JP2006156535A - Driving electrolyte of electrolytic capacitor - Google Patents
Driving electrolyte of electrolytic capacitor Download PDFInfo
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- JP2006156535A JP2006156535A JP2004341819A JP2004341819A JP2006156535A JP 2006156535 A JP2006156535 A JP 2006156535A JP 2004341819 A JP2004341819 A JP 2004341819A JP 2004341819 A JP2004341819 A JP 2004341819A JP 2006156535 A JP2006156535 A JP 2006156535A
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- acid
- electrolytic capacitor
- electrolytic solution
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- 239000003990 capacitor Substances 0.000 title claims abstract description 26
- 239000003792 electrolyte Substances 0.000 title abstract description 4
- -1 diethylamine Chemical class 0.000 claims abstract description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 35
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- BWUMHQBLGOKCNB-UHFFFAOYSA-N ethyl 2-ethoxy-1h-quinoline-2-carboxylate Chemical compound C1=CC=C2C=CC(C(=O)OCC)(OCC)NC2=C1 BWUMHQBLGOKCNB-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- OWCLRJQYKBAMOL-UHFFFAOYSA-N 2-butyloctanedioic acid Chemical compound CCCCC(C(O)=O)CCCCCC(O)=O OWCLRJQYKBAMOL-UHFFFAOYSA-N 0.000 abstract description 2
- 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
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 abstract description 2
- 235000019253 formic acid Nutrition 0.000 abstract description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- XREULDWVGLXLDZ-UHFFFAOYSA-N butyl quinoline-2-carboperoxoate Chemical compound C1=CC=CC2=NC(C(=O)OOCCCC)=CC=C21 XREULDWVGLXLDZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 5
- YQUVCSBJEUQKSH-UHFFFAOYSA-N 3,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000006068 polycondensation reaction Methods 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000003254 radicals Chemical group 0.000 description 3
- 150000005846 sugar alcohols 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
- 239000004327 boric acid Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000000203 mixture Substances 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
- 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
- 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
- RBLWHLQHEWPZHQ-UHFFFAOYSA-N CC(C(=O)O)CCCCCCC(=O)O.C(CCCCCCCCC(=O)O)(=O)O Chemical compound CC(C(=O)O)CCCCCCC(=O)O.C(CCCCCCCCC(=O)O)(=O)O RBLWHLQHEWPZHQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-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
- 229930195725 Mannitol Natural products 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
- 239000004372 Polyvinyl alcohol 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 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
- ZRXGCJAFQUBZCG-UHFFFAOYSA-N carbonic acid;4-methyl-1,3-dioxolan-2-one Chemical class OC(O)=O.CC1COC(=O)O1 ZRXGCJAFQUBZCG-UHFFFAOYSA-N 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 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
- 239000003999 initiator Substances 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
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000000034 method Methods 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
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-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
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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、特に高温下での製品信頼性を向上させた電解液に関するものである。 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 product reliability at high temperatures.
従来、中高圧用アルミニウム電解コンデンサの電解液はエチレングリコール等の溶媒にカルボン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、およびマンニトール等の多価アルコール類を溶解している。この電解液において、カルボン酸やホウ酸と、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とされている（例えば、特許文献１〜３参照）。
しかしながら、上記エステル化合物は電解コンデンサ内部の発熱や雰囲気温度等により、アミド類を生成する。そして、このアミド類がコンデンサ素子内部や電解液に残存する酸素および陽極で発生する酸素ガスによってラジカル連鎖熱酸化反応を起こし、そのアミド類の酸化反応によって発生する生成物が原因で電解液の比抵抗上昇を招くという問題点がある。
また、カルボン酸も酸素ラジカルが開始剤となって重縮合反応を起こし、電解液の比抵抗上昇を招くという問題点がある。
However, the ester compound generates amides due to heat generated in the electrolytic capacitor, atmospheric temperature, and the like. The amides cause a radical chain thermal oxidation reaction with oxygen remaining in the capacitor element or in the electrolytic solution and oxygen gas generated in the anode, and the product generated by the oxidation reaction of the amides causes a ratio of the electrolytic solution. There is a problem of increasing resistance.
In addition, carboxylic acid also has a problem that oxygen radicals act as initiators to cause a polycondensation reaction and increase the specific resistance of the electrolytic solution.
