JP3987837B2 - Electrolytic solution for electrolytic capacitor drive - Google Patents
Electrolytic solution for electrolytic capacitor drive Download PDFInfo
- Publication number
- JP3987837B2 JP3987837B2 JP2004103658A JP2004103658A JP3987837B2 JP 3987837 B2 JP3987837 B2 JP 3987837B2 JP 2004103658 A JP2004103658 A JP 2004103658A JP 2004103658 A JP2004103658 A JP 2004103658A JP 3987837 B2 JP3987837 B2 JP 3987837B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- electrolytic solution
- electrolytic
- acid
- driving
- 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.)
- Expired - Lifetime
Links
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- 239000003990 capacitor Substances 0.000 title claims description 15
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Chemical group OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical group [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-L phosphoramidate Chemical compound NP([O-])([O-])=O PTMHPRAIXMAOOB-UHFFFAOYSA-L 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Chemical group CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、電解コンデンサの駆動用電解液（以下、電解液と称す）の改良に関するものであり、特に耐電圧を改善した電解液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 referred to as an electrolytic solution), and particularly relates to an electrolytic solution having improved withstand voltage.
従来、中高圧用アルミニウム電解コンデンサ用の電解液は、エチレングリコール等の溶媒に、高級二塩基酸またはそのアンモニウム塩、ホウ酸またはそのアンモニウム塩およびマンニトール等の多価アルコール類を溶解しており、ホウ酸と多価アルコール類とはエステル化合物を形成し、その構造的な特性により電解液の耐電圧が向上することが知られている。さらに合成高分子であるポリビニルアルコールを溶解していた（例えば、特許文献１〜３参照）。
しかしながら、炭素数が６程度のマンニトール、ソルビトール等は添加量を増加させても電解液の耐電圧の向上が緩慢であり、耐電圧を大幅に向上させるには、比抵抗の顕著な上昇を伴う。一方、ポリビニルアルコールはマンニトールより少量の添加で電解液の耐電圧向上が図れるが、エチレングリコールを主成分とする溶媒に対して溶解性が著しく低いため多量に添加ができない上、電解液の加熱と攪拌が長時間必要になるという問題がある。また、多価アルコール類は主溶質である高級二塩基酸ともエステル反応を起こすことがあるため、電解液自身の特性変化が大きくなるという問題があった。
本発明は上記課題を解決し、比抵抗上昇を抑えながら耐電圧の上昇を図ることができる電解コンデンサの駆動用電解液を提供するものである。
However, for mannitol, sorbitol, etc. having about 6 carbon atoms, the improvement in the withstand voltage of the electrolyte is slow even if the addition amount is increased, and in order to greatly improve the withstand voltage, there is a marked increase in specific resistance. . Polyvinyl alcohol, on the other hand, can improve the withstand voltage of the electrolyte solution by adding a smaller amount than mannitol, but it cannot be added in a large amount because it has extremely low solubility in a solvent mainly composed of ethylene glycol. There is a problem that stirring is required for a long time. In addition, polyhydric alcohols may cause an ester reaction with a higher dibasic acid, which is a main solute, and there has been a problem that the characteristic change of the electrolytic solution itself increases.
This invention solves the said subject and provides the electrolyte solution for a drive of the electrolytic capacitor which can aim at the raise of a withstand voltage, suppressing a specific resistance raise.
本発明は、上記の課題を解決するため各種検討した結果、見出されたものであり、分子鎖中にオキシアルキレン基を含有する不飽和単量体と酢酸ビニルとの共重合体をケン化して得られるポリビニルアルコール系樹脂（以下ポリオキシアルキレン変性ＰＶＡ系樹脂と略す）を用いることに着目した。この構造により電解液と電極箔との化学反応を抑制し、また、この構造はエチレングリコール等に容易に溶解する特徴を有していることから、耐電圧の上昇、溶解性の向上を図ろうとするものである。 The present invention has been found as a result of various studies to solve the above problems, and saponifies a copolymer of an unsaturated monomer containing an oxyalkylene group in a molecular chain and vinyl acetate. Attention was focused on using a polyvinyl alcohol-based resin (hereinafter abbreviated as polyoxyalkylene-modified PVA-based resin). This structure suppresses the chemical reaction between the electrolyte solution and the electrode foil, and this structure has a feature that it can be easily dissolved in ethylene glycol, etc., so it is intended to increase the withstand voltage and improve the solubility. To do.
