JPH03145713A - Electrolyte for driving of electrolytic capacitor - Google Patents
Electrolyte for driving of electrolytic capacitorInfo
- Publication number
- JPH03145713A JPH03145713A JP28416389A JP28416389A JPH03145713A JP H03145713 A JPH03145713 A JP H03145713A JP 28416389 A JP28416389 A JP 28416389A JP 28416389 A JP28416389 A JP 28416389A JP H03145713 A JPH03145713 A JP H03145713A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- residue
- carboxyl group
- tertiary carboxyl
- electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 13
- 239000003792 electrolyte Substances 0.000 title claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 abstract description 6
- 125000002723 alicyclic group Chemical group 0.000 abstract description 3
- 239000004721 Polyphenylene oxide Chemical group 0.000 abstract description 2
- 125000001931 aliphatic group Chemical group 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 229920000570 polyether Chemical group 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 3
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- -1 unsaturated aliphatic polyols Chemical class 0.000 description 14
- 229920005862 polyol Polymers 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 7
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 125000002887 hydroxy group Chemical class [H]O* 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- LXVSANCQXSSLPA-UHFFFAOYSA-N 2-Ethyl-2-hydroxy-butyric acid Chemical compound CCC(O)(CC)C(O)=O LXVSANCQXSSLPA-UHFFFAOYSA-N 0.000 description 2
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical class C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- SDXXIJKVQADFED-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene-1,6-diol Chemical compound OC1CCCC2CC(O)CCC21 SDXXIJKVQADFED-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- RVBUZBPJAGZHSQ-UHFFFAOYSA-N 2-chlorobutanoic acid Chemical compound CCC(Cl)C(O)=O RVBUZBPJAGZHSQ-UHFFFAOYSA-N 0.000 description 1
- RRDPWAPIJGSANI-UHFFFAOYSA-N 2-cyclohexyl-2-hydroxyacetic acid Chemical compound OC(=O)C(O)C1CCCCC1 RRDPWAPIJGSANI-UHFFFAOYSA-N 0.000 description 1
- MBIQENSCDNJOIY-UHFFFAOYSA-N 2-hydroxy-2-methylbutyric acid Chemical compound CCC(C)(O)C(O)=O MBIQENSCDNJOIY-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- YBJGQSNSAWZZHL-UHFFFAOYSA-N 3-chloro-2,2-dimethylpropanoic acid Chemical compound ClCC(C)(C)C(O)=O YBJGQSNSAWZZHL-UHFFFAOYSA-N 0.000 description 1
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 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
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 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
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZITKDVFRMRXIJQ-UHFFFAOYSA-N dodecane-1,2-diol Chemical compound CCCCCCCCCCC(O)CO ZITKDVFRMRXIJQ-UHFFFAOYSA-N 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- WGTGQGJDNAGBCC-UHFFFAOYSA-N hex-5-ene-1,2-diol Chemical compound OCC(O)CCC=C WGTGQGJDNAGBCC-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- UXGHWJFURBQKCJ-UHFFFAOYSA-N oct-7-ene-1,2-diol Chemical compound OCC(O)CCCCC=C UXGHWJFURBQKCJ-UHFFFAOYSA-N 0.000 description 1
- TZSZOUXLMCRLSU-UHFFFAOYSA-N octane-1,2,7,8-tetrol Chemical compound OCC(O)CCCCC(O)CO TZSZOUXLMCRLSU-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 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
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、電解コンデンサに関するものであシ、さらに
詳しくは、電解コンデンサ駆動用電解液に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an electrolytic capacitor, and more particularly to an electrolytic solution for driving an electrolytic capacitor.
従来の技術
従来、特に中高圧級の電解液としてはエチレングリコー
ル−はう酸系のものが用いられているが。BACKGROUND OF THE INVENTION Conventionally, ethylene glycol-acid-based electrolytes have been used as electrolytes, particularly for medium and high pressures.
この種の電解液は、エチレングリコールとほう酸のエス
テル化反応により水が生成するため１０゜Ｃ以上では蒸
気圧が高く、また電極であるアルミニウムと反応しやす
く高温での使用に適さなかった。このような欠点を改良
するために、溶質として、アゼライン酸、セバシン酸１
１１１０−デカンジカルボン酸、ノナンニ酸（特開昭６
１−１７２３２３号公報）＋’＋６−デカンジカルボン
酸、またはその塩を用いる電解液がある。This type of electrolytic solution produces water through the esterification reaction of ethylene glycol and boric acid, so its vapor pressure is high at temperatures above 10°C, and it tends to react with aluminum, which is the electrode, making it unsuitable for use at high temperatures. In order to improve these drawbacks, azelaic acid and sebacic acid 1 were added as solutes.
