TW200951993A - Dispersion of conducting composition, conducting composition and use thereof - Google Patents
Dispersion of conducting composition, conducting composition and use thereof Download PDFInfo
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- TW200951993A TW200951993A TW098112959A TW98112959A TW200951993A TW 200951993 A TW200951993 A TW 200951993A TW 098112959 A TW098112959 A TW 098112959A TW 98112959 A TW98112959 A TW 98112959A TW 200951993 A TW200951993 A TW 200951993A
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- 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
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
Abstract
Description
200951993 六、發明說明： 【發明所屬之技術領域】 本發明係關於導電性組成物之分散液、將前述導電性 組成物之分散液進行乾燥所得到之導電性組成物、將前述 導電性組成物當做導電體使用之防靜電膜及防靜電片、以 及將前述導電性組成物當做固體電解質使用之固體電解電 容器。 【先前技術】 ❹ 導電性高分子，藉由其高導電性，而被當做例如鉬固 體電解電容器、鈮固體電解電容器、鋁固體電解電容器等 之固體電解電容器的固體電解質來使用。 其次，該用途之導電性高分子，係使用例如使噻吩或 其衍生物等之聚合性單體進行氧化聚合而合成者。 上述噻吩或其衍生物等之聚合性單體之氧化聚合，尤 其是’進行化學氧化聚合時之摻雜劑，主要係使用有機磺 〇 酸，其中’又以芳香族磺酸較適合，氧化劑係使用過渡金 屬’其中，又以三價鐵較適合，通常，芳香族磺酸之三價 鐵鹽被當做噻吩或其衍生物等之聚合性單體之化學氧化聚 合時之氧化劑兼摻雜劑來使用。 其次’有報告指出，芳香族磺酸之三價鐵鹽當中，又 以甲苯磺酸三價鐵鹽及甲氧苯磺酸三價鐵鹽等最爲有用， 利用上述之導電性高分子的合成，可將該等氧化劑兼摻雜 劑與噻吩或其衍生物等聚合性單體進行混合來進行，簡單 的適合工業化（專利文獻1、專利文獻2) -4 - 200951993 , 然而，將甲苯磺酸三價鐵鹽當做氧化劑兼摻雜劑使用 所得到之導電性高分子，對於初期電阻値及耐熱性不具有 可充份滿足之特性，此外，將甲氧苯磺酸三價鐵鹽當做氧 化劑兼摻雜劑使用所得到之導電性高分子，相較於利用甲 苯磺酸三價鐵鹽之導電性高分子，初期電阻値較低，亦具 有優良耐熱性，然而，也無法得到可充份滿足之特性。 因爲甲苯磺酸三價鐵鹽及甲氧苯磺酸三價鐵鹽係固 體，一般，係以溶解於乙醇之狀態來使用，然而，該等溶 M 液於保存期間會發生沈澱。 亦即，使用發生沈澱之甲苯磺酸三價鐵鹽及甲氧苯磺 酸三價鐵鹽的乙醇溶液，均一性會降低，利用所得到之導 電性高分子的固體電解電容器之ESR(等效串聯電阻）會增 加，高溫條件下之信賴性則會降低。 此外，將所得到之導電性高分子當做固體電解電容器 之固體電解質使用時，利用化學氧化聚合法所合成之導電 @ 性高分子，通常，因爲對溶劑不具溶解性，必須在具有由 姐、鈮、鋁等電子管金屬（valve metal)之多孔體所構成之陽 極、及由前述電子管金屬之氧化皮膜所構成之介電質層的 元件上直接形成導電性高分子層。 然而，如上所示，於元件上直接形成導電性高分子層， 會有成爲條件非常困難的作業、缺乏再現性、以及工程管 理非常困難之問題。 有鑑於上述狀況，積極地針對可溶化導電性高分子進 行檢討（專利文獻3)。依據該專利文獻3之報告，混合聚苯 200951993 乙烯磺酸、過硫酸銨、鐵鹽、伸乙二氧嚷吩等使其產生反 應，可得到導電性高分子之分散液。然而’以此方式所得 到之導電性高分子，無法得到充份之高導電性’要當做固 體電解電容器之固體電解質使用的話’必須進一步提高導 電性。 此外，有報告提出將酚磺酸酚醛樹脂摻雜於聚苯胺之 導電性高分子（專利文獻4〜5)。然而，該導電性高分子亦 沒有充份之高導電率，當做固體電解電容器之固體電解質 使用時，必須進一步提高導電性。 此外，亦針對利用電解氧化聚合法之可溶化導電性高 分子進行檢討（專利文獻6〜7)。然而，利用上述等時，必 須取出形成於電極上之不溶性導電性高分子來進行可溶化 之處理，而有不利應用於工業上之問題。 先前技術文獻 專利文獻 專利文獻1:日本特開2003-160647號公報 專利文獻2:日本特開2004-265 927號公報 專利文獻3 :特許第2636968號公報 專利文獻4:特許第3906071號公報 專利文獻5:曰本特開2007-277 5 69號公報 專利文獻6:日本特開平號公報 專利文獻7:日本特開昭62-181328號公報 【發明內容】 有鑑於上述情形，本發明之目的係在提供高導電性且 .200951993 優良耐熱性之導電性組成物，且將上述導電性組成物當做 導電體使用，提供高導電性且優良耐熱性的防靜電膜’此 外，將上述導電組成物當做固體電解質使用’提供ESR較 小、高溫條件下具高信賴性的固體電解電容器。 本發明者們重複進行以解決上述課題爲目的之硏究’ 結果發現，在具有下述一般式（I)所表示之重複單位之酚磺 酸酚醛樹脂、磺化聚酯或聚苯乙烯磺酸的存在下，由將噻 吩或其衍生物混入水中、或水與水互溶性溶劑之混合液所 構成之水性液中進行電解氧化聚合時，幾乎不會黏著於電 極’而以均勻分散於水中或水性液中之狀態得到導電性高 分子分散液’由在該導電性高分子之分散液中含有高沸點 溶劑或具環狀構造之有機酸而成的導電性組成物分散液所 得到之導電性組成物’具有高導電性、及優良耐熱性，並 依據其完成本發明。In the present invention, the present invention relates to a conductive composition of a conductive composition, a conductive composition obtained by drying a dispersion of the conductive composition, and the conductive composition. The antistatic film and the antistatic sheet used as the conductor, and the solid electrolytic capacitor in which the conductive composition is used as a solid electrolyte. [Prior Art] The conductive polymer is used as a solid electrolyte of a solid electrolytic capacitor such as a molybdenum solid electrolytic capacitor, a tantalum solid electrolytic capacitor, or an aluminum solid electrolytic capacitor, because of its high electrical conductivity. Next, the conductive polymer for the purpose is synthesized by, for example, oxidative polymerization of a polymerizable monomer such as thiophene or a derivative thereof. Oxidative polymerization of a polymerizable monomer such as the above thiophene or a derivative thereof, in particular, a dopant used in chemical oxidative polymerization, mainly using an organic sulfonic acid, wherein 'an aromatic sulfonic acid is more suitable, and an oxidizing agent is used. The transition metal is used, and trivalent iron is more suitable. Usually, the trivalent iron salt of the aromatic sulfonic acid is used as an oxidant and a dopant in the chemical oxidation polymerization of a polymerizable monomer such as thiophene or a derivative thereof. use. Secondly, it has been reported that among the trivalent iron salts of aromatic sulfonic acids, trivalent iron salts of toluenesulfonic acid and trivalent iron salts of methoxybenzenesulfonic acid are most useful, and the synthesis of the above conductive polymers is utilized. The oxidant-and-dopant can be mixed with a polymerizable monomer such as thiophene or a derivative thereof, and is easily industrialized (Patent Document 1 and Patent Document 2) -4 - 200951993, however, toluenesulfonic acid The conductive polymer obtained by using the trivalent iron salt as an oxidizing agent and a dopant does not have sufficient characteristics for initial resistance enthalpy and heat resistance, and further, ternary iron oxybenzenesulfonate is used as an oxidizing agent. The conductive polymer obtained by using the conductive polymer has a lower initial resistance and lower heat resistance than the conductive polymer using a trivalent iron salt of toluenesulfonic acid. However, it cannot be satisfactorily satisfied. Characteristics. The trivalent iron salt of toluenesulfonic acid and the trivalent iron salt of methoxybenzenesulfonic acid are generally used in a state of being dissolved in ethanol. However, these molten liquids precipitate during storage. That is, the homogeneity is lowered by using the ethanol solution of the precipitated toluenesulfonic acid trivalent iron salt and the methoxybenzenesulfonic acid trivalent iron salt, and the ESR of the solid electrolytic capacitor obtained by using the obtained conductive polymer (equivalent The series resistance) increases, and the reliability under high temperature conditions decreases. In addition, when the obtained conductive polymer is used as a solid electrolyte of a solid electrolytic capacitor, a conductive@-polymer which is synthesized by a chemical oxidative polymerization method is usually used because it has no solubility in a solvent. A conductive polymer layer is directly formed on the anode formed of the porous body of the valve metal such as aluminum and the element of the dielectric layer composed of the oxide film of the valve metal. However, as described above, the formation of the conductive polymer layer directly on the element has a problem that it is extremely difficult to perform the work, the lack of reproducibility, and the engineering management is extremely difficult. In view of the above, the soluble conductive polymer has been actively reviewed (Patent Document 3). According to the report of Patent Document 3, a polyphenylene 200951993 ethylene sulfonic acid, ammonium persulfate, iron salt, ethylene dioxin or the like is reacted to cause a reaction, and a dispersion of a conductive polymer can be obtained. However, the conductive polymer obtained in this manner cannot obtain sufficient high conductivity. If it is used as a solid electrolyte of a solid electrolytic capacitor, it is necessary to further improve the electrical conductivity. Further, there has been reported a conductive polymer in which a phenolsulfonic acid phenol resin is doped with polyaniline (Patent Documents 4 to 5). However, the conductive polymer does not have a sufficiently high electrical conductivity, and when it is used as a solid electrolyte of a solid electrolytic capacitor, it is necessary to further improve conductivity. In addition, it is also reviewed for solubilized conductive high molecular weights by electrolytic oxidation polymerization (Patent Documents 6 to 7). However, when the above-mentioned or the like is used, it is necessary to take out the insoluble conductive polymer formed on the electrode and perform the solubilization treatment, which is disadvantageously applied to industrial problems. CITATION LIST Patent Literature Patent Literature 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. 62-181328. Providing a conductive composition having high conductivity and excellent heat resistance of .200951993, and using the above conductive composition as a conductor to provide an antistatic film having high conductivity and excellent heat resistance. Further, the above conductive composition is regarded as a solid. The electrolyte is used to provide a solid electrolytic capacitor with low ESR and high reliability under high temperature conditions. The present inventors have repeatedly conducted research to solve the above problems. As a result, it has been found that a phenolsulfonic acid phenol resin, a sulfonated polyester or a polystyrenesulfonic acid having the repeating unit represented by the following general formula (I) When it is subjected to electrolytic oxidative polymerization in an aqueous liquid composed of a mixture of thiophene or a derivative thereof in water or a water-miscible solvent, it hardly adheres to the electrode and is uniformly dispersed in water or In the state of the aqueous liquid, the conductivity of the conductive polymer dispersion liquid is obtained by the conductive composition dispersion liquid containing a high boiling point solvent or an organic acid having a cyclic structure in the dispersion liquid of the conductive polymer. The composition 'has high conductivity, and excellent heat resistance, and the present invention has been completed in accordance with the same.
