JPH0240208B2 - DENKAIKONDENSA - Google Patents
DENKAIKONDENSAInfo
- Publication number
- JPH0240208B2 JPH0240208B2 JP27914984A JP27914984A JPH0240208B2 JP H0240208 B2 JPH0240208 B2 JP H0240208B2 JP 27914984 A JP27914984 A JP 27914984A JP 27914984 A JP27914984 A JP 27914984A JP H0240208 B2 JPH0240208 B2 JP H0240208B2
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic capacitor
- chlorine
- corrosion
- electrolytic
- elastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003990 capacitor Substances 0.000 claims description 35
- 238000007789 sealing Methods 0.000 claims description 21
- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 15
- 238000005260 corrosion Methods 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- -1 chlorine ions Chemical class 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000012459 cleaning agent Substances 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000012812 sealant material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
Landscapes
- Oscillators With Electromechanical Resonators (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Description
〔産業上の利用分野〕
この発明は、電解コンデンサの改良に係り、特
に電解コンデンサの耐腐食特性の改善に関する。
〔従来の技術〕
電解コンデンサは、アルミニウム、タンタルな
どの皮膜形成性金属を陽極に用い、この陽極表面
に誘電体となる絶縁性の酸化皮膜を陽極酸化処理
等により形成し、陰極として酸化皮膜のない同種
もしくは他の金属を対抗配置し、これらの電極間
に紙、多孔質プラスチツクなどのセパレータを介
在させて巻回あるいは、層状に重ね合わせてコン
デンサ素子を形成している。
図面は、一般的な電解コンデンサの構造をあら
わしたもので、アルミニウムからなる帯状の陽
極、陰極双方の電極箔とセパレータとが層状に重
ね合わされ、巻回された円筒状のコンデンサ素子
１が、有底筒状の外装ケース２に収納され、外装
ケース２の開口部が各種の合成ゴム、弾性プラス
チツクなどの弾性部材からなる円盤状の弾性封口
体３で閉じられ、外装ケース２の開口端を巻き締
めて密閉がなされている。
なお、前記コンデンサ素子１の上端からは、陽
極、陰極双方の電極と電気的に接続された内部リ
ード４が突出している。この内部リード４は弾性
封口体３３に設けられた貫通孔５に挿通され、そ
の先端には、外部との電気的接続を行うための外
部リード６が各々接続されている。
この構造のもの以外に、図示はしないが弾性封
口体３に代えて、硬質の絶縁板状部材に弾性部材
のシートを貼り合わせた構造の封口体も一般に用
いられている。
この電解コンデンサは、誘導体が陽極の皮膜形
成性金属の表面に形成された酸化皮膜であり、電
解液がこの酸化皮膜と接触して、真の陰極として
作用し、コンデンサの機能を持つことになる。ま
た、電解液はこの酸化皮膜の劣化部分に作用し
て、皮膜を修復させる機能を有している。このこ
とは、酸化皮膜と電解液の接触面で常に局所的に
陽極酸化反応が常におこなわれているといえる。
ところが、この陽極酸化反応の部位に塩素イオ
ンが存在すると、アルミニウムは塩素と化合し塩
化アルミニウムとなり、さらに加水分解して水酸
化アルミニウムが形成される。そして塩素イオン
はあたかも触媒のように作用してアルミニウムの
腐食を進行させ、漏れ電流の増加、内圧上昇等に
始まり、ついには内部リードの断線等により電解
コンデンサの機能を全く損ねてしまうことにな
る。
このため、電解コンデンサの内部は、塩素の存
在を極力排除しなければならない。しかしなが
ら、各種合成ゴム等からなる弾性封口体には、架
橋剤、架橋促進剤、老化防止剤など、封口機能の
維持、改善のため多くの添加殺が添加されるが、
この中の不純物に塩素が含まれているおそれがあ
り、これが原因で腐食の発生を起こすことがあ
る。
従来からもこの対策として、上述のような添加
剤を含まない。ウレタンゴム、ポリオフイン系の
熱可塑性エラストマーなどを電解コンデンサの封
口体に用いることが提案されている。ところが、
これらの封口体、耐熱性、コストなどの面から実
用的でない。
また、電解コンデンサは、印刷配線基板上に半
田により取り付けられるが、この半田付け後の基
板洗浄に、トリクロロエタン等のハロゲン系洗浄
剤が使用されるので、残存洗浄剤が電解コンデン
サの封口体部分やリード引き出し部分から内部に
浸透し、腐食発生の原因となることもある。この
対策として、ハロゲン系洗浄剤に対して強い抵抗
力を有する弗素ゴムを封口体のゴムに分散させ、
実質的に洗浄剤が電解コンデンサ内部に到達する
距離が遠くなるようにする工夫もあるが、実効が
小さく、かつコスト面での問題もあり実用的でな
い。また、封口体の外面に樹脂を塗布することも
おこなわれているが、製造工程が複雑になるこ
と、製品の全長が長くなるなどの欠点がある。
このように、電解コンデンサは塩素に対し、極
めて弱いので、信頼度の高い電解コンデンサを得
るには、腐食を抑制するための手段が必要とな
る。
〔発明が解決しようとする問題点〕
この発明は、従来のこのような技術背景に対
し、封口体に含まれる塩素あるいは外部から侵入
する塩素による腐食発生を防止し、信頼度の高い
電解コンデンサを得ることにある。
〔問題点を解決するための手段〕
この発明は、陽極電極、陰極電極間にセパレー
タを介在させ、電解液を含浸したコンデンサ素子
を、外装ケース内部に収納し、外装ケース開口部
を封口部材で密閉してなる電解コンデンサにおい
て、前記封口部材にビスマス酸塩とアンチモン酸
とが含有されていることを特徴としている。
〔作用〕
ビスマスの酸は、その詳細な理由は明らかでは
ないが、塩素等の陰イオンを吸着する能力に優れ
る。
一方、アンチモン酸は、陽イオン殊にナトリウ
ムイオンをはじめとするアルカリ金属イオンに対
し選択的に吸着をおこなうことが知られている。
そこで、発明者はこれら２つの化合物の特性に
着目し、双方を混合して存在させることにより、
例えば塩化アルミニウムような形で封口体内に存
在する塩素分に対し、陽イオン、陰イオン双方か
ら選択的に吸着をおこなうことで、塩素イオン捕
捉の効率を高めようとするものである。
また、塩素イオンの捕捉は、ビスマスの酸の形
でおこなわれるものと推定されるが、ビスマス酸
は単体でなく、アルカリ金属との塩の形でしか得
られていない。従つてアンチモン酸との共存によ
り、ビスマス酸塩の陽イオンがアンチモン酸に捕
捉され、ビスマス酸の形で塩素イオンの捕捉が促
進されるものと考えられる。
〔実施例〕
次に、実際の電解コンデンサを製作して腐食の
抑制について調べた結果を示す。
実験は、電解コンデンサの弾性封口体材料に一
定量の塩素イオンを含有させ、さらにこの発明の
ものについては、前述の腐食抑制物質も添加して
弾性封口体を製作し、これを電解コンデンサに装
着して寿命試験をおこない、腐食の発生割合をみ
たものである。
製作した電解コンデンサは、帯状のアルミニウ
ム電極をセパータ紙とともに巻回し、電解液を含
浸し、外装ケースに収納した第１図に示す通常の
構造のもので、定格電圧400V、静電容量4.7μF、
外形寸法は10φ×30mmである。
弾性封口体は、エチレンプロピレンターポリマ
ー（EPT）を用い、材料段階で塩化ナトリウム
を添加し、塩素イオン濃度で300ppmになるよう
に調整した。以下の表に示す比較例は、この組成
で加硫成形したものを弾性封口体として用いた。
また、この発明例のものは、表に示すようなビス
マス酸塩と、アンチモン酸をEPT原材料に対し、
