JPH0611021B2 - Electrolytic solution for electrolytic capacitors - Google Patents
Electrolytic solution for electrolytic capacitorsInfo
- Publication number
- JPH0611021B2 JPH0611021B2 JP28698385A JP28698385A JPH0611021B2 JP H0611021 B2 JPH0611021 B2 JP H0611021B2 JP 28698385 A JP28698385 A JP 28698385A JP 28698385 A JP28698385 A JP 28698385A JP H0611021 B2 JPH0611021 B2 JP H0611021B2
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic
- electrolytic solution
- acid
- solvent
- quaternary ammonium
- 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
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、電解コンデンサ用電解液に関するものであ
る。Description: TECHNICAL FIELD The present invention relates to an electrolytic solution for an electrolytic capacitor.
本発明によれば、電導度の高い優れた電解コンデンサ用
電解液（以下単に電解液と称することがある）が得られ
る。According to the present invention, an excellent electrolytic solution for electrolytic capacitors having high electrical conductivity (hereinafter sometimes simply referred to as electrolytic solution) can be obtained.
従来の技術 電解コンデンサ用電解液としてエチレングリコール溶媒
に、溶質として硼酸やアジピン酸のアンモニウム塩を溶
解させたものがよく知られている。また、低温特性の優
れた電解液としては、更に凝固点の低いN,N−ジメチル
ホルムアミドやγ−ブチロラクトン等の溶媒に、アジピ
ン酸やマレイン酸のアミン塩を溶解させたものが知られ
ている。2. Description of the Related Art As an electrolytic solution for electrolytic capacitors, a solution in which an ammonium salt of boric acid or adipic acid is dissolved as a solute in an ethylene glycol solvent is well known. In addition, as an electrolytic solution having excellent low-temperature characteristics, it is known that an amine salt of adipic acid or maleic acid is dissolved in a solvent such as N, N-dimethylformamide or γ-butyrolactone having a lower freezing point.
発明が解決しようとする問題点 しかしながら、電解コンデンサの低インピーダンス化に
伴い更に電導度の高い電解液が望まれており、特開昭５
９−７８５２２には、二塩基性カルボン酸HOOC-(CH2)n-
COOH（４ｎ８）の四級アンモニウム塩を２〜１０重
量％の水を含有したアミド溶媒に溶解させた電導度の高
い電解液が開示されているが、十分とはいえない。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention However, as the impedance of an electrolytic capacitor is lowered, an electrolytic solution having higher conductivity is desired.
The 9-78522, dibasic carboxylic acid HOOC- (CH 2) n -
An electrolytic solution having a high electric conductivity in which a quaternary ammonium salt of COOH (4n8) is dissolved in an amide solvent containing 2 to 10% by weight of water is disclosed, but it cannot be said to be sufficient.
問題点を解決するための手段 本発明者等は、電導度の更に高い新規な電解液を見い出
すべく鋭意検討を行ない、脂環式カルボン酸の四級アン
モニウム塩が、従来のアジピン酸等の直鎖の二塩基性カ
ルボン酸の四級アンモニウム塩より高い電導度を示すこ
とを見い出し本発明を完成した。Means for Solving the Problems The inventors of the present invention have conducted diligent studies to find a novel electrolytic solution having higher conductivity, and found that the quaternary ammonium salt of alicyclic carboxylic acid is a direct salt of adipic acid or the like. The present invention has been completed by finding that the chain shows higher conductivity than the quaternary ammonium salt of dibasic carboxylic acid.
即ち、本発明は脂環式カルボン酸の四級アンモニウム塩
を溶質として使用することを特徴とする電解コンデンサ
用電解液を提供するものである。That is, the present invention provides an electrolytic solution for an electrolytic capacitor, which comprises using a quaternary ammonium salt of an alicyclic carboxylic acid as a solute.
発明の効果 本発明で溶質として使用する脂環式カルボン酸の四級ア
ンモニウム塩は溶媒に対する溶解性が良く、また高い電
導度を示し、凝固点〜沸点範囲の広い溶媒と伴に用いる
ことにより、使用温度範囲の広い優れた電解コンデンサ
用電解液となる。The quaternary ammonium salt of an alicyclic carboxylic acid used as a solute in the present invention has good solubility in a solvent and exhibits high conductivity, and is used by being used in combination with a solvent having a wide range of freezing point to boiling point. An excellent electrolytic solution for electrolytic capacitors with a wide temperature range.
