JP4727160B2 - Valve action metal sintered body, manufacturing method thereof and solid electrolytic capacitor - Google Patents

Description

  The present invention relates to a method for producing a valve action metal sintered body for an anode of a solid electrolytic capacitor and a solid electrolytic capacitor using the sintered body as an anode. More specifically, niobium, niobium compound, niobium alloy powder, tantalum, tantalum compound, and tantalum alloy powder are used as the valve action metal, and a method for producing a niobium sintered body for anode and a tantalum sintered body having a high capacity per unit mass and The present invention relates to a solid electrolytic capacitor using the sintered body as an anode.

  Capacitors used in electronic devices such as mobile phones and personal computers are desired to be small and have a large capacity. Among such capacitors, tantalum capacitors and niobium capacitors are preferred because of their large capacity and good performance. Furthermore, recent electronic devices are required to operate at low voltage, operate at high frequency, and reduce noise. Even in solid electrolytic capacitors, higher capacity, lower ESR (equivalent series resistance), and improved tanδ characteristics Is required.

Generally, a sintered body of valve action metal powder is used as an anode body of a capacitor using a valve action metal. For example, niobium powder is granulated by mixing niobium powder and a liquid binder, this is molded by compression molding, and the anode lead is implanted in the molded body at high temperature and high vacuum sintering. Thus, an electrode called a sintered body is obtained.
The inside of the sintered body has a three-dimensional complicated shape in which the powder is electrically and mechanically connected. A dielectric film layer is formed on the surface of the sintered body including the surface of the internal voids, and then a capacitor is formed by impregnating a material serving as a counter electrode. The capacitance of the produced capacitor greatly depends on the contact state between the counter electrode material and the dielectric coating layer as long as the dielectric coating layer is uniformly attached to the surface outside the sintered body.

  In order to increase the capacity of these valve metal capacitors, it is necessary to increase the mass of the sintered body or to use a sintered body having a surface area increased by pulverizing the valve metal powder.

  In the method of increasing the mass of the sintered body, the shape of the capacitor inevitably increases and does not satisfy the demand for downsizing. On the other hand, in the method of increasing the specific surface area by pulverizing the valve action metal powder, the pore diameter of the valve action metal sintered body is reduced and the number of closed holes is increased in the sintering stage, and impregnation with the cathode agent in the post-process. Becomes difficult.

  For example, when a phosphoric acid aqueous solution is used as the counter electrode material, the contact state with the dielectric coating layer is perfect, and the capacity appearance rate (also referred to as the cathode agent impregnation rate) at that time is 100%. When using a material, particularly a solid electrode material, it was difficult to set the capacity appearance rate to 100%. In particular, when the average particle diameter of the valve action metal powder is small, or when the shape of the sintered body produced from the valve action metal powder is large, the difficulty increases. In an extreme case, the capacity appearance rate is 50%. Sometimes it was less than. In addition, in such a low capacity appearance rate, it is not possible to produce a high-capacity valve metal capacitor, but ESR cannot be lowered, tan δ characteristics are inferior, and sufficient moisture resistance can be obtained. There wasn't.

  As one of the means to solve these drawbacks in the high capacity valve action metal sintered body, the pores of the sintered body are enlarged, and the negative electrode impregnation property of the counter electrode material having a large viscosity, particularly the solid electrode material, is improved. A capacitor having a valve action metal sintered body that can be improved and has high capacity, low ESR, low tan δ value, and long-term reliability can be considered.

  In Patent Document 1 (Japanese Patent Application Laid-Open No. 48-25859), a compound having an evaporation point lower than the sintering temperature is added to a metal powder such as tantalum or niobium, and vaporized and scattered during sintering to form pores. A method of manufacturing a porous electrode for a capacitor is disclosed. Examples of the compound to be added include aluminum fluoride, bismuth fluoride, zinc fluoride, lead fluoride, and cadmium fluoride powders. It is described that these compounds gradually evaporate in the sintering process and completely evaporate at a set temperature. Since the pores formed by transpiration are exposed to a high temperature of 1500 ° C., they are baked and do not remain effectively. As a result, the capacitance of the manufactured capacitor is as extremely small as 10 to 16 μF, and tan δ is as extremely large as 7 to 9%.

  In Patent Document 2 (Japanese Patent Laid-Open No. 56-45015), a substance having a melting point lower than that of the powder is added to a valve action metal powder such as tantalum or niobium, and the added substance is evaporated by exposure to high temperature in a vacuum. A method of manufacturing an anode body that is dispersed to form pores is disclosed. Zinc and aluminum metal are described as substances to be added. Also in this method, evaporation is scattered during sintering, so that baking is performed and pores do not remain effectively. As a result, the capacitance of the manufactured capacitor is as extremely small as 2.4 to 2.5 μF, and the ESR is as extremely large as 140 mΩ.

  In Patent Document 3 (Japanese Patent Laid-Open No. 10-275746), a valve action metal powder mixed with a granular binder of 50 μm or less is sintered in a vacuum at a high temperature of about 2000 ° C. to leave pores. A method for producing a knot is disclosed. As the granular binder, polyvinyl alcohol, polyvinyl butyrate, polyvinyl acetate, polyethylene carbonate, methyl methacrylate, polyethylene resin, polyester resin, methacrylic resin and the like are described. Since these binders are organic polymers, they cause decomposition such as depolymerization during sintering and decompose and fly, so that pores do not remain effectively.

  In Patent Document 4 (Japanese Patent Application Laid-Open No. 11-181505), a valve-acting metal agglomerated powder or granulated powder such as tantalum, niobium, and aluminum is combined with a solid organic material, and the formed body is baked at high temperature and high vacuum. A manufacturing method of an anode sintered body for a solid electrolytic capacitor to be bonded is disclosed. There is a description that it is preferable to use PVA (polyvinyl alcohol) or acrylic solid binder or camphor as the solid organic matter. These solid organic substances are compounds of the same type as the binder described in Patent Document 3 (Japanese Patent Laid-Open No. 10-275746), and cause pores to decompose and scatter by causing a reaction such as depolymerization during sintering. Does not remain effectively. As a result, although ESR is improved, it is extremely high at about 150 mΩ.

  Patent Document 5 (Japanese Patent Application Laid-Open No. 9-74051) discloses a methacrylic acid ester polymer, polyethylene carbonate, polypropylene carbonate, polybutylene carbonate, etc., processed into a thread-like metal powder such as tantalum, titanium, niobium, and aluminum. A method for producing a sintered body for a solid electrolytic capacitor is disclosed in which a fiber made of is added and mixed, molded, and then sintered in a high-temperature vacuum. Since these compounds are only in the form of fibers, they are the same kind of compounds as the binder described in Patent Document 3 (Japanese Patent Laid-Open No. 10-275746) and have the same physical properties. As a result of this reaction, the fine particles do not remain effectively.

  In Patent Document 6 (Japanese Patent Application Laid-Open No. 6-252011), a thin sintered body is used to shorten the pore path when forming a porous sintered body for a capacitor by molding and sintering a valve action metal powder. The manufacturing method which produces a body and laminates many sintered compacts is indicated. This method is economically disadvantageous because a large number of thin sintered bodies must be laminated on the unit volume of the capacitor, and it is economically disadvantageous, as compared to the case of producing a capacitor with a single sintered body. The volumetric efficiency deteriorates and a capacitor with a large capacity cannot be produced.

  In Patent Document 7 (Japanese Patent Application Laid-Open No. 4-136102), after mixing a liquid binder with tantalum powder for electrolytic capacitors, the particle size is adjusted to 20 to 400 μm in order to improve the flowability of the granulated powder. Techniques for molding and sintering are disclosed. By adjusting the particle size, fine particles are removed, and the gaps between the granulated powders are once increased. However, the compression process at the time of molding reduces the gap, and as a result, the gap becomes almost the same as when not sized, and physical properties such as ESR cannot be improved.

In Patent Document 8 (Japanese Patent Laid-Open No. 2001-345238), a powder obtained by reducing tantalum potassium fluoride at 850 ° C. is pulverized by a bead mill to obtain a tantalum powder having an average particle diameter of about 2 μm. A granulated powder with weak cohesive force obtained by spray drying after mixing the emulsion is heated to 1100 ° C. to produce a hard agglomerated powder, then magnesium chip is added and deoxygenated at 800 ° C. for 1 to 20 μm. An agglomerated powder of tantalum or niobium having pores of 5 to 5.0 g / cm ³ is obtained by press molding, sintering at 1000 to 1400 ° C., and 0.08 to 0. A method for producing a porous sintered body having pore peaks in the range of .5 μm and in the range of 1 to 20 μm, and having a pore diameter of 1 to 20 μm in 5% by volume or more of the total pore volume is disclosed. . In the examples, a sintered body in which 7 to 9% by volume of the total pore volume has a pore diameter of 1 to 20 μm is disclosed, but the pores of 1 μm or less are 90% by volume or more of the total pore volume. And the peak peak of the pores are very small pores in the range of 0.08 to 0.5 μm, so the impregnation of the cathode agent is insufficient, and the sintered body is 99000 to 101000 μFV / g. ESR is a very high value of 550 to 600 mΩ. Further, the number of times of exposure to a high temperature of 800 ° C. or more is as many as 4, and there is a problem that CV decreases with the number of thermal histories.

Patent Document 9 (WO02 / 092864) has two peak tops in the pore diameter distribution at 0.2 to 0.7 μm and 0.7 to 3 μm, and the relative intensity of the latter peak top. A method for producing a niobium sintered body having a large size is disclosed. It is described that the niobium sintered body having these two peaks can be manufactured by adjusting the pressure during molding to a specific pressure value. In this method, when the pressurization value is lowered, the adhesion strength between the lead wire of the electrode wire and the molded body is lowered, and the LC is sometimes increased. For large sintered bodies with a sintered body volume exceeding 25 mm ³ , pore formation is insufficient and the impregnation rate of the cathode agent may be less than 80%, achieving high capacity and low ESR at the same time. There were cases where it was not possible.

  In Patent Document 10 (Japanese Patent Laid-Open No. 6-128604), a metal that forms a matrix such as tungsten, molybdenum, tantalum, niobium, chromium, cobalt, rhenium, iron, nickel, copper, or the like, free energy of oxide formation from the matrix metal. A method of manufacturing a dense sintered member by adding and sintering an oxide having a low oxygen content and lower than the stoichiometric composition is disclosed. This method utilizes the action of an oxygen deficient oxide as a reducing agent. Examples of these oxygen-deficient oxides include aluminum and yttrium. The relative density of the member produced by this method is 93 to 99%, and there are almost no voids. Therefore, impregnation with the cathode agent cannot be performed, and the capacitor does not have a high capacity and low ESR.

JP-A-48-25859 JP-A-56-45015 JP-A-10-275746 JP-A-11-181505 JP-A-9-74051 JP-A-6-252011 JP-A-4-136102 JP 2001-345238 A International Publication No. 02/092864 Pamphlet JP-A-6-128604

The present invention has been made in view of the above circumstances, and is a valve metal sintered body for an anode of a solid electrolytic capacitor having a valve metal, a valve metal compound and / or a valve metal alloy as a main component. In addition, a sintered body capable of producing a capacitor having high cathode agent impregnation, high capacity appearance rate, low ESR, good tan δ characteristics, and excellent long-term reliability such as moisture resistance and high temperature load, in particular a CV value of 40000 CV / An object of the present invention is to provide a sintered body having a high capacity exceeding g, particularly a large-sized sintered body having a sintered body volume of 10 mm ³ or more, and a method for producing the same.

  The method for producing a sintered body for a solid electrolytic capacitor according to the present invention comprises a step of compressing and forming a valve-acting metal powder for a capacitor to form a formed body, and a step of sintering the formed body at a high temperature. In the manufacturing method of a body, the said molded object is formed with the mixed granulated material containing the primary powder of the valve action metal for capacitors, secondary agglomerated powder or granulated powder, a pore formation agent, and an organic binder, The molded object It is characterized in that it has a step of removing the pore-forming agent after sintering. The formed body can also be formed by applying and printing a dispersion of the mixed granulated product. Sintering is performed using a pore-forming agent that is not removed at the sintering temperature, and pores are formed in the sintered body by removing the pore-forming agent remaining in the sintered body after sintering. By controlling the type, average particle size, and amount of addition of the pore forming agent, the optimum pore peak position, number, and amount for the type of cathode agent can be adjusted, and the impregnation property of the cathode material can be improved.

According to the method of the present invention, it is possible to adjust the position, number and amount of the pore diameter distribution peak of the sintered body used as the anode, and in particular, when the volume of the sintered body is 10 mm ³ or more For large sintered bodies having a rate of 55% by volume or more, the pore volume of 1 μm or more is 10% by volume or more of the total pore volume, the capacity is high, the impregnation property of the cathode agent is high, and the low ESR and tan δ characteristics It is possible to produce a solid electrolytic capacitor that is excellent in long-term reliability.

  That is, this invention relates to the manufacturing method of the valve action metal sintered compact for anodes of the following solid electrolytic capacitors, and the solid electrolytic capacitor using the sintered compact as an anode.

