙烯基聚合物的摻 合單體存在於PANI中、或有著成爲非常不均勻且不安定 之物質的問題。 又’專利文獻7中揭示，溶解於實質上不與水混合的 有機溶劑之含有具有（a )經質子化的取代或未取代聚苯 Ο 胺複合體、及（b )具有酚性羥基之化合物的導電性聚苯 胺組成物。 然而’該專利文獻中揭示對於溶劑/水/單體/乳化劑之 聚合時’因使用水溶性氧化劑進行聚苯胺的合成，故本質 上水溶苯胺單體一邊進行聚合，一邊介著乳化劑分散於甲 苯的系統中成爲聚苯胺，實質上於除甲苯以外對於水有著 幾分溶解的溶劑之展開係爲不可能，特別爲使用醇或酮類 的溶劑時’於導電性聚合物既行聚合時，氧化劑之氧化還 原電位顯著變化，不僅無法得到充分聚苯胺之聚合度，亦 201041964 不會引起對聚苯胺之摻雜物的***，故所得之聚苯胺未顯 示充分電氣特性，又作爲收率亦會顯著降低。此由本發明 者們的追加試驗中得到確認。又’在本專利文獻之發明中 ，實際上以所使用之二異辛基磺基琥珀酸鈉（AOT ) ’因 無法充分抑制聚苯胺之重疊，故必須倂用酚類（甲酚）等 。此雖未充分地記載於說明書中’但爲非專利文獻1所記 載之技術，其中揭示藉由聚苯胺被膜中之供給強度的調整 ，可使酚性化合物之親和性顯著’對於聚苯胺被膜中之導 電性的提高爲有用。換言之藉由混合如酚類一般對於甲苯 之溶解性良好且對聚苯胺之相溶性良好的不揮發性添加劑 ，不僅可提高乾燥塗膜之導電性，酚類亦可抑制甲苯可溶 中之聚苹胺彼此疊模（Stack )’沒有這些添加劑之情況時 ，如Α Ο T之立體障害性的聚苯胺之結晶性控制下，得到 充分可溶性之安定化爲不可能，且對於醇或酮系溶劑中， 聚苯胺與酚性化合物與其藉由局部化，其爲微凝集化後最 終完全由溶劑分離沈澱。這些亦由本發明者們經追加試驗 得到確認。 作爲最合理方法，專利文獻5中揭示將具有分子量 2,000〜5〇0,000範圍之分子量，在聚苯乙烯磺酸的聚陰離 子之存在下使其氧化化學聚合的聚噻吩、與分子量2,〇〇〇 〜5〇〇,〇〇〇之來自聚苯乙烯磺酸的聚陰離子含於水或水與 水混合性有機溶劑之混合溶劑中所成的聚噻吩之溶液。 該專利文獻係爲提出在聚苯乙烯磺酸（p s S )與氧化 劑共存下之氧化聚合’可於水或醇溶劑中溶解或分散的聚 -8 - 201041964 (伸乙基二氧化物取代噻吩）（ 所得之PEDOT/PSS雖分散於水 抑制部分P E D Ο T間之重疊，對 並非充分。又，所使用的聚苯乙 具有離子解離能之水或對於極性 控制聚噻吩之結晶性，僅爲聚苯 難，且對於實質上未含水分的酮 0 及相溶性的骨架時極難使其溶解 另一方面，作爲使用導電性 著色素增感型太陽電池用對極或 中揭示於設有透明導電層之塑質 所成的色素增感型太陽電池之對 然而，該專利文獻中，塗佈 液，除去溶劑後形成導電性高分 爲微粒子之分散膜，故對於透明 〇 須預先進行電漿處理等而提高透 ，該專利文獻之實施例中，雖記 磺酸，此時存在著摻合於導電性 溶劑成爲水溶液，塗敷於薄膜基 表面之選擇性非常大，將容易產 之不均勻性的針孔、由藉由殘存 高，在電解質溶液中使得對於一 液體等之耐久性變差而容易產生 可舉出透明導電膜因電解液中之 PEDOT )之製造法，於此 中’並非完全溶解，難以 於溶解導電性聚合物而言 烯磺酸之結構中，雖對於 溶劑可能顯示相溶性，欲 乙烯磺酸的結構時極爲困 類’若未附帶具有溶解性 〇 聚合物組成物之用途，有 防帶電薄膜。專利文獻9 薄膜設置導電性高分子層 極。 含有導電性高分子之分散 子層’但因導電性高分子 導電層之密著性較差，必 明導電層之表面能量。又 載於分散劑使用聚苯乙烯 高分子之自由磺酸，欲使 板上時，溶劑與薄膜基板 生來自導電性高分子塗膜 磺酸基使得塗膜之極性提 般所使用的乙腈或離子性 塗膜之剝落等作爲原因， 碘而被腐蝕的問題，因作 -9 - 201041964 爲對極的長期安定性上有著問題，對於取代鈾對極來說並 非充分。 又，專利文獻1 〇中揭示將含有聚噻吩系化合物、酸 性聚合物及糖醇之防帶電材料塗佈於熱可塑性樹脂薄膜的 防帶電薄膜。 然而，該專利文獻中作爲防帶電材料將糖醇作爲必須 成分時，雖所得之防帶電薄膜的透明性或防帶電性爲良好 ，但作爲對於聚噻吩系化合物之摻合劑因僅使用聚苯乙烯 磺酸等酸性聚合物，藉由防帶電膜之經時性吸濕，有著密 著性及防帶電性降低之問題。 [先前技術文獻] [專利文獻] [專利文獻1]特表2002-5 3 928 7 [專利文獻2]特開平0 1 -3 1 3 52 1 [專利文獻3]特表2004-5 1 4753 [專利文獻4]特表2007-5 1 8 8 59 [專利文獻5]專利第2636968 [專利文獻6]特開2007-3 1 4606 [專利文獻 7] W02005/052058 [專利文獻8]特開2009-344823 [專利文獻9]特開2006-155907 [專利文獻1 〇 ]特開2 0 0 8 _ 1 7 9 8 0 9 [非專利文獻] [非專利文獻 1] Y. Cao et al· / Synthetic Metals 69 -10- 201041964 (1995) 187-190 【發明內容】 於此本發明係以提供對溶劑之溶解性優良、自立膜即 在單獨不會產生針孔等之均質膜、或成爲成形體之導電性 高分子組成物及其製造方法等爲課題。 本發明者們欲解決上述課題，追加試驗檢討前述先行 〇 技術之結果’ 〇具有在兀共軛系高分子之聚合時使用充 分電解資質溶劑，必須對進行氧化之陰離子情況賦予安定 且均勻系統、<2>欲控制聚合成長中之π共軛系高分子的 重疊且賦予安定單體供給時之情況成爲必要、<3>在這些 聚合成長情況的對π共軛系聚合物之摻合爲積極地進行、 <4 >在這些摻合過程中，可能由水等初期聚合情況的電解 資質溶劑析出、<5 >聚合後的π共軛系高分子會藉由某種 立體分子障害而使主鏈骨架之重疊受到抑制、<6>這些立 〇 體障害性因子爲該物質本身並不具有結晶性，且可在溶劑 或熱寺之熔融等要素由導電性聚合物合成之初期至純化、 對溶劑之再溶解係爲必要之事實成爲明確。 其中’本發明者們進一步檢討結果，發現將共聚合特 疋單體的闻分子化合物’於π共軛系高分子的聚合時作爲 添加劑使用時’除可發揮作爲乳化劑之使聚合場均勻狀態 化的功能以外，亦可發揮作爲摻合材之功能的同時，因具 有對π共軛系高分子之適度立體障害性，故可得到對特定 溶劑之可溶性優良的複合導電性高分子組成物。又，本發 -11 - 201041964 明者們發現前述複合導電性高分子組成物可利用於色素增 感型太陽電氣用對極或防帶電薄膜等而完成本發明。 即，本發明爲將以下成分（a-l)至（a-3) (a-1)具有磺酸基與聚合性乙烯基之單體 20 〜60mol% (a-2 )具有親水性基與聚合性乙烯基之極性單體 20 〜60mol% (a-3)具有芳香族基或脂環族基與聚合性乙烯基之 卓體 20〜35mol% 進行聚合所得之高分子化合物摻合於以選自次式（Ϊ )〜（III) 【化3】201041964 VI. Description of the Invention: [Technical Field] The present invention relates to a composite conductive polymer composition, a method for producing the same, a solution containing the composition, and the use of the composition, and more specifically When a π-conjugated polymer having an aromatic or heterocyclic compound such as aniline, thiophene or pyrrole as a monomer component is added to a solvent, the composite conductive polymer composition of the polymer compound is blended. A production method, a solution containing the composition, and a dye-sensitized solar electric electrode or an antistatic film of the composition. [Prior Art] When high conductivity is imparted to a π-conjugated polymer, it is necessary to blend with a dopant. However, the polymer which is originally π-conjugated and developed is a structure in which the planarity of the polymer chain is high, and the crystallinity (overlapping) between the polymer chains by the affinity of the π bond is high. Moreover, the planarity of the blended π-conjugated polymer and the affinity by π-conjugate are further improved by the dopant, so that the overlap is more remarkable. Therefore, it is difficult to dissolve the π-conjugated polymer (heat or solvent) and electrical conductivity. Among them, a polymer in which an alkyl group or an alkoxy group is introduced into a side chain of a π-conjugated polymer has been proposed (Patent Document 1), and it is actually intended to increase the S·m of 1 〇_5 of a so-called sufficient conductor. The following electrical conductivity must be blended. As a result of the blending, the planarity of the conductive polymer is developed and the π-conjugated affinity is developed, so that sufficient solvent solubility cannot be obtained. -4 - 201041964 When considering the use of a conductive polymer, it is possible to dissolve by a solvent or melt by heat in view of ease of handling, and it is expected to have sufficient electrical conductivity after film formation. In the past, when these conductive polymers were used, they were subjected to electrolytic polymerization or vapor exposure, immersion of an oxidizing agent and a conductive polymer precursor monomer solution, heating, etc. on a substrate to which direct conductivity is to be imparted. The film is polymerized, followed by a treatment such as blending. 〇 However, at this time, the substrate must be a semiconductor or an electric conductor during electrolytic polymerization, and the corrosion resistance to the electrolyte is also desired, and the usable substrate is limited. Further, in the film polymerization by direct vapor, the oxidizing agent must be homogeneously present on the film to be a polymerization site, and it is not sufficient in terms of film formation control, and in the polymer condenser application used in these methods, When fine surface irregularities are formed when the surface area is to be enlarged, it is difficult to form a conductive polymer on a sufficiently homogeneous surface. Therefore, attempts have been made to dissolve the conductive polymer in an organic solvent, and the means 〇 have been proposed several items. Patent Document 2 discloses a method for producing a poly(3,4-disubstituted thiophene) in which a 3,4-disubstituted thiophene is polymerized using an inorganic high-iron salt and an oxidizing agent, and Patent Document 3 discloses a main repeating thiophene unit. A water-dispersible powder of the polymer T and at least one other polyanionic polymer p. However, the method of Patent Document 2 is a method of obtaining a powder or a method of performing oxidative polymerization directly on the surface of a target coating, and it is impossible to dissolve the polymer obtained by the method in a solvent or water, and the like. The revealer is also only a dispersion with good water dispersibility, and is not molecularly soluble for organic solvents. -5- 201041964 Further, as a method for more direct solvent nano-dispersion, although various methods have been reviewed, Patent Document 4 discloses that polyaniline which is insoluble in a solvent in nature is pulverized and micronized to nanometer. A sulfonic acid anion emulsifier such as SDS (dodecylbenzenesulfonic acid) or PTS (p-toluenesulfonic acid) having a high affinity for polyaniline or a solvent is used as a dispersing agent, and is dispersed in a solvent together. The provision of the microdispersion solution at the nano level is not substantially soluble in the solvent, so the surface of the coated film becomes convex and concave, and cannot be a self-standing film of polyaniline alone (also referred to as a homogeneous film. When the film is not formed by a combination of an adhesive or the like, it is impossible to form a film. Furthermore, in Patent Document 5, in the presence of an anionic surfactant having a large hydrophobicity, aniline or an aniline derivative is oxidatively polymerized in a solvent containing an organic acid or an inorganic acid, and precipitated, separated, and purified. After the 'extraction with an organic solvent which is not mixed with water to form an organic solution, the emulsifier used in the patent document is a low molecular sulfonic acid system, and the aniline is subjected to hydrochloric acid chlorination before polymerization, and then emulsified by a sulfonic acid system. Although the aniline salt is substituted, it is difficult to carry out sufficient salt exchange, and the polyaniline obtained by the synthesis method of this patent document is practically insoluble in a solvent, and has a problem that only a solvent dispersion liquid in a slightly dispersed state is obtained. Moreover, since the hydrophobicity of the surfactant used is increased, the obtained polyaniline does not exhibit dissolution or stable microdispersion of a polar solvent of a hydrogen or a ketone having strong hydrogen bonding, which promotes these polar solvents. Crystallinity of polyaniline. Further, Patent Document 6 discloses that (A) a monomer having a sulfonic acid functional group and a -6 - 201041964 radical polymerizable functional group and (B) a monomer formed from aniline or a derivative thereof is dissolved in water or The solution of the organic solvent is emulsified, and after introducing the sulfonic acid structure of the monomer of (A) into the monomer of (B), the polymerization initiator is polymerized in the following coexistence of the monomers (A) and (B). A method of producing a conductive polymer in association with the polymer of (B) and the polymer state of (A). However, in the method of the patent document, when an ammonium persulfate salt is used as a water-based oxidizing agent and a free sulfhydryl starter, it is practically difficult to form a mutual network structure of an ideal vinyl polymer and polyaniline as described in the present specification. . Therefore, in the method of the patent document, there is actually a considerable amount of vinyl polymer not containing PANI. The opposite monomer which is not put into the vinyl polymer is present in the PANI, or has become very uneven and does not The problem of stable matter. Further, Patent Document 7 discloses that an organic solvent dissolved in a substance which is substantially not mixed with water has (a) a protonated substituted or unsubstituted polyphenyleneamine complex, and (b) a compound having a phenolic hydroxyl group. Conductive polyaniline composition. However, 'the patent document discloses that when a solvent/water/monomer/emulsifier is polymerized, the synthesis of polyaniline is carried out by using a water-soluble oxidizing agent, so that the water-soluble aniline monomer is polymerized while being dispersed in the emulsifier. In the system of toluene, polyaniline is formed, and it is substantially impossible to develop a solvent which dissolves a little bit of water other than toluene, especially when a solvent of an alcohol or a ketone is used. The oxidation-reduction potential of the oxidant changes remarkably, and not only the polymerization degree of the polyaniline is not obtained well, but also the insertion of the polyaniline dopant is not caused in 201041964, so the obtained polyaniline does not exhibit sufficient electrical properties, and the yield is also obtained as a yield. Significantly lower. This was confirmed by an additional test by the present inventors. Further, in the invention of the patent document, in practice, the sodium diisooctylsulfosuccinate (AOT) used is not sufficiently inhibited from overlapping with polyaniline, so that phenol (cresol) or the like must be used. Though it is not fully described in the specification, the technique described in Non-Patent Document 1 discloses that the affinity of the phenolic compound can be significantly improved by adjusting the supply strength in the polyaniline film. The improvement in conductivity is useful. In other words, by mixing a non-volatile additive such as a phenol which has good solubility in toluene and good compatibility with polyaniline, the conductivity of the dried coating film can be improved, and the phenol can also inhibit the polycondensation in toluene. When the amines are stacked on one another (in the absence of these additives, it is impossible to obtain sufficient solubility stability under the control of the crystallinity of the sterically hindered polyaniline of Α T, and in the alcohol or ketone solvent The polyaniline and the phenolic compound are localized by localization, which is microaggregation and finally completely separated by solvent separation. These were also confirmed by the inventors by additional tests. As a most rational method, Patent Document 5 discloses a polythiophene having a molecular weight of 2,000 to 5 Å to 0,000 in a molecular weight, which is oxidatively chemically polymerized in the presence of a polyanion of polystyrenesulfonic acid, and a molecular weight of 2, 〇〇〇 ～5〇〇, a solution of polythiophene formed from a polyanion of polystyrenesulfonic acid contained in water or a mixed solvent of water and a mixed organic solvent of water. This patent document proposes an oxidative polymerization in the presence of polystyrenesulfonic acid (ps S ) and an oxidizing agent, which can be dissolved or dispersed in water or an alcohol solvent. Poly-8 - 