JP2005117034A - Solid electrolytic capacitor - Google Patents
Solid electrolytic capacitor Download PDFInfo
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- JP2005117034A JP2005117034A JP2004269333A JP2004269333A JP2005117034A JP 2005117034 A JP2005117034 A JP 2005117034A JP 2004269333 A JP2004269333 A JP 2004269333A JP 2004269333 A JP2004269333 A JP 2004269333A JP 2005117034 A JP2005117034 A JP 2005117034A
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G2/00—Details of capacitors not covered by a single one of groups H01G4/00-H01G11/00
- H01G2/02—Mountings
- H01G2/06—Mountings specially adapted for mounting on a printed-circuit support
- H01G2/065—Mountings specially adapted for mounting on a printed-circuit support for surface mounting, e.g. chip capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
Description
本発明は、等価直列抵抗（ＥＳＲ）が低く、漏れ電流（ＬＣ）性能が良好な固体電解コンデンサに関する。 The present invention relates to a solid electrolytic capacitor having a low equivalent series resistance (ESR) and good leakage current (LC) performance.
携帯電話やパーソナルコンピュータ等の電子機器に使用されるコンデンサは、小型、大容量、低ＥＳＲで信頼性の高いものが望まれている。このようなコンデンサの１つとして弁作用金属もしくは導電性酸化物の焼結体を利用した固体電解コンデンサがある。該固体電解コンデンサは、内部に微小な細孔を有する焼結体に陽極リード端子が接続されていて、細孔を含む焼結体全表面に誘電体酸化皮膜層が形成され、さらに半導体層、カーボンペースト層及び導電体層が順次積層されたコンデンサ素子を外装して作製される。 Capacitors used in electronic devices such as mobile phones and personal computers are desired to be small, large capacity, low ESR and highly reliable. As one of such capacitors, there is a solid electrolytic capacitor using a valve action metal or a sintered body of a conductive oxide. In the solid electrolytic capacitor, an anode lead terminal is connected to a sintered body having minute pores therein, and a dielectric oxide film layer is formed on the entire surface of the sintered body including the pores. A capacitor element in which a carbon paste layer and a conductor layer are sequentially laminated is packaged.
ＥＳＲ値は半導体層、カーボンペースト層、導電体層の抵抗により大まかな値が決まるため、目標とする低いＥＳＲ値を達成するために各種工夫がなされている。また、信頼性の中でも最も重要な誘電体酸化皮膜から生じる漏れ電流値（以下、ＬＣ値と略す。）を良くするために、半導体層を形成した後に再化成を行うことや、作製した固体電解コンデンサをエージング処理することによりＬＣ値を減少させている。 Since the ESR value is roughly determined by the resistance of the semiconductor layer, the carbon paste layer, and the conductor layer, various measures have been taken to achieve the target low ESR value. In addition, in order to improve the leakage current value (hereinafter abbreviated as LC value) generated from the dielectric oxide film, which is the most important of reliability, re-formation after forming the semiconductor layer, The LC value is reduced by aging the capacitor.
昨今の要求である小型で容量の大きな固体電解コンデンサを作製するには、粒径の小さい弁作用金属もしくは導電性酸化物の粉末を使用し表面積が大きい焼結体を利用することになるが、このような焼結体を用いて作製した固体電解コンデンサのＬＣ値は、再化成やエージング処理という従来の手段を使っても減少させることが困難な場合があった。とりわけ多数個の固体電解コンデンサを同時に作製する場合に、ＬＣ値が飛び抜けて高いものが発生する問題があり、この問題を解決して、良品率を上昇させる必要があった。 In order to manufacture a solid electrolytic capacitor having a small size and a large capacity, which is a recent requirement, a sintered body having a large surface area using a valve metal or conductive oxide powder having a small particle size is used. In some cases, it has been difficult to reduce the LC value of a solid electrolytic capacitor produced using such a sintered body even by using conventional means such as re-forming or aging treatment. In particular, when a large number of solid electrolytic capacitors are produced at the same time, there is a problem that the LC value is excessively high and a high product is generated. It is necessary to solve this problem and increase the yield rate.
本発明者等は、鋭意検討した結果、陽極リード接続面にカーボンペースト層を設けないことによって前記課題が解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that the above problem can be solved by not providing a carbon paste layer on the anode lead connection surface, and have completed the present invention.
すなわち、本発明は、以下の固体電解コンデンサ及び該固体電解コンデンサを使用した電子機器に関する。
１．陽極リードが接続された弁作用金属もしくは導電性酸化物の焼結体の表面に、誘電体酸化皮膜層、半導体層、カーボンペースト層及び導電体層を順次積層したコンデンサ素子を外装した固体電解コンデンサにおいて、陽極リードが接続された焼結体面のみカーボンペースト層が形成されていないことを特徴とする固体電解コンデンサ。
２．弁作用金属もしくは導電性酸化物が、タンタル、アルミニウム、ニオブ、チタン、これら弁作用金属を主成分とする合金または酸化ニオブである前記１に記載の固体電解コンデンサ。
３．陽極リードが、線状または箔状である前記１に記載の固体電解コンデンサ。
４．陽極リードが、陽極リードの材質が、タンタル、アルミニウム、ニオブ、チタン、またはこれら弁作用金属を主成分とする合金である前記１に記載の固体電解コンデンサ。
５．半導体層が、有機半導体層及び無機半導体層から選ばれる少なくとも１種である前記１に記載の固体電解コンデンサ。
６．有機半導体が、ベンゾピロリン４量体とクロラニルからなる有機半導体、テトラチオテトラセンを主成分とする有機半導体、テトラシアノキノジメタンを主成分とする有機半導体、下記一般式（１）または（２）
で示される繰り返し単位を含む高分子にドーパントをドープした導電性高分子を主成分とした有機半導体から選択される少なくとも１種である前記５に記載の固体電解コンデンサ。
７．一般式（１）で示される繰り返し単位を含む導電性高分子が、下記一般式（３）
で示される構造単位を繰り返し単位として含む導電性高分子である前記６に記載のチップ状固体電解コンデンサ。
８．導電性高分子が、ポリアニリン、ポリオキシフェニレン、ポリフェニレンサルファイド、ポリチオフェン、ポリフラン、ポリピロール、ポリメチルピロール、及びこれらの置換誘導体及び共重合体から選択される前記７に記載の固体電解コンデンサ。
９．導電性高分子、ポリ（３，４−エチレンジオキシチオフェン）である前記８に記載の固体電解コンデンサ。
１０．無機半導体が、二酸化モリブデン、二酸化タングステン、二酸化鉛、及び二酸化マンガンから選ばれる少なくとも１種の化合物である前記５に記載の固体電解コンデンサ。
１１．半導体の電導度が１０-2〜１０3Ｓ／ｃｍの範囲である前記５に記載の固体電解コンデンサ。
１２．前記１乃至１１のいずれかに記載の固体電解コンデンサを使用した電子回路。
１３．前記１乃至１１のいずれかに記載の固体電解コンデンサを使用した電子機器。
That is, the present invention relates to the following solid electrolytic capacitor and an electronic device using the solid electrolytic capacitor.
1. Solid electrolytic capacitor having a capacitor element in which a dielectric oxide film layer, a semiconductor layer, a carbon paste layer, and a conductor layer are sequentially laminated on the surface of a sintered body of a valve metal or conductive oxide to which an anode lead is connected A solid electrolytic capacitor, wherein a carbon paste layer is not formed only on the surface of the sintered body to which the anode lead is connected.
