Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/004—Details
  • H01G9/022—Electrolytes; Absorbents
  • H01G9/035—Liquid electrolytes, e.g. impregnating materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/145—Liquid electrolytic capacitors

Definitions

• the present invention relates to an electrolytic solution for electrolytic capacitors having a high spark voltage and excellent heat resistance in terms of spark voltage and conductivity, and an electrolytic capacitor using the same.
• an organic solvent, an inorganic acid, or a salt thereof dissolved in an organic solvent is used as an electrolytic solution for an electrolytic capacitor.
• Patent Document 1 sulfamic acid, suberic acid, dodecyl phosphate, porous polyimide and the like are known as additives for improving the spark voltage.
• the initial spark voltage was excellent, but it deteriorated as soon as it was used, resulting in poor heat resistance.
• Patent Document 2 discloses a technique using silica colloid particles, which are inorganic oxide colloid particles, in order to improve the spark voltage while maintaining high electrical conductivity.
• the electrolyte containing silica colloidal particles has a problem of short-circuiting because it gels during use, although the initial spark voltage is high.
• Patent Document 3 discloses an electrolytic solution for an electrolytic capacitor containing colloidal silica stabilized with ammonia. Although this electrolytic solution has a certain spark voltage and heat resistance, it has further heat resistance. There was a need for improvement.
• an object of the present invention is to provide an electrolytic solution for an electrolytic capacitor that has a high spark voltage and is excellent in heat resistance at the spark voltage and conductivity, and an electrolytic capacitor using the electrolytic solution.
• an electrolytic salt containing an electrolytic salt containing a nitrogen-containing cation, an acidic colloidal silica, and an electrolytic solution for an electrolytic capacitor containing an organic solvent has an acidic colloidal silica.
• the present invention has found that by agglomerating within a range of a certain average particle size and present as an aggregate in the electrolyte, a high spark voltage is exhibited, and the heat resistance in the spark voltage and conductivity is remarkably improved. It came to complete.
• the present invention provides an electrolytic solution for an electrolytic capacitor containing an electrolyte salt containing a nitrogen-containing cation, acid-type colloidal silica, and an organic solvent, and the acid-type colloidal silica aggregates to form an aggregate.
• the present invention is an electrolytic capacitor using the above electrolytic solution.
• the present invention includes a step of adding ammonia to an aqueous dispersion of acid-type colloidal silica so that the pH is 8 to 11.
• the water is distilled off by heating, and the acid-type colloidal silica is aggregated to obtain an organic solvent dispersion of the acid-type colloidal silica aggregate Process, Mixing an organic solvent dispersion of acid-type colloidal silica aggregates with an electrolyte salt containing a nitrogen-containing cation and an organic solvent; The manufacturing method of the said electrolyte solution for electrolytic capacitors containing these.
• the present invention also relates to an electrolyte for electrolytic capacitors containing an electrolyte salt containing a nitrogen-containing cation and an organic solvent, and adding an aggregate of acid-type colloidal silica having an average particle size of 30 to 200 nm.
• a method for improving a spark voltage or a method for improving heat resistance of an electrolytic solution for an electrolytic capacitor is also referred to.
• the electrolytic solution for an electrolytic capacitor of the present invention has a high spark voltage and excellent heat resistance in terms of spark voltage and conductivity. By using this, a high withstand voltage is maintained over a long period of time even at high temperatures. An electrolytic capacitor that can be obtained can be obtained.
• the acid colloidal silica used in the present invention has an OH group as a surface modifying group.
• the acid type colloidal silica itself (primary particles) preferably has an average particle size of 4 to 100 nm, preferably 10 to 50 nm, and two or more types having different average particle sizes may be used in combination.
• the acid-type colloidal silica used in the present invention is such that primary particles having such an average particle size aggregate to form an aggregate, and the average particle size becomes 30 to 200 nm, more preferably 40 to 150 nm. And particularly preferably 50 to 100 nm.
• a material having such an average particle size By using a material having such an average particle size, a high spark voltage can be obtained, and further aggregation during use can be prevented, so that the electrolytic capacitor has excellent heat resistance in terms of spark voltage and conductivity.
• An electrolytic solution can be obtained.
• the average particle diameter of colloidal silica is a value measured by the method as described in an Example (manufacture example).
• colloidal silica is in the acid form can be determined by, for example, applying an organic solvent dispersion of colloidal silica onto a calcium fluoride tablet and completely evaporating the solvent under vacuum to form a uniform thin film. and then, the thin film of the obtained sample was measured by infrared absorption spectrum method, no peak of ONH 4 groups wavelength 3030cm -1 ⁇ 3330cm -1, a peak of OH groups of wavelength 3700 cm -1 is present Can be confirmed by. Moreover, it can also confirm that there is no Na group in colloidal silica surface modification group by measuring sodium content with an atomic absorption analyzer.
• Such an aggregate of acid-type colloidal silica includes, for example, a step (1) of adding ammonia to an aqueous dispersion of acid-type colloidal silica so that the pH becomes 8 to 11, and an aqueous dispersion of acid-type colloidal silica to which ammonia is added.
• a step (1) of adding ammonia to an aqueous dispersion of acid-type colloidal silica so that the pH becomes 8 to 11, and an aqueous dispersion of acid-type colloidal silica to which ammonia is added After adding an organic solvent to the mixture, heating to distill off the water and coagulating the acid type colloidal silica to obtain an organic solvent dispersion of the acid type colloidal silica aggregate (2),
• the organic solvent dispersion can be obtained by a production method including an electrolyte salt containing a nitrogen-containing cation and a step (3) of mixing with an organic solvent.
