JP2012028752A - Electrolyte for electrolytic capacitor - Google Patents
Electrolyte for electrolytic capacitor Download PDFInfo
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- JP2012028752A JP2012028752A JP2011135921A JP2011135921A JP2012028752A JP 2012028752 A JP2012028752 A JP 2012028752A JP 2011135921 A JP2011135921 A JP 2011135921A JP 2011135921 A JP2011135921 A JP 2011135921A JP 2012028752 A JP2012028752 A JP 2012028752A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 25
- 239000003990 capacitor Substances 0.000 title claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- -1 oxypropylene group Chemical group 0.000 claims abstract description 22
- 125000006353 oxyethylene group Chemical group 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 239000002798 polar solvent Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 44
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 16
- 235000005985 organic acids Nutrition 0.000 claims description 4
- 239000013078 crystal Substances 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 13
- 230000008021 deposition Effects 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 238000000926 separation method Methods 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 125000002947 alkylene group Chemical group 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 229940021013 electrolyte solution Drugs 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229920005604 random copolymer Polymers 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Chemical group 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 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
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-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
- 229940126062 Compound A Drugs 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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- GAGSAAHZRBTRGD-UHFFFAOYSA-N oxirane;oxolane Chemical compound C1CO1.C1CCOC1 GAGSAAHZRBTRGD-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
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
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- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
Abstract
Description
本発明は、電解コンデンサ用電解液に関する。 The present invention relates to an electrolytic solution for an electrolytic capacitor.
アルミ電解コンデンサは、高純度のアルミニウム箔からなる陽極に形成する酸化被膜を誘電体として利用するものであり、−４０℃程度から１００℃を超える温度までの幅広い温度領域において安定に使用できることが必須となる。近年のデジタル家電の普及や自動車の電装化にともないデジタル機器や車載機器用途での需要が拡がっているが、高電圧下で使用した場合にショート等の不具合を発生することがあり、火花発生電圧の向上が要求されている。
アルミ電解コンデンサ用電解液としては、エチレングリコールやγ−ブチロラクトン等を主成分とする極性溶媒に、ホウ酸等の無機酸やアジピン酸、マレイン酸、フタル酸、安息香酸等の二塩基酸及びその塩を溶質とした駆動用電解液が知られている。しかしながら、溶質としてこれらのカルボン酸を使用した電解液は、電導性は高いものの火花発生電圧が低いことが問題となっていた。
この問題を解決するため、添加剤の添加により火花発生電圧を向上させる種々の検討がなされており、ポリエチレングリコールを添加する方法、オキシエチレンオキシプロピレンランダム共重合体を添加する方法（例えば特許文献１）、グリセリンのオキシプロピレンオキシエチレンランダム共重合体を添加する方法（例えば特許文献２）が報告されている。このような化合物を添加した電解液は火花発生電圧の向上に効果を有するが、車載用コンデンサに要望される−４０℃付近の低温領域では、経時的に凝固して結晶が析出することがあり、酸化皮膜の化成性が低下して火花発生電圧の向上に十分な効果を発現しないことがあった。
An aluminum electrolytic capacitor uses an oxide film formed on an anode made of high-purity aluminum foil as a dielectric, and must be able to be used stably in a wide temperature range from about −40 ° C. to over 100 ° C. It becomes. With the recent spread of digital home appliances and the electrification of automobiles, the demand for digital devices and in-vehicle devices is expanding, but when used under high voltage, problems such as short-circuits may occur, and spark generation voltage Improvement is demanded.
As electrolytic solutions for aluminum electrolytic capacitors, polar solvents mainly composed of ethylene glycol, γ-butyrolactone, inorganic acids such as boric acid, dibasic acids such as adipic acid, maleic acid, phthalic acid, benzoic acid, and the like A driving electrolyte using a salt as a solute is known. However, electrolytes using these carboxylic acids as solutes have a problem of low electrical spark generation voltage although they are highly conductive.
In order to solve this problem, various studies have been made to improve the spark generation voltage by the addition of an additive. A method of adding polyethylene glycol, a method of adding an oxyethyleneoxypropylene random copolymer (for example, Patent Document 1). ), And a method of adding an oxypropyleneoxyethylene random copolymer of glycerin (for example, Patent Document 2) has been reported. An electrolyte containing such a compound is effective in improving the spark generation voltage. However, in the low temperature region around −40 ° C., which is required for an on-vehicle capacitor, it may solidify over time and crystals may precipitate. In some cases, the chemical conversion of the oxide film is lowered, and the effect sufficient for improving the spark generation voltage is not exhibited.
また、エチレンオキシド及び他のアルキレンオキシドのランダム共重合体を添加する方法（例えば特許文献３）が報告されており、具体例としてエチレンオキシドブチレンオキシドランダム共重合体が記載されている。このようなエチレンオキシドとブチレンオキシドをランダム状に付加した化合物は、エチレンオキシド及びプロピレンオキシドからなる化合物と比べて火花発生電圧の向上効果は高いが、分子量中のブチレンオキシドの含有率が高くなると溶媒への溶解性が低下して電解液中で分離してしまうことがあった。したがって、親水基であるオキシエチレン基の含有率を高める必要があるが、この場合は低温で凝固して電解液に結晶が析出し、火花発生電圧の向上に十分な効果を発現しないことがあった。
このように、火花発生電圧の向上に十分な効果を有するとともに、電解液の分離及び低温での結晶の析出を抑制することのできる電解コンデンサ用電解液は未だ得られていない。
In addition, a method of adding a random copolymer of ethylene oxide and other alkylene oxide has been reported (for example, Patent Document 3), and an ethylene oxide butylene oxide random copolymer is described as a specific example. Such a compound in which ethylene oxide and butylene oxide are randomly added has a higher effect of improving the spark generation voltage than a compound composed of ethylene oxide and propylene oxide, but if the content of butylene oxide in the molecular weight increases, In some cases, the solubility was lowered and the electrolyte was separated in the electrolytic solution. Therefore, it is necessary to increase the content of the oxyethylene group, which is a hydrophilic group, but in this case, it may solidify at a low temperature and crystals may precipitate in the electrolyte, which may not produce a sufficient effect for improving the spark generation voltage. It was.