2. 2. The solid electrolytic capacitor as described in 1 above, wherein the valve action metal or conductive oxide is tantalum, aluminum, niobium, titanium, an alloy mainly containing these valve action metals, or niobium oxide.
3. 2. The solid electrolytic capacitor as described in 1 above, wherein the anode lead is linear or foil-like.
4). 2. The solid electrolytic capacitor as described in 1 above, wherein the anode lead is made of tantalum, aluminum, niobium, titanium, or an alloy containing these valve action metals as a main component.
5. 2. The solid electrolytic capacitor as described in 1 above, wherein the semiconductor layer is at least one selected from an organic semiconductor layer and an inorganic semiconductor layer.
6). The organic semiconductor is an organic semiconductor composed of benzopyrroline tetramer and chloranil, an organic semiconductor mainly composed of tetrathiotetracene, an organic semiconductor mainly composed of tetracyanoquinodimethane, the following general formula (1) or (2)
6. The solid electrolytic capacitor as described in 5 above, which is at least one selected from organic semiconductors whose main component is a conductive polymer obtained by doping a polymer containing a repeating unit represented by formula (1) with a dopant.
7). The conductive polymer containing the repeating unit represented by the general formula (1) is represented by the following general formula (3).
7. The chip-shaped solid electrolytic capacitor as described in 6 above, which is a conductive polymer containing the structural unit represented by
8). 8. The solid electrolytic capacitor as described in 7 above, wherein the conductive polymer is selected from polyaniline, polyoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, polypyrrole, polymethylpyrrole, and substituted derivatives and copolymers thereof.
9. 9. The solid electrolytic capacitor as described in 8 above, which is a conductive polymer, poly (3,4-ethylenedioxythiophene).
10. 6. The solid electrolytic capacitor as described in 5 above, wherein the inorganic semiconductor is at least one compound selected from molybdenum dioxide, tungsten dioxide, lead dioxide, and manganese dioxide.
11. 6. The solid electrolytic capacitor as described in 5 above, wherein the electrical conductivity of the semiconductor is in the range of 10 −2 to 10 3 S / cm.
12 An electronic circuit using the solid electrolytic capacitor according to any one of 1 to 11 above.
13. An electronic apparatus using the solid electrolytic capacitor according to any one of 1 to 11 above.
本発明の固体電解コンデンサの１形態を添付図面を参照して説明する。
図１は本発明の固体電解コンデンサの１例の断面図である（図１では各部の大きさは説明の便宜のために誇張して示してある。）。
One embodiment of the solid electrolytic capacitor of the present invention will be described with reference to the accompanying drawings.
FIG. 1 is a cross-sectional view of an example of a solid electrolytic capacitor of the present invention (in FIG. 1, the size of each part is exaggerated for convenience of explanation).
弁作用金属または導電性酸化物の粉末からなる焼結体（１）に陽極リード（２）が植設され、陽極リードの一部と焼結体表面に誘電体酸化皮膜（３）が形成され（図１では省略されているが、焼結体細孔内の表面にも誘電体酸化皮膜が形成されている。）、さらに焼結体部分に半導体層（４）、陽極リードが植設されている面を除いてカーボンペースト層（５）、導電体層（６）が順次積層された固体電解コンデンサ素子が陰陽端子（９ａ，９ｂ）に各接続され、陰陽端子の一部を除いて外装（７）されて固体電解コンデンサ（８）が作製される。 An anode lead (2) is implanted in a sintered body (1) made of a valve action metal or conductive oxide powder, and a dielectric oxide film (3) is formed on a part of the anode lead and the surface of the sintered body. (Although omitted in FIG. 1, a dielectric oxide film is also formed on the surface in the pores of the sintered body.) Further, a semiconductor layer (4) and an anode lead are implanted in the sintered body portion. The solid electrolytic capacitor element in which the carbon paste layer (5) and the conductor layer (6) are sequentially laminated except for the surface is connected to the yin and yang terminals (9a and 9b), and the exterior is removed except for some of the yin and yang terminals. (7) The solid electrolytic capacitor (8) is manufactured.
本発明に使用される焼結体は、陽極リードを成形体面に植設した弁作用金属もしくは導電性酸化物の粉末の成形体を焼結して作製される。成形圧力（例えば、0.1〜５０Ｋｇ／ｍｍ2）と焼結条件（例えば、温度８００〜1800℃・時間１分〜１０時間）を適宜選択することにより焼結体の表面積を大きくすることができる。焼結後に焼結体の表面積をさらに増加させるために、焼結体表面を化学的及び／または電気的にエッチング処理を行っていてもよい。
The sintered body used in the present invention is produced by sintering a molded body of a valve metal or conductive oxide powder in which an anode lead is implanted on the surface of the molded body. Molding pressure (e.g., 0.1~50Kg / mm 2) and the sintering conditions (e.g., temperature 800 to 1,800 ° C. ·
焼結体の形状は、特に限定されず、通常は柱状形状であるが、角柱形状の場合には、各隅のうち少なくとも１隅を面取りまたは球面状にＲをとって、焼結体を使用して作製される固体電解コンデンサの漏れ電流（ＬＣ）値の平均値を良好にしておいてもよい。また、成形時に金型から成形体が脱離しやすいようにテーパをきっておいてもよい。この場合は作製焼結体の形状は略角錐台状となる。 The shape of the sintered body is not particularly limited and is usually a columnar shape. However, in the case of a prismatic shape, at least one of the corners is chamfered or spherically shaped and R is used. The average value of the leakage current (LC) value of the solid electrolytic capacitor manufactured in this manner may be good. Further, the taper may be cut so that the molded body is easily detached from the mold during molding. In this case, the produced sintered body has a substantially truncated pyramid shape.
本発明においては、陽極リードは、リード線であってもリード箔であってもよい。また陽極リードを成形体に植設せずに、焼結体を作製した後に接続してもよい。陽極リードの材質としては、タンタル、アルミニウム、ニオブ、チタン、これら弁作用金属を主成分とする合金が使用される。また、陽極リードの一部を、炭化、燐化、ホウ化、窒化、硫化、酸化から選ばれる少なくとも１種の処理を行ってから使用してもよい。 In the present invention, the anode lead may be a lead wire or a lead foil. Further, the anode lead may be connected after the sintered body is produced without being implanted in the molded body. As the material of the anode lead, tantalum, aluminum, niobium, titanium, or an alloy mainly composed of these valve metals is used. Further, a part of the anode lead may be used after being subjected to at least one treatment selected from carbonization, phosphide, boride, nitridation, sulfidation, and oxidation.
陽極リードを成形体に植設する場合、陽極リードの焼結体内の深さは、焼結体の１／３以上、好ましくは２／３以上とすると焼結体の強度が維持できて後述するコンデンサ素子の外装封口時の熱的、物理的な封止応力に耐えることができるために好ましい。 When the anode lead is implanted in the molded body, the depth of the sintered body of the anode lead is 1/3 or more, preferably 2/3 or more of the sintered body, and the strength of the sintered body can be maintained. It is preferable because it can withstand thermal and physical sealing stress when the capacitor element is sealed.
