1357083 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】 導電性高分子，藉由其高導電性，而被當做例如鉅固 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 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- 1357083 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 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 鉬、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 1357083 乙烯磺酸、過硫酸銨、鐵鹽、伸乙二氧噻吩等使其產生反 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2004-265927號公報 專利文獻3:特許第2636968號公報 專利文獻4 :特許第390607 1號公報 專利文獻5:日本特開2007-277569號公報 專利文獻6 :日本特開平丨_丨6 1 〇 1 3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 1357083 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。1357083. EMBODIMENT OF THE INVENTION The present invention relates to a dispersion 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 giant solid electrolytic capacitor, a tantalum solid electrolytic capacitor, or an aluminum solid electrolytic capacitor by virtue 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. a transition metal in which trivalent iron is more suitable, and generally, a trivalent iron salt of an aromatic sulfonic acid is used as an oxidizing agent and a dopant in chemical oxidative polymerization of a polymerizable monomer such as thiophene or a derivative thereof. . Secondly, it has been reported that among the trivalent iron salts of aromatic sulfonic acid, trivalent iron salt of toluenesulfonic acid and trivalent iron salt of methoxybenzenesulfonic acid are most useful, and the synthesis of the above conductive polymer 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- 1357083 However, toluenesulfonic acid III The ferrous salt is used as an oxidizing agent and a dopant to obtain a conductive polymer, which does not have sufficient characteristics for initial resistance enthalpy and heat resistance. In addition, ternary iron oxybenzenesulfonate is used as an oxidizing agent. The conductive polymer obtained by using the dopant has lower initial resistance and lower heat resistance than the conductive polymer using the ferric acid of the toluenesulfonic acid. However, it cannot be satisfactorily satisfied. characteristic. Since 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, these solutions 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. Further, when the obtained conductive polymer is used as a solid electrolyte of a solid electrolytic capacitor, the conductive polymer synthesized by a chemical oxidative polymerization method usually has molybdenum, rhodium, or the like 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 formed 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 1357083 ethylenesulfonic acid, ammonium persulfate, iron salt, ethylenedioxythiophene or the like is mixed 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, and if it is used as a solid electrolyte of a solid electrolytic capacitor, it is necessary to further improve the conductivity. Further, it has been reported that phenolsulfonic acid phenolic A conductive polymer in which a 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: JP-A-2003-160647, JP-A-2004-265927, JP-A-2004-265927, Patent Document 3: Patent No. 2,636,968, Patent Document 4: Patent No. 390,607, In the case of the above, in view of the above circumstances, Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. An object of the present invention is to provide an electroconductive composition having high conductivity and a high heat resistance of 1570083 and using the above-mentioned electroconductive composition as a conductor to provide an antistatic film which provides high conductivity and excellent heat resistance. The conductive composition is used as a solid electrolyte to provide a solid electrolytic capacitor having a small ESr and high reliability under high temperature conditions. The inventors of the present invention have repeatedly conducted research aimed at solving the above problems, and as a result, have found that a phenolsulfonic acid phenol resin, a sulfonated polyester or a polystyrenesulfonic acid having a 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 conductive polymer dispersion is obtained, and the conductivity of the conductive composition dispersion liquid containing a high boiling point solvent or an organic acid having a cyclic structure in the dispersion of the conductive polymer is obtained. The composition has high electrical 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，本發明係關於一種導電性組成物之分散液，其 特徵爲在具有上述一般式⑴所表示之重複單位之酚磺酸酚 醛樹脂、磺化聚酯、或聚苯乙烯磺酸之存在下，含有藉由 將噻吩或其衍生物混入水中、或水與水互溶性溶劑之混合 1357083 液所構成之水性液進行電解氧化聚合而得到之導 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 乾燥而得到之導電性組成物，將前述導電性組成 電體使用之防靜電膜及防靜電片，以及將前述導 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 熱性優良。又，本發明之導電性組成物爲高透明 於其導電性高分子係利用電解氧化聚合所合成者 學氧化聚合所合成之導電性高分子會出現之氧化 的硫酸根含有量較少，故殘留硫酸根所導致之導 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 性，藉由將其當做導電體使用，可以得到高透明 電性且耐熱性優良之防靜電膜、防靜電樹脂、以 片等。此外，藉由將此種高導電性且耐熱性優良 的導電性組成物當做固體電解質使用，可以得至 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 一般式（I)所表示之重複單位的酚磺酸酚醛樹脂、 或聚苯乙烯磺酸，其係於導電性高分子之合成時 分散劑之機能，使作爲聚合性單體之噻吩或其衍 對應需要所添加之觸媒等均勻分散於水中或水性 電性高分 之分散液 物當做導 電性組成 性、且耐 性，且由 ，利用化 劑所導致 電性降低 成物的特 性、高導 及防靜電 之本發明 U ESR 較 使用具有 磺化聚酯 具有優良 生物、及 液中，且 1357083 於合成聚合物中添加摻雜劑，使導電性高分子成爲具有高 物I。其次’上述摻雜劑具有優良分散劑之機能， ί系可以合成高透明性、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400,000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 1357083 差。此外，上述磺化聚酯之平均分子量數大於300,000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1〇〇,〇〇〇以下者，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10,〇〇〇〜 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，所得到之導電性高分子的導電性變低，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- ^)/083 上述闻沸點溶劑，以沸點爲l50〇C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189r )、r -丁內醋（沸點204 °C)、環丁碾（沸點285 eC)、N-甲基吡咯啶（沸 點202 C )、二甲碾（沸點233。(：）、乙二醇（沸點198°C )、二 乙一醇（沸點244°C )等，尤其是，以二甲亞楓爲佳。