JP2002217067A - Electrolyte for driving electrolytic capacitor - Google Patents
Electrolyte for driving electrolytic capacitorInfo
- Publication number
- JP2002217067A JP2002217067A JP2001013359A JP2001013359A JP2002217067A JP 2002217067 A JP2002217067 A JP 2002217067A JP 2001013359 A JP2001013359 A JP 2001013359A JP 2001013359 A JP2001013359 A JP 2001013359A JP 2002217067 A JP2002217067 A JP 2002217067A
- Authority
- JP
- Japan
- Prior art keywords
- graft copolymer
- polyacrylic acid
- electrolytic capacitor
- polypropylene glycol
- polyethylene glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電解コンデンサの
駆動用電解液(以下、電解液と称す)の改良に関するもの
であり、特に耐電圧を向上させた電解液に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in an electrolytic solution for driving an electrolytic capacitor (hereinafter referred to as an electrolytic solution), and more particularly to an electrolytic solution having an improved withstand voltage.
【０００２】[0002]
【従来の技術】従来、中高圧用電解コンデンサの電解液
は、エチレングリコールを主成分とする溶媒に、高級二
塩基酸またはそのアンモニウム塩と、ホウ酸またはその
アンモニウムとを溶解し、さらに電解液の耐電圧を向上
させるためポリエチレングリコールやポリプロピレング
リコール、ポリアクリレート等の合成高分子を添加して
いた。しかし、ポリエチレングリコールやポリプロピレ
ングリコールはエチレングリコールを主溶媒とする電解
液に対して高い溶解性を示すが、耐電圧を上昇させるた
めには多量に加えなければならず、比抵抗が上昇する。
また、ポリアクリレートは高電導度を示すため、比抵抗
を上昇させずに耐電圧を向上できるが、エチレングリコ
ールを主溶媒とする電解液に対する溶解性が非常に低
く、ごく少量しか添加することができない。2. Description of the Related Art Conventionally, an electrolytic solution for a medium-to-high pressure electrolytic capacitor has been prepared by dissolving a higher dibasic acid or its ammonium salt and boric acid or its ammonium in a solvent containing ethylene glycol as a main component. In order to improve the withstand voltage, synthetic polymers such as polyethylene glycol, polypropylene glycol and polyacrylate have been added. However, polyethylene glycol and polypropylene glycol exhibit high solubility in an electrolyte containing ethylene glycol as a main solvent, but must be added in a large amount to increase the withstand voltage, and the specific resistance increases.
In addition, since polyacrylate exhibits high electrical conductivity, it can improve the withstand voltage without increasing the specific resistance.However, the solubility in an electrolytic solution containing ethylene glycol as a main solvent is very low, and only a small amount can be added. Can not.
【０００３】[0003]
【発明が解決しようとする課題】上記のような問題があ
ったため、比抵抗の上昇を抑制しつつ、耐電圧の向上を
図ることができ、かつ、溶解性の向上も可能な電解液が
求められていた。SUMMARY OF THE INVENTION In view of the above-mentioned problems, there is a need for an electrolytic solution that can improve the withstand voltage while suppressing an increase in the specific resistance and can also improve the solubility. Had been.