• the content of the acid colloidal silica in the aqueous dispersion of the acid colloidal silica in the step (1) is not particularly limited, but is preferably 1 to 70% by mass, for example, and more preferably 5 to 60% by mass.
• Ammonia is added to such an aqueous dispersion of acid-type colloidal silica so as to have a pH of 8-11.
• the organic solvent used in the step (2) the same organic solvents as described later can be used. For example, ethylene glycol, ⁇ -butyrolactone, sulfolane, ethyl isopropyl sulfone, and the like are preferably used.
• the addition amount of the organic solvent is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 1 part by mass of the acid-type colloidal silica.
• the mixture is heated to distill off water and form an aggregate of acid-type colloidal silica.
• the heating temperature is about 40 to 100 ° C., and water is distilled off until the water content is preferably 5% by mass or less, more preferably 3% by mass or less.
• the average particle size of the aggregate of the acid-type colloidal silica can be adjusted by the heating time, and the longer the heating time, the larger the average particle size. Therefore, the heating time is appropriately set so as to be within the above average particle size range. Adjust it.
• the electrolyte solution of the present invention is prepared by mixing the organic solvent dispersion of the acid-type colloidal silica aggregate thus obtained with an electrolyte salt containing a nitrogen-containing cation and an organic solvent according to a conventional method. be able to. Even in the electrolytic solution thus prepared, the acid-type colloidal silica exists as an aggregate.
• a commercially available product such as Snowtex-O (acid type, average particle size of 10 to 20 nm, manufactured by Nissan Chemical Co., Ltd.) can be used as the aqueous dispersion of acid type colloidal silica.
• a solution obtained by adding ammonia to an aqueous dispersion of acid-type colloidal silica so as to have a pH of 8-11 commercially available ammonia-stable colloidal silica, SNOWTEX-N (ammonia stable type, average particle size of 10-20 nm, (Manufactured by Nissan Chemical Co., Ltd.), which can be directly applied to the step (2) as an aqueous dispersion of acid-type colloidal silica to which ammonia has been added.
• the aqueous dispersion of acid-type colloidal silica is replaced with an organic solvent as it is, it does not easily aggregate and is not included in the average particle diameter described above.
• the pH of the aqueous dispersion is once adjusted to 8 to 11, and then the organic solvent is added and then water is distilled off to volatilize the ammonia. Gradually become neutral.
• Colloidal silica is unstable in the vicinity of neutrality and easily aggregates, so that the dispersed colloidal silica aggregates, and an aggregate of acid colloidal silica having the above average particle diameter can be obtained.
• alkali compounds such as dimethylethylamine and trimethylamine other than ammonia, may be used, since it is desirable to remove the alkali compound together with water, ammonia that is easily volatilized is preferable.
• the content of colloidal silica in the electrolytic solution for electrolytic capacitors of the present invention is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, and particularly preferably 0.3 to 10% by mass. It is. If the amount is less than 0.1% by mass, the effect of improving the electrical characteristics of the electrolytic capacitor may be small.
• the electrolyte salt used in the present invention contains a nitrogen-containing cation, and specifically, one or more selected from the group consisting of compounds represented by the following general formulas (1) to (5) Is used.
• the groups R 1 to R 25 are hydrogen, alkyl groups having 1 to 18 carbon atoms, alkoxy groups having 1 to 18 carbon atoms or hydroxyl groups, which may be the same or different, and R Adjacent groups of 1 to R 25 may be linked to form an alkylene group having 2 to 6 carbon atoms.
• X ⁇ is a carboxylate anion or a boron compound anion.
• cation moiety of the compound represented by the general formula (1) include an ammonium cation; a tetramethylammonium cation, a tetraethylammonium cation, a tetrapropylammonium cation, a tetraisopropylammonium cation, a tetrabutylammonium cation, and a trimethylethylammonium cation.
• Triethylmethylammonium cation dimethyldiethylammonium cation, dimethylethylmethoxyethylammonium cation, dimethylethylmethoxymethylammonium cation, dimethylethylethoxyethylammonium cation, trimethylpropylammonium cation, dimethylethylpropylammonium cation, triethylpropylammonium cation, spiro- (1,1 ' -Quaternary ammonium cations such as bipyrrolidinium cation, piperidine-1-spiro-1'-pyrrolidinium cation, spiro- (1,1 ')-bipiperidinium cation; trimethylamine cation, triethylamine cation, tripropyl Amine cation, triisopropylamine cation, tributylamine cation, diethyl
• ammonium cation, tetraethylammonium cation, triethylmethylammonium cation, spiro- (1,1 ′)-bipyrrolidinium cation are superior because they are excellent in improving spark voltage and / or conductivity and heat resistance.
• N-methylpyrrolidine cation, dimethylethylamine cation, diethylmethylamine cation, trimethylamine cation, triethylamine cation, diethylamine cation and the like are preferably used.
• cation moiety of the compound represented by the general formula (2) include tetramethylimidazolium cation, tetraethylimidazolium cation, tetrapropylimidazolium cation, tetraisopropylimidazolium cation, tetrabutylimidazolium cation, 1, 3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1,3-dipropylimidazolium cation, 1,3-diisopropylimidazolium cation, 1,3-dibutylimidazolium cation, 1-methyl-3- Ethyl imidazolium cation, 1-ethyl-3-methyl imidazolium cation, 1-butyl-3-methyl imidazolium cation, 1-butyl-3-ethyl imidazolium cation, 1,2,3
• tetramethylimidazolium cation tetraethylimidazolium cation, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl have high conductivity and are excellent in heat resistance improvement effect.
