TW201602080A

TW201602080A - Polybasic carboxylic acid compound with ether groups, useful as electrolyte for electrolytic solution for electrochemical device

Info

Publication number: TW201602080A
Application number: TW104110139A
Authority: TW
Inventors: 弘津健二; 福田泰久; 里村哲也; 吉田佳弘; 遠藤健太
Original assignee: 宇部興產股份有限公司
Priority date: 2014-03-28
Filing date: 2015-03-27
Publication date: 2016-01-16
Also published as: WO2015147321A1; JPWO2015147321A1

Abstract

The invention discloses an electrolyte for an electrochemical device, the electrolyte containing a polybasic carboxylic acid compound having ether groups represented by general formula (1) shown below. In general formula (1), G represents an (n+1)-valent hydrocarbon group having a carbon number of 2 to 36 that may have a substituent, each of R1 to R4 is selected from among a hydrogen atom, an alkyl group having a carbon number of 1 to 4 and a hydroxyl group, n represents an integer of 1 to 10, R<SP>a+</SP> is selected from among a hydrogen ion, an ammonium ion and an organic amine ion, and the total carbon number of the compound represented by general formula (1) is at least 8 but not more than 70. An electrolytic solution for an electrolytic capacitor that uses this compound is stable, with no precipitation of the electrolyte compound, and exhibits a high withstand voltage.

Description

可用作為電化學元件用電解液的電解質之具有醚基的多元羧酸化合物Polycarboxylic acid compound having an ether group which can be used as an electrolyte for an electrolyte for an electrochemical element

本發明係關於例如鋁電解電容般的電化學元件用電解液，更詳細而言係關於一種新穎的含有具有醚基的多元羧酸化合物之電解質。The present invention relates to an electrolyte for an electrochemical element such as an aluminum electrolytic capacitor, and more particularly to a novel electrolyte containing a polycarboxylic acid compound having an ether group.

在分子內具有多個羧基的多元羧酸化合物之中，例如關於具有2個羧基的二羧酸，已知其作為電解電容電解液的電解質或聚醯胺的原料等之可用性(例如參照專利文獻1～專利文獻5)。 [先前技術文獻] [專利文獻]Among the polycarboxylic acid compounds having a plurality of carboxyl groups in the molecule, for example, the dicarboxylic acid having two carboxyl groups is known as an electrolyte of an electrolytic capacitor electrolyte or a raw material of polyamine (for example, refer to the patent literature). 1 to Patent Document 5). [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本特開2005-072182號公報 [專利文獻2]日本特開平6-61103號公報 [專利文獻3]美國專利3994959號公報 [專利文獻4]日本特開平6-104144號公報 [專利文獻5]日本特開平3-145713號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-61103 (Patent Document 3) Japanese Patent No. 3994959 (Patent Document 4) Japanese Patent Publication No. Hei 6-104144 [ Patent Document 5] Japanese Patent Laid-Open No. Hei 3-145713

[發明所欲解決之課題][Problems to be solved by the invention]

然而，此等多元羧酸化合物之中，經報告作為電解電容用電解液的電解質成分之大多數的化合物，例如作為鋁電解電容用電解液成分使用時之高火花起始電壓或高導電度、對電解液的溶解度等以電解質而言必要的物性，難以稱為充分滿足。However, among these polycarboxylic acid compounds, most of the compounds which are reported as electrolyte components of the electrolytic solution for electrolytic capacitors, for example, are used as high-sparking starting voltages or high electrical conductivity when used as an electrolytic solution component for aluminum electrolytic capacitors. It is difficult to say that the physical properties necessary for the electrolyte such as the solubility of the electrolytic solution are sufficiently satisfied.

因此，本發明係以提供一種電化學元件用電解液的電解質為課題，該電化學元件用電解液的電解質具有尤其作為鋁電解電容用電解液成分所要求之物性的高火花起始電壓、高導電度，並且更具有在低溫下操作中亦難以析出結晶(固體)之特徵。 [用以解決課題之手段]Therefore, the present invention has an object of providing an electrolyte for an electrolyte for an electrochemical device having a high spark initiation voltage and a high physical property required for an electrolyte component for an aluminum electrolytic capacitor. Conductivity, and more difficult to precipitate crystals (solids) during operation at low temperatures. [Means to solve the problem]

本案發明人為了解決上述課題而專心探討，結果發現前述課題可藉由下述所示之含有多元羧酸化合物之電解質來解決，繼而完成本發明。The inventors of the present invention have intensively studied to solve the above problems, and as a result, have found that the above problems can be solved by an electrolyte containing a polyvalent carboxylic acid compound shown below, and the present invention has been completed.

[1]一種電化學元件用電解質，含有下述通式(1)所表示之具有醚基的多元羧酸化合物；[1] An electrolyte for an electrochemical device comprising a polyvalent carboxylic acid compound having an ether group represented by the following formula (1);

【化1】[通式(1)中，G表示可具有取代基之碳數2～36的(n＋1)價之烴基，惟具有芳香族基時亦可包含雜原子； R¹ ～R⁴ 分別表示選自由氫原子、碳數1～6的烷基、碳數1～6的烷氧基、及羥基構成之群組中的一種取代基，R¹ ～R⁴ 彼此可為相同亦可為不同，出現多次時可各表示相同或不同之基，惟R³ 與R⁴ 不會同時表示烷基及烷氧基； n係1～10的整數，當n為2以上時，於分子末端具有羧酸部位之氧基不存在於同一碳上； R^a ^＋表示選自由氫離子、銨離子及有機胺離子構成之群組中的離子，又，虛線之鍵結表示離子鍵；通式(1)所表示之化合物的碳數係8以上70以下]。 [2]如上述[1]記載之電解質，其中G表示選自由碳數2～36的飽和烴基、碳數4～36的不飽和脂肪族烴基、可包含雜原子之碳數6～36的芳香族基、及具有芳香族部分及脂肪族部分的可包含雜原子之碳數7～36的烴基構成之群組中的可具有取代基之烴基。 [3]如上述[1]或[2]記載之電解質，其中含有n為1～3的通式(1)所表示之化合物。 [4]如上述[1]～[3]中任1項記載之電解質，其中含有R¹ ～R⁴ 全為氫的通式(1)所表示之化合物。 [5]如上述[1]～[4]中任1項記載之電解質，其中含有G為選自由碳數3～12的直鏈狀伸烷基、主鏈的碳數為3以上且側鏈的碳數為1以上之碳數4～12的分支鏈烷-二、三或四-基、式(2)所表示之伸烷基、及碳數4～8的直鏈狀之伸烯基構成之群組中的基之通式(1)之化合物；【化1】 [In the formula (1), G represents a (n+1)-valent hydrocarbon group having 2 to 36 carbon atoms which may have a substituent, and may have a hetero atom even when it has an aromatic group; and R ¹ to R ⁴ each represent a group selected from hydrogen; One of the substituents in the group consisting of an atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a group consisting of hydroxyl groups, and R ¹ to R ⁴ may be the same or different and may be present multiple times. Each of R ³ and R ^{4 may} not represent an alkyl group or an alkoxy group at the same time; n is an integer of 1 to 10, and when n is 2 or more, it has a carboxylic acid moiety at a molecular terminal. The oxy group is not present on the same carbon; R ^a ⁺ represents an ion selected from the group consisting of a hydrogen ion, an ammonium ion, and an organic amine ion, and the bond of a broken line represents an ionic bond; represented by the formula (1) The carbon number of the compound is 8 or more and 70 or less]. [2] The electrolyte according to [1] above, wherein G represents an aromatic hydrocarbon group selected from the group consisting of a saturated hydrocarbon group having 2 to 36 carbon atoms, an unsaturated aliphatic hydrocarbon group having 4 to 36 carbon atoms, and a carbon number of 6 to 36 which may contain a hetero atom. A hydrocarbon group which may have a substituent in the group consisting of a hydrocarbon group having a hetero atom and a carbon number of 7 to 36 having an aromatic moiety and an aliphatic moiety. [3] The electrolyte according to the above [1] or [2], which contains a compound represented by the formula (1) wherein n is 1 to 3. [4] The electrolyte according to any one of the above [1], wherein the compound represented by the formula (1) in which all of R ¹ to R ⁴ are hydrogen is contained. [5] The electrolyte according to any one of [1] to [4] wherein G is selected from a linear alkyl group having 3 to 12 carbon atoms, and the carbon number of the main chain is 3 or more and a side chain. a branched alkane having two or more carbon atoms of 4 to 12, a di-, tri- or tetra-yl group, an alkylene group represented by the formula (2), and a linear alkenyl group having 4 to 8 carbon atoms. a compound of the formula (1) in the group consisting of;

【化2】(式中，v、w、x及z分別表示0～6之數，v＋w＋x＋z係2～6；惟當v為0時及z為0時，表示環員碳為鍵結部位，當x為0時及w為0時，表示單鍵)。 [6]如上述[1]～[5]中任1項記載之電解質，其中更含有選自由碳數4～16的羧酸及羧酸之鹽構成之群組中的至少1種化合物。 [7]如上述[1]～[6]中任1項記載之電解質，其中更含有選自由碳數4～10的腈化合物及碳數4～10的醚化合物構成之群組中的至少1種化合物。 [8]一種電化學元件用電解液，其含有如上述[1]～[7]中任1項記載之電解質、及水與選自乙二醇及γ-丁內酯之一種以上的有機溶媒之混合溶媒。 [9]如上述[8]記載之電解液，其中前述混合溶液中之水的含量為30質量%以下。 [10]如上述[8]或[9]記載之電解液，其中以0.01～50質量%之量含有如上述1～7中任1項記載之電解質。 [11]如上述[8]～[10]中任1項記載之電解液，其為鋁電化學元件用電解液。 [12]一種電解電容，其含有如上述[8]～[11]中任1項記載之電解液。 [13]如上述[12]記載之電解電容，其為鋁電解電容。 [14]一種化合物，其係以式(3)所表示；[Chemical 2] (wherein, v, w, x, and z represent the number of 0 to 6, respectively, v + w + x + z is 2 to 6; but when v is 0 and z is 0, it means ring member carbon is the bonding site, when x is 0 When w and 0 are 0, it means a single key). [6] The electrolyte according to any one of the above [1] to [5], further comprising at least one compound selected from the group consisting of a carboxylic acid having 4 to 16 carbon atoms and a salt of a carboxylic acid. [7] The electrolyte according to any one of the above [1], wherein the electrolyte further contains at least one selected from the group consisting of a nitrile compound having 4 to 10 carbon atoms and an ether compound having 4 to 10 carbon atoms. Kind of compound. [8] An electrolyte solution for an electrochemical device, comprising the electrolyte according to any one of the above [1] to [7], and water and one or more organic solvents selected from the group consisting of ethylene glycol and γ-butyrolactone. Mixed solvent. [9] The electrolytic solution according to the above [8], wherein the content of the water in the mixed solution is 30% by mass or less. [10] The electrolyte according to the above [8] or [9], wherein the electrolyte according to any one of the above 1 to 7 is contained in an amount of from 0.01 to 50% by mass. [11] The electrolytic solution according to any one of the above [8] to [10], which is an electrolytic solution for an aluminum electrochemical device. [12] An electrolytic capacitor comprising the electrolytic solution according to any one of the above [8] to [11]. [13] The electrolytic capacitor according to [12] above, which is an aluminum electrolytic capacitor. [14] A compound represented by formula (3);

【化3】(式中，A係選自由COOH、CN及COOR⁵ 構成之群組中的基，R⁵ 表示碳數1～6的烷基)。 [15]一種化合物，其係以式(4)所表示；[化3] (In the formula, A is selected from the group consisting of COOH, CN, and COOR ⁵ , and R ⁵ is an alkyl group having 1 to 6 carbon atoms). [15] a compound represented by formula (4);

【化4】(式中，B表示COOH或CN)。 [發明之效果]【化4】 (wherein B represents COOH or CN). [Effects of the Invention]

根據本發明，可提供一種電化學元件用電解液的電解質，其具有高火花起始電壓、高導電度，並且更具有在低溫下操作中亦難以析出結晶(固體)之特徵。According to the present invention, it is possible to provide an electrolyte of an electrolyte for an electrochemical element which has a high spark initiation voltage, high conductivity, and is more characterized in that it is difficult to precipitate crystals (solids) during operation at a low temperature.

本發明所使用之具有醚基的多元羧酸化合物具有良好的傳導性及火花電壓，同時對水及多數的有機溶媒顯示良好的溶解性，可期待低溫下的特性優異。因此，該多元羧酸化合物利用這種溶解性，尤其利用從水溶液之析出為少的特徵，可期待作為鋁電解電容用電解液的電解質成分之用途，此外，還期待作為例如清潔劑、洗淨劑之補助劑(builder)；潤滑油；抗水垢劑；環氧樹脂硬化劑；聚合物用原料等新的可用性。The polyvalent carboxylic acid compound having an ether group used in the present invention has good conductivity and spark voltage, and exhibits good solubility to water and many organic solvents, and is excellent in characteristics at a low temperature. Therefore, the polycarboxylic acid compound is used in such a solvent, and is particularly useful in that it is used as an electrolyte component of an electrolytic solution for aluminum electrolytic capacitors, and is expected to be used as, for example, a cleaning agent and a cleaning agent. Agents; lubricants; anti-scaling agents; epoxy resin hardeners; new materials for polymer materials.

首先，針對具有醚基的多元羧酸化合物進行說明。＜可用作為電化學元件用電解液的電解質之具有醚基的多元羧酸化合物：通式(1)＞本發明所使用之多元羧酸化合物，係在分子內具有2個以上的羧基，碳數為8以上70以下，並且以下述通式(1)所表示。First, a description will be given of a polyvalent carboxylic acid compound having an ether group. <Polycarboxylic acid compound having an ether group which can be used as an electrolyte for an electrochemical device electrolyte: Formula (1)> The polycarboxylic acid compound used in the present invention has two or more carboxyl groups in the molecule, and the number of carbon atoms It is 8 or more and 70 or less, and is represented by the following general formula (1).

【化5】【化5】

[通式(1)中，G表示可具有取代基之碳數2～36的(n＋1)價之烴基，惟具有芳香族基時亦可包含雜原子； R¹ ～R⁴ 分別表示選自由氫原子、碳數1～6的烷基、碳數1～6的烷氧基、及羥基構成之群組中的一種取代基，R¹ ～R⁴ 彼此可為相同亦可為不同，出現多次時可各表示相同或不同之基，惟R³ 與R⁴ 不會同時表示烷基及烷氧基； n係1～10的整數，當n為2以上時，於分子末端具有羧酸部位之氧基不存在於同一碳上； R^a ^＋表示選自由氫離子、銨離子及有機胺離子構成之群組中的離子，又，虛線之鍵結表示離子鍵；通式(1)所表示之化合物的碳數係8以上70以下]。[In the formula (1), G represents a (n+1)-valent hydrocarbon group having 2 to 36 carbon atoms which may have a substituent, and may have a hetero atom even when it has an aromatic group; and R ¹ to R ⁴ each represent a group selected from hydrogen; One of the substituents in the group consisting of an atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a group consisting of hydroxyl groups, and R ¹ to R ⁴ may be the same or different and may be present multiple times. Each of R ³ and R ^{4 may} not represent an alkyl group or an alkoxy group at the same time; n is an integer of 1 to 10, and when n is 2 or more, it has a carboxylic acid moiety at a molecular terminal. The oxy group is not present on the same carbon; R ^a ⁺ represents an ion selected from the group consisting of a hydrogen ion, an ammonium ion, and an organic amine ion, and the bond of a broken line represents an ionic bond; represented by the formula (1) The carbon number of the compound is 8 or more and 70 or less].

(關於G) 通式(1)之定義中，G較佳為選自由碳數2～36的飽和烴基、碳數4～36的不飽和脂肪族烴基、可包含雜原子之碳數6～36的芳香族基、及具有芳香族部分及脂肪族部分的可包含雜原子之碳數7～36的烴基構成之群組。此等基可具有取代基。(G) In the definition of the formula (1), G is preferably selected from a saturated hydrocarbon group having 2 to 36 carbon atoms, an unsaturated aliphatic hydrocarbon group having 4 to 36 carbon atoms, and a carbon number 6 to 36 which may contain a hetero atom. The aromatic group and the hydrocarbon group having an aromatic moiety and an aliphatic moiety which may contain a hetero atom and having 7 to 36 carbon atoms. These groups may have a substituent.