後記する半導体層が陽極リードの上部にまで付着してコンデンサがショートすることを防ぐために、焼結体と陽極リードの境界部（陽極リード側）に絶縁性樹脂を鉢巻状に付着させて絶縁を計ってもよい。 In order to prevent the semiconductor layer, which will be described later, from adhering to the upper part of the anode lead and shorting out the capacitor, an insulating resin is attached to the boundary (anode lead side) between the sintered body and the anode lead to form an insulation. It may be measured.
弁作用金属または導電性酸化物としては、タンタル、アルミニウム、ニオブ、チタン、これら弁作用金属を主成分とする合金または酸化ニオブであるか、または前記弁作用金属、合金及び導電性酸化物から選択される２種以上の混合物が挙げられる。 The valve action metal or conductive oxide is tantalum, aluminum, niobium, titanium, an alloy based on these valve action metals or niobium oxide, or selected from the valve action metal, alloy and conductive oxide. Or a mixture of two or more thereof.
弁作用金属または導電性酸化物の形状は、通常粉体である。
弁作用金属または前記合金または導電性化合物あるいは前記焼結体等の一部を、炭化、燐化、ホウ素化、窒化、硫化、酸化から選ばれる少なくとも１種の処理を行ってから使用してもよい。
The shape of the valve metal or conductive oxide is usually a powder.
A part of the valve action metal, the alloy, the conductive compound, the sintered body, or the like may be used after being subjected to at least one treatment selected from carbonization, phosphation, boronation, nitridation, sulfurization, and oxidation. Good.
本発明の固体電解コンデンサは、前記焼結体に誘電体酸化皮膜層、半導体層、カーボンペースト層および導電体層を順次積層して陰極部を形成した固体電解コンデンサ素子の陽極リードの一部と陰極部の一部を、陽極端子と陰極端子に各々接続して前記陰陽両端子の一部を残して外装封口して作製される。 The solid electrolytic capacitor of the present invention includes a part of an anode lead of a solid electrolytic capacitor element in which a cathode portion is formed by sequentially laminating a dielectric oxide film layer, a semiconductor layer, a carbon paste layer, and a conductor layer on the sintered body. A part of the cathode part is connected to the anode terminal and the cathode terminal, respectively, and the outer and outer terminals are partly sealed to leave the part.
本発明の焼結体及び陽極リードの一部の表面に形成させる誘電体酸化皮膜層としては、Ｔａ2Ｏ5、Ａｌ2Ｏ3、ＴｉＯ2、Ｎｂ2Ｏ5等の金属酸化物から選ばれる少なくとも１つを主成分とする誘電体層が挙げられる。該誘電体層は、前記陽極基体を電解液中で化成することによって得ることができる。また、金属酸化物から選ばれた少なくとも１つを主成分とする誘電体層とセラミックコンデンサで使用される誘電体層を混合した誘電体層であってもよい（国際公開第００／７５９４３号パンフレット）。 The dielectric oxide film layer formed on a part of the surface of the sintered body and the anode lead of the present invention is selected from metal oxides such as Ta 2 O 5 , Al 2 O 3 , TiO 2 , and Nb 2 O 5. A dielectric layer containing at least one as a main component can be mentioned. The dielectric layer can be obtained by forming the anode substrate in an electrolytic solution. Further, it may be a dielectric layer in which a dielectric layer mainly composed of at least one selected from metal oxides and a dielectric layer used in a ceramic capacitor are mixed (WO 00/75943 pamphlet). ).
本発明の誘電体層上に形成される半導体層の代表例として、有機半導体および無機半導体から選ばれる少なくとも１種の化合物が挙げられる。 A typical example of the semiconductor layer formed on the dielectric layer of the present invention is at least one compound selected from an organic semiconductor and an inorganic semiconductor.
有機半導体の具体例としては、ベンゾピロリン４量体とクロラニルからなる有機半導体、テトラチオテトラセンを主成分とする有機半導体、テトラシアノキノジメタンを主成分とする有機半導体、下記一般式（１）または（２）で示される繰り返し単位を含む高分子にドーパントをドープした導電性高分子を主成分とした有機半導体が挙げられる。 Specific examples of the organic semiconductor include an organic semiconductor composed of benzopyrroline tetramer and chloranil, an organic semiconductor mainly composed of tetrathiotetracene, an organic semiconductor mainly composed of tetracyanoquinodimethane, and the following general formula (1) Or the organic semiconductor which has as a main component the conductive polymer which doped the dopant to the polymer containing the repeating unit shown by (2) is mentioned.
式（１）及び（２）において，Ｒ1〜Ｒ4は各々独立して水素原子、炭素数１〜６のアルキル基または炭素数１〜６のアルコキシ基を表わし、Ｘは酸素、イオウまたは窒素原子を表わし、Ｒ5はＸが窒素原子のときのみ存在して水素原子または炭素数１〜６のアルキル基を表わし、Ｒ1とＲ2及びＲ3とＲ4は、互いに結合して環状になっていてもよい。 In the formula (1) and (2), R 1 to R 4 each independently represents a hydrogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms having 1 to 6 carbon atoms, X is oxygen, sulfur or nitrogen R 5 represents an atom only when X is a nitrogen atom and represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R 1 and R 2 and R 3 and R 4 are bonded to each other to form a ring It may be.
さらに、本発明においては、前記一般式（１）で示される繰り返し単位を含む導電性高分子は、好ましくは下記一般式（３）で示される構造単位を繰り返し単位として含む導電性高分子が挙げられる。 Furthermore, in the present invention, the conductive polymer containing a repeating unit represented by the general formula (1) is preferably a conductive polymer containing a structural unit represented by the following general formula (3) as a repeating unit. It is done.
式中、Ｒ6及びＲ7は、各々独立して水素原子、炭素数１〜６の直鎖状もしくは分岐状の飽和もしくは不飽和のアルキル基、または該アルキル基が互いに任意の位置で結合して、２つの酸素原子を含む少なくとも１つ以上の５〜７員環の飽和炭化水素の環状構造を形成する置換基を表わす。また、前記環状構造には置換されていてもよいビニレン結合を有するもの、置換されていてもよいフェニレン構造のものが含まれる。 In the formula, R 6 and R 7 are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 6 carbon atoms, or the alkyl group is bonded to each other at an arbitrary position. And a substituent that forms a cyclic structure of at least one 5- to 7-membered saturated hydrocarbon containing two oxygen atoms. The cyclic structure includes those having a vinylene bond which may be substituted and those having a phenylene structure which may be substituted.
このような化学構造を含む導電性高分子は、荷電されており、ドーパントがドープされる。ドーパントには公知のドーパントが制限なく使用できる。 A conductive polymer containing such a chemical structure is charged and doped with a dopant. A well-known dopant can be used for a dopant without a restriction | limiting.
一般式（１）乃至（３）で示される繰り返し単位を含む高分子としては、例えば、ポリアニリン、ポリオキシフェニレン、ポリフェニレンサルファイド、ポリチオフェン、ポリフラン、ポリピロール、ポリメチルピロール、およびこれらの置換誘導体や共重合体などが挙げられる。中でもポリピロール、ポリチオフェン及びこれらの置換誘導体（例えば、ポリ（３，４−エチレンジオキシチオフェン）等）が好ましい。 Examples of the polymer containing the repeating units represented by the general formulas (1) to (3) include polyaniline, polyoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, polypyrrole, polymethylpyrrole, and substituted derivatives and co-polymers thereof. Examples include coalescence. Of these, polypyrrole, polythiophene, and substituted derivatives thereof (for example, poly (3,4-ethylenedioxythiophene)) are preferable.