【０００４】[0004]
【課題を解決するための手段】本発明は、上記の課題を
解決するために種々検討した結果、見出されたものであ
り、エチレングリコールを主成分とする溶媒に高級二塩
基酸またはそのアンモニウム塩と、ホウ酸またはそのア
ンモニウム塩と、ポリエチレングリコール−ポリアクリ
ル酸グラフト共重合体またはポリプロピレングリコール
−ポリアクリル酸グラフト共重合体とを溶解したことを
特徴とする電解コンデンサの電解液である。また、上記
のポリエチレングリコール−ポリアクリル酸グラフト共
重合体またはポリプロピレングリコール−ポリアクリル
酸グラフト共重合体が０．１〜１０．０ｗｔ％であるこ
とを特徴とする電解コンデンサの駆動用電解液である。
さらに、上記のグラフト共重合体における主鎖のポリア
クリル酸に対する側鎖のポリエチレングリコールまたは
ポリプロピレングリコールの結合数の割合が２０〜１０
０％であることを特徴とする電解コンデンサの駆動用電
解液である。DISCLOSURE OF THE INVENTION The present invention has been found as a result of various studies to solve the above-mentioned problems, and a higher dibasic acid or its ammonium salt has been added to a solvent containing ethylene glycol as a main component. An electrolytic solution for an electrolytic capacitor, wherein a salt, boric acid or its ammonium salt, and a polyethylene glycol-polyacrylic acid graft copolymer or a polypropylene glycol-polyacrylic acid graft copolymer are dissolved. In addition, the above-mentioned polyethylene glycol-polyacrylic acid graft copolymer or polypropylene glycol-polyacrylic acid graft copolymer is 0.1 to 10.0 wt%, and is an electrolytic solution for driving an electrolytic capacitor. .
Further, the ratio of the number of bonds of the side chain polyethylene glycol or polypropylene glycol to the main chain polyacrylic acid in the above graft copolymer is 20 to 10%.
0% is an electrolytic solution for driving an electrolytic capacitor.
【０００５】[0005]
【発明の実施の形態】ポリエチレングリコール−ポリア
クリル酸グラフト共重合体、ポリプロピレングリコール
−ポリアクリル酸グラフト共重合体添加により、比抵抗
の上昇を抑制しつつ、耐電圧を向上させる。上記共重合
体は、アクリル酸にポリエチレングリコール、ポリプロ
ピレングリコールがグラフト重合し、側鎖結合した構造
を有する。電解液中においてはグラフト化したポリエチ
レングリコール、ポリプロピレングリコールが溶解性向
上に寄与し、主鎖となるポリアクリレートが耐電圧向上
に寄与する。また、上記共重合体は三次元網目構造を有
するため、イオンの移動を妨げずに耐電圧の向上が可能
である。BEST MODE FOR CARRYING OUT THE INVENTION By adding a polyethylene glycol-polyacrylic acid graft copolymer or a polypropylene glycol-polyacrylic acid graft copolymer, the withstand voltage is improved while suppressing an increase in specific resistance. The above copolymer has a structure in which polyethylene glycol and polypropylene glycol are graft-polymerized to acrylic acid and are bonded to a side chain. In the electrolyte, the grafted polyethylene glycol and polypropylene glycol contribute to the improvement in solubility, and the polyacrylate serving as the main chain contributes to the improvement in the withstand voltage. Further, since the copolymer has a three-dimensional network structure, the withstand voltage can be improved without hindering the movement of ions.
【０００６】[0006]
【実施例】以下、本発明の実施例を表１により具体的に
説明する。溶媒にはエチレングリコール、溶質にはアゼ
ライン酸とホウ酸、ｐＨ調整用のアンモニア水を用い、
添加剤としてマンニトール、オルトリン酸を用い、他
に、耐電圧向上を目的としてポリエチレングリコール−
ポリアクリル酸グラフト共重合体、ポリプロピレングリ
コール−ポリアクリル酸グラフト共重合体を添加した電
解液を調合した。また、比較例として、上記のグラフト
共重合体の代わりにポリエチレングリコール、ポリプロ
ピレングリコール、ポリアクリル酸を添加した電解液と
これらを全く添加しない従来の電解液を調合し、３０℃
における比抵抗および８５℃における火花発生電圧（電
解液の耐電圧）を測定した。EXAMPLES Examples of the present invention will be specifically described below with reference to Table 1. Use ethylene glycol for the solvent, azelaic acid and boric acid for the solute, ammonia water for pH adjustment,
Mannitol and orthophosphoric acid were used as additives, and polyethylene glycol-
An electrolytic solution to which a polyacrylic acid graft copolymer and a polypropylene glycol-polyacrylic acid graft copolymer were added was prepared. Further, as a comparative example, an electrolyte solution in which polyethylene glycol, polypropylene glycol and polyacrylic acid were added in place of the above graft copolymer and a conventional electrolyte solution in which these were not added at all were prepared.
