JP2021040087A - Modifier of capacitor electrolyte solution, electrolytic solution for aluminum electrolytic capacitor, which is arranged by use thereof, and aluminum electrolytic capacitor - Google Patents
Modifier of capacitor electrolyte solution, electrolytic solution for aluminum electrolytic capacitor, which is arranged by use thereof, and aluminum electrolytic capacitor Download PDFInfo
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- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 45
- 239000003990 capacitor Substances 0.000 title claims abstract description 33
- 239000003607 modifier Substances 0.000 title claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 title claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 53
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 3
- -1 ester compound Chemical class 0.000 description 28
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 229920001451 polypropylene glycol Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 3
- 150000003839 salts Chemical class 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 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229930195725 Mannitol Natural products 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000000594 mannitol Substances 0.000 description 2
- 235000010355 mannitol Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N n-Dodecanedioic acid Natural products OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-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
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-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
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-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
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- FOFMIZPXOAUNDQ-UHFFFAOYSA-N azane;2-methylnonanedioic acid Chemical compound N.N.OC(=O)C(C)CCCCCCC(O)=O FOFMIZPXOAUNDQ-UHFFFAOYSA-N 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
Abstract
Description
本発明は、コンデンサ電解液用の改質剤、ならびにそれを用いた電解液及び電解コンデンサに関するものである。 The present invention relates to a modifier for a capacitor electrolytic solution, and an electrolytic solution and an electrolytic capacitor using the modifier.
アルミニウム電解コンデンサは、粗面化処理を施したアルミニウムの表面に絶縁性の酸化皮膜層を形成した陽極電極箔と、集電用の陰極電極箔とを電解紙を介して巻回してコンデンサ素子を形成するとともに、電解液を含浸し、外装ケースに収納した構成から成る。電解液は、陽極箔上に形成された誘電体層と集電用の陰極箔の間に介入して、その抵抗分が電解コンデンサに直列に挿入され、電解液の特性がコンデンサの特性を左右させる大きな要因となることが知られている。 In an aluminum electrolytic capacitor, an anode electrode foil having an insulating oxide film layer formed on the surface of roughened aluminum and a cathode electrode foil for collecting electricity are wound around an electrolytic paper to form a capacitor element. It is formed, impregnated with an electrolytic solution, and stored in an outer case. The electrolytic solution intervenes between the dielectric layer formed on the anode foil and the cathode foil for current collection, and its resistance is inserted in series with the electrolytic capacitor, and the characteristics of the electrolytic solution affect the characteristics of the capacitor. It is known to be a major factor in causing this.
一般に、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やγ−ブチロラクトンなどの有機溶媒に、高級ジカルボン酸、又はそのアンモニウム塩、ホウ酸、又はそのアンモニウム塩、及びマンニトールなどの多価アルコール類を溶解したものである。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（特許文献１）。また、ポリエチレングリコールを電解液に添加することでも耐電圧が向上することが知られている（特許文献２）。しかしながら、近年、スイッチング電源を使用した電子機器において、アルミニウム電解コンデンサの安全性に対する要求が高まっている。スイッチング電源に使用されるアルミニウム電解コンデンサには、供給電力の不安定さによって過電圧が印加される場合があり、その際にはコンデンサの破裂、発火、燃焼という事態を招くことがあり、これを防止するためには電解コンデンサ用電解液の火花電圧、すなわち耐電圧をさらに向上させる必要がある。これに対して、ホウ酸と多価アルコール類の添加量を増加して耐電圧の向上を図ろうとすると、ホウ酸エステル化により生成する水分の増加によってコンデンサの内圧上昇を招くという問題があった。また、ポリエチレングリコールの添加量を増加して耐電圧特性の向上を図ろうとした場合には、低温下で電解液の著しい増粘あるいは固化により著しい電導度の低下が生じ、電解コンデンサのインピーダンス特性の低下を招くという問題が存在した。そのため、添加量を増加させた場合においても、低温下で電解液の流動性を維持しつつ、高い耐電圧を付与できる改質剤が求められていた。 Generally, an electrolytic solution for an aluminum electrolytic capacitor dissolves a higher dicarboxylic acid or its ammonium salt, boric acid, or its ammonium salt, and polyhydric alcohols such as mannitol in an organic solvent such as ethylene glycol or γ-butyrolactone. It was done. 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 properties (Patent Document 1). It is also known that the withstand voltage is improved by adding polyethylene glycol to the electrolytic solution (Patent Document 2). However, in recent years, there has been an increasing demand for the safety of aluminum electrolytic capacitors in electronic devices using switching power supplies. Overvoltage may be applied to the aluminum electrolytic capacitor used in the switching power supply due to the instability of the supplied power, which may cause the capacitor to burst, ignite, or burn, which is prevented. In order to do so, it is necessary to further improve the spark voltage, that is, the withstand voltage of the electrolytic solution for the electrolytic capacitor. On the other hand, if an attempt is made to improve the withstand voltage by increasing the amount of boric acid and polyhydric alcohols added, there is a problem that the internal pressure of the capacitor increases due to the increase in the water content generated by boric acid esterification. .. In addition, when an attempt is made to improve the withstand voltage characteristics by increasing the amount of polyethylene glycol added, the impedance characteristics of the electrolytic capacitor are significantly reduced due to the significant thickening or solidification of the electrolytic solution at low temperatures. There was a problem of causing a decline. Therefore, there has been a demand for a modifier capable of imparting a high withstand voltage while maintaining the fluidity of the electrolytic solution at a low temperature even when the addition amount is increased.
