JP2008205496A - Method of manufacturing solid electrolytic capacitor - Google Patents

Method of manufacturing solid electrolytic capacitor Download PDF

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JP2008205496A
JP2008205496A JP2008099058A JP2008099058A JP2008205496A JP 2008205496 A JP2008205496 A JP 2008205496A JP 2008099058 A JP2008099058 A JP 2008099058A JP 2008099058 A JP2008099058 A JP 2008099058A JP 2008205496 A JP2008205496 A JP 2008205496A
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conductive polymer
capacitor element
solid electrolytic
electrolytic capacitor
solid electrolyte
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JP4831108B2 (en
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Yoshiyuki Mori
義幸 森
Yukihiro Nitta
幸弘 新田
Hiroki Kusayanagi
弘樹 草柳
Akira Harada
晃 原田
Yoshihiro Watanabe
善博 渡辺
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a solid electrolytic capacitor having a high capacitance achievement rate with excellent high frequency property by forming relatively easily a conductive polymer solid electrolyte layer in a winding type capacitor element. <P>SOLUTION: The method of manufacturing the solid electrolytic capacitor includes a step of forming a capacitor element by winding a positive electrode foil formed with an oxidized dielectric film layer, a negative electrode foil that is etched or chemically treated after etching, and a separator held therebetween, a step of forming a first solid electrolyte material layer by impregnating a conductive polymer fine particle with dispersed solution prepared by dispersing fine particles selected from polypyrrol, polythiophen, polyaniline or a derivative thereof into a solution containing an organic binder and a surfactant to regulate the viscosity between 5 to 100 cp, and a step of impregnating the capacitor element formed a first solid electrolyte layer with an electrolyte solution. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は導電性高分子を固体電解質層に用いた固体電解コンデンサの製造方法に関するものである。   The present invention relates to a method for producing a solid electrolytic capacitor using a conductive polymer in a solid electrolyte layer.

電子機器の高周波化に伴って、電子部品である電解コンデンサにも従来よりも高周波領域でのインピーダンス特性に優れる大容量のコンデンサが求められてきている。最近では、この高周波領域でのインピーダンス低減のために電気伝導度の高い導電性高分子を電解質に用いた固体電解コンデンサが検討されてきており、また大容量化の要求に対しては電極箔を積層させる場合と比較して、構造的に大容量化が容易な巻回形（陽極箔と陰極箔をその間にセパレータを介して巻回した構造のもの）による導電性高分子を用いた固体電解コンデンサが製品化されてきている。   With the increase in frequency of electronic equipment, electrolytic capacitors that are electronic components have been required to have a large capacity capacitor that is superior in impedance characteristics in a high frequency region than before. Recently, in order to reduce impedance in this high-frequency region, solid electrolytic capacitors using a conductive polymer with high electrical conductivity as an electrolyte have been studied. Solid electrolysis using a conductive polymer of a wound type (a structure in which an anode foil and a cathode foil are wound with a separator between them), which makes it easy to increase the capacity compared to the case of stacking Capacitors have been commercialized.

この巻回形の固体電解コンデンサにおいて、導電性高分子の形成方法についてこれまで多くの発明がなされており、一般的には導電性高分子のモノマー溶液と酸化剤溶液で交互に電解重合または化学重合して固体電解質層を形成するか、導電性高分子のモノマー溶液と酸化剤溶液の混合溶液で電解重合または化学重合して固体電解質層を形成させていた。ここで用いられている導電性高分子のモノマーとしてはピロール、チオフェン、エチレンジオキシチオフェン、アニリンまたはその誘導体であり、酸化剤溶液としてはｐ−トルエンスルホン酸第二鉄塩、ドデシルベンゼンスルホン酸第二鉄塩、ナフタレンスルホン酸第二鉄塩、トリイソプロピルナフタレンスルホン酸第二鉄塩や長鎖脂肪族スルホン酸等の第二鉄塩を含有したアルコール（メタノール、エタノール、イソプロピルアルコール、ｎ−ブタノール、エチレングリコール等）溶液が用いられている。   In this wound-type solid electrolytic capacitor, many inventions have been made so far regarding a method for forming a conductive polymer. Generally, an electropolymerization or chemical reaction is alternately performed between a monomer solution and an oxidant solution of a conductive polymer. The solid electrolyte layer is formed by polymerization, or the solid electrolyte layer is formed by electrolytic polymerization or chemical polymerization using a mixed solution of a conductive polymer monomer solution and an oxidizing agent solution. The conductive polymer monomer used here is pyrrole, thiophene, ethylenedioxythiophene, aniline or a derivative thereof, and the oxidizing agent solution is p-toluenesulfonic acid ferric salt, dodecylbenzenesulfonic acid Alcohol (methanol, ethanol, isopropyl alcohol, n-butanol, ferric salt such as ferric salt, naphthalenesulfonic acid ferric salt, ferric salt of triisopropylnaphthalenesulfonic acid and long chain aliphatic sulfonic acid Ethylene glycol etc.) solution is used.