201041964 (Extended Ethylene Dioxide Substituted Thiophene) (The obtained PEDOT/PSS is not sufficient even if it is dispersed in the water-inhibiting portion PED Ο T. Moreover, the polyphenylene used has water having ionic dissociation energy or crystallinity for polarity-controlled polythiophene, only poly It is difficult to dissolve benzene, and it is extremely difficult to dissolve ketone 0 and a compatible skeleton which are substantially free of water. On the other hand, it is disclosed as a counter electrode for using a conductive dye-sensitized solar cell or a transparent conductive material. However, in the patent document, the coating liquid removes the solvent to form a dispersion film having high conductivity and is divided into fine particles, so that the transparent whisker is previously subjected to plasma treatment. In the examples of the patent documents, although the sulfonic acid is present, the conductive solvent is added to the aqueous solution, and the selectivity to the surface of the film base is very large, which is easy to produce. The pinhole of the non-uniformity is produced by a method in which the durability of the liquid or the like is deteriorated in the electrolyte solution, and the transparent conductive film (PEDOT in the electrolytic solution) is easily produced. In the structure of the olefinic sulfonic acid, which is not completely soluble and difficult to dissolve the conductive polymer, although it may exhibit compatibility with the solvent, the structure of the ethylene sulfonic acid is extremely difficult to be trapped. The use of the composition has an antistatic film. Patent Document 9 A film is provided with a conductive polymer layer. The dispersion layer containing the conductive polymer' is inferior in adhesion to the conductive polymer conductive layer, and the surface energy of the conductive layer is required. Further, the free sulfonic acid of the polystyrene polymer is used in the dispersing agent. When the plate is to be used, the solvent and the film substrate are made of a conductive polymer film sulfonic acid group, so that the polarity of the coating film is improved. The problem of peeling off of the coating film, etc., is caused by iodine, and the problem of long-term stability of the pole is -9 - 201041964, and it is not sufficient for the replacement of uranium. Further, Patent Document 1 discloses an antistatic film in which an antistatic material containing a polythiophene compound, an acid polymer, and a sugar alcohol is applied to a thermoplastic resin film. However, when the sugar alcohol is an essential component as an antistatic material in this patent document, although the transparency and antistatic property of the antistatic film obtained are good, as a blending agent for a polythiophene compound, only polystyrene is used. An acidic polymer such as a sulfonic acid has a problem in that the adhesion and the antistatic property are lowered by the time-dependent moisture absorption of the antistatic film. [Prior Art Document] [Patent Document 1] [Patent Document 1] Special Table 2002-5 3 928 7 [Patent Document 2] Japanese Patent Laid-Open No. 0 1 - 3 1 3 52 1 [Patent Document 3] Special Table 2004-5 1 4753 [ Patent Document 4] Special Table 2007-5 1 8 8 59 [Patent Document 5] Patent No. 2636968 [Patent Document 6] JP 2007-3 1 4606 [Patent Document 7] W02005/052058 [Patent Document 8] Special Opening 2009- [Patent Document 9] JP-A-2006-155907 [Patent Document 1 〇] Special Opening 2 0 0 8 _ 1 7 9 8 0 9 [Non-Patent Document] [Non-Patent Document 1] Y. Cao et al· / Synthetic Metals 69 -10- 201041964 (1995) 187-190 SUMMARY OF THE INVENTION The present invention provides a homogeneous film having excellent solubility in a solvent, a self-standing film, that is, a pinhole or the like, or a conductive body. A polymer composition, a method for producing the same, and the like are problems. The inventors of the present invention have tried to solve the above-mentioned problems, and have added a test to review the results of the above-mentioned prior art technique. 〇In the polymerization of a ruthenium-conjugated polymer, a sufficiently electrolytic solvent is used, and it is necessary to provide a stable and uniform system for the anion to be oxidized. <2> In order to control the superposition of the π-conjugated polymer during polymerization growth and to supply a stable monomer, <3> blending of the π-conjugated polymer in the case of these polymerization growths In order to carry out actively, <4 > in these blending processes, it may be precipitated by an electrolytic qualification solvent in the initial polymerization state such as water, and the <5 > polymerized π-conjugated polymer may be formed by a certain stereo The molecular barrier causes the overlap of the main chain skeleton to be suppressed, and <6> These scorpion damaging factors are that the substance itself does not have crystallinity, and can be synthesized by a conductive polymer in a solvent or a melting of a hot temple. The fact that it is necessary to purify and re-dissolve the solvent from the initial stage is clear. In the above, the present inventors further examined the results and found that when the polymer compound of the copolymerization of the special monomer is used as an additive in the polymerization of the π-conjugated polymer, the polymerization field can be used as an emulsifier. In addition to the function of the blending material, it also exhibits a moderate steric hindrance to the π-conjugated polymer, and thus a composite conductive polymer composition excellent in solubility in a specific solvent can be obtained. Further, the present inventors have found that the composite conductive polymer composition can be used in a dye-sensitized solar electric counter electrode or an antistatic film or the like to complete the present invention. That is, the present invention has a hydrophilic group and a polymerizable property in the following components (al) to (a-3) (a-1) having a sulfonic acid group and a polymerizable vinyl monomer of 20 to 60 mol% (a-2). 20 to 60 mol% of a polar monomer of a vinyl group (a-3) 20 to 35 mol% of an aromatic group or an alicyclic group and a polymerizable vinyl group. The polymer compound obtained by polymerization is selected from the group consisting of Formula (Ϊ)~(III) 【化3】

⑴ (II)(1) (II)

Oil) (各式中’ 1^至7表示氫原子或碳數丨至12的院基） 的化α物作爲單體構成成分之π共輕系高分子（β) 而成之複合導電性高分子組成物。 又’本發明爲耢由將以下成分（a-l)至（a_3) -12- 201041964 (a-1)具有磺酸基與聚合性乙烯基之單體 2 0 〜6 0 m ο 10/〇 (a-2 )具有親水性基與聚合性乙烯基之極性單體 20 〜60mol% (a-3 )具有芳香族基或脂環族基與聚合性乙烯基之 單體 20〜35mol% 進行聚合所得之高分子化合物、與選自前述式（I) 〇 〜（111)之化合物在電解性基質溶劑中使其共存下，使用 氧化劑進行化學氧化聚合爲特徵的複合導電性高分子組成 物之製法。 且本發明爲將前述複合導電性高分子組成物於醇系溶 劑及酮系溶劑中以0.1〜1 0質量％且溶解狀態下含有所成 的複合導電性高分子組成物溶液。 又’本發明爲使用前述複合導電性高分子組成物所成 的色素增感型太陽電池用對極。 〇 且’本發明爲使用前述複合導電性高分子組成物所成 的防帶電薄膜。 [發明之效果] 在本發明的高分子化合物之存在下，藉由氧化劑之作 用進行聚合所得的複合導電性高分子係爲可安定地溶解於 醇系、或酮系之溶劑中者。 因此，將於芳香族溶劑中溶解該複合導電性高分子之 溶液’塗佈於必須賦予導電性之部位上，藉由乾燥此可簡 -13- 201041964 單地得到導電性皮膜。 [實施發明的形態] 本發明中所使用的高分子化合物（A)可依據常法， 將成分（a-Ι)之具有磺酸基與聚合性乙烯基之單體、成 分（a-2 )之具有親水性基與聚合性乙烯基之極性單體及 成分（a-3)之具有芳香族基或脂環族基與聚合性乙烯基 之單體，在聚合啓始劑的存在下使其聚合而製造。 成分（a-Ι)之具有磺酸基與聚合性乙烯基之單體爲 苯乙烯磺酸基、或磺基乙基等具有磺酸基之單體，作爲該 例子’可舉出苯乙烯磺酸或苯乙烯磺酸鈉、苯乙烯磺酸鉀 、苯乙烯磺酸鈣等苯乙烯磺酸鹽、（甲基）丙烯酸乙基2-磺酸、或（甲基）丙烯酸乙基2 -磺酸鈉、（甲基）丙烯酸 乙基2-磺酸鉀 '(甲基）丙烯酸乙基2 _磺酸鈣等（甲基） 丙烯酸乙基2 -磺酸鹽。 又，成分（a-2 )之具有親水性基與聚合性乙烯基之 極性單體對於在室溫的pH7.0之蒸餾水以 0 · 1 m m ο 1 /1 進行 溶解時’該溶液之pH可能顯示超過5.5而未達8.0 ( 5·5<ρΗ<8_0 )者，作爲該具體例，可舉出丙烯酸、甲基丙 嫌酸、2-甲基丙烯氧基乙基琥珀酸、（無水）馬來酸、2-羥基乙基（甲基）丙烯酸酯、2 -羥基丙基（甲基）丙烯酸 酯、4 -羥基丁基（甲基）丙烯酸酯、2_乙醯乙酸乙基（甲 基）丙烯酸酯、甲氧基乙基（甲基）丙烯酸酯、乙氧基乙 基（甲基）丙烯酸酯、丁氧基乙基（甲基）丙烯酸酯、乙 -14- 201041964 基卡必醇（甲基）丙烯酸酯、甲氧基三乙二醇（甲基）丙 烯酸酯、甲氧基聚乙二醇（甲基）丙烯酸酯、β_ (甲基） 丙嫌醒氧基乙基氨號拍酸酯等。 且，作爲成分（a-3)之具有芳香族或脂環族基與聚 合性乙烯基之單體的例子，可舉出苯甲基（甲基）丙烯酸 酯、苯氧基乙基（甲基）丙烯酸酯、（甲基）丙烯酸乙基 2-苯二甲酸甲基酯、（甲基）丙烯酸乙基2-苯二甲酸乙基 〇 酯、環己基（甲基）丙烯酸酯、二環戊基（甲基）丙烯酸 酯、二環戊氧基乙基（甲基）丙烯酸酯、異冰片基（甲基 )丙烯酸酯、t-丁基環己基（甲基）丙烯酸酯、環己基（ 甲基）丙烯酸酯、（甲基）丙烯酸酯嗎啉、苯乙烯、二甲 基苯乙烯、萘（甲基）丙烯酸酯、乙烯基萘、N-乙烯基咔 唑、乙烯基η-乙基咔唑、乙烯基芴等。 於本發明所使用的高分子化合物（A )的製造時，單 體（a-Ι)、單體（a-2)及單體（a-3)之莫耳比爲重要。 〇 即，本發明的高分子化合物藉由適宜平衡以芳香族或脂環 族基的疏水性、與以磺酸基及親水性基的親水性，作用於 導電性高分子組成物，其爲欲使此溶解於溶劑中。 製造本發明之高分子化合物（A)時的成分（a-1)的 配合量爲20〜60mol%，較佳爲25〜50mol%。又，成分（ a-2)之配合量爲20〜60mol%’較佳爲25〜55mol%。且 成分（a-3)之配合量爲 20〜35mol。/。’較佳爲 25〜 3 0 m ο 1 %。 本發明的高分子化合物中，可含有上述單體（a_i) -15- 201041964 ' (a-2)及（a-3)以外之聚合性成分。作爲該聚合性成 分之例子，可舉出甲基（甲基）丙烯酸酯、乙基（甲基） 丙嫌酸酯、η-丙基（甲基）丙燒酸酯、i-丙基（甲基）丙 烯酸酯、η-丁基（甲基）丙烯酸酯、i-丁基（甲基）丙烯 酸酯、i-丙基（甲基）丙烯酸酯、t-丁基（甲基）丙烯酸 酯、2-乙基己基（甲基）丙烯酸酯、異辛基（甲基）丙烯 酸酯、月桂基（甲基）丙烯酸酯、硬脂醯（甲基）丙烯酸 酯、四糠基（甲基）丙烯酸酯、Ν,Ν-二甲基胺基乙基甲基 丙烯酸酯、乙烯基吡啶' (甲基）丙烯醯基嗎啉等，添加 時的配合量爲〇〜20mol%程度。 上述成分（a-1 )、成分（a-2 )、成分（a-3 )及視必 要所添加的聚合性成分之聚合反應可以公知方法進行。例 如可將這些各成分進行混合後，於此添加聚合啓始劑，藉 由加熱、光照射等開始聚合而製造。 欲製造上述高分子化合物（A)可採用之聚合法，僅 由單體混合物成分（a·3 )不會成爲分離狀態的狀態下可 實施的方法即可，並無特別限定，例如採用溶液聚合法、 塊狀（bulk)聚合法、析出聚合法等。 又’使用於聚合反應之聚合啓始劑若爲上述各成分、 或可溶解於反應時所使用之溶劑者即可，並無特別限定。 作爲該聚合啓始劑之例子，可舉出過氧化苯甲醯基（BP0 )等油溶性過氧化物系熱聚合啓始劑、偶氮二異丁腈（ AIBN )等油溶性偶氮系熱聚合啓始劑、偶氮雙氰基吉草 酸（ACVA )等水溶性偶氮系熱聚合啓始劑等。又，溶液 -16- 201041964 聚合之溶劑中的水比率較多時，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啓始劑、過氧化氫水等 。且，亦可使用二茂鐵或胺類等氧化還原劑之組合。 這些聚合啓始劑之使用範圍對於上述化合物1莫耳而 言可任意使用0.001〜0.1莫耳之範圍，亦可利用一括投入 、滴下投入、逐次投入之任一方法。又，使用塊狀聚合或 少量（對於單體爲5 Owt%以下）溶劑的溶液聚合之情況， 〇 亦可藉由硫醇與金屬芳香類之組合的聚合方法（專利文獻 8 ) 〇 進一步作爲使用於上述聚合反應之溶劑，可舉出甲醇 、乙醇、異丙基醇、丁醇等醇系溶劑、丙酮、甲基乙酮、 甲基異丁酮等酮系溶劑、甲基賽路蘇、乙基賽路蘇、丙二 醇甲基醚、丙二醇乙基醚等二醇系溶劑、乳酸甲酯、乳酸 乙酯等乳酸系溶劑等。 且聚合時除聚合啓始劑以外亦可並用連鎖移動劑，若 〇 要調整分子量時可適宜使用。作爲可使用之連鎖移動劑， 若爲上述單體或可溶解於溶劑的物質即可，可使用任何化 合物，例如亦可適宜地使用如十二烷基硫醇或庚基硫醇等 烷硫醇、氫硫基丙酸（BMPA )等具有極性基之水溶性硫 醇、α苯乙烯二聚物（ASD )等油性自由基抑止劑等。 又進一步該聚合反應可在所使用之溶劑（除塊狀聚合 之情況以外）的沸點以下進行爲佳，例如以6 5 °C〜8 0 °C程 度爲佳。但，進行如塊狀聚合或以硫醇與金屬芳香類進行 的如專利文獻9之聚合時，在25 °C〜8 0°C下進行爲佳。 -17- 201041964 該所得之聚合物視必要可經純化 A )。作爲該純化方法的例子，可舉 出於聚合溶劑的導電性高分子聚合物 行數次洗淨後取出水系雜質，其後使 ，取出油性低分子雜質及殘存單體、 又，作爲純化方法之其他例子，可舉 A)之聚合後對於聚合添加乙腈等離 調整聚合媒的離子解離定數、或以添 聚合溶劑中之離子濃度、或鹽酸水等 溶液之添加來調整聚合媒之pH，由 劑析出導電性高分子，於此添加己烷 液萃取時取出油性低分子雜質及殘存 其後藉由離子交換水取出水系雜質、 如此純化爲佳的理由爲，高分子 電性高分子組成物中作爲摻合劑而被 stack )抑止劑，且溶劑可溶劑作用， 存物的除此以外的聚合啓始劑殘物、 勻組成物等殘存時，導電性高分子組 問題，故必須除去此等。然而如此純 專利文獻7的不均勻自由基聚合物， 性高分子組成物的組成與高分子化启 樣地相溶化的可溶狀態者。 如以上所得之高分子化合物（A : 均分子量以 3，000〜150,000爲佳。 成爲高分子化合物（ 出過濾分離單純下析 ，藉由離子交換水進 用己烷等油性弱溶劑 低分子雜質的方法。 出於高分子化合物（ 子解離性水性溶劑而 加飽和食鹽水等增加 質子釋出性的酸性水 聚合終了後之聚合溶 等油性弱溶劑進行分 單體、低分子雜質， 殘存物的方法。 •化合物（A )對於導 導入，因作爲疊模（ 故若作爲聚合後之殘 單體、寡聚物、不均 成物之功能降低成爲 化結果，不會混合如 其爲可表現均勻導電 「物（A )之組成爲一 )的GPC換算重量平 重量平均分子量未達 -18- 201041964 3’ααα時’作爲高分子乳化劑之功能並不充分。相反地成 爲15胃以上時，導電性聚合物合成時對於聚合情況（酸 性#胃液）的溶解性會有不充分的情況產生，又高分子化 合物J Φ身的溶劑溶解性變差、或對於導電性聚合物之可溶 化性有著賦予顯著壞影響之情況。 本發明的複合導電性高分子組成物使用如上述所得之 高分子化合物（a)，以如下述製造。即，將上述高分子 〇 化合物（A )溶解於電解性基質溶劑，其次在溶液中，添 加成爲兀共軛系高分子（β)之原料的前述式（1)至（ΠΙ )所示化合物，進一步地將此藉由氧化劑進行氧化，可得 到於將前述式（I )至（III )所示化合物作爲單體構成成 分的π共轭系局分子（β)慘合則述高分子化合物（a)的 複合導電性高分子化合物。 原料之化合物中’式（I )所示化合物係取代基爲氫 原子或院基之苯胺。作爲該化合物之具體例，可舉出苯胺 〇 、ο -甲苯胺、m -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-n -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-卜萘基胺、2,6_二乙基苯胺等。 又’式（II)所示化合物係取代基爲氫或烷基之噻吩 ，作爲該具體例’可舉出噻吩、3 -甲基噻吩、3_乙基唾吩 、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-n-辛基噻吩等。 -19- 201041964 且，式（III )所示化合物係取代基爲氫或烷基之吡略 ，作爲該具體例，可舉出吡咯、3 -甲基吡咯、3 -庚基吡咯 、3-n-辛基吡咯等。 作爲藉由本發明方法製造複合導電性高分子組成物之 具體方法的一例子，可舉出首先將作爲電解性基質溶劑之 離子交換水，視必要成爲酸性後，於其中添加如前述之所 得之高分子化合物（A )，其次於其中添加原料之式（I ) 至（III )的化合物之1種或2種以上，進一步加入氧化劑 使其氧化聚合的方法。且，藉由高分子化合物（A)對於 離子交換水之溶解性，亦可適宜倂用丙酮、甲基乙酮等酮 系溶劑、甲醇、乙醇、異丙基醇等醇系溶劑、乙腈等親水 性高之有機溶劑。 作爲上述反應中將電解性基質溶劑成爲酸性所使用的 酸性成分，可舉出鹽酸、硫酸、過氯酸、過碘酸、氯化鐵 (II)、硫酸鐵（II)等，其量對於式（I)〜（III)之化 合物lmol而言，以0_5〜3.0mol程度即可。 又，於反應所使用的氧化劑亦必須藉由形成複合導電 性高分子組成物之芳香族化合物（單體）的氧化還原電位 做適宜調整’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（111 )、四氟硼酸鐵 (III )、六氟燐酸鐵（III)、硫酸銅（Π)、氯化銅（II )、四氟硼酸銅（Π) '六氟燐酸銅（II)等。 又，反應中之高分子化合物（A )與化合物（I )至（ 111 )的比率因亦取決於最終所得之複合導電性高分子組成 -20 - 201041964 物的性質’故雖非可單純決定者，例如較佳範圍之例子中 ’高分子化合物（A)中的磺酸基數與所使用的化合物（1 )〜（III )之莫耳比可如以下所示。 即’對於選自式（I )〜（III )之化合物i莫耳，將 高分子化合物（A )以該化合物中之磺酸基的莫耳比成爲 〇·2〜1.5的量下共存即可。 且’氧化劑之使用量一般對於化合物（I )至（III ) 1 〇 莫耳而言可使用1.5〜2·5莫耳（1價換算）程度，但藉由 系統內之氧化度（酸性度），對於單體1莫耳而言即使爲 1莫耳以下亦可充分進行聚合。 且’欲得到複合導電性高分子組成物之聚合反應的溫 度’氧化反應後之發熱量或去除氫的容易度依化合物（I )至（111 )的種類而相異，故較佳溫度範圍亦相異。 —般而言，利用化合物（I )時，以4 0 °c以下爲佳， 利用化合物（II )時，以90°C以下爲佳，利用化合物（III 〇 )時，以20°C以下爲佳。 又，欲使複合導電性高分子組成物進行高分子量化時 ，僅使反應溫度相對地降低，使反應時間相對地延長即可 ，若欲進行低分子量化之情況時，僅與上述相反即可。 如此所得之聚合物，視必要進一步進行洗淨等後，可 爲目的物之複合導電性高分子組成物。此爲如後述不溶解 過去導電性高分子組成物之醇系或酮系的溶劑中可安定地 溶解者。 作爲該所得之本發明的複合導電性尚分子組成物之利 -21 - 201041964 用方法的例子’將此於醇系、或酮系溶劑中以均質狀態下 溶解的複合導電性高分子組成物溶液。該複合導電性高分 子組成物溶液爲’將此塗佈於要求導電性皮膜之形成的部 分，其次藉由乾燥等手段’發揮該組成物中之溶劑，可於 目的部分形成均勻導電性皮膜。 調製上述複合導電性筒分子組成物溶液時，較佳爲將 複合導電性高分子組成物於甲醇、乙醇、異丙基醇、甲基 賽路蘇、丙二醇單甲基醚乙酸醋等醇系溶劑'或丙酮、甲 基乙酮、甲基異丁酮等酮系溶劑以0.1〜10質量％程度進 行溶解者。 又’上述複合導電性高分子組成物溶液中，將溶液安 定性提高及在塗膜狀態之導電性提高作爲目的，可進一步 添加苯甲基醇、酣' m -甲酣、〇 -甲紛、2_萘院醇、丨_萘院 醇、鄰甲氧基苯酚、2,6-二甲基酚等具有羥基之芳香族化 合物。具有這些羥基之化合物對於複合導電性高分子組成 物溶液之溶劑量100重量份而言，添加〇.01〜45重量份 程度爲佳。 又’上述複合導電性高分子組成物溶液中，將作爲防 帶電塗料的自立膜之導電性提高及作爲太陽電池用對極材 之觸媒性能提高作爲目的，可進一步含有將銅、銀、鋁、 鉑等金屬、氧化鈦、氧化銦錫、氟摻合氧化錫、氧化鋁、 二氧化砂等金屬氧化物、導電性聚合物組成物、奈米碳管 (CNT ) '富勒烯、碳黑等碳粉末、或分散體作爲塡充物 成分° ΪΙ些粉末或分散體對於複合導電性高分子組成物溶 -22- 201041964 液之固體成分100重量份而言，添加固體成分0.01〜50 重量份程度爲佳。 且，上述複合導電性高分子組成物可使用色素增感型 太陽電池用對極。該色素增感型太陽電池用對極若被要求 透明性時，於透明基板之片面層合上述複合導電性高分子 組成物、或於透明基板的一面上配置光透過性電極，於該 光透過性電極層合上述複合導電性高分子組成物而可形成 0 。又，若透明性不被要求時，可藉由於金屬箔等進行層合 而形成。該複合導電性高分子組成物之厚度一般爲0.01〜 ΙΟΟμηι，較佳爲0.1〜50μπι之範圍內。 作爲本發明的色素增感之上述所使用的透明基板，光 透過率通常爲50%以上，較佳爲可使用80%以上之薄膜或 板。作爲如此透明板之例子，可舉出玻璃等無機透明基板 、聚對苯二甲酸乙二酯（PET )、聚碳酸酯（PC )、聚伸 苯基硫化物、聚颯、聚酯颯、聚烷基（甲基）丙烯酸酯、 ❹ 聚萘二甲酸乙二酯（PEN)、聚醚颯（PES)、聚環烯烴 等高分子透明基板等。又，作爲金屬箔，可舉出金、鉑、 銀、錫、銅、鋁、不鏽鋼、鎳等金屬箔。 這些透明基板之厚度於無機透明基板之情況時，一般 爲200〜700 Ομηι之範圔內，於高分子透明基板之情況時’ 一般爲20〜4000μιη，較佳爲20〜2000μηι之範圍內。於金 屬箱基板之情況時爲 Ο.ΐμπι〜ΙΟΟΟμιη，較佳爲Ιμηι〜 500μιη之範圍內。