JP4877229B2 - Solid electrolytic capacitor and manufacturing method thereof - Google Patents
Solid electrolytic capacitor and manufacturing method thereof Download PDFInfo
- Publication number
- JP4877229B2 JP4877229B2 JP2007522361A JP2007522361A JP4877229B2 JP 4877229 B2 JP4877229 B2 JP 4877229B2 JP 2007522361 A JP2007522361 A JP 2007522361A JP 2007522361 A JP2007522361 A JP 2007522361A JP 4877229 B2 JP4877229 B2 JP 4877229B2
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- JP
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- Prior art keywords
- solid electrolytic
- electrolytic capacitor
- porous layer
- substrate
- reduced
- Prior art date
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- 239000007787 solid Substances 0.000 title claims description 86
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Landscapes
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Description
この出願は、米国法典第３５巻第１１１条（ｂ）項の規定に従い、２００５年７月６日に提出した米国仮出願第６０／６９６，５３７の出願日の利益を同第１１９条（ｅ）項（１）により主張する同第１１１条（ａ）項の規定に基づく出願である。 This application is filed in accordance with the provisions of 35 U.S.C. 111 (b) of US Code No. 119 (e) of the filing date of US Provisional Application No. 60 / 696,537 filed July 6, 2005. ) Is an application based on the provisions of Article 111 (a) claimed in paragraph (1).
本発明は、固体電解コンデンサ及びその製造方法に関する。さらに詳しく言えば、陽極部と陰極部とを確実に絶縁できる遮蔽構造を有する固体電解コンデンサ基材及びそれを用いた固体電解コンデンサ並びにその製造方法に関する。 The present invention relates to a solid electrolytic capacitor and a method for manufacturing the same. More specifically, the present invention relates to a solid electrolytic capacitor base material having a shielding structure capable of reliably insulating an anode portion and a cathode portion, a solid electrolytic capacitor using the same, and a method for manufacturing the same.
固体電解コンデンサは、一般的にアルミニウム、タンタル、ニオブ、チタン及びその合金などの弁作用金属からなる陽極体の表面をエッチングにより粗面化してミクロンオーダーの微細孔を形成して表面積を拡大し、その上に化成工程によって誘電体酸化皮膜を形成し、さらに陽極部との間にセパレータを介して固体電解質を含浸させまたは固体電解質層を形成し、その上にカーボンペースト、金属含有導電性ペーストからなる陰極導電層を形成した後に、外部電極となるリードフレームに溶接し、エポキシ樹脂等の外装部を形成して構成される。 Solid electrolytic capacitors are generally roughened by etching the surface of an anode body made of a valve metal such as aluminum, tantalum, niobium, titanium and alloys thereof to form micron-order micropores to increase the surface area. A dielectric oxide film is formed thereon by a chemical conversion process, and further, impregnated with a solid electrolyte or a solid electrolyte layer through a separator between the anode portion and a carbon paste or a metal-containing conductive paste. After forming the cathode conductive layer to be formed, it is welded to a lead frame serving as an external electrode to form an exterior portion such as an epoxy resin.
特に、固体電解質として導電性重合物を用いた固体電解コンデンサは、二酸化マンガンなどを固体電解質とする固体電解コンデンサに比べて等価直列抵抗及び漏れ電流を小さくでき、電子機器の高性能化、小型化に対応できるコンデンサとして有用であるため、多くの製造方法が提案されている。 In particular, solid electrolytic capacitors using a conductive polymer as the solid electrolyte can reduce the equivalent series resistance and leakage current compared to solid electrolytic capacitors using manganese dioxide or the like as the solid electrolyte, improving the performance and size of electronic devices. Therefore, many manufacturing methods have been proposed.
導電性重合物を用いて高性能の固体電解コンデンサを製造する際、特に弁作用金属箔を使用する場合には、陽極端子となる陽極部と導電性重合体を含む導電体層からなる陰極部とを電気的に確実に絶縁することが不可欠である。しかし、固体電解質の含浸または形成工程では、固体電解質が陽極領域側に侵入するいわゆる這い上がりが起こることがあり、この場合、陽極部と陰極部との間で絶縁不良が発生する。 When producing a high performance solid electrolytic capacitor using a conductive polymer, particularly when a valve metal foil is used, a cathode part comprising an anode part serving as an anode terminal and a conductor layer containing a conductive polymer. It is essential to electrically insulate them from each other. However, in the step of impregnating or forming the solid electrolyte, so-called creeping in which the solid electrolyte enters the anode region side may occur. In this case, insulation failure occurs between the anode part and the cathode part.
固体電解コンデンサの陽極部と陰極部を絶縁する遮蔽手段としては、例えば弁作用金属の固体電解質を形成しない部分の少なくとも一部に、ポリアミック酸塩を含む溶液を電着してポリアミック酸の膜を形成した後、加熱により脱水硬化させてポリイミド膜を形成する方法（特開平５−４７６１１号公報）、固体電解質の這い上がり防止のためにポリプロピレン、ポリエステル、シリコン系樹脂またはフッ素系樹脂製のテープもしくは樹脂コートフィルム部を形成する方法（特開平５−１６６６８１号公報）、誘電体皮膜中に浸透し、かつ前記浸透部の上にマスキング層を形成するマスキング材溶液を塗布する工程を有した固体電解質の製造方法（国際出願公開第００／６７２６７号パンフレット（EP1193727））などが提案されている。 As a shielding means for insulating the anode portion and the cathode portion of the solid electrolytic capacitor, for example, a solution containing a polyamic acid salt is electrodeposited on at least a part of the portion of the valve metal that does not form the solid electrolyte to form a polyamic acid film. After forming, a method of forming a polyimide film by dehydrating and curing by heating (Japanese Patent Laid-Open No. 5-47611), a tape made of polypropylene, polyester, silicon resin, or fluorine resin to prevent the solid electrolyte from creeping up or A method for forming a resin-coated film portion (Japanese Patent Laid-Open No. 5-166681), a solid electrolyte having a step of applying a masking material solution which penetrates into a dielectric film and forms a masking layer on the permeation portion A manufacturing method (International Application Publication No. 00/67267 pamphlet (EP1193727)) has been proposed.
電着法でポリイミド膜を形成する方法（特開平５−４７６１１号公報）は通常の塗布法に比べて細孔部まで膜を形成できるが、電着工程を必要とするため生産コストが嵩み、またポリイミド膜を形成させるために高温の脱水工程を必要とする。作製時における固体電解質の這い上がり防止のため絶縁樹脂製のテープもしくはコートフィルムを利用する方法（特開平５−１６６６８１号公報）は、基材の端部をテープ（フィルム）で確実に貼付することが困難であり、固体電解質が陽極側に進入することがある。誘電体皮膜中に浸透し、かつ前記浸透部の上にマスキング層を形成するマスキング材溶液を塗布する工程を有した固体電解質の製造方法（国際出願公開第００／６７２６７号パンフレット）は、マスキング材の粘性等の影響と考えられるが、使用する誘電体皮膜の表面状態や細孔分布等の細孔形成状態によっては、細孔内深部への浸透性が十分でない。 The method of forming a polyimide film by electrodeposition (Japanese Patent Laid-Open No. 5-47611) can form a film up to the pores as compared with the usual coating method, but it requires an electrodeposition process, which increases the production cost. Also, a high temperature dehydration process is required to form a polyimide film. In order to prevent the solid electrolyte from creeping up during production, a method using an insulating resin tape or a coated film (Japanese Patent Laid-Open No. 5-166681) is to securely attach the end of the substrate with a tape (film). Is difficult, and the solid electrolyte may enter the anode side. A method for producing a solid electrolyte (International Application Publication No. 00/67267 pamphlet) having a step of applying a masking material solution that penetrates into a dielectric film and forms a masking layer on the permeation part is disclosed in However, depending on the surface state of the dielectric film used and the pore formation state such as the pore distribution, the permeability to the deep part in the pores is not sufficient.
以上のように、従来のマスキング手段はいずれも十分満足できるものではなく、固体電解コンデンサの陽極部と陰極部とを確実に絶縁できるマスキング形態（構造）が求められていた。 As described above, none of the conventional masking means is sufficiently satisfactory, and a masking configuration (structure) capable of reliably insulating the anode portion and the cathode portion of the solid electrolytic capacitor has been demanded.
従って、本発明は上記従来技術の問題点を解決し、固体電解コンデンサの品質を安定化させ、かつ生産性を向上させるため、陽極部領域と陰極部領域をより確実に絶縁した固体電解コンデンサ用陽極基体（本明細書及び特許請求の範囲において「固体電解コンデンサ用基材」という。）及びその製造方法を提供することを目的とするものである。 Therefore, the present invention solves the above-mentioned problems of the prior art, stabilizes the quality of the solid electrolytic capacitor, and improves the productivity, so that the anode region and the cathode region are more reliably insulated. An object of the present invention is to provide an anode substrate (referred to as “substrate for solid electrolytic capacitor” in the present specification and claims) and a method for producing the same.
上記課題に鑑み鋭意検討した結果、本発明者らは、表面に多孔質層を有する固体電解コンデンサ用基材において、陽極部領域と陰極部領域の間の多孔質層の少なくとも一部を縮少し、好ましくは縮少により形成された凹部をマスキング材で充填することにより、陰陽両極が確実に分離される構造が得られ、コンデンサ諸特性の向上がもたらされることを見出し本発明を完成するに至った。
すなわち、本発明によれば、以下の固体電解コンデンサ用基材、固体電解コンデンサ及びその製造方法が提供される。As a result of intensive studies in view of the above problems, the present inventors reduced at least part of the porous layer between the anode region and the cathode region in the solid electrolytic capacitor substrate having a porous layer on the surface. It has been found that a structure in which the negative and positive electrodes are reliably separated by filling the recesses formed by shrinkage with a masking material, and that various characteristics of the capacitor are improved, and the present invention has been completed. It was.
That is, according to the present invention, the following solid electrolytic capacitor substrate, solid electrolytic capacitor, and manufacturing method thereof are provided.