(式中之R係氫或甲基） 亦即，本發明係關於— 特徵爲在具有上述一般式Π 醛樹脂、磺化聚酯、 將噻吩或其衍生物混入水中、 關於一種導電性組成物之分散液，其 & $ 表示之重複單位之酚磺酸酚 &聚本乙燦磺酸之存在下，含有藉由 A 7jc中 '或水與水互溶性溶劑之混合 200951993 液所構成之水性液進行電解氧化聚合而得到之導電性高分 子’及高沸點溶劑或具有環狀構造之有機酸。 此外’本發明係與藉由將前述導電性組成物之分散液 乾燥而得到之導電性組成物，將前述導電性組成物當做導 電體使用之防靜電膜及防靜電片，以及將前述導電性組成 物當做固體電解質使用之固體電解電容器相關。 本發明之導電性組成物爲高透明性、高導電性、且耐 熱性優良。又，本發明之導電性組成物爲高透明性，且由 Ο 於其導電性高分子係利用電解氧化聚合所合成者，利用化 學氧化聚合所合成之導電性高分子會出現之氧化劑所導致 的硫酸根含有量較少，故殘留硫酸根所導致之導電性降低 及透明性降低等也較少。 所以，依據如上所示之本發明之導電性組成物的特 性，藉由將其當做導電體使用，可以得到高透明性、高導 電性且耐熱性優良之防靜電膜、防靜電樹脂、以及防靜電 Q 片等。此外，藉由將此種高導電性且耐熱性優良之本發明 的導電性組成物當做固體電解質使用，可以得到ESR較 小、且在高溫條件下信賴性高的固體電解電容器。 【實施方式】 於本發明中，在導電性高分子的合成時，係使用具有 一般式（I)所表示之重複單位的酚磺酸酚醛樹脂、磺化聚酯 或聚苯乙烯磺酸，其係於導電性高分子之合成時具有優良 分散劑之機能，使作爲聚合性單體之噻吩或其衍生物、及 對應需要所添加之觸媒等均勻分散於水中或水性液中，且 200951993 於合成聚合物中添加摻雜劑，使導電性高分子成爲具有高 導電性之物。其次，上述摻雜劑具有優良分散劑之機能， 係可以合成高透明性、高導電性且耐熱性優良之導電性高 分子的重要原因。 上述一般式（I)所表示之酚磺酸酚醛樹脂，其數量平均 分子量以5,000〜500,000爲佳。其係基於以下之理由。 亦即，上述酚磺酸酚醛樹脂之數量平均分子量數小於 5,000時，所得到之導電性高分子的導電性變低，此外，透 明性亦恐怕變差。此外，上述酚磺酸酚醛樹脂之數量平均 分子量數大於500,000時，導電性組成物之分散液之黏度 變高，恐怕難以使用於固體電解電容器等之製作。其次， 此酚磺酸酚醛樹脂，其數量平均分子量位於上述範圍內 時，較佳爲10,0 00以上者，此外，較佳爲400,00 0以下者， 更佳爲80,000以下者。 此外，上述磺化聚酯係使磺基異酞酸、磺基對苯二甲 酸等之二羧基苯磺酸或磺基異酞酸酯、磺基對苯二甲酸酯 等之二羧基苯磺酸二酯、及伸烷二醇之混合物在氧化銻或 氧化鋅等之觸媒之存在下進行縮聚合者，或使上述二羧基 苯磺酸或二羧基苯磺酸二酯 '與伸烷二醇、及對苯二甲酸 或對苯二甲酸二甲酯之混合物在氧化銻或氧化鋅等之觸媒 之存在下進行縮聚合者’該磺化聚酯’其數量平均分子量 以5,000〜300,000者爲佳。 亦即，上述磺化聚酯之數量平均分子量小於5，000時’ 所得到之導電性高分子的導電性變低’透明性亦恐怕變 200951993 差。此外，上述磺化聚酯之平均分子量數大於3 00,000時， 導電性組成物之分散液的黏度變高，恐怕難以使用於固體 電解電容器等之製作。其次，此種磺化聚酯，其平均分子 量數在上述範圍內，較佳爲10,000以上者，更佳爲20,000 以上者，此外較佳爲1 00,000以下者，更佳爲80,000以下 者。 此外，聚苯乙烯磺酸，以數量平均分子量爲10，0 00〜 1,000,000 者爲佳。 亦即，上述聚苯乙烯磺酸之數量平均分子量小於 10,000時，所得到之導電性髙分子的導電性變低，此外， 透明性亦恐怕變差。此外，上述聚苯乙烯磺酸之平均分子 量數大於1，000,000時，導電性組成物之分散液的黏度變 高，恐怕難以使用於固體電解電容器之製作。其次，上述 聚苯乙烯磺酸，其數量平均分子量在上述範圍內，較佳爲 20,000以上者，更佳爲40,000以上者，此外較佳爲800,000 以下者，更佳爲300,000以下者。 本發明之分散液中，含有高沸點溶劑或具有環狀構造 之有機酸，像這樣含有高沸點溶劑係爲了可以提高所得到 之導電性組成物的製膜性，藉此提高導電性。像這樣藉由 含有高沸點溶劑而提高導電性高分子之導電性的理由，目 前並不明確，然而，認爲係例如將導電性組成物之分散液 塗布於基材並進行乾燥時，隨著高沸點溶劑的脫離而提高 厚度方向之層密度，藉此，導電性高分子間之面間隔變窄， 而提高了導電性高分子的導電性。 -10- • 200951993 上述高沸點溶劑，以沸點爲15CTC以上者爲佳，此種高 沸點溶劑之具體實例，例如，二甲亞碾（沸點189°C )、r -丁內酯（沸點204t )、環丁碾（沸點285 °C )、Ν·甲基吡咯啶（沸 點202°C )、二甲硒（沸點233 °C )、乙二醇（沸點198〇c )、二 乙二醇（沸點244°C )等，尤其是，以二甲亞碾爲佳。其次， 該高沸點溶劑之含有量，相對於分散液中之導電性高分 子，質量基準以5〜3,000%(亦即，相對於1〇〇質量份之導 電性高分子，高沸點溶劑爲5〜3,000質量份）爲佳，尤其 ® 是，20〜700%更佳。高沸點溶劑之含有量少於上述時，導 電性組成物之製膜性降低，結果，恐怕導致提高導電性組 成物之導電性的作用降低，高沸點溶劑之含有量較上述多 時，分散液之乾燥需要較多時間，此外，可能反而導致導 電性的降低。 此外’本發明之分散液亦可含有具有環狀構造之有機 酸來取代上述高沸點溶劑，像這樣含有有機酸係爲了可提 φ 高所得到之導電性組成物的製膜性，藉此提髙導電性。藉 由含有此種具有環狀構造之有機酸，可提高導電性高分子 之導電性的理由，目前尙不明確，認爲係例如將導電性組 成物之分散液塗布於基材並進行乾燥時，具有環狀構造之 有機酸進入導電性高分子之層間，而容易發生導電性高分 子之層間之電洞的輸送的緣故。 上述具有環狀構造之有機酸，例如，酞酸、酞醛酸、 羧基酚、羧基甲酚、羧基萘、二羧基萘、噻吩磺酸、甲苯 磺酸、酚磺酸、甲酚磺酸'萘磺酸、萘二磺酸，萘三磺酸、 -11- 200951993 蒽醌磺酸、蒽醌二磺酸等，尤其是，以酚磺酸、萘磺酸、 蒽醌磺酸等之芳香族系有機酸爲佳。其次，具有該環狀構 造之有機酸的含有量，相對於分散液中之導電性高分子， 質量基準以5〜500 % (亦即，相對於100質量份之導電性高 分子，具有環狀構造之有機酸爲5〜500質量份）爲佳，特 佳爲20〜150%。具有環狀構造之有機酸的含有量少於上述 時，導電性組成物之製膜性降低，結果恐怕導致提高導電 性組成物之導電性的作用降低，具有環狀構造之有機酸的 β 含有量多於上述時，因爲雜質之作用，導電性組成物之製 膜性降低，此外，恐怕導致導電性的降低。 又，因爲分散液中之導電性高分子的含有量會對使導 電性組成物之分散液乾燥而形成膜狀等時之作業性等產生 影響’故通常以1〜10質量％程度爲佳。換言之，導電性高 分子之含有量少於上述時，乾燥需要較多時間，此外，導 電性高分子之含有量多於上述時，黏度變高，而恐怕降低 Ρ 塗布時等之作業性。 將含有導電性高分子及高沸點溶劑之分散液進行乾燥 所得到的乾燥物’因爲係認爲以導電性高分子作爲主要成 份而曰有若干高沸點溶劑，故本說明書中，係將導電性組 成物之分散液進行乾燥所得到者以導電性組成物來表現。 只是，因爲高沸點溶劑也是溶劑，以進一步之高溫進行乾 燥的話，可能全部都會蒸發，在本發明中，使含有導電性 高分子及高沸點溶劑之導電性組成物進行乾燥而得到之乾 燥物’例如’即使其中幾乎未含有高沸點溶劑帛，亦以導 -12- 200951993 電性組成物來表現。此外，含有具有環狀構造之有機酸來 取代高沸點溶劑時，因爲具有上述環狀構造之有機酸於通 常之乾燥不會蒸發，使含有導電性高分子及具有環狀構造 之有機酸的分散液進行乾燥所得到之乾燥物，通常爲含有 導電性高分子及具有環狀構造之有機酸的導電性組成物。 此外，本發明之導電性高分子之分散液，亦可同時含有高 沸點溶劑及具有環狀構造之有機酸。 本發明時，藉由使導電性高分子進行電解氧化聚合之 Ο 合成的聚合性單體係使用噻吩或其衍生物，然而，該噻吩 或其衍生物之噻吩衍生物，例如，3,4-伸乙二氧噻吩、3-烷基噻吩、3-烷氧基噻吩、3-烷基-4-烷氧基噻吩，3，4-烷基 噻吩、3，4-烷氧基噻吩等，其烷基及烷氧基之碳數較佳爲1 〜16，更佳爲1〜4，總之，以碳數爲2之3,4-伸乙二氧唾 吩爲佳。 導電性高分子之合成時之電解氧化聚合，因爲做爲摻 ϋ 雜劑之具有以一般式（I)表示之重複單位的酚磺酸酚醛樹 脂、磺化聚酯、聚苯乙烯磺酸（以下，也以「摻雜劑」之用 詞來進行說明）之任一者，皆對由水或水與水互溶性溶劑之 混合物所構成之水性液具有溶解性，故係於水中或水性液 中進行。 構成上述水性液之水互溶性溶劑，例如，甲醇、乙醇、 丙醇、丙酮、乙腈等，該等水互溶性溶劑之水的混合比例， 應爲水性液整體中之50質量％以下。 上述電解氧化聚合時之摻雜劑及聚合性單體的使用 -13- 200951993 量，並無特別限制’然而’例如’以摻雜劑爲具 式（I)表示之重複單位之酚磺酸酚醛樹脂、聚合性 噻吩之衍生物3,心伸乙二氧噻吩時爲例來進行說 等之使用比率，以質量比而言’較佳爲酚磺酸酚(In the formula, R is hydrogen or methyl). In other words, the present invention relates to a method characterized by having the above-mentioned general formula furfural resin, sulfonated polyester, thiophene or a derivative thereof mixed in water, and a conductive composition. a dispersion comprising a mixture of phenolic phenolic phenolic phenolic sulfonic acid & PEG in the presence of a repeating unit of & $, comprising a mixture of water and water-miscible solvent 200951993 in A 7jc The conductive polymer obtained by electrolytic oxidation polymerization of the aqueous liquid and a high boiling point solvent or an organic acid having a cyclic structure. Further, the present invention relates to an electroconductive composition obtained by drying a dispersion of the electroconductive composition, an antistatic film and an antistatic sheet using the conductive composition as a conductor, and the electroconductive property. The composition is related to a solid electrolytic capacitor used as a solid electrolyte. The conductive composition of the present invention is highly transparent, highly conductive, and excellent in heat resistance. Further, the conductive composition of the present invention is highly transparent, and is formed by an oxidizing agent which is formed by electroless oxidative polymerization of a conductive polymer which is synthesized by electrolytic oxidative polymerization. Since the sulfate content is small, the conductivity due to residual sulfate is lowered and the transparency is lowered. Therefore, according to the characteristics of the conductive composition of the present invention as described above, by using it as a conductor, an antistatic film, an antistatic resin, and an antistatic film having high transparency, high conductivity, and excellent heat resistance can be obtained. Static Q sheets, etc. Further, by using such a conductive composition of the present invention which is excellent in electrical conductivity and heat resistance as a solid electrolyte, a solid electrolytic capacitor having a small ESR and high reliability under high temperature conditions can be obtained. [Embodiment] In the present invention, in the synthesis of a conductive polymer, a phenolsulfonic acid phenol resin, a sulfonated polyester or a polystyrenesulfonic acid having a repeating unit represented by the general formula (I) is used. It is a function of an excellent dispersing agent in the synthesis of a conductive polymer, and thiophene or a derivative thereof as a polymerizable monomer, and a catalyst to be added as needed, are uniformly dispersed in water or an aqueous liquid, and 200951993 A dopant is added to the synthetic polymer to make the conductive polymer highly conductive. Further, the above dopant has an excellent function as a dispersant, and is an important factor for synthesizing a highly conductive polymer having high transparency, high conductivity, and excellent heat resistance. The phenolsulfonic acid phenol resin represented by the above general formula (I) preferably has a number average molecular weight of 5,000 to 500,000. It is based on the following reasons. In other words, when the number average molecular weight of the phenolsulfonic acid phenol resin is less than 5,000, the conductivity of the obtained conductive polymer is lowered, and the transparency is likely to be deteriorated. Further, when the number average molecular weight of the phenolsulfonic acid phenol resin is more than 500,000, the viscosity of the dispersion of the conductive composition becomes high, which may be difficult to use for production of a solid electrolytic capacitor or the like. When the number average molecular weight of the phenolsulfonic acid phenol resin is in the above range, it is preferably 10,000 or more, and more preferably 400,000 or less, more preferably 80,000 or less. Further, the sulfonated polyester is a dicarboxybenzenesulfonic acid such as sulfoisophthalic acid or sulfoisophthalic acid such as dicarboxybenzenesulfonic acid or sulfoisophthalic acid ester or sulfophthalic acid ester. a mixture of an acid diester and an alkylene glycol in a polycondensation in the presence of a catalyst such as cerium oxide or zinc oxide, or a dicarboxy sulfonic acid or a dicarboxy benzene sulfonic acid diester a mixture of an alcohol and a terephthalic acid or a dimethyl terephthalate in the presence of a catalyst such as cerium oxide or zinc oxide. The sulfonated polyester has a number average molecular weight of 5,000 to 300,000. It is better. That is, when the number average molecular weight of the sulfonated polyester is less than 5,000, the conductivity of the obtained conductive polymer becomes low, and the transparency may be deteriorated in 200951993. Further, when the average molecular weight of the sulfonated polyester is more than 30,000, the viscosity of the dispersion of the conductive composition becomes high, which may be difficult to use in the production of a solid electrolytic capacitor or the like. Next, the sulfonated