[G：碳數2～36的飽和烴基] 在本發明之1種態樣中，G係以(n＋1)價之碳數2～36的飽和烴基為較佳，其表示從飽和烴(即烷)除去(n＋1)個氫原子後之殘基。飽和烴基可為直鏈狀烴基，又可為分支鏈烴基(碳數3以上)，亦可為分子內包含飽和環之烴基(碳數3以上)。具體而言係以伸烷基(烷二基)、烷三基、烷四基為較佳。又，當為分子內包含飽和環之烴基時，鍵結部位可為環員碳或鏈狀碳之任一者。飽和環較佳為3～8員環，更佳為4～6員環，最佳為6員環(環己烷環)。[G: saturated hydrocarbon group having 2 to 36 carbon atoms] In one aspect of the present invention, G is preferably a saturated hydrocarbon group having a carbon number of 2 to 36 of (n+1), which is represented by a saturated hydrocarbon (i.e., an alkane). The residue after removal of (n+1) hydrogen atoms. The saturated hydrocarbon group may be a linear hydrocarbon group or a branched hydrocarbon group (having a carbon number of 3 or more), or may be a hydrocarbon group having a saturated ring in the molecule (having a carbon number of 3 or more). Specifically, an alkylene group (alkanediyl group), an alkanetriyl group or an alkanetetrayl group is preferred. Further, when it is a hydrocarbon group containing a saturated ring in the molecule, the bonding site may be either ring member carbon or chain carbon. The saturated ring is preferably a 3 to 8 membered ring, more preferably a 4 to 6 membered ring, and most preferably a 6 membered ring (cyclohexane ring).

再者，鍵結於此等飽和烴基中之碳原子的氫原子之一部份或全部，可例如經碳數1～6的烷基(直鏈狀、分支鏈狀、環狀)、碳數1～6的烷氧基(其中，烷基係直鏈狀、分支鏈狀或環狀的烷基)、碳數6～24的芳基(例如苯基、萘基、聯苯基等)、碳數7～25的芳烷基(例如苯甲基、苯乙基等)取代。又，同一碳上的2個氫原子可經側氧基(＝O)、硫基(thioxo)(＝S)取代。取代基之個數並未特別限制，通式(1)之化合物的碳數係8以上70以下。Further, part or all of the hydrogen atoms of the carbon atoms bonded to the saturated hydrocarbon group may be, for example, an alkyl group having 1 to 6 carbon atoms (linear, branched, cyclic), carbon number An alkoxy group of 1 to 6 (wherein an alkyl group is a linear, branched or cyclic alkyl group), an aryl group having 6 to 24 carbon atoms (for example, a phenyl group, a naphthyl group, a biphenyl group, etc.), An aralkyl group having 7 to 25 carbon atoms (e.g., benzyl, phenethyl, etc.) is substituted. Further, two hydrogen atoms on the same carbon may be substituted with a pendant oxy group (=O) or a thioxo group (=S). The number of the substituents is not particularly limited, and the compound of the formula (1) has a carbon number of 8 or more and 70 or less.

[G：碳數4～36的不飽和脂肪族烴基] 在本發明之1種態樣中，G係以(n＋1)價之碳數4～36的不飽和脂肪族烴基為較佳，其表示從不飽和脂肪族烴除去(n＋1)個氫原子後之殘基。不飽和脂肪族烴基可為直鏈狀，又可為分支鏈狀。較佳為從烯衍生之殘基，而以碳數4～12的直鏈狀之伸烯基、碳數4～18的分支鏈狀之伸烯基為較佳。進一步更佳為碳數4～8的直鏈狀之伸烯基、分支鏈狀之伸烯基。[G: unsaturated aliphatic hydrocarbon group having 4 to 36 carbon atoms] In one aspect of the present invention, G is preferably an unsaturated aliphatic hydrocarbon group having a carbon number of 4 to 36 of (n+1). A residue after removing (n+1) hydrogen atoms from an unsaturated aliphatic hydrocarbon. The unsaturated aliphatic hydrocarbon group may be linear or branched. The residue derived from an alkene is preferably a linear alkenyl group having 4 to 12 carbon atoms and a branched alkenyl group having 4 to 18 carbon atoms. Further, it is more preferably a linear alkenyl group having 4 to 8 carbon atoms or an extended alkenyl group having a branched chain.

再者，鍵結於此等伸烷基中之碳原子的氫原子之一部份或全部，可例如經碳數1～6的烷基(直鏈狀、分支鏈狀、環狀)、碳數1～6的烷氧基(烷基部分可為直鏈狀、分支鏈狀、環狀之任一者)、碳數6～24的芳基(例如苯基、萘基、聯苯基等)、碳數7～25的芳烷基(例如苯甲基、苯乙基等)取代。又，同一碳上的2個氫原子可經側氧基(＝O)、硫基(＝S)取代。此外，此等取代基之個數並未特別限制，通式(1)之化合物的碳數係8以上70以下。Further, a part or all of a hydrogen atom bonded to a carbon atom in the alkyl group may be, for example, an alkyl group having 1 to 6 carbon atoms (linear, branched, cyclic), carbon The alkoxy group of 1 to 6 (the alkyl moiety may be a linear chain, a branched chain or a ring) or an aryl group having 6 to 24 carbon atoms (for example, a phenyl group, a naphthyl group, a biphenyl group, etc.) And an aralkyl group having 7 to 25 carbon atoms (e.g., benzyl, phenethyl, etc.) is substituted. Further, two hydrogen atoms on the same carbon may be substituted with a pendant oxy group (=O) or a thio group (=S). Further, the number of such substituents is not particularly limited, and the compound of the formula (1) has a carbon number of 8 or more and 70 or less.

[G：可包含雜原子之碳數6～36的芳香族基] 在本發明之1種態樣中，G係選自(n＋1)價之可包含雜原子之碳數6～36的芳香族基，其表示從芳香族化合物除去(n＋1)個氫原子後之殘基。較佳為例如伸苯基、伸萘基或聯伸苯基等碳數6～36的2價之伸芳基。再者，在此等芳香族基中，芳香族基中之碳原子可例如經碳數1～6的烷基、碳數1～6的烷氧基、苯基取代。此外，此等取代基之個數並未特別限制，通式(1)之化合物的碳數係8以上70以下。[G: an aromatic group having 6 to 36 carbon atoms which may contain a hetero atom] In one aspect of the present invention, G is an aromatic group having a carbon number of 6 to 36 which may be contained in a (n+1)-valent hetero atom. A group which represents a residue obtained by removing (n+1) hydrogen atoms from an aromatic compound. Preferred are, for example, a divalent aryl group having 6 to 36 carbon atoms such as a phenyl group, a naphthyl group or a phenyl group. Further, in these aromatic groups, the carbon atom in the aromatic group may be substituted, for example, with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group. Further, the number of such substituents is not particularly limited, and the compound of the formula (1) has a carbon number of 8 or more and 70 or less.

在此，包含雜原子之芳香族基係表示從雜芳香族化合物除去(n＋1)個氫後之殘基。雜芳香族化合物係指呋喃、苯并呋喃、噻吩、苯并噻吩、吡咯吲哚、吡啶、嘧啶等。Here, the aromatic group containing a hetero atom means a residue obtained by removing (n+1) hydrogen from the heteroaromatic compound. The heteroaromatic compound means furan, benzofuran, thiophene, benzothiophene, pyrrolidine, pyridine, pyrimidine or the like.

[G：具有芳香族部分及脂肪族部分的可包含雜原子之碳數7～36的烴基] 在本發明之1種態樣中，G可為具有芳香族部分及脂肪族部分的(n＋1)價之烴基，其表示從具有芳香族部分與脂肪族部分之烴化合物除去(n＋1)個氫原子後之殘基。基G中之鍵結部位(經除去氫原子之部位)可僅為芳香族部分、亦可僅為脂肪族部分、亦可為芳香族部分與脂肪族部分之兩者。[G: a hydrocarbon group having 7 to 36 carbon atoms which may have a hetero atom and an aliphatic moiety] In one aspect of the invention, G may be (n+1) having an aromatic moiety and an aliphatic moiety A hydrocarbon group of a valence, which represents a residue obtained by removing (n+1) hydrogen atoms from a hydrocarbon compound having an aromatic moiety and an aliphatic moiety. The bonding site in the group G (the portion from which the hydrogen atom is removed) may be only an aromatic moiety, or may be only an aliphatic moiety, or both an aromatic moiety and an aliphatic moiety.

作為該「具有芳香族部分及脂肪族部分的基」之說明，針對2價(n＋1＝2)之伸芳烷基、伸芳基二伸烷基及伸烷基二伸芳基進行說明。The description of the "base having an aromatic moiety and an aliphatic moiety" is described for a divalent (n+1=2) exoaralkyl group, an aryl dialkylene group, and an alkylene diaryl group.

[伸芳烷基] 伸芳烷基係指例如甲伸苯基、萘亞甲基、聯苯亞甲基等在芳香族環部分與伸烷基部分均具有鍵結部位(與醚基之鍵結部位)之碳數7～36的基。又，此等基係芳香族環部分中之碳原子可例如經碳數1～6的烷基、碳數1～6的烷氧基、碳數6～12的芳基、碳數7～12的芳烷基取代。此外，此等取代基之個數並未特別限制，通式(1)之化合物的碳數係8以上70以下。[Extended aralkyl] aralkyl group means, for example, a methylphenyl group, a naphthylene group, a biphenylmethylene group, etc., having a bonding moiety (an bond with an ether group) in an aromatic ring moiety and an alkylene moiety. The junction portion has a carbon number of 7 to 36. Further, the carbon atom in the base aromatic ring moiety may, for example, be an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a carbon number of 7 to 12 Aromatic alkyl substitution. Further, the number of such substituents is not particularly limited, and the compound of the formula (1) has a carbon number of 8 or more and 70 or less.

[伸芳基二伸烷基] 伸芳基二伸烷基係指例如伸茬基、萘二亞甲基、聯苯二亞甲基等在伸烷基部分具有鍵結部位(與醚基之鍵結部位)，碳數8～36的伸烷基-伸芳基-伸烷基結構所表示之基。又，此等基的芳香族環部分中之碳原子可例如經碳數1～6的烷基、碳數1～6的烷氧基、碳數6～12的芳基、碳數7～12的芳烷基取代。此外，此等取代基之個數並未特別限制，通式(1)之化合物的碳數係8以上70以下。[Rhenyl dialkylene] aryl aryl dialkyl refers to, for example, an exomethyl group, a naphthalene dimethylene group, a biphenyl dimethylene group, etc. having a bonding moiety in the alkylene moiety (with an ether group) The bonding site) is a group represented by an alkylene-arylene-alkylene structure having a carbon number of 8 to 36. Further, the carbon atom in the aromatic ring portion of the group may be, for example, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a carbon number of 7 to 12 Aromatic alkyl substitution. Further, the number of such substituents is not particularly limited, and the compound of the formula (1) has a carbon number of 8 or more and 70 or less.

[伸烷基二伸芳基] 伸烷基二伸芳基係指例如亞甲基二伸苯基(-C₆ H₄ -CH₂ -C₆ H₄ -)、二甲基亞甲基二伸苯基(-C₆ H₄ -C(Me)₂ -C₆ H₄ -)、二苯基亞甲基二伸苯基(-C₆ H₄ -CF₂ -C₆ H₄ -)等在伸芳基部分具有2個與醚基之鍵結之碳數13～36的伸芳基-伸烷基-伸芳基結構所表示之基。又，此等基之芳香族環部分中之碳原子可例如經碳數1～6的烷基、碳數1～6的烷氧基、碳數6～12的芳基、碳數7～12的芳烷基取代。此外，此等取代基之個數並未特別限制，通式(1)之化合物的碳數係8以上70以下。[alkylalkyl diaryl) alkylene diaryl refers to, for example, methylene diphenyl (-C ₆ H ₄ -CH ₂ -C ₆ H ₄ -), dimethylmethylene phenylene _{_{(-C 6 H 4 -C (Me}} ) 2 -C 6 H 4 -), diphenylmethylene-phenylene _{_{_{(-C 6 H 4 -CF 2 -C}}} 6 H 4 -) , etc. The aryl group has two groups represented by an extended aryl-alkylene-arylene structure having a carbon number of 13 to 36 bonded to an ether group. Further, the carbon atom in the aromatic ring portion of the group may be, for example, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a carbon number of 7 to 12 Aromatic alkyl substitution. Further, the number of such substituents is not particularly limited, and the compound of the formula (1) has a carbon number of 8 or more and 70 or less.

上述通式(1)中，以G而言，較佳為碳數2～12的直鏈狀飽和烴基、主鏈的碳數為3以上且側鏈的碳數為1以上之碳數4～18的分支鏈飽和烴基、具有飽和環之碳數3～18的飽和烴基、碳數4～12的直鏈狀之伸烯基、可具有前述取代基之伸芳基；可具有前述取代基之伸烷基二伸芳基，更佳為碳數3～12的直鏈狀伸烷基、主鏈的碳數為3以上且側鏈的碳數為1以上之碳數4～12的分支鏈烷-二、三或四-基、碳數3～8的具有飽和環之碳數3～18的伸烷基(烷二基)、碳數4～12的直鏈狀之伸烯基、伸苯基、伸茬基、亞甲基二伸苯基(-C₆ H₄ -CH₂ -C₆ H₄ -)、二甲基亞甲基二伸苯基(-C₆ H₄ -C(Me)₂ -C₆ H₄ -)。In the above formula (1), G is preferably a linear saturated hydrocarbon group having 2 to 12 carbon atoms, a carbon number of the main chain of 3 or more, and a carbon number of the side chain of 1 or more and 4 to 4 carbon atoms. a branched chain saturated hydrocarbon group of 18, a saturated hydrocarbon group having a saturated ring having 3 to 18 carbon atoms, a linear alkenyl group having 4 to 12 carbon atoms, an extended aryl group which may have the aforementioned substituent; may have the aforementioned substituent The alkyl diaryl group is more preferably a linear alkyl group having 3 to 12 carbon atoms, a branched chain having a carbon number of 3 or more in the main chain and a carbon number of 1 or more in the side chain of 4 to 12 An alkane-di-, tri- or tetra-yl group, a C 3-8 alkyl group having a saturated ring having 3 to 18 carbon atoms (alkylenediyl group), a linear alkyl group having 4 to 12 carbon atoms, and a stretching group Phenyl, fluorenyl, methylene diphenyl (-C ₆ H ₄ -CH ₂ -C ₆ H ₄ -), dimethylmethylene diphenyl (-C ₆ H ₄ -C ( Me) ₂ -C ₆ H ₄ -).

特佳為碳數3～12的直鏈狀伸烷基、主鏈的碳數為3以上且側鏈的碳數為1以上之碳數4～12的分支鏈烷-二、三或四-基、式(2)所表示之伸烷基(烷二基)、及碳數4～8的直鏈狀之伸烯基，最佳為碳數5～12的直鏈狀伸烷基、主鏈的碳數為3以上且側鏈的碳數為1～3的碳數6～12的分支鏈烷-二、三或四-基、式(2)中x及w同為1之伸烷基、及碳數4～6的直鏈狀之伸烯基。Particularly preferred is a linear alkyl group having 3 to 12 carbon atoms, a branched chain alkane having a carbon number of 3 or more in the main chain and a carbon number of 1 or more in the side chain of 4 to 12 - two, three or four - The alkyl group (alkyl dialkyl group) represented by the formula (2) and the linear alkenyl group having 4 to 8 carbon atoms are preferably a linear alkyl group having a carbon number of 5 to 12 and a main chain. a branched alkane having a carbon number of 3 or more and having a carbon number of 1 to 3 in the side chain of 6 to 12, a dialkyl, a di-, a tri- or a tetra-yl group having a carbon number of 1 to 3 in the formula (2) a base and a linear alkenyl group having 4 to 6 carbon atoms.

【化6】(式中，v、w、x及z分別表示0～6之數，v＋w＋x＋z係2～6；惟當v為0時及z為0時，表示環員碳為鍵結部位，當x為0時及w為0時，表示單鍵)。【化6】 (wherein, v, w, x, and z represent the number of 0 to 6, respectively, v + w + x + z is 2 to 6; but when v is 0 and z is 0, it means ring member carbon is the bonding site, when x is 0 When w and 0 are 0, it means a single key).

(取代基R¹ ～R⁴ ) 通式(1)中，取代基R¹ ～R⁴ 係選自由氫原子、碳數1～6的烷基、碳數1～6的烷氧基或羥基構成之群組中的一種取代基。烷基及烷氧基中的烷基可為直鏈狀、分支鏈狀及環狀之任一者。作為烷基之具體例，可列舉甲基、乙基、丙基、異丙基、丁基、異丁基、二級丁基、三級丁基、正戊基、異戊基、二級戊基、新戊基、正己基、異己基、二級環己基，較佳為甲基、乙基。R¹ ～R⁴ 彼此可為相同亦可為不同，出現多次時可各表示相同或不同之基。惟R³ 與R⁴ 不會同時表示烷基及烷氧基。最佳為取代基R¹ ～R⁴ 全為氫原子。(Substituent R ¹ to R ⁴ ) In the formula (1), the substituents R ¹ to R ⁴ are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a hydroxyl group. a substituent in the group. The alkyl group in the alkyl group and the alkoxy group may be any of a linear chain, a branched chain, and a cyclic group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a n-pentyl group, an isopentyl group, and a secondary pentane group. Base, neopentyl, n-hexyl, isohexyl, secondary cyclohexyl, preferably methyl or ethyl. R ¹ to R ⁴ may be the same or different from each other, and each of them may represent the same or different groups when it appears multiple times. However, R ³ and R ⁴ do not simultaneously represent an alkyl group and an alkoxy group. Preferred substituents R ¹ ~ R ⁴ are all a hydrogen atom.

(n：醚基之個數) n係於分子末端具有羧酸部位之氧基的數，係1～10的整數。當n為2以上時，於分子末端具有羧酸部位之氧基不存在於同一碳上。又，R¹ ～R⁴ 每次出現時可為不同或相同。n係較佳為1～3。(n: the number of ether groups) n is a number of oxy groups having a carboxylic acid moiety at the molecular terminal, and is an integer of 1 to 10. When n is 2 or more, the oxy group having a carboxylic acid moiety at the terminal of the molecule is not present on the same carbon. And it may be different or the same as R ¹ ~ R ⁴ at each occurrence. The n system is preferably from 1 to 3.

(R^a ^＋：氫離子、銨離子或有機胺離子) 在本發明之通式(1)所表示之具有醚基的多元羧酸化合物中，R^a ^＋表示氫離子、銨離子或有機胺離子之任一者。(R ^a ⁺ : a hydrogen ion, an ammonium ion or an organic amine ion) In the polyvalent carboxylic acid compound having an ether group represented by the formula (1) of the present invention, R ^a ⁺ represents a hydrogen ion, an ammonium ion or an organic amine ion. Either.

通式(1)中，作為R^a ^＋，例如可列舉銨離子；甲胺、乙胺、三級丁胺等一級胺之離子(一級胺離子)；二甲胺、乙甲胺、二乙胺、啉、哌啶、哌等二級胺之離子(二級胺離子)；三甲胺、二乙甲胺、乙二甲胺、三乙胺、N-甲基啉等三級胺鹽之離子(三級胺離子)；四甲基銨離子、三乙基甲基銨離子、四乙基銨離子等四級銨離子；1,2,3,4-四甲基咪唑鎓、1,3,4-三甲基-2-乙基咪唑鎓、1,3-二甲基-2,4-二乙基咪唑鎓、1,2-二甲基-3,4-二乙基咪唑鎓、1-甲基-2,3,4-三乙基咪唑鎓、1,2,3,4-四乙基咪唑鎓、1,2,3-三甲基咪唑鎓、1,3-二甲基-2-乙基咪唑鎓、1-乙基-2,3-二甲基咪唑鎓、1,2,3-三乙基咪唑鎓、4-氰基-1,2,3-三甲基咪唑鎓、3-氰基甲基-1,2-二甲基咪唑鎓、2-氰基甲基-1,3-二甲基咪唑鎓、4-乙醯基-1,2,3-三甲基咪唑鎓、3-乙醯基甲基-1,2-二甲基咪唑鎓、4-甲基羧基甲基-1,2,3-三甲基咪唑鎓、3-甲基羧基甲基-1,2-二甲基咪唑鎓、4-甲氧基-1,2,3-三甲基咪唑鎓、3-甲氧基甲基-1,2-二甲基咪唑鎓、4-甲醯基-1,2,-三甲基咪唑鎓、3-甲醯基甲基-1,2-二甲基咪唑鎓、3-羥基乙基-1,2-二甲基咪唑鎓、4-羥基甲基-1,2,3-三甲基咪唑鎓、2-羥基乙基-1,3-二甲基咪唑鎓等咪唑鎓離子等，較佳為銨離子(銨鹽)。In the general formula (1), examples of R ^a ⁺ include ammonium ions; ions of a primary amine such as methylamine, ethylamine or tertiary butylamine (primary amine ion); dimethylamine, ethylamine and diethylamine. , Porphyrin, piperidine, piperazine Secondary amine ion (secondary amine ion); trimethylamine, diethylamine, ethyldimethylamine, triethylamine, N-methyl Ions of a tertiary amine salt such as porphyrin (tribasic amine ion); tetra-ammonium ion such as tetramethylammonium ion, triethylmethylammonium ion or tetraethylammonium ion; 1,2,3,4-tetra Imidazolium, 1,3,4-trimethyl-2-ethylimidazolium, 1,3-dimethyl-2,4-diethylimidazolium, 1,2-dimethyl-3,4 -diethylimidazolium, 1-methyl-2,3,4-triethylimidazolium, 1,2,3,4-tetraethylimidazolium, 1,2,3-trimethylimidazolium, 1,3-Dimethyl-2-ethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1,2,3-triethylimidazolium, 4-cyano-1,2 ,3-trimethylimidazolium, 3-cyanomethyl-1,2-dimethylimidazolium, 2-cyanomethyl-1,3-dimethylimidazolium, 4-ethenyl-1 , 2,3-trimethylimidazolium, 3-ethylidylmethyl-1,2-dimethylimidazolium, 4-methylcarboxymethyl-1,2,3-trimethylimidazolium, 3 -methylcarboxymethyl-1,2-dimethylimidazolium, 4-methoxy-1,2,3-trimethylimidazolium, 3-methoxymethyl-1,2-dimethyl Imidazolium, 4-mercapto-1,2,-trimethylimidazolium, 3-methylmethylidene-1,2-dimethylimidazolium, 3-hydroxyethyl-1,2-dimethyl Imidazolium, 4-hydroxymethyl-1,2,3-trimethylimidazolium 1,3-dimethyl-2-hydroxyethyl imidazolium imidazolium ion, preferably an ammonium ion (salt).

＜電化學元件用電解質＞通式(1)所表示之多元羧酸化合物係作為電化學元件用，例如作為電解電容用的電解質成分使用。本發明之電化學元件用電解質，可僅以通式(1)所表示之多元羧酸化合物構成，亦可包含其它成分。作為電解液的成分而後述之「其它添加物」，依據實施態樣，可為本發明之「電化學元件用電解質」的構成成分，亦可為不同於「電化學元件用電解質」的「其它添加物」。惟作成電解液時，兩者無區別。<Electrolyte for Electrochemical Element> The polyvalent carboxylic acid compound represented by the formula (1) is used as an electrochemical element, and is used, for example, as an electrolyte component for an electrolytic capacitor. The electrolyte for an electrochemical device of the present invention may be composed only of the polyvalent carboxylic acid compound represented by the formula (1), and may contain other components. The "other additive" which will be described later as a component of the electrolytic solution may be a constituent component of the "electrolyte for electrochemical device" of the present invention, or may be "other than the electrolyte for electrochemical device" depending on the embodiment. Additives." When making an electrolyte, there is no difference between the two.

在電化學元件用，尤其電解電容用電解液中，式(1)之多元羧酸化合物的用量，只要是不對電解電容用電解液的性能造成不良影響的量，則並未特別限制，而作為其含量，較佳為0.01～50質量%，進一步更佳為0.05～40質量%，特佳為0.05～30質量%。In the electrolytic element, particularly the electrolytic solution for electrolytic capacitors, the amount of the polyvalent carboxylic acid compound of the formula (1) is not particularly limited as long as it does not adversely affect the performance of the electrolytic solution for electrolytic capacitors. The content thereof is preferably from 0.01 to 50% by mass, still more preferably from 0.05 to 40% by mass, particularly preferably from 0.05 to 30% by mass.

＜電化學元件用電解液＞以下，針對電化學元件、尤其電解電容用電解液進行說明。 [溶媒] 使用於本發明之電解液的溶媒，只要可溶解本發明溶質的具有醚基之多元羧酸及/或其鹽者，則並未特別限制。因此，作為可使用於本發明之電解液的溶媒，例如可列舉水；乙二醇、二乙二醇、丙二醇、丙三醇、1,4-丁二醇、甲基賽路蘇、乙基賽路蘇等醇類；γ-丁內酯、β-丁內酯、γ-戊內酯、δ-戊內酯等內酯類；碳酸二甲酯、碳酸二乙酯、碳酸伸乙酯、碳酸伸丙酯等碳酸酯類；甲醯胺、甲基甲醯胺、二甲基甲醯胺、乙基甲醯胺、二乙基甲醯胺、甲基乙醯胺、二甲基乙醯胺、乙基乙醯胺、二乙基乙醯胺、N-甲基吡咯啶酮等醯胺類；乙腈、丙腈、丁二腈、戊二腈、2-甲基戊二腈、己二腈、苯甲腈等腈類；二甲基亞碸等亞碸類；二甲基碸、環丁碸等碸類等。此外，此等溶媒可單獨使用，亦可作為混合有多種之混合溶媒來使用。又，作為使用於本發明之電解電容用電解液的溶媒，較佳為使用水、乙二醇、或γ-丁內酯。再者，當將水使用於本發明之電解電容用電解液時，電解液中之水的含量並未特別限制，而較佳為以成為90質量%以下，特佳為30質量%以下的方式設定。<Electrolyte for Electrochemical Device> Hereinafter, an electrochemical device, particularly an electrolytic solution for electrolytic capacitor, will be described. [Solvent] The solvent used in the electrolytic solution of the present invention is not particularly limited as long as it has an ether group-containing polycarboxylic acid and/or a salt thereof which can dissolve the solute of the present invention. Therefore, examples of the solvent which can be used in the electrolytic solution of the present invention include water; ethylene glycol, diethylene glycol, propylene glycol, glycerin, 1,4-butanediol, methyl stilbene, and ethyl. Alcohols such as 赛路苏; γ-butyrolactone, β-butyrolactone, γ-valerolactone, δ-valerolactone and other lactones; dimethyl carbonate, diethyl carbonate, ethyl carbonate Carbonic acid esters such as propyl carbonate; formamide, methylformamide, dimethylformamide, ethylformamide, diethylformamide, methylacetamide, dimethylacetamide Amidoxime such as amine, ethyl acetamide, diethyl acetamide, N-methyl pyrrolidone; acetonitrile, propionitrile, succinonitrile, glutaronitrile, 2-methylglutaronitrile, hexane Nitriles such as nitrile and benzonitrile; hydrazines such as dimethyl hydrazine; hydrazines such as dimethyl hydrazine and cyclobutyl hydrazine. Further, these solvents may be used singly or as a mixture of a plurality of mixed solvents. Moreover, as a solvent used for the electrolytic solution for electrolytic capacitors of the present invention, water, ethylene glycol or γ-butyrolactone is preferably used. In addition, when water is used for the electrolytic solution for electrolytic capacitors of the present invention, the content of water in the electrolytic solution is not particularly limited, but is preferably 90% by mass or less, and particularly preferably 30% by mass or less. set up.

[其它添加物] 電解液中除了式(1)之多元羧酸化合物及上述溶媒以外，亦可添加以減低漏電流、提升耐電壓、吸收氣體等為目的之各種添加劑。在此，作為添加劑，例如可列舉以磷酸化合物、磷酸酯化合物、硝基化合物、腈化合物、醚化合物、硼酸化合物、磺酸化合物、苯酚類、多元醇類、聚乙烯醇、聚乙烯醚、聚乙二醇、聚丙二醇、聚氧乙烯・聚氧丙烯無規共聚物、及嵌段共聚物為代表之高分子化合物。[Other Additives] In addition to the polycarboxylic acid compound of the formula (1) and the above solvent, various additives for the purpose of reducing leakage current, increasing withstand voltage, and absorbing gas may be added to the electrolytic solution. Here, examples of the additive include a phosphoric acid compound, a phosphate compound, a nitro compound, a nitrile compound, an ether compound, a boric acid compound, a sulfonic acid compound, a phenol, a polyhydric alcohol, a polyvinyl alcohol, a polyvinyl ether, and a poly A polymer compound represented by ethylene glycol, polypropylene glycol, polyoxyethylene, polyoxypropylene random copolymer, and block copolymer.

作為上述磷酸化合物及磷酸酯化合物，例如可列舉正磷酸、焦磷酸、次亞磷酸、次二磷酸、亞磷酸、二亞磷酸、焦亞磷酸、異次磷酸、次磷酸、磷酸丁酯、磷酸異丁酯、磷酸辛酯、磷酸十二酯等，進一步可列舉此等化合物之銨鹽、鋁鹽等。Examples of the phosphoric acid compound and the phosphate compound include orthophosphoric acid, pyrophosphoric acid, hypophosphorous acid, hypophosphorous acid, phosphorous acid, diphosphoric acid, pyrophosphoric acid, isophosphoric acid, hypophosphorous acid, butyl phosphate, and phosphoric acid. Examples of the butyl ester, the octyl phosphate, the dodecyl phosphate, and the like include ammonium salts and aluminum salts of these compounds.

作為硝基化合物，例如可列舉硝基甲烷、硝基乙烷、硝基丙烷、硝基丁烷、硝基苯、硝基苯甲醚、硝基苯胺、硝基苯甲酸、硝基甲苯、硝基苯酚、硝基苯甲醇、硝基苯乙酮等。Examples of the nitro compound include nitromethane, nitroethane, nitropropane, nitrobutane, nitrobenzene, nitroanisole, nitroaniline, nitrobenzoic acid, nitrotoluene, and nitrate. Phenolic, nitrobenzyl alcohol, nitroacetophenone, and the like.

作為腈化合物，只要是具有腈基者則無特別限定，可列舉乙腈、丙腈、丁腈、特戊腈(pivalonitrile)、戊腈、己腈、丙烯腈、甲基丙烯腈、丁二腈、戊二腈、2-甲基戊二腈、己二腈、1,5-二氰基戊烷、1,6-二氰基己烷、1,7-二氰基庚烷、1,8-二氰基辛烷、1,9-二氰基壬烷、1,10-二氰基癸烷、1,12-二氰基十二烷、2,4-二甲基戊二腈、1,6-二氰基癸烷、丙二腈、1,3-丁二烯二腈、1,2,3-戊三烯二腈、1,2,3,4-庚四烯二腈、1,2,3,4,5-辛五烯二腈、苯甲腈等。The nitrile compound is not particularly limited as long as it has a nitrile group, and examples thereof include acetonitrile, propionitrile, butyronitrile, pivalonitrile, valeronitrile, hexanenitrile, acrylonitrile, methacrylonitrile, and succinonitrile. Glutaronitrile, 2-methylglutaronitrile, adiponitrile, 1,5-dicyanopentane, 1,6-dicyanohexane, 1,7-dicyanoheptane, 1,8- Dicyanooctane, 1,9-dicyanodecane, 1,10-dicyanodecane, 1,12-dicyanododecane, 2,4-dimethylglutaronitrile, 1, 6-dicyanodecane, malononitrile, 1,3-butadiene dinitrile, 1,2,3-pentatrienonitrile, 1,2,3,4-heptylenedicarbonitrile, 1, 2,3,4,5-octapentenedionitrile, benzonitrile, and the like.

較佳可列舉丁腈、特戊腈、戊腈、己腈、丁二腈、戊二腈、2-甲基戊二腈、己二腈、1,5-二氰基戊烷、1,6-二氰基己烷、1,7-二氰基庚烷、1,8-二氰基辛烷、1,9-二氰基壬烷、1,10-二氰基癸烷、1,12-二氰基十二烷、2,4-二甲基戊二腈、1,6-二氰基癸烷、丙二腈、1,3-丁二烯二腈、1,2,3-戊三烯二腈、1,2,3,4-庚四烯二腈、1,2,3,4,5-辛五烯二腈。Preferred examples are butyronitrile, pivalonitrile, valeronitrile, hexanenitrile, succinonitrile, glutaronitrile, 2-methylglutaronitrile, adiponitrile, 1,5-dicyanopentane, 1,6 -dicyanohexane, 1,7-dicyanoheptane, 1,8-dicyanooctane, 1,9-dicyanodecane, 1,10-dicyanodecane, 1,12 -Dicyanododecane, 2,4-dimethylglutaronitrile, 1,6-dicyanodecane, malononitrile, 1,3-butadiene dinitrile, 1,2,3-pentane Trieniconitrile, 1,2,3,4-heptylenedicarbonitrile, 1,2,3,4,5-octopentadicdonitrile.

進一步更佳可列舉丁腈、特戊腈、戊腈、己腈、丁二腈、戊二腈、2-甲基戊二腈、己二腈、1,5-二氰基戊烷、1,6-二氰基己烷、1,7-二氰基庚烷、1,8-二氰基辛烷、2,4-二甲基戊二腈、苯甲腈。Further preferred are butyronitrile, pivalonitrile, valeronitrile, hexanenitrile, succinonitrile, glutaronitrile, 2-methylglutaronitrile, adiponitrile, 1,5-dicyanopentane, 1, 6-dicyanohexane, 1,7-dicyanoheptane, 1,8-dicyanooctane, 2,4-dimethylglutaronitrile, benzonitrile.

作為醚化合物，可列舉二乙二醇、三乙二醇、四乙二醇、五乙二醇、二丙二醇、三丙二醇、四丙二醇、五丙二醇之二烷基醚，作為二烷基醚的烷基，可列舉碳原子數1～4的直鏈或分支烷基。Examples of the ether compound include dialkyl ethers of diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and pentapropylene glycol, and alkylene as a dialkyl ether. Examples of the group include a linear or branched alkyl group having 1 to 4 carbon atoms.

較佳可列舉二乙二醇、三乙二醇、四乙二醇、五乙二醇、二丙二醇、三丙二醇、四丙二醇、五丙二醇之二烷基醚，作為二烷基醚的烷基，可列舉碳原子數1～4的直鏈烷基。進一步更佳可列舉二乙二醇二甲基醚、二乙二醇二乙基醚、三乙二醇二甲基醚、三乙二醇二乙基醚、四乙二醇二甲基醚、二丙二醇二甲基醚、二丙二醇二乙基醚。Preferred examples thereof include dialkyl ethers of diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and pentapropylene glycol, and alkyl groups as dialkyl ethers. A linear alkyl group having 1 to 4 carbon atoms is exemplified. Further preferably, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, Dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether.

作為硼酸化合物，可列舉硼酸、硼酸酯、環狀硼酸等。Examples of the boric acid compound include boric acid, boric acid ester, and cyclic boronic acid.

再者，在本發明之電解電容用電解液中，因應需要，以電解液的電導度增加及特性提升等為目的，除了通式(1)所表示之多元羧酸及/或其鹽以外，可進一步添加其它羧酸或羧酸之鹽。因此，作為羧酸，例如除了甲酸、乙酸、三甲基乙酸、3,3-二甲基丁酸、2,2-二異丙基丙酸、己酸、2-乙基己酸、2-乙基丁酸、2,2-二甲基己酸、環己烷羧酸、山梨酸、桂皮酸、氰乙酸、氰丙酸、4-氰丁酸、5-氰戊酸、11-氰十一酸、7-氰十一酸、月桂酸、硬脂酸、癸酸、苯甲酸等單羧酸；順丁烯二酸、鄰苯二甲酸、反丁烯二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、1,7-辛烷二羧酸、癸二酸、1,10-癸烷二羧酸、2-甲基壬二酸、1,6-癸烷二羧酸、5,6-癸烷二羧酸、7-乙烯基十六烯-1,16-二羧酸等二羧酸；1,3,6-己烷三羧酸、1,3-二甲基-1,3,9-壬烷三羧酸等三羧酸等以外，可列舉四羧酸以上的多元羧酸。又，作為羧酸之鹽，例如可列舉前述羧酸之鹽等。In addition, in the electrolytic solution for electrolytic capacitors of the present invention, in addition to the polycarboxylic acid and/or its salt represented by the general formula (1), for the purpose of increasing the electrical conductivity of the electrolytic solution and improving the properties, etc., Further salts of other carboxylic acids or carboxylic acids may be added. Thus, as the carboxylic acid, for example, in addition to formic acid, acetic acid, trimethylacetic acid, 3,3-dimethylbutyric acid, 2,2-diisopropylpropionic acid, caproic acid, 2-ethylhexanoic acid, 2- Ethyl butyric acid, 2,2-dimethylhexanoic acid, cyclohexanecarboxylic acid, sorbic acid, cinnamic acid, cyanoacetic acid, cyanopropionic acid, 4-cyanobutyric acid, 5-cyanovaleric acid, 11-cyanide Monocarboxylic acid such as monoacid, 7-cyanuronic acid, lauric acid, stearic acid, citric acid, benzoic acid; maleic acid, phthalic acid, fumaric acid, succinic acid, glutaric acid Acid, adipic acid, pimelic acid, suberic acid, sebacic acid, 1,7-octane dicarboxylic acid, sebacic acid, 1,10-decane dicarboxylic acid, 2-methylsebacic acid, Dicarboxylic acid such as 1,6-decanedicarboxylic acid, 5,6-decanedicarboxylic acid, 7-vinylhexadecene-1,16-dicarboxylic acid; 1,3,6-hexanetricarboxylic acid Examples of the tricarboxylic acid such as an acid or 1,3-dimethyl-1,3,9-decanetricarboxylic acid include a polycarboxylic acid having a tetracarboxylic acid or higher. Further, examples of the salt of the carboxylic acid include a salt of the above carboxylic acid.

較佳可列舉三甲基乙酸、3,3-二甲基丁酸、2,2-二異丙基丙酸、己酸、2-乙基己酸、2-乙基丁酸、2,2-二甲基己酸、環己烷羧酸、山梨酸、桂皮酸、11-氰十一酸、7-氰十一酸、月桂酸、硬脂酸、癸酸、苯甲酸、順丁烯二酸、鄰苯二甲酸、反丁烯二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、1,7-辛烷二羧酸、癸二酸、1,10-癸烷二羧酸、2-甲基壬二酸、1,6-癸烷二羧酸、5,6-癸烷二羧酸、7-乙烯基十六烯-1,16-二羧酸、1,3,6-己烷三羧酸、1,3-二甲基-1,3,9-壬烷三羧酸、庚烷-1,3,7-三羧酸、辛烷-1,5,7-三羧酸、庚烷-1,4,6-三羧酸、辛烷-1,3,6,8-四羧酸、癸烷-2,4,7,9-四羧酸。進一步更佳可列舉三甲基乙酸、3,3-二甲基丁酸、己酸、2-乙基己酸、2-乙基丁酸、2,2-二甲基己酸、環己烷羧酸、山梨酸、桂皮酸、苯甲酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、1,7-辛烷二羧酸、癸二酸、1,10-癸烷二羧酸、2-甲基壬二酸、1,6-癸烷二羧酸、5,6-癸烷二羧酸、1,3,6-己烷三羧酸、1,3-二甲基-1,3,9-壬烷三羧酸、庚烷-1,3,7-三羧酸、辛烷-1,5,7-三羧酸、庚烷-1,4,6-三羧酸、辛烷-1,3,6,8-四羧酸、癸烷-2,4,7,9-四羧酸。Preferred examples thereof include trimethylacetic acid, 3,3-dimethylbutyric acid, 2,2-diisopropylpropionic acid, caproic acid, 2-ethylhexanoic acid, 2-ethylbutyric acid, and 2,2. -Dimethylhexanoic acid, cyclohexanecarboxylic acid, sorbic acid, cinnamic acid, 11-cyandecanoic acid, 7-cyanuric acid, lauric acid, stearic acid, citric acid, benzoic acid, maleic acid Acid, phthalic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, 1,7-octane dicarboxylic acid, sebacic acid 1,10-decanedicarboxylic acid, 2-methylsebacic acid, 1,6-decanedicarboxylic acid, 5,6-decanedicarboxylic acid, 7-vinylhexadecene-1,16 -dicarboxylic acid, 1,3,6-hexanetricarboxylic acid, 1,3-dimethyl-1,3,9-decanetricarboxylic acid, heptane-1,3,7-tricarboxylic acid, Octane-1,5,7-tricarboxylic acid, heptane-1,4,6-tricarboxylic acid, octane-1,3,6,8-tetracarboxylic acid, decane-2,4,7, 9-tetracarboxylic acid. Further more preferably, trimethylacetic acid, 3,3-dimethylbutyric acid, caproic acid, 2-ethylhexanoic acid, 2-ethylbutyric acid, 2,2-dimethylhexanoic acid, cyclohexane Carboxylic acid, sorbic acid, cinnamic acid, benzoic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, 1,7-octane dicarboxylic acid, sebacic acid, 1,10-decanedicarboxylic acid, 2-methylsebacic acid, 1,6-decanedicarboxylic acid, 5,6-decanedicarboxylic acid, 1,3,6-hexanetricarboxylic acid, 1,3-Dimethyl-1,3,9-decanetricarboxylic acid, heptane-1,3,7-tricarboxylic acid, octane-1,5,7-tricarboxylic acid, heptane-1 4,6-tricarboxylic acid, octane-1,3,6,8-tetracarboxylic acid, decane-2,4,7,9-tetracarboxylic acid.

此等添加物可單獨使用，亦可混合多種來使用。例如本發明之多元羧酸與羧酸、本發明之多元羧酸與腈化合物、本發明之多元羧酸與醚化合物、本發明之多元羧酸與羧酸與腈化合物等。具體而言，可混合本發明之多元羧酸與三甲基乙酸或2-乙基己酸、山梨酸、桂皮酸等飽和及不飽和單羧酸或己二酸、壬二酸、癸二酸、1,6-癸烷二羧酸、1,3,6-己烷三羧酸等多元羧酸、或進一步組合己二腈、苯甲腈等腈化合物、二甘二甲醚等醚化合物來添加。These additives may be used singly or in combination of two or more. For example, the polycarboxylic acid and the carboxylic acid of the present invention, the polycarboxylic acid and nitrile compound of the present invention, the polyvalent carboxylic acid and ether compound of the present invention, the polycarboxylic acid of the present invention, the carboxylic acid and the nitrile compound, and the like. Specifically, the polycarboxylic acid of the present invention and trimethylacetic acid or a saturated or unsaturated monocarboxylic acid such as 2-ethylhexanoic acid, sorbic acid or cinnamic acid, or adipic acid, sebacic acid or sebacic acid may be mixed. a polycarboxylic acid such as 1,6-decanedicarboxylic acid or 1,3,6-hexanetricarboxylic acid, or a combination of a nitrile compound such as adiponitrile or benzonitrile or an ether compound such as diglyme. Add to.

在本發明之電解電容用電解液中，由於該電解液的溶媒量與溶質量係因電解電容的用途及額定電壓等而異，因此並未特別限制，而以溶媒量為50.0～99.5質量%、溶質量為0.5～50.0質量%為較佳。In the electrolytic solution for electrolytic capacitors of the present invention, the amount of the solvent and the mass of the electrolytic solution vary depending on the use of the electrolytic capacitor, the rated voltage, and the like, and therefore are not particularly limited, and the amount of the solvent is 50.0 to 99.5% by mass. The melt mass is preferably 0.5 to 50.0% by mass.

在本發明之電解電容用電解液中，由於該電解液的溶媒量與溶質量係因電解電容的用途及額定電壓等而異，因此並未特別限制，而以電導度為0.5mS/cm以上為較佳，1.0mS/cm以上為更佳。In the electrolytic solution for electrolytic capacitors of the present invention, the amount of the solvent and the mass of the electrolytic solution vary depending on the use of the electrolytic capacitor, the rated voltage, and the like, and therefore are not particularly limited, and the electrical conductivity is 0.5 mS/cm or more. Preferably, it is more preferably 1.0 mS/cm or more.

＜電化學元件＞本發明之電解液係適合作為電化學元件、尤其適合作為電解電容用使用。電解電容並未特別限定，例如可列舉一種捲繞形之鋁電解電容，其係藉由在陽極表面形成有氧化鋁之陽極(氧化鋁箔)與陰極鋁箔之間，隔著間隔物捲繞構成之電容等。藉由在該電解電容，將本發明之電解液作為驅動用電解液含浸間隔物，與陽陰極一同收納於例如有底筒狀的鋁盒後，以封口材料密封鋁盒之開口部，而可製造鋁電解電容。<Electrochemical Element> The electrolytic solution of the present invention is suitable as an electrochemical element, and is particularly suitable for use as an electrolytic capacitor. The electrolytic capacitor is not particularly limited, and examples thereof include a wound aluminum electrolytic capacitor which is formed by winding a separator between an anode (aluminum foil) and a cathode aluminum foil having an alumina surface formed thereon. Capacitor and so on. In the electrolytic capacitor, the electrolyte solution of the present invention is used as a driving electrolyte solution impregnated with a spacer, and is housed in a bottomed cylindrical aluminum case together with the anode, and the opening of the aluminum case is sealed with a sealing material. Manufacturing aluminum electrolytic capacitors.

在電解液中，鹵化物離子的量(鹵化物離子容許量)係相對於該電解液的總質量而言為500ppm(0.05質量%)以下為較佳，200ppm(0.02質量%)以下為更佳，150ppm(0.015質量%)以下為進一步更佳，50ppm(0.005質量%)以下為特佳。依據本案發明人之探討，已經確認只要是該範圍內的容許量，則不僅是電極的腐蝕問題，以電解電容用電解液而言亦不會在性能上造成影響。In the electrolytic solution, the amount of halide ions (halide ion allowable amount) is preferably 500 ppm (0.05% by mass) or less based on the total mass of the electrolytic solution, and more preferably 200 ppm (0.02% by mass) or less. 150 ppm (0.015% by mass) or less is further more preferable, and 50 ppm (0.005 mass%) or less is particularly preferable. According to the investigation by the inventors of the present invention, it has been confirmed that as long as the allowable amount within the range is not only the corrosion problem of the electrode, but also the electrolytic solution for electrolytic capacitor does not affect the performance.

＜式(3)的化合物＞下式(3)所表示之化合物均為新穎化合物。A為COOH之化合物(實施例的式(k))係可用作為電解質成分的化合物，A為CN之化合物(參考例的式(i))及A為COOR⁵ 之化合物(例如參考例的式(j))係可用作為其合成中間產物的化合物。R⁵ 可為直鏈狀、分支鏈狀及環狀之任一者。作為具體例，可列舉甲基、乙基、丙基、異丙基、丁基、異丁基、二級丁基、三級丁基、正戊基、異戊基、二級戊基、新戊基、正己基、異己基、二級環己基，較佳為甲基、乙基。<Compound of the formula (3)> The compounds represented by the following formula (3) are all novel compounds. A compound in which A is COOH (formula (k) of the embodiment) is a compound which can be used as an electrolyte component, A is a compound of CN (formula (i) of the reference example), and A is a compound of COOR ⁵ (for example, the formula of the reference example ( j)) can be used as a compound for the synthesis of intermediates thereof. R ⁵ may be any of a linear chain, a branched chain, and a ring. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a n-pentyl group, an isopentyl group, a secondary pentyl group, and a new one. A pentyl group, a n-hexyl group, an isohexyl group, or a secondary cyclohexyl group is preferably a methyl group or an ethyl group.

【化7】(式中，A係選自由COOH、CN及COOR⁵ 構成之群組中的基，R⁵ 表示碳數1～6的烷基)。【化7】 (In the formula, A is selected from the group consisting of COOH, CN, and COOR ⁵ , and R ⁵ is an alkyl group having 1 to 6 carbon atoms).

＜式(4)的化合物＞下式(4)所表示之化合物均為新穎化合物。B為COOH之化合物(實施例的式(m))係可用作為電解質成分的化合物，B為CN之化合物(參考例的式(l))係可用作為其合成中間產物的化合物。<Compound of the formula (4)> The compounds represented by the following formula (4) are all novel compounds. A compound in which B is COOH (formula (m) of the example) is a compound which can be used as an electrolyte component, and a compound in which B is a CN (formula (l) of the reference example) can be used as a compound for which an intermediate product is synthesized.

【化8】(式中，B表示COOH或CN)。 [實施例]【化8】 (wherein B represents COOH or CN). [Examples]

以下列舉實施例以具體說明本發明。此外，實施例所示之材料、用量、比例、操作等，只要不脫離本發明之精神，則可適當變更。亦即，本發明之範圍並不受以下所示之具體例所限制。此外，氯離子濃度係藉由離子層析(Tosoh離子層析儀IC-2001)所測定。The following examples are given to illustrate the invention. In addition, the materials, the amounts, the ratios, the operations, and the like shown in the examples can be appropriately changed without departing from the spirit of the invention. That is, the scope of the present invention is not limited by the specific examples shown below. Further, the chloride ion concentration was measured by ion chromatography (Tosoh Ion Chromatograph IC-2001).

＜參考例1：3,3’-(己烷-1,6-二基雙(氧基))二丙腈之合成：式(a)＞將丙烯腈495.6g(9.34mol)保持於內溫25～31℃，花費約1小時15分鐘滴液於混合有1,6-己二醇490.6g(4.15mol)、50質量%氫氧化鉀水溶液32.9g(0.29mol)及四氫呋喃587mL之溶液。滴液後，接著於室溫下進行攪拌20小時。<Reference Example 1: Synthesis of 3,3'-(hexane-1,6-diylbis(oxy))dipropionitrile: Formula (a)> 495.6 g (9.34 mol) of acrylonitrile was kept at the internal temperature At 25 to 31 ° C, a solution of 49. 6 g (4.15 mol) of 1,6-hexanediol, 32.9 g (0.29 mol) of a 50% by mass potassium hydroxide aqueous solution, and 587 mL of tetrahydrofuran was mixed for about 1 hour and 15 minutes. After the dropwise addition, stirring was carried out for 20 hours at room temperature.

反應結束後，於所得之反應液添加5M鹽酸水溶液74mL以使反應液成為酸性。在減壓下餾去所得之反應液中之四氫呋喃，添加水(670mL)，以乙酸乙酯745mL與甲醇30mL之混合液進行3次萃取。混合有機相，以0.63M碳酸氫鈉水溶液1116mL洗滌，添加硫酸鈉(乾燥劑)而處理有機相後，濃縮所得之濾液以獲得褐色的粗製品(crude product)939.7g。藉由管柱層析(矽膠：313g，展開液：乙酸乙酯：正己烷＝1：4至2：3)精製所得之粗製品，獲得下述式(a)所表示之3,3’-(己烷-1,6-二基雙(氧基))二丙腈798.4g(產率：84%，純度：98%(¹ H-NHR定量値))。又，所得之3,3’-(己烷-1,6-二基雙(氧基))二丙腈的分析數據係如下述。After completion of the reaction, 74 mL of a 5 M aqueous hydrochloric acid solution was added to the obtained reaction mixture to make the reaction liquid acidic. The tetrahydrofuran in the obtained reaction liquid was distilled off under reduced pressure, water (670 mL) was added, and the mixture was extracted three times with a mixture of ethyl acetate 745 mL and methanol 30 mL. The organic phase was combined, washed with a 1163 mL aqueous solution of 0.63 M sodium hydrogencarbonate, and the organic phase was treated with sodium sulfate (drying agent), and the obtained filtrate was concentrated to obtain a brown crude product (939.7 g). The obtained crude product was purified by column chromatography (silicone: 313 g, developing solvent: ethyl acetate: n-hexane = 1:4 to 2:3) to obtain 3,3'- represented by the following formula (a). (hexane-1,6-diyl bis (oxy)) dipropanenitrile 798.4g (yield: 84%, purity: 98% ⁽¹ H-NHR Zhi quantitative)). Further, the analytical data of the obtained 3,3'-(hexane-1,6-diylbis(oxy))dipropionitrile was as follows.

【化9】【化9】

(分析數據：式(a))¹ H NMR(CDCl₃ , δppm)：1.28～1.44(m, 4H), 1.46～1.66(m, 4H), 2.52～2.68(tr, 4H),3.40～3.58(tr, 4H) ,3.62～3.82(tr, 4H) IR(neat,cm^-1 )：2140, 1120(Analytical data: formula (a)) ¹ H NMR (CDCl ₃ , δ ppm): 1.28 to 1.44 (m, 4H), 1.46 to 1.66 (m, 4H), 2.52 to 2.68 (tr, 4H), 3.40 to 3.58 ( Tr, 4H) , 3.62 to 3.82 (tr, 4H) IR (neat, cm ^-1 ): 2140, 1120

＜實施例1：3,3’-(己烷-1,6-二基雙(氧基))二丙酸之合成：式(b)＞將3,3’-(己烷-1,6-二基雙(氧基))二丙腈783.2g(3.42mol)溶解於37質量%鹽酸水溶液(1200mL)，加溫至60℃，使其反應22小時。反應結束後，放置冷卻所得之反應液，其次將反應液中所析出之無機鹽作為固體進行分濾，以丙酮2.4L洗淨無機鹽，進行濃縮。濃縮後，添加水1.5 L與乙酸乙酯2L進行分液，添加飽和食鹽水(300mL)而以乙酸乙酯2.5L進行2次萃取。混合所得之有機相，以硫酸鈉(乾燥劑)進行乾燥，對其進行分濾後，以蒸發器濃縮所得之濾液，獲得3,3’-(己烷-1,6-二基雙(氧基))二丙酸的粗製物1254.8g(濕晶體)作為濃縮物。於所得之粗製物添加乙酸乙酯1.6L，於50℃使其溶解。於該溶液添加己烷2L並且於冷藏室靜置1晩。瀝濾析出之固體，獲得白色固體972.5g(濕晶體)。於該白色固體添加乙酸乙酯1.5L，於50℃使其溶解。於該溶液添加己烷1.5L，並且於冷藏室靜置3小時。<Example 1: Synthesis of 3,3'-(hexane-1,6-diylbis(oxy))dipropionic acid: Formula (b)> 3,3'-(hexane-1,6 783.2 g (3.42 mol) of -diylbis(oxy))dipropionitrile was dissolved in a 37% by mass aqueous hydrochloric acid solution (1200 mL), and the mixture was heated to 60 ° C to carry out a reaction for 22 hours. After completion of the reaction, the reaction liquid obtained by cooling was placed, and then the inorganic salt precipitated in the reaction liquid was subjected to filtration as a solid, and the inorganic salt was washed with 2.4 L of acetone and concentrated. After concentration, 1.5 L of water and 2 L of ethyl acetate were added to conduct liquid separation, and saturated brine (300 mL) was added thereto, and extracted twice with ethyl acetate 2.5 L. The obtained organic phase was mixed, dried over sodium sulfate (drying agent), and then filtered, and the filtrate was concentrated by an evaporator to obtain 3,3'-(hexane-1,6-diylbis(oxygen) Base)) A crude product of dipropionic acid 1254.8 g (wet crystal) was used as a concentrate. 1.6 L of ethyl acetate was added to the obtained crude product, and it was dissolved at 50 °C. 2 L of hexane was added to the solution and allowed to stand in a refrigerator for 1 Torr. The precipitated solid was leached to give a white solid, 972.5 g (wet crystal). 1.5 L of ethyl acetate was added to the white solid, which was dissolved at 50 °C. 1.5 L of hexane was added to the solution, and it was allowed to stand in a refrigerator for 3 hours.

其次，分濾析出之固體，獲得白色固體701.0g(濕晶體)。於所得之白色固體添加乙酸乙酯1.5L並且於50℃使其溶解後，於該溶液添加己烷1.5L並且於冷藏室靜置3小時以進行再結晶。以再結晶析出之結晶，使用乙酸乙酯/己烷(容量比例v/v＝30/1)的混合溶媒2L洗淨同時瀝濾。所得之固體330g(濕晶體)進一步溶解於乙酸乙酯3L，以超純水500mL洗淨4次，濃縮所得之有機相，於45～60℃使析出之白色固體真空乾燥10日，藉此獲得下述式(b)所表示之3,3’-(己烷-1,6-二基雙(氧基))二丙酸147.3g(取得產率：16%，氣相層析純度(面積%)：98%)。此外，所得之化合物的分析數據係如下述。Next, the precipitated solid was separated to give a white solid (yield: 701.0 g). After 1.5 L of ethyl acetate was added to the obtained white solid and dissolved at 50 ° C, 1.5 L of hexane was added to the solution and allowed to stand in a refrigerator for 3 hours to carry out recrystallization. The crystals precipitated by recrystallization were washed with 2 L of a mixed solvent of ethyl acetate/hexane (capacity ratio v/v = 30/1) while leaching. 330 g (wet crystals) of the obtained solid was further dissolved in 3 L of ethyl acetate, and washed four times with 500 mL of ultrapure water, and the obtained organic phase was concentrated, and the precipitated white solid was vacuum dried at 45 to 60 ° C for 10 days. 147.3 g of 3,3'-(hexane-1,6-diylbis(oxy))dipropionic acid represented by the following formula (b) (yield: 16%, gas chromatography purity (area) %): 98%). Further, the analytical data of the obtained compound is as follows.

【化10】【化10】

¹ H NMR(DMSO-d6, δppm)：1.22～1.38(m, 4H), 1.39～1.50(m, 4H), 2.38～2.48 (tr, 4H),3.20～3.50 (tr, 4H), 2.52～3.64 (tr, 4H), 12.1(brs, 2H) IR(KBr,cm^-1 )：1710, 1120 氯離子(Cl^- )含量：＜10ppm 硫酸離子(SO₄ ^2- )含量：＜10ppm ¹ H NMR (DMSO-d6, δ ppm): 1.22 to 1.38 (m, 4H), 1.39 to 1.50 (m, 4H), 2.38 to 2.48 (tr, 4H), 3.20 to 3.50 (tr, 4H), 2.52 to 3.64 (tr, 4H), 12.1(brs, 2H) IR(KBr, cm ^-1 ): 1710, 1120 Chloride (Cl ^- ) content: <10ppm Sulfate ion (SO ₄ ^2- ) content: <10ppm

＜參考例2：3,3’-(戊烷-1,5-二基雙(氧基))二丙腈之合成：式(c)＞藉由與參考例1同樣的操作獲得3,3’-(戊烷-1,5-二基雙(氧基))二丙腈(GCarea%：96.0%、產率：78%)。蒸餾操作如下所示。浴溫：230℃ 壓力：0.3kPa 餾出溫度：193～194℃ 又，所得之化合物的分析數據係如下述。<Reference Example 2: Synthesis of 3,3'-(pentane-1,5-diylbis(oxy))dipropionitrile: Formula (c)> 3, 3 was obtained by the same operation as Reference Example 1. '-(Pentane-1,5-diylbis(oxy))dipropionitrile (GCarea%: 96.0%, yield: 78%). The distillation operation is as follows. Bath temperature: 230 ° C Pressure: 0.3 kPa Distillation temperature: 193 to 194 ° C Further, the analysis data of the obtained compound are as follows.

【化11】【化11】

(分析數據：式(c))¹ H NMR(CDCl₃ ,δppm)：1.40～1.48(m,2H),1.58～1.65(dtr,4H),2.59～2.62(tr,4H),3.48～3.51(tr,4H),3.62～3.65(tr,4H) IR(neat,cm^-1 )：2251,1116(Analytical data: Formula ^{(c)) 1 H NMR (} CDCl 3, δppm): 1.40 ~ 1.48 (m, 2H), 1.58 ~ 1.65 (dtr, 4H), 2.59 ~ 2.62 (tr, 4H), 3.48 ~ 3.51 ( Tr,4H), 3.62~3.65(tr,4H) IR(neat,cm ^-1 ): 2251,1116

＜參考例3：3,3’-(戊烷-1,5-二基雙(氧基))二丙酸甲酯之合成：式(d)＞於氬氣環境下將由甲醇(75.38g、2.353mol)與90%硫酸(97.03g、0.890mol)製備之溶液，花費20分鐘滴液於參考例2所得之3,3’-(戊烷-1,5-二基雙(氧基))二丙腈(65.01g、0.297mol、GCarea%：96.0%)。滴液結束後，將內溫升溫至90℃並且攪拌18小時後，將內溫冷卻至40℃，藉由過濾除去析出之硫酸銨，以甲苯(400mL)洗淨過濾物。以水(100mL)洗淨所得之濾液後，為了除去有機相中之甲醇而進行甲苯取代。具體而言，以蒸發器將有機相濃縮至一半左右，對其添加甲苯(100g)並且進行再度濃縮而重覆2次僅餾去甲苯添加分量之操作。濃縮後進行GC分析，結果溶液中之甲醇的含量係1wt%以下。以飽和碳酸氫鈉水溶液(100mL)洗淨濃縮殘渣2次，其次以水(100mL)洗淨。以硫酸鎂(10g)乾燥所得之有機相約30分鐘並且進行過濾後，以蒸發器進行濃縮並且獲得茶色油狀的粗製品(77.81g)。藉由減壓蒸餾(浴溫：205℃，壓力：0.2kPa，頂溫：158～159℃)精製該粗製品，獲得3,3’-(戊烷-1,5-二基雙(氧基))二丙酸甲酯(40.86g、0.145mol、GCarea%：98.2%、產率：49%)作為無色的液體。所得之化合物的分析數據係如下述。<Reference Example 3: Synthesis of methyl 3,3'-(pentane-1,5-diylbis(oxy))dipropionate: Formula (d)> Under argon atmosphere, methanol (75.38 g, 2.353 mol) of a solution prepared with 90% sulfuric acid (97.03 g, 0.890 mol), which took 20 minutes to drip 3,3'-(pentane-1,5-diylbis(oxy)) obtained in Reference Example 2. Dipropionitrile (65.01 g, 0.297 mol, GCarea%: 96.0%). After completion of the dropwise addition, the internal temperature was raised to 90 ° C and stirred for 18 hours, and then the internal temperature was cooled to 40 ° C, and the precipitated ammonium sulfate was removed by filtration, and the filtrate was washed with toluene (400 mL). After washing the obtained filtrate with water (100 mL), toluene substitution was carried out in order to remove methanol in the organic phase. Specifically, the organic phase was concentrated to about half with an evaporator, toluene (100 g) was added thereto, and re-concentration was carried out to repeat the operation of only distilling off the toluene addition component twice. After concentration and GC analysis, the content of methanol in the solution was 1 wt% or less. The concentrated residue was washed twice with a saturated aqueous sodium hydrogen carbonate solution (100 mL), and then washed with water (100 mL). The obtained organic phase was dried over magnesium sulfate (10 g), and filtered, evaporated, evaporated, The crude product was purified by distillation under reduced pressure (bath temperature: 205 ° C, pressure: 0.2 kPa, top temperature: 158 to 159 ° C) to obtain 3,3'-(pentane-1,5-diylbis(oxyl) )) Methyl dipropionate (40.86 g, 0.145 mol, GCarea%: 98.2%, yield: 49%) was used as a colorless liquid. The analytical data of the obtained compound is as follows.