其次， 胃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5〜3,〇〇〇質量份）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 高所得到之導電性組成物的製膜性，藉此提高導電性。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 - 1357083 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1〇〇質量份之導電性高 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 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 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 份而含有若干高沸點溶劑，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者，亦以導 -12-(In the formula, R is a hydrogen or a methyl group). In other words, the present invention relates to a dispersion of a conductive composition characterized by having a phenolic phenolic resin having a repeating unit represented by the above general formula (1), and being sulfonated. In the presence of polyester or polystyrene sulfonic acid, a derivative obtained by electrolytic oxidative polymerization of an aqueous liquid composed of a mixture of thiophene or a derivative thereof in water or a mixture of water and a water-miscible solvent, 1570073, is obtained. 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 the electroconductive composition, an antistatic film and an antistatic sheet using the electroconductive composition, and the use of the above-mentioned conductor as a solid electrolyte. Solid electrolytic capacitors are related. The conductive composition of the present invention is excellent in high transparency and high in heat conductivity. Further, the conductive composition of the present invention is highly transparent, and the conductive polymer synthesized by the oxidative polymerization of the conductive polymer by electrolysis oxidative polymerization has a small amount of sulfate which is oxidized, so that remains. Sulfate leads to less conductivity and reduced transparency. Therefore, according to the conductive composition of the present invention as described above, by using it as a conductor, an antistatic film, an antistatic resin, a sheet or the like which is highly transparent and excellent in heat resistance can be obtained. In addition, by using such a conductive composition having high conductivity and excellent heat resistance as a solid electrolyte, it is possible to obtain a solid electrolytic capacitor which is small and has high reliability under high temperature conditions. [Embodiment] In the present invention, In the synthesis of the conductive polymer, the phenol sulfonic acid phenol resin or the polystyrene sulfonic acid, which is a repeating unit represented by the general formula (I), is a function of a dispersing agent during the synthesis of the conductive polymer. The thiophene which is a polymerizable monomer or a derivative thereof which requires a catalyst or the like to be uniformly dispersed in water or an aqueous electrical high-concentration is required to be electrically conductive and resistant, and is caused by a chemical agent. The U ESR of the present invention has the characteristics of high-conductivity, high conductivity and anti-static. The U ESR has excellent bio- and liquid content in the sulfonated polyester, and 1357083 is added to the synthetic polymer to make the conductive polymer Has a high object I. Secondly, the above-mentioned dopant has a function as an excellent dispersant, and it 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. That is, the conductivity of the conductive polymer obtained when the number average molecular weight of the phenolsulfonic acid phenol resin is less than 5,000 is lowered, and the transparency may 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, and it is difficult to use it in the 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, more preferably 400,000 or less, and still 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 having 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 to 1,357,083. Further, when the average molecular weight of the sulfonated polyester is more than 300,000, 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 of the above range, preferably 10,000 or more, more preferably 20,000 or more, further preferably 1 Å, or less, more preferably 80,000. The following. Further, the polystyrene sulfonic acid preferably has a number average molecular weight of 10, 〇〇〇 1,000,000. In other words, when the number average molecular weight of the polystyrenesulfonic acid is less than 10,000, the conductivity of the obtained conductive polymer 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 present. However, it is considered that, for example, when a dispersion of the conductive composition is applied to a substrate and dried, The detachment of the high-boiling solvent increases the layer density in the thickness direction, whereby the surface interval between the conductive polymers is narrowed, and the conductivity of the conductive polymer is improved. -10- ^) / 083 The above-mentioned scent boiling point solvent is preferably a boiling point of l50 〇 C or more, and specific examples of such a high boiling point solvent, for example, dimethyl sub-milling (boiling point 189r), r-butane vinegar (boiling point) 204 °C), cyclobutyl milling (boiling point 285 eC), N-methylpyrrolidine (boiling point 202 C), dimethyl milling (boiling point 233. (:), ethylene glycol (bp 198 ° C), diethyl alcohol (boiling point: 244 ° C), etc., especially, dimethyl sulfoxide is preferred. Second, the content of the high-boiling solvent of the stomach is 5 to 3,000% based on the mass of the conductive polymer in the dispersion (that is, Preferably, the conductive polymer '5 to 3 parts by mass of the high-boiling solvent is 1 part by mass, more preferably 2 to 700%. The content of the high-boiling solvent is less than the above. When the film forming property of the conductive composition is lowered, the effect of improving the conductivity of the conductive composition may be lowered. When the content of the high-boiling solvent