JP2021190712A - Modifier for capacitor electrolytic solution including (meth) acrylate, electrolytic solution for aluminum electrolytic capacitor using the same, and aluminum electrolytic capacitor - Google Patents
Modifier for capacitor electrolytic solution including (meth) acrylate, electrolytic solution for aluminum electrolytic capacitor using the same, and aluminum electrolytic capacitor Download PDFInfo
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- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 41
- 239000003990 capacitor Substances 0.000 title claims abstract description 26
- 239000003607 modifier Substances 0.000 title claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 title claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 11
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims abstract description 33
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- 235000011187 glycerol Nutrition 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract 1
- -1 ester compound Chemical class 0.000 description 38
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 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
- 238000000034 method Methods 0.000 description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 239000001488 sodium phosphate Substances 0.000 description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 4
- MYNCBIPQQBNHCA-UHFFFAOYSA-N C(C(O)CO)OCC(O)CO.C(C=C)(=O)O Chemical compound C(C(O)CO)OCC(O)CO.C(C=C)(=O)O MYNCBIPQQBNHCA-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000000654 additive Substances 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
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 229940105990 diglycerin Drugs 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010410 layer Substances 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
- 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
- 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
- 238000010992 reflux Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 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
- 239000005711 Benzoic acid Substances 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
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 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
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000007664 blowing Methods 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
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001923 cyclic compounds Chemical class 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
- 235000019253 formic acid Nutrition 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 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
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 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
- 238000005809 transesterification reaction Methods 0.000 description 1
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- Polyethers (AREA)
- Macromonomer-Based Addition Polymer (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 same.
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 influence the characteristics of the capacitor. It is known to be a major factor in causing it to occur.
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やポリエチレングリコールジアクリレート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、３）。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る。その際にコンデンサの破裂、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。 Generally, an electrolytic solution for an aluminum electrolytic capacitor dissolves a higher dicarboxylic acid or a polyhydric alcohol such as an ammonium salt thereof, a boric acid or an ammonium salt thereof, and 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 can be improved by adding polyethylene glycol or polyethylene glycol diacrylate to the electrolytic solution (Patent Documents 2 and 3). However, in recent years, there has been an increasing demand for the safety of aluminum electrolytic capacitors in electronic devices using switching power supplies. An overvoltage may be applied to the aluminum electrolytic capacitor used in the switching power supply due to the instability of the supplied power. At that time, the capacitor may explode, ignite, or burn, and in order to prevent this, it is necessary to further improve the spark voltage, that is, the withstand voltage of the electrolytic solution for the electrolytic capacitor.
本発明は、耐電圧の向上効果に優れるコンデンサ電解液用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 a capacitor electrolytic solution having an excellent effect of improving withstand voltage.
ポリオキシアルキレン（ポリ）グリセリルエーテルの末端基を（メタ）アクリレート変性させたポリオキシアルキレン（ポリ）グリセリルエーテル（メタ）アクリレートを改質剤として使用することにより、耐電圧特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 polyoxyalkylene (poly) glyceryl ether (meth) acrylate in which the terminal group of polyoxyalkylene (poly) glyceryl ether is modified with (meth) acrylate as a modifier, a capacitor electrolytic solution with excellent withstand voltage characteristics. It was found that the above was obtained, and the present invention was completed.
本発明のコンデンサ電解液用の改質剤を使用することにより、耐電圧特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 for 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.
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, "~" indicating a range includes an upper limit and a lower limit.
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（メタ）アクリレート（以下、（メタ）アクリレートと言う）は、ポリオキシアルキレン（ポリ）グリセリルエーテルとアクリル酸またはメタクリル酸がエステル結合した化合物である。 The polyoxyalkylene (poly) glyceryl ether (meth) acrylate (hereinafter referred to as (meth) acrylate) used in the modifier of the present invention is an ester bond of polyoxyalkylene (poly) glyceryl ether and acrylic acid or methacrylic acid. It is a compound.