• -3-Methylimidazolium cation or the like is preferably used.
• cation moiety of the compound represented by the general formula (3) examples include tetramethylimidazolinium cation, tetraethylimidazolinium cation, tetrapropylimidazolinium cation, tetraisopropylimidazolinium cation, and tetrabutylimidazoli.
• tetramethylimidazolinium cation tetraethylimidazolinium cation, 1,2,3-trimethylimidazolinium cation, 1,2,3-triethyl are shown because of their high conductivity and excellent heat resistance improvement effect.
• An imidazolinium cation and a 1-ethyl-3-methylimidazolinium cation are preferably used.
• cation moiety of the compound represented by the general formula (4) include tetramethyl pyrazolium cation, tetraethyl pyrazolium cation, tetrapropyl pyrazolium cation, tetraisopropyl pyrazolium cation, tetrabutyl pyrazo Rium cation, 1,2-dimethylpyrazolium cation, 1-methyl-2-ethylpyrazolium cation, 1,2-diethylpyrazolium cation, 1,2-dipropylpyrazolium cation, 1,2- Dibutylpyrazolium cation, 1-methyl-2-propylpyrazolium cation, 1-methyl-2-butylpyrazolium cation, 1-methyl-2-hexylpyrazolium cation, 1-methyl-2-octylpyra Zorium cation, 1-methyl-2-dodecylpyrazolium cation, 1
• tetramethylpyrazolium cation tetraethylpyrazolium cation, 1,2-dimethylpyrazolium cation, 1,2-diethylpyrazolium cation because of high conductivity and excellent heat resistance improvement effect
• a cation, a 1-methyl-2-ethylpyrazolium cation, etc. are preferably used.
• cation moiety of the compound represented by the general formula (5) include N-methylpyridinium cation, N-ethylpyridinium cation, N-propylpyridinium cation, N-isopropylpyridinium cation, N-butylpyridinium cation, N -Hexylpyridinium cation, N-octylpyridinium cation, N-dodecylpyridinium cation, N-methyl-3-methylpyridinium cation, N-ethyl-3-methylpyridinium cation, N-propyl-3-methylpyridinium cation, N-butyl Examples include -3-methylpyridinium cation, N-butyl-4-methylpyridinium cation, and N-butyl-4-ethylpyridinium cation.
• N-methylpyridinium cation, N-ethylpyridinium cation, N-butylpyridinium cation, N-butyl-3-methylpyridinium cation and the like are preferably used because they exhibit high conductivity and are excellent in heat resistance improvement effect. It is done.
• the anion X ⁇ combined with the cation is a carboxylate anion or a boron compound anion.
• the carboxylic acid anion is an anion of an organic carboxylic acid such as an aromatic carboxylic acid or an aliphatic carboxylic acid, and the organic carboxylic acid may have a substituent.
• Aromatic carboxylic acid anions such as: oxalate anion, malonate anion, succinate anion, glutarate anion, adipate anion, pimelate anion, suberate anion, azelaic acid anion, sebacic acid anion, undecanedioic acid anion, dodecane Diacid anion, tridecanedioic acid anion, tetradecanedioic acid anion, pentadecanedioic acid anion, hexadecanedioic acid anion, 3-tert-butyladipate anion, methylmalonate anion,
• a phthalate anion a maleate anion, a salicylate anion, a benzoate anion, an adipate anion, an azelate anion, a 1,6-decanedicarboxylate anion
• Preferable examples include 3-tert-butyl adipate anion.
• Examples of the boron compound anion include a borate anion, a borodiazelate anion, a borodisalicylate anion, a borodiglycolate anion, a borodilactic acid anion, and a borodisoxalate anion.
• a borate anion, a borodisalicylate anion, a borodiglycolate anion, etc. are preferably used from the point which is excellent in a spark voltage.
• phthalate anion, maleate anion, salicylate anion, benzoate anion, adipate anion, borodisalicylate anion, borodiglycolate anion, etc. are preferably used. High electrical conductivity and excellent heat resistance.
• the compound represented by the general formula (1) is stable over a long period of time, can provide a high spark voltage, and has high heat resistance. Since it is excellent, it is preferably used.
• electrolyte salts used for low and medium pressure electrolytic capacitors include dimethylethylamine phthalate, tetraethylammonium maleate, diethylamine phthalate, spiro- (1,1 ′)-bipyrrolidinium maleate, 1-ethyl phthalate Examples include 3-methylimidazolinium, 1-methyl-2-ethylpyrazolium phthalate, N-butylpyridinium phthalate, and tetramethylimidazolinium phthalate.
• electrolyte salts used for high-voltage electrolytic capacitors include diethylamine azelate, trimethylamine azelate, ammonium azelate, ammonium 1,6-decanedicarboxylate, diethylamine 1,6-decanedicarboxylate, 1,6-decanedicarboxylic acid.
• Trimethylamine, N-methylpyrrolidine borodisalicylate and the like are preferably used.
• the content of the electrolyte salt selected from the group consisting of the compounds represented by the general formulas (1) to (5) in the electrolytic solution for electrolytic capacitors of the present invention is preferably 1 to 70% by mass, and 3 to 60% by mass. More preferred is 5 to 50% by mass. If it is less than 1% by mass, sufficient electrical conductivity may not be obtained, and if it exceeds 70% by mass, the viscosity of the electrolytic solution may be increased and sufficient electrical conductivity may not be obtained.