各々1.5wt％の割合でさらに添加し、加硫成形し
たものを弾性封口体として用いた。
そして、この電解コンデンサを110℃で400Vの
電圧を印加して寿命試験をおこない、腐食の発生
割合をみた。この結果を以下の表に示す。
[Industrial Application Field] The present invention relates to improvement of electrolytic capacitors, and particularly to improvement of corrosion resistance properties of electrolytic capacitors. [Prior art] Electrolytic capacitors use a film-forming metal such as aluminum or tantalum as an anode, and an insulating oxide film that serves as a dielectric is formed on the surface of the anode by anodizing treatment, and the oxide film is used as a cathode. A capacitor element is formed by arranging metals of the same type or other metals opposite each other, and winding or stacking them in layers with a separator such as paper or porous plastic interposed between these electrodes. The drawing shows the structure of a general electrolytic capacitor, in which a cylindrical capacitor element 1 is formed by layering aluminum band-shaped electrode foils for both the anode and cathode and a separator, and winding the electrode foils for the anode and cathode. It is housed in a bottom cylindrical outer case 2, and the opening of the outer case 2 is closed with a disc-shaped elastic sealing body 3 made of an elastic material such as various synthetic rubbers or elastic plastics, and the opening end of the outer case 2 is wrapped around the opening. It is tightened and sealed. Note that an internal lead 4 protrudes from the upper end of the capacitor element 1 and is electrically connected to both the anode and cathode electrodes. The internal leads 4 are inserted into through holes 5 provided in the elastic sealing body 33, and external leads 6 for electrical connection with the outside are connected to their tips. In addition to this structure, although not shown, a sealing body having a structure in which a sheet of an elastic member is bonded to a hard insulating plate-like member in place of the elastic sealing body 3 is also generally used. In this electrolytic capacitor, the dielectric is an oxide film formed on the surface of the film-forming metal as the anode, and when the electrolyte comes into contact with this oxide film, it acts as a true cathode and has the function of a capacitor. . Furthermore, the electrolytic solution has the function of acting on the deteriorated portions of this oxide film and repairing the film. This means that an anodic oxidation reaction is always occurring locally at the contact surface between the oxide film and the electrolyte. However, when chlorine ions are present at the site of this anodic oxidation reaction, aluminum combines with chlorine to form aluminum chloride, which is further hydrolyzed to form aluminum hydroxide. The chlorine ions then act as if they were a catalyst, accelerating the corrosion of aluminum, causing an increase in leakage current, an increase in internal pressure, etc., and eventually causing the electrolytic capacitor to lose its functionality due to internal lead breakage, etc. . Therefore, the presence of chlorine must be eliminated as much as possible inside the electrolytic capacitor. However, many additives such as cross-linking agents, cross-linking accelerators, and anti-aging agents are added to elastic sealing bodies made of various synthetic rubbers in order to maintain and improve the sealing function.
The impurities in this may contain chlorine, which may cause corrosion. Conventionally, as a countermeasure to this problem, additives such as those mentioned above are not included. It has been proposed to use urethane rubber, polyoffine-based thermoplastic elastomers, and the like for the sealing bodies of electrolytic capacitors. However,
