JP2008121025A - Oxidizer and dopant for synthesizing electrically-conductive polymer, electrically-conductive polymer and solid electrolytic capacitor - Google Patents
Oxidizer and dopant for synthesizing electrically-conductive polymer, electrically-conductive polymer and solid electrolytic capacitor Download PDFInfo
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本発明は、導電性高分子合成用酸化剤兼ドーパント、それを用いて化学酸化重合して得られた導電性高分子、該導電性高分子を固体電解質として用いた固体電解コンデンサに関する。 The present invention relates to an oxidizing agent and dopant for conductive polymer synthesis, a conductive polymer obtained by chemical oxidative polymerization using the same, and a solid electrolytic capacitor using the conductive polymer as a solid electrolyte.
導電性高分子は、その高い導電性により、アルミニウムコンデンサ、タンタルコンデンサなどの固体電解コンデンサの固体電解質などに用いられている。 Conductive polymers are used for solid electrolytes of solid electrolytic capacitors such as aluminum capacitors and tantalum capacitors because of their high conductivity.
そのような用途における導電性高分子としては、ピロール、チオフェン、アニリンまたはそれらの誘導体を化学酸化重合または電解酸化重合することによって合成したものが用いられている。 As the conductive polymer in such applications, those synthesized by chemical oxidative polymerization or electrolytic oxidative polymerization of pyrrole, thiophene, aniline or their derivatives are used.
酸化重合を行う際のドーパントには、主に有機スルホン酸が用いられ、それらの中でも特に芳香族スルホン酸が多用されている。 An organic sulfonic acid is mainly used as a dopant for oxidative polymerization, and among them, aromatic sulfonic acid is frequently used.
しかしながら、芳香族スルホン酸の出発材料であるアルキルベンゼンのアルキル鎖は、長鎖の場合、混合アルキルであって単一化合物として一定していないので、得られる導電性高分子の導電性がばらつく原因となる。例えば、ドデシルベンゼンスルホン酸（分子量３２６）のように単一分子量であっても、構造異性体の存在が電気特性に影響する。また、長鎖アルキル基を有する長鎖型芳香族スルホン酸は、分子サイズが大きいため、ドーピングしづらく、結果として初期重合段階では充分な導電性が得られない。 However, the alkyl chain of the alkylbenzene, which is the starting material of the aromatic sulfonic acid, is a mixed alkyl in the case of a long chain and is not constant as a single compound. Therefore, the conductivity of the resulting conductive polymer varies. Become. For example, even with a single molecular weight such as dodecylbenzenesulfonic acid (molecular weight 326), the presence of structural isomers affects the electrical properties. In addition, a long-chain aromatic sulfonic acid having a long-chain alkyl group has a large molecular size and is difficult to be doped. As a result, sufficient conductivity cannot be obtained in the initial polymerization stage.
一方、短鎖型芳香族スルホン酸、例えばベンゼンスルホン酸（分子量１５８）やトルエンスルホン酸（分子量１７２）は、分子サイズが小さく、ドーピングしやすいので初期重合段階では良好な導電性が得られるものの、その小さい分子サイズのため、脱ドーピングが起こりやすく、特に高温・高湿条件下で放置した場合には、顕著な導電性の低下が認められる。 On the other hand, short-chain aromatic sulfonic acids such as benzene sulfonic acid (molecular weight 158) and toluene sulfonic acid (molecular weight 172) are small in molecular size and easy to be doped, so that good conductivity is obtained in the initial polymerization stage. Due to its small molecular size, dedoping is likely to occur, and a remarkable decrease in conductivity is observed particularly when left under high temperature and high humidity conditions.
上記のような状況から、初期重合段階で良好な導電性が得られ、しかも高温・高湿条件下で放置しても大きな導電性の低下が認められず、導電性のばらつきが少ない導電性高分子を構成することができるドーパントが求められている。 From the above situation, good conductivity can be obtained in the initial polymerization stage, and even if it is left under high temperature and high humidity conditions, there is no significant decrease in conductivity, and there is little variation in conductivity. There is a need for dopants that can constitute molecules.