発明の具体的説明 本発明において用いられる脂環式カルボン酸の四級アン
モニウム塩の脂環式カルボン酸とはモノシクロ、及びビ
シクロ体の１価あるいは多価カルボン酸である。環の大
きさは炭素数３〜１０の範囲で、カルボキシル基の数は
１〜４である。又、環内に不飽和結合を有していても良
い。脂環式カルボン酸の総炭素数は４〜３０の範囲であ
るが、６〜１２のものが好ましい。Detailed Description of the Invention The alicyclic carboxylic acid of the quaternary ammonium salt of the alicyclic carboxylic acid used in the present invention is a monocyclo or bicyclo monovalent or polyvalent carboxylic acid. The size of the ring is in the range of 3 to 10 carbon atoms, and the number of carboxyl groups is 1 to 4. Further, it may have an unsaturated bond in the ring. The total carbon number of the alicyclic carboxylic acid is in the range of 4 to 30, but 6 to 12 is preferable.
具体的には、シクロペンタンカルボン酸、シクロヘキサ
ンカルボン酸、1,1−シクロペンタンジカルボン酸、1,2
−シクロペンタンジカルボン酸、1,1シクロヘキサンジ
カルボン酸、1,2−シクロヘキサンジカルボン酸、４−
シクロヘキセン−1,2−ジカルボン酸、５−ノルボルネ
ン−2,3−ジカルボン酸等を例示することができる。Specifically, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2
-Cyclopentanedicarboxylic acid, 1,1 cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-
Examples thereof include cyclohexene-1,2-dicarboxylic acid and 5-norbornene-2,3-dicarboxylic acid.
四級アンモニウム塩としては、テトラエチルアンモニウ
ム、テトラプロピルアンモニウム、テトラブチルアンモ
ニウム、メチルトリエチルアンモニウム等の脂肪族四級
アンモニウム塩、N,N−ジメチルピロリジニウム、N,N−
ジメチルピペリジニウム、N,N−ペンタメチレンピペリ
ジニウム等の脂環式四級アンモニウム塩、およびＮ−エ
チルピリジニウム等の芳香族四級アンモニウム塩を例示
することができる。The quaternary ammonium salt, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, aliphatic quaternary ammonium salts such as methyltriethylammonium, N, N-dimethylpyrrolidinium, N, N-
Examples thereof include alicyclic quaternary ammonium salts such as dimethylpiperidinium and N, N-pentamethylenepiperidinium, and aromatic quaternary ammonium salts such as N-ethylpyridinium.
本発明の脂環式カルボン酸の四級アンモニウム塩を溶解
させる溶媒としては、Ｎ−メチルホルムアミド、Ｎ−エ
チルホルムアミド、N,N−ジメチルホルムアミド、N,N−
ジエチルホルムアミド、Ｎ−メチルアセトアミド、Ｎ−
エチルアセトアミド、N,N−ジメチルアセトアミド、N,N
−ジエチルアセトアミド、Ｎ−メチルピロリジノン等の
アミド溶媒、γ−ブチロラクトン、γ−バレロラクト
ン、δ−バレロラクトン等のラクトン溶媒、エチレンカ
ーボネート、プロピレンカーボネート、ブチレンカーボ
ネート等のカーボネート溶媒、エチレングリコール、グ
リセリン、メチルセロソルブ等のアルコール溶媒、３−
メトキシプロピオニトリル等のニトリル溶媒、およびト
リメチルホスフェート等の燐酸エステル溶媒の単独ある
いは混合溶媒を例示することができる。これらの中で
も、γ−ブチロラクトンを主体とする溶媒が毒性が低
く、電解コンデンサの封孔剤のアタックやハロゲンの混
入が少ない等のことから特に好ましい。As a solvent for dissolving the quaternary ammonium salt of the alicyclic carboxylic acid of the present invention, N-methylformamide, N-ethylformamide, N, N-dimethylformamide, N, N-
Diethylformamide, N-methylacetamide, N-
Ethylacetamide, N, N-dimethylacetamide, N, N
-Amide solvents such as diethylacetamide and N-methylpyrrolidinone, lactone solvents such as γ-butyrolactone, γ-valerolactone and δ-valerolactone, carbonate solvents such as ethylene carbonate, propylene carbonate and butylene carbonate, ethylene glycol, glycerin, methyl Alcohol solvent such as cellosolve, 3-
Examples thereof include nitrile solvents such as methoxypropionitrile, and phosphoric acid ester solvents such as trimethyl phosphate, either alone or as a mixed solvent. Among these, a solvent mainly composed of γ-butyrolactone is particularly preferable because it has a low toxicity, and the attack of the sealing agent of the electrolytic capacitor and the mixing of halogen are small.