前記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から選ばれる１種以上を用いることが好ましく、アルキレンオキサイド中のエチレンオキサイドのモル比率を５０％以上とすることがさらに好ましい。 The polyoxyalkylene (poly) glyceryl ether is a compound in which an alkylene oxide is added to the hydroxyl group of (poly) glycerin. Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and the like, and it is particularly preferable to use one or more selected from ethylene oxide and propylene oxide, and among the alkylene oxides. It is more preferable that the molar ratio of ethylene oxide is 50% or more.
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）グリセリンは平均重合度が１〜２０であることが好ましく、２〜１０であることがさらに好ましい。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、グリセリン、ジグリセリン、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、ジグリセリンＳ、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 (poly) glycerin constituting the polyoxyalkylene (poly) glyceryl ether has a structure in which the hydroxyl group of the glycerin is ether-bonded by dehydration condensation, and the ether bond may be linear or branched, or a molecule. It may contain a cyclic compound condensed within. The (poly) glycerin used preferably has an average degree of polymerization of 1 to 20, and more preferably 2 to 10. Here, the average degree of polymerization is the average degree of polymerization (n) of (poly) glycerin 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 (poly) glycerin, and is a numerical value of 1 g (formula 2). Poly) The number of milligrams of potassium hydroxide required to neutralize the acetic acid required to acetylate the free OH groups contained in glycerin. The number of milligrams of potassium hydroxide is calculated according to the editorial of the Japan Oil Chemists'Association, "Established by the Japan Oil Chemists' Society, Standard Oil and Fat Analysis Test Method, 2013 Edition". Specific examples of (poly) glycerin include glycerin, diglycerin, triglycerin, tetraglycerin, hexaglycerin, decaglycerin and the like, and commercially available products include diglycerin S, PGL-S, polyglycerin # 310 and poly. Glycerin # 500 and polyglycerin # 750 (both manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) can be used.
前記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ＯＨ基１つに対して、アルキレンオキサイド（ＡＯ）の平均付加数が５〜３０であることが好ましい。ＯＨ基当たりのＡＯの平均付加数を５〜３０とすることで優れた耐電圧特性が得られる。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（２０）ジグリセリルエーテル、ポリオキシエチレン（４０）ジグリセリルエーテル、ポリオキシエチレン（６０）ジグリセリルエーテル、ポリオキシエチレン（８０）ジグリセリルエーテル、ポリオキシエチレン（１００）ジグリセリルエーテル、ポリオキシエチレン（１２０）ジグリセリルエーテル、ポリオキシエチレン（６０）テトラグリセリルエーテル、ポリオキシエチレン（１２０）テトラグリセリルエーテル、ポリオキシエチレン（６０）デカグリセリルエーテル、ポリオキシエチレン（１２０）デカグリセリルエーテル、ポリオキシプロピレン（２４）ジグリセリルエーテル、ポリオキシプロピレン（１４）ポリオキシエチレン（１００）ジグリセリルエーテル、ポリオキシプロピレン（２５）ポリオキシエチレン（４５）ジ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（２４）ポリオキシエチレン（２４０）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 (poly) glyceryl ether preferably has an average addition number of alkylene oxide (AO) of 5 to 30 with respect to one OH group of (poly) glycerin. Excellent withstand voltage characteristics can be obtained by setting the average number of AOs added per OH group to 5 to 30. Specific examples of the polyoxyalkylene (poly) glyceryl ether include polyoxyethylene (20) diglyceryl ether, polyoxyethylene (40) diglyceryl ether, polyoxyethylene (60) diglyceryl ether, and polyoxyethylene (80). Diglyceryl ether, polyoxyethylene (100) diglyceryl ether, polyoxyethylene (120) diglyceryl ether, polyoxyethylene (60) tetraglyceryl ether, polyoxyethylene (120) tetraglyceryl ether, polyoxyethylene (60) Decaglyceryl ether, polyoxyethylene (120) decaglyceryl ether, polyoxypropylene (24) diglyceryl ether, polyoxypropylene (14) polyoxyethylene (100) diglyceryl ether, polyoxypropylene (25) polyoxyethylene (25) 45) Diglyceryl ether, polyoxypropylene (24) polyoxyethylene (60) tetraglyceryl ether, polyoxypropylene (24) polyoxyethylene (240) decaglyceryl ether and the like, but are not limited thereto. No.
