JP2000223364A - Manufacture of electrolytic capacitor - Google Patents
Manufacture of electrolytic capacitorInfo
- Publication number
- JP2000223364A JP2000223364A JP11026165A JP2616599A JP2000223364A JP 2000223364 A JP2000223364 A JP 2000223364A JP 11026165 A JP11026165 A JP 11026165A JP 2616599 A JP2616599 A JP 2616599A JP 2000223364 A JP2000223364 A JP 2000223364A
- Authority
- JP
- Japan
- Prior art keywords
- capacitor element
- conductive polymer
- capacitor
- solution containing
- dropping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、陽極化成箔と対向
陰極箔とをセパレータを介して巻回してなるコンデンサ
素子に、導電性ポリマーを含む陰極材を含浸した電解コ
ンデンサに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic capacitor obtained by impregnating a cathode element containing a conductive polymer into a capacitor element formed by winding an anodized foil and a counter cathode foil via a separator.
【０００２】[0002]
【従来の技術】電子機器のデジタル化に伴い、それに使
用されるコンデンサにも小型、大容量で高周波領域にお
ける等価直列抵抗（以下、ＥＳＲと略す）の小さいもの
が求められるようになってきている。2. Description of the Related Art Along with the digitization of electronic equipment, capacitors used therein are required to be small in size, large in capacity, and low in equivalent series resistance (hereinafter abbreviated as ESR) in a high frequency region. .
【０００３】従来、高周波領域用のコンデンサとしては
プラスチックフイルムコンデンサ、積層セラミックコン
デンサ等が多用されているが、これらは比較的小容量で
ある。Conventionally, plastic film capacitors, multilayer ceramic capacitors, and the like have been frequently used as capacitors for a high frequency region, but these have relatively small capacities.
【０００４】小型、大容量で低ＥＳＲのコンデンサとし
ては、二酸化マンガン、ＴＣＮＱ錯塩等の電子電導性固
体を陰極材として用いた固体電解コンデンサがある。こ
こでＴＣＮＱとは７，７，８，８−テトラシアノキノジ
メタンを意味する。As a small, large-capacity, low-ESR capacitor, there is a solid electrolytic capacitor using an electron conductive solid such as manganese dioxide, TCNQ complex salt or the like as a cathode material. Here, TCNQ means 7,7,8,8-tetracyanoquinodimethane.
【０００５】又、ポリピロール、ポリチオフェン、ポリ
フラン、ポリアニリン等の導電性ポリマーを陰極材とし
て用いた固体電解コンデンサも有望である。[0005] A solid electrolytic capacitor using a conductive polymer such as polypyrrole, polythiophene, polyfuran, or polyaniline as a cathode material is also promising.
【０００６】[0006]
【発明が解決しようとする課題】前記導電性ポリマーを
陰極材として用いた固体電解コンデンサの従来製法にお
いては、アルミニウム、タンタル等の弁作用金属からな
る陽極焼結体あるいは陽極箔の表面に、化成皮膜、導電
性ポリマー層、グラファイト層、銀ペイント層が順次形
成され、そこへ陰極リード線が導電性接着剤等により接
続されるが、この製法は、化成皮膜を形成した陽極箔と
対向陰極箔とをセパレータを介して巻回したコンデンサ
素子に電解液を含浸するという通常の電解コンデンサの
製法に比べて、かなり煩雑である。又、上述の如き陰極
引き出し法では、対向陰極箔を用いる場合に比べてＥＳ
Ｒが大きくなる。In the conventional method for producing a solid electrolytic capacitor using a conductive polymer as a cathode material, a method of forming a cathode on a surface of an anode sintered body or an anode foil made of a valve metal such as aluminum or tantalum is used. A film, a conductive polymer layer, a graphite layer, and a silver paint layer are sequentially formed, and a cathode lead wire is connected thereto with a conductive adhesive or the like. This is considerably complicated as compared with a normal electrolytic capacitor manufacturing method in which a capacitor element obtained by winding the above through a separator is impregnated with an electrolytic solution. In addition, the cathode extraction method as described above has a higher ES than the case where the opposing cathode foil is used.
R increases.
【０００７】一方、前記導電性ポリマー層は電解重合法
や気相重合法等により形成されるが、巻回型のコンデン
サ素子内に電解重合法や気相重合法により導電性ポリマ
ー層を形成するのは容易でない。陽極箔上に化成皮膜及
び導電性ポリマー層を形成した後、対向陰極箔とともに
巻き取るという製法も考えられるが、化成皮膜や導電性
ポリマー層を損傷することなく巻き取るのは困難であ
る。On the other hand, the conductive polymer layer is formed by an electrolytic polymerization method or a gas phase polymerization method. The conductive polymer layer is formed in a wound capacitor element by an electrolytic polymerization method or a gas phase polymerization method. Not easy. A method of forming the chemical conversion film and the conductive polymer layer on the anode foil and then winding the same together with the opposite cathode foil is also conceivable, but it is difficult to wind the chemical conversion film and the conductive polymer layer without damage.