These sealing bodies are not practical in terms of heat resistance, cost, etc. In addition, electrolytic capacitors are attached to printed circuit boards by soldering, and halogen-based cleaning agents such as trichloroethane are used to clean the board after soldering, so residual cleaning agents may be left behind on the sealing body of the electrolytic capacitor. It may also seep into the interior through the lead extraction area and cause corrosion. As a countermeasure to this, fluororubber, which has strong resistance to halogen-based cleaning agents, is dispersed in the rubber of the sealing body.
Although there is a method of increasing the distance through which the cleaning agent actually reaches the inside of the electrolytic capacitor, it is not practical because it is not effective and there are problems in terms of cost. In addition, coating resin on the outer surface of the sealing body has also been practiced, but this method has drawbacks such as complicating the manufacturing process and increasing the overall length of the product. As described above, electrolytic capacitors are extremely susceptible to chlorine, so in order to obtain highly reliable electrolytic capacitors, means for suppressing corrosion are required. [Problems to be Solved by the Invention] Against this conventional technical background, the present invention provides a highly reliable electrolytic capacitor that prevents corrosion caused by chlorine contained in the sealing body or chlorine that enters from the outside. It's about getting. [Means for Solving the Problems] The present invention involves interposing a separator between an anode electrode and a cathode electrode, storing a capacitor element impregnated with an electrolyte inside an outer case, and sealing the opening of the outer case with a sealing member. The sealed electrolytic capacitor is characterized in that the sealing member contains bismuthate and antimonic acid. [Function] Bismuth acid has an excellent ability to adsorb anions such as chlorine, although the detailed reason is not clear. On the other hand, antimonic acid is known to selectively adsorb cations, particularly alkali metal ions including sodium ions. Therefore, the inventor focused on the characteristics of these two compounds, and by making them exist in a mixture,
For example, by selectively adsorbing both cations and anions of chlorine present in the sealing body in the form of aluminum chloride, the efficiency of trapping chlorine ions is increased. Furthermore, it is presumed that chloride ions are captured in the form of bismuth acid, but bismuth acid is not obtained as a simple substance, but only in the form of a salt with an alkali metal. Therefore, it is considered that by coexistence with antimonic acid, the cations of bismuthate are captured by antimonic acid, and the capture of chloride ions in the form of bismuth acid is promoted. [Example] Next, we will show the results of an investigation into inhibition of corrosion by manufacturing an actual electrolytic capacitor. In the experiment, a certain amount of chlorine ions were added to the elastic sealant material of an electrolytic capacitor, and in the case of the present invention, the above-mentioned corrosion inhibiting substance was also added to produce an elastic sealant, which was then attached to the electrolytic capacitor. A lifespan test was conducted to determine the rate of corrosion occurrence. The fabricated electrolytic capacitor has the usual structure shown in Figure 1, in which a band-shaped aluminum electrode is wound together with separator paper, impregnated with electrolyte, and stored in an external case.The rated voltage is 400V, the capacitance is 4.7μF,
External dimensions are 10φ x 30mm. The elastic sealant was made of ethylene propylene terpolymer (EPT), and sodium chloride was added at the material stage to adjust the chloride ion concentration to 300 ppm. In the comparative examples shown in the table below, a product vulcanized and molded with this composition was used as an elastic sealant.