本発明は、従来のポリエチレングリコールよりも耐電圧向上効果に優れ、かつ低温での流動性に優れたコンデンサ用電解液の改質剤を提供することを課題とする。 An object of the present invention is to provide a modifier for an electrolytic solution for a capacitor, which is superior in withstand voltage improving effect and excellent in fluidity at low temperature as compared with conventional polyethylene glycol.
平均重合度が３〜１０であるポリグリセリンに対して、水酸基１つ当たりのアルキレンオキサイド（ＡＯ）の平均付加数が１０〜３０であるポリオキシアルキレンポリグリセリルエーテルを改質剤として使用することにより、耐電圧特性に優れ、かつ低温流動性に優れたコンデンサ電解液が得られることを見出し、本発明を完成するに至った。 By using a polyoxyalkylene polyglyceryl ether having an average addition number of alkylene oxide (AO) per hydroxyl group of 10 to 30 as a modifier with respect to polyglycerin having an average degree of polymerization of 3 to 10. We have found that a capacitor electrolytic solution having excellent withstand voltage characteristics and excellent low-temperature fluidity can be obtained, and have completed the present invention.
本発明のコンデンサ電解液の改質剤を使用することにより、耐電圧特性ならびに低温下での流動性に優れたアルミニウム電解コンデンサ用の電解液を製造することができる。 By using the modifier of the capacitor electrolytic solution of the present invention, it is possible to produce an electrolytic solution for an aluminum electrolytic capacitor having excellent withstand voltage characteristics and fluidity at a low temperature.
以下に本説明を実施するための形態をより詳細に説明するが、本発明の範囲はこの実施形態に限定されるものではなく、本発明の趣旨を損なわない範囲で、変更等が加えられた形態も本発明に属する。なお、範囲を表す「〜」は上限と下限を含むものである。 Hereinafter, embodiments for carrying out the present invention will be described in more detail, but the scope of the present invention is not limited to this embodiment, and changes and the like have been made to the extent that the gist of the present invention is not impaired. The form also belongs to the present invention. In addition, "~" representing a range includes an upper limit and a lower limit.
ポリオキシアルキレンポリグリセリルエーテルは、ポリグリセリンの水酸基に対してアルキレンオキサイドを付加した化合物である。アルキレンオキサイドはエチレンオキサイド、プロピレンオキサイド、１，２−ブチレンオキサイド、２，３−ブチレンオキサイドなどが挙げられ、特にエチレンオキサイド、ならびにプロピレンオキサイドを用いることが好ましい。 Polyoxyalkylene polyglyceryl ether is a compound in which an alkylene oxide is added to the hydroxyl group of polyglycerin. Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide, and it is particularly preferable to use ethylene oxide and propylene oxide.