１．表面に多孔質層を有する固体電解コンデンサ用基材において、陽極部領域と陰極部領域の間の多孔質層の少なくとも一部が縮少されていることを特徴とする固体電解コンデンサ用基材。
２．多孔質層の少なくとも一部が縮少されている部位における多孔質層の厚みが、縮少されていない多孔質層の部位の厚みを１として０〜０．９５の範囲である前記１に記載の固体電解コンデンサ用基材。
３．多孔質層の少なくとも一部が縮少されている部位の幅が、陰極部領域の長軸方向の長さを１として０．０００５〜０．１の範囲である前記１または２に記載の固体電解コンデンサ用基材。
４．多孔質層の少なくとも一部が縮少されている部位に凹部が形成され、その凹部がマスキング材で充填されている前記１〜３のいずれかに記載の固体電解コンデンサ用基材。
５．マスキング材が耐熱性樹脂である前記４に記載の固体電解コンデンサ用基材。
６．基材が弁作用金属材料からなる前記１〜５のいずれかに記載の固体電解コンデンサ用基材。
７．弁作用金属材料が、アルミニウム、タンタル、ニオブ、チタン、ジルコニウムのうち少なくとも一種の金属を含むことを特徴とする前記６に記載の固体電解コンデンサ用基材。
８．基材の表面に誘電体皮膜が形成されている前記１〜７のいずれかに記載の固体電解コンデンサ用基材。
９．基材が平板状であり、陽極部領域と陰極部領域の間において基材の両面で多孔質層が縮少されている前記１〜８のいずれかに記載の固体電解コンデンサ用基材。
１０．基材が平板状であり、陽極部領域と陰極部領域の間において、基材の横断面を巡って周状に多孔質層が縮少されている前記１〜８のいずれかに記載の固体電解コンデンサ用基材。
１１．前記１〜１０のいずれかに記載の固体電解コンデンサ用基材を用いたことを特徴とする固体電解コンデンサ。
１２．前記１〜１０のいずれかに記載の固体電解コンデンサ用基材を用いたことを特徴とする固体電解コンデンサ素子。
１３．固体電解コンデンサ用基材の陽極部領域と陰極部領域の間の多孔質層の少なくとも一部を縮少する工程を含むことを特徴とする固体電解コンデンサの製造方法。
１４．縮少が、多孔質層を除去することにより行なわれる前記１３に記載の固体電解コンデンサの製造方法。
１５．縮少が、多孔質層を圧縮することにより行なわれる前記１３に記載の固体電解コンデンサの製造方法。
１６．固体電解コンデンサ用基材の陽極部領域と陰極部領域の間の多孔質層の少なくとも一部を縮小する工程がレーザ光を照射する工程を含む前記１３〜１５のいずれかに記載の固体電解コンデンサの製造方法。
１７．水流コラム内に封じ込めたレーザ光を照射する工程を含む前記１３〜１６のいずれかに記載の固体電解コンデンサの製造方法。
１８．レーザ光が０．１〜１１ミクロンの波長を有している前記１６または１７に記載の固体電解コンデンサの製造方法。1. A substrate for a solid electrolytic capacitor having a porous layer on a surface thereof, wherein at least a part of the porous layer between the anode region and the cathode region is reduced.
2. 2. The thickness of the porous layer in a portion where at least a part of the porous layer is reduced is in the range of 0 to 0.95, where 1 is the thickness of the portion of the porous layer that is not reduced. Base material for solid electrolytic capacitors.
3. 3. The solid according to 1 or 2 above, wherein the width of the portion where at least a part of the porous layer is reduced is in the range of 0.0005 to 0.1, where the length in the major axis direction of the cathode region is 1. Electrolytic capacitor substrate.
4). 4. The substrate for a solid electrolytic capacitor as described in any one of 1 to 3, wherein a concave portion is formed in a portion where at least a part of the porous layer is reduced, and the concave portion is filled with a masking material.
5. 5. The substrate for a solid electrolytic capacitor as described in 4 above, wherein the masking material is a heat resistant resin.
6). 6. The substrate for a solid electrolytic capacitor as described in any one of 1 to 5 above, wherein the substrate is made of a valve action metal material.
7). 7. The solid electrolytic capacitor base material as described in 6 above, wherein the valve action metal material contains at least one metal selected from aluminum, tantalum, niobium, titanium, and zirconium.
8). 8. The solid electrolytic capacitor substrate according to any one of 1 to 7, wherein a dielectric film is formed on the surface of the substrate.
9. 9. The substrate for a solid electrolytic capacitor as described in any one of 1 to 8 above, wherein the substrate is flat and the porous layer is reduced on both surfaces of the substrate between the anode part region and the cathode part region.
10. The solid according to any one of 1 to 8 above, wherein the substrate is flat and the porous layer is reduced in a circumferential shape around the cross section of the substrate between the anode region and the cathode region. Electrolytic capacitor substrate.
11. 11. A solid electrolytic capacitor using the solid electrolytic capacitor base material according to any one of 1 to 10 above.
12 11. A solid electrolytic capacitor element using the solid electrolytic capacitor base material according to any one of 1 to 10 above.
13. A method for producing a solid electrolytic capacitor comprising a step of reducing at least a part of a porous layer between an anode region and a cathode region of a substrate for a solid electrolytic capacitor.
14 14. The method for producing a solid electrolytic capacitor as described in 13 above, wherein the reduction is performed by removing the porous layer.
15. 14. The method for producing a solid electrolytic capacitor as described in 13 above, wherein the reduction is performed by compressing the porous layer.
16. The solid electrolytic capacitor according to any one of 13 to 15, wherein the step of reducing at least a part of the porous layer between the anode region and the cathode region of the substrate for a solid electrolytic capacitor includes a step of irradiating laser light. Manufacturing method.
17. The method for producing a solid electrolytic capacitor as described in any one of 13 to 16 above, comprising a step of irradiating a laser beam contained in a water flow column.
18. 18. The method for producing a solid electrolytic capacitor as described in 16 or 17 above, wherein the laser beam has a wavelength of 0.1 to 11 microns.
本発明の好ましい実施態様によれば、表面に多孔質層を有する固体電解コンデンサ用基材において、陽極部領域と陰極部領域の間の多孔質層の少なくとも一部を除去または圧し、好ましくは除去により形成された凹部をマスキング材で充填することにより、コンデンサ製造工程における固体電解質または固体電解質形成用処理液の這い上がりを防止して陰極部と陽極部の絶縁性をより高め、絶縁不良に起因する漏れ電流特性の悪化を防ぎ、収率及び信頼性の向上に寄与する。 According to a preferred embodiment of the present invention, in the solid electrolytic capacitor substrate having a porous layer on the surface, at least a part of the porous layer between the anode region and the cathode region is removed or pressed, preferably removed. By filling the recesses formed by the masking material with the masking material, it is possible to prevent the rise of the solid electrolyte or the processing solution for forming the solid electrolyte in the capacitor manufacturing process, and to further improve the insulation between the cathode and anode, resulting from poor insulation This prevents the leakage current characteristics from deteriorating and contributes to the improvement of yield and reliability.
以下、添付の図面を参照しつつ、本発明の好ましい実施態様における固体電解コンデンサ用基材及びそれを用いたコンデンサ及びその製造方法を説明する。
本発明の好ましい実施態様における固体電解コンデンサ基材は、表面に多孔質層を有するコンデンサ用材料であり、好ましくは、微細孔を有する弁作用金属材料、特に好ましくは、表面に誘電体酸化皮膜を有する弁作用金属である。弁作用金属はアルミニウム、タンタル、ニオブ、チタン、ジルコニウムあるいはこれらを基質とする合金系の弁作用を有する金属箔、棒、あるいはこれらを主成分とする焼結体等から選ばれる。これらの金属は空気中の酸素により表面が酸化された結果としての誘電体酸化皮膜を有しているが、予め公知の方法によりエッチング処理等をして多孔質化する。次に公知の方法等に従って、化成処理し確実に誘電体酸化皮膜を形成しておくことが好ましい。Hereinafter, a substrate for a solid electrolytic capacitor, a capacitor using the same, and a method for manufacturing the same according to preferred embodiments of the present invention will be described with reference to the accompanying drawings.
The solid electrolytic capacitor base material in a preferred embodiment of the present invention is a capacitor material having a porous layer on the surface, preferably a valve metal material having micropores, particularly preferably a dielectric oxide film on the surface. It has a valve metal. The valve metal is selected from aluminum, tantalum, niobium, titanium, zirconium, or an alloy-based metal foil, rod, or a sintered body containing these as a main component. These metals have a dielectric oxide film as a result of oxidation of the surface by oxygen in the air, but are made porous by etching in advance by a known method. Next, it is preferable to form a dielectric oxide film reliably by chemical conversion according to a known method or the like.
弁作用を有する金属基材は、粗面化後、予め固体電解コンデンサの形状に合わせた寸法に裁断したものを使用するのが好ましい。
弁作用を有する金属箔としては、使用目的によって厚さが変わるが、一般的に厚みが約４０〜１５０μｍの箔が使用される。また、弁作用を有する金属箔の大きさ及び形状は用途により異なるが、平板形素子単位として幅約１〜５０ｍｍ、長さ約１〜５０ｍｍの矩形のものが好ましく、より好ましくは幅約２〜２０ｍｍ、長さ約２〜２０ｍｍ、さらに好ましくは幅約２〜５ｍｍ、長さ約２〜６ｍｍである。As the metal base material having a valve action, it is preferable to use a metal base material that has been cut into a size that matches the shape of the solid electrolytic capacitor after roughening.
As the metal foil having a valve action, the thickness varies depending on the purpose of use, but generally a foil having a thickness of about 40 to 150 μm is used. Moreover, although the size and shape of the metal foil having a valve action vary depending on the use, a rectangular element having a width of about 1 to 50 mm and a length of about 1 to 50 mm is preferable as a flat element unit, and more preferably a width of about 2 to 2 mm. It is 20 mm, length is about 2-20 mm, more preferably width is about 2-5 mm, and length is about 2-6 mm.