すなわち、本発明は、
（１）エチレングリコールを主成分とする溶媒と、カルボン酸またはその塩と、ポリオキシアルキレン変性ＰＶＡ系樹脂とを含むことを特徴とする電解コンデンサの駆動用電解液である。
That is, the present invention
(1) An electrolytic solution for driving an electrolytic capacitor comprising a solvent containing ethylene glycol as a main component, a carboxylic acid or a salt thereof, and a polyoxyalkylene-modified PVA resin.
（２）前記の不飽和単量体が、下記の一般式（１）： (2) The unsaturated monomer is represented by the following general formula (1):
［但し、上式中のＡＯは、オキシエチレン、オキシプロピレン、オキシブチレン、オキシテトラメチレン基であり、Ｒは炭素数１〜１８の炭化水素基であり、ｎは１〜５０の整数である。］
で表されることを特徴とする前記（１）記載の電解コンデンサの駆動用電解液である。
[However, AO in the above formula is an oxyethylene, oxypropylene, oxybutylene, or oxytetramethylene group, R is a hydrocarbon group having 1 to 18 carbon atoms, and n is an integer of 1 to 50. ]
The electrolytic solution for driving an electrolytic capacitor as described in (1) above, characterized in that
（３）前記（１）〜（２）記載のポリオキシアルキレン変性ＰＶＡ系樹脂の溶解量が０．１０〜５．００ｗｔ％であることを特徴とする電解コンデンサの駆動用電解液である。 (3) An electrolytic solution for driving an electrolytic capacitor, wherein the polyoxyalkylene-modified PVA resin according to (1) to (2) is dissolved in an amount of 0.10 to 5.00 wt%.
（４）前記（１）〜（３）記載のポリオキシアルキレン変性ＰＶＡ系樹脂の平均重合度が５０〜２０００であり、ケン化度が１０〜１００モル％であることを特徴とする電解コンデンサの駆動用電解液である。 (4) The average polymerization degree of the polyoxyalkylene-modified PVA resin described in (1) to (3) is 50 to 2000, and the saponification degree is 10 to 100 mol%. It is a driving electrolyte.
（５）前記（１）〜（４）記載のポリオキシアルキレン変性ＰＶＡ系樹脂のオキシアルキレン基含有構成単量体部分の占める割合（変性量）が０．０１〜５０モル％であることを特徴とする電解コンデンサの駆動用電解液である。 (5) The proportion (modified amount) of the oxyalkylene group-containing constituent monomer portion of the polyoxyalkylene-modified PVA resin described in (1) to (4) is 0.01 to 50 mol%. An electrolytic solution for driving an electrolytic capacitor.
本発明の電解コンデンサ用電解液中に含有されるポリオキシアルキレン変性ＰＶＡ系樹脂は、エチレングリコールに対する溶解性が高いので、容易に溶解させることができ、溶解した電解液は、主溶質のカルボン酸とのエステル化反応が少なく、比抵抗の上昇を抑制しながら、耐電圧の向上を図ることができ、かつ熱安定性にも優れるため、高温下での製品の信頼性を高めることができる。 The polyoxyalkylene-modified PVA resin contained in the electrolytic solution for electrolytic capacitors of the present invention has high solubility in ethylene glycol, so it can be easily dissolved, and the dissolved electrolytic solution is a main solute carboxylic acid. Thus, the withstand voltage can be improved while suppressing an increase in specific resistance, and the thermal stability is also excellent. Therefore, the reliability of the product at high temperatures can be improved.
本発明では、エチレングリコールを主溶媒とする電解液中において、ポリオキシアルキレン変性ＰＶＡ系樹脂の水酸基、およびエーテル基部分が電極箔の酸化皮膜と反応し耐水性の皮膜を形成するため、電解液と電極箔との化学反応が抑えられ、耐電圧向上を図ることができる。 In the present invention, in the electrolytic solution containing ethylene glycol as the main solvent, the hydroxyl group and ether group portion of the polyoxyalkylene-modified PVA resin react with the oxide film of the electrode foil to form a water-resistant film. The chemical reaction between the electrode foil and the electrode foil is suppressed, and the withstand voltage can be improved.