そこで、上記のような要求に応えるべく、導電性高分子用ドーパントとして、ＯＨ基が付いた芳香族スルホン酸を用いて、電解酸化重合により導電性高分子を形成することが提案されている（非特許文献１）。しかしながら、一般的に上記のような芳香族スルホン酸は、乳化力が弱く、モノマーを完全に乳化できないため、均一な導電性高分子を合成することができないという問題があった。また、乳化力を高めるため、別途アルキル基を付加することも考えられるが、反応が繁雑になり、かつ経済的ではない。 Therefore, in order to meet the above requirements, it has been proposed to form an electroconductive polymer by electrolytic oxidation polymerization using an aromatic sulfonic acid with an OH group as a dopant for the electroconductive polymer ( Non-patent document 1). However, in general, the aromatic sulfonic acid as described above has a problem that the emulsifying power is weak and the monomer cannot be completely emulsified, so that a uniform conductive polymer cannot be synthesized. In order to increase the emulsifying power, it may be possible to add an alkyl group separately, but the reaction becomes complicated and it is not economical.
また、化学酸化重合の場合は、酸化剤としての機能を持たせるため、上記芳香族スルホン酸を遷移金属塩、例えば第二鉄塩や第二銅塩に仕上げる必要があるが、水酸基またはカルボキシル基が付いた芳香族スルホン酸は、キレート作用が強いため、均一な鉄塩を調製することができず、そのため、均一な導電性高分子が得ることができなかった。 In addition, in the case of chemical oxidative polymerization, in order to have a function as an oxidizing agent, it is necessary to finish the aromatic sulfonic acid to a transition metal salt, for example, a ferric salt or a cupric salt. Aromatic sulfonic acids marked with have a strong chelating action, so a uniform iron salt could not be prepared, and a uniform conductive polymer could not be obtained.
本発明は、上記のような従来技術における問題点を解決し、導電性が優れ、かつ耐熱性が優れた導電性高分子を化学酸化重合により合成できる酸化剤兼ドーパントと、上記のような導電性が優れ、かつ耐熱性が優れた導電性高分子を提供し、また、その導電性高分子を固体電解質として用いて高温・高湿条件下での信頼性の高い固体電解コンデンサを提供することを目的とする。 The present invention solves the problems in the prior art as described above, an oxidizing agent / dopant capable of synthesizing a conductive polymer having excellent conductivity and heat resistance by chemical oxidative polymerization, and the above-described conductivity. To provide a conductive polymer with excellent heat resistance and heat resistance, and to provide a solid electrolytic capacitor with high reliability under high temperature and high humidity conditions using the conductive polymer as a solid electrolyte With the goal.
本発明者らは、上記課題を解決するため鋭意研究を重ねた結果、メトキシベンゼンスルホン酸第二鉄塩またはエトキシベンゼンスルホン酸第二鉄塩を酸化剤兼ドーパントとしてチオフェンまたはその誘導体を化学酸化重合して得られる導電性高分子が、導電性が優れ、かつ耐熱性が優れていて、上記課題を解決できることを見出し、それに基づいて本発明を完成するにいたった。 As a result of intensive studies to solve the above problems, the present inventors have conducted chemical oxidative polymerization of thiophene or its derivatives using ferric salt of methoxybenzene sulfonic acid or ferric salt of ethoxybenzene sulfonic acid as an oxidizing agent and dopant. The conductive polymer obtained in this way was found to be excellent in conductivity and heat resistance and to solve the above problems, and based on this, the present invention was completed.
すなわち、本願の第１の発明はメトキシベンゼンスルホン酸第二鉄塩またはエトキシベンゼンスルホン酸第二鉄塩からなる導電性高分子合成用酸化剤兼ドーパントに関するものであり、第２の発明は上記導電性高分子合成用酸化剤兼ドーパントを用いてチオフェンまたはその誘導体を化学酸化重合して得られたことを特徴とする導電性高分子に関するものであり、第３の発明は上記導電性高分子を固体電解質として用いたことを特徴とする固体電解コンデンサに関するものである。 That is, the first invention of the present application relates to an oxidizing agent / dopant for synthesizing a conductive polymer comprising ferric salt of methoxybenzenesulfonic acid or ferric salt of ethoxybenzenesulfonic acid, and the second invention relates to the above-mentioned conductive material. The present invention relates to a conductive polymer obtained by chemical oxidative polymerization of thiophene or a derivative thereof using an oxidizing agent / dopant for the synthesis of a conductive polymer, and a third invention relates to the conductive polymer described above. The present invention relates to a solid electrolytic capacitor that is used as a solid electrolyte.
本発明の導電性高分子合成用酸化剤兼ドーパントを用いてチオフェンまたはその誘導体を化学酸化重合することにより、導電性が優れ、かつ耐熱性が優れた導電性高分子が得られる。
そして、その導電性が優れ、かつ耐熱性が優れた導電性高分子を固体電解質として用いることにより、高温・高湿条件下における信頼性の高い固体電解コンデンサが得られる。
By conducting chemical oxidative polymerization of thiophene or a derivative thereof using the oxidant and dopant for conductive polymer synthesis of the present invention, a conductive polymer having excellent conductivity and excellent heat resistance can be obtained.
