JP4540244B2 - Electrolytic solution for driving electrolytic capacitors - Google Patents
Electrolytic solution for driving electrolytic capacitors Download PDFInfo
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- JP4540244B2 JP4540244B2 JP2001092063A JP2001092063A JP4540244B2 JP 4540244 B2 JP4540244 B2 JP 4540244B2 JP 2001092063 A JP2001092063 A JP 2001092063A JP 2001092063 A JP2001092063 A JP 2001092063A JP 4540244 B2 JP4540244 B2 JP 4540244B2
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- Prior art keywords
- electrolytic solution
- electrolytic
- acid
- withstand voltage
- methacrylic acid
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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)に関するものであり、特に電解液の耐電圧を改善するものである。
【0002】
【従来の技術】
従来、中高圧用電解コンデンサの電解液としては、エチレングリコールを主成分とする溶媒に、安息香酸、二塩基酸、ホウ酸またはそのアンモニウム塩を溶解し、さらに、マンニトール、ソルビトール等の炭素数6程度の多価アルコール類を添加することで、ホウ酸と多価アルコールとがエステル化合物を形成し、電解液の耐電圧が向上することが知られている。また、合成高分子であるポリエチレングリコールやポリビニルアルコールを添加することでも、電解液の耐電圧が向上することが知られている。
【0003】
【発明が解決しようとする課題】
しかし、マンニトール、ソルビトール等は添加量を増加させても電解液の耐電圧の向上効果が緩慢であり、耐電圧を大幅に向上させるためにマンニトール、ソルビトールを多量に溶解すると、電解液の比抵抗が大幅に上昇するという問題があった。また、平均分子量が1000以下の比較的重合度の小さいポリエチレングリコールは、電解液に対する溶解性は高いが耐電圧向上の効果が少なく、平均分子量が1000を超えるポリエチレングリコールは、耐電圧向上の効果は高いが、電解液に対する溶解性が低く、多量に添加できないという問題がある。そして、ポリビニルアルコールも、少量の添加で電解液の耐電圧向上を図れるが、電解液に対する溶解性が著しく低い上、その他の溶質量にも問題が出てくるため、長時間の加熱、撹拌を必要とし、作業性にも問題があった。
したがって、耐電圧の向上とともに、溶解性の向上も可能な電解液が望まれていた。
【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各種検討した結果、見出したものであり、電解液の比抵抗の上昇を抑えながら耐電圧向上を図ったものである。すなわち、有機極性溶媒に、有機カルボン酸またはその塩と、ホウ酸またはそのアンモニウム塩と、メタクリル酸−ビニルフェノール共重合体とを溶解し、前記メタクリル酸−ビニルフェノール共重合体の溶解量が、1.0〜20.0wt%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。
【0005】
そして、上記メタクリル酸−ビニルフェノール共重合体の平均分子量が、200〜5000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。
【0007】
そして、有機カルボン酸としては、安息香酸、アジピン酸、アゼライン酸、セバシン酸、1,6−デカンジカルボン酸、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。
【0008】
さらに、有機カルボン酸の塩としては、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。
【0009】
また、有機極性溶媒としては、エチレングリコール、プロピレングリコール等のグリコール類、γ−ブチロラクトン、N−メチル−2−ピロリドン等のラクトン類、N−メチルホルムアミド、N,N−ジメチルホルムアミド、N−エチルホルムアミド、N,N−ジエチルホルムアミド、N−メチルアセトアミド、N,N−ジメチルアセトアミド、N−エチルアセトアミド、N,N−ジエチルアセトアミド、ヘキサメチルホスホリックアミド等のアミド類、エチレンカーボネート、プロピレンカーボネート、イソブチレンカーボネート等の炭酸類、アセトニトリル等のニトリル類、ジメチルスルホキシド等のオキシド類、エーテル類、ケトン類、エステル類等を例示することができる。
【0010】
【発明の実施の形態】
メタクリル酸−ビニルフェノール共重合体は、メタクリル酸とビニルフェノールの共重合で得られるポリマーである。メタクリル酸とビニルフェノールの共重合体構造を持つことにより、単独では得られなかった電解液の比抵抗上昇を抑えながら耐電圧の向上を図ることができる。また、ビニルフェノールの水酸基が電極箔を保護し、製品の特性安定化が図れる。
【0011】
【実施例】
以下、本発明を実施例に基づき具体的に説明する。
表1,2の組成で電解液を調合し、30℃における電解液の比抵抗および85℃における電解液の火花発生電圧(耐電圧)を測定し、表1,2の結果を得た。
【0012】
【表1】
【0013】
【表2】
【0014】
表1より、メタクリル酸−ビニルフェノール共重合体を溶解した実施例は、マンニトールを多量に溶解した従来例2や、ポリエチレングリコール、ポリビニルアルコールを溶解した従来例3,5より比抵抗の上昇を抑えながら、耐電圧を向上させていることが分かる。また、ポリエチレングリコールやポリビニルアルコールの量を増やした従来例4,6は、完全に溶解しなかった。メタクリル酸−ビニルフェノール共重合体の溶解量が1.0wt%未満では耐電圧向上の効果が少なく、20.0wt%を超えると耐電圧は向上するが、比抵抗が高くなり低比抵抗用途に不適となる。よって、メタクリル酸−ビニルフェノール共重合体の溶解量は、1.0〜20.0wt%の範囲が好ましい。
【0015】
実施例3の電解液組成で、メタクリル酸−ビニルフェノール共重合体の平均分子量と電解液の耐電圧との関係を検討し、図1の結果を得た。図1より平均分子量が200未満では耐電圧向上の効果が少ないが、200以上で耐電圧向上の効果が得られることが分かる。
但し、平均分子量が5000を超えるとメタクリル酸−ビニルフェノール共重合体の粘度が高くなるため、電解液の調合に時間がかかるようになる。
よって、メタクリル酸−ビニルフェノール共重合体の平均分子量は、200〜5000の範囲が好ましい。
【0016】
なお、本発明による電解液に、火花発生電圧安定化のために、マンニトール、ソルビトール等の多価アルコールや、リン酸またはその塩等の無機酸類を溶解してもよい。
【0017】
また、本発明による電解液が含有する水分量は、低いほど好ましいが、8.0wt%以下が好ましい。さらに電解液のpHは、必要に応じアンモニア水等のpH調整剤でpH4〜8、好ましくはpH5〜7に調整する。
【0018】
【発明の効果】
以上のように、本発明によるメタクリル酸−ビニルフェノール共重合体を溶解した電解液は、溶質を容易に溶解させることが可能であり、電解液の比抵抗の上昇を抑えながら耐電圧を向上させることが可能である。
【図面の簡単な説明】