しかしながら上記巻回形の固体電解コンデンサにおいて、導電性高分子を巻回形のコンデンサ素子の内部に均一かつ十分に含浸させることは困難であり、特にエチレンジオキシチオフェンを重合してなるポリエチレンジオキシチオフェンにおいては、種々の酸化剤や重合条件の微妙な変化、さらには酸化剤溶液を調合してから導電性高分子のモノマーを重合するまでの経過時間等によって、電気特性のバラツキ（特に導電性高分子の誘電体酸化皮膜層上への被覆率により決定される静電容量のバラツキや導電性高分子の充填率により決定される高周波域でのインピーダンスのバラツキ）が大きいという課題を有していた。   However, in the above wound solid electrolytic capacitor, it is difficult to uniformly and sufficiently impregnate the conductive polymer inside the wound capacitor element, and in particular, polyethylene dioxypolymer formed by polymerizing ethylenedioxythiophene. In thiophene, there are variations in electrical properties (particularly conductivity) due to subtle changes in various oxidizing agents and polymerization conditions, and the elapsed time from the preparation of the oxidizing agent solution to the polymerization of the conductive polymer monomer. There is a problem that the capacitance variation determined by the coating rate of the polymer on the dielectric oxide film layer and the impedance variation in the high frequency range determined by the filling rate of the conductive polymer are large. It was.

また、導電性高分子のモノマー溶液は粘性が高いため、コンデンサ素子の陽極箔および陰極箔のピット内に充填させるには低温雰囲気や真空含浸などの工夫が必要であった。   Further, since the monomer solution of the conductive polymer has a high viscosity, a device such as a low temperature atmosphere or vacuum impregnation is required to fill the pits of the anode foil and the cathode foil of the capacitor element.

本発明はこのような従来の課題を解決し、巻回形のコンデンサ素子に導電性高分子の固体電解質層を比較的容易に形成させて、容量達成率の高い高周波特性に優れた固体電解コンデンサの製造方法を提供することを目的とするものである。   The present invention solves such a conventional problem, and a solid electrolytic layer of a conductive polymer is formed on a wound capacitor element relatively easily, so that a solid electrolytic capacitor excellent in high frequency characteristics with a high capacity achievement rate is obtained. An object of the present invention is to provide a manufacturing method.

上記課題を解決するために本発明の請求項１に記載の発明は、誘電体酸化皮膜層を形成した陽極箔とエッチング処理あるいはエッチング後化成処理された陰極箔とをその間にセパレータを介在させて巻回することによりコンデンサ素子を形成する工程と、有機バインダーおよび界面活性剤を含む溶液にポリピロール、ポリチオフェン、ポリアニリンおよびそれらの誘導体のいずれかの微粒子を分散させ、粘度を５〜１００ｃｐに調整した導電性高分子微粒子分散水溶液をコンデンサ素子に含浸させて微粒子の導電性高分子を有した第１の固体電解質層を形成する工程と、この第１の固体電解質層を形成したコンデンサ素子に電解液を含浸する工程とを具備した製造方法とするもので、この方法により、誘電体酸化皮膜層上に微粒子の導電性高分子を有した第１の固体電解質層を比較的容易に形成することができ、導電性高分子微粒子分散体の導電層と電解液を含浸することにより、比較的容易に高周波領域のインピーダンス特性を低くすることができ、固体電解コンデンサの内部抵抗の低い、容量達成率の高い高周波特性に優れた固体電解コンデンサを得ることができるという作用を有する。   In order to solve the above-mentioned problems, according to the first aspect of the present invention, an anode foil on which a dielectric oxide film layer is formed and a cathode foil that has been subjected to etching treatment or post-etching chemical conversion treatment are interposed between them. A step of forming a capacitor element by winding, and a conductive material in which fine particles of polypyrrole, polythiophene, polyaniline and their derivatives are dispersed in a solution containing an organic binder and a surfactant, and the viscosity is adjusted to 5 to 100 cp. Forming a first solid electrolyte layer having a conductive polymer fine particle by impregnating a capacitor element with an aqueous solution of a conductive polymer fine particle, and an electrolytic solution for the capacitor element on which the first solid electrolyte layer is formed. And impregnating the conductive oxide particles on the dielectric oxide film layer by this method. The first solid electrolyte layer having a child can be formed relatively easily, and by impregnating the conductive polymer fine particle dispersion with the conductive layer and the electrolytic solution, impedance characteristics in the high frequency region can be relatively easily achieved. The solid electrolytic capacitor can be reduced, and a solid electrolytic capacitor having a low internal resistance and a high capacity achievement rate and excellent high frequency characteristics can be obtained.