前記ポリオキシアルキレンポリグリセリルエーテルを構成するポリグリセリンは、グリセリンの水酸基が脱水縮合によりエーテル結合した構造であり、エーテル結合は直鎖状、または分岐状のいずれでもよく、また、分子内で縮合した環状化合物を含有してもよい。使用するポリグリセリンは、電解液の耐電圧特性の観点から平均重合度が３以上であることが好ましい。また、電解液の粘度や低温下での電導度特性の観点から平均重合度が１０以下であることが好ましい。ここで、平均重合度は、末端基分析法によるヒドロキシル価（ＯＨＶ）から算出されるポリグリセリンの平均重合度（ｎ）である。詳しくは、次式（式１）、及び（式２）から平均重合度（ｎ）が算出される。
（式１）分子量＝７４ｎ＋１８
（式２）ＯＨＶ＝５６１１０（ｎ＋２）／分子量
上記（式２）中のＯＨＶとは、ポリグリセリンに含まれるヒドロキシル基（ＯＨ基）数の大小の指標となる数値であり、１ｇのポリグリセリンに含まれる遊離ＯＨ基をアセチル化するために必要な酢酸を中和するのに要する水酸化カリウムのミリグラム数をいう。水酸化カリウムのミリグラム数は、社団法人日本油化学会編集、「日本油化学会制定、基準油脂分析試験法、２０１３年度版」に準じて算出される。
ポリグリセリンの具体例としては、トリグリセリン、テトラグリセリン、ヘキサグリセリン、デカグリセリンなどが挙げられ、市販品としては、ＰＧＬ−Ｓ、ポリグリセリン＃３１０、ポリグリセリン＃５００、ポリグリセリン＃７５０（いずれも阪本薬品工業株式会社製）を使用することができる。
The polyglycerin constituting the polyoxyalkylene polyglyceryl ether has a structure in which the hydroxyl groups of glycerin are ether-bonded by dehydration condensation, and the ether bond may be linear or branched, and the cyclic condensed in the molecule. It may contain a compound. The polyglycerin used preferably has an average degree of polymerization of 3 or more from the viewpoint of the withstand voltage characteristics of the electrolytic solution. Further, the average degree of polymerization is preferably 10 or less from the viewpoint of the viscosity of the electrolytic solution and the conductivity characteristics at low temperatures. Here, the average degree of polymerization is the average degree of polymerization (n) of polyglycerin calculated from the hydroxyl value (OHV) by the end group analysis method. Specifically, the average degree of polymerization (n) is calculated from the following equations (Equation 1) and (Equation 2).
(Equation 1) Molecular weight = 74n + 18
(Equation 2) OHV = 56110 (n + 2) / molecular weight OHV in the above (Equation 2) is a numerical value that is an index of the number of hydroxyl groups (OH groups) contained in polyglycerin, and can be added to 1 g of polyglycerin. The number of milligrams of potassium hydroxide required to neutralize the acetic acid required to acetylate the free OH groups contained. The number of milligrams of potassium hydroxide is calculated according to "The Japan Oil Chemists'Association, Established by the Japan Oil Chemists' Society, Standard Oil and Fat Analysis Test Method, 2013 Edition".
Specific examples of polyglycerin include triglycerin, tetraglycerin, hexaglycerin, decaglycerin and the like, and commercially available products include PGL-S, polyglycerin # 310, polyglycerin # 500 and polyglycerin # 750 (all of which). Sakamoto Yakuhin Kogyo Co., Ltd.) can be used.
本発明の改質剤に用いられるポリオキシアルキレンポリグリセリルエーテルは、ポリグリセリンの水酸基１つ当たりのアルキレンオキサイドの平均付加数が１０〜３０である。アルキレンオキサイドはエチレンオキサイド（ＥＯ）およびプロピレンオキサイド（ＰＯ）が好ましく、ＥＯとＰＯの付加モル比がＥＯ：ＰＯ＝５５：４５〜８５：１５であることがより好ましい。アルキレンオキサイドの平均付加数、ならびにＥＯとＰＯの付加モル比が上記範囲であることにより、アルミニウム電解コンデンサの耐電圧特性の向上に繋がる。さらに、ポリグリセリンの水酸基１つ当たりのＥＯの平均付加数が５〜１５であれば低温条件においても電解液の流動性を損なうことなく、低温特性に優れたアルミニウム電解コンデンサが得られる。