【０００８】そこで、巻回型のコンデンサ素子に、酸化
重合により導電性ポリマーとなるモノマーを適量含浸し
た後、該コンデンサ素子を酸化剤の水溶液に浸漬する
か、該コンデンサ素子に酸化剤の水溶液を適量滴下する
方法が提案されている。この方法によれば、巻回型のコ
ンデンサ素子内に導電性ポリマー層を直接形成すること
ができ、陽極化成皮膜も損傷し難い。[0008] Therefore, after winding a capacitor element of a winding type with an appropriate amount of a monomer that becomes a conductive polymer by oxidative polymerization, the capacitor element is immersed in an aqueous solution of an oxidizing agent, or an aqueous solution of an oxidizing agent is added to the capacitor element. A method of dropping an appropriate amount has been proposed. According to this method, the conductive polymer layer can be directly formed in the wound capacitor element, and the anodized film is hardly damaged.
【０００９】本発明は、陽極化成箔と対向陰極箔とをセ
パレータを介して巻回してなるコンデンサ素子に、導電
性ポリマーを含む陰極材を含浸した電解コンデンサにお
いて、上記従来製法を改良してＥＳＲを更に低減させる
ことを目的とするものである。The present invention relates to an electrolytic capacitor in which a cathode element containing a conductive polymer is impregnated with a capacitor element formed by winding an anodized foil and an opposing cathode foil via a separator. Is intended to be further reduced.
【００１０】[0010]
【課題を解決するための手段】本発明の第１の局面に従
った電解コンデンサの製造方法は、陽極化成箔と対向陰
極箔とをセパレータを介して巻回してなるコンデンサ素
子内に導電性ポリマー層を形成した電解コンデンサの製
造方法において、（１）前記コンデンサ素子をドーピン
グ剤を含む溶液に浸漬した後乾燥するか、前記コンデン
サ素子にドーピング剤を含む溶液を滴下した後乾燥する
工程と、（２）前記コンデンサ素子を酸化重合により導
電性ポリマーとなるモノマー又はその溶液に浸漬する
か、前記コンデンサ素子に酸化重合により導電性ポリマ
ーとなるモノマー又はその溶液を滴下する工程と、
（３）前記コンデンサ素子を酸化剤を含む溶液に浸漬す
るか、前記コンデンサ素子に酸化剤を含む溶液を滴下す
る工程とを順に経ることにより、前記コンデンサ素子内
に導電性ポリマー層を形成することを特徴とするもので
ある。According to a first aspect of the present invention, there is provided a method of manufacturing an electrolytic capacitor, comprising: a conductive element in a capacitor element formed by winding an anodized foil and a counter cathode foil via a separator. (1) a step of immersing the capacitor element in a solution containing a doping agent and then drying, or dropping a solution containing a doping agent on the capacitor element and drying the capacitor element; 2) immersing the capacitor element in a monomer or a solution thereof that becomes a conductive polymer by oxidative polymerization, or dropping a monomer or a solution thereof that becomes a conductive polymer by oxidative polymerization in the capacitor element;
(3) forming a conductive polymer layer in the capacitor element by sequentially immersing the capacitor element in a solution containing an oxidant or dropping a solution containing an oxidant on the capacitor element. It is characterized by the following.
【００１１】本発明の第２の局面に従った電解コンデン
サの製造方法は、陽極化成箔と対向陰極箔とをセパレー
タを介して巻回してなるコンデンサ素子内に導電性ポリ
マー層を形成した電解コンデンサの製造方法において、
（１）前記コンデンサ素子を酸化重合により導電性ポリ
マーとなるモノマー又はその溶液に浸漬するか、前記コ
ンデンサ素子に酸化重合により導電性ポリマーとなるモ
ノマー又はその溶液を滴下する工程と、（２）前記コン
デンサ素子をドーピング剤及び酸化剤を含む溶液に浸漬
するか、前記コンデンサ素子にドーピング剤及び酸化剤
を含む溶液を滴下する工程とを順に経ることにより、前
記コンデンサ素子内に導電性ポリマー層を形成すること
を特徴とするものである。A method of manufacturing an electrolytic capacitor according to a second aspect of the present invention is directed to an electrolytic capacitor having a conductive polymer layer formed in a capacitor element formed by winding an anodized foil and a counter cathode foil via a separator. In the manufacturing method of
(1) immersing the capacitor element in a monomer or a solution thereof that becomes a conductive polymer by oxidative polymerization, or dropping a monomer or a solution thereof that becomes a conductive polymer by oxidative polymerization in the capacitor element; Forming a conductive polymer layer in the capacitor element by immersing the capacitor element in a solution containing a doping agent and an oxidizing agent, or by sequentially dropping a solution containing a doping agent and an oxidizing agent on the capacitor element. It is characterized by doing.
【００１２】本発明の第３の局面に従った電解コンデン
サの製造方法は、上記本発明の第１の局面に従った製法
と第２の局面に従った製法とを組み合わせて、（１）前
記コンデンサ素子をドーピング剤を含む溶液に浸漬した
後乾燥するか、前記コンデンサ素子にドーピング剤を含
む溶液を滴下した後乾燥する工程と、（２）前記コンデ
ンサ素子を酸化重合により導電性ポリマーとなるモノマ
ー又はその溶液に浸漬するか、前記コンデンサ素子に酸
化重合により導電性ポリマーとなるモノマー又はその溶
液を滴下する工程と、（３）前記コンデンサ素子をドー
ピング剤及び酸化剤を含む溶液に浸漬するか、前記コン
デンサ素子にドーピング剤及び酸化剤を含む溶液を滴下
する工程とを順に経ることにより、前記コンデンサ素子
内に導電性ポリマー層を形成することを特徴とするもの
である。The method for manufacturing an electrolytic capacitor according to the third aspect of the present invention is characterized in that the manufacturing method according to the first aspect of the present invention and the manufacturing method according to the second aspect are combined, and A step of immersing the capacitor element in a solution containing a doping agent and then drying, or a method of dropping a solution containing a doping agent onto the capacitor element and then drying, and (2) a monomer which becomes a conductive polymer by oxidative polymerization of the capacitor element Or a step of dropping a monomer that becomes a conductive polymer by oxidative polymerization or a solution thereof into the capacitor element, or (3) immersing the capacitor element in a solution containing a doping agent and an oxidizing agent, And a step of dropping a solution containing a doping agent and an oxidizing agent onto the capacitor element in order, thereby forming a conductive polymer in the capacitor element. It is characterized in forming a layer.