該範圍內厚度之高分子透明基板及金屬 箔基板可對所得的色素增感太陽電池賦予可撓性。 -23- 201041964 又，於上述透明基板之一面上視必要亦可配置光透過 性電極。作爲於此所使用的光透過性電極，可舉出膜狀導 電性金屬電極、篩狀導電性金屬電極等。 上述膜狀導電性金屬電極係爲將氧化錫、錫摻合氧化 銦（ITO )、氟摻合氧化錫（FTO )等形成爲膜狀者。該 膜狀導電性金屬電極爲於透明基板表面上，將氧化錫、 ITO、FTO等可藉由蒸鍍或濺鑛等而形成。該膜狀導電性 金屬電極之厚度一般爲0.01〜Ιμηι，較佳爲0.01〜0.5μιη 之範圍內。 另一方面，篩狀導電性金屬電極係將銅、鎳、鋁等導 電性金屬形成爲篩狀者。具體爲篩狀導電性金屬電極使用 銅、鎳、鋁等導電性金屬，例如藉由光微影技術法，可藉 由餓刻至線寬一般爲1 〇〜7 0 μ m，較佳爲1 0〜2 0 μ m，節距 寬一般爲50〜300μιη，較佳爲50〜200μηι之篩而形成。此 時的篩狀導電性金屬電極的導線厚度，成爲與所使用之導 電性金屬的厚度略相同，一般爲8〜150μηι，較佳爲8〜 15μιη之範圍內。該篩狀導電性金屬電極的透明基板表面 上可使用黏著劑等貼著。 製造上述色素增感型太陽電池用對極時，作爲將複合 導電性高分子組成物層合於配置於上述透明基板片面或透 明基板一面上的光透過性電極之方法，例如可舉出於配置 於上述透明基板片面或透明基板一面上的光透過性電極塗 佈上述複合導電性高分子組成物溶液，進行1次至複數次 的將溶液中的溶劑除去之方法。 -24- 201041964 上述複合導電性高分子組成物溶液之塗佈可適用浸漬 塗佈、微棒塗佈、輥塗佈、缺角輪塗佈（comma coate〇 、模具塗佈、凹版塗佈等公知塗佈。 又，溶劑之除去可適用藉由放置之自然乾燥、藉由熱 風·紅外線之加熱條件下的強制乾燥等方法。 上述色素增感型太陽電池用對極爲，使用於此的上述 複合導電性高分子組成物於有機溶劑爲可溶，故與將過去 〇 複合導電性高分子組成物分散於水性媒體的分散液相比， 其塗佈步驟較爲容易，生產性亦較優。又，可抑制來自酸 性水溶液之對極製作段階時的金屬腐鈾劣化。 又，上述色素增感型太陽電池用對極爲，使用於此的 上述複合導電性高分子組成物，藉由使用經上述成分（a-1)、成分（a-2)及成分（a-3)以所定範圍下進行共聚合 所得的高分子化合物（A )，因對上述透明基板或光透過 性電極或金屬箔的密著性優良，故可長期間使用。 〇 且，上述色素增感型太陽電池用對極爲，使用於此的 上述複合導電性高分子組成物，藉由使用抑制將上述成分 (a-ι )、成分（a-2 )及成分（a-3 )以所定範圍進行共聚 合所得的酸性度之高分子化合物（A )，可使光透過性電 極（導電性金屬）難被腐蝕下，因可提高對於電解液的耐 久性，故可長期間使用。 又’上述色素增感型太陽電池用對極爲，對於作爲對 過去電解液具有耐氧化性之電極使用的高價鉑電極，因作 爲均勻耐氧化性膜可發揮複合導電性高分子膜，可提供廉 -25- 201041964 價可使用的各種金屬。 又，使用上述複合導電性高分子組成物所成的防帶電 薄膜爲，上述複合導電性高分子組成物於單獨下進行塗敷 •乾燥，欲成膜爲自立膜可加工低電阻的防帶電薄膜。又 ，視必要混合複合導電性高分子組成物與熱可塑性樹脂及 /或熱硬化性樹脂時，可藉由（1 )將以押出機或擠出機等 進行熔融混煉者使用T塑模等進行成膜之方法、（2 )於 熱可塑性樹脂、熱硬化性樹脂、及玻璃製之薄膜片面或雙 面上塗佈上述複合導電性高分子組成物溶液，除去溶液中 之溶劑形成防帶電層的方法等而得到。 作爲上述防帶電薄膜所使用的熱可塑性樹脂，可舉出 聚烯烴、聚氯化乙烯、聚氯化亞乙烯、聚苯乙烯、聚乙酸 乙烯酯、聚四氟伸乙基、聚丙烯腈丁二烯苯乙烯、聚丙烯 腈苯乙烯、聚甲基丙烯、聚丙烯、飽和聚酯、聚醯胺、聚 碳酸酯、聚變性伸苯基醚、聚伸苯基硫化物、聚颯、聚丙 烯酸酯、液晶聚合物、聚醚醚酮、聚醯胺亞胺等，亦包含 這些熱可塑性樹脂之聚合物合金或熱可塑性彈性體。 作爲本發明的上述防帶電薄膜所使用的熱硬化性樹脂 ’可舉出聚酚、聚環氧、不飽和聚酯、聚尿烷、聚亞胺、 聚尿素、聚矽氧樹脂、三聚氰胺樹脂、氟樹脂、醇酸樹脂 等。 又’上述防帶電薄膜爲’藉由使用將上述成分（a」 )、成分（a-2 )及成分（a_3 )以所定範圍下進行共聚合 所得之筒分子化合物（A )，可形成各種高濕低濕環境條 -26- 201041964 件下之性能偏差較少，且具有較高透過性之防帶電膜。 【實施方式】 [實施例] 以下舉出實施例，對本發明做更詳細說明，但本發明 並未受到這些實施例之任何限制。且，本實施例中之分子 量及表面電阻値藉由下述方法進行測定。 ❸ <分子量> 藉由下述條件下的GPC進行測定。 裝置名：HLC-8120( TOSOH (股）製） 管柱：GF-1G7B + GF-510HQ ( Asahipak :註冊商標、 昭和電工（股）製） 基準物質：聚苯乙烯及聚苯乙烯磺酸鈉 取樣濃度：1 . 〇mg/ml 〇 溶離液：50mmol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> 使用（股）DIA INSTRUMENTS 製之低電阻率計 L 〇 r e s t a G P、P S P型探針，藉由四端子四探針法進行測定。 -27- 201041964 合成例1 高分子化合物之合成（2-NaSEMA/BzMA/HEMA = 40/25/35) 於具備攪拌機、氮氣導入管、迴流冷卻器、投入口及 溫度計之容量1000cm3的四口燒杯中投入2 -鈉磺基乙基甲 基丙烯酸酯68.9g、苯甲基甲基丙烯酸酯35.7g、2-羥基乙 基甲基丙烯酸酯36.9g、離子水150g及異丙基醇300g。 一邊於燒杯內導入氮氣下，將燒杯內的混合物昇溫至 迴流溫度。其次，將偶氮二異丁腈〇.7g投入於燒杯內， 保持迴流狀態下，進行1 8小時聚合反應後得到聚合物溶 液（A-1)。 ‘ 將所得之聚合物溶液（A-1 )的全量移至2〇〇〇cm3的 燒杯，藉由攪拌器一邊攪拌一邊添加己烷5〇〇g ’其後靜置 1小時後除去含有雜質之油層。將水層側的溶液使用乾燥 機，於1 0 〇 °C下進行2 4小時乾燥。將所得之固體物於減壓 下在1 0 0 t：進行2 4小時乾燥後，以乳鉢進行粉碎後得到高 分子化合物之粉體（AP-1 )。 將所得之高分子化合物（AP_ 1 )以凝膠滲透層析法（ GPC)進行測定後得到重量平均分子量（Mw) =58,000。 合成例2〜5及比較合成例6〜9 將單體如表1所示添加，由與合成例1之同樣方法得 到高分子化合物之粉體（AP-2〜9 )。所得之高分子化合 物（AP_2〜9 )之Mw及對於水的溶解性如表1所示。 -28- 201041964 TJ lx 表 璧) 0ss^i 〇 〇o 〇 〇 〇 〇 〇o 〇〇〇 εε 000-ooo ·ε9 000·" 00°Z9 ooo ,s°0°9S000-s 000 s (I)Ϊ屮Φ o o roro ro ro ro 「0 ro 「0 「0iv ai卸) VVW vs〒z isvwcsssezVw3se〒z (豳蜱堪 《 ) UO f—t .in 〇 r— CT> r^—\ r—I "^· r*—i r~* CO r—» .LO . O . L〇 . O . 〇 tOCOCNlLOtOCNj^—CMCOtO C〇 i—I 1^3 i—I i_j c%| i_i ① k—j 对S I CO ·—» co r—i »*— ί—I .r~*» Uf3 . O 〇0 LO ~CVJ LD L〇 CM '—«· r*-Oil) (In each formula, the compound α of 1 to 7 represents a hydrogen atom or a carbon number of 丨 to 12) is a composite component of a π-co-light polymer (β) having a monomer component. Molecular composition. Further, the present invention is a monomer having a sulfonic acid group and a polymerizable vinyl group from the following components (al) to (a_3) -12 to 201041964 (a-1) 2 0 to 6 0 m ο 10/〇 (a) -2) 20 to 60 mol% (a-3) of a polar monomer having a hydrophilic group and a polymerizable vinyl group (a-3) having an aromatic group or an alicyclic group and a monomer of a polymerizable vinyl group of 20 to 35 mol% A method for producing a composite conductive polymer composition characterized by chemical oxidative polymerization using a polymer compound and a compound selected from the group consisting of the above formula (I) 〇 to (111) in an electrolytic matrix solvent. In the present invention, the composite conductive polymer composition is contained in an alcohol-based solvent and a ketone solvent in an amount of 0.1 to 10% by mass in a dissolved state to form a solution of the composite conductive polymer composition. Further, the present invention is a counter electrode for a dye-sensitized solar cell using the composite conductive polymer composition. Further, the present invention is an antistatic film formed using the above composite conductive polymer composition. [Effect of the Invention] The composite conductive polymer obtained by the polymerization of the oxidizing agent in the presence of the polymer compound of the present invention is stably dissolved in an alcohol-based or ketone-based solvent. Therefore, the solution in which the composite conductive polymer is dissolved in an aromatic solvent is applied to a portion where conductivity is required, and the conductive film is obtained by drying it in a simple manner from 13 to 201041964. [Mode for Carrying Out the Invention] The polymer compound (A) used in the present invention may have a monomer (a-2) having a sulfonic acid group and a polymerizable vinyl group as a component (a-Ι) according to a usual method. a polar monomer having a hydrophilic group and a polymerizable vinyl group, and a monomer having an aromatic group or an alicyclic group and a polymerizable vinyl group of the component (a-3), in the presence of a polymerization initiator Manufactured by polymerization. The monomer having a sulfonic acid group and a polymerizable vinyl group as a component (a-Ι) is a monomer having a sulfonic acid group such as a styrenesulfonic acid group or a sulfoethyl group, and as this example, styrene sulfonate may be mentioned. Styrene sulfonate such as acid or sodium styrene sulfonate, potassium styrene sulfonate or calcium styrene sulfonate, ethyl 2-sulfonic acid (meth) acrylate, or ethyl 2- sulfonic acid (meth) acrylate Sodium (ethyl) ethyl 2-sulfonate (ethyl) 2-(sulfonate) ethyl (ethyl) 2-sulfonate (meth) acrylate (ethyl) acrylate 2-ethyl sulfonate. Further, when the polar monomer having the hydrophilic group and the polymerizable vinyl group of the component (a-2) is dissolved at 0. 1 mm ο 1 /1 in distilled water at pH 7.0 at room temperature, the pH of the solution may be When it exceeds 5.5 and does not reach 8.0 (5·5 < ρ Η < 8 _0 ), examples of the specific examples include acrylic acid, methacrylic acid, 2-methylacryloxyethyl succinic acid, and (anhydrous) horse. Acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-ethyl acetoacetate ethyl (methyl) Acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, B-14- 201041964 carbitol (A) Acrylate, methoxytriethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, β_(methyl) propyl smear oxyethylamine Wait. Further, examples of the monomer having an aromatic or alicyclic group and a polymerizable vinyl group as the component (a-3) include benzyl (meth) acrylate and phenoxyethyl (methyl). Acrylate, ethyl 2-methyl phthalate (meth) acrylate, ethyl decyl 2-ethyl phthalate, cyclohexyl (meth) acrylate, dicyclopentyl (Meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclohexyl (methyl) Acrylate, (meth) acrylate morpholine, styrene, dimethyl styrene, naphthalene (meth) acrylate, vinyl naphthalene, N-vinyl carbazole, vinyl η-ethyl carbazole, ethylene Basics and so on. In the production of the polymer compound (A) used in the present invention, the molar ratio of the monomer (a-fluorene), the monomer (a-2) and the monomer (a-3) is important. In other words, the polymer compound of the present invention acts on the conductive polymer composition by appropriately balancing the hydrophobicity of the aromatic or alicyclic group and the hydrophilicity of the sulfonic acid group and the hydrophilic group. This was dissolved in a solvent. The amount of the component (a-1) to be produced in the production of the polymer compound (A) of the present invention is 20 to 60 mol%, preferably 25 to 50 mol%. Further, the compounding amount of the component (a-2) is 20 to 60 mol%', preferably 25 to 55 mol%. Further, the amount of the component (a-3) is 20 to 35 mol. /. ' is preferably 25 to 30 m ο 1 %. The polymer compound of the present invention may contain a polymerizable component other than the above monomers (a_i) -15 to 201041964 ' (a-2) and (a-3). Examples of the polymerizable component include methyl (meth) acrylate, ethyl (methyl) propyl acrylate, η-propyl (methyl) propionate, and i-propyl (A). Acrylate, η-butyl (meth) acrylate, i-butyl (meth) acrylate, i-propyl (meth) acrylate, t-butyl (meth) acrylate, 2 -ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearic acid (meth) acrylate, tetradecyl (meth) acrylate, Ν, Ν-dimethylaminoethyl methacrylate, vinyl pyridine '(meth) propylene hydrazino morpholine, etc., when added, the amount is 〇 20 mol%. The polymerization reaction of the above component (a-1), component (a-2), component (a-3), and the polymerizable component to be added may be carried out by a known method. For example, after mixing these components, a polymerization initiator is added thereto, and polymerization is started by heating, light irradiation, or the like. The polymerization method which can be used for the production of the polymer compound (A) is not particularly limited as long as the monomer mixture component (a·3) is not in a separated state, and is, for example, solution polymerization. Method, bulk polymerization method, precipitation polymerization method, and the like. Further, the polymerization initiator used in the polymerization reaction is not particularly limited as long as it is the above-mentioned respective components or a solvent which can be dissolved in the reaction. Examples of the polymerization initiator include an oil-soluble peroxide-based thermal polymerization initiator such as benzoyl peroxide (BP0) and an oil-soluble azo heat such as azobisisobutyronitrile (AIBN). A water-soluble azo-based thermal polymerization initiator such as a polymerization initiator or azobiscyanojimic acid (ACVA). Further, when the ratio of water in the solvent to be polymerized 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, a combination of a redox agent such as ferrocene or an amine may also be used. The range of use of these polymerization initiators may be arbitrarily used in the range of 0.001 to 0.1 mol per mol of the above-mentioned compound 1, and any of the methods of including input, dripping, and successive input may be employed. Further, in the case of solution polymerization using a bulk polymerization or a small amount (for a monomer of 5% by weight or less), hydrazine may be further used as a polymerization method by a combination of a thiol and a metal aryl (Patent Document 8). The solvent for the polymerization reaction may, for example, be an alcohol solvent such as methanol, ethanol, isopropyl alcohol or butanol, or a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone, or meth. A diol solvent such as ketiselus, propylene glycol methyl ether or propylene glycol ethyl ether; a lactic acid solvent such as methyl lactate or ethyl lactate. Further, in the polymerization, a chain shifting agent may be used in addition to the polymerization initiator, and if it is desired to adjust the molecular weight, it may be suitably used. As the chain-transporting agent which can be used, any of the above monomers or a substance soluble in a solvent may be used, and for example, an alkanethiol such as dodecyl mercaptan or heptyl mercaptan may be suitably used. An oily radical inhibitor such as a water-soluble thiol having a polar group such as mercaptopropionic acid (BMPA) or an α-styrene dimer (ASD). Further, the polymerization reaction is preferably carried out at a temperature below the boiling point of the solvent to be used (except in the case of bulk polymerization), and is preferably, for example, 65 ° C to 80 ° C. However, when polymerization is carried out as in the case of block polymerization or thiol and metal aryl, as in Patent Document 9, it is preferably carried out at 25 ° C to 80 ° C. -17- 201041964 The resulting polymer can be purified, if necessary, A). As an example of the purification method, the conductive polymer obtained by the polymerization solvent is washed several times, and the water-based impurities are taken out, and then the oily low molecular impurities and the residual monomers are taken out, and the purification method is used. In another example, after the polymerization of A), the ionic dissociation number of the acetonitrile isolating polymerization medium added by polymerization or the addition of a solution such as an ion concentration in a polymerization solvent or hydrochloric acid water may be used to adjust the pH of the polymerization medium. The reason why the conductive polymer is precipitated, and the oily low molecular impurities are taken out after the extraction of the hexane liquid, and the water-based impurities are removed by the ion-exchanged water, and the purification is preferably carried out in the polymer electrical polymer composition. When the solvent is allowed