JP3705864B2 - Electrolytic solution for electrolytic capacitor drive - Google Patents
Electrolytic solution for electrolytic capacitor drive Download PDFInfo
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- JP3705864B2 JP3705864B2 JP11471996A JP11471996A JP3705864B2 JP 3705864 B2 JP3705864 B2 JP 3705864B2 JP 11471996 A JP11471996 A JP 11471996A JP 11471996 A JP11471996 A JP 11471996A JP 3705864 B2 JP3705864 B2 JP 3705864B2
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- JP
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- Prior art keywords
- polyvinyl alcohol
- electrolytic
- electrolytic solution
- dissolved
- polyvinyl acetate
- 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.)
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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、単に電解液と称す）の改良に関するものであり、特に耐電圧を改善した電解液に関するものである。
【０００２】
【従来の技術】
従来、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、及びホウ酸またはホウ酸アンモニウムを溶解した電解コンデンサ用電解液に、ポリビニルアルコールを添加すると、ホウ酸や、添加剤として用いたリン酸等とエステル化合物を形成しその構造的な特性により電解液の耐電圧が向上するとされている。
【０００３】
【発明が解決しようとする課題】
ポリビニルアルコールはエチレングリコールを主成分とする溶媒に対して溶解性が非常に乏しく、同重合度のポリビニルアルコールの場合、その溶解性はケン化度、及びポリ酢酸ビニルとポリビニルアルコールの分布状態にわずかに依存している。しかし一直鎖上にポリ酢酸ビニルとポリビニルアルコールが分布している部分ケン化ポリビニルアルコールは、溶媒や溶解状態によって、溶解度が低下することがあり、また溶解しても高分子の利点である高耐電圧性を十分に生かしきれないという欠点をもっている。
本発明は上記の欠点を改善し、電解液に対するポリビニルアルコールの溶解性を向上させ、ポリビニルアルコールの高分子であるが故の利点、すなわち高耐電圧性を充分活用することができる電解コンデンサ用電解液を提供するものである。
【０００４】
【課題を解決する手段】
本発明は上記の課題を解決するために各種検討した結果、見い出されたものである。本発明者はグラフト化ポリ酢酸ビニル−ポリビニルアルコール共重合体がその構造上の特性より電解液に対する溶解性が高いことに着目し、その特性を電解液に適用することにより課題の解決を図った。すなわち、本発明は、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、及びホウ酸またはホウ酸アンモニウムを溶解し、グラフト化ポリ酢酸ビニル−ポリビニルアルコール共重合体を０．１〜１．０重量％溶解し、耐電圧性を向上させた電解コンデンサ用電解液である。
【０００５】
【発明の実施の形態】
部分ケン化ポリビニルアルコールの場合、一直鎖上にポリ酢酸ビニルとポリビニルアルコールが分布した構造を示すが、エチレングリコールを主成分とする溶媒中では、部分ケン化ポリビニルアルコール上に分布する水酸基同士がミセル状に集合し、静電的な結合により溶解性が低下する。また、溶解しても糸屑状に絡み合った状態で電解液に存在するため、高分子の利点が十分生かされない場合がある。ポリビニルアルコールを保護コロイドに用いた酢酸ビニルのグラフト重合によって得られるグラフト化ポリ酢酸ビニル−ポリビニルアルコール共重合体はポリビニルアルコールの直鎖からポリ酢酸ビニルが枝分かれした、魚の骨のような構造を示す。その枝分かれしたポリ酢酸ビニルがポリビニルアルコールの水酸基の静電的結合を抑制し、そのため直鎖が絡み合わずに電解液中に存在するため高分子である特性が生かされ、火花電圧を上昇させることが可能となった。
【０００６】
【実施例】
以下、実施例の具体的内容について説明する。溶媒にはエチレングリコールを、溶質には７−ビニル−９−ヘキサデセン−１，１６ジカルボン酸またはそのアンモニウム塩を用い、添加剤としてはマンニトール、オルトリン酸、グラフト化ポリ酢酸ビニル−ポリビニルアルコール共重合体を、ｐＨ調整剤としてアンモニア水を用いた。表１に実施例、比較例、従来例の組成および測定結果を示す。但し、比抵抗は３０℃、火花発生電圧は８５℃において測定した。また比較例に用いた部分ケン化ポリビニルアルコールと、グラフト化ポリ酢酸ビニル−ポリビニルアルコール共重合体の重合度、及びアセチル基と水酸基の比率はほぼ等しいものを使用した。
従来例に比べ比較例２の部分ケン化ポリビニルアルコールを０．５％添加したものは比抵抗は１０Ω・ｃｍ程の上昇がみられたが、火花発生電圧は３０Ｖ上昇した。実施例２のグラフト化ポリ酢酸ビニル−ポリビニルアルコール共重合体を添加したものでは部分ケン化ポリビニルアルコールを用いたときとほぼ同じ位の比抵抗であったが、火花電圧はさらに１５Ｖ高く、４３５Ｖにまで達した。
ここで、グラフト化ポリ酢酸ビニル−ポリビニルアルコール共重合体の添加量は０．１重量％未満では上記の効果は得られず、１．０重量％を超えると、溶解性の低下伴うため不適である。
【０００７】
【表１】
【発明の効果】
上述した通り、グラフト化ポリ酢酸ビニル−ポリビニルアルコールを用いることで、溶媒に対する溶解性を高めることができ、かつ火花発生電圧を向上させ得る電解コンデンサ用電解液を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an improvement in an electrolytic solution for driving an electrolytic capacitor (hereinafter simply referred to as an electrolytic solution), and particularly relates to an electrolytic solution with improved withstand voltage.
[0002]
[Prior art]
Conventionally, when polyvinyl alcohol is added to an electrolytic solution for electrolytic capacitors in which a higher dibasic acid or an ammonium salt thereof and boric acid or ammonium borate are dissolved in a solvent containing ethylene glycol as a main component, boric acid or an additive It is said that the withstand voltage of the electrolytic solution is improved by forming an ester compound with the phosphoric acid used and the structural characteristics thereof.
[0003]
[Problems to be solved by the invention]
Polyvinyl alcohol is very poorly soluble in solvents based on ethylene glycol. In the case of polyvinyl alcohol having the same degree of polymerization, the solubility is slightly affected by the degree of saponification and the distribution of polyvinyl acetate and polyvinyl alcohol. Depends on. However, partially saponified polyvinyl alcohol, in which polyvinyl acetate and polyvinyl alcohol are distributed on a straight chain, may have reduced solubility depending on the solvent and dissolved state. It has the disadvantage of not being able to make full use of voltage characteristics.
The present invention improves the above-mentioned drawbacks, improves the solubility of polyvinyl alcohol in the electrolytic solution, and makes it possible to fully utilize the advantages of being a polymer of polyvinyl alcohol, that is, high voltage resistance. A liquid is provided.
[0004]
[Means for solving the problems]
The present invention has been found as a result of various studies to solve the above-described problems. The present inventor paid attention to the fact that the grafted polyvinyl acetate-polyvinyl alcohol copolymer has higher solubility in the electrolytic solution than its structural characteristics, and attempted to solve the problem by applying the characteristics to the electrolytic solution. . That is, in the present invention, a higher dibasic acid or an ammonium salt thereof and boric acid or ammonium borate are dissolved in a solvent containing ethylene glycol as a main component, and a grafted polyvinyl acetate-polyvinyl alcohol copolymer is added in an amount of 0.1. It is an electrolytic solution for electrolytic capacitors which is dissolved by 1.0% by weight and has improved withstand voltage.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In the case of partially saponified polyvinyl alcohol, it shows a structure in which polyvinyl acetate and polyvinyl alcohol are distributed on a straight chain, but in a solvent mainly composed of ethylene glycol, the hydroxyl groups distributed on partially saponified polyvinyl alcohol are micelles. As a result, the solubility decreases due to electrostatic bonding. Moreover, since it exists in electrolyte solution in the state entangled with the lint-like shape even if it melt | dissolves, the advantage of a polymer | macromolecule may not fully be utilized. A grafted polyvinyl acetate-polyvinyl alcohol copolymer obtained by graft polymerization of vinyl acetate using polyvinyl alcohol as a protective colloid has a structure like a fish bone in which polyvinyl acetate is branched from a straight chain of polyvinyl alcohol. The branched polyvinyl acetate suppresses the electrostatic bonding of the hydroxyl groups of polyvinyl alcohol, so that the straight chain is not entangled in the electrolyte and the polymer property is utilized to increase the spark voltage. Became possible.
[0006]
【Example】
Hereinafter, specific contents of the embodiment will be described. Ethylene glycol is used as the solvent, 7-vinyl-9-hexadecene-1,16 dicarboxylic acid or its ammonium salt is used as the solute, mannitol, orthophosphoric acid, grafted polyvinyl acetate-polyvinyl alcohol copolymer as additives. Ammonia water was used as a pH adjuster. Table 1 shows compositions and measurement results of Examples, Comparative Examples, and Conventional Examples. However, the specific resistance was measured at 30 ° C., and the spark generation voltage was measured at 85 ° C. The partially saponified polyvinyl alcohol used in the comparative example and the grafted polyvinyl acetate-polyvinyl alcohol copolymer had a polymerization degree and a ratio of acetyl groups to hydroxyl groups substantially equal.
As compared with the conventional example, the specific resistance of 0.5% of the partially saponified polyvinyl alcohol of Comparative Example 2 increased by about 10 Ω · cm, but the spark generation voltage increased by 30V. When the grafted polyvinyl acetate-polyvinyl alcohol copolymer of Example 2 was added, the specific resistance was almost the same as when partially saponified polyvinyl alcohol was used, but the spark voltage was further increased by 15V to 435V. Reached.
Here, if the addition amount of the grafted polyvinyl acetate-polyvinyl alcohol copolymer is less than 0.1% by weight, the above effect cannot be obtained, and if it exceeds 1.0% by weight, the solubility is lowered, which is not suitable. is there.
[0007]
[Table 1]
【The invention's effect】
As described above, by using grafted polyvinyl acetate-polyvinyl alcohol, it is possible to provide an electrolytic solution for an electrolytic capacitor that can improve solubility in a solvent and can improve a spark generation voltage.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11471996A JP3705864B2 (en) | 1996-05-09 | 1996-05-09 | Electrolytic solution for electrolytic capacitor drive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11471996A JP3705864B2 (en) | 1996-05-09 | 1996-05-09 | Electrolytic solution for electrolytic capacitor drive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09298132A JPH09298132A (en) | 1997-11-18 |
| JP3705864B2 true JP3705864B2 (en) | 2005-10-12 |
Family
ID=14644915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11471996A Expired - Fee Related JP3705864B2 (en) | 1996-05-09 | 1996-05-09 | Electrolytic solution for electrolytic capacitor drive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3705864B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4481516B2 (en) * | 2001-03-16 | 2010-06-16 | ニチコン株式会社 | Electrolytic solution for driving electrolytic capacitors |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0722087B2 (en) * | 1988-08-12 | 1995-03-08 | 日立エーアイシー株式会社 | Electrolytic solution for electrolytic capacitors |
| JPH0690992B2 (en) * | 1988-09-01 | 1994-11-14 | 日立エーアイシー株式会社 | Electrolytic solution for electrolytic capacitors |
| JPH0722088B2 (en) * | 1988-09-22 | 1995-03-08 | 日立エーアイシー株式会社 | Electrolytic solution for electrolytic capacitors |
| JPH0513275A (en) * | 1991-07-04 | 1993-01-22 | Matsushita Electric Ind Co Ltd | Electrolytic solution for driving electrolytic capacitors |
| JPH05182870A (en) * | 1991-12-27 | 1993-07-23 | Matsushita Electric Ind Co Ltd | Aluminum electrolytic capacitor |
| JPH0745482A (en) * | 1993-07-29 | 1995-02-14 | Sanyo Chem Ind Ltd | Electrolyte for driving electrolytic capacitor |
| JP3078171B2 (en) * | 1994-03-14 | 2000-08-21 | ニチコン株式会社 | Electrolyte for driving electrolytic capacitors |
-
1996
- 1996-05-09 JP JP11471996A patent/JP3705864B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09298132A (en) | 1997-11-18 |
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