本発明は、上記のような表面に多孔質層を有する固体電解コンデンサ基材において、陽極部領域と陰極部領域の間の多孔質層の少なくとも一部を縮少したことを特徴とする。
すなわち、多孔質層を有する固体電解コンデンサ基材、例えば、微細孔を有する弁作用金属材料の表面に誘電体皮膜が形成された固体電解コンデンサ用基材において陽極が形成される領域（陽極部領域）と陰極が形成される領域（陰極部領域）との間の領域、通常はその境界部分の多孔質層の少なくとも一部について多孔質層の縮少を行なう。
多孔質層の縮少には、多孔質層そのものを基材から取り除くだけでなく、前記処理液の這い上り可能な細孔をできるだけなくすことも含まれる。例えば、多孔質層の除去、多孔質層の圧縮等が挙げられるほか、多孔質層の部分的な溶融、及びこれら以外の方法による緻密化が含まれる。
固体電解コンデンサ基材の形状は特に限定されないが、図１に断面を示す平板型素子単位用エッチング済みアルミ箔を例とすると、市販されているこのエッチングされたアルミ箔は、箔の中心部に芯材（アルミニウム）５を有し、その両側にエッチングされた多孔質層４を有する。通常、これを固体電解コンデンサ基材として用いる場合、一方の端部近傍領域を陽極部領域１、反対側の領域を陰極部領域２とする（図１（ａ））。その中間領域３が、陽極部領域１と陰極部領域２を隔離する境界部領域３であり、従来はこの領域にマスキング材７が塗布されている（図１（ｂ））。The present invention is characterized in that in the solid electrolytic capacitor base material having a porous layer on the surface as described above, at least a part of the porous layer between the anode region and the cathode region is reduced.
That is, a region (anode portion region) where an anode is formed in a solid electrolytic capacitor substrate having a porous layer, for example, a solid electrolytic capacitor substrate in which a dielectric film is formed on the surface of a valve metal material having micropores ) And a region where the cathode is formed (cathode portion region), usually at least part of the porous layer at the boundary portion is reduced.
The reduction of the porous layer includes not only removing the porous layer itself from the base material but also eliminating as much as possible the pores that can be swept up by the treatment liquid. For example, removal of the porous layer, compression of the porous layer, and the like are included, and partial melting of the porous layer and densification by other methods are included.
The shape of the solid electrolytic capacitor base material is not particularly limited, but when an etched aluminum foil for a flat-type element unit whose cross section is shown in FIG. It has a core material (aluminum) 5 and has a porous layer 4 etched on both sides thereof. Usually, when this is used as a solid electrolytic capacitor base material, one end portion vicinity region is an anode portion region 1 and the opposite region is a cathode portion region 2 (FIG. 1A). The intermediate region 3 is a boundary region 3 that separates the anode region 1 and the cathode region 2, and conventionally, a masking material 7 is applied to this region (FIG. 1B).
本発明では、この領域の少なくとも一部について多孔質層の縮少を行なう。例えば、図２に示すように、前記境界部領域３において除去または圧縮を行なう。このように多孔質層の縮少を行なった場合、多孔質層の厚みが減少するため、凹部６が形成される。この結果、陰極部領域２に固体電解質形成処理を行なった場合、陽極部領域１への固体電解質の這い上がりが抑制される。
特に図３に示すように、マスキング材（陰極部領域と陽極部領域とを電気的に絶縁し、固体電解質または固体電解質形成用処理液が陰極部領域から陽極部領域に侵入するのを防止する遮蔽材）７を凹部６に充填した場合、マスキング材７による遮蔽層は、多孔質内部への浸透部分８を含め、基材深部まで形成される。圧縮処理を行なった場合には、圧縮後に残っている多孔質層が緻密化されるため、固体電解質または固体電解質形成用処理液が浸透して陰極部領域から陽極部領域に浸み上がる現象が確実に防止される。In the present invention, the porous layer is reduced in at least a part of this region. For example, as shown in FIG. 2, removal or compression is performed in the boundary region 3. When the porous layer is reduced in this way, the thickness of the porous layer decreases, so that the recess 6 is formed. As a result, when the solid electrolyte forming process is performed on the cathode region 2, creeping of the solid electrolyte to the anode region 1 is suppressed.
In particular, as shown in FIG. 3, the masking material (the cathode part region and the anode part region are electrically insulated to prevent the solid electrolyte or the solid electrolyte forming treatment liquid from entering the anode part region from the cathode part region. When the concave portion 6 is filled with the shielding material 7, the shielding layer made of the masking material 7 is formed up to the deep part of the base material including the permeation portion 8 into the porous interior. When the compression treatment is performed, the porous layer remaining after the compression is densified, so that the solid electrolyte or the treatment solution for forming the solid electrolyte permeates and soaks into the anode region from the cathode region. It is surely prevented.
多孔質層の除去方法は、多孔質体を精度良く除去でき、他の領域、特に陰極部へ悪影響を及ぼさない手法であれば、いかなる手法でも良く、例えば機械的、電気的、化学的（例えば、溶解）、熱的（例えば、揮散）手法等が利用できる。好ましくはレーザ光を利用した切削手法、水流コラム内に封じ込められたレーザ光を利用した切削手法、針状金属片で削り取る手法、円盤状金属板で回転研磨しながら切削する手法等が挙げられる。 The removal method of the porous layer may be any method as long as the porous body can be removed with high accuracy and does not adversely affect other regions, particularly the cathode portion. For example, mechanical, electrical, chemical (for example, , Dissolution), thermal (for example, volatilization) methods, and the like. Preferably, a cutting method using laser light, a cutting method using laser light confined in a water flow column, a method of scraping with a needle-shaped metal piece, a method of cutting while rotating and polishing with a disk-shaped metal plate, and the like can be mentioned.
レーザー光を利用した切削方法では、０．１〜１１ミクロンの波長を有するレーザ光が使用でき、具体的にはルビー、ガラス、ＹＡＧ等の固体レーザ、ＧａＡｓ、ＩｎＧａＡｓＰ等の半導体レーザ、色素レーザ等の液体レーザ、Ｈｅ−Ｎｅ、Ａｒ、ＡｒＦ、Ｆ２、ＣＯ２等の気体レーザ等が挙げられる。特に好ましくは、ＹＡＧ、ＣＯ２のレーザ光を使用した切削方法及び水流コラム内に封じ込められたＹＡＧのレーザ光を利用した切削方法が好ましい。In the cutting method using laser light, laser light having a wavelength of 0.1 to 11 microns can be used. Specifically, solid lasers such as ruby, glass and YAG, semiconductor lasers such as GaAs and InGaAsP, dye lasers and the like Liquid laser, He—Ne, Ar, ArF, F 2 , CO 2 and other gas lasers. A cutting method using YAG and CO 2 laser light and a cutting method using YAG laser light enclosed in a water flow column are particularly preferable.
例えば、水圧１０〜５０ＭＰａ、コラム径３０〜１８０μｍとして、水を細い糸のように吹き出し、ＹＡＧレーザをこの水の中に導いて切削することができる。水流コラム内に封じ込められたＹＡＧのレーザ光は、レーザ光照射部分に発生する熱を照射と同時に水流によって除去することができる。このため基板に残存する多孔質層の表面が溶解するのを低減することができるため、マスキング材の浸透性が良くなり、さらに溶解粉による汚染やバリの発生が防止される点で、切削方法として有効である。
水流コラム内に封じ込められたＹＡＧのレーザ光を利用した場合の切削の幅は水流圧力とレーザによる相乗効果のため、コラム径の１〜３倍の範囲に拡大される。For example, the water pressure is 10 to 50 MPa, the column diameter is 30 to 180 μm, and water can be blown out like a thin thread, and the YAG laser can be guided into the water and cut. The YAG laser light confined in the water flow column can remove the heat generated in the laser light irradiation portion by the water flow simultaneously with the irradiation. For this reason, it is possible to reduce the dissolution of the surface of the porous layer remaining on the substrate, so that the permeability of the masking material is improved, and further, contamination by the dissolved powder and generation of burrs are prevented. It is effective as
The cutting width when using the YAG laser light confined in the water flow column is expanded to a range of 1 to 3 times the column diameter due to the synergistic effect of the water pressure and the laser.
圧縮方法も多孔質体を精度良く圧縮でき、他の領域、特に陰極部へ悪影響を及ぼさない手法であれば、いかなる手法でも良く、例えば、機械的手法が利用できる。さらに詳しく言えば、針状金属片や薄片の縁部を押し当てる、円盤状金属板を回転させつつ押し当てる方法などが挙げられるが、これに限られるものではない。 As the compression method, any method may be used as long as it can compress the porous body with high accuracy and does not adversely affect other regions, particularly the cathode portion. For example, a mechanical method can be used. More specifically, a method of pressing an edge of a needle-shaped metal piece or a thin piece or a method of pressing a disk-shaped metal plate while rotating it may be mentioned, but it is not limited thereto.
多孔質層を縮少することにより形成される凹部の割合は、好ましくは、多孔質層の全体の厚み（縮少されていない部位の多孔質層の厚みを）を１とした場合、縮少された部位の多孔質層の厚みが０〜０．９５の比となる範囲である。例えば１１０μｍの厚みの箔で、多孔質層がその両面に３５μｍずつ対称に存在しているとすると、縮少部位とそうでない部位の多孔質層の厚みの差が１．７５μｍ（多孔質の表裏面を合わせた深さで３．５μｍ）未満では、前記比は０．９５を超えるため、本発明の効果は少なくなる。更に好ましい範囲としては、多孔質層の全体の厚みを１とした時、縮少された多孔質層の厚みが０．０５〜０．９０であり、更に好ましくは０．２〜０．８である。 The ratio of the recesses formed by reducing the porous layer is preferably reduced when the total thickness of the porous layer (the thickness of the porous layer at the portion not reduced) is 1. In this range, the thickness of the porous layer at the site is a ratio of 0 to 0.95. For example, if the foil is 110 μm thick and the porous layers are symmetrically present on both sides of 35 μm, the difference in the thickness of the porous layer between the reduced portion and the other portion is 1.75 μm (porous surface). If the depth of the back surface is less than 3.5 μm), the ratio exceeds 0.95, so the effect of the present invention is reduced. As a more preferable range, when the total thickness of the porous layer is 1, the reduced thickness of the porous layer is 0.05 to 0.90, more preferably 0.2 to 0.8. is there.