なお、上記有機バインダーとしては、ポリビニルアルコール、ポリ酢酸ビニル、ポリカーボネート、ポリアクリレート、ポリメタアクリレート、ポリスチレン、ポリウレタン、ポリアクリロニトリル、ポリブタジエン、ポリイソプレン、ポリエーテル、ポリエステル、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリアミド、ポリイミド、ブチラール樹脂、シリコーン樹脂、メラミン樹脂、アルキッド樹脂、セルロース、ニトロセルロース、ビスフェノールＡ型エポキシ、ビスフェノールＦ型エポキシ、脂環式エポキシおよびこれらの誘導体よりなる群より選ばれる１つ以上を含有する高分子または共重合体の１つ以上からなるものが挙げられ、これらの高分子または共重合体は導電性の乏しい高分子であり、かつこれらの抵抗率を１．０×１０10Ω／□を超える値に設定することが容易であるため、電子なだれ現象を局所的な範囲に止めるに十分な絶縁性能を有する誘電体酸化皮膜上の層を構成できるので、漏れ電流が非常に小さく、かつエージング中にショートの発生しにくい固体電解質層を得ることができる。 Examples of the organic binder include polyvinyl alcohol, polyvinyl acetate, polycarbonate, polyacrylate, polymethacrylate, polystyrene, polyurethane, polyacrylonitrile, polybutadiene, polyisoprene, polyether, polyester, polyethylene terephthalate, polybutylene terephthalate, polyamide, High containing at least one selected from the group consisting of polyimide, butyral resin, silicone resin, melamine resin, alkyd resin, cellulose, nitrocellulose, bisphenol A type epoxy, bisphenol F type epoxy, alicyclic epoxy and derivatives thereof And those composed of one or more molecules or copolymers, these polymers or copolymers are polymers with poor conductivity, and these Since it is easy to set the anti-factor to a value greater than 1.0 × 10 10 Ω / □, a layer on the dielectric oxide film having a sufficient insulation performance in stopping the local range of the electron avalanche Since it can be configured, it is possible to obtain a solid electrolyte layer that has a very small leakage current and is less likely to cause a short circuit during aging.

請求項２に記載の発明は、導電性高分子微粒子分散水溶液の微粒子が２００〜１００００ｎｍとした製造方法としたもので、上記請求項１に記載の発明により得られる作用と同様の作用を有する。   The invention according to claim 2 is a production method in which the fine particles of the aqueous dispersion of fine conductive polymer particles are 200 to 10,000 nm, and has the same action as that obtained by the invention according to claim 1.

上記導電性高分子微粒子分散水溶液を超音波、ホモジナイザー、ハイブリッドミキサー、ハイシェアミキサーの少なくとも１種で分散処理して粘度を調整することにより、流体せん断作用および機械的せん断作用により導電性高分子微粒子分散水溶液中の微粒子および有機バインダーの分散性を高めることができ、上記水溶液を低粘度にして誘電体酸化皮膜層上に第１の固体電解質層を緻密に形成することができるという作用を有する。   Conductive polymer fine particles are dispersed by a fluid shearing action and a mechanical shearing action by dispersing the conductive polymer fine particle-dispersed aqueous solution with at least one of an ultrasonic wave, a homogenizer, a hybrid mixer, and a high shear mixer to adjust the viscosity. The dispersibility of the fine particles and the organic binder in the dispersed aqueous solution can be enhanced, and the aqueous solution has a low viscosity so that the first solid electrolyte layer can be densely formed on the dielectric oxide film layer.

なお、上記超音波は周波数４０〜６０ｋＨｚ、出力５０〜１００Ｗを有する一般的な超音波処理装置で処理するもの、ホモジナイザーはポンプで液体をオリフィス機構を通過させることにより、高いせん断作用を液体に与えることができる装置で処理するもの、ハイブリッドミキサーは液体を公転および自転させながら攪拌することができる装置で処理するもの、ハイシェアミキサーはロータとスクリーンを高速で回転させ、ロータとスクリーンの間に液体を通過させることにより、高いせん断作用を液体に与えながら攪拌することができる装置で処理するもので、これらの各分散処理のいずれか、あるいはそれらの組み合わせで導電性高分子微粒子分散水溶液を分散処理することができる。   The ultrasonic wave is processed by a general ultrasonic processing apparatus having a frequency of 40-60 kHz and an output of 50-100 W. The homogenizer gives a high shearing action to the liquid by passing the liquid through the orifice mechanism with a pump. That can be processed with a device that can handle, a hybrid mixer that processes with a device that can stir while revolving and rotating the liquid, a high shear mixer that rotates the rotor and the screen at high speed, and the liquid between the rotor and the screen Is processed with an apparatus that can stir while giving a high shearing action to the liquid, and the conductive polymer fine particle dispersion aqueous solution is dispersed by any of these dispersion treatments or a combination thereof. can do.

上記複素環式モノマーがポリピロール、ポリチオフェン、ポリアニリンおよびそれらの誘導体のいずれかを用いるもので、これらの電子導電性高分子は導電率が非常に高いため、陽極誘電体酸化皮膜上に設けた層の電子導電性高分子の抵抗率を１．０×１０10Ω／□以下に設定しやすい上、前記した第１の固体電解質層の有機バインダーであるグリシジル変性ポリエステル、スルホン酸変性ポリエステル、カルボン酸変性ポリエステル等との相溶性が極めて高いので、これらの非電子伝導性高分子との併用により誘電体酸化皮膜上へこれらの電子導電性高分子の被覆率が高められるという効果を有するので、漏れ電流が非常に小さく、かつエージング中にショートが発生しにくい上、容量引き出し率の高い大容量の固体電解コンデンサを構成することができるという作用を有する。 The heterocyclic monomer uses any one of polypyrrole, polythiophene, polyaniline, and derivatives thereof, and these electronic conductive polymers have very high conductivity, so that the layer provided on the anode dielectric oxide film It is easy to set the resistivity of the electron conductive polymer to 1.0 × 10 10 Ω / □ or less, and the glycidyl-modified polyester, sulfonic acid-modified polyester, and carboxylic acid-modified organic binder for the first solid electrolyte layer described above. Since the compatibility with polyester, etc. is extremely high, the combined use of these non-electron conductive polymers has the effect of increasing the coverage of these electronic conductive polymers on the dielectric oxide film, so that leakage current This is a very small capacitor that does not easily cause a short circuit during aging. It has the effect that it is Rukoto.