• Organic solvent used for the electrolytic solution for the electrolytic capacitor can be a protic polar solvent or an aprotic polar solvent, and may be used alone or in combination of two or more.
• Protic polar solvents include monohydric alcohols (methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclobutanol, cyclopentanol, cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols and oxyalcohol compounds ( Ethylene glycol, propylene glycol, glycerin, methyl cellosolve, ethyl cellosolve, methoxypropylene glycol, dimethoxypropanol, etc.).
• monohydric alcohols methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclobutanol, cyclopentanol, cyclohexanol, benzyl alcohol, etc.
• polyhydric alcohols and oxyalcohol compounds Ethylene glycol, propylene glycol, glycerin, methyl cellosolv
• aprotic polar solvents examples include ⁇ -butyrolactone, ⁇ -valerolactone, amides (N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, hexamethylphosphoricamide, etc.), sulfolane (sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane, etc.), chain sulfone (Dimethylsulfone, ethylmethylsulfone, ethylisopropylsulfone), cyclic amide (N-methyl-2-pyrrolidone, etc.), carbonates (ethylene carbonate, propylene carbonate, isobutylene carbonate, etc.), nitrile (acetonitrile, etc.)
• a solvent containing ⁇ -butyrolactone as a main solvent is preferably used.
• the content of ⁇ -butyrolactone in the organic solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.
• the water content in the case of low and medium pressure is specifically preferably 10% by mass or less, more preferably 5.0% by mass or less, and particularly preferably 2.0% by mass or less.
• the solvent used in the electrolytic capacitor for high voltage is preferably one having ethylene glycol as the main solvent, preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more in the organic solvent. .
• it may contain moisture, specifically 10.0% by mass or less, more preferably 5.0% by mass or less. By using such a moisture content, the chemical conversion to the electrode foil is enhanced and a high spark voltage is obtained.
• the electrolytic solution for electrolytic capacitors of the present invention may contain an additive.
• Additives include polyvinyl alcohol, dibutyl phosphoric acid or phosphoric acid compound of phosphorous acid, boric acid, mannit, complex compounds such as boric acid and mannit, sorbit and boric acid and polyhydric alcohols such as ethylene glycol and glycerin And nitro compounds such as o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, o-nitrophenol, m-nitrophenol, and p-nitrophenol.
• the amount of the additive is preferably 0.1 to 10% by mass, more preferably 0.5 to 5.0% by mass. If it is less than 0.1% by mass, a sufficient spark voltage may not be obtained, and if it exceeds 10% by mass, the conductivity may decrease.
• the electrolytic solution of the present invention can be produced by mixing the above essential components and optional components added as necessary according to a conventional method.
• the electrolytic capacitor of the present invention is characterized by using the above-described electrolytic solution for electrolytic capacitors.
• an aluminum electrolytic capacitor will be described as an example.
• An aluminum electrolytic capacitor uses, as an anode electrode, a chemical conversion foil in which an oxide film is formed on a surface of an aluminum foil by anodization as a dielectric, and a cathode electrode is disposed opposite to the anode electrode.
• An electrolytic capacitor is formed by interposing a separator and holding an electrolytic solution therein.
• the conductivity is preferably 5 to 50 mS / cm, more preferably 6 to 30 mS / cm, and particularly preferably 7 to 20 mS / cm.
• the spark voltage is preferably 160 to 400V, more preferably 190 to 350V, and particularly preferably 220 to 300V.
• the electrical conductivity is preferably 1 to 7 mS / cm, more preferably 1.5 to 6 mS / cm, and particularly preferably 2 to 5 mS / cm.
• the spark voltage is preferably 500 to 1000 V, more preferably 550 to 900 V, particularly preferably 600 to 850 V, and further preferably 650 to 800 V.
• the electrolytic capacitor using the electrolytic solution of the present invention has a spark voltage higher than that of the conventional one, and has a high heat resistance with almost no decrease in the spark voltage even under high temperature conditions. That is, colloidal silica is agglomerated in advance to form an agglomerate having a certain average particle diameter, so that it is difficult to agglomerate further during use and gelation can be prevented. Therefore, high spark voltage and spark voltage And heat resistance in electrical conductivity can be obtained.
• Production Example 1 (Preparation of ethylene glycol dispersion of colloidal silica 1) Ammonia is added to 500 parts of a 20% aqueous dispersion adjusted to pH 9.0 by commercially available acid-type colloidal silica (Snowtex-O, manufactured by Nissan Chemical Co., Ltd., average particle size 10-20 nm, surface modifying group is OH group). Thereafter, 400 parts of ethylene glycol was mixed and heated for 3 hours while reducing the pressure at 60 ° C. and 25 Torr to obtain 500 parts of colloidal silica ethylene glycol dispersion. The average particle size of the colloidal silica aggregates in the resulting ethylene glycol dispersion of colloidal silica was measured by the method described below.
• the average particle size of the aggregate (secondary particles) of acid-type colloidal silica was 36 nm.
• Production Example 2 An ethylene glycol dispersion of colloidal silica was obtained in the same manner as in Production Example 1 except that the heating time was changed from 3 hours to 3 hours 30 minutes. The average particle size of the aggregate of acid-type colloidal silica was measured in the same manner as in Production Example 1 and found to be 61 nm.