is larger than the above, it takes a long time to dry the dispersion, and further, Conversely, the conductivity may be lowered. Further, the dispersion of the present invention may also have a ring structure. The organic acid is used in place of the high-boiling solvent, and the organic acid is contained in order to improve the film formability of the obtained conductive composition, thereby improving conductivity. By including such an organic acid having a cyclic structure, The reason why the conductivity of the conductive polymer can be improved is not clear. For example, when a dispersion of a conductive composition is applied to a substrate and dried, an organic acid having a cyclic structure enters the conductive polymer. Between the layers, the transport of the holes between the layers of the conductive polymer is likely to occur. The organic acid having a cyclic structure, for example, citric acid, lauric acid, carboxyphenol, carboxycresol, carboxynaphthalene, dicarboxyl Naphthalene, thiophenesulfonic acid, toluenesulfonic acid, phenolsulfonic acid, cresolsulfonic acid, naphthalenesulfonic acid, naphthalene disulfonic acid, naphthalene trisulfonic acid, -11 - 1357083 sulfonic acid, sulfonic acid, etc., especially The aromatic organic acid such as phenolsulfonic acid, naphthalenesulfonic acid or sulfonic acid is preferred. Secondly, the content of the organic acid having the cyclic structure is relative to the conductive polymer in the dispersion. The quality benchmark is 5~500% ( In other words, the conductive polymer having a cyclic structure is preferably 5 to 500 parts by mass, particularly preferably 20 to 150%, based on 1 part by mass of the conductive polymer. The organic acid having a cyclic structure is contained. When the amount 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 is lowered, and the content of the organic acid having a cyclic structure is more than that described above because of the action of impurities. In addition, the film forming property of the conductive composition is lowered, and the conductivity is lowered. In addition, the content of the conductive polymer in the dispersion is such that the dispersion of the conductive composition is dried to form a film. In the case of the workability and the like, it 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 the content of the conductive polymer is large. At the above, the viscosity becomes high, and it is feared that the workability at the time of coating or the like is lowered. The dried product obtained by drying a dispersion containing a conductive polymer and a high-boiling solvent is considered to contain a high-boiling solvent by using a conductive polymer as a main component. Therefore, in the present specification, the conductive composition is formed. When the dispersion of the substance is dried, it is expressed by a conductive composition. "Because the high-boiling solvent is also a solvent, and drying at a higher temperature, all may evaporate. In the present invention, the conductive polymer is contained. And a dried product obtained by drying the conductive composition of the high-boiling solvent, for example, even if it contains almost no high-boiling solvent, it is also a derivative-12-
1357083 電性組成物來表現。此外，含有具有環狀構造；; 取代高沸點溶劑時，因爲具有上述環狀構造之；^ 常之乾燥不會蒸發，使含有導電性高分子及具；f 之有機酸的分散液進行乾燥所得到之乾燥物，3 導電性高分子及具有環狀構造之有機酸的導電t 此外，本發明之導電性高分子之分散液，亦可[i 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讀 合成的聚合性單體係使用噻吩或其衍生物，然ΪΙ 或其衍生物之噻吩衍生物，例如，3,4-伸乙二^ 烷基唾吩、3-烷氧基噻吩、3-烷基-4-烷氧基噻吩 噻吩、3，4-烷氧基噻吩等，其烷基及烷氧基之碳 〜16，更佳爲1〜4，總之，以碳數爲2之3,4-·ί 吩爲佳。 導電性高分子之合成時之電解氧化聚合， 雜劑之具有以一般式（I)表示之重複單位的酚擴 脂、磺化聚酯、聚苯乙烯磺酸（以下，也以「摻丨 詞來進行說明）之任一者，皆對由水或水與水互i 混合物所構成之水性液具有溶解性，故係於水I 中進行。 構成上述水性液之水互溶性溶劑，例如，甲 丙醇、丙酮、乙腈等，該等水互溶性溶劑之水的 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】 :有機酸來 _機酸於通 _環狀構造 丨常爲含有 :組成物。 丨時含有高 :化聚合之 ί，該噻吩 ί噻吩、3-，3,4-烷基 致較佳爲1 3乙二氧噻 3爲做爲慘 酸酚醛樹 I劑」之用 麥性溶劑之 3或水性液 醇、乙醇、 昆合比例， .體的使用 -13- 1357083 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3,4-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 3,4-伸乙二氧噻吩=1: 0.05〜1: 5,特佳爲酚磺酸i 3,4 -伸乙二氧噻吩=1: 〇·1〜1: 1。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 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//m以下，更佳爲l〇vm以下。其後，利用乙淫 有以一般 單體使用 明時，該 醛樹脂： f醛樹脂： 使用其他 可，例如 05mA/cm2 電壓實施 _ 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 I沈澱法、 -14- 1357083 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、鉬固體電解電容器、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、 且在高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、耐腐鈾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- 1357083 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鉬固體電解電容 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- 1357083 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、銀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 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 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- 1357083 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⑴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ORGANO公司製之陽離子交換樹脂 八1\0丑1^心1206(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.131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 濾裝置[SARTORIUS公司製 Vivaflow200(商品名稱）、分子 1357083 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，二甲亞諷約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 CHROMATO 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 2-561(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0.05g以外，二甲亞颯之添加等， 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，二甲亞颯之添加等，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- 1357083 外，二甲亞硒之添加等，進行與實施例i相同之操作，胃 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蔡碌酸 〇.4g(相對於導電性筒分子，萘磺酸33%)取代高沸點溶劑之 一甲亞楓以外，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6 除了添加作具有環狀構造之有機酸的恵醒碌酸 〇.5g(相對於導電性高分子，蒽醌磺酸42%)取代高沸點溶劑 之二甲亞颯以外，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酚磺酸〇.5g(相對於 導電性高分子，酚磺酸4 2%)取代高沸點溶劑之二甲亞颯以 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倒入內容積之容器， -20- 1357083 添加過硫酸銨2g後，以攪拌機進行攪拌使其溶解。