【化12】【化12】

(分析數據：式(d))¹ H NMR(CDCl₃ ,δppm)：1.32～1.40(m,2H),1.53～1.61(dtr,4H),2.56～2.60(tr,4H),3.41～3.45(tr,4H),3.67～3.70(tr,4H),3.69(s,6H) IR(neat,cm^-1 )：1742,1115(Analytical data: formula (d)) ¹ H NMR (CDCl ₃ , δ ppm): 1.32 to 1.40 (m, 2H), 1.53 to 1.61 (dtr, 4H), 2.56 to 2.60 (tr, 4H), 3.41 to 3.45 ( Tr, 4H), 3.67 to 3.70 (tr, 4H), 3.69 (s, 6H) IR (neat, cm ^-1 ): 1742, 1115

＜實施例2：3,3’-(戊烷-1,5-二基雙(氧基))二丙酸之合成：式(e)＞於參考例3所得之3,3’-(戊烷-1,5-二基雙(氧基))二丙酸甲酯(38.11g、0.135mol、GCarea%：98.2%)添加10.1wt%氫氧化鈉水溶液(117.91g、0.298mol、2.2eq.)後，於室溫攪拌8小時。以HPLC分析確認原料消失，以甲苯(50mL)洗淨2次。分離之水相以冰浴冷卻至15℃，添加45wt%硫酸水溶液(38.9g)，結果結晶析出(pH＝2)。以MTBE(甲基三級丁醚)(200mL)溶解析出之固體，使水相分離後，以水(30mL)洗淨5次。以離子層析分析第5次的水相，結果離子(Cl^- 、SO₄ ^2- )為檢測界限以下。以硫酸鎂(10g)乾燥經確認未含有離子之有機相後進行過濾。在卡耳費雪分析中，溶液中之水分量為0.5wt%。接著，藉由蒸發器濃縮MTBE直到目的化合物之理論產量的約2倍重量(60.15g)為止。對其滴液庚烷(78.78g)並且使結晶析出，進行過濾，以庚烷洗淨。於室溫對瀝濾之固體進行真空乾燥8小時，獲得3,3’-(戊烷-1,5-二基雙(氧基))二丙酸(19.62g、0.077mol、GCarea%：98.0%、產率：57%)作為白色的固體。所得之化合物的分析數據係如下述。<Example 2: Synthesis of 3,3'-(pentane-1,5-diylbis(oxy))dipropionic acid: Formula (e)>3,3'-(pentane) obtained in Reference Example 3 Methyl alkal-1,5-diylbis(oxy))dipropionate (38.11 g, 0.135 mol, GCarea%: 98.2%) was added 10.1 wt% aqueous sodium hydroxide solution (117.91 g, 0.298 mol, 2.2 eq. After that, it was stirred at room temperature for 8 hours. The disappearance of the starting material was confirmed by HPLC analysis, and the mixture was washed twice with toluene (50 mL). The separated aqueous phase was cooled to 15 ° C in an ice bath, and a 45 wt% aqueous sulfuric acid solution (38.9 g) was added to crystallize (pH = 2). The precipitated solid was dissolved in MTBE (methyl tertiary butyl ether) (200 mL), and the aqueous phase was separated, and then washed five times with water (30 mL). The fifth aqueous phase was analyzed by ion chromatography, and the ions (Cl ^- , SO ₄ ^2- ) were below the detection limit. The organic phase which was confirmed to contain no ions was dried over magnesium sulfate (10 g), followed by filtration. In the Karl Fischer analysis, the amount of water in the solution was 0.5% by weight. Next, MTBE was concentrated by an evaporator until about 2 times the weight (60.15 g) of the theoretical yield of the objective compound. Heptane (78.78 g) was added dropwise thereto, and crystals were precipitated, filtered, and washed with heptane. The leached solid was vacuum dried at room temperature for 8 hours to obtain 3,3'-(pentane-1,5-diylbis(oxy))dipropionic acid (19.62 g, 0.077 mol, GCarea%: 98.0). %, yield: 57%) as a white solid. The analytical data of the obtained compound is as follows.

【化13】【化13】

(分析數據：式(e))¹ H NMR(DMSO-d6,δppm)：1.24～1.32(m,2H),1.43～1.50(dtr,4H),2.41～2.44(tr,4H),3.32～3.36(tr,4H),3.53～3.56(tr,4H),12.14(brs,2H) IR(KBr,cm^-1 )：1693,1112 氯離子(Cl^- )含量：＜10ppm 硫酸離子(SO₄ ^2- )含量：18ppm 鈉離子(Na^＋ )含量：＜5ppm 鉀離子(K^＋ )含量：＜5ppm(Analytical data: formula (e)) ¹ H NMR (DMSO-d6, δ ppm): 1.24 to 1.32 (m, 2H), 1.43 to 1.50 (dtr, 4H), 2.41 to 2.44 (tr, 4H), 3.32 to 3.36 (tr, 4H), 3.53 to 3.56 (tr, 4H), 12.14 (brs, 2H) IR (KBr, cm ^-1 ): 1693, 1112 Chloride (Cl ^- ) content: <10 ppm Sulfate ion (SO ₄ ^2- ) Content: 18ppm Sodium ion (Na ⁺ ) content: <5ppm Potassium ion (K ⁺ ) content: <5ppm

＜參考例4：3,3’-(丁烷-1,4-二基雙(氧基))二丙腈之合成：式(f)＞藉由與參考例1同樣的操作獲得3,3’-(丁烷-1,4-二基雙(氧基))二丙腈(GCarea%：96.7%、產率：81%)。蒸餾條件如下所示。浴溫：215℃ 壓力：0.2kPa 餾出溫度：176～180℃ 又，所得之化合物的分析數據係如下述。<Reference Example 4: Synthesis of 3,3'-(butane-1,4-diylbis(oxy))dipropionitrile: Formula (f)> 3, 3 was obtained by the same operation as Reference Example 1. '-(Butane-1,4-diylbis(oxy))dipropionitrile (GCarea%: 96.7%, yield: 81%). The distillation conditions are as follows. Bath temperature: 215 ° C Pressure: 0.2 kPa Distillation temperature: 176 to 180 ° C Further, the analysis data of the obtained compound are as follows.

【化14】【化14】

(分析數據：式(f))¹ H NMR(CDCl₃ ,δppm)：1.64～1.71(m,4H),2.59～2.62(tr,4H),3.50～3.54(m,4H),3.63～3.66(tr,4H) IR(neat,cm^-1 )：2251,1115(Analytical data: formula (f)) ¹ H NMR (CDCl ₃ , δ ppm): 1.64 to 1.71 (m, 4H), 2.59 to 2.62 (tr, 4H), 3.50 to 3.54 (m, 4H), 3.63 to 3.66 ( tr, 4H) IR (neat, cm -1): 2251,1115

＜參考例5：3,3’-(丁烷-1,4-二基雙(氧基))二丙酸甲酯之合成：式(g)＞藉由與參考例3同樣的操作獲得3,3’-(丁烷-1,4-二基雙(氧基))二丙酸甲酯(GCarea%：91.3%、產率：27%)。蒸餾條件如下所示。浴溫：170℃ 壓力：0.2kPa 餾出溫度：144～151℃ 又，所得之化合物的分析數據係如下述。<Reference Example 5: Synthesis of methyl 3,3'-(butane-1,4-diylbis(oxy))dipropionate: Formula (g)> Obtained by the same operation as Reference Example 3 Methyl 3'-(butane-1,4-diylbis(oxy))dipropionate (GCarea%: 91.3%, yield: 27%). The distillation conditions are as follows. Bath temperature: 170 ° C Pressure: 0.2 kPa Distillation temperature: 144 to 151 ° C Further, the analysis data of the obtained compound are as follows.

【化15】【化15】

(分析數據：式(g))¹ H NMR(CDCl₃ ,δppm)：1.59～1.62(m,4H),2.56～2.59(tr,4H),3.43～3.46(m,4H),3.67～3.70(tr,4H),3.69(s,6H) IR(neat,cm^-1 )：1742,1114(Analytical data: formula (g)) ¹ H NMR (CDCl ₃ , δ ppm): 1.59 to 1.62 (m, 4H), 2.56 to 2.59 (tr, 4H), 3.43 to 3.46 (m, 4H), 3.67 to 3.70 ( Tr,4H), 3.69(s,6H) IR(neat,cm ^-1 ):1742,1114

＜實施例3：3,3’-(丁烷-1,4-二基雙(氧基))二丙酸之合成：式(h)＞藉由與參考例2同樣的操作獲得3,3’-(丁烷-1,4-二基雙(氧基))二丙酸(GCarea%：87.2%、產率：70%)。又，所得之化合物的分析數據係如下述。<Example 3: Synthesis of 3,3'-(butane-1,4-diylbis(oxy))dipropionic acid: Formula (h)> 3, 3 was obtained by the same operation as Reference Example 2. '-(Butane-1,4-diylbis(oxy))dipropionic acid (GCarea%: 87.2%, yield: 70%). Further, the analytical data of the obtained compound is as follows.

【化16】【化16】

(分析數據：式(h))¹ H NMR(DMSO-d6,δppm)：1.47～1.50(m,4H),2.41～2.44(tr,4H),3.34～3.37(m,4H),3.53～3.56(tr,4H),12.14(brs,2H) IR(KBr,cm^-1 )：1706,1110 氯離子(Cl^- )含量：＜10ppm 硫酸離子(SO₄ ^2- )含量：50ppm 鈉離子(Na^＋ )含量：30ppm 鉀離子(K^＋ )含量：＜10ppm(Analytical data: formula (h)) ¹ H NMR (DMSO-d6, δ ppm): 1.47 to 1.50 (m, 4H), 2.41 to 2.44 (tr, 4H), 3.34 to 3.37 (m, 4H), 3.53 to 3.56 (tr, 4H), 12.14 (brs, 2H) IR (KBr, cm ^-1 ): 1706, 1110 Chloride (Cl ^- ) content: <10ppm Sulfate ion (SO ₄ ^2- ) content: 50ppm sodium ion (Na ⁺ ) Content: 30ppm Potassium ion (K ⁺ ) content: <10ppm

＜參考例6：3,3’-(壬烷-1,9-二基雙(氧基))二丙腈之合成：式(i)＞藉由與參考例1同樣的操作獲得3,3’-(壬烷-1,9-二基雙(氧基))二丙腈(GCarea%：95.2%、產率：87%)。<Reference Example 6: Synthesis of 3,3'-(decane-1,9-diylbis(oxy))dipropionitrile: Formula (i)> 3, 3 was obtained by the same operation as Reference Example 1. '-(decane-1,9-diylbis(oxy))dipropionitrile (GCarea%: 95.2%, yield: 87%).

惟精製係實施管柱層析(展開溶媒：35%乙酸乙酯/65%正己烷)。又，所得之化合物的分析數據係如下述。The purification was carried out by column chromatography (developing solvent: 35% ethyl acetate / 65% n-hexane). Further, the analytical data of the obtained compound is as follows.

【化17】【化17】

(分析數據：式(i))¹ H NMR(CDCl₃ ,δppm)：1.30～1.38(m,10H),1.55～1.62(dtr,4H),2.58～2.61(tr,4H),3.46～3.49(tr,4H),3.63～3.66(tr,4H) IR(neat,cm^-1 )：2251,1117(Analytical data: formula (i)) ¹ H NMR (CDCl ₃ , δ ppm): 1.30 to 1.38 (m, 10H), 1.55 to 1.62 (dtr, 4H), 2.58 to 2.61 (tr, 4H), 3.46 to 3.49 ( Tr, 4H), 3.63 to 3.66 (tr, 4H) IR (neat, cm ^-1 ): 2251, 1117

＜參考例7：3,3’-(壬烷-1,9-二基雙(氧基))二丙酸甲酯之合成：式(j)＞使用參考例6所得之化合物，藉由與參考例3同樣的操作獲得3,3’-(壬烷-1,9-二基雙(氧基))二丙酸甲酯(GCarea%：84.3%、產率：63%)。又，所得之化合物的分析數據係如下述。<Reference Example 7: Synthesis of methyl 3,3'-(decane-1,9-diylbis(oxy))dipropionate: Formula (j)> Using the compound obtained in Reference Example 6, by The same procedure as in Reference Example 3 gave methyl 3,3'-(decane-1,9-diylbis(oxy))dipropionate (GCarea%: 84.3%, yield: 63%). Further, the analytical data of the obtained compound is as follows.

【化18】【化18】

(分析數據：式(j))¹ H NMR(CDCl₃ ,δppm)：1.24～1.34(m,10H), 1.50～1.69(m,4H), 2.58 (tr, 4H), 3.33～3.52 (m,4H), 3.58～3.76(m,10H) IR(neat,cm^-1 )：1742, 1115(Analytical data: formula (j)) ¹ H NMR (CDCl ₃ , δ ppm): 1.24 to 1.34 (m, 10H), 1.50 to 1.69 (m, 4H), 2.58 (tr, 4H), 3.33 to 3.52 (m, 4H), 3.58~3.76(m,10H) IR(neat,cm ^-1 ):1742, 1115

＜實施例4：3,3’-(壬烷-1,9-二基雙(氧基))二丙酸之合成：式(k)＞使用參考例7所得之化合物，藉由與參考例2同樣的操作獲得3,3’-(壬烷-1,9-二基雙(氧基))二丙酸(GCarea%：91.5%、產率：85%)。又，所得之化合物的分析數據係如下述。<Example 4: Synthesis of 3,3'-(decane-1,9-diylbis(oxy))dipropionic acid: Formula (k)> The compound obtained in Reference Example 7 was used, with reference examples. 2 The same operation gave 3,3'-(decane-1,9-diylbis(oxy))dipropionic acid (GCarea%: 91.5%, yield: 85%). Further, the analytical data of the obtained compound is as follows.

【化19】【化19】

(分析數據：式(k))¹ H NMR(DMSO-d6,δppm)：1.21～1.30(m,10H), 1.38～1.50(m,4H), 2.42 (tr, 4H), 3.34(tr, 4H), 3.54(tr, 4H), 12.1(brs, 2H) IR(KBr,cm^-1 )：1694, 1117 氯離子(Cl^- )含量：＜10ppm 硫酸離子(SO₄ ^2- )含量：＜10ppm 鈉離子(Na^＋ )含量：＜10ppm 鉀離子(K^＋ )含量：＜10ppm(Analytical data: formula (k)) ¹ H NMR (DMSO-d6, δ ppm): 1.21 to 1.30 (m, 10H), 1.38 to 1.50 (m, 4H), 2.42 (tr, 4H), 3.34 (tr, 4H) ), 3.54(tr, 4H), 12.1(brs, 2H) IR(KBr, cm ^-1 ): 1694, 1117 Chloride (Cl ^- ) content: <10ppm Sulfate ion (SO ₄ ^2- ) content: <10ppm sodium Ion (Na ⁺ ) content: <10ppm Potassium ion (K ⁺ ) content: <10ppm

＜參考例8：3,3’-((2,4-二乙基戊烷-1,5-二基)雙(氧基))二丙腈之合成：式(l)＞除了未實施減壓蒸餾以外，進行與參考例1同樣的操作，獲得3,3’-((2,4-二乙基戊烷-1,5-二基)雙(氧基))二丙腈(GCarea%：80.7%、產率：70%)。又，所得之化合物的分析數據係如下述。<Reference Example 8: Synthesis of 3,3'-((2,4-diethylpentane-1,5-diyl)bis(oxy))dipropionitrile: Formula (l)> Except that no reduction was carried out The same operation as in Reference Example 1 was carried out except for pressure distillation to obtain 3,3'-((2,4-diethylpentane-1,5-diyl)bis(oxy))dipropionitrile (GCarea%). : 80.7%, yield: 70%). Further, the analytical data of the obtained compound is as follows.