ポリオキシアルキレンポリグリセリルエーテルの具体例としては、ポリオキシエチレン（５０）ポリオキシプロピレン（１０）トリグリセリルエーテル、ポリオキシエチレン（５０）ポリオキシプロピレン（２０）トリグリセリルエーテル、ポリオキシエチレン（６０）ポリオキシプロピレン（２４）テトラグリセリルエーテル、ポリオキシエチレン（６０）ポリオキシプロピレン（３６）テトラグリセリルエーテル、ポリオキシプロピレン（１２）ポリオキシエチレン（６０）テトラグリセリルエーテル、ポリオキシプロピレン（２４）ポリオキシエチレン（６０）テトラグリセリルエーテル、ポリオキシプロピレン（１２）ポリオキシエチレン（９０）テトラグリセリルエーテル、ポリオキシプロピレン（３６）ポリオキシエチレン（９０）テトラグリセリルエーテル、ポリオキシプロピレン（２４）ポリオキシエチレン（８０）ヘキサグリセリルエーテル、ポリオキシエチレン（８０）ポリオキシプロピレン（３２）ヘキサグリセリルエーテル、ポリオキシエチレン（１２０）ポリオキシプロピレン（４８）デカグリセリルエーテルなどが挙げられるが、これらに限定されるものではない。
The polyoxyalkylene polyglyceryl ether used in the modifier of the present invention has an average number of alkylene oxides added per hydroxyl group of polyglycerin of 10 to 30. Ethylene oxide (EO) and propylene oxide (PO) are preferable as the alkylene oxide, and the addition molar ratio of EO to PO is more preferably EO: PO = 55:45 to 85:15. When the average addition number of alkylene oxides and the addition molar ratio of EO and PO are within the above ranges, the withstand voltage characteristics of the aluminum electrolytic capacitor can be improved. Further, if the average number of EOs added per hydroxyl group of polyglycerin is 5 to 15, an aluminum electrolytic capacitor having excellent low temperature characteristics can be obtained without impairing the fluidity of the electrolytic solution even under low temperature conditions.
Specific examples of the polyoxyalkylene polyglyceryl ether include polyoxyethylene (50) polyoxypropylene (10) triglyceryl ether, polyoxyethylene (50) polyoxypropylene (20) triglyceryl ether, and polyoxyethylene (60) poly. Oxypropylene (24) tetraglyceryl ether, polyoxyethylene (60) polyoxypropylene (36) tetraglyceryl ether, polyoxypropylene (12) polyoxyethylene (60) tetraglyceryl ether, polyoxypropylene (24) polyoxyethylene (60) Tetraglyceryl ether, polyoxypropylene (12) polyoxyethylene (90) tetraglyceryl ether, polyoxypropylene (36) polyoxyethylene (90) tetraglyceryl ether, polyoxypropylene (24) polyoxyethylene (80) ) Hexaglyceryl ether, polyoxyethylene (80) polyoxypropylene (32) hexaglyceryl ether, polyoxyethylene (120) polyoxypropylene (48) decaglyceryl ether and the like, but are not limited thereto. ..
本発明の電解液は、ポリオキシアルキレンポリグリセリルエーテルの含有量が好ましくは５重量％から４０重量％であり、より好ましくは１０重量％から３０重量％であり、最も好ましくは１５重量％から２５重量％である。ポリオキシアルキレンポリグリセリルエーテルの含有量が５重量％から４０重量％であることにより、アルミニウム電解コンデンサの耐電圧の向上に繋がる。 The electrolytic solution of the present invention has a polyoxyalkylene polyglyceryl ether content of preferably 5% by weight to 40% by weight, more preferably 10% by weight to 30% by weight, and most preferably 15% by weight to 25% by weight. %. When the content of the polyoxyalkylene polyglyceryl ether is 5% by weight to 40% by weight, the withstand voltage of the aluminum electrolytic capacitor is improved.