接著 —邊攪拌一邊緩慢滴入3,4-伸乙二氧噻吩3mL，花費24 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 波均質器[日本精機公司製、US-T300(商品名稱）]進行30 鐘之分散處理。其後，添加100g之ORGANO公司製之陽 子交換樹脂AMBERLITE120B(商品名稱），以攪拌機進行 小時之攪拌。其次，以東洋濾紙公司製之濾紙No. 131進 過濾，重複3次該陽離子交換樹脂之處理及過濾，除去 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 濾裝置[SARTORIUS公司製Vivaflow200(商品名稱）、分 量分離5萬]對該通過液進行處理，除去液中之遊離低分 成份。以水稀釋該處理後之液將濃度調整成3 %，針對該 液40g，添加4g二甲亞颯，得到導電性組成物之分散液 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 除了未添加二甲亞楓4g以外，進行與實施例1相同 操作，得到導電性組成物之分散液。此外，因爲該分散 未添加高沸點溶劑之二甲亞颯，正確而言，應以導電性 分子之分散液來表現，然而，該比較例2之分散液，爲 說明上之方便，配合實施例1〜7及比較例1之導電性箱 物的分散液，以導電性組成物之分散液來表現。其次， 小 音 分 離 1 行 液 過 子 子 3% 之 液 高 了 成 對 -21 - 1357083 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。 [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之導電性組成物之 分散液分別在2.8cmx4.8cm之玻璃板上滴下50gL，以No.8 之棒塗布器（bar coater)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，於玻璃板上形 成導電性組成物之薄片，該導電性組成物之片的導電率， 在室溫（約25°C)下，依據JISK7194，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。結果如表1所示。此外，各試料之測定係各針對5點 進行’表1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。1357083 Electrical composition to express. Further, it has a cyclic structure; when it is substituted for a high-boiling solvent, it has the above-mentioned cyclic structure; and the drying does not evaporate, and the dispersion containing the conductive polymer and the organic acid having f is dried. The obtained dry product, the conductive polymer of the conductive polymer and the organic acid having a cyclic structure, and the dispersion of the conductive polymer of the present invention may be [i boiling point solvent and organic acid having a cyclic structure. In the present invention, thiophene or a derivative thereof is used as a polymerizable single system for electrically interpreting a conductive polymer, and then a thiophene derivative of a derivative thereof or a derivative thereof, for example, 3,4-ethylenediazine a thiophene, a 3-alkoxythiophene, a 3-alkyl-4-alkoxythiophene thiophene, a 3,4-alkoxythiophene or the like, the alkyl group of the alkyl group and the alkoxy group, preferably 16 ~4, in short, with a carbon number of 2, 3, 4-·ί is preferred. Electrolytic oxidative polymerization in the synthesis of a conductive polymer, the phenolic resin having a repeating unit represented by the general formula (I), a sulfonated polyester, and a polystyrene sulfonic acid (hereinafter, also referred to as "doping" Any one of them is soluble in water or a water-based mixture of water and water, and is carried out in water I. A water-miscible solvent constituting the above aqueous liquid, for example, A Propanol, acetone, acetonitrile, etc., the water of the water-miscible solvent should be 50% by mass or less of the entire aqueous liquid. The dopant and the polymerizability in the above electrolytic oxidation polymerization: organic acid The _ ring structure 丨 often contains: a composition. 丨 含有 含有 含有 : : : : , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , For the phenolic phenolic acid I agent, the amount of the wheat solvent 3 or the aqueous liquid alcohol, ethanol, and ketone ratio is not particularly limited, but 'for example, the dopant is a phenolic phenolic resin having a repeating unit represented by the formula (I), a derivative of a polymerizable thiophene When using 3,4-ethylenedioxythiophene as an example, the ratio of use is used, and in terms of mass ratio, it is preferably phenolsulfonic acid phenol 3,4-ethylenedioxythiophene = 1: 0.05 to 1: 5 Particularly preferred is phenolsulfonic acid i 3,4 -ethylenedioxythiophene=1: 〇·1~1: 1. Next, the dopant substance and the polymerizable monomer are also substantially the same when other substances are used. The electrolytic oxidative polymerization is carried out at a constant current and a constant voltage, and the current enthalpy is preferably 〇. 〜10 mA/cm 2 , more preferably 2 2 mA/cm 2 〜 4 mA/cm 2 , in the stationary electrolysis. In the oxidative polymerization, 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. Further, in the electrolytic oxidation polymerization, ferrous sulfate or iron sulfate is used as a catalyst. Electrolytic oxidative polymerization is carried out in water or aqueous liquid containing iron ions to promote the polymerization of thilytes. The conductive polymer obtained as described above is obtained by being dispersed in water or an aqueous liquid, and contains an iron sulfate salt and a decomposition product thereof. In this case, the dispersion containing the electropolymer is placed in a dispersion machine 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/m or less, more preferably 10 〇vm or less. Thereafter, the aldehyde resin is used as a general monomer, and the aldehyde resin: f aldehyde resin: using other voltages, for example, a voltage of 05 mA/cm 2 , ≤ 1.5 V 〜 , more preferably an hour, or may be added thereto. The contact phenotype or its derivative can be used as a catalyst to make the impurity of the guide ball mill cation cross-flow is preferably I precipitation method, -14-1357083 ultrafiltration method, anion exchange resin, etc., removing sulfuric acid generated by decomposition of the catalyst, etc. Further, a high boiling point solvent or an organic acid having a cyclic structure is added. 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 molybdenum solid electrolytic capacitor, or a tantalum solid electrolytic capacitor, and is provided. A solid electrolytic capacitor with low ESR and high reliability under high temperature 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. Base material resin for active materials, coatings for resisting uranium, etc. 