Thus, an electrolytic solution for an electrolytic capacitor that has a sufficient effect for improving the spark generation voltage and that can suppress separation of the electrolytic solution and precipitation of crystals at a low temperature has not yet been obtained.
本発明が解決しようとする課題は、火花発生電圧の向上に十分な効果を有するとともに、比抵抗の上昇度に比べて火花発生電圧の向上度が高く、さらに電解液の分離及び低温での結晶の析出を抑制することのできる電解コンデンサ用電解液を提供することにある。 The problem to be solved by the present invention has a sufficient effect for improving the spark generation voltage, and has a higher degree of improvement of the spark generation voltage than the increase of the specific resistance. It is in providing the electrolyte solution for electrolytic capacitors which can suppress precipitation of this.
本発明者は、鋭意研究の結果、多価アルコールのブチレンオキシド−アルキレンオキシドブロック付加物、又はアルキレンオキシド−ブチレンオキシド−アルキレンオキシドブロック付加物、又はそれらの末端アルキルエーテル化物を、電解コンデンサ用電解液の火花発生電圧向上剤として使用すれば、電解液の分離が生じず、低温での結晶の析出も回避されることを見出し、本発明を完成するに至った。 As a result of diligent research, the present inventor obtained polybutyl alcohol butylene oxide-alkylene oxide block adducts, alkylene oxide-butylene oxide-alkylene oxide block adducts, or terminal alkyl etherified products thereof as electrolytic solutions for electrolytic capacitors. When used as a spark generating voltage improver, it has been found that separation of the electrolytic solution does not occur and precipitation of crystals at a low temperature is avoided, and the present invention has been completed.
すなわち、本発明は、
［１］次の（ａ）、（ｂ）、及び（ｃ）成分を含有する、電解コンデンサ用電解液、
（ａ）式（１）で示される化合物
（ｂ）極性溶媒
（ｃ）有機酸、無機酸又はそれらの塩からなる群から選択される１種以上の電解質
Ｘ−［Ｏ−(ＥＯ)ａ/(ＰＯ)ｂ−(ＢＯ)ｃ−(ＥＯ)ｄ/(ＰＯ)ｅ−Ｒ］ｋ （１）
（式中、Ｘは、２〜６価のアルコールの水酸基を除いた残基を表す。ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基、ＢＯはオキシブチレン基、Ｒは水素原子又は炭素数１〜４の炭化水素基を示す。ａ及びｄはオキシエチレン基の平均付加モル数であって０〜４０を示し、（ａ＋ｄ）は２〜４０である。ｂ及びｅはオキシプロピレン基の平均付加モル数であって０〜２０を示し、（ｂ＋ｅ）は１〜２０である。ｃはオキシブチレン基の平均付加モル数であって１〜１２を示す。（ａ＋ｄ）／（ａ＋ｂ＋ｄ＋ｅ）は０．６〜０．９５であり、ｃ／（ａ＋ｂ＋ｃ＋ｄ＋ｅ）は０．１〜０．３５である。ｋは２〜６であり、(ＥＯ)ａ/(ＰＯ)ｂ及び(ＥＯ)ｄ/(ＰＯ)ｅは、ＥＯとＰＯのランダム状付加を表す。）
［２］式（１）で示される化合物のＲが水素原子である、［１］記載の電解コンデンサ用電解液、
［３］式（１）で示される化合物のＸが２又は３価のアルコールの水酸基を除いた残基である、［１］又は［２］記載の電解コンデンサ用電解液、
に関する。
That is, the present invention
[1] An electrolytic solution for electrolytic capacitors containing the following components (a), (b), and (c):
(A) Compound represented by formula (1) (b) Polar solvent (c) One or more electrolytes selected from the group consisting of organic acids, inorganic acids or salts thereof
X- [O- (EO) a / (PO) b- (BO) c- (EO) d / (PO) e- R] k (1)
(In the formula, X represents a residue excluding a hydroxyl group of a divalent to hexavalent alcohol. EO is an oxyethylene group, PO is an oxypropylene group, BO is an oxybutylene group, and R is a hydrogen atom or a carbon number of 1 to 1. 4 represents a hydrocarbon group of 4. a and d are average addition moles of an oxyethylene group and represent 0 to 40, and (a + d) is 2 to 40. b and e are average addition moles of an oxypropylene group. The number is 0 to 20, and (b + e) is 1 to 20. c is the average added mole number of the oxybutylene group and is 1 to 12. (a + d) / (a + b + d + e) is 0.6. C / (a + b + c + d + e) is 0.1 to 0.35, k is 2 to 6, (EO) a / (PO) b and (EO) d / (PO) e Represents a random addition of EO and PO.)
[2] The electrolytic solution for electrolytic capacitors according to [1], wherein R of the compound represented by the formula (1) is a hydrogen atom,
[3] The electrolytic solution for electrolytic capacitors according to [1] or [2], wherein X of the compound represented by the formula (1) is a residue obtained by removing a hydroxyl group of a divalent or trivalent alcohol,
About.
本発明に係る式（１）で示される化合物は、ポリエーテル系化合物でありながら、電解コンデンサ用電解液に添加しても電解液の分離を生じにくく、火花発生電圧を向上させ、低温における結晶の析出も抑制することができるため、耐電圧向上剤として有用である。当該化合物を含有する本発明に係る電解コンデンサ用電解液は、火花発生電圧の向上効果に優れるとともに、比抵抗の上昇度に比べて火花発生電圧の向上度が高く、さらに電解液の分離が生じにくく、低温における結晶の析出をも回避することができ、幅広い温度域における安定性が求められる車載用コンデンサなど、各種用途に実用上極めて有用である。 Although the compound represented by the formula (1) according to the present invention is a polyether compound, it is difficult to cause separation of the electrolytic solution even when added to the electrolytic solution for an electrolytic capacitor, improves spark generation voltage, and crystal at low temperature. Is also useful as a withstand voltage improver. The electrolytic solution for an electrolytic capacitor according to the present invention containing the compound is excellent in the effect of improving the spark generation voltage, has a high degree of improvement in the spark generation voltage compared to the increase in specific resistance, and further causes separation of the electrolytic solution. It is difficult to prevent precipitation of crystals at low temperatures, and is extremely useful in various applications such as an in-vehicle capacitor that requires stability in a wide temperature range.