• Production Example 3 An ethylene glycol dispersion of colloidal silica was obtained in the same manner as in Production Example 1 except that the heating time was changed from 3 hours to 4 hours.
• the average particle size of the aggregate of acid colloidal silica was measured in the same manner as in Production Example 1, it was 80 nm.
• Production Example 4 An ethylene glycol dispersion of colloidal silica was obtained in the same manner as in Production Example 1 except that the heating time was changed from 3 hours to 5 hours. When the average particle size of the aggregate of acid-type colloidal silica was measured in the same manner as in Production Example 1, it was 124 nm.
• Production Example 5 An ethylene glycol dispersion of colloidal silica was obtained in the same manner as in Production Example 1 except that the heating time was changed from 3 hours to 6 hours. The average particle size of the aggregate of acid-type colloidal silica was measured in the same manner as in Production Example 1, and it was 168 nm.
• Production Example 6 An ethylene glycol dispersion of colloidal silica was obtained in the same manner as in Production Example 1 except that the heating time was changed from 3 hours to 8 hours. The average particle size of the aggregate of acid-type colloidal silica was measured in the same manner as in Production Example 1 and found to be 198 nm.
• Production Comparative Example 1 400 parts of ethylene glycol is mixed with 500 parts of a 20% aqueous dispersion of acid-type colloidal silica (Snowtex-O, manufactured by Nissan Chemical Industries, average particle size of 10 to 20 nm, surface modifying group is OH group), The mixture was heated for 3 hours while reducing the pressure at 60 ° C. and 25 Torr to obtain 500 parts of an ethylene glycol dispersion of colloidal silica.
• the average particle size of the colloidal silica in the ethylene glycol dispersion of the obtained colloidal silica was measured in the same manner as in Production Example 1, it was 13 nm corresponding to the average particle size of the primary particles of the acid-type colloidal silica and was agglomerated. It was confirmed that there was no.
• Production Comparative Example 2 An ethylene glycol dispersion of colloidal silica was obtained in the same manner as in Production Example 1 except that the heating time was changed from 3 hours to 12 hours. The average particle size of the aggregate of acid-type colloidal silica was measured in the same manner as in Production Example 1 and found to be 247 nm.
• Production Comparative Example 3 Commercially available sodium-stable colloidal silica (Snowtex-20, manufactured by Nissan Chemical Co., Ltd., average particle size 10-20 nm) 20% aqueous dispersion and 500 parts of ethylene glycol are mixed, and the degree of vacuum at 60 ° C. and 25 Torr. The mixture was heated for 3 hours under reduced pressure to obtain 500 parts of colloidal silica ethylene glycol dispersion. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 38 nm.
• Production Comparative Example 4 An ethylene glycol dispersion of colloidal silica was obtained in the same manner as in Production Comparative Example 3, except that the heating time was changed from 3 hours to 5 hours. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 84 nm.
• Production Comparative Example 5 An ethylene glycol dispersion of colloidal silica was obtained in the same manner as in Production Comparative Example 3, except that the heating time was changed from 3 hours to 9 hours. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 180 nm.
• Example 1 (Preparation of electrolyte 1) After mixing 188 parts (1.0 mol) of azelaic acid and 1670 parts of ethylene glycol as a solvent and stirring, 146 parts (2.0 mol) of diethylamine was dropped to obtain an azelaic acid diethylamine ethylene glycol solution, 223 parts of the colloidal silica ethylene glycol dispersion prepared in Production Example 1 was mixed with stirring to obtain an azelaic acid diethylamine ethylene glycol solution containing colloidal silica (colloidal silica content 2%). When the average particle size of the colloidal silica aggregate in the diethylamine ethylene glycol solution of azelaic acid was measured in the same manner as described above, the average particle size of the aggregate did not change and was 36 nm.
• Examples 2 to 6 Preparation of electrolyte 2-6) An electrolyte solution was prepared in the same manner as in Example 1 except that the ethylene glycol dispersion of colloidal silica in Production Example 1 was replaced with the ethylene glycol dispersion of colloidal silica in Production Examples 2-6. Similarly, the average particle diameter of the colloidal silica aggregate was measured, and it was confirmed that there was no change in the average particle diameter of the aggregate.
• Comparative Example 1 An electrolytic solution was prepared in the same manner as in Example 1 except that the ethylene glycol dispersion of colloidal silica of Production Example 1 was replaced with the ethylene glycol dispersion of colloidal silica of Production Comparative Example 1. Similarly, the average particle diameter of colloidal silica was measured, and it was confirmed that there was no change in the average particle diameter.
• Comparative Example 2 An electrolytic solution was prepared in the same manner as in Example 1 except that the ethylene glycol dispersion of colloidal silica in Production Example 1 was replaced with the ethylene glycol dispersion of colloidal silica in Production Comparative Examples 2 to 5. Similarly, the average particle diameter of the colloidal silica aggregate was measured, and it was confirmed that there was no change in the average particle diameter of the aggregate.
• Test example 1 With respect to the electrolyte solutions obtained in Examples 1 to 6 and Comparative Examples 1 to 5, the electrical conductivity and spark voltage after the initial stage and after the heat resistance test (after 2000 hours at 105 ° C.) were measured by the following measurement methods. The results are shown in Table 1.
• Ethylene glycol 400 was prepared by adding ammonia to 250 parts of a 40% aqueous dispersion of acid-type colloidal silica (Snowtex-O-40, manufactured by Nissan Chemical Co., Ltd., average particle size 20 to 25 nm) and adjusting the pH to 9.0. The components were mixed and heated for 3 hours while reducing the pressure at 60 ° C. and a reduced pressure of 25 Torr to obtain 500 parts of an ethylene glycol dispersion of colloidal silica. The average particle size of the colloidal silica aggregates in the resulting colloidal silica ethylene glycol dispersion was measured in the same manner as in Production Example 1. As a result of measurement, the average particle size of the aggregate (secondary particles) of acid-type colloidal silica was 51 nm.
• Production Example 8 An ethylene glycol dispersion of colloidal silica was obtained in the same manner as in Production Example 7 except that the heating time was changed from 3 hours to 4 hours. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 89 nm.
• Production Example 9 An ethylene glycol dispersion of colloidal silica was obtained in the same manner as in Production Example 7 except that the heating time was changed from 3 hours to 5 hours. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 126 nm.
• Production Example 10 An ethylene glycol dispersion of colloidal silica was obtained in the same manner as in Production Example 7 except that the heating time was changed from 3 hours to 8 hours. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 191 nm.
• Production Comparative Example 6 Mix 400 parts of ethylene glycol with 250 parts of 40% aqueous dispersion of commercially available acid-type colloidal silica (Snowtex-O-40, manufactured by Nissan Chemical Co., Ltd., average particle size 20-25 nm, surface modifying group is OH group). Then, the mixture was heated for 3 hours while reducing the pressure at 60 ° C. and 25 Torr to obtain 500 parts of colloidal silica ethylene glycol dispersion. When the average particle size of the colloidal silica was measured in the same manner as in Production Example 1, it was 24 nm corresponding to the average particle size of the primary particles of acid-type colloidal silica, and it was confirmed that no aggregation occurred.
• Snowtex-O-40 commercially available acid-type colloidal silica
• Production Comparative Example 7 An ethylene glycol dispersion of colloidal silica was obtained in the same manner as in Production Example 1 except that the heating time was changed from 3 hours to 12 hours. The average particle size of the aggregate of acid-type colloidal silica was measured in the same manner as in Production Example 1, and it was 239 nm.
• Production Comparative Example 8 Commercially available sodium stable colloidal silica (Snowtex-50, manufactured by Nissan Chemical Co., Ltd., average particle size 20 to 25 nm) 48% aqueous dispersion 208 parts and ethylene glycol 400 parts are mixed and heated at 60 ° C. for 3 hours. Thus, 500 parts of an ethylene glycol dispersion of colloidal silica was obtained. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 59 nm.
• Production Comparative Example 9 An ethylene glycol dispersion of colloidal silica was obtained in the same manner as in Production Comparative Example 8, except that the heating time was changed from 3 hours to 5 hours. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 120 nm.
• Production Comparative Example 10 An ethylene glycol dispersion of colloidal silica was obtained in the same manner as in Production Comparative Example 8, except that the heating time was changed from 3 hours to 9 hours. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 183 nm.
• Example 7 (Preparation of electrolyte 7) While mixing 230 parts of 1,6-decanedicarboxylic acid (1.0 mol) and 1322 parts of ethylene glycol as a solvent and stirring, 34.1 parts (2.0 mol) of ammonia was added dropwise, and 1,6- A solution of ammonium decanedicarboxylate ethylene glycol was obtained. 176 parts of an ethylene glycol dispersion of colloidal silica prepared in Production Example 7 was mixed with stirring to obtain 1,6-decanedicarboxylic acid ammonium ethylene glycol solution (colloidal silica content 2%) to which colloidal silica was added. It was.
• Examples 8-10 (Preparation of electrolyte 8-1010) An electrolyte solution was prepared in the same manner as in Example 7, except that the ethylene glycol dispersion of colloidal silica in Production Example 7 was replaced with the ethylene glycol dispersion of colloidal silica in Production Examples 8-10. Similarly, the average particle diameter of the colloidal silica aggregate was measured, and it was confirmed that there was no change in the average particle diameter of the aggregate.
• Test example 2 In the same manner as in Test Example 1, the electrolytes obtained in Examples 7 to 10 and Comparative Examples 6 to 10 were measured for electrical conductivity and spark voltage after the initial test and after the heat resistance test (after 2000 hours at 105 ° C.). The results are shown in Table 2.
• Comparative Examples 8 to 10 using an aqueous dispersion of sodium-stable colloidal silica have a small effect of improving the spark voltage even if they are aggregated in the same average particle size range as in the Examples. It can be seen that the decrease in conductivity is significant.
• Production Example 11 (Preparation of ⁇ -butyrolactone dispersion of colloidal silica 1) Ammonia is added to 500 parts of a 20% aqueous dispersion adjusted to pH 9.0 by commercially available acid-type colloidal silica (Snowtex-O, manufactured by Nissan Chemical Co., Ltd., average particle size 10-20 nm, surface modifying group is OH group). Thereafter, 400 parts of ⁇ -butyrolactone was mixed and heated for 3 hours under reduced pressure at 60 ° C. and 25 Torr to obtain 500 parts of a ⁇ -butyrolactone dispersion of colloidal silica.
• Snowtex-O commercially available acid-type colloidal silica
• the average particle size of the colloidal silica aggregate in the resulting colloidal silica ⁇ -butyrolactone dispersion was measured by the following method. As a result of measurement, the average particle size of the aggregate (secondary particles) of acid-type colloidal silica was 42 nm. ⁇ Measuring method of average particle diameter of colloidal silica> The average particle size of the colloidal silica aggregate was measured under the following conditions using Microtrac Nanotrac 150 (manufactured by Nikkiso Co., Ltd., particle size distribution measuring instrument).