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 using the conductive composition of the present invention as a conductor to produce an antistatic cloth, the dispersion of the conductive composition is applied to a cloth or the cloth is immersed in a dispersion of a 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, polyamide, 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, a solid electrolytic capacitor can be produced as described below. First, when the conductive composition of the present invention is used as a solid electrolyte such as a molybdenum 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- 1357083 After the solid electrolyte layer is formed, a carbon paste and a silver paste are applied and dried, and then packaged to prepare a solid electrolytic capacitor such as a tantalum solid electrolytic capacitor, a tantalum solid electrolytic capacitor, or a silver laminated solid electrolytic capacitor. . Further, for example, the non-iron salt-based organic sulfonate can be used as a dopant, and the capacitor element is immersed in a liquid containing a polymerizable monomer or an oxidizing agent, and then taken out, polymerized at room temperature, and immersed in After the water is taken out and washed, it is further dried to synthesize a conductive polymer, and then the whole is immersed in the dispersion liquid of the conductive composition of the present invention, and taken out and dried, and the conductive material of the present invention can be formed. The solid electrolyte layer composed of the composition 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, the surface of the aluminum foil is etched, and then 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 an anode and a cathode to which the lead terminals are attached are wound through a separator to prepare a capacitor element, and the capacitor element is immersed in the conductive composition of the present invention. The dispersion is taken out, dried, 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 repeating the operations, the package is packed in a packaging material. Aluminum wound solid electrolytic capacitors can be fabricated. EXAMPLES -17- 1357083 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 phenol resin (lot EW00130 (trade name), average molecular weight number 60,000, R-hydrogen], which is a repeating unit represented by the general formula (1), into an internal volume. A 1 L stainless steel container was added with ferrous sulfate·7 water and 0.3 g, and 4 mL of 3,4-ethylenedioxythiophene was slowly dropped thereinto. The mixture was stirred with a stirring blade made of stainless steel, and the anode was placed in a container, and the cathode was placed at the root of the stirring blade, and electrolytic oxidation 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 dispersion treatment for 30 minutes using an ultrasonic homogenizer [manufactured by Nippon Seiki Co., Ltd., US-T3 00 (trade name)]. Thereafter, 100 g of a cation exchange resin (manufactured by ORGANO Co., Ltd.) was added, and the mixture was stirred by a stirrer. Next, the filter paper No. 131 manufactured by Toyo Filter Co., Ltd. was filtered, and the treatment with the cation exchange resin and filtration were repeated 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 above treated liquid was passed through a sieve having a pore size of l#m, and was subjected to an ultrafiltration device [Vivaflow 200 (trade name) manufactured by SARTORIUS Co., Ltd., molecular weight of 1357083 (molecular weight fraction). Id) 50,000] treatment of the passing liquid 'removal of the 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 dimethyl sulphide (relative to conductive polymer, dimethyl sulphate about 3 30%) 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 CHROMATO DX 120 (trade name) manufactured by DI0NEX Co., Ltd., and the content of sulfuric acid was 25 ppm. Example 2 In addition to the 3% aqueous solution 600 of sulfonated polyester [Plascoa.T 2-561 (trade name), number average molecular weight 27,000] manufactured by Mutual Chemical Industry Co., Ltd., § ferrous sulfate, water and 0.05 g were added. The addition of dimethyl hydrazine or the like was carried out in the same manner as in Example 1 to obtain a dispersion of a 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 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 Co., Ltd., 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. 600 g of the dispersion of the stomach and the conductive composition was carried out in the same manner as in Example i except for the addition of dimethylene selenide, such as -19 to 1357,083. 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 Example 3 was carried out except that 4 g of succinic acid as a organic acid having a cyclic structure (with respect to a conductive cylinder molecule, naphthalenesulfonic acid 33%) was substituted for one of the high boiling solvents, jasmine. 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 In addition to being added as an organic acid having a cyclic structure, 5 g (relative to conductivity) The same procedure as in Example 3 was carried out, except that the dimethyl hydrazine of the high boiling point solvent was replaced by a polymer, 42% of hydrazine sulfonic acid, 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. Example 7 Example 3 was carried out except that ruthenium phenolate sulfonate (5 g of an organic acid having a cyclic structure (with respect to a conductive polymer, phenolsulfonic acid 42%) was substituted for dimethyl hydrazine of a high boiling point solvent. 