無機半導体の具体例として、二酸化モリブデン、二酸化タングステン、二酸化鉛、二酸化マンガン等から選ばれた少なくとも１種の化合物が挙げられる。 Specific examples of the inorganic semiconductor include at least one compound selected from molybdenum dioxide, tungsten dioxide, lead dioxide, manganese dioxide and the like.
上記有機半導体および無機半導体として、電導度１０-2〜１０3Ｓ／ｃｍの範囲のものを使用すると、作製したコンデンサのＥＳＲ値が小さくなり好ましい。 When the organic semiconductor and the inorganic semiconductor have an electric conductivity in the range of 10 −2 to 10 3 S / cm, the ESR value of the manufactured capacitor is preferably reduced.
上記半導体層を形成する方法として、電解重合による方法（特開昭６０−３７１１４号公報）、酸化剤処理した陽極基体を電解重合する方法（特許２０５４５０６号）、化学的析出させる方法（特許２０４４３３４号）等従来公知の方法を採用することができる。 As a method for forming the semiconductor layer, a method by electrolytic polymerization (Japanese Patent Laid-Open No. 60-37114), a method of electrolytic polymerization of an oxidant-treated anode substrate (Japanese Patent No. 20450506), a method of chemical deposition (Japanese Patent No. 2043434). A conventionally known method such as) can be employed.
また、半導体層を形成途中及び／または形成後に再化成を行って半導体層形成によって引き起こされた誘電体酸化皮膜層の微小な欠陥部を修復しておいてもよい。 Further, re-chemical conversion may be performed during and / or after the formation of the semiconductor layer to repair minute defects in the dielectric oxide film layer caused by the formation of the semiconductor layer.
本発明では、前述した方法等で形成された半導体層の上にカーボンペースト層が設けられるが、このカーボンペースト層は、陽極リードが接続された焼結体の面を除いて設けることが肝要である。このようにカーボンペースト層の形成方法を多数個の固体電解コンデンサ素子作製時に応用することにより、ＬＣ値が飛びぬけて高い固体電解コンデンサの発生率を減少させることができる。 In the present invention, a carbon paste layer is provided on the semiconductor layer formed by the above-described method or the like. However, it is important to provide this carbon paste layer except for the surface of the sintered body to which the anode lead is connected. is there. Thus, by applying the carbon paste layer forming method when manufacturing a large number of solid electrolytic capacitor elements, the LC value can be skipped and the generation rate of high solid electrolytic capacitors can be reduced.
陽極リードと焼結体の接続面は、異種形状の材料が出会う箇所であり、接続時の応力を持っているために、この部分に形成された誘電体酸化皮膜層は不安定である。この部分に微細な粒子を含有するカーボンペースト層が付着すると、不安定な誘電体酸化皮膜層内に侵入するためにＬＣ値の回復が困難になるものと思われる。 The connecting surface between the anode lead and the sintered body is a place where materials of different shapes meet and has a stress at the time of connection, so the dielectric oxide film layer formed on this portion is unstable. If a carbon paste layer containing fine particles adheres to this part, it will be difficult to recover the LC value because it penetrates into an unstable dielectric oxide film layer.
また、粒径が小さい弁作用金属もしくは導電性酸化物の粉を使用した焼結体の場合ほど、誘電体酸化皮膜層の曲率半径が短いために、誘電体酸化皮膜層の不安定性が大きく、一般にＬＣ値が大きくなるが、このような素子であっても、前記本発明の方法を適用することにより固体電解コンデンサのＬＣ値を十分下げられるため、不良素子の発生率を下げることができる。すなわち、本発明によれば、小粒径粉（ＣＶが大きな粉）の焼結体ほど、大きな効果が得られる。 In addition, the more the sintered body using a valve metal or conductive oxide powder having a smaller particle diameter, the shorter the radius of curvature of the dielectric oxide film layer, the greater the instability of the dielectric oxide film layer, In general, the LC value increases, but even in such an element, the LC value of the solid electrolytic capacitor can be sufficiently lowered by applying the method of the present invention, so that the incidence of defective elements can be reduced. That is, according to the present invention, a larger effect can be obtained with a sintered body of small particle size powder (powder having a large CV).
さらにカーボンペーストに含有されるカーボン粒子の大きさが小さいと、半導体層とカーボンペースト層の密着性が強くなり、その結果作製した固体電解コンデンサのＥＳＲ値が良好になるが、このようなカーボン粒子が小さい場合に陽極リード接続面にカーボンペースト層を設けない本発明はＬＣ改良に好都合である。 Furthermore, if the carbon particles contained in the carbon paste are small in size, the adhesion between the semiconductor layer and the carbon paste layer becomes strong, and as a result, the ESR value of the produced solid electrolytic capacitor is improved. The present invention in which the carbon paste layer is not provided on the anode lead connecting surface when the value is small is advantageous for LC improvement.
本発明に使用されるカーボンペーストは、カーボン粒子を水及び／または有機溶媒に分散させたものであり、界面活性剤、アンモニア等の各種分散剤及びアルキッド樹脂、アクリル樹脂、エポキシ樹脂、フェノール樹脂、イミド樹脂、フッ素樹脂、エステル樹脂、イミドアミド樹脂、アミド樹脂、スチレン樹脂等の公知の各種樹脂や樹脂の硬化剤が含有されていてもよい。カーボンペーストを半導体層上に付着させた後に乾燥することによって水及び／または有機溶媒が飛散しカ−ボンペースト層が形成される。 The carbon paste used in the present invention is obtained by dispersing carbon particles in water and / or an organic solvent, and includes a surfactant, various dispersants such as ammonia, an alkyd resin, an acrylic resin, an epoxy resin, a phenol resin, Various known resins such as imide resins, fluororesins, ester resins, imidoamide resins, amide resins, styrene resins, and resin curing agents may be contained. Carbon paste is deposited on the semiconductor layer and then dried, whereby water and / or an organic solvent is scattered to form a carbon paste layer.
カーボンとしては、通常、平均粒径0.001〜1000μｍのものが使用され、一次粒子が化学的または物理的に融着して二次または三次粒子になったものも使用できる。前述したように、一般に粒径が細かいカーボンを使用するほど作製した固体電解コンデンサのＥＳＲ値が低くなるので好ましい。 As the carbon, those having an average particle diameter of 0.001 to 1000 μm are usually used, and those in which primary particles are chemically or physically fused to form secondary or tertiary particles can also be used. As described above, since the ESR value of a solid electrolytic capacitor produced is generally lower as carbon having a smaller particle size is used, it is preferable.
カーボンペースト層の厚みは、薄いほど作製した固体電解コンデンサのＥＳＲ値が良好になる。しかし、薄すぎると固体電解コンデンサの耐湿性が劣化するため、通常0.1〜１００μｍ、好ましくは0.1〜３０μｍの範囲に設定される。 The thinner the carbon paste layer is, the better the ESR value of the produced solid electrolytic capacitor. However, if the thickness is too thin, the moisture resistance of the solid electrolytic capacitor is deteriorated, so the thickness is usually set in the range of 0.1 to 100 μm, preferably 0.1 to 30 μm.
本発明では、前述した方法等で形成されたカーボンペースト層と陽極リードが接続している面の半導体層の上に導電体層が設けられる。 In the present invention, the conductor layer is provided on the semiconductor layer on the surface where the carbon paste layer formed by the above-described method and the like and the anode lead are connected.