A highly reliable solid electrolytic capacitor under high temperature and high humidity conditions can be obtained by using a conductive polymer having excellent conductivity and heat resistance as a solid electrolyte.
本発明の酸化剤兼ドーパントを構成するメトキシベンゼンスルホン酸第二鉄塩またはエトキシベンゼンスルホン酸第二鉄塩のメトキシベンゼンスルホン酸部分またはエトキシベンゼンスルホン酸部分は、メトキシベンゼンやエトキシベンゼンなどのアルコキシベンゼンを濃硫酸に混合してスルホン化した後、苛性ソーダなどのアルカリ剤で中和し、晶析分離などの精製処理をすることによって合成することができる。そして、メトキシベンゼンスルホン酸第二鉄塩またはエトキシベンゼンスルホン酸第二鉄塩は、後記の実施例で示すように、上記メトキシベンゼンスルホン酸またはエトキシベンゼンスルホン酸と水酸化第二鉄とを反応させることによって得られる。 The methoxybenzenesulfonic acid ferric salt or ethoxybenzenesulfonic acid ferric salt constituting the oxidizing agent and dopant of the present invention is an alkoxybenzene such as methoxybenzene or ethoxybenzene. Is mixed with concentrated sulfuric acid to be sulfonated, then neutralized with an alkaline agent such as caustic soda, and then subjected to purification treatment such as crystallization separation. Then, the ferric salt of methoxybenzene sulfonic acid or ferric salt of ethoxybenzene sulfonic acid reacts the methoxybenzene sulfonic acid or ethoxybenzene sulfonic acid with ferric hydroxide, as shown in the examples below. Can be obtained.
本発明で導電性高分子を合成するためのモノマーとしては、チオフェンまたはその誘導体が用いられる。 As a monomer for synthesizing the conductive polymer in the present invention, thiophene or a derivative thereof is used.
つぎに、本発明の導電性高分子の合成および上記導電性高分子を固体電解質として用いた固体電解コンデンサについて説明する。 Next, the synthesis of the conductive polymer of the present invention and a solid electrolytic capacitor using the conductive polymer as a solid electrolyte will be described.
本発明の導電性高分子の合成にあたっては、まず、チオフェンまたはその誘導体を、上記メトキシベンゼンスルホン酸第二鉄塩またはエトキシベンゼンスルホン酸第二鉄塩を酸化剤兼ドーパントとして用いて、化学酸化重合が行われる。 In the synthesis of the conductive polymer of the present invention, first, thiophene or a derivative thereof is chemically oxidatively polymerized using the above-mentioned methoxybenzene sulfonic acid ferric salt or ethoxybenzene sulfonic acid ferric salt as an oxidant and dopant. Is done.
上記化学酸化重合においては、メトキシベンゼンスルホン酸第二鉄塩またはエトキシベンゼンスルホン酸第二鉄塩とチオフェンまたはその誘導体とを、有機溶媒で特定濃度となるよう、それぞれ別途あらかじめ希釈しておき、溶液同士を混合して一定時間反応させた後、洗浄、乾燥して導電性高分子を合成することができる（ここで、酸化剤兼ドーパントとして用いているメトキシベンゼンスルホン酸第二鉄塩またはエトキシベンゼンスルホン酸第二鉄塩の鉄成分がチオフェンまたはその誘導体の酸化重合剤として働き、残りのスルホン酸成分は高分子マトリックス中に含有され、ドーパントとしての役割を果たす）。上記重合に際して用いる有機溶媒としては、例えば、メタノール、エタノール、ｎ−プロパノール、ｎ−ブタノールなどが挙げられ、洗浄の際にも上記溶媒のいずれかを用いればよい。 In the above-mentioned chemical oxidative polymerization, methoxybenzene sulfonic acid ferric salt or ethoxybenzene sulfonic acid ferric salt and thiophene or a derivative thereof are separately diluted beforehand with an organic solvent so as to have a specific concentration, After mixing and reacting for a certain period of time, it can be washed and dried to synthesize a conductive polymer (wherein methoxybenzene sulfonic acid ferric salt or ethoxybenzene used as an oxidizing agent and dopant) The iron component of the ferric sulfonic acid salt acts as an oxidative polymerization agent for thiophene or its derivative, and the remaining sulfonic acid component is contained in the polymer matrix and serves as a dopant). Examples of the organic solvent used for the polymerization include methanol, ethanol, n-propanol, and n-butanol. Any of the above solvents may be used for washing.