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. Comparative Example 1 200 g of a 4% aqueous solution of the same phenolsulfonic acid phenol resin (number average molecular weight: 60,000) used in Example 1 was poured into a container of internal volume, -20 - 1357083, 2 g of ammonium persulfate was added, and then agitator was used. Stir to dissolve. Next, 3 mL of 3,4-extended ethylenedioxythiophene was slowly added dropwise while stirring, and chemical oxidation polymerization of 3,4-extended ethylenedioxythiophene was carried out at 24 hours. After the above chemical oxidative polymerization, it was diluted with water to four times, and then subjected to dispersion treatment for 30 minutes by a superwave homogenizer [manufactured by Nippon Seiki Co., Ltd., US-T300 (trade name)]. Thereafter, 100 g of a male exchange resin AMBERLITE 120B (trade name) manufactured by ORGANO Co., Ltd. was added, and the mixture was stirred for a while with a stirrer. Next, the filter paper No. 131 manufactured by Toyo Filter Co., Ltd. was filtered, and the cation exchange resin was treated and filtered three times to remove all the cationic components. 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 apparatus [Vivaflow 200 (trade name) manufactured by SARTORIUS Co., Ltd., component separation 50,000] to remove free low-component components in the liquid. . The liquid after the treatment was diluted with water to adjust the concentration to 3%, and 4 g of dimethyl hydrazine was added to 40 g of the liquid to obtain a dispersion of the conductive composition, which was the same as in Example 1, and the sulfuric acid content in the dispersion was measured. The content of sulfuric acid was determined to be 123 ppm. Comparative Example 2 A dispersion of a conductive composition was obtained in the same manner as in Example 1 except that 4 g of dimethylsulfoxide was not added. In addition, since the dimethyl hydrazine which is not added with a high boiling point solvent is dispersed, it should be represented by a dispersion of a conductive molecule. However, the dispersion of Comparative Example 2 is convenient for explanation, and the examples are blended. The dispersion liquid of the conductive case of 1 to 7 and Comparative Example 1 was expressed as a dispersion of the conductive composition. Next, the small sound was separated by one line of liquid 3%, and the liquid content was -21 - 1357083. 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. [Evaluation of Conductive Composition] The dispersions of the conductive compositions of the above Examples 1 to 7 and Comparative Examples 1 and 2 were each dropped on 50 g of a 2.8 cm x 4.8 cm glass plate, and coated with a bar of No. 8. After the bar coater was uniformly applied, it was dried at 60 ° C for 10 minutes, and then dried at 150 ° C for 10 minutes to form a sheet of a conductive composition on a glass plate, and a sheet of the conductive composition. The conductivity was measured at room temperature (about 25 ° C) in accordance with JIS K7194 using a four-probe conductivity measuring instrument [MCP-T600 (trade name) manufactured by Mitsubishi Chemical Corporation]. The results are shown in Table 1. Further, the measurement of each sample was carried out for each of the five points shown in Table 1. The average of the five points was obtained and the decimal point was rounded off.
-22· 1357083 [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 如表1所示，實施例1〜7相較於比較例1〜2，導電率 較高，導電性較優良。亦即，以電解氧化聚合法合成導電 性高分子之實施例1〜7，相較於以化學氧化聚合法合成導 電性高分子之比較例1，導電率較高，導電性較優良，此 外，相較於未添加高沸點溶劑或具有環狀構造之有機酸之 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之導電性 組成物之各薄片進行導電率之測定後，將各薄片於15 0°C之 恆溫槽中靜置100小時後取出，對各別的導電率進行與前 述相同之測定。結果如表2所示。但是，關於導電率係以 在i’5(TC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15 0°C下經過1〇〇小時 後之導電率除以初期導電率（表1記載之導電率），並以百 -23- 1357083 保持率 ，代表 分比（％)來表示。以公式來表示的話，則如下所示。 較高之一方，較不易發生相對於熱之導電率的降低 其耐熱性優良。 導電率之保持率(％)= 100小時後之導電率 1 ~初期導電率~ 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 8 1 比 較 例 1 69 比 較 例 2 70 高溫保 如表2所示，實施例1〜7相較於比較例1〜2， 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8〜1 2及比較例3〜4 之導電 成份分 工業公 針對前述實施例1〜4、實施例7及比較例1〜2 性組成物之分散液，以相對於導電性高分子，樹脂 別爲約150%之方式，添加磺化聚酯樹脂[互應化學 -24- 1357083 司製PLASCOAT Z-561(商品名稱）]，攪拌後，將該含有磺化 聚酯樹脂之分散液滴5〇#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6(TC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 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- 1357083 〜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。 [作爲钽固體電解電容器之評估] 實施例1 3 在將鉬燒結體浸漬於濃度爲0.1 %之磷酸水溶液的狀 態，施加20 V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，將上述鉬燒結體浸漬 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5 0% 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，將上述鉬燒結體浸漬於水 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15(TC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鉬固體電解電容器。 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1 3相同 -26- 1357083 之操作，製作鉅固體電解電容器。 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13相同 之操作，製作鉬固體電解電容器。 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13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，製作鉅固體電解電容器。 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。 針對如上面所製作之實施例1 3〜1 6及比較例5〜6的 鉬固體電解電容器，進行ESR及靜電電容之測定。結果如 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，於靜電電容 之測定，使用 HEWLETT PACKARD公司製之 LCR計 (4284A)，於25°C下以120Hz進行靜電電容之測定。該等測 -27- 1357083 定，各試料皆針對10個來實施，表4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。 [表 _____ . ESR(mQ) 靜電電容（#F) 實施例U 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 如表4所示，實施例13〜16之組固體電解電容器相較 於比較例5〜6之钽固體電解電容器，ESR較小，靜電電容 較大，可知電容器之機能較優。 ESR(mQ) 靜電電容（μ 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 其次，將分別10個之上述實施例13〜16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] _ -28- 1357083 如表5所示，實施例13〜16之钽固體電解電容 於比較例5〜6之鉅固體電解電容器，即使高溫儲存彳 也較小，靜電電容也較大，於高溫條件下具有高信丨 [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 介電體層之陽極裝設導線端子，此外，於由鋁箔所 陰極裝設導線端子，介由隔片捲繞裝設著該等引線 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 散液中和成pH 5.5，將上述電容器元件浸漬於該液， 後取出，於150 °C乾燥30分鐘。重複4次該操作後， °C乾燥120分鐘，形成由導電性組成物所構成之固 質層。其後’將形成上述固體電解質層後之電容器 入鋁之包裝殼體，密封後，於130°C —邊施加25V 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 成物之分散液中和成pH 5.5所得到之液以外，進行 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 成物之分散液中和成pH 5.5所得到之液以外，進行 例17相同之操作，製作鋁捲繞型固體電解電容器。 器相較 麦，ESR 瞋性。 