1110-decanedicarboxylic acid, nonanninic acid (Japanese Patent Application Laid-open No. 6
1-172323) There is an electrolytic solution using +'+6-decanedicarboxylic acid or a salt thereof.
発明が解決しようとする課題
しかしながら、従来用いられている上記のようなカルボ
ン酸およびその塩１ｄエチレングリコール等の溶媒に対
する溶解性が１分でない。Problems to be Solved by the Invention However, the solubility of conventionally used carboxylic acids and their salts in solvents such as 1d ethylene glycol is not 1 minute.
また、従来のカルボン酸は、火花電圧を比較的高くでき
るものの、１−分ではなく、これらのカルボン酸または
その塩を単独で溶質として用いる場合、定格電圧３５０
Ｖが限度であった。In addition, although conventional carboxylic acids can produce a relatively high spark voltage, when these carboxylic acids or their salts are used alone as a solute, the rated voltage is 350.
V was the limit.
また、電解液を高温中に放置した場合、従来のカルボン
酸あるいはそのアンモニウムＩは、エチレングリコール
とエステル化反応全起こす等、高温中での変化が大きか
った。Further, when the electrolytic solution is left at high temperature, conventional carboxylic acids or their ammonium I undergo a large change at high temperatures, such as causing a complete esterification reaction with ethylene glycol.
上記のような従来の欠点を改良するために、本発明者ら
は、時開１１Ｐ１−１０３８２１号公報における第２級
および／または第３級のカルボキシル基を合計で２個以
上有する分子量２６０以上のポリカルボン酸の塩を用い
ることにより、火花電圧が高く、高温での比電導度変化
の少ない電解液となることを見いだした。しかし、よシ
高性能のコンデンサへの適用に当たっては、その特性は
充分ではなかった。In order to improve the above-mentioned conventional drawbacks, the present inventors have developed a method of manufacturing a carbon fiber with a molecular weight of 260 or more and having a total of two or more secondary and/or tertiary carboxyl groups as disclosed in Jikai No. 11P1-103821. It has been found that by using a polycarboxylic acid salt, an electrolytic solution with a high spark voltage and little change in specific conductivity at high temperatures can be obtained. However, its characteristics were not sufficient for application to high-performance capacitors.
本発明はＬ記従来の欠点を解決するもので、中高田級電
解コンデンサの長寿命化、高信頼化が可能となる電解コ
ンデンサ駆動用電解液を提供することを目的とするもの
である。The present invention solves the drawbacks of the prior art as described in L above, and aims to provide an electrolytic solution for driving an electrolytic capacitor that can extend the life of a Nakada-class electrolytic capacitor and increase its reliability.
課題を解決するための手段
本発明者らは、より高温での安定性に優れた電解液を見
い出すべく鋭意検討した結果、本発明に到達した。すな
わち、本発明は第２級および／または第３級のカルボキ
シル基′ｆ：２個以上有するポリカルボン酸であって、
エーテル結合を有し、かつエステル結合を有さないもの
の塩全溶質として用いる電解液である。Means for Solving the Problems The present inventors conducted intensive studies to find an electrolytic solution with excellent stability at higher temperatures, and as a result, they arrived at the present invention. That is, the present invention provides a polycarboxylic acid having two or more secondary and/or tertiary carboxyl groups'f,
It is an electrolytic solution that has an ether bond and no ester bond, but is used as a salt total solute.
ポリカルボン酸としては、一般式（１）！、たけ（２）
０ （−Ａ−ＧＯＯＨ）２ （１）Ｒ
（−〇−Ａ−Ｃ００Ｈ）ｎ １２）（式中
、Ａは第２級または第３級のカルボキシル基を有する、
エステル結合を有さないカルボン酸の残基で、同一また
は異なる。Ｒはエステル結合を有さない有機残基、ｎは
２以上の整数である。）で表されるポリカルボン酸があ
げられる。As polycarboxylic acid, general formula (1) is used! , Take (2)
0 (-A-GOOH)2 (1)R
(-〇-A-C00H)n 12) (wherein A has a secondary or tertiary carboxyl group,
Carboxylic acid residues that do not have an ester bond and can be the same or different. R is an organic residue having no ester bond, and n is an integer of 2 or more. ) are polycarboxylic acids represented by
ポリカルボン酸の分子量としては、例えば１６０から５
，０００またはそれ以上、通常２５Ｑから３．０００、
好ましくは２５０から２，０００、さらに好ましくは３
５０から１，５ＱＱである。The molecular weight of polycarboxylic acid is, for example, 160 to 5.