上記ポリチオフェンとしてポリエチレンジオキシチオフェンを用いることができる。   Polyethylenedioxythiophene can be used as the polythiophene.

以上のように本発明によれば、誘電体酸化皮膜層を形成した陽極箔とエッチング処理あるいはエッチング後化成処理された陰極箔とをその間にセパレータを介在して巻回することによりコンデンサ素子を形成する工程と、有機バインダーおよび界面活性剤を含む溶液にポリピロール、ポリチオフェン、ポリアニリンおよびそれらの誘導体のいずれかの微粒子を分散させ、粘度を５〜１００ｃｐに調整した導電性高分子微粒子分散水溶液をコンデンサ素子に含浸させて微粒子の導電性高分子を有した第１の固体電解質層を形成する工程と、この第１の固体電解質層を形成したコンデンサ素子に電解液を含浸する工程とを具備した製造方法としたもので、この方法により、誘電体酸化皮膜層上に微粒子の導電性高分子を有した第１の固体電解質層を比較的容易に形成することができ、導電性高分子微粒子分散体の導電層と電解液を含浸することにより、比較的容易に高周波領域のインピーダンス特性を低くすることができ、固体電解コンデンサの内部抵抗の低い、容量達成率の高い高周波特性に優れた固体電解コンデンサを得ることができるものであり、その工業的な価値は大なるものである。   As described above, according to the present invention, the capacitor element is formed by winding the anode foil formed with the dielectric oxide film layer and the cathode foil subjected to etching treatment or post-etching chemical conversion treatment with a separator interposed therebetween. And a conductive polymer fine particle dispersed aqueous solution in which fine particles of any of polypyrrole, polythiophene, polyaniline and derivatives thereof are dispersed in a solution containing an organic binder and a surfactant and the viscosity is adjusted to 5 to 100 cp. A method of forming a first solid electrolyte layer having a conductive polymer of fine particles by impregnating with a capacitor, and a step of impregnating a capacitor element formed with the first solid electrolyte layer with an electrolytic solution By this method, the first solid electrolyte layer having a fine conductive polymer on the dielectric oxide film layer It can be formed relatively easily, and by impregnating the conductive layer of the conductive polymer fine particle dispersion with the electrolytic solution, the impedance characteristics in the high frequency region can be lowered relatively easily. A solid electrolytic capacitor having a low resistance and a high capacity achievement rate and excellent high frequency characteristics can be obtained, and its industrial value is great.

次に、本発明の具体的な実施の形態について説明する。   Next, specific embodiments of the present invention will be described.

（実施の形態１）
誘電体酸化皮膜の耐電圧が３０Ｖの陽極アルミニウム箔と陰極アルミニウム箔との間にポリエチレンテレフタレート製のセパレータ（厚さ５０μｍ、秤量２５ｇ／ｍ2）を介在させて巻回することにより巻回形のコンデンサ素子を作製した（このコンデンサ素子にアジピン酸アンモニウム１０重量％エチレングリコール溶液を含浸させた際の周波数１２０Ｈｚにおける静電容量は２５０μＦであった）。 (Embodiment 1)
A dielectric oxide film is wound by interposing a polyethylene terephthalate separator (thickness 50 μm, weighing 25 g / m 2 ) between an anode aluminum foil and a cathode aluminum foil having a withstand voltage of 30 V. A capacitor element was produced (the capacitance at a frequency of 120 Hz when this capacitor element was impregnated with an ammonium adipate 10 wt% ethylene glycol solution was 250 μF).

次に、ポリエチレンジオキシチオフェンポリスチレンスルホン酸の微粒子（平均粒径２００ｎｍ）の濃度が１．０重量％と、グリシジル変性ポリエステルの濃度が３．０重量％と界面活性剤を添加した導電性高分子微粒子分散水溶液に上記コンデンサ素子を浸漬して引き上げた後、１５０℃で５分間乾燥処理を行い、少なくとも誘電体酸化皮膜上に電子導電性高分子であるポリエチレンジオキシチオフェンポリスチレンスルホン酸とグリシジル変性ポリエステルを含有する第１の固体電解質層を形成した。   Next, a conductive polymer in which the concentration of fine particles of polyethylenedioxythiophene polystyrene sulfonic acid (average particle size 200 nm) is 1.0% by weight, the concentration of glycidyl-modified polyester is 3.0% by weight, and a surfactant is added. After the capacitor element is immersed in the fine particle dispersed aqueous solution and pulled up, it is dried at 150 ° C. for 5 minutes, and at least a dielectric oxide film is formed of polyethylenedioxythiophene polystyrenesulfonic acid and glycidyl-modified polyester, which are electronically conductive polymers. A first solid electrolyte layer containing was formed.

