JP4405908B2 - Electrolytic solution for driving electrolytic capacitors - Google Patents
Electrolytic solution for driving electrolytic capacitors Download PDFInfo
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- JP4405908B2 JP4405908B2 JP2004380121A JP2004380121A JP4405908B2 JP 4405908 B2 JP4405908 B2 JP 4405908B2 JP 2004380121 A JP2004380121 A JP 2004380121A JP 2004380121 A JP2004380121 A JP 2004380121A JP 4405908 B2 JP4405908 B2 JP 4405908B2
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- electrolytic solution
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- 239000003990 capacitor Substances 0.000 title claims description 26
- 239000008151 electrolyte solution Substances 0.000 title claims description 20
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 18
- SZUPZARBRLCVCB-UHFFFAOYSA-N 3-(2-undecylimidazol-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=CN1CCC#N SZUPZARBRLCVCB-UHFFFAOYSA-N 0.000 claims description 15
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 12
- -1 tertiary amine salt Chemical class 0.000 claims description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 2
- 229910000679 solder Inorganic materials 0.000 description 12
- 238000012856 packing Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- JLIOOYQWWAUHRC-UHFFFAOYSA-N 2-carboxybenzoate;triethylazanium Chemical compound CCN(CC)CC.OC(=O)C1=CC=CC=C1C(O)=O JLIOOYQWWAUHRC-UHFFFAOYSA-N 0.000 description 2
- KWEIPWPXMKCFDH-UHFFFAOYSA-N 2-ethyl-1,3-dimethylimidazolidin-1-ium;phthalate Chemical compound CCC1N(C)CC[NH+]1C.CCC1N(C)CC[NH+]1C.[O-]C(=O)C1=CC=CC=C1C([O-])=O KWEIPWPXMKCFDH-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- YHOASSVIZSHRKO-UHFFFAOYSA-N n,n-dimethylmethanamine;phthalic acid Chemical compound CN(C)C.OC(=O)C1=CC=CC=C1C(O)=O YHOASSVIZSHRKO-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- VSKIZLPBNBFXMZ-UHFFFAOYSA-N 2-carboxybenzoate;1-ethyl-2,3-dimethylimidazolidin-1-ium Chemical compound CC[NH+]1CCN(C)C1C.OC(=O)C1=CC=CC=C1C([O-])=O VSKIZLPBNBFXMZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- SVQYZXLFQJMFNR-UHFFFAOYSA-N CCC1=C(CC)[N+](CC)=C(CC)N1.[O-]C(C1=CC=CC=C1C(O)=O)=O Chemical compound CCC1=C(CC)[N+](CC)=C(CC)N1.[O-]C(C1=CC=CC=C1C(O)=O)=O SVQYZXLFQJMFNR-UHFFFAOYSA-N 0.000 description 1
- UCMIQVIZOQLNHC-UHFFFAOYSA-N CCN(C)CC.OC(=O)c1ccccc1C(O)=O Chemical compound CCN(C)CC.OC(=O)c1ccccc1C(O)=O UCMIQVIZOQLNHC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- HCZWNJMKAQGNDP-UHFFFAOYSA-N n,n-dimethylethanamine;phthalic acid Chemical compound CCN(C)C.OC(=O)C1=CC=CC=C1C(O)=O HCZWNJMKAQGNDP-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- JLSPTMAJOFCBDK-UHFFFAOYSA-N phthalate 2,3,4,5-tetraethyl-1H-imidazol-3-ium Chemical group [O-]C(=O)c1ccccc1C([O-])=O.CCc1[nH]c(CC)[n+](CC)c1CC.CCc1[nH]c(CC)[n+](CC)c1CC JLSPTMAJOFCBDK-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-M phthalate(1-) Chemical compound OC(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-M 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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- Electric Double-Layer Capacitors Or The Like (AREA)
Description
本発明は、電解コンデンサの駆動用電解液(以下、単に電解液と称す)の改良に関するものであり、特に電解コンデンサのはんだリフロー耐熱安定性向上に関するものである。 The present invention relates to an improvement of an electrolytic solution for driving an electrolytic capacitor (hereinafter simply referred to as an electrolytic solution), and particularly relates to improvement of solder reflow heat stability of the electrolytic capacitor.
従来の低圧用アルミニウム電解コンデンサでは、γ−ブチロラクトンを主成分とする溶媒に、主電解質となるフタル酸の三級アミン塩またはそのイミダゾリニウム塩などを配合してなる電解液が用いられている（例えば、特許文献１参照）。 In a conventional low-voltage aluminum electrolytic capacitor, an electrolytic solution in which a tertiary amine salt of phthalic acid or an imidazolinium salt as a main electrolyte is blended with a solvent mainly composed of γ-butyrolactone is used. (For example, refer to Patent Document 1).