（ａ）式（１）で示される化合物
式（１）において、Ｘは２〜６価のアルコールから水酸基を除いた残基を表し、エチレングリコール、プロピレングリコール、ブチレングリコール、ネオペンチルグリコール、グリセリン、ジグリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスルトール、ジペンタエリスリトール、キシロース、アルキルグルコシド、キシリトール、ガラクトース、グルコース、ソルビトール、ソルビタン等が挙げられる。
そのうち、２〜４価のアルコールの水酸基を除いた残基が好ましく、より好ましくは２〜３価のアルコールの水酸基を除いた残基であり、具体的には、エチレングリコール、プロピレングリコール、ブチレングリコール、ネオペンチルグリコール、グリセリン、トリメチロールエタン、トリメチロールプロパン等が挙げられる。アルコールの水酸基の価数が２より小さいと、親油基−親水基のジブロック型界面活性剤となるために、電解液の泡立ちが高くなる。
(A) Compound represented by formula (1) In formula (1), X represents a residue obtained by removing a hydroxyl group from a divalent to hexavalent alcohol, and ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, glycerin, Examples include diglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, xylose, alkylglucoside, xylitol, galactose, glucose, sorbitol, sorbitan and the like.
Among them, a residue from which a hydroxyl group of a divalent to tetravalent alcohol is removed is preferable, and a residue from which a hydroxyl group of a divalent to trivalent alcohol is removed is more preferable. Specific examples include ethylene glycol, propylene glycol, butylene glycol. , Neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane and the like. When the valence of the hydroxyl group of the alcohol is less than 2, since it becomes a lipophilic group-hydrophilic diblock type surfactant, the foaming of the electrolyte is increased.
式（１）において、Ｒは水素原子又は炭素数１〜４の炭化水素基であり、炭素数１〜４の炭化水素基である場合は直鎖であっても分岐であってもよく、具体的にはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基が挙げられる。Ｒは好ましくは水素原子である。Ｒの炭素数が４より大きくなると溶媒への溶解性が低下する。
式（１）において、ａ及びｄはオキシエチレン基の平均付加モル数を表し、０〜４０である。（ａ＋ｄ）は２〜４０であり、好ましくは３〜３０、より好ましくは３〜２５である。（ａ＋ｄ）が２より小さいと溶媒への溶解性が低下し、４０より大きくなると低温で電解液に結晶が析出しやすくなる。
In the formula (1), R is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and when it is a hydrocarbon group having 1 to 4 carbon atoms, it may be linear or branched. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. R is preferably a hydrogen atom. When the carbon number of R is larger than 4, the solubility in a solvent is lowered.
In Formula (1), a and d represent the average addition mole number of an oxyethylene group, and are 0-40. (A + d) is 2-40, preferably 3-30, more preferably 3-25. When (a + d) is smaller than 2, the solubility in a solvent is lowered, and when it is larger than 40, crystals are likely to precipitate in the electrolyte at a low temperature.
式（１）において、ｂ及びｅはオキシプロピレン基の平均付加モル数を表し、０〜２０である。（ｂ＋ｅ）は１〜２０であり、好ましくは２〜１５、より好ましくは２〜１０である。（ｂ＋ｅ）が１より小さいと低温で電解液に結晶が析出し、２０より大きくなると溶媒への溶解性が低下する傾向がある。
式（１）において、ｃはオキシブチレン基の平均付加モル数を表し、１〜１２であり、好ましくは１〜１０、より好ましくは１〜８である。
式（１）において、（ａ＋ｄ）／（ａ＋ｂ＋ｄ＋ｅ）は、０．６〜０．９５であり、好ましくは０．６〜０．９、より好ましくは０．６〜０．８５である。（ａ＋ｄ）／（ａ＋ｂ＋ｄ＋ｅ）が０．６より小さいと溶媒への溶解性が低下し、０．９５より大きくなると低温で電解液に結晶が析出しやすくなる。
式（１）において、ｃ／（ａ＋ｂ＋ｃ＋ｄ＋ｅ）は０．１〜０．３５であり、好ましくは０．１〜０．３である。ｃ／（ａ＋ｂ＋ｃ＋ｄ＋ｅ）が０．１より小さいと低温で電解液に結晶が析出し、０．３５より大きい場合は溶媒への溶解性が低下する傾向がある。
式（１）において、ｋは２〜６であり、好ましくは２〜４、より好ましくは２〜３である。
式（１）において、ＥＯ及びＰＯの付加形態はランダム状である。ブロック状の場合は低温で電解液に結晶が析出する。
式（１）で示される化合物の分子量は、好ましくは５００〜１０，０００であり、より好ましくは８００〜５，０００である。分子量が５００より小さいと火花発生電圧の向上に十分な効果が得られず、分子量が１０，０００より大きくなると電解液の粘度が高くなり、泡立ちが強くなりやすい。
In Formula (1), b and e represent the average addition mole number of an oxypropylene group, and are 0-20. (B + e) is 1-20, preferably 2-15, more preferably 2-10. When (b + e) is smaller than 1, crystals are precipitated in the electrolyte at a low temperature, and when it is larger than 20, the solubility in a solvent tends to decrease.
In formula (1), c represents the average number of added moles of the oxybutylene group, and is 1 to 12, preferably 1 to 10, and more preferably 1 to 8.
In the formula (1), (a + d) / (a + b + d + e) is 0.6 to 0.95, preferably 0.6 to 0.9, and more preferably 0.6 to 0.85. When (a + d) / (a + b + d + e) is less than 0.6, the solubility in a solvent is lowered, and when it is more than 0.95, crystals tend to precipitate in the electrolyte at a low temperature.