to act as a binder and the solvent is solvent-soluble, and the polymerization initiator residue, the homogenous composition, and the like remain, the conductive polymer group has a problem. Therefore, it is necessary to remove the catalyst. However, in the case of the heterogeneous radical polymer of Patent Document 7, the composition of the polymer composition is soluble in the melted state in which the polymerization is dissolved. The polymer compound obtained as above (A: the average molecular weight is preferably 3,000 to 150,000. It is a polymer compound (the filtration separation is simply carried out, and the oil-based weak solvent such as hexane is used as the low molecular impurity by ion exchange water. Method for separating monomer, low molecular impurities, and residual substances by using a polymer compound (a dissociable aqueous solvent, a saturated aqueous solution such as a saturated aqueous solution of salt water, etc.) • The compound (A) is introduced into the lead-in method because it is a stacking mold (so that the function as a residual monomer, an oligomer, or a heterogeneous product after polymerization is reduced, and it is not mixed as if it can exhibit uniform conductivity. The composition of the substance (A) is a GPC-equivalent weight average molecular weight of less than -18-201041964. When 3'ααα is used, the function as a polymer emulsifier is not sufficient. Conversely, when it is 15 or more, conductive polymerization When the substance is synthesized, the solubility in the polymerization (acid #gastric juice) may be insufficient, and the solvent solubility of the polymer compound J Φ body may be deteriorated, or The polymerizable polymer composition of the present invention has a polymer compound (a) obtained as described above, and is produced as follows. The hydrazine compound (A) is dissolved in an electrolytic matrix solvent, and then the compound represented by the above formulas (1) to (ΠΙ) which is a raw material of the fluorene-conjugated polymer (β) is added to the solution, and this is further When the oxidizing agent is oxidized, the π-conjugated system molecule (β) having the compound represented by the above formulas (I) to (III) as a monomer constituent component is mismatched, and the polymer compound (a) has high composite conductivity. In the compound of the raw material, the compound represented by the formula (I) is a hydrogen atom or an aniline of a hospital group. Specific examples of the compound include aniline, ο-toluidine, and m-toluidine. 3,5-Dimethylaniline, 2,3-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 2-ethylaniline, 3-ethylaniline, 2- Isopropylaniline, 3-isopropylaniline, 2-methyl-6-ethylaniline, 2-n-propylaniline, 2-methyl-: 5-isopropylaniline, 2-butylaniline, 3-butylaniline, 5,6,7,8-tetrahydro-p-naphthylamine, 2,6_ Further, the compound represented by the formula (II) is a thiophene in which the substituent is hydrogen or an alkyl group, and examples of the specific example include thiophene, 3-methylthiophene, and 3-ethylpyrylene. -propylthiophene '3-butylthiophene, 3-pentylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-n-octylthiophene, etc. -19- 201041964 Further, a compound of the formula (III) The substituent is a hydrogen or an alkyl group. Examples of the specific examples thereof include pyrrole, 3-methylpyrrole, 3-heptylpyrrole, and 3-n-octylpyrrole. An example of a specific method for producing a composite conductive polymer composition by the method of the present invention is to first add an ion exchange water as an electrolytic matrix solvent, if necessary, to be acidic, and then add the above-mentioned high The molecular compound (A) is secondarily added to the compound of the formula (I) to (III) in which the raw material is added, and a method of further oxidizing and polymerizing the oxidizing agent is further added. Further, the solubility of the polymer compound (A) in ion-exchanged water may be preferably a ketone solvent such as acetone or methyl ethyl ketone, an alcohol solvent such as methanol, ethanol or isopropyl alcohol or a hydrophilic solvent such as acetonitrile. High organic solvent. Examples of the acidic component used to make the electrolytic matrix solvent acidic in the above reaction include hydrochloric acid, sulfuric acid, perchloric acid, periodic acid, iron (II) chloride, iron (II) sulfate, and the like. The compound (I) to (III) may be used in an amount of from 0 to 5 mol. Further, the oxidizing agent used in the reaction must be appropriately adjusted by the oxidation-reduction potential of the aromatic compound (monomer) forming the composite conductive polymer composition, and ammonium peroxodisulfate or potassium peroxodisulfate can be used. Sodium peroxodisulfate, iron (III) chloride, iron (111), iron (III) tetrafluoroborate, iron (III) hexafluoroantimonate, copper (ruthenium) sulfate, copper (II) chloride, tetrafluoroethylene Copper borate (bismuth) 'copper hexafluoroantimonate (II) and the like. Further, the ratio of the polymer compound (A) to the compound (I) to (111) in the reaction depends on the nature of the finally obtained composite conductive polymer composition -20 - 201041964, so it may not be determined simply. For example, in the example of the preferred range, the molar ratio of the sulfonic acid group in the polymer compound (A) to the compound (1) to (III) to be used can be as shown below. That is, for the compound i mol selected from the formulae (I) to (III), the polymer compound (A) can be coexisted in an amount such that the molar ratio of the sulfonic acid group in the compound becomes 〇·2 to 1.5. . And 'the amount of oxidizing agent used is generally 1.5 to 2.5 mM (1 valent conversion) for compounds (I) to (III) 1 〇 Moule, but by the degree of oxidation (acidity) in the system For the monomer 1 mole, the polymerization can be sufficiently carried out even if it is 1 mol or less. Further, 'the temperature at which the polymerization reaction of the composite conductive polymer composition is desired', the heat generation amount after the oxidation reaction or the ease of hydrogen removal differs depending on the types of the compounds (I) to (111), so the preferred temperature range is also Different. In general, when the compound (I) is used, it is preferably 40 ° C or less, and when the compound (II ) is used, it is preferably 90 ° C or less, and when the compound (III 〇 ) is used, it is 20 ° C or less. good. Further, when the composite conductive polymer composition is subjected to high molecular weight, the reaction temperature may be relatively lowered, and the reaction time may be relatively extended. If the molecular weight is to be lowered, the reverse is only possible. . The polymer thus obtained may be a composite conductive polymer composition of the object after further washing as necessary. This is a solvent which can be stably dissolved in an alcohol-based or ketone-based solvent which does not dissolve the conductive polymer composition in the past. The composite conductive polymer composition of the present invention is obtained as a composite conductive polymer composition solution which is dissolved in an alcohol-based or ketone solvent in a homogeneous state. . The composite conductive polymer composition solution is applied to the portion where the conductive film is required to be formed, and then the solvent in the composition is applied by means of drying or the like to form a uniform conductive film in the target portion. When the composite conductive molecular composition solution is prepared, it is preferred to use the composite conductive polymer composition in an alcohol solvent such as methanol, ethanol, isopropyl alcohol, methyl stilbene, or propylene glycol monomethyl ether acetate vinegar. 'A ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone is dissolved in an amount of 0.1 to 10% by mass. Further, in the above-mentioned composite conductive polymer composition solution, for the purpose of improving the stability of the solution and improving the conductivity in the coating state, benzyl alcohol, 酣'm-methyl hydrazine, hydrazine-methyl ketone may be further added. An aromatic compound having a hydroxyl group such as 2_naphthalene alcohol, 丨_naphthalene alcohol, o-methoxyphenol or 2,6-dimethylphenol. The compound having such a hydroxyl group is preferably added in an amount of from 0.01 to 45 parts by weight based on 100 parts by weight of the solvent of the composite conductive polymer composition solution. Further, in the above-mentioned composite conductive polymer composition solution, the conductivity of the self-supporting film as an antistatic paint is improved, and the catalyst performance of the solar cell is improved, and copper, silver, and aluminum may be further contained. , metal such as platinum, titanium oxide, indium tin oxide, fluorine-doped tin oxide, aluminum oxide, metal oxide such as alumina, conductive polymer composition, carbon nanotube (CNT) 'fullerene, carbon black The carbon powder or the dispersion is used as the chelating component. The powder or the dispersion is added to the solid component of the composite conductive polymer composition, -22 - 201041964, and the solid component is added in an amount of 0.01 to 50 by weight. The degree is good. Further, as the composite conductive polymer composition, a counter electrode for a dye-sensitized solar cell can be used. When the transparency of the dye-sensitized solar cell is required to be transparent, the composite conductive polymer composition is laminated on one surface of the transparent substrate, or a light-transmitting electrode is disposed on one surface of the transparent substrate, and the light is transmitted through the light-transmitting electrode. The composite electrode is formed by laminating the above composite conductive polymer composition to form 0. Further, when transparency is not required, it can be formed by lamination by a metal foil or the like. The thickness of the composite conductive polymer composition is generally 0.01 to ΙΟΟμηι, preferably 0.1 to 50 μm. The transparent substrate used as the above-described dye sensitization of the present invention has a light transmittance of usually 50% or more, and preferably 80% or more of a film or a sheet can be used. Examples of such a transparent plate include inorganic transparent substrates such as glass, polyethylene terephthalate (PET), polycarbonate (PC), polyphenylene sulfide, polyfluorene, polyester fluorene, and poly. A polymer transparent substrate such as an alkyl (meth) acrylate, a polyethylene naphthalate (PEN), a polyether oxime (PES) or a polycycloolefin. Further, examples of the metal foil include metal foils such as gold, platinum, silver, tin, copper, aluminum, stainless steel, and nickel. The thickness of the transparent substrate is generally in the range of 200 to 700 Å μηι in the case of the inorganic transparent substrate, and is generally in the range of 20 to 4000 μm, preferably 20 to 2000 μm in the case of the polymer transparent substrate. In the case of a metal substrate, it is preferably Ομπι~ΙΟΟΟμιη, preferably in the range of Ιμηι to 500μιη. The polymer transparent substrate and the metal foil substrate having a thickness in the range can impart flexibility to the obtained dye-sensitized solar cell. -23- 201041964 Further, a light transmissive electrode may be disposed on one surface of the transparent substrate as necessary. The light transmissive electrode used herein may be a film-shaped conductive metal electrode or a mesh-shaped conductive metal electrode. The film-shaped conductive metal electrode is formed by forming tin oxide, tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), or the like into a film. The film-shaped conductive metal electrode is formed on the surface of the transparent substrate by tin oxide, ITO, FTO or the like by vapor deposition or sputtering. The thickness of the film-shaped conductive metal electrode is generally in the range of 0.01 to Ιμηι, preferably 0.01 to 0.5 μm. On the other hand, the mesh-shaped conductive metal electrode is formed of a conductive metal such as copper, nickel or aluminum. Specifically, the mesh-shaped conductive metal electrode is made of a conductive metal such as copper, nickel or aluminum. For example, by photolithography, it can be hungry to a line width of generally 1 〇 to 70 μm, preferably 1 0 to 2 0 μ m, and the pitch is generally 50 to 300 μm, preferably 50 to 200 μm. The thickness of the wire of the sieve-like conductive metal electrode at this time is slightly the same as the thickness of the conductive metal to be used, and is generally in the range of 8 to 150 μm, preferably 8 to 15 μm. The surface of the transparent substrate of the mesh-shaped conductive metal electrode can be adhered with an adhesive or the like. When the counter electrode for a dye-sensitized solar cell is produced, a method of laminating a composite conductive polymer composition on a light-transmitting electrode disposed on one surface of the transparent substrate or the transparent substrate may be, for example, a configuration. The composite conductive polymer composition solution is applied to the