この種の電解コンデンサは、ケースの開口部を、全体がゴム製のゴムパッキング、あるいは樹脂板が貼られたゴムパッキングで封口した構造を有しており、ゴムパッキングを貫通する端子を基板のランドにはんだによって接続する。
近年、鉛入りのはんだに代えて鉛フリーはんだが使用される傾向にあるが、鉛フリーはんだは、従来の鉛入りはんだに比べ融点が高いため、はんだリフロー温度を上昇させる必要がある。しかしながら、アルミニウム電解コンデンサでは、ケースの開口部をゴムパッキングで封口した構造が採用されているため、はんだリフロー温度を高めると、電解液からのガス発生によってケースの内圧が上昇し、その結果、ゴムパッキングが膨張するか、またはケース底が膨張して、電解コンデンサの高さ寸法値（ゴムパッキングの外側端面からケース底までの寸法）が増加するという問題点がある。このような寸法増加が発生すると、基板に実装した電解コンデンサの高さ寸法が増大し、基板の機器への搭載に支障が発生する他、電解コンデンサの信頼性も低下するため、好ましくない。 In recent years, lead-free solder tends to be used in place of lead-containing solder. However, lead-free solder has a higher melting point than conventional lead-containing solder, so it is necessary to increase the solder reflow temperature. However, since aluminum electrolytic capacitors have a structure in which the opening of the case is sealed with rubber packing, increasing the solder reflow temperature increases the internal pressure of the case due to gas generation from the electrolyte, resulting in rubber There is a problem that the packing expands or the case bottom expands to increase the height dimension value of the electrolytic capacitor (the dimension from the outer end face of the rubber packing to the case bottom). When such an increase in dimensions occurs, the height dimension of the electrolytic capacitor mounted on the substrate increases, which causes troubles in mounting the substrate on equipment, and also reduces the reliability of the electrolytic capacitor, which is not preferable.
以上の問題点に鑑みて、本発明の課題は、はんだリフロー温度が上昇しても高さ寸法の増大を発生させない電解コンデンサの駆動用電解液を提供することにある。 In view of the above problems, an object of the present invention is to provide an electrolytic solution for driving an electrolytic capacitor that does not increase in height even when the solder reflow temperature increases.
上記課題を解決するために、本発明では、γ−ブチロラクトンを主成分とする溶媒に、少なくとも、カルボン酸またはその塩が配合された電解コンデンサの駆動用電解液において、上記溶媒に対して、さらに、以下の化学式で示される１−シアノエチル−２−ウンデシルイミダゾールが配合されていることを特徴とする。 In order to solve the above problems, in the present invention, in an electrolytic solution for driving an electrolytic capacitor in which at least a carboxylic acid or a salt thereof is blended in a solvent mainly composed of γ-butyrolactone, 1-cyanoethyl-2-undecylimidazole represented by the following chemical formula is blended.
本発明において、１−シアノエチル−２−ウンデシルイミダゾールの配合量は、電解液全体に対して５〜１５ｗｔ％の範囲であることが好ましい。配合量が５ｗｔ％未満では高さ寸法値抑制効果が小さく、配合量が１５ｗｔ％を超えると、電解液の比抵抗が上昇し、製品のｔａｎδの増大を招く傾向にある。 In this invention, it is preferable that the compounding quantity of 1-cyanoethyl-2-undecyl imidazole is the range of 5-15 wt% with respect to the whole electrolyte solution. When the blending amount is less than 5 wt%, the height dimension value suppressing effect is small, and when the blending amount exceeds 15 wt%, the specific resistance of the electrolytic solution increases, and the tan δ of the product tends to increase.
本発明において、上記カルボン酸としてはフタル酸を用い、その塩としては三級アミン塩またはイミダゾリニウム塩を用いることが好ましい。 In the present invention, phthalic acid is preferably used as the carboxylic acid, and a tertiary amine salt or imidazolinium salt is preferably used as the salt thereof.
フタル酸の三級アミン塩としては、フタル酸水素トリメチルアミン、フタル酸水素トリエチルアミン、フタル酸水素エチルジメチルアミン、フタル酸水素ジエチルメチルアミン等を例示することができる。 Examples of the tertiary amine salt of phthalic acid include trimethylamine hydrogen phthalate, triethylamine hydrogen phthalate, ethyldimethylamine hydrogen phthalate, and diethylmethylamine hydrogen phthalate.