,000 or more, usually 25Q to 3,000,
Preferably from 250 to 2,000, more preferably 3
50 to 1.5QQ.
これらのポリカルボン酸は、例えばオキシカルボン酸（
ＨＯ−Ａ−ＣＯＯＨ’）とハロゲン置換基含有−）Ｊ
／ｌ／ ホ７酸（Ｘ−Ａ−ＣＯＯＨ−Ｘｑハロゲン原’
ｊ’−’を示す）またはポリハライド（Ｒ（−Ｘ）ｎ）
との反応、ハロゲン置換基含有カルボン酸とポリオール
（Ｒ（−０Ｈ）Ｈ，ｍはｎ以上の整数。）との反応等に
よって得ることができる。These polycarboxylic acids are, for example, oxycarboxylic acids (
HO-A-COOH') and halogen substituent-containing -)J
/l/ 7-acid (X-A-COOH-Xq halogen base)
j'-') or polyhalide (R(-X)n)
It can be obtained by a reaction between a halogen substituent-containing carboxylic acid and a polyol (R(-0H)H, m is an integer of n or more).
人で示される第２級または第３級のカルボキシル基金有
する、エステル結合を有さないカルボン酸の残基のカル
ボン酸の例としては、オキシカルボン酸の場合次のもの
がある。Examples of carboxylic acids of carboxylic acid residues having a secondary or tertiary carboxyl group and not having an ester bond include the following in the case of oxycarboxylic acids.
１、脂肪族オキシカルボン酸
例えば、２−ヒドロキシイン酪酸、２−ヒドロキシ−２
−メチル酪酸、２−エチル−２−ヒドロキシ酪酸、ヒド
ロキシピバリン酸。1. Aliphatic oxycarboxylic acids such as 2-hydroxyinbutyric acid, 2-hydroxy-2
-Methylbutyric acid, 2-ethyl-2-hydroxybutyric acid, hydroxypivalic acid.
２、脂環式オキシカルボン酸
例、ｔ ハ、１−ヒドロキシ−１−７クロプロパンカル
ボン酸、ヘキサヒドロマンデル酸。2. Examples of alicyclic oxycarboxylic acids, t, 1-hydroxy-1-7 chloropropanecarboxylic acid, hexahydromandelic acid.
３、芳香族オキシカルボン酸 例えば、サリチル酸。3. Aromatic oxycarboxylic acid For example, salicylic acid.
また、ハロゲン置換基含有カルボン酸残基のカルボン酸
の例としては、上記オキシカルボン酸の水酸基のハロゲ
ン置換体等があり、例えばクロロピバリン酸等があげら
れる。Further, examples of the carboxylic acid of the halogen substituent-containing carboxylic acid residue include halogen-substituted hydroxyl groups of the above-mentioned oxycarboxylic acids, such as chloropivalic acid.
Ｒで示されるエステル結合を含まない有機残基の例とし
ては、炭化水素基、ポリエーテル基等があげられる。Ｒ
がポリオールの残基の場合のポリオールとしては次のも
のがある。Examples of the organic residue not containing an ester bond represented by R include a hydrocarbon group, a polyether group, and the like. R
When is a polyol residue, the polyols include the following.
１、飽和及び不飽和脂肪族ポリオール
例エバ、エチレングリコール、１．３−クロパンジオー
ル、１．４−ブタンジオール、１．５−ベンタンジオー
ル、１．６−ヘキサンジオール、１．１２−ドデカンジ
オール、プロピレングリコール、２−ブチル−２−エチ
ル−１，３−プロパンジオール、２．３−または２．４
−ブタンジオール、１．５ヘキサンジオ−／Ｌ／、１．
２−デカンジオール、１．２−ドデカンジオール等の直
鎖および分校の飽和脂肪族ジオール。1. Examples of saturated and unsaturated aliphatic polyols EVA, ethylene glycol, 1.3-cropanediol, 1.4-butanediol, 1.5-bentanediol, 1.6-hexanediol, 1.12-dodecanediol, Propylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 2.3- or 2.4
-butanediol, 1.5 hexanedio-/L/, 1.
