JP4739148B2 - Solid electrolytic capacitor - Google Patents

Solid electrolytic capacitor Download PDF

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JP4739148B2
JP4739148B2 JP2006231165A JP2006231165A JP4739148B2 JP 4739148 B2 JP4739148 B2 JP 4739148B2 JP 2006231165 A JP2006231165 A JP 2006231165A JP 2006231165 A JP2006231165 A JP 2006231165A JP 4739148 B2 JP4739148 B2 JP 4739148B2
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electrolytic capacitor
solid electrolytic
acid
layer
formed
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JP2007096284A (en
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勝洋 吉田
剛 戸井田
健男 春日
猛 齋藤
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Necトーキン株式会社
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/54Electrolytes
    • H01G11/56Solid electrolytes, e.g. gels; Additives therein
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/48Conductive polymers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/13Ultracapacitors, supercapacitors, double-layer capacitors

Description

  The present invention relates to a solid electrolytic capacitor, and more particularly to a solid electrolytic capacitor having an improved precoat provided between an oxide film of the solid electrolytic capacitor and a solid electrolyte.

  In recent years, a dielectric oxide film (hereinafter referred to as an anodic oxide film) is formed on a porous body of valve action metal such as aluminum by an anodic oxidation method, and then a conductive polymer layer as a solid electrolyte is formed on the anodic oxide film. The formed solid electrolytic capacitor was developed. In this solid electrolytic capacitor, the conductivity of the solid electrolyte is 10 to 100 times higher than that of a solid electrolytic capacitor using manganese dioxide as a solid electrolyte. Furthermore, this solid electrolytic capacitor can reduce the equivalent series resistance value (hereinafter referred to as ESR), and the high frequency characteristics are greatly improved. Therefore, this type of solid electrolytic capacitor has begun to be used in various electronic devices in order to remove high frequency noise from small devices.

  Increasing the density and speed of electronic components are increasingly demanding smaller and larger capacitors and lower ESR. Corresponding to these, attempts have been made to increase the capacitance per unit area. These attempts have progressed in increasing the etching magnification of an aluminum substrate as a valve action metal, increasing the volumetric efficiency, which is the ratio of the product volume to the volume of the part forming the capacitor, and laminating.

  The inventors of the present application improve the adhesion of the anodized film and the polypyrrole conductive polymer layer, improve the substantial coverage of the conductive polymer on the anodized film, and improve the characteristics of the capacitor. Therefore, Patent Document 1 discloses a method for forming the following solid electrolytic capacitor. In the method of Patent Document 1, first, the surface of the aluminum substrate is roughened by etching. An aluminum dielectric film (anodized film layer) is formed on the surface of the roughened aluminum substrate in an aqueous solution containing ammonium adipate, phosphoric acid, ammonium phosphate or the like to form an anode part. Next, it is immersed in a polystyrene sulfonic acid aqueous solution and dried to form a polystyrene sulfonic acid thin film as a precoat layer on the anodized film surface. Next, the aluminum substrate having the anodized film layer on which the precoat layer is formed is immersed in a solution containing a conductive polymer monomer. Furthermore, it is immersed in a solution of protonic acid, metal halide, peroxide or the like to form a conductive polymer film (internal polymer film layer) such as a polypyrrole film, a polythiophene film, or a polyoxythiophene film. The polypyrrole layer and the polystyrene sulfonic acid precoat layer are reacted to improve the adhesion between the anodized film layer and the polypyrrole layer. Next, a plurality of conductive polymer films (external polymer film layers) such as a polypyrrole film, a polythiophene film, and a polyoxythiophene film are formed on the inner polymer film layer by chemical oxidative polymerization. A graphite layer and a silver paste layer are formed thereon to form a cathode portion.

  By the way, in order to reduce the size and increase the capacity of the solid electrolytic capacitor, it is most effective to improve the coverage ratio. However, as the etching magnification increases, the structure of the porous body becomes more precise and complicated. Thus, there is a demand for a method of expanding the capacitance by improving the covering ratio and lowering the resistance (reducing the ESR value) associated therewith.

  The pre-coating layer of polystyrene sulfonic acid in the solid electrolytic capacitor of Patent Document 1 described above exhibits a great effect for improving the coverage. However, since polystyrene sulfonic acid is a water-soluble polymer compound, the portion reacted with polypyrrole formed thereon is insoluble in water, but the unreacted portion may be dissolved in water. A very small portion of polystyrene sulfonic acid dissolved in water has a strong acidity of pH≈0.5 to 1, has an adverse effect on the anodized film, and has a leakage current (LC) value when used at high humidity. An increase could occur.

JP 2005-159154 A

  SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a solid electrolytic capacitor that eliminates the drawbacks of the prior art and has excellent moisture resistance, small size, large capacity, and low ESR characteristics.

  Another object of the present invention is to provide a method for producing a solid electrolytic capacitor having excellent moisture resistance.

  Yet another object of the present invention is to provide a solid electrolytic capacitor having a transmission line structure with improved moisture resistance.

  Another object of the present invention is to provide a method for manufacturing a solid electrolytic capacitor having a transmission line structure with improved moisture resistance.

  According to the present invention, a roughened aluminum substrate, an anodized film layer formed on the surface of the roughened aluminum substrate, and a polystyrene sulfonate formed on a part of the anodized film layer And a conductive polymer film layer formed as a solid electrolyte on the polystyrene sulfonate layer, the polystyrene sulfonate layer comprising the anodized film layer and the conductive polymer film layer. A solid electrolytic capacitor characterized by being formed in between is obtained.

