JP4637374B2 - Electrolytic solution for electrolytic capacitor drive - Google Patents
Electrolytic solution for electrolytic capacitor drive Download PDFInfo
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- JP4637374B2 JP4637374B2 JP2001013359A JP2001013359A JP4637374B2 JP 4637374 B2 JP4637374 B2 JP 4637374B2 JP 2001013359 A JP2001013359 A JP 2001013359A JP 2001013359 A JP2001013359 A JP 2001013359A JP 4637374 B2 JP4637374 B2 JP 4637374B2
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- Prior art keywords
- graft copolymer
- polyacrylic acid
- polyethylene glycol
- glycol
- polypropylene glycol
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Description
【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。
【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。
【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。
【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、前記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溶解量が０．１〜１０．０ｗｔ％であり、前記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２０〜５０％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。
【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。
【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。
【０００７】
【表１】
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、８５℃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１．０ｗｔ％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。
【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。
【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。
【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。[0001]
BACKGROUND 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 particularly relates to an electrolytic solution with improved withstand voltage.
[0002]
[Prior art]
Conventionally, electrolytes for medium- and high-voltage electrolytic capacitors have a higher dibasic acid or its ammonium salt and boric acid or its ammonium dissolved in a solvent mainly composed of ethylene glycol to further improve the withstand voltage of the electrolyte. Therefore, synthetic polymers such as polyethylene glycol, polypropylene glycol, and polyacrylate have been added.
However, although polyethylene glycol or polypropylene glycol shows high solubility in an electrolyte solution containing ethylene glycol as a main solvent, it must be added in a large amount in order 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, but it has very low solubility in an electrolytic solution containing ethylene glycol as a main solvent, and only a small amount can be added. Can not.
[0003]
[Problems to be solved by the invention]
Because of the above problems, there has been a demand for an electrolytic solution that can improve the withstand voltage while suppressing an increase in specific resistance and can also improve the solubility.
[0004]
[Means for Solving the Problems]
The present invention has been found as a result of various studies to solve the above-described problems, and has been found as a solvent mainly composed of ethylene glycol, a higher dibasic acid or an ammonium salt thereof, and boric acid or an ammonium salt thereof. And polyethylene glycol-polyacrylic acid graft copolymer or polypropylene glycol-polyacrylic acid graft copolymer, and the polyethylene glycol-polyacrylic acid graft copolymer or polypropylene glycol-polyacrylic acid graft copolymer it amount of dissolution is 0.1~10.0wt%, the ratio of the number of bonds polyethylene glycol or polypropylene glycol having a side chain with respect to polyacrylic acid backbone of the graft copolymer between 20 and 50% Electrolytic capacitor drive power characterized by It is a liquid.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
By adding the polyethylene glycol-polyacrylic acid graft copolymer and the polypropylene glycol-polyacrylic acid graft copolymer, the withstand voltage is improved while suppressing an increase in specific resistance. The copolymer has a structure in which polyethylene glycol and polypropylene glycol are graft-polymerized with acrylic acid and side chain bonded. In the electrolytic solution, grafted polyethylene glycol and polypropylene glycol contribute to improvement in solubility, and polyacrylate as a main chain contributes to improvement in 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]
【Example】
Examples of the present invention will be specifically described below with reference to Table 1. Ethylene glycol as solvent, azelaic acid and boric acid as solute, ammonia water for pH adjustment, mannitol and orthophosphoric acid as additives, polyethylene glycol-polyacrylic acid graft for the purpose of improving withstand voltage An electrolyte solution to which a copolymer and a polypropylene glycol-polyacrylic acid graft copolymer were added was prepared. As a comparative example, an electrolytic solution to which polyethylene glycol, polypropylene glycol, polyacrylic acid was added instead of the above graft copolymer and a conventional electrolytic solution to which none of these were added were prepared, and a specific resistance at 30 ° C. and 85 Spark generation voltage (withstand voltage of electrolyte) at ℃ was measured.
[0007]
[Table 1]
As is apparent from Table 1, Examples 1 to 4 to which a polyethylene glycol-polyacrylic acid graft copolymer was added and Examples 5 to 8 to which a polypropylene glycol-polyacrylic acid graft copolymer was added were polyethylene glycol. In comparison with Comparative Examples 5 to 8 to which PP was added and Comparative Examples 9 to 12 to which polypropylene glycol was added, the increase rate of the specific resistance at 30 ° C. when the addition amount was increased from 0.1 wt% to 10.0 wt% is Small, the increase in spark voltage of 85 ° C. is large.
That is, when 10.0 wt% of polyethylene glycol-polyacrylic acid graft copolymer is added, the spark voltage rises to 410 V with a specific resistance of 685 Ω · cm, and when 10.0 wt% of polypropylene glycol-polyacrylic acid graft copolymer is added, The spark voltage rises to 400 V at a specific resistance of 680 Ω · cm.
Next, although the result of having examined about addition of polyacrylic acid is shown in comparative examples 13 and 14, it was not able to be dissolved completely with the addition amount of 1.0 wt%.
Moreover, when the addition amount of the polyethylene glycol-polyacrylic acid graft copolymer or the polypropylene glycol-polyacrylic acid graft copolymer is less than 0.10 wt%, the effect of improving the withstand voltage is exhibited as shown in Comparative Examples 1 and 3. 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 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 exceeds 50%, the withstand voltage decreases, which is not suitable.
[0009]
In addition to the above azelaic acid, higher dibasic acids include sebacic acid (Example 9), 1,6-decanedicarboxylic acid (Example 10), 5,6-decanedicarboxylic acid, 7-vinylhexadecene. Examples include -1,16-dicarboxylic acid.
[0010]
As salts of higher dibasic acids, in addition to ammonium salts, primary amine salts such as methylamine, ethylamine and t-butylamine, secondary amine salts such as dimethylamine, ethylmethylamine and diethylamine, trimethylamine and diethylmethyl Examples thereof include tertiary amine salts such as amine, ethyldimethylamine and triethylamine, and quaternary ammonium salts such as tetramethylammonium, triethylmethylammonium and tetraethylammonium.
[0011]
【The invention's effect】
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, an increase in specific resistance is suppressed, The voltage can be improved.
Claims (1)
前記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溶解量が０．１〜１０．０ｗｔ％であり、
前記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２０〜５０％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。A higher dibasic acid or an ammonium salt thereof, boric acid or an ammonium salt thereof, and a polyethylene glycol-polyacrylic acid graft copolymer or a polypropylene glycol-polyacrylic acid graft copolymer in an ethylene glycol-based solvent. Dissolve,
The amount of the polyethylene glycol-polyacrylic acid graft copolymer or polypropylene glycol-polyacrylic acid graft copolymer is 0.1 to 10.0 wt%,
Driving electrolyte for an electrolytic capacitor characterized in that the ratio of the number of bonds polyethylene glycol or polypropylene glycol having a side chain with respect to polyacrylic acid backbone of the graft copolymer between 20 and 50%.
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 |
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| 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 JP2002217067A (en) | 2002-08-02 |
| JP4637374B2 true JP4637374B2 (en) | 2011-02-23 |
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| 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 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005303062A (en) | 2004-04-13 | 2005-10-27 | Rubycon Corp | Electrolytic capacitor and electrolytic solution for driving the same |
| JP4653593B2 (en) * | 2005-08-22 | 2011-03-16 | ニチコン株式会社 | Electrolytic solution for electrolytic capacitor drive |
| WO2011099261A1 (en) | 2010-02-15 | 2011-08-18 | 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 |
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| Publication number | Publication date |
|---|---|
| JP2002217067A (en) | 2002-08-02 |
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