Linear and branched saturated aliphatic diols such as 2-decanediol, 1,2-dodecanediol.
マタハ、２−エチル−２−ヒドロキシメチル１．３−プ
ロパンジオール、１．２．３−へブタントリオール、１
，１．１−トリス（ヒドロキシメチル）エタン、ペンタ
エリスリトール、１，２，７．８−オクタンテトロール
等の飽和脂肪族ポリオール。Mataha, 2-ethyl-2-hydroxymethyl 1.3-propanediol, 1.2.3-hebutanetriol, 1
, 1.1-tris(hydroxymethyl)ethane, pentaerythritol, 1,2,7.8-octanetetrol and other saturated aliphatic polyols.
または、５−ヘキセン−１，２−ジオール％７−オクテ
ンー１．２−ジオール等の不飽和脂肪族ポリオール。Or unsaturated aliphatic polyols such as 5-hexene-1,2-diol%7-octene-1,2-diol.
２、飽和および不飽和脂環式ポリオール例工Ｉｄ、１．
３−シクロペンタンジオ−／Ｉ／、（メチル−）１．２
−または１．３−または１．４−シクロヘキサンジオー
ル、１．４−シクロヘキサンジメタツール、１．２−シ
クロへブタンジオール、１．４−または１．６−シクロ
オクタンジオール等の飽和単環脂環式ポリオール。2. Saturated and unsaturated alicyclic polyol examples Id, 1.
3-cyclopentanedio-/I/, (methyl-)1.2
- or saturated monocyclic aliphatic resins such as 1.3- or 1.4-cyclohexanediol, 1.4-cyclohexane dimetatool, 1.2-cyclohebutanediol, 1.4- or 1.6-cyclooctanediol Cyclic polyol.
または１．６−デカリンジオール、水素化ビスフェノー
ルＡ、水素化ビスフェノールＢ、４．８−ビス（ヒドロ
キシメチル）トリシクロ（５，２゜１０〕デカン等の飽
和多環脂環式ポリオ−μ。or saturated polycyclic alicyclic polyol-μ such as 1,6-decalindiol, hydrogenated bisphenol A, hydrogenated bisphenol B, and 4,8-bis(hydroxymethyl)tricyclo(5,2°10]decane.
マタハ、３−シクロヘキセン−１−−ジメタツール、３
．６−シクロへキサジエン−１，２−ジオール等の不飽
和脂環式ポリオ−μ。mataha, 3-cyclohexene-1-dimethatol, 3
．． Unsaturated alicyclic polyolefins such as 6-cyclohexadiene-1,2-diol.
３、芳香族ポリオール
例エバ、レゾルシン、ビスフェノール人、ビスフェノー
ルＢ、２．２−ビス（４−ヒドロキシ−３−メチルフェ
ニル）プロパン、ビス（２−ｔた１ｄ４−ヒドロキシフ
エニル）メタン。3. Examples of aromatic polyols: EVA, resorcinol, bisphenol, bisphenol B, 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(2-t-1d4-hydroxyphenyl)methane.
４、ポリアルキレングリコール
例えば、分子量１０６から４，５００または、それ以上
のポリエチレングリコール、ポリプロピレングリコール
、ポリブチレングリコール、またはそれらの共重合体。4. Polyalkylene glycols, such as polyethylene glycol, polypropylene glycol, polybutylene glycol, or copolymers thereof, having a molecular weight of 106 to 4,500 or more.
６、糖類
例えば、グルコース、ガラクトース、マンノース、フル
クトース等の単糖類。6. Sugars, such as monosaccharides such as glucose, galactose, mannose, and fructose.
マタハ、マルトース、ラクトース、スクロース等の多糖
類。Polysaccharides such as mataha, maltose, lactose, and sucrose.
６、複素環式ポリオール類 例エバ、２．６−フランジメタノール等。6. Heterocyclic polyols Examples include Eva, 2,6-furandimethanol, etc.