• Production Example 12 A ⁇ -butyrolactone dispersion of colloidal silica was obtained in the same manner as in Production Example 11 except that the heating time was changed from 3 hours to 4 hours.
• the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 72 nm.
• Production Example 13 A ⁇ -butyrolactone dispersion of colloidal silica was obtained in the same manner as in Production Example 11 except that the heating time was changed from 3 hours to 5 hours. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 89 nm.
• Production Example 14 A ⁇ -butyrolactone dispersion of colloidal silica was obtained in the same manner as in Production Example 11 except that the heating time was changed from 3 hours to 6 hours.
• the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 138 nm.
• Production Example 15 A colloidal silica ⁇ -butyrolactone dispersion was obtained in the same manner as in Production Example 11 except that the heating time was changed from 3 hours to 8 hours. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 170 nm.
• Production Example 16 A colloidal silica ⁇ -butyrolactone dispersion was obtained in the same manner as in Production Example 11, except that the heating time was changed from 3 hours to 10 hours. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 195 nm.
• Production Comparative Example 11 400 parts of ⁇ -butyrolactone is mixed with 500 parts of a 20% aqueous dispersion of acid-type colloidal silica (Snowtex-O, manufactured by Nissan Chemical Co., Ltd., average particle size 10-20 nm, surface modifying group is OH group). The mixture was heated at 60 ° C. under a reduced pressure of 25 Torr for 3 hours to obtain 500 parts of colloidal silica ⁇ -butyrolactone. When the average particle size of the colloidal silica was measured in the same manner as in Production Example 1, it was 13 nm corresponding to the average particle size of the primary particles of acid-type colloidal silica, indicating that no aggregation occurred.
• Snowtex-O manufactured by Nissan Chemical Co., Ltd., average particle size 10-20 nm, surface modifying group is OH group
• Production Comparative Example 12 A colloidal silica ⁇ -butyrolactone dispersion was obtained in the same manner as in Production Example 11, except that the heating time was changed from 3 hours to 12 hours. The average particle size of the aggregate of acid-type colloidal silica was measured in the same manner as in Production Example 1 and found to be 232 nm.
• Production Comparative Example 13 Commercially available sodium stable colloidal silica (Snowtex-20, manufactured by Nissan Chemical Co., Ltd., average particle size 10-20 nm) 20% aqueous dispersion and 400 parts of ⁇ -butyrolactone are mixed, and reduced pressure at 60 ° C. and 25 Torr. The mixture was heated for 3 hours under reduced pressure to obtain 500 parts of a ⁇ -butyrolactone dispersion of colloidal silica. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 39 nm.
• Snowtex-20 manufactured by Nissan Chemical Co., Ltd., average particle size 10-20 nm
• Production Comparative Example 14 A ⁇ -butyrolactone dispersion of colloidal silica was obtained in the same manner as in Production Comparative Example 13, except that the heating time was changed from 3 hours to 5 hours. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 94 nm.
• Production Comparative Example 15 A ⁇ -butyrolactone dispersion of colloidal silica was obtained in the same manner as in Production Comparative Example 13, except that the heating time was changed from 3 hours to 9 hours.
• the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 187 nm.
• Example 11 (Preparation of electrolyte solution 11) While mixing and stirring 166 parts (1.0 mol) of phthalic acid and 838 parts of ⁇ -butyrolactone as a solvent, 73.1 parts (1.0 mol) of dimethylethylamine was added dropwise, and dimethylethylamine phthalate ⁇ -butyrolactone was added. After obtaining the solution, 120 parts of the colloidal silica ⁇ -butyrolactone dispersion prepared in Production Example 11 was mixed with stirring, and dimethylethylamine phthalate ⁇ -butyrolactone solution containing colloidal silica (content of colloidal silica 2 %). The average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, and it was confirmed that there was no change in the average particle size of the aggregate.
• Examples 12-16 (Preparation of electrolyte solution 12-16) An electrolyte solution was prepared in the same manner as in Example 11 except that the colloidal silica ⁇ -butyrolactone dispersion of Production Example 11 was replaced with the colloidal silica ⁇ -butyrolactone dispersion of Production Examples 12-16. Similarly, the average particle diameter of the colloidal silica aggregate was measured, and it was confirmed that there was no change in the average particle diameter of the aggregate.
• Comparative Examples 11-15 An electrolyte solution was prepared in the same manner as in Example 11, except that the colloidal silica ⁇ -butyrolactone dispersion of Production Example 11 was replaced with the colloidal silica ⁇ -butyrolactone dispersion of Production Comparative Examples 11-15. Similarly, the average particle diameter of the colloidal silica aggregate was measured, and it was confirmed that there was no change in the average particle diameter of the aggregate.
• Test example 3 In the same manner as in Test Example 1, the electrolytes obtained in Examples 11 to 16 and Comparative Examples 11 to 15 were measured for electrical conductivity and spark voltage after the initial stage and after the heat resistance test (after 2000 hours at 105 ° C.). The results are shown in Table 3.