上記の問題点を解消する方法として、例えば、プロトカテキュ酸によってラジカル連鎖熱反応を抑制することが考えられる。しかしながら、プロトカテキュ酸を多量に溶解した電解液を高温放置して比抵抗変化を調べると、比抵抗上昇の抑制効果が十分でなく、信頼性試験における電解コンデンサの損失の増大などを防止するものとしては、効果が十分でない。 As a method for solving the above problems, for example, it is conceivable to suppress radical chain thermal reaction with protocatechuic acid. However, if the electrolytic solution in which a large amount of protocatechuic acid is dissolved is allowed to stand at high temperature and the change in specific resistance is examined, the effect of suppressing the increase in specific resistance is not sufficient, and the increase in loss of the electrolytic capacitor in the reliability test is prevented. Is not effective.
以上の問題点に鑑みて、本発明の課題は、電解コンデンサの信頼性を向上可能な電解コンデンサ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 an electrolytic solution for driving an electrolytic capacitor that can improve the reliability of the electrolytic capacitor.
上記課題を解決するため各種検討した結果、本願発明者は、電解液にエチル−２−エトキシキノリンカルボン酸エステルを添加することにより、電解液中におけるアミド類の酸化反応、カルボン酸の重縮合反応を長時間抑制できることを見出した。 As a result of various studies to solve the above problems, the present inventor added an ethyl-2-ethoxyquinolinecarboxylic acid ester to the electrolytic solution to thereby oxidize amides in the electrolytic solution and polycondensation reaction of carboxylic acid. It was found that it can be suppressed for a long time.
本発明はかかる知見に基づいてなされたものであり、本発明に係る電解コンデンサの駆動用電解液は、エチレングリコール等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、以下の化学式で示すエチル−２−エトキシキノリンカルボン酸エステルを溶解したことを特徴とする。 The present invention has been made on the basis of such knowledge, and the electrolytic solution for driving an electrolytic capacitor according to the present invention includes at least a carboxylic acid or a salt thereof and a chemical formula shown below in a solvent mainly composed of ethylene glycol or the like. It is characterized by dissolving ethyl-2-ethoxyquinolinecarboxylic acid ester represented by
本発明において、上記エチル−２−エトキシキノリンカルボン酸エステルの溶解量は、０．１０〜５．００ｗｔ％であることが好ましい。５．００ｗｔ％を超えると、電解液の初期比抵抗値の上昇がみられ、また、０．１０ｗｔ％未満では、容量減少やｔａｎδ上昇を抑制する効果が減少する傾向にある。 In the present invention, the amount of the ethyl-2-ethoxyquinolinecarboxylic acid ester dissolved is preferably 0.10 to 5.00 wt%. If it exceeds 5.00 wt%, an increase in the initial specific resistance value of the electrolytic solution is observed, and if it is less than 0.10 wt%, the effect of suppressing the decrease in capacity and the increase in tan δ tends to decrease.
本発明で用いられるカルボン酸の例としては、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−ジカルボン酸等が挙げられる。 Examples of carboxylic acids used in the present invention 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 and the like.
また、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。 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, diethylmethylamine and ethyl Examples thereof include tertiary amine salts such as dimethylamine and 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、水の他、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, water, glycols such as propylene glycol, lactones such as γ-butyrolactone and N-methyl-2-pyrrolidone, N-methylformamide, N, N-dimethylformamide, N -Amides such as ethylformamide, N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, hexamethylphosphoricamide, ethylene carbonate, propylene carbonate Carbonates such as isobutylene carbonate, nitriles such as acetonitrile, oxides such as dimethyl sulfoxide, ethers, ketones, esters, sulfolane and sulfolane derivatives can be exemplified. 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、カルボン酸とその塩、溶媒の他、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及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。 In addition to the carboxylic acid, its salt and solvent, various additives can be added to the above electrolyte for the purpose of reducing leakage current, improving withstand voltage, gas absorption, and the like. Examples of additives include phosphoric acid compounds, boric acid compounds, polyhydric alcohols, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene glycol random copolymers and block copolymers A molecular compound, a nitro compound, etc. are mentioned.
本発明では、電解液に対してエチル−２−エトキシキノリンカルボン酸エステルを添加したので、高温での電解コンデンサの静電容量変化、損失（ｔａｎδ）の上昇を抑制することができ、電解コンデンサの信頼性の向上を図ることができる。 In the present invention, since ethyl-2-ethoxyquinolinecarboxylic acid ester is added to the electrolytic solution, it is possible to suppress a change in the capacitance of the electrolytic capacitor at a high temperature and an increase in loss (tan δ). Reliability can be improved.