７、主鎖に炭素、酸素以外の原子を含有するポリオール
例えば、２．２’−（デカメチレンジチオ）ジメタツー
ル、ジェタノールアミン、トリエタノールアミン、 ２
．２’−ビス（ヒドロキシメチ１ｖ）−２，２’、２”
−ニトリロエタノール、１．４−ビス（２−ヒドロキシ
エチル）ヒペラジン、トリス（ヒドロキシメチル）アミ
ノメタン、トリス（ヒドロキシメチル）フナスフィンオ
キサイド、ビスフェノールＳ等。7. Polyol containing atoms other than carbon and oxygen in the main chain, e.g. 2'-(decamethylenedithio)dimethazole, jetanolamine, triethanolamine, 2
．． 2'-bis(hydroxymethyv)-2,2',2"
-Nitriloethanol, 1,4-bis(2-hydroxyethyl)hyperazine, tris(hydroxymethyl)aminomethane, tris(hydroxymethyl)funasphine oxide, bisphenol S, etc.
８、水酸基を有するモノマーの重合体および共重合体
例えば、分子量９０から４，５００または、それ以上の
ポリビニルアルコール等。8. Polymers and copolymers of monomers having hydroxyl groups, such as polyvinyl alcohol with a molecular weight of 90 to 4,500 or more.
これらのポリオールで、３価以上のものについては、す
べての水酸基がエーテル結合に供される必要はなく、１
つ以上の水酸基が残存してもかまわない。Among these polyols, for those with a valence of 3 or more, it is not necessary that all hydroxyl groups be provided for ether bonding;
It does not matter if more than one hydroxyl group remains.
また、Ｒがポリハライドの残基の場合のポリハライドの
例としては、上記ポリオールの水酸基のハロゲン置換体
、例えばジクロロエタン、１．６−ジブロモヘキサン等
があげられる。Examples of the polyhalide when R is a polyhalide residue include halogen-substituted hydroxyl groups of the polyols, such as dichloroethane and 1,6-dibromohexane.
１Ｑ、、７
これらの、ポリハライドのハロゲン基は、すべて、エー
テル結合生成に費やされ、反応後分子内に残存していな
いことが好ましい。1Q, , 7 It is preferable that all of the halogen groups of these polyhalides are used for forming ether bonds and do not remain in the molecule after the reaction.
作用
通常、高温での劣化は、溶媒とエステル化反応を引キ起
こす等のカルボン酸のカルボキシル基の反応で起こる。Effect Usually, deterioration at high temperatures occurs due to reactions between the carboxyl groups of carboxylic acids, such as esterification reactions with solvents.
本発明はこの点に着目し第２級および／または第３級の
カルボキシル基を有するカルボン酸を用いた。第２級お
よび／または第３級のカルボキシル基は立体障害により
エステル化反応を起こしにくく、高温で安定な電解液が
得られると考えられる。The present invention focused on this point and used a carboxylic acid having a secondary and/or tertiary carboxyl group. It is thought that secondary and/or tertiary carboxyl groups are less likely to cause an esterification reaction due to steric hindrance, resulting in an electrolytic solution that is stable at high temperatures.
また、エーテル結合を有し、エステル結合を有さないポ
リカルボン酸を用いることによって、より高温安定性を
高めだ電解液とすることができる。Further, by using a polycarboxylic acid having an ether bond and no ester bond, an electrolytic solution with higher high temperature stability can be obtained.
実施例
以Ｆ、実施例により本発明を更に説明するが、本発明は
これに限定されるものではない。EXAMPLES The present invention will be further explained with reference to Examples F and F, but the present invention is not limited thereto.
表１に本発明の実施例および従来の電解液、並びにその
常温における比電導度、火花電圧を示す。Table 1 shows examples of the present invention and conventional electrolytes, as well as their specific conductivities and spark voltages at room temperature.
この表１から明らかなように本発明においては、従来例
１．２．３と比較して比電導度を下げずに、火花電圧を
高くすることができる。As is clear from Table 1, in the present invention, the spark voltage can be increased without lowering the specific conductivity compared to Conventional Examples 1.2.3.
第１図は実施例１．２．３．４、従来例２．４および５
の１２６０における電解液の比電導度経時変化を示した
もので、この第１図からも明らかなように、本発明は、
従来例と比較して高温での変化が小さく、高温での長寿
命化が可能であることが判る。Figure 1 shows Example 1.2.3.4, Conventional Examples 2.4 and 5.
This figure shows the change in specific conductivity of the electrolytic solution over time at 1260, and as is clear from this figure, the present invention
It can be seen that the change at high temperatures is small compared to the conventional example, and it is possible to extend the life at high temperatures.