本発明のアルミニウム電解コンデンサ用電解液は、ポリオキシアルキレンポリグリセリルエーテルを含有する他に各種有機溶媒、電解質、添加剤を含有する。有機溶媒としては、エチレングリコール、γ−ブチロラクトン、グリセリンなどが挙げられるが、これらに限定されるものではない。電解質としては、有機酸、無機酸、又はその塩が挙げられる。有機酸、又はその塩としては、ギ酸、酢酸、プロピオン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、アゼライン酸、セバシン酸、１，１０−デカンジカルボン酸、１，６−デカンジカルボン酸、５，６−デカンジカルボン酸、１，７−オクタンジカルボン酸、７−ビニルヘキサデセン−１，１６−ジカルボン酸、マレイン酸、安息香酸、フタル酸、又はそのアンモニウム塩、アミン塩などが挙げられる。さらに、無機酸、又はその塩としては、炭酸、次亜リン酸、亜リン酸、リン酸、ホウ酸、過塩素酸、又はそのアンモニウム塩、アミン塩などが挙げられる。但し、これらに限定されるものではない。添加剤としては、マンニトールなどの多価アルコール類、ポリビニルアルコール、ポリビニルピロリドンなどの親水性高分子化合物、二酸化ケイ素、アルミノケイ酸などの金属酸化物、ｐ−ニトロ安息香酸、ｐ−ニトロフェノールなどのニトロ化合物、水などが挙げられるが、これらに限定されるものではない。 The electrolytic solution for an aluminum electrolytic capacitor of the present invention contains various organic solvents, electrolytes, and additives in addition to containing polyoxyalkylene polyglyceryl ether. Examples of the organic solvent include, but are not limited to, ethylene glycol, γ-butyrolactone, and glycerin. Examples of the electrolyte include organic acids, inorganic acids, and salts thereof. Organic acids or salts thereof include formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, 1,10-decandicarboxylic acid, 1,6-decane. Dicarboxylic acid, 5,6-decandicarboxylic acid, 1,7-octanedicarboxylic acid, 7-vinylhexadecene-1,16-dicarboxylic acid, maleic acid, oxalic acid, phthalic acid, or ammonium salt, amine salt, etc. Be done. Further, examples of the inorganic acid or a salt thereof include carbonic acid, hypophosphorous acid, phosphorous acid, phosphoric acid, boric acid, perchloric acid, or ammonium salts and amine salts thereof. However, it is not limited to these. Additives include polyhydric alcohols such as mannitol, hydrophilic polymer compounds such as polyvinyl alcohol and polyvinylpyrrolidone, metal oxides such as silicon dioxide and aluminosilicate, and nitro such as p-nitrobenzoic acid and p-nitrophenol. Examples include, but are not limited to, compounds and water.
次に、本発明を実施例及び比較例により詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。以下、本発明の実施例及び比較例を示す。 Next, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Hereinafter, examples and comparative examples of the present invention will be shown.
（実施例１）
加熱装置のついた耐圧容器に、ポリグリセリン＃３１０（阪本薬品工業株式会社製、平均重合度：４）を３１０ｇ（１モル）、及び水酸化カリウムを７．２ｇ添加し、窒素雰囲気とした。エチレンオキサイド２６４０ｇ（６０モル）を添加し、１２０℃で３時間反応させた。その後、プロピレンオキサイド６９６ｇ（１２モル）を添加し、１２０℃で３時間反応させた。反応物を８０℃に冷却して、１０％りん酸を添加して反応液のｐＨを７．０に調整した後、１００ｍｍＨｇ以下の減圧下、１００〜１２０℃の条件にて水分０．１％以下まで脱水し、反応液を８０℃に冷却して粗生成物を得た。吸着剤としてキョーワード５００（協和化学株式会社製）を３６．５ｇ添加して１時間撹拌後に濾過してイオン成分を吸着除去し、ＥＯとＰＯの付加モル比（ＥＯ：ＰＯ）が８３：１７のポリオキシプロピレン（１２）ポリオキシエチレン（６０）テトラグリセリルエーテル（４Ｇ６０ＥＯ１２ＰＯ、水酸基価：９２ｍｇＫＯＨ／ｇ）を得た。改質剤として４Ｇ６０ＥＯ１２ＰＯ、電解質として１，７−オクタンジカルボン酸二アンモニウム、溶媒としてエチレングリコール、およびイオン交換水を用い、表１に示した重量比（ｗｔ％）で混合してコンデンサ電解液を調製した。調製した電解液の耐電圧、電導度、低温下における流動性を評価した結果を表１に示した。
(Example 1)
310 g (1 mol) of polyglycerin # 310 (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., average degree of polymerization: 4) and 7.2 g of potassium hydroxide were added to a pressure-resistant container equipped with a heating device to create a nitrogen atmosphere. 2640 g (60 mol) of ethylene oxide was added and reacted at 120 ° C. for 3 hours. Then, 696 g (12 mol) of propylene oxide was added, and the mixture was reacted at 120 ° C. for 3 hours. The reaction product was cooled to 80 ° C., 10% phosphoric acid was added to adjust the pH of the reaction solution to 7.0, and then the water content was 0.1% under the conditions of 100 to 120 ° C. under a reduced pressure of 100 mmHg or less. After dehydration to the following, the reaction solution was cooled to 80 ° C. to obtain a crude product. 36.5 g of Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added as an adsorbent, and after stirring for 1 hour, the ionic component was adsorbed and removed by filtration, and the added molar ratio of EO to PO (EO: PO) was 83:17. Polyoxypropylene (12) polyoxyethylene (60) tetraglyceryl ether (4G60EO12PO, hydroxyl value: 92 mgKOH / g) was obtained. Using 4G60EO12PO as a modifier, diammonium 1,7-octanedicarboxylic acid as an electrolyte, ethylene glycol as a solvent, and ion-exchanged water, mix them at the weight ratio (wt%) shown in Table 1 to prepare a capacitor electrolyte. did. Table 1 shows the results of evaluating the withstand voltage, conductivity, and fluidity of the prepared electrolyte at low temperatures.