除去の場合、除去部位の多孔質層をすべて除去する（図２（ａ））ことも可能であるが、その場合、基材の強度が相対的に減少し、後の加工工程に影響を及ぼす。従って、後工程に影響を及ぼさない範囲で除去（図２（ｂ））することが好ましい。 In the case of removal, it is also possible to remove all of the porous layer at the removal site (FIG. 2 (a)), but in that case, the strength of the base material is relatively reduced, affecting the subsequent processing steps. . Therefore, it is preferable to remove (FIG. 2B) within a range that does not affect the subsequent process.
縮少される多孔質層の幅は、陰極部領域の長軸方向の長さを１とした場合、０．０００５〜０．１の比で表される。例えば、陰極部領域の長軸方向の長さが５ｍｍであるとすると、縮少される領域の長軸方向の長さは２．５μｍ〜５００μｍとなる。更に好ましい範囲としては、０．００１〜０．０７５の範囲、更に好ましくは０．００２〜０．０５の範囲である。縮少される領域が長軸方向の長さに対して０．００１以下であると、マスキング材が内部に浸透しにくくなり、陰極部領域と陽極部領域とを電気的に絶縁し、固体電解質または固体電解質形成用処理液が陰極部領域から陽極部領域に侵入するのを防止する遮蔽効果が少なくなる。また０．１以上であると、コンデンサの基本特性である容量への影響を無視することができず、必要容量を得るためには基材面積を大きくする必要がある。なお、本発明の目的から、固体電解コンデンサ用基材が平板状である場合、陽極部領域と陰極部領域の間において基材の両面で、または基材の横断面を巡って周状に多孔質層の除去または圧縮処理を施すことが好ましい。 The width of the porous layer to be reduced is represented by a ratio of 0.0005 to 0.1, where 1 is the length in the major axis direction of the cathode region. For example, if the length in the major axis direction of the cathode region is 5 mm, the length in the major axis direction of the region to be reduced is 2.5 μm to 500 μm. As a more preferable range, it is the range of 0.001-0.075, More preferably, it is the range of 0.002-0.05. When the area to be reduced is 0.001 or less with respect to the length in the major axis direction, the masking material is less likely to penetrate into the inside, and the cathode part area and the anode part area are electrically insulated, and the solid electrolyte Alternatively, the shielding effect for preventing the solid electrolyte forming treatment liquid from entering the anode region from the cathode region is reduced. If it is 0.1 or more, the influence on the capacity, which is a basic characteristic of the capacitor, cannot be ignored, and it is necessary to increase the substrate area in order to obtain the required capacity. For the purpose of the present invention, when the substrate for a solid electrolytic capacitor is flat, it is porous on both sides of the substrate between the anode region and the cathode region or circumferentially around the cross section of the substrate. It is preferable to perform removal or compression treatment of the material layer.
所定の形状に裁断された弁作用を有する金属の化成処理は種々の方法によって行なうことができる。化成処理の条件は特に限定されるものではないが、例えばシュウ酸、アジピン酸、ホウ酸、リン酸等の少なくとも１種を含む電解液を用い、その電解液濃度が０．０５質量％〜２０質量％、温度が０℃〜９０℃、電流密度が０．１ｍＡ／ｃｍ２〜２００ｍＡ／ｃｍ２、電圧は処理する化成箔の既に形成されている皮膜の化成電圧に応じた数値、化成時間が６０分以内の条件で化成を行なう。さらに好ましくは前記電解液濃度が０．１質量％〜１５質量％、温度が２０℃〜７０℃、電流密度が１ｍＡ／ｃｍ２〜１００ｍＡ／ｃｍ２、化成時間が３０分以内の範囲で条件を選定する。The chemical conversion treatment of the metal having a valve action cut into a predetermined shape can be performed by various methods. The conditions for the chemical conversion treatment are not particularly limited. For example, an electrolytic solution containing at least one of oxalic acid, adipic acid, boric acid, phosphoric acid and the like is used, and the electrolytic solution concentration is 0.05% by mass to 20%. Mass%, temperature is 0 ° C. to 90 ° C., current density is 0.1 mA / cm 2 to 200 mA / cm 2 , voltage is a numerical value according to the conversion voltage of the already formed film of the conversion foil to be processed, formation time Chemical conversion is performed within 60 minutes. More preferably the electrolyte solution concentration is 0.1% by mass to 15% by weight, temperature is 20 ° C. to 70 ° C., a current density of 1mA / cm 2 ~100mA / cm 2 , the chemical conversion time conditions within a range of 30 minutes Select.
前記の化成処理の条件は工業的方法として好適なものではあるが、弁作用金属材料表面に既に形成されている誘電体酸化皮膜を破壊または劣化させない限り、電解液の種類、電解液濃度、温度、電流密度、化成時間等の諸条件は任意に選定することができる。 The conditions of the chemical conversion treatment are suitable as an industrial method, but unless the dielectric oxide film already formed on the surface of the valve metal material is destroyed or deteriorated, the type of electrolyte, concentration of electrolyte, temperature Various conditions such as current density and formation time can be arbitrarily selected.
マスキング材７（図３）は、陰極部領域と陽極部領域とを電気的に絶縁し、固体電解質または固体電解質形成用処理液が陰極部領域から陽極部領域に侵入するのを防止するための遮蔽材として設けられる。
このようなマスキング材（遮蔽材）としては、上記の目的に適合する限りにおいて特に限定されず、一般的な耐熱性樹脂、好ましくは溶剤に可溶あるいは膨潤しうる耐熱性樹脂またはその前駆体、無機質微粉とセルロース系樹脂からなる組成物（特開平１１−８０５９６号公報）などが使用できる。具体例としてはポリフェニルスルホン（ＰＰＳ）、ポリエーテルスルホン（ＰＥＳ）、シアン酸エステル樹脂、フッ素樹脂（テトラフルオロエチレン、テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体）、ポリイミド及びそれらの誘導体などが挙げられる。ポリイミド、ポリエーテルスルホン、フッ素樹脂及びそれらの前駆体が好ましく、特に弁作用金属に十分な密着力、充填性を有し、約４５０℃までの高温処理に耐えられる絶縁性に優れたポリイミドが好ましい。ポリイミドとしては、２００℃以下、好ましくは１００〜２００℃の低温度での熱処理により硬化が十分可能であり、陽極箔の表面上の誘電体層の熱による破損・破壊などの外的衝撃が少ないポリイミドが好適に使用できる。
ポリイミドの好ましい平均分子量としては約１０００〜１００００００であり、より好ましくは約２０００〜２０００００である。The masking material 7 (FIG. 3) electrically insulates the cathode part region and the anode part region, and prevents the solid electrolyte or the processing solution for forming a solid electrolyte from entering the anode part region from the cathode part region. Provided as a shielding material.
Such a masking material (shielding material) is not particularly limited as long as it meets the above-mentioned purpose, and is a general heat-resistant resin, preferably a heat-resistant resin that can be dissolved or swelled in a solvent or a precursor thereof, A composition comprising an inorganic fine powder and a cellulose resin (Japanese Patent Laid-Open No. 11-80596) can be used. Specific examples include polyphenylsulfone (PPS), polyethersulfone (PES), cyanate ester resin, fluororesin (tetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), polyimide, and derivatives thereof. Can be mentioned. Polyimide, polyethersulfone, fluororesin and their precursors are preferred, and in particular, a polyimide having sufficient adhesion and filling properties to the valve action metal and excellent in insulation capable of withstanding high temperature processing up to about 450 ° C. . As polyimide, it can be sufficiently cured by heat treatment at a low temperature of 200 ° C. or less, preferably 100 to 200 ° C., and there is little external impact such as damage or destruction due to heat of the dielectric layer on the surface of the anode foil. Polyimide can be suitably used.
The preferred average molecular weight of the polyimide is about 1000 to 1000000, more preferably about 2000 to 200000.
これらは、有機溶剤に溶解あるいは分散可能であり、塗布操作に適した任意の固形分濃度（従って粘度）の溶液あるいは分散液を容易に調製することができる。好ましい濃度としては、約１０〜６０質量％、より好ましい濃度としては、約１５〜４０質量％である。濃度が低すぎるとマスキング材（遮蔽材）による描線がにじみ、高過ぎると糸引き等が起こり、線幅が不安定になる。 These can be dissolved or dispersed in an organic solvent, and a solution or dispersion having an arbitrary solid content concentration (and therefore viscosity) suitable for coating operation can be easily prepared. A preferable concentration is about 10 to 60% by mass, and a more preferable concentration is about 15 to 40% by mass. If the concentration is too low, the drawn line by the masking material (shielding material) blurs, and if it is too high, stringing or the like occurs and the line width becomes unstable.
ポリイミド溶液の具体例としては、塗布後の加熱処理により硬化する低分子ポリイミドを２−メトキシエチルエーテルやトリエチレングリコールジメチルエーテルなどの吸湿性の少ない溶剤に溶した（例えば宇部興産(株)から「ユピコートＴＭＦＳ−１００Ｌ」として販売されている。）、あるいは前記式（５）で示されるポリイミド樹脂をＮＭＰ（Ｎ−メチル−２−ピロリドン）やＤＭＡｃ（ジメチルアセトアミド）に溶解した溶液（例えば、新日本理化(株)から「リカコートＴＭ」として販売されている。）が好ましく使用できる。
本発明の好適実施態様においては、上に述べた液状のマスキング材を前述のように縮小した多孔質層上に塗布して遮蔽材層を形成する。溶液状のマスキング材を用いることにより多孔質層の縮小部分がマスキング材によって確実に充填される。マスキング材（遮蔽材）溶液によって形成される遮蔽材層は、遮蔽材溶液の塗布後、必要に応じて乾燥、加熱、光照射などの処理を行なっても良い。As a specific example of the polyimide solution, a low molecular weight polyimide that is cured by a heat treatment after coating was dissolved in a solvent having low hygroscopicity such as 2-methoxyethyl ether or triethylene glycol dimethyl ether (for example, “Iupicoat from Ube Industries, Ltd.”). TMFS-100L "), or a solution in which the polyimide resin represented by the formula (5) is dissolved in NMP (N-methyl-2-pyrrolidone) or DMAc (dimethylacetamide) (for example, Shin Nippon Rika Co., Ltd.) Can be used preferably.
In a preferred embodiment of the present invention, the liquid masking material described above is applied on the porous layer reduced as described above to form a shielding material layer. By using a solution-like masking material, the reduced portion of the porous layer is reliably filled with the masking material. The shielding material layer formed of the masking material (shielding material) solution may be subjected to treatments such as drying, heating, and light irradiation as necessary after application of the shielding material solution.