light-transmissive electrode on the transparent substrate sheet surface or the transparent substrate surface, and the solvent in the solution is removed one to several times. -24- 201041964 The coating of the above composite conductive polymer composition solution is suitable for dip coating, microrod coating, roll coating, corner wheel coating (comma coate, die coating, gravure coating, etc.). Further, the solvent can be removed by a method such as natural drying by standing, forced drying by heating under hot air or infrared rays, etc. The dye-sensitized solar cell is extremely useful for the above composite conductive use. Since the polymer composition is soluble in an organic solvent, the coating step is easier and the productivity is superior to that of the dispersion in which the conventional ruthenium-based composite conductive polymer composition is dispersed in an aqueous medium. It is possible to suppress the deterioration of the metal humus in the production of the step from the opposite side of the acidic aqueous solution. Further, the above-mentioned composite conductive polymer composition used in the above-described dye-sensitized solar cell is excellent in the use of the above-mentioned components ( A-1), the polymer compound (A) obtained by copolymerizing the component (a-2) and the component (a-3) in a predetermined range, and the transparent substrate or the light transmissive electrode or the metal In addition, the above-mentioned composite conductive polymer composition used in the above-mentioned dye-sensitized solar cell is excellent in the adhesion, and the above-mentioned component (a-ι) is suppressed by use. The polymer compound (A) having a degree of acidity obtained by copolymerization of the component (a-2) and the component (a-3) in a predetermined range makes it difficult to corrode the light-transmitting electrode (conductive metal). Since the durability of the electrolytic solution can be improved, it can be used for a long period of time. The above-mentioned dye-sensitized solar cell is extremely useful, and the high-priced platinum electrode used as an electrode having oxidation resistance to the past electrolyte is uniformly resistant. The oxidizable film can exhibit a composite conductive polymer film, and can provide various metals which can be used at a low price of -25-201041964. Further, the antistatic film formed using the composite conductive polymer composition has high composite conductivity. The molecular composition is coated and dried separately, and the film is formed into a self-standing film to process a low-resistance anti-charged film. Further, the composite conductive polymer composition and heat may be mixed as necessary. In the case of a plastic resin and/or a thermosetting resin, (1) a method of forming a film by a T-die or the like by melt-kneading by an extruder or an extruder, and (2) a thermoplastic resin, The thermosetting resin and the glass film are coated on the surface of the film or both surfaces, and the solution of the composite conductive polymer composition is applied to remove the solvent in the solution to form an antistatic layer. The antistatic film is used as the antistatic film. The thermoplastic resin may, for example, be a polyolefin, a polyvinyl chloride, a polyvinylidene chloride, a polystyrene, a polyvinyl acetate, a polytetrafluoroethylene, a polyacrylonitrile butadiene styrene or a polyacrylonitrile benzene. Ethylene, polymethacryl, polypropylene, saturated polyester, polyamide, polycarbonate, poly-derivative phenyl ether, polyphenylene sulfide, polyfluorene, polyacrylate, liquid crystal polymer, polyether ether Ketones, polyamidines, and the like, also include polymer alloys or thermoplastic elastomers of these thermoplastic resins. Examples of the thermosetting resin used in the above antistatic film of the present invention include polyphenol, polyepoxy, unsaturated polyester, polyurethane, polyimine, polyurea, polyoxyxylene resin, melamine resin, Fluorine resin, alkyd resin, and the like. Further, the above-mentioned antistatic film can be formed into various types by using a tubular molecular compound (A) obtained by copolymerizing the above component (a), component (a-2) and component (a-3) in a predetermined range. Wet low humidity environment strip -26- 201041964 under the performance of less variation, and has a higher permeability anti-charge film. [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the examples. Further, the molecular weight and surface resistance 本 in the present example were measured by the following methods. ❸ <Molecular weight> The measurement was carried out by GPC under the following conditions. Device name: HLC-8120 (manufactured by TOSOH Co., Ltd.) Column: GF-1G7B + GF-510HQ (Asahipak: registered trademark, Showa Denko Co., Ltd.) Reference material: Sampling of polystyrene and sodium polystyrene sulfonate Concentration: 1. 〇mg/ml 〇Dissolution: 50mmol lithium chloride aqueous solution/CH3CN = 60/40wt Flow rate: 0.6ml/min Column temperature: 30°C Detector: UV254nm <Surface resistance> Use (share) DIA INSTRUMENTS low resistivity meter L 〇resta GP, PSP type probe, measured by four-terminal four-probe method. -27- 201041964 Synthesis Example 1 Synthesis of polymer compound (2-NaSEMA/BzMA/HEMA = 40/25/35) Four beakers with a capacity of 1000 cm3 equipped with a stirrer, a nitrogen gas introduction tube, a reflux cooler, an input port, and a thermometer 68.9 g of 2-sodium sulfoethyl methacrylate, 35.7 g of benzyl methacrylate, 36.9 g of 2-hydroxyethyl methacrylate, 150 g of ionized water, and 300 g of isopropyl alcohol were charged. The mixture in the beaker was heated to reflux temperature while introducing nitrogen into the beaker. Next, 7 g of azobisisobutyronitrile was placed in a beaker, and while maintaining a reflux state, a polymerization reaction was carried out for 18 hours to obtain a polymer solution (A-1). 'The total amount of the obtained polymer solution (A-1) was transferred to a beaker of 2 〇〇〇cm3, and hexane 5 〇〇g was added while stirring with a stirrer, and then left to stand for 1 hour to remove impurities. Oil layer. The solution on the aqueous layer side was dried using a drier at 10 ° C for 24 hours. The obtained solid was dried under reduced pressure at 100 Torr for 24 hours, and then pulverized in a mortar to obtain a powder (AP-1) of a high molecular compound. The obtained polymer compound (AP-1) was measured by gel permeation chromatography (GPC) to obtain a weight average molecular weight (Mw) = 58,000. Synthesis Examples 2 to 5 and Comparative Synthesis Examples 6 to 9 The monomers were added as shown in Table 1, and powders of polymer compounds (AP-2 to 9) were obtained in the same manner as in Synthesis Example 1. The Mw of the obtained polymer compound (AP_2 to 9) and the solubility in water are shown in Table 1. -28- 201041964 TJ lx 表璧) 0ss^i 〇〇o 〇〇〇〇〇o 〇〇〇εε 000-ooo ·ε9 000·" 00°Z9 ooo ,s°0°9S000-s 000 s (I )Ϊ屮Φ oo roro ro ro ro "0 ro "0" "0iv ai unloading" VVW vs〒z isvwcsssezVw3se〒z (豳蜱堪" ) UO f-t .in 〇r— CT> r^—\ r—I "^· r*—ir~* CO r—» .LO . O . L〇. O . 〇tOCOCNlLOtOCNj^—CMCOtO C〇i—I 1^3 i—I i_j c%| i_i 1 k—j SI CO ·—» co r—i »*— ί—I .r~*» Uf3 . O 〇0 LO ~CVJ LD L〇CM '—«· r*-

C7 CO I-» CO i—C3 f~~* I-ί I OO 1—1 «—* to ί . ιλ . m . o ί . u〇 . ir> CM l 寸对 OCOCOCVJ! I CVJ to »— i— <0 *>—' ΙΛ ♦—* CM *—1C7 CO I-» CO i—C3 f~~* I-ί I OO 1—1 «—* to ί . ιλ . m . o ί . u〇. ir> CM l inch to OOCOCVJ! I CVJ to »— I— <0 *>—' ΙΛ ♦—* CM *—1

CO COCO CO

> r—♦ .o i CSJ OO i——» ί—I .in ο 〇 CO CO LO O *—· T— r— 〇5 r-—« r— r~» Γ~* ι~τ r-^ · dD · O C〇-«3-C〇C^J*— CO·»— CO <rt i—j »—» jj-> i_j t/3 «—j ι—in-- ι—ι .O . O r- t— co L·—« tn * 6 —dv 8 —dv Γ —& 9 —dv s—dvTdv ε—dv N 1¾ t丨dvI1¾ 承时赇^豳酹堪*^«^*£旮【Γ(3)_γ«胺*密蚱親一r 蘅遐卸离1|*堪聰(csa 趑«E«s-: vvs 避囊 §.*-2*15-0):< 圉 H-o) ®越涯EMs-wnJK __ VWHU if - —m 避趑sMwfrwKl»堪程-cs: vwh^ncn。长友H-K1n$ssse鋇卸靶|3蚺««( i 切 實施例1 (1 )聚苯胺聚合與純化： 於具備攪拌機、氮氣導入管、迴流冷卻器、投入口及 溫度計之容量5 00cm3的四口燒杯中投入合成例1所得之 -29- 201041964 高分子化合物（八？-1)1〇.98、離子交換水10(^及35%鹽 酸水溶液6 g，其次於6 0 °C進行加熱，進行3小時攪拌， 得到均勻乳化劑水溶液。且，於該乳化劑水溶液添加25 °C 飽和食鹽水l〇〇g，在60°C進行1小時攪拌後，冷卻至25 °C。燒杯內之乳化劑溶液爲均勻者。 繼續，於該乳化劑溶液投入苯胺4.65g，經攪拌成爲 均勻乳化液。將l〇g之過氧二硫酸銨溶解於離子交換水 3 0g者，於保持〇°C的燒杯內經2小時滴下。滴下終了後 回復至室溫（25°C )，繼續進行48小時聚合反應。 將聚合反應終了後之聚合溶液進行濾別，將所得之固 體物於水再分散並進行攪拌洗淨，進行再度濾別。取出重 複進行4次前述洗淨所得之含水的固體物，減壓下在4〇°C 進行96小時乾燥後得到複合導電性高分子組成物（E-1 ) 。測定該導電性高分子組成物之揮發分後，得到2%以下 。且揮發分爲，將導電性高分子組成物投入於l〇5°C之熱 風循環式乾燥機中3小時，由該前後之質量減量率求得（ 以下相同）。 (2 )塗膜評估： 於燒杯投入上述所得之複合導電性高分子組成物（E-1 ) 5g、環戊酮60g及甲基乙酮35g，在室溫進行攪拌溶解 ，得到複合導電性高分子組成物溶液。該溶液之外觀爲具 有透明感之綠色。 繼續將該複合導電性高分子組成物溶液使用刮刀，欲 -30- 201041964 使乾燥後的厚度成爲1 Ομηι，於玻璃基板上進行塗敷並乾 燥後，得到綠色之均勻塗膜。該塗膜之表面電阻値爲 2001ίΩ/〇。 實施例2 (1 )聚吡略聚合與純化： 於具備攪拌機、氮氣導入管、迴流冷卻器、投入口及 0 溫度計之容量500cm3的四口燒杯中投入合成例2所得之 高分子化合物（八？-2)10.6§、離子交換水20(^及35%鹽 酸水溶液6g，其次於60t進行加熱，進行3小時攪拌後 ，冷卻至2 5 t。燒杯內之乳化劑溶液爲均勻者。 繼續，於該乳化劑溶液投入吡咯3.3 5 g，經攪拌得到 均勻乳化液。將58g的硫酸第二鐵溶解於離子交換水30g 者，於保持的燒杯內經2小時滴下。滴下終了後回復 室溫（25°C )，繼續進行73小時聚合反應。 〇 將聚合反應終了後之聚合溶液進行濾別，將所得之固 體物於水再次分散並進行攪拌洗淨，進行再度濾別。取出 重複進行4次前述洗淨所得之含水的固體物，減壓下40 °C 中進行96小時乾燥後得到複合導電性高分子組成物（E-2 )。測定該複合導電性高分子組成物之揮發分後得到2% 以下。 (2 )塗膜評估： 於燒杯投入上述所得之複合導電性高分子組成物5g、 -31 - 201041964 甲基乙酮45g及甲基醇50g，在室溫進行攪拌溶解後得到 複合導電性高分子組成物溶液。該溶液之外觀爲黑色。 繼續，將該複合導電性高分子組成物溶液使用刮刀， 欲使乾燥後的厚度成爲1 Ομιη，於玻璃基板上進行塗敷並 乾燥後，得到黑色之均勻塗膜。該塗膜之表面電阻値爲 60kQ/[]。 實施例3 (1 )聚噻吩聚合與純化： 於具備攪拌機、氮氣導入管、迴流冷卻器、投入口及 溫度計之容量500cm3的四口燒杯中投入合成例3所得之 高分子化合物（入？-3)11.68、離子交換水2008及35%鹽 酸水溶液6 g，於6 0 °C進行加熱，進行3小時攪拌後，冷 卻至2 5 °C。燒杯內之乳化劑溶液爲均勻者。 繼續’於該乳化劑溶液投入噻吩4.2 g，攪拌下成爲均 勻乳化液。將1 6 · 5 g的氯化第二鐵溶解於離子交換水3 〇 g 者，於保持8 0 °C的燒杯內經2小時滴下。滴下終了後保持 8 0 °C下，繼續進行5 8小時聚合反應。 將聚合反應終了後之聚合溶液進行濾別，將所得之固 體物於水再次分散後進行攪拌洗淨，進行再度濾別。取出 重複進行4次前述洗淨所得之含水的固體物，減壓下4 0 °C 中進行96小時乾燥後得到複合導電性高分子組成物（e-3 )。測定該複合導電性高分子組成物之揮發分後得到2% 以下。 -32- 201041964 (2 )塗膜評估： 於燒杯投入上述所得之複合導電性高分子組成物（E-3 ) 5g、甲基乙酮50g及異丙基醇45g，在室溫進行攪抻溶 解後得到複合導電性高分子組成物溶液。此溶液的外觀爲 透明感之濃綠色。 其次，將該複合導電性高分子組成物溶液使用刮刀， 〇 欲使乾燥後的厚度成爲1 Ομιη，於玻璃基板上進行塗敷並 乾燥後，得到黑綠色之均勻塗膜。該塗膜之表面電阻値爲 301(Ω/〇。 實施例4 (1 )聚苯胺聚合與純化： 於具備攪拌機、氮氣導入管、迴流冷卻器、投入口及 溫度計之容量5〇〇cm3的四口燒杯中投入合成例2所得之 Ο 高分子化合物（八？-2)13.32、離子交換水20(^及35%鹽 酸水溶液6 g，於6 〇 °C進行加熱，進行3小時攪拌後，冷 卻至2 5 °C。燒杯內之乳化劑溶液爲均勻者。 繼續，於該乳化劑溶液投入苯胺4.65g，攪拌後成爲 均勻乳化液。將5 8 g的硫酸鐵（111 )溶解於離子交換水 1 0 0 g者，於保持3 0 °c之燒杯內經2小時滴下。滴下終了 後昇溫至50°C，繼續進行48小時聚合反應。 將聚合反應終了後之聚合溶液進行濾別，將所得之固 體物於水再次分散後進行攪拌洗淨，進行再度濾別。取出 -33- 201041964 重複進行4次前述洗淨所得之含水的固體物，減壓下40°C 中進行96小時乾燥後得到複合導電性高分子組成物（E-4 )。測定該複合導電性高分子組成物之揮發分後得到2% 以下。 (2 )塗膜評估： 於燒杯投入上述所得之複合導電性高分子組成物（E-4) 5g、環戊酮50g及異丙基醇45g，在室溫進行攪拌溶解 |-| 後得到複合導電性高分子組成物溶液。該溶液之外觀爲具 有透明感之綠色。 繼續，將該複合導電性高分子組成物溶液使用刮刀， 欲使乾燥後的厚度成爲1 〇μιη ’於玻璃基板上進行塗敷並 乾燥後，得到綠色之均勻塗膜。該塗膜之表面電阻値爲 3〇〇kn/〇。 實施例5 (1 )聚苯胺聚合與純化： 將高分子化合物（AP-2) 13.3g變更爲高分子化合物 (AP-4 ) 14.6g以外，與實施例4同樣地，得到複合導電 性高分子組成物（E - 5 )。測定該複合導電性高分子組成 物之揮發分後得到2 %以下。 (2 )塗膜評估： 於燒杯投入上述所得之複合導電性高分子組成物（E- -34- 201041964 5) 5g、環戊酮65g及甲基乙酮3〇g，在室溫進行攪拌溶解 後得到複合導電性高分子組成物溶液。該溶液之外觀爲具 有透明感之綠色。 繼續，將該複合導電性高分子組成物溶液使用刮刀， 欲使乾燥後的厚度成爲1 Ομιη，於玻璃基板上進行塗敷並 乾燥後，得到綠色均勻之塗膜。該塗膜之表面電阻値爲 5 50kn/[H。 〇 實施例6 (1 )聚苯胺聚合與純化： 將高分子化合物（AP-2) 13.3g變更爲高分子化合物 (AP-5 ) 1 3.7g以外，與實施例4同樣地得到複合導電性 高分子組成物（E-6 )。測定該複合導電性高分子組成物 之揮發分後得到2%以下。 〇 ( 2 )塗膜評估： 於燒杯投入上述所得之複合導電性高分子組成物（E- 6) 5g、環戊酮65g及異丙基醇30g’在室溫下進行攪拌溶 解後得到複合導電性高分子組成物溶液。該溶液之外觀爲 具有透明感之黑綠色。 繼續，將該複合導電性高分子組成物溶液使用刮刀， 欲使乾燥後的厚度成爲1 Ομιη，於玻璃基板上進行塗敷並 乾燥後，得到綠色均勻塗膜。該塗膜之表面電阻値爲 1 5 01<;Ω/[Ι|。 -35- 201041964 比較例1 (1 )聚苯胺聚合與純化： 將高分子化合物（AP-2) 13.3g變更爲高分子化合物 (AP _ 6 ) 3 7.9 g以外，與實施例4同樣下得到導電性高分 子組成物（E C -1 )。測定該導電性高分子組成物之揮發分 後得到2%以下。 (2 )塗膜評估： 於燒杯投入上述所得之導電性高分子組成物（EC-1 ) 5g及甲基乙酮95g，在室溫進行攪拌溶解後得到導電性高 分子組成物溶液。該溶液之外觀爲不均質之綠色。 繼續將該導電性高分子組成物溶液使用刮刀，欲使乾 燥後的厚度成爲1 0 μηι，於玻璃基板上進行塗敷並乾燥後 ，得到綠色不均勻塗膜。該塗膜之表面電阻値爲8 ΜΩ/口 比較例2 (1 )聚苯胺聚合與純化： 將高分子化合物（AP-2 ) 13.3g變更爲高分子化合物 (AP-7 ) 1 5.4g以外，與實施例4同樣地得到導電性高分 子組成物（EC-2 )。測定該導電性高分子組成物之揮發分 後得到2%以下。 -36- 201041964 (2 )塗膜評估： 於燒杯投入上述所得之導電性高分子組成物（EC_2 ) 5 g及環戊酮9 5 g，在室溫進行攪拌溶解後得到導電性高分 子組成物溶液。該溶液之外觀爲不均質之綠色° 繼續將該導電性高分子組成物溶液使用刮刀’欲使乾 燥後的厚度成爲1 〇μπι，於玻璃基板上進行塗敷並乾燥後 ，得到綠色不均勻塗膜。該塗膜之表面電阻値爲ιμω/口 比較例3 (1 )聚苯胺聚合與純化： 將高分子化合物（AP-2) l3.3g變更爲高分子化合物 (AP-8 ) 7.2g以外，與實施例4同樣下得到導電性高分子 組成物（EC-3 )。測定該導電性高分子組成物之揮發分後 得到2%以下。 ❹ (2 )塗膜評估： 於燒杯投入上述所得之導電性高分子組成物（EC-3 ) 5g及甲醇95g，在室溫進行攪拌溶解後得到導電性高分子 組成物溶液。該溶液之外觀爲稍微不均質之綠色。 繼續將該導電性高分子組成物溶液使用刮刀，欲使乾 燥後的厚度成爲1 〇μϊη，於玻璃基板上進行塗敷並乾燥後 ’得到綠色不均勻塗膜。該塗膜之表面電阻値爲5ΜΩ/Π -37- 201041964 比較例4 (1 )聚苯胺聚合與純化： 將高分子化合物（AP-2) 13.3g變更爲高分子化合物 (AP-9 ) 5.1 5g以外，與實施例4同樣下，得到導電性高 分子組成物（EC-4 )。測定該導電性高分子組成物之揮發 分後得到2%以下。 (2 )塗膜評估： 於燒杯投入上述所得之導電性高分子組成物（EC-4 ) 5g及甲醇95g，在室溫進行攪拌溶解後得到導電性高分子 組成物溶液。該溶液之外觀爲稍不均質之綠色。 繼續將該導電性高分子組成物溶液使用刮刀，欲使乾 燥後的厚度成爲1 〇 μιη，於玻璃基板上進行塗敷並乾燥後 ，得到綠色不均勻塗膜。該塗膜之表面電阻値爲12ΜΩ/〇 比較例5 (1 )聚苯胺聚合與純化： 將高分子化合物（AP-2) 13.3g變更爲高分子化合物 (AP-9 ) 20.6g，將35%鹽酸水溶液6g變更爲10g以外， 與實施例4同樣下得到導電性高分子組成物（EC_5 )。測 定該導電性高分子組成物之揮發分後得到2%以下。 -38- 201041964 (2 )塗膜評估·· 於燒杯投入上述所得之導電性高分子組成物（EC-5 ) 5g及離子交換水95g，在室溫進行攪拌溶解後得到導電性 高分子組成物溶液。該溶液之外觀爲具有透明感之綠色。 繼續將該導電性高分子組成物溶液使用刮刀，欲使乾 燥後的厚度成爲1 Ομηι，於玻璃基板上進行塗敷並乾燥後 ，得到綠色均勻之塗膜。該塗膜之表面電阻値爲3ΜΩ/Π 比較例6 (1 )聚吡咯聚合與純化： 於具備攪拌機、氮氣導入管、迴流冷卻器、投入口及 溫度計之容量500cm3的四口燒杯中投入合成例2所得之 高分子化合物（八？-2)10.68、離子交換水20(^、35%鹽 酸水溶液6g，在6(TC經加熱並進行3小時攪拌後，冷卻 〇 至25°C。燒杯內之乳化劑溶液爲均句者。 繼續於該乳化劑溶液投入吡咯3 . 3 5 g，經攪拌成爲均 勻乳化液。將16.5g的氯化第二鐵溶解於離子交換水30g 者，於保持〇 °C的燒杯內經2小時滴下。滴下終了後回復 室溫（25 °C )，繼續進行43小時聚合反應。 將聚合反應終了後之聚合溶液進行濾別，將所得之固 體物於水再次分散後進行攪拌洗淨，進行再度濾別。取出 重複進行4次前述洗淨所得之含水的固體物，減壓下4 0 °C 進行96小時乾燥後得到導電性高分子組成物（ec-6 )。 -39- 201041964 測定該導電性高分子組成物之揮發分後得到2%以下。 (2 )塗膜評估： 於燒杯投入上述所得之導電性高分子組成物（E C - 6 ) 5 g及甲基乙酮9 5 g，在室溫進行攪拌溶解後得到導電性高 分子組成物溶液。該溶液之外觀爲不均質之黑色。 繼續將該導電性高分子組成物溶液使用刮刀，欲使乾 燥後的厚度成爲1 〇 μ m，於玻璃基板上進行塗敷並乾燥後 ，得到具有凹凸之黑色塗膜。該塗膜之表面電阻値爲 20ΜΩ/□以上。又，塗膜的表面以手指擦拭時會使粉狀物 剝離。 