続いて、このコンデンサ素子を複素環式モノマーであるエチレンジオキシチオフェン１部と酸化剤であるｐ−トルエンスルホン酸第二鉄２部と重合溶剤であるｎ−ブタノール４部を含む混合溶液に浸漬して引き上げた後、８５℃で６０分間放置することにより導電性高分子であるポリエチレンジオキシチオフェンの第２の固体電解質層を電極箔間に形成した。   Subsequently, the capacitor element is immersed in a mixed solution containing 1 part of ethylenedioxythiophene as a heterocyclic monomer, 2 parts of ferric p-toluenesulfonate as an oxidizing agent and 4 parts of n-butanol as a polymerization solvent. After being pulled up, it was left at 85 ° C. for 60 minutes to form a second solid electrolyte layer of polyethylenedioxythiophene, which is a conductive polymer, between the electrode foils.

このコンデンサ素子を樹脂加硫ブチルゴム封口材（ブチルゴムポリマー３０部、カーボン２０部、無機充填剤５０部から構成、封口体硬度：７０ＩＲＨＤ［国際ゴム硬さ単位］）と共にアルミニウム製の外装ケースに封入した後、カーリング処理により開口部を封止し固体電解コンデンサを作製した。   This capacitor element was encapsulated in an aluminum outer case together with a resin vulcanized butyl rubber sealant (30 parts butyl rubber polymer, 20 parts carbon, 50 parts inorganic filler, sealant hardness: 70 IRHD [international rubber hardness unit]). Thereafter, the opening was sealed by curling treatment to produce a solid electrolytic capacitor.

（実施の形態２）
上記実施の形態１において、陰極アルミニウム箔を化成処理したアルミニウム箔（化成皮膜耐圧５．０Ｖ）を用いた以外は実施の形態１と同様にして固体電解コンデンサを作製した。 (Embodiment 2)
A solid electrolytic capacitor was produced in the same manner as in the first embodiment except that an aluminum foil (chemical conversion film withstand voltage 5.0 V) obtained by chemical conversion of the cathode aluminum foil was used.

（実施の形態３）
上記実施の形態１において、導電性高分子微粒子分散水溶液をポリエチレンジオキシチオフェンポリスチレンスルホン酸の微粒子（平均粒径５００ｎｍ）の濃度が１．５重量％と、グリシジル変性ポリエステルの濃度が３．０重量％と界面活性剤を添加したものを用いた以外は実施の形態１と同様にして固体電解コンデンサを作製した。 (Embodiment 3)
In the first embodiment, in the conductive polymer fine particle dispersion aqueous solution, the concentration of polyethylenedioxythiophene polystyrenesulfonic acid fine particles (average particle size 500 nm) is 1.5% by weight, and the concentration of glycidyl-modified polyester is 3.0% by weight. A solid electrolytic capacitor was produced in the same manner as in the first embodiment except that a material with a% and a surfactant added was used.

（実施の形態４）
上記実施の形態１において、導電性高分子微粒子分散水溶液を超音波装置（出力１００Ｗ）により２時間処理を行った後に用いた以外は実施の形態１と同様にして固体電解コンデンサを作製した。 (Embodiment 4)
A solid electrolytic capacitor was produced in the same manner as in the first embodiment except that the aqueous conductive polymer fine particle dispersion was used after being treated for 2 hours by an ultrasonic device (output 100 W).

（実施の形態５）
上記実施の形態１において、導電性高分子微粒子分散水溶液を超音波装置（出力１００Ｗ）により４時間処理を行った後に用いた以外は実施の形態１と同様にして固体電解コンデンサを作製した。 (Embodiment 5)
A solid electrolytic capacitor was produced in the same manner as in the first embodiment except that the aqueous conductive polymer fine particle dispersion was used after being treated for 4 hours by an ultrasonic device (output 100 W).

（実施の形態６）
上記実施の形態１において、導電性高分子微粒子分散水溶液をホモジナイザー（ヒスコトロン製ＮＳ−５６）により１時間処理した後に用いた以外は実施の形態１と同様にして固体電解コンデンサを作製した。 (Embodiment 6)
A solid electrolytic capacitor was produced in the same manner as in Embodiment 1 except that the aqueous conductive polymer fine particle dispersion was used after being treated for 1 hour with a homogenizer (NS-56 manufactured by Hiscotron).

（実施の形態７）
上記実施の形態１において、導電性高分子微粒子分散水溶液をハイブリッドミキサー（キーエンス製ＨＭ−５００）で３時間処理した後に用いた以外は実施の形態１と同様にして固体電解コンデンサを作製した。 (Embodiment 7)
A solid electrolytic capacitor was produced in the same manner as in Embodiment 1 except that the aqueous conductive polymer fine particle dispersion was used after being treated with a hybrid mixer (Keyence HM-500) for 3 hours.

（実施の形態８）
上記実施の形態１において、導電性高分子微粒子分散水溶液をハイシェアミキサー（エム・テクニック製ＣＬＭ−０．８Ｓ）で１０分間処理した後に用いた以外は実施の形態１と同様にして固体電解コンデンサを作製した。 (Embodiment 8)
A solid electrolytic capacitor in the same manner as in the first embodiment except that the aqueous conductive polymer fine particle dispersion was used after being treated with a high shear mixer (CLM-0.8S manufactured by M Technique) for 10 minutes. Was made.

