JPH03180014A - Electrolyte for electrolytic capacitor - Google Patents
Electrolyte for electrolytic capacitorInfo
- Publication number
- JPH03180014A JPH03180014A JP31975489A JP31975489A JPH03180014A JP H03180014 A JPH03180014 A JP H03180014A JP 31975489 A JP31975489 A JP 31975489A JP 31975489 A JP31975489 A JP 31975489A JP H03180014 A JPH03180014 A JP H03180014A
- Authority
- JP
- Japan
- Prior art keywords
- ester
- phosphide
- electrolyte
- added
- phosphorous acid
- 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.)
- Pending
Links
- 239000003990 capacitor Substances 0.000 title claims description 13
- 239000003792 electrolyte Substances 0.000 title abstract description 8
- 150000003014 phosphoric acid esters Chemical class 0.000 claims abstract description 11
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 6
- 238000003763 carbonization Methods 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 4
- 150000002148 esters Chemical class 0.000 abstract 3
- 239000002075 main ingredient Substances 0.000 abstract 2
- 150000003018 phosphorus compounds Chemical class 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000010407 anodic oxide Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 2
- OWCLRJQYKBAMOL-UHFFFAOYSA-N 2-butyloctanedioic acid Chemical compound CCCCC(C(O)=O)CCCCCC(O)=O OWCLRJQYKBAMOL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- SATJMZAWJRWBRX-UHFFFAOYSA-N azane;decanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCCCCCCCC([O-])=O SATJMZAWJRWBRX-UHFFFAOYSA-N 0.000 description 1
- ORKKMKUDEPWHTG-UHFFFAOYSA-N azane;nonanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCCCCCCC([O-])=O ORKKMKUDEPWHTG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- -1 phosphorus compound Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 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、電解コンデンサ用電解液に関し、特に難燃性
の電解コンデンサ用電解液に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an electrolytic solution for electrolytic capacitors, and particularly to a flame-retardant electrolytic solution for electrolytic capacitors.
（従来の技＃Ｉ）
一般、に、電解コンデンサに用いられている電解液は、
溶媒としてエチレングリコール等の有機物質を主体とし
ているために、可燃性のものが多い。(Conventional Technique #I) Generally, the electrolyte used in electrolytic capacitors is:
Many of them are flammable because they mainly contain organic substances such as ethylene glycol as solvents.
しかし、電解コンデンサに対して要求される安全性が厳
しくなり、破壊しても火災が発生することのない難燃性
のものが必要とされるようになってきた。However, safety requirements for electrolytic capacitors have become stricter, and flame-retardant capacitors that will not cause a fire even if destroyed have become necessary.
そのために、Ｗｊ質としてｉｌｌ酸や１１Ｍアンモニウ
ムを溶解したり、また、特開平１−９５５１２号の通り
リン酸エステルを溶媒や助溶媒として用い、自己消火性
を付与している。For this purpose, ill acid or 11M ammonium is dissolved as a Wj substance, and phosphoric acid ester is used as a solvent or co-solvent as disclosed in JP-A-1-95512 to impart self-extinguishing properties.
（発明が解決しようとする課題）
しかしながら、エチレングリコール１１１Ｍ系の電解液
は、自己消火性を示すが、％１ｍ！１ｌ１１度が大きい
ためにエステル化により水分が多く生成し、それにより
陽極酸化皮膜を著しく劣化し、また、比抵抗も比較的に
大きい欠点がある。この欠点を解決するために、有ｍＷ
１アンモニウム塩を溶質とし難燃剤を添加した電解液も
あるが、例えばプラスチック等の代表的難燃剤であるリ
ン含有ハロゲン化合物は火花電圧が低下する欠点がある
。(Problems to be Solved by the Invention) However, the ethylene glycol 111M electrolyte exhibits self-extinguishing properties, but only %1M! Since the 1l11 degree is large, a large amount of water is produced by esterification, which significantly deteriorates the anodic oxide film, and the specific resistance is also relatively large. In order to solve this drawback, mW
Although there is an electrolytic solution containing an ammonium salt as a solute and a flame retardant added, for example, a phosphorus-containing halogen compound, which is a typical flame retardant for plastics, etc., has the disadvantage that the spark voltage decreases.
また、電解液中にリン酸エステル等を溶解すると陽極酸
化皮膜を溶解して火花電圧を低下する欠点がある。Furthermore, when phosphoric acid ester or the like is dissolved in the electrolytic solution, the anodic oxide film is dissolved and the spark voltage is reduced.
本発明の目的は、以上の欠点を改良し、難燃性を向上す
るとともに、火花電圧を改善しろる電解コンデンサ用電
解液を提供するものである。An object of the present invention is to provide an electrolytic solution for electrolytic capacitors that can improve the above-mentioned drawbacks, improve flame retardancy, and improve spark voltage.