polyester has an average molecular weight in the above range, preferably 10,000 or more, more preferably 20,000 or more, further preferably 10,000 or less, more preferably 80,000 or less. Further, polystyrenesulfonic acid preferably has a number average molecular weight of from 10,00 to 1,000,000. That is, when the number average molecular weight of the above polystyrenesulfonic acid is less than 10,000, the conductivity of the obtained conductive germanium molecule is lowered, and transparency may be deteriorated. Further, when the average molecular weight of the polystyrenesulfonic acid is more than 1,000,000, the viscosity of the dispersion of the conductive composition becomes high, which may be difficult to use in the production of a solid electrolytic capacitor. Further, the polystyrenesulfonic acid has a number average molecular weight within the above range, preferably 20,000 or more, more preferably 40,000 or more, more preferably 800,000 or less, still more preferably 300,000 or less. The dispersion liquid of the present invention contains a high boiling point solvent or an organic acid having a cyclic structure, and contains a high boiling point solvent as described above in order to improve the film formability of the obtained conductive composition, thereby improving conductivity. The reason why the conductivity of the conductive polymer is improved by containing a high-boiling solvent is not known at this time. However, it is considered that, for example, when a dispersion of the conductive composition is applied to a substrate and dried, When the high-boiling point solvent is detached and the layer density in the thickness direction is increased, the surface interval between the conductive polymers is narrowed, and the conductivity of the conductive polymer is improved. -10- • 200951993 The above high boiling point solvent, preferably having a boiling point of 15 CTC or more, specific examples of such a high boiling point solvent, for example, dimethyl sub-milling (boiling point 189 ° C), r-butyrolactone (boiling point 204 t) , cyclobutyl milling (boiling point 285 ° C), Ν · methyl pyrrolidine (boiling point 202 ° C), dimethyl selenium (boiling point 233 ° C), ethylene glycol (boiling point 198 〇 c), diethylene glycol (boiling point 244 ° C) and the like, in particular, it is preferred to use dimethyl argon. Next, the content of the high-boiling solvent is 5 to 3,000% based on the mass of the conductive polymer in the dispersion (that is, 5 to 5 parts by mass of the conductive polymer, and the high-boiling solvent is 5). ~ 3,000 parts by mass) is preferred, especially ® is, 20 to 700% better. When the content of the high-boiling solvent is less than the above, the film formability of the conductive composition is lowered, and as a result, the effect of improving the conductivity of the conductive composition may be lowered, and when the content of the high-boiling solvent is larger than the above, the dispersion may be used. Drying requires more time and, in addition, may result in a decrease in electrical conductivity. Further, the dispersion liquid of the present invention may contain an organic acid having a cyclic structure instead of the above-mentioned high-boiling solvent, and the organic acid-based film may have a film-forming property of a conductive composition obtained by extracting φ.髙 Conductivity. The reason why the conductivity of the conductive polymer can be improved by including such an organic acid having a cyclic structure is not clear, and it is considered that, for example, when a dispersion of the conductive composition is applied to a substrate and dried. The organic acid having a cyclic structure enters between the layers of the conductive polymer, and the transport of the holes between the layers of the conductive polymer is likely to occur. The above organic acid having a cyclic structure, for example, citric acid, uronic acid, carboxy phenol, carboxy cresol, carboxy naphthalene, dicarboxy naphthalene, thiophene sulfonic acid, toluene sulfonic acid, phenolsulfonic acid, cresol sulfonic acid 'naphthalene Sulfonic acid, naphthalene disulfonic acid, naphthalene trisulfonic acid, -11- 200951993 sulfonic acid, sulfonic acid, etc., especially aromatic phenolsulfonic acid, naphthalenesulfonic acid, sulfonic acid, etc. Organic acids are preferred. In addition, the content of the organic acid having the cyclic structure is 5 to 500% based on the mass of the conductive polymer in the dispersion (that is, it has a ring shape with respect to 100 parts by mass of the conductive polymer). The organic acid of the structure is preferably 5 to 500 parts by mass, and particularly preferably 20 to 150%. When the content of the organic acid having a cyclic structure is less than the above, the film forming property of the conductive composition is lowered, and as a result, the effect of improving the conductivity of the conductive composition is lowered, and the β content of the organic acid having a cyclic structure is contained. When the amount is more than the above, the film forming property of the conductive composition is lowered by the action of impurities, and further, the conductivity may be lowered. In addition, the content of the conductive polymer in the dispersion liquid is generally affected by the workability of the dispersion of the conductive composition to form a film or the like, and is usually about 1 to 10% by mass. In other words, when the content of the conductive polymer is less than the above, it takes a lot of time for drying, and when the content of the conductive polymer is more than the above, the viscosity is high, and the workability such as coating at the time of coating may be lowered. The dried product obtained by drying a dispersion containing a conductive polymer and a high-boiling solvent is considered to have a high-boiling solvent by using a conductive polymer as a main component, and therefore, conductivity is used in the present specification. The dispersion of the composition is dried and expressed as a conductive composition. However, since the high-boiling point solvent is also a solvent and may be evaporated at a higher temperature, it may evaporate. In the present invention, the conductive composition obtained by drying the conductive composition containing the conductive polymer and the high-boiling point solvent is dried. For example, 'even if it contains almost no high-boiling solvent, it is expressed by the conductive composition of -12-200951993. In addition, when an organic acid having a cyclic structure is substituted for a high boiling point solvent, the organic acid having the above-described cyclic structure does not evaporate during normal drying, and the organic polymer containing a conductive polymer and a cyclic structure is dispersed. The dried product obtained by drying the liquid is usually a conductive composition containing a conductive polymer and an organic acid having a cyclic structure. Further, the dispersion of the conductive polymer of the present invention may contain both a high boiling point solvent and an organic acid having a cyclic structure. In the present invention, thiophene or a derivative thereof is used as a polymerizable single system which is synthesized by electrolytic oxidative polymerization of a conductive polymer, however, a thiophene derivative of the thiophene or a derivative thereof, for example, 3,4- Ethylene dioxythiophene, 3-alkylthiophene, 3-alkoxythiophene, 3-alkyl-4-alkoxythiophene, 3,4-alkylthiophene, 3,4-alkoxythiophene, etc. The number of carbon atoms of the alkyl group and the alkoxy group is preferably from 1 to 16, more preferably from 1 to 4, and more preferably, the number of carbon atoms is 2, and 4-ethylenedioxypropene is preferred. Electrolytic oxidative polymerization in the synthesis of a conductive polymer, as a phenolic phenolic phenolic resin having a repeating unit represented by the general formula (I), a sulfonated polyester, or a polystyrenesulfonic acid (hereinafter referred to as an antimony dopant) Any one of the terms "dopant" is used to dissolve in an aqueous liquid composed of water or a mixture of water and water-miscible solvent, so it is in water or aqueous liquid. get on. The water-miscible solvent constituting the aqueous liquid, for example, methanol, ethanol, propanol, acetone, acetonitrile or the like, and the mixing ratio of the water of the water-miscible solvent should be 50% by mass or less based on the entire aqueous liquid. The amount of the dopant and the polymerizable monomer used in the above electrolytic oxidation polymerization is not particularly limited. However, the dopant is a repeating unit of the phenolsulfonic acid phenolic aldehyde represented by the formula (I). The ratio of the resin, the derivative of the polymerizable thiophene 3, and the ethylene dioxythiophene is taken as an example, and the ratio is preferably 'phenol sulfonate phenol by mass ratio.