And the spark generation voltage at 85 ° C. (withstand voltage of the electrolytic solution) were measured.
【０００７】[0007]
【表１】 [Table 1]
【０００８】表１より明らかなように、ポリエチレング
リコール−ポリアクリル酸グラフト共重合体を添加した
実施例１〜４、およびポリプロピレングリコール−ポリ
アクリル酸グラフト共重合体を添加した実施例５〜８
は、ポリエチレングリコールを添加した比較例５〜８、
およびポリプロピレングリコールを添加した比較例９〜
１２と比べて、添加量が０．１ｗｔ％から１０．０ｗｔ
％に増加した時の３０℃の比抵抗の増加率は小さく、８
５℃の火花電圧の上昇が大きくなっている。すなわち、
ポリエチレングリコール−ポリアクリル酸グラフト共重
合体１０．０ｗｔ％添加では、比抵抗６８５Ω・ｃｍで
火花電圧は４１０Ｖまで上昇し、ポリプロピレングリコ
ール−ポリアクリル酸グラフト共重合体１０．０ｗｔ％
添加では、比抵抗６８０Ω・ｃｍで火花電圧が４００Ｖ
まで上昇する。次に、ポリアクリル酸の添加について検
討した結果を比較例１３、１４に示すが、添加量１．０
ｗｔ％では完全に溶解させることができなかった。ま
た、ポリエチレングリコール−ポリアクリル酸グラフト
共重合体、またはポリプロピレングリコール−ポリアク
リル酸グラフト共重合体の添加量が０．１０ｗｔ％未満
では、比較例１、３に示したとおり耐電圧向上の効果が
なく、１０．０ｗｔ％を超える場合は十分に溶解せず析
出するため不適である。また、上記のグラフト共重合体
における主鎖のポリアクリル酸に対する側鎖のポリエチ
レングリコールまたはポリプロピレングリコールの結合
数の割合は２０〜１００％の範囲内にあることが望まし
い。２０％未満では溶解性向上の効果がなく、５０％を
超えると耐電圧が低下するので不適である。As apparent from Table 1, Examples 1 to 4 in which a polyethylene glycol-polyacrylic acid graft copolymer was added, and Examples 5 to 8 in which a polypropylene glycol-polyacrylic acid graft copolymer was added.
Are Comparative Examples 5 to 8 to which polyethylene glycol was added,
And Comparative Examples 9 and 10 in which polypropylene glycol was added
12 compared with 0.1 wt% to 10.0 wt%
% Increase in resistivity at 30 ° C. is small,
The increase in the spark voltage at 5 ° C. is large. That is,
When the polyethylene glycol-polyacrylic acid graft copolymer was added at 10.0 wt%, the spark voltage increased to 410 V at a specific resistance of 685 Ω · cm, and the polypropylene glycol-polyacrylic acid graft copolymer was added at 10.0 wt%.
In addition, the specific resistance is 680Ω · cm and the spark voltage is 400V
To rise. Next, Comparative Examples 13 and 14 show the results of studies on the addition of polyacrylic acid.
At wt%, it could not be completely dissolved. When the amount of the polyethylene glycol-polyacrylic acid graft copolymer or the amount of the polypropylene glycol-polyacrylic acid graft copolymer added is less than 0.10 wt%, the effect of improving the withstand voltage as shown in Comparative Examples 1 and 3 is not obtained. On the other hand, if it exceeds 10.0 wt%, it is not suitable because it does not dissolve sufficiently and precipitates. Further, the ratio of the number of bonds of the side chain polyethylene glycol or polypropylene glycol to the main chain polyacrylic acid in the above graft copolymer is preferably in the range of 20 to 100%. If it is less than 20%, there is no effect of improving the solubility, and if it is more than 50%, the withstand voltage is lowered, so it is not suitable.