（式中、Ｒ¹〜Ｒ⁴はそれぞれ独立して水素原子、炭素数１〜１０の直鎖状もしくは分岐状の飽和もしくは不飽和のアルキル基、アルコキシ基あるいはアルキルエステル基、またはハロゲン原子、ニトロ基、シアノ基、１級、２級もしくは３級アミノ基、ＣＦ₃基、フェニル基及び置換フェニル基からなる群から選ばれる一価基を表わし、
Ｒ¹とＲ²及びＲ³とＲ⁴の炭化水素鎖は互いに任意の位置で結合して、かかる基により置換を受けている炭素原子と共に少なくとも１つ以上の３〜７員環の飽和または不飽和炭化水素の環状構造を形成する二価鎖を形成してもよく、
前記環状の結合鎖は、その任意の位置にカルボニル、エーテル、エステル、アミド、スルフィド、スルフィニル、スルホニル、イミノの結合を含んでもよく、
Ｘは酸素、硫黄または窒素原子を表し、Ｒ⁵はＸが窒素原子の時のみ存在して、独立して水素原子または炭素数１〜１０の直鎖状もしくは分岐状の飽和もしくは不飽和のアルキル基を表す。）
で示される繰り返し単位を含む重合体に、ドーパントをドープした導電性高分子である前記５５に記載の固体電解コンデンサ。
６７．導電性高分子が、下記一般式（３）

（式中、Ｒ⁶及びＲ⁷は、各々独立して水素原子、炭素数１〜６の直鎖状もしくは分岐状の飽和もしくは不飽和のアルキル基、または該アルキル基が互いに任意の位置で結合して、２つの酸素元素を含む少なくとも１つ以上の５〜７員環の飽和炭化水素の環状構造を形成する置換基を表わし、
前記環状構造には置換されていてもよいビニレン結合を有するもの、置換されていてもよいフェニレン構造のものが含まれる。）
で示される繰り返し単位を含む導電性高分子である前記６６に記載の固体電解コンデンサ。
６９．対電極の材料が、有機スルホン酸アニオンをドーパントとして含む前記５４乃至５７および６６、６７のいずれかに記載の固体電解コンデンサ。 1. Disperse a mixture containing at least one primary powder, secondary agglomerated powder or a granulated powder thereof, a pore-forming agent, and an organic binder selected from a valve metal, a valve metal compound and a valve metal alloy Coating and molding, or compressing and molding the granulated product of the mixture, sintering the resulting molded body, and removing the pore forming agent contained in the obtained sintered body The manufacturing method of the valve action metal sintered compact for anodes of a solid electrolytic capacitor characterized by including a process.
2. Compression and molding of a granulated mixture of at least one primary powder selected from niobium, a niobium compound and a niobium alloy, a secondary agglomerated powder or a granulated powder thereof, a pore forming agent, and an organic binder. A niobium sintered body for an anode of a solid electrolytic capacitor, comprising: a step of sintering, a step of sintering the obtained molded body, and a step of removing a pore forming agent contained in the obtained sintered body Production method.
3. Before the step of forming a molded body, the granulated product of the mixture has a step of doping at least one element selected from the group consisting of nitrogen, oxygen, boron, phosphorus, sulfur, selenium, tellurium 3. The production method according to 1 or 2.
4). After the step of forming the formed body and before the sintering step, the step of doping the formed body with at least one element selected from the group consisting of nitrogen, oxygen, boron, phosphorus, sulfur, selenium, and tellurium. The manufacturing method according to 1 or 2 above.
5. After the sintering step and before the pore forming agent removing step, at least one selected from the group consisting of nitrogen, oxygen, boron, phosphorus, sulfur, selenium and tellurium is applied to the sintered body containing the pore forming agent. 3. The manufacturing method according to 1 or 2 above, comprising a step of doping an element.
6). Valve action metal compounds and valve action metal alloys are hydrogen, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, titanium, zirconium, hafnium, vanadium, tantalum, niobium, chromium, molybdenum, tungsten, manganese, rhenium, ruthenium , Osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium, carbon, silicon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth , Oxygen, sulfur, selenium, tellurium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosym, holmium, erbium, thulium, ytte The process according to any one of the 1 to 5 comprising at least one element selected from the group consisting of Biumu and lutetium.
7). 7. The manufacturing method according to 6, wherein the valve action metal compound and the valve action metal alloy contain an element of tantalum or niobium.
8). 7. The production method according to 6 above, wherein the valve metal compound and the valve metal alloy include at least one selected from the group consisting of niobium monoxide, silicon nitride, and antimony.
9. 9. The production method according to 8 above, wherein the silicon nitride is a compound represented by SiαNβ (wherein α and β represent a positive integer).
10. 10. The production method according to 9 above, wherein the silicon nitride is at least one selected from SiN, Si ₂ N ₂ , Si ₂ N ₃ and Si ₃ N ₄ .
11. 11. The production method according to any one of 1 to 3 to 10, wherein an average particle diameter of at least one primary powder selected from a valve action metal, a valve action metal compound, and a valve action metal alloy is 0.01 to 2 μm.
12 The production according to any one of 1 to 3 and 10, wherein an average particle size of at least one secondary agglomerated powder selected from a valve metal, a valve metal compound and a valve metal alloy is 0.1 to 20 μm. Method.
13. The above 1, 3 to 10 wherein the granulated powder of at least one primary powder or secondary agglomerated powder selected from a valve action metal, a valve action metal compound and a valve action metal alloy has an average particle diameter of 0.2 to 200 µm. The manufacturing method in any one of.
14 14. The manufacturing method according to any one of 11 to 13, wherein the valve action metal, the valve action metal compound, and the valve action metal alloy are niobium, a niobium compound, and a niobium alloy.
15. 15. The production method according to any one of 1 to 14, wherein the pore forming agent is an oxide present as a solid at a temperature at which the molded body is sintered.
16. 16. The production method according to 15 above, wherein the oxide is an oxide of Groups 1 to 5 and Groups 7 to 15 of the Periodic Table.
17. The oxide is lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, rhenium, iron, ruthenium, cobalt, rhodium, iridium, nickel, copper, From cadmium, mercury, boron, aluminum, gallium, indium, thallium, silicon, germanium, lead, antimony, bismuth, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium 16. The production method according to 15 above, which is at least one oxide selected from the group consisting of:
18. 16. The production method according to 15 above, wherein the oxide-providing compound is at least one selected from the group consisting of hydroxide, carbonate and bicarbonate.
19. Pore forming agent is sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, lithium oxide, lithium carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium hydrogen carbonate, magnesium calcium carbonate, calcium oxide, calcium hydroxide , Calcium carbonate, barium oxide, barium carbonate, hafnium oxide, yttrium oxide, yttrium hydroxide, yttrium carbonate, lanthanum oxide, lanthanum hydroxide, lanthanum carbonate, cerium oxide, cerium hydroxide, cerium carbonate, neodymium oxide, neodymium hydroxide, Neodymium carbonate, samarium oxide, samarium hydroxide, samarium carbonate, manganese carbonate, iron oxide, iron hydroxide, iron carbonate, magnesium oxide, lead iron oxide, barium zinc oxide, boron oxide, aluminum oxide, Aluminum oxide, a manufacturing method according to any one of the 15 is at least one compound selected from the group consisting of lead oxide, and lead carbonate.
20. 20. The production method according to any one of 1 to 19, wherein the pore forming agent used for the preparation of the granulated product is a powder having an average particle size of 0.1 μm to 100 μm.
21. 21. The production method according to 20, wherein the pore forming agent has a particle size distribution having a plurality of peaks.
22. 22. The production method according to 21 above, wherein the plurality of peaks are present at least one in a particle diameter of 0.1 to 1.0 μm and at least one in a particle diameter of 1.0 μm or more.
23. 1 to 22 above, wherein the organic binder is at least one selected from the group consisting of camphor, naphthalene, soap fatty acid, carbowax, vegetable wax, purified paraffin, acrylic polymer, methacrylic polymer, vinyl polymer and polyethylene carbonate. The manufacturing method in any one.
24. The pore-forming agent removal step is selected from the group consisting of water, organic solvents, acidic solvents, alkaline solvents, amine solvents, amino acid solvents, polyphosphoric acid solvents, crown ether solvents, chelating solvents, ammonium salt solvents, and ion exchange resin dispersion solvents. 24. The production method according to any one of 1 to 23, which is a step of removing with at least one selected solvent.
25. Furthermore, the manufacturing method in any one of said 1-24 including the process of providing the lead | read | reed of a valve action metal.
26. The manufacturing method according to 25, wherein the step of providing the lead is performed by compressing and molding the granulated material together with the valve metal lead and implanting the valve metal lead in the compression / molding step.
27. The manufacturing method according to 25, wherein the step of providing the lead is performed by welding the valve action metal lead to the sintered body after the removing step.
28. It comprises at least one kind of primary powder selected from valve action metal, valve action metal compound and valve action metal alloy, secondary agglomerated powder, or a mixture of these granulated powder, pore former and organic binder, 3. The production method according to 1 or 2 above, wherein the average particle diameter of the granules is 10 to 1000 μm.
29. It comprises at least one kind of primary powder selected from valve action metal, valve action metal compound and valve action metal alloy, secondary agglomerated powder, or a mixture of these granulated powder, pore former and organic binder, 3. The method according to 1 or 2 above, wherein the repose angle of the granules is 60 ° or less.
30. It comprises at least one kind of primary powder selected from valve action metal, valve action metal compound and valve action metal alloy, secondary agglomerated powder, or a mixture of these granulated powder, pore former and organic binder, ^3. The production method according to 1 or 2 above, wherein the flowability of the granules is 0.1 cm ³ / g or more.
31. Granulation comprising at least one primary powder selected from valve action metals, valve action metal compounds and valve action metal alloys, secondary agglomerated powders, or a mixture of these granulated powders, a pore-forming agent and an organic binder A granulated product, wherein the ratio of the minor axis diameter to the major axis diameter of the product is 50 or less with respect to the minor axis 1.
32. Valve action metal compounds and valve action metal alloys are hydrogen, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, titanium, zirconium, hafnium, vanadium, tantalum, niobium, chromium, molybdenum, tungsten, manganese, rhenium, ruthenium , Osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium, carbon, silicon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth , Oxygen, sulfur, selenium, tellurium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosym, holmium, erbium, thulium, ytte Biumu, and granulated product according to the 31 containing at least one element selected from the group consisting of lutetium.
33. 33. The granulated product according to 31 or 32, wherein the valve action metal compound and the valve action metal alloy contain an element of tantalum or niobium.
34. 33. The granulated product as described in 31 or 32 above, wherein the valve action metal compound and the valve action metal alloy contain at least one selected from the group consisting of niobium monoxide, silicon nitride and antimony.
35. 35. The granulated product as described in 34 above, wherein the silicon nitride is a compound represented by SiαNβ (wherein α and β represent a positive integer).
36. A sintered body of a valve metal, a valve metal compound or a valve metal alloy for a solid electrolytic capacitor anode, having a volume of 10 mm ³ or more and a specific surface area of 0.005 m ² / mm ³ or more.
37. The volume is 10 mm ³ or more, the porosity is 55% by volume or more, the maximum peak of the pore diameter distribution is 0.1 μm or more and 10 μm or less, and the volume of pores having a diameter of 1 μm or more is 10% by volume of the total pore volume. A sintered body of a valve action metal, a valve action metal compound or a valve action metal alloy for an anode of a solid electrolytic capacitor, characterized in that it is as described above.
38. 38. The sintered body according to 36 or 37, wherein a plurality of pore diameter distribution peaks are present at 0.3 μm or more.
39. The sintered body according to any one of 36 to 38, wherein the volume of pores having a diameter of 1 μm or more is 13% by volume or more of the total pore volume.
40. Valve action metal compounds and valve action metal alloys are hydrogen, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, titanium, zirconium, hafnium, vanadium, tantalum, niobium, chromium, molybdenum, tungsten, manganese, rhenium, ruthenium , Osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium, carbon, silicon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth , Oxygen, sulfur, selenium, tellurium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosym, holmium, erbium, thulium, ytter Um, and a sintered body according to any one of the 36 to 39 comprising at least one element selected from the group consisting of lutetium.
41. It contains at least one primary powder, secondary agglomerated powder or granulated powder thereof, a pore forming agent, an organic binder and a solvent selected from a valve metal, a valve metal compound and a valve metal alloy, 2. The dispersion according to 1 above, wherein the solid content concentration is 1 to 80% by mass.
42. The dispersion according to 41, wherein the viscosity at 20 ° C. is 0.1 Pa · s or more.
43. The dispersion according to 41, wherein the thixotropy index at 20 ° C. is 0.2 to 2.
44. The coating body formed by coating the dispersion liquid in any one of said 41-43.
45. A molded body comprising the dispersion according to any one of 41 to 43 in a mold.
46. Granulated product of at least one kind of primary powder, secondary agglomerated powder selected from valve action metal, valve action metal compound and valve action metal alloy, or a mixture containing these granulated powder, pore former and organic binder A molded product characterized by being compressed and molded.
47. 47. The molded article according to 46, wherein the valve action metal, the valve action metal compound, and the valve action metal alloy are niobium, a niobium compound, and a niobium alloy.
48. 48. A sintered body containing a pore forming agent obtained by sintering the coated body according to 44 or the molded body according to any one of 45 to 47.
49. 49. A sintered body for an anode of a solid electrolytic capacitor containing no pore forming agent, wherein the pore forming agent contained in the sintered body according to 48 is removed.
50. The sintered body for an anode according to any one of 36 to 40 and 48 and 49, wherein the sintered body has a CV value of 40000 to 400,000 400,000 FV / g when sintered at 50.200 ° C.
51. 50. A solid electrolytic capacitor comprising the anode sintered body of the solid electrolytic capacitor according to any one of 36 to 40 and 48 and 49 as one electrode, and a dielectric interposed between the counter electrode .
52. 52. The solid electrolytic capacitor as described in 51 above, wherein the main component of the dielectric is niobium oxide or tantalum oxide.
53. 53. The solid electrolytic capacitor according to 51 or 52, wherein the counter electrode material is at least one selected from the group consisting of a solid electrolyte, an organic semiconductor, and an inorganic semiconductor.
54. The material of the counter electrode is an organic semiconductor, and the organic semiconductor is an organic semiconductor composed of benzopyrroline tetramer and chloranil, an organic semiconductor mainly composed of tetrathiotetracene, and an organic composed mainly of tetracyanoquinodimethane. 54. The solid electrolytic capacitor as described in 53 above, which is at least one selected from the group consisting of a semiconductor and a conductive polymer.
55. 55. The solid electrolytic capacitor as described in 54 above, wherein the organic semiconductor is a conductive polymer, and the conductive polymer is at least one selected from polypyrrole, polythiophene, polyaniline and substituted derivatives thereof.
56. 56. The solid electrolytic capacitor as described in 55 above, wherein the conductive polymer is a conductive polymer obtained by doping a dopant in poly (3,4-ethylenedioxythiophene).
57. The solid electrolytic capacitor according to any one of 54 to 56, wherein the counter electrode material has a layered structure at least in part.
58. 58. An electronic circuit using the solid electrolytic capacitor according to any one of 51 to 57.
59. 58. An electronic device using the solid electrolytic capacitor according to any one of 51 to 57.
60. 58. A device using the solid electrolytic capacitor according to any one of 51 to 57, which is an oscillator-mounted device, an IC-mounted device, a CPU-mounted device, or a power supply device.
61. Valve action metal compounds and valve action metal alloys are hydrogen, yttrium, zirconium, hafnium, vanadium, tantalum, niobium, molybdenum, tungsten, manganese, rhenium, zinc, boron, aluminum, silicon, nitrogen, antimony, oxygen, neodymium, erbium 7. The production method according to 6 above, comprising at least one element selected from the group consisting of ytterbium and lutetium.
62. The manufacturing method according to 61, wherein the valve action metal compound and the valve action metal alloy contain silicon and nitrogen.
63. Valve action metal compounds and valve action metal alloys are hydrogen, yttrium, zirconium, hafnium, vanadium, tantalum, niobium, molybdenum, tungsten, manganese, rhenium, zinc, boron, aluminum, silicon, nitrogen, antimony, oxygen, neodymium, erbium 33. The granulated product according to 32, comprising at least one element selected from the group consisting of ytterbium and lutetium.
64. 64. The granulated product according to 63, wherein the valve action metal compound and the valve action metal alloy contain at least one element selected from the group consisting of tantalum, niobium, silicon, nitrogen, antimony and oxygen.
65. Valve action metal compounds and valve action metal alloys are hydrogen, yttrium, zirconium, hafnium, vanadium, tantalum, molybdenum, tungsten, manganese, rhenium, zinc, boron, aluminum, silicon, nitrogen, antimony, oxygen, neodymium, erbium, ytterbium 41. The sintered body according to 40, comprising at least one element selected from the group consisting of lutetium and lutetium.
66. The conductive polymer is represented by the following general formula (1) or general formula (2).

Wherein R ^{1 to} R ⁴ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, a halogen atom, a nitro group, A monovalent group selected from the group consisting of a group, a cyano group, a primary, secondary or tertiary amino group, a CF ₃ group, a phenyl group and a substituted phenyl group;
The hydrocarbon chains of R ¹ and R ² and R ³ and R ⁴ are bonded to each other at any position, and at least one or more 3- to 7-membered saturated or unsaturated groups with carbon atoms substituted by such groups. It may form a divalent chain that forms a cyclic structure of a saturated hydrocarbon,
The cyclic bond chain may include a bond of carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino at any position thereof,
X represents an oxygen, sulfur or nitrogen atom, R ⁵ is present only when X is a nitrogen atom, and is independently a hydrogen atom or a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms. Represents a group. )
56. The solid electrolytic capacitor as described in 55 above, which is a conductive polymer obtained by doping a polymer containing a repeating unit represented by the following formula:
67. The conductive polymer is represented by the following general formula (3)

(Wherein R ⁶ and R ⁷ are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 6 carbon atoms, or the alkyl group is bonded to each other at an arbitrary position. And represents a substituent that forms a cyclic structure of at least one 5- to 7-membered saturated hydrocarbon containing two oxygen elements,
The cyclic structure includes those having a vinylene bond which may be substituted and those having a phenylene structure which may be substituted. )
67. The solid electrolytic capacitor as described in 66 above, which is a conductive polymer containing a repeating unit represented by:
69. 68. The solid electrolytic capacitor according to any one of 54 to 57 and 66, 67, wherein the counter electrode material contains an organic sulfonate anion as a dopant.

  Hereinafter, the present invention will be specifically described.

[1] Granulated product The granulated product used in the production of the sintered body of the present invention is at least one primary powder, secondary agglomerated powder selected from a valve action metal, a valve action metal compound and a valve action metal alloy. These granulated powders (hereinafter simply referred to as “valve action metal powder” or “valve action metal powder for capacitors”), a mixture containing a pore forming agent and an organic binder. The valve action metal is preferably niobium and tantalum, particularly preferably niobium.

  The valve action metal, the valve action metal compound, and the valve action metal alloy used in the present invention refer to those containing niobium or tantalum as a main component and being a material for producing a capacitor. In addition to pure niobium or pure tantalum, conductive (semiconductor) containing components such as alloys and composites of niobium or tantalum and other components, nitrogen (50 to 50000 ppm) and / or oxygen (2000 to 200000 ppm). Niobium or tantalum compounds. In niobium, the form of the conductive (including semiconductor) compound containing nitrogen and / or oxygen may be niobium mononitride and / or niobium monoxide and / or niobium monoxide. These compounds may be in the form of amorphous, amorphous, glassy, colloidal or crystalline. Further, pure niobium or pure tantalum, niobium alloy, tantalum alloy, niobium compound or hydride of tantalum compound may be used.

Components other than the valve action metal of the valve action metal alloy and the valve action metal compound include hydrogen, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, titanium, zirconium, hafnium, vanadium, tantalum, niobium, chromium, Molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium, carbon, silicon, germanium, tin, lead, Nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium, tellurium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosim, hormiu , Erbium, thulium, ytterbium, and at least one element and the like are selected from the group consisting of lutetium. Preferably, hydrogen, yttrium, zirconium, hafnium, vanadium, tantalum, niobium, molybdenum, tungsten, manganese, rhenium, zinc, boron, aluminum, silicon, nitrogen, phosphorus, antimony, oxygen, neodymium, erbium, ytterbium and lutetium At least one element selected from the group. These valve action metal alloys and valve action metal compounds may be in the form of amorphous, amorphous, glassy, colloidal, crystalline or the like. In order to obtain a valve action metal powder for a capacitor having a higher capacity and a lower ESR, it is preferable to contain at least one element of nitrogen, oxygen, tantalum, antimony and silicon. In the case of a niobium compound containing nitrogen and silicon, the form may be silicon nitride. Specific examples of silicon nitride include SiN, Si ₂ N ₂ , Si ₂ N ₃ , Si ₃ N ₄ , etc., and the forms thereof are amorphous, amorphous, glassy, colloidal, crystal, etc. The thing which is taking the form of may be sufficient.

  In the production method of the present invention, as the valve action metal powder, any of a primary powder, a secondary agglomerated powder obtained by agglomerating it, and a granulated powder obtained by granulating the primary powder or the secondary agglomerated powder can be used. . The primary powder preferably has an average particle size of 0.01 to 2 μm, the secondary agglomerated powder preferably has an average particle size of 0.1 to 20 μm, and the granulated powder has an average particle size of 0.2. The thing of -200 micrometers is preferable. The valve action metal powder can be suitably used regardless of the shape such as a spherical shape, a rod shape, a flat shape, and a flake shape. In order to obtain a valve capacitor metal sintered body for a capacitor having a higher capacity, it is desirable to use a valve metal powder having a small heat history and a large specific surface area.

  Such valve-acting metal powder is produced by pulverization of niobium powder, niobium compound powder, niobium alloy powder described in US Pat. No. 4,084,965, JP-A-10-242004, JP-A-2002-25864, etc. Using a known method such as niobium powder or niobium powder by reduction of niobium oxide or niobium halide described in U.S. Pat.No. 1,728,941, U.S. Pat. Can be manufactured.

The pore forming agent used in the present invention does not react with the valve action metal, the valve action metal compound or the valve action metal alloy before or during the subsequent sintering process, and the sintering temperature (usually 700 A substance that remains in a solid state at a temperature higher than or equal to ° C., specifically, an oxide or a compound that gives such an oxide through a sintering process is preferable. By using a pore-forming agent that remains solid at the sintering temperature, the valve action metal powder is prevented from agglomerating more than necessary during sintering, so that the fusion of the valve action metals only at the contact points of the valve action metals. Can be awakened. A pore forming agent that becomes a liquid or gas at the sintering temperature can also be used, but in that case, the effect of blocking the aggregation of the valve action metal powder is reduced, and a pore smaller than the desired pore may be formed.
Also, blocking unnecessary aggregation of the valve action metal powder can control the density of the sintered body that is optimal for the impregnation of the cathode agent during capacitor production, leaving a large specific surface area of the sintered body. The capacity per unit volume of the sintered body can be increased.

Examples of the pore forming agent include lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, rhenium, iron, ruthenium, cobalt, rhodium, iridium. , Nickel, copper, cadmium, mercury, boron, aluminum, gallium, indium, thallium, silicon, germanium, lead, antimony, bismuth, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosym, holmium, erbium, thulium , Ytterbium and lutetium oxides, and hydroxides, carbonates or hydrogencarbonates that give these oxides can be used alone or in combination. That.
In the present invention, the pore forming agent after the sintering step includes those in which the pore forming agent used at the time of forming the molded body becomes an oxide by the sintering treatment.

  Since the pore-forming agent is removed by the solvent in the step after sintering, those having good solubility in the solvent are preferable. Furthermore, an inexpensive pore forming agent is economically advantageous because it is dissolved and removed. Therefore, particularly preferred pore-forming agents include sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium oxide, lithium carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium bicarbonate, magnesium calcium carbonate, oxidation Calcium, calcium hydroxide, calcium carbonate, barium oxide, barium carbonate, hafnium oxide, yttrium oxide, yttrium hydroxide, yttrium carbonate, lanthanum oxide, lanthanum hydroxide, lanthanum carbonate, cerium oxide, cerium hydroxide, cerium carbonate, neodymium oxide , Neodymium hydroxide, neodymium carbonate, samarium oxide, samarium hydroxide, samarium carbonate, manganese carbonate, iron oxide, iron hydroxide, iron carbonate, magnesium iron oxide, lead iron oxide, barium zinc oxide, Boron, aluminum oxide, aluminum hydroxide, lead oxide, at least one compound selected from the group consisting of lead carbonate.

The particle diameter of the pore forming agent affects the pore diameter of the sintered body of the present invention, and the pore diameter of the sintered body affects the capacity of the capacitor and the impregnation property of the cathode agent in the capacitor manufacturing process. When the impregnation property of the cathode agent is good, a capacitor having a high capacity and a low ESR can be obtained. In particular, the difference in impregnation is noticeable for large-sized capacitor anode sintered bodies having a thickness of 1 mm or more and a sintered body volume of 10 mm ³ or more. Since the sintered compact with a small peak of pore diameter distribution is not well impregnated with the cathode agent, the desirable pore diameter of the valve action metal sintered body for capacitors is 0.1 μm or more as an average diameter, and more than 0.3 μm. It is. In particular, in the case of a valve capacitor metal sintered body for an anode of a large capacitor having a sintered body volume of 10 mm ³ or more and a porosity of 55 volume% or more, the total pore volume of 1 μm or more is the total pore volume. It is preferable that it is 10 volume% or more. More preferably, there are a plurality of pore diameter distribution peaks at 0.3 μm or more, and the total pore volume of 1 μm or more is 13% by volume or more of the total pore volume.

  As described above, since the pore-forming agent exists as a solid at the sintering temperature and is removed with an appropriate solvent, the average pore diameter of the sintered body of the present invention is the average particle diameter of the pore-forming agent. Almost unchanged. Therefore, the average particle diameter of the pore-forming agent is preferably 0.1 μm or more and 100 μm or less, more preferably 0.5 μm or more and 20 μm or less. When only one kind of pore forming agent having an average particle size of 1.0 μm or less is used, it is preferable that the distribution of 1 μm or more in the particle size distribution of the pore forming agent is 10% by volume or more.

  Moreover, a plurality of pore forming agents having different average particle diameters can be mixed and used as a pore forming agent having a plurality of peaks in the particle size distribution. Specifically, a pore forming agent having an average particle diameter of 0.1 to 1 μm, preferably 0.3 to 1 μm, and a fine particle having an average particle diameter of 1 μm or more, preferably 1 to 20 μm, more preferably 1 to 5 μm. By using in combination with the hole forming agent, the impregnation property of the cathode agent into the anode sintered body is improved. These pore forming agents having different average particle diameters can be used by mixing a plurality of pore forming agents having different average particle diameters. Even when a plurality of pore-forming agents having different average particle diameters are used in combination, the pore-forming agent mixture preferably has a particle diameter of 1 μm or more, and is preferably 10% by volume or more, and further 13 to 80% by volume. It is preferable that it is, and it is especially preferable that it is 15-50 volume%. For example, in order to adjust the pore diameter distribution peak of the sintered body to 0.7 μm and 2 μm and to adjust the pore volume having a diameter of 1 μm or more to 13 volume% or more of the total pore volume, A pore forming agent having an average particle diameter of about 0.7 μm and about 2 μm may be used in combination, and the ratio of the pore forming agent having an average particle diameter of 2 μm or more may be 13% by volume or more.

  The amount of pore-forming agent added to the valve metal is related to the density of the compact and the density of the sintered body. The density of the sintered body of the present invention is preferably 2.5 to 4.0 g / ml with respect to niobium, considering the ease of impregnation of the cathode agent and the strength of the sintered body. 3.8 g / ml is more preferable, and 3.0 to 3.6 g / ml is particularly preferable. For tantalum, it is preferably 4.5 to 7.8 g / ml, more preferably 4.8 to 7.3 g / ml, and particularly preferably 5.0 to 6.8 g / ml. Also, the valve metal equivalent density (the density of the above-mentioned valve action metal, valve action metal compound, valve action metal alloy, etc. excluding the pore forming agent, binder and lead wire) of the compact is related to shrinkage. To niobium is preferably 2.0 to 3.8 g / ml, more preferably 2.5 to 3.6 g / ml, and particularly preferably 2.8 to 3.4 g / ml. For tantalum, 4.0 to 7.5 g / ml is preferable, 4.5 to 7.0 g / ml is more preferable, and 4.8 to 6.3 g / ml is particularly preferable.

  What is necessary is just to select the quantity of the pore formation agent to add so that a sintered compact density may become in the said range. Although it varies depending on the molecular weight, shape, average particle diameter, bulk density, and tapping density of the pore forming agent, it is usually preferably 70% by mass or less based on the total amount of the valve action metal powder and the pore forming agent. A mass% or less is more preferable.

  A known organic binder can be used as the binder used in the mixture of the valve metal powder, the pore forming agent and the binder in the present invention. For example, soap fatty acids such as camphor, naphthalene, stearic acid, carbowax, vegetable wax, refined paraffin, acrylic polymers such as polyacrylic acid, polyacrylic acid ester, polyacrylamide, polymethacrylic acid, polymethacrylic acid ester, polymethacrylic acid Methacrylic polymers such as amide, polyvinyl alcohols such as polyvinyl alcohol, polyvinyl butyral, and polyvinyl acetate, and polyethylene carbonate can be used. These binders are usually used after being dissolved in a solution. Examples of the solvent that can be used include water, alcohols, ethers, cellosolves, ketones, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and the like.

  The amount of the organic binder used cannot be generally specified depending on the type thereof, but is usually 1 to 15 parts by mass, preferably 3 to 3 parts when the total of the valve action metal powder and the pore forming agent is 100 parts by mass. It is 10 mass parts, More preferably, it is 4-8 mass parts.

  The granulated product comprising the mixture of the valve action metal powder, the pore forming agent and the binder in the present invention can be produced, for example, as follows.

  Capacitor valve metal powder, pore forming agent and organic binder are put in a solvent (toluene or the like) and mixed thoroughly. A mixer can be used for mixing. As the mixer, ordinary apparatuses such as a shake mixer, a V-type mixer, a bead mixer, and a nauter mixer can be used without any problem. Although the temperature in mixing is limited by the boiling point and freezing point of the solvent, it is generally −50 ° C. or higher and 120 ° C. or lower, preferably −50 ° C. or higher and 50 ° C. or lower, more preferably −10 ° C. or higher and 30 ° C. or lower. The time required for mixing is not particularly limited as long as it is 5 minutes or longer, but is usually 1 to 6 hours. It is desirable to perform in an oxygen-free atmosphere using an inert gas such as nitrogen or argon. Then, it granulates, distilling a solvent off.

A dry granulator can be used for distilling off the solvent. Examples of the drying granulator include a conical dryer, a fluid dryer, a nauter mixer, and a Henschel mixer. Although the solvent is distilled off, it is carried out from room temperature to 200 ° C. under an appropriate pressure from reduced pressure to increased pressure, although it depends on the boiling point of the solvent used. In general, the temperature is preferably from normal temperature to 120 ° C. under reduced pressure.
The granulated product in the present invention preferably has an average particle size of 10 μm to 1000 μm, more preferably 15 μm to 500 μm, and particularly preferably 20 μm to 300 μm.

As described above, the valve action metal powder and the pore forming agent may each be used alone to prepare a mixture, or the valve action metal powder and the pore forming agent are mixed and granulated in advance and then an organic binder is used. A mixture may be prepared. When mixing and granulating the valve action metal powder and the pore forming agent in advance, for example, put the valve action metal powder and the pore forming agent in an organic solvent such as toluene and mix using the above mixer and dry granulator. Prepare a dispersion.
This dispersion can be applied or printed. In this case, the portion of the dispersion excluding the solvent, that is, the concentration range of the solid content is preferably 1 to 80% by mass, particularly preferably 1 to 50% by mass.
The viscosity of the dispersion at this time is determined by the method described in JIS Z 8803. Viscosity can be measured with a general apparatus such as a B type viscometer or an E type viscometer. The viscosity range is preferably 0.1 Pa · s or more at 20 ° C., particularly preferably 0.2 Pa · s or more. Moreover, it is preferable that the range of the thixotropy index at this time is 0.2-2, and 0.3-1.6 are especially preferable.
In order to prepare a mixture using the above dispersion, the mixture can be granulated, dried, and then heated at an appropriate pressure at a temperature of 300 ° C. to 1700 ° C. for 1 minute to 100 hours. At this time, an inorganic binder or an organic binder may be used. Although the heat history (temperature, time, number of times) depends on the temperature, the specific surface area of the sintered body is reduced, and as a result, the capacity is reduced. Therefore, it is desirable that the heat history is small.

  In the present invention, a step of doping at least one element selected from the group consisting of nitrogen, boron, phosphorus, sulfur, selenium, and tellurium is provided on the granulated product before forming the valve action metal powder or molded body. Also good. For example, in nitrogen doping, methods such as gas nitriding, ion nitriding, and solid nitriding are used. Among them, the gas nitriding method is preferable because nitrogen can be uniformly doped on the surface of the niobium particles. The dope treatment may be performed on the molded body before sintering, or after sintering, before the step of removing the pore forming agent, or after the step of removing the pore forming agent. May be.

[2] Molded body In the present invention, molding refers to a method of printing or coating the dispersion, and a method of compression molding a granulated product composed of a mixture of a valve metal powder, a pore forming agent and a binder. The molded product refers to a product molded by the above method.
Molding by a method of printing or applying the dispersion is, for example, a method of printing the dispersion on a substrate by a known printing method such as a doctor blade, a roll coating method such as squeeze coating, a screen printing method using a metal mask or the like, an intaglio printing method, A method of forming by casting a dispersion into a mold (pillow molding, mud casting) or the like can be used.
In the present invention, a molded product of a granulated product composed of a mixture of a valve action metal powder, a pore-forming agent and a binder (hereinafter sometimes simply referred to as “molded product”) can be preferably produced by an automatic molding machine. . Specifically, the granulated material is weighed while being naturally dropped from a hopper of an automatic molding machine to a mold, and molded together with a lead wire. For this reason, in the case of a granulated product having no suitable flowability and angle of repose, it cannot flow stably from the hopper to the mold and cannot be stably molded. As a result, the mass of the molded body, the strength of the sintered body, and variations in shape increase, chipping and cracking may occur, and the leakage current value may deteriorate. When the average particle size of the granulated product is 10 μm or less, the flowability is poor, and when it is 1000 μm or more, the filling amount in the corners of the mold varies. Therefore, the average particle diameter of the granulated product is preferably 10 μm to 1000 μm, more preferably 15 μm to 500 μm, and particularly preferably 20 μm to 300 μm, as described above. The granulated product of the present invention preferably has an angle of repose of 60 ° or less, particularly 10 to 50 ° in the tilt method. As the flowability of the granulated product in the present invention (measured by the method of Japanese Industrial Standard Z2504), the larger the volume flowing per unit time, the better. Usually, it is preferably 0.1 cm ³ / s or more, more preferably 0.2 cm ³ / s or more, and particularly preferably 0.3 cm ³ / s or more. If the flowability is good, it can be suitably used regardless of the shape, such as a spherical shape, a rod shape, a flat shape, or a flake shape, but usually a spherical shape or a rod shape is preferred. The ratio of the minor axis diameter to the major axis diameter of the granulated product is preferably 50 or less, more preferably 10 or less, and particularly preferably 5 or less for the major axis with respect to the minor axis 1.

  Even if a molded body is prepared without using a lead wire, and the lead wire is welded to the sintered body containing the pore forming agent after sintering or the sintered body after sintering and removing the pore forming agent, good. For this welding, spot welding is preferably used. As the lead wire, tantalum, niobium, aluminum having a valve action, and compounds and alloys thereof can be preferably used. For example, niobium, partially nitrided niobium due to the adhesive property with sintered niobium powder, Niobium alloys are preferred. A niobium lead wire having the same composition as the niobium powder of the present invention is more preferred. That is, when using a partially nitrided niobium powder, it is preferable to use a partially nitrided niobium lead wire, and when using a niobium alloy powder, it is preferable to use a niobium alloy lead wire.

[3] Sintering treatment The molded body thus obtained is subjected to a sintering treatment. The sintering conditions depend on the melting point and boiling point of the pore-forming agent used and / or the melting point and boiling point of the valve metal powder, valve metal compound and valve metal alloy used. It is carried out by heating at 700 ° C. to 2000 ° C. for 1 minute to 100 hours in the presence of an inert gas or under a high reduced pressure (eg 10 ⁻⁴ to 10 ⁻¹ Pa). A preferable sintering temperature is 800 ° C to 1500 ° C, and a more preferable sintering temperature is 1000 ° C to 1300 ° C.

A step of removing the organic binder before reaching the sintering temperature can be provided. The removal of the organic binder can be performed, for example, by treating at 200 to 600 ° C., which is lower than the sintering temperature, for 10 minutes to 10 hours under reduced pressure (10 ¹ to 10 ³ Pa). By providing the organic binder removal treatment step before the sintering treatment, the organic binder can be more completely removed.
Further, when a hydride of a valve action metal, a valve action metal compound, or a valve action metal alloy is used as the metal powder, a step of removing hydrogen can be provided during or before the sintering step. Removal of hydrogen (dehydrogenation) can be performed, for example, by treating at 300 to 600 ° C. for 10 minutes to 100 hours under reduced pressure (10 ¹ to 10 ³ Pa).

  After the sintering is completed, the valve action metal sintered body is cooled until the temperature (also referred to as product temperature) is 30 ° C. or less, and is 0.01 vol% to 10 vol%, preferably 0.1 vol% to 1 An inert gas such as nitrogen or argon containing volume% oxygen is gradually added so that the product temperature does not exceed 30 ° C., and the mixture is left for 8 hours or longer and then taken out.

[4] Removal of pore-forming agent After sintering, the pore-forming agent contained in the sintered body is removed to produce the valve-acting metal sintered body for capacitor anode of the present invention. Examples of the method for removing the pore forming agent include a method for removing it by dissolving in a solvent. The solvent to be used may be any solvent that can sufficiently obtain the solubility of the pore-forming agent to be dissolved, and is preferably an inexpensive one that hardly remains.
For example, if the pore forming agent is water-soluble, water can be used as the solvent.
If the pore forming agent is soluble in an organic solvent, an organic solvent can be used as the solvent. As the organic solvent, alcohols such as methanol and ethanol, ketones such as acetone and methyl isobutyl ketone, dimethylsulfoylside (DMSO) and the like can be used.
If the pore-forming agent is acid-soluble, an acidic solvent such as nitric acid, sulfuric acid, phosphoric acid, boric acid, carbonic acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, or organic acid may be used as the solvent. it can.
If the pore-forming agent is alkali-soluble, an alkaline solvent such as an alkali metal hydroxide, an alkaline earth metal hydroxide, or ammonia can be used as the solvent.
If the pore-forming agent forms a soluble complex, ammonia as its ligand, amines such as ethylenediamine, amino acids such as glycine, polyphosphoric acids such as sodium tripolyphosphate, crown ethers, sodium thiosulfate A solution of a chelating agent such as thiosulfate such as ethylenediaminetetraacetic acid can be used.
Also, ammonium salt solutions such as ammonium chloride, ammonium nitrate, and ammonium sulfate, cation exchange resins, and anion exchange resins can be suitably used.

  The combination of the pore-forming agent and the solvent when considering removal of the pore-forming agent with a solvent includes, for example, barium oxide and water, calcium carbonate and hydrochloric acid, aluminum oxide and sodium hydroxide aqueous solution, hafnium oxide and methyl isobutyl. Examples include ketones, magnesium carbonate, and ethylenediaminetetraacetic acid tetrasodium salt aqueous solution.

  It is desirable that the temperature for dissolving and removing the pore forming agent is low. Since the valve metal has high affinity with oxygen, the surface of the valve metal is oxidized when the temperature for dissolving and removing is high. Therefore, the temperature for dissolving and removing is preferably 50 ° C. or less. Furthermore, −10 ° C. to 40 ° C. is preferable, and 0 ° C. to 30 ° C. is particularly preferable. For the above reasons, it is preferable to select a method that generates less heat when dissolved and removed. For example, when a metal oxide or metal carbonate is used as the pore forming agent, the method of dissolving and removing with an acid generates heat of neutralization. Therefore, for example, select a method that hardly generates heat, such as a method of dissolving in water or an organic solvent, a method of forming a soluble complex using an aqueous ammonium nitrate salt solution or ethylenediaminetetraacetic acid, or a method of dissolving in a solution containing an ion exchange resin. It is preferable.

  After removing the pore-forming agent using these solvents, the solvent is removed by washing thoroughly with water. For example, when the pore forming agent is removed using nitric acid or ammonium chloride as a solvent and the nitric acid or ammonium chloride solvent is removed by washing with ion exchange water, the electric conductivity of the ion exchange water after washing is 5 μS / cm or less. It is desirable to wash with water until After sufficient washing, drying is performed at an appropriate pressure of 120 ° C. or lower, preferably 80 ° C. or lower, more preferably 50 ° C. or lower. Under reduced pressure, the drying time is shorter and the drying temperature can be lowered. After completion of drying, it is gradually oxidized to obtain the sintered body of the present invention.

In the sintered body produced by the production method of the present invention, the peak top of the pore diameter distribution suitable for impregnation with the cathode agent is in the range of 0.01 μm to 100 μm. Of course, not only a small sintered body having a volume of less than 10 mm ³ , particularly a large sintered body having a thickness of 1 mm or more at the thinnest portion of the sintered body and a volume of the sintered body of 10 mm ³ or more, It is possible to adjust the pore peak top to 0.3 μm or more, and further to 0.5 μm or more.
Furthermore, even for a large sintered body having a sintered body volume of 10 mm ³ or more and a porosity of 55 volume% or more, the pore volume having a diameter of 1 μm or more can be adjusted to 10 volume% or more of the total pore volume. A plurality of pore diameter distribution peaks can be present at 0.3 μm or more, further 0.5 μm or more, and the pore volume with a diameter of 1 μm or more can be made 13 volume% or more of the total pore volume. Is possible.

The density of the sintered body obtained by the production method of the present invention is usually 4.0 g / ml or less for niobium, and usually 8.0 g / ml or less for tantalum. If the density is 4.0 g / ml or less for niobium and 8.0 g / ml or less for tantalum, the impregnation property is good, depending on the type of the cathode agent. For example, when a high-capacity niobium powder having a CV value of 200,000 μFV / g is adjusted to a compact density of 2.8 g / ml and a compact volume of 25 mm ³ by the method of the present invention and sintered at 1150 ° C., The body volume is about 22 mm ³ , the sintered body density is 3.2 g / ml, and the specific surface area is 0.17 m ² (0.0007 m ² / mm ³ ). Sintering proceeds to a sintered body volume of about 17 mm ³ , a sintered body density of 4.2 g / ml, and a specific surface area of 0.10 m ² (0.0059 m ² / mm ³ ).
Increasing the density of the sintered body makes it more difficult to impregnate the cathode agent and lowers the capacity appearance rate in the capacitor, and decreasing the specific surface area causes a decrease in the capacity of the sintered body. In the method using no pore forming agent, only a capacitor of about 400 μF / piece (about 20 mm ³ sintered body) can be obtained even if a high-capacity niobium powder of 200,000 μF / g is used.

By using the method of the present invention, a high capacity appearance rate and a high capacity of a sintered body can be achieved simultaneously, and a capacitor of about 750 μF / piece (about 20 mm ³ sintered body) can be manufactured. If the primary powder having a low thermal history is used as described above, sintering at a lower temperature is possible. As a result, a capacity of 800 μF / piece or more, further 1000 μF / piece or more for a sintered body of about 20 mm ^3. It is also possible to produce a sintered body having

When a 10 mm ³ sintered body is produced by the method of the present invention, the specific surface area is 0.005 m ² / mm ³ or more. If the primary powder having a small thermal history is used as described above, the specific surface area is set to 0.005. It can also be set to 01 m ² / mm ³ or more. Further, even if the volume of the sintered body was as large as 50 mm ^3, 100 mm ³ showed no significant reduction in the cathode agent impregnation ratio, ESR is stable.

  As an example, when the sintered body of the present invention is sintered at 1200 ° C., the CV value (formation voltage value in the case of 120 ° C. 120 ° C. differentiation in a 0.1 mass% phosphoric acid aqueous solution and the capacity at 120 Hz) Product) is 40000-400000 μFV / g.

[5] Capacitor Element Next, the production of the capacitor element will be described.
A capacitor can be manufactured from the above-mentioned sintered body as one electrode and a dielectric interposed between the counter electrode. For example, a niobium sintered body is used as one electrode, a dielectric is formed on the surface of the sintered body (including the surface in the pores), and a counter electrode is provided on the dielectric to constitute a capacitor.

  Here, as the dielectric of the capacitor, a dielectric mainly composed of niobium oxide is preferable, and a dielectric mainly composed of niobium pentoxide is particularly preferable. A dielectric body mainly composed of niobium pentoxide can be obtained, for example, by electrolytic oxidation of a niobium sintered body that is one of the electrodes. Electrolytic oxidation of the niobium electrode in the electrolytic solution is usually performed using a protonic acid aqueous solution, for example, a 0.1% phosphoric acid aqueous solution, a sulfuric acid aqueous solution, a 1% acetic acid aqueous solution, an adipic acid aqueous solution, or the like. Thus, when a niobium electrode is formed in an electrolytic solution to obtain a niobium oxide dielectric, the capacitor of the present invention becomes an electrolytic capacitor and the niobium electrode becomes an anode.

  In the capacitor of the present invention, the counter electrode (counter electrode) of the niobium sintered body is not particularly limited. For example, at least one selected from an electrolyte, an organic semiconductor, and an inorganic semiconductor known in the aluminum electrolytic capacitor industry. These materials (compounds) can be used.

  Specific examples of the electrolyte include a mixed solution of dimethylformamide and ethylene glycol in which 5% by mass of isobutyltripropylammonium borotetrafluoride electrolyte is dissolved, propylene carbonate and ethylene glycol in which 7% by mass of tetraethylammonium borotetrafluoride is dissolved. Examples thereof include mixed solutions.

  Specific examples of the organic semiconductor include an organic semiconductor composed of benzopyrroline tetramer and chloranil, an organic semiconductor composed mainly of tetrathiotetracene, an organic semiconductor composed mainly of tetracyanoquinodimethane, or the following general formula (1 ) Or a conductive polymer containing a repeating unit represented by the general formula (2).

In the formula, R ^{1 to} R ⁴ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, a halogen atom, or a nitro group. , A monovalent group selected from the group consisting of a cyano group, a primary, secondary or tertiary amino group, a CF ₃ group, a phenyl group and a substituted phenyl group. The hydrocarbon chains of R ¹ and R ² and R ³ and R ⁴ are bonded to each other at any position, and at least one or more 3- to 7-membered saturated or unsaturated groups with carbon atoms substituted by such groups. You may form the bivalent chain | strand which forms the cyclic structure of a saturated hydrocarbon. The cyclic bond chain may include a bond of carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, or imino at any position. X represents an oxygen, sulfur or nitrogen atom, R ⁵ is present only when X is a nitrogen atom, and is independently a hydrogen atom or a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms. Represents a group.

Further, in the present invention, R ^{1 to} R ⁴ in the general formula (1) or the general formula (2) are preferably each independently a hydrogen atom or a linear or branched saturated group having 1 to 6 carbon atoms. Alternatively, it represents an unsaturated alkyl group or alkoxy group, and R ¹ and R ² and R ³ and R ⁴ may be bonded to each other to form a ring.

  In the present invention, the conductive polymer containing a repeating unit represented by the general formula (1) is preferably a conductive polymer containing a structural unit represented by the following general formula (3) as a repeating unit.

In the formula, R ⁶ and R ⁷ are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 6 carbon atoms, or the alkyl group is bonded to each other at an arbitrary position. And a substituent that forms a cyclic structure of at least one 5- to 7-membered saturated hydrocarbon containing two oxygen elements. The cyclic structure includes those having a vinylene bond which may be substituted and those having a phenylene structure which may be substituted.

  The conductive polymer containing such a chemical structure is doped with a dopant. A well-known dopant can be used for a dopant without a restriction | limiting.

  Examples of the polymer containing the repeating unit represented by the general formula (1) or (2) include polyaniline, polyoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, polypyrrole, polymethylpyrrole, and substituted derivatives thereof. And copolymers. Of these, polypyrrole, polythiophene, and substituted derivatives thereof (for example, poly (3,4-ethylenedioxythiophene)) are preferable.

  Specific examples of the inorganic semiconductor include an inorganic semiconductor mainly composed of lead dioxide or manganese dioxide, and an inorganic semiconductor composed of iron trioxide. Such semiconductors may be used alone or in combination of two or more.

When the organic semiconductor and the inorganic semiconductor having a conductivity in the range of 10 ⁻² S / cm to 10 ³ S / cm are used, the impedance value of the manufactured capacitor is further reduced, and the capacitance at high frequency is further increased. Can do.

  As the method for producing the conductive polymer layer, for example, aniline, thiophene, furan, pyrrole, methylpyrrole or a polymerizable compound of these substituted derivatives may be oxidized enough to cause an oxidation reaction of dehydrogenative two-electron oxidation. A method of polymerizing by the action of the agent is employed. The polymerization reaction from the polymerizable compound (monomer) includes, for example, vapor phase polymerization of a monomer, solution polymerization, and the like, and is formed on the surface of a niobium sintered body having a dielectric. When the conductive polymer is soluble in an organic solvent and can be applied as a solution, a method of applying it to the surface is employed.

  As one of preferred production methods by solution polymerization, a niobium sintered body having a dielectric layer formed is immersed in a solution containing an oxidizing agent (solution 1), and then immersed in a solution containing a monomer and a dopant (solution 2). And a method of polymerizing and forming a conductive polymer layer on the surface. Further, the sintered body may be immersed in the solution 1 after being immersed in the solution 2. Moreover, the said solution 2 is good also as a monomer solution which does not contain a dopant. Moreover, when using a dopant, you may use it making it coexist in the solution containing an oxidizing agent.

  By repeating this polymerization step operation once or more, preferably 3 to 20 times, with respect to the niobium sintered body having a dielectric, a dense and layered conductive polymer layer can be easily formed. it can.

  In the method for producing a capacitor of the present invention, the oxidizing agent may be any one that can improve the electric power of the conductive polymer by using the reduced form of the oxidizing agent as a dopant without adversely affecting the capacitor performance. An oxidizing agent that is industrially inexpensive and easy to handle in production is preferred.

Specific examples of such an oxidizing agent include FeCl (III) compounds such as FeCl ₃ , FeClO ₄ , Fe (organic acid anion) salt, anhydrous aluminum chloride / cuprous chloride, alkali metal peroxide. Sulfates, ammonium persulfates, peroxides, manganese such as potassium permanganate, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetrachloro-1,4-benzoquinone Quinones such as tetracyano-1,4-benzoquinone, halogens such as iodine and bromine, sulfonic acids such as peracid, sulfuric acid, fuming sulfuric acid, sulfur trioxide, chlorosulfuric acid, fluorosulfuric acid and amidosulfuric acid, ozone and the like A combination of these plural oxidizing agents can be mentioned.

  Among these, examples of the basic compound of the organic acid anion that forms the Fe (organic acid anion) salt include organic sulfonic acid or organic carboxylic acid, organic phosphoric acid, and organic boric acid. Specific examples of the organic sulfonic acid include benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, α-sulfo-naphthalene, β-sulfo-naphthalene, naphthalene disulfonic acid, alkylnaphthalenesulfonic acid (alkyl group). As butyl, triisopropyl, di-t-butyl, etc.).

On the other hand, specific examples of the organic carboxylic acid include acetic acid, propionic acid, benzoic acid, oxalic acid and the like. Furthermore, in the present invention, polyelectrolyte anions such as polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyvinyl sulfate poly-α-methyl sulfonic acid, polyethylene sulfonic acid, and polyphosphoric acid are also used. These organic sulfonic acids or organic carboxylic acids are merely examples, and are not limited thereto. Examples of the counter anion of the anion include alkali metal ions such as H ⁺ , Na ⁺ , K ⁺ , or ammonium ions substituted with hydrogen atoms, tetramethyl groups, tetraethyl groups, tetrabutyl groups, tetraphenyl groups, or the like. Although illustrated, it is not limited to these. Of the above oxidizing agents, particularly preferred are oxidizing agents containing trivalent Fe compounds, or cuprous chloride, alkali persulfates, ammonium persulfates, and quinones.

An anion having an ability to coexist as necessary in the method for producing a conductive polymer (anion other than the reductant anion of the oxidant) is an oxidant anion (reductant of the oxidant) produced from the above-mentioned oxidant. An electrolyte anion having a counter ion or other electrolyte anion can be used. Specifically, for example, a halide anion of a group 15 element such as PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , a halide anion of a group 13 element such as BF ₄ ⁻ , I ⁻ (I ₃ ⁻ ), Br ⁻ , Halogen anions such as Cl ⁻ , perhalogenate anions such as ClO ₄ ⁻ , Lewis acid anions such as AlCl ₄ ⁻ , FeCl ₄ ⁻ and SnCl ₅ ⁻ , or inorganic acid anions such as NO ₃ ⁻ and SO ₄ ²⁻ Or sulfonate anions such as p-toluenesulfonic acid and naphthalenesulfonic acid, alkyl-substituted naphthalenesulfonic acid having 1 to 5 carbon atoms, organic sulfonate anions such as CF ₃ SO ₃ ⁻ and CH ₃ SO ₃ ^— , or CH ₃ Examples include proton acid anions such as carboxylic acid anions such as COO ⁻ and C ₆ H ₅ COO ⁻ .

  Similarly, anions of polymer electrolytes such as polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyvinyl sulfuric acid, poly-α-methyl sulfonic acid, polyethylene sulfonic acid, and polyphosphoric acid can be exemplified. However, it is not limited to these. Preferred examples include anions of high molecular weight and low molecular weight organic sulfonic acid compounds or polyphosphoric acid compounds. Desirably, aromatic sulfonic acid compounds (sodium dodecylbenzene sulfonate, sodium naphthalene sulfonate, etc.) are supplied as anions. Used as a compound.

Among the organic sulfonate anions, more effective dopants include sulfoquinone compounds having one or more sulfo anion groups (—SO ₃ ⁻ ) and a quinone structure in the molecule, and anthracene sulfonate anions.

  As the basic skeleton of the sulfoquinone anion of the sulfoquinone compound, p-benzoquinone, o-benzoquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, 2,6-naphthoquinone, 9,10-anthraquinone, 1,4-anthraquinone, 1,2-anthraquinone, 1,4-chrysenequinone, 5,6-chrysenequinone, 6,12-chrysenequinone, acenaphthoquinone, acenaphthenequinone, camphorquinone, 2,3-bornanedione, 9,10-phenanthrenequinone, 2,7- Examples include pyrenequinone.

  When the counter electrode (counter electrode) is solid, a conductor layer may be provided thereon in order to improve electrical contact with an external lead (for example, a lead frame) used as desired.

  The conductor layer can be formed, for example, by solidifying conductive paste, plating, metal vapor deposition, heat-resistant conductive resin film, or the like. As the conductive paste, a silver paste, a copper paste, an aluminum paste, a carbon paste, a nickel paste, and the like are preferable, but these may be used alone or in combination of two or more. When using 2 or more types, they may be mixed or may be stacked as separate layers. After applying the conductive paste, it is left in the air or heated to solidify. Examples of the plating include nickel plating, copper plating, silver plating, and aluminum plating. Moreover, aluminum, nickel, copper, silver etc. are mentioned as a vapor deposition metal.

  Specifically, for example, a carbon paste and a silver paste are sequentially laminated on the second electrode and sealed with a material such as an epoxy resin to constitute a capacitor. The capacitor may have niobium or tantalum leads that are sintered integrally with the niobium sintered body or later welded.

  The capacitor of the present invention having the above-described configuration can be made into a capacitor product for various uses by, for example, a resin mold, a resin case, a metallic outer case, resin dipping, and a laminate film.

  Further, when the counter electrode is liquid, the capacitor composed of the two electrodes and the dielectric is housed in, for example, a can electrically connected to the counter electrode to form a capacitor. In this case, the electrode side of the niobium sintered body is designed to be led out to the outside through the niobium or tantalum lead described above, and at the same time, insulated from the can by an insulating rubber or the like.

As described above, the valve action metal sintered body for a capacitor manufactured according to the embodiment of the present invention described above is particularly effective in impregnating the cathode agent of a large sintered body having a sintered body volume of 10 mm ³ or more. By manufacturing a capacitor from the sintered body, high capacity, low ESR, and low tan δ can be achieved, and a capacitor with a small leakage current value and good long-term reliability can be obtained.

  In addition, the capacitor of the present invention has a larger capacitance than the conventional tantalum capacitor, and a smaller capacitor product can be obtained.

  The capacitor of the present invention having such characteristics is, for example, a conventional tantalum capacitor for use as a bypass capacitor, a coupling capacitor, a smoothing power supply circuit, or a noise filter in analog circuits and digital circuits. It can be applied to applications.

  In general, such a capacitor is frequently used in an electronic circuit. Therefore, by using the capacitor of the present invention, restrictions on the arrangement of electronic components and exhaust heat are alleviated, and a highly reliable electronic circuit can be made in a narrower space than before. Can fit.

  Furthermore, if the capacitor of the present invention is used, electronic devices that are smaller and more reliable than conventional devices, for example, computer peripheral devices such as computers and PC cards, mobile devices such as mobile phones, home appliances, in-vehicle devices, artificial satellites, communication Equipment etc. can be obtained.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these examples. The tapping density, angle of repose, particle diameter, pore diameter, capacitor capacity, leakage current value, capacity appearance rate, and moisture resistance in each example were measured by the following methods.

(1) Porosity of sintered body The bulk density of the sintered body is obtained from the external dimensions and mass of the sintered body, the true density of the sintered body is obtained by a pycnometer, and the porosity of the sintered body is calculated according to the following formula. Calculated.

(2) Particle size measurement The particle size distribution was measured by a laser diffraction scattering method using a particle size distribution measuring apparatus (Microtrac, Inc; HRA 9320-X100) manufactured by Microtrac. The average particle diameter was defined as a particle size value (D ₅₀ ; μm) corresponding to the cumulative volume% of 50 volume%.

(3) Pore diameter measurement The pore distribution was measured by a mercury intrusion method using an apparatus (Micromeritics Instrument Corporation; Poresier 9320).
In the present invention, the maximum value is obtained from the rate of change of the press-fitting amount, and the pore diameter indicated by the maximum value is set as the peak top. When there were a plurality of maximum values, each was set as a peak top.

(4) Pore volume ratio of 1 μm or more The pore distribution was measured by a mercury intrusion method using an apparatus manufactured by Micromeritics Instrument Corporation (Poresier 9320).
In the present invention, the ratio of the pore volume (ml) of 1 μm or more in the total pore volume (ml) is defined as the pore volume ratio (volume%) of 1 μm or more.

(5) Capacity of Anode Sintered Body When sintered in a 0.1% phosphoric acid aqueous solution at 80 ° C. and 20 V for 600 minutes, the sintered body was subjected to a bias of 1.5 V and 120 Hz in 30% sulfuric acid at room temperature. The capacity measured in step 1 was taken as the capacity of the anode sintered body.

(6) Capacitor capacity and tan δ measurement At room temperature, a Hewlett Packard LCR measuring instrument was connected between the terminals of the fabricated chip, and the capacitance and tan δ measurement values at a bias of 1.5 V and 120 Hz were processed into chips. The capacity and tan δ were used.

(7) Capacitor Leakage Current Measurement At room temperature, the current value measured after applying a DC voltage of 6.3 V for 1 minute between the terminals of the fabricated chip was taken as the leakage current value of the capacitor processed into the chip.

(8) ESR measurement of capacitor At room temperature, an ESR measurement value at 100 kHz, 1.5 VDC, and 0.5 Vrms. It was.

(9) Capacitance Appearance Rate Capacitance measured in a 0.1% phosphoric acid aqueous solution for 600 minutes under conditions of 80 ° C. and 20 V, measured in 30% sulfuric acid with a bias of 1.5 V and 120 Hz. It was expressed as a ratio (%) of capacitance after capacitor formation with respect to.
(10) Moisture resistance of capacitor The capacity when the produced capacitor was allowed to stand at 60 ° C. and 95% RH for 2000 hours was expressed as a number less than 110% of the initial value. It was judged that the more the number was less than 110%, the better the moisture resistance.
(11) ESR Stability of Capacitor The ESR value when the produced capacitor was allowed to stand at 60 ° C. and 95% RH for 2000 hours was expressed as a number less than 100 ± 10% of the initial value. It was judged that the stability of ESR was better as the number was less than 100 ± 10%.

  Moreover, the production of capacitors from the sintered bodies of Examples and Comparative Examples was performed by any of the following methods 1 to 4.

Capacitor manufacturing method 1:
100 valve metal anode sintered bodies each having a dielectric oxide film formed on the surface thereof by electrolytic oxidation using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V for 6 hours were prepared. Next, the operation of heating at 220 ° C. for 30 minutes after being immersed in a 60% manganese nitrate aqueous solution was repeated to form a manganese dioxide layer as a counter electrode layer on the dielectric oxide film. Subsequently, a carbon layer and a silver paste layer were sequentially laminated thereon. Next, after the lead frame was mounted, the whole was sealed with an epoxy resin to produce a chip capacitor.

Capacitor manufacturing method 2:
100 valve metal sintered bodies each having a dielectric oxide film formed on the surface thereof by electrolytic oxidation at a voltage of 20 V using a 0.1% phosphoric acid aqueous solution for 6 hours were prepared. Next, after being immersed in a 1: 1 (volume ratio) mixed solution of 35% lead acetate aqueous solution and 35% ammonium persulfate aqueous solution, an operation of reacting at 40 ° C. for 1 hour is repeated to form a counter electrode layer on the dielectric oxide film. A mixed layer of lead dioxide and lead sulfate was formed. Subsequently, a carbon layer and a silver paste layer were sequentially laminated thereon. Next, after the lead frame was mounted, the whole was sealed with an epoxy resin to produce a chip capacitor.

Capacitor manufacturing method 3:
100 valve metal sintered bodies each having a dielectric oxide film formed on the surface thereof by electrolytic oxidation at a voltage of 20 V using a 0.1% phosphoric acid aqueous solution for 6 hours were prepared. Next, an equivalent mixture of 10% aqueous solution of ammonium persulfate and 0.5% aqueous solution of anthraquinone sulfonic acid was brought into contact with the dielectric oxide film, and then contacted with pyrrole vapor was performed at least 5 times. The counter electrode (counter electrode) consisting of was formed. Subsequently, a carbon layer and a silver paste layer were sequentially laminated thereon. Next, after the lead frame was mounted, the whole was sealed with an epoxy resin to produce a chip capacitor.

Capacitor fabrication method 4:
100 valve metal sintered bodies each having a dielectric oxide film formed on the surface thereof by electrolytic oxidation at a voltage of 20 V using a 0.1% phosphoric acid aqueous solution for 6 hours were prepared. Next, the valve action metal sintered body was dipped in an aqueous solution (solution 1) containing 25% by mass of ammonium persulfate, then lifted, dried at 80 ° C. for 30 minutes, and then the sintered body on which the dielectric was formed was After immersing in an isopropanol solution (solution 2) containing 18% by mass of 4-ethylenedioxythiophene, it was pulled up and left to stand in an atmosphere at 60 ° C. for 10 minutes for oxidative polymerization. This was again immersed in solution 1 and further treated in the same manner as described above. The operation from immersion in solution 1 to oxidative polymerization was repeated 8 times, followed by washing with warm water at 50 ° C. for 10 minutes, and drying at 100 ° C. for 30 minutes, whereby conductive poly (3, A counter electrode (counter electrode) composed of 4-ethylenedioxythiophene) was formed. Subsequently, a carbon layer and a silver paste layer were sequentially laminated thereon. Next, after the lead frame was mounted, the whole was sealed with an epoxy resin to produce a chip capacitor.

Example 1:
At room temperature, 500 g of camphor was dissolved in 10 L of toluene. To this solution, 8.4 kg of niobium hydride powder having an average particle size of 0.5 μm, 800 g of barium oxide powder having an average particle size of 0.7 μm, and 800 g of barium oxide powder having an average particle size of 2 μm, prepared by pulverizing niobium hydride. Was dispersed. Using zirconia beads, the mixture was mixed with a dynomill for 1 hour. This slurry is put into a Nauta mixer, dried under reduced pressure at 1 × 10 ² Pa and 80 ° C., and granulated to obtain a mixed granulated product of niobium hydride, barium oxide and camphor having an average particle size of 120 μm. It was. This mixed granulated product was dehydrogenated at 480 ° C. under a reduced pressure of 1 × 10 ² Pa or less to convert niobium hydride to niobium and remove camphor and to remove hard niobium having an average particle size of 120 μm and barium oxide. 10 kg of mixed granulated material was obtained. Disperse a hard granulated product of niobium and barium oxide in a solution of 300 g of polyisobutyl methacrylate in 5 L of toluene, and dry under reduced pressure using a conical dryer under the conditions of 1 × 10 ² Pa and 80 ° C. Produced a granulated product of 120 μm of niobium, barium oxide and polyisobutyl methacrylate.

The mixed granulated material thus obtained is put into a hopper of a tantalum element automatic molding machine (manufactured by Seiko Co., Ltd., TAP-2R) and automatically molded with a niobium wire having a diameter of 0.3 mm. A molded body was obtained so as to be ³ mm × 1.8 mm × 4.3 mm (about 25 mm ³ ). The molded body density of the molded body in terms of niobium was 2.8 g / ml (niobium amount: 72 mg).

Next, these molded bodies were heated at 10 ⁻² to 10 ² Pa and 250 to 400 ° C. for 3 hours to decompose and remove polyisobutyl methacrylate and left at 1150 ° C. for 30 minutes under a reduced pressure of 4 × 10 ⁻³ Pa. After sintering, the product was cooled until the product temperature was 30 ° C. or lower. The process of gradually adding nitrogen gas containing 0.1 vol% oxygen so that the product temperature does not exceed 30 ° C. and removing it under reduced pressure is repeated until the product temperature does not change, and then left for 8 hours or longer to oxidize. The niobium sintered body mixed with barium was taken out.

  1000 pieces of this niobium sintered body mixed with barium oxide and 1000 g of ion-exchanged water were placed in a polytetrafluoroethylene container and cooled to 15 ° C. or lower. Separately, a mixed aqueous solution of 60% nitric acid 600 g, 30% hydrogen peroxide 150 g, and ion-exchanged water 750 g cooled to 15 ° C. or lower is prepared, and the water temperature does not exceed 20 ° C. while stirring 500 g of this aqueous solution. Thus, it was dripped at the container containing the niobium sintered compact mixed with barium oxide and ion-exchanged water to dissolve barium oxide. After completion of the dropwise addition, stirring was continued for another 2 hours, the mixture was allowed to stand for 30 minutes, and then decanted. After adding 2000 g of ion-exchanged water and stirring for 30 minutes, the mixture was allowed to stand for 30 minutes and then decanted. This operation was repeated 5 times. Further, the niobium sintered body was placed in a polytetrafluoroethylene column and washed with water for 4 hours while flowing ion exchange water to remove barium oxide as a barium salt. The electrical conductivity of the washing water at this time was 0.9 μS / cm.

The niobium sintered body was dried under reduced pressure at 1 × 10 ² Pa and 50 ° C., and then cooled until the product temperature was 30 ° C. or lower. The process of gradually adding nitrogen gas containing 0.1% by volume of oxygen so that the product temperature does not exceed 30 ° C. and removing under reduced pressure is repeated until the product temperature does not change, and then left for 8 hours or longer to read niobium lead. A sintered niobium body in which wires were implanted was obtained. This sintered body had a volume of about 22 mm ³ , a sintered body density of 3.2 g / ml, a specific surface area of 0.0007 m ² / mm ³ , and a porosity of 63%. The pore diameter peak tops were 0.7 μm and 2 μm, and the pore volume of 1 μm or more was 17% by volume of the total pore volume.

Next, 100 sintered bodies were prepared and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface.
A chip-type capacitor was fabricated using the capacitor fabrication method 4 for this formed niobium anode sintered body. The capacity appearance rate of this capacitor was 98%, and the capacity was 766 μF / piece.

Examples 2-4:
Before forming (Example 2), before forming and then sintering (Example 3), or after sintering and before removing barium oxide (Example 4), nitriding in a nitrogen atmosphere at 300 ° C. for 2 hours A niobium sintered body in which niobium lead wires were implanted was obtained in the same manner as in Example 1 except for the treatment. 100 sintered bodies were prepared, and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface. Further, with respect to these formed niobium anode sintered bodies, chip type capacitors were produced using capacitor production methods 1 to 3. Tables 1 to 3 show the physical properties of the sintered body, the capacity appearance rate of the capacitor, and the electrical characteristics.

Example 5:
Niobium secondary agglomerated powder having an average particle diameter of 7 μm in which primary particles having an average particle diameter of about 0.5 μm were aggregated by a method of reducing niobium oxide was prepared. At room temperature, 300 g of polymethylmethacrylic acid methyl ester was dissolved in 10 L of toluene. In this solution, 8.5 kg of niobium aggregated powder and 1.5 kg of calcium oxide powder having an average particle size of 0.9 μm were dispersed. Using zirconia beads, the mixture was mixed with a dynomill for 1 hour. This slurry is put into a Nauter mixer, dried under reduced pressure at 1 × 10 ² Pa and 80 ° C. and granulated, and mixed granulated polymethylmethacrylic acid methyl ester of niobium having an average particle size of 180 μm and calcium oxide. I got a thing. The mixed granulated material thus obtained is put into a tantalum element automatic molding machine (TAP-2R manufactured by Seken Co., Ltd.) hopper and automatically molded without using a lead wire, and the size is about 3.3 mm × 1. A molded body was prepared so as to be 8 mm × 4.3 mm (about 25 mm ³ ). The density of the molded body in terms of niobium was 3.0 g / ml (amount of niobium of 76 mg).

Next, this molded body was heated at 10 ⁻² to 10 ² Pa at 250 to 400 ° C. for 3 hours to decompose and remove polymethylmethacrylic acid methyl ester, and at a reduced pressure of 4 × 10 ⁻³ Pa at 1200 ° C. for 30 minutes. After leaving it to sinter, it was cooled until the product temperature was 30 ° C. or lower. After repeating the operation of gradually adding nitrogen gas containing 0.1% by volume of oxygen so that the product temperature does not exceed 30 ° C. and removing it under reduced pressure until the product temperature does not change, leave it for 8 hours or more to leave calcium oxide The mixed niobium sintered body was taken out.

  1000 pieces of this calcium oxide mixed niobium sintered body and 1000 g of ion exchange water were put into a polytetrafluoroethylene container and cooled to 15 ° C. or lower. Separately, a mixed aqueous solution of 60% nitric acid 600 g, 30% hydrogen peroxide 150 g, and ion-exchanged water 750 g cooled to 20 ° C. or less is prepared, and the water temperature does not exceed 20 ° C. while stirring 500 g of this aqueous solution. Thus, it was dripped at the container containing the niobium sintered compact with which calcium oxide was mixed, and ion-exchange water, and the calcium oxide was melt | dissolved. After completion of the dropwise addition, stirring was continued for another 2 hours, the mixture was allowed to stand for 30 minutes, and then decanted. After adding 2000 g of ion-exchanged water and stirring for 30 minutes, the mixture was allowed to stand for 30 minutes and then decanted. This operation was repeated five times, and the niobium sintered body was placed in a polytetrafluoroethylene column and washed with water for 4 hours while flowing ion exchange water to remove calcium oxide as a calcium salt. The electrical conductivity of the washing water at this time was 0.9 μS / cm.

The niobium sintered body was dried under reduced pressure under conditions of 1 × 10 ² Pa and 50 ° C., and then cooled until the product temperature was 30 ° C. or lower. After gradually adding nitrogen gas containing 0.1% by volume of oxygen so that the product temperature does not exceed 30 ° C. and repeating the removal under reduced pressure until the product temperature does not change, leave it for more than 8 hours. A niobium sintered body was obtained. A niobium lead wire having a diameter of 0.3 mmφ was spot-welded to the sintered body to prepare a niobium sintered body for an anode.

This sintered body had a volume of about 23 mm ³ , a sintered body density of 3.3 g / ml, a specific surface area of 0.0073 m ² / mm ³ , and a porosity of 61%. In addition, the pore diameter peak top was 0.8 μm, and the pore volume of 1 μm or more was 19% by volume of the total pore volume.

  Next, 100 sintered bodies were prepared and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface. Further, with respect to these formed niobium anode sintered bodies, chip type capacitors were produced using the capacitor production method 4. Tables 1 to 3 show the capacitance appearance rate and electrical characteristics of this capacitor.

Examples 6-24:
In the same manner as in Example 1 or Example 5, using niobium powder having different average particle diameters and a plurality of pore forming agents having different average particle diameters, paraffin, vegetable oil, camphor, polyacrylic polymer, polymethacrylic system After obtaining a mixed granulated product of niobium, a pore-forming agent and a binder using a polymer or polyvinyl polymer binder, it is molded and sintered at 1000 ° C to 1500 ° C, and a solvent suitable for the pore-forming agent is used. Used to remove the pore former. This sintered body was processed in the same manner as in Example 1 or 5 to obtain a niobium sintered body for anode. Further, 100 sintered bodies were prepared and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface. Further, with respect to these formed niobium sintered bodies, chip type capacitors were produced using capacitor production methods 1 to 4. Tables 1 to 3 show the physical properties of the sintered body, the capacity appearance rate of the capacitor, and the electrical characteristics.

Example 25:
Niobium monoxide secondary agglomerated powder having an average particle diameter of 6 μm in which primary particles having an average particle diameter of about 0.3 μm were aggregated by a method of reducing niobium pentoxide was prepared. At room temperature, 300 g of polymethylmethacrylic acid methyl ester was dissolved in 10 L of toluene. In this solution, 8.5 kg of niobium aggregated powder and 1.5 kg of calcium oxide powder having an average particle size of 0.9 μm were dispersed. Using zirconia beads, the mixture was mixed with a dynomill for 1 hour. This slurry is put into a Nauter mixer, dried under reduced pressure at 1 × 10 ² Pa and 80 ° C. and granulated, and mixed with polymethylmethacrylic acid methyl ester of niobium monoxide and calcium oxide having an average particle size of 170 μm. A granulated product was obtained. The mixed granulated material thus obtained is put into a tantalum element automatic molding machine (TAP-2R manufactured by Seken Co., Ltd.) hopper and automatically molded without using a lead wire, and the size is about 3.3 mm × 1. A molded body was prepared so as to be 8 mm × 4.3 mm (about 25 mm ³ ). The density of the compact in terms of niobium monoxide was 3.0 g / ml (the amount of niobium monoxide was 76 mg).

Next, this molded body was heated at 10 ⁻² to 10 ² Pa at 250 to 400 ° C. for 3 hours to decompose and remove polymethylmethacrylic acid methyl ester, and at a reduced pressure of 4 × 10 ⁻³ Pa at 1200 ° C. for 30 minutes. After leaving it to sinter, it was cooled until the product temperature was 30 ° C. or lower. After repeating the operation of gradually adding nitrogen gas containing 0.1% by volume of oxygen so that the product temperature does not exceed 30 ° C. and removing it under reduced pressure until the product temperature does not change, leave it for 8 hours or more to leave calcium oxide The mixed niobium monoxide sintered body was taken out.

  1000 calcium oxide mixed niobium monoxide sintered bodies and 1000 g of ion-exchanged water were put in a polytetrafluoroethylene container and cooled to 15 ° C. or lower. Separately, a mixed aqueous solution of 60% nitric acid 600 g, 30% hydrogen peroxide 150 g, and ion-exchanged water 750 g cooled to 20 ° C. or less is prepared, and the water temperature does not exceed 20 ° C. while stirring 500 g of this aqueous solution. Thus, it was dripped at the container containing the niobium monoxide sintered compact mixed with calcium oxide and ion-exchanged water to dissolve calcium oxide. After completion of the dropwise addition, stirring was continued for another 2 hours, the mixture was allowed to stand for 30 minutes, and then decanted. After adding 2000 g of ion-exchanged water and stirring for 30 minutes, the mixture was allowed to stand for 30 minutes and then decanted. This operation was repeated 5 times. Further, the niobium monoxide sintered body was placed in a polytetrafluoroethylene column and washed with water for 4 hours while flowing ion exchange water to remove calcium oxide as a calcium salt. The electrical conductivity of the washing water at this time was 0.8 μS / cm.

The niobium monoxide sintered body was dried under reduced pressure under the conditions of 1 × 10 ² Pa and 50 ° C., and then cooled until the product temperature was 30 ° C. or lower. After gradually adding nitrogen gas containing 0.1% by volume of oxygen so that the product temperature does not exceed 30 ° C. and repeating the removal under reduced pressure until the product temperature does not change, leave it for more than 8 hours. A sintered niobium monoxide was obtained. A niobium lead wire having a diameter of 0.3 mmφ was spot welded to the sintered body to prepare a niobium monoxide sintered body for an anode.

This sintered body had a volume of about 23 mm ³ , a sintered body density of 3.3 g / ml, a specific surface area of 0.0115 m ² / mm ³ , and a porosity of 61%. Moreover, it had a pore diameter peak top at 0.7 μm, and the pore volume of 1 μm or more was 17% by volume of the total pore volume. Next, 100 sintered bodies were prepared and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface. Further, with respect to these formed niobium monoxide anode sintered bodies, chip-type capacitors were produced using the capacitor production method 4. Tables 2 to 3 show the capacitance appearance rate and electrical characteristics of this capacitor.

Comparative Example 1:
A niobium powder was formed and sintered in the same manner as in Example 1 without using a pore forming agent to obtain a niobium sintered body. Further, 100 sintered bodies were prepared and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface. A chip-type capacitor was manufactured using the capacitor manufacturing method 4 for the formed sintered body. Tables 1 to 3 show the physical properties of the sintered body, the capacity appearance rate of the capacitor, and the electrical characteristics.

Comparative Example 2:
A niobium sintered body was obtained by molding and sintering niobium powder without using a pore-forming agent in the same manner as in Example 5. Further, 100 sintered bodies were prepared and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface. A chip-type capacitor was manufactured using the capacitor manufacturing method 4 for the formed sintered body. Tables 1 to 3 show the physical properties of the sintered body, the capacity appearance rate of the capacitor, and the electrical characteristics.

Example 26:
At room temperature, 300 g of polymethylmethacrylic acid methyl ester was dissolved in 10 L of toluene. In this solution, 8.5 kg of niobium hydride powder having an average particle diameter of 0.5 μm and 1.5 kg of calcium oxide powder having an average particle diameter of 0.9 μm prepared by pulverizing niobium hydride were dispersed. Using zirconia beads, the mixture was mixed with a dynomill for 1 hour. This slurry was put into a rotary evaporator, and the solvent was removed under conditions of 1 × 10 ² Pa and 40 ° C. to obtain a polymethylmethacrylic acid methyl ester mixed dispersion of niobium and calcium oxide. Next, a 10 mm × 5 mm pattern was printed on the clean niobium foil using this dispersion using a metal mask and a metal blade having a thickness of 0.2 mm. The printed matter was dried under normal pressure and at a temperature of 80 ° C., and the dispersion was fixed on the foil.

Next, these printed materials were heated at 10 ⁻² to 10 ² Pa at 250 to 400 ° C. for 3 hours to decompose and remove polymethylmethacrylic acid methyl ester and dehydrogenate at the same time under reduced pressure of 4 × 10 ⁻³ Pa. After being allowed to sinter at 1150 ° C. for 30 minutes, it was cooled until the product temperature was 30 ° C. or lower. The process of gradually adding nitrogen gas containing 0.1 vol% oxygen so that the product temperature does not exceed 30 ° C. and removing it under reduced pressure is repeated until the product temperature does not change, and then left for 8 hours or longer to oxidize. The niobium sintered body mixed with calcium was taken out.
100 sheets of this niobium sintered body mixed with calcium oxide and 1000 g of ion-exchanged water were put in a polytetrafluoroethylene container and cooled to 15 ° C. or lower. Separately, a mixed aqueous solution of 60% nitric acid 600 g, 30% hydrogen peroxide 150 g, and ion-exchanged water 750 g cooled to 15 ° C. or lower is prepared, and the water temperature does not exceed 20 ° C. while stirring 500 g of this aqueous solution. Thus, it was dripped at the container containing the niobium sintered compact with which calcium oxide was mixed, and ion-exchange water, and the calcium oxide was melt | dissolved. After completion of the dropwise addition, stirring was continued for another 2 hours, the mixture was allowed to stand for 30 minutes, and then decanted. After adding 2000 g of ion-exchanged water and stirring for 30 minutes, the mixture was allowed to stand for 30 minutes and then decanted. This operation was repeated 5 times. Further, the niobium sintered body was placed in a polytetrafluoroethylene column and washed with water for 4 hours while flowing ion exchange water to remove calcium oxide as a calcium salt. The electrical conductivity of the washing water at this time was 0.9 μS / cm.

The niobium sintered body was dried under reduced pressure at 1 × 10 ² Pa and 50 ° C., and then cooled until the product temperature was 30 ° C. or lower. After repeating the operation of gradually adding nitrogen gas containing 0.1% by volume of oxygen so that the product temperature does not exceed 30 ° C. and removing under reduced pressure until the product temperature does not change, and then leaving it for 8 hours or more, The foil was cut along the printed surface and a niobium lead wire was welded to obtain a niobium sintered body. This sintered body had a volume of about 50 mm ³ and a porosity of 74%. Moreover, it had a pore diameter peak top at 0.9 μm, and the pore volume of 1 μm or more was 16% by volume of the total pore volume. The printed niobium powder was 14.2 mg.

  Next, this sintered body was subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface.

  A chip-type capacitor was fabricated using the capacitor fabrication method 4 for this formed niobium anode sintered body. The capacity appearance rate of this capacitor was 98%, and the capacity was 149 μF / piece. Moreover, when the weight of the powder used for this capacitor was converted to the niobium weight (72 mg) in the case of compression molding, the capacity was 755 μF / piece, which was the same level as in Examples 1-5.

Examples 27-34:
A mixed granulated product of niobium, barium oxide and polyisobutyl methacrylate was obtained in the same manner as in Example 1. This mixed granulated product is placed in the hopper of a tantalum element automatic molding machine (TAP-2R manufactured by Seken Co., Ltd.) so that the sintered body has a volume of about 1 to about 500 mm ^3, and is automatically molded with a niobium wire. A molded product having a value approximately equal to that in Table 4 was obtained and sintered at 1150 ° C. Furthermore, 100 sintered bodies were prepared and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface. A chip-type capacitor was produced by using it. The capacity appearance rate of this capacitor is shown in Table 4 and FIG.

Comparative Examples 3 to 10:
Hopper of tantalum element automatic molding machine (TAP-2R manufactured by Seiko Co., Ltd.) so that the volume of the sintered body is about 1 to about 500 mm ³ without using a pore forming agent in the same manner as in Comparative Example 1. And molded automatically together with the niobium wire to obtain a molded product having a size of about the value shown in Table 4, which was sintered at 1150 ° C. Further, 100 sintered bodies were prepared and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface. A chip-type capacitor was manufactured using the capacitor manufacturing method 4. The capacity appearance rate of this capacitor is shown in Table 4 and FIG.

As is apparent from Table 4 and FIG. 1, the capacitors produced in Comparative Examples 3 to 10 show excellent capacity appearance rates up to about 5 mm ³ or less, but the sintered body volume exceeds 10 mm ³ . From around, the capacity appearance rate drops sharply. On the other hand, in the capacitors produced in Examples 27 to 34, a high capacity appearance rate is maintained even when the sintered body volume is 10 mm ³ or more. That is, it can be seen that the capacitor produced in the example shows a particularly excellent capacity appearance rate when a large sintered body having a volume of 10 mm ³ or more is used.

Example 35:
100 sintered bodies were produced in the same manner as in Examples 1, 2, 5, 6, 8, 10, 14, 19, 31, 32, 33 and 34, and each sintered body was 0.1% phosphorus. Chemical conversion was carried out in an acid aqueous solution at 80 ° C. for 600 minutes at 20 V to form a dielectric oxide film layer on the surface of the sintered body. Next, each of the formed sintered bodies is divided into 50 pieces, and each of the 50 sets of formed sintered bodies is impregnated with two kinds of cathode agents by the capacitor production methods 2 and 4, followed by carbon paste, A silver paste was laminated in order and sealed with an epoxy resin to produce a chip capacitor. Table 5 shows the capacity appearance rate, moisture resistance, and ESR stability of the manufactured capacitors.

Comparative Example 11:
100 sintered bodies were produced in the same manner as in Comparative Examples 1, 2, 7, 8, 9 and 10, and each sintered body was produced in a 0.1% phosphoric acid aqueous solution at 80 ° C., 600 minutes, 20 V. Then, a dielectric oxide film layer was formed on the surface of the sintered body. Next, each of the formed sintered bodies is divided into 50 pieces, and each of the 50 sets of formed sintered bodies is impregnated with two kinds of cathode agents by the capacitor production methods 2 and 4, followed by carbon paste, A silver paste was laminated in order and sealed with an epoxy resin to produce a chip capacitor. Table 5 shows the capacity appearance rate, moisture resistance, and ESR stability of the manufactured capacitors.

  From Table 5, it can be seen that the capacitor produced in Example 35 is superior in moisture resistance and ESR stability to the capacitor produced in Comparative Example 11.

Example 36:
9 kg of tantalum hydride powder having an average particle diameter of 0.5 μm, 500 g of barium oxide powder having an average particle diameter of 0.7 μm, and oxidation having an average particle diameter of 2 μm, prepared by a method of pulverizing tantalum hydride in the same manner as in Example 1. Using 500 g of barium powder, a mixed granulated product of tantalum, barium oxide and polyisobutyl methacrylate having an average particle size of 120 μm was obtained. The obtained mixed granulated product was automatically molded to obtain a molded body having a size of about 3.3 mm × 1.8 mm × 4.2 mm (about 25 mm ³ ). This molded body had a tantalum-converted molded body density of 5.0 g / ml (tantalum amount 125 mg).

Next, these compacts were sintered to obtain a tantalum sintered body mixed with barium oxide, and a tantalum sintered body was obtained after acid cleaning and drying. This sintered body had a volume of about 22 mm ³ , a sintered body density of 5.7 g / ml, a specific surface area of 0.0059 m ² / mm ³ , and a porosity of 66%. The pore diameter peak tops were 0.7 μm and 2 μm, and the pore volume of 1 μm or more was 18% by volume of the total pore volume.

  Next, 100 sintered bodies were prepared and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface.

  About this formed tantalum anode sintered body, a chip type capacitor was manufactured by using capacitor manufacturing method 4. The capacity appearance rate of this capacitor was 98%, and the capacity was 703 μF / piece.

Examples 37-39:
Before forming (Example 37), before forming and then sintering (Example 38), or after sintering and before removing barium oxide (Example 39), nitriding at 300 ° C. for 2 hours in a nitrogen atmosphere A tantalum sintered body in which a tantalum lead wire was implanted was obtained in the same manner as in Example 36 except that the treatment was performed. 100 sintered bodies were prepared, and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface. Further, with respect to these formed tantalum anode sintered bodies, chip type capacitors were produced using capacitor production methods 1 to 3. Tables 6 to 8 show the physical properties of this sintered body, the capacity appearance rate of this capacitor, and the electrical characteristics.

Example 40:
A tantalum secondary agglomerated powder having an average particle size of 5 μm in which primary particles having an average particle size of about 0.5 μm were aggregated by a method of reducing potassium tantalum fluoride was prepared. At room temperature, 300 g of polymethylmethacrylic acid methyl ester was dissolved in 10 L of toluene. In this solution, 9 kg of aggregated tantalum powder and 1 kg of calcium oxide powder having an average particle size of 0.9 μm were dispersed, and a molded body was produced using the method of Example 34. The molded body density of this molded body in terms of tantalum was 5.5 g / ml (tantalum amount 135 mg).

Next, these molded bodies were sintered to obtain a tantalum sintered body mixed with calcium oxide, and a tantalum sintered body was obtained after acid cleaning and drying. This sintered body had a volume of about 22 mm ³ , a sintered body density of 5.9 g / ml, a specific surface area of 0.0053 m ² / mm ³ , and a porosity of 61%. In addition, the pore diameter peak top was 0.8 μm, and the pore volume of 1 μm or more was 19% by volume of the total pore volume.

  Next, 100 sintered bodies were prepared and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface. Further, with respect to these formed tantalum anode sintered bodies, a chip type capacitor was manufactured by using capacitor manufacturing method 4. Tables 6 to 8 show the capacity appearance rate and electrical characteristics of this capacitor.

Examples 41-59:
In the same manner as in Example 36 or Example 40, using tantalum powder having different average particle diameters and a plurality of pore forming agents having different average particle diameters, paraffin, vegetable oil, camphor, polyacrylic polymer, polymethacrylic polymer A mixed granulated product of tantalum, a pore forming agent and a binder is obtained using a polymer or polyvinyl polymer binder, and then molded, sintered at 1000 ° C. to 1500 ° C., and a solvent suitable for the pore forming agent is obtained. Used to remove the pore former. This sintered body was processed in the same manner as in Example 36 or 40 to obtain a tantalum sintered body for an anode. Further, 100 sintered bodies were prepared and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface. Further, with respect to these formed tantalum sintered bodies, chip type capacitors were produced using capacitor production methods 1 to 4. Tables 6 to 8 show the physical properties of this sintered body, the capacity appearance rate of this capacitor, and the electrical characteristics.

Comparative Example 12:
Tantalum powder was molded and sintered in the same manner as in Example 36 without using a pore-forming agent to obtain a tantalum sintered body. Further, 100 sintered bodies were prepared and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface. A chip-type capacitor was manufactured using the capacitor manufacturing method 4 for the formed sintered body. Tables 6 to 8 show the physical properties of this sintered body, the capacity appearance rate of this capacitor, and the electrical characteristics.

Comparative Example 13:
Tantalum powder was molded and sintered in the same manner as in Example 40 without using a pore-forming agent to obtain a tantalum sintered body. Further, 100 sintered bodies were prepared and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface. A chip-type capacitor was manufactured using the capacitor manufacturing method 4 for the formed sintered body. Tables 6 to 8 show the physical properties of this sintered body, the capacity appearance rate of this capacitor, and the electrical characteristics.

Examples 60-67:
A mixed granulated product of tantalum, barium oxide and polyisobutyl methacrylate was obtained in the same manner as in Example 36. This mixed granulated product is placed in the hopper of a tantalum element automatic molding machine (TAP-2R manufactured by Seken Co., Ltd.) so that the sintered body has a volume of about 1 to about 500 mm ^3, and is automatically molded with a tantalum wire. Was obtained and sintered at 1250 ° C. Furthermore, 100 sintered bodies were prepared and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface. A chip-type capacitor was produced by using it. The capacity appearance rate of this capacitor is shown in Table 9 and FIG.

Comparative Examples 14-21:
Hopper of tantalum element automatic molding machine (TAP-2R manufactured by Seken Co., Ltd.) so that the volume of the sintered body is about 1 to about 500 mm ³ without using a pore forming agent in the same manner as in Comparative Example 12. And molded automatically together with the tantalum wire to obtain a molded body having a size of approximately the value shown in Table 9, and sintered at 1250 ° C. Further, 100 sintered bodies were prepared and subjected to electrolytic conversion for 600 minutes using a 0.1% phosphoric acid aqueous solution at a voltage of 20 V to form a dielectric oxide film on the surface. A chip-type capacitor was manufactured using the capacitor manufacturing method 4. The capacity appearance rate of this capacitor is shown in Table 9 and FIG.

As apparent from Table 9 and FIG. 2, the capacitors produced in Comparative Examples 14 to 21 show an excellent capacity appearance rate up to about 5 mm ³ or less, but the sintered body volume exceeds 10 mm ³ . From around, the capacity appearance rate drops sharply. On the other hand, in the capacitors produced in Examples 60 to 67, a high capacity appearance rate is maintained even when the sintered body volume is 10 mm ³ or more. That is, it can be seen that the capacitor produced in the example shows a particularly excellent capacity appearance rate when a large sintered body having a volume of 10 mm ³ or more is used.

Example 68:
100 sintered bodies were produced in the same manner as in Examples 36, 37, 40, 41, 43, 45, 49, 54, 64, 65, 66 and 67, and each sintered body was 0.1% phosphorus. Chemical conversion was carried out in an acid aqueous solution at 80 ° C. for 600 minutes at 20 V to form a dielectric oxide film layer on the surface of the sintered body. Next, each of the formed sintered bodies is divided into 50 pieces, and each of the 50 sets of formed sintered bodies is impregnated with two kinds of cathode agents by the capacitor production methods 2 and 4, followed by carbon paste, A silver paste was laminated in order and sealed with an epoxy resin to produce a chip capacitor. Table 10 shows the capacity appearance rate, moisture resistance, and ESR stability of the manufactured capacitors.

Comparative Example 22:
100 sintered bodies were produced in the same manner as in Comparative Examples 12, 13 , 18, 19, 20 and 21, and each sintered body was produced in a 0.1% phosphoric acid aqueous solution at 80 ° C., 600 minutes, 20 V. Then, a dielectric oxide film layer was formed on the surface of the sintered body. Next, each of the formed sintered bodies is divided into 50 pieces, and each of the 50 sets of formed sintered bodies is impregnated with two kinds of cathode agents by the capacitor production methods 2 and 4, followed by carbon paste, A silver paste was laminated in order and sealed with an epoxy resin to produce a chip capacitor. Table 10 shows the capacity appearance rate, moisture resistance, and ESR stability of the manufactured capacitors.

  From Table 10, it can be seen that the capacitor produced in Example 68 is superior in moisture resistance and ESR stability to the capacitor produced in Comparative Example 22.

It is a graph which shows the capacity | capacitance appearance rate of the capacitor | condenser of Examples 27-34 and Comparative Examples 3-10. It is a graph which shows the capacity | capacitance appearance rate of the capacitor | condenser of Examples 60-67 and Comparative Examples 14-21.

Claims (48)

Disperse a mixture containing at least one primary powder, secondary agglomerated powder or a granulated powder thereof, a pore-forming agent, and an organic binder selected from a valve metal, a valve metal compound and a valve metal alloy Coating / molding step, or compressing / molding the granulated product of the mixture, sintering the obtained molded body to obtain a sintered body having a volume of 49 mm ³ or more , and the obtained sintered body Removing the pore-forming agent contained in the particle, wherein the pore-forming agent has a plurality of peaks in a particle size distribution, and the plurality of peaks are particles having at least one particle size of 0.1 to 0.9 μm. The valve action for an anode of a solid electrolytic capacitor having a plurality of peaks in the pore diameter distribution, wherein at least one having a diameter of 1.0 μm or more and 10% by volume or more having a particle diameter of 1 μm or more A method for producing a sintered metal body. Compression and molding of a granulated mixture of at least one primary powder selected from niobium, a niobium compound and a niobium alloy, a secondary agglomerated powder or a granulated powder thereof, a pore forming agent, and an organic binder. Forming the pores, sintering the obtained molded body to obtain a sintered body having a volume of 49 mm ³ or more , and removing the pore-forming agent contained in the obtained sintered body. The agent has a plurality of peaks in the particle size distribution, and the plurality of peaks are present in at least one particle size of 0.1 to 0.9 μm, at least one particle size of 1.0 μm or more, and a particle size of 1 μm or more. A method for producing a niobium sintered body for an anode of a solid electrolytic capacitor having a plurality of peaks in pore diameter distribution, characterized in that the content is 10% by volume or more.   Prior to the step of forming the molded body, the granulated product of the mixture has a step of doping at least one element selected from the group consisting of nitrogen, oxygen, boron, phosphorus, sulfur, selenium and tellurium Item 3. The method according to Item 1 or 2.   After the step of forming the formed body and before the sintering step, the step of doping the formed body with at least one element selected from the group consisting of nitrogen, oxygen, boron, phosphorus, sulfur, selenium, and tellurium. The manufacturing method according to claim 1 or 2.   After the sintering step and before the pore forming agent removing step, at least one selected from the group consisting of nitrogen, oxygen, boron, phosphorus, sulfur, selenium and tellurium is applied to the sintered body containing the pore forming agent. The manufacturing method of Claim 1 or 2 which has the process of doping an element.   Valve action metal compounds and valve action metal alloys are hydrogen, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, titanium, zirconium, hafnium, vanadium, tantalum, niobium, chromium, molybdenum, tungsten, manganese, rhenium, ruthenium , Osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium, carbon, silicon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth , Oxygen, sulfur, selenium, tellurium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosym, holmium, erbium, thulium, ytte Biumu and process according to any one of claims 1, 3 to 5 comprises at least one element selected from the group consisting of lutetium.   The manufacturing method according to claim 6, wherein the valve action metal compound and the valve action metal alloy contain an element of tantalum or niobium.   The manufacturing method according to claim 6, wherein the valve action metal compound and the valve action metal alloy include at least one selected from the group consisting of niobium monoxide, silicon nitride, and antimony.   The manufacturing method according to claim 8, wherein the silicon nitride is a compound represented by SiαNβ (wherein α and β represent positive integers). The manufacturing method according to claim 9, wherein the silicon nitride is at least one selected from SiN, Si ₂ N ₂ , Si ₂ N ₃ and Si ₃ N ₄ .   The production method according to any one of claims 1, 3 and 10, wherein an average particle diameter of at least one primary powder selected from a valve metal, a valve metal compound and a valve metal alloy is 0.01 to 2 µm. .   The average particle size of at least one secondary agglomerated powder selected from a valve action metal, a valve action metal compound, and a valve action metal alloy is 0.1 to 20 µm. Production method.   The average particle diameter of the granulated powder of at least one primary powder or secondary agglomerated powder selected from valve action metals, valve action metal compounds and valve action metal alloys is 0.2 to 200 µm. The manufacturing method in any one of 10.   The manufacturing method according to claim 11, wherein the valve action metal, the valve action metal compound, and the valve action metal alloy are niobium, a niobium compound, and a niobium alloy.   The production method according to claim 1, wherein the pore forming agent is an oxide that exists as a solid at a temperature at which the molded body is sintered.   The manufacturing method according to claim 15, wherein the oxide is an oxide of Groups 1 to 5 and Groups 7 to 15 of the Periodic Table.   The oxide is lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, rhenium, iron, ruthenium, cobalt, rhodium, iridium, nickel, copper, From cadmium, mercury, boron, aluminum, gallium, indium, thallium, silicon, germanium, lead, antimony, bismuth, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium The production method according to claim 15, which is at least one oxide selected from the group consisting of:   The production method according to claim 15, wherein the oxide-providing compound is at least one selected from the group consisting of hydroxide, carbonate and bicarbonate.   Pore forming agent is sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, lithium oxide, lithium carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium hydrogen carbonate, magnesium calcium carbonate, calcium oxide, calcium hydroxide , Calcium carbonate, barium oxide, barium carbonate, hafnium oxide, yttrium oxide, yttrium hydroxide, yttrium carbonate, lanthanum oxide, lanthanum hydroxide, lanthanum carbonate, cerium oxide, cerium hydroxide, cerium carbonate, neodymium oxide, neodymium hydroxide, Neodymium carbonate, samarium oxide, samarium hydroxide, samarium carbonate, manganese carbonate, iron oxide, iron hydroxide, iron carbonate, magnesium oxide, lead iron oxide, barium zinc oxide, boron oxide, aluminum oxide, Aluminum oxide, process according to any one of claims 1 to 15 is at least one compound selected from the group consisting of lead oxide, and lead carbonate. The method according to any one of claims 1 to 19, wherein the pore-forming agent is a powder having an average particle diameter of 0.1 µm to 100 µm.   21. The organic binder is at least one selected from the group consisting of camphor, naphthalene, soap fatty acid, carbowax, vegetable wax, purified paraffin, acrylic polymer, methacrylic polymer, vinyl polymer, and polyethylene carbonate. The manufacturing method in any one of.   The pore-forming agent removal step is selected from the group consisting of water, organic solvents, acidic solvents, alkaline solvents, amine solvents, amino acid solvents, polyphosphoric acid solvents, crown ether solvents, chelating solvents, ammonium salt solvents, and ion exchange resin dispersion solvents. The method according to any one of claims 1 to 21, which is a step of removing with at least one selected solvent.   Furthermore, the manufacturing method in any one of Claims 1-22 including the process of providing the lead | read | reed of a valve action metal.   24. The manufacturing method according to claim 23, wherein the step of providing the lead is performed by implanting the valve action metal lead by compressing and forming the granulated material together with the valve action metal lead in the compression / forming process.   The manufacturing method according to claim 23, wherein the step of providing the lead is performed by welding the valve action metal lead to the sintered body after the removing step.   The production method according to claim 1 or 2, wherein the granulated product of the mixture has an average particle size of 10 to 1000 µm.   The production method according to claim 1 or 2, wherein an angle of repose of the granulated product of the mixture is 60 ° or less. The production method according to claim 1 or 2, wherein the flowability of the granulated product of the mixture is 0.1 cm ³ / g or more. It contains at least one primary powder, secondary agglomerated powder or granulated powder thereof, a pore forming agent, an organic binder and a solvent selected from a valve metal, a valve metal compound and a valve metal alloy, The solid content concentration is 1 to 80% by mass, the pore-forming agent has a plurality of peaks in the particle size distribution, and the plurality of peaks are at least one in a particle size of 0.1 to 0.9 μm and a particle size of 1 The dispersion used in the production method according to claim 1, wherein at least one particle having a particle diameter of 1 μm or more is 10% by volume or more at 0.0 μm or more.   The dispersion according to claim 29, which has a viscosity at 20 ° C of 0.1 Pa · s or more.   30. The dispersion according to claim 29, wherein the thixotropy index at 20 [deg.] C. is 0.2-2.   The coating body obtained by the method including the process of applying the dispersion liquid in any one of Claims 29-31.   A molded body obtained by a method comprising the step of placing the dispersion according to any one of claims 29 to 31 into a mold. Granulated product of at least one kind of primary powder, secondary agglomerated powder selected from valve action metal, valve action metal compound and valve action metal alloy, or a mixture containing these granulated powder, pore former and organic binder The pore-forming agent has a plurality of peaks in the particle size distribution, and the plurality of peaks have at least one particle diameter of 0.1 to 0.9 μm and a particle diameter of 1.0 μm or more. A molded article having at least one and having a particle size of 1 μm or more is 10% by volume or more.   The molded article according to claim 34, wherein the valve action metal, the valve action metal compound, and the valve action metal alloy are niobium, a niobium compound, and a niobium alloy. A sintered body having a volume of 49 mm ³ or more containing a pore-forming agent obtained by sintering the coated body according to claim 32 or the molded body according to any of claims 33 to 35. A sintered body for an anode of a solid electrolytic capacitor having a volume of 49 mm ³ or more, which does not contain a pore forming agent, wherein the pore forming agent is removed from the sintered body according to claim 36.   The sintered body for an anode according to claim 37, wherein when sintered at 1200 ° C, the sintered body has a CV value of 40000 to 400000 µFV / g.   A solid electrolytic capacitor comprising a sintered body for an anode of a solid electrolytic capacitor according to claim 37 as one electrode and a dielectric interposed between the counter electrode.   The solid electrolytic capacitor according to claim 39, wherein a main component of the dielectric is niobium oxide or tantalum oxide.   The solid electrolytic capacitor according to claim 39 or 40, wherein the material of the counter electrode is at least one selected from the group consisting of a solid electrolyte, an organic semiconductor, and an inorganic semiconductor.   The material of the counter electrode is an organic semiconductor, and the organic semiconductor is an organic semiconductor composed of benzopyrroline tetramer and chloranil, an organic semiconductor mainly composed of tetrathiotetracene, and an organic composed mainly of tetracyanoquinodimethane. The solid electrolytic capacitor according to claim 41, which is at least one selected from the group consisting of a semiconductor and a conductive polymer.   The solid electrolytic capacitor according to claim 42, wherein the organic semiconductor is a conductive polymer, and the conductive polymer is at least one selected from polypyrrole, polythiophene, polyaniline, and substituted derivatives thereof.   44. The solid electrolytic capacitor according to claim 43, wherein the conductive polymer is a conductive polymer obtained by doping poly (3,4-ethylenedioxythiophene) with a dopant.   45. The solid electrolytic capacitor according to claim 42, wherein the counter electrode material has a layered structure at least in part.   The electronic circuit using the solid electrolytic capacitor in any one of Claims 39-45.   The electronic device using the solid electrolytic capacitor in any one of Claims 39-45.   The device using the solid electrolytic capacitor according to any one of claims 39 to 45, which is an oscillator-mounted device, an IC-mounted device, a CPU-mounted device, or a power supply device.

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