In addition, in this invention example, bismuthate and antimonic acid as shown in the table are added to the EPT raw material.
Each was further added at a ratio of 1.5 wt%, and the product was vulcanized and used as an elastic sealant. A lifespan test was then performed on this electrolytic capacitor by applying a voltage of 400V at 110°C, and the rate of corrosion was observed. The results are shown in the table below.
以上述べたようにこの発明によれば、電解コン
デンサの封口部材に不純物として含まれる塩素イ
オン、あるいは、基板洗浄剤等などに含まれ、外
部から電解コンデンサに侵入してくる塩素イオン
が、ビスマス酸塩とアンチモン酸により捕捉され
るので、電解コンデンサの塩素による腐食を抑制
することができる。
これにより、電解コンデンサの漏れ電流の増
加、内部リードの断線、封口部の開弁等の致命的
な事故の発生を防止することができ、極めて信頼
度の高い電解コンデンサを得ることができる。
As described above, according to the present invention, chlorine ions contained as impurities in the sealing member of an electrolytic capacitor or chlorine ions contained in substrate cleaning agents and the like and entering the electrolytic capacitor from the outside are removed from bismuth acid. Since it is captured by salt and antimonic acid, corrosion of electrolytic capacitors caused by chlorine can be suppressed. As a result, it is possible to prevent fatal accidents such as an increase in leakage current of the electrolytic capacitor, breakage of internal leads, and opening of the sealing part, and it is possible to obtain an extremely reliable electrolytic capacitor.
図面は、一般的な電解コンデンサの構造をあら
わした断面図である。
１……コンデンサ素子、２……外装ケース、３
……弾性封口体、４……内部リード、５……貫通
孔、６……外部リード。
The drawing is a cross-sectional view showing the structure of a general electrolytic capacitor. 1...Capacitor element, 2...Exterior case, 3
...Elastic sealing body, 4...Internal lead, 5...Through hole, 6...External lead.
Claims (1)
せ、電解液を含浸したコンデンサ素子を、外装ケ
ース内部に収納し、外装ケース開口部を封口部材
で密閉してなる電解コンデンサにおいて、前記封
口部材にビスマス酸塩とアンチモン酸とが含有さ
れていることを特徴とする電解コンデンサ。1. An electrolytic capacitor in which a separator is interposed between an anode electrode and a cathode electrode, a capacitor element impregnated with an electrolyte is housed inside an exterior case, and an opening of the exterior case is sealed with a sealing member, wherein the sealing member is made of bismuth. An electrolytic capacitor characterized by containing an acid salt and antimonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27914984A JPH0240208B2 (en) | 1984-12-29 | 1984-12-29 | DENKAIKONDENSA |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27914984A JPH0240208B2 (en) | 1984-12-29 | 1984-12-29 | DENKAIKONDENSA |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61158135A JPS61158135A (en) | 1986-07-17 |
| JPH0240208B2 true JPH0240208B2 (en) | 1990-09-10 |
Family
ID=17607126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27914984A Expired - Lifetime JPH0240208B2 (en) | 1984-12-29 | 1984-12-29 | DENKAIKONDENSA |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0240208B2 (en) |
-
1984
- 1984-12-29 JP JP27914984A patent/JPH0240208B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61158135A (en) | 1986-07-17 |
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