In the formula (1), c / (a + b + c + d + e) is 0.1 to 0.35, preferably 0.1 to 0.3. When c / (a + b + c + d + e) is smaller than 0.1, crystals are precipitated in the electrolyte at a low temperature, and when it is larger than 0.35, the solubility in a solvent tends to decrease.
In Formula (1), k is 2-6, Preferably it is 2-4, More preferably, it is 2-3.
In Formula (1), the addition form of EO and PO is random. In the case of the block shape, crystals are precipitated in the electrolyte at a low temperature.
The molecular weight of the compound represented by the formula (1) is preferably 500 to 10,000, more preferably 800 to 5,000. When the molecular weight is less than 500, a sufficient effect for improving the spark generation voltage cannot be obtained, and when the molecular weight is greater than 10,000, the viscosity of the electrolytic solution increases and foaming tends to be strong.
式（１）で示される化合物は、公知の方法で製造することができる。例えば、アルカリ触媒の存在下、２〜６価のアルコールにブチレンオキシド、炭素数２及び３のアルキレンオキシドを順に付加重合させることにより多価アルコールのブチレンオキシド−炭素数２及び３のアルキレンオキシド−ブロック付加物が得られる。さらに、この多価アルコールのブチレンオキシド−炭素数２及び３のアルキレンオキシド−ブロック付加物をアルカリ触媒の存在下においてハロゲン化アルキルと反応させることにより、末端アルキルエーテル化物が得られる。
また、アルカリ触媒の存在下、２〜６価のアルコールに 炭素数２及び３のアルキレンオキシド、ブチレンオキシドを順に付加重合させることにより多価アルコールのアルキレンオキシド−ブチレンオキシド−ブロック付加物が得られる。さらに、この多価アルコールのアルキレンオキシド−ブチレンオキシド−ブロック付加物をアルカリ触媒の存在下において炭素数２及び３のアルキレンオキシドと反応させることにより、多価アルコールのアルキレンオキシド−ブチレンオキシド−アルキレンオキシド−ブロック付加物が得られる。さらに、この多価アルコールのアルキレンオキシド−ブチレンオキシド−アルキレンオキシド−ブロック付加物をアルカリ触媒の存在下においてハロゲン化アルキルと反応させることにより、末端アルキルエーテル化物が得られる。
The compound represented by the formula (1) can be produced by a known method. For example, in the presence of an alkali catalyst, butylene oxide and alkylene oxides having 2 and 3 carbon atoms are sequentially added to a 2 to 6 valent alcohol to polymerize butylene oxide of a polyhydric alcohol-alkylene oxide blocks having 2 and 3 carbon atoms. An adduct is obtained. Furthermore, a terminal alkyl etherified product is obtained by reacting this polyhydric alcohol butylene oxide-C2 and C3 alkylene oxide block adduct with an alkyl halide in the presence of an alkali catalyst.
Further, an alkylene oxide-butylene oxide-block adduct of a polyhydric alcohol can be obtained by addition polymerization of a C2-C3 alkylene oxide and a butylene oxide to a divalent to hexavalent alcohol in the presence of an alkali catalyst. Furthermore, by reacting the alkylene oxide-butylene oxide-block adduct of the polyhydric alcohol with an alkylene oxide having 2 and 3 carbon atoms in the presence of an alkali catalyst, the polyhydric alcohol alkylene oxide-butylene oxide-alkylene oxide- A block adduct is obtained. Furthermore, a terminal alkyl etherified product is obtained by reacting the alkylene oxide-butylene oxide-alkylene oxide-block adduct of this polyhydric alcohol with an alkyl halide in the presence of an alkali catalyst.
上記のとおり、式（１）で示される化合物において、多価アルコールへのオキシブチレン基と（オキシエチレン基／オキシプロピレン基）の付加順序はいずれが先でもよく、また（オキシエチレン基／オキシプロピレン基）−オキシブチレン基−（オキシエチレン基／オキシプロピレン基）のように付加してもよい。付加順序がオキシブチレン基−（オキシエチレン基／オキシプロピレン基）である場合及び（オキシエチレン基／オキシプロピレン基）−オキシブチレン基−（オキシエチレン基／オキシプロピレン基）である場合は、極性溶媒への溶解性が向上する。また、付加順序が（オキシエチレン基／オキシプロピレン基）−オキシブチレン基である場合は、電解液の泡立ちが低減する。 As described above, in the compound represented by the formula (1), any order of addition of the oxybutylene group and (oxyethylene group / oxypropylene group) to the polyhydric alcohol may be first, and (oxyethylene group / oxypropylene group). Group) -oxybutylene group- (oxyethylene group / oxypropylene group). When the addition order is oxybutylene group- (oxyethylene group / oxypropylene group) and (oxyethylene group / oxypropylene group) -oxybutylene group- (oxyethylene group / oxypropylene group), a polar solvent Solubility is improved. Further, when the addition order is (oxyethylene group / oxypropylene group) -oxybutylene group, foaming of the electrolytic solution is reduced.
（ｂ）極性溶媒
本発明における極性溶媒としては、エタノール、プロパノール等の１価アルコール、エチレングリコール、プロピレングリコール、ジエチレングリコール、１，３−ブタンジオール、１，４−ブタンジオール等の２価アルコール、グリセリン等の３価アルコール、エチレングリコールモノメチルエーテル、ジエチレングリコールジエチルエーテル等のエーテル系溶媒、γ−ブチロラクトン等のラクトン系溶媒、Ｎ−メチルホルムアミド等のアミド系溶媒、水等が挙げられ、単独で使用してもよく２種類以上を混合して使用してもよく、好ましくはエチレングリコール及びγ−ブチロラクトンである。
(B) Polar solvent The polar solvent in the present invention includes monohydric alcohols such as ethanol and propanol, dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,3-butanediol, and 1,4-butanediol, and glycerin. Examples include trihydric alcohols such as ethylene glycol monomethyl ether and diethylene glycol diethyl ether, lactone solvents such as γ-butyrolactone, amide solvents such as N-methylformamide, water, and the like. Alternatively, two or more types may be used in combination, and ethylene glycol and γ-butyrolactone are preferred.