【００１３】上記本発明の各製法におけるドーピング剤
としては、例えば、ｐ−トルエンスルホン酸ナトリウ
ム、ｍ−ベンゼンジスルホン酸ジナトリウム等の芳香族
スルホン酸塩を用いることができる。As the doping agent in each of the production methods of the present invention, for example, aromatic sulfonates such as sodium p-toluenesulfonate and disodium m-benzenedisulfonate can be used.
【００１４】上記本発明の各製法によれば、コンデンサ
素子内に導電性ポリマー層が形成される際に、導電性ポ
リマー中にドーピング剤が取り込まれ、該導電性ポリマ
ーの比抵抗が小さくなってコンデンサ完成品としてのＥ
ＳＲが小さくなる。According to each of the production methods of the present invention, when the conductive polymer layer is formed in the capacitor element, the doping agent is incorporated into the conductive polymer, and the specific resistance of the conductive polymer is reduced. E as a finished capacitor
SR decreases.
【００１５】又、上記本発明の各製法に従ってコンデン
サ素子内に導電性ポリマー層を形成した後、該コンデン
サ素子に電解液を含浸させてもよい。この電解液として
は、例えば、γブチロラクトン、エチレングリコール等
を主溶媒とし、フタル酸、アジピン酸等のアミジン塩、
アミン塩、アンモニウム塩等を主溶質とするものを用い
ることができる。After the conductive polymer layer is formed in the capacitor element according to each of the above-mentioned methods of the present invention, the capacitor element may be impregnated with an electrolytic solution. As the electrolyte, for example, γ-butyrolactone, ethylene glycol and the like as a main solvent, phthalic acid, amidine salts such as adipic acid,
Those having an amine salt, an ammonium salt or the like as a main solute can be used.
【００１６】導電性ポリマー層を形成したコンデンサ素
子に電解液を含浸させることにより、陽極化成皮膜の損
傷部の修復力が向上して、コンデンサ完成品としての漏
れ電流が低減する。By impregnating the capacitor element on which the conductive polymer layer is formed with the electrolytic solution, the ability to repair the damaged portion of the anodized film is improved, and the leakage current as a completed capacitor is reduced.
【００１７】[0017]
【発明の実施の形態】本発明の実施形態に従った固体電
解コンデンサの製造方法においては、図１に示すような
巻回型のコンデンサ素子７内に、ポリピロール、ポリチ
オフェン、ポリフラン、ポリアニリン等からなる導電性
ポリマー層を形成する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In a method for manufacturing a solid electrolytic capacitor according to an embodiment of the present invention, a winding type capacitor element 7 as shown in FIG. 1 is made of polypyrrole, polythiophene, polyfuran, polyaniline or the like. Form a conductive polymer layer.
【００１８】前記コンデンサ素子７は、アルミニウム、
タンタル、ニオブ、チタン等の弁作用金属からなる箔に
粗面化のためのエッチング処理及び誘電体皮膜形成のた
めの化成処理を施した陽極化成箔１と、対向陰極箔２と
をセパレータ３を介して巻き取ることにより形成され
る。前記陽極化成箔１及び対向陰極箔２には、それぞれ
リードタブ６１、６２を介してリード線５１、５２が取
り付けられている。４は巻き止めテープである。The capacitor element 7 is made of aluminum,
An anode forming foil 1 in which a foil made of a valve metal such as tantalum, niobium, titanium or the like is subjected to an etching treatment for surface roughening and a chemical conversion treatment for forming a dielectric film, and a counter cathode foil 2 into a separator 3 It is formed by winding through. Lead wires 51 and 52 are attached to the anodized foil 1 and the opposing cathode foil 2 via lead tabs 61 and 62, respectively. Reference numeral 4 denotes a winding tape.
【００１９】前記コンデンサ素子内に導電性ポリマー層
を形成する工程及びそれ以後の工程について、以下、４
種類の例を挙げて説明する。The steps of forming a conductive polymer layer in the capacitor element and the subsequent steps are described below.
A description will be given using examples of types.
【００２０】尚、コンデンサ素子内に導電性ポリマー層
を形成する工程の前に、加熱処理等を施すことによりコ
ンデンサ素子内のセパレータを炭化（すなわち、低密度
化）しておけば、該コンデンサ素子内に導電性ポリマー
層が形成されやすくなる。If the separator in the capacitor element is carbonized (ie, reduced in density) by performing a heat treatment or the like before the step of forming the conductive polymer layer in the capacitor element, A conductive polymer layer is easily formed in the inside.
【００２１】［製法Ａ］前記コンデンサ素子を、ドーピ
ング剤としてのｐ−トルエンスルホン酸ナトリウム又は
ｍ−ベンゼンジスルホン酸ジナトリウムを含む水溶液に
浸漬し、引き上げた後、８５℃の乾燥炉で３０分間乾燥
する。[Production Method A] The capacitor element is immersed in an aqueous solution containing sodium p-toluenesulfonate or disodium m-benzenedisulfonate as a doping agent, pulled up, and dried in a drying oven at 85 ° C. for 30 minutes. I do.
【００２２】次に、該コンデンサ素子に素子体積の１０
容量％のピロールモノマーを滴下する。Next, 10 times of the element volume is stored in the capacitor element.
The volume% of pyrrole monomer is added dropwise.
【００２３】次に、該コンデンサ素子を、酸化剤として
の過硫酸アンモニウムを３０重量％含む水溶液に浸漬
し、引き上げて水洗した後、８５℃の乾燥炉で３０分間
乾燥する。Next, the capacitor element is immersed in an aqueous solution containing 30% by weight of ammonium persulfate as an oxidizing agent, pulled up and washed with water, and then dried in a drying oven at 85 ° C. for 30 minutes.
【００２４】このようにしてポリピロール層を形成した
コンデンサ素子７を、図２に示すように有底筒状のアル
ミニウム製ケース８に収納し、その開口部をエポキシ樹
脂９により封止し、定格電圧を印加しながら１２０℃で
１時間のエージング処理を行うことにより、所望の電解
コンデンサが完成する。The capacitor element 7 having the polypyrrole layer formed as described above is housed in a bottomed cylindrical aluminum case 8 as shown in FIG. 2 and its opening is sealed with an epoxy resin 9 to obtain a rated voltage. The desired electrolytic capacitor is completed by performing an aging treatment at 120 ° C. for 1 hour while applying a voltage.
【００２５】［製法Ｂ］前記コンデンサ素子を、ドーピ
ング剤としてのｐ−トルエンスルホン酸ナトリウム又は
ｍ−ベンゼンジスルホン酸ジナトリウムを含む水溶液に
浸漬し、引き上げた後、８５℃の乾燥炉で３０分間乾燥
する。[Production Method B] The capacitor element is immersed in an aqueous solution containing sodium p-toluenesulfonate or disodium m-benzenedisulfonate as a doping agent, pulled up, and dried in a drying oven at 85 ° C. for 30 minutes. I do.
【００２６】次に、該コンデンサ素子に素子体積の１０
容量％のピロールモノマーを滴下する。Next, 10 times of the element volume is stored in the capacitor element.
The volume% of pyrrole monomer is added dropwise.
【００２７】次に、該コンデンサ素子を、酸化剤として
の過硫酸アンモニウムを３０重量％含む水溶液に浸漬
し、引き上げて水洗した後、８５℃の乾燥炉で３０分間
乾燥する。Next, the capacitor element is immersed in an aqueous solution containing 30% by weight of ammonium persulfate as an oxidizing agent, pulled up, washed with water, and dried in a drying oven at 85 ° C. for 30 minutes.
【００２８】このようにしてポリピロール層を形成した
コンデンサ素子７に、γブチロラクトン、エチレングリ
コール等を主溶媒としてフタル酸、アジピン酸等のアミ
ジン塩、アミン塩、アンモニウム塩等を主溶質とする電
解液を含浸させた後、図３に示すように有底筒状のアル
ミニウム製ケース８に収納し、その開口部をゴムパッキ
ング１０により封止し、定格電圧を印加しながら１２０
℃で１時間のエージング処理を行うことにより、所望の
電解コンデンサが完成する。In the capacitor element 7 having the polypyrrole layer formed in this manner, an electrolytic solution containing γ-butyrolactone, ethylene glycol or the like as a main solvent and an amidine salt such as phthalic acid or adipic acid, an amine salt, an ammonium salt or the like as a main solute. Then, as shown in FIG. 3, it is housed in a bottomed cylindrical aluminum case 8, its opening is sealed with a rubber packing 10, and 120
The desired electrolytic capacitor is completed by performing the aging treatment at 1 ° C. for 1 hour.
【００２９】［製法Ｃ］前記コンデンサ素子に、該素子
の体積の１０容量％のピロールモノマーを滴下する。[Production Method C] A pyrrole monomer of 10% by volume of the volume of the capacitor element is dropped on the capacitor element.
【００３０】次に、該コンデンサ素子を、ドーピング剤
としてのｐ−トルエンスルホン酸ナトリウム又はｍ−ベ
ンゼンジスルホン酸ジナトリウムを含むと共に酸化剤と
しての過硫酸アンモニウムを３０重量％含む水溶液に浸
漬し、引き上げて水洗した後、８５℃の乾燥炉で３０分
間乾燥する。Next, the capacitor element was immersed in an aqueous solution containing sodium p-toluenesulfonate or disodium m-benzenedisulfonate as a doping agent and containing 30% by weight of ammonium persulfate as an oxidizing agent, and pulled up. After washing with water, it is dried in a drying oven at 85 ° C. for 30 minutes.
【００３１】このようにしてポリピロール層を形成した
コンデンサ素子７を、図２に示すように有底筒状のアル
ミニウム製ケース８に収納し、その開口部をエポキシ樹
脂９により封止し、定格電圧を印加しながら１２０℃で
１時間のエージング処理を行うことにより、所望の電解
コンデンサが完成する。The capacitor element 7 on which the polypyrrole layer is formed is housed in a bottomed cylindrical aluminum case 8 as shown in FIG. 2 and its opening is sealed with an epoxy resin 9 to obtain a rated voltage. The desired electrolytic capacitor is completed by performing an aging treatment at 120 ° C. for 1 hour while applying a voltage.
【００３２】［製法Ｄ］前記コンデンサ素子に該素子の
体積の１０容量％のピロールモノマーを滴下する。[Production Method D] A pyrrole monomer of 10% by volume of the volume of the capacitor element is dropped on the capacitor element.
【００３３】次に、該コンデンサ素子を、ドーピング剤
としてのｐ−トルエンスルホン酸ナトリウム又はｍ−ベ
ンゼンジスルホン酸ジナトリウムを含むと共に酸化剤と
しての過硫酸アンモニウムを３０重量％含む水溶液に浸
漬し、引き上げて水洗した後、８５℃の乾燥炉で３０分
間乾燥する。Next, the capacitor element was immersed in an aqueous solution containing sodium p-toluenesulfonate or disodium m-benzenedisulfonate as a doping agent and containing 30% by weight of ammonium persulfate as an oxidizing agent, and pulled up. After washing with water, it is dried in a drying oven at 85 ° C. for 30 minutes.
【００３４】このようにしてポリピロール層を形成した
コンデンサ素子７に、γブチロラクトン、エチレングリ
コール等を主溶媒とし、フタル酸、アジピン酸等のアミ
ジン塩、アミン塩、アンモニウム塩等を主溶質とする電
解液を含浸させた後、図３に示すように有底筒状のアル
ミニウム製ケース８に収納し、その開口部をゴムパッキ
ング１０により封止し、定格電圧を印加しながら１２０
℃で１時間のエージング処理を行うことにより、所望の
電解コンデンサが完成する。In the capacitor element 7 having the polypyrrole layer formed in this way, an electrolytic solution containing γ-butyrolactone, ethylene glycol or the like as a main solvent and an amidine salt such as phthalic acid or adipic acid, an amine salt, an ammonium salt or the like as a main solute. After being impregnated with the liquid, it is housed in a bottomed aluminum case 8 as shown in FIG.
The desired electrolytic capacitor is completed by performing the aging treatment at 1 ° C. for 1 hour.
【００３５】ここで、外形φ６．３ｍｍ×Ｈ５ｍｍ、定
格１０Ｖ−３３μＦのアルミニウム巻回型コンデンサ素
子を用い、上記Ａ〜Ｄの製法に準じながら、ドーピング
剤の種類やその溶液濃度を変えて試作した実施例１〜１
２及び比較例１、２の電解コンデンサについて、１０５
℃×１０００時間の高温負荷試験を行った。各実施例及
び比較例の試作条件を表１に示し、高温負荷試験の前後
における静電容量：Ｃ（μＦ）、損失角の正接：ｔａｎ
δ、定格電圧を印加して１５秒後の漏れ電流：ＬＣ（μ
Ａ）、１００ｋＨｚでの等価直列抵抗：ＥＳＲ（ｍΩ）
の測定結果を表２に示す。尚、表２における高温負荷試
験後のＣについては、試験前のＣを基準とした変化率Δ
Ｃ／Ｃの値を掲載している。Here, a prototype was produced using an aluminum wound capacitor element having an outer diameter of 6.3 mm × H5 mm and a rating of 10 V-33 μF while changing the type of the doping agent and the solution concentration thereof in accordance with the production methods A to D described above. Examples 1 to 1
2 and Comparative Examples 1 and 2, 105
A high temperature load test at 1000C for 1000 hours was performed. Table 1 shows the trial production conditions of each example and comparative example. The capacitance before and after the high-temperature load test: C (μF), the tangent of the loss angle: tan.
δ, leakage current 15 seconds after application of the rated voltage: LC (μ
A), Equivalent series resistance at 100 kHz: ESR (mΩ)
Table 2 shows the measurement results. In Table 2, the C after the high-temperature load test was a rate of change Δ based on the C before the test.
The values of C / C are listed.
【００３６】[0036]
【表１】 [Table 1]
【００３７】[0037]
【表２】 [Table 2]
【００３８】表１及び表２を対照すればわかるように、
製法Ａ又はＢに従ってドーピング剤を使用した実施例１
〜６においては、製法Ａに準じながらドーピング剤を使
用しない比較例１に比べて、高温負荷試験の前後いずれ
においてもＥＳＲが小さくなっている。As can be seen by comparing Tables 1 and 2,
Example 1 using doping agent according to process A or B
In Nos. To 6, the ESR was smaller before and after the high-temperature load test than in Comparative Example 1 in which a doping agent was not used in accordance with Production Method A.
【００３９】又、製法Ｃ又はＤに従ってドーピング剤を
使用した実施例７〜１２においては、製法Ｃに準じなが
らドーピング剤を使用しない比較例２に比べて、高温負
荷試験の前後いずれにおいてもＥＳＲが小さくなってい
る。Further, in Examples 7 to 12 in which a doping agent was used in accordance with Production Method C or D, the ESR before and after the high-temperature load test was lower than in Comparative Example 2 in which no doping agent was used according to Production Method C. It is getting smaller.
【００４０】更に詳述すれば、ＥＳＲが特に小さくなっ
ているのはドーピング剤の濃度が０．５重量％以上の場
合であり、好ましくは５重量％以上の場合である。More specifically, the ESR is particularly low when the concentration of the doping agent is 0.5% by weight or more, preferably 5% by weight or more.
【００４１】本発明の実施形態は上記製法Ａ〜Ｄに限定
されるものでなく、例えば、上記製法Ａ〜Ｄにおけいて
ドーピング剤や酸化剤を含む溶液にコンデンサ素子を浸
漬する工程は、ドーピング剤や酸化剤を含む溶液をコン
デンサ素子に滴下する工程に置き換えてもよい。The embodiment of the present invention is not limited to the above-mentioned production methods A to D. For example, in the above-mentioned production methods A to D, the step of immersing the capacitor element in a solution containing a doping agent or an oxidizing agent includes It may be replaced with a step of dropping a solution containing an agent or an oxidizing agent onto the capacitor element.
【００４２】又、ピロールモノマーをコンデンサ素子に
滴下する工程は、ピロールモノマーを溶媒に溶かした溶
液をコンデンサ素子に滴下する工程、或いはピロールモ
ノマー又はその溶液にコンデンサ素子を浸漬する工程に
置き換えてもよい。The step of dropping the pyrrole monomer onto the capacitor element may be replaced by a step of dropping a solution of the pyrrole monomer in a solvent onto the capacitor element, or a step of dipping the capacitor element in the pyrrole monomer or its solution. .
【００４３】更に、上記製法Ａ又はＢとＣ又はＤとを組
み合わせて、コンデンサ素子を、ドーピング剤を含む水
溶液に浸漬し、引き上げた後、８５℃の乾燥炉で３０分
間乾燥する工程と、該コンデンサ素子に素子体積の１０
容量％のピロールモノマーを滴下する工程と、該コンデ
ンサ素子を、ドーピング剤及び酸化剤を含む水溶液に浸
漬し、引き上げて水洗した後、８５℃の乾燥炉で３０分
間乾燥という工程とを順に経ることにより、コンデンサ
素子内に導電性ポリマー層を形成してもよい。Further, a step of dipping the capacitor element in an aqueous solution containing a doping agent by combining the above-mentioned production methods A or B and C or D, pulling it up, and then drying it in a drying oven at 85 ° C. for 30 minutes; 10 times the element volume of the capacitor element
A step of dropping a volume% of a pyrrole monomer, a step of immersing the capacitor element in an aqueous solution containing a doping agent and an oxidizing agent, pulling it up, washing it with water, and then drying it for 30 minutes in a drying oven at 85 ° C. Thus, a conductive polymer layer may be formed in the capacitor element.
【００４４】一方、上記各実施形態において例示したピ
ロールモノマーの代わりに、チオフェン、フラン、アニ
リン、或いはそれらの誘導体等、酸化重合により導電性
ポリマーとなる各種モノマーを用いてもよい。On the other hand, instead of the pyrrole monomer exemplified in each of the above embodiments, various monomers that become a conductive polymer by oxidative polymerization, such as thiophene, furan, aniline, or derivatives thereof, may be used.
【００４５】又、コンデンサ完成品の外装に関して、コ
ンデンサ素子をアルミケースに収納して樹脂又はゴムパ
ッキングにて封止する代わりに、ディッピング法等によ
り外装樹脂層を形成してもよい。Regarding the exterior of the completed capacitor, an exterior resin layer may be formed by a dipping method or the like instead of housing the capacitor element in an aluminum case and sealing it with resin or rubber packing.
【００４６】[0046]
【発明の効果】本発明によれば、陽極化成箔と対向陰極
箔とをセパレータを介して巻回してなるコンデンサ素子
内に導電性ポリマー層を形成した電解コンデンサにおい
て、コンデンサ素子内に導電性ポリマー層が形成される
際に導電性ポリマー中にドーピング剤が取り込まれ、該
導電性ポリマー層の比抵抗が小さくなってコンデンサ完
成品としてのＥＳＲが小さくなる。According to the present invention, there is provided an electrolytic capacitor having a conductive polymer layer formed in a capacitor element formed by winding an anodized foil and an opposing cathode foil via a separator. When the layer is formed, a doping agent is incorporated into the conductive polymer, and the specific resistance of the conductive polymer layer is reduced, so that the ESR as a finished capacitor is reduced.
【００４７】又、本発明に従ってコンデンサ素子内に導
電性ポリマー層を形成した後、該コンデンサ素子に電解
液を含浸させれば、陽極化成皮膜の損傷部の修復力が向
上し、コンデンサ完成品としての漏れ電流が低減する。After the conductive polymer layer is formed in the capacitor element according to the present invention, if the capacitor element is impregnated with an electrolytic solution, the repairing ability of the damaged portion of the anodized chemical film is improved, and the capacitor is completed. Leakage current is reduced.
【図１】本発明実施例及び従来例において用いられるコ
ンデンサ素子の分解斜視図である。FIG. 1 is an exploded perspective view of a capacitor element used in an embodiment of the present invention and a conventional example.
【図２】本発明実施例による電解コンデンサの断面図で
ある。FIG. 2 is a sectional view of an electrolytic capacitor according to an embodiment of the present invention.
【図３】本発明実施例による電解コンデンサの断面図で
ある。FIG. 3 is a sectional view of an electrolytic capacitor according to an embodiment of the present invention.
１ 陽極化成箔 ２ 対向陰極箔 ３ セパレータ ４ 巻き止めテープ ５１ 陽極リード線 ５２ 陰極リード線 ６１ 陽極リードタブ ６２ 陰極リードタブ ７ コンデンサ素子 ８ 外装ケース ９ 封口樹脂 １０ 封口ゴム DESCRIPTION OF SYMBOLS 1 Anodized chemical foil 2 Counter cathode foil 3 Separator 4 Winding tape 51 Anode lead wire 52 Cathode lead wire 61 Anode lead tab 62 Cathode lead tab 7 Capacitor element 8 Outer case 9 Sealing resin 10 Sealing rubber
Claims (6)
を介して巻回してなるコンデンサ素子内に導電性ポリマ
ー層を形成した電解コンデンサの製造方法において、
（１）前記コンデンサ素子をドーピング剤を含む溶液に
浸漬した後乾燥するか、前記コンデンサ素子にドーピン
グ剤を含む溶液を滴下した後乾燥する工程と、（２）前
記コンデンサ素子を酸化重合により導電性ポリマーとな
るモノマー又はその溶液に浸漬するか、前記コンデンサ
素子に酸化重合により導電性ポリマーとなるモノマー又
はその溶液を滴下する工程と、（３）前記コンデンサ素
子を酸化剤を含む溶液に浸漬するか、前記コンデンサ素
子に酸化剤を含む溶液を滴下する工程とを順に経ること
により、 前記コンデンサ素子内に導電性ポリマー層を形成するこ
とを特徴とする電解コンデンサの製造方法。1. A method for manufacturing an electrolytic capacitor in which a conductive polymer layer is formed in a capacitor element formed by winding an anodized foil and a counter cathode foil via a separator,
(1) a step of immersing the capacitor element in a solution containing a doping agent and then drying, or a method of dropping a solution containing a doping agent on the capacitor element and then drying; and (2) making the capacitor element conductive by oxidative polymerization. A step of dipping a monomer to be a polymer or a solution thereof, or a step of dropping a monomer or a solution thereof to be a conductive polymer by oxidative polymerization on the capacitor element; and (3) immersing the capacitor element in a solution containing an oxidizing agent. And a step of dropping a solution containing an oxidizing agent onto the capacitor element, thereby forming a conductive polymer layer in the capacitor element.
を介して巻回してなるコンデンサ素子内に導電性ポリマ
ー層を形成した電解コンデンサの製造方法において、
（１）前記コンデンサ素子を酸化重合により導電性ポリ
マーとなるモノマー又はその溶液に浸漬するか、前記コ
ンデンサ素子に酸化重合により導電性ポリマーとなるモ
ノマー又はその溶液を滴下する工程と、（２）前記コン
デンサ素子をドーピング剤及び酸化剤を含む溶液に浸漬
するか、前記コンデンサ素子にドーピング剤及び酸化剤
を含む溶液を滴下する工程とを順に経ることにより、 前記コンデンサ素子内に導電性ポリマー層を形成するこ
とを特徴とする電解コンデンサの製造方法。2. A method for producing an electrolytic capacitor comprising a conductive polymer layer formed in a capacitor element formed by winding an anodized foil and a counter cathode foil via a separator,
(1) immersing the capacitor element in a monomer or a solution thereof that becomes a conductive polymer by oxidative polymerization, or dropping a monomer or a solution thereof that becomes a conductive polymer by oxidative polymerization in the capacitor element; Forming a conductive polymer layer in the capacitor element by sequentially immersing the capacitor element in a solution containing a doping agent and an oxidizing agent, or dropping a solution containing a doping agent and an oxidizing agent on the capacitor element. A method for manufacturing an electrolytic capacitor.
を介して巻回してなるコンデンサ素子内に導電性ポリマ
ー層を形成した電解コンデンサの製造方法において、
（１）前記コンデンサ素子をドーピング剤を含む溶液に
浸漬した後乾燥するか、前記コンデンサ素子にドーピン
グ剤を含む溶液を滴下した後乾燥する工程と、（２）前
記コンデンサ素子を酸化重合により導電性ポリマーとな
るモノマー又はその溶液に浸漬するか、前記コンデンサ
素子に酸化重合により導電性ポリマーとなるモノマー又
はその溶液を滴下する工程と、（３）前記コンデンサ素
子をドーピング剤及び酸化剤を含む溶液に浸漬するか、
前記コンデンサ素子にドーピング剤及び酸化剤を含む溶
液を滴下する工程とを順に経ることにより、 前記コンデンサ素子内に導電性ポリマー層を形成するこ
とを特徴とする電解コンデンサの製造方法。3. A method for manufacturing an electrolytic capacitor in which a conductive polymer layer is formed in a capacitor element formed by winding an anodized aluminum foil and a counter cathode foil via a separator,
(1) a step of immersing the capacitor element in a solution containing a doping agent and then drying, or a method of dropping a solution containing a doping agent on the capacitor element and then drying; and (2) making the capacitor element conductive by oxidative polymerization. A step of dipping in a monomer to be a polymer or a solution thereof, or a method of dropping a monomer or a solution thereof to be a conductive polymer by oxidative polymerization on the capacitor element; and (3) converting the capacitor element to a solution containing a doping agent and an oxidizing agent. Soak or
A step of dropping a solution containing a doping agent and an oxidizing agent onto the capacitor element, thereby forming a conductive polymer layer in the capacitor element.
層を形成した後、該コンデンサ素子に電解液を含浸させ
る工程を備えることを特徴とする請求項１、２又は３記
載の電解コンデンサの製造方法。4. The method for producing an electrolytic capacitor according to claim 1, further comprising a step of impregnating said capacitor element with an electrolytic solution after forming a conductive polymer layer in said capacitor element. .
塩であることを特徴とする請求項１、２、３又は４記載
の電解コンデンサの製造方法。5. The method for producing an electrolytic capacitor according to claim 1, wherein the doping agent is an aromatic sulfonate.
ンスルホン酸ナトリウム又はｍ−ベンゼンジスルホン酸
ジナトリウムであることを特徴とする請求項５記載の電
解コンデンサの製造方法。6. The method according to claim 5, wherein the aromatic sulfonate is sodium p-toluenesulfonate or disodium m-benzenedisulfonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02616599A JP3548035B2 (en) | 1999-02-03 | 1999-02-03 | Manufacturing method of electrolytic capacitor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02616599A JP3548035B2 (en) | 1999-02-03 | 1999-02-03 | Manufacturing method of electrolytic capacitor |
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| Publication Number | Publication Date |
|---|---|
| JP2000223364A true JP2000223364A (en) | 2000-08-11 |
| JP3548035B2 JP3548035B2 (en) | 2004-07-28 |
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ID=12185946
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02616599A Expired - Lifetime JP3548035B2 (en) | 1999-02-03 | 1999-02-03 | Manufacturing method of electrolytic capacitor |
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| Country | Link |
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| JP (1) | JP3548035B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004088689A1 (en) * | 2003-03-31 | 2004-10-14 | Matsushita Electric Industrial Co., Ltd. | Conductive separator and electrolytic capacitor including the same |
| WO2012144608A1 (en) | 2011-04-20 | 2012-10-26 | 三菱レイヨン株式会社 | Conductive composition, conductor using conductive composition, and solid electrolytic capacitor |
| JP2014192427A (en) * | 2013-03-28 | 2014-10-06 | Carlit Holdings Co Ltd | Oxidant solution for conductive polymer production, solid electrolytic capacitor arranged by use thereof, and method for producing solid electrolytic capacitor by use thereof |
| US9799420B2 (en) | 2010-10-26 | 2017-10-24 | Mitsubishi Chemical Corporation | Conductive aniline polymer, method for producing same, and method for producing conductive film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07122461A (en) * | 1993-10-20 | 1995-05-12 | Nec Corp | Manufacture of solid electrolytic capacitor |
| JPH07249543A (en) * | 1994-03-14 | 1995-09-26 | Matsushita Electric Ind Co Ltd | Electrolytic capacitor |
| JPH0859599A (en) * | 1994-08-16 | 1996-03-05 | Nec Corp | Disulfonic acid compound, electrically conductive polymer with the same as dopant, electrically conductive material and solid electrolytic capacitor using the material |
| JPH0974050A (en) * | 1995-06-26 | 1997-03-18 | Matsushita Electric Ind Co Ltd | Capacitor and its manufacture |
| JPH1012497A (en) * | 1996-06-27 | 1998-01-16 | Nec Corp | Manufacture of solid electrolytic capacitor using conductive polymer |
-
1999
- 1999-02-03 JP JP02616599A patent/JP3548035B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07122461A (en) * | 1993-10-20 | 1995-05-12 | Nec Corp | Manufacture of solid electrolytic capacitor |
| JPH07249543A (en) * | 1994-03-14 | 1995-09-26 | Matsushita Electric Ind Co Ltd | Electrolytic capacitor |
| JPH0859599A (en) * | 1994-08-16 | 1996-03-05 | Nec Corp | Disulfonic acid compound, electrically conductive polymer with the same as dopant, electrically conductive material and solid electrolytic capacitor using the material |
| JPH0974050A (en) * | 1995-06-26 | 1997-03-18 | Matsushita Electric Ind Co Ltd | Capacitor and its manufacture |
| JPH1012497A (en) * | 1996-06-27 | 1998-01-16 | Nec Corp | Manufacture of solid electrolytic capacitor using conductive polymer |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004088689A1 (en) * | 2003-03-31 | 2004-10-14 | Matsushita Electric Industrial Co., Ltd. | Conductive separator and electrolytic capacitor including the same |
| US7379289B2 (en) | 2003-03-31 | 2008-05-27 | Matsushita Electric Industrial Co., Ltd. | Conductive separator and electrolytic capacitor including the same |
| US9799420B2 (en) | 2010-10-26 | 2017-10-24 | Mitsubishi Chemical Corporation | Conductive aniline polymer, method for producing same, and method for producing conductive film |
| WO2012144608A1 (en) | 2011-04-20 | 2012-10-26 | 三菱レイヨン株式会社 | Conductive composition, conductor using conductive composition, and solid electrolytic capacitor |
| US9679673B2 (en) | 2011-04-20 | 2017-06-13 | Mitsubishi Rayon Co., Ltd. | Conductive composition, conductor and solid electrolytic capacitor using conductive composition |
| JP2014192427A (en) * | 2013-03-28 | 2014-10-06 | Carlit Holdings Co Ltd | Oxidant solution for conductive polymer production, solid electrolytic capacitor arranged by use thereof, and method for producing solid electrolytic capacitor by use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3548035B2 (en) | 2004-07-28 |
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