表２は、表１に示した実施例１から４、従来例４．６の
電解液を使用したアルミ電解コンデンサ（定格４００Ｖ
、２２ＱμＦ ）の１２５０におけるライフ試倹での特
性変化を示したものである。Table 2 shows aluminum electrolytic capacitors (rated at 400 V) using the electrolytes of Examples 1 to 4 and Conventional Examples 4 and 6 shown in Table 1.
, 22QμF) during a life test at 1250.
なお、従来例１から３は４００Ｖの電圧が印加できなか
った。Note that in Conventional Examples 1 to 3, a voltage of 400V could not be applied.
表２から明らかなように、実施例１から４を使用したコ
ンデンサは従来例４．６と比較して静電容量変化、損失
角の正接変化のいずれも小さく、寿命特性に優れた信頼
性の高いコンデンサを得ることができる。As is clear from Table 2, the capacitors using Examples 1 to 4 have smaller capacitance changes and smaller loss angle tangent changes than conventional examples 4.6, and are highly reliable with excellent life characteristics. You can get higher capacitors.
発明の効果
以北のように本発明によれば、従来の電解液と比較して
、火花電圧が高く、かつ高温中での変化が小さく、さら
には中高圧級電解コンデンサの長寿命化、高信頼化が可
能となるもので、工業価値の大なるものである。Effects of the Invention According to the present invention, compared to conventional electrolytes, the spark voltage is higher and the change in high temperature is smaller, and furthermore, the life of medium and high voltage class electrolytic capacitors is extended, and the It enables reliability and is of great industrial value.
第１図は本発明の実施例による電解液の１２５０中での
比電導度経時変化を従来の電解液と比較して示した特性
図である。FIG. 1 is a characteristic diagram showing the change in specific conductivity over time of an electrolytic solution according to an embodiment of the present invention in 1250 ml as compared with a conventional electrolytic solution.
Claims (2)
２個以上有するポリカルボン酸であって、エーテル結合
を有し、かつエステル結合を有さないものの塩を溶質と
して用いることを特徴とする電解コンデンサ駆動用電解
液。(1) A polycarboxylic acid having two or more secondary and/or tertiary carboxyl groups, which has an ether bond and no ester bond, is used as a solute. Electrolyte for driving electrolytic capacitors.
（−Ａ−ＣＯＯＨ）＿２ （１） Ｒ（−Ｏ−Ａ−ＣＯＯＨ）＿ｎ （２） （式中、Ａは第２級または第３級のカルボキシル基を有
する、エステル結合を有さないカルボン酸の残基で、同
一または異なる。Ｒはエステル結合を有さない有機残基
、ｎは２以上の整数である。）で表される特許請求の範
囲第１項記載の電解コンデンサ駆動用電解液。(2) The polycarboxylic acid has the general formula (1) or (2) O
(-A-COOH)_2 (1) R(-O-A-COOH)_n (2) (wherein, A is a carboxylic acid having a secondary or tertiary carboxyl group and having no ester bond) (R is an organic residue having no ester bond, and n is an integer of 2 or more.) The electrolyte solution for driving an electrolytic capacitor according to claim 1, .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1284163A JP2695254B2 (en) | 1989-10-31 | 1989-10-31 | Electrolyte for driving electrolytic capacitors |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1284163A JP2695254B2 (en) | 1989-10-31 | 1989-10-31 | Electrolyte for driving electrolytic capacitors |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03145713A true JPH03145713A (en) | 1991-06-20 |
| JP2695254B2 JP2695254B2 (en) | 1997-12-24 |
Family
ID=17675000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1284163A Expired - Fee Related JP2695254B2 (en) | 1989-10-31 | 1989-10-31 | Electrolyte for driving electrolytic capacitors |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2695254B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011099261A1 (en) * | 2010-02-15 | 2011-08-18 | パナソニック株式会社 | Electrolytic capacitor |
| JP2015019015A (en) * | 2013-07-12 | 2015-01-29 | 日油株式会社 | Electrolyte for electrolytic capacitor |
| JP2017112389A (en) * | 2017-02-01 | 2017-06-22 | 国立大学法人三重大学 | Driving electrolyte of electrolytic capacitor and electrolytic capacitor using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0218919A (en) * | 1988-07-07 | 1990-01-23 | Matsushita Electric Ind Co Ltd | Electrolyte for driving electrolytic capacitor and electrolytic capacitor |
-
1989
- 1989-10-31 JP JP1284163A patent/JP2695254B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0218919A (en) * | 1988-07-07 | 1990-01-23 | Matsushita Electric Ind Co Ltd | Electrolyte for driving electrolytic capacitor and electrolytic capacitor |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011099261A1 (en) * | 2010-02-15 | 2011-08-18 | パナソニック株式会社 | Electrolytic capacitor |