（実施の形態９）
上記実施の形態１において、導電性高分子微粒子分散水溶液をポリアニリンの微粒子（平均粒径１０００ｎｍ）の濃度が５．０重量％と、ポリエチレンテレフタレートの濃度が３．０重量％と界面活性剤を添加したものを、超音波装置により２時間処理を行った後に用いた以外は実施の形態１と同様にして固体電解コンデンサを作製した。 (Embodiment 9)
In the first embodiment, a conductive polymer fine particle-dispersed aqueous solution is added with a surfactant having a polyaniline fine particle concentration (average particle size of 1000 nm) of 5.0% by weight and a polyethylene terephthalate concentration of 3.0% by weight. A solid electrolytic capacitor was produced in the same manner as in Embodiment 1 except that the obtained product was used after being treated for 2 hours with an ultrasonic device.

（実施の形態１０）
上記実施の形態１において、導電性高分子微粒子分散水溶液をポリピロールの微粒子（平均粒径８００ｎｍ）の濃度が３．０重量％と、ポリエチレンテレフタレートの濃度が３．０重量％と界面活性剤を添加したものを、超音波装置により１時間処理を行った後に用いた以外は実施の形態１と同様にして固体電解コンデンサを作製した。 (Embodiment 10)
In the first embodiment, a conductive polymer fine particle dispersed aqueous solution is added with a surfactant having a polypyrrole fine particle (average particle size of 800 nm) concentration of 3.0% by weight and a polyethylene terephthalate concentration of 3.0% by weight. A solid electrolytic capacitor was produced in the same manner as in Embodiment 1 except that the obtained product was used after being treated with an ultrasonic device for 1 hour.

（実施の形態１１）
上記実施の形態１において、第１の固体電解質層を形成したコンデンサ素子を、複素環式モノマーであるピロール１部と酸化剤であるナフタレンスルホン酸第二鉄２部と重合溶剤であるｎ−ブタノール３部を含む混合溶液に浸漬して引き上げた後、８５℃で６０分間放置することにより導電性高分子であるポリピロールの第２の固体電解質層を電極箔間に形成した以外は実施の形態１と同様にして固体電解コンデンサを作製した。 (Embodiment 11)
In the first embodiment, the capacitor element formed with the first solid electrolyte layer is composed of 1 part of pyrrole as a heterocyclic monomer, 2 parts of ferric naphthalene sulfonate as an oxidizing agent, and n-butanol as a polymerization solvent. Embodiment 1 Except that a second solid electrolyte layer of polypyrrole, which is a conductive polymer, was formed between electrode foils by dipping in a mixed solution containing 3 parts and pulling it up and then standing at 85 ° C. for 60 minutes. A solid electrolytic capacitor was produced in the same manner as described above.

（実施の形態１２）
上記実施の形態１１において、酸化剤であるナフタレンスルホン酸第二鉄の代わりにメタンスルホン酸第二鉄塩を用いた以外は実施の形態１１と同様にして固体電解コンデンサを作製した。 (Embodiment 12)
In the eleventh embodiment, a solid electrolytic capacitor was fabricated in the same manner as in the eleventh embodiment except that ferric methanesulfonate was used instead of ferric naphthalene sulfonate, which is an oxidizing agent.

（実施の形態１３）
誘電体酸化皮膜の耐電圧が３０Ｖの陽極アルミニウム箔と化成処理された陰極アルミニウム箔（化成皮膜耐圧５．０Ｖ）との間にポリエチレンテレフタレート製のセパレータ（厚さ５０μｍ、秤量２５ｇ／ｍ2）を介在させて巻回することにより巻回形のコンデンサ素子を作製した（このコンデンサ素子にアジピン酸アンモニウム１０重量％エチレングリコール溶液を含浸させた際の周波数１２０Ｈｚにおける静電容量は２５０μＦであった）。 (Embodiment 13)
A separator made of polyethylene terephthalate (thickness 50 μm, weighing 25 g / m 2 ) between an anode aluminum foil with a dielectric oxide film with a withstand voltage of 30 V and a chemically treated cathode aluminum foil (chemical conversion film withstand voltage 5.0 V). A wound capacitor element was produced by interposing and winding (capacitance at a frequency of 120 Hz when this capacitor element was impregnated with a 10 wt% ethylene adipate ethylene glycol solution was 250 μF).

次に、ポリエチレンジオキシチオフェンポリスチレンスルホン酸の微粒子（平均粒径５００ｎｍ）の濃度が１．０重量％と、グリシジル変性ポリエステルの濃度が３．０重量％と界面活性剤を添加した導電性高分子微粒子分散水溶液に上記コンデンサ素子を浸漬して引き上げた後、１５０℃で５分間乾燥処理を行い、少なくとも誘電体酸化皮膜上に電子導電性高分子であるポリエチレンジオキシチオフェンポリスチレンスルホン酸とグリシジル変性ポリエステルを含有する第１の固体電解質層を形成した。   Next, a conductive polymer in which the concentration of fine particles of polyethylenedioxythiophene polystyrene sulfonic acid (average particle size 500 nm) is 1.0% by weight, the concentration of glycidyl-modified polyester is 3.0% by weight, and a surfactant is added. After the capacitor element is immersed in the fine particle dispersed aqueous solution and pulled up, it is dried at 150 ° C. for 5 minutes, and at least a dielectric oxide film is formed of polyethylenedioxythiophene polystyrenesulfonic acid and glycidyl-modified polyester, which are electronically conductive polymers. A first solid electrolyte layer containing was formed.