比較例7 (1 )聚噻吩聚合與純化： 將高分子化合物（AP-3) 11.6g變更爲高分子化合物 (AP-8 ) 4.3g以外，與實施例3同樣下得到導電性高分子 組成物（EC-7 )。測定該導電性高分子組成物之揮發分後 得到2%以下。 (2 )塗膜評估： 於燒杯投入上述所得之導電性高分子組成物（EC-6 ) 5 g及甲醇9 5 g，在室溫進行攪拌溶解後得到導電性高分子 組成物溶液。該溶液之外觀爲稍不均質之黑綠色。 繼續將該導電性高分子組成物溶液使用刮刀，欲使乾 -40 - 201041964 燥後的厚度成爲ΙΟμιη，於玻璃基板上進行塗敷並乾燥後 ，黑得到綠色不均勻塗膜。該塗膜之表面電阻値爲2ΜΩ/ □。 實施例7〜實施例1 3及比較例8〜比較例1 0 將國際公開號碼WO/2009/0 1 3 942的實施例1所使用 的對向電極（開口銅篩電極）以及對向電極基板（厚度 0 80μιη之PET薄膜），使實施例1〜4所調製的複合導電性 高分子組成物溶液或比較例2所調製之導電性高分子組成 物溶液，使用刮刀使乾燥後的厚度成爲5 μπι後，取代塗敷 於SUS箔、ITO PEN薄膜、玻璃基板、ΙΤΟ玻璃基板或 FTO玻璃基板上者而製造出色素增感型太陽電池元件。 所得之色素增感型太陽電池元件評估則使用山下電裝 (股）製之 Solar simulatorYSS-80A。對於晶胞面積 lcm2 的元件，調查AM1.5(1 sun; 100mW/cm2 )照射下之I-V特 Q 性，進而評估晶胞的短路電流、開放電壓、塡充因子及發 電效率。其結果如表2所示。 -41 - 201041964 [表2] 對向電極及對向電極基板 短路電流 (Jsc/mA) 開放電壓 (Voc/v) 塡充因子 (FF) 發電效率 (Eff%) 實施例7 ITO玻璃基板+實施例1之 複合導電性高分子組成物 7.9 0.81 45 2.9 實施例8 ITO玻璃基板+實施例2之 複合導電性高分子組成物 8.5 0.80 46 3.2 實施例9 SUS箔+實施例3之 複合導電性高分子組成物 8.7 0.81 48 3.4 實施例10 ITO玻璃基板+實施例4之 複合導電性高分子組成物 8.3 0.81 44 3.0 實施例11 FTO玻璃基板+實施例1之 複合導電性高分子組成物 8.1 0.80 44 2.9 實施例12 ITO PEN薄膜+實施例1之 複合導電性高分子組成物 7.9 0.81 43 2.8 實施例13 玻璃基板+實施例1之 複合導電性高分子組成物 1.2 0.55 60 0.4 比較例8 ITO玻璃基板+比較例2之 複合導電性高分子組成物 1.3 0.71 6 0.06 比較例9 ITO玻璃基板 1.3 0.56 7 0.05 比較例10 FTO玻璃基板 1.3 0.56 7 0.05 由以上結果得知，使用本發明的複合導電性高分子組 成物所成的色素增感型太陽電池元件顯示高光電變換效率 實施例1 4〜實施例1 5及比較例1 1〜比較例1 2 將實施例1〜2所調製之複合導電性高分子組成物溶 液或以比較例2所調製之導電性高分子組成物溶液，各再 次調整爲固體成分 2.5%，將這些藉由轉動塗佈法以 -42- 201041964 4000rPm-15SeC的條件下，對於厚度ι〇〇〇μιη之玻璃基板及 ΙΟΟμιη之PET薄膜基板進行塗佈，以熱風乾燥機將溶劑除 去製造出形成防帶電層之防帶電薄膜。且，將防帶電層的 膜厚以觸針式表面形狀測定器（Dektak 6M : ULVAC製） 進行測定後，防帶電層的厚度皆約爲25nm。 對於所得之防帶電薄膜，在如以下條件下靜置後進行 表面電阻値之評估。評估結果如表3所示。 Q 條件（1 ):在23°C 50%RH爲192小時 條件（2 ):在40 °C 8 0%RH爲1 6 8小時 [表3] 玻璃面板 PET薄膜基板 條件⑴ 條件(2) 條件(1) 條件(2) 防帶電薄膜 上:膜之狀態 上:膜之狀態 上:膜之狀態 上:膜之狀態 下:表面電阻 下:表面電阻 下:表面電阻 下:表面電阻 (Ω/Π ) (Ω/Π ) (Ω/〇 ) (Ω/Π ) 實施例Η 實施例1之複合導 〇 〇 〇 〇 電性高分子組成物 4.78 χΙΟ8 8.2x10s 9.73 χΙΟ8 2.0x109 實施例15 實施例2之複合導 〇 〇 〇 〇 電性高分子組成物 3.31χ107 7.2xl08 8.5xl08 9.3χ108 比較例11 比較例5之導電性 X X X X 高分子組成物 >1.0〇xl015 >1.0〇χ1015 >1.00xl015 >1.0〇χ1015 比較例5之導電性 〇 X 〇 X 比較例12 高分子組成物溶解 1.5χ109 因吸濕而無 6.〇χ1〇10 因吸濕而無 於水之物質 法測定 法測定 由以上之結果得知’本發明的防帶電薄膜即使使用於 高溫多濕下之環境，亦充分顯示防帶電特性。 [產業上可利用性] -43- 201041964 本發明的複合導電性高分子組成物爲，將以具有親水 性基與聚合性乙烯基之極性單體作爲主成分的高分子化合 物（A )作爲摻合劑使用者，於醇系或酮系溶劑中可安定 地溶化成爲可能者。 因此所得之複合導電性高分子組成物在醇系或酮系溶 劑中以透明狀態下溶解的複合導電性高分子組成物溶液， 可於被要求導電性的部分上簡單地形成導電性皮膜，對於 電子零件等領域而言，可於極有利之狀況下使用。 且’使用本發明的複合導電性高分子組成物之色素增 感型太陽電氣用電極或防帶電薄膜具有優良的性能。> r—♦ .oi CSJ OO i——» ί—I .in ο 〇CO CO LO O *—· T— r— 〇5 r-—« r— r~» Γ~* ι~τ r- ^ · dD · OC〇-«3-C〇C^J*— CO·»— CO <rt i—j »—» jj-> i_j t/3 «—j ι—in-- ι—ι .O . O r- t — co L·—« tn * 6 —dv 8 —dv Γ —& 9 —dv s—dvTdv ε—dv N 13⁄4 t丨dvI13⁄4 Time-honored 豳酹^豳酹*^«^ *£旮[Γ(3)_γ«amine*密蚱亲一 r 蘅遐卸离1|*可聪(csa 趑«E«s-: vvs escaping §.*-2*15-0):&lt ; 圉Ho) ®越涯EMs-wnJK __ VWHU if -m avoid sMwfrwKl» 堪程-cs: vwh^ncn. Changyou H-K1n$ssse unloading target|3蚺««( i cut example 1 (1) polyaniline polymerization and purification: with a mixer, nitrogen inlet tube, reflux cooler, input port and thermometer capacity 5000 cm3 In the four beakers, the polymer compound (eight?-1)1〇.98 obtained from the synthesis example 1 was used, and the ion exchange water 10 (^ and 35% aqueous hydrochloric acid solution 6 g, followed by 6 0 ° C). The mixture was heated and stirred for 3 hours to obtain a homogeneous emulsifier aqueous solution, and 100 g of saturated brine at 25 ° C was added to the emulsifier aqueous solution, and the mixture was stirred at 60 ° C for 1 hour, and then cooled to 25 ° C. The emulsifier solution is uniform. Continuing, 4.65 g of aniline is added to the emulsifier solution, and the mixture is stirred to form a uniform emulsion. Dissolving 10 g of ammonium peroxodisulfate in ion-exchanged water is maintained at 0°. The beaker of C was dropped over 2 hours, and after the completion of the dropwise addition, it was returned to room temperature (25 ° C), and polymerization was continued for 48 hours. The polymerization solution after the completion of the polymerization was filtered, and the obtained solid was redispersed in water. Wash and stir again, and filter again. Take out and repeat The aqueous solid obtained by the above washing was washed four times at a reduced pressure of 96 ° C for 96 hours to obtain a composite conductive polymer composition (E-1). The volatile polymer composition was measured for volatilization. After the separation, 2% or less was obtained, and the volatile polymer composition was placed in a hot air circulation type dryer at 10 ° C for 3 hours, and the mass reduction rate before and after was determined (the same applies hereinafter). (2) Coating evaluation: 5 g of the composite conductive polymer composition (E-1) obtained above, 60 g of cyclopentanone, and 35 g of methyl ethyl ketone were placed in a beaker, and stirred and dissolved at room temperature to obtain composite conductivity. The polymer composition solution has a transparent green color. The composite conductive polymer composition solution is continuously used as a doctor blade, and the thickness after drying is 1 Ομηι, which is performed on a glass substrate. After coating and drying, a green uniform coating film was obtained. The surface resistance 値 of the coating film was 2001 ίΩ/〇. Example 2 (1) Polypyridyl polymerization and purification: equipped with a stirrer, a nitrogen gas introduction tube, a reflux cooler, Cast 0 The polymer compound (eight?-2) 10.6 § obtained in Synthesis Example 2, ion-exchanged water 20 (^ and 6 g of a 35% hydrochloric acid aqueous solution) were placed in a four-necked beaker having a capacity of 500 cm3, followed by heating at 60 t for 3 hours. After stirring, it was cooled to 25 t. The emulsifier solution in the beaker was uniform. Continue, 3.3 g of pyrrole was added to the emulsifier solution, and a uniform emulsion was obtained by stirring. 58 g of the second iron sulfate was dissolved in the ion exchange. 30 g of water was dropped in a kept beaker for 2 hours, and after the end of the dropping, the temperature was returned to room temperature (25 ° C), and the polymerization was continued for 73 hours.聚合 The polymerization solution after the completion of the polymerization reaction is filtered, and the obtained solid matter is redispersed in water, stirred and washed, and filtered again. The aqueous solid obtained by the above-described washing was washed four times, and dried at 40 ° C for 96 hours under reduced pressure to obtain a composite conductive polymer composition (E-2). The volatile matter of the composite conductive polymer composition was measured and found to be 2% or less. (2) Evaluation of coating film: In the beaker, 5 g of the composite conductive polymer composition obtained above, -31 - 201041964, 45 g of methyl ethyl ketone and 50 g of methyl alcohol were placed, and stirred and dissolved at room temperature to obtain a composite conductive polymer. Composition solution. The appearance of the solution was black. Then, the composite conductive polymer composition solution was subjected to a doctor blade, and the thickness after drying was adjusted to 1 μm, and the film was coated on a glass substrate and dried to obtain a black uniform coating film. The surface resistance of the coating film was 60 kQ/[]. Example 3 (1) Polymerization and purification of polythiophene: The polymer compound obtained in Synthesis Example 3 was placed in a four-pot beaker having a capacity of 500 cm 3 equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, an inlet, and a thermometer (into -3) 11.68, ion exchange water 2008 and 6 g of a 35% hydrochloric acid aqueous solution were heated at 60 ° C, stirred for 3 hours, and then cooled to 25 ° C. The emulsifier solution in the beaker is uniform. Continuing with the addition of 4.2 g of thiophene to the emulsifier solution, it became a homogeneous emulsion with stirring. Dissolving 1 6 · 5 g of the second iron chloride in the ion exchange water 3 〇 g was dropped in a beaker maintained at 80 ° C for 2 hours. After the end of the dropwise addition, the polymerization was continued at 80 ° C for 48 hours. The polymerization solution after the completion of the polymerization reaction was filtered, and the obtained solid matter was redispersed in water, stirred and washed, and filtered again. The aqueous solid obtained by the above-described washing was washed four times, and dried at 40 ° C for 96 hours under reduced pressure to obtain a composite conductive polymer composition (e-3). The volatile matter of the composite conductive polymer composition was measured and found to be 2% or less. -32- 201041964 (2) Evaluation of coating film: 5 g of the composite conductive polymer composition (E-3) obtained above, 50 g of methyl ethyl ketone and 45 g of isopropyl alcohol were placed in a beaker, and the mixture was dissolved at room temperature. Thereafter, a composite conductive polymer composition solution was obtained. The appearance of this solution is a dark green with a transparent feel. Then, the composite conductive polymer composition solution was subjected to a doctor blade, and the thickness after drying was set to 1 μm, and the film was coated on a glass substrate and dried to obtain a black-green uniform coating film. The surface resistance 値 of the coating film was 301 (Ω/〇. Example 4 (1) Polyaniline polymerization and purification: Four having a capacity of 5 〇〇 cm 3 with a stirrer, a nitrogen introduction tube, a reflux cooler, an input port, and a thermometer In the mouth beaker, Ο polymer compound (octa-2) 13.32, ion-exchanged water 20 (^ and 35% aqueous hydrochloric acid solution 6 g) were added to the beaker, and the mixture was heated at 6 ° C for 3 hours, and then cooled. To 2 5 ° C. The emulsifier solution in the beaker is uniform. Continue, 4.65 g of aniline is added to the emulsifier solution, and stirred to form a uniform emulsion. 5 8 g of iron sulfate (111 ) is dissolved in ion-exchanged water. 1 0 0 g, dropped in a beaker kept at 30 ° C for 2 hours. After the completion of the dropwise addition, the temperature was raised to 50 ° C, and the polymerization reaction was continued for 48 hours. The polymerization solution after the completion of the polymerization reaction was filtered, and the obtained solution was obtained. The solid was re-dispersed in water, washed with stirring, and filtered again. The -33-201041964 was taken out and the aqueous solid obtained by the above washing was repeated four times, and dried at 40 ° C for 96 hours under reduced pressure to obtain a composite. Conductive polymer composition E-4) The volatile matter of the composite conductive polymer composition was measured to obtain 2% or less. (2) Evaluation of coating film: 5 g of the composite conductive polymer composition (E-4) obtained above was placed in a beaker. 50 g of cyclopentanone and 45 g of isopropyl alcohol were stirred and dissolved at room temperature at --| to obtain a composite conductive polymer composition solution. The appearance of the solution was green with transparency. Continued, the composite conductivity was high. The molecular composition solution was sprayed with a doctor blade to a thickness of 1 〇μιη after drying, and dried to obtain a green uniform coating film. The surface resistance of the coating film was 3 〇〇 kn / 〇 Example 5 (1) Polymerization and purification of polyaniline: In the same manner as in Example 4, 13.3 g of the polymer compound (AP-2) was changed to 14.6 g of the polymer compound (AP-4), and composite electric conductivity was high. Molecular composition (E - 5 ). The volatile component of the composite conductive polymer composition was measured to obtain 2% or less. (2) Evaluation of coating film: The composite conductive polymer composition obtained above was placed in a beaker (E- -34- 201041964 5) 5g, cyclopentanone 65g and A Ethyl ketone 3 〇g was stirred and dissolved at room temperature to obtain a composite conductive polymer composition solution. The appearance of the solution was green with transparency. Continued, the composite conductive polymer composition solution was squeegee, The thickness after drying was 1 μm, and the coating was applied to a glass substrate and dried to obtain a green uniform coating film. The surface resistance of the coating film was 5 50 kn/[H. 〇 Example 6 (1) Polyaniline Polymerization and purification: A composite conductive polymer composition (E-6) was obtained in the same manner as in Example 4 except that 13.3 g of the polymer compound (AP-2) was changed to 13.7 g of the polymer compound (AP-5). The volatile matter of the composite conductive polymer composition was measured to obtain 2% or less. 