本発明においては、上記の固体電解コンデンサ用基材を用い、その陰極部領域に固体電解質を設けることにより、陽極部と陰極部との絶縁性に優れた固体電解コンデンサが得られる。
固体電解質としてはチオフェン骨格を有する化合物、多環状スルフィド骨格を有する化合物、ピロール骨格を有する化合物、フラン骨格を有する化合物、アニリン骨格を有する化合物等で示される構造を繰り返し単位として含む導電性重合物が挙げられるが、固体電解質を形成する導電性重合物はこれに限られるものではない。In the present invention, a solid electrolytic capacitor excellent in insulation between the anode part and the cathode part can be obtained by using the solid electrolytic capacitor base material and providing a solid electrolyte in the cathode part region.
As the solid electrolyte, there is a conductive polymer containing as a repeating unit a structure represented by a compound having a thiophene skeleton, a compound having a polycyclic sulfide skeleton, a compound having a pyrrole skeleton, a compound having a furan skeleton, a compound having an aniline skeleton, or the like. The conductive polymer forming the solid electrolyte is not limited to this.
チオフェン骨格を有する化合物としては、３−メチルチオフェン、３−エチルオフェン、３−プロピルチオフェン、３−ブチルチオフェン、３−ペンチルチオフェン、３−ヘキシルチオフェン、３−ヘプチルチオフェン、３−オクチルチオフェン、３−ノニルチオフェン、３−デシルチオフェン、３−フルオロチオフェン、３−クロロチオフェン、３−ブロモチオフェン、３−シアノチオフェン、３，４−ジメチルチオフェン、３，４−ジエチルチオフェン、３，４−ブチレンチオフェン、３，４−メチレンジオキシチオフェン、３，４−エチレンジオキシチオフェン等の誘導体を挙げることができる。これらの化合物は、一般には市販されている化合物または公知の方法（例えばＳｙｎｔｈｅｔｉｃ Ｍｅｔａｌｓ誌、１９８６年、１５巻、１６９頁）で準備できるが、本発明においてはこれらに限るものではない。 Examples of the compound having a thiophene skeleton include 3-methylthiophene, 3-ethyloffene, 3-propylthiophene, 3-butylthiophene, 3-pentylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3- Nonylthiophene, 3-decylthiophene, 3-fluorothiophene, 3-chlorothiophene, 3-bromothiophene, 3-cyanothiophene, 3,4-dimethylthiophene, 3,4-diethylthiophene, 3,4-butylenethiophene, 3 , 4-methylenedioxythiophene, 3,4-ethylenedioxythiophene and the like. These compounds can be prepared by generally commercially available compounds or by known methods (for example, Synthetic Metals, 1986, Vol. 15, 169), but the present invention is not limited thereto.
また、例えば、多環状スルフィド骨格を有する化合物としては、具体的には１，３−ジヒドロ多環状スルフィド（別名、１，３−ジヒドロベンゾ［ｃ］チオフェン）骨格を有する化合物、１，３−ジヒドロナフト［２，３−ｃ］チオフェン骨格を有する化合物が使用できる。さらには１，３−ジヒドロアントラ［２，３−ｃ］チオフェン骨格を有する化合物、１，３−ジヒドロナフタセノ［２，３−ｃ］チオフェン骨格を有する化合物を挙げることができ、公知の方法、例えば特開平８−３１５６号公報（US5530139）記載の方法により準備することができる。 For example, as a compound having a polycyclic sulfide skeleton, specifically, a compound having a 1,3-dihydropolycyclic sulfide (also known as 1,3-dihydrobenzo [c] thiophene) skeleton, 1,3-dihydro A compound having a naphtho [2,3-c] thiophene skeleton can be used. Furthermore, a compound having a 1,3-dihydroanthra [2,3-c] thiophene skeleton and a compound having a 1,3-dihydronaphthaceno [2,3-c] thiophene skeleton can be exemplified, and a known method, For example, it can be prepared by the method described in JP-A-8-3156 (US5530139).
また、例えば、１，３−ジヒドロナフト［１，２−ｃ］チオフェン骨格を有する化合物が、１，３−ジヒドロフェナントラ［２，３−ｃ］チオフェン誘導体や、１，３−ジヒドロトリフェニロ［２，３−ｃ］チオフェン骨格を有する化合物が、１，３−ジヒドロベンゾ［ａ］アントラセノ［７，８−ｃ］チオフェン誘導体なども使用できる。 In addition, for example, a compound having a 1,3-dihydronaphtho [1,2-c] thiophene skeleton is a 1,3-dihydrophenanthra [2,3-c] thiophene derivative or 1,3-dihydrotriphenylo. The compound having a [2,3-c] thiophene skeleton may be a 1,3-dihydrobenzo [a] anthraceno [7,8-c] thiophene derivative.
縮合環に窒素またはＮ−オキシドを任意に含んでいる場合もあり、１，３−ジヒドロチエノ［３，４−ｂ］キノキサリンや、１，３−ジヒドロチエノ［３，４−ｂ］キノキサリン−４−オキシド、１，３−ジヒドロチエノ［３，４−ｂ］キノキサリン−４，９−ジオキシド等を挙げることができるがこれらに限定されるものではない。 The condensed ring may optionally contain nitrogen or N-oxide, such as 1,3-dihydrothieno [3,4-b] quinoxaline or 1,3-dihydrothieno [3,4-b] quinoxaline-4-oxide 1,3-dihydrothieno [3,4-b] quinoxaline-4,9-dioxide, and the like, but are not limited thereto.
また、ピロール骨格を有する化合物としては、３−メチルピロール、３−エチルピロール、３−プロピルピロール、３−ブチルピロール、３−ペンチルピロール、３−ヘキシルピロール、３−ヘプチルピロール、３−オクチルピロール、３−ノニルピロール、３−デシルピロール、３−フルオロピロール、３−クロロピロール、３−ブロモピロール、３−シアノピロール、３，４−ジメチルピロール、３，４−ジエチルピロール、３，４−ブチレンピロール、３，４−メチレンジオキシピロール、３，４−エチレンジオキシピロール等の誘導体を挙げることができる。これらの化合物は、市販品または公知の方法で準備できるが、本発明においてはこれらに限るものではない。 Examples of the compound having a pyrrole skeleton include 3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole, 3-butylpyrrole, 3-pentylpyrrole, 3-hexylpyrrole, 3-heptylpyrrole, 3-octylpyrrole, 3-nonylpyrrole, 3-decylpyrrole, 3-fluoropyrrole, 3-chloropyrrole, 3-bromopyrrole, 3-cyanopyrrole, 3,4-dimethylpyrrole, 3,4-diethylpyrrole, 3,4-butylenepyrrole , Derivatives of 3,4-methylenedioxypyrrole, 3,4-ethylenedioxypyrrole, and the like. These compounds can be prepared commercially or by known methods, but are not limited to these in the present invention.
また、フラン骨格を有する化合物としては、３−メチルフラン、３−エチルフラン、３−プロピルフラン、３−ブチルフラン、３−ペンチルフラン、３−ヘキシルフラン、３−ヘプチルフラン、３−オクチルフラン、３−ノニルフラン、３−デシルフラン、３−フルオロフラン、３−クロロフラン、３−ブロモフラン、３−シアノフラン、３，４−ジメチルフラン、３，４−ジエチルフラン、３，４−ブチレンフラン、３，４−メチレンジオキシフラン、３，４−エチレンジオキシフラン等の誘導体を挙げることができる。これらの化合物は市販品または公知の方法で準備できるが、本発明においてはこれらに限るものではない。 Examples of the compound having a furan skeleton include 3-methyl furan, 3-ethyl furan, 3-propyl furan, 3-butyl furan, 3-pentyl furan, 3-hexyl furan, 3-heptyl furan, 3-octyl furan, 3-nonylfuran, 3-decylfuran, 3-fluorofuran, 3-chlorofuran, 3-bromofuran, 3-cyanofuran, 3,4-dimethylfuran, 3,4-diethylfuran, 3,4-butylenefuran, 3,4 -Derivatives such as methylenedioxyfuran and 3,4-ethylenedioxyfuran can be mentioned. These compounds can be prepared commercially or by known methods, but are not limited to these in the present invention.
また、アニリン骨格を有する化合物としては、２−メチルアニリン、２−エチルアニリン、２−プロピルアニリン、２−ブチルアニリン、２−ペンチルアニリン、２−ヘキシルアニリン、２−ヘプチルアニリン、２−オクチルアニリン、２−ノニルアニリン、２−デシルアニリン、２−フルオロアニリン、２−クロロアニリン、２−ブロモアニリン、２−シアノアニリン、２，５−ジメチルアニリン、２，５−ジエチルアニリン、３，４−ブチレンアニリン、３，４−メチレンジオキシアニリン、３，４−エチレンジオキシアニリン等の誘導体を挙げることができる。これらの化合物は、市販品または公知の方法で準備できるが、本発明においてはこれらに限るものではない。 Examples of the compound having an aniline skeleton include 2-methylaniline, 2-ethylaniline, 2-propylaniline, 2-butylaniline, 2-pentylaniline, 2-hexylaniline, 2-heptylaniline, 2-octylaniline, 2-nonylaniline, 2-decylaniline, 2-fluoroaniline, 2-chloroaniline, 2-bromoaniline, 2-cyanoaniline, 2,5-dimethylaniline, 2,5-diethylaniline, 3,4-butyleneaniline , Derivatives of 3,4-methylenedioxyaniline, 3,4-ethylenedioxyaniline, and the like. These compounds can be prepared commercially or by known methods, but are not limited to these in the present invention.
また上記化合物群から選ばれる化合物を併用し、３元系共重合体として用いても良い。その際重合性単量体の組成比などは重合条件等に依存するものであり、好ましい組成比、重合条件は簡単なテストにより確認できる。 Moreover, you may use the compound chosen from the said compound group together, and may use it as a ternary system copolymer. In this case, the composition ratio of the polymerizable monomer depends on the polymerization conditions, and the preferred composition ratio and polymerization conditions can be confirmed by a simple test.