而形成 構成之 端子之 物之分 120秒 以150 體電解 元件置 之規格 〇 電性組 與實施 電性組 與實施 -29- 1357083 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17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1 7〜20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之孭！I定時，使用HEWLETT PACKARD公司製之 LCR計（4284A)，於25°C下以100kHz進行ESR之測定，於 靜電電容之測定時，使用HEWLETT PACKARD公司製之LCR 計（4284 A)，於25 °C下以120Hz進行靜電電容之測定。該等 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- 1357083 [表6] ESR(mQ) 靜電電容（#F) 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UF) 實施例17 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- 1357083 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】 無。 【主要元件符號說明】 無。 -32--22·1357083 [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 Comparative Example 2 0.6 As shown in Table 1, Examples 1 to 7 were superior in electrical conductivity and superior in electrical conductivity to Comparative Examples 1 to 2. That is, Examples 1 to 7 in which a conductive polymer was synthesized by an electrolytic oxidation polymerization method, compared with Comparative Example 1 in which a conductive polymer was synthesized by a chemical oxidation polymerization method, had high conductivity and excellent conductivity, and further, In Comparative Example 2, in which an organic acid having a high boiling point solvent or a cyclic structure was not 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 to 2 were measured for electrical conductivity, and then each sheet was allowed to stand in a thermostat at 150 ° C for 100 hours, and then taken out. The respective conductivity was measured in the same manner as described above. The results are shown in Table 2. However, the conductivity is expressed by the retention of conductivity after resting for 100 hours at i'5 (TC). In addition, the retention of conductivity is after 1 hour at 150 °C. The conductivity is divided by the initial conductivity (the conductivity described in Table 1), and is expressed as a percentage (%) in the holding ratio of -23 - 1357083. If expressed by the formula, the following is shown. It is less prone to decrease in thermal conductivity with respect to heat. Maintainance of conductivity (%) = conductivity after 100 hours 1 ~ initial conductivity ~ X 1 〇〇 [Table 2] Conductivity retention Rate (%) Example 1 81 Example 2 80 Example 3 83 Example 4 81 Example 5 84 - Example 6 85 Example 7 8 1 Comparative Example 1 69 Comparative Example 2 70 High temperature maintenance as shown in Table 2, In Examples 1 to 7, the retention ratio of the electrical conductivity after storage was higher than that of Comparative Examples 1 to 7, and the heat resistance was excellent. [As Evaluation of Antistatic Film] Examples 8 to 12 and Comparative Examples 3 to 4 The conductive component is divided into the above embodiments 1 to 4, the embodiment 7 and the comparative example 1 A sulfonated polyester resin is added to the dispersion of the composition of the composition of the second to the second, and the resin is added to the conductive polymer and the resin is about 150%. [Compound Chemical-24- 1357083 manufactured by PLASCOAT Z-561 (trade name) After stirring, the dispersed droplets containing the sulfonated polyester resin were placed on a polyethylene sheet of 2.8 cm x 4.8 cm, uniformly coated with a bar coater of No. 8, and then subjected to 6 (TC for 10 minutes). After drying, the film was dried at 150 ° C for 10 minutes, and each of the conductive compositions was made into an antistatic film of a conductor. The surface resistances of the obtained antistatic films of Examples 8 to 12 and Comparative Examples 3 to 4 were obtained. According to J1SK7194, a four-probe conductivity measuring device [MCP-T600 (product name) manufactured by Mitsubishi Chemical Corporation] was used at room temperature (about 25 ° C), and UV-VIS-NIR RECORDING SPECTROPHOTOMETER was used. [UV3100 (product name) manufactured by Shimadzu Corporation] The measurement of the visible light transmittance at a wavelength of 400 nm to 700 nm was carried out. The results are shown in Table 3 together with the type of the conductive composition to be used. Implemented at 5 o'clock, the number shown in Table 3 is obtained from the 5 points. The average 値 and the decimal point are rounded off. [Table 3] Conductive composition used for the antistatic film 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 Example 7 750 91 Comparative Example 3 Comparative Example 1 51,200 90 Comparative Example 4 Comparative Example 2 629, 100 90 As shown in Table 3, Examples The antistatic film of 8 to 1 2 has a smaller surface resistance than the antistatic film of Comparative Example 3 -25-1357083 to 4, 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 of 钽Solid Electrolytic Capacitor] Example 1 3 A immersion of a molybdenum sintered body in a phosphoric acid aqueous solution having a concentration of 0.1% was carried out by applying a voltage of 20 V to form an oxide film on the surface of the molybdenum sintered body. Dielectric layer. Next, the above-mentioned molybdenum 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 oxidizing agent and doped with 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 above-mentioned molybdenum sintered body was immersed in water, left for 30 minutes, 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 the above operation was repeated three times, the solid electrolyte layer composed of the conductive composition was formed at 15 (TC) for 60 minutes. Thereafter, the solid electrolyte layer was coated with a carbon paste or a silver paste to prepare a molybdenum solid electrolytic capacitor. [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 2 was used instead of the dispersion of the conductive composition of Example 1. Example 1 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 Example 3 was used instead of the dispersion of the conductive composition of Example 1. 