陽極リードが接続している面の半導体層の上に導電体層を設けないと作製した固体電解コンデンサのＬＣの平均値は良好になるが、ＥＳＲ値が不良になるために好ましくない。 If the conductor layer is not provided on the semiconductor layer on the surface to which the anode lead is connected, the average value of LC of the manufactured solid electrolytic capacitor is good, but it is not preferable because the ESR value becomes poor.
導電体層は、例えば、導電ペーストの固化、メッキ、金属蒸着、耐熱性の導電樹脂フイルムの付着等により形成することができる。 The conductor layer can be formed, for example, by solidifying a conductive paste, plating, metal vapor deposition, attaching a heat-resistant conductive resin film, or the like.
導電ペーストとしては、銀ペースト、銅ペースト、アルミニウムペースト、金ペースト、ニッケルペースト等が好ましい。これらは１種を用いても２種以上を用いてもよい。２種以上を用いる場合、混合してもよく、または別々の層として重ねてもよい。導電ペーストを適用した後、空気中に放置するか、または加熱して固化せしめる。 As the conductive paste, silver paste, copper paste, aluminum paste, gold paste, nickel paste and the like are preferable. These may be used alone or in combination of two or more. When using 2 or more types, they may be mixed or may be stacked as separate layers. After applying the conductive paste, it is left in the air or heated to solidify.
導電ペーストは、樹脂と金属等の導電粉を主成分とするが、場合によっては、樹脂を溶解するための溶媒や樹脂の硬化剤等が加えられていて、前記固化時に溶媒が飛散する。 The conductive paste is mainly composed of conductive powder such as resin and metal, but in some cases, a solvent for dissolving the resin, a curing agent for the resin, or the like is added, and the solvent is scattered during the solidification.
樹脂として、アルキッド樹脂、アクリル樹脂、エポキシ樹脂、フェノール樹脂、イミド樹脂、フッ素樹脂、エステル樹脂、イミドアミド樹脂、アミド樹脂、スチレン樹脂等の公知の各種樹脂が使用される。 As the resin, various known resins such as alkyd resin, acrylic resin, epoxy resin, phenol resin, imide resin, fluorine resin, ester resin, imidoamide resin, amide resin, and styrene resin are used.
導電粉としては、銀、銅、アルミニウム、金、ニッケルおよびこれら金属を主成分とする合金の粉、これら金属が表層にあるコート粉やこれらの混合物粉の少なくとも１種が使用される。導電粉は、通常４０〜９７質量％含まれている。４０質量％未満であると作製した導電ペーストの導電性が小さく、９７質量％を超えると、導電ペーストの接着性が不良になるために好ましくない。導電ペーストに前述した半導体層を形成する導電性高分子や金属酸化物の粉を混合して使用してもよい。 As the conductive powder, at least one kind of powder of silver, copper, aluminum, gold, nickel and an alloy containing these metals as a main component, coat powder having these metals on the surface layer, or a mixture of these powders is used. The conductive powder is usually contained in an amount of 40 to 97% by mass. If it is less than 40% by mass, the conductivity of the produced conductive paste is small, and if it exceeds 97% by mass, the adhesiveness of the conductive paste becomes poor, which is not preferable. You may mix and use the conductive polymer and metal oxide powder which form the semiconductor layer mentioned above in the electrically conductive paste.
メッキとしては、ニッケルメッキ、銅メッキ、銀メッキ、アルミニウムメッキ等が挙げられる。また蒸着金属としては、アルミニウム、ニッケル、銅、銀等が挙げられる。 Examples of the plating include nickel plating, copper plating, silver plating, and aluminum plating. Examples of the deposited metal include aluminum, nickel, copper, and silver.
このようにして陽極基体に導電体層まで積層して陰極部を形成した固体電解コンデンサ素子が作製される。 In this way, a solid electrolytic capacitor element in which the cathode layer is formed by laminating the conductor layer on the anode substrate is produced.
以上のような構成の本発明の固体電解コンデンサ素子は、例えば、樹脂モールド、樹脂ケース、金属性の外装ケース、樹脂のディッピング、ラミネートフイルムによる外装などの外装により各種用途のコンデンサ製品とすることができる。 The solid electrolytic capacitor element of the present invention having the above-described configuration may be made into a capacitor product for various uses by using, for example, a resin mold, a resin case, a metallic outer case, a resin dipping, or a laminate film. it can.
これらの中でも、とりわけ樹脂モールド外装を行ったチップ状固体電解コンデンサが、小型化と低コスト化が簡単に行えるので好ましい。 Among these, a chip-shaped solid electrolytic capacitor with a resin mold exterior is particularly preferable because it can be easily reduced in size and cost.
樹脂モールド外装の場合について具体的に説明すると、本発明の固体電解コンデンサは、前記固体電解コンデンサ素子の導電体層の一部を、別途用意した一対の対向して配置された先端部を有するリードフレームの一方の先端部に載置し、さらに陽極リードの一部（寸法を合わすために陽極リードの先端を切断して使用してもよい。）を前記リードフレームの他方の先端部に載置し、前者は、例えば導電ペーストの固化で、後者は、溶接で各々電気的・機械的に接合した後、前記リードフレームの先端部の一部を残して樹脂封口し、樹脂封口外の所定部所でリードフレームを切断・折り曲げ加工（リードフレームが樹脂封口の下面にあり、リードフレームの下面または下面と側面のみを残して封口されている場合は、切断加工のみ）して作製される。 The solid electrolytic capacitor according to the present invention will be specifically described in the case of a resin mold exterior. The solid electrolytic capacitor according to the present invention is a lead having a pair of oppositely arranged tip portions prepared separately from a part of the conductor layer of the solid electrolytic capacitor element. Placed on one end of the frame, and further, a part of the anode lead (the end of the anode lead may be cut to match the dimensions) may be placed on the other end of the lead frame. The former is, for example, solidification of the conductive paste, and the latter is electrically and mechanically joined by welding, and then resin-sealed leaving a part of the tip of the lead frame, and a predetermined portion outside the resin seal Cut and bend the lead frame at the location (if the lead frame is on the bottom surface of the resin seal and is sealed with only the bottom or bottom and side surfaces of the lead frame sealed, only cut processing) It is.
リードフレームは、前述したように切断加工されて最終的には固体電解コンデンサの外部端子となるが、形状は箔または平板状であり、材質としては、鉄、銅、アルミニウムまたはこれら金属を主成分とする合金が使用される。リードフレームの一部または全部に半田、錫、ニッケル、銀、金、チタン等のメッキが施されていてもよい。リードフレームとメッキとの間に、ニッケルまたは銅等の下地メッキがあってもよい。リードフレームには、一対の対向して配置された先端部が存在し、先端部間に隙間があることにより、各固体電解コンデンサ素子の陽極リードと陰極部とが絶縁される。 The lead frame is cut and processed as described above, and finally becomes an external terminal of the solid electrolytic capacitor. The shape of the lead frame is foil or flat plate, and the material is iron, copper, aluminum or these metals as main components. An alloy is used. Part or all of the lead frame may be plated with solder, tin, nickel, silver, gold, titanium, or the like. There may be a base plating such as nickel or copper between the lead frame and the plating. The lead frame has a pair of opposed tip portions, and a gap is provided between the tip portions, whereby the anode lead and the cathode portion of each solid electrolytic capacitor element are insulated.