上記のようにして合成された導電性高分子は、導電性が優れ、しかも耐熱性が優れている。その理由は現在のところ必ずしも明確ではないが、メトキシベンゼンスルホン酸やエトキシベンゼンスルホン酸がＯＨ基のようにキレート作用を有しないため、均一な第二鉄塩を得ることができることに基づくものと考えられる。すなわち、上記メトキシベンゼンスルホン酸第二鉄塩またはエトキシベンゼンスルホン酸第二鉄塩を酸化重合剤として使用すると、均一な導電性高分子が形成されるので、初期重合段階から優れた特性が得られるようになるものと考えられる。そして、そのようにして導電性高分子中に取り込まれたメトキシ基またはエトキシ基は、長期保存中に分解されやすく、その際、メトキシ基またはエトキシ基がＯＨ基に変わるので、優れた耐熱性が得られるようになるものと考えられる。 The conductive polymer synthesized as described above has excellent conductivity and heat resistance. The reason for this is not necessarily clear at present, but it is thought that methoxybenzene sulfonic acid and ethoxybenzene sulfonic acid do not have a chelating action like OH groups, and thus are based on the ability to obtain a uniform ferric salt. It is done. That is, when the above methoxybenzene sulfonic acid ferric salt or ethoxybenzene sulfonic acid ferric salt is used as an oxidative polymerization agent, a uniform conductive polymer is formed, so that excellent characteristics can be obtained from the initial polymerization stage. It is thought that it will become. The methoxy group or ethoxy group thus incorporated into the conductive polymer is easily decomposed during long-term storage, and at that time, the methoxy group or ethoxy group is changed to an OH group. It is thought that it will be obtained.
上記のように、本発明の導電性高分子は、導電性が優れ、しかも耐熱性が優れているので、コンデンサ、バッテリー、帯電防止シート、耐腐食用塗料などの用途において有用である。 As described above, the conductive polymer of the present invention is excellent in conductivity and heat resistance, and thus is useful in applications such as capacitors, batteries, antistatic sheets, and anticorrosion paints.
以下に実施例を挙げて本発明をより具体的に説明する。ただし、本発明はそれらの実施例に例示のもののみに限定されることはない。また、実施例に先立ち、実施例の導電性高分子のドーパントとなるメトキシベンゼンスルホン酸の合成例を合成例１として示し、エトキシベンゼンスルホン酸の合成例を合成例２として示す。なお、以下において、溶液や分散液などの濃度を示す％は質量基準によるものである。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples illustrated in these examples. Prior to the examples, a synthesis example of methoxybenzene sulfonic acid serving as a dopant for the conductive polymer of the example is shown as synthesis example 1, and a synthesis example of ethoxybenzene sulfonic acid is shown as synthesis example 2. In the following, “%” indicating the concentration of a solution or dispersion is based on mass.
合成例１
室温下で攪拌しながら、９８％硫酸５６０ｇをメトキシベンゼン６００ｇに滴下した。上記硫酸の滴下後、反応液の温度を７５℃に上げ、その温度を保ちながら３時間攪拌した。反応終了後、５００ｇの蒸留水を加え、エーテル２００ｇを添加し、２層に分離した下層部分のみを取り出し、さらに蒸留による濃縮と水の添加を２度繰り返して、未反応のメトキシベンゼンを除去することにより、メトキシベンゼンスルホン酸を得た。さらに２ｍｏｌ／ｌの水酸化ナトリウムにより中和してメトキシベンゼンスルホン酸のナトリウム塩も得た。
Synthesis example 1
While stirring at room temperature, 560 g of 98% sulfuric acid was added dropwise to 600 g of methoxybenzene. After dropwise addition of the sulfuric acid, the temperature of the reaction solution was raised to 75 ° C. and stirred for 3 hours while maintaining the temperature. After completion of the reaction, 500 g of distilled water is added, 200 g of ether is added, only the lower layer part separated into two layers is taken out, and concentration by distillation and addition of water are repeated twice to remove unreacted methoxybenzene. As a result, methoxybenzenesulfonic acid was obtained. Further, neutralization with 2 mol / l sodium hydroxide gave a sodium salt of methoxybenzenesulfonic acid.
合成例２
メトキシベンゼンに代えてエトキシベンゼン６７８ｇを用いた以外は、実施例１と同様の操作を行い、エトキシベンゼンスルホン酸を得た。
Synthesis example 2
Except for using 678 g of ethoxybenzene instead of methoxybenzene, the same operation as in Example 1 was performed to obtain ethoxybenzenesulfonic acid.