6 A giant solid electrolytic capacitor was produced in the same manner 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 In addition to the use of the comparative example The same operation as in Example 13 was carried out, except that the dispersion of the conductive composition of 1 was replaced by the dispersion of the conductive composition of Example 1. Solid electrolytic capacitor. 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 electrostatic capacitance were measured for the molybdenum solid electrolytic capacitors of Examples 13 to 16 and Comparative Examples 5 to 6 produced as above. The results are shown in Table 4. Further, the measurement methods of ESR and electrostatic capacitance were as follows: As shown in the measurement of ESR, ESR was measured at 100 kHz at 25 ° C using an LCR meter (4284A) manufactured by HEWLETT PACKARD Co., Ltd., and an LCR meter (4284A) manufactured by HEWLETT PACKARD Co., Ltd. was used for measurement of electrostatic capacitance. The electrostatic capacitance was measured at 120 Hz at 25 ° C. These tests were carried out for each of the samples -27 - 1357083, and the ESR and electrostatic capacitance 所示 shown in Table 4 were obtained for each of the 10 samples. Average 値 and round off the decimal point. [Table_____ . ESR (mQ) Electrostatic capacitance (#F) Example U 27 150 Example 14 28 150 Example 15 24 152 Example 16 25 151 Comparative Example 5 220 134 comparison Example 6 2199 121 As shown in Table 4, the solid electrolytic capacitors of the groups 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. ESR (mQ) Electrostatic capacitance (μ 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 Next, 10 of the above examples After the solid electrolytic capacitors of 13 to 16 and Comparative Examples 5 to 6 were stored at 125 ° C for 200 hours, the same ESR and electrostatic capacitance were measured. The results are shown in Table 5. [Table 5] _ -28 - 1357083 As shown in Table 5, the solid electrolytic capacitors of Examples 13 to 16 were compared with the giant solid electrolytic capacitors of Comparative Examples 5 to 6, even if the storage was high at a high temperature, and the electrostatic capacitance was large. High-stacking under high temperature conditions [Evaluation of aluminum-wound solid electrolytic capacitor] Example 1 7 After performing an etching treatment on the surface of the aluminum foil, an anode-mounted lead terminal for forming a dielectric layer is formed, and further, A lead terminal is mounted on the cathode of the aluminum foil, and the lead anode and the cathode are wound around the separator to form a capacitor element. Next, the conductive composition dispersion liquid obtained in Example 3 was neutralized to pH 5.5 with butylamine, and the capacitor element was immersed in the liquid, and then taken out, and dried at 150 ° C for 30 minutes. After repeating this operation four times, it was dried at °C for 120 minutes to form a solid layer composed of a conductive composition. Thereafter, the capacitor 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. 2-methylimidazole The same procedure as in Example 17 was carried out except that the dispersion of the derivative obtained in Example 5 was neutralized to a pH of 5.5 to prepare an aluminum wound solid electrolytic capacitor. Example 1 9 The same operation as in Example 17 was carried out except that the liquid obtained by neutralizing the dispersion of the derivative obtained in Example 6 with 2-methylimidazole to pH 5.5 was used to prepare aluminum-wound solid electrolytic Capacitor. Compared with wheat, ESR is ambiguous. And the object forming the terminal is divided into 120 seconds, the 150-electrolytic element is placed in the specification, the electrical group is set, and the electrical group is implemented. -29- 1357083. Example 20 except that 4-methylimidazole is used. An aluminum wound solid electrolytic capacitor was produced in the same manner as in Example 17 except that the obtained liquid dispersion of the conductive composition was neutralized to a liquid obtained in pH 5.5. Comparative Example 7 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 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. At the top of ESR! At the time of I, the LCR meter (4284A) manufactured by HEWLETT PACKARD Co., Ltd. was used to measure ESR at 100 kHz at 25 ° C. For the measurement of electrostatic capacitance, the LCR meter (4284 A) manufactured by HEWLETT PACKARD Co., Ltd. was used at 25 °. The measurement of the electrostatic capacitance was performed at 120 Hz under C. For each of these measurements, each of the samples was carried out for 10, and the ESR and the electrostatic capacitance 所示 shown in Table 6 were obtained by taking the average of the 10 値 and rounding off the decimal point. • 30-1357083 [Table 6] ESR (mQ) Electrostatic Capacitance (#F) 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-wound solid electrolytic capacitors of Examples 17 to 20 have 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 UF) Example 17 26 99 Example 18 25 105 Example 19 25 104 Example 20 26 104 Comparative Example 7 5500 41 As shown in Table 7, the aluminum of Examples 17 to 20 Compared with the aluminum-wound solid electrolytic capacitor of Comparative Example 7, the wound-type solid electrolytic capacitor has a small ESR and a large electrostatic capacitance even after high-temperature storage, and represents high reliability under high temperature conditions -31-1357083. 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 shown above, by using it as an electric conductor, it is possible to provide an antistatic film, an antistatic resin, and an antistatic film which are excellent in transparency, high electrical conductivity, and excellent heat resistance. Electrostatic 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] None. [Main component symbol description] None. -32-