本発明の固体電解コンデンサの封口に使用される樹脂としては、エポキシ樹脂、フェノール樹脂、アルキッド樹脂等固体電解コンデンサの封止に使用される公知の樹脂が採用できるが、各樹脂とも一般に市販されている低応力樹脂を使用すると、封止時におきるコンデンサ素子への封止応力の発生を緩和することができるために好ましい。また、樹脂封口するための製造機としてトランスファーマシンが好んで使用される。封止後に所定温度で樹脂の硬化を行ってもよい。 As a resin used for sealing the solid electrolytic capacitor of the present invention, a known resin used for sealing a solid electrolytic capacitor such as an epoxy resin, a phenol resin, or an alkyd resin can be adopted, but each resin is generally commercially available. It is preferable to use a low-stress resin that can reduce the generation of sealing stress on the capacitor element that occurs at the time of sealing. A transfer machine is preferably used as a manufacturing machine for sealing the resin. The resin may be cured at a predetermined temperature after sealing.
このように作製された固体電解コンデンサは、導電体層形成時や外装時の熱的および／または物理的な誘電体層の劣化を修復するために、エージング処理を行ってもよい。 The solid electrolytic capacitor thus manufactured may be subjected to an aging treatment in order to repair the deterioration of the thermal and / or physical dielectric layer during the formation of the conductor layer and during the exterior.
エージング方法は、固体電解コンデンサに所定の電圧（通常、定格電圧の２倍以内）を印加することによって行われる。エージング時間や温度は、コンデンサの種類、容量、定格電圧によって最適値が変化するので予め実験によって決定されるが、通常、時間は数分から数日間、温度は電圧印加冶具の熱劣化を考慮して３００℃以下で行われる。エージングの雰囲気は、空気中でもよいし、Ａｒ、Ｎ2、Ｈｅ等の不活性ガス中でもよい。また、減圧、常圧、加圧下のいずれの条件で行ってもよい。エージング中のすべてあるいは一部で、水蒸気を供給しながら、または水蒸気を供給した後に前記エージングを行うと誘電体層の安定化が進む場合がある。水蒸気の供給方法の１例として、エージングの炉中に置いた水溜めから熱により水蒸気を供給する方法が挙げられる。 The aging method is performed by applying a predetermined voltage (usually within twice the rated voltage) to the solid electrolytic capacitor. Aging time and temperature are determined in advance by experiment because optimum values vary depending on the type, capacity, and rated voltage of the capacitor.Normally, the time is several minutes to several days, and the temperature is determined in consideration of thermal degradation of the voltage application jig. It is performed at 300 ° C. or lower. The aging atmosphere may be air or an inert gas such as Ar, N 2 , or He. Moreover, you may carry out on any conditions of pressure reduction, a normal pressure, and pressurization. When the aging is performed while supplying water vapor or after supplying water vapor in all or part of the aging, stabilization of the dielectric layer may progress. One example of a method for supplying water vapor is a method for supplying water vapor by heat from a water reservoir placed in an aging furnace.
電圧印加方法として、直流、任意の波形を有する交流、直流に重畳した交流やパルス電流等の任意の電流を流すように設計することができる。エージングの途中に一旦電圧印加を止め、再度電圧印加を行うことも可能である。 As a voltage application method, it can be designed to flow an arbitrary current such as a direct current, an alternating current having an arbitrary waveform, an alternating current superimposed on the direct current, or a pulse current. It is also possible to stop the voltage application once during the aging and apply the voltage again.
本発明で製造された固体電解コンデンサは、例えば、中央演算回路や電源回路等の高容量のコンデンサを用いる回路に好ましく用いることができ、これらの回路は、パソコン、サーバー、カメラ、ゲーム機、ＤＶＤ、ＡＶ機器、携帯電話等の各種デジタル機器や、各種電源等の電子機器に利用可能である。本発明で製造された固体電解コンデンサは、容量が大きく、ＥＳＲ値が良好で、またＬＣ値が飛び抜けて不良なものが無いことから、これを用いることにより信頼性の高い電子回路及び電子機器を得ることができる。 The solid electrolytic capacitor manufactured by the present invention can be preferably used for a circuit using a high-capacitance capacitor such as a central processing circuit and a power supply circuit, and these circuits are used for personal computers, servers, cameras, game machines, DVDs. It can be used for various digital devices such as AV devices and mobile phones, and electronic devices such as various power sources. Since the solid electrolytic capacitor manufactured by the present invention has a large capacity, a good ESR value, and an LC value that skips and is not defective, a highly reliable electronic circuit and electronic device can be obtained by using this. Can be obtained.
本発明は、焼結体の陽極リードが接続された面のみカーボンペースト層を形成しない固体電解コンデンサを提供したものであって、本発明によれば、ＬＣ値が極端に大きな固体電解コンデンサの発生率を減少させることができる。 The present invention provides a solid electrolytic capacitor that does not form a carbon paste layer only on the surface to which the anode lead of the sintered body is connected. According to the present invention, the generation of a solid electrolytic capacitor having an extremely large LC value is provided. The rate can be reduced.
以下、本発明の具体例についてさらに説明するが、以下の例により本発明は限定されるものではない。 Specific examples of the present invention will be further described below, but the present invention is not limited to the following examples.
実施例１：
ＣＶ（容量と化成電圧の積）１０万μＦ・Ｖ／ｇのタンタル粉と0.24ｍｍφのタンタルリード線を使用して成形し、大きさ4.5×1.0×3.0ｍｍの焼結体を作製した（焼結温度1300℃、焼結時間２０分、焼結体密度6.6ｇ／ｃｍ3、焼結体の1.0×3.0ｍｍの面中央部に垂直にＴａリード線が植設されていて焼結体内部に４ｍｍ入り、外部に１０ｍｍ出ている）。別途用意した長さ２５０ｍｍ幅２０ｍｍ厚さ２ｍｍのステンレス製長尺金属板に左右３０ｍｍを残して前記焼結体３２個の各リード線を等間隔かつ等寸に整列接続した。このような長尺金属板２０枚を５ｍｍ間隔に並列に並べ、長尺金属板の左右１５ｍｍのところで電気的に接続するように金属製フレームに配設した。金属製フレームに焼結体が６４０個等間隔に配置されていて、各焼結体はリード線を通して金属性フレームに設けた給電端子に電気的に接続されている。この金属製フレームに連なった焼結体を１ロットとして以下の各種操作を行った。
Example 1:
CV (product of capacity and conversion voltage) was formed using 100,000μF · V / g tantalum powder and 0.24mmφ tantalum lead wire to produce a sintered body of 4.5 × 1.0 × 3.0mm in size (baked) The sintering temperature is 1300 ° C, the sintering time is 20 minutes, the sintered body density is 6.6 g / cm 3 , and the Ta lead wire is implanted vertically in the center of the 1.0 × 3.0 mm surface of the sintered body. 4mm and 10mm outside). The lead wires of the 32 sintered bodies were aligned and equidistantly arranged at equal intervals, leaving 30 mm left and right on a separately prepared stainless steel long metal plate having a length of 250 mm, a width of 20 mm, and a thickness of 2 mm. Twenty such long metal plates were arranged in parallel at intervals of 5 mm, and arranged on a metal frame so as to be electrically connected at 15 mm on the left and right sides of the long metal plate. 640 sintered bodies are arranged at equal intervals on the metal frame, and each sintered body is electrically connected to a power supply terminal provided on the metallic frame through a lead wire. The following various operations were performed with one sintered body connected to the metal frame as one lot.