実施例１
室温下、１０００ｍｌの蒸留水にＦｅ２ （ＳＯ４ ）３ ・８Ｈ２ Ｏを１０８．６ｇ（０．２ｍｏｌ）溶解して調製した溶液を激しく攪拌しながら、その中に５ｍｏｌ／ｌの水酸化ナトリウム水溶液をゆっくりと添加してｐＨ７に調整した後、遠心分離により上澄みを取り除いて水酸化第二鉄の沈殿を得た。余分の水溶性塩を取り除くため、４０００ｍｌの蒸留水に上記水酸化第二鉄の沈殿を分散させた後、遠心分離で上清を取り除く操作を２回繰り返した。得られた水酸化第二鉄の沈殿を５００ｇのノルマルブタノールに分散させた。
Example 1
A solution prepared by dissolving 108.6 g (0.2 mol) of Fe 2 (SO 4 ) 3 · 8H 2 O in 1000 ml of distilled water at room temperature was vigorously stirred, and 5 mol / l sodium hydroxide was added therein. The aqueous solution was slowly added to adjust the pH to 7, and then the supernatant was removed by centrifugation to obtain a ferric hydroxide precipitate. In order to remove excess water-soluble salts, the operation of dispersing the ferric hydroxide precipitate in 4000 ml of distilled water and then removing the supernatant by centrifugation was repeated twice. The obtained ferric hydroxide precipitate was dispersed in 500 g of normal butanol.
これとは別に、合成例１で得たメトキシベンゼンスルホン酸２０３ｇをあらかじめ５００ｇのノルマルブタノールに溶解しておき、その溶液中に上記方法で調製した水酸化第二鉄の分散液を添加した。室温下、１２時間かきまぜて反応させた後、蒸留して濃度５０％のメトキシベンゼンスルホン酸第二鉄塩のノルマルブタノール溶液を得た。 Separately, 203 g of methoxybenzenesulfonic acid obtained in Synthesis Example 1 was previously dissolved in 500 g of normal butanol, and a dispersion of ferric hydroxide prepared by the above method was added to the solution. The mixture was reacted at room temperature for 12 hours, and then distilled to obtain a normal butanol solution of ferric methoxybenzenesulfonic acid having a concentration of 50%.
上記メトキシベンゼンスルホン酸第二鉄塩のノルマルブタノール溶液に、メトキシベンゼンスルホン酸第二鉄塩の濃度が０．５ｍｏｌ／ｌになるようにｎ−ブタノールを添加して濃度調整した後、その溶液に３，４−エチレンジオキシチオフェンを濃度が０．５ｍｏｌ／ｌになるように添加し、充分にかき混ぜ、上記メトキシベンゼンスルホン酸第二鉄塩を酸化剤兼ドーパントとして、３，４−エチレンジオキシチオフェンの化学酸化重合を開始させ、それを直ちに、３ｃｍ×５ｃｍのセラミックプレート上に１８０μｌ滴下した。そして、そのセラミックプレート上で湿度５５％、温度２５℃で１２時間重合した後、エタノール中に上記プレートをその上に形成された重合物膜と共に入れ、洗浄し、１３０℃で３０分間乾燥した。乾燥後、上記プレートに１．５ｔの荷重をかけたまま５分間放置して、膜厚を均等にした後、その重合物であるポリエチレンジオキシチオフェンの電導度を４探針方式の電導度測定器（三菱化学社製のＭＣＰ−Ｔ６００）により測定した。その結果を後記の表１に示す。 After adjusting the concentration of n-butanol by adding n-butanol to the above-mentioned normal butanol solution of ferric methoxybenzene sulfonate so that the concentration of ferric salt of methoxybenzene is 0.5 mol / l, 3,4-ethylenedioxythiophene was added so that the concentration was 0.5 mol / l, and the mixture was thoroughly stirred, and the above methoxybenzene sulfonic acid ferric salt was used as an oxidizing agent and a dopant, and 3,4-ethylenedioxy The chemical oxidative polymerization of thiophene was initiated and immediately dropped 180 μl onto a 3 cm × 5 cm ceramic plate. Then, after polymerizing on the ceramic plate at a humidity of 55% and a temperature of 25 ° C. for 12 hours, the plate was placed in ethanol together with the polymer film formed thereon, washed, and dried at 130 ° C. for 30 minutes. After drying, leave the plate with a load of 1.5t for 5 minutes to equalize the film thickness, and then measure the conductivity of polyethylenedioxythiophene, the polymer, using a 4-probe method. Measured with an instrument (MCP-T600 manufactured by Mitsubishi Chemical Corporation). The results are shown in Table 1 below.