〇( 2 ) Evaluation of coating film: 5 g of the composite conductive polymer composition (E-6) obtained in the above-mentioned beaker, 65 g of cyclopentanone, and 30 g of isopropyl alcohol were stirred and dissolved at room temperature to obtain a composite conductive layer. A solution of a polymer composition. The appearance of the solution was a blackish green with a transparent feel. Then, the composite conductive polymer composition solution was subjected to a doctor blade, and the thickness after drying was adjusted to 1 μm, and the film was coated on a glass substrate and dried to obtain a green uniform coating film. The surface resistance 値 of the coating film is 1 5 01 <; Ω / [Ι |. -35-201041964 Comparative Example 1 (1) Polymerization and Purification of Polyaniline: Conduction was carried out in the same manner as in Example 4 except that 13.3 g of the polymer compound (AP-2) was changed to a polymer compound (AP _ 6 ) 3 7.9 g. Polymer composition (EC-1). The volatile matter of the conductive polymer composition was measured to obtain 2% or less. (2) Coating film evaluation: 5 g of the conductive polymer composition (EC-1) and 95 g of methyl ethyl ketone obtained above were placed in a beaker, and stirred and dissolved at room temperature to obtain a conductive polymer composition solution. The appearance of the solution is an uneven green color. The conductive polymer composition solution was continuously dried using a doctor blade, and after drying to a thickness of 10 μm, it was applied onto a glass substrate and dried to obtain a green uneven coating film. The surface resistance 値 of the coating film was 8 ΜΩ/port. Comparative Example 2 (1) Polyaniline polymerization and purification: 13.3 g of the polymer compound (AP-2) was changed to a polymer compound (AP-7) 1 5.4 g, A conductive polymer composition (EC-2) was obtained in the same manner as in Example 4. The volatile matter of the conductive polymer composition was measured to obtain 2% or less. -36- 201041964 (2) Evaluation of coating film: 5 g of the conductive polymer composition (EC 2 ) and 95 g of cyclopentanone obtained in the above-mentioned beaker were placed in a beaker, and stirred and dissolved at room temperature to obtain a conductive polymer composition. Solution. The appearance of the solution is uneven green. The continuation of the conductive polymer composition solution is carried out using a doctor blade. The thickness after drying is 1 〇μπι, coated on a glass substrate and dried to obtain a green uneven coating. membrane. The surface resistance 値 of the coating film was ι μω / port. Comparative Example 3 (1) Polyaniline polymerization and purification: The polymer compound (AP-2) was changed to 3.3 g, and the polymer compound (AP-8) was changed to 7.2 g. In the same manner as in Example 4, a conductive polymer composition (EC-3) was obtained. The volatile matter of the conductive polymer composition was measured to obtain 2% or less. (2) Coating film evaluation: 5 g of the conductive polymer composition (EC-3) and 95 g of methanol obtained above were placed in a beaker, and stirred and dissolved at room temperature to obtain a conductive polymer composition solution. The appearance of the solution was slightly heterogeneous green. The conductive polymer composition solution was continuously dried using a doctor blade, and the thickness after drying was changed to 1 〇μϊη, and the coating was applied to a glass substrate and dried to obtain a green uneven coating film. The surface resistance 値 of the coating film was 5 Μ Ω / Π -37 - 201041964 Comparative Example 4 (1) Polyaniline polymerization and purification: 13.3 g of the polymer compound (AP-2) was changed to a polymer compound (AP-9) 5.1 5 g A conductive polymer composition (EC-4) was obtained in the same manner as in Example 4 except for the above. The volatile matter of the conductive polymer composition was measured to obtain 2% or less. (2) Coating film evaluation: 5 g of the conductive polymer composition (EC-4) and 95 g of methanol obtained above were placed in a beaker, and stirred and dissolved at room temperature to obtain a conductive polymer composition solution. The appearance of the solution was slightly heterogeneous green. The conductive polymer composition solution was continuously dried using a doctor blade, and after drying to a thickness of 1 μm, the film was coated on a glass substrate and dried to obtain a green uneven coating film. The surface resistance 値 of the coating film was 12 ΜΩ/〇. Comparative Example 5 (1) Polyaniline polymerization and purification: 13.3 g of the polymer compound (AP-2) was changed to a polymer compound (AP-9) 20.6 g, and 35% was obtained. A conductive polymer composition (EC_5) was obtained in the same manner as in Example 4 except that 6 g of the aqueous hydrochloric acid solution was changed to 10 g. The volatile matter of the conductive polymer composition was measured to obtain 2% or less. -38- 201041964 (2) Evaluation of coating film · 5 g of conductive polymer composition (EC-5) and 95 g of ion-exchanged water obtained in the above-mentioned beaker were stirred and dissolved at room temperature to obtain a conductive polymer composition. Solution. The appearance of the solution is green with a transparent feel. The conductive polymer composition solution was continuously dried using a doctor blade, and after drying to a thickness of 1 μm, it was applied onto a glass substrate and dried to obtain a green uniform coating film. The surface resistance 値 of the coating film was 3 Μ Ω / Π Comparative Example 6 (1) Polypyrrole polymerization and purification: A synthesis example was put into a four-mouth beaker having a capacity of 500 cm 3 equipped with a stirrer, a nitrogen gas introduction tube, a reflux condenser, an input port, and a thermometer. 2 obtained polymer compound (octa-2) 10.68, ion-exchanged water 20 (^, 35% hydrochloric acid aqueous solution 6g, after 6 (TC is heated and stirred for 3 hours, then cooled to 25 ° C. In the beaker The emulsifier solution is a uniform sentence. The emulsifier solution is further charged with 3.35 g of pyrrole and stirred to form a uniform emulsion. 16.5 g of the second iron chloride is dissolved in 30 g of ion-exchanged water to maintain 〇° The beaker of C was dropped over 2 hours, and after the completion of the dropping, the temperature was returned to room temperature (25 ° C), and the polymerization was continued for 43 hours. The polymerization solution after the completion of the polymerization was filtered, and the obtained solid was redispersed in water. The mixture was washed with stirring and filtered again. The aqueous solid obtained by the above-mentioned washing was washed four times, and dried at 40 ° C for 96 hours under reduced pressure to obtain a conductive polymer composition (ec-6 ). 39- 201041964 Determination of the guide After the volatile component of the electropolymer composition, 2% or less was obtained. (2) Evaluation of coating film: 5 g of the conductive polymer composition (EC - 6 ) and 95 g of methyl ethyl ketone obtained in the above-mentioned beaker were placed in a beaker. After stirring and dissolving at room temperature, a conductive polymer composition solution is obtained. The appearance of the solution is black which is uneven. Continue to use a doctor blade for the conductive polymer composition solution, and the thickness after drying is 1 μm. After coating and drying on a glass substrate, a black coating film having irregularities is obtained. The surface resistance 値 of the coating film is 20 ΜΩ/□ or more. Further, when the surface of the coating film is wiped with a finger, the powder is peeled off. Comparative Example 7 (1) Polymerization and Purification of Polythiophene: A conductive polymer composition was obtained in the same manner as in Example 3 except that 11.6 g of the polymer compound (AP-3) was changed to 4.3 g of the polymer compound (AP-8). (EC-7). The volatile matter of the conductive polymer composition was measured to obtain 2% or less. (2) Evaluation of coating film: 5 g of the conductive polymer composition (EC-6) obtained above was placed in a beaker. 9 5 g of methanol, stirred and dissolved at room temperature An electropolymer composition solution. The appearance of the solution is a slightly heterogeneous black-green color. Continue to use the doctor blade for the conductive polymer composition solution, and the thickness of the dry--40-201041964 is ΙΟμιη, on the glass substrate. After coating and drying, black gave a green uneven coating film. The surface resistance 値 of the coating film was 2 Μ Ω / □. Example 7 to Example 1 3 and Comparative Example 8 to Comparative Example 1 0 International public number WO /2009/0 1 3 942 The counter electrode (open copper screen electrode) used in Example 1 and the counter electrode substrate (PET film having a thickness of 80 μm) were made to have high composite conductivity prepared in Examples 1 to 4. The molecular composition solution or the conductive polymer composition solution prepared in Comparative Example 2 was applied to a SUS foil, an ITO PEN film, a glass substrate, a bismuth glass substrate, or an FTO after using a doctor blade to have a thickness of 5 μm after drying. A dye-sensitized solar cell element was produced on a glass substrate. The obtained solar sensitized solar cell element was evaluated using Solar Simulator YSS-80A manufactured by Yamashita Electric Co., Ltd. For the element with a cell area of 1 cm2, the I-V characteristic Q under the irradiation of AM1.5 (1 sun; 100 mW/cm2) was investigated, and the short-circuit current, open voltage, charging factor and power generation efficiency of the unit cell were evaluated. The results are shown in Table 2. -41 - 201041964 [Table 2] Short-circuit current (Jsc/mA) of the counter electrode and the counter electrode substrate Open voltage (Voc/v) Charge factor (FF) Power generation efficiency (Eff%) Example 7 ITO glass substrate + implementation Composite conductive polymer composition of Example 1 7.9 0.81 45 2.9 Example 8 ITO glass substrate + composite conductive polymer composition of Example 2 8.5 0.80 46 3.2 Example 9 SUS foil + Example 3 has high composite conductivity Molecular composition 8.7 0.81 48 3.4 Example 10 ITO glass substrate + composite conductive polymer composition of Example 4 8.3 0.81 44 3.0 Example 11 FTO glass substrate + composite conductive polymer composition of Example 1 8.1 0.80 44 2.9 Example 12 ITO PEN film + composite conductive polymer composition of Example 1 7.9 0.81 43 2.8 Example 13 Glass substrate + composite conductive polymer composition of Example 1 1.2 0.55 60 0.4 Comparative Example 8 ITO glass substrate + Composite conductive polymer composition of Comparative Example 2 1.3 0.71 6 0.06 Comparative Example 9 ITO glass substrate 1.3 0.56 7 0.05 Comparative Example 10 FTO glass substrate 1.3 0.56 7 0.05 From the above results, the use of the present invention The dye-sensitized solar cell element formed of the conductive polymer composition showed high photoelectric conversion efficiency. Example 14 to Example 1 5 and Comparative Example 1 1 to Comparative Example 1 2 The composite prepared in Examples 1 to 2 The conductive polymer composition solution or the conductive polymer composition solution prepared in Comparative Example 2 was again adjusted to a solid content of 2.5%, and these were subjected to a spin coating method at -42 to 201041964 4000rPm-15SeC. Next, the glass substrate of the thickness ι〇〇〇μηη and the PET film substrate of ΙΟΟμιη were coated, and the solvent was removed by a hot air dryer to produce an antistatic film forming an antistatic layer. Further, the film thickness of the antistatic layer was measured by a stylus type surface measuring device (Dektak 6M: manufactured by ULVAC), and the thickness of the antistatic layer was about 25 nm. With respect to the obtained antistatic film, the surface resistance 値 was evaluated after standing under the following conditions. The evaluation results are shown in Table 3. Q Condition (1): at 23 ° C 50% RH is 192 hours Condition (2 ): at 40 ° C 80 ° RH is 168 hours [Table 3] Glass panel 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/Π (Ω/Π) (Ω/〇) (Ω/Π) Example 复合 Composite conductive polymer composition of Example 1 4.78 χΙΟ8 8.2×10s 9.73 χΙΟ8 2.0x109 Example 15 Example 2 Composite conductive polymer composition 3.31χ107 7.2xl08 8.5xl08 9.3χ108 Comparative Example 11 Conductivity XXXX of Comparative Example 5 Polymer composition > 1.0〇xl015 >1.0〇χ1015 >1.00xl015 > 1.0〇χ1015 Conductivity 比较X 〇X of Comparative Example 5 Comparative Example 12 Polymer composition dissolved 1.5χ109 No moisture due to moisture absorption 6. 〇χ1〇10 Determination by mass spectrometry due to moisture absorption without water As a result, it was found that the antistatic film of the present invention is sufficiently used even in an environment of high temperature and high humidity. Illustrates antistatic properties. [Industrial Applicability] -43- 201041964 The composite conductive polymer composition of the present invention contains a polymer compound (A) having a hydrophilic group and a polar monomer having a hydrophilic group as a main component. It is possible for the user of the mixture to be stably dissolved in an alcohol-based or ketone-based solvent. Therefore, the composite conductive polymer composition obtained by dissolving the composite conductive polymer composition in an alcohol-based or ketone-based solvent in a transparent state can easily form a conductive film on a portion where conductivity is required. In the field of electronic parts and the like, it can be used under extremely favorable conditions. Further, the dye-sensitized solar electric electrode or the antistatic film using the composite conductive polymer composition of the present invention has excellent performance.