本発明の（メタ）アクリレートの製造方法には特に制限はない。例えば、特定の（ポリ）グリセリンに任意の量のアルキレンオキサイドを公知の方法で付加反応させたポリオキシアルキレン（ポリ）グリセリルエーテルの末端水酸基に（メタ）アクリル酸を反応させて生成水を系外に抜き出しながらエステル化物を得る脱水エステル化法、末端水酸基に低級アルコールの（メタ）アクリル酸エステルを反応させて生成した低級アルコールを系外に抜き出しながらエステル化物を得るエステル交換法が挙げられる。 The method for producing the (meth) acrylate of the present invention is not particularly limited. For example, (meth) acrylic acid is reacted with the terminal hydroxyl group of a polyoxyalkylene (poly) glyceryl ether obtained by adding an arbitrary amount of alkylene oxide to a specific (poly) glycerin by a known method to remove the generated water. Examples thereof include a dehydration esterification method for obtaining an esterified product while extracting the esterified product, and a transesterification method for obtaining an esterified product while extracting the lower alcohol produced by reacting a (meth) acrylic acid ester of a lower alcohol with a terminal hydroxyl group to the outside of the system.
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（メタ）アクリレートの含有量が好ましくは１重量％〜３０重量％であり、より好ましくは３重量％〜２５重量％であり、最も好ましくは５重量％〜２０重量％である。（メタ）アクリレートの含有量が１重量％〜３０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 (poly) glyceryl ether (meth) acrylate content of preferably 1% by weight to 30% by weight, more preferably 3% by weight to 25% by weight, and most preferably. Is 5% by weight to 20% by weight. The content of the (meth) acrylate is 1% by weight to 30% by weight, which leads to an improvement in the withstand voltage of the aluminum electrolytic capacitor.
本発明の電解液は、（メタ）アクリレートを含有する他に、各種有機溶媒、電解質、添加剤を含有することができる。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、フタル酸ならびに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、ならびに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 of the present invention may contain various organic solvents, electrolytes, and additives in addition to containing (meth) acrylate. 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 and 1,6-decane. Examples thereof include dicarboxylic acid, 5,6-decandicarboxylic acid, 1,7-octanedicarboxylic acid, 7-vinylhexadecene-1,16-dicarboxylic acid, maleic acid, benzoic acid, phthalic acid and ammonium salts and amine salts thereof. .. Further, examples of the inorganic acid or a salt thereof include carbonic acid, hypophosphoric acid, phosphoric acid, phosphoric acid, boric acid, perchloric acid, and 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。ただし、％は重量基準である。 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. However,% is based on weight.
（実施例１）
温度計、撹拌機、空気吹き込み管、ディーン・スターク還流装置を備えた反応容器に、ポリオキシエチレン（４０）ジグリセリルエーテル２６９．６ｇ（０．１４１ｍｏｌ）、トルエン３００．０ｇ、ｐ−トルエンスルホン酸１５．０ｇ、ハイドロキノンモノメチルエーテル０．３ｇ、塩化銅（ＩＩ）０．１ｇ、次亜リン酸ナトリウム０．３ｇ、アクリル酸６０．８ｇ（０．８４３ｍｏｌ）を仕込み、空気吹き込み下において撹拌しながら、トルエン還流雰囲気まで昇温し、約６時間かけて脱水エステル化反応を行った。反応終了後、アルカリ水洗、水洗を行い、有機層のトルエンを減圧留去することで、ポリオキシエチレン（４０）ジグリセリルエーテルアクリレート（２Ｇ４０ＥＯ４Ａ）を得た。改質剤として２Ｇ４０ＥＯ４Ａを用い、電解質（１，７−オクタンジカルボン酸二アンモニウム）、エチレングリコール（ＥＧ）およびイオン交換水を、表１に示した比率で配合し、電解液を調製した。電解液の性能評価として耐電圧、電導度を測定した結果を表１に示す。
(Example 1)
Polyoxyethylene (40) diglyceryl ether 269.6 g (0.141 mol), toluene 300.0 g, p-toluenesulfonic acid in a reaction vessel equipped with a thermometer, agitator, air blow tube, and Dean Stark reflux device. 15.0 g, hydroquinone monomethyl ether 0.3 g, copper (II) chloride 0.1 g, sodium hypophosphite 0.3 g, acrylic acid 60.8 g (0.843 mol) were charged, and while stirring under air blowing, The temperature was raised to a toluene reflux atmosphere, and the dehydration esterification reaction was carried out over about 6 hours. After completion of the reaction, the reaction was carried out with alkaline water and water, and toluene in the organic layer was distilled off under reduced pressure to obtain polyoxyethylene (40) diglyceryl ether acrylate (2G40EO4A). Using 2G40EO4A as a modifier, an electrolyte (diammonium 1,7-octanedicarboxylic acid), ethylene glycol (EG) and ion-exchanged water were blended in the ratios shown in Table 1 to prepare an electrolytic solution. Table 1 shows the results of measuring the withstand voltage and conductivity as the performance evaluation of the electrolytic solution.