【化20】【化20】

(分析數據：式(l))¹ H NMR(DMSO-d6,δppm)：0.86～0.92(m,6H),1.15～1.25(m,4H),1.32～1.44(m,2H),1.56～1.68(m,2H), 2.56～2.62(tr,4H),3.32～3.40(m,4H),3.62～3.74(tr,4H) IR(KBr,cm^-1 )：2251,1113(Analytical data: Formula (1)) ¹ H NMR (DMSO-d6, δ ppm): 0.86 to 0.92 (m, 6H), 1.15 to 1.25 (m, 4H), 1.32 to 1.44 (m, 2H), 1.56 to 1.68 (m, 2H), 2.56 to 2.62 (tr, 4H), 3.32 to 3.40 (m, 4H), 3.62 to 3.74 (tr, 4H) IR (KBr, cm ^-1 ): 2251, 1113

＜實施例5：3,3’-((2,4-二乙基戊烷-1,5-二基)雙(氧基))二丙酸之合成：式(m)＞於參考例8所合成之3,3’-((2,4-二乙基戊烷-1,5-二基)雙(氧基))二丙腈8.0g(24.3mmol)添加37質量%鹽酸水溶液(20mL)並且加溫至80～85℃，使其反應24小時。冷卻反應液，添加MTBE(100ml)與水(50ml)，進行分液操作。分離MTBE層，對水層添加MTBE(100ml)並且進行分液操作。分離MTBE層，與先前的MTBE層一起添加水(20ml)並且進行分液操作。分離MTBE層，以無水硫酸鎂(10g)實施脫水操作後，減壓濃縮MTBE層而獲得淡黃色油狀物9.3g(GCarea%：58.6%、產率：73.6%)。又，所得之化合物的分析數據係如下述。<Example 5: Synthesis of 3,3'-((2,4-diethylpentane-1,5-diyl)bis(oxy))dipropionic acid: Formula (m)> Reference Example 8 Synthesis of 3,3'-((2,4-diethylpentane-1,5-diyl)bis(oxy))dipropanenitrile 8.0 g (24.3 mmol), 37% by mass aqueous hydrochloric acid solution (20 mL) And heating to 80-85 ° C, and allowing to react for 24 hours. The reaction solution was cooled, and MTBE (100 ml) and water (50 ml) were added to carry out a liquid separation operation. The MTBE layer was separated, MTBE (100 ml) was added to the aqueous layer and a liquid separation operation was carried out. The MTBE layer was separated, water (20 ml) was added along with the previous MTBE layer and a liquid separation operation was performed. The MTBE layer was separated, and the residue was subjected to a water-dehydration operation (MgSO4). Further, the analytical data of the obtained compound is as follows.

【化21】【化21】

(分析數據：式(m))¹ H NMR(DMSO-d6,δppm)：0.82～0.90(m,6H),1.20～1.40(m,6H),1.52～1.62(m,2H), 2.56～2.62(tr,4H),3.32～3.38(m,4H),3.64～3.72(tr,4H), 9.80～11.20(brs,2H) IR(neat,cm^-1 )：1716,1112 氯離子(Cl^- )含量：＜20ppm 硫酸離子(SO₄ ^2- )含量：＜20ppm 鈉離子(Na^＋ )含量：＜20ppm 鉀離子(K^＋ )含量：＜20ppm(Analytical data: formula (m)) ¹ H NMR (DMSO-d6, δ ppm): 0.82 to 0.90 (m, 6H), 1.20 to 1.40 (m, 6H), 1.52 to 1.62 (m, 2H), 2.56 to 2.62 (tr, 4H), 3.32 ~ 3.38 (m, 4H), 3.64 ~ 3.72 (tr, 4H), 9.80 ~ 11.20 (brs, 2H) IR (neat, cm -1): 1716,1112 chloride ion (Cl ^-) Content: <20ppm Sulfate ion (SO ₄ ^2- ) content: <20ppm Sodium ion (Na ⁺ ) content: <20ppm Potassium ion (K ⁺ ) content: <20ppm

＜參考例9：3,3’-((環己烷-1,4-二基雙(亞甲基))雙(氧基))二丙腈之合成：式(o)＞除了未實施減壓蒸餾以外，與參考例1進行同樣的操作，獲得3,3’-((環己烷-1,4-二基雙(亞甲基))雙(氧基))二丙腈(GCarea%：79.4%、產率：67.8%)。又，所得之化合物的分析數據係如下述。<Reference Example 9: Synthesis of 3,3'-((cyclohexane-1,4-diylbis(methylene))bis(oxy))dipropionitrile: Formula (o)> Except that no reduction was performed The same operation as in Reference Example 1 was carried out except for pressure distillation to obtain 3,3'-((cyclohexane-1,4-diylbis(methylene))bis(oxy))dipropionitrile (GCarea%). : 79.4%, yield: 67.8%). Further, the analytical data of the obtained compound is as follows.

【化22】【化22】

(分析數據：式(o))¹ H NMR(DMSO-d6,δppm)：1.24～1.46(m,8H),1.72～1.88(m,2H),2.60～2.68(tr,4H),3.28～3.42(m,4H),3.60～3.68(tr,4H) IR(KBr,cm^-1 )：2252,1114(Analytical data: formula (o)) ¹ H NMR (DMSO-d6, δ ppm): 1.24 to 1.46 (m, 8H), 1.72 to 1.88 (m, 2H), 2.60 to 2.68 (tr, 4H), 3.28 to 3.42 (m, 4H), 3.60 to 3.68 (tr, 4H) IR (KBr, cm ^-1 ): 2252, 1114

＜實施例6：3,3’-((環己烷-1,4-二基雙(亞甲基))雙(氧基))二丙酸之合成：式(p)＞藉由與實施例5同樣的操作獲得3,3’-((環己烷-1,4-二基雙(亞甲基))雙(氧基))二丙酸(GCarea%：56.6%、產率：76.7%)。又，所得之化合物的分析數據係如下述。<Example 6: Synthesis of 3,3'-((cyclohexane-1,4-diylbis(methylene))bis(oxy))dipropionic acid: Formula (p)> by and with Example 5, the same procedure gave 3,3'-((cyclohexane-1,4-diylbis(methylene))bis(oxy))dipropionic acid (GCarea%: 56.6%, yield: 76.7 %). Further, the analytical data of the obtained compound is as follows.

【化23】【化23】

(分析數據：式(p))¹ H NMR(DMSO-d6,δppm)：1.20～1.48(m,8H),1.65～1.80(m,2H),2.40～2.57(tr,4H),3.25～3.40(m,4H),3.55～3.65(tr,4H), 9.94～11.82(brs,2H) IR(KBr,cm^-1 )：1735,1116 氯離子(Cl^- )含量：＜20ppm 硫酸離子(SO₄ ^2- )含量：＜20ppm 鈉離子(Na^＋ )含量：＜20ppm 鉀離子(K^＋ )含量：＜20ppm(Analytical data: formula (p)) ¹ H NMR (DMSO-d6, δ ppm): 1.20 to 1.48 (m, 8H), 1.65 to 1.80 (m, 2H), 2.40 to 2.57 (tr, 4H), 3.25 to 3.40 (m, 4H), 3.55 to 3.65 (tr, 4H), 9.94 to 11.82 (brs, 2H) IR (KBr, cm ^-1 ): 1735, 1116 Chloride ion (Cl ^- ) content: <20 ppm Sulfate ion (SO ₄ ^2-) content: <20ppm sodium ions (Na ⁺⁾ content: <20ppm potassium ion (K ⁺⁾ content: <20ppm

＜參考例10：3,3’-(順2-丁烯-1,4-二基雙(氧基))二丙酸三級丁酯之合成：式(q)＞於氬氣環境下於室溫混合順2-丁烯-1,4-二醇(50.00g、0.533mol、純度：94%)、50wt%氫氧化鉀水溶液(4.22g、0.038mol、7mol%)及THF(80mL)。花費40分鐘於該溶液滴液丙烯酸三級丁酯(153.8g、1.20mol、2.25eq.)。於室溫攪拌38小時後，添加47wt%硫酸水溶液(4.70g)以使反應液成為酸性(pH＝4)，藉此停止反應。藉由蒸發器餾去反應液中之THF，對其添加水(100mL)並且以MTBE(200mL)進行萃取。經分離之有機相以水(100mL)洗淨4次，以硫酸鎂(15g)乾燥所得之有機相約30分鐘並且進行過濾後，藉由蒸發器進行濃縮而獲得淡黃色的油狀粗製品(108.59g)。藉由管柱層析(展開溶媒：10%乙酸乙酯/己烷)精製該粗製品，獲得3,3’-(順2-丁烯-1,4-二基雙(氧基))二丙酸三級丁酯(29.44g、0.084mol、GCarea%：98.2%、產率：16%)。所得之化合物的分析數據係如下述。<Reference Example 10: Synthesis of 3,3'-(cis-2-butene-1,4-diylbis(oxy))dipropionic acid tert-butyl butyl ester: Formula (q)> under argon atmosphere The cis 2-butene-1,4-diol (50.00 g, 0.533 mol, purity: 94%), 50 wt% aqueous potassium hydroxide solution (4.22 g, 0.038 mol, 7 mol%) and THF (80 mL) were mixed at room temperature. It took 40 minutes to drip the solution of tributyl acrylate (153.8 g, 1.20 mol, 2.25 eq.). After stirring at room temperature for 38 hours, a 47 wt% aqueous sulfuric acid solution (4.70 g) was added to make the reaction liquid acidic (pH = 4), thereby stopping the reaction. The THF in the reaction mixture was evaporated by an evaporator, water (100 mL) was added and extracted with MTBE (200 mL). The separated organic phase was washed 4 times with water (100 mL), and the obtained organic phase was dried over magnesium sulfate (15 g) for about 30 minutes and filtered, and concentrated by evaporation to give a pale yellow oily crude product (108.59 g). The crude product was purified by column chromatography (developing solvent: 10% ethyl acetate /hexane) to give 3,3'-(cis-2-butene-1,4-diylbis(oxy)) Tert-butyl propionate (29.44 g, 0.084 mol, GCarea%: 98.2%, yield: 16%). The analytical data of the obtained compound is as follows.

【化24】【化24】

(分析數據：式(q))¹ H NMR(CDCl₃ ,δppm)：1.45(s,18H),2.47～2.51(tr,4H),3.64～3.67(tr,4H),4.05～4.06(d,4H),5.69～5.71(m,2H) IR(neat,cm^-1 )：1732,1160(Analytical data: formula (q)) ¹ H NMR (CDCl ₃ , δ ppm): 1.45 (s, 18H), 2.47 to 2.51 (tr, 4H), 3.64 to 3.67 (tr, 4H), 4.05 to 4.06 (d, 4H), 5.69~5.71 (m, 2H) IR (neat, cm ^-1 ): 1732, 1160

＜實施例7：3,3’-(順2-丁烯-1,4-二基雙(氧基))二丙酸之合成：式(r)＞於氬氣環境下，於室溫混合參考例10所合成之3,3’-(順2-丁烯-1,4-二基雙(氧基))二丙酸三級丁酯(27.01g、0.077mol、GCarea%：98.2%)與二氯甲烷(81.0mL)。花費20分鐘於該溶液滴液三氟乙酸(81.0mL、1.058mol、13.7eq.)。於室溫攪拌22小時並且在HPLC分析中確認3,3’-(順2-丁烯-1,4-二基雙(氧基))二丙酸三級丁酯消失後，藉由蒸發器餾去二氯甲烷及過剩量的三氟乙酸。於濃縮殘渣添加MTBE(250mL)並且以水(20mL)進行8次逆萃取。藉由蒸發器濃縮乾燥硬化水相並且以甲苯(100mL)使其共沸3次後，藉由進行真空乾燥而獲得3,3’-(順2-丁烯-1,4-二基雙(氧基))二丙酸(12.95g、0.054mol、GCarea%：96.4%、產率：70%)作為黃色的固體。所得之化合物的分析數據係如下述。<Example 7: Synthesis of 3,3'-(cis-2-butene-1,4-diylbis(oxy))dipropionic acid: Formula (r)> Mixed under argon at room temperature 3,3'-(cis-2-butene-1,4-diylbis(oxy))dipropionic acid tert-butyl ester synthesized in Reference Example 10 (27.01 g, 0.077 mol, GCarea%: 98.2%) With dichloromethane (81.0 mL). The solution was added dropwise trifluoroacetic acid (81.0 mL, 1.058 mol, 13.7 eq.) over 20 minutes. Stir at room temperature for 22 hours and confirm the disappearance of 3,3'-(cis-2-butene-1,4-diylbis(oxy))dipropionic acid tert-butyl ester in the HPLC analysis, by means of an evaporator Dichloromethane and excess amount of trifluoroacetic acid were distilled off. MTBE (250 mL) was added to the concentrated residue and 8 times of reverse extraction was carried out with water (20 mL). The organic phase was dried and hardened by an evaporator and azeotroped three times with toluene (100 mL), followed by vacuum drying to obtain 3,3'-(cis-2-butene-1,4-diylbis( Oxy))dipropionic acid (12.95 g, 0.054 mol, GCarea%: 96.4%, yield: 70%) was taken as a yellow solid. The analytical data of the obtained compound is as follows.

【化25】【化25】

(分析數據：式(r))¹ H NMR(DMSO-d6,δppm)：2.43～2.46(tr,4H),3.55～3.58(tr,4H),3.98～3.99(d,4H),5.58～5.60(d,2H),11.95(brs,2H) IR(KBr,cm^-1 )：1712,1107 氯離子(Cl^- )含量：＜10ppm 硫酸離子(SO₄ ^2- )含量：＜10ppm 鈉離子(Na^＋ )含量：＜10ppm 鉀離子(K^＋ )含量：＜10ppm(Analytical data: formula (r)) ¹ H NMR (DMSO-d6, δ ppm): 2.43 to 2.46 (tr, 4H), 3.55 to 3.58 (tr, 4H), 3.98 to 3.99 (d, 4H), 5.58 to 5.60 (d, 2H), 11.95 (brs, 2H) IR (KBr, cm ^-1 ): 1712, 1107 Chloride (Cl ^- ) content: <10 ppm Sulfate ion (SO ₄ ^2- ) content: <10 ppm sodium ion (Na ⁺ ) Content: <10ppm Potassium ion (K ⁺ ) content: <10ppm

＜參考例11：3,3’-((2,2-雙((2-氰基乙氧基)甲基)丙烷-1,3-二基雙(氧基))二丙腈之合成：式(s)＞於氬氣環境下，於室溫混合季戊四醇(80.26g、0.578mol、純度：98%)、50wt%氫氧化鉀水溶液(4.57g、0.041mol、7mol%)及THF(100mL)。花費40分鐘於該溶液滴液丙烯腈(137.72g、2.596mol、4.5eq.)。於室溫攪拌26小時後，添加47wt%硫酸水溶液(5.10g)以使反應液成為酸性(pH3)，藉此停止反應。藉由矽藻土過濾除去析出之無機鹽，藉由蒸發器餾去反應液中之THF。於濃縮溶液添加飽和食鹽水(150mL)與甲苯(250mL)，藉由過濾除去不溶物後進行萃取。以硫酸鎂(5g)使經分離之有機相乾燥約30分鐘並且進行過濾後，藉由蒸發器進行濃縮而獲得3,3’-((2,2-雙((2-氰基乙氧基)甲基)丙烷-1,3-二基雙(氧基))二丙腈作為淡黃色的油狀粗製品(136.67g、純度：89.4%(NMR定量値)、產率：61%)。所得之化合物的分析數據係如下述。<Reference Example 11: Synthesis of 3,3'-((2,2-bis((2-cyanoethoxy)methyl)propane-1,3-diylbis(oxy)))dipropionitrile: Formula (s)> Pentaerythritol (80.26 g, 0.578 mol, purity: 98%), 50 wt% potassium hydroxide aqueous solution (4.57 g, 0.041 mol, 7 mol%) and THF (100 mL) were mixed at room temperature under an argon atmosphere. The solution was stirred for 40 minutes to acrylonitrile (137.72 g, 2.596 mol, 4.5 eq.). After stirring at room temperature for 26 hours, a 47 wt% aqueous sulfuric acid solution (5.10 g) was added to make the reaction solution acidic (pH 3). The reaction was stopped, and the precipitated inorganic salt was removed by filtration through celite, and the THF in the reaction mixture was distilled off by an evaporator. Saturated brine (150 mL) and toluene (250 mL) were added to the concentrated solution to remove insoluble by filtration. The extract was post-extracted. The separated organic phase was dried with magnesium sulfate (5 g) for about 30 minutes and filtered, and concentrated by an evaporator to obtain 3,3'-((2,2-bis((2- Cyanethoxy)methyl)propane-1,3-diylbis(oxy))dipropionitrile as a pale yellow oily crude product (136.67 g, purity: 89.4% (NMR quantitative enthalpy), yield : 61%) The analytical data of the obtained compound is as follows.

