Niobium monoxide powder, niobium monoxide sintered product and capacitor using niobium monoxide sint

专利摘要:
(1) Formula: NbOx (x = 0.8-1.2), it may contain 50-200,000 ppm of ellipsoids, the tapping density is 0.5-2.5 g / ml, the average particle diameter is 10-1000 micrometers, and the angle of repose is A niobium monoxide powder for a capacitor having a 10 to 60 °, a BET specific surface area of 0.5 to 40 m 2 / g, and a pore distribution having a plurality of pore diameter peak tops, and a method of manufacturing the same. (2) It has a pore diameter peak top within the range of 0.01 μm to 500 μm obtained by sintering the niobium monoxide powder. Preferably, among the plurality of pore diameter peak tops, the peak tops of the two peaks having the largest relative strengths are Niobium monoxide sintered compact in the range of 0.2-7 micrometers and 0.7-3 micrometers, respectively, whose peak top with the largest relative intensity is larger than the peak top with the next largest intensity, and its manufacturing method, (3 ) A capacitor using the sintered body and a method of manufacturing the same, (4) An electronic circuit and an electronic device using the capacitor.
公开号:KR20030020366A
申请号:KR10-2003-7000517
申请日:2002-05-14
公开日:2003-03-08
发明作者:오모리카즈히로；나이토카즈미；카와사키토시야；와다코우이치
申请人:쇼와 덴코 가부시키가이샤；
IPC主号:

专利说明:

NIOBIUM MONOXIDE POWDER, NIOBIUM MONOXIDE SINTERED PRODUCT AND CAPACITOR USING NIOBIUM MONOXIDE SINTERED PRODUCT}
[3] Condensers used in electronic devices such as mobile phones and personal computers are desired to be small and large in capacity. Among these capacitors, tantalum capacitors are frequently used because of their large capacity and good performance.
[4] Furthermore, in recent years, electronic devices have been requested to operate at low voltages, to operate at high frequencies, and to reduce noise, and even lower individual ESR (equivalent series resistance) is required in individual electrolytic capacitors.
[5] In general, a sintered body of tantalum powder is used as the anode body of a tantalum capacitor. The powder is sintered after molding to be integrated into an electrode called a sintered body. The sintered compact has a three-dimensional complex shape in which the particles of the powder are electrically and mechanically connected. After forming a dielectric film layer on the surface including the surface of the internal void of this sintered compact, a capacitor is comprised by impregnating the material used as a counter electrode. The capacity of the produced capacitor depends largely on the contact situation of the counter electrode material and the dielectric coating layer as long as the dielectric coating layer is uniformly attached to the surfaces inside and outside the sintered body.
[6] In order to increase the capacity of these tantalum capacitors, it is necessary to use a sintered compact in which the sintered compact mass is increased or the tantalum powder is micronized to increase the surface area.
[7] In the method of increasing the sintered body mass, the shape of the condenser inevitably increases and does not meet the demand for miniaturization. On the other hand, in the method of micronizing the tantalum powder to increase the specific surface area, the pore diameter of the tantalum sintered compact becomes small, and the number of closed holes is increased in the sintering step, making impregnation of the negative electrode agent in the later step difficult.
[8] For example, when a phosphoric acid aqueous solution is used as the counter electrode material, the contact state with the dielectric film layer becomes perfect, and the capacity expression rate (also referred to as cathode impregnation rate) at that time is 100%. In the case of using a material, especially a solid electrode material, it was difficult to set the capacity expression rate to 100%. In particular, when the average particle diameter of the tantalum powder is small or when the shape of the sintered body made of the tantalum powder is large, difficulty increases, and in extreme cases, the capacity emergence rate does not reach 50%. In addition, in the case of such a low capacity appearance rate, the moisture resistance of the produced capacitor could not be fully obtained.
[9] Moreover, when the pore diameter which a tantalum powder for producing a tantalum sintered compact has is small, the pore diameter which a sintered compact has inevitably becomes small, and a capacity | capacitance output rate becomes low. As a result, there arises a problem that the ESR cannot be lowered. As one of the methods to solve these drawbacks, the capacitor | condenser which made the sintered compact which can obtain a high capacity | capacitance yield rate using the electrode material which can obtain the dielectric of a dielectric constant larger than tantalum can be considered.
[10] As such an electrode material which can be supplied industrially, niobium is known to have a higher dielectric constant and a higher reserve than tantalum.
[11] In Japanese Patent Application Laid-Open No. 55-157226, agglomerated powder is press-molded and sintered by a valve-action metal fine powder having a particle diameter of 2.0 µm or less, finely cut the molded sintered body, and then joining the lead portion to it. Disclosed is a method of manufacturing a sintered element for a capacitor which is sintered again. However, the publication does not show details regarding the manufacturing method and characteristics of the niobium capacitor.
[12] U.S. Patent No. 4,084,965 discloses a capacitor in which niobium ingots are hydrogenated and pulverized to obtain niobium powder having an average particle diameter of 5.1 mu m, and then sintered and used. However, the capacitor | condenser disclosed is large in leakage current (it may abbreviate as LC hereafter), and lacks practicality.
[13] Japanese Patent Laid-Open No. 10-242004 discloses that the LC value is improved by nitriding a part of niobium powder or the like.
[14] In Japanese Patent Laid-Open No. 2000-119710, niobium pentoxide is added to molten magnesium to reduce the reaction, and then, NbOx (x = 0.5 to 1.5) generated is taken out, and NbOx (x = 0.5 to 0.5) produced in molten magnesium is subsequently removed. A method for producing a high purity niobium powder by a two-stage reduction reaction in which 1.5) is added to reduce the reaction to obtain metal niobium is disclosed.
[15] The tapping density of niobium powder, such as niobium monoxide, which can be used in a condenser, is an important factor in forming a niobium powder. As for the former, the tapping density is larger than 2.5 g / ml and is about 4 g / ml. It wasn't enough to do that.
[16] That is, when such a niobium monoxide powder was molded and sintered to form a sintered body, the flow from the molding machine hopper of the niobium monoxide powder was poor, and it was difficult to always weigh a certain amount of niobium monoxide powder into the mold. For this reason, the shape of a molded object is not always fully stabilized, the strength of a molded object and a sintered compact is insufficient, and, as a result, the capacitor | condenser with a bad LC was produced in high frequency. In addition, in the case of using a special molding apparatus that can handle poor flowability powder, the molding price becomes too high and is not practical.
[17] For this reason, the conventional niobium monoxide powder for capacitors known in the art is not sufficiently adaptable to continuous molding and has a problem of low productivity of the capacitors.
[1] This application is filed under U.S. Application No. 60/291925, filed May 21, 2001, and U.S. Application No. 60/331200, filed November 9, 2001, pursuant to Section 35 (b) of US Code 35. It is an application based on the provisions of Article 111 (a) which claims the benefit of Article 119 (e) (1).
[2] The present invention provides a niobium monoxide powder and a sintered body which can stably produce a capacitor having a large capacity per unit mass, a low equivalent series resistance (ESR), and good leakage current characteristics and moisture resistance, a capacitor using them, and a manufacturing method thereof. It is about.
[18] An object of the present invention is to provide a capacitor having a large capacity per unit mass, a low equivalent series resistance (ESR), a low leakage current value, a capacitor having high moisture resistance, a sintered body which can obtain a high capacity appearance rate by using this electrode material, It is desirable to provide a niobium monoxide powder which is preferable as the sintered compact material, has good flowability during molding, facilitates continuous formation, and enables stable production of a capacitor, and a method for producing the same.
[19] MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined the above subject. As a result, when a niobium monoxide sintered body having a specific pore distribution, preferably a niobium monoxide sintered body having a pore distribution having a plurality of pore diameter peak tops, is used for the capacitor electrode, a high capacity expression rate can be obtained and the leakage current is low. It was found that a capacitor having good moisture resistance can be produced. Further, niobium monoxide powder having a tapping density of preferably 0.5 to 2.5 g / ml, and more preferably an average particle diameter of 10 to 1000 µm, is preferred as the sintered compact material because of its good flowability and continuous molding. Using this niobium monoxide powder, it was found that a capacitor having a low leakage current value can be stably produced.
[20] More preferably, when the niobium monoxide sintered body made of niobium monoxide powder having a large pore distribution, a plurality of pore diameter peak saws, and all of the pore diameter peak saws made of niobium monoxide powder of 0.5 mu m or more is used for the capacitor electrode, Together we found something that could achieve that ESR.
[21] That is, the present invention relates to the following niobium monoxide powder, niobium monoxide sintered compact, a capacitor using the same, and a method for producing them.
[22] [1] Formula: Niobium monoxide powder for a capacitor represented by NbOx (x = 0.8 to 1.2) and having a tapping density of 0.5 to 2.5 g / ml.
[23] [2] magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, ruthetium, titanium, zirconium, hafnium, Vanadium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium, carbon, silicon, germanium, The niobium monoxide powder according to the preceding item [1], which contains at least one ellipsoid selected from the group consisting of tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, sulfur, selenium, and tellurium.
[24] [3] The niobium monoxide powder according to the above [1] or [2], wherein the ellipsoid forms a composite oxide with niobium.
[25] [4] The niobium monoxide powder according to the above [2] or [3], wherein the content of the elliptical element is 50 to 200,000 ppm.
[26] [5] The niobium monoxide powder according to any one of [1] to [4], wherein the average particle diameter is l0 to 1000 µm.
[27] [6] The niobium monoxide powder according to any one of [1] to [5], wherein the angle of repose is 10 to 60 °.
[28] [7] The niobium monoxide powder according to any one of [1] to [6], wherein the BET specific surface area is 0.5 to 40 m 2 / g.
[29] [8] The niobium monoxide powder according to any one of [1] to [7], which has a pore distribution having a pore diameter peak top within a range of 0.01 µm to 500 µm.
[30] [9] The niobium monoxide powder according to the above [8], wherein the pore distribution has a plurality of pore diameter peak tops.
[31] [10] The niobium monoxide powder according to the above [8] or [9], wherein all of the pore diameter peak tops are in the range of 0.5 to 100 µm.
[32] [11] A sintered body using the niobium monoxide powder according to any one of [1] to [10].
[33] [12] The sintered compact according to the above [11], which has a pore distribution having a pore diameter peak top within a range of 0.01 µm to 500 µm.
[34] [13] A niobium monoxide sintered compact for capacitor electrodes, wherein the pore distribution of the niobium monoxide sintered compact has a plurality of pore diameter peak tops.
[35] [14] The niobium monoxide sintered body according to any one of [11] to [13], wherein the pore distribution is composed of two pore diameter peak saws.
[36] [15] The monoxide according to the preceding item [13] or [14], wherein the peak tops of the two peaks having the largest relative strengths among the plurality of pore diameter peak tops are in the range of 0.2 to 0.7 µm and 0.7 to 3 µm, respectively. Niobium sintered body.
[37] [16] The niobium monoxide sintered body according to the item [13], wherein the peak top of the peak having the largest relative strength is larger than the peak top having the next largest relative strength among the plurality of pore diameter peak saws.
[38] [17] The niobium monoxide sintered body according to any one of [11] to [16], in which the sintered body has a volume of 10 GPa or more including the pore pore volume.
[39] [18] The niobium monoxide sintered body according to any one of [11] to [17], in which the sintered body has a specific surface area of 0.2 to 7 m 2 / g.
[40] [19] The niobium monoxide sintered body according to any one of the above [11] to [18], wherein a part of the sintered body is nitrided.
[41] [20] The niobium monoxide sintered body according to any one of [11] to [19], which is a sintered body obtained from a niobium monoxide molded body which gives a sintered body having a CV value of 40000 to 200000 µFV / g when the sintered body is sintered at 1400 ° C.
[42] [21] A capacitor comprising the dielectric niobium monoxide sintered body according to any one of [11] to [20] as one electrode and interposed between a counter electrode.
[43] [22] The capacitor as described in the above [21], wherein the main component of the dielectric is diniobium pentoxide.
[44] [23] The capacitor according to the above [21], wherein the counter electrode is at least one material selected from the group consisting of an electrolyte solution, an organic semiconductor, and an inorganic semiconductor.
[45] [24] The counter electrode is an organic semiconductor, and the organic semiconductor is an organic semiconductor consisting of a benzopyrroline tetramer and chloranyl, an organic semiconductor mainly composed of tetrathiotetracene, and an organic semiconductor mainly composed of tetracyanoquinomimethane. And the capacitor according to the above [23], which is at least one material selected from the group consisting of a conductive polymer.
[46] [25] The capacitor according to the above [24], wherein the conductive polymer is at least one selected from polypyrrole, polythiophene, polyaniline, and substituted derivatives thereof.
[47] [26] The conductive polymer is represented by the following General Formula (1) or (2).
[48]
[49] Wherein R ¹ to R ⁴ each independently represent a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom, a nitro group, a cyano group, or a primary And a monovalent group selected from the group consisting of secondary or tertiary amino groups, CF ₃ groups, phenyl groups and substituted phenyl groups, wherein the hydrocarbon chains of R ¹ and R ² and R ³ and R ⁴ are bonded to each other at arbitrary positions, You may form a bivalent chain which forms the cyclic structure of one or more 3-7 membered saturated or unsaturated hydrocarbons with the carbon atom substituted by such group. In the said cyclic bond chain, carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, may already contain the combination of the furnace at any position. X represents an oxygen, sulfur or nitrogen atom, R ⁵ is present only when X is to the nitrogen atom, and independently Or a capacitor of 1 to 10 carbon atoms in the straight-chain or branched saturated or unsaturated alkyl group.) A polymer substrate containing a repeating unit, with the preceding paragraph [24] of the conductive polymer doped with a dopant represented by the following on.
[50] [27] The conductive polymer is formula (3)
[51]
[52] (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 any position and includes two oxygen elements; The substituent refers to a substituent which forms a cyclic structure of at least one saturated hydrocarbon of 5 to 7 membered rings, and the cyclic structure includes those having a vinylene bond which may be substituted and those having a substituted phenylene structure. The capacitor as described in the preceding item [26], which is a conductive polymer containing a repeating unit represented by the above formula.
[53] [28] The capacitor according to the above [27], wherein the conductive polymer is a conductive polymer obtained by doping a poly (3,4-ethylenedioxythiophene) with a dopant.
[54] [29] The capacitor according to the above [21], wherein the counter electrode is made of a material having at least a part of a layer structure.
[55] [30] The condenser according to the above [21], wherein the counter electrode is a material containing an organic technical anion as a dopant.
[56] [31] A method for producing the niobium monoxide powder according to any one of [1] to [10], wherein the niobium monoxide or niobium monoxide compound is activated (also referred to as "pore forming treatment"). Method for preparing the powder.
[57] [32] The method for producing the niobium monoxide powder according to the above [31], wherein the activation treatment of the niobium monoxide or niobium monoxide compound is performed in at least one step selected from the group consisting of a sintering step and a crushing step.
[58] [33] The niobium monoxide powder according to the above [31] or [32], wherein the activation treatment of the niobium monoxide or niobium monoxide compound is performed using a mixture containing niobium monoxide or a niobium monoxide compound and an activator. Manufacturing method.
[59] [34] The method for producing the niobium monoxide powder according to any one of [31] to [33], wherein the average particle diameter of the niobium monoxide or niobium monoxide compound to be activated is 0.01 µm to 10 µm.
[60] [35] Niobium or niobium monoxide compounds include magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, ruthetium , Titanium, zirconium, hafnium, vanadium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium Containing 50 to 200,000 ppm of at least one element selected from the group consisting of carbon, silicon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, sulfur, selenium and tellurium [31] The method for producing the niobium monoxide powder according to any one of [34] to [34].
[61] [36] The method for producing the niobium monoxide powder according to the above [35], wherein the ellipsoid contained in the niobium monoxide or niobium monoxide compound forms a complex oxide with niobium.
[62] [37] The method for producing the niobium monoxide powder according to the above [33], wherein the niobium monoxide or a mixture containing the niobium monoxide compound and the activator is mixed using a solvent.
[63] [38] The niobium monoxide powder according to the above [37], wherein the solvent is at least one solvent selected from the group consisting of water, alcohols, ethers, cellosolves, ketones, aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons. Manufacturing method.
[64] [39] The method for producing the niobium monoxide powder according to the above [33], wherein the activator is used in an amount of 1 to 40% by mass based on the total amount of niobium monoxide or niobium monoxide compound.
[65] [40] The method for producing the niobium monoxide powder according to the above [33] or [39], wherein the average particle diameter of the activator is 0.01 to 500 µm.
[66] [41] The method for producing the niobium monoxide powder according to any one of [33], [37], [39] and [40], wherein the particle diameter peak top of the activator is plural.
[67] [42] The method for producing the niobium monoxide powder according to any one of [33], [37], [39] to [41], wherein the activator is a substance which is removed as a gas at 2000 ° C or lower.
[68] [43] The activator is naphthalene, anthracene, quinone, camphor, polyacrylic acid, polyacrylic acid ester, polyacrylamide, polymethacrylic acid, polymethacrylic acid ester, polymethacrylamide, polyvinyl alcohol, NH ₄ Cl, ZnO, A method for producing a niobium monoxide powder according to the preceding item [42], which is at least one member selected from the group consisting of WO ₂ , SnO ₂ , MnO ₃ .
[69] [44] One kind of activator selected from the group consisting of water-soluble substances, organic solvent soluble substances, acidic solution soluble substances, alkaline solution soluble substances, complexes to form soluble substances thereof, and those soluble substances below 2000 ° C. The process for producing the niobium monoxide powder according to any one of the above [33], [37], and [39] to [4l].
[70] [45] The activator consists of a metal, a compound of carbonic acid, sulfuric acid, sulfurous acid, halogen, perhalogenic acid, hypohalogenic acid, nitric acid, nitrous acid, phosphoric acid, acetic acid, oxalic acid or boric acid, or a metal, metal hydroxide and metal oxide. A method for producing niobium monoxide powder as described in the preceding item [44], which is at least one member selected from the group.
[71] [46] The method for producing the niobium monoxide powder according to the above [45], wherein the activator is at least one selected from the group consisting of metal carbonates, metal carbonates, metal hydroxides and metal oxides.
[72] [47] The niobium monoxide powder according to the preceding item [46], wherein the activator is at least one selected from the group consisting of metal carbonates, metal carbonates, metal hydroxides and metal oxides and has a melting point higher than the temperature in the sintering step. Manufacturing method.
[73] [48] The activator is lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium , Holmium, erbium, thulium, ytterbium, lutetium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, silver, gold At least one selected from the group consisting of zinc, cadmium, boron, aluminum, gallium, indium, thallium, carbon, silicon, germanium, tin, lead, arsenic, antimony, bismuth, selenium, tellurium, polonium, and these compounds The manufacturing method of niobium monoxide powder as described in [44].
[74] [49] The niobium monoxide powder according to any one of the above [31] to [33], wherein the activation treatment is a treatment for removing the activator by heating and / or depressurization before or during the sintering step. Manufacturing method.
[75] [50] The method of any one of the above [31] to [33], wherein the activation treatment is a treatment for removing a activator component by contacting a solvent with the sintered or crushed product after the sintering step, during the crushing step, or after the crushing step. The manufacturing method of the niobium monoxide powder of a base material.
[76] [51] The method for producing the niobium monoxide powder according to the above [50], wherein the solvent is at least one selected from the group consisting of water, an organic solvent, an acidic solution, an alkaline solution, and a solution containing a ligand that forms a soluble complex.
[77] [52] The method for producing the niobium monoxide powder according to the above [51], wherein the acidic solution is at least one solution selected from the group consisting of nitric acid, sulfuric acid, hydrofluoric acid, and hydrochloric acid.
[78] [53] The method for producing the niobium monoxide powder according to the above [51], wherein the alkaline solution contains at least one member selected from the group consisting of hydroxides of alkali metals and ammonia.
[79] [54] The method for producing the niobium monoxide powder according to the above [51], wherein the ligand is at least one member selected from the group consisting of ammonia, glycine, and ethylenediamine tetraacetic acid.
[80] [55] Nitrogen monoxide powder according to any one of [1] to [10], wherein the niobium monoxide powder is treated by at least one method selected from the group consisting of liquid nitriding, ion nitriding and gas nitriding. Method for producing niobium monoxide powder containing a.
[81] [56] Carbon containing niobium monoxide powder as described in any one of the preceding items [1] to [10] is treated by at least one method selected from the group consisting of solid phase carbonization and liquid carbonization. Method for producing niobium monoxide powder.
[82] [57] Boron, wherein the niobium monoxide powder according to any one of [1] to [10] is treated by at least one method selected from the group consisting of gas boronation and solid boronation. Method for producing niobium monoxide powder containing a.
[83] [58] Sulfur characterized by treating the niobium monoxide powder according to any one of [1] to [10] by at least one method selected from the group consisting of gas sulfidation, ion sulfidation and solid phase sulfidation. Method for producing niobium monoxide powder containing a.
[84] [59] A niobium monoxide powder obtained by the production method according to any one of [31] to [58].
[85] [60] A method for producing a niobium monoxide sintered compact, wherein the niobium monoxide powder according to any one of [1] to [10] and [59] is used.
[86] [61] A method for producing a capacitor comprising a niobium monoxide sintered body as one electrode, a dielectric formed on the surface of the sintered body, and a counter electrode formed on the dielectric, wherein the sintered niobium monoxide is the above-mentioned [1] to [10] And the niobium monoxide powder according to any one of the above [59].
[87] [62] The method for producing a capacitor according to the above [61], wherein the dielectric is formed by electrolytic oxidation.
[88] [63] A method for producing a capacitor comprising a niobium monoxide sintered body as one electrode, a dielectric formed on the surface of the sintered body, and a counter electrode formed on the dielectric, wherein the sintered niobium monoxide is the above-mentioned [11] to [20] It is a niobium-monoxide monoxide sintered compact in any one of Claims 1-9 characterized by the above-mentioned.
[89] [64] An electronic circuit using the capacitor according to any one of [21] to [30].
[90] [65] An electronic device using the capacitor according to any one of [21] to [30].
[91] Hereinafter, a high-capacity, low equivalent series resistance (ESR), a capacitor having good leakage current characteristics and moisture resistance, a niobium monoxide sintered body which can draw out its characteristics to obtain a high capacity expression rate, and a good flowability as a sintered body material is continuous. The niobium monoxide powder which can be shape | molded, and its manufacturing method are demonstrated.
[92] In the present invention, a niobium monoxide powder that satisfies the characteristics of the capacitor and improves the productivity of capacitor manufacturing, and has a tapping density of 0.5 to 2.5 g / ml (also abbreviated as niobium monoxide powder only). Is used).
[93] The niobium monoxide powder for condensers means that it can be used as a material for producing a condenser based on the formula: NbOx (wherein x is 0.8 to 1.2).
[94] Three types of niobium oxides are known, niobium monoxide, niobium dioxide, and niobium pentoxide.
[95] In niobium oxide where x is between 0 and 1, metal niobium and niobium monoxide coexist. Metal niobium is more easily sintered than niobium monoxide, and when a large amount of metal niobium is present, it is difficult to increase the specific surface area of the sintered body, and the capacity of the capacitor tends to be small.
[96] In the niobium oxide where x is between 1 and 2, niobium monoxide and niobium dioxide coexist. Niobium monoxide is conductive while niobium dioxide is insulating. The presence of a large amount of niobium dioxide is disadvantageous for the formation of a dielectric by electrolytic oxidation.
[97] In consideration of these, the range of x is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and particularly preferably 0.95 to 1.05.
[98] The niobium monoxide powder may contain, for example, one or more of components which form a composite oxide with niobium and components other than niobium such as nitrogen, phosphorus, antimony, sulfur, selenium, and tellurium. Thus, by containing components other than niobium, it becomes possible to change sinterability and can improve the characteristic as a capacitor | condenser. As elements other than such niobium, for example, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium , Titanium, zirconium, hafnium, vanadium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium And carbon, silicon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, sulfur, selenium and tellurium.
[99] For example, niobium monoxide powder may be molded and sintered to obtain a sintered compact for a capacitor by the following method.
[100] A niobium monoxide powder for a capacitor is added to a solution in which a binder described later is dissolved in an organic solvent such as toluene or methanol, and this is sufficiently mixed using a vibration mixer, a V-type mixer, or the like. Thereafter, using a dryer such as a conical dryer, the organic solvent is distilled off under reduced pressure to prepare a niobium monoxide combination powder including a binder. This combination powder is placed in an automatic molding machine hopper. The niobium monoxide combination powder is flowed from the hopper into the mold of the molding machine, automatically weighed while falling naturally into the mold, and molded together with the lead wire. After the molded object is removed under reduced pressure, the binder is sintered at 500 ° C to 2000 ° C to produce a niobium monoxide sintered body.
[101] Then, for example, the niobium monoxide sintered compact is elevated to 20 to 60 V in an electrolytic solution such as phosphoric acid or azipine acid at a temperature of 30 to 90 ° C. and a concentration of about 0.1% by mass, and chemically treated for 1 to 30 hours to form niobium pentoxide. Create a dielectric layer mainly composed of. On this dielectric layer, solid electrolyte layers, such as manganese dioxide, lead dioxide, and a conductive polymer, are formed, followed by forming a graphite layer and a silver paste layer. Next, after connecting the negative electrode terminal with soldering etc. on it, it seals with resin and creates a solid electrolytic capacitor.
[102] At the time of molding, in a combination powder having no proper flowability or angle of repose, it is difficult to flow from the hopper into the mold and cannot be molded stably. In particular, since it is transported from the hopper using a method such as vibration, even if the tapping density and the average particle diameter of the combination powder are too large or too small, the mass of the molded body, the stiffness of the molded body and the shape imbalance increases, and chipping and cracking may occur. As a result, the leakage current value worsens. Thus, the tapping density, average particle diameter, flowability, and angle of repose of the combination powder are important factors in producing a good sintered compact and a capacitor.
[103] Such physical properties of the combination powder hardly change before and after the combination with the binder, and the physical properties of the combination powder are determined by the properties of the niobium monoxide powder for the capacitor used. For this reason, the tapping density, average particle diameter, flowability, and angle of repose of the niobium monoxide powder to be used become important. Since the flowability and the angle of repose of the niobium monoxide powder are greatly influenced by the tapping density and the average particle diameter, the tapping density and the average particle diameter become important factors.
[104] In order to obtain the effect of improving the productivity, the strength of the sintered compact, and the reduction of the leakage current value according to the improvement of the flowability and the angle of repose, in the present invention, the tapping density is preferably 0.5 to 2.5 g / ml, and 0.7 to 1.9 g. / Ml is more preferable, and 0.7-1.6g / ml is especially preferable. Moreover, 10-1000 micrometers is preferable and, as for the average particle diameter of the niobium monoxide powder of this invention, 50-200 micrometers is especially preferable.
[105] In order to naturally fall a niobium monoxide powder from a molding machine hopper into a metal mold | die, the angle of repose of the niobium monoxide powder of this invention has preferable 10-60 degrees, and 10-50 degrees is especially preferable.
[106] The niobium monoxide powder having the above-described physical properties includes niobium monoxide powder or niobium monoxide compound powder (hereinafter, these are referred to as "raw niobium monoxide powder") and an activator ("pore-forming agent"). It can be manufactured using a mixture (hereinafter sometimes referred to as "raw material mixture") containing "may be described as a raw material" as a raw material, at least through a sintering step and a crushing step.
[107] The activator is removed by either the sintering step or the crushing step of producing the niobium monoxide powder of the present invention from the raw material mixture. The activator may be removed independently of the sintering step and the disintegration step.
[108] The method of removing an activator can employ | adopt various methods arbitrarily according to the chemical property of an activator, and what is necessary is just to use the method which is easy to remove an activator, combining any one or several.
[109] As a method of removing an activator, the method of evaporating, subliming, or pyrolyzing an activator and removing it as a gas, and the method of removing by dissolving an activator with a solvent are mentioned, for example.
[110] When removing an activator as a gas, you may provide in the sintering process or the process of removing an activator by heating and / or reduced pressure before sintering.
[111] In the case of dissolving and removing the activator, the activator is dissolved and removed by contacting the solvent described later with the sintered material or its pulverized product after sintering, during crushing, or after crushing.
[112] Further, in any of the steps of producing the niobium monoxide powder of the present invention from the raw material mixture, a step of nitriding, boronizing, carbonizing or sulfiding a part of the niobium monoxide powder may be provided.
[113] Hereinafter, the manufacturing method of the niobium monoxide powder of this invention is demonstrated in detail.
[114] As raw material niobium monoxide powder, niobium monoxide (NbOx: x = 0.8-1.2) and magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium , Erbium, thulium, ytterbium, lutetium, titanium, zirconium, hafnium, vanadium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, water, silver At least one element selected from the group consisting of boron, aluminum, gallium, indium, thallium, carbon, silicon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, sulfur, selenium and tellurium One or more powders selected from niobium monoxide, and composite oxides thereof can be used. In addition, some of these may be further nitrided, sulfided, carbonized or boronated.
[115] 0.01-10 micrometers is preferable, as for the average particle diameter of the raw material niobium monoxide powder used by this invention, 0.02-5 micrometers is more preferable, 0.05-2 micrometers is especially preferable.
[116] Moreover, from the improvement of the sintering property and the electrical performance of the obtained capacitor | condenser, the quantity of the other element to contain is preferable from 50 mass ppm to 500000 mass ppm, and 50-200000 mass ppm is especially preferable.
[117] The method for obtaining niobium monoxide, which is a raw niobium monoxide powder, is, for example, a method of reducing diniobium pentoxide using a reducing metal such as calcium or magnesium, or a method of reducing niobium dioxide powder by heating in a hydrogen stream. And a niobium metal powder and a niobium dioxide powder are mixed, followed by heating in argon.
[118] The method for obtaining niobium monoxide containing an ellipsoid consisting of a raw niobium monoxide powder is obtained by heating a composite oxide with other components, a mixture of niobium pentaoxide and an elliptic oxide oxide, niobium dioxide and an ellipsoid oxide with starting materials in a hydrogen stream. Reduction or reduction using metals with reducing action such as calcium, magnesium, yttrium, lanthanum, cerium, samarium, and misch metals, oxidation of niobium and ellipsoids in air, oxidation of niobium monoxide and The method of heating the mixture of an ellipsoid compound, the method of reacting with a gas, solid, a liquid ellipsoid, and niobium monoxide, etc. are mentioned. These powders can be pulverized in a usual manner to adjust the particle size.
[119] For example, in order to obtain a niobium monoxide powder containing boron as an ellipsoid, a method of mixing and heating a niobium boride powder and a niobium monoxide powder, a method of heating a niobium boride powder in air, or a gaseous boron and monoxide The niobium is heated, and the method etc. are mentioned.
[120] An activator is a substance which can be removed in any of the processes for preparing the niobium monoxide powder of the present invention from a raw material mixture. Usually, the part in which the activator is removed in the niobium monoxide powder of the present invention forms pores.
[121] The particle diameter of the activator affects the pore diameter of the niobium monoxide powder of the present invention, the pore diameter of the niobium monoxide powder affects the pore diameter of the niobium monoxide sintered compact, and the pore diameter of the sintered compact is the capacity of the capacitor and the manufacturing process of the capacitor. It affects the impregnation property of the negative electrode agent in.
[122] Impregnation of the negative electrode has a high capacity and greatly affects the fabrication of low ESR capacitors. Since the niobium monoxide sintered compact is produced by press-molding niobium monoxide powder, the pore diameter of the sintered compact inevitably becomes smaller than the pore diameter of the niobium monoxide powder. In view of the difficulty in impregnation of the negative electrode with respect to the sintered compact made of powder having a small pore diameter peak, the pore diameter of the niobium monoxide powder is preferably 0.5 µm or more, particularly 1 µm or more as an average diameter.
[123] These pore diameters are preferably 0.01 to 500 µm, more preferably 0.03 to 300 µm, and particularly preferably 0.1 to 200 µm as the average diameter. Therefore, 0.01-500 micrometers is preferable, as for the average particle diameter of an activator, 0.03-300 micrometers is more preferable, 0.1-200 micrometers is especially preferable.
[124] The pore diameter of most preferable niobium monoxide powder is 0.5 micrometer-100 micrometers as an average diameter, and the average particle diameter of the most preferable activator which produces this pore diameter is 0.5 micrometer-100 micrometers.
[125] In order to reduce these pore diameters, an activator having a small particle size may be used, and an activator having a large particle size may be used to increase the pore size.
[126] In addition, the pore diameter distribution can be adjusted by adjusting the particle size distribution of the activator.
[127] In order to obtain a capacitor having a sufficient capacity without impregnation of the negative electrode agent, pores small enough to obtain a predetermined capacity in the niobium monoxide sintered body and pores large enough to sufficiently impregnate the negative electrode agent in accordance with the properties of the negative electrode agent It is preferable to install suitably.
[128] In order to adjust the pore diameter distribution of the niobium monoxide powder or the niobium monoxide sintered compact, for example, using an activator (powder) having a particle size distribution having two or more peak tops, two or more peak tops are used in the niobium monoxide powder. It can have a pore diameter distribution. By sintering this niobium monoxide powder, a niobium monoxide sintered compact having a pore diameter distribution having two or more peak tops of equivalent pore diameter can be obtained. In this case, it is preferable that a pore diameter peak top exists in the range of 0.01-500 micrometers, 0.03-300 micrometers is more preferable, 0.1-200 micrometers is still more preferable, 0.1-30 micrometers is especially preferable, 0.2- 3 μm is most preferred.
[129] The niobium monoxide powder giving such a niobium monoxide sintered compact has two or more pore diameter peak tops. It is preferable that all the two or more pore diameter peak tops of this niobium monoxide powder are 0.5 micrometer or more. For example, when producing a niobium monoxide sintered body having two pore diameter peak tops at 0.7 mu m and 3 mu m, the two pore diameter top saws of the niobium monoxide powder are, for example, about 1.5 mu m and about 25 mu m. You can adjust it. The average particle diameter of the activator giving a small pore diameter of about 1.5 μm is about 1.5 μm, and the average particle diameter of the activator giving a large pore diameter of about 25 μm is about 25 μm. Usually, when small pores and large pores exist in niobium monoxide powder, large pores are crushed and become small at the time of press molding. Therefore, it is preferable that a large pore diameter peak top exists in 20 micrometers or more. Even when there are three pore diameter peak tops, it is preferable that a large pore diameter peak top is 20 micrometers or more. Moreover, it is preferable that 30 volume% or more of all the pore volumes have a pore diameter of 20 micrometers or more, and it is especially preferable that it is 40 volume% or more.
[130] An activator having two or more peak tops in the particle size distribution can be obtained, for example, by mixing two or more types of activators having different peak tops in the particle size distribution.
[131] As a substance used as an activator, the substance used as a gas below sintering temperature, or the substance soluble in a solvent at least after sintering is mentioned, for example.
[132] Examples of the substance which becomes a gas at a sintering temperature or lower include, for example, a substance which becomes a gas by evaporation, sublimation, or pyrolysis. An inexpensive substance which easily becomes a gas without leaving a residue even at a low temperature is preferable. As such a material includes, for example, a naphthalene, an aromatic compound such as anthracene, quinone, camphor, NH ₄ Cl, ZnO, WO _2, SnO _2, MnO _3, organic polymer.
[133] Examples of the organic polymer include polyacrylic acid, polyacrylic acid ester, polyacrylamide, polymethacrylic acid, polymethacrylic acid ester, polymethacrylamide, and polyvinyl alcohol.
[134] The substance which is soluble at least after sintering is particularly preferable as long as the residue of the activator or its thermal decomposition product is a substance soluble in the solvent, and the substance readily dissolves in the solvent described later after sintering, during crushing or after crushing. Combinations with can select from many materials.
[135] Examples of such materials include compounds with metals, carbonic acid, sulfuric acid, sulfurous acid, halogens, perhalogenic acid, hypohalogenic acid, nitric acid, nitrous acid, phosphoric acid, acetic acid, oxalic acid, or boric acid, metal oxides, metal hydroxides and metals. Can be mentioned.
[136] Preferably, the compound is a compound having high solubility in a solvent such as an acid, alkali, ammonium salt solution described later, and the like, for example, lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, Radium, scandium, yttrium, cerium, neodymium, erbium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, silver, Compounds containing at least one compound selected from the group consisting of gold, zinc, cadmium, aluminum, gallium, indium, thallium, germanium, tin, lead, antimony, bismuth, selenium, tellurium, polonium, boron, silicon, and arsenic Can be mentioned. Among them, metal salts are preferable, and barium oxide, manganese nitrate (II), calcium carbonate, and the like are more preferable.
[137] These said activators may be used independently and there is no problem even if it uses them in combination of 2 or more types.
[138] In consideration of efficiently forming specific pores, a material present as a solid at the sintering temperature is preferred. This is because the activating agent is present at the sintering temperature to block the aggregation of niobium monoxide primary powders more than necessary and cause fusion of niobium monoxide only at the contacts between the niobium monoxides. At the sintering temperature, when present as a liquid or a gas, there is little effect of blocking and may form pores smaller than desired pores. Therefore, a high melting point material, such as barium oxide, calcium carbonate, aluminum oxide, magnesium oxide, etc., is used as an activator than when a low melting point material such as zinc metal, tin metal, antimony oxide, or the like is used as an activator. The pore diameter is stabilized when used as.
[139] If the amount of the activator added is small, the tapping density and the angle of repose are large, and if the amount is large, the tapping density is small and the closing holes in the sintering step are increased. In order to obtain a tapping density of 0.5 to 2.5 g / ml at a repose angle of 60 ° or less without a problem of the closing hole in the sintering step, it is also changed depending on the average particle diameter of the activator. -40 mass% (Hereinafter, unless otherwise indicated, a mass% is abbreviated as only%.), Preferably it is 5 to 25%, More preferably, it is 10 to 20%.
[140] The raw material mixture may be a mixture of the above-mentioned activator and the above niobium monoxide raw material in a solvent-free manner, or may be dried by mixing both using a suitable solvent.
[141] Examples of the solvent that can be used include water, alcohols, ethers, cellulsolves, ketones, aliphatic hydrocarbons, aromatic hydrocarbons and halogenated hydrocarbons.
[142] A mixer may be used for mixing. As the mixer, conventional apparatuses such as a vibration mixer, a V-type mixer, and a Nauter mixer can be used without any problem. The temperature in the mixing is limited depending on the boiling point and the solidification point of the solvent, but is generally -50 ° C to 120 ° C, preferably -50 ° C to 50 ° C, and more preferably -10 ° C to 30 ° C. . There is no restriction | limiting in particular if the time to mix is 10 minutes or more, Usually, it is preferable to carry out in 1 to 6 hours.
[143] When using a solvent, the mixture obtained is dried to less than 80 degreeC, Preferably it is less than 50 degreeC using a conical dryer, a partition type dryer, etc.
[144] If the activator becomes a gas at or below the sintering temperature, it is possible to remove the activator at the time of sintering. You may install independently the process of removing. In this case, for example, the activator is distilled off under a reduced pressure at 100 ° C to 800 ° C for several hours.
[145] The sintering step is performed at 500 ° C to 2000 ° C, preferably 800 ° C to 1500 ° C, more preferably 1000 ° C to 1400 ° C under reduced pressure or under a reducing atmosphere such as argon. Preferably, after the end of the sintering, the niobium monoxide is cooled until the temperature of the niobium monoxide (abbreviated as the product temperature) is 30 ° C. or lower, and the oxygen is 0.01% by volume to 10% by volume, preferably 0.1% by volume to 1% by volume. Inert gas, such as nitrogen or argon, containing is gradually added so that the product temperature does not exceed 30 ℃, left for 8 hours or more and taken out to obtain a sintered mass.
[146] In the disintegration step, the sintered mass is disintegrated to an appropriate particle diameter by using a disintegrator such as a roll granulator.
[147] If the activator is soluble in the solvent at least after the sintering step, a suitable solvent is contacted with the sintered mass or pulverized powder after sintering, before crushing, during crushing, after crushing, or in a plurality of these processes to dissolve and remove the activator component. do. It is preferable to dissolve and remove by disintegration powder after disintegration from the ease of removal.
[148] As a solvent used here, it is a solvent in which the solubility of the activator to be melt | dissolved is obtained sufficiently, Preferably it is inexpensive and it is hard to remain. For example, if the activator is water-soluble, water is used. If the organic solvent is soluble, organic solvents such as methyl isobutyl ketone, ethanol, dimethyl sulfoxide (DMSO) are used, and if acid-soluble, nitric acid, sulfuric acid, phosphoric acid, boric acid, If acid solutions such as carbonic acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, and organic acid are used, and alkali-soluble, alkaline solutions such as hydroxides of alkali metals, hydroxides of alkaline earth metals, ammonia, and the like are formed. Ammonia, amines such as ethylenediamine, amino acids such as glycine, polyphosphates such as sodium tripolyphosphate, thiosulfates such as crown ether and sodium thiophosphate, and chelating agents such as ethylenediamine tetraacetic acid. It is good to use.
[149] In addition, solutions of ammonium salts such as ammonium chloride, ammonium nitrate and ammonium sulfate, cation exchange resins and anion exchange resins can also be preferably used. The temperature at which the activator is dissolved and removed is preferably low, and preferably 50 ° C. or lower. It is more preferable to dissolve and remove at -10 degreeC-40 degreeC, and it is especially preferable to carry out at 0 degreeC-30 degreeC. Moreover, when dissolving and removing, it is preferable to select the method with few heat generation. For example, when a metal oxide or a metal is used as an activator, the heat of neutralization may generate | occur | produce in the method of dissolving and removing with an acid, and temperature may become high too much. Therefore, for example, it is difficult to generate heat such as a method of dissolving in water or an organic solvent, a method of forming a soluble complex using an aqueous solution of ammonium nitrate, ethylenediamine tetraacetic acid, or the like, and a method of dissolving in a solution containing an ion exchange resin. You can also choose a method.
[150] More specifically, the combination of the activator and the solvent is, for example, barium oxide and water, calcium oxalate and hydrochloric acid, aluminum oxide and sodium hydroxide aqueous solution, hafnium oxide and methyl isobutyl ketone, magnesium carbonate and ethylenediamine tetraacetate Aqueous solution etc. are mentioned.
[151] After dissolving and removing the activator, it is sufficiently washed and dried. For example, when barium oxide is removed with water, it is sufficiently washed with ion-exchanged water until the electrical conductivity of the washing water is 5 µS / cm or less. Next, under reduced pressure, the product temperature is dried at 50 캜 or lower. The amount of the activator and the solvent component remaining here is usually 100 ppm or less, depending on the washing conditions.
[152] In order to further improve the sintering property, the niobium monoxide powder, the sintered mass or the niobium monoxide raw material powder thus obtained may further be subjected to nitriding, boronization, carbonization, sulfidation or a plurality of these treatments. .
[153] The obtained nitride of niobium monoxide, boronide of niobium monoxide, carbide of niobium monoxide, sulfide of niobium monoxide, or plural kinds thereof may be contained in the niobium monoxide powder of the present invention. Although the sum total of content of each element of nitrogen, boron, carbon, and sulfur changes also with the shape of niobium monoxide powder, it is 0 ppm-200,000 ppm, Preferably it is 50 ppm-100,000 ppm, More preferably, 200 ppm-20,000 ppm to be. If it exceeds 200,000 ppm, the capacity characteristics deteriorate and are not suitable as a capacitor.
[154] The niobium monoxide powder nitriding method can be carried out by any one of liquid nitriding, ion nitriding, gas nitriding or the like, or a combination thereof. Gas nitriding in a nitrogen gas atmosphere is preferable because the apparatus is simple and the operation is easy. For example, the method of gas nitriding by nitrogen gas atmosphere is achieved by leaving the said niobium monoxide powder in a nitrogen atmosphere. The niobium monoxide powder of the target amount of nitriding can be obtained within the temperature of the atmosphere to be nitrided at 2000 degrees C or less, and the leaving time within 100 hours. Moreover, processing time can be shortened by processing at higher temperature.
[155] The boronation method of niobium monoxide powder may be gas boronation or solid boronation. For example, the niobium monoxide powder may be left to stand for 1 minute to 100 hours under a reduced pressure with a boron source of boron halide such as boron pellets or trifluoroboron.
[156] The carbonization of the niobium monoxide powder may be any of gas carbonization, solid carbonization and liquid carbonization. For example, the niobium monoxide powder may be left to stand for 1 minute to 100 hours under a reduced pressure, together with a carbon source such as an organic material having carbon such as a carbon material or methane.
[157] The sulfidation method of niobium monoxide powder may be any of gas sulfidation, ion sulfidation and solid phase sulfidation. For example, the method of gas sulfidation in a sulfur gas atmosphere is achieved by leaving the niobium monoxide powder in a sulfur atmosphere. The temperature of the sulfiding atmosphere is 2000 degrees C or less, and the leaving time can obtain the niobium monoxide powder of the target amount of sulfide within 100 hours. Moreover, processing time can be shortened by processing at higher temperature.
[158] The BET specific surface area of the niobium monoxide powder of this invention obtained as mentioned above is 0.5-40 m <2> / g normally, Preferably it is 0.7-10 m <2> / g, More preferably, it is 0.9-2 m <2> / g.
[159] The niobium monoxide powder of the present invention may be used by mixing niobium monoxide powders having different tapping densities, particle diameters, angles of repose, BET specific surface area, pore size distribution, nitriding, boronization, carbonization, and sulfidation.
[160] It is preferable that the sintered compact of this invention which can be used for the electrode for capacitors is manufactured by sintering the niobium monoxide powder of this invention mentioned above, for example. For example, after niobium monoxide powder is press-molded to a predetermined shape for 1 minute to 10 hours at 10 ^-5 to 10 ² Pa, 500 to 2000 캜, preferably 800 to 1500 캜, more preferably 1000 It can heat in the range of 1 degreeC-1400 degreeC, and can obtain a sintered compact.
[161] The pore diameter distribution of the sintered compact obtained from the niobium monoxide powder of the present invention usually has a pore diameter peak top in the range of 0.01 μm to 500 μm.
[162] Moreover, by adjusting the pressurization at the time of shaping | molding to a specific pressurization value, a sintered compact can have more pore diameter peak saws than the number of pore diameter peak saws which a niobium monoxide powder has. The pressurization value varies depending on the physical properties of the niobium monoxide powder, the shape of the molded body, or the press molding conditions such as a molding machine, but is within a range not less than the pressure at which pressure molding is possible and the pressure at which the pores of the sintered compact are not closed. Preferred pressurization values can be determined by preliminary experiments in accordance with the physical properties of the niobium monoxide powder to be molded so as to have a plurality of pore diameter peak tops. In addition, a pressurization value can be adjusted by adjusting the weight added to the molded object of a molding machine, for example.
[163] The pore diameter distribution of the sintered compact preferably has at least two pore diameter peak tops such that pores small enough to obtain a predetermined capacity and pores large enough to sufficiently impregnate the negative electrode agent in accordance with the physical properties of the negative electrode agent. Thus, from the sintered compact in which a pore diameter distribution has several peak tops, the capacitor | condenser which has a favorable impregnation of a counter electrode and has a high capacity | capacitance output rate can be obtained.
[164] In addition, among the plurality of pore diameter peak tops, the peak tops of the two peaks having the largest relative strengths are present at 0.2 to 0.7 µm and 0.7 to 3 µm, respectively, preferably at 0.2 to 0.7 µm and 0.9 to 3 µm, respectively. In this case, moisture resistance of the capacitor | condenser produced from this sintered compact becomes favorable. Moreover, the peak top of the peak with the largest relative intensity among the plurality of pore diameter peak saws is particularly preferable since the moisture resistance is better condenser when the relative top is on the larger diameter side than the peak top of the next largest peak.
[165] The specific surface area of the sintered compact thus produced is generally 0.2 m 2 / g to 7 m 2 / g.
[166] Usually, the larger the shape of the sintered body, the more difficult the impregnation of the counter electrode is. For example, when the size of a sintered compact is 10 GPa or more, the sintered compact which has a pore diameter distribution with several peak tops of this invention can be used especially effectively.
[167] The sintered compact of this invention may be partially nitrided. As the nitriding method, the method and reaction conditions applied to the niobium monoxide powder described above can be adopted. It is also possible to nitride a part of the niobium monoxide powder for producing the sintered body and to nitride a part of the sintered body produced from the powder.
[168] On the other hand, in such a sintered body, the oxygen element usually contains 0.8 to 1.2 times mol relative to the niobium element. This includes oxygen contained in the niobium monoxide powder before sintering and oxygen added by natural oxidation during sintering. In addition, content of elements other than niobium monoxide, the added element, oxygen, and nitrogen of the sintered weight of this invention are 400 mass ppm or less normally.
[169] In the sintered compact of the present invention, for example, when sintered at 1400 ° C, the CV value (the product of the chemical conversion voltage value at the time of 120 ° C 120 min in 0.1 mass% phosphate aqueous solution and the capacity at 120 kPa) is 40000. It becomes -200000 micro FV / g.
[170] Next, the manufacturing of the capacitor element will be described.
[171] For example, a lead wire having an appropriate shape and length, which is made of a valve action metal such as niobium or tantalum, is prepared, and the lead wire is integrally inserted so that a part of the lead wire is inserted into the molded body during press molding of the niobium monoxide powder described above. It is molded and designed so that the lead wire is assembled to be the lead of the sintered compact, or the lead wire prepared separately after the molding and sintering without the lead wire is connected by welding or the like.
[172] Using the above-mentioned sintered compact as one electrode, a capacitor can be manufactured from a dielectric interposed between the counter electrode. For example, a niobium monoxide sintered body is used as one electrode, a dielectric is formed on the surface of the sintered body (including the inner surface of the pore), and a counter electrode is provided on the dielectric to form a capacitor.
[173] Here, as the dielectric of the capacitor, a dielectric mainly composed of niobium oxide is preferable, and more preferably a dielectric mainly composed of niobium pentoxide. A dielectric mainly composed of niobium pentoxide can be obtained by electrooxidizing, for example, a niobium monoxide sintered compact which is one electrode. In order to electrolytically oxidize the niobium monoxide electrode in an electrolytic solution, it is usually performed using an aqueous solution of protonic acid, for example, an aqueous 0.1% phosphoric acid solution, an aqueous sulfuric acid solution or an aqueous acetic acid solution of 1%, an aqueous azipic acid solution, or the like. In this way, when the niobium monoxide electrode is converted into an electrolytic solution to obtain a niobium oxide dielectric, the capacitor of the present invention becomes an electrolytic capacitor, and the niobium monoxide electrode becomes an anode.
[174] In the capacitor of the present invention, the counter electrode (counter electrode) of the niobium monoxide sintered body is not particularly limited, and for example, at least one material (compound) selected from electrolytes, organic semiconductors, and inorganic semiconductors known in the aluminum electrolytic capacitor industry. Can be used.
[175] As a specific example of electrolyte solution, the mixed solution of dimethylformamide and ethylene glycol which melt | dissolved 5 mass% of isobutyl tripropyl ammonium borotetrafluoride electrolyte, and the mixed solution of propylene carbonate and ethylene glycol which melt | dissolved 7 mass% of tetraethylammonium borotetrafluoride electrolyte Etc. can be mentioned.
[176] As a specific example of an organic semiconductor, the organic semiconductor which a benzopyrroline tetramer consists of chloranyl, the organic semiconductor which has a tetrathiotetracene as a main component, the organic semiconductor whose main component is tetracyanoquinomimethane, or following General formula (1) Or the conductive polymer containing the repeating unit represented by General formula (2) is mentioned.
[177]
[178] Wherein R ¹ to R ⁴ each independently represent a hydrogen atom, a linear or branched, saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom, a nitro group, a cyano group, a primary, The monovalent group chosen from the group which consists of a secondary or tertiary amino group, a CF ₃ group, a phenyl group, and a substituted phenyl group is shown. The hydrocarbon chains of R ¹ and R ² and R ³ and R ⁴ are bonded to each other at arbitrary positions, and form a cyclic structure of saturated or unsaturated hydrocarbons of at least one or three to seven membered rings together with the carbon atoms substituted by such groups. You may form the bivalent chain to form. The cyclic bond chain may contain a bond of carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino at an arbitrary position. X represents oxygen, sulfur or a nitrogen atom, and R ⁵ is present only when X is a nitrogen atom, and independently represents hydrogen or a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms.
[179] In the present invention, R ¹ to R ⁴ in the general formula (1) or (2) are preferably each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 6 carbon atoms. Or an alkoxy group may be represented and R <^1> and R <^2> and R <^3> and R <^4> may combine with each other and may be cyclic.
[180] In addition, in this invention, the conductive polymer containing the repeating unit represented by the said General formula (1), Preferably the conductive polymer containing the structural unit represented by following General formula (3) as a repeating unit is mentioned. have.
[181]
[182] In formula, R <^6> and R <^7> respectively independently represents a hydrogen atom, a C1-C6 linear or branched saturated or unsaturated alkyl group, or the said alkyl group couple | bonds in arbitrary positions with each other, and contains two oxygen elements, It means the substituent which forms the cyclic structure of at least 1 or more 5-7 membered saturated hydrocarbon. In addition, the said cyclic structure includes the thing which has a vinylene bond which may be substituted, and the thing of the phenylene structure which may be substituted.
[183] Dopants are doped in the conductive polymer including the chemical structure. As the dopant, a known dopant can be used without limitation.
[184] As an example of an inorganic semiconductor, the inorganic semiconductor which consists of lead dioxide or manganese dioxide as a main component, the inorganic semiconductor which consists of iron tetratrioxide, etc. are mentioned. You may use these semiconductors individually or in combination of 2 or more types.
[185] As a polymer containing the repeating unit represented by General formula (1) or (2), for example, polyaniline, polyoxyphenylene, polyphenylene sulfide, polythiophene, polyfuran, polypyrrole, polymethylpyrrole And these substituted derivatives, a copolymer, etc. are mentioned. Among them, polypyrrole, polythiophene and substituted derivatives thereof (for example, poly (3,4-ethylenedioxythiophene) and the like) are preferable.
[186] When the organic semiconductor and the inorganic semiconductor are in the range of conductivity 0 ^-2 S / cm-10 ³ S / cm, the impedance value of the produced capacitor becomes smaller and the capacity | capacitance at a high frequency can be further enlarged.
[187] As a method for producing the conductive polymer layer, for example, an oxidizing agent capable of sufficiently conducting a dehydrogenated bielectron oxidation reaction of a polymeric compound of aniline, thiophene, furan, pyrrole, methylpyrrole or a substituted derivative thereof. The method of superposing | polymerizing by the action of is employ | adopted. The polymerization reaction from the polymerizable compound (monomer) is, for example, gas phase polymerization or solution polymerization of monomers, and is formed on the surface of the niobium monoxide sintered body having a dielectric. The conductive polymer is an organic solvent soluble polymer capable of solution coating. In this case, a method of coating and forming the surface is adopted.
[188] As one of the preferable manufacturing methods by solution polymerization, the niobium monoxide sintered compact in which the dielectric layer was formed is immersed in the solution containing the oxidizing agent (solution 1), and then immersed in the solution containing the monomer and the dopant (solution 2) and polymerized. And the method which can form a conductive polymer layer on the said surface is illustrated. Moreover, you may immerse in the solution 1, after immersing the said sintered compact in solution 2. In addition, in the said solution 2, you may use for the said method as a monomer solution which does not contain a dopant. In addition, when using a dopant, you may use coexisting in the solution containing an oxidizing agent.
[189] By repeating this polymerization step operation more than once, preferably 3 to 20 times, with respect to the niobium monoxide sintered body having a dielectric, a dense, layered conductive polymer layer can be easily formed.
[190] In the manufacturing method of the capacitor | condenser of this invention, an oxidizing agent should just be an oxidizing agent which does not adversely affect a capacitor | condenser performance, and the reducing agent of the oxidizing agent becomes a dopant, and can improve the electrical conductivity of a conductive polymer, and it is industrially cheap and manufacture handling This easy compound is preferred.
[191] Specific examples of such oxidizing agents include Fe (III) -based compounds such as FeCl ₃ , FeClO ₄ , and Fe (organic acid anion) salts, or anhydrous aluminum chloride / copper chloride, alkali metal persulfates, and persulfate. Manganese such as ammonium salts, peroxides, potassium permanganate, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetrachloro-l, 4-benzoquinone, tetracyano- Quinones such as 1,4-benzoquinone, halogens such as urea and bromine, peracids, sulfuric acid, fuming sulfuric acid, sulfur trioxide, sulphonic acid such as chlorosulfuric acid, fluorosulfuric acid and amidic sulfuric acid, ozone and the like, and combinations of a plurality of these oxidizing agents Can be mentioned.
[192] Among these, examples of the basic compound of the organic acid anion forming the Fe (organic acid anion) salt include organic technical acid or organic carboxylic acid, organophosphoric acid and organoboric acid. Specific examples of the euphonic acid include benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, α-sulfonaphthalene, β-sulfonaphthalene, naphthalenedisulphonic acid, alkylnaphthalenesulfonic acid (butyl as an alkyl group, triisopropyl, di-t- Butyl and the like).
[193] On the other hand, examples of the organic carboxylic acid include acetic acid, propionic acid, benzoic acid, oxalic acid, and the like. In the present invention, polymer electrolyte anions such as polyacrylic acid, polymethacrylic acid, polystyrenesulfonic acid, polyvinylsulfonic acid, polyvinyl sulfate poly-α-methylsulfonic acid, polyethylenesulfonic acid and polyphosphoric acid are also used. On the other hand, examples of these eutechonic acids or organic carboxylic acids are merely illustrative and are not limited to these. In addition, examples of the counter cation of the anion include an alkali metal ion such as H ⁺ , Na ⁺ , K ⁺ , or an ammonium ion substituted with a hydrogen atom or a tetramethyl group, a tetraethyl group, a tetrabutyl group, a tetraphenyl group, or the like. It is not limited to. Among the above oxidizing agents, particularly preferred are oxidizing agents including trivalent Fe-based compounds or cuprous chloride-based compounds, alkali persulfate salts, ammonium persulfate salts and quinones.
[194] In the method for producing a polymer composition of a conductive polymer, an anion (an anion other than a reducing anion of an oxidant) having a dopant ability to coexist as needed is a oxidant anion (reducing agent of an oxidant) produced from the oxidizing agent described above as a counter ion. It is possible to use an electrolyte anion having or other electrolyte anions. Specifically, for example, PF ₆ ^-, SbF ₆ ^- halide anions of 3B group elements, such as, I ^{- -} 5B Group halide anion of an element, BF _4, as _{^{-, AsF 6 (I 3 -}} ), Br ^-, Cl ^- anions such as inorganic acid, SO ₄ ^{2-, -} halogen acid anions such as AlCl and _{^{4 - -, FeCl 4 -,}} SnCl 5 - Lewis acid anions or halogen anions such as NO _3, ClO _4, such as p- or acid anions, such as toluenesulfonic acid or naphthalenesulfonic acid, alkyl-substituted naphthalenesulfonic acid having from 1 to 5 (hereinafter referred to ^{_{C1~5), CF 3 SO 3 -,}} CH 3 SO 3 -, and an organic acid anion, or the like CH ₃ COO ^- there may be mentioned a protonic acid anions such as carboxylic acid anion such as ^-, C ₆ H ₅ CO0.
[195] Similarly, anions of polymer electrolytes such as polyacrylic acid, polymethacrylic acid, polystyrenesulfonic acid, polyvinylsulfonic acid, polyvinylsulfuric acid, poly-α-methylsulfonic acid, polyethylenesulfonic acid, polyphosphoric acid, and the like, and the like, are limited thereto. It is not. However, preferably an anion of a polymer-based and low molecular-weight eutechonic acid compound or a polyphosphate compound is preferable, and aromatic sulfonic acid compounds (sodium dodecylbenzene sulfonate, sodium naphthalene sulfonate, etc.) are preferably used as anion-coating compounds. Used.
[196] Further, as the organic acid anions, more effective dopants, at least one sulfo anion group (-SO ₃ ^-) in the molecule there may be mentioned the quinone compound or sulfonyl, anthracene sulfonic acid anion having a quinone structure.
[197] As a 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-crissenquinone, 5,6-crissenquinone, 6,12-crissenquinone, acenaphthoquinone, acenaphthequinone, Camphorquinone, 2,3-bonandion, 9,10-phenanthrenequinone, and 2,7-pyrenquinone.
[198] In the case where the counter electrode (the counter electrode) is solid, a conductor layer may be provided thereon in order to improve electrical contact with an external lead lead (for example, a lead frame or the like) that can be used as desired.
[199] As the conductor layer, for example, the conductive paste can be formed by solidification, plating, metal deposition, heat resistant conductive resin film, or the like. As the conductive paste, silver paste, copper paste, aluminum paste, carbon paste, nickel paste and the like are preferable, but these may use one kind or two or more kinds. When using 2 or more types, you may mix, or you may make it into each layer and overlap. After the conductive paste is applied, it is left in air or heated to solidify. As plating, nickel plating, copper plating, silver plating, aluminum plating, etc. are mentioned. Moreover, as vapor deposition metal, aluminum, nickel, copper, silver, etc. are mentioned.
[200] Specifically, for example, a carbon paste and a silver paste are sequentially laminated on the second electrode and sealed with a material such as epoxy resin to form a capacitor. This capacitor may have a niobium or tantalum lead which is sintered integrally with the niobium monoxide sintered compact or welded later.
[201] The capacitor | condenser of this invention of the above structure can be made into the capacitor | condenser product of various uses by the resin mold, the resin case, the metallic exterior case, the immersion of resin, and the exterior of a laminated film, for example.
[202] In the case where the counter electrode is a liquid, the capacitor formed of the anode and the dielectric is housed in a can electrically connected to the counter electrode, for example. In this case, the electrode side of the niobium monoxide sintered body is designed to lead to the outside through the niobium or tantalum lead described above, and to insulate the can with an insulating rubber or the like.
[203] As described above, by producing a sintered compact for a capacitor using the niobium monoxide powder produced according to the embodiment of the present invention described above, and manufacturing a capacitor using the sintered compact, a capacitor having good reliability with a small leakage current value can be obtained.
[204] In addition, the capacitor of the present invention has a larger capacitance than a conventional tantalum capacitor and can obtain a smaller capacitor product.
[205] The capacitor of the present invention having such a characteristic can be applied to, for example, a bypass capacitor and a coupling capacitor which are widely used in analog circuits and digital circuits, and to the use of conventional tantalum capacitors. In general, since such a capacitor is widely used in an electronic circuit, the use of the capacitor of the present invention can alleviate constraints on arrangement and heat dissipation of an electronic component, and can store a highly reliable electronic circuit in a narrower space than before.
[206] In addition, when the capacitor of the present invention is used, a smaller and more reliable electronic device than the conventional one, for example, a computer peripheral device such as a computer or a PC card, a mobile device such as a mobile phone, a home appliance, a vehicle loading device, a satellite, a communication Equipment and the like can be obtained.
[207] Hereinafter, although an Example and a comparative example are given and this invention is concretely demonstrated, this invention is not limited to these examples.
[208] On the other hand, the tapping density, angle of repose, particle diameter and pore diameter of the niobium monoxide powder in each example, and the capacity, leakage current value, capacity expression rate, and moisture resistance of the capacitor were measured by the following method.
[209] (1) tapping density measurement
[210] The tapping density was measured according to the method by a tapping apparatus and the measuring apparatus in the external gravity measurement method of the industrial sodium carbonate prescribed | regulated to JIS (Japanese Industrial Standards 2000 edition) K1201-1.
[211] (2) repose angle measurement
[212] The angle of repose is measured by using a flow measuring device and a sample quantity specified in JIS (Japanese Industrial Standards 2000 Edition) Z2504, and the horizontal surface from the apex of the cone formed by dropping niobium monoxide powder from the height of 6 cm below the hopper to the horizontal surface. The angle with respect to the horizontal surface of the slope with respect to was made into the angle of repose.
[213] (3) particle diameter measurement
[214] The particle size distribution was measured by the laser diffraction scattering method using the apparatus of the microtruck company (HRA 9320-X100). The cumulative volume percent, particle size value (D _50; ㎛) corresponding to 50% by volume had a mean particle size.
[215] (4) pore diameter measurement
[216] The pore distribution was measured by mercury intrusion using a Poresier 9320 from Micro Meritics.
[217] On the other hand, in this invention, the maximum value was calculated | required from the rate of change of an indentation amount, the pore diameter represented by the maximum value was made into the peak top, and the maximum value was made into the magnitude | size of the relative intensity of the peak to which this peak top belongs.
[218] (5) Capacitor measurement
[219] At room temperature, a Hewlett-Packard Co., Ltd. LCR measuring instrument was connected between the terminals of the produced chip, and the capacitance measured value at 120 Hz was used as the capacity of the chip | tip processed chip | tip.
[220] (6) Measuring leakage current of capacitor
[221] At room temperature, after continuously applying for 1 minute between the terminals of the chip | tip which produced DC voltage 6.3V, the measured electric current value was made into the leakage current value of the capacitor processed by the chip | tip.
[222] (7) Capacity appearance rate of capacitor
[223] In the 0.1% phosphoric acid aqueous solution, the sintered compact when it was chemically formed at 80 ° C. and 20 V for 1000 minutes was expressed as a ratio of the capacity measured at 30% sulfuric acid to 100% and the capacity after the capacitor formation.
[224] (8) Moisture resistance value of capacitor
[225] The capacity | capacitance at which the produced capacitor was left to stand at 60 degreeC 95% RH for 500 hours was represented by the number less than 110% and less than 120% of an initial value. It was judged that the moisture resistance value was good, so that there were many more than 110%.
[226] (9) ESR measurement value of capacitor
[227] At room temperature, a Hewlett-Packard LCR measuring instrument was connected between the terminals of the produced chip, and the ESR measurement value at 100 kV, 1.5 VDC, and 0.5 Vrms. Was used as the ESR of the capacitor.
[228] (10) content of nitrogen, oxygen, sulfur, and carbon elements
[229] The analysis was carried out using an oxygen nitrogen analyzer or a carbon sulfur analyzer (both manufactured by LECO).
[230] (11) Metal element content
[231] The analysis was performed using an atomic absorption spectrometer, an ICP luminescence spectrometer, or an ICP mass spectrometer (all devices manufactured by Shimadzu Corporation).
[232] (12) Niobium Oxide Composition
[233] The value of x when niobium oxide was represented by NbOx was calculated by determining the molar ratio of the oxygen element content measured in the above (10) to the niobium element content measured in the above (11).
[234] Example 1:
[235] A cylindrical stainless steel container having an inner diameter of 150 mm and an inner volume of 5 L was lined up from the sheet of tantalum. The vessel was provided with an argon gas supply and discharge pipe, a powder material feeder, a stirrer, a temperature controller, a heater, and a cooler. 400 g of shaved metal magnesium was placed in a cylindrical container, flashed with argon, and then heated to 750 ° C (reduction temperature). After maintaining this temperature for 15 minutes and melting the magnesium metal, the stirrer was started. About 10 g of Nb ₂ O ₅ powder was introduced into the powder feeder. The temperature in the reactor rose about 30 ° C. After waiting for the temperature in the reactor to reach a reduction temperature, about 10 g of Nb ₂ O ₅ powder was added to the powder feeder again. This operation was repeated until the addition of the total amount of 350g of the Nb ₂ O ₅ powder. After the addition was completed, stirring was continued at a 30 minute reduction temperature. The reactor was then cooled down to 10 ° C. or lower and the flashing of argon was stopped. After reducing pressure, air was slowly added so that the temperature in the reactor did not exceed 50 ° C. The reaction product was taken out and washed alternately with a mixed aqueous solution of hydrogen peroxide and nitric acid and ion exchanged water. The composition of the produced niobium monoxide powder was NbO _0.98 .
[236] 200 g of this niobium monoxide powder was put into a pot made of niobium, and water and zirconia ball were added and ground for 10 hours. The average particle diameter of the obtained niobium monoxide powder was 1.0 micrometer. 20 g of polymethyl methacrylate butyl ester whose average particle diameter is 1 micrometer was added to this slurry. The mixture was mixed for 1 hour in a vibrating mixer, and the mixture from which zirconia balls were removed was placed in a conical drier and vacuum dried under conditions of 1 × 10 ² Pa and 80 ° C.
[237] Subsequently, the niobium monoxide powder was heated at 1 × 10 ⁻² Pa and 250 to 400 ° C. for 12 hours to decompose and remove the polymethyl methacrylate butyl ester, and further, under reduced pressure of 4 × 10 ⁻³ Pa, 120 It sintered at 2 degreeC. After cooling until the product temperature became 30 degrees C or less, air was added gradually so that a product temperature might not exceed 50 degreeC. The obtained niobium monoxide sintered mass was pulverized with a roll granulator to obtain niobium pulverized powder having an average particle diameter of 100 µm.
[238] Table 1 shows the values of physical properties (tapping density, average particle diameter, angle of repose, BET specific surface area, pore diameter peak top) measured for this niobium monoxide powder.
[239] The niobium monoxide powder (about 0.lg) obtained in this manner was put in a hopper of a tantalum element automatic molding machine (TAP-2R manufactured by Seiken Co., Ltd.), and automatically molded with a niobium wire of 0.3 mm Φ, and the size was about 0.3 cm x 0.18 cm. The molded object was produced so that it might become * 0.45 cm. Table 1 shows the appearance (chipping, cracking, deformation) and mass deviation of the molded body.
[240] Next, these molded bodies were left to stand for 30 minutes at 1400 degreeC under the vacuum of 4x10 <^-3> Pa, and the sintered compact was obtained. 100 of these sintered bodies were prepared, and electrolytically formed for 200 minutes using 0.1% phosphoric acid aqueous solution at a voltage of 20V to form a dielectric oxide film on the surface.
[241] Subsequently, after immersion in 60% manganese nitrate aqueous solution, heating was repeated for 30 minutes at 220 degreeC, and the manganese dioxide layer was formed as a counter electrode layer on the dielectric oxide film. Next, the carbon layer and the silver paste layer were laminated | stacked on it in order. Next, after the lead frame was mounted, the whole was sealed with an epoxy resin to produce a chip capacitor. Table 1 shows the capacity appearance rate of this capacitor and the average (n = 100) of the capacity and leakage current value (hereinafter abbreviated as "LC") of the chip capacitor.
[242] Example 2:
[243] 1000 g of niobium ingots were placed in a reaction vessel made of SUS304, and hydrogen was continuously introduced at 400 ° C for 10 hours. After cooling, the hydrogenated niobium mass was put into a pot made of SUS containing zirconia balls and ground for 10 hours. Next, the hydride was made into a 20 volume% slurry of water and a zirconia ball in a spike mill, and wet pulverized at 40 ° C. or less for 7 hours to obtain crushed slurry of niobium hydride to obtain a zirconia ball. After removing, it dried on the conditions of l * 10 <^2> Pa and 50 degreeC. Subsequently, the obtained niobium hydride powder was heated at 1 × 10 ⁻² Pa and 