（電解液の耐電圧）
調製した電解液を８５℃に加温し、定格皮膜耐電圧が６６５Ｖ、静電容量が０．４５μＦ／ｃｍ２の陽極用酸化アルミニウム箔（１０４ＨＤ５Ｂ−６６５Ｖｆ：日本蓄電器工業株式会社製）を電解液に浸し、直流安定化電源（ＰＬ−６５０−０．１：松定プレシジョン製）を用いて、電流密度０．６ｍＡ／ｃｍ２、電圧の上昇速度１．７Ｖ／ｓの条件にて陽極箔に電流を印加した。耐電圧の評価は、電流−電圧曲線をモニタリングし、電流値が５ｍＡを超えた時点の電圧値を破壊電圧として読み取った。
(Withstand voltage of electrolyte)
The prepared electrolytic solution is heated to 85 ° C., and an aluminum oxide foil for an anode (104HD5B-665Vf: manufactured by Nippon Denki Kogyo Co., Ltd.) having a rated film withstand voltage of 665V and a capacitance of 0.45μF / cm 2 is used as an electrolytic solution. Immerse in the anode foil using a regulated DC power supply (PL-650-0.1: manufactured by Matsusada Precision) under the conditions of a current density of 0.6 mA / cm 2 and a voltage rise rate of 1.7 V / s. A current was applied. For the evaluation of the withstand voltage, the current-voltage curve was monitored, and the voltage value at the time when the current value exceeded 5 mA was read as the breaking voltage.
（電解液の電導度）
調製した電解液を２５℃に調温し、導電率計（ＤＳ−５２：堀場製作所製）を用いて電導度を測定した。
(Conductivity of electrolyte)
The temperature of the prepared electrolytic solution was adjusted to 25 ° C., and the conductivity was measured using a conductivity meter (DS-52: manufactured by Horiba, Ltd.).
（−２０℃における電解液の性状の評価）
電解液の低温特性の指標として−２０℃における性状を以下の方法で評価した。透明なガラス管に電解液を入れて密栓したものを−２０℃に調温したエタノール浴中で静置し、２時間後に試験管を傾けて目視にて電解液の外観ならびに流動性を観察し、以下の基準で評価した。
＜評価基準＞
〇：流動性があり、且つ外観が透明
△：流動性があるが外観が白濁、または一部に析出物がみられる
×：流動性がない
(Evaluation of the properties of the electrolytic solution at -20 ° C)
As an index of the low temperature characteristics of the electrolytic solution, the properties at −20 ° C. were evaluated by the following method. Put the electrolytic solution in a transparent glass tube, seal it tightly, and let it stand in an ethanol bath adjusted to -20 ° C. After 2 hours, tilt the test tube and visually observe the appearance and fluidity of the electrolytic solution. , Evaluated according to the following criteria.
<Evaluation criteria>
〇: Fluid and transparent in appearance Δ: Fluid but cloudy in appearance or some precipitates ×: No fluidity
（実施例２）
改質剤として２０％の４Ｇ６０ＥＯ１２ＰＯを用いた以外は実施例１と同様に電解液の各物性を評価し、結果を表１に示した。
(Example 2)
The physical characteristics of the electrolytic solution were evaluated in the same manner as in Example 1 except that 20% of 4G60EO12PO was used as the modifier, and the results are shown in Table 1.