  According to the present invention, in the solid electrolytic capacitor, the polystyrene sulfonate layer is an amine salt obtained by reacting an amine, an amine and an organic acid in a 0.1 to 10 wt% polystyrene sulfonic acid aqueous solution, It is characterized in that it is formed by adding an ammonium salt of any one of an organic acid and an inorganic acid and at least one of ammonia water, immersing it in an aqueous solution adjusted to a pH value of 2 to 6, and drying it. A solid electrolytic capacitor is obtained.

  According to the present invention, in the solid electrolytic capacitor, the amine is at least one of triethylamine and triethanolamine, and the amine salt is the amine and boric acid, malonic acid, maleic acid, adipic acid, At least one of amine salts obtained by reacting at least one of sebacic acid, dodecanoic acid, citric acid, phthalic acid, terephthalic acid, and pyromellitic acid, and each ammonium salt of the organic acid and inorganic acid Is a solid electrolytic capacitor characterized in that it is at least one of ammonium borate, ammonium adipate, ammonium sebacate, and ammonium dodecanoate.

  According to the present invention, in any one of the solid electrolytic capacitors, after forming the polystyrene sulfonate layer, voltage treatment was performed with an aqueous solution containing an ammonium salt of an organic acid such as adipic acid or citric acid. Thus, a solid electrolytic capacitor can be obtained.

  According to the present invention, in any one of the solid electrolytic capacitors, an anode part composed of the part of the anodized film layer of the aluminum base, and a polystyrene salt on the part of the anodized film. A cathode portion having the conductive polymer layer formed thereon, and comprising an anode terminal connection portion formed in a portion other than the portion of the aluminum base, the cathode portion being the conductive polymer layer A solid electrolytic capacitor having a cathode terminal connection portion formed thereon is obtained.

  Further, according to the present invention, the solid electrolytic capacitor includes a terminal connected to one of the cathode terminal connection portions and one of the anode terminal connection portions, and an encapsulating member made of a synthetic resin or an insulating material. A solid electrolytic capacitor characterized by the above can be obtained.

According to the present invention, in any one of the solid electrolytic capacitors, the solid electrolytic capacitor includes a transmission line element structure, and the transmission line element structure has the rough surface having an anodized film formed on a surface thereof. An anode part included in the central part of the formed aluminum substrate, first and second anode terminal connection parts located on both sides of the anode part, and a part on the anodized film facing the anode part A solid electrolytic capacitor comprising the polystyrene sulfonate layer formed on the surface and the conductive polymer film layer on the polystyrene sulfonate layer is obtained.

  According to the invention, the solid electrolytic capacitor includes a terminal connected to the cathode terminal connecting portion and the first and second anode terminal connecting portions, and an encapsulating member made of a synthetic resin or an insulating material. A solid electrolytic capacitor characterized by that.

Further, according to the present invention, the step of roughening the surface of the aluminum substrate, the step of forming the anodized film layer on the surface of the aluminum substrate, and the polystyrene sulfonate on a part of the anodized film layer There is obtained a method for producing a solid electrolytic capacitor comprising a step of forming a layer and a step of forming a conductive conductive polymer film layer as a solid electrolyte on the polystyrene sulfonate layer.

  According to the present invention, in the method for producing a solid electrolytic capacitor, the step of forming the polystyrene sulfonate layer includes an amine, an amine and an organic acid in a 0.1 to 10 wt% polystyrene sulfonic acid aqueous solution. The aluminum substrate is immersed in an aqueous solution adjusted to have a pH value of 2 to 6 by adding at least one of an amine salt obtained by reacting, an ammonium salt of an organic acid or an inorganic acid, and aqueous ammonia, and dried. A method of manufacturing a solid electrolytic capacitor characterized in that it is formed is obtained.

  Further, according to the present invention, in the method for producing any one of the solid electrolytic capacitors, the amine is at least one amine of triethylamine and triethanolamine, and the amine salt is the amine, boric acid, malonic acid. , An amine salt obtained by reacting at least one of maleic acid, adipic acid, sebacic acid, dodecanoic acid, citric acid, phthalic acid, terephthalic acid, and pyromellitic acid. A method for producing a solid electrolytic capacitor is obtained, wherein the ammonium salt is at least one of ammonium borate, ammonium adipate, ammonium sebacate, and ammonium dotecanate.

  According to the invention, in any one of the above-described solid electrolytic capacitor manufacturing methods, after forming the polystyrene sulfonate layer, voltage treatment is performed with an aqueous solution containing an ammonium salt of an organic acid such as adipic acid or citric acid. The manufacturing method of the solid electrolytic capacitor characterized by having a process is obtained.

  According to the present invention, in the method for manufacturing any one of the solid electrolytic capacitors, an anode part composed of a part of the anodized film on the aluminum base and the part of the anodized film on the anode part The conductive polymer film layer is formed thereon via the precoat layer, and a cathode terminal connection portion is formed thereon to form a cathode portion, and an anode terminal connection portion is formed in a portion other than the cathode portion of the aluminum substrate. Thus, a method for manufacturing a solid electrolytic capacitor is obtained.

Further, according to the present invention, in the manufacturing method of the solid electrolytic capacitor, the solid electrolytic capacitor, and terminals respectively connected to said cathode terminal connecting portion and the anode terminal connection unit, made of a synthetic resin or an insulating material A method for manufacturing a solid electrolytic capacitor comprising an enclosing member is obtained.

Also, aluminum according to the present invention, in the manufacturing method of the solid electrolytic capacitor, the solid electrolytic capacitor comprises a transmission line element structure, the transmission line element structure mentioned above roughened with an anodic oxide film on the front surface An anode portion formed at the center of the substrate; first and second anode terminal connecting portions formed on both sides of the anode portion; and facing the anode portion and on the part of the anodized film A method for producing a solid electrolytic capacitor comprising a formed polystyrene sulfonate layer and a cathode portion including the conductive polymer layer formed on the polystyrene sulfonate layer is obtained.

  According to the present invention, in the method of manufacturing the solid electrolytic capacitor, the solid electrolytic capacitor includes a transmission line element structure, and the transmission line element structure includes the cathode terminal connection portion and the first and second anode terminal connections. The manufacturing method of the solid electrolytic capacitor characterized by including the terminal connected to the part and the encapsulating member formed of a synthetic resin or an insulating material.

  According to the present invention, it is possible to provide a solid electrolytic capacitor that is excellent in moisture resistance and has small, large capacity and low ESR characteristics.

  Moreover, according to this invention, the manufacturing method of the solid electrolytic capacitor excellent in moisture resistance can be provided.

  Moreover, according to the present invention, a solid electrolytic capacitor having a transmission line structure with improved moisture resistance can be provided.

  In addition, according to the present invention, a method for manufacturing a solid electrolytic capacitor having a transmission line structure with improved moisture resistance can be provided.

  The present invention will be further described in detail with reference to FIGS. Similar parts are given the same reference numerals and are not called repeatedly. The present invention is a further improvement of the invention described in Patent Document 1 filed earlier.

  FIG. 1A is a diagram showing a solid electrolytic capacitor according to an embodiment of the present invention, and FIG. 1B is an enlarged view of a portion A in FIG.

  As shown in FIGS. 1A and 1B, a solid electrolytic capacitor 100 of the present invention has an aluminum substrate 1 made of an aluminum foil. The aluminum substrate 1 has a surface roughened by etching or the like. Solid electrolytic capacitor 100 has anodized film layer 2 on the roughened surface of aluminum substrate 1. In the solid electrolytic capacitor 100, a conductive polymer film layer 20 that is a solid electrolyte layer is formed on the anodized film layer 2. The conductive polymer film layer 20 has an inner polymer film layer 5 and an outer polymer film layer 6. A polystyrene sulfonate layer 4 as a precoat layer is provided between the anodized film layer 2 and the conductive polymer layer 20.

  More specifically, the surface of the aluminum substrate 1 of the aluminum etching foil is roughened by etching. An anodized film is formed on the roughened surface of the aluminum substrate in an aqueous solution containing adipic acid, citric acid, phosphoric acid, or a salt thereof, and the aluminum substrate 1 is coated with aluminum on the roughened surface. Anodized film layer 2 is formed. Thereafter, in order to divide the aluminum substrate 1 into a capacity forming region and a region (hereinafter referred to as an anode terminal connecting portion) 9 connected to the anode lead or anode terminal, a thermosetting resin resist band 3 is provided. The aluminum substrate 1 in the capacity forming region constitutes the anode part 11. The resist band 3 uses an epoxy resin which is a thermosetting resin, but a thermoplastic resin can also serve its purpose. Thereafter, the polystyrenesulfonate precoat layer 4 which is the main object of the present invention is formed until reaching the inside of the porous body of the anodized film layer 2. Thereafter, an internal chemical polymerization layer (internal polymerization film layer) 5 is formed by chemical oxidative polymerization of a conductive polymer such as polypyrrole. Further, a slurry polymer of 3,4-ethylenedioxythiophene is applied on the inner polymer film layer 5 and dried to form a slurry polymer layer 6 as an outer chemical polymer layer (outer polymer film layer). Further, a graphite layer 7 and a silver paste layer 8 which are conductor layers are sequentially formed thereon to form a solid electrolytic capacitor 100 having a transmission line structure. The graphite layer 7 and the silver paste layer 8 together with the precoat layer 4 and the conductive polymer layer 6 form a cathode portion 10. Here, the silver paste layer 8 constitutes a cathode terminal connection portion connected to a cathode lead or a cathode terminal. The capacity forming region is formed in a region where the cathode portion 10 and the anode portion 11 face each other with the anodic oxide film layer 2 interposed therebetween.

  In the illustrated solid electrolytic capacitor 100, the anode lead or terminal connected to the anode terminal connecting portion 9 and the cathode lead or cathode terminal connected to the silver paste layer 8 are omitted.

  Specifically, the polystyrene sulfonate precoat layer 4 described above is prepared by first reacting an amine and an organic acid in a 0.1 to 10% by mass (hereinafter referred to as wt%) polystyrene sulfonic acid aqueous solution. An aqueous solution adjusted to a pH value of 2 to 6 by adding an amine salt or an ammonium salt of an organic acid or an inorganic acid, and immersing the aluminum substrate 1 on which the anodized film layer 2 is formed And dried to form.

  In the present invention, amines, amine salts, aqueous ammonia, and / or ammonium salts of organic acids or inorganic acids may be used as the base added to the polystyrene sulfonic acid solution to form the polystyrene sulfonate precoat layer 4. it can. As a result of various investigations among these bases, it has been found preferable to use the following.

  Examples of amines include 4-methoxy-2,2 ′, 4′-trimethyldiphenylamine, 2-ethylhexylamine, hexadecylamine, octadecylamine, dimethylamine, diethylamine, diisopropylamine, dibutylamine, trimethylamine, triethylamine, triethylamine, and the like. Examples include organic compounds having amino groups such as butylamine, triallylamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, hexamethylenediamine, triethanolamine, diethylenetriamine, but triethylamine, triethanolamine. Is preferred.

  Examples of amine salts include organic acids such as adipic acid, dodecanoic acid, sebacine (sebacin) acid, citric acid, maleic acid, malonic acid, phthalic acid, terephthalic acid, and pyromellitic acid. It is preferable to use a product formed by reacting inorganic acid such as boric acid.

  Examples of the ammonium salts include ammonium borate which is an inorganic acid ammonium salt. Further, organic acid ammonium salts, which are ammonium adipate, ammonium sebacate, and ammonium dodecanoate, can be mentioned.

  In addition, as an organic acid for forming organic acid ammonium salt, adipic acid, dodecanoic acid, sebacine (sebacin) acid, citric acid, maleic acid, malonic acid, phthalic acid, terephthalic acid, pyromellitic acid, etc. It is preferable to use the organic fatty acid. Moreover, as an inorganic acid, it is preferable to use the boric acid etc. which were mentioned above.

  Further, examples of the base added to the polystyrene sulfonic acid solution include ammonia water which is an inorganic compound.

  In the present invention, it has been described that the conductive polymer layer is formed after the polystyrene sulfonate layer is formed. However, after the polystyrene sulfonate layer is formed, an organic acid such as adipic acid or citric acid is used. It is preferable to perform voltage treatment with an aqueous solution containing an ammonium salt, and then form a conductive polymer layer on the polystyrene sulfonate.

  In the present invention, the precoat layer of Patent Document 1 is improved, and the results of tests conducted to evaluate the characteristics of the precoat layer 4 of the present invention will be described below.

(Voltage drop rate of precoat layer)
As a precoat layer 4 according to Example 1 of the present invention, an aluminum foil cut into a predetermined size was anodized at 8 V to form an anodized film, and then 1.5 wt% polystyrene sulfonic acid, triethanolamine 1 It was immersed in an aqueous solution mixed with 0.1 wt% for 30 minutes and dried to form a polystyrenesulfonate precoat thin film layer.

  In addition, as a precoat layer according to Example 2 of the present invention, after anodized film was formed in the same manner as in Example 1, 1.5% by weight of polystyrene sulfonic acid, 1.0% by weight of triethanolamine, 0.5% by weight of adipic acid Was immersed in an aqueous solution for 30 minutes and dried to form a polystyrenesulfonate precoat thin film layer.

  Further, as Comparative Example 1, as in Example 1, a sample was prepared in which an anodized film was formed and no precoat thin film layer was formed.

  Further, as Comparative Example 2, after anodized film was formed in the same manner as in Example 1, it was immersed in a 1.5 wt% aqueous polystyrene sulfonate solution for 30 minutes and dried to form a polystyrene sulfonate pre-coated thin film layer. Formed.

The sample according to Example 1 was put in a high-humidity resistance test tank maintained at 65 ° C., 95% constant temperature and constant humidity, and held for 24 hours (H), 48H, and 72H. Similarly, each sample according to Example 2 and Comparative Examples 1 and 2 was also placed in a high humidity resistance test tank maintained at 65 ° C., 95% constant temperature and constant humidity, and 24 hours (H), 48 H, 72 H. Retained. After each holding time, after removing the samples from the humid chamber, each sample was tested to determine its withstand voltage. The voltage behavior was observed by passing a constant current of current density (I) = 2 A / m 2 in an aqueous solution (chemical conversion solution) of 7.5 wt% ammonium adipate and 0.05 wt% ammonium dihydrogen phosphate. It was done. In particular, the sample was immersed in the solution in the container, and a constant current was applied for 10 minutes between the aluminum substrate with the sample as the anode and the container with the cathode. The voltage behavior was obtained by measuring the voltage between the anode and cathode over time. The voltage 5 minutes after the start of current supply was determined as the withstand voltage. In addition, another sample of Examples 1 and 2 and Comparative Examples 1 and 2 was prepared in order to measure the initial withstand voltage without being put in the high humidity test tank. Each sample was subjected to a current of 10 minutes at the same current density in the chemical conversion solution. The withstand voltage of these other samples was taken as the initial withstand voltage, and the ratio of the withstand voltage change of each sample to these was plotted against time as shown in FIG.

  As shown in FIG. 2, the precoat layer according to Comparative Example 2 according to the conventional method has a higher resistance to resistance than the one without the precoat layer according to Comparative Example 1 indicated by the line segment 21 as indicated by the line segment 22. Since the voltage change rate by the high-humidity test is large and the withstand voltage when originally formed cannot be maintained, the rated voltage had to be set below the withstand voltage.

  However, in the precoat layers according to Examples 1 and 2 of the present invention indicated by the line segments 23 and 24, the withstand voltage is hardly lowered, and the rated voltage can be increased even with the same conversion voltage.

  Next, Examples 3 and 4 will be described. In Example 1 described above, an aqueous solution in which 1.5 wt% of polystyrene sulfonic acid is mixed with 1.1 wt% of triethanolamine is used, and an aluminum substrate on which an anodized film is formed is immersed in these aqueous solutions for 30 minutes. In Example 3, an aqueous solution using triethylamine instead of triethanolamine was used, and an aluminum substrate on which an anodized film was formed was immersed for 30 minutes in the same manner as in Example 1. And dried to form a precoat layer.

  In Example 4, an aqueous solution using 1.3 wt% ammonium adipate was used instead of the triethanolamine of Example 1, and an aluminum substrate on which an anodized film was formed was immersed for 30 minutes in the same manner as in Example 1. It dried and the precoat layer was formed.

  The obtained samples on which the precoat layers of Examples 3 and 4 were formed were subjected to a high humidity resistance test in the same manner as described above. The results are shown in FIG. 3 together with the measurement results of the samples according to Comparative Example 1 and Comparative Example 2 described above. From the result of FIG. 3, as shown by the broken line 53, in Example 3 of the present invention provided with the polystyrenesulfonate precoat layer, it is almost the same as the sample without precoat treatment (without forming the precoat layer) according to Comparative Example 1. The same effect was shown. Moreover, as shown in the line segment 54, it turns out that Example 4 of this invention provided with the precoat layer of the polystyrene sulfonate also shows the same effect as the sample without the precoat process which concerns on the comparative example 1. FIG.

  Next, Examples 5 and 6 will be described. In Example 2 described above, an aluminum solution in which 1.1 wt% of triethanolamine and 0.5 wt% of adipic acid were mixed with 1.5 wt% of polystyrene sulfonic acid, and an anodized film formed in the aqueous solution was used. The substrate was immersed for 30 minutes and dried to form a precoat layer. In Example 5, an anodized film was formed in the same manner as in Example 2 using an aqueous solution of 0.69 wt% dodecanoic acid instead of adipic acid. The prepared aluminum substrate was immersed for 30 minutes and dried to form a precoat layer.

  In Example 6, an aqueous solution of sebacic acid (sebacic acid) 0.69 wt% was used instead of adipic acid of Example 2, and an aluminum substrate on which an anodized film was formed was immersed for 30 minutes in the same manner as Example 2. And dried to form a precoat layer.

  The high humidity resistance test of Examples 5 and 6 was performed in the same manner as in Examples 3 and 4 described above. The result is shown in FIG. In the same figure, the results of the high-humidity standing test of the precoat layers according to Examples 1 and 2 are also shown.

  From the results shown in FIG. 4, samples having polystyrene sulfonate precoat layers according to Examples 5 and 6 of the present invention are shown in Curves 61 and 62 as shown in Curves 63 and 64. It was found that the same effect as that of the sample provided with the polystyrene sulfonate precoat layer according to No. 2 can be expected.

(Measurement of coverage)
Next, the influence of the polystyrene sulfonic acid concentration on the coverage of the polystyrene sulfonate was examined.

  First, an aluminum foil cut into a predetermined size is anodized at 8 V to form an anodized film, and then each polystyrene sulfonic acid solution in which the polystyrene sulfonic acid concentration is changed in the range of 0 to 20 wt%, and ethanolamine are used. A precoat layer was formed by immersing in the mixed solution and drying. Thereafter, as described in Patent Document 1, a conductive polymer film such as a polypyrrole film and a polythiophene film is formed on the precoat layer by chemical oxidation polymerization, and a graphite layer and a silver paste layer are sequentially formed to form a solid electrolytic capacitor element. Formed. The element was measured for capacity C at 120 Hz, and the rate of change ΔC / CO (%) with respect to capacity CO (%) with a polystyrene sulfonic acid concentration of 0 wt% was determined. This relationship is shown in FIG.

  From the results of FIG. 5, when the polystyrene sulfonate thin film layer was formed at a polystyrene sulfonic acid concentration of 0.01 to 10 wt%, the capacity increased. This shows that a solid electrolytic capacitor with a good coverage can be provided by polystyrene sulfonate.

(Change characteristics of leakage current in high humidity test and effect of voltage treatment)
Next, the change characteristics of the leakage current of the solid electrolytic capacitor elements according to Examples 7 to 10 which were left in the high humidity test tank were examined.

First, in Example 7, a precoat layer was formed as in Example 1 described above. That is, an anodized film was formed by anodizing an aluminum foil cut to a predetermined size at 8V. Then, it was immersed in an aqueous solution in which 1.5 wt% of polystyrene sulfonic acid and 1.1 wt% of triethanolamine were mixed, and dried to form a precoat layer. Thereafter, voltage treatment was performed by applying a constant current of current density (I) = 2 A / m 2 for 10 minutes in an aqueous solution of 7.5 wt% ammonium adipate and 0.05 wt% ammonium dihydrogen phosphate. In the voltage treatment, the pressure is increased to 7.8 V at 12 V / min using an aluminum conversion foil formed with a precoat layer as an anode and the container (tank) containing the conversion solution as a cathode, followed by 7.8 V. And kept for 10 minutes. Next, as in Patent Document 1, conductive polymer layers of a polypyrrole film and a polythiophene film were formed by chemical oxidative polymerization. Further, a solid electrolytic capacitor was formed by sequentially forming a graphite layer and a silver paste layer.

  Next, as Example 8, after forming a precoat layer in the same manner as in Example 7, a solid electrolytic capacitor in which a conductive polymer layer of a polypyrrole film and a polythiophene film was formed by chemical oxidative polymerization without performing voltage treatment. Produced.

Further, as Example 9, after anodized film was formed in the same manner as in Example 2 above, in an aqueous solution in which 1.5% by weight of polystyrene sulfonic acid, 1.0% by weight of triethanolamine, and 0.5% by weight of adipic acid were mixed. And dried for 30 minutes to form a precoat layer similar to that of Example 2. Thereafter, voltage treatment was performed by applying a constant current of current density (I) = 2 A / m 2 for 10 minutes in an aqueous solution of 7.5 wt% ammonium adipate and 0.05 wt% ammonium dihydrogen phosphate. Next, similarly to Patent Document 1, a polypyrrole film and a polythiophene film were formed by chemical oxidative polymerization. Further, a solid electrolytic capacitor was formed by sequentially forming a graphite layer and a silver paste layer.

  Next, as Example 10, after forming a precoat layer in the same manner as in Example 9, a solid electrolytic capacitor in which a conductive polymer layer of a polypyrrole film and a polythiophene film was formed by chemical oxidative polymerization without performing voltage treatment. Produced.

Further, as Comparative Example 3, an anodized film was formed on an aluminum substrate in the same manner as Comparative Example 2, and then immersed in a 1.5 wt% aqueous polystyrene sulfonate solution for 30 minutes and dried to form a precoat layer. . Thereafter, voltage treatment was performed by applying a constant current of current density (I) = 2 A / m 2 in an aqueous solution of 7.5 wt% ammonium adipate and 0.05 wt% ammonium dihydrogen phosphate for 10 minutes. Next, similarly to Patent Document 1, a polypyrrole film and a polythiophene film were formed by chemical oxidative polymerization. Further, a solid electrolytic capacitor was formed by sequentially forming a graphite layer and a silver paste layer.

  Further, as Comparative Example 4, a solid electrolytic capacitor in which a precoat layer was formed in the same manner as in Comparative Example 3 and then a conductive polymer layer of a polypyrrole film and a polythiophene film was formed by chemical oxidative polymerization without voltage treatment was produced. did.

  Each sample was allowed to stand in the above-mentioned high-humidity test tank for 72 hours, then removed from the high-humidity test tank, and applied with voltages of 2.5 V, 4.0 V, and 6.3 V for 1 minute, and LC (Leakage current) was measured. The result is shown in FIG.

  From the results shown in FIG. 6, the solid electrolytic capacitors according to Examples 7, 8, 9 and 10 of the present invention in which the polystyrenesulfonate precoat thin film layer was formed, as shown by the broken lines 43 to 46, are broken lines 41 and 42. Similarly to the solid electrolytic capacitor according to Comparative Example 3 shown in FIG. In addition, the solid electrolytic capacitors according to Comparative Example 4 and Examples 8 and 10 of the present invention, which were subjected to voltage treatment after the formation of the precoat layer, were compared with Comparative Example 3 which was not subjected to voltage treatment and 7 and 8 of the present invention. It can be seen that the LC is less than the capacitor.

  As described above, according to the embodiment of the present invention, by pre-coating with polystyrene sulfonate, the leakage current generated when a conventional polystyrene sulfonic acid is used as a pre-coat layer is reduced, and the coverage is reduced. Therefore, it has been found that a solid electrolytic capacitor having small, large capacity and low ESR characteristics can be provided.

  Further, according to the embodiment of the present invention, the solid electrolytic capacitor can be made small and large by pre-coating the anodized film with polystyrene sulfonate to reduce the leakage current of the solid electrolytic capacitor and increase the coverage. It has been found that it is possible to provide a method for manufacturing a solid electrolytic capacitor that can have characteristics of capacitance and low ESR.

  In the above-described embodiment, the first and second anode terminal connection regions (anode terminal connection portions) 9 serving as current inflow paths or current outflow portions are provided at both ends of the anode portion 11, and further, the first and second The first and second anode terminals are provided in the anode connection region, a power supply voltage is applied between the first anode terminal and the cathode portion, and a load is connected between the second anode terminal and the cathode portion. An element having a transmission line structure has been described. However, the solid electrolytic capacitor of the present invention may be a solid electrolytic capacitor having a normal structure in which one anode connection region is formed and one anode terminal is provided in the anode connection region.

  Further, the solid electrolytic capacitor according to the present invention is a capacitor element mounted on a substrate of an electronic device or an electric device, and further, the solid electrolytic capacitor having a transmission line structure is a power supply coupling circuit or a power supply circuit stabilization. Applies to

  In the embodiments described above, only the polypyrrole and 3,4-ethylenedioxythiophene are listed as the conductive polymer layer constituting the solid electrolyte of the present invention. The present invention is not limited to the conductive polymer, and various modifications can be made without departing from the scope of the present invention.

  As described above, the solid electrolytic capacitor according to the present invention is particularly applied to a circuit element of a backup power supply or a decoupling circuit as a circuit element mounted on an electric / electronic circuit board.