実施例２
合成例１で得たメトキシベンゼンスルホン酸に代えて、合成例２で得たエトキシベンゼンスルホン酸２１８ｇを用いた以外は、実施例１と同様に３，４−エチレンジオキシチオフェンの化学酸化重合を行い、得られたポリエチレンジオキシチオフェンについて電導度を測定した。その結果を後記の表１に示す。
Example 2
In place of the methoxybenzenesulfonic acid obtained in Synthesis Example 1 and using 218 g of ethoxybenzenesulfonic acid obtained in Synthesis Example 2, chemical oxidative polymerization of 3,4-ethylenedioxythiophene was performed in the same manner as in Example 1. The electrical conductivity of the obtained polyethylenedioxythiophene was measured. The results are shown in Table 1 below.
比較例１
合成例１で得たメトキシベンゼンスルホン酸に代えて、ｐ−トルエンスルホン酸１８６ｇを用いた以外は、実施例１と同様に３，４−エチレンジオキシチオフェンの化学酸化重合を行い、得られたポリエチレンジオキシチオフェンについて電導度を測定した。その結果を後記の表１に示す。
Comparative Example 1
A chemical oxidative polymerization of 3,4-ethylenedioxythiophene was carried out in the same manner as in Example 1 except that 186 g of p-toluenesulfonic acid was used instead of methoxybenzenesulfonic acid obtained in Synthesis Example 1. Electrical conductivity was measured for polyethylenedioxythiophene. The results are shown in Table 1 below.
比較例２
合成例１で得たメトキシベンゼンスルホン酸に代えて、分岐型ドデシルベンゼンスルホン酸３５２ｇを用いた以外は、実施例１と同様に３，４−エチレンジオキシチオフェンの化学酸化重合を行い、得られたポリエチレンジオキシチオフェンについて電導度を測定した。その結果を後記の表１に示す。
Comparative Example 2
In place of methoxybenzenesulfonic acid obtained in Synthesis Example 1, 352 g of branched dodecylbenzenesulfonic acid was used, except that chemical oxidation polymerization of 3,4-ethylenedioxythiophene was performed in the same manner as in Example 1 to obtain The electrical conductivity of polyethylenedioxythiophene was measured. The results are shown in Table 1 below.
比較例３
合成例１で得たメトキシベンゼンスルホン酸に代えて、ナフタレンスルホン酸２２５ｇを用いた以外は、実施例１と同様に３，４−エチレンジオキシチオフェンの化学酸化重合を行い、得られたポリエチレンジオキシチオフェンについて電導度を測定した。その結果を後記の表１に示す。
Comparative Example 3
In place of methoxybenzenesulfonic acid obtained in Synthesis Example 1, 225 g of naphthalenesulfonic acid was used, except that chemical oxidation polymerization of 3,4-ethylenedioxythiophene was performed in the same manner as in Example 1 to obtain the obtained polyethylene The conductivity was measured for oxythiophene. The results are shown in Table 1 below.
上記実施例１〜２および比較例１〜３で得たポリエチレンジオキシチオフェンの電導度を表１に、その合成にあたって使用した酸化剤兼ドーパントと共に示す。 The electrical conductivity of the polyethylenedioxythiophene obtained in Examples 1-2 and Comparative Examples 1-3 is shown in Table 1 together with the oxidizing agent and dopant used in the synthesis.
表１に示すように、実施例１〜２のポリエチレンジオキシチオフェンは、比較例１〜３のポリエチレンジオキシチオフェンに比べて、電導度が高く、導電性が優れていた。 As shown in Table 1, the polyethylene dioxythiophenes of Examples 1 and 2 had higher electrical conductivity and excellent electrical conductivity than the polyethylene dioxythiophenes of Comparative Examples 1 to 3.
すなわち、メトキシベンゼンスルホン酸第二鉄塩を酸化剤兼ドーパントとして用いて合成した実施例１のポリエチレンジオキシチオフェンおよびエトキシベンゼンスルホン酸第二鉄塩を酸化剤兼ドーパントとして合成した実施例２のポリエチレンジオキシチオフェンは、ｐ−トルエンスルホン酸第二鉄塩を酸化剤兼ドーパントとして合成した比較例１のポリエチレンジオキシチオフェン、分岐型ドデシルベンゼンスルホン酸第二鉄塩を酸化剤兼ドーパントとして合成した比較例２のポリエチレンジオキシチオフェンおよびナフタレンスルホン酸第二鉄塩を酸化剤兼ドーパントとして合成した比較例３のポリエチレンジオキシチオフェンより、高い電導度を有していて、導電性が優れていた。 That is, the polyethylene of Example 2 synthesized using polyethylenedioxythiophene of Example 1 and ferric salt of ethoxybenzene sulfonic acid as dopants and dopants synthesized using ferric salt of methoxybenzenesulfonic acid as an oxidant and dopant The dioxythiophene was synthesized using polyethylene dioxythiophene of Comparative Example 1 synthesized with p-toluenesulfonic acid ferric salt as an oxidizing agent and dopant, and branched dodecylbenzenesulfonic acid ferric salt as an oxidizing agent and dopant. The polyethylene dioxythiophene of Example 2 and ferric naphthalenesulfonic acid ferric salt synthesized as an oxidant and dopant had higher electrical conductivity and superior conductivity than the polyethylene dioxythiophene of Comparative Example 3.