続いて、第１の固体電解質層を形成したコンデンサ素子にアジピン酸アンモニウム１０％を溶かしたエチレングリコール電解液を含浸した。   Subsequently, the capacitor element on which the first solid electrolyte layer was formed was impregnated with an ethylene glycol electrolytic solution in which 10% ammonium adipate was dissolved.

このコンデンサ素子を樹脂加硫ブチルゴム封口材（ブチルゴムポリマー３０部、カーボン２０部、無機充填剤５０部から構成、封口体硬度：７０ＩＲＨＤ［国際ゴム硬さ単位］）と共にアルミニウム製の外装ケースに封入した後、カーリング処理により開口部を封止して固体電解コンデンサを作製した。   This capacitor element was encapsulated in an aluminum outer case together with a resin vulcanized butyl rubber sealant (30 parts butyl rubber polymer, 20 parts carbon, 50 parts inorganic filler, sealant hardness: 70 IRHD [international rubber hardness unit]). Thereafter, the opening was sealed by curling treatment to produce a solid electrolytic capacitor.

（比較例）
誘電体酸化皮膜の耐電圧が３０Ｖの陽極アルミニウム箔と陰極アルミニウム箔との間にポリエチレンテレフタレート製のセパレータ（厚さ５０μｍ、秤量２５ｇ／ｍ2）を介在させて巻回することにより巻回形のコンデンサ素子を作製した（このコンデンサ素子にアジピン酸アンモニウム１０重量％のエチレングリコール溶液を含浸させた際の周波数１２０Ｈｚにおける静電容量は２５０μＦであった）。 (Comparative example)
A dielectric oxide film is wound by interposing a polyethylene terephthalate separator (thickness 50 μm, weighing 25 g / m 2 ) between an anode aluminum foil and a cathode aluminum foil having a withstand voltage of 30 V. A capacitor element was produced (the capacitance at a frequency of 120 Hz when this capacitor element was impregnated with an ethylene glycol solution containing 10% by weight of ammonium adipate was 250 μF).

このコンデンサ素子を複素環式モノマーであるエチレンジオキシチオフェン１部と酸化剤であるｐ−トルエンスルホン酸第二鉄２部と重合溶剤であるｎ−ブタノール４部を含む混合溶液に浸漬して引き上げた後、８５℃で６０分間放置することにより導電性高分子であるポリエチレンジオキシチオフェンを電極箔間に形成した。   Immerse this capacitor element in a mixed solution containing 1 part of ethylenedioxythiophene as a heterocyclic monomer, 2 parts of ferric p-toluenesulfonate as an oxidizing agent and 4 parts of n-butanol as a polymerization solvent, and pull it up. Then, the conductive polymer, polyethylenedioxythiophene, was formed between the electrode foils by leaving it at 85 ° C. for 60 minutes.

このコンデンサ素子を樹脂加硫ブチルゴム封口材（ブチルゴムポリマー３０部、カーボン２０部、無機充填剤５０部から構成、封口体硬度：７０ＩＲＨＤ［国際ゴム硬さ単位］）と共にアルミニウム製の外装ケースに封入した後、カーリング処理により開口部を封止し固体電解コンデンサを作製した。   This capacitor element was encapsulated in an aluminum outer case together with a resin vulcanized butyl rubber sealant (30 parts butyl rubber polymer, 20 parts carbon, 50 parts inorganic filler, sealant hardness: 70 IRHD [international rubber hardness unit]). Thereafter, the opening was sealed by curling treatment to produce a solid electrolytic capacitor.

上記実施の形態１〜１３と比較例の固体電解コンデンサについて、その静電容量（測定周波数１２０Ｈｚ）、ｔａｎδ（測定周波数１２０Ｈｚ）、インピーダンス（測定周波数１００ｋＨｚ）を比較した結果を（表１）に示す。なお、試験個数はいずれも５０個であり、静電容量、インピーダンスはショート品を除いたサンプルについての平均値で示した。   About the solid electrolytic capacitor of the said Embodiments 1-13 and a comparative example, the result of having compared the electrostatic capacitance (measuring frequency 120Hz), tan-delta (measuring frequency 120Hz), and impedance (measuring frequency 100kHz) is shown in (Table 1). . The number of tests was 50, and the capacitance and impedance were shown as average values for samples excluding short-circuited products.

Figure 2008205496
Figure 2008205496

（表１）より明らかなように、本発明の実施の形態１〜１２の固体電解コンデンサは、誘電体酸化皮膜層上に導電性高分子の微粒子を有した第１の固体電解質層を比較的容易に形成することができ、この第１の固体電解質層の表面に形成される第２の固体電解質層との密着性も向上することができるので、固体電解コンデンサの内部抵抗を低くし、容量達成率の高い高周波特性に優れた固体電解コンデンサを得ることができる。   As is clear from Table 1, the solid electrolytic capacitors according to the first to twelfth embodiments of the present invention are obtained by relatively disposing the first solid electrolyte layer having conductive polymer fine particles on the dielectric oxide film layer. Since it can be easily formed and the adhesion to the second solid electrolyte layer formed on the surface of the first solid electrolyte layer can also be improved, the internal resistance of the solid electrolytic capacitor is reduced, and the capacitance A solid electrolytic capacitor having a high achievement rate and excellent high frequency characteristics can be obtained.