（ｃ）有機酸、無機酸又はそれらの塩からなる群から選択される１種以上の電解質
本発明における無機酸としては、ホウ酸等が挙げられ、有機酸としては、アジピン酸、アゼライン酸、セバシン酸、ブチルオクタン二酸、５，６−デカンジカルボン酸、マレイン酸等の脂肪族カルボン酸、安息香酸、サリチル酸、フタル酸、トリメリット酸等の芳香族カルボン酸が挙げられる。これらは１種でも２種以上を混合して使用してもよく、塩基性化合物との中和塩として使用してもよい。塩基性化合物としては、アンモニア、アンモニア水、トリエチルアミン、トリエタノールアミン等の３級アミン、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン等のポリアルキレンポリアミン、ポリアルキレンポリアミンのアルキレンオキシド付加物等が挙げられる。好ましくはアンモニア及びアンモニア水である。
(C) One or more electrolytes selected from the group consisting of organic acids, inorganic acids or salts thereof Examples of inorganic acids in the present invention include boric acid, and examples of organic acids include adipic acid, azelaic acid, Examples thereof include aliphatic carboxylic acids such as sebacic acid, butyloctanedioic acid, 5,6-decanedicarboxylic acid and maleic acid, and aromatic carboxylic acids such as benzoic acid, salicylic acid, phthalic acid and trimellitic acid. These may be used alone or in combination of two or more, and may be used as a neutralized salt with a basic compound. Examples of basic compounds include tertiary amines such as ammonia, aqueous ammonia, triethylamine, and triethanolamine, polyalkylene polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, and alkylene oxide adducts of polyalkylenepolyamine. Can be mentioned. Ammonia and aqueous ammonia are preferred.
式（１）で示される化合物は、オキシブチレン基を含有しているため、アルミ電解コンデンサの陽極上の保護皮膜としては、オキシエチレン基やオキシプロピレン基のみからなる化合物と比べて電気絶縁性が高く、さらにオキシブチレン基の分岐のエチル基により嵩高い立体構造を形成することから、酸化皮膜の化成性を向上させることができる。これにより、オキシブチレン基を含有する化合物は火花発生電圧の向上に優れた効果を有する。
式（１）で示される化合物において、オキシブチレン基と（オキシエチレン基／オキシプロピレン基）の付加形態はブロック型であり、親油基であるポリオキシブチレン鎖と酸化皮膜を形成する酸との親和性により、酸化皮膜の化成性が向上して優れた火花発生電圧向上効果が得られる。
また、式（１）で示される化合物は、オキシブチレン基の分岐のエチル基を有し、さらにオキシエチレン基とオキシプロピレン基のランダム状の共重合体を有することにより、結晶性が低下し、低温における式（１）で示される化合物自体の結晶の析出を抑制することができる。これにより、低温においても性能を低下させることがなく、幅広い温度領域で安定にコンデンサを使用することができる。
Since the compound represented by the formula (1) contains an oxybutylene group, the protective film on the anode of the aluminum electrolytic capacitor is more electrically insulating than a compound consisting of only an oxyethylene group or an oxypropylene group. Further, since a bulky steric structure is formed by the branched ethyl group of the oxybutylene group, the chemical conversion property of the oxide film can be improved. Thereby, the compound containing an oxybutylene group has the effect excellent in the improvement of a spark generation voltage.
In the compound represented by the formula (1), the addition form of an oxybutylene group and (oxyethylene group / oxypropylene group) is a block type, and a polyoxybutylene chain that is a lipophilic group and an acid that forms an oxide film. Due to the affinity, the chemical conversion property of the oxide film is improved, and an excellent spark generation voltage improvement effect is obtained.
Further, the compound represented by the formula (1) has a branched ethyl group of an oxybutylene group, and further has a random copolymer of an oxyethylene group and an oxypropylene group, so that the crystallinity is lowered. Precipitation of crystals of the compound itself represented by formula (1) at a low temperature can be suppressed. As a result, the capacitor can be stably used in a wide temperature range without degrading the performance even at a low temperature.
本発明の電解液において、式（１）で示される化合物の添加量は、０．１〜５０質量％である。添加量が０．１質量％より少ないと火花発生電圧の向上効果が不十分であり、５０質量％より多いと、電解液の粘度が上昇する傾向にあるため適切でない。
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれに限定されるものではない。
In the electrolytic solution of the present invention, the amount of the compound represented by the formula (1) is 0.1 to 50% by mass. When the addition amount is less than 0.1% by mass, the effect of improving the spark generation voltage is insufficient, and when it is more than 50% by mass, the viscosity of the electrolytic solution tends to increase.
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.
［実施例１］
＜合成例１＞
プロピレングリコール７６．１ｇ（１．０モル）と触媒として水酸化カリウム４．５ｇを５Ｌ容量オートクレーブ中に仕込み、オートクレーブ内の空気を窒素で置換した後、撹拌しながら１２０℃にて触媒を完全に溶解させた。次に滴下装置よりブチレンオキシド２８８．４ｇ（４．０モル）を滴下し、４時間撹拌した。その後、さらに滴下装置よりエチレンオキシド８８２．０ｇ（２０．０モル）とプロピレンオキシド２３２．４ｇ（４．０モル）の混合物を滴下し、４時間撹拌した。その後、オートクレーブより生成物を取り出し、塩酸で中和してｐＨ６〜７とし、含有する水分を除去するために、減圧−０．０９５Ｍｐａ（ゲージ圧、５０ｍｍＨｇ）、１００℃で１時間処理した。さらに処理後生成した塩を除去するためにろ過を行い、表１の化合物Ａを得た。
[Example 1]
<Synthesis Example 1>
76.1 g (1.0 mol) of propylene glycol and 4.5 g of potassium hydroxide as a catalyst were charged into a 5 L autoclave, the air in the autoclave was replaced with nitrogen, and the catalyst was completely removed at 120 ° C. with stirring. Dissolved. Next, 288.4 g (4.0 mol) of butylene oxide was added dropwise from the dropping device, followed by stirring for 4 hours. Thereafter, a mixture of 882.0 g (20.0 mol) of ethylene oxide and 232.4 g (4.0 mol) of propylene oxide was further added dropwise from a dropping device and stirred for 4 hours. Thereafter, the product was taken out from the autoclave, neutralized with hydrochloric acid to pH 6 to 7, and treated at 100 ° C. for 1 hour at a reduced pressure of −0.095 MPa (gauge pressure, 50 mmHg) in order to remove the contained water. Further, filtration was carried out to remove the salt produced after the treatment, and compound A in Table 1 was obtained.