また、イミダゾリウム塩としてはフタル酸水素テトラエチルイミダゾリウム、フタル酸水素テトラメチルイミダゾリニウム、フタル酸水素１，３−ジメチルイミダゾリニウム、フタル酸水素１−エチル−２，３−ジメチルイミダゾリニウム、フタル酸水素２−エチル−１，３−ジメチルイミダゾリニウム、フタル酸水素１，３，４−トリメチルイミダゾリニウム、フタル酸水素２−エチル−１，３−ジメチルイミダゾリニウム、フタル酸水素１．３−ジメチル−２−ｎ−ペンチル等を例示することができる。 Examples of imidazolium salts include tetraethylimidazolium hydrogen phthalate, tetramethylimidazolium hydrogen phthalate, 1,3-dimethylimidazolinium hydrogen phthalate, and 1-ethyl-2,3-dimethylimidazolinium hydrogen phthalate. 2-ethyl-1,3-dimethylimidazolinium phthalate, hydrogen 1,3,4-trimethylimidazolinium phthalate, 2-ethyl-1,3-dimethylimidazolinium phthalate, hydrogen phthalate Examples thereof include 1.3-dimethyl-2-n-pentyl.
本発明では、電解液に１−シアノエチル−２−ウンデシルイミダゾールが配合され、この１−シアノエチル−２−ウンデシルイミダゾールは、γ−ブチロラクトンに比べて蒸気圧が低い。このため、はんだリフロー温度が高い場合でも、電解コンデンサの内部圧力の上昇を抑制することができるので、ケース底の膨張やゴムパッキングの膨張を防止でき、電解コンデンサの高さ寸法値の増加を防止することができる。 In the present invention, 1-cyanoethyl-2-undecylimidazole is blended in the electrolytic solution, and this 1-cyanoethyl-2-undecylimidazole has a lower vapor pressure than γ-butyrolactone. For this reason, even when the solder reflow temperature is high, the rise in the internal pressure of the electrolytic capacitor can be suppressed, so that expansion of the bottom of the case and expansion of the rubber packing can be prevented, and an increase in the height dimension value of the electrolytic capacitor can be prevented. can do.
本発明では、γ−ブチロラクトンを主成分とする溶媒に、少なくとも、カルボン酸またはその塩が配合された電解コンデンサの駆動用電解液において、上記溶媒に対して、さらに、上記の１−シアノエチル−２−ウンデシルイミダゾールを配合したことを特徴とする。
ここで、カルボン酸としてはフタル酸を用い、その塩としては三級アミン塩またはイミダゾリニウム塩を用いることが好ましい。カルボン酸としてフタル酸を用いれば、マレイン酸を用いた場合と比較して電解コンデンサのｔａｎδの経時的な増大を抑えることができるからである。
また、１−シアノエチル−２−ウンデシルイミダゾールの配合量は、電解液全体に対して５〜１５ｗｔ％までの範囲であることが好ましい。
In the present invention, in an electrolyte for driving an electrolytic capacitor in which at least a carboxylic acid or a salt thereof is blended in a solvent containing γ-butyrolactone as a main component, the 1-cyanoethyl-2 is further added to the solvent. -It is characterized by blending undecylimidazole.
Here, phthalic acid is preferably used as the carboxylic acid, and a tertiary amine salt or imidazolinium salt is preferably used as the salt thereof. This is because if phthalic acid is used as the carboxylic acid, an increase in tan δ of the electrolytic capacitor over time can be suppressed as compared with the case where maleic acid is used.
Moreover, it is preferable that the compounding quantity of 1-cyanoethyl-2-undecylimidazole is the range to 5-15 wt% with respect to the whole electrolyte solution.
このように構成した電解液は、それをコンデンサ素子に含浸した後、コンデンサ素子をケースに収納するとともに、ケースの開口部を、全体がゴム製のゴムパッキング、あるいは樹脂板が貼られたゴムパッキングで封口する。このように構成した電解コンデンサは、ゴムパッキングを貫通する端子を基板のランドにはんだ付けすることで接続する。 The electrolytic solution thus configured is impregnated in the capacitor element, and then the capacitor element is accommodated in the case, and the opening of the case is entirely made of rubber or rubber packing with a resin plate attached. Seal with. The electrolytic capacitor configured as described above is connected by soldering a terminal penetrating the rubber packing to a land of the substrate.
ここで、本形態の電解コンデンサでは、電解液に１−シアノエチル−２−ウンデシルイミダゾールが配合され、この１−シアノエチル−２−ウンデシルイミダゾールはγ−ブチロラクトンに比べて蒸気圧が低い。
このため、鉛フリーはんだを用いて実装したためにはんだリフロー温度が高い場合でも、電解コンデンサの内部圧力の上昇を抑制することができるので、ケース底の膨張やゴムパッキングの膨張を防止でき、電解コンデンサの高さ寸法値の増加を防止することができる。
Here, in the electrolytic capacitor of this embodiment, 1-cyanoethyl-2-undecylimidazole is blended in the electrolytic solution, and this 1-cyanoethyl-2-undecylimidazole has a lower vapor pressure than γ-butyrolactone.
For this reason, even if the solder reflow temperature is high because it is mounted using lead-free solder, the rise in the internal pressure of the electrolytic capacitor can be suppressed, so that expansion of the bottom of the case and expansion of the rubber packing can be prevented. It is possible to prevent an increase in the height dimension value.
以下、実施例に基づいて、本発明をより具体的に説明する。まず、表１に示す組成で電解液を調合し、その電解液を用いて、５０ＷＶ／１００μＦのアルミニウム電解コンデンサを製作し、リフロー耐熱性試験を実施した。リフロー耐熱性試験としては、２５０℃３１秒間放置後のアルミニウム電解コンデンサの高さ寸法値の変化を測定した。その測定結果を表１に示す。 Hereinafter, based on an Example, this invention is demonstrated more concretely. First, an electrolytic solution was prepared with the composition shown in Table 1, and a 50 WV / 100 μF aluminum electrolytic capacitor was manufactured using the electrolytic solution, and a reflow heat resistance test was performed. As a reflow heat resistance test, a change in the height dimension value of the aluminum electrolytic capacitor after being left at 250 ° C. for 31 seconds was measured. The measurement results are shown in Table 1.
表１に基づいて、まず、フタル酸の三級アミン塩としてフタル酸トリエチルアミンを用いた場合の実施例１〜８について説明する。１−シアノエチル−２−ウンデシルイミダゾールを配合していないもの（比較例１）と、例えば、１−シアノエチル−２−ウンデシルイミダゾールを１０ｗｔ％配合したもの（実施例５）を比較すると、実施例５での寸法値変化率の方が極めて小さく、高さ寸法変化率を２％以下に抑制することできた。その他の実施例でも同様である。
但し、１−シアノエチル−２−ウンデシルイミダゾールの配合量が５ｗｔ％未満では高さ寸法値抑制効果が小さく（実施例１、２）、また、１５ｗｔ％を超える場合（実施例８）では、電解液の比抵抗が上昇し、製品のｔａｎδの増大を招くため、好ましくない。よって、１−シアノエチル−２−ウンデシルイミダゾールの配合量は５〜１５ｗｔ％の範囲が好ましい。
Based on Table 1, first, Examples 1 to 8 in the case where triethylamine phthalate is used as the tertiary amine salt of phthalic acid will be described. When comparing the one not containing 1-cyanoethyl-2-undecylimidazole (Comparative Example 1) with the one containing 10 wt% of 1-cyanoethyl-2-undecylimidazole (Example 5), Example The dimension value change rate at 5 was much smaller, and the height dimension change rate could be suppressed to 2% or less. The same applies to other embodiments.
However, when the blending amount of 1-cyanoethyl-2-undecylimidazole is less than 5 wt%, the height dimension value suppressing effect is small (Examples 1 and 2), and when it exceeds 15 wt% (Example 8), electrolysis is performed. This is not preferable because the specific resistance of the liquid is increased and the tan δ of the product is increased. Therefore, the blending amount of 1-cyanoethyl-2-undecylimidazole is preferably in the range of 5 to 15 wt%.
また、フタル酸の三級アミン塩をフタル酸水素トリメチルアミンとした場合（実施例９〜１５）、およびイミダゾリニウム塩として、フタル酸テトラエチルイミダゾリウムを用いた場合（実施例１４〜２１）でも上記と同様、１−シアノエチル−２−ウンデシルイミダゾールによる高さ寸法値抑制効果が見られた。 In addition, when the tertiary amine salt of phthalic acid is trimethylamine phthalate (Examples 9 to 15), and when imidazolinium salt is tetraethylimidazolium phthalate (Examples 14 to 21), Similarly, the height dimension value suppression effect by 1-cyanoethyl-2-undecylimidazole was seen.
尚、１−シアノエチル−２−ウンデシルイミダゾールを配合した効果は、上記実施例に限定されるものではなく、先に記載したフタル酸の三級アミン塩やそのイミダゾリニウム塩を単独または複数配合した電解液に用いても同等の効果があった。
In addition, the effect of blending 1-cyanoethyl-2-undecylimidazole is not limited to the above-described examples, and the above-described tertiary amine salt of phthalic acid or its imidazolinium salt is blended alone or in combination. Even when used in the electrolyte solution, the same effect was obtained.
Claims (3)
上記溶媒に対して、さらに、以下の化学式で示される１−シアノエチル−２−ウンデシルイミダゾールが配合されていることを特徴とする電解コンデンサの駆動用電解液。
An electrolytic solution for driving an electrolytic capacitor, wherein 1-cyanoethyl-2-undecylimidazole represented by the following chemical formula is further blended with the solvent.
3. The electrolytic solution for driving an electrolytic capacitor according to claim 1, wherein the carboxylic acid is phthalic acid, and the salt thereof is a tertiary amine salt or an imidazolinium salt.
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