焼結体を１％燐酸水溶液中にリード線の一部を除いて浸漬し、リード線を陽極とし水溶液中に配置したＴａ陰極板との間に１４Ｖを印加し、８０℃で１０時間化成してＴａ2Ｏ5からなる誘電体酸化皮膜層を形成した。この焼結体のリード線部分を除いて、２０％酢酸鉛水溶液と３５％過硫酸アンモニウム水溶液の１：１混合液に浸漬し、４０℃で１時間放置した後引き上げ水洗後乾燥すること及び１５％酢酸アンモニウム水溶液で洗浄することを４５回繰り返して、誘電体酸化皮膜層上に二酸化鉛と酢酸鉛との混合物（二酸化鉛が９６％）からなる半導体層を形成した。半導体層形成途中と最後に複数回0.1％酢酸水溶液中で再化成を行った。ついでリード線が植設されている面を除いて半導体層上にカーボンペースト（平均粒径0.2μｍのカーボン粒子が水に分散している。）を付着させ乾燥しカーボンペースト層を形成した。ついで焼結体の６面全部にエポキシ樹脂１０質量部と銀粉９０質量部からなる銀ペーストを積層した導電体層を設けて陰極部を形成して固体電解コンデンサ素子を作製した。 The sintered body is immersed in a 1% phosphoric acid aqueous solution with a part of the lead wire removed, 14 V is applied between the lead wire as the anode and a Ta cathode plate placed in the aqueous solution, and the resultant is formed at 80 ° C. for 10 hours. Thus, a dielectric oxide film layer made of Ta 2 O 5 was formed. Except for the lead wire portion of this sintered body, it was immersed in a 1: 1 mixture of 20% lead acetate aqueous solution and 35% ammonium persulfate aqueous solution, left at 40 ° C. for 1 hour, then washed with water, dried and 15% Washing with an aqueous ammonium acetate solution was repeated 45 times to form a semiconductor layer made of a mixture of lead dioxide and lead acetate (96% lead dioxide) on the dielectric oxide film layer. During the formation of the semiconductor layer and finally, re-formation was performed several times in a 0.1% acetic acid aqueous solution. Next, a carbon paste (carbon particles having an average particle size of 0.2 μm are dispersed in water) was deposited on the semiconductor layer except for the surface where the lead wires were implanted, and dried to form a carbon paste layer. Next, a conductor layer in which a silver paste consisting of 10 parts by mass of epoxy resin and 90 parts by mass of silver powder was provided on all six surfaces of the sintered body to form a cathode part to produce a solid electrolytic capacitor element.
別途用意した、表面に錫メッキした厚さ１００μｍの銅合金リードフレーム（幅3.4ｍｍの一対の先端部が３２個存在し、両先端部には同一平面に投影して1.0ｍｍの隙間がある。）の一対の先端部の上面に、前記した固体電解コンデンサ素子の陰極部面（4.5ｍｍ×3.0ｍｍの面）と一部切断除去した陽極リード線を各々載置し、前者は、陰極部と同一の銀ペーストの固化で、後者は、スポット溶接で電気的・機械的に接続した。ついで前記リードフレームの一部を残してエポキシ樹脂でトランスファー成形して樹脂外装し、さらに、リードフレームの樹脂外部の所定部を切断後外装部に沿って折り曲げ加工した。引き続き２００℃で外装樹脂を硬化させた後に、１０５℃、６Ｖで４時間エージング処理を行い、大きさ7.3×4.3×1.8ｍｍのチップ状固体電解コンデンサを作製した。 Separately prepared 100 μm thick copper alloy lead frame with tin plating on the surface (32 pairs of tip portions having a width of 3.4 mm are present, and both tip portions are projected on the same plane and have a gap of 1.0 mm. ) Are placed on the cathode part surface (4.5 mm × 3.0 mm surface) of the solid electrolytic capacitor element and the anode lead wire partially cut and removed, respectively. With the solidification of the same silver paste, the latter was electrically and mechanically connected by spot welding. Subsequently, a part of the lead frame was left and transfer molded with epoxy resin to coat the resin, and a predetermined portion outside the resin of the lead frame was cut and then bent along the outer package. Subsequently, the exterior resin was cured at 200 ° C., and then subjected to aging treatment at 105 ° C. and 6 V for 4 hours to produce a chip-shaped solid electrolytic capacitor having a size of 7.3 × 4.3 × 1.8 mm.
比較例１：
実施例１でカーボンペースト層を焼結体の６面すべてに形成した以外は実施例１と同様にしてチップ状固体電解コンデンサを作製した。
Comparative Example 1:
A chip-shaped solid electrolytic capacitor was produced in the same manner as in Example 1 except that the carbon paste layer was formed on all six surfaces of the sintered body in Example 1.
実施例２：
実施例１でタンタル焼結体の代わりにニオブ焼結体（ＣＶ２０万μＦ・Ｖ／ｇの粉末から調製、窒化量１万ｐｐｍ，表面の自然酸化酸素量8.2万ｐｐｍ、焼結温度1280℃、焼結時間３０分、焼結体密度3.5ｇ／ｃｍ3）を、タンタルリード線の代わりにニオブリード線を使用して、３０Ｖの化成で誘電体酸化皮膜層をＮｂ2Ｏ5とした。次に焼結体を３％３，４−エチレンジオキシチオフェンアルコール溶液と1.5％過硫酸アンモニウムが溶解した１３％アントラキノン−２−スルホン酸水溶液とに交互に浸漬することを７回繰り返すことにより誘電体層上にエチレンジオキシポリマーを主成分とする多数の微小接触物を付着させ誘電体層に電気的な微小欠陥部分を多数個作製した後に、0.1％酢酸水溶液中で再化成して乾燥した。ついで焼結体を３，４−エチレンジオキシチオフェン（モノマーが飽和濃度以下となる水溶液として使用）とアントラキノン−２−スルホン酸が溶解した水と２０％エチレングリコール電解液に漬け、金属製フレームの給電端子から電解液中に配置した負極のタンタル電極板との間に室温で２０ｍＡの直流定電流を４５分流し、半導体層を形成するための通電を行った。引き上げ洗浄乾燥した後、0.1％酢酸水溶液中で誘電体層の微小なＬＣの欠陥を修復するための再化成（８０℃、３０分、１７Ｖ）を行った。前記通電と再化成を１５回繰り返した後水洗浄乾燥して半導体層を形成した。ついで実施例１と同様にしてカーボンペースト層（平均粒径1.8μｍのカーボン粒子を使用）、導電体層（アクリル樹脂１０質量部と銀粉９０質量部からなる銀ペースト）を形成し、さらに樹脂外装、硬化、エージング（８５℃、９Ｖ）処理を行ってチップ状固体電解コンデンサを作製した。
Example 2:
In Example 1, instead of the tantalum sintered body, a niobium sintered body (prepared from a powder having a CV of 200,000 μF · V / g, the nitriding amount is 10,000 ppm, the surface natural oxygen oxide amount is 82,000 ppm, the sintering temperature is 1280 ° C., Using a niobium lead wire instead of a tantalum lead wire with a sintering time of 30 minutes and a sintered body density of 3.5 g / cm 3 ), the dielectric oxide film layer was made Nb 2 O 5 by chemical conversion at 30V. Next, by alternately immersing the sintered body in a 3% 3,4-ethylenedioxythiophene alcohol solution and a 13% anthraquinone-2-sulfonic acid aqueous solution in which 1.5% ammonium persulfate is dissolved, the dielectric is obtained by repeating the process seven times. A large number of microcontacts mainly composed of ethylenedioxy polymer were deposited on the layer to produce a large number of electrical microdefects on the dielectric layer, and then re-formed in 0.1% acetic acid aqueous solution and dried. Next, the sintered body is immersed in 3,4-ethylenedioxythiophene (used as an aqueous solution in which the monomer is less than the saturated concentration) and anthraquinone-2-sulfonic acid dissolved in 20% ethylene glycol electrolyte, A constant current of 20 mA was passed for 45 minutes at room temperature between the power supply terminal and the negative tantalum electrode plate disposed in the electrolyte, and energization was performed to form the semiconductor layer. After pulling up, drying and drying, re-formation (80 ° C., 30 minutes, 17 V) was performed in 0.1% acetic acid aqueous solution to repair minute LC defects in the dielectric layer. The energization and re-chemical conversion were repeated 15 times, followed by washing with water and drying to form a semiconductor layer. Then, a carbon paste layer (using carbon particles having an average particle size of 1.8 μm) and a conductor layer (silver paste comprising 10 parts by weight of acrylic resin and 90 parts by weight of silver powder) were formed in the same manner as in Example 1, and further the resin exterior Then, curing and aging (85 ° C., 9 V) were performed to produce a chip-shaped solid electrolytic capacitor.