＜電解液の調製＞
表２に示す組成で混合し、６０℃で均一になるまで撹拌して電解液を得た。
＜分離の有無の評価＞
電解液５０ｇをガラス瓶に入れ、２５℃の恒温槽で１時間静置したときの分離の有無を以下の基準で評価した。
○：分離することなく均一である
×：分離している
結果を表２に示す。
＜結晶の析出の有無の評価＞
電解液５０ｇをガラス瓶に入れ、２５℃及び−４０℃の恒温槽で１時間静置したときの結晶の析出の有無を以下の基準で評価した。
○：結晶が析出せず均一である
×：結晶が析出している
結果を表２に示す。
<Preparation of electrolyte>
It mixed by the composition shown in Table 2, and it stirred until it became uniform at 60 degreeC, and obtained electrolyte solution.
<Evaluation of presence / absence of separation>
The presence or absence of separation was evaluated according to the following criteria when 50 g of the electrolytic solution was put in a glass bottle and allowed to stand in a thermostatic bath at 25 ° C. for 1 hour.
○: Uniform without separation ×: Separation The results are shown in Table 2.
<Evaluation of Presence of Crystal Precipitation>
The following criteria evaluated the presence or absence of crystal precipitation when 50 g of the electrolytic solution was put in a glass bottle and allowed to stand for 1 hour in a thermostatic bath at 25 ° C. and −40 ° C.
○: Crystal is not precipitated and is uniform ×: Crystal is precipitated Table 2 shows the results.
＜比抵抗の測定＞
電気伝導度計（東亜電波工業（株）製ＣＭ−６０Ｓ）により、電解液の３０℃での比抵抗を測定した。結果を表２に示す。
＜火花発生電圧の測定＞
１Ｌ容量ステンレス製容器に電解液７００ｇを入れ、６０ｍｍ×１０ｍｍに切断した純度９９．９９％以上のアルミ箔を浸漬し、直流電源を繋げて２５℃における電解液の火花発生電圧を測定した。火花発生電圧向上効果を次式にしたがって算出し、以下の基準で評価した。結果を表２に示す。
[火花発生電圧向上度（Ｖ）＝（ａ）の化合物を添加した電解液の火花発生電圧−
（ａ）の化合物を添加していない電解液の火花発生電圧]
○：火花発生電圧向上度が３０Ｖ以上
×：火花発生電圧向上度が３０Ｖ未満
また、比抵抗上昇度に対する火花発生電圧向上度を次式にしたがって算出し、以下の基準で評価した。結果を表２に示す。
[火花発生電圧向上度／比抵抗上昇度＝（（ａ）の化合物を添加した電解液の火花発生電圧−（ａ）の化合物を添加していない電解液の火花発生電圧）／（（ａ）の化合物を添加した電解液の比抵抗−（ａ）の化合物を添加していない電解液の比抵抗）]
○：火花発生電圧向上度／比抵抗上昇度が１．２０以上
×：火花発生電圧向上度／比抵抗上昇度が１．２０未満
<Measurement of specific resistance>
The specific resistance at 30 ° C. of the electrolytic solution was measured with an electric conductivity meter (CM-60S manufactured by Toa Radio Industry Co., Ltd.). The results are shown in Table 2.
<Measurement of spark generation voltage>
700 g of the electrolytic solution was put into a 1 L capacity stainless steel container, aluminum foil having a purity of 99.99% or more cut to 60 mm × 10 mm was immersed, and a spark generation voltage of the electrolytic solution at 25 ° C. was measured by connecting a DC power source. The spark generation voltage improvement effect was calculated according to the following equation and evaluated according to the following criteria. The results are shown in Table 2.
[Spark generation voltage improvement degree (V) = Spark generation voltage of electrolyte added with compound of (a) −
Spark generation voltage of electrolyte without adding compound (a)]
○: Spark generation voltage improvement degree is 30 V or more ×: Spark generation voltage improvement degree is less than 30 V Further, the spark generation voltage improvement degree with respect to the specific resistance increase degree is calculated according to the following formula and evaluated according to the following criteria. The results are shown in Table 2.
[Spark generation voltage improvement / specific resistance increase = (spark generation voltage of electrolyte added with compound (a) −spark generation voltage of electrolyte not added compound (a)) / ((a) Specific Resistance of Electrolytic Solution with Addition of Compound-Specific Resistance of Electrolytic Solution without Addition of Compound (a))]
○: Spark generation voltage improvement / specific resistance increase is 1.20 or more ×: Spark generation voltage improvement / specific resistance increase is less than 1.20
［実施例２〜９］
実施例１の方法に準じて、表１に示す化合物Ｂ〜Ｇを合成し、表２に示す電解液を調製して、分離の有無及び結晶析出の有無の評価を行った。また、比抵抗及び火花発生電圧を測定し、火花発生電圧向上度を算出し、火花発生電圧向上度の評価及び比抵抗上昇度に対する火花発生電圧向上度の評価を行った。結果を表２に示す。
［比較例１〜１０］
実施例１と同様の方法で、表１に示す化合物Ｈ〜Ｑを合成し、表２に示す電解液を調製して、分離の有無及び結晶析出の有無の評価を行った。また、比抵抗及び火花発生電圧を測定し、火花発生電圧向上度を算出し、火花発生電圧向上度の評価及び比抵抗上昇度に対する火花発生電圧向上度の評価を行った。結果を表２に示す。なお、電解液の分離の評価において、２５℃で分離が見られた場合には、結晶の析出の有無の評価、比抵抗の測定、火花発生電圧の測定は行わなかった。
[Examples 2 to 9]
According to the method of Example 1, compounds B to G shown in Table 1 were synthesized, and an electrolyte solution shown in Table 2 was prepared, and the presence or absence of separation and the presence or absence of crystal precipitation were evaluated. Moreover, the specific resistance and the spark generation voltage were measured, the spark generation voltage improvement degree was calculated, the spark generation voltage improvement degree was evaluated, and the spark generation voltage improvement degree with respect to the specific resistance increase degree was evaluated. The results are shown in Table 2.