以下、本発明を詳細に説明する。
本発明の電解液に用いられる溶媒としてはエチレングリコールが挙げられ、エチレングリコールに混合する副溶媒としては、プロピレングリコール等のグリコール類、γ−ブチロラクトン、Ｎ−メチル−２−ピロリドン等のラクトン類、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−エチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−エチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、ヘキサメチルホスホリックアミド等のアミド類、エチレンカーボネート、プロピレンカーボネート、イソブチレンカーボネート等の炭酸類、アセトニトリル等のニトリル類、ジメチルスルホキシド等のオキシド類、エーテル類、ケトン類、エステル類、スルホラン、スルホラン誘導体、水等を例示することができる。これらの溶媒は一種類だけでなく、二種類以上を混合して使用することができる。
Hereinafter, the present invention will be described in detail.
Examples of the solvent used in the electrolytic solution of the present invention include ethylene glycol. Examples of the auxiliary solvent mixed with ethylene glycol include glycols such as propylene glycol, lactones such as γ-butyrolactone and N-methyl-2-pyrrolidone, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, hexamethyl Amides such as phosphoric amide, carbonates such as ethylene carbonate, propylene carbonate, isobutylene carbonate, nitriles such as acetonitrile, oxides such as dimethyl sulfoxide, ethers, ketones, esters, sulfolane, Ruhoran derivatives, water, etc. can be exemplified. These solvents can be used by mixing not only one type but also two or more types.
本発明の電解液に用いられるカルボン酸としては、ギ酸、酢酸、ラウリン酸、ステアリン酸、デカン酸、安息香酸、サリチル酸、マレイン酸、フタル酸、フマル酸、コハク酸、グルタル酸、アゼライン酸、セバシン酸、２−メチルアゼライン酸、１，６−デカンジカルボン酸、５，６−デカンジカルボン酸、７−ビニルヘキサデセン−１，１６−ジカルボン酸などが挙げられる。 Examples of the carboxylic acid used in the electrolytic solution of the present invention include formic acid, acetic acid, lauric acid, stearic acid, decanoic acid, benzoic acid, salicylic acid, maleic acid, phthalic acid, fumaric acid, succinic acid, glutaric acid, azelaic acid, sebacin Acid, 2-methyl azelaic acid, 1,6-decanedicarboxylic acid, 5,6-decanedicarboxylic acid, 7-vinylhexadecene-1,16-dicarboxylic acid and the like.
また、カルボン酸の塩としては、アンモニウム塩の他、メチルアミン、エチルアミン、ｔ−ブチルアミン等の一級アミン塩、ジメチルアミン、エチルメチルアミン、ジエチルアミン等の二級アミン塩、トリメチルアミン、ジエチルメチルアミン、エチルジメチルアミン、トリエチルアミン等の三級アミン塩、テトラメチルアンモニウム、トリエチルメチルアンモニウム、テトラエチルアンモニウム等の四級アンモニウム塩、イミダゾリニウム塩等の溶融塩などが挙げられる。 In addition to ammonium salts, primary amine salts such as methylamine, ethylamine and t-butylamine, secondary amine salts such as dimethylamine, ethylmethylamine and diethylamine, trimethylamine, diethylmethylamine and ethyl Examples thereof include tertiary amine salts such as dimethylamine and triethylamine, quaternary ammonium salts such as tetramethylammonium, triethylmethylammonium and tetraethylammonium, and molten salts such as imidazolinium salts.