【図1】メタクリル酸−ビニルフェノール共重合体の平均分子量と電解液の耐電圧との特性図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrolytic solution for driving an electrolytic capacitor (hereinafter referred to as an electrolytic solution), and particularly to improve the withstand voltage of the electrolytic solution.
[0002]
[Prior art]
Conventionally, as an electrolytic solution for an electrolytic capacitor for medium to high voltage, benzoic acid, dibasic acid, boric acid or ammonium salt thereof is dissolved in a solvent mainly composed of ethylene glycol, and further, carbon number of 6 such as mannitol, sorbitol and the like. It is known that by adding about a certain amount of polyhydric alcohols, boric acid and polyhydric alcohol form an ester compound, and the withstand voltage of the electrolytic solution is improved. It is also known that the withstand voltage of the electrolytic solution can be improved by adding polyethylene glycol or polyvinyl alcohol, which are synthetic polymers.
[0003]
[Problems to be solved by the invention]
However, even if mannitol, sorbitol, etc. are added, the effect of improving the withstand voltage of the electrolyte is slow, and if mannitol and sorbitol are dissolved in a large amount in order to greatly improve the withstand voltage, the specific resistance of the electrolyte There was a problem that would rise significantly. In addition, polyethylene glycol having a relatively low degree of polymerization having an average molecular weight of 1000 or less has high solubility in an electrolyte solution, but has little effect of improving withstand voltage. Polyethylene glycol having an average molecular weight exceeding 1000 has an effect of improving withstand voltage. Although it is high, there is a problem that the solubility in the electrolytic solution is low and a large amount cannot be added. Polyvinyl alcohol can also improve the withstand voltage of an electrolytic solution by adding a small amount, but the solubility in the electrolytic solution is remarkably low, and there are problems with other dissolved masses. There was a problem in workability.
Therefore, an electrolytic solution capable of improving the withstand voltage and the solubility has been desired.
[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 is intended to improve the withstand voltage while suppressing an increase in the specific resistance of the electrolytic solution. That is, an organic carboxylic acid or a salt thereof, boric acid or an ammonium salt thereof, and a methacrylic acid-vinylphenol copolymer are dissolved in an organic polar solvent, and the dissolved amount of the methacrylic acid-vinylphenol copolymer is An electrolytic solution for driving an electrolytic capacitor characterized by being 1.0 to 20.0 wt% .
[0005]
And the average molecular weight of the said methacrylic acid-vinylphenol copolymer is 200-5000, It is electrolyte solution for a drive of the electrolytic capacitor characterized by the above-mentioned.
[0007]
Examples of organic carboxylic acids include benzoic acid, adipic acid, azelaic acid, sebacic acid, 1,6-decanedicarboxylic acid, 5,6-decanedicarboxylic acid, 7-vinylhexadecene-1,16-dicarboxylic acid, and the like. can do.
[0008]
Furthermore, as salts of organic carboxylic 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 diethylmethylamine And tertiary amine salts such as ethyldimethylamine and triethylamine, and quaternary ammonium salts such as tetramethylammonium, triethylmethylammonium and tetraethylammonium.