比較例２：
実施例２でカーボンペースト層を焼結体の６面すべてに形成した以外は実施例２と同様にしてチップ状固体電解コンデンサを作製した。
Comparative Example 2:
A chip-shaped solid electrolytic capacitor was produced in the same manner as in Example 2 except that the carbon paste layer was formed on all six surfaces of the sintered body in Example 2.
以上作製したコンデンサ（各例６４０個測定）の平均容量、ＥＳＲ、ＬＣを以下の方法で測定し、各測定値及び1000μＡ以上のＬＣ値を示す個数を表１にまとめて示した。
コンデンサの容量：ヒューレットパッカード社製ＬＣＲ測定器を用い、室温、１２０Ｈｚで容量を測定した。
ＥＳＲ値：コンデンサの等価直列抵抗を１００ｋＨｚで測定した。
ＬＣ値：室温において、所定の定格電圧（実施例１及び比較例１は４Ｖ値、実施例２及び比較例２は６Ｖ値）を作製したコンデンサの端子間に３０秒間印加し続けた後に測定した。
The average capacity, ESR, and LC of the thus-prepared capacitors (measured by 640 in each example) were measured by the following methods, and the measured values and the numbers indicating the LC values of 1000 μA or more are shown in Table 1.
Capacitor capacity: The capacity was measured at room temperature and 120 Hz using an LCR measuring instrument manufactured by Hewlett-Packard Company.
ESR value: The equivalent series resistance of the capacitor was measured at 100 kHz.
LC value: measured at room temperature after applying a predetermined rated voltage (4V value for Example 1 and Comparative Example 1 and 6V value for Example 2 and Comparative Example 2) between terminals of the capacitor produced for 30 seconds. .
実施例１と比較例１、実施例２と比較例２を比べることにより、焼結体の陽極リードが接続された面のみカーボンペースト層を形成しないと、ＬＣ値が極端に大きな固体電解コンデンサの発生率が減少することがわかる。 By comparing Example 1 with Comparative Example 1 and Example 2 with Comparative Example 2, if a carbon paste layer is not formed only on the surface of the sintered body to which the anode lead is connected, a solid electrolytic capacitor having an extremely large LC value is obtained. It can be seen that the incidence decreases.
１ 焼結体
２ 陽極リード
３ 誘電体酸化皮膜層
４ 半導体層
５ カーボンペースト層
６ 導電体層
７ 外装
８ 固体電解コンデンサ
９ａ 陰極端子
９ｂ 陽極端子
DESCRIPTION OF
Claims (13)
で示される繰り返し単位を含む高分子にドーパントをドープした導電性高分子を主成分とした有機半導体から選択される少なくとも１種である請求項５に記載の固体電解コンデンサ。 An organic semiconductor composed of a benzopyrroline tetramer and chloranil, an organic semiconductor mainly composed of tetrathiotetracene, an organic semiconductor mainly composed of tetracyanoquinodimethane, the following general formula (1) or (2)
The solid electrolytic capacitor according to claim 5, which is at least one selected from organic semiconductors mainly composed of a conductive polymer obtained by doping a polymer containing a repeating unit represented by formula 1 with a dopant.
で示される構造単位を繰り返し単位として含む導電性高分子である請求項６に記載のチップ状固体電解コンデンサ。 The conductive polymer containing the repeating unit represented by the general formula (1) is represented by the following general formula (3).
The chip-shaped solid electrolytic capacitor according to claim 6, which is a conductive polymer including a structural unit represented by
The electronic device using the solid electrolytic capacitor in any one of Claims 1 thru | or 11.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008001630A1 (en) * | 2006-06-27 | 2008-01-03 | Showa Denko K.K. | Solid electrolytic capacitor |
| JP2008004744A (en) * | 2006-06-22 | 2008-01-10 | Nec Tokin Corp | Solid-state electrolytic capacitor manufacturing method |
| JP2008028137A (en) * | 2006-07-21 | 2008-02-07 | Nec Tokin Corp | Solid-state electrolytic capacitor |
| JP2008186881A (en) * | 2007-01-29 | 2008-08-14 | Japan Carlit Co Ltd:The | Solid electrolytic capacitor |
| JP2010021217A (en) * | 2008-07-09 | 2010-01-28 | Japan Carlit Co Ltd:The | Solid electrolytic capacitor, and method of manufacturing the same |
| JP2010267866A (en) * | 2009-05-15 | 2010-11-25 | Murata Mfg Co Ltd | Solid electrolytic capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008004744A (en) * | 2006-06-22 | 2008-01-10 | Nec Tokin Corp | Solid-state electrolytic capacitor manufacturing method |
| JP4662368B2 (en) * | 2006-06-22 | 2011-03-30 | Ｎｅｃトーキン株式会社 | Manufacturing method of solid electrolytic capacitor |
| WO2008001630A1 (en) * | 2006-06-27 | 2008-01-03 | Showa Denko K.K. | Solid electrolytic capacitor |
| JP4955000B2 (en) * | 2006-06-27 | 2012-06-20 | 昭和電工株式会社 | Solid electrolytic capacitor |
| JP2008028137A (en) * | 2006-07-21 | 2008-02-07 | Nec Tokin Corp | Solid-state electrolytic capacitor |
| JP2008186881A (en) * | 2007-01-29 | 2008-08-14 | Japan Carlit Co Ltd:The | Solid electrolytic capacitor |
| JP2010021217A (en) * | 2008-07-09 | 2010-01-28 | Japan Carlit Co Ltd:The | Solid electrolytic capacitor, and method of manufacturing the same |
| JP2010267866A (en) * | 2009-05-15 | 2010-11-25 | Murata Mfg Co Ltd | Solid electrolytic capacitor |
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