また、導電性高分子微粒子分散水溶液を超音波処理（実施の形態４および５）、ホモジナイザー処理（実施の形態６）、ハイブリッドミキサー処理（実施の形態７）、ハイシェアミキサー処理（実施の形態８）することにより、第１の固体電解質層を緻密で均一に形成することができることから、容量およびインピーダンス特性に優れた固体電解コンデンサを得ることができる。   In addition, the conductive polymer fine particle-dispersed aqueous solution is subjected to ultrasonic treatment (Embodiments 4 and 5), homogenizer treatment (Embodiment 6), hybrid mixer treatment (Embodiment 7), and high shear mixer treatment (Embodiment 8). ), The first solid electrolyte layer can be formed densely and uniformly, so that a solid electrolytic capacitor having excellent capacitance and impedance characteristics can be obtained.

特に実施の形態８の固体電解コンデンサは、導電性高分子微粒子分散水溶液の分散処理時間を短くしても分散効率を高めることができ、容量およびインピーダンス特性をさらに高めることができる。   In particular, the solid electrolytic capacitor of Embodiment 8 can increase the dispersion efficiency even if the dispersion treatment time of the conductive polymer fine particle-dispersed aqueous solution is shortened, and can further increase the capacitance and impedance characteristics.

上記超音波処理およびハイシェアミキサー処理において、導電性高分子微粒子分散水溶液の分散処理時間と粘性の関係をＢＲＡＮＳＯＮ製のＢＲＡＮＳＯＮＩＣ２２０を用いて測定した結果を図１に示す。同図より超音波処理では１〜４時間処理することにより低粘性（１００ｃｐ以下）にすることができ、また、ハイシェアミキサー処理では１０分で低粘性になり、この低粘性（５〜１００ｃｐ）の導電性高分子微粒子分散水溶液を用いることにより、緻密で均一な第１の固体電解質層を形成することができるものである。   FIG. 1 shows the results of measuring the relationship between the dispersion treatment time and the viscosity of the aqueous conductive polymer fine particle dispersion using the BRANSONIC 220 manufactured by BRANSON in the ultrasonic treatment and the high shear mixer treatment. From the figure, ultrasonic treatment can reduce the viscosity (100 cp or less) by processing for 1 to 4 hours, and high shear mixer treatment reduces the viscosity in 10 minutes. This low viscosity (5 to 100 cp) By using the aqueous conductive polymer fine particle dispersion aqueous solution, a dense and uniform first solid electrolyte layer can be formed.

さらに、実施の形態１３においては、導電性高分子微粒子分散水溶液により第１の固体電解質層を形成したコンデンサ素子に、エチレングリコール電解液を含浸した固体電解コンデンサで、比較的容易に高周波領域のインピーダンス特性の低い固体電解コンデンサを得ることができるものである。   Further, in the thirteenth embodiment, a capacitor element in which the first solid electrolyte layer is formed with the conductive polymer fine particle dispersed aqueous solution is a solid electrolytic capacitor impregnated with an ethylene glycol electrolytic solution. A solid electrolytic capacitor having low characteristics can be obtained.

本発明の実施の形態における超音波およびハイシェアミキサーで導電性高分子微粒子分散水溶液を分散処理したときの処理時間と粘性の関係を示すグラフThe graph which shows the relationship between the processing time and viscosity when carrying out the dispersion process of the electroconductive polymer fine particle dispersion | distribution aqueous solution with the ultrasonic wave and high shear mixer in embodiment of this invention

Claims (2)

誘電体酸化皮膜層を形成した陽極箔とエッチング処理あるいはエッチング後化成処理された陰極箔とをその間にセパレータを介在させて巻回することによりコンデンサ素子を形成する工程と、有機バインダーおよび界面活性剤を含む溶液にポリピロール、ポリチオフェン、ポリアニリンおよびそれらの誘導体のいずれかの微粒子を分散させ、粘度を５〜１００ｃｐに調整した導電性高分子微粒子分散水溶液をコンデンサ素子に含浸させて微粒子の導電性高分子を有した第１の固体電解質層を形成する工程と、この第１の固体電解質層を形成したコンデンサ素子に電解液を含浸する工程とを具備した固体電解コンデンサの製造方法。 A step of forming a capacitor element by winding an anode foil formed with a dielectric oxide film layer and a cathode foil subjected to etching treatment or post-etching chemical conversion treatment with a separator interposed therebetween, an organic binder and a surfactant In the solution containing polypyrrole, polythiophene, polyaniline and their derivatives, the capacitor element is impregnated with a conductive polymer fine particle-dispersed aqueous solution whose viscosity is adjusted to 5 to 100 cp, and the fine conductive polymer A method for producing a solid electrolytic capacitor, comprising: a step of forming a first solid electrolyte layer having a liquid crystal; and a step of impregnating a capacitor element having the first solid electrolyte layer with an electrolytic solution. 微粒子が２００〜１００００ｎｍである請求項１に記載の固体電解コンデンサの製造方法。 The method for producing a solid electrolytic capacitor according to claim 1, wherein the fine particles are 200 to 10,000 nm.
JP2008099058A 2001-07-16 2008-04-07 Manufacturing method of solid electrolytic capacitor Expired - Fee Related JP4831108B2 (en)

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