本発明の電解液中に含有されるポリオキシアルキレン変性ＰＶＡ系樹脂は、末端または分子鎖中にオキシアルキレン基を含有するものであれば特に制限はなく、その変性量は通常０．０１〜５０モル％が好ましく、より好ましくは０．１〜３０モル％であり、さらに好ましくは０．３〜１５モル％である。変性量が０．０１モル％未満の場合、耐電圧向上効果が少なく、かつエチレングリコール等の溶媒への溶解性が低下するため好ましくない。また５０モル％を超えるとエチレングリコール等の溶媒への溶解性は上昇するが、比抵抗が上昇するため好ましくない。
その中でも酢酸ビニルとオキシアルキレン不飽和単量体との共重合体ケン化物が好適に用いられ、好ましくは平均重合度が５０〜２０００、ケン化度が１０〜１００モル％である。平均重合度が５０未満の場合、耐電圧向上の効果が十分に現れず、２０００を超えるとエチレングリコール等の溶媒に溶解し難くなるため好ましくない。また、ケン化度が１０モル％未満では耐電圧向上の効果が十分に現れない。末端または分子鎖中にオキシアルキレン基を含有するポリビニルアルコール系樹脂の好ましい平均重合度の範囲は１００〜１０００、ケン化度の範囲は２０〜１００モル％である。
The polyoxyalkylene-modified PVA resin contained in the electrolytic solution of the present invention is not particularly limited as long as it contains an oxyalkylene group at the terminal or molecular chain, and the amount of modification is usually 0.01 to 50. Mol% is preferable, More preferably, it is 0.1-30 mol%, More preferably, it is 0.3-15 mol%. When the modification amount is less than 0.01 mol%, the effect of improving the withstand voltage is small, and the solubility in a solvent such as ethylene glycol is lowered, which is not preferable. If it exceeds 50 mol%, the solubility in a solvent such as ethylene glycol increases, but the specific resistance increases, which is not preferable.
Among them, a saponified copolymer of vinyl acetate and an oxyalkylene unsaturated monomer is suitably used, preferably having an average degree of polymerization of 50 to 2000 and a degree of saponification of 10 to 100 mol%. When the average degree of polymerization is less than 50, the effect of improving the withstand voltage is not sufficiently exhibited, and when it exceeds 2000, it is difficult to dissolve in a solvent such as ethylene glycol. Further, when the degree of saponification is less than 10 mol%, the effect of improving the withstand voltage is not sufficiently exhibited. The range of the preferable average polymerization degree of the polyvinyl alcohol-based resin containing an oxyalkylene group in the terminal or molecular chain is 100 to 1000, and the range of the saponification degree is 20 to 100 mol%.
本発明で言うオキシアルキレン基とは一般式（１）： The oxyalkylene group referred to in the present invention is represented by the general formula (1):
［但し、上式中のＡＯは、オキシエチレン、オキシプロピレン、オキシブチレン、オキシテトラメチレン基であり、Ｘは、水素、アルキル基、アルキルエステル基、アルキルアミド基またはその塩であり、ｎは１〜５０の整数である。］
で表される構造を有するものであり、中でもＡＯで表されるオキシアルキレン基はオキシエチレン基が好ましい。また、オキシアルキレン基は、単独または２種以上を含んでいてもよい。２種以上のオキシアルキレン基を含む場合には、ブロック状付加またはランダム状付加のいずれでもよい。エチレングリコール等の溶媒に対して溶解度をより高く得られる点から、一方にオキシエチレン基を有することが好ましい。
また、Ｘは水素、アルキル基、アルキルエステル基、アルキルアミド基、スルホン酸またはその塩などが挙げられるが、エチレングリコール等の溶媒への溶解性などの点から水素が好ましい。また、ｎはオキシアルキレン基の数を表しており、ｎの範囲は１〜５０、好ましくは１〜３０である。
[However, AO in the above formula is oxyethylene, oxypropylene, oxybutylene, oxytetramethylene group, X is hydrogen, alkyl group, alkyl ester group, alkylamide group or a salt thereof, and n is 1 It is an integer of ~ 50. ]
In particular, the oxyalkylene group represented by AO is preferably an oxyethylene group. Moreover, the oxyalkylene group may contain single or 2 types or more. When two or more oxyalkylene groups are contained, either block addition or random addition may be used. It is preferable that one side has an oxyethylene group from the viewpoint of obtaining higher solubility in a solvent such as ethylene glycol.
