JP2006332266A - Electrolyte for driving electrolytic capacitor - Google Patents
Electrolyte for driving electrolytic capacitor Download PDFInfo
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- JP2006332266A JP2006332266A JP2005152705A JP2005152705A JP2006332266A JP 2006332266 A JP2006332266 A JP 2006332266A JP 2005152705 A JP2005152705 A JP 2005152705A JP 2005152705 A JP2005152705 A JP 2005152705A JP 2006332266 A JP2006332266 A JP 2006332266A
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- Prior art keywords
- acid
- electrolyte
- electrolytic capacitor
- electrolytic solution
- diethoxypyrimidine
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- 239000003990 capacitor Substances 0.000 title claims abstract description 10
- 239000003792 electrolyte Substances 0.000 title abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 31
- WFUDIWSUZYDRST-UHFFFAOYSA-N 4,6-diethoxypyrimidine Chemical compound CCOC1=CC(OCC)=NC=N1 WFUDIWSUZYDRST-UHFFFAOYSA-N 0.000 claims description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 abstract description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 abstract description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005711 Benzoic acid Substances 0.000 abstract description 2
- 235000010233 benzoic acid Nutrition 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- 235000019253 formic acid Nutrition 0.000 abstract description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 235000011037 adipic acid Nutrition 0.000 abstract 1
- 239000001361 adipic acid Substances 0.000 abstract 1
- -1 ester compound Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 3
- 229930195725 Mannitol Natural products 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000000594 mannitol Substances 0.000 description 3
- 235000010355 mannitol Nutrition 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PMDCZENCAXMSOU-UHFFFAOYSA-N N-ethylacetamide Chemical compound CCNC(C)=O PMDCZENCAXMSOU-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- BQNDPALRJDCXOY-UHFFFAOYSA-N 2,3-dibutylbutanedioic acid Chemical compound CCCCC(C(O)=O)C(C(O)=O)CCCC BQNDPALRJDCXOY-UHFFFAOYSA-N 0.000 description 1
- OWCLRJQYKBAMOL-UHFFFAOYSA-N 2-butyloctanedioic acid Chemical compound CCCCC(C(O)=O)CCCCCC(O)=O OWCLRJQYKBAMOL-UHFFFAOYSA-N 0.000 description 1
- XWVFEDFALKHCLK-UHFFFAOYSA-N 2-methylnonanedioic acid Chemical compound OC(=O)C(C)CCCCCCC(O)=O XWVFEDFALKHCLK-UHFFFAOYSA-N 0.000 description 1
- GZKBIHXVOPRVQS-UHFFFAOYSA-N 8-ethenyloctadec-2-enedioic acid Chemical compound OC(=O)CCCCCCCCCC(C=C)CCCCC=CC(O)=O GZKBIHXVOPRVQS-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004653 carbonic acids Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- YHLVIDQQTOMBGN-UHFFFAOYSA-N methyl prop-2-enyl carbonate Chemical compound COC(=O)OCC=C YHLVIDQQTOMBGN-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
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、特に耐電圧を改善した電解液に関するものである。 The present invention relates to an improvement of an electrolytic solution for driving an electrolytic capacitor (hereinafter referred to as an electrolytic solution), and particularly relates to an electrolytic solution having improved withstand voltage.
従来、中高圧用アルミニウム電解コンデンサ用の電解液は、エチレングリコール等の溶媒に、高級二塩基酸またはそのアンモニウム塩、ホウ酸またはそのアンモニウム塩、マンニトール等の多価アルコール類を配合したものが用いられている。
この種の電解液において、ホウ酸と多価アルコール類とは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ことが知られている。
さらに、合成高分子であるポリビニルアルコールを配合することも提案されている（例えば、特許文献１〜３参照）。
In this type of electrolytic solution, it is known that boric acid and polyhydric alcohols form an ester compound, and the withstand voltage of the electrolytic solution is improved due to its structural characteristics.
Furthermore, blending polyvinyl alcohol, which is a synthetic polymer, has also been proposed (see, for example, Patent Documents 1 to 3).
しかしながら、炭素数が６程度のマンニトール、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が緩慢であるため、耐電圧を大幅に向上させるには、大量に添加する必要があり、その結果、比抵抗の顕著な上昇を伴うという問題点がある。 However, mannitol, sorbitol, etc. having about 6 carbon atoms are slow to improve the withstand voltage of the electrolyte even if the addition amount is increased, so it is necessary to add a large amount to greatly improve the withstand voltage. As a result, there is a problem that the resistivity is significantly increased.
一方、ポリビニルアルコールはマンニトールより少量の添加で電解液の耐電圧向上が図れるが、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著しく低いため、多量に添加ができない。また、電解液を調製するのに長時間の加熱と攪拌とを必要とするため、調合に多大な手間がかかるという問題がある。 On the other hand, polyvinyl alcohol can improve the withstand voltage of the electrolytic solution by adding a smaller amount than mannitol, but it cannot be added in a large amount because it has extremely low solubility in a solvent containing ethylene glycol as a main component. Moreover, since long time heating and stirring are required in order to prepare electrolyte solution, there exists a problem that preparation takes much effort.