[Comparative Examples 1 to 10]
In the same manner as in Example 1, the compounds H to Q shown in Table 1 were synthesized and the electrolyte solutions shown in Table 2 were prepared, and the presence or absence of separation and the presence or absence of crystal precipitation were evaluated. Moreover, the specific resistance and the spark generation voltage were measured, the spark generation voltage improvement degree was calculated, the spark generation voltage improvement degree was evaluated, and the spark generation voltage improvement degree with respect to the specific resistance increase degree was evaluated. The results are shown in Table 2. In the evaluation of the separation of the electrolytic solution, when separation was observed at 25 ° C., the evaluation of the presence or absence of crystal precipitation, the measurement of the specific resistance, and the measurement of the spark generation voltage were not performed.
表２から明らかなとおり、実施例１〜９の電解液は、分離することがなく、かつ低温において結晶が析出することもなく均一であった。また、実施例１〜９の電解液は火花発生電圧向上度が高く、さらに比抵抗上昇度に対する火花発生電圧向上度も高いことがわかった。すなわち、これらの電解液をアルミ電解コンデンサに使用した場合、高い電導度を示すとともに、高い火花発生電圧向上効果を示すことが確認された。 As is clear from Table 2, the electrolyte solutions of Examples 1 to 9 were uniform without separation and without precipitation of crystals at low temperatures. Moreover, it turned out that the electrolyte solution of Examples 1-9 has a high spark generation voltage improvement degree, and also has a high spark generation voltage improvement degree with respect to a specific resistance increase degree. That is, when these electrolytic solutions were used for aluminum electrolytic capacitors, it was confirmed that they showed high conductivity and a high spark generation voltage improvement effect.
これに対し、比較例１の電解液はｃが本発明の範囲より大きく、ｃ／（ａ＋ｂ＋ｃ＋ｄ＋ｅ）が本発明の範囲より大きいために、電解液が分離する結果となった。
比較例２は、ｃ／（ａ＋ｂ＋ｃ＋ｄ＋ｅ）が本発明の範囲より大きいために、電解液が分離した。
比較例３は、ａ及び（ａ＋ｄ）が本発明の範囲より大きいために、低温で電解液に結晶が析出した。また、比抵抗上昇度に対する火花発生電圧向上度が不十分であった。
比較例４は、（ａ＋ｄ）が本発明の範囲より小さく、（ａ＋ｄ）／（ａ＋ｂ＋ｄ＋ｅ）が本発明の範囲より小さいために、電解液が分離した。
比較例５は、ｅ及び（ｂ＋ｅ）が本発明の範囲より大きく、（ａ＋ｄ）／（ａ＋ｂ＋ｄ＋ｅ）が本発明の範囲より小さいために、電解液が分離した。
比較例６は、ｃが本発明の範囲より小さく、ｃ／（ａ＋ｂ＋ｃ＋ｄ＋ｅ）が本発明の範囲より小さいために、電解液が分離した。
比較例７は、ｃが本発明の範囲より小さく、（ｂ＋ｅ）が本発明の範囲より小さく、（ａ＋ｄ）／（ａ＋ｂ＋ｄ＋ｅ）が本発明の範囲より大きく、ｃ／（ａ＋ｂ＋ｃ＋ｄ＋ｅ）が本発明の範囲より小さいために、低温で電解液に結晶が析出した。また、火花発生電圧向上度が不十分であり、比抵抗上昇度に対する火花発生電圧向上度が不十分であった。
比較例８は、ｃが本発明の範囲より小さく、ｄ及び（ａ＋ｄ）が本発明の範囲より大きく、ｃ／（ａ＋ｂ＋ｃ＋ｄ＋ｅ）が本発明の範囲より小さいために、電解液に低温で結晶が析出した。また、火花発生電圧向上度が不十分であり、比抵抗上昇度に対する火花発生電圧向上度が不十分であった。
比較例９は、ｃが本発明の範囲より小さく、ｃ／（ａ＋ｂ＋ｃ＋ｄ＋ｅ）が本発明の範囲より小さいために、低温で電解液に結晶が析出した。また、火花発生電圧向上度が不十分であり、比抵抗上昇度に対する火花発生電圧向上度が不十分であった。
比較例１０は、ｃが本発明の範囲より大きく、（ｂ＋ｅ）が本発明の範囲より小さく、（ａ＋ｄ）／（ａ＋ｂ＋ｄ＋ｅ）が本発明の範囲より大きく、ｃ／（ａ＋ｂ＋ｃ＋ｄ＋ｅ）が本発明の範囲より大きく、ｋが本発明の範囲より小さいことにより、電解液が分離した。
On the other hand, the electrolytic solution of Comparative Example 1 was separated from the electrolytic solution because c was larger than the range of the present invention and c / (a + b + c + d + e) was larger than the range of the present invention.
In Comparative Example 2, since c / (a + b + c + d + e) was larger than the range of the present invention, the electrolytic solution was separated.
In Comparative Example 3, since a and (a + d) were larger than the range of the present invention, crystals were precipitated in the electrolytic solution at a low temperature. Moreover, the spark generation voltage improvement degree with respect to the specific resistance increase degree was insufficient.
In Comparative Example 4, since (a + d) was smaller than the range of the present invention and (a + d) / (a + b + d + e) was smaller than the range of the present invention, the electrolytic solution was separated.