Examples of X include hydrogen, an alkyl group, an alkyl ester group, an alkylamide group, a sulfonic acid or a salt thereof, and hydrogen is preferable from the viewpoint of solubility in a solvent such as ethylene glycol. N represents the number of oxyalkylene groups, and the range of n is 1 to 50, preferably 1 to 30.
前記ポリオキシアルキレン変性ＰＶＡ系樹脂は、通常、オキシアルキレン基を有する不飽和単量体と酢酸ビニルとを共重合させ、その後ケン化を行うことにより製造される。 The polyoxyalkylene-modified PVA-based resin is usually produced by copolymerizing an unsaturated monomer having an oxyalkylene group and vinyl acetate, and then performing saponification.
前記のオキシアルキレン基を含有する不飽和単量体としては、ポリオキシエチレン（メタ）アクリレート、ポリオキプロピレン（メタ）アクリレート等のポリオキシアルキレン（メタ）アクリレート類、ポリオキシエチレン（メタ）アクリル酸アミド、ポリオキシプロピレン（メタ）アクリル酸アミド等のポリオキシアルキレン（メタ）アクリル酸アミド類、ポリオキシエチレンビニルエーテル、ポリオキシプロピレンビニルエーテル等のポリオキシアルキレンビニルエーテル類、ポリオキシエチレンアリルエーテル、ポリオキシプロピレンアリルエーテル、ポリオキシエチレンブチルビニルエーテル、ポリオキシプロピレンブチルビニルエーテル等のポリオキシアルキレンアルキルビニルエーテル類等があげられるが、中でも下記の一般式（２）： Examples of the unsaturated monomer containing an oxyalkylene group include polyoxyalkylene (meth) acrylates such as polyoxyethylene (meth) acrylate and polyoxypropylene (meth) acrylate, and polyoxyethylene (meth) acrylic acid. Amides, polyoxyalkylene (meth) acrylic amides such as polyoxypropylene (meth) acrylic amide, polyoxyalkylene vinyl ethers such as polyoxyethylene vinyl ether and polyoxypropylene vinyl ether, polyoxyethylene allyl ether, polyoxypropylene Examples include polyoxyalkylene alkyl vinyl ethers such as allyl ether, polyoxyethylene butyl vinyl ether, polyoxypropylene butyl vinyl ether, etc. 2):
［但し、上式中のＡＯは、オキシエチレン、オキシプロピレン、オキシブチレン、オキシテトラメチレン基であり、Ｒは炭素数１〜１８の炭化水素基であり、ｎは１〜５０の整数である。］
で表されるポリオキシアルキレンアルキルビニルエーテル類が好適に用いられる。Ｒは炭素数１〜１８の炭化水素基であり、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ｎ−ヘキシル基、イソヘキシル基、ｎ−オクチル基、２−エチルヘキシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、オレイル基などが挙げられるがこれに限らない。なかでもメチル基、エチル基、ｎ−ブチル基のものが好ましい。また、ＡＯで表されるオキシアルキレン基は前記同様オキシエチレン基が好ましく、単独または２種以上を含んでいてもよい。２種以上のオキシアルキレン基を含む場合には、ブロック状付加またはランダム状付加のいずれでもよく、エチレングリコール等の溶媒に対して溶解度をより高く得られる点から、一方にオキシエチレン基を有することが好ましい。
[However, AO in the above formula is an oxyethylene, oxypropylene, oxybutylene, or oxytetramethylene group, R is a hydrocarbon group having 1 to 18 carbon atoms, and n is an integer of 1 to 50. ]
The polyoxyalkylene alkyl vinyl ether represented by these is used suitably. R is a hydrocarbon group having 1 to 18 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, n-hexyl group, isohexyl. Group, n-octyl group, 2-ethylhexyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, oleyl group and the like, but are not limited thereto. Of these, those having a methyl group, an ethyl group or an n-butyl group are preferred. Further, the oxyalkylene group represented by AO is preferably an oxyethylene group as described above, and may contain one or two or more. When two or more oxyalkylene groups are included, either block addition or random addition may be used, and one has an oxyethylene group from the viewpoint of obtaining higher solubility in a solvent such as ethylene glycol. Is preferred.
また、本発明の効果を損なわない範囲で共重合可能な他の不飽和単量体、例えば、（メタ）アクリル酸、マレイン酸、無水マレイン酸、フマル酸、クロトン酸、イタコン酸等のカルボキシル基含有単量体、マレイン酸モノメチル、イタコン酸モノメチル等の不飽和二塩基酸モノアルキルエステル類、アクリルアミド、ジメチルアクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−ビニルアセトアミド等のアミド基含有単量体、Ｎ−ビニル−２−ピロリドン、Ｎ−ビニル−３−プロピル−２−ピロリドン、Ｎ−ビニル−５−メチル−２−ピロリドン、Ｎ−ビニル−５，５−ジメチル−２−ピロリドン、Ｎ−ビニル−３，５−ジメチル−２−ピロリドン、Ｎ−アリル−２−ピロリドン等の２−ピロリドン環含有単量体、ラウリルビニルエーテル、ステアリルビニルエーテル等のアルキルビニルエーテル類、アリルアルコール、ジメチルアリルアルコール、イソプロペニルアリルアルコール、ヒドロキシエチルビニルエーテル、ヒドロキシブチルビニルエーテル等の水酸基含有単量体、アリルアセテート、ジメチルアリルアセテート、イソプロペニルアリルアセテート等のアセチル基含有単量体、メタクリル酸メチル、メタクリル酸エチル、アクリル酸−２−エチルヘキシル、アクリル酸−ｎ−ブチル等のアクリル酸エステル類、トリメトキシビニルシラン、トリブチルビニルシラン、ジフェニルメチルビニルシラン等のビニルシラン類、エチレン、プロピレン等のα―オレフィン類、スチレン等の芳香族系単量体、ダイアセトンアクリルアミド、ビニルエチレンカーボネート等と共重合してもよい。 In addition, other unsaturated monomers copolymerizable within the range of not impairing the effects of the present invention, for example, (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid and other carboxyl groups -Containing monomers, unsaturated dibasic acid monoalkyl esters such as monomethyl maleate and monomethyl itaconate, amide group-containing monomers such as acrylamide, dimethylacrylamide, N-methylolacrylamide and N-vinylacetamide, N-vinyl -2-pyrrolidone, N-vinyl-3-propyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, N-vinyl-3,5 -2-pyrrolidone ring-containing monomers such as dimethyl-2-pyrrolidone and N-allyl-2-pyrrolidone, lauryl vinyl ether Alkyl vinyl ethers such as stearyl vinyl ether, hydroxyl-containing monomers such as allyl alcohol, dimethylallyl alcohol, isopropenyl allyl alcohol, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, and acetyl groups such as allyl acetate, dimethylallyl acetate, isopropenyl allyl acetate Containing monomer, acrylic acid esters such as methyl methacrylate, ethyl methacrylate, acrylic acid-2-ethylhexyl, acrylic acid-n-butyl, vinylsilanes such as trimethoxyvinylsilane, tributylvinylsilane, diphenylmethylvinylsilane, ethylene, Copolymerized with α-olefins such as propylene, aromatic monomers such as styrene, diacetone acrylamide, vinyl ethylene carbonate, etc. May be.
共重合の方法は公知の方法でよく、ラジカル重合、例えば塊状重合法、溶液重合法、懸濁重合法、乳化重合方法等により重合されるが、中でもメチルアルコール等の溶剤中でα，α’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）等のアゾ系または、過酸化ベンゾイル、過酢酸、ジ−ｎ−プロピルパーオキシジカーボネート等の過酸化物系の開始剤を用いて重合する方法が一般的である。メルカプタン類、アルデヒド類等を添加して重合度を調整したり、分子鎖末端を変性したりすることも可能である。また、未反応の単量体の除去方法および乾燥、粉砕方法等も公知の方法でよく、特に制限はない。 The copolymerization method may be a known method, and is polymerized by radical polymerization, for example, bulk polymerization method, solution polymerization method, suspension polymerization method, emulsion polymerization method, etc., among which α, α ′ in a solvent such as methyl alcohol. -Azo-based compounds such as azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile), or peroxides such as benzoyl peroxide, peracetic acid, and di-n-propyl peroxydicarbonate A polymerization method using a system initiator is common. Mercaptans, aldehydes and the like can be added to adjust the degree of polymerization, and the molecular chain terminals can be modified. Also, a method for removing unreacted monomers, a drying method, a grinding method, and the like may be known methods, and there is no particular limitation.