（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 breakdown 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.).
（実施例２）
ポリオキシエチレン（１００）ジグリセリルエーテル２５７．８ｇ（０．０５６３ｍｏｌ）、トルエン２７０．０ｇ、ｐ−トルエンスルホン酸１３．５ｇ、ハイドロキノンモノメチルエーテル０．３ｇ、塩化銅（ＩＩ）０．１ｇ、次亜リン酸ナトリウム０．３ｇ、アクリル酸２４．４ｇ（０．３３８ｍｏｌ）を仕込み、実施例１と同様の条件で反応および精製を実施し、ポリオキシエチレン（１００）ジグリセリルエーテルアクリレート（２Ｇ１００ＥＯ４Ａ）を得た。改質剤として２Ｇ１００ＥＯ４Ａ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 2)
Polyoxyethylene (100) diglyceryl ether 257.8 g (0.0563 mol), toluene 270.0 g, p-toluenesulfonic acid 13.5 g, hydroquinone monomethyl ether 0.3 g, copper (II) chloride 0.1 g, hypophosphite 0.3 g of sodium phosphate and 24.4 g (0.338 mol) of acrylic acid were charged, and the reaction and purification were carried out under the same conditions as in Example 1 to obtain polyoxyethylene (100) diglyceryl ether acrylate (2G100EO4A). rice field. Using 2G100EO4A as a modifier, each physical property of the electrolytic solution was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
（実施例３）
ポリオキシエチレン（１００）ポリオキシプロピレン（１４）ジグリセリルエーテル２４０．３ｇ（０．０４４７ｍｏｌ）、トルエン２５０．０ｇ、ｐ−トルエンスルホン酸１７．５ｇ、ハイドロキノンモノメチルエーテル０．３ｇ、塩化銅（ＩＩ）０．１ｇ、次亜リン酸ナトリウム０．３ｇ、アクリル酸１９．３ｇ（０．２６８ｍｏｌ）を仕込み、実施例１と同様の条件で反応および精製を実施し、ポリオキシエチレン（１００）ポリオキシプロピレン（１４）ジグリセリルエーテルアクリレート（２Ｇ１４ＰＯ１００ＥＯ４Ａ）を得た。改質剤として２Ｇ１４ＰＯ１００ＥＯ４Ａ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)
Polyoxyethylene (100) Polyoxypropylene (14) Diglyceryl ether 240.3 g (0.0447 mol), toluene 250.0 g, p-toluenesulfonic acid 17.5 g, hydroquinone monomethyl ether 0.3 g, copper (II) chloride 0.1 g, 0.3 g of sodium hypophosphite, and 19.3 g (0.268 mol) of acrylic acid were charged, and the reaction and purification were carried out under the same conditions as in Example 1, and polyoxyethylene (100) polyoxypropylene was carried out. (14) Diglyceryl ether acrylate (2G14PO100EO4A) was obtained. Using 2G14PO100EO4A as a modifier, each physical property of the electrolytic solution was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
（実施例４）
ポリオキシエチレン（６０）テトラグリセリルエーテル６３７．６ｇ（０．２１６ｍｏｌ）、トルエン５７７．０ｇ、ｐ−トルエンスルホン酸２８．２ｇ、ハイドロキノンモノメチルエーテル０．７ｇ、塩化銅（ＩＩ）０．３ｇ、次亜リン酸ナトリウム０．７ｇ、アクリル酸１３５．２ｇ（１．８８ｍｏｌ）を仕込み、実施例１と同様の条件で反応および精製を実施し、ポリオキシエチレン（６０）テトラグリセリルエーテルアクリレート（４Ｇ６０ＥＯ６Ａ）を得た。改質剤として４Ｇ６０ＥＯ６Ａ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 4)
Polyoxyethylene (60) tetraglyceryl ether 637.6 g (0.216 mol), toluene 577.0 g, p-toluenesulfonic acid 28.2 g, hydroquinone monomethyl ether 0.7 g, copper (II) chloride 0.3 g, hypophosphite 0.7 g of sodium phosphate and 135.2 g (1.88 mol) of acrylic acid were charged, and the reaction and purification were carried out under the same conditions as in Example 1 to obtain polyoxyethylene (60) tetraglyceryl ether acrylate (4G60EO6A). rice field. Using 4G60EO6A as a modifier, each physical property of the electrolytic solution was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