【０００９】さらに、高級二塩基酸としては、上記のア
ゼライン酸の他に、セバシン酸（実施例９）、１，６−
デカンジカルボン酸（実施例１０）、５，６−デカンジ
カルボン酸、７−ビニルヘキサデセン−１，１６−ジカ
ルボン酸等を例示することができる。Further, as the higher dibasic acid, besides the above-mentioned azelaic acid, sebacic acid (Example 9), 1,6-
Decanedicarboxylic acid (Example 10), 5,6-decanedicarboxylic acid, 7-vinylhexadecene-1,16-dicarboxylic acid and the like can be exemplified.
【００１０】また、高級二塩基酸の塩としては、アンモ
ニウム塩の他、メチルアミン、エチルアミン、ｔ−ブチ
ルアミン等の１級アミン塩、ジメチルアミン、エチルメ
チルアミン、ジエチルアミン等の２級アミン塩、トリメ
チルアミン、ジエチルメチルアミン、エチルジメチルア
ミン、トリエチルアミン等の３級アミン塩、テトラメチ
ルアンモニウム、トリエチルメチルアンモニウム、テト
ラエチルアンモニウム等の４級アンモニウム塩等を例示
することができる。The salts of higher dibasic acids include ammonium salts, primary amine salts such as methylamine, ethylamine and t-butylamine, secondary amine salts such as dimethylamine, ethylmethylamine and diethylamine, and trimethylamine. And tertiary amine salts such as diethylmethylamine, ethyldimethylamine and triethylamine, and quaternary ammonium salts such as tetramethylammonium, triethylmethylammonium and tetraethylammonium.
【００１１】[0011]
【発明の効果】上述したとおり、ポリエチレングリコー
ル−ポリアクリル酸グラフト共重合体、またはポリプロ
ピレングリコール−ポリアクリル酸グラフト共重合体を
エチレングリコールを主溶媒とする電解液に添加するこ
とにより、比抵抗の上昇を抑え、耐電圧の改善を図るこ
とができる。As described above, by adding a polyethylene glycol-polyacrylic acid graft copolymer or a polypropylene glycol-polyacrylic acid graft copolymer to an electrolyte containing ethylene glycol as a main solvent, the specific resistance can be reduced. The rise can be suppressed and the withstand voltage can be improved.
Claims (3)
に高級二塩基酸またはそのアンモニウム塩と、ホウ酸ま
たはそのアンモニウム塩と、ポリエチレングリコール−
ポリアクリル酸グラフト共重合体またはポリプロピレン
グリコール−ポリアクリル酸グラフト共重合体とを溶解
したことを特徴とする電解コンデンサの駆動用電解液。1. A solvent containing ethylene glycol as a main component, a higher dibasic acid or its ammonium salt, boric acid or its ammonium salt, and polyethylene glycol-
An electrolytic solution for driving an electrolytic capacitor, comprising a polyacrylic acid graft copolymer or a polypropylene glycol-polyacrylic acid graft copolymer dissolved therein.
クリル酸グラフト共重合体またはポリプロピレングリコ
ール−ポリアクリル酸グラフト共重合体が０．１〜１
０．０ｗｔ％であることを特徴とする請求項１記載の電
解コンデンサの駆動用電解液。2. The method according to claim 1, wherein the polyethylene glycol-polyacrylic acid graft copolymer or the polypropylene glycol-polyacrylic acid graft copolymer is 0.1 to 1%.