（課題を解決するための手段）
本発明は、上記の目的を達成するために、多価アルコー
ルを主成分とする電解コンデンサ用電解液に、リン酸エ
ステルまたはその縮合体と、亜リン酸またはその塩とを
添加することを特徴とする電解コンデンサ用電解液を提
供するものである。(Means for Solving the Problems) In order to achieve the above object, the present invention adds phosphoric acid or a phosphorous acid or The present invention provides an electrolytic solution for an electrolytic capacitor, which is characterized by adding the salt thereof.
（作用）
リン酸エステルまたはリン酸エステルの縮重合体、亜リ
ン酸また曝よこの塩を多価アルコールに溶解すると、燃
焼したときにリン化合物が多価アルコールの炭化を促進
し、可燃性ガスの発生を抑制する。(Function) When a phosphoric acid ester or a condensation polymer of a phosphoric acid ester, a phosphorous acid, or a salt of phosphorous acid is dissolved in a polyhydric alcohol, when burned, the phosphorus compound accelerates the carbonization of the polyhydric alcohol, producing flammable gas. suppress the occurrence of
なお、リン酸エステルは、単独では多量に添加しないと
炭化を促進する効果が低いが、亜リン酸やその塩をとも
に添加すると添加量が少なくても、かなりの効果を生じ
る。そのために、電解液を他の特性を損うことなく難燃
性を向上できる。Note that phosphoric acid ester alone has a low effect of promoting carbonization unless added in a large amount, but when phosphorous acid or a salt thereof is added together, a considerable effect is produced even if the amount added is small. Therefore, the flame retardance of the electrolyte can be improved without impairing other properties.
また、硼酸系の電解液にこれらの物質を添り口すると、
必要な硼酸の溶質′ｆａ度を低下でき、これによりガス
発生量を低減でき、１００℃以上の高温でも使用できる
。Also, when these substances are added to a boric acid electrolyte,
The required solute degree of boric acid can be reduced, thereby reducing the amount of gas generated, and it can be used even at high temperatures of 100° C. or higher.
（実施例） 以下、本発明を実施例に基づいて説明する。(Example) Hereinafter, the present invention will be explained based on examples.
溶媒としてはエチレングリコール等の多価アルコールを
用いる。A polyhydric alcohol such as ethylene glycol is used as the solvent.
溶質には、ブチルオクタンニ酸や（Ｉｌｌ、硼酸アンモ
ニウム、セバシン酸アンモニウム、アゼライン酸アンモ
ニウム等を用いる。As the solute, butyloctane diic acid, ammonium borate, ammonium sebacate, ammonium azelaate, etc. are used.
添加剤としては、リン酸エステルまたはその縮重合体を
０．１〜１２．０ｗｔ％、亜リン酸またはその塩を０．
０１〜７．Ｑｗｔ％を用いる。各々の添１＋１１ ｆｆ
ｉがこの数値より少ないと難燃性の効果が低く、多いと
火花電圧が低下する。なお、リン酸エステルまたはその
＠重合体のアルキル基の炭素数は１〜８がよく、９以上
だと溶解し難くなる。また、縮重合体の重合度は２〜１
５がよく、１６以上になると溶解し難くなる。As additives, 0.1 to 12.0 wt% of phosphoric acid ester or its condensation polymer, and 0.1 to 12.0 wt% of phosphorous acid or its salt.
01-7. Qwt% is used. Each addition 1+11 ff
If i is less than this value, the flame retardant effect will be low, and if it is more than this value, the spark voltage will decrease. Note that the number of carbon atoms in the alkyl group of the phosphoric acid ester or its @polymer is preferably 1 to 8, and if it is 9 or more, it becomes difficult to dissolve. In addition, the degree of polymerization of the condensation polymer is 2 to 1.
5 is good, and when it is 16 or more, it becomes difficult to dissolve.
次に表１の１１戊からなる上記実施例及び従来例につい
て、難燃性、電導度及び火花電圧を調べた。Next, the flame retardance, electrical conductivity, and spark voltage of the above examples and conventional examples consisting of 11 items in Table 1 were examined.
表１
難燃性の測定には、径３５Ｍ１長さ４０闇のアルミ電解
コンデンサ素子に電解液を含浸した素子を用いる。この
素子をガスバーナーの先端から１５關上方に、かつ垂線
に対して４５度傾けて火焔を５秒間あて、次に３秒間離
す処理を１０回繰り返す。そして燃焼した場合には素子
を火焔から離して消火するまでの時間を測定し、難燃性
を判断した。また、電導反は３０℃のときの値とし、火
花電圧は８５℃のときの値とする。Table 1 For flame retardancy measurements, an aluminum electrolytic capacitor element with a diameter of 35 M and a length of 40 mm is used, which is impregnated with an electrolyte. This process is repeated 10 times by placing this element 15 degrees above the tip of the gas burner and tilting it at 45 degrees with respect to the perpendicular, applying the flame for 5 seconds and then releasing it for 3 seconds. If the element burns, the element is removed from the flame and the time taken to extinguish the flame is measured to determine flame retardancy. Further, the conductivity is the value at 30°C, and the spark voltage is the value at 85°C.