（実施例５）
ポリオキシエチレン（６０）デカグリセリルエーテル６７２．３ｇ（０．１９８ｍｏｌ）、トルエン６５４．６ｇ、ｐ−トルエンスルホン酸３２．０ｇ、ハイドロキノンモノメチルエーテル０．８ｇ、塩化銅（ＩＩ）０．３ｇ、次亜リン酸ナトリウム０．８ｇ、アクリル酸２５５．８ｇ（３．５５ｍｏｌ）を仕込み、実施例１と同様の条件で反応および精製を実施し、ポリオキシエチレン（６０）デカグリセリルエーテルアクリレート（１０Ｇ６０ＥＯ１２Ａ）を得た。改質剤として１０Ｇ６０ＥＯ１２Ａ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 5)
Polyoxyethylene (60) decaglyceryl ether 672.3 g (0.198 mol), toluene 654.6 g, p-toluenesulfonic acid 32.0 g, hydroquinone monomethyl ether 0.8 g, copper (II) chloride 0.3 g, hypophosphite 0.8 g of sodium phosphate and 255.8 g (3.55 mol) of acrylic acid were charged, and the reaction and purification were carried out under the same conditions as in Example 1 to obtain polyoxyethylene (60) decaglyceryl ether acrylate (10G60EO12A). rice field. Using 10G60EO12A as a modifier, each physical property of the electrolytic solution was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
（実施例６）
ポリオキシエチレン（１２０）デカグリセリルエーテル２４２．８ｇ（０．０４１８ｍｏｌ）、トルエン２７０．０ｇ、ｐ−トルエンスルホン酸１３．５ｇ、ハイドロキノンモノメチルエーテル０．３ｇ、塩化銅（ＩＩ）０．１ｇ、次亜リン酸ナトリウム０．３ｇ、アクリル酸５４．３ｇ（０．７５３ｍｏｌ）を仕込み、実施例１と同様の条件で反応および精製を実施し、ポリオキシエチレン（１２０）デカグリセリルエーテルアクリレート（１０Ｇ１２０ＥＯ１２Ａ）を得た。改質剤として１０Ｇ１２０ＥＯ１２Ａ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 6)
Polyoxyethylene (120) decaglyceryl ether 242.8 g (0.0418 mol), toluene 270.0 g, p-toluenesulfonic acid 13.5 g, hydroquinone monomethyl ether 0.3 g, copper (II) chloride 0.1 g, hypophosphite 0.3 g of sodium phosphate and 54.3 g (0.753 mol) of acrylic acid were charged, and the reaction and purification were carried out under the same conditions as in Example 1 to obtain polyoxyethylene (120) decaglyceryl ether acrylate (10G120EO12A). rice field. Using 10G120EO12A as a modifier, each physical property of the electrolytic solution was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
（実施例７）
改質剤として２０％の２Ｇ４０ＥＯ４Ａ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 7)
The physical characteristics of the electrolytic solution were evaluated in the same manner as in Example 1 except that 20% 2G40EO4A was used as the 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と同様の方法で電解液を調製し、耐電圧と電導度を評価した結果を表１に示した。
(Comparative Example 1)
Table 1 shows the results of preparing an electrolytic solution by the same method as in Example 1 except that no modifier was added, and evaluating the withstand voltage and conductivity.