つぎに、上記実施例１〜２および比較例１〜３のポリエチレンジオキシチオフェンについて高温貯蔵による電導度の低下率を調べた。その結果を表２に示す。その高温貯蔵試験の方法は次の通りである。 Next, the rate of decrease in electrical conductivity due to high-temperature storage was examined for the polyethylene dioxythiophenes of Examples 1-2 and Comparative Examples 1-3. The results are shown in Table 2. The method of the high temperature storage test is as follows.
高温貯蔵試験：
上記実施例１〜２および比較例１〜３のポリエチレンジオキシチオフェンのシートについて、前記のように電導度を測定した後、各シートを１３０℃の恒温槽中に貯蔵し、経時的にシートを取り出して電導度を測定して、高温貯蔵による電導度の低下率を調べた。なお、電導度の低下率は、初期電導度値（すなわち、貯蔵前に測定した電導度値）から貯蔵後の電導度値を引いた時の差を初期電導度値で割り、パーセント（％）で示した。これを式で表すと次の通りである。
High temperature storage test:
For the polyethylene dioxythiophene sheets of Examples 1-2 and Comparative Examples 1-3 above, after measuring the conductivity as described above, each sheet was stored in a thermostatic bath at 130 ° C. The electrical conductivity was taken out and measured to examine the rate of decrease in electrical conductivity due to high temperature storage. Note that the rate of decrease in conductivity is calculated by dividing the difference when the conductivity value after storage is subtracted from the initial conductivity value (that is, the conductivity value measured before storage) by the initial conductivity value. It showed in. This is expressed as follows.
表２に示す結果から明らかなように、実施例１〜２のポリエチレンジオキシチオフェンは、比較例１〜３のポリエチレンジオキシチオフェンに比べて、２４時間貯蔵後、４８時間貯蔵後とも、電導度の低下が少なく、耐熱性が優れていた。 As is clear from the results shown in Table 2, the polyethylene dioxythiophenes of Examples 1 and 2 are more conductive than the polyethylene dioxythiophenes of Comparative Examples 1 to 3 after 24 hours of storage and 48 hours of storage. The heat resistance was excellent.
すなわち、メトキシベンゼンスルホン酸第二鉄塩を酸化剤兼ドーパントとして合成した実施例１のポリエチレンジオキシチオフェンおよびエトキシベンゼンスルホン酸第二鉄塩を酸化剤兼ドーパントとして合成した実施例２のポリエチレンジオキシチオフェンは、ｐ−トルエンスルホン酸第二鉄塩を酸化剤兼ドーパントとして合成した比較例１のポリエチレンジオキシチオフェン、分岐型ドデシルベンゼンスルホン酸第二鉄塩を酸化剤兼ドーパントとして合成した比較例２のポリエチレンジオキシチオフェンおよびナフタレンスルホン酸第二鉄塩を酸化剤兼ドーパントとして合成した比較例３のポリエチレンジオキシチオフェンに比べて、高温貯蔵による電導度の低下が少なく、耐熱性が優れていた。 That is, the polyethylenedioxythiophene of Example 1 synthesized using ferric methoxybenzene sulfonate as an oxidant and dopant and the polyethylene dioxy of Example 2 synthesized using ferric salt of ethoxybenzene sulfonic acid and a dopant as oxidant As for thiophene, Comparative Example 2 in which polyethylene dioxythiophene of Comparative Example 1 synthesized using p-toluenesulfonic acid ferric salt as an oxidizing agent and dopant, and branched-type dodecylbenzenesulfonic acid ferric salt as synthetic agent and dopant were synthesized. Compared with the polyethylene dioxythiophene of Comparative Example 3 synthesized using polyethylene dioxythiophene of the above and ferric naphthalenesulfonic acid salt as an oxidant and dopant, the electrical conductivity decreased with high temperature storage and was excellent in heat resistance.