3.4 -伸乙二氧噻吩=1: 〇·〇5〜1: 5’特佳爲酚磺酸K 3.4 -伸乙二氧噻吩=1: 0·1〜1:丨。其次，摻雜劑 物質、聚合性單體使用其他物質時亦大致相同。 電解氧化聚合，在定電流及定電壓下實施皆 ® 於定電流實施電解氧化聚合時’電流値較佳爲〇· 〜10mA/cm2，更佳爲 〇.2mA/cm2 〜4mA/cm2’ 於定 電解氧化聚合時’電壓較佳爲0.5V〜10V，更佳: 5V。電解氧化聚合時之溫度’較佳爲5 °C〜95 °C 10°C〜30°C。此外，聚合時間較佳爲1小時〜72 佳爲8小時〜24小時。此外’電解氧化聚合時’ 硫酸亞鐵或硫酸鐵當做觸媒。電解氧化聚合在含 ❹ 媒之鐵離子的水中或水性液中實施’可以促進噻 生物之聚合。 以如上所述之方式所得到之導電性高分子’ 合後分散在水中或水性液中之狀態得到’含有當 用之硫酸鐵鹽及其分解物等。此時’應以將含有 電性高分子的分散液裝設至超音波均質器或行星 (planet ball mill)等之分散機使雜質分散後，再以 換樹脂除去金屬成份。此時之導電性高分子之粒 100/im以下，更佳爲l〇#m以下。其後，利用乙程 有以一般 單體使用 明時，該 醛樹脂： >醛樹脂： 使用其他 可，例如 0 5 m A/cm2 電壓實施 專1.5V〜 ，更佳爲 小時，更 亦可添加 有該等觸 吩或其衍 可以於聚 做觸媒使 雜質之導 式球磨機 陽離子交 徑較佳爲 寡沈澱法、 -14- 200951993 超過濾法、陰離子交換樹脂等，除去觸媒之分解所生成之 硫酸等，再添加高沸點溶劑或具有環狀構造之有機酸。 本發明之導電性組成物，因爲高導電性、耐熱性優良、 且透明性優良，故適合用作爲防靜電膜、防靜電布、防靜 電樹脂等之防靜電材料的導電體。此外，本發明之導電性 組成物，因爲高導電性且耐熱性優良，故適合使用於包括 鋁固體電解電容器、钽固體電解電容器、鈮固體電解電容 器等之固體電解電容器的固體電解質，而可提供低ESR、 且在髙溫條件下之信賴性高的固體電解電容器。 此外，本發明之導電性組成物，係利用其高導電性且 耐熱性優良之特性，不但可應用於上述固體電解電容器之 固體電解質及防靜電材之導電體以外，尙可適用於電池之 正極活性物質、耐腐蝕用塗料之基材樹脂等。 如上所述，將本發明之導電性組成物當做防靜電材之 導電體或固體電解電容器之固體電解質使用時，雖可以直 接使用，但亦適合使用將導電性組成物分散於水中或水性 液中之分散液，其後，將進行乾燥所得到之導電性組成物 當做導電體或固體電解質來使用。 使用本發明之導電性組成物做爲導電體來製作防靜電 膜時，將前述導電性組成物之分散液塗布於基材片、或將 基材片浸漬於導電性組成物之分散液，取出後，進行乾燥 而形成防靜電膜，再將該膜從基材片剝離即可，然而，當 然也可以不從基材片剝離形成於基材片之一面或兩面之防 靜電膜，而將該基材片當做支持材之防靜電片來使用。此 -15- 200951993 外，使用本發明之導電性組成物做爲導電體來製作防靜電 布時，將前述導電性組成物之分散液塗布於布、或將布浸 漬於導電性組成物之分散液，取出後，進行乾燥即可。其 次，如上所述，製作防靜電片及防靜電布時，應先於上述 導電性組成物之分散液添加黏結樹脂，可提高導電性組成 物對基材片或布的黏著性。如上所示，先於導電性組成物 之分散液添加黏結劑，將導電性組成物當做固體電解電容 器之固體電解質使用時亦相同。 上述之黏結樹脂，例如，聚胺酯、聚酯、丙烯酸樹脂、 聚醯胺'聚醯亞胺'環氧樹脂、聚丙烯腈樹脂、聚甲基丙 烯腈樹脂、聚苯乙烯樹脂、酚醛樹脂、矽烷偶合劑等，特 佳爲聚酯、聚胺酯、丙烯酸樹脂等。此外，如磺化聚丙烯、 磺化聚乙烯、磺化聚苯乙烯之附加了磺酸基時，可以提高 導電性組成物之導電性而更佳。 其次，將上述黏結樹脂或其他樹脂添加於前述導電性 組成物之分散體並進行乾燥，即可得到防靜電樹脂》此外， 將導電性組成物使用於固體電解電容器時，如以下所示， 可以製作固體電解電容器。 首先，將本發明之導電性組成物當做钽固體電解電容 器、鈮固體電解電容器、鋁積層型固體電解電容器等之固 體電解質使用時，將具有由鉅、鈮、鋁等之管金屬的多孔 體所構成之陽極、由該等管金屬之氧化皮膜所構成之介電 體層的電容器元件，重複進行浸漬於本發明之導電性組成 物的分散液、取出後乾燥之步驟而形成由導電性組成物所 -16- 200951993 構成之固體電解質層後，塗布碳糊、銀糊並進行乾燥後， 再進行包裝，即可製作钽固體電解電容器、鈮固體電解電 容器、鋁積層型固體電解電容器等之固體電解電容器。 此外，例如可以將非鐵鹽系有機磺酸鹽當做摻雜劑使 用，而將前述電容器元件浸漬於含有聚合性單體、氧化劑 之液中並取出後，在室溫下進行聚合，並浸漬於水中並取 出進行洗淨後，再進行乾燥，合成導電性高分子後，進一 步重複進行將整體浸漬於本發明之導電性組成物之分散液3.4 - Ethylene dioxythiophene = 1: 〇·〇 5~1: 5' is preferably phenolsulfonic acid K 3.4 - EDTA = 1: 0·1~1: 丨. Next, the dopant substance and the polymerizable monomer are also substantially the same when other substances are used. Electrolytic oxidation polymerization, at constant current and constant voltage, when performing electrolytic oxidation polymerization at a constant current, the current 値 is preferably 〇·10mA/cm2, more preferably 22mA/cm2 〜4mA/cm2' When the electrolytic oxidation polymerization is carried out, the voltage is preferably 0.5 V to 10 V, more preferably 5 V. The temperature at the time of electrolytic oxidation polymerization is preferably from 5 ° C to 95 ° C and from 10 ° C to 30 ° C. Further, the polymerization time is preferably from 1 hour to 72 times, preferably from 8 hours to 24 hours. In addition, 'electrolytic oxidative polymerization' ferrous sulfate or iron sulphate acts as a catalyst. Electrolytic oxidative polymerization can be carried out in water or aqueous solution containing iron ions of ruthenium to promote the polymerization of thilytes. The conductive polymer obtained as described above is combined and dispersed in water or an aqueous liquid to obtain an iron sulfate salt and a decomposition product thereof. At this time, the dispersion containing the electropolymer is placed in a disperser such as an ultrasonic homogenizer or a planetary ball mill to disperse the impurities, and the metal component is removed by replacing the resin. The particles of the conductive polymer at this time are 100/im or less, more preferably 10 Å or less. Thereafter, the aldehyde resin is used in the case of using a general monomer, and the aldehyde resin: > aldehyde resin: using a voltage of, for example, 0 5 m A/cm 2 , a specific 1.5 V 〜 , more preferably an hour, or The cation exchange path of the guide ball mill to which the phenotype or the derivative thereof can be used as a catalyst to make impurities is preferably an oligoprecipitation method, -14-200951993 ultrafiltration method, an anion exchange resin, etc., to remove the decomposition of the catalyst. The generated sulfuric acid or the like is further added with a high boiling point solvent or an organic acid having a cyclic structure. Since the conductive composition of the present invention is excellent in high conductivity and heat resistance and excellent in transparency, it is suitably used as an electric conductor of an antistatic material such as an antistatic film, an antistatic cloth, or an antistatic resin. Further, since the conductive composition of the present invention is excellent in high conductivity and heat resistance, it is suitably used for a solid electrolyte including a solid electrolytic capacitor such as an aluminum solid electrolytic capacitor, a tantalum solid electrolytic capacitor, or a tantalum solid electrolytic capacitor, and is provided. A solid electrolytic capacitor with low ESR and high reliability under enthalpy conditions. Further, the conductive composition of the present invention is excellent in heat resistance and excellent in heat resistance, and can be applied not only to the solid electrolyte of the solid electrolytic capacitor but also to the conductor of the antistatic material, and can be applied to the positive electrode of the battery. A base material resin of an active material or a coating for corrosion resistance. As described above, when the conductive composition of the present invention is used as a conductor of an antistatic material or a solid electrolyte of a solid electrolytic capacitor, it can be used as it is, but it is also suitable to use a conductive composition in water or an aqueous liquid. After the dispersion, the conductive composition obtained by drying is used as an electric conductor or a solid electrolyte. When the antistatic film is produced by using the conductive composition of the present invention as a conductor, the dispersion of the conductive composition is applied to a substrate sheet, or the substrate sheet is immersed in a dispersion of the conductive composition, and taken out. Thereafter, drying is performed to form an antistatic film, and the film may be peeled off from the substrate sheet. However, of course, the antistatic film formed on one surface or both surfaces of the substrate sheet may not be peeled off from the substrate sheet. The base material sheet is used as an antistatic sheet for a support material. In the case of producing an antistatic cloth using the conductive composition of the present invention as a conductor, the dispersion of the conductive composition is applied to the cloth or the cloth is immersed in the dispersion of the conductive composition. After the liquid is taken out, it can be dried. Then, as described above, when the antistatic sheet and the antistatic cloth are produced, the binder resin is added to the dispersion of the above conductive composition, and the adhesion of the conductive composition to the substrate sheet or the cloth can be improved. As described above, the addition of the binder to the dispersion of the conductive composition is the same as when the conductive composition is used as the solid electrolyte of the solid electrolytic capacitor. The above-mentioned bonding resin, for example, polyurethane, polyester, acrylic resin, polyamidamine 'polyimide' epoxy resin, polyacrylonitrile resin, polymethacrylonitrile resin, polystyrene resin, phenolic resin, decane A mixture or the like is particularly preferably a polyester, a polyurethane, an acrylic resin or the like. Further, when a sulfonic acid group is added to the sulfonated polypropylene, the sulfonated polyethylene or the sulfonated polystyrene, the conductivity of the conductive composition can be improved and it is more preferable. Next, the above-mentioned binder resin or other resin is added to the dispersion of the above-mentioned conductive composition and dried to obtain an antistatic resin. Further, when the conductive composition is used in a solid electrolytic capacitor, as shown below, A solid electrolytic capacitor is fabricated. First, when the conductive composition of the present invention is used as a solid electrolyte such as a tantalum solid electrolytic capacitor, a tantalum solid electrolytic capacitor, or an aluminum laminated solid electrolytic capacitor, a porous body having a tube metal such as giant, bismuth, or aluminum is used. A capacitor element constituting the anode and the dielectric layer formed of the oxide film of the tube metal is repeatedly subjected to a step of immersing in the dispersion of the conductive composition of the present invention, followed by drying, and forming a conductive composition. -16- 200951993 After the solid electrolyte layer is formed, the carbon paste and the silver paste are applied and dried, and then packaged to produce a solid electrolytic capacitor such as a tantalum solid electrolytic capacitor, a tantalum solid electrolytic capacitor, or an aluminum laminated solid electrolytic capacitor. . Further, for example, a non-iron salt-based organic sulfonate can be used as a dopant, and the capacitor element can be immersed in a liquid containing a polymerizable monomer or an oxidizing agent and taken out, and then polymerized at room temperature and immersed in After the water is taken out and washed, and then dried to synthesize a conductive polymer, the entire dispersion of the conductive composition of the present invention is further repeated.