| JPWO2011099261A1 (en) * | 2010-02-15 | 2013-06-13 | パナソニック株式会社 | Electrolytic capacitor |
| JP5810292B2 (en) * | 2010-02-15 | 2015-11-11 | パナソニックＩｐマネジメント株式会社 | Electrolytic capacitor |
| US9208954B2 (en) | 2010-02-15 | 2015-12-08 | Panasonic Intellectual Property Management Co., Ltd. | Electrolytic capacitor |
| US9595396B2 (en) | 2010-02-15 | 2017-03-14 | Panasonic Intellectual Property Management Co., Ltd. | Electrolytic capacitor and manufacturing method therefor |
| US9966200B2 (en) | 2010-02-15 | 2018-05-08 | Panasonic Intellectual Property Management Co., Ltd. | Electrolytic capacitor and manufacturing method therefor |
| US10559432B2 (en) | 2010-02-15 | 2020-02-11 | Panasonic Intellectual Property Management Co., Ltd. | Electrolytic capacitor and manufacturing method therefor |
| US10679800B2 (en) | 2010-02-15 | 2020-06-09 | Panasonic Intellectual Property Management Co., Ltd. | Electrolytic capacitor and manufacturing method therefor |
| US11398358B2 (en) | 2010-02-15 | 2022-07-26 | Panasonic Intellectual Property Management Co., Ltd. | Electrolytic capacitor and manufacturing method therefor |
| JP2015019015A (en) * | 2013-07-12 | 2015-01-29 | 日油株式会社 | Electrolyte for electrolytic capacitor |
| JP2017112389A (en) * | 2017-02-01 | 2017-06-22 | 国立大学法人三重大学 | Driving electrolyte of electrolytic capacitor and electrolytic capacitor using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2695254B2 (en) | 1997-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5321555B2 (en) | Liquid crystal light modulation element and optical head device | |
| Netzel et al. | Benzoquinone quenching of diporphyrin excited states: Kinetic evidence for distinguishing electron transfer photoproducts from (. pi.,. pi.*) states | |
| WO2021019998A1 (en) | Perfluoropolyether compound, lubricant, and magnetic disc | |
| JPWO2016031436A1 (en) | Curable composition, polymer functional cured product, stack or apparatus provided with polymer functional film, amide compound, and method for producing the same | |
| US20090039321A1 (en) | Supramolecular composite film material and method for fabricating | |
| JPH03145713A (en) | Electrolyte for driving of electrolytic capacitor | |
| WO2002035636A1 (en) | Solid polymer electrolyte and cell containing the electrolyte | |
| Park et al. | Self‐healable supramolecular hydrogel formed by nor‐seco‐cucurbit [10] uril as a supramolecular crosslinker | |
| Shigehara et al. | Langmuir-Blodgett ultrathin membranes of fumarate polymers | |
| JP5377830B2 (en) | POLYESTER RESIN, POLYESTER RESIN AQUEOUS LIQUE | |
| JP7162308B2 (en) | Draw solute and water treatment equipment | |
| JP5042513B2 (en) | Two-photon absorption materials and their applications | |
| JPH01103821A (en) | Electrolyte for driving electrolytic capacitor | |
| CN111748273B (en) | Double-component solvent-free adhesive and use method thereof | |
| JPH04366563A (en) | Electrolyte composition and high molecular solid electrolyte | |
| JPH06145384A (en) | Method for forming antistatic film | |
| EP0196497B1 (en) | Functional elastomer | |
| WO2021085099A1 (en) | Layered body | |
| Wan et al. | Influence of Side‐Chain Composition on Polythiophene Properties and Supramolecular Assembly of Anionic Polythiophene Derivatives | |
| JP3376749B2 (en) | Electrolyte for driving electrolytic capacitors | |
| JP3281945B2 (en) | Electrolyte for driving electrolytic capacitors | |
| CN108831997A (en) | A kind of sandwich structure memory device and preparation method thereof | |
| JPS63158540A (en) | Optical recording material | |
| JP3393673B2 (en) | Electrolyte for driving electrolytic capacitors | |
| JPH0442911A (en) | Electrolyte for driving electrolytic capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |