• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    PURPOSE: An aluminum electrolytic condenser is provided to elevate reliability by preventing the transformation of the appearance despite of long use at high temperature and the degradation of property and by eliminating an ignition point. CONSTITUTION: An electrolytic condenser contains 20-90wt% of moisture content of electrolyte. Herein, the electrolyte contains at least one of compounds selected from ammonium formate, ammonia lactate, ammonium glycol, ammonium oxalate, ammonium succinate, ammonium malonic acid, ammonium adipate, ammonium benzoate, ammonium glutaric acid, and ammonium azelaic acid as main electrolyte. And, the electrolyte includes more than 1wt% of compound selected from organic carboxyl acid of a certain structure and ammonium chloride thereof. The condensing point of the electrolyte is under 10°C below zero point. The content of chlorine in the sealing agent of the condenser is under 300ppm to the weight of the sealing agent. The electrolytic condenser is formed by interposing a separator(4) between an anode foil(2) and a cathode foil(3) for impregnating electrolyte for driving. Then, the separator is inserted into an aluminum case(5) for sealing the aperture of the aluminum case by using a rubber sealing agent(6).
    公开号:KR20000029050A
    申请号:KR1019990044421
    申请日:1999-10-13
    公开日:2000-05-25
    发明作者:쯔바키유이찌로；마쯔우라히로유키；모로쿠마무네히로；미나토코이찌로；닛타유키히로
    申请人:모리시타 요이찌；마쯔시다덴기산교 가부시키가이샤；
    IPC主号:
    专利说明:

    Aluminum electrolytic condenser
    The present invention relates to a highly reliable aluminum electrolytic capacitor (hereinafter referred to as an electrolytic capacitor) that is excellent in low-temperature characteristics using an electrolyte of a non-flash point and has little appearance change and deterioration in characteristics even when used for a long time at a high temperature.
    As shown in FIG. 1, the conventional electrolytic capacitor is wound around the separator foil 4 such as Manila hemp and kraft paper between the positive electrode foil 2 and the negative electrode foil 3, and the driving electrolyte solution. After impregnating (hereinafter referred to as electrolyte solution) and inserting it into the aluminum case 5, the opening of the aluminum case 5 is sealed by a sealing member 6 made of rubber. The positive electrode foil 2 is a dielectric layer formed by anodizing after surface enlargement (roughening) the aluminum foil by etching.
    The electrolyte is in close contact with the roughened positive electrode 2 to generate an electrostatic capacity. In addition, since the electrolyte solution can repair the dielectric layer of the aluminum oxide film by its carrying capacity, it is responsible for maintaining a low leakage current. In addition, among the properties of the electrolyte, the electrical conductivity has a great influence on the impedance performance of the electrolytic capacitor.
    In view of the above, the low-pressure and low-impedance electrolytic capacitors having a guaranteed temperature of 105 ° C. or higher and a rated voltage of 100 V or lower, and γ-butylolactone excellent in low temperature characteristics and chemical conversion are used as solvents. A stable electrolyte has been used even at a high temperature with high electrical conductivity using a quaternary ammonium salt as an electrolyte. (See Japanese Patent Application Laid-Open No. 62-145713 and Japanese Patent Application Laid-Open No. 62-145715)
    However, when the electrolytic capacitor using the electrolyte solution which melt | dissolved the quaternary ammonium salt of phthalic acid or maleic acid in the said (gamma)-butyrolactone solvent is used for continuous energization in an environment with high humidity, a strong alkali compound is produced | generated at a negative electrode part. In particular, this strong alkaline compound erodes the cathode lead and the sealing material 6 in contact with it, so that there is a problem that an electrolyte solution leaks outside the capacitor.
    In order to avoid such a problem, it is effective to use an electrolyte solution having low alkali compound generation, that is, an electrolyte solution containing ethylene glycol and water as a solvent and an ammonium salt such as ammonium adipic acid as an electrolyte.
    In addition, since the electrolyte solution using the γ-butyrolactone solvent has a flash point around 100 ° C, there is no assertion that there is no risk of ignition even when the electrolyte is ejected due to abnormal operation of the electronic device.
    On the other hand, in a low pressure electrolytic capacitor having a guaranteed temperature of 85 ° C. and a rated voltage of 100 V or less, a mixed solvent of ethylene glycol and water is used as a solvent of an electrolyte solution, and an electrolyte solution containing ammonium salts such as ammonium adipic acid as an electrolyte is used. Can be. Water is added for the purpose of increasing the electrical conductivity. In electrolytic capacitors using this type of electrolyte, it is difficult to maintain long-term electrical performance at temperatures above the boiling point (100 ° C.) of water, which is one of the solvent components. For example, in a rated voltage application test with a temperature of 110 ° C., a large amount of hydrogen gas generated as a result of the reaction between aluminum and water is generated. Due to this increase in internal pressure, the safety valve at the bottom of the aluminum case may operate. Moreover, in the no load leaving test at a temperature of 110 ° C., inconveniences such as the rate of change of the leakage current value after the test exceeded + 5000% occurred within 1000 hours.
    In order to solve these problems, a method of adding various phosphorus compounds to the electrolyte for the purpose of suppressing the reaction between the electrode foil and water, or adding various nitro compounds for the purpose of absorbing the generated hydrogen gas. And the like have been proposed. Even if these methods were used, it was difficult to maintain the electrical performance of the capacitor for a long time at a temperature of 100 ° C. or more using a high moisture content electrolyte solution having a water content of more than 20% in a capacitor having a rated voltage of 100 V or less.
    In addition, when the electrolyte having a high conductivity of 20% or more is used for a long time at a temperature of 100 ° C or more, chlorine in the sealing rubber, which has not been a problem in the electrolyte having a low moisture content of less than 20%, becomes a problem. That is, in the long-term high temperature load test, corrosion of the anode aluminum lead occurs, and as a result, leakage current may increase or lead to corrosion disconnection of the anode aluminum lead.
    An object of the present invention is to solve such a conventional problem and to provide a highly reliable electrolytic capacitor.
    1 is a partially cutaway perspective view showing the configuration of an electrolytic capacitor including an embodiment of the present invention.
    [Explanation of symbols on the main parts of the drawings]
    2: anode foil 3: cathode foil
    4: Separator 5: Aluminum Case
    6: sewing materials
    The electrolytic capacitor of the present invention has a water content of 20 to 90 wt%, and the electrolyte solution is ammonium formate, ammonium acetate, ammonium lactate, ammonium glycolate, ammonium oxalate, ammonium succinate, ammonium malonate, ammonium adipic acid or ammonium benzoate. Containing at least one compound selected from ammonium glutarate and ammonium azelaate as the main electrolyte, and also trimethyladipic acid, 1,6-decanedicarboxylic acid, sebacic acid, 1,7-octanedicarboxylic acid, butyloctane Dicarboxylic acid, 3-tert-butyladipic acid, 3-tert-octylhexanoic acid, 3-n-dodecylhexanoic acid, free carboxylic acid represented by (Compound 1), free carboxylic acid represented by (Compound 2) Or 1 wt% or more of at least one compound selected from the ammonium salts of these organic acids.
    (Compound 1)
    Provided that R 2 is a lower alkyl group, R 1 is a hydrogen atom, or
    (Compound 2)
    Provided that R 3 and R 4 are lower alkyl groups and R 5 is a phenyl group
    The electrolyte solution of the present invention does not have a flash point and has a freezing point of -10 deg. In the electrolytic capacitor of the present invention, the chlorine content of the sealing material is 300 ppm or less with respect to the weight of the sealing material, and the impedance ratio of -10 ° C and 100 Hz to the impedance at 20 ° C and 100 Hz is 4 or less. will be. According to the present invention, it is possible to realize an aluminum electrolytic capacitor having a rated voltage of 100 V or less, which is high in reliability and has a low risk of ignition even when an electrolyte is ejected, and excellent in impedance performance and low temperature characteristics.
    EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described.
    The electrolytic capacitor of the present invention is impregnated with an electrolytic solution in a condenser element formed by winding a cathode aluminum foil and a cathode aluminum foil having a dielectric layer made of aluminum oxide on the surface with a separator therebetween, and then stored in an aluminum case. The opening of the aluminum case is sealed with a sealing material and closed.
    The moisture content of electrolyte solution which concerns on this invention is 20-90 wt%. The electrolyte solution contains at least one compound selected from ammonium formate, ammonium acetate, ammonium lactate, ammonium glycolate, ammonium oxalate, ammonium succinate, ammonium malonate, ammonium adipic acid, ammonium benzoate, ammonium glutarate, and ammonium azelaate. It contains as a "main electrolyte", and also trimethyl adipic acid, 1,6-decanedicarboxylic acid, sebacic acid, 1,7-octanedicarboxylic acid, butyloctanedicarboxylic acid, 3-tert- butyladipic acid, 3-tert At least one compound selected from -octylhexanoic acid, 3-n-dodecylhexanoic acid, an organic carboxylic acid represented by (Compound 1), an organic carboxylic acid represented by (Compound 2), or an ammonium salt of these organic acids (hereinafter, Reaction inhibitors) 1 wt% or more. In addition, the electrolyte solution of the present invention does not have a flash point, and the solidification point of the driving electrolyte is -10 deg.
    The electrolytic capacitor of the present invention has a rated voltage of 100 V or less, and an impedance ratio of -10 ° C. and 100 Hz to an impedance at 20 ° C. 100 Hz is 4 or less.
    Moreover, in the range whose water content of electrolyte solution is less than 20%, electrical conductivity in low temperature is inadequate. For this reason, since the impedance ratio of -10 degreeC and 100 Hz to the impedance in 20 degreeC and 100 Hz is more than 4, it is unpreferable. Moreover, in the range whose moisture content exceeds 90%, the solidification point of electrolyte solution may become temperature higher than -10 degreeC. For this reason, although the impedance performance at 20 degreeC mentioned above can be ensured, since the guaranteed temperature range in the low temperature side of a capacitor becomes more than -10 degreeC and a guarantee range becomes narrow, it is not preferable.
    In addition, the reaction inhibitor is adsorbed on the surface of the electrode foil to inhibit the reaction with water, and in particular, the effect in the state of high temperature speed load is large. Moreover, since the effect of anodic foil protection becomes extremely weak in the content rate of these organic carboxylic acid components being 1 weight% or less, it is unpreferable.
    Moreover, the amount of chlorine contained in the sealing material of this invention is 300 ppm or less with respect to the sealing material weight. If the chlorine content of the condenser is composed of a sealing material of more than 300 ppm relative to the weight of the sealing material, the chloride extracted from the sealing rubber dissociates into ions when the rated voltage test is performed at a temperature of 100 ° C or higher. As a result, the anode aluminum lead is corroded under high temperature, which is not preferable.
    In addition, the electrolytic capacitor of the present invention has a valve expansion amount of +1 mm in the bottom portion of the aluminum casing within 1000 hours in a rated voltage load and a no-load standing test at a temperature of 100 ° C. or higher. In addition, the rate of change of the leakage current value within 1000 hours of the no-load standing test at 100 ° C or higher is within + 5000% of the initial leakage current value. When the expansion ratio of the leakage current value in the aluminum casing bottom portion of 1 mm or more and within 1000 hours of no load unloading test becomes + 5000% or more, it is not preferable because it causes a significant change in product appearance and characteristics.
    Hereinafter, the specific material and compounding ratio of this invention are demonstrated.
    The electrolyte solution according to the present invention contains an organic solvent composed of one or more selected from alcohols, polyhydric alcohols, polyethylene glycols, copolymers of ethylene oxide and propylene oxide, and contains a main electrolyte, a reaction inhibitor, an alkyl phosphate ester, and a tea. 0.01 wt% or more of at least one phosphorus compound selected from phosphorous acid, pyrophosphoric acid and salts thereof, and also contains p-nitrophenol, m-nitrophenol, o-nitrophenol, p-nitrobenzoic acid, m-nitrobenzoic acid, It contains 0.01 wt% or more of one or more nitro compounds selected from o-nitrobenzoic acid, p-nitroanisole, m-nitroanisole and o-nitroanisole.
    As a specific example of the solvent used, Alcohols [monohydric alcohol (butyl alcohol, diacetone alcohol, benzo alcohol, amino alcohol, etc.); Dihydric alcohols (ethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol , 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, hexylene glycol, phenyl glycol and the like); Trihydric alcohols (glycerine, polyglycerol, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 1,2,6-hexanetriol, 3-methylpentane-1,3,5-triol, etc. Hexitol, etc.], Ethers (monoether (ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monophenyl ether, etc.)); Diethers (ethylene glycol dimethyl ether), ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc.), copolymers of ethylene oxide and propylene oxide, and mixtures of two or more thereof. Can be mentioned. Of these, ethylene glycol having high solubility in various solutes and excellent in temperature characteristics is preferable.
    When the reaction ratio of the reaction inhibitor of the electrolyte solution is ethylene glycol as a solvent, the ratio of the total content of the reaction inhibitor to the main electrolyte is in the range of 0.05 or more and less than 5.0, and the total content of the main electrolyte and the reaction inhibitor It is preferable that the composition is 10 wt% or more with respect to the weight of the electrolyte solution. In the above composition range, the electrode foil of these compounds can be adsorbed with their respective functions to suppress the hydration reaction between the electrode foil and water without impairing the capacitor characteristics.
    In addition, by incorporating 0.01 wt% or more of one or more phosphorus compounds selected from alkyl phosphate esters, hypophosphorous acid, pyrophosphoric acid and ammonium salts thereof in the electrolyte solution, these compounds are adsorbed onto the electrode foil, without damaging the capacitor characteristics. Suppress the reaction of gourd and water. From p-nitrophenol, m-nitrophenol, o-nitrophenol, p-nitrobenzoic acid, m-nitrobenzoic acid, o-nitrobenzoic acid, p-nitroanisole, m-nitroanisole and o-nitroanisole At least one nitro compound to be selected plays a role of hydrogen gas absorption by reducing the nitro group.
    The phosphorus compound is particularly adsorbed on the negative electrode foil, but the nitro compound further enhances the adsorption effect of the reaction inhibitor on the negative electrode foil. As a result of these, the nitro compound can efficiently increase the protective effect against water of the negative electrode foil. At this time, the concentration of the nitro compound is preferably 0.01 wt% or more with respect to the electrolyte, and below 0.01 wt% impairs the combined effect.
    In addition, the electrolytic capacitor of the present invention has at least one compound selected from alkyl phosphate esters, hypophosphorous acid, pyrophosphoric acid, salts thereof, or a silicon compound of the general formula (Compound 6) on either the separator or the electrode foil. The silane coupling agent and the alkoxysilane adhered.
    (Compound 6)
    Examples of the silicone compound include hydroxy-modified silicon, amino-modified silicon, carboxyl-modified silicon, alcohol-modified silicon, and reactive silicon which is epoxy-modified silicon. Specific examples of X 1 to X 6 of the silicone compound represented by General Formula (Compound 6) include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, alkenyl groups such as vinyl group and allyl group, phenyl group and naphthyl group Hydrocarbon groups such as aralkyl groups such as aryl group, benzyl group and phenethyl group, oxyhydrocarbon group or hydroxyl group such as methoxy group, ethoxy group, propoxy group, butoxy group, vinyloxy group, phenoxy group and benzyloxy group Can be mentioned. As another example, aliphatic carboxyl groups, such as a methyl carboxyl group, an ethyl carboxyl group, and a propyl carboxyl group, etc. are mentioned. Moreover, amino hydrocarbon groups, such as a methylamine group, an ethylamine group, a propylamine group, and a phenylamine group, etc. are mentioned. The silicon compound to be used is not limited to the above, and may be a general reactive silicone compound.
    As the silane coupling agent, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane and N-β (aminoethyl) γ-aminopropyltrie Oxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxysilane), β- (3,4-ethoxycyclohexyl) ethyl Trimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ -Aminopropyl triethoxysilane, N-phenyl- (gamma)-aminopropyl trimethoxysilane, (gamma)-mercaptopropyl trimethoxysilane, etc. are mentioned. Examples of the alkoxysilane include tetramethoxysilane and tetraethoxysilane.
    Examples of the phosphorus compound (alkyl phosphate ester) that can be used in the present invention include monomethyl phosphate ester, monoethyl phosphate ester, monopropyl phosphate ester, monobutyl phosphate ester, monohexyl phosphate ester, monooctyl phosphate ester, monodecyl phosphate ester, Dimethyl Phosphate, Diethyl Phosphate, Dipropyl Phosphate, Dibutyl Phosphate, Dihexyl Phosphate, Dioctyl Phosphate, Didecyl Phosphate, Trimethyl Phosphate, Triethyl Phosphate, Tripropyl Phosphate, Tributyl Phosphate There is at least one alkyl phosphate ester selected from phosphate ester, trihexyl phosphate ester, trioctyl phosphate ester and tridecyl phosphate ester.
    According to the configuration of the present invention, it is easier to distribute the phosphorus compound and the silicon compound to the center of the element as compared to the case where the electrolyte containing the same kind of phosphorus compound and the silicon compound is impregnated in the roll type capacitor element simply. It becomes possible. For this reason, since the fall of the capacitance by the hydration of electrode foil, and the grade of hydrogen gas generation can be improved further, a more reliable capacitor | condenser can be comprised.
    On the other hand, according to the conventional manufacturing method of simply impregnating an electrolytic solution containing a phosphorus compound in advance in a roll type capacitor element, the phosphorus additive and the silicon compound do not sufficiently spread to the center of the element, resulting in uneven distribution. As a result, the electrolytic capacitor by the conventional manufacturing method produces the deterioration of the electrode foil by hydration.
    If the adhesion amount of the phosphorus compound and the silicon compound to the separator is less than 5.0 mg / g per unit weight of the separator, the hydration deterioration inhibitory effect is not sufficient, which is not preferable. In addition, in the range where the adhesion amount exceeds 50.0 mg / g per unit weight of the separator, the permeability of the electrolyte solution to the separator is lowered due to the influence of the hydrophobic long chain alkyl chain of the phosphorus compound. It is not preferable because the impedance of the capacitor becomes large.
    Moreover, when the adhesion amount of the said phosphorus compound and a silicon compound to electrode foil is less than 0.5 mg / g per unit weight of electrode foil, since the hydration deterioration suppression effect is not enough, it is unpreferable. Moreover, in the range whose adhesion amount exceeds 5.0 mg / g per unit weight of electrode foil, since the resistance component of electrolyte solution / electrode foil interface becomes large and the impedance of a capacitor becomes large, it is unpreferable. In the case of the negative electrode foil, the same effect can be exhibited in both the chemical conversion and the fine chemical, but in order to further increase the reliability, it is preferable to perform chemical conversion treatment of about 1 to 2 V on the negative electrode.
    As the sealing material of the present invention, isobutylene isoprene rubber, ethylene propylene terpolymer and mixtures thereof are used. The hardness of the sealing material is preferably 65 to 100 IRHD (International Rubber Hardness Unit). If the hardness of the sealing material is less than 65 IRHD, even in a capacitor with less gas generation, it is not preferable because the appearance deformation of the condenser occurs or the sealing rubber sticks out at a temperature exceeding 100 ° C. This is due to vaporization of moisture contained in the electrolyte solution. Moreover, when hardness exceeds 100 IRHD, rubber | gum becomes weak and it is unpreferable since inconvenience, such as a crack generate | occur | produces in rubber | gum, arises during a test. In addition, when the silicon compound is contained inside the sealing material or adhered to the surface, the corrosion reaction of the anode lead can be suppressed in particular. Moreover, since the evaporation of the solvent in electrolyte solution can be suppressed, the fall of a capacitance can be suppressed.
    Next, the present invention will be described with reference to specific examples.