• Production Example 17 (Preparation of ⁇ -butyrolactone dispersion of colloidal silica 2) Ammonia was added to 250 parts of a 40% aqueous dispersion of acid-type colloidal silica (Snowtex-O-40, manufactured by Nissan Chemical Co., Ltd., average particle size 20 to 25 nm, surface modifying group is OH group), pH 9.0 After that, 400 parts of ⁇ -butyrolactone was mixed and heated for 3 hours while reducing the pressure at 60 ° C. and a reduced pressure of 25 Torr to obtain 500 parts of a ⁇ -butyrolactone dispersion of colloidal silica.
• Snowtex-O-40 manufactured by Nissan Chemical Co., Ltd., average particle size 20 to 25 nm, surface modifying group is OH group
• the average particle size of the colloidal silica aggregates in the obtained colloidal silica ⁇ -butyrolactone dispersion was measured in the same manner as in Production Example 11. As a result, the average particle size of the acid type colloidal silica aggregates (secondary particles) was measured. The diameter was 53 nm.
• Production Example 18 A colloidal silica ⁇ -butyrolactone dispersion was obtained in the same manner as in Production Example 17 except that the heating time was changed from 3 hours to 4 hours. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 82 nm.
• Production Example 19 A ⁇ -butyrolactone dispersion of colloidal silica was obtained in the same manner as in Production Example 17 except that the heating time was changed from 3 hours to 5 hours.
• the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 131 nm.
• Production Example 20 A ⁇ -butyrolactone dispersion of colloidal silica was obtained in the same manner as in Production Example 17 except that the heating time was changed from 3 hours to 8 hours. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 193 nm.
• Production Comparative Example 16 Commercially available acid-type colloidal silica (Snowtex-O-40, manufactured by Nissan Chemical Co., Ltd., average particle size 20 to 25 nm, surface modifying group is OH group) mixed with 250 parts of 40% aqueous dispersion and 400 parts of ⁇ -butyrolactone The mixture was heated at 60 ° C. under a reduced pressure of 25 Torr for 3 hours to obtain 500 parts of a ⁇ -butyrolactone dispersion of colloidal silica. When the average particle size of the colloidal silica was measured in the same manner as in Production Example 1, it was 24 nm corresponding to the average particle size of the primary particles of the acid-type colloidal silica, indicating that no aggregation occurred.
• Snowtex-O-40 manufactured by Nissan Chemical Co., Ltd., average particle size 20 to 25 nm, surface modifying group is OH group
• Production Comparative Example 17 A ⁇ -butyrolactone dispersion of colloidal silica was obtained in the same manner as in Production Example 17 except that the heating time was changed from 3 hours to 12 hours. The average particle size of the aggregate of acid-type colloidal silica was measured in the same manner as in Production Example 1 and found to be 241 nm.
• Production Comparative Example 18 Commercially available sodium stable colloidal silica (Snowtex-50, manufactured by Nissan Chemical Co., Ltd., average particle size 20 to 25 nm) 48% aqueous dispersion 208 parts and 400 parts of ⁇ -butyrolactone were mixed, and reduced pressure at 60 ° C. and 25 Torr. The mixture was heated for 3 hours under reduced pressure to obtain 500 parts of a ⁇ -butyrolactone dispersion of colloidal silica. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 56 nm.
• Snowtex-50 manufactured by Nissan Chemical Co., Ltd., average particle size 20 to 25 nm
• Production Comparative Example 19 A ⁇ -butyrolactone dispersion of colloidal silica was obtained in the same manner as in Production Comparative Example 18, except that the heating time was changed from 3 hours to 5 hours. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 117 nm.
• Production Comparative Example 20 A ⁇ -butyrolactone dispersion of colloidal silica was obtained in the same manner as in Production Comparative Example 18, except that the heating time was changed from 3 hours to 9 hours. When the average particle size of the colloidal silica aggregate was measured in the same manner as in Production Example 1, it was 196 nm.
• Example 17 (Electrolytic Solution Preparation 17) While mixing and stirring 116 parts (1.0 mol) of maleic acid and 843 parts of ⁇ -butyrolactone as a solvent, 705 parts (1.0 mol) of a 20% aqueous tetraethylammonium hydroxide solution was dropped and reacted. The pressure is reduced at 80 ° C. to obtain a tetraethylammonium hydrogen maleate ⁇ -butyrolactone solution.
• Examples 18-20 (Preparation of electrolyte 18-20) An electrolyte solution was prepared in the same manner as in Example 17 except that the colloidal silica ⁇ -butyrolactone dispersion of Production Example 17 was replaced with the colloidal silica ⁇ -butyrolactone dispersion of Production Examples 18-20. Similarly, the average particle diameter of the colloidal silica aggregate was measured, and it was confirmed that there was no change in the average particle diameter of the aggregate.
• Comparative Examples 16-20 An electrolytic solution was prepared in the same manner as in Example 17 except that the colloidal silica ⁇ -butyrolactone dispersion of Production Example 17 was replaced with the colloidal silica ⁇ -butyrolactone dispersion of Production Comparative Examples 16 to 20. Similarly, the average particle diameter of the colloidal silica aggregate was measured, and it was confirmed that there was no change in the average particle diameter of the aggregate.
• Test example 4 In the same manner as in Test Example 1, the electrolytes obtained in Examples 17 to 20 and Comparative Examples 16 to 20 were measured for electrical conductivity and spark voltage after the initial stage and after the heat resistance test (after 2000 hours at 105 ° C.). The results are shown in Table 4.
• the electrolytic solution of the present invention is extremely useful as an electrolytic solution for electrolytic capacitors because it has a high spark voltage and is excellent in heat resistance in terms of spark voltage and conductivity.

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