つぎに、導電性高分子を固体電解質として用いた固体電解コンデンサを実施例３〜４および比較例４〜６として示す。 Next, solid electrolytic capacitors using conductive polymers as solid electrolytes are shown as Examples 3 to 4 and Comparative Examples 4 to 6.
実施例３〜４および比較例４〜６
アルミニウム箔の表面をエッチング処理した後、化成処理を行い、誘電体皮膜を形成した陽極箔と陰極箔としてのアルミニウム箔とをセパレータを介して巻回してコンデンサ素子を作製した。そして、このコンデンサ素子のセパレータ部分に３，４−エチレンジオキシチオフェンを含浸させ、さらに実施例１〜２および比較例１〜３の過程で得られたそれぞれのスルホン酸の第二鉄塩をそれぞれ別々に含浸させ、６０℃で２時間加熱することによりポリエチレンジオキシチオフェンからなる固体電解質層を形成した。そして、それを外装材で外装して、固体電解コンデンサを得た。
Examples 3-4 and Comparative Examples 4-6
After etching the surface of the aluminum foil, a chemical conversion treatment was performed, and an anode foil on which a dielectric film was formed and an aluminum foil as a cathode foil were wound through a separator to produce a capacitor element. Then, the separator portion of this capacitor element was impregnated with 3,4-ethylenedioxythiophene, and each ferric salt of sulfonic acid obtained in the process of Examples 1-2 and Comparative Examples 1-3 was further added. A solid electrolyte layer made of polyethylene dioxythiophene was formed by impregnating separately and heating at 60 ° C. for 2 hours. And it was armored with an exterior material to obtain a solid electrolytic capacitor.
このようにして作製した実施例３〜４および比較例４〜６の固体電解コンデンサの等価直列抵抗（ＥＳＲ）の測定をした。その結果を酸化剤兼ドーパントの種類と共に表３に示す。 The equivalent series resistance (ESR) of the solid electrolytic capacitors of Examples 3 to 4 and Comparative Examples 4 to 6 thus produced was measured. The results are shown in Table 3 together with the type of oxidizing agent and dopant.
表３に示すように、実施例３〜４の固体電解コンデンサは、比較例４〜６の固体電解コンデンサに比べて、ＥＳＲ値が小さかった。 As shown in Table 3, the solid electrolytic capacitors of Examples 3 to 4 had smaller ESR values than the solid electrolytic capacitors of Comparative Examples 4 to 6.
すなわち、メトキシベンゼンスルホン酸第二鉄塩を酸化剤兼ドーパントとして合成した導電性高分子を固体電解質として用いた実施例３の固体電解コンデンサおよびエトキシベンゼンスルホン酸第二鉄塩を酸化剤兼ドーパントとして合成した導電性高分子を固体電解質として用いた実施例４の固体電解コンデンサは、ｐ−トルエンスルホン酸第二鉄塩を酸化剤兼ドーパントとして合成した導電性高分子を固体電解質として用いた比較例４の固体電解コンデンサ、分岐型ドデシルベンゼンスルホン酸第二鉄塩を酸化剤兼ドーパントとして合成した導電性高分子を固体電解質として用いた比較例５の固体電解コンデンサ、ナフタレンスルホン酸第二鉄塩を酸化剤兼ドーパントとして合成した導電性高分子を固体電解質として用いた比較例６の固体電解コンデンサに比べて、ＥＳＲが低く、高温・高湿条件下における特性の信頼性が高かった。 That is, the solid electrolytic capacitor of Example 3 using a conductive polymer synthesized with ferric methoxybenzene sulfonate as an oxidant and dopant as a solid electrolyte and ferric ethoxybenzene sulfonate as an oxidant and dopant The solid electrolytic capacitor of Example 4 using the synthesized conductive polymer as a solid electrolyte is a comparative example using a conductive polymer synthesized as a solid electrolyte with p-toluenesulfonic acid ferric salt as an oxidizing agent and a dopant. The solid electrolytic capacitor of No. 4, the solid electrolytic capacitor of Comparative Example 5 using a conductive polymer synthesized by using branched-type dodecylbenzenesulfonic acid ferric salt as an oxidizing agent and a dopant as the solid electrolyte, and naphthalenesulfonic acid ferric salt Solid of Comparative Example 6 using conductive polymer synthesized as oxidant and dopant as solid electrolyte Compared to solutions capacitance, ESR is low, higher reliability characteristics under high temperature and high humidity conditions.
Claims (4)
A solid electrolytic capacitor using the conductive polymer according to claim 2 as a solid electrolyte.
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