    Table 1 shows the amount of phosphorus or silicon compound attached to the separator used in Embodiments 1 to 25 and Comparative Examples 1 to 8 of the present invention, the amount of phosphorus or silicon compound attached to the electrode foil used, the amount of chlorine contained in the used sealing material, the hardness and surface of the sealing material. The treated silicon compound, the thickness of the bottom surface of the aluminum case and the inner surface of the aluminum case are indicated.
    As the sealing rubber, one having a hardness (IRHD) of 70 and a chlorine content of 100 ppm was used. For comparison, as Comparative Example 8, 100 mg / g of ammonium hypophosphite adhered to the separator was also tested.
    The flash point of the electrolyte solution of Embodiments 1-25 of this invention was measured by the Cleveland opening method, As a result, these electrolyte solution did not have a flash point in the temperature range of 128 degreeC-134 degreeC. Moreover, when the electrolyte solution of Embodiments 1-25 of this invention was left to stand for 24 hours in -30 degreeC low temperature thermostat, the change of the property of electrolyte solution was not confirmed. This experiment also confirmed that the solidification point of the electrolyte solution was -10 ° C or lower.
    In addition, the chemical formulas of the compounds 7 to 14 shown in Table 1 are shown in separate sheets.
    Impedance ratio of -10 degreeC / 100 Hz with respect to the impedance in 20 degreeC / 100 Hz of the electrolytic capacitor comprised using the electrolyte solution of Embodiments 1-25 and Comparative Examples 1-8 of Table 2-Table 5, The expansion of the bottom surface of the product, the rate of change of leakage current, the amount of solvent permeated from the sealing rubber, the corrosiveness of the anode aluminum lead, and the sealing rubber after the rated voltage for 1000 hours at 110 ° C and no load unloading test. The aluminum electrolytic capacitors provided in this test are of two types: rated voltage of 6.3 V-capacitance 560 μF (size: ø8 x 11 L) and rated voltage of 50 V-capacitance of 1500 μF (size: ø16 x 35.5 L).
    In addition, phosphorus compounds or silicone compounds of any concentration for the adhesion treatment of the phosphorus compound or the silicon compound of the separator (manila hemp fiber material), electrode foil and sealing rubber (resin vulcanized isobutylene isopropylene rubber [butyl rubber]) The separator, electrode foil, and sealing rubber were immersed in an aqueous solution of, and then dried at 100 ° C. for 1 hour. In addition, the amount of chlorine in the sealing rubber is measured by a total chlorine analyzer (product number: TS × 10) manufactured by Mitsubishi Chemical Co., Ltd. in Japan, and converted into the amount of chlorine per weight of the sealing rubber. did.
    From the results of Tables 2 to 5, the aluminum electrolytic capacitor of the present invention has a low impedance ratio, a small rate of change in the amount of expansion (L value change) and a leakage current value at the bottom of the aluminum case even in a life test at 110 ° C. It can be seen that there is no corrosion of anodized aluminum lead or sticking out of sealing rubber.
    As described above, the electrolytic capacitor of the present invention has an impedance ratio of -10 ° C and 100 mA to an impedance at 20 ° C and 100 mA of 4 or less, and a rated voltage at a temperature of 100 ° C or more and 1000 hours of unloading test. The valve expansion amount of the bottom part of the aluminum casing at +1 mm or less. Moreover, the ratio of the leakage current value within 1000 hours to the initial leakage current value at 100 ° C or more to the initial leakage current value is less than + 5000%, and there is little change in appearance and deterioration even when used for a long time at high temperature. In addition, since the electrolyte has excellent low temperature characteristics and a high water content, the safety valve operates because an abnormal voltage or reverse voltage is applied to the aluminum electrolytic capacitor due to abnormal operation of the electronic device, and the risk of ignition is small even when the electrolyte is ejected. Therefore, according to the present invention, an aluminum electrolytic capacitor having a rated voltage of 100 V or less, which is highly reliable, has excellent impedance performance and low temperature characteristics.



    [Compound 7]
    [Compound 8]
    [Compound 9]
    [Compound 10]
    Compound 11
    Compound 12
    Compound 13
    Compound 14
    权利要求:
    Claims (17)
    [1" claim-type="Currently amended] The water content of the driving electrolyte is 20 to 90 wt%, and the driving electrolyte is ammonium formate, ammonium acetate, ammonium lactate, ammonium glycolate, ammonium oxalate, ammonium succinate, ammonium malonate, ammonium adipic acid, ammonium benzoate or glue. It contains at least one compound selected from ammonium tartrate and ammonium azelaate as the main electrolyte, and also trimethyladipic acid, 1,6-decanedicarboxylic acid, sebacic acid, 1,7-octanedicarboxylic acid, butyloctanedicarboxylic acid , 3-tert-butyladipic acid, 3-tert-octylhexanoic acid, 3-n-dodecylhexanoic acid, an organic carboxylic acid represented by formula 1, an organic carboxylic acid represented by formula 2, or an ammonium salt of these carboxylic acids An aluminum electrolytic capacitor, characterized by containing 1 wt% or more of at least one compound selected.
    Structural Formula 1
    Provided that R 2 is a lower alkyl group, R 1 is a hydrogen atom, or

    Structural Formula 2
    With the proviso that R 3 and R 4 are lower alkyl groups and R 5 is a phenyl group.
    [2" claim-type="Currently amended] The content of the main electrolyte and the organic carboxylic acid or at least one compound selected from the ammonium salts thereof is in the range of 0.05 or more and less than 5.0, and the main electrolyte and the organic An aluminum electrolytic capacitor, wherein a driving electrolyte is used in which the total content of at least one compound selected from carboxylic acids or ammonium salts thereof is 10 wt% or more based on the weight of the electrolyte.
    [3" claim-type="Currently amended] 2. The driving electrolyte according to claim 1, wherein the driving electrolyte contains one or more organic solvents selected from polyhydric alcohols, polyglycerols, polyethylene glycols, copolymers of ethylene oxide and propylene oxide, and also alkyl phosphate esters and teas. Containing at least 0.01 wt% of at least one phosphorus compound selected from phosphorous acid, pyrophosphoric acid and salts thereof, and also contains p-nitrophenol, m-nitrophenol, o-nitrophenol, p-nitrobenzoic acid, m-nitrobenzoic acid, An aluminum electrolytic capacitor, characterized in that it contains 0.01 wt% or more of one or more nitro compounds selected from o-nitrobenzoic acid, p-nitroanisole, m-nitroanisole, and o-nitroanisole.
    [4" claim-type="Currently amended] 4. The alkyl phosphate ester according to claim 3, wherein the alkyl phosphate ester is at least one compound selected from monoalkyl phosphate esters, dialkyl phosphate esters and trialkyl phosphate esters, wherein the alkyl chains per molecule have 3 to 36 carbon atoms. Aluminum electrolytic capacitor
    [5" claim-type="Currently amended] The method of claim 4, wherein the alkyl phosphate ester is monomethyl phosphate ester, monoethyl phosphate ester, monopropyl phosphate ester, monobutyl phosphate ester, monohexyl phosphate ester, monooctyl phosphate ester, monodecyl phosphate ester, dimethyl phosphate ester, Diethyl Phosphate, Dipropyl Phosphate, Dibutyl Phosphate, Dihexyl Phosphate, Dioctyl Phosphate, Didecyl Phosphate, Trimethyl Phosphate, Triethyl Phosphate, Tripropyl Phosphate, Tributyl Phosphate, Tri An aluminum electrolytic capacitor, characterized in that at least one compound selected from hexyl phosphate ester, trioctyl phosphate ester, and tridecyl phosphate ester.
    [6" claim-type="Currently amended] An aluminum electrolytic capacitor characterized by adhering one or more compounds selected from alkyl phosphate esters, hypophosphorous acid, prophosphoric acid or salts thereof, and silicone compounds, silane coupling agents, or alkoxysilanes represented by the following structural formulas to the separator.

    Provided that X 1 , X 5 and X 6 are alkyl groups, alkenyl groups, allyl groups, aralkyl groups, X 2 , X 3 and X 4 are alkyloxy groups or hydroxyl groups.
    [7" claim-type="Currently amended] 7. The aluminum electrolytic capacitor according to claim 6, wherein the adhesion amount of the compound is 5.0 to 50.0 mg / g per unit weight of the separator.
    [8" claim-type="Currently amended] An aluminum electrolytic capacitor, comprising at least one of aluminum foil and cathode aluminum foil attached with at least one compound selected from alkyl phosphate esters, hypophosphorous acid, pyrophosphoric acid or salts thereof, silicone compounds represented by the following structural formulas, and alkoxysilanes. .

    Provided that X 1 , X 5 and X 6 are alkyl groups, alkenic, allyl groups, aralkyl groups, X 2 , X 3 and X 4 are alkyloxy groups or hydroxyl groups.
    [9" claim-type="Currently amended] 9. The aluminum electrolytic capacitor according to claim 8, wherein the adhesion amount of the compound is 0.5 to 5.0 mg / g per unit weight of the electrode foil.
    [10" claim-type="Currently amended] The aluminum electrolytic capacitor according to claim 1, wherein the sealing material is composed of isobutylene isoprene rubber, ethylene propylene terpolymer and mixtures thereof, and the sealing material has a hardness of 65 to 100 IRHD (International Rubber Hardness Unit).
    [11" claim-type="Currently amended] The aluminum electrolytic capacitor according to claim 10, wherein the chlorine content of the sealing material is 300 ppm or less with respect to the weight of the sealing material.
    [12" claim-type="Currently amended] The aluminum electrolytic capacitor according to claim 10, wherein at least one compound selected from silicone compounds, silane coupling agents, and alkoxysilanes represented by the following structural formulas is contained in the interior of the sealing material or adhered to the surface.

    Provided that X 1 , X 5 and X 6 are alkyl groups, alkenyl groups, allyl groups, aralkyl groups, X 2 , X 3 and X 4 are alkyloxy groups or hydroxyl groups.
    [13" claim-type="Currently amended] An aluminum electrolyte comprising an alkyl phosphate ester, hypophosphorous acid, pyrophosphoric acid or salts thereof, or at least one compound selected from a silicone compound, a silane coupling agent, or an alkoxysilane represented by the following structural formula attached to an inner surface of an aluminum case. Condenser.

    Provided that X 1 , X 5 and X 6 are alkyl groups, alkenyl groups, allyl groups, aralkyl groups, X 2 , X 3 and X 4 are alkyloxy groups or hydroxyl groups.
    [14" claim-type="Currently amended] The aluminum electrolytic capacitor according to claim 1, wherein the solidification point of the driving electrolyte is -10 deg.
    [15" claim-type="Currently amended] The aluminum electrolytic capacitor according to claim 1, wherein an impedance ratio of -10 ° C and 100 Hz to an impedance at 20 ° C and 100 Hz is 4 or less.
    [16" claim-type="Currently amended] The valve expansion amount of the bottom part of the aluminum case within 1000 hours in the rated voltage load and no load leaving test at a temperature of 100 ° C. or higher is within +1 mm, and 100 ° C. with respect to the initial leakage current value. The aluminum electrolytic capacitor, characterized in that the rate of change of the leakage current value within 1000 hours after the no-load stand-by test is within + 5000%.
    [17" claim-type="Currently amended] The aluminum electrolytic capacitor according to any one of claims 1 to 10, wherein the aluminum case is made of aluminum or an aluminum alloy, and the plate thickness of the bottom portion of the aluminum case is 0.30 mm or more.
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    同族专利:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-10-13|Priority to JP1998-290333
    1998-10-13|Priority to JP29033398
    1999-09-09|Priority to JP25524999A
    1999-09-09|Priority to JP1999-255249
    1999-10-13|Application filed by 모리시타 요이찌, 마쯔시다덴기산교 가부시키가이샤
    2000-05-25|Publication of KR20000029050A
    2004-03-18|Application granted
    2004-03-18|Publication of KR100423196B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP1998-290333|1998-10-13|
    JP29033398|1998-10-13|
    JP25524999A|JP4554012B2|1998-10-13|1999-09-09|Aluminum electrolytic capacitor|
    JP1999-255249|1999-09-09|
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