A w 中並取出乾燥之步驟，亦可形成由本發明之導電性組成物 所構成之固體電解質層，此外，亦可以爲其相反之形態。 其次’對像這樣爲導電性組成物所覆蓋之元件塗布碳 糊、銀糊後，進行包裝，亦可製作钽固體電解電容器、鈮 固體電解電容器、鋁層積型固體電解電容器等。 此外’將本發明之導電性組成物當做鋁捲繞型固體電 解電容器之固體電解質使用時，對鋁箔表面進行蝕刻處理 Q 後，將導線端子裝設於進行形成處理形成著介電質層之陽 極’此外，將導線端子裝設於由鋁箔所構成之陰極，介由 隔片捲繞附有該等導線端子之陽極及陰極來製作電容器元 件，將該電容器元件浸漬於本發明之導電性組成物之分散 液並取出進行乾燥’乾燥後以除去未因爲鋁箔之蝕刻而形 成細孔之導電性組成物爲目的，浸漬於純水並取出進行乾 燥’重複該等操作後’以包裝材料進行包裝，可製作鋁捲 繞型固體電解電容器。 實施例 -17- 200951993 下面以實施例針對本發明更具體地進行說明，然而本 發明並未受限於該等實施例所例示者。此外，以下之實施 例中表示濃度及使用量時的％，尤其是未附記其基準時，係 依據質量基準之％。 實施例1 將具有以一般式（I)所表示之重複單位之酚磺酸酚醛樹 脂[小西化學工業公司製lotEW00130(商品名稱）、平均分子 量數60,000、R係氫]之4%水溶液600g倒入內容積1L之不 鏽鋼製容器，添加硫酸亞鐵·7水和物0.3g，將3,4-伸乙二 氧噻吩4mL緩慢地滴入其中》以不鏽鋼製之攪拌翼進行攪 拌，將陽極裝設於容器裝設，將陰極裝設於攪拌翼之根部， 以ImA/cm2之定電流實施18小時的電解氧化聚合。上述電 解氧化聚合後，以水稀釋爲6倍後，以超音波均質器[日本 精機公司製、US-T3 00(商品名稱）]進行30分鐘分散處理》 其後，添加100g之0RGAN0公司製之陽離子交換樹脂 AMBERLITE120B(商品名稱），以攪拌機進行攪拌。其次， 東洋濾紙公司製之濾紙No. 1 3 1進行過濾，以該陽離子交換 樹脂進行之處理及過濾重複3次，將液中之鐵離子等陽離 子成份全部除去。此外，上述電解氧化聚合時作爲摻雜劑 之酚磺酸酚醛樹脂與聚合性單體之3,4-伸乙二氧噻吩的比 率，以質量比而言，爲酚磺酸酚醛樹脂：3,4-伸乙二氧噻吩 =1:0.2。 使上述經過處理之液通過孔徑爲l^m之濾網，以超過 爐裝置[SARTORIUS公司製Vivaflow200(商品名稱）、分子 -18 - 200951993 量分離（molecular weight fraction ation)5 萬]處理該通過液， 除去液中遊離之低分子成份。以水稀釋該處理後之液將濃 度調整成3%，對該3%液40g，添加二甲亞碾4g(相對於導 電性高分子，二甲亞碾約3 30%)做爲高沸點溶劑，得到導 電性組成物之分散液。以DI0NEX公司製之ION CHR0MAT0 DX 120(商品名稱）測定該分散液中之硫酸的含有量，硫酸之 含有量爲25ppm。 實施例2 除了於磺化聚酯[互應化學工業公司製 PLASCOA.T 乙-561(商品名稱）、數量平均分子量27,000]之3%水溶液600£ 添加硫酸亞鐵· 7水和物〇.〇5g以外，二甲亞楓之添加等， 進行與實施例1相同之操作，得到導電性組成物之分散 液。對該分散液中之硫酸含有量進行與實施例1相同的測 定，硫酸之含有量爲22ppm。 實施例3 除了使用聚苯乙烯磺酸（TIC A公司製、數量平均分子 量100,000)之4 %水溶液600g以外，二甲亞碾之添加等，進 行與實施例1相同之操作，得到導電性組成物之分散液。 對該分散液中之硫酸含有量進行與實施例1相同的測定， 硫酸之含有量爲26ppm。 實施例4 除了使用具有以一般式（I)表示之重複單位之酚磺酸酚 醛樹脂[小西化學工業公司製lotEG0727(商品名稱）、數量 平均分子量20,000、式中之R係氫]之4%水溶液600g以 -19- 200951993 外，二甲亞砸之添加等，進行與實施例1相同之操作，得 到導電性組成物之分散液。對該分散液中之硫酸含有量進 行與實施例1相同的測定，硫酸之含有量爲27ppm。 實施例5 除了添加作爲具有環狀構造之有機酸的萘擴酸 〇.4g(相對於導電性高分子，萘磺酸3 3%)取代高沸點溶劑之 二甲亞碾以外，進行與實施例3相同之操作，得到導電性 組成物之分散液。對該分散液中之硫酸含有量進行與實施 例1相同的測定，硫酸之含有量爲2 6ppm。 實施例6 除了添加作具有環狀構造之有機酸的惠醒磺酸 〇.5g(枏對於導電性高分子，蒽醌磺酸42%)取代高沸點溶劑 之二甲亞碾以外，進行與實施例3相同之操作，得到導電 性組成物之分散液。對該分散液中之硫酸含有量進行與實 施例1相同的測定，硫酸之含有量爲26ppm » 實施例7 除了以具有環狀構造之有機酸之酣碯酸〇.5g(相對於 導電性高分子，酚磺酸42%)取代髙沸點溶劑之二甲亞砸以 外，進行與實施例3相同之操作，得到導電性組成物之分 散液。對該分散液中之硫酸含有量進行與實施例1相同的 測定，硫酸之含有量爲26ppm。 比較例1 將與實施例1所使用之相同的酚磺酸酚醛樹脂（數量平 均分子量60,000)之4 %水溶液200g倒入內容積il之容器， -20- 200951993 添加過硫酸銨2g後’以攪拌機進行攪拌使其溶解。接著’ 一邊攪拌一邊緩慢滴入3,4-伸乙二氧噻吩3mL，花費24小 時進行3,4-伸乙二氧噻吩之化學氧化聚合。 上述化學氧化聚合後’以水稀釋爲4倍後，利用超音 波均質器[日本精機公司製、US-T300(商品名稱）]進行30分 鐘之分散處理。其後’添加l〇〇g之ORGANO公司製之陽離 子交換樹脂AMBERLITE120B(商品名稱），以攪拌機進行1 小時之攪拌。其次，以東洋濾紙公司製之濾紙No. 1 3 1進行 ® 過濾，重複3次該陽離子交換樹脂之處理及過濾，除去液 中之全部陽離子成份。 使經過上述處理之液通過孔徑爲l^m之濾網，以超過 濾裝置[SARTORIUS公司製Vivaflow200(商品名稱）、分子 量分離5萬]對該通過液進行處理，除去液中之遊離低分子 成份。以水稀釋該處理後之液將濃度調整成3 %，針對該3 % 液40g，添加4g二甲亞楓，得到導電性組成物之分散液》 ❹ 與實施例1相同，進行該分散液中之硫酸含有量的測定， 硫酸之含有量爲123ppm » 比較例2 除了未添加二甲亞颯4g以外，進行與實施例1相同之 操作，得到導電性組成物之分散液。此外，因爲該分散液 未添加高沸點溶劑之二甲亞碾，正確而言，應以導電性高 分子之分散液來表現，然而，該比較例2之分散液，爲了 說明上之方便，配合實施例1〜7及比較例1之導電性組成 物的分散液，以導電性組成物之分散液來表現。其次，對 -21 - 200951993 該分散液中之硫酸含有量進行與實施例1相同的測定 酸之含有量爲22ppm。 [作爲導電性組成物之評估] 將上述實施例1〜7及比較例1〜2之導電性組成 分散液分別在2.8cmx4.8cm之玻璃板上滴下50# L，以 之棒塗布器（barcoater)塗布均句後，以60°C進行10分 乾燥，接著，以15(TC實施10分鐘之乾燥，於玻璃板 成導電性組成物之薄片，該導電性組成物之片的導電 ❹ 在室溫（約25°C)下，依據JISK7194，以4探針方式之 度測定器[三菱化學公司製MCP-T600(商品名稱）]進 定。結果如表1所示。此外，各試料之測定係各針對 進行’表1所示之數値係求取該5點之平均値並將小 以下進行四捨五入者。 ，硫 物之 No.8 鐘之 上形 率， 電導 行測 5點 數點The step of drying is taken out in A w , and the solid electrolyte layer composed of the conductive composition of the present invention may be formed, or may be in the opposite form. Then, a carbon paste or a silver paste is applied to the element covered with the conductive composition, and then packaged, and a solid electrolytic capacitor, a tantalum solid electrolytic capacitor, an aluminum laminated solid electrolytic capacitor, or the like can be produced. Further, when the conductive composition of the present invention is used as a solid electrolyte of an aluminum wound solid electrolytic capacitor, after etching the surface of the aluminum foil Q, the lead terminal is mounted on the anode which is formed to form a dielectric layer. Further, a lead terminal is attached to a cathode made of an aluminum foil, and a capacitor element is formed by winding an anode and a cathode to which the lead terminals are attached via a separator, and the capacitor element is immersed in the conductive composition of the present invention. The dispersion is taken out and dried to remove the conductive composition which is not formed by etching of the aluminum foil, and is immersed in pure water, taken out and dried, and after repeated operations, it is packaged in a packaging material. Aluminum wound solid electrolytic capacitors can be fabricated. EXAMPLES -17-200951993 The present invention will now be described more specifically by way of examples, but the invention is not limited by the examples. Further, in the following examples, the % when the concentration and the amount of use are expressed, especially when the basis is not attached, is based on the mass basis. Example 1 Pour 600 g of a 4% aqueous solution of a phenolsulfonic acid phenolic resin (lot EW00130 (trade name), average molecular weight number 60,000, R-hydrogen], which is a repeating unit represented by the general formula (I). 1L stainless steel container, adding ferrous sulfate·7 water and 0.3g, 3,4-ethylenedioxythiophene 4mL slowly dripping into it. Stirring with stainless steel stirring wing, the anode is installed In the vessel, the cathode was placed at the root of the stirring blade, and electrolytic oxidative polymerization was carried out for 18 hours at a constant current of 1 mA/cm 2 . After the electrolytic oxidative polymerization, the mixture was diluted to 6 times with water, and then subjected to a dispersion treatment for 30 minutes by a sonic homogenizer [manufactured by Nippon Seiki Co., Ltd., US-T3 00 (trade name)]. Thereafter, 100 g of 0RGAN0 company was added. The cation exchange resin AMBERLITE 120B (trade name) was stirred with a stirrer. Next, the filter paper No. 133 manufactured by Toyo Filter Co., Ltd. was filtered, and the cation exchange resin was subjected to treatment and filtration three times to remove all the cation components such as iron ions in the liquid. Further, the ratio of the phenolsulfonic acid phenol resin as the dopant to the 3,4-ethylenedioxythiophene of the polymerizable monomer in the above electrolytic oxidation polymerization is phenolsulfonic acid phenol resin in a mass ratio: 4-Exoethylenedioxythiophene = 1:0.2. The treated liquid was passed through a sieve having a pore size of 1 μm, and the passage liquid was treated in excess of the furnace apparatus [Vivaflow 200 (trade name) manufactured by SARTORIUS Co., Ltd., molecular weight 50,000 - 200951993 molecular weight fractionation 50,000]. , remove the free low molecular components in the liquid. Diluting the treated solution with water to adjust the concentration to 3%, adding 40 g of 3% liquid to 40 g of 3% liquid (relative to conductive polymer, about 30% by weight of dimethyl sulphide) as a high boiling point solvent A dispersion of the conductive composition was obtained. The content of sulfuric acid in the dispersion was measured by ION CHR0MAT0 DX 120 (trade name) manufactured by DI0NEX Co., Ltd., and the sulfuric acid content was 25 ppm. Example 2 In addition to a 3% aqueous solution of sulfonated polyester [Plascoa.T B-561 (trade name), number average molecular weight 27,000] manufactured by Mutual Chemical Industry Co., Ltd., 600 sulphur sulphate sulphate and water sulphate were added. In the same manner as in Example 1, except for the addition of 5 g of dimethyl sulfoxide, a dispersion of the conductive composition was obtained. The sulfuric acid content in the dispersion was measured in the same manner as in Example 1, and the sulfuric acid content was 22 ppm. Example 3 The same procedure as in Example 1 was carried out except that 600 g of a 4% aqueous solution of polystyrenesulfonic acid (manufactured by TIC A, number average molecular weight: 100,000) was used, and the same procedure as in Example 1 was carried out to obtain a conductive composition. Dispersion. The sulfuric acid content in the dispersion was measured in the same manner as in Example 1, and the sulfuric acid content was 26 ppm. Example 4 A 4% aqueous solution of a phenolsulfonic phenolic resin having a repeating unit represented by the general formula (I) [lot EG 0727 (trade name) manufactured by Xiaoxi Chemical Industry Co., Ltd., a number average molecular weight of 20,000, and an R-based hydrogen in the formula] was used. The same operation as in Example 1 was carried out in the same manner as in Example 1 except for the addition of dimethyl hydrazine at 600 g to -19 to 20095, and a dispersion of the conductive composition was obtained. The sulfuric acid content in the dispersion was measured in the same manner as in Example 1, and the sulfuric acid content was 27 ppm. Example 5 In addition to the addition of dimethyl arsenite which is a high boiling point solvent to 4 g of naphthalene sulphate as an organic acid having a cyclic structure (3 3% of a conductive polymer, naphthalenesulfonic acid) 3 In the same operation, a dispersion of the conductive composition was obtained. The sulfuric acid content in the dispersion was measured in the same manner as in Example 1, and the sulfuric acid content was 26 ppm. Example 6 Except for addition of dimethyl sulfite which is added to a high boiling point solvent instead of a high-boiling solvent, which is added as an organic acid having a cyclic structure, 5 g (a conductive polymer, sulfonic acid 42%). In the same manner as in Example 3, a dispersion of the conductive composition was obtained. The sulfuric acid content in the dispersion was measured in the same manner as in Example 1, and the sulfuric acid content was 26 ppm. » Example 7 In addition to the organic acid having a cyclic structure, bismuth ruthenate. 