上記溶媒に対する脂環式カルボン酸の四級アンモニウム
塩の溶解量は飽和濃度以下、好ましくは５〜４０重量％
の範囲である。また上記電解液中の溶解塩は中性塩であ
る必要はなく酸性塩でも良い。The amount of the quaternary ammonium salt of alicyclic carboxylic acid dissolved in the solvent is not more than the saturation concentration, preferably 5 to 40% by weight.
Is the range. The dissolved salt in the electrolytic solution does not have to be a neutral salt, and may be an acidic salt.
脂環式カルボン酸の第四アンモニウム塩は、例えば、脂
環式カルボン酸１モルに対し、１モルの水酸化テトラエ
チルアンモニウム水溶液で中和した後、水を減圧留去
し、得られた生成物をメタノールより再結晶し、真空乾
燥して得られるが、本発明の電解液は、溶媒に脂環式カ
ルボン酸と水酸化第四アンモニウム水溶液を加え、溶解
後脱水して調整することも出来る。The quaternary ammonium salt of an alicyclic carboxylic acid is, for example, a product obtained by neutralizing with 1 mol of an aqueous solution of tetraethylammonium hydroxide relative to 1 mol of an alicyclic carboxylic acid, and then distilling off water under reduced pressure Is obtained by recrystallization from methanol and vacuum drying, and the electrolytic solution of the present invention can also be prepared by adding an alicyclic carboxylic acid and an aqueous solution of quaternary ammonium hydroxide to a solvent, dissolving and dehydrating.
本発明の電解液は、本質的には、脂環式カルボン酸の四
級アンモニウム塩と溶媒よりなるが、電蝕防止、漏れ電
流の低減、水素ガス吸収等の目的で種々の助溶質、例え
ば、燐酸誘導体、ニトロベンゼン誘導体等を添加するこ
とができる。本発明に用いられる溶媒は実質的に無水の
状態で使用可能であるが、電導度の向上、化成性改善等
の目的で１〜１０重量％の水を添加することもできる。The electrolytic solution of the present invention essentially consists of a quaternary ammonium salt of an alicyclic carboxylic acid and a solvent, but various co-solutes for the purpose of preventing electrolytic corrosion, reducing leakage current, absorbing hydrogen gas, etc. , Phosphoric acid derivative, nitrobenzene derivative and the like can be added. The solvent used in the present invention can be used in a substantially anhydrous state, but 1 to 10% by weight of water can be added for the purpose of improving the electric conductivity and the chemical conversion property.
実験例 以下に実施例、比較例を挙げて本発明を更に具体的に説
明する。Experimental Example The present invention will be described more specifically with reference to Examples and Comparative Examples below.
実施例１ γ−ブチロラクトン溶媒に２０重量％の1,2−シクロヘ
キサンジカルボン酸のモノテトラエチルアンモニウム塩
を溶解させて電解液を得た。この電解液の２５℃におけ
る電導度は8.2mS/cmであり、＋，−一組のアルミニウム
平滑箔に２mA/cm2の定電流印加時の火花発生電圧は105
Ｖであった。Example 1 An electrolyte solution was obtained by dissolving 20% by weight of monotetraethylammonium salt of 1,2-cyclohexanedicarboxylic acid in a γ-butyrolactone solvent. The conductivity of this electrolytic solution at 25 ° C is 8.2 mS / cm, and the spark generation voltage is 105 when a constant current of 2 mA / cm 2 is applied to a pair of + and-aluminum smooth foils.
It was V.