測定結果は表２に示した。The measurement results are shown in Table 2.
以下余白。Margin below.
表２
表２から明らかな通り、本発明の実施例１〜１４によれ
ば難燃性の試験を１０回繰り返してもコンデンサ素子は
燃焼しないが、従来例１〜４、従来例６〜７は１〜４回
で燃焼する。なお、従来例５は１０回でも燃焼しないが
電導度が低く比抵抗が高い。また、従来例５は硼酸アン
モンの含有量が３０，０ｗｔ％と多いが、本発明の実施
例１，８゜１３は５〜１２ｗｔ％と少なくできる。Table 2 As is clear from Table 2, according to Examples 1 to 14 of the present invention, the capacitor element does not burn even if the flame retardancy test is repeated 10 times, but in Conventional Examples 1 to 4 and Conventional Examples 6 to 7. Burns in 1-4 times. Note that although Conventional Example 5 does not burn even after 10 cycles, its conductivity is low and its specific resistance is high. Further, although the content of ammonium borate in Conventional Example 5 is as high as 30.0 wt%, it can be reduced to 5 to 12 wt% in Examples 1, 8 and 13 of the present invention.
電樽度については、実浦例１〜１４が１．１５９〜１．
５１２であるのに対して、従来例１〜７が０．６３０〜
１．５１０となり、前者の方が全体的に高く従って比抵
抗を低くできる。Regarding electric barrel strength, Miura Examples 1 to 14 have a range of 1.159 to 1.159.
512, whereas in conventional examples 1 to 7 it is 0.630 to
1.510, the former is higher overall and can therefore lower the specific resistance.
火花電圧についても、実施例１〜１４が４００〜４５０
Ｖ、従来例１〜７が１５０〜４５０Ｖとなり、前者の方
が全体に高い値を示している。Regarding the spark voltage, Examples 1 to 14 were 400 to 450.
V was 150 to 450 V in Conventional Examples 1 to 7, with the former showing a higher value overall.
（発明の効果）
以上の通り、本発明によれば、リン酸エステルまたはそ
の縮重合体、亜リン酸またはこの塩を添加することによ
り難燃性を向上でき、比抵抗を低下でき、火花電圧の高
い電解コンデンサ用電解液が得られる。(Effects of the Invention) As described above, according to the present invention, by adding phosphoric acid ester or its condensation polymer, phosphorous acid or its salt, flame retardancy can be improved, specific resistance can be reduced, and spark voltage can be improved. An electrolytic solution for electrolytic capacitors with a high temperature can be obtained.
Claims (1)
電解液に、リン酸エステルまたはその縮合体と、亜リン
酸またはその塩とを添加することを特徴とする電解コン
デンサ用電解液。(1) An electrolytic solution for an electrolytic capacitor, which is characterized in that a phosphoric acid ester or a condensate thereof, and a phosphorous acid or a salt thereof are added to an electrolytic solution for an electrolytic capacitor containing a polyhydric alcohol as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31975489A JPH03180014A (en) | 1989-12-08 | 1989-12-08 | Electrolyte for electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31975489A JPH03180014A (en) | 1989-12-08 | 1989-12-08 | Electrolyte for electrolytic capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03180014A true JPH03180014A (en) | 1991-08-06 |
Family
ID=18113801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31975489A Pending JPH03180014A (en) | 1989-12-08 | 1989-12-08 | Electrolyte for electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03180014A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012067097A1 (en) * | 2010-11-16 | 2012-05-24 | 日本ケミコン株式会社 | Fire retardant electrolytic capacitor |
| WO2014024603A1 (en) | 2012-08-10 | 2014-02-13 | 日本ケミコン株式会社 | Flame-retardant electrolytic capacitor |
-
1989
- 1989-12-08 JP JP31975489A patent/JPH03180014A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012067097A1 (en) * | 2010-11-16 | 2012-05-24 | 日本ケミコン株式会社 | Fire retardant electrolytic capacitor |
| JPWO2012067097A1 (en) * | 2010-11-16 | 2014-05-12 | 日本ケミコン株式会社 | Flame retardant electrolytic capacitor |
| WO2014024603A1 (en) | 2012-08-10 | 2014-02-13 | 日本ケミコン株式会社 | Flame-retardant electrolytic capacitor |
| KR20150040801A (en) | 2012-08-10 | 2015-04-15 | 닛뽄 케미콘 가부시끼가이샤 | Flame-retardant electrolytic capacitor |
| US9496092B2 (en) | 2012-08-10 | 2016-11-15 | Nippon Chemi-Con Corporation | Flame-retardant electrolytic capacitor |
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