（実施例３）
水酸化カリウムの添加量を８．６ｇとし、エチレンオキサイドの添加量を２６４０ｇ（６０モル）、プロピレンオキサイドの添加量を１３９２ｇ（２４モル）、キョーワード５００の添加量を４３．４ｇとした以外は実施例１と同様の方法で、ＥＯ：ＰＯ＝７１：２９のポリオキシプロピレン（２４）ポリオキシエチレン（６０）テトラグリセリルエーテル（４Ｇ６０ＥＯ２４ＰＯ、水酸基価：７８ｍｇＫＯＨ／ｇ）を得た。改質剤として２０％の４Ｇ６０ＥＯ２４ＰＯを用いて実施例１と同様に電解液の各物性を評価し、結果を表１に示した。
(Example 3)
Except that the amount of potassium hydroxide added was 8.6 g, the amount of ethylene oxide added was 2640 g (60 mol), the amount of propylene oxide added was 1392 g (24 mol), and the amount of Kyoward 500 added was 43.4 g. Polyoxypropylene (24) polyoxyethylene (60) tetraglyceryl ether (4G60EO24PO, hydroxyl value: 78 mgKOH / g) having EO: PO = 71: 29 was obtained in the same manner as in Example 1. Each physical property of the electrolytic solution was evaluated in the same manner as in Example 1 using 20% 4G60EO24PO as a modifier, and the results are shown in Table 1.
（比較例１）
改質剤を添加しなかった以外は実施例１と同様に電解液の各物性を評価し、結果を表１に示した。
(Comparative Example 1)
The physical characteristics of the electrolytic solution were evaluated in the same manner as in Example 1 except that no modifier was added, and the results are shown in Table 1.
（比較例２、比較例３）
改質剤として表１に示した添加量のポリエチレングリコール１０００（ＰＥＧ１０００、平均分子量１０００）を用いた以外は実施例１と同様に電解液の各物性を評価し、結果を表１に示した。
(Comparative Example 2, Comparative Example 3)
The physical characteristics of the electrolytic solution were evaluated in the same manner as in Example 1 except that the added amount of polyethylene glycol 1000 (PEG1000, average molecular weight 1000) shown in Table 1 was used as the modifier, and the results are shown in Table 1.
実施例１では、改質剤を添加しなかった比較例１に比べて約１０Ｖの耐電圧の向上が見られ、ＰＥＧ１０００を５％添加した比較例２と同等以上の効果が得られた。さらに、改質剤の添加量を２０％に増量した実施例２、３では、耐電圧４９０Ｖを超える電解液が得られることが明らかとなった。また、−２０℃の低温下における電解液の外観評価では、実施例１〜３は電解液が透明かつ流動性を示した。
一方、ＰＥＧ１０００の添加量を２０％とした比較例３では、耐電圧は添加量５％の比較例２より向上したものの、電解液が固化して流動性を示さなかった。
これらより、ポリオキシアルキレンポリグリセリルエーテルを改質剤として用いることにより、耐電圧の向上効果に優れ、且つ低温下においても流動性に優れた電解液が得られることが明らかとなった。
In Example 1, an improvement in withstand voltage of about 10 V was observed as compared with Comparative Example 1 to which no modifier was added, and an effect equal to or higher than that of Comparative Example 2 to which 5% of PEG1000 was added was obtained. Further, in Examples 2 and 3 in which the amount of the modifier added was increased to 20%, it was clarified that an electrolytic solution having a withstand voltage exceeding 490 V could be obtained. Further, in the appearance evaluation of the electrolytic solution at a low temperature of −20 ° C., the electrolytic solution was transparent and fluid in Examples 1 to 3.
On the other hand, in Comparative Example 3 in which the addition amount of PEG1000 was 20%, the withstand voltage was improved as compared with Comparative Example 2 in which the addition amount was 5%, but the electrolytic solution solidified and did not show fluidity.
From these, it was clarified that by using polyoxyalkylene polyglyceryl ether as a modifier, an electrolytic solution having an excellent effect of improving withstand voltage and excellent fluidity even at a low temperature can be obtained.
本発明の改質剤を含有したコンデンサ用電解液を用いることにより、耐電圧特性と低温特性に優れたアルミニウム電解コンデンサの製造に有用である。 By using the electrolytic solution for a capacitor containing the modifier of the present invention, it is useful for producing an aluminum electrolytic capacitor having excellent withstand voltage characteristics and low temperature characteristics.
Claims (4)
An aluminum electrolytic capacitor using the electrolytic solution according to claim 3.
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