5 g (relative to high conductivity) The same procedure as in Example 3 was carried out except that the molecule, phenolsulfonic acid (42%) was replaced by dimethyl hydrazine in the hydrazine boiling solvent to obtain a dispersion of the conductive composition. The sulfuric acid content in the dispersion was measured in the same manner as in Example 1, and the sulfuric acid content was 26 ppm. Comparative Example 1 200 g of a 4% aqueous solution of the phenolsulfonic acid phenolic resin (number average molecular weight 60,000) used in Example 1 was poured into a container of internal volume il, -20-200951993, after adding 2 g of ammonium persulfate, the mixer was used. Stir and dissolve. Then, while stirring, 3 mL of 3,4-ethylenedioxythiophene was slowly added dropwise, and it took 24 hours to carry out chemical oxidative polymerization of 3,4-ethylenedioxythiophene. After the above chemical oxidative polymerization, the mixture was diluted to 4 times with water, and then subjected to dispersion treatment for 30 minutes using an ultrasonic homogenizer [manufactured by Nippon Seiki Co., Ltd., US-T300 (trade name)]. Thereafter, the AM-ion exchange resin AMBERLITE 120B (trade name) manufactured by ORGANO Co., Ltd. was added and stirred for 1 hour with a stirrer. Next, filtration was carried out by filter paper No. 1 3 1 manufactured by Toyo Filter Co., Ltd., and the cation exchange resin was treated and filtered three times to remove all the cationic components in the liquid. The liquid subjected to the above treatment was passed through a sieve having a pore size of 1 μm, and the passage liquid was treated with an ultrafiltration device [Vivaflow 200 (trade name) manufactured by SARTORIUS Co., Ltd., molecular weight separation of 50,000] to remove free low molecular components in the liquid. . The liquid after the treatment was diluted with water to adjust the concentration to 3%, and 4 g of dimethyl sulfoxide was added to 40 g of the 3% liquid to obtain a dispersion of the conductive composition. ❹ In the same manner as in Example 1, the dispersion was carried out. The content of the sulfuric acid was measured, and the content of the sulfuric acid was 123 ppm. - Comparative Example 2 The same procedure as in Example 1 was carried out except that 4 g of dimethyl hydrazine was not added to obtain a dispersion of the conductive composition. In addition, since the dispersion is not added with a high-boiling solvent, it is represented by a dispersion of a conductive polymer. However, the dispersion of Comparative Example 2 is used for convenience of explanation. The dispersion liquids of the conductive compositions of Examples 1 to 7 and Comparative Example 1 were expressed as a dispersion of a conductive composition. Next, the sulfuric acid content in the dispersion was measured in the same manner as in Example 1 from -21 to 200951993, and the acid content was 22 ppm. [Evaluation as Conductive Composition] The conductive composition dispersion liquids of the above Examples 1 to 7 and Comparative Examples 1 and 2 were each dropped on a glass plate of 2.8 cm x 4.8 cm by 50# L, and the bar coater was used. After coating the average sentence, it was dried at 60 ° C for 10 minutes, and then dried at 15 (TC for 10 minutes to form a sheet of a conductive composition on the glass plate, and the conductive enthalpy of the sheet of the conductive composition was in the chamber. At the temperature (about 25 ° C), according to JIS K7194, a 4-probe method measuring device [MCP-T600 (trade name) manufactured by Mitsubishi Chemical Corporation] was used. The results are shown in Table 1. In addition, the measurement of each sample was carried out. For each of the numbers shown in Table 1, the average 値 of the 5 points is obtained and the following is rounded off. The No. 8 volume of the sulfur is above, and the conductivity is measured by 5 points.
-22- [表1] 導電率（S/cm) 實 施 例1 230 實 施 例2 220 實 施 例3 450 實 施 例4 280 實 施 例5 410 實 施 例6 400 實 施 例7 430 比 較 例1 12 比 較 例2 0.6-22- [Table 1] Conductivity (S/cm) Example 1 230 Example 2 220 Example 3 450 Example 4 280 Example 5 410 Example 6 400 Example 7 430 Comparative Example 1 12 Comparison Example 2 0.6
200951993 Ο 如表1所不，實施例1〜7相較於比較例1〜2，導電 較高’導電性較優良。亦即，以電解氧化聚合法合成導 性高分子之實施例1〜7’相較於以化學氧化聚合法合成 電性高分子之比較例1，導電率較高，導電性較優良， 外’相較於未添加高沸點溶劑或具有環狀構造之有機酸 比較例2，導電率較高，導電性較優良。 其次’針對上述實施例1〜7及比較例1〜2之導電 組成物之各薄片進行導電率之測定後，將各薄片於150。<： 恆溫槽中靜置100小時後取出，對各別的導電率進行與 述相同之測定。結果如表2所示。但是，關於導電率係 在150 °C下靜置100小時後之導電率的保持率表示。 此外，導電率之保持率，係將在l5〇〇c下經過100小 後之導電率除以初期導電率（表1記載之導電率），並以 率 電 導 此 之 性 之 刖 以 時 百 -23- 200951993 分比（％)來表示。以公式來表示的話，則如下所示。保持率 較高之一方，較不易發生相對於熱之導電率的降低，代表 其耐熱性優良。 導電率之保持率(％)= 100小時後之導電率 '~初期導電率 X 1 〇 〇200951993 Ο As shown in Table 1, Examples 1 to 7 have higher conductivity and better conductivity than Comparative Examples 1 and 2. That is, the examples 1 to 7' in which the conductive polymer was synthesized by the electrolytic oxidation polymerization method were compared with the comparative example 1 in which the electrochemical polymer was synthesized by the chemical oxidation polymerization method, and the conductivity was high and the conductivity was excellent. Compared with the organic acid Comparative Example 2 in which no high boiling point solvent or a cyclic structure was added, the electrical conductivity was high and the electrical conductivity was excellent. Next, the respective sheets of the conductive compositions of the above Examples 1 to 7 and Comparative Examples 1 and 2 were subjected to measurement of electrical conductivity, and then each sheet was 150. <: It was taken out after standing for 100 hours in a thermostatic chamber, and the same conductivity was measured for each of the respective electrical conductivity. The results are shown in Table 2. However, the conductivity was expressed as the conductivity retention after standing at 150 ° C for 100 hours. In addition, the conductivity retention rate is obtained by dividing the conductivity after 100 hours at 15 〇〇c by the initial conductivity (the conductivity described in Table 1), and at the rate of conductance. 23- 200951993 The ratio (%) is expressed. If it is expressed by a formula, it is as follows. One of the higher retention ratios is less likely to cause a decrease in electrical conductivity with respect to heat, and it is excellent in heat resistance. Conductivity retention (%) = conductivity after 100 hours '~ initial conductivity X 1 〇 〇
[表2] 導電率之保持率（％) 實施例1 81 實施例2 80 實施例3 83 實施例4 81 實施例5 84 實施例6 85 實施例7 81 比較例1 69 比較例2 70 如表2所示，實施例1〜7相較於比較例1〜2，高溫保 存後之導電率的保持率較高，耐熱性較優良。 [作爲防靜電膜之評估] 實施例8〜12及比較例3〜4 針對前述實施例1〜4、實施例7及比較例1〜2之導電 性組成物之分散液，以相對於導電性高分子，樹脂成份分 別爲約150%之方式，添加磺化聚酯樹脂[互應化學工業公 -24- .200951993 司製PLASCQAT Z-5 6l(商品名稱）]，攪拌後，將該含有磺化 聚酯樹脂之分散液滴 50;/ L於2.8cmx4.8cm之聚乙烯片 上，以No.8之棒塗布器塗布均勻後，以60°C進行10分鐘 之乾燥，接著以150°C實施10分鐘之乾燥，將各導電性組 成物製成導電體之防靜電膜。 所得到之實施例8〜12及比較例3〜4之防靜電膜之表 面電阻，於室溫（約25°C)下，依據J1SK7194，以4探針方 式之電導度測定器[三菱化學公司製MCP-T600(商品名稱）] © 進行測定，並以 UV-VIS-NIR RECORDING SPECTROPHOTOMETER[島 津公司製UV3100(商品名稱）]進行波長400nm〜700nm之可 見光透射率之測定。其結果與所使用之導電性組成物的種 類同時列示於表3。此外，各試料之測定係分別針對5點 來實施，表3所示之數値係求取該5點之平均値並將小數 點以下進行四捨五入者》 [表3] 防靜電膜 所使用之導電性組成物 表面電阻（Ω) 可見光透射率(％) 實施例8 實施例1 2.100 90 實施例9 實施例2 2,400 90 實施例10 實施例3 740 91 實施例11 實施例4 1,800 90 實施例12 實施例7 750 91 比較例3 比較例1 51,200 90 比較例4 1 比較例2 629,100 90 如表3所示，實施例8〜1 2之防靜電膜相較於比較例3 -25- • 200951993 〜4之防靜電膜，表面電阻較小，依此結果可推測，導電 性較高，防靜電機能較優良。此外，實施例8〜12之防靜 電膜具有與比較例3〜4之防靜電膜相同的高可見光透射 率，得知具有優良透明性。 [作爲鉅固體電解電容器之評估] 實施例1 3 在將钽燒結體浸漬於濃度爲0.1 %之磷酸水溶液的狀 態，施加20V之電壓來實施形成處理，構成於鉬燒結體表 ® 面形成氧化皮膜之介電體層。其次，將上述鉅燒結體浸漬 於濃度爲35 %之3,4-伸乙二氧噻吩之乙醇溶液，1分鐘後取 出，放置5分鐘。其後，將其浸漬於預先準備之濃度50% 之酚磺酸丁胺水溶液（pH5)及濃度爲30%之過硫酸銨水溶液 以質量比1 : 1混合之混合物所構成之氧化劑兼摻雜劑溶液 中，30秒鐘後取出，於室溫放置30分鐘後，以50°C進行 10分鐘加熱，實施聚合。其後，將上述钽燒結體浸漬於水 0 中’放置30分鐘後，取出並進行70°C之30分鐘乾燥。重 複6次上述操作後，浸漬於實施例1之導電性組成物之分 散液，30秒後取出，進行70 °C之30分鐘乾燥。重複3次 上述操作後，於150 °C下放置60分鐘，形成由導電性組成 物所構成之固體電解質層。其後，以碳糊、銀糊塗覆上述 固體電解質層來製作钽固體電解電容器。 實施例1 4 除了使用實施例2之導電性組成物之分散液取代實施 例1之導電性組成物之分散液以外，進行與實施例13相同 -26- .200951993 之操作，製作鉬固體電解電容器。 實施例1 5 除了使用實施例3之導電性組成物之分散液取代實施 例1之導電性組成物之分散液以外，進行與實施例1 3相同 之操作，製作钽固體電解電容器。 實施例1 6 除了使用實施例4之導電性組成物之分散液取代實施 例1之導電性組成物之分散液以外，進行與實施例1 3相同 ® 之操作，製作鉅固體電解電容器。 比較例5 除了使用比較例1之導電性組成物之分散液取代實施 例1之導電性組成物之分散液以外，進行與實施例1 3相同 之操作，製作鉬固體電解電容器。 比較例6 除了使用比較例2之導電性組成物之分散液取代實％ Q 例1之導電性組成物之分散液以外，進行與實施例1 3相同 之操作，製作鉬固體電解電容器。 針對如上面所製作之實施例1 3〜1 6及比較例5〜6 % 钽固體電解電容器，進行ESR及靜電電容之測定。結 表4所示。此外，ESR及靜電電容之測定方法如下所示。 於ESR之測J定，使用HEWLETT PACKARD公司製之LCR計 (4284A)於25°C下以100kHz進行ESR之測定，於靜電電$ 之測定，使用 HEWLETT PACKARD公司製之 LCR g-j-(4 284 A)，於25°C下以120Hz進行靜電電容之測定。該等測 -27- 200951993 點以 > 進行 % Bg 定’各試料皆針對10個來實施，表4所示之 電容値，係求取該等10個之平均値並將小數 捨五入者。 [表4] ESR(mQ) 靜電電容（从F) 實施例13 27 150 實施例14 28 150 實施例15 24 152 實施例16 25 151 比較例5 220 134 比較例6 2199 121[Table 2] Conductivity retention (%) Example 1 81 Example 2 80 Example 3 83 Example 4 81 Example 5 84 Example 6 85 Example 7 81 Comparative Example 1 69 Comparative Example 2 70 As shown in Fig. 2, in Examples 1 to 7, the retention ratio of the electrical conductivity after high-temperature storage was higher than that of Comparative Examples 1 to 2, and the heat resistance was excellent. [Evaluation as Antistatic Film] Examples 8 to 12 and Comparative Examples 3 to 4 The dispersions of the conductive compositions of the above Examples 1 to 4, Example 7 and Comparative Examples 1 to 2 were compared with respect to conductivity. The polymer and resin components are respectively about 150%, and a sulfonated polyester resin is added [Plastic Chemical Industry Co., Ltd. - 200951993, manufactured by PLASCQAT Z-5 6l (trade name)], and after stirring, the sulfonate is contained. The dispersed droplets of the polyester resin were 50; / L on a polyethylene sheet of 2.8 cm x 4.8 cm, uniformly coated with a bar coater of No. 8, and then dried at 60 ° C for 10 minutes, followed by 150 ° C. After drying for 10 minutes, each of the conductive compositions was made into an antistatic film of an electric conductor. The surface resistance of the obtained antistatic films of Examples 8 to 12 and Comparative Examples 3 to 4 was measured by a 4-probe conductivity measuring device according to J1SK7194 at room temperature (about 25 ° C) [Mitsubishi Chemical Co., Ltd. MCP-T600 (product name)] The measurement was carried out, and the visible light transmittance at a wavelength of 400 nm to 700 nm was measured by UV-VIS-NIR RECORDING SPECTROPHOTOMETER [UV3100 (trade name) manufactured by Shimadzu Corporation). The results are shown in Table 3 together with the types of conductive compositions used. In addition, the measurement of each sample was carried out for 5 points, and the number shown in Table 3 was obtained by taking the average of the 5 points and rounding off the decimal point. [Table 3] Conductive electricity used for the antistatic film Sex composition surface resistance (Ω) visible light transmittance (%) Example 8 Example 1 2.100 90 Example 9 Example 2 2,400 90 Example 10 Example 3 740 91 Example 11 Example 4 1,800 90 Example 12 Implementation Example 7 750 91 Comparative Example 3 Comparative Example 1 51,200 90 Comparative Example 4 1 Comparative Example 2 629, 100 90 As shown in Table 3, the antistatic films of Examples 8 to 12 were compared with Comparative Examples 3 - 25 - • 200951993 〜 4 The antistatic film has a small surface resistance, and as a result, it is presumed that the conductivity is high and the antistatic function is excellent. Further, the antistatic films of Examples 8 to 12 had the same high visible light transmittance as those of the antistatic films of Comparative Examples 3 to 4, and were found to have excellent transparency. [Evaluation as a giant solid electrolytic capacitor] Example 1 3 A ruthenium sintered body was immersed in a phosphoric acid aqueous solution having a concentration of 0.1%, and a voltage of 20 V was applied thereto to carry out a forming treatment to form an oxide film on the surface of the molybdenum sintered body. Dielectric layer. Next, the above giant sintered body was immersed in an ethanol solution of 3,4-ethylenedioxythiophene at a concentration of 35%, and taken out after 1 minute, and left for 5 minutes. Thereafter, it is immersed in an oxidant-dopant composed of a mixture of a 50% aqueous solution of butyl phenolsulfonate (pH 5) and a 30% aqueous ammonium persulfate solution mixed at a mass ratio of 1:1. The solution was taken out after 30 seconds, left at room temperature for 30 minutes, and then heated at 50 ° C for 10 minutes to carry out polymerization. Thereafter, the tantalum sintered body was immersed in water 0 for 30 minutes, and then taken out and dried at 70 ° C for 30 minutes. After repeating the above operation six times, the dispersion of the conductive composition of Example 1 was immersed, taken out after 30 seconds, and dried at 70 ° C for 30 minutes. After repeating the above operation three times, it was allowed to stand at 150 ° C for 60 minutes to form a solid electrolyte layer composed of a conductive composition. Thereafter, the solid electrolyte layer was coated with a carbon paste or a silver paste to prepare a tantalum solid electrolytic capacitor. [Example 1] A molybdenum solid electrolytic capacitor was produced by the same procedure as in Example 13 except that the dispersion of the conductive composition of Example 2 was used instead of the dispersion of the conductive composition of Example 1. . [Example 1] A ruthenium solid electrolytic capacitor was produced in the same manner as in Example 13 except that the dispersion of the conductive composition of Example 3 was used instead of the dispersion of the conductive composition of Example 1. [Example 1] A giant solid electrolytic capacitor was produced by the same procedure as in Example 13 except that the dispersion of the conductive composition of Example 4 was used instead of the dispersion of the conductive composition of Example 1. Comparative Example 5 A molybdenum solid electrolytic capacitor was produced in the same manner as in Example 13 except that the dispersion of the conductive composition of Comparative Example 1 was used instead of the dispersion of the conductive composition of Example 1. Comparative Example 6 A molybdenum solid electrolytic capacitor was produced in the same manner as in Example 13 except that the dispersion of the conductive composition of Comparative Example 2 was used instead of the dispersion of the conductive composition of Example 1. The ESR and the capacitance were measured for the solid electrolytic capacitors of Examples 13 to 16 and Comparative Examples 5 to 6 % produced as described above. Table 4 shows. In addition, the measurement methods of ESR and electrostatic capacitance are as follows. For ESR measurement, ESR was measured at 100 kHz at 25 ° C using an LCR meter (4284A) manufactured by HEWLETT PACKARD Co., Ltd., and LCR gj- (4 284 A manufactured by HEWLETT PACKARD) was used for the measurement of electrostatic electricity $ The measurement of the electrostatic capacitance was performed at 25 ° C at 120 Hz. The measurements are -27-200951993 and the % Bg is determined as 'each sample is implemented for 10, and the capacitance shown in Table 4 is obtained by taking the average of 10 and decimating the decimals. . [Table 4] ESR (mQ) electrostatic capacitance (from F) Example 13 27 150 Example 14 28 150 Example 15 24 152 Example 16 25 151 Comparative Example 5 220 134 Comparative Example 6 2199 121
如表4所示，實施例13〜16之钽固體電解電容器相較 於比較例5〜6之鉬固體電解電容器，ESR較小，靜電電容 較大，可知電容器之機能較優。 其次，將分別1 〇個之上述實施例1 3〜1 6及比較例5 〜6之钽固體電解電容器於125 °C儲存200小時後，進行與 前述相同之ESR及靜電電容之測定。其結果如表5所示。 [表5] ESR(mQ) 靜電電容（从F) 實施例13 29 146 實施例14 30 147 實施例15 26 149 實施例16 27 147 比較例5 279 125 比較例6 4261 108 -28- 200951993 如表5所示，實施例13〜16之鉅固體電解電容器相較 於比較例5〜6之鉬固體電解電容器’即使高溫儲存後’ESR 也較小，靜電電容也較大，於高溫條件下具有高信賴性° [鋁捲繞型固體電解電容器之評估] 實施例1 7 於進行鋁箔表面之蝕刻處理後，實施形成處理而形成 介電體層之陽極裝設導線端子，此外，於由鋁箔所構成之 陰極裝設導線端子，介由隔片捲繞裝設著該等引線端子之 〇 w 陽極及陰極，製作電容器元件。 其次，以丁胺將實施例3所得到之導電性組成物之分 散液中和成PH5.5，將上述電容器元件浸漬於該液，120秒 後取出，於150°C乾燥30分鐘。重複4次該操作後，以150 t乾燥120分鐘，形成由導電性組成物所構成之固體電解 質層。其後，將形成上述固體電解質層後之電容器元件置 入鋁之包裝殼體，密封後，於130°C —邊施加25V之規格 Q 電壓一邊進行老化，製作鋁捲繞型固體電解電容器。 實施例1 8 除了使用以2-甲基咪唑將實施例5所得到之導電性組 成物之分散液中和成pH 5 · 5所得到之液以外，進行與實施 例17相同之操作，製作鋁捲繞型固體電解電容器。 實施例1 9 除了使用以2-甲基咪唑將實施例6所得到之導電性組 成物之分散液中和成PH5.5所得到之液以外，進行與實施 例17相同之操作，製作鋁捲繞型固體電解電容器。 -29- 200951993 實施例20 除使用以4 -甲基咪唑將實施例7所得到之導電性組成 物之分散液中和成PH5.5所得到之液以外，進行與實施例 17相同之操作，製作鋁捲繞型固體電解電容器。 比較例7 除了使用以丁胺將比較例1所得到之導電性組成物之 分散液中和成PH5.5所得到之液以外，進行與實施例π相 同之操作，製作鋁捲繞型固體電解電容器。 針對如上面所製作之實施例17〜20及比較例7之鋁捲 繞型固體電解電容器，進行ESR及靜電電容之測定。其結 果如表6所示。此外，ESR及靜電電容之測定方法如下所 示。於ESR之測定時，使用HEWLETT PACKARD公司製之 LCR計（42 8 4A)，於25°C下以100kHz進行ESR之測定，於 靜電電容之測定時，使用HEWLETT PACKARD公司製之LCR 計（42 84 A)，於25 °C下以120Hz進行靜電電容之測定。該等 0 測定，各試料皆針對10個來實施，表6所示之ESR値及靜 電電容値，係求取該等10個之平均値並將小數點以下進行 四捨五入者》 -30- 200951993 [表6] ESR(mQ) 靜電電容UF) 實施例17 24 107 實施例18 23 107 實施例19 23 108 實施例20 24 107 比較例7 940 59 如表6所示，實施例17〜20之鋁捲繞型固體電解電容 器相較於比較例7之鋁捲繞型固體電解電容器，ESR較小， 靜電電容較大，可知電容器之機能較優良。 其次，將分別爲10個之上述實施例17〜20及比較例7 之鋁捲繞型固體電解電容器於125 °C下儲存500小時後，與 前述相同，進行ESR及靜電電容之測定。其結果如表7所 不 ° [表7] ESR(mQ) 靜電電容（yF) 實施例Π 26 99 實施例18 25 105 實施例19 25 104 實施例20 26 104 比較例7 5500 41 如表7所示，實施例17〜20之鋁捲繞型固體電解電容 器相較於比較例7之鋁捲繞型固體電解電容器，即使高溫 儲存後，ESR也較小，靜電電容也較大，代表高溫條件下 -31 - 200951993 · 具有高信賴性。 產業之可利用性 依據本發明，可以提供高透明性、高導電性且耐熱性 優良之導電性組成物。其次，上述本發明之導電性組成物 因爲透明性高，而且其導電性高分子係利用電解氧化聚合 所合成者，利用化學氧化聚合所合成之導電性高分子所出 現之氧化劑所導致的硫酸根含有量較少，故殘留硫酸根所 導致之導電性降低及透明性降低等也較少。 ® 所以，依據如上所示之本發明之導電性組成物的特 性，藉由將其當做導電體使用，可以提供高透明性、高導 電性且耐熱性優良之防靜電膜、防靜電樹脂、以及防靜電 片等。此外，藉由將此種高導電性且優良耐熱性之本發明 的導電性組成物當做固體電解質使用，可以提供ESR小、 且在高溫條件下信賴性高的固體電解電容器。 【圖式簡單說明】 〇 無。 【主要元件符號說明】 無。 -32-As shown in Table 4, the solid electrolytic capacitors of Examples 13 to 16 had smaller ESR and larger electrostatic capacitance than the solid electrolytic capacitors of Comparative Examples 5 to 6, and it was found that the function of the capacitor was superior. Next, the solid electrolytic capacitors of the above Examples 13 to 16 and Comparative Examples 5 to 6 were stored at 125 ° C for 200 hours, and then the same ESR and capacitance were measured. The results are shown in Table 5. [Table 5] ESR (mQ) electrostatic capacitance (from F) Example 13 29 146 Example 14 30 147 Example 15 26 149 Example 16 27 147 Comparative Example 5 279 125 Comparative Example 6 4261 108 -28- 200951993 As shown in Fig. 5, the giant solid electrolytic capacitors of Examples 13 to 16 have smaller ESR and higher electrostatic capacitance than those of Comparative Examples 5 to 6 of the molybdenum solid electrolytic capacitors, even after high temperature storage, and have high temperatures under high temperature conditions. Reliability [Evaluation of Aluminum-wound Solid Electrolytic Capacitor] Example 1 7 An anode-mounted lead terminal for forming a dielectric layer after performing an etching treatment on the surface of an aluminum foil, and further comprising an aluminum foil The cathode is provided with a lead terminal, and the anode and the cathode of the lead terminal are wound around the separator to form a capacitor element. Then, the dispersion of the conductive composition obtained in Example 3 was neutralized to pH 5.5 with butylamine, and the capacitor element was immersed in the liquid, taken out after 120 seconds, and dried at 150 ° C for 30 minutes. After repeating this operation four times, it was dried at 150 t for 120 minutes to form a solid electrolyte layer composed of a conductive composition. Then, the capacitor element in which the solid electrolyte layer was formed was placed in a package of aluminum, sealed, and then aged at a temperature of 130 ° C while applying a voltage of 25 V to prepare an aluminum wound solid electrolytic capacitor. Example 1 8 The same operation as in Example 17 was carried out except that the liquid obtained by neutralizing the dispersion of the conductive composition obtained in Example 5 with 2-methylimidazole was used to prepare aluminum. Winding type solid electrolytic capacitor. Example 1 9 An aluminum coil was produced in the same manner as in Example 17 except that the dispersion of the conductive composition obtained in Example 6 was neutralized to a pH of 5.5 with 2-methylimidazole. Winding solid electrolytic capacitors. -29-200951993 Example 20 The same operation as in Example 17 was carried out, except that the dispersion obtained by neutralizing the dispersion of the conductive composition obtained in Example 7 with a solution of pH 5.5 was used. An aluminum wound solid electrolytic capacitor was fabricated. Comparative Example 7 The same operation as in Example π was carried out except that the liquid obtained by neutralizing the dispersion of the conductive composition obtained in Comparative Example 1 with butylamine was used to prepare aluminum-wound solid electrolysis. Capacitor. The ESR and the capacitance were measured for the aluminum coiled solid electrolytic capacitors of Examples 17 to 20 and Comparative Example 7 produced as described above. The results are shown in Table 6. In addition, the measurement methods of ESR and electrostatic capacitance are as follows. For the measurement of ESR, the LCR meter (42 8 4A) manufactured by HEWLETT PACKARD Co., Ltd. was used to measure ESR at 100 kHz at 25 ° C, and the LCR meter manufactured by HEWLETT PACKARD was used for the measurement of electrostatic capacitance (42 84). A) The capacitance was measured at 120 Hz at 25 °C. For each of the 0 measurements, each sample is implemented for 10, and the ESR and electrostatic capacitance 所示 shown in Table 6 are obtained by taking the average of 10 and 小 and rounding off the decimal point. -30- 200951993 [ Table 6] ESR (mQ) electrostatic capacitance UF) Example 17 24 107 Example 18 23 107 Example 19 23 108 Example 20 24 107 Comparative Example 7 940 59 As shown in Table 6, the aluminum rolls of Examples 17 to 20 The wound-type solid electrolytic capacitor has a smaller ESR and a larger electrostatic capacitance than the aluminum-wound solid electrolytic capacitor of Comparative Example 7, and it is understood that the function of the capacitor is excellent. Then, the aluminum-wound solid electrolytic capacitors of the above-described Examples 17 to 20 and Comparative Example 7 were stored at 125 ° C for 500 hours, and then the ESR and the capacitance were measured in the same manner as described above. The results are shown in Table 7. [Table 7] ESR (mQ) Electrostatic capacitance (yF) Example Π 26 99 Example 18 25 105 Example 19 25 104 Example 20 26 104 Comparative Example 7 5500 41 The aluminum-wound solid electrolytic capacitors of Examples 17 to 20 are smaller than the aluminum-wound solid electrolytic capacitors of Comparative Example 7 even after high-temperature storage, and the electrostatic capacitance is also large, representing high temperature conditions. -31 - 200951993 · High reliability. Industrial Applicability According to the present invention, it is possible to provide a conductive composition having high transparency, high conductivity, and excellent heat resistance. Next, the conductive composition of the present invention has a high transparency, and the conductive polymer is synthesized by electrolytic oxidation polymerization, and the sulfate generated by the oxidizing agent formed by the conductive polymer synthesized by chemical oxidative polymerization is used. Since the content is small, the conductivity due to residual sulfate is lowered and the transparency is lowered. Therefore, according to the characteristics of the conductive composition of the present invention as described above, by using it as an electric conductor, it is possible to provide an antistatic film, an antistatic resin, and a film having high transparency, high electrical conductivity, and excellent heat resistance. Anti-static sheet, etc. Further, by using such a conductive composition of the present invention having high conductivity and excellent heat resistance as a solid electrolyte, it is possible to provide a solid electrolytic capacitor having a small ESR and high reliability under high temperature conditions. [Simple description of the diagram] 〇 No. [Main component symbol description] None. -32-
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| JP5607441B2 (en) * | 2010-07-01 | 2014-10-15 | カーリットホールディングス株式会社 | Conductive polymer fine particles, conductive polymer fine particle dispersions and methods for producing them |
| JP5682887B2 (en) * | 2010-11-02 | 2015-03-11 | 学校法人東京理科大学 | Conductive polymer nanoparticle dispersion solution, conductive thin film using the dispersion solution, and method for producing conductive thin film |
| JP5507484B2 (en) * | 2011-02-28 | 2014-05-28 | 信越ポリマー株式会社 | Conductive polymer composite and method for producing the same, and conductive polymer solution and antistatic film |
| KR101644770B1 (en) | 2011-09-06 | 2016-08-01 | 데이카 가부시키가이샤 | Dispersion of electrically conductive polymer, and electrically conductive polymer and use thereof |
| JP5655745B2 (en) * | 2011-09-08 | 2015-01-21 | コニカミノルタ株式会社 | Transparent electrode and organic electroluminescence device |
| JP5952551B2 (en) | 2011-12-12 | 2016-07-13 | Ｎｅｃトーキン株式会社 | Conductive polymer composition and method for producing the same, method for producing conductive polymer material, method for producing conductive substrate, method for producing electrode, method for producing electronic device, and method for producing solid electrolytic capacitor |
| JP5872872B2 (en) | 2011-12-12 | 2016-03-01 | Ｎｅｃトーキン株式会社 | Method for producing conductive polymer composition, method for producing conductive polymer material, method for producing conductive substrate, method for producing electrode, and method for producing solid electrolytic capacitor |
| KR102025194B1 (en) * | 2013-01-29 | 2019-09-25 | 주식회사 한국엔티켐 | A high molecule copolymer-complex with a excellent water-resisting, chemical-resisting, and weather-resisting property, and the fabrciation method of the same. |
| WO2014025200A1 (en) * | 2012-08-07 | 2014-02-13 | 주식회사 한국엔티켐 | Composite including high molecular weight copolymer having good water resistance, chemical resistance, and weather resistance, and method for preparing same |
| JP5988824B2 (en) * | 2012-10-22 | 2016-09-07 | テイカ株式会社 | Electrolytic capacitor manufacturing method |
| JP5988831B2 (en) * | 2012-10-31 | 2016-09-07 | テイカ株式会社 | Electrolytic capacitor manufacturing method |
| JP6485457B2 (en) | 2014-06-26 | 2019-03-20 | パナソニック株式会社 | Electrolytic capacitor |
| CN104672786B (en) * | 2015-03-11 | 2017-05-17 | 中国科学院理化技术研究所 | Water-soluble PEDOT-PSS dispersion and homogeneous polymerization preparation method thereof |
| JP6832724B2 (en) * | 2017-01-30 | 2021-02-24 | 信越ポリマー株式会社 | Manufacturing method of antistatic film |
| JP7462172B2 (en) * | 2017-12-28 | 2024-04-05 | パナソニックＩｐマネジメント株式会社 | Electrolytic capacitor and its manufacturing method |
| US11031187B2 (en) | 2018-03-30 | 2021-06-08 | Showa Denko K.K. | Method of manufacturing solid electrolytic capacitor, and method of manufacturing dispersion containing conjugated electrically conductive polymer |
| JP7083280B2 (en) * | 2018-06-25 | 2022-06-10 | テイカ株式会社 | How to manufacture electrolytic capacitors |
| JP7357238B2 (en) | 2019-06-28 | 2023-10-06 | パナソニックＩｐマネジメント株式会社 | Electrolytic capacitors and electrolytic capacitor manufacturing methods |
| WO2021186942A1 (en) * | 2020-03-19 | 2021-09-23 | 東レ株式会社 | Conductive composition, and conductive film, sensor, biosensor and flexible device including same, as well as conductive fabric, and bioelectrode and wearable device including same |
| JP2023058759A (en) * | 2020-03-25 | 2023-04-26 | パナソニックＩｐマネジメント株式会社 | Capacitor element and electrolytic capacitor |
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| WO2004106404A1 (en) * | 2003-05-27 | 2004-12-09 | Fujitsu Limited | Organic conductive polymer composition, transparent conductive film and transparent conductor both comprising the composition, and input device comprising the transparent conductor and its manufacturing method |
| US20060223976A1 (en) * | 2003-08-11 | 2006-10-05 | Tayca Corporation | Conductive polymer and solid electrolytic capacitor using same |
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| JP2009235127A (en) * | 2008-03-25 | 2009-10-15 | Fujifilm Corp | Method for producing conductive polymer particulate, conductive polymer particulate obtained by the method, and aqueous dispersion thereof |
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