本発明に係る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、少なくとも、カルボン酸またはその塩と、上記の化学式で示すエチル−２−エトキシキノリンカルボン酸エステルを溶解したものであり、後述するように、電解コンデンサの信頼性を向上することができる。ここで、エチル−２−エトキシキノリンカルボン酸エステルの溶解量は、電解液全体に対して０．１０〜５．００ｗｔ％であることが好ましい。 The electrolytic solution of the electrolytic capacitor according to the present invention is obtained by dissolving at least carboxylic acid or a salt thereof and ethyl-2-ethoxyquinolinecarboxylic acid ester represented by the above chemical formula in a solvent mainly composed of ethylene glycol. As will be described later, the reliability of the electrolytic capacitor can be improved. Here, it is preferable that the dissolution amount of ethyl-2-ethoxyquinolinecarboxylic acid ester is 0.10 to 5.00 wt% with respect to the entire electrolytic solution.
本発明に係る電解コンデンサの電解液において、信頼性が向上する理由としては、以下のように考えられる。まず、エチル−２−エトキシキノリンカルボン酸エステルはカルボニル基を有する化合物であり、このカルボニル基が電解コンデンサ内の残存酸素と優先的に反応して、酸素のラジカル性を消失させ、アミド類の酸化反応、カルボン酸の重縮合反応を抑制すると考えられる。
また、上記構造を有するため、電極箔との反応性が比較的低く、長期間にわたって酸化反応、重縮合反応を抑制することができ、電解コンデンサを高温雰囲気下で長時間、使用または放置した場合でも、製品の初期特性を長時間持続できる。さらに、カルボン酸が陽極箔へ過度に吸着することを抑制する作用もある。
The reason why the reliability is improved in the electrolytic solution of the electrolytic capacitor according to the present invention is considered as follows. First, ethyl-2-ethoxyquinolinecarboxylic acid ester is a compound having a carbonyl group, and this carbonyl group reacts preferentially with residual oxygen in the electrolytic capacitor to eliminate the radical nature of oxygen and oxidize amides. It is thought that the reaction and the polycondensation reaction of carboxylic acid are suppressed.
In addition, because of the above structure, the reactivity with the electrode foil is relatively low, and the oxidation reaction and polycondensation reaction can be suppressed over a long period. When the electrolytic capacitor is used or left in a high temperature atmosphere for a long time However, the initial characteristics of the product can be maintained for a long time. Furthermore, it also has an effect of suppressing the excessive adsorption of carboxylic acid to the anode foil.
以下、実施例に基づき本発明をさらに具体的に説明する。まず、表１に各種電解液の組成を示すように、実施例、比較例、および従来例に係る電解液を各々、調合した後、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に示す。なお、表１中、ラジカル反応抑制剤「Ａ」は、エチル−２−エトキシキノリンカルボン酸エステルを表している。 Hereinafter, the present invention will be described more specifically based on examples. First, as shown in Table 1, the compositions of various electrolytic solutions are prepared, and after preparing the electrolytic solutions according to Examples, Comparative Examples, and Conventional Examples, the specific resistance of the electrolytic solution at 30 ° C. and the spark generation voltage at 85 ° C. (The withstand voltage of electrolyte solution) was measured. The results are shown in Table 1. In Table 1, the radical reaction inhibitor “A” represents ethyl-2-ethoxyquinolinecarboxylic acid ester.
次に、表１に示す組成で電解液を調合した後、該電解液をコンデンサ素子に含浸し、直径１０．０ｍｍ、長さ１２．５ｍｍ、定格電圧３５０Ｖ、静電容量１０μＦのアルミ電解コンデンサを各２０個作成した。
これらの試料のうち、１０個を１０５℃の恒温槽中で５０００時間定格電圧を印加後、静電容量と損失（ｔａｎδ）を測定し、表２の結果を得た。
そして、残りの１０個を１１５℃の恒温槽中で５０００時間定格電圧を印加後、静電容量と損失（ｔａｎδ）を測定し、表３の結果を得た。
Next, after preparing an electrolytic solution with the composition shown in Table 1, a capacitor element was impregnated with the electrolytic solution to obtain an aluminum electrolytic capacitor having a diameter of 10.0 mm, a length of 12.5 mm, a rated voltage of 350 V, and a capacitance of 10 μF. 20 pieces were prepared each.
Ten of these samples were applied with a rated voltage for 5000 hours in a constant temperature bath at 105 ° C., and then the capacitance and loss (tan δ) were measured. The results shown in Table 2 were obtained.
Then, after applying the rated voltage for 5000 hours in a constant temperature bath at 115 ° C. for the remaining 10 pieces, the capacitance and loss (tan δ) were measured, and the results shown in Table 3 were obtained.