さらに、多価アルコール類は、主溶質である高級二塩基酸ともエステル反応を起こすことがあるため、電解液自身の特性変化が大きくなるという問題があった。 Furthermore, polyhydric alcohols may cause an ester reaction with a higher dibasic acid that is a main solute, so that there has been a problem that the characteristic change of the electrolytic solution itself becomes large.
以上の問題点に鑑みて、本発明の課題は、低比抵抗化および耐電圧の上昇の双方を図ることができるアルミニウム電解コンデンサ用の駆動用電解液を提供することにある。 In view of the above problems, an object of the present invention is to provide a driving electrolytic solution for an aluminum electrolytic capacitor that can achieve both a reduction in specific resistance and an increase in withstand voltage.
本発明は、上記の課題を解決するため各種検討した結果、見出されたものであり、ジエトキシピリミジンがエーテル基を有することに着目し、この構造により電解液と電極箔との化学反応を抑制し、耐電圧の上昇を図ろうとするものである。 The present invention has been found as a result of various studies to solve the above-mentioned problems. It has been found that diethoxypyrimidine has an ether group, and this structure allows a chemical reaction between the electrolytic solution and the electrode foil. It is intended to suppress and increase the withstand voltage.
すなわち、本発明に係るアルミニウム電解コンデンサ用の駆動用電解液では、エチレングリコールを主成分とする溶媒に、少なくとも、カルボン酸またはその塩と、以下の化学式で示されるジエトキシピリミジンとを配合したことを特徴とする。 That is, in the driving electrolytic solution for an aluminum electrolytic capacitor according to the present invention, at least carboxylic acid or a salt thereof and diethoxypyrimidine represented by the following chemical formula are blended in a solvent mainly composed of ethylene glycol. It is characterized by.
本発明において、ジエトキシピリミジンの配合量は、電解液全体に対して０．１０〜５．００ｗｔ％であることが好ましい。 In this invention, it is preferable that the compounding quantity of diethoxypyrimidine is 0.10 to 5.00 wt% with respect to the whole electrolyte solution.
本発明において、カルボン酸の例として、ギ酸、酢酸、ラウリン酸、ステアリン酸、デカン酸、安息香酸、サリチル酸、マレイン酸、フタル酸、フマル酸、コハク酸、グルタル酸、アゼライン酸、セバシン酸、２−メチルアゼライン酸、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−ジカルボン酸が挙げられる。 In the present invention, examples of carboxylic acids include formic acid, acetic acid, lauric acid, stearic acid, decanoic acid, benzoic acid, salicylic acid, maleic acid, phthalic acid, fumaric acid, succinic acid, glutaric acid, azelaic acid, sebacic acid, 2 -Methyl azelaic acid, 1,6-decanedicarboxylic acid, 5,6-decanedicarboxylic acid, 7-vinylhexadecene-1,16-dicarboxylic acid.
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−ブチルアミン等の一級アミン塩、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二級アミン塩、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三級アミン塩、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四級アンモニウム塩、イミダゾリニウム塩等の溶融塩を例示することができる。 Examples of carboxylic acid salts include ammonium salts, primary amine salts such as methylamine, ethylamine, and t-butylamine, secondary amine salts such as dimethylamine, ethylmethylamine, and diethylamine, trimethylamine, diethylmethylamine, and ethyldimethylamine. And tertiary amine salts such as triethylamine, quaternary ammonium salts such as tetramethylammonium, triethylmethylammonium and tetraethylammonium, and molten salts such as imidazolinium salts.
エチレングリコールに混合する副溶媒としては、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、スルホラン、スルホラン誘導体、水等を例示することができる。これらの溶媒は一種類だけでなく、二種類以上を混合して使用することができる。 As a co-solvent mixed with ethylene glycol, glycols such as propylene glycol, lactones such as γ-butyrolactone and N-methyl-2-pyrrolidone, N-methylformamide, N, N-dimethylformamide, 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, etc. Examples thereof include carbonic acids, nitriles such as acetonitrile, oxides such as dimethyl sulfoxide, ethers, ketones, esters, sulfolane, sulfolane derivatives, water and the like. These solvents can be used by mixing not only one type but also two or more types.
上記の電解液には、漏れ電流の低減、耐電圧向上、ガス吸収等の目的で種々の添加剤を加えることができる。添加剤の例として、リン酸化合物、ホウ酸化合物、多価アルコール類、ポリビニルアルコール、ポリエチレングリコール、ポリプロピレングリコール、ポリオキシエチレンポリオキシプロピレングリコールのランダム共重合体およびブロック共重合体に代表される高分子化合物、ニトロ化合物等が挙げられる。 Various additives can be added to the electrolytic solution for the purpose of reducing leakage current, improving withstand voltage, and absorbing gas. Examples of additives include phosphoric acid compounds, boric acid compounds, polyhydric alcohols, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol random copolymers and block copolymers. A molecular compound, a nitro compound, etc. are mentioned.