この他、ポリオキシアルキレン変性ＰＶＡ系樹脂は本発明の効果を損なわない範囲で部分的にウレタン化、アセタール化、エーテル化、グラフト化、リン酸エステル化などの反応によって変性させた樹脂であってもよい。 In addition, the polyoxyalkylene-modified PVA resin is a resin that has been partially modified by a reaction such as urethanization, acetalization, etherification, grafting, or phosphoric esterification within a range that does not impair the effects of the present invention. Also good.
本発明の電解液に用いられるポリオキシアルキレン変性ＰＶＡ系樹脂の溶解量は０．１０〜５．００ｗｔ％であり、溶解量が０．１０ｗｔ％未満では耐電圧向上の効果が十分でなく、５．００ｗｔ％を超えると比抵抗が高くなり過ぎ、低比抵抗用途には不向きとなる。 The dissolution amount of the polyoxyalkylene-modified PVA resin used in the electrolytic solution of the present invention is 0.10 to 5.00 wt%. If the dissolution amount is less than 0.10 wt%, the effect of improving the withstand voltage is not sufficient. If it exceeds 0.000 wt%, the specific resistance becomes too high, and it is not suitable for low specific resistance applications.
上記の電解液には、漏れ電流の低減、耐電圧向上、ガス吸収等の目的で種々の添加剤を加えることができる。添加剤の具体例としては、リン酸化合物、ホウ酸化合物、多価アルコール類、ポリビニルアルコール、ポリエチレングリコール、ポリプロピレングリコール、ポリオキシエチレンポリオキシプロピレングリコールのランダム共重合体およびブロック共重合体に代表される高分子化合物、ニトロ化合物等が挙げられる。 Various additives can be added to the electrolytic solution for the purpose of reducing leakage current, improving withstand voltage, and absorbing gas. Specific examples of additives include phosphoric acid compounds, boric acid compounds, polyhydric alcohols, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene glycol random copolymers and block copolymers. And high molecular compounds and nitro compounds.
以下、本発明の実施例に基づき具体的に説明する。表１の組成で電解液を調合し、３０℃における電解液の比抵抗と８５℃における火花発生電圧（電解液の耐電圧）を測定し、表１の結果を得た。又、同様にして、表２の組成で電解液を調合し、３０℃における電解液の比抵抗と８５℃における火花発生電圧（電解液の耐電圧）を測定し、表２の結果を得た。本発明において、ポリオキシアルキレン変性ＰＶＡ系樹脂ならびにポリビニルアルコールの重合度およびケン化度はＪＩＳ−Ｋ６７２６に従って測定される。 The present invention will be specifically described below based on examples of the present invention. An electrolytic solution was prepared with the composition shown in Table 1, and the specific resistance of the electrolytic solution at 30 ° C. and the spark generation voltage (withstand voltage of the electrolytic solution) at 85 ° C. were measured. Similarly, an electrolyte solution was prepared with the composition shown in Table 2, and the specific resistance of the electrolyte solution at 30 ° C. and the spark generation voltage (withstand voltage of the electrolyte solution) at 85 ° C. were measured. The results shown in Table 2 were obtained. . In the present invention, the polymerization degree and saponification degree of the polyoxyalkylene-modified PVA resin and polyvinyl alcohol are measured according to JIS-K6726.