表２に示す結果から明らかなように、エチル−２−エトキシキノリンカルボン酸エステルを溶解した実施例に係る電解コンデンサでは、従来例や比較例に比べて、１０５℃という高温下において容量減少やｔａｎδ上昇が抑えられている。
また、表３に示す結果から明らかなように、エチル−２−エトキシキノリンカルボン酸エステルを溶解した実施例に係る電解コンデンサでは、従来例や比較例に比べて、１１５℃という高温下においても容量減少やｔａｎδ上昇が抑制されている。
As is clear from the results shown in Table 2, in the electrolytic capacitor according to the example in which ethyl-2-ethoxyquinolinecarboxylic acid ester was dissolved, the capacitance decreased and tan δ at a high temperature of 105 ° C. compared to the conventional example and the comparative example. The rise is suppressed.
Further, as is apparent from the results shown in Table 3, the electrolytic capacitor according to the example in which ethyl-2-ethoxyquinolinecarboxylic acid ester is dissolved has a capacity even at a high temperature of 115 ° C. as compared with the conventional example and the comparative example. Reduction and tan δ increase are suppressed.
また、表１〜３に示す結果からすれば、エチル−２−エトキシキノリンカルボン酸エステルの溶解量が多いほど、容量減少やｔａｎδ上昇を抑制する効果が大きくなる傾向にあるが、エチル−２−エトキシキノリンカルボン酸エステルの溶解量が５．０ｗｔ％を超えると（実施例６参照）、電解液の初期比抵抗値の上昇がみられる。
また、０．１ｗｔ％未満では（実施例１参照）、容量減少やｔａｎδ上昇を抑制する効果が減少する傾向にある。
よって、エチル−２−エトキシキノリンカルボン酸エステルの溶解量は、電解液全体に対して０．１〜５．０ｗｔ％の範囲が好ましい。
Further, according to the results shown in Tables 1 to 3, the larger the amount of ethyl-2-ethoxyquinolinecarboxylate dissolved, the greater the effect of suppressing the decrease in capacity and the increase in tan δ. When the amount of ethoxyquinolinecarboxylic acid ester dissolved exceeds 5.0 wt% (see Example 6), an increase in the initial specific resistance value of the electrolytic solution is observed.
Moreover, if it is less than 0.1 wt% (refer Example 1), it exists in the tendency for the effect which suppresses a capacity | capacitance reduction and a tan-delta rise to reduce.
Therefore, the dissolution amount of ethyl-2-ethoxyquinolinecarboxylic acid ester is preferably in the range of 0.1 to 5.0 wt% with respect to the entire electrolytic solution.
なお、本発明は上記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、上述した添加剤を加えた電解液、副溶媒を混合した電解液でも上記実施例と同等の効果があった。
また、本発明は、中高圧用アルミニウム電解コンデンサの電解液に限らず、低圧用アルミニウム電解コンデンサの電解液にも適用することができる。
In addition, this invention is not limited to the said Example, The electrolyte solution which melt | dissolved various solutes illustrated previously individually or in multiple, the electrolyte solution which added the additive mentioned above, and the electrolyte solution which mixed the subsolvent are also used. There was an effect equivalent to the said Example.
Further, the present invention is not limited to the electrolytic solution of the medium / high pressure aluminum electrolytic capacitor but can be applied to the electrolytic solution of the low pressure aluminum electrolytic capacitor.
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| CN112763296A (en) * | 2020-12-30 | 2021-05-07 | 上海大学 | Three-dimensional etching method for chromium-manganese stainless steel inclusions |
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| JPH0368120A (en) * | 1989-08-07 | 1991-03-25 | Hitachi Aic Inc | Electrolyte for electrolytic capacitor |
| JPH04214728A (en) * | 1990-12-14 | 1992-08-05 | Chisso Corp | Production of polyisoimide |
| JP2003037026A (en) * | 2001-07-26 | 2003-02-07 | Nichicon Corp | Driving electrolyte for electrolytic capacitor |
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| JPH0368120A (en) * | 1989-08-07 | 1991-03-25 | Hitachi Aic Inc | Electrolyte for electrolytic capacitor |
| JPH04214728A (en) * | 1990-12-14 | 1992-08-05 | Chisso Corp | Production of polyisoimide |
| JP2003037026A (en) * | 2001-07-26 | 2003-02-07 | Nichicon Corp | Driving electrolyte for electrolytic capacitor |
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| CN103887070A (en) * | 2012-12-19 | 2014-06-25 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of electrolyte functional additive and electrolyte prepared by using electrolyte functional additive |
| CN112763296A (en) * | 2020-12-30 | 2021-05-07 | 上海大学 | Three-dimensional etching method for chromium-manganese stainless steel inclusions |
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