本発明に係る電解液では、ジエトキシピリミジンの少量の添加で、電解液と電極箔との化学反応が抑えられるので、低比抵抗化および耐電圧の向上を図ることができる。また、ジエトキシピリミジンによって高温での安定性も高められる。さらに、ジエトキシピリミジンは、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高く、主溶質のカルボン酸とのエステル化反応が少ないことから、高温雰囲気下での比抵抗の経時的な増大を防止することもできる。 In the electrolytic solution according to the present invention, the chemical reaction between the electrolytic solution and the electrode foil can be suppressed by adding a small amount of diethoxypyrimidine, so that the specific resistance can be reduced and the withstand voltage can be improved. Also, stability at high temperatures is enhanced by diethoxypyrimidine. In addition, diethoxypyrimidine is highly soluble in solvents based on ethylene glycol and has little esterification reaction with the main solute carboxylic acid, which increases the specific resistance over time in a high-temperature atmosphere. Can also be prevented.
このように構成した電解液を用いてアルミニウム電解コンデンサを構成すると、ジエトキシピリミジンの少量の添加で、電解液と電極箔との化学反応が抑えられるため、電解液の低比抵抗化および耐電圧の向上を図ることができる。その理由は、ジエトキシピリミジンのエーテル基部分が電解液中でアルミニウム電極箔の酸化皮膜と反応し、耐水性の皮膜を形成するためと考えられる。
また、ジエトキシピリミジンがピリミジン環を有することで、高温での安定性も高められる。
さらに、ジエトキシピリミジンは、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高く、主溶質のカルボン酸とのエステル化反応が少ないことから、高温雰囲気下での比抵抗の経時的な増大を防止することができる。
When an aluminum electrolytic capacitor is configured using the electrolytic solution thus configured, the chemical reaction between the electrolytic solution and the electrode foil can be suppressed with the addition of a small amount of diethoxypyrimidine. Can be improved. The reason is considered to be that the ether group portion of diethoxypyrimidine reacts with the oxide film of the aluminum electrode foil in the electrolytic solution to form a water-resistant film.
In addition, since diethoxypyrimidine has a pyrimidine ring, stability at high temperatures can be enhanced.
In addition, diethoxypyrimidine is highly soluble in solvents based on ethylene glycol and has little esterification reaction with the main solute carboxylic acid, which increases the specific resistance over time in a high-temperature atmosphere. Can be prevented.
以下、本発明を実施例に基づき、より具体的に説明する。まず、表１および表２に示す組成で電解液を調合し、３０℃における電解液の比抵抗と８５℃における火花発生電圧（電解液の耐電圧）を測定した。その結果を表１および表２に示す。 Hereinafter, the present invention will be described more specifically based on examples. First, an electrolyte solution was prepared according to the composition shown in Tables 1 and 2, and the specific resistance of the electrolyte solution at 30 ° C. and the spark generation voltage at 85 ° C. (withstand voltage of the electrolyte solution) were measured. The results are shown in Tables 1 and 2.
表１および表２より、ジエトキシピリミジンを溶解した実施例に係る電解液は、従来例に係る電解液より比抵抗が低く、耐電圧を向上していることが分かる。ここで、ジエトキシピリミジンの配合量が電解液全体に対して０．１０ｗｔ％未満では耐電圧向上の効果が十分でなく（実施例１）、５．００ｗｔ％を超えると比抵抗が高くなり過ぎ、低比抵抗用途に不向きとなる（実施例５）。よって、ジエトキシピリミジンの配合量は、電解液全体に対して０．１０〜５．００ｗｔ％の範囲が好ましい。 From Table 1 and Table 2, it can be seen that the electrolytic solution according to the example in which diethoxypyrimidine is dissolved has a lower specific resistance than that of the electrolytic solution according to the conventional example and has improved withstand voltage. Here, when the blending amount of diethoxypyrimidine is less than 0.10 wt% with respect to the entire electrolyte solution, the effect of improving the withstand voltage is not sufficient (Example 1), and when it exceeds 5.00 wt%, the specific resistance becomes too high. This is not suitable for low specific resistance applications (Example 5). Therefore, the blending amount of diethoxypyrimidine is preferably in the range of 0.10 to 5.00 wt% with respect to the entire electrolyte solution.
なお、本発明は実施例に限定されるものではなく、先に例示した各種溶質を単独または複数溶解した電解液や、その他添加剤を加えた電解液、副溶媒を混合した電解液でも実施例と同等の効果があった。 In addition, this invention is not limited to an Example, It is an Example also in the electrolyte solution which mixed the various solutes illustrated previously individually or severally, the electrolyte solution which added the other additive, and the subsolvent. Had the same effect.
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| JP2003338431A (en) * | 2002-05-22 | 2003-11-28 | Nichicon Corp | Electrolyte for driving of electrolytic capacitor |
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| JP2003338431A (en) * | 2002-05-22 | 2003-11-28 | Nichicon Corp | Electrolyte for driving of electrolytic capacitor |
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