(A) is sectional drawing which shows an example of the solid electrolytic capacitor of this invention. (B) is an enlarged view of the A part of (a). Constant current density for the sample in which the precoat layer according to Examples 1 and 2 of the present invention was formed, the sample in which the precoat layer according to Comparative Example 1 was not formed, and the sample in which the precoat layer according to Comparative Example 2 was formed It is a figure which shows the relationship between the voltage behavior at the time of flowing, and the leaving time in a high humidity test tank. The figure which shows the relationship between the voltage behavior at the time of flowing a fixed current density to the sample in which the precoat layer based on Example 3 and 4 of this invention was formed, and the leaving time in a high-humidity-proof test tank, and also compared A sample in which the precoat layer according to Example 1 is not formed and a sample in which the precoat layer according to Comparative Example 2 is formed are also shown. It is a figure which shows the relationship between the voltage behavior at the time of flowing a fixed current density to the sample in which the precoat layer based on Example 5 and 6 of this invention was formed, and the leaving time in a high-humidity-proof test tank, and it implemented together The sample on which the precoat layer according to Examples 1 and 2 is formed is also shown. It is a figure which shows the influence which the density | concentration of the polystyrene sulfonic acid used for forming the polystyrene sulfonate of a solid electrolytic capacitor has on a capacity | capacitance. 6 gives constant voltages of 2.5 V, 4 V, and 6.3 V to the solid electrolytic capacitors according to Examples 7, 8, 9, and 10 of the present invention and the solid electrolytic capacitors according to Comparative Examples 3 and 4, respectively. It is a figure which shows the leakage current (LC) in the case of.

Explanation of symbols

1 Aluminum substrate 2 Anodized film layer 3 Resist band 4 Precoat layer (polystyrene sulfonate layer)
5 Internal Polymerized Film Layer 6 External Polymerized Film Layer 7 Graphite Layer 8 Silver Paste Layer 9 Anode Terminal Connection Part 10 Cathode Part 11 Anode Part 20 Conductive Polymer Film Layer 100 Solid Electrolytic Capacitor

Claims (16)