In Comparative Example 5, since e and (b + e) were larger than the range of the present invention and (a + d) / (a + b + d + e) was smaller than the range of the present invention, the electrolytic solution was separated.
In Comparative Example 6, since c was smaller than the range of the present invention and c / (a + b + c + d + e) was smaller than the range of the present invention, the electrolytic solution was separated.
In Comparative Example 7, c is smaller than the range of the present invention, (b + e) is smaller than the range of the present invention, (a + d) / (a + b + d + e) is larger than the range of the present invention, and c / (a + b + c + d + e) is within the range of the present invention. Because it was smaller, crystals precipitated in the electrolyte at low temperatures. Moreover, the spark generation voltage improvement degree was insufficient, and the spark generation voltage improvement degree with respect to the specific resistance increase degree was insufficient.
In Comparative Example 8, c is smaller than the range of the present invention, d and (a + d) are larger than the range of the present invention, and c / (a + b + c + d + e) is smaller than the range of the present invention. did. Moreover, the spark generation voltage improvement degree was insufficient, and the spark generation voltage improvement degree with respect to the specific resistance increase degree was insufficient.
In Comparative Example 9, since c was smaller than the range of the present invention and c / (a + b + c + d + e) was smaller than the range of the present invention, crystals were precipitated in the electrolytic solution at a low temperature. Moreover, the spark generation voltage improvement degree was insufficient, and the spark generation voltage improvement degree with respect to the specific resistance increase degree was insufficient.
In Comparative Example 10, c is larger than the range of the present invention, (b + e) is smaller than the range of the present invention, (a + d) / (a + b + d + e) is larger than the range of the present invention, and c / (a + b + c + d + e) is within the range of the present invention. The electrolyte was separated because it was larger and k was smaller than the range of the present invention.
Claims (3)
（ａ）式（１）で示される化合物
（ｂ）極性溶媒
（ｃ）有機酸、無機酸又はそれらの塩からなる群から選択される１種以上の電解質
Ｘ−［Ｏ−(ＥＯ)ａ/(ＰＯ)ｂ−(ＢＯ)ｃ−(ＥＯ)ｄ/(ＰＯ)ｅ−Ｒ］ｋ （１）
（式中、Ｘは２〜６価のアルコールの水酸基を除いた残基である。ＥＯはオキシエチレン基であり、ＰＯはオキシプロピレン基であり、ＢＯはオキシブチレン基である。Ｒは水素原子又は炭素数１〜４の炭化水素基である。ａ及びｄはオキシエチレン基の平均付加モル数であって０〜４０を示し、（ａ＋ｄ）は２〜４０である。ｂ及びｅはオキシプロピレン基の平均付加モル数であって０〜２０を示し、（ｂ＋ｅ）は１〜２０である。ｃはオキシブチレン基の平均付加モル数であって１〜１２を示す。（ａ＋ｄ）／（ａ＋ｂ＋ｄ＋ｅ）は０．６〜０．９５である。ｃ／（ａ＋ｂ＋ｃ＋ｄ＋ｅ）は０．１〜０．３５である。ｋは２〜６であり、(ＥＯ)ａ/(ＰＯ)ｂ及び(ＥＯ)ｄ/(ＰＯ)ｅは、ＥＯとＰＯのランダム状付加を表す。） An electrolytic solution for an electrolytic capacitor containing the following components (a), (b), and (c):
(A) Compound represented by formula (1) (b) Polar solvent (c) One or more electrolytes selected from the group consisting of organic acids, inorganic acids or salts thereof
X- [O- (EO) a / (PO) b- (BO) c- (EO) d / (PO) e- R] k (1)
(In the formula, X is a residue obtained by removing a hydroxyl group of a divalent to hexavalent alcohol. EO is an oxyethylene group, PO is an oxypropylene group, BO is an oxybutylene group. R is a hydrogen atom. Or it is a C1-C4 hydrocarbon group, a and d are the average addition mole numbers of an oxyethylene group, 0-40 are shown, (a + d) is 2-40, b and e are oxypropylene. The average added mole number of the group is from 0 to 20, and (b + e) is from 1 to 20. c is the average added mole number of the oxybutylene group and is from 1 to 12. (a + d) / (a + b + d + e ) Is 0.6 to 0.95, c / (a + b + c + d + e) is 0.1 to 0.35, k is 2 to 6, and (EO) a / (PO) b and (EO) d / (PO) e represents random addition of EO and PO.)
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| JP2019134179A (en) * | 2015-03-11 | 2019-08-08 | 三洋化成工業株式会社 | Electrolytic solution for aluminum electrolytic capacitor and aluminum electrolytic capacitor using the same |
| US10607786B2 (en) | 2015-03-11 | 2020-03-31 | Sanyo Chemical Industries, Ltd. | Electrolytic solution for aluminum electrolytic capacitor and aluminum electrolytic capacitor using same |
| JP2022002341A (en) * | 2015-03-11 | 2022-01-06 | 三洋化成工業株式会社 | Electrolyte for aluminum electrolytic capacitor and aluminum electrolytic capacitors using the same |
| JP7181366B2 (en) | 2015-03-11 | 2022-11-30 | 三洋化成工業株式会社 | Electrolyte for aluminum electrolytic capacitor and aluminum electrolytic capacitor using the same |
| JP2021022753A (en) * | 2020-11-06 | 2021-02-18 | 日本ケミコン株式会社 | Solid electrolytic capacitor and method of manufacturing the same |
| JP7067598B2 (en) | 2020-11-06 | 2022-05-16 | 日本ケミコン株式会社 | Solid electrolytic capacitors and their manufacturing methods |
| JP2022100375A (en) * | 2020-11-06 | 2022-07-05 | 日本ケミコン株式会社 | Solid electrolytic capacitor and method of manufacturing the same |
| JP7294494B2 (en) | 2020-11-06 | 2023-06-20 | 日本ケミコン株式会社 | Solid electrolytic capacitor and its manufacturing method |
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