表１および表２の実験結果より、本発明によるポリオキシアルキレン変性ＰＶＡ系樹脂を溶解した実施例の電解液は、従来例の電解液より比抵抗の上昇が抑えられ、耐電圧を向上していることが分かる。また、従来例１〜５より、ポリビニルアルコールは３％以上添加すると完全に溶解せず、電解液に不向きであるが、実施例に示されるように、本発明によるポリオキシアルキレン変性ＰＶＡ系樹脂は１０％を添加（実施例６）しても完全に溶解し、電解コンデンサの駆動用電解液として機能する。
ポリオキシアルキレン変性ＰＶＡ系樹脂の溶解量が０．１０ｗｔ％未満（実施例１）では耐電圧向上の効果が十分でなく、５．００ｗｔ％を超える（実施例６）と比抵抗が高くなり過ぎ、低比抵抗用途に不向きとなる。よって、ポリオキシアルキレン変性ＰＶＡ系樹脂の溶解量は、０．１０〜５．００ｗｔ％の範囲が好ましい。
耐電圧向上効果の高い溶質は、どうしても比抵抗が上昇するという問題があるが、本発明によるポリオキシアルキレン変性ＰＶＡ系樹脂が溶解された電解液の場合には、比抵抗の上昇が少なくて耐電圧向上効果の高いという利点がある。又、実施例３および４と、従来例２および３を比較すると、同じ溶解量であっても実施例３および４（本発明品）の方が比抵抗が低く、耐電圧が高くなっていることがわかる。本発明の電解液にあっては、従来例とほぼ同じ比抵抗であれば、耐電圧が１０Ｖ以上向上し、耐電圧を低下させる他の溶質を使用することが可能である。
From the experimental results in Table 1 and Table 2, the electrolyte solution of the example in which the polyoxyalkylene-modified PVA resin according to the present invention is dissolved can suppress an increase in specific resistance and improve the withstand voltage compared to the electrolyte solution of the conventional example. I understand that. In addition, from conventional examples 1 to 5, when 3% or more of polyvinyl alcohol is added, it does not completely dissolve and is unsuitable for an electrolytic solution. However, as shown in the examples, the polyoxyalkylene-modified PVA resin according to the present invention is Even when 10% is added (Example 6), it completely dissolves and functions as an electrolyte for driving an electrolytic capacitor.
When the amount of polyoxyalkylene-modified PVA resin dissolved is less than 0.10 wt% (Example 1), the effect of improving the withstand voltage is not sufficient, and when it exceeds 5.00 wt% (Example 6), the specific resistance becomes too high. Unsuitable for low specific resistance applications. Therefore, the dissolution amount of the polyoxyalkylene-modified PVA resin is preferably in the range of 0.10 to 5.00 wt%.
A solute having a high withstand voltage improving effect inevitably increases the specific resistance. However, in the case of an electrolytic solution in which the polyoxyalkylene-modified PVA resin according to the present invention is dissolved, the specific resistance does not increase so much and the resistance is increased. There is an advantage that the voltage improving effect is high. In addition, when Examples 3 and 4 are compared with Conventional Examples 2 and 3, Examples 3 and 4 (product of the present invention) have lower specific resistance and higher withstand voltage even if the amount of dissolution is the same. I understand that. In the electrolytic solution of the present invention, if the specific resistance is substantially the same as that of the conventional example, it is possible to use another solute that improves the withstand voltage by 10 V or more and lowers the withstand voltage.
なお、本発明は、上述の実施例に限定されるものではなく、先に例示した各種溶質を単独または複数溶解した電解液や、その他添加剤を加えた電解液、副溶媒を混合した電解液でも上記の実施例の場合と同等の効果があった。 In addition, this invention is not limited to the above-mentioned Example, The electrolyte solution which mix | blended the various solutes illustrated previously individually or severally, the electrolyte solution which added the other additive, and the electrolyte solution which mixed the subsolvent However, there was an effect equivalent to the case of the above embodiment.
Claims (5)
［但し、上式中のＡＯは、オキシエチレン、オキシプロピレン、オキシブチレン、オキシテトラメチレン基であり、Ｒは炭素数１〜１８の炭化水素基であり、ｎは１〜５０の整数である。］
で表されることを特徴とする請求項１記載の電解コンデンサの駆動用電解液。 The unsaturated monomer is represented by the following general formula (1):
[However, AO in the above formula is an oxyethylene, oxypropylene, oxybutylene, or oxytetramethylene group, R is a hydrocarbon group having 1 to 18 carbon atoms, and n is an integer of 1 to 50. ]
The electrolytic solution for driving an electrolytic capacitor according to claim 1, wherein
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