  1.   A roughened aluminum substrate, an anodized film layer formed on the surface of the roughened aluminum substrate, a polystyrene sulfonate layer formed on a part of the anodized film layer, and the polystyrene sulfone A conductive polymer film layer formed as a solid electrolyte on the acid salt layer, and the polystyrene sulfonate layer is formed between the anodized film layer and the conductive polymer film layer A solid electrolytic capacitor characterized by that.
  2.   2. The solid electrolytic capacitor according to claim 1, wherein the polystyrene sulfonate layer comprises an amine salt obtained by reacting an amine, an amine and an organic acid, an organic acid, and 0.1 to 10 wt% polystyrene sulfonic acid aqueous solution. A solid electrolytic capacitor formed by adding at least one ammonium salt of an inorganic acid and at least one of aqueous ammonia, soaking in an aqueous solution adjusted to a pH value of 2 to 6, and drying the solution. .
  3.   The solid electrolytic capacitor according to claim 2, wherein the amine is at least one of triethylamine and triethanolamine, and the amine salt is the amine and boric acid, malonic acid, maleic acid, adipic acid, sebacic acid, At least one of amine salts obtained by reacting at least one of dodecanoic acid, citric acid, phthalic acid, terephthalic acid, and pyromellitic acid, and each ammonium salt of the organic acid and inorganic acid is boron. A solid electrolytic capacitor characterized by being at least one of ammonium acid, ammonium adipate, ammonium sebacate, and ammonium dodecanoate.
  4.   The solid electrolytic capacitor according to any one of claims 1 to 3, wherein after forming the polystyrene sulfonate layer, voltage treatment is performed with an aqueous solution containing an ammonium salt of an organic acid such as adipic acid or citric acid. A solid electrolytic capacitor characterized by having been performed.
  5.   5. The solid electrolytic capacitor according to claim 1, wherein the anode part formed of the part of the anodized film layer of the aluminum base and polystyrene acid on the part of the anodized film are formed. A cathode part on which the conductive polymer layer is formed via a salt, and an anode terminal connection part formed on a part other than the part of the aluminum base, wherein the cathode part has the conductivity high A solid electrolytic capacitor comprising a cathode terminal connection portion formed on a molecular layer.
  6.   The solid electrolytic capacitor according to claim 5, further comprising: a terminal connected to one of the cathode terminal connection portions and one of the anode terminal connection portions; and an encapsulating member made of a synthetic resin or an insulating material. Solid electrolytic capacitor.
  7. In the solid electrolytic capacitor according to any one of claims 1 to 5, the solid electrolytic capacitor comprises a transmission line element structure, the transmission line element structure, said having the anodized film formed on the surface The anode part included in the center part of the roughened aluminum substrate, the first and second anode terminal connecting parts located on both sides of the anode part, the anode part facing the anode part, and on the anodized film A solid electrolytic capacitor comprising: the polystyrene sulfonate layer formed in part; and the conductive polymer film layer on the polystyrene sulfonate layer.
  8.   8. The solid electrolytic capacitor according to claim 7, further comprising: a terminal connected to the cathode terminal connecting portion and the first and second anode terminal connecting portions; and an encapsulating member made of a synthetic resin or an insulating material. Solid electrolytic capacitor.
  9. A step of surface roughening of the aluminum substrate, forming an anodized film layer on the surface of the aluminum substrate, forming a polystyrene sulfonate layer on a part of the anodized film layer, wherein And a step of forming a conductive conductive polymer film layer as a solid electrolyte on the polystyrene sulfonate layer.
  10.   The method for producing a solid electrolytic capacitor according to claim 9, wherein the step of forming the polystyrene sulfonate layer comprises reacting an amine, an amine and an organic acid in a 0.1 to 10 wt% polystyrene sulfonic acid aqueous solution. The aluminum substrate is immersed in an aqueous solution adjusted to a pH value of 2-6 by adding at least one of an amine salt, an organic acid or an inorganic acid ammonium salt, and aqueous ammonia, and dried. A method for producing a solid electrolytic capacitor characterized by the above.
  11.   11. The method for producing a solid electrolytic capacitor according to claim 9, wherein the amine is at least one of triethylamine and triethanolamine, and the amine salt is the amine and boric acid, malonic acid, maleic acid, adipine. An amine salt obtained by reacting at least one of acid, sebacic acid, dodecanoic acid, citric acid, phthalic acid, terephthalic acid, and pyromellitic acid, and the ammonium salt of the organic acid or inorganic acid is boron. A method for producing a solid electrolytic capacitor, wherein the solid electrolytic capacitor is at least one of ammonium acetate, ammonium adipate, ammonium sebacate, and ammonium dotecanate.
  12.   12. The method for producing a solid electrolytic capacitor according to claim 9, wherein after forming the polystyrene sulfonate layer, voltage treatment is performed with an aqueous solution containing an ammonium salt of an organic acid such as adipic acid or citric acid. The manufacturing method of the solid electrolytic capacitor characterized by having the process of performing.
  13.   13. The method for producing a solid electrolytic capacitor according to claim 9, wherein an anode part formed of a part of the anodized film on the aluminum base and the part of the anodized film on the anode part. The conductive polymer film layer is formed thereon via the precoat layer, and a cathode terminal connection portion is formed thereon to form a cathode portion, and an anode terminal connection portion is formed in a portion other than the cathode portion of the aluminum substrate. A method for producing a solid electrolytic capacitor, wherein:
  14. The method of manufacturing a solid electrolytic capacitor according to claim 13, wherein the solid electrolytic capacitor, and terminals respectively connected to said cathode terminal connecting portion and the anode terminal connection unit, and a sealing member made of a synthetic resin or an insulating material A method for producing a solid electrolytic capacitor, comprising:
  15. The method of manufacturing a solid electrolytic capacitor according to claim 13, wherein the solid electrolytic capacitor comprises a transmission line element structure, the transmission line element structure, the center of the roughened aluminum substrate having an anodic oxide film on the front surface An anode part formed on the part, first and second anode terminal connecting parts formed on both sides of the anode part, and formed on the part of the anodic oxide film facing the anode part and A method for producing a solid electrolytic capacitor, comprising: a polystyrene sulfonate layer; and a cathode portion including the conductive polymer layer formed on the polystyrene sulfonate layer.
  16.   16. The method of manufacturing a solid electrolytic capacitor according to claim 15, wherein the solid electrolytic capacitor includes a transmission line element structure, and the transmission line element structure is connected to the cathode terminal connection portion and the first and second anode terminal connection portions. And a sealing member formed of a synthetic resin or an insulating material.
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JP5063448B2 (en) * 2008-03-31 2012-10-31 三井化学株式会社 Nonaqueous electrolyte and nonaqueous electrolyte secondary battery including the nonaqueous electrolyte
JP5273726B2 (en) * 2009-04-07 2013-08-28 Necトーキン株式会社 Solid electrolytic capacitor and manufacturing method thereof
JP5444057B2 (en) 2010-03-16 2014-03-19 信越ポリマー株式会社 Solid electrolytic capacitor, manufacturing method thereof, and solution for solid electrolytic capacitor
TWI559348B (en) 2011-12-01 2016-11-21 Nippon Chemicon Solid electrolytic capacitor and method of manufacturing same
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JPH0590081A (en) * 1991-09-27 1993-04-09 Marcon Electron Co Ltd Manufacture of solid electrolytic capacitor
JPH05152168A (en) * 1991-11-28 1993-06-18 Nec Corp Manufacture of solid electrolytic capacitor
JPH05262981A (en) * 1992-03-18 1993-10-12 Japan Carlit Co Ltd:The Water-dispersible polyaniline composition and its production
JP2002373832A (en) * 2001-06-14 2002-12-26 Matsushita Electric Ind Co Ltd Manufacturing method for solid electrolytic capacitor
JP2005039040A (en) * 2003-07-14 2005-02-10 Nec Tokin Corp Surface mounting thin capacitor
JP2005159154A (en) * 2003-11-27 2005-06-16 Nec Tokin Corp Manufacturing method of solid electrolytic capacitor

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0590081A (en) * 1991-09-27 1993-04-09 Marcon Electron Co Ltd Manufacture of solid electrolytic capacitor
JPH05152168A (en) * 1991-11-28 1993-06-18 Nec Corp Manufacture of solid electrolytic capacitor
JPH05262981A (en) * 1992-03-18 1993-10-12 Japan Carlit Co Ltd:The Water-dispersible polyaniline composition and its production
JP2002373832A (en) * 2001-06-14 2002-12-26 Matsushita Electric Ind Co Ltd Manufacturing method for solid electrolytic capacitor
JP2005039040A (en) * 2003-07-14 2005-02-10 Nec Tokin Corp Surface mounting thin capacitor
JP2005159154A (en) * 2003-11-27 2005-06-16 Nec Tokin Corp Manufacturing method of solid electrolytic capacitor

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