2. The electrolytic solution for driving an electrolytic capacitor according to claim 1, wherein the amount is 0.0 wt%.
ポリアクリル酸に対する側鎖のポリエチレングリコール
またはポリプロピレングリコールの結合数の割合が２０
〜１００％であることを特徴とする請求項１記載の電解
コンデンサの駆動用電解液。3. The graft copolymer according to claim 1, wherein the ratio of the number of the side chain polyethylene glycol or polypropylene glycol bonded to the main chain polyacrylic acid is 20.
2. The electrolytic solution for driving an electrolytic capacitor according to claim 1, wherein the amount is from 100% to 100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001013359A JP4637374B2 (en) | 2001-01-22 | 2001-01-22 | Electrolytic solution for electrolytic capacitor drive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001013359A JP4637374B2 (en) | 2001-01-22 | 2001-01-22 | Electrolytic solution for electrolytic capacitor drive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002217067A true JP2002217067A (en) | 2002-08-02 |
| JP4637374B2 JP4637374B2 (en) | 2011-02-23 |
Family
ID=18880226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001013359A Expired - Fee Related JP4637374B2 (en) | 2001-01-22 | 2001-01-22 | Electrolytic solution for electrolytic capacitor drive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4637374B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007059478A (en) * | 2005-08-22 | 2007-03-08 | Nichicon Corp | Electrolyte for driving electrolytic capacitor |
| US7667953B2 (en) | 2004-04-13 | 2010-02-23 | Rubycon Corporation | Electrolytic capacitor |
| JPWO2011099261A1 (en) * | 2010-02-15 | 2013-06-13 | パナソニック株式会社 | Electrolytic capacitor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04337618A (en) * | 1991-05-14 | 1992-11-25 | Mitsubishi Petrochem Co Ltd | Solid state electrolyte capacitor and manufacture thereof |
| JP2000058396A (en) * | 1998-08-10 | 2000-02-25 | Nichicon Corp | Electrolytic solution for driving electrolytic capacitor |
-
2001
- 2001-01-22 JP JP2001013359A patent/JP4637374B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04337618A (en) * | 1991-05-14 | 1992-11-25 | Mitsubishi Petrochem Co Ltd | Solid state electrolyte capacitor and manufacture thereof |
| JP2000058396A (en) * | 1998-08-10 | 2000-02-25 | Nichicon Corp | Electrolytic solution for driving electrolytic capacitor |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7667953B2 (en) | 2004-04-13 | 2010-02-23 | Rubycon Corporation | Electrolytic capacitor |
| JP2007059478A (en) * | 2005-08-22 | 2007-03-08 | Nichicon Corp | Electrolyte for driving electrolytic capacitor |
| JP4653593B2 (en) * | 2005-08-22 | 2011-03-16 | ニチコン株式会社 | Electrolytic solution for electrolytic capacitor drive |
| JPWO2011099261A1 (en) * | 2010-02-15 | 2013-06-13 | パナソニック株式会社 | Electrolytic capacitor |
| JP5810292B2 (en) * | 2010-02-15 | 2015-11-11 | パナソニックＩｐマネジメント株式会社 | Electrolytic capacitor |
| US9208954B2 (en) | 2010-02-15 | 2015-12-08 | Panasonic Intellectual Property Management Co., Ltd. | Electrolytic capacitor |
| US9595396B2 (en) | 2010-02-15 | 2017-03-14 | Panasonic Intellectual Property Management Co., Ltd. | Electrolytic capacitor and manufacturing method therefor |
| US9966200B2 (en) | 2010-02-15 | 2018-05-08 | Panasonic Intellectual Property Management Co., Ltd. | Electrolytic capacitor and manufacturing method therefor |
| US10559432B2 (en) | 2010-02-15 | 2020-02-11 | Panasonic Intellectual Property Management Co., Ltd. | Electrolytic capacitor and manufacturing method therefor |
| US10679800B2 (en) | 2010-02-15 | 2020-06-09 | Panasonic Intellectual Property Management Co., Ltd. | Electrolytic capacitor and manufacturing method therefor |
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|---|---|
| JP4637374B2 (en) | 2011-02-23 |
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