Claims (1)

201041964 七、申請專利範圍： 1 · 一種複合導電性高分子組成物，其特徵爲將聚合下 述成分（a-l )至（a_3 )所得之高分子化合物（A )，摻 合於'選自下述式（〗）〜（m )的化合物作爲單體構成成 分的κ共軛系高分子（β )所成者； (a-l)具有磺酸基與聚合性乙烯基之單體 20 ~ 60mol% 〇 ( a-2 )具有親水性基與聚合性乙烯基之極性單體 2 0 〜6 0 m ο 1 % (a_3 )具有芳香族基或脂環族基與聚合性乙烯基之 單體 2 0〜3 5 m ο 1 % 式 〇 I )〜（III201041964 VII. Patent Application Range: 1 · A composite conductive polymer composition characterized in that the polymer compound (A) obtained by polymerizing the following components (al) to (a_3) is blended in the following a compound of the formula (I) to (m) as a monomer component of a κ-conjugated polymer (β); (al) a monomer having a sulfonic acid group and a polymerizable vinyl group of 20 to 60 mol% 〇 ( A-2) a polar monomer having a hydrophilic group and a polymerizable vinyl group 2 0 to 6 0 m ο 1 % (a_3 ) a monomer having an aromatic group or an alicyclic group and a polymerizable vinyl group 2 0 to 3 5 m ο 1 % 〇I )~(III nh2 r3 r4 /R5 ⑴ (II) Re ,R5Nh2 r3 r4 /R5 (1) (II) Re , R5 (各式中，：^^至7表示氫原子或碳數丨至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-l)的具有磺酸基與聚合性乙烯基之單體 -45- 201041964 爲選自苯乙烯磺酸鈉、苯乙烯磺酸、2-鈉磺基乙基（甲基 )丙烯酸酯及2 -磺基乙基（甲基）丙嫌酸醋所成群者。 3 .如申請專利範圍第1項或第2項之複合導電性高分 子組成物，其中成分（a-2)之具有親水性基與聚合性乙 烯基之極性單體爲選自丙烯酸、甲基丙烯酸、2 -甲基丙烯 氧基乙基琥珀酸、（無水）馬來酸、2_徑基乙基（甲基） 丙烯酸酯、2-羥基丙基（甲基）丙烯酸醋、4_羥基丁基（ 甲基）丙烯酸酯、2-乙醯乙酸乙基（甲基）丙烯酸酯、甲 氧基乙基（甲基）丙烯酸酯、乙氧基乙基（甲基）丙烯酸 酯、丁氧基乙基（甲基）丙烯酸酯、乙基卡必醇（甲基） 丙烯酸酯、甲氧基三乙二醇（甲基）丙烯酸酯、甲氧基聚 乙二醇（甲基）丙烯酸酯及β-(甲基）丙烯醯氧基乙基氫 琥珀酸酯所成群者。 4.如申請專利範圍第1項至第3項中任一項之複合導 電性高分子組成物，其中成分（a-3 )之具有芳香族基或 脂環族基與聚合性乙烯基之單體爲選自苯甲基（甲基）丙 烯酸酯、苯氧基乙基（甲基）丙烯酸酯、2-(甲基）丙烯 醯氧基乙基苯二甲酸、2-(甲基）丙烯醯氧基乙基六氫苯 二甲酸、新戊二醇（甲基）丙烯酸安息香酸酯、2 -羥基-3-苯氧基丙基（甲基）丙烯酸酯 '羥基乙基化〇-酚（甲基） 丙烯酸酯、〇-苯基酚環氧丙基醚（甲基）丙烯酸酯、環己 基（甲基）丙烯酸酯、異冰片基（甲基）丙烯酸酯、二環 戊基（甲基）丙烯酸酯、t-丁基環己基（甲基）丙丨希酸酯 、二環戊烯基（甲基）丙烯酸酯、二環戊烯氧基乙基（甲 -46- 201041964 基）丙烯酸酯、四氫糠基（甲基）丙烯酸酯、乙烯基吡啶 及（甲基）丙烯醯基嗎啉所成群者。 5 . —種複合導電性高分子組成物的製造方法，其特徵 爲將聚合下述成分（a-Ι )至（a-3 )所得之高分子化合物 (A)、與選自下述式（1)〜（111)之化合物共存於電解 性基質溶劑中，使用氧化劑進行化學氧化聚合者； (a-1)具有磺酸基與聚合性乙烯基之單體 〇 20 〜60mol% (a-2 )具有親水性基與聚合性乙烯基之極性單體 20 〜60mol% (a·3 )具有芳香族基或脂環族基與聚合性乙烯基之 單體 20〜35m。1 % 式（I )〜（III )(In the formula, ^^ to 7 represents a hydrogen atom or an alkyl group having a carbon number of 12 to 12). 2. The composite conductive polymer composition of claim 1 wherein the component (al) having a sulfonic acid group and a polymerizable vinyl group-45-201041964 is selected from sodium styrene sulfonate and benzene. A group of ethylene sulfonic acid, 2-sodium sulfoethyl (meth) acrylate and 2- sulfoethyl (methyl) propylene vinegar. 3. The composite conductive polymer composition according to claim 1 or 2, wherein the polar monomer having a hydrophilic group and a polymerizable vinyl group of the component (a-2) is selected from the group consisting of acrylic acid and methyl group. Acrylic acid, 2-methylacryloxyethyl succinic acid, (anhydrous) maleic acid, 2_diabase ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate vinegar, 4 hydroxy butyl (meth) acrylate, 2-ethyl acetonitrile ethyl (meth) acrylate, methoxy ethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxy B (meth) acrylate, ethyl carbitol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate and β- A group of (methyl) acryloxyethyl hydrosuccinate. 4. The composite conductive polymer composition according to any one of claims 1 to 3, wherein the component (a-3) has an aromatic group or an alicyclic group and a polymerizable vinyl group The body is selected from the group consisting of benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-(meth) propylene methoxy ethoxy phthalate, 2- (meth) propylene hydride Oxyethylhexahydrophthalic acid, neopentyl glycol (meth)acrylic acid benzoate, 2-hydroxy-3-phenoxypropyl (meth)acrylate 'hydroxyethylated oxime-phenol (A Base) acrylate, fluorene-phenylphenol epoxypropyl ether (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentyl (meth) acrylate Ester, t-butylcyclohexyl (methyl) propionate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (methyl-46-201041964) acrylate, four A group of hydroquinone (meth) acrylate, vinyl pyridine, and (meth) propylene morpholine. A method for producing a composite conductive polymer composition, which comprises polymerizing the polymer compound (A) obtained by polymerizing the following components (a-Ι) to (a-3) and a compound selected from the following formula ( 1) The compound of (111) coexists in an electrolytic matrix solvent and is chemically oxidized by an oxidizing agent; (a-1) a monomer having a sulfonic acid group and a polymerizable vinyl group 〇20 to 60 mol% (a-2) The polar monomer having a hydrophilic group and a polymerizable vinyl group is 20 to 60 mol% (a·3) and has a monomer having an aromatic group or an alicyclic group and a polymerizable vinyl group of 20 to 35 m. 1 % of formula (I ) ~ (III ) (I) (II) (m) (各式中’1^至7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 -47- 201041964 的製造方法，其中成分（a-l)之具有磺酸基與聚合性乙 烯基之單體爲選自苯乙烯磺酸鈉、苯乙烯磺酸、2-鈉磺基 乙基（甲基）丙烯酸酯及2 -磺基乙基（甲基）丙烯酸酯所 成群者。 7 如申請專利範圍第5項或第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 )之具有親水性基 與聚合性乙烯基之極性單體爲選自丙烯酸、甲基丙烯酸、 2_甲基丙烯醯氧基乙基琥珀酸、（無水）馬來酸、2-羥基 乙基（甲基）丙烯酸酯、2-羥基丙基（甲基）丙烯酸酯、 4-羥基丁基（甲基）丙烯酸酯、2-乙醯乙酸乙基（甲基） 丙烯酸酯、甲氧基乙基（甲基）丙烯酸酯、乙氧基乙基（ 甲基）丙烯酸酯、丁氧基乙基（甲基）丙烯酸酯、乙基卡 必醇（甲基）丙烯酸酯、甲氧基三乙二醇（甲基）丙烯酸 酯、甲氧基聚乙二醇（甲基）丙烯酸酯及β-(甲基）丙烯 醯氧基乙基氫琥珀酸酯所成群者。 8 ·如申請專利範圍第5項至第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 )之具有 芳香族基或脂環族基與聚合性乙烯基之單體（甲基）丙稀 酸單體爲選自苯甲基（甲基）丙烯酸酯、苯氧基乙基（甲 基）丙烯酸酯、2-(甲基）丙烯醯氧基乙基苯二甲酸、2_ (甲基）丙烯醯氧基乙基六氫苯二甲酸、新戊二醇（甲基 )丙烯酸安息香酸酯、2 -羥基-3-苯氧基丙基（甲基）丙烯 酸酯、羥基乙基化〇 -酚（甲基）丙烯酸酯、〇 -苯基酚環氧 丙基醚（甲基）丙烯酸酯、環己基（甲基）丙烯酸酯、異 -48- 201041964 冰片基（甲基）丙烯酸酯、二環戊基（甲基）丙烯酸酯、 t-丁基環己基（甲基）丙烯酸酯、二環戊烯基（甲基）丙 烯酸酯、二環戊烯氧基乙基（甲基）丙烯酸酯、四氫糠基 (甲基）丙烯酸酯、乙烯基吡啶及（甲基）丙烯醯基嗎啉 所成群者。 9 ·如申請專利範圍第5項至第8項中任一項之複合導 電性高分子組成物的製造方法，其中對於選自式（I )〜 〇 ( 111 )的化合物1莫耳而言，將高分子化合物（A )以該 磺酸基莫耳比成爲0.2〜1.5下使其共存。 1 0 .如申請專利範圍第5項至第9項中任一項之複合 導電性高分子組成物的製造方法，其中氧化劑爲選自過氧 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（III)、六氟燐酸鐵（III )、硫酸銅（Π )、氯化銅（11 )、四氟硼酸銅（11 )、 六氟燐酸銅（11 )及一氧二硫酸銨所成群之氧化劑。 〇 1 1 如申請專利範圍第5項至第1 0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。 1 2 ·如申請專利範圍第5項至第U項中任一項之複合 導電性高分子組成物的製造方法，其中化學氧化聚合係對 於lmol之選自式（I)〜（III)的化合物而言，加入0.5 〜3. Omol的選自鹽酸、硫酸、過氯酸、過碘酸、氯化鐵（ Π )及硫化鐵（II )的酸性成分而進行。 1 3 · —種複合導電性高分子組成物溶液，其特徵爲將 -49- 201041964 如申專利範圍第丨項至第4項中任一項之複合導電性高 分子組成物於醇系溶劑或酮系溶劑中，以〇 . i〜i 〇質量％ 的溶解狀態下含有而成。 1 4 .如申請專利範圍第丨3項之複合導電性高分子組成 物溶液’其中進一步含有金屬、氧化金屬、導電性聚合物 組成物、碳粉末或分散體。 15.—種色素增感型太陽電池用對極，其特徵爲使用 如申請專利範圍第1項至第4項中任一項之複合導電性高 分子組成物所成者。 1 6. —種防帶電薄膜’其特徵爲使用如申請專利範圍 第1項至第4項中任一項之複合導電性高分子組成物所成 者。 -50 - 201041964 四、指定代表圖： (一） 、本案指定代表圖為：無 (二） 、本代表圖之元件代表符號簡單說明：無(I) (II) (m) (wherein '1^ to 7 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms). 6. The method for producing a composite conductive polymer composition of the invention of claim 5, wherein the monomer having a sulfonic acid group and a polymerizable vinyl group as the component (al) is selected from the group consisting of styrenesulfonic acid A group of sodium, styrenesulfonic acid, 2-sodium sulfoethyl (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 polar monomer having a hydrophilic group and a polymerizable vinyl group of the component (a-2) is selected from the group consisting of acrylic acid, Methacrylic acid, 2-methacryloxyethyl succinic acid, (anhydrous) maleic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, 2-ethyl acetoxyethyl (meth) acrylate, methoxy ethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxy Ethyl (meth) acrylate, ethyl carbitol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate and A group of β-(meth)acrylomethoxyethyl hydrosuccinates. The method for producing a composite conductive polymer composition according to any one of claims 5 to 7, wherein the component (a-3) has an aromatic group or an alicyclic group and a polymerizable ethylene. The monomeric (meth)acrylic acid monomer is selected from the group consisting of benzyl (meth) acrylate, phenoxy ethyl (meth) acrylate, 2-(methyl) propylene methoxyethyl Phthalic acid, 2-(meth)acryloxyethyl hexahydrophthalic acid, neopentyl glycol (meth)acrylic acid benzoate, 2-hydroxy-3-phenoxypropyl (meth)acrylic acid Ester, hydroxyethylated oxime-phenol (meth) acrylate, fluorene-phenylphenol epoxidized propyl ether (meth) acrylate, cyclohexyl (meth) acrylate, iso-48-201041964 borneol base ( Methyl) acrylate, dicyclopentyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl a group of (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, vinyl pyridine, and (meth) propylene hydrazinomorphThe method for producing a composite conductive polymer composition according to any one of claims 5 to 8, wherein, for the compound 1 selected from the group consisting of the formula (I) to the oxime (111), The polymer compound (A) was allowed to coexist with the sulfonic acid molar ratio of 0.2 to 1.5. 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 peroxydialdehyde Sodium sulfate, iron (III) chloride, iron (III) sulfate, iron (III) tetrafluoroborate, iron (III) hexafluoroantimonate, copper (Π) sulfate, copper (11) chloride, copper tetrafluoroborate ( 11), an oxidant of a group of copper hexafluoroantimonate (11) and ammonium monooxydisulfate. 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. The method for producing a composite conductive polymer composition according to any one of claims 5 to 5, wherein the chemical oxidative polymerization is for 1 mol of a compound selected from the group consisting of the formulae (I) to (III) In addition, 0.5 to 3. Omol of an acidic component selected from the group consisting of hydrochloric acid, sulfuric acid, perchloric acid, periodic acid, iron chloride (ruthenium), and iron sulfide (II) is added. And a composite conductive polymer composition according to any one of the above-mentioned claims, in the alcohol-based solvent or In the ketone solvent, it is contained in a dissolved state of 〇. i~i 〇 mass%. The composite conductive polymer composition solution of claim 3, further comprising a metal, a metal oxide, a conductive polymer composition, a carbon powder or a dispersion. 15. A counter electrode for a dye-sensitized solar cell, which is characterized by using a composite conductive high molecular composition according to any one of claims 1 to 4. A 6. The antistatic film is characterized in that the composite conductive polymer composition according to any one of claims 1 to 4 is used. -50 - 201041964 IV. Designated representative map: (1) The designated representative figure of this case is: None (2), the representative symbol of the representative figure is simple: No 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5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none
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