【化26】【化26】

(分析數據：式(s))¹ H NMR(CDCl₃ ,δppm)：2.59～2.62(tr,8H),3.50(s,8H),3.66～3.69(tr,8H) IR(neat,cm^-1 )：2251,1108(Analytical data: formula (s)) ¹ H NMR (CDCl ₃ , δ ppm): 2.59 to 2.62 (tr, 8H), 3.50 (s, 8H), 3.66 to 3.69 (tr, 8H) IR (neat, cm ^-1) ): 2251, 1108

＜實施例8：3,3’-((2,2-雙((2-羰乙氧基)甲基)丙烷-1,3-二基雙(氧基))二丙酸之合成：式(t)＞於氬氣環境下，使參考例11所合成之化合物(50.16g、0.129mol、NMR純度：89.4%)懸浮於水(20.0mL)，花費25分鐘於其滴液37%鹽酸水溶液(80.0mL、0.966mol、7.5eq.)。於90℃攪拌10小時後，添加水(60mL)並且以MTBE(300mL)進行萃取，藉由蒸發器濃縮乾燥硬化有機相。其次使濃縮殘渣溶解於乙酸乙酯(300mL)，以水(30mL)洗淨7次。以離子層析分析第7次的水相，結果離子(Cl^- 、SO₄ ^2- )為檢測界限以下。以硫酸鎂(20g)使經確認未含有離子之有機相乾燥並且進行過濾後，藉由蒸發器進行濃縮乾燥硬化，獲得3,3’-((2,2-雙((2-羰乙氧基)甲基)丙烷-1,3-二基雙(氧基))二丙酸(33.87g、0.043mol、純度：53.5%(NMR定量値)、產率：33%)作為淡黃色的油。所得之化合物的分析數據係如下述。<Example 8: Synthesis of 3,3'-((2,2-bis((2-carbonylethoxy)methyl)propane-1,3-diylbis(oxy))dipropionic acid: Formula (t)> The compound synthesized in Reference Example 11 (50.16 g, 0.129 mol, NMR purity: 89.4%) was suspended in water (20.0 mL) under an argon atmosphere, and it took 25 minutes to drip 37% hydrochloric acid aqueous solution. (80.0 mL, 0.966 mol, 7.5 eq.) After stirring at 90 ° C for 10 hours, water (60 mL) was added and extracted with MTBE (300 mL), and the organic phase was dried by evaporation and concentrated by evaporation. Ethyl acetate (300 mL) was washed 7 times with water (30 mL). The 7th aqueous phase was analyzed by ion chromatography, and the ions (Cl ^- , SO ₄ ^2- ) were below the detection limit. After drying and confirming the organic phase which has been confirmed to contain no ions, it is concentrated and dried and hardened by an evaporator to obtain 3,3'-((2,2-bis((2-carbonylethoxy)methyl)) Propane-1,3-diylbis(oxy))dipropionic acid (33.87 g, 0.043 mol, purity: 53.5% (NMR quantitative enthalpy), yield: 33%) as a pale yellow oil. The analytical data is as follows.

【化27】【化27】

(分析數據：式(t))¹ H NMR(DMSO-d6,δppm)：2.39～2.42(tr,8H),3.24(s,8H),3.51～3.54(tr,8H),12.20(brs,4H) IR(neat,cm^-1 )：1745,1125 氯離子(Cl^- )含量：＜20ppm 硫酸離子(SO₄ ^2- )含量：＜20ppm 鈉離子(Na^＋ )含量：＜20ppm 鉀離子(K^＋ )含量：＜20ppm(Analytical data: formula (t)) ¹ H NMR (DMSO-d6, δ ppm): 2.39 to 2.42 (tr, 8H), 3.24 (s, 8H), 3.51 to 3.54 (tr, 8H), 12.20 (brs, 4H) IR(neat,cm ^-1 ):1745,1125 Chloride ion (Cl ^- ) content: <20ppm Sulfate ion (SO ₄ ^2- ) content: <20ppm Sodium ion (Na ⁺ ) content: <20ppm Potassium ion (K ⁺ ) Content: <20ppm

[物性評價] ＜電解液例1＞其次，將實施例1所合成之式(b)所表示之二羧酸、乙二醇及水以下述表1之質量比的欄位所示之比例製備混合液，於該製備液添加氨，調整至pH6而獲得電解電容用電解液。所得之電解電容用電解液，係使用鋁箔測定以10mA/cm² 之電流密度的定電流所轉化時之耐電壓(火花電壓)。轉化性表示到達火花電壓為止之時間(分鐘)時的電壓上升率。電導度表示於30℃之値。再者，以目視評價各電解液於-25℃之溶解性。此等結果示於表1。[Evaluation of physical properties] <Example of electrolytic solution 1> Next, the dicarboxylic acid, ethylene glycol and water represented by the formula (b) synthesized in Example 1 were prepared in a ratio shown by the column of the mass ratio of the following Table 1. The mixed solution was added with ammonia to the preparation liquid, and adjusted to pH 6 to obtain an electrolytic solution for electrolytic capacitor. The obtained electrolytic solution for electrolytic capacitors was measured for withstand voltage (spark voltage) at a constant current of a current density of 10 mA/cm ² using an aluminum foil. The conversion rate indicates the rate of voltage rise at the time (minutes) until the spark voltage is reached. The electrical conductivity is expressed at 30 ° C. Further, the solubility of each electrolytic solution at -25 ° C was visually evaluated. These results are shown in Table 1.

＜電解液例2～19＞使用實施例所合成之化合物，以表1中電解液成分的欄位及質量比的欄位所示之組成製備混合液，與電解液例1同樣地製備電解液，並且同樣地測定各物性。<Electrolyte Examples 2 to 19> Using the compound synthesized in the examples, a mixed liquid was prepared in the composition shown by the column of the electrolyte component in Table 1 and the column of the mass ratio, and an electrolytic solution was prepared in the same manner as in the electrolytic solution example 1. And the physical properties were measured in the same manner.

＜比較電解液例1＞作為對照化合物，使用壬二酸(比較例1)，以表1中電解液成分的欄位及質量比的欄位所示之組成製備混合液，與電解液例1同樣地製備電解液，並且進行各種物性測定。<Comparative Electrolyte Example 1> As a control compound, a mixed solution was prepared using azelaic acid (Comparative Example 1), and the composition shown in the column of the electrolyte component in Table 1 and the column of the mass ratio, and the electrolytic solution example 1 The electrolytic solution was prepared in the same manner, and various physical properties were measured.

【表1】【Table 1】

【表2】【Table 2】

*1：未溶解，無法測定。 *2：於-25℃之溶解性的評價；○：溶解、×：固體析出、－：未探討。表中，1,6-DDA：2-丁基辛二酸表中，四羧酸：癸烷-2,4,7,9-四羧酸*1: Not dissolved, cannot be measured. *2: Evaluation of solubility at -25 ° C; ○: dissolution, ×: solid precipitation, -: not investigated. In the table, 1,6-DDA: 2-butyl suberic acid, in the table, tetracarboxylic acid: decane-2,4,7,9-tetracarboxylic acid

含有本發明之具有醚基的多元羧酸化合物之電解液，係鹵化物離子的含量為500ppm(0.05質量%)以下，又，其物性係如上述表1所明示，相較於比較例的電解液，在耐電壓、轉化性、溶解性等方面優異。如實施例所明示，本發明之電解液具有高耐電壓、適度的轉化性與良好的溶解性，因此，可用作為中高電壓用的電解電容用電解液。 [產業上之可利用性]The electrolytic solution containing the polyvalent carboxylic acid compound having an ether group of the present invention has a halide ion content of 500 ppm (0.05% by mass) or less, and the physical properties thereof are as shown in Table 1 above, and compared with the electrolytic solution of the comparative example. The liquid is excellent in resistance to voltage, conversion, solubility, and the like. As is apparent from the examples, the electrolytic solution of the present invention has high withstand voltage, moderate conversion property, and good solubility, and therefore can be used as an electrolytic solution for electrolytic capacitors for medium and high voltages. [Industrial availability]

本發明所揭示之具有醚基的多元羧酸化合物，係除了可用作為電化學元件用電解液的電解質、電解電容用電解液的電解質以外，還期待作為例如清潔劑、洗淨劑之補助劑；潤滑油；抗水垢劑；環氧樹脂硬化劑；聚合物用原料等新的可用性。The polyvalent carboxylic acid compound having an ether group disclosed in the present invention is expected to be an auxiliary agent such as a detergent or a detergent, in addition to an electrolyte which can be used as an electrolyte for an electrochemical device or an electrolyte for an electrolytic capacitor; Lubricating oil; anti-scaling agent; epoxy resin hardener; new availability of raw materials for polymers.

無。no.

Claims

一種電化學元件用電解質，含有下述通式(1)所表示之具有醚基的多元羧酸化合物；【化1】[通式(1)中，G表示可具有取代基之碳數2～36的(n＋1)價之烴基，惟具有芳香族基時亦可包含雜原子； R¹ ～R⁴ 分別表示選自由氫原子、碳數1～6的烷基、碳數1～6的烷氧基、及羥基構成之群組中的一種取代基，R¹ ～R⁴ 彼此可為相同亦可為不同，出現多次時可各表示相同或不同之基，惟R³ 與R⁴ 不會同時表示烷基及烷氧基； n係1～10的整數，當n為2以上時，於分子末端具有羧酸部位之氧基不存在於同一碳上； R^a ^＋表示選自由氫離子、銨離子及有機胺離子構成之群組中的離子，又，虛線之鍵結表示離子鍵；通式(1)所表示之化合物的碳數係8以上70以下]。An electrolyte for an electrochemical element comprising a polycarboxylic acid compound having an ether group represented by the following formula (1); [In the formula (1), G represents a (n+1)-valent hydrocarbon group having 2 to 36 carbon atoms which may have a substituent, and may have a hetero atom even when it has an aromatic group; and R ¹ to R ⁴ each represent a group selected from hydrogen; One of the substituents in the group consisting of an atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a group consisting of hydroxyl groups, and R ¹ to R ⁴ may be the same or different and may be present multiple times. Each of R ³ and R ^{4 may} not represent an alkyl group or an alkoxy group at the same time; n is an integer of 1 to 10, and when n is 2 or more, it has a carboxylic acid moiety at a molecular terminal. The oxy group is not present on the same carbon; R ^a ⁺ represents an ion selected from the group consisting of a hydrogen ion, an ammonium ion, and an organic amine ion, and the bond of a broken line represents an ionic bond; represented by the formula (1) The carbon number of the compound is 8 or more and 70 or less].

如申請專利範圍第1項之電化學元件用電解質，其中G表示選自由碳數2～36的飽和烴基、碳數4～36的不飽和脂肪族烴基、可包含雜原子之碳數6～36的芳香族基、及具有芳香族部分及脂肪族部分的可包含雜原子之碳數7～36的烴基構成之群組中的可具有取代基之烴基。An electrolyte for an electrochemical device according to claim 1, wherein G represents a saturated hydrocarbon group selected from carbon number 2 to 36, an unsaturated aliphatic hydrocarbon group having 4 to 36 carbon atoms, and a carbon number 6 to 36 which may contain a hetero atom. The aromatic group and the hydrocarbon group having a substituent in the group of the hydrocarbon group having 7 to 36 carbon atoms which may have a hetero atom and an aromatic moiety and an aliphatic moiety.

如申請專利範圍第1或2項之電化學元件用電解質，其中含有n為1～3的通式(1)所表示之化合物。An electrolyte for an electrochemical device according to claim 1 or 2, which contains a compound represented by the formula (1) wherein n is 1 to 3.

如申請專利範圍第1或2項之電化學元件用電解質，其中含有R¹ ～R⁴ 全為氫的通式(1)所表示之化合物。An electrolyte for an electrochemical device according to claim 1 or 2, which comprises a compound represented by the formula (1) in which all of R ¹ to R ⁴ are hydrogen.

如申請專利範圍第1或2項之電化學元件用電解質，其中含有G為選自由碳數3～12的直鏈狀伸烷基、主鏈的碳數為3以上且側鏈的碳數為1以上之碳數4～12的分支鏈烷-二、三或四-基、式(2)所表示之伸烷基、及碳數4～8的直鏈狀之伸烯基構成之群組中的基之通式(1)之化合物；【化2】(式中，v、w、x及z分別表示0～6之數，v＋w＋x＋z係2～6；惟當v為0時及z為0時，表示環員碳為鍵結部位，當x為0時及w為0時，表示單鍵)。An electrolyte for an electrochemical device according to claim 1 or 2, wherein G is selected from a linear alkyl group having 3 to 12 carbon atoms, a carbon number of the main chain of 3 or more, and a carbon number of the side chain. a group consisting of 1 or more carbon atoms of 4 to 12 branched alkane-di, tri- or tetra-yl, an alkylene group represented by the formula (2), and a linear alkenyl group having 4 to 8 carbon atoms a compound of the formula (1); (wherein, v, w, x, and z represent the number of 0 to 6, respectively, v + w + x + z is 2 to 6; but when v is 0 and z is 0, it means ring member carbon is the bonding site, when x is 0 When w and 0 are 0, it means a single key).

如申請專利範圍第1或2項之電化學元件用電解質，更含有選自由碳數4～16的羧酸及羧酸之鹽構成之群組中的至少1種化合物。The electrolyte for an electrochemical device according to claim 1 or 2 further contains at least one compound selected from the group consisting of a carboxylic acid having 4 to 16 carbon atoms and a salt of a carboxylic acid.

如申請專利範圍第1或2項之電化學元件用電解質，更含有選自由碳數4～10的腈化合物及碳數4～10的醚化合物構成之群組中的至少1種化合物。The electrolyte for electrochemical devices according to claim 1 or 2 further contains at least one compound selected from the group consisting of a nitrile compound having 4 to 10 carbon atoms and an ether compound having 4 to 10 carbon atoms.

一種電化學元件用電解液，含有如申請專利範圍第1至7項中任1項之電化學元件用電解質、及水與選自乙二醇及γ-丁內酯之一種以上的有機溶媒之混合溶媒。An electrolyte for an electrochemical device, comprising an electrolyte for an electrochemical device according to any one of items 1 to 7 of the patent application, and water and one or more organic solvents selected from the group consisting of ethylene glycol and γ-butyrolactone. Mixed solvent.

如申請專利範圍第8項之電化學元件用電解液，其中該混合溶液中之水的含量為30質量%以下。The electrolyte solution for electrochemical devices according to the eighth aspect of the invention, wherein the content of the water in the mixed solution is 30% by mass or less.

如申請專利範圍第8或9項之電化學元件用電解液，其中以0.01～50質量%之量含有如申請專利範圍第1至7項中任1項之電化學元件用電解質。An electrolyte for an electrochemical device according to any one of claims 1 to 7, wherein the electrolyte for an electrochemical device according to any one of claims 1 to 7 is contained in an amount of from 0.01 to 50% by mass.

如申請專利範圍第8或9項之電化學元件用電解液，其為鋁電化學元件用電解液。An electrolyte for an electrochemical device according to claim 8 or 9, which is an electrolyte for an aluminum electrochemical device.

一種電解電容，含有如申請專利範圍第8至11項中任1項之電化學元件用電解液。An electrolytic capacitor comprising an electrolyte for an electrochemical device according to any one of claims 8 to 11.

如申請專利範圍第12項之電解電容，其為鋁電解電容。For example, in the electrolytic capacitor of claim 12, it is an aluminum electrolytic capacitor.

一種化合物，其係以式(3)所表示；【化3】(式中，A係選自由COOH、CN及COOR⁵ 構成之群組中的基，R⁵ 表示碳數1～6的烷基)。a compound represented by formula (3); (In the formula, A is selected from the group consisting of COOH, CN, and COOR ⁵ , and R ⁵ is an alkyl group having 1 to 6 carbon atoms).

一種化合物，其係以式(4)所表示；【化4】(式中，B表示COOH或CN)。a compound represented by formula (4); (wherein B represents COOH or CN).