本発明において、固体電解質として用いる導電性重合物の製造に用いられる酸化剤は脱水素的４電子酸化反応の酸化反応を十分行なわせ得る酸化剤であれば良い。詳しくは、工業的に安価であり、製造上取り扱いが容易である化合物が好まれる。具体的には例えば、ＦｅＣｌ３、ＦｅＣｌＯ４、Ｆｅ（有機酸アニオン）塩等のＦｅ（III）系化合物、または無水塩化アルミニウム／塩化第一銅、アルカリ金属過硫酸塩類、過硫酸アンモニウム塩類、過酸化物類、過マンガン酸カリウム等のマンガン類、２，３−ジクロロ−５，６−ジシアノ−１，４−ベンゾキノン（ＤＤＱ）、テトラクロロ−１，４−ベンゾキノン、テトラシアノ−１，４−ベンゾキノン等のキノン類、沃素、臭素等のハロゲン類、過酸、硫酸、発煙硫酸、三酸化硫黄、クロロ硫酸、フルオロ硫酸、アミド硫酸等のスルホン酸、オゾン等及びこれら複数の酸化剤の組み合わせが挙げられる。In the present invention, the oxidizing agent used for the production of the conductive polymer used as the solid electrolyte may be any oxidizing agent that can sufficiently perform the dehydrogenative four-electron oxidation reaction. Specifically, a compound that is industrially inexpensive and easy to handle in production is preferred. Specifically, for example, FeCl 3 , FeClO 4 , Fe (III) -based compounds such as Fe (organic acid anion) salt, or anhydrous aluminum chloride / cuprous chloride, alkali metal persulfates, ammonium persulfates, peroxides Products, manganese such as potassium permanganate, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetrachloro-1,4-benzoquinone, tetracyano-1,4-benzoquinone, etc. Quinones, halogens such as iodine and bromine, peracid, sulfuric acid, fuming sulfuric acid, sulfur trioxide, sulfonic acid such as chlorosulfuric acid, fluorosulfuric acid and amidosulfuric acid, ozone and the like, and combinations of these oxidizing agents. .
この中で、前記Ｆｅ（有機酸アニオン）塩を形成する有機酸アニオンの基本化合物としては、有機スルホン酸または有機カルボン酸、有機燐酸、有機硼酸が挙げられる。有機スルホン酸の具体例としては、ベンゼンスルホン酸やｐ−トルエンスルホン酸、メタンスルホン酸、エタンスルホン酸、α−スルホ−ナフタレン、β−スルホ−ナフタレン、ナフタレンジスルホン酸、アルキルナフタレンスルホン酸（アルキル基としてはブチル、トリイソプロピル、ジ−ｔ−ブチル等）等が使用される。 Among these, the basic compound of the organic acid anion that forms the Fe (organic acid anion) salt includes organic sulfonic acid, organic carboxylic acid, organic phosphoric acid, and organic boric acid. Specific examples of the organic sulfonic acid include benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, α-sulfo-naphthalene, β-sulfo-naphthalene, naphthalene disulfonic acid, alkylnaphthalenesulfonic acid (alkyl group). As butyl, triisopropyl, di-t-butyl, etc.).
一方、有機カルボン酸の具体例としては、酢酸、プロピオン酸、安息香酸、蓚酸等が挙げられる。さらに本発明においては、ポリアクリル酸、ポリメタクリル酸、ポリスチレンスルホン酸、ポリビニルスルホン酸、ポリビニル硫酸、ポリ−α−メチルスルホン酸、ポリエチレンスルホン酸、ポリリン酸等の高分子電解質アニオンも使用されるが、これら有機スルホン酸または有機カルボン酸の例は単なる例示であってこの限りではない。また、前記アニオンの対カチオンはＨ＋、Ｎａ＋、Ｋ＋等のアルカリ金属イオン、または水素原子やテトラメチル基、テトラエチル基、テトラブチル基、テトラフェニル基等で置換されたアンモニウムイオンであるが、本発明においては特に限定を受けない。前記の酸化剤のうち、特に好ましくは３価のＦｅ系化合物、または塩化第一銅系、過硫酸アルカリ塩類、過硫酸アンモニウム塩類、マンガン酸類、キノン類を含む酸化剤が好適に使用できる。On the other hand, specific examples of the organic carboxylic acid include acetic acid, propionic acid, benzoic acid, and succinic acid. Furthermore, in the present invention, polyelectrolyte anions such as polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyvinyl sulfuric acid, poly-α-methyl sulfonic acid, polyethylene sulfonic acid and polyphosphoric acid are also used. Examples of these organic sulfonic acids or organic carboxylic acids are merely examples and are not limited thereto. The counter cation of the anion is an alkali metal ion such as H + , Na + , K + , or an ammonium ion substituted with a hydrogen atom, a tetramethyl group, a tetraethyl group, a tetrabutyl group, a tetraphenyl group, or the like. The present invention is not particularly limited. Among the oxidizing agents described above, trivalent Fe-based compounds or oxidizing agents containing cuprous chloride-based, alkali persulfates, ammonium persulfates, manganic acids, and quinones can be preferably used.
本発明において、固体電解質として用いる導電性重合物の製造において、必要に応じて共存されるドーパント能を有する対アニオンは、前記酸化剤から産生される酸化剤アニオン（酸化剤の還元体）を対イオンに持つ電解質化合物または他のアニオン系電解質を挙げることができる。具体的には例えば、ＰＦ６ −、ＳｂＦ６ −、ＡｓＦ６ −の如き５Ｂ族元素のハロゲン化アニオン、ＢＦ４ −の如き３Ｂ族元素のハロゲン化アニオン、Ｉ−（Ｉ３ −）、Ｂｒ−、Ｃｌ−の如きハロゲンアニオン、ＣｌＯ４ −の如きハロゲン酸アニオン、ＡｌＣｌ４ −やＦｅＣｌ４ −、ＳｎＣｌ５ −等の如きルイス酸アニオン、あるいはＮＯ３ −、ＳＯ４ ２−の如き無機酸アニオン、またはｐ−トルエンスルホン酸やナフタレンスルホン酸、炭素数１乃至５のアルキル置換スルホン酸、ＣＨ３ＳＯ３ −、ＣＦ３ＳＯ３ −の如き有機スルホン酸アニオン、またはＣＦ３ＣＯＯ−、Ｃ６Ｈ５ＣＯＯ−の如きカルボン酸アニオン等のプロトン酸アニオンを挙げることができる。また同じく、ポリアクリル酸、ポリメタクリル酸、ポリスチレンスルホン酸、ポリビニルスルホン酸、ポリビニル硫酸、ポリ−α−メチルスルホン酸、ポリエチレンスルホン酸、ポリリン酸等の高分子電解質アニオン等を挙げることができるが、必ずしも限定されるものではない。In the present invention, in the production of a conductive polymer used as a solid electrolyte, a counter anion having a dopant ability that coexists as necessary is an oxidant anion (reduced form of an oxidant) produced from the oxidant. Examples thereof include electrolyte compounds possessed by ions or other anionic electrolytes. Specifically, for example, a halogenated anion of a group 5B element such as PF 6 − , SbF 6 − , AsF 6 − , a halogenated anion of a group 3B element such as BF 4 − , I − (I 3 − ), Br −. Halogen anions such as Cl − , halogen acid anions such as ClO 4 − , Lewis acid anions such as AlCl 4 − , FeCl 4 − and SnCl 5 − , or inorganic acid anions such as NO 3 − and SO 4 2− . Or p-toluenesulfonic acid or naphthalenesulfonic acid, an alkyl-substituted sulfonic acid having 1 to 5 carbon atoms, an organic sulfonate anion such as CH 3 SO 3 − or CF 3 SO 3 — , or CF 3 COO − or C 6 H 5. COO - can be given such a protonic acid anions such as carboxylate anions. Similarly, polymer electrolyte anions such as polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyvinyl sulfuric acid, poly-α-methyl sulfonic acid, polyethylene sulfonic acid, polyphosphoric acid, etc. It is not necessarily limited.
しかしながら好ましくは高分子系または低分子系の有機スルホン酸化合物、あるいはポリリン酸が挙げられ、望ましくはアリールスルホン酸塩系ドーパントが好適に使用される。例えば、ベンゼンスルホン酸、トルエンスルホン酸、ナフタレンスルホン酸、アントラセンスルホン酸、アントラキノンスルホン酸及びそれらの誘導体などの塩を用いることができる。 However, a high molecular or low molecular organic sulfonic acid compound or polyphosphoric acid is preferable, and an aryl sulfonate dopant is preferably used. For example, salts such as benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, anthracenesulfonic acid, anthraquinonesulfonic acid and derivatives thereof can be used.
本発明に用いられる固体電解質に使用する導電性重合物を形成するモノマーの濃度はその化合物の置換基の種類や溶媒等の種類によって異なるが、一般的には１０−３〜１０モル／リットルの範囲が望ましく、また１０−２〜５モル／リットルの範囲がさらに好ましい。また反応温度はそれぞれ反応方法によって定められるもので特に限定できるものではないが、一般的には−７０℃〜２５０℃の温度範囲で選ばれる。望ましくは−３０℃〜１５０℃であり、さらに−１０℃〜３０℃の温度範囲で行なわれることが望ましい。The concentration of the monomer that forms the conductive polymer used in the solid electrolyte used in the present invention varies depending on the type of the substituent of the compound, the type of the solvent, etc., but is generally 10 −3 to 10 mol / liter. The range is desirable, and the range of 10 −2 to 5 mol / liter is more preferable. The reaction temperature is determined by the reaction method and is not particularly limited, but is generally selected within a temperature range of -70 ° C to 250 ° C. Desirably, it is -30 degreeC-150 degreeC, and also it is desirable to carry out in the temperature range of -10 degreeC-30 degreeC.
本発明において、用いられる反応溶媒は単量体あるいは酸化剤、ドーパント能を有する対アニオンを共に、またはそれぞれ単独に溶解可能な溶媒であれば良く、例えばテトラヒドロフランやジオキサン、ジエチルエーテル等のエーテル類、あるいはジメチルホルムアミドやアセトニトリル、ベンゾニトリル、Ｎ−メチルピロリドン、ジメチルスルホキシド等の非プロトン性極性溶媒、酢酸エチルや酢酸ブチル等のエステル類、クロロホルムや塩化メチレン等の非芳香族性の塩素系溶媒、ニトロメタンやニトロエタン、ニトロベンゼン等のニトロ化合物、あるいはメタノールやエタノール、プロパノール等のアルコール類、または蟻酸や酢酸、プロピオン酸等の有機酸または該有機酸の酸無水物（例、無水酢酸等）、水、アルコール類またはケトン類あるいはこれらの混合溶媒を用いることができる。また前記酸化剤または／及びドーパント能を有する対アニオン及び単量体はそれぞれ単独に溶解した溶媒系、すなわち二液系、もしくは三液系で取り扱っても良い。 In the present invention, the reaction solvent used may be any solvent that can dissolve the monomer, the oxidizing agent, the counter anion having the dopant ability, or each independently, for example, ethers such as tetrahydrofuran, dioxane, diethyl ether, Or aprotic polar solvents such as dimethylformamide, acetonitrile, benzonitrile, N-methylpyrrolidone, dimethyl sulfoxide, esters such as ethyl acetate and butyl acetate, non-aromatic chlorinated solvents such as chloroform and methylene chloride, nitromethane Nitro compounds such as nitroethane, nitrobenzene, alcohols such as methanol, ethanol and propanol, organic acids such as formic acid, acetic acid and propionic acid, or acid anhydrides of the organic acids (eg, acetic anhydride, etc.), water, alcohol Kind or Emissions such or may be used a mixed solvent thereof. The counter anion and / or monomer having the oxidant or / and dopant ability may be handled in a solvent system dissolved independently, that is, a two-component system or a three-component system.
このようにして製造された固体電解質の電導度は、１Ｓ／ｃｍ以上であるが、望ましい条件では５Ｓ／ｃｍ以上、さらに好ましくは１０Ｓ／ｃｍ以上である。 The electric conductivity of the solid electrolyte thus produced is 1 S / cm or more, but it is 5 S / cm or more, more preferably 10 S / cm or more under desirable conditions.
更に、固体電解質層の表面にカーボンペースト層と金属粉含有導電性層を設けてコンデンサの陰極部が形成される。金属粉含有導電性層は固体電解質層と密着接合し、陰極として作用すると同時に最終コンデンサ製品の陰極リード端子を接合するための接着層となるものであり、金属含有導電性層の厚さは限定されないが、一般には１〜１００μｍ程度、好ましくは５〜５０μｍ程度である。 Further, a carbon paste layer and a metal powder-containing conductive layer are provided on the surface of the solid electrolyte layer to form the cathode portion of the capacitor. The metal powder-containing conductive layer is in close contact with the solid electrolyte layer and acts as a cathode, and at the same time serves as an adhesive layer for bonding the cathode lead terminal of the final capacitor product. The thickness of the metal-containing conductive layer is limited However, it is generally about 1 to 100 μm, preferably about 5 to 50 μm.
本発明の固体電解コンデンサ用基材は、通常、積層型のコンデンサ素子に用いられる。積層型固体電解コンデンサにおいては、リードフレームを面取り、つまり稜角の部分を若干平らに削ったり、丸みをつけたりするリードフレーム形状にしても良い。またリード端子の役目を、リードフレームの対向する陰極ボンディング部に持たせたものとして使用しても良い。 The substrate for a solid electrolytic capacitor of the present invention is usually used for a multilayer capacitor element. In a multilayer solid electrolytic capacitor, the lead frame may be chamfered, that is, a lead frame shape in which a ridge angle portion is slightly flattened or rounded. Moreover, you may use as what gave the role of the lead terminal to the cathode bonding part which the lead frame opposes.
リードフレームの材料は、一般的に使用されるものであれば特に制限は無いが、好ましくは銅系（例えばＣｕ−Ｎｉ系、Ｃｕ−Ａｇ系、Ｃｕ−Ｓｕ系、Ｃｕ−Ｆｅ系、Ｃｕ−Ｎｉ−Ａｇ系、Ｃｕ−Ｎｉ−Ｓｎ系、Ｃｕ−Ｃｏ−Ｐ系、Ｃｕ−Ｚｎ−Ｍｇ系、Ｃｕ−Ｓｎ−Ｎｉ−Ｐ系合金等）の材料もしくは表面に銅系の材料のめっき処理を施した材料で構成すればリードフレームの面取り作業性が良好になる等の効果が得られる。 The lead frame material is not particularly limited as long as it is generally used, but is preferably copper-based (for example, Cu-Ni-based, Cu-Ag-based, Cu-Su-based, Cu-Fe-based, Cu--based). Ni-Ag-based, Cu-Ni-Sn-based, Cu-Co-P-based, Cu-Zn-Mg-based, Cu-Sn-Ni-P-based alloys, etc.) or copper-based material plating treatment on the surface If it is made of the applied material, effects such as good chamfering workability of the lead frame can be obtained.
固体電解コンデンサは陽極部に接合したリードフレームにリード端子を接合し、固体電解質層、カーボンペースト層及び金属粉含有導電性層からなる陰極部にリード線を接合し、さらに全体をエポキシ樹脂等の絶縁性樹脂で封止して得られる。
但し、本発明は、表面に多孔質層を有する固体電解コンデンサ用基材を用いたコンデンサ全般に及び、上に詳述した固体電解質やその他の構成によって限定されるものではない。The solid electrolytic capacitor has a lead terminal joined to a lead frame joined to the anode part, a lead wire joined to a cathode part made of a solid electrolyte layer, a carbon paste layer, and a metal powder-containing conductive layer, and the whole is made of an epoxy resin or the like. Obtained by sealing with an insulating resin.
However, the present invention covers all capacitors using a solid electrolytic capacitor base material having a porous layer on the surface, and is not limited by the solid electrolyte detailed above or other configurations.
以下、実施例を挙げて本発明を詳しく説明するが、本発明はこれらの実施例により何ら限定されるものではない。なお、以下の例において、切削／圧縮深さは箔両面の合計値である。
（実施例１）
厚み１１０μｍの化成アルミ箔（片面当たり厚さ約３５μｍの多孔質層を有する。）を３．５ｍｍ幅に切断したものを１３ｍｍずつの長さに切り取り、この箔片の一方の短辺部を金属製ガイドに溶接により固定した。切断部を化成処理するために、固定していない端から７ｍｍの箇所にポリイミド樹脂溶液（宇部興産（株）製）を０．８ｍｍ幅に線状に描き、約１８０℃で３０分乾燥させた。固定していないアルミ箔の先端から塗布されたポリイミド樹脂までの部分をアジピン酸アンモニウム水溶液中に浸漬して３Ｖの電圧を印加して切口部の未化成部を化成し、誘電体皮膜を形成した。EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited at all by these Examples. In the following examples, the cutting / compression depth is the total value on both sides of the foil.
Example 1
A 110 μm-thick chemical aluminum foil (having a porous layer with a thickness of about 35 μm per side) cut to 3.5 mm width is cut into lengths of 13 mm, and one short side of this foil piece is made of metal. It fixed to the guide made by welding. In order to subject the cut portion to chemical conversion treatment, a polyimide resin solution (manufactured by Ube Industries) was linearly drawn to a width of 7 mm from a non-fixed end and dried at about 180 ° C. for 30 minutes. . A portion from the tip of the unfixed aluminum foil to the applied polyimide resin was immersed in an aqueous solution of ammonium adipate and a voltage of 3 V was applied to form an unformed portion of the cut portion to form a dielectric film. .
次にアルミ箔の先端から５ｍｍの部分を中心として、針状突起を有する金属棒を走らせ、深さ２０μｍ、幅４０μｍの切削溝を形成した（図４に切削部位近傍の断面写真（３００倍）を示す）。この上に、陽極部と陰極部を遮蔽するポリイミド樹脂を、アルミ箔の先端から５ｍｍの部分を中心として０．８ｍｍ幅に線状に描き、塗布した。
陰極部領域には以下のようにして固体電解質を形成した。Next, a metal rod having needle-like protrusions was run around a 5 mm portion from the tip of the aluminum foil to form a cutting groove having a depth of 20 μm and a width of 40 μm (FIG. 4 is a cross-sectional photograph of the vicinity of the cutting site (300 times)). Showing). On top of this, a polyimide resin that shields the anode portion and the cathode portion was linearly drawn and applied in a width of 0.8 mm centering on a portion 5 mm from the tip of the aluminum foil.
A solid electrolyte was formed in the cathode region as follows.
すなわち、陰極部領域（３．５ｍｍ×４．６ｍｍ）を３，４−エチレンジオキシチオフェン２０質量％を含むイソプロパノール溶液（溶液１）に浸漬し、引き上げて２５℃で５分放置した。次に過硫酸アンモニウム３０質量％を含む水溶液（溶液２）に浸漬し、これを４５℃で１０分間乾燥し、酸化重合を行なった。溶液１に浸漬してから溶液２に浸漬し、酸化重合を行なう操作を１５回繰り返した。次に５０℃の温水で３０分洗浄した後、１００℃で３０分乾燥させた。固体電解質層を形成した。更に、陰極部にカーボンペースト、銀ペーストで電極を形成し、コンデンサ素子を完成させた。 That is, the cathode region (3.5 mm × 4.6 mm) was immersed in an isopropanol solution (solution 1) containing 20% by mass of 3,4-ethylenedioxythiophene, pulled up, and left at 25 ° C. for 5 minutes. Next, it was immersed in an aqueous solution (solution 2) containing 30% by mass of ammonium persulfate, which was dried at 45 ° C. for 10 minutes to carry out oxidative polymerization. The operation of immersing in solution 1 and then immersing in solution 2 and performing oxidative polymerization was repeated 15 times. Next, it was washed with hot water at 50 ° C. for 30 minutes and then dried at 100 ° C. for 30 minutes. A solid electrolyte layer was formed. Further, an electrode was formed on the cathode portion with carbon paste and silver paste to complete a capacitor element.
切削された領域に塗布した遮蔽材層を含む部分をリードフレーム上にＡｇペーストで接合しながら３枚重ね、固体電解質のついていない部分に陽極リード端子を溶接により接続し、全体をエポキシ樹脂で封止し、１３５℃で定格電圧を印加して３時間エージングして合計３０個のチップ型固体電解コンデンサを作製した。 Three parts including the shielding material layer applied to the cut area are joined on the lead frame while being joined with Ag paste, and the anode lead terminal is connected to the part without the solid electrolyte by welding, and the whole is sealed with epoxy resin. Then, a rated voltage was applied at 135 ° C. and aged for 3 hours to produce a total of 30 chip-type solid electrolytic capacitors.
これら３０個のコンデンサについて、初期特性として１２０Ｈｚにおける容量と損失係数（ｔａｎδ）、１００ｋＨｚにおける等価直列抵抗（以下ＥＳＲとする。）及び漏れ電流を測定した。なお、漏れ電流は定格電圧を印加して１分後に測定した。測定結果は以下の通りであった。
容量（平均値） ：９８μＦ
ｔａｎδ（平均値） ：１．２％
ＥＳＲ（平均値） ：７ｍΩ
漏れ電流（平均値） ：０．１５μＡ
また１．０μＡ（０．００５ＣＶ）以上の漏れ電流を不良品とした時の不良率は０％であった。For these 30 capacitors, the initial characteristics were measured for capacity and loss factor (tan δ) at 120 Hz, equivalent series resistance (hereinafter referred to as ESR) at 100 kHz, and leakage current. The leakage current was measured 1 minute after applying the rated voltage. The measurement results were as follows.
Capacity (average value): 98 μF
tan δ (average value): 1.2%
ESR (average value): 7 mΩ
Leakage current (average value): 0.15 μA
Further, the defective rate when a leakage current of 1.0 μA (0.005 CV) or more was regarded as a defective product was 0%.
さらにリフロー試験及びこれに続いて行なった耐湿試験での結果を示した。リフロー試験（ハンダ耐熱性試験）は次の方法で評価した。すなわち３０個のコンデンサ素子を準備し、該素子を２４５℃の温度下に１０秒間通過させ、この作業を３回繰り返し、定格電圧印加１分後の漏れ電流を測定し、そしてその値が８．０μＡ（０．０４ＣＶ）以上の素子を不良品とした。また、耐湿試験は６０℃、９０％ＲＨの高温高湿下に５００時間放置し、定格電圧印加１分後漏れ電流値が６０μＡ（０．３ＣＶ）以上を不良品とした。
リフロー試験後の漏れ電流 ：０．２０μＡ
耐湿試験後の漏れ電流 ：１１．７μＡ
いずれも不良率０であった。
これらの結果を他の実施例及び比較例の結果とともに表１に示す。なお、表１中、「切削／圧縮比（深さ）」は多孔質層の全体の厚み（除去または圧縮していない多孔質層の厚み）を１とした場合の除去または圧縮後の多孔質層の厚みを示す。「処理部の寸法比（幅）」は、陰極部領域の長軸方向の長さを１とした場合の除去または圧縮した多孔質層の幅を示す。Further, the results of a reflow test and a subsequent moisture resistance test are shown. The reflow test (solder heat resistance test) was evaluated by the following method. That is, 30 capacitor elements were prepared, the elements were passed for 10 seconds at a temperature of 245 ° C., this operation was repeated three times, the leakage current after 1 minute application of the rated voltage was measured, and the value was 8. An element having 0 μA (0.04 CV) or more was regarded as a defective product. Further, the moisture resistance test was allowed to stand for 500 hours under high temperature and high humidity of 60 ° C. and 90% RH, and a leakage current value of 60 μA (0.3 CV) or more after 1 minute of application of the rated voltage was regarded as a defective product.
Leakage current after reflow test: 0.20μA
Leakage current after moisture resistance test: 11.7 μA
In all cases, the defect rate was zero.
These results are shown in Table 1 together with the results of other examples and comparative examples. In Table 1, “cutting / compression ratio (depth)” is the porous after removal or compression when the total thickness of the porous layer (the thickness of the porous layer not removed or compressed) is 1. Indicates the thickness of the layer. “Dimension ratio (width) of the processing portion” indicates the width of the removed or compressed porous layer when the length in the major axis direction of the cathode portion region is 1.
（実施例２）
除去工程として、深さ６μｍ、幅４μｍの切削溝を形成した以外は実施例１と同様にコンデンサを作成し、評価した。(Example 2)
As a removing step, a capacitor was prepared and evaluated in the same manner as in Example 1 except that a cutting groove having a depth of 6 μm and a width of 4 μm was formed.
（実施例３）
除去工程として、深さ７０μｍ、幅４００μｍの切削溝を形成した以外は実施例１と同様にコンデンサを作成し、評価した。(Example 3)
As a removing step, a capacitor was prepared and evaluated in the same manner as in Example 1 except that a cutting groove having a depth of 70 μm and a width of 400 μm was formed.
（実施例４）
針状突起を有する金属棒の代わりに、幅０．１ｍｍの金属円盤を箔に押し当てながら回転させ、箔両面の多孔質層を圧縮し、深さ２０μｍ、幅１３０μｍの圧縮溝を形成した以外は実施例１と同様にコンデンサを作成し、評価した。Example 4
Instead of a metal bar having needle-like protrusions, a metal disk having a width of 0.1 mm is rotated while being pressed against the foil, and the porous layer on both sides of the foil is compressed to form a compressed groove having a depth of 20 μm and a width of 130 μm. Were made and evaluated in the same manner as in Example 1.
（実施例５）
除去工程として、深さ３μｍ、幅１μｍの切削溝を形成した以外は実施例１と同様にコンデンサを作成し、評価した。(Example 5)
As a removing step, a capacitor was prepared and evaluated in the same manner as in Example 1 except that a cutting groove having a depth of 3 μm and a width of 1 μm was formed.
（実施例６）
除去工程として、深さ３μｍ、幅５００μｍの切削溝を形成した以外は実施例１と同様にコンデンサを作成し、評価した。(Example 6)
As a removing step, a capacitor was prepared and evaluated in the same manner as in Example 1 except that a cutting groove having a depth of 3 μm and a width of 500 μm was formed.
（実施例７）
除去工程として、レーザ光（ＹＡＧ（MIYACHI製ECOMARKER，ML-7064A，波長1064nm））を使用し、深さ１０μｍ、幅７０μｍの切削溝を形成した以外は実施例１と同様にコンデンサを作成し、評価した。なお、図５に切削部位近傍の断面写真（３００倍）を示す。(Example 7)
As a removal process, a laser was produced (YAG (Ecomarker, manufactured by MIYACHI, ML-7064A, wavelength 1064 nm)), and a capacitor was formed in the same manner as in Example 1 except that a cutting groove having a depth of 10 μm and a width of 70 μm was formed. evaluated. In addition, the cross-sectional photograph (300 times) of the cutting site vicinity is shown in FIG.
（実施例８）
除去工程として、水流コラム内に封じ込められたレーザ光（ＹＡＧ（澁谷工業(株)製アクアレーザ，波長532nm））を使用し、深さ６５〜６６μｍ、幅５５〜１２０μｍの切削溝を形成した以外は実施例１と同様にコンデンサを作成し、評価した。なお、図６に切削部位近傍の断面写真（３００倍）を示す。(Example 8)
As a removal process, laser light (YAG (Aqua laser manufactured by Kabuya Kogyo Co., Ltd., wavelength 532 nm)) contained in a water flow column was used, except that a cutting groove having a depth of 65 to 66 μm and a width of 55 to 120 μm was formed. Were made and evaluated in the same manner as in Example 1. In addition, the cross-sectional photograph (300 times) of the cutting site vicinity is shown in FIG.
（比較例１）
除去または圧縮を行なわずに化成アルミ箔上に陽極部と陰極部を遮蔽するポリイミド樹脂を塗布した以外は上記各実施例と同様にしてコンデンサを作成し、評価した。(Comparative Example 1)
Capacitors were prepared and evaluated in the same manner as in each of the above examples, except that a polyimide resin that shields the anode and cathode portions was coated on the chemical conversion aluminum foil without removing or compressing.
これらの結果に示されるように、本発明によれば、全般的に漏れ電流が低減し、不良品発生率も有意に改善されている。特に多孔質層の除去／圧縮を好適範囲内で行なった場合（実施例１〜４）の改善効果は著しく、本発明の手法が非常に有効であることが確認できる。 As shown in these results, according to the present invention, the leakage current is generally reduced, and the defective product occurrence rate is significantly improved. In particular, when the removal / compression of the porous layer is performed within a suitable range (Examples 1 to 4), the improvement effect is remarkable, and it can be confirmed that the method of the present invention is very effective.
本発明によれば、表面に多孔質層を有する固体電解コンデンサ用基材において、陽極部領域と陰極部領域の間の多孔質層の少なくとも一部を除去し、好ましくは除去により形成した凹部をマスキング材で充填する簡便な操作により、コンデンサ製造工程における固体電解質または固体電解質形成用処理液の這い上がりを防止して陰極部と陽極部間の絶縁性をより高めることができる。この結果、絶縁不良に起因する漏れ電流特性の悪化を防ぎ、収率及び信頼性の改善がもたらされる。従って、本発明は表面に多孔質層を有する固体電解コンデンサを基材とする固体電解コンデンサに広く利用できる。 According to the present invention, in the substrate for a solid electrolytic capacitor having a porous layer on the surface, at least a part of the porous layer between the anode region and the cathode region is removed, and preferably a recess formed by the removal is provided. By the simple operation of filling with the masking material, the solid electrolyte or the solid electrolyte forming treatment liquid can be prevented from creeping up in the capacitor manufacturing process, and the insulation between the cathode part and the anode part can be further enhanced. As a result, deterioration of leakage current characteristics due to insulation failure is prevented, and yield and reliability are improved. Therefore, the present invention can be widely used for solid electrolytic capacitors based on a solid electrolytic capacitor having a porous layer on the surface.
１ 陽極部領域
２ 陰極部領域
３ 境界部
４ 多孔質層
５ 芯
６ 除去または圧縮した領域
７ 遮蔽材（マスキング材）
８ 多孔質層内における遮蔽材（マスキング材）浸透領域DESCRIPTION OF SYMBOLS 1 Anode part area | region 2 Cathode part area | region 3 Boundary part 4 Porous layer 5 Core 6 Area | region 7 removed or compressed 7 Shielding material (masking material)
8 Shielding material (masking material) penetration area in the porous layer
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