（比較例２）
改質剤を５％のポリオキシエチレン（４０）ジグリセリルエーテル（２Ｇ４０ＥＯ）に変えた以外は実施例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)
The physical characteristics of the electrolytic solution were evaluated in the same manner as in Example 1 except that the modifier was changed to 5% polyoxyethylene (40) diglyceryl ether (2G40EO), and the results are shown in Table 1.
（比較例３）
改質剤を２０％のポリオキシエチレン（４０）ジグリセリルエーテル（２Ｇ４０ＥＯ）に変えた以外は実施例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 3)
The physical characteristics of the electrolytic solution were evaluated in the same manner as in Example 1 except that the modifier was changed to 20% polyoxyethylene (40) diglyceryl ether (2G40EO), and the results are shown in Table 1.
（比較例４）
改質剤を５％のポリエチレングリコールジアクリレート（ＰＥＧ−２Ａ、ＰＥＧ重合度９）に変えた以外は実施例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 4)
The physical characteristics of the electrolytic solution were evaluated in the same manner as in Example 1 except that the modifier was changed to 5% polyethylene glycol diacrylate (PEG-2A, PEG polymerization degree 9), and the results are shown in Table 1.
改質剤として５％のポリオキシアルキレンポリグリセリルエーテルアクリレートを用いた実施例１〜６では、改質剤を添加しなかった比較例１に比べて１０Ｖ以上の耐電圧の向上が見られた。同添加量の２Ｇ４０ＥＯを用いた比較例２よりも耐電圧、電導度ともに高い電解液が得られた。さらに、２Ｇ４０ＥＯ４Ａの添加量を２０％に増量した実施例７では、耐電圧値は５１７Ｖを示しており、同添加量の２Ｇ４０ＥＯを用いた比較例３と比べても耐電圧、電導度ともに高い電解液が得られた。末端水酸基をアクリレート変性することで、添加剤同士の重合が起こり、より優れた耐電圧特性が得られたものと考えられる。また、実施例１〜６は同添加量のＰＥＧ−２Ａを用いた比較例４よりも耐電圧の高い電解液が得られた。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（メタ）アクリレートを改質剤として用いることにより、耐電圧特性に優れた電解液が得られることが明らかとなった。 In Examples 1 to 6 in which 5% polyoxyalkylene polyglyceryl ether acrylate was used as the modifier, an improvement in withstand voltage of 10 V or more was observed as compared with Comparative Example 1 in which the modifier was not added. An electrolytic solution having a higher withstand voltage and higher conductivity than that of Comparative Example 2 using the same amount of 2G40EO was obtained. Further, in Example 7 in which the addition amount of 2G40EO4A was increased to 20%, the withstand voltage value was 517V, and the withstand voltage and the conductivity were higher than those of Comparative Example 3 using the same addition amount of 2G40EO. Liquid was obtained. It is considered that by acrylate-modifying the terminal hydroxyl group, polymerization of the additives occurred and more excellent withstand voltage characteristics were obtained. Further, in Examples 1 to 6, an electrolytic solution having a higher withstand voltage than that of Comparative Example 4 using the same amount of PEG-2A was obtained. From these, it was clarified that an electrolytic solution having excellent withstand voltage characteristics can be obtained by using polyoxyalkylene (poly) glyceryl ether (meth) acrylate as a modifier.
Claims (5)
An aluminum electrolytic capacitor using the electrolytic solution according to claim 4.
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