[0009]
Examples of the organic polar solvent include glycols such as ethylene glycol and propylene glycol, lactones such as γ-butyrolactone and N-methyl-2-pyrrolidone, N-methylformamide, N, N-dimethylformamide, and N-ethylformamide. Amides such as N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, hexamethylphosphoricamide, ethylene carbonate, propylene carbonate, isobutylene carbonate Examples thereof include carbonic acids such as acetonitrile, nitriles such as acetonitrile, oxides such as dimethyl sulfoxide, ethers, ketones, esters and the like.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The methacrylic acid-vinylphenol copolymer is a polymer obtained by copolymerization of methacrylic acid and vinylphenol. By having a copolymer structure of methacrylic acid and vinylphenol, it is possible to improve the withstand voltage while suppressing an increase in specific resistance of the electrolytic solution that could not be obtained alone. Moreover, the hydroxyl group of vinylphenol protects the electrode foil, and the product characteristics can be stabilized.
[0011]
【Example】
Hereinafter, the present invention will be specifically described based on examples.
Electrolytic solutions were prepared according to the compositions shown in Tables 1 and 2, and the specific resistance of the electrolytic solution at 30 ° C. and the spark generation voltage (withstand voltage) of the electrolytic solution at 85 ° C. were measured.
[0012]
[Table 1]
[0013]
[Table 2]
[0014]
From Table 1, the example in which the methacrylic acid-vinylphenol copolymer was dissolved suppressed the increase in specific resistance compared to Conventional Example 2 in which mannitol was dissolved in a large amount and Conventional Examples 3 and 5 in which polyethylene glycol and polyvinyl alcohol were dissolved. However, it can be seen that the withstand voltage is improved. Further, Conventional Examples 4 and 6 in which the amount of polyethylene glycol or polyvinyl alcohol was increased did not completely dissolve. When the amount of methacrylic acid-vinylphenol copolymer dissolved is less than 1.0 wt%, the effect of improving the withstand voltage is small. It becomes inappropriate. Therefore, the amount of methacrylic acid-vinylphenol copolymer dissolved is preferably in the range of 1.0 to 20.0 wt%.
[0015]
With the electrolytic solution composition of Example 3, the relationship between the average molecular weight of the methacrylic acid-vinylphenol copolymer and the withstand voltage of the electrolytic solution was examined, and the result of FIG. 1 was obtained. As can be seen from FIG. 1, when the average molecular weight is less than 200, the effect of improving the withstand voltage is small, but when the average molecular weight is 200 or more, the effect of improving the withstand voltage is obtained.
However, when the average molecular weight exceeds 5000, the viscosity of the methacrylic acid-vinylphenol copolymer becomes high, so that it takes time to prepare the electrolytic solution.
Therefore, the average molecular weight of the methacrylic acid-vinylphenol copolymer is preferably in the range of 200 to 5000.
[0016]
In the electrolytic solution according to the present invention, a polyhydric alcohol such as mannitol or sorbitol, or an inorganic acid such as phosphoric acid or a salt thereof may be dissolved in order to stabilize the spark generation voltage.
[0017]
Moreover, although the water content which the electrolyte solution by this invention contains is so preferable that it is low, 8.0 wt% or less is preferable. Further, the pH of the electrolytic solution is adjusted to pH 4 to 8, preferably pH 5 to 7, with a pH adjusting agent such as ammonia water as required.
[0018]
【The invention's effect】
As described above, the electrolytic solution in which the methacrylic acid-vinylphenol copolymer according to the present invention is dissolved can easily dissolve the solute, and improves the withstand voltage while suppressing an increase in the specific resistance of the electrolytic solution. It is possible.
[Brief description of the drawings]
FIG. 1 is a characteristic diagram of an average molecular weight of a methacrylic acid-vinylphenol copolymer and a withstand voltage of an electrolytic solution.
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JP2001092063A JP4540244B2 (en) | 2001-03-28 | 2001-03-28 | Electrolytic solution for driving electrolytic capacitors |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61291606A (en) * | 1985-06-20 | 1986-12-22 | Cosmo Co Ltd | Production of copolymer from p-vinylphenol and acrylic monomer |
JPH0745482A (en) * | 1993-07-29 | 1995-02-14 | Sanyo Chem Ind Ltd | Electrolyte for driving electrolytic capacitor |
JPH10106892A (en) * | 1996-09-30 | 1998-04-24 | Matsushita Electric Ind Co Ltd | Electrolyte solution for driving electrolytic capacitor and electrolytic capacitor using the same |
JPH1174159A (en) * | 1997-08-28 | 1999-03-16 | Nichicon Corp | Drive electrolyte of electrolytic capacitor |
-
2001
- 2001-03-28 JP JP2001092063A patent/JP4540244B2/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61291606A (en) * | 1985-06-20 | 1986-12-22 | Cosmo Co Ltd | Production of copolymer from p-vinylphenol and acrylic monomer |
JPH0745482A (en) * | 1993-07-29 | 1995-02-14 | Sanyo Chem Ind Ltd | Electrolyte for driving electrolytic capacitor |
JPH10106892A (en) * | 1996-09-30 | 1998-04-24 | Matsushita Electric Ind Co Ltd | Electrolyte solution for driving electrolytic capacitor and electrolytic capacitor using the same |
JPH1174159A (en) * | 1997-08-28 | 1999-03-16 | Nichicon Corp | Drive electrolyte of electrolytic capacitor |
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