実施例２、３ 実施例１において、1,2−シクロヘキサンジカルボン酸
のモノテトラエチルアンモニウム塩の代わりに、1,1−
シクロペンタンジカルボン酸（実施例２）、シクロヘキ
サンカルボン酸（実施例３）を使用した電解液の電導度
および火花発生電圧を測定した。その結果を第１表に示
した。Examples 2, 3 In Example 1, 1,1-cyclohexanedicarboxylic acid was replaced by 1,1-
The electric conductivity and the spark generation voltage of the electrolytic solution using cyclopentanedicarboxylic acid (Example 2) and cyclohexanecarboxylic acid (Example 3) were measured. The results are shown in Table 1.
実施例４ 実施例１において、γ−ブチロラクトンの代わりに、N,
N−ジメチルホルムアミドを使用した電解液の電導度
は、12.3mS/cmであった。Example 4 In Example 1, instead of γ-butyrolactone, N,
The conductivity of the electrolytic solution using N-dimethylformamide was 12.3 mS / cm.
実施例５、６ 実施例２において、γ−ブチロラクトンの代わりに、３
−メトキシプロピオニトリル（実施例５）、トリメチル
ホスフェート（実施例６）を使用した電解液の電導度お
よび火花発生電圧を第１表に示した。Examples 5, 6 In Example 2, instead of γ-butyrolactone, 3
Table 1 shows the electric conductivity and the spark generation voltage of the electrolytic solution using -methoxypropionitrile (Example 5) and trimethyl phosphate (Example 6).
比較例１ 実施例１において、1,2−シクロヘキサンジカルボン酸
塩の代わりに、アジピン酸のモノテトラエチルアンモニ
ウム塩を使用した電解液の電導度および火花発生電圧を
第１表に示した。Comparative Example 1 In Example 1, the conductivity and the spark generation voltage of the electrolytic solution in which the monotetraethylammonium salt of adipic acid was used instead of the 1,2-cyclohexanedicarboxylic acid salt are shown in Table 1.
比較例２〜４ アジピン酸のモノテトラエチルアンモニウム塩２０重量
％をN,N−ジメチルホルムアミド（比較例２）、３−メ
トキシプロピオニトリル（比較例３）、トリメチルホス
フェート（比較例４）溶媒に溶解して電解液を得た。そ
の電解液の電導度および火花発生電圧を第１表に示し
た。Comparative Examples 2 to 4 20% by weight of the monotetraethylammonium salt of adipic acid was dissolved in a solvent of N, N-dimethylformamide (Comparative Example 2), 3-methoxypropionitrile (Comparative Example 3) and trimethylphosphate (Comparative Example 4). Then, an electrolytic solution was obtained. Table 1 shows the electric conductivity and the spark generation voltage of the electrolytic solution.
なお、第１表では次の略号を使用した。In Table 1, the following abbreviations are used.
ＧＢＬ：γ−ブチロラクトン ＤＭＦ：N,N−ジメチルホルムアミド ＭＰＮ：３−メトキシプロピオニトリル ＴＭＰ：トリメチルホスフェート GBL: γ-butyrolactone DMF: N, N-dimethylformamide MPN: 3-methoxypropionitrile TMP: trimethyl phosphate
Claims (1)
溶質として溶媒に溶解したことを特徴とする電解コンデ
ンサ用電解液。1. An electrolytic solution for an electrolytic capacitor, wherein a quaternary ammonium salt of an alicyclic carboxylic acid is dissolved as a solute in a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28698385A JPH0611021B2 (en) | 1985-12-20 | 1985-12-20 | Electrolytic solution for electrolytic capacitors |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28698385A JPH0611021B2 (en) | 1985-12-20 | 1985-12-20 | Electrolytic solution for electrolytic capacitors |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62145716A JPS62145716A (en) | 1987-06-29 |
| JPH0611021B2 true JPH0611021B2 (en) | 1994-02-09 |
Family
ID=17711496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28698385A Expired - Lifetime JPH0611021B2 (en) | 1985-12-20 | 1985-12-20 | Electrolytic solution for electrolytic capacitors |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0611021B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01119010A (en) * | 1987-10-31 | 1989-05-11 | Nichicon Corp | Electrolytic solution for driving electrolytic capacitor |
| CN113913163B (en) * | 2020-07-07 | 2024-03-19 | 中国石油化工股份有限公司 | Heat conduction medium and preparation method and application thereof |
-
1985
- 1985-12-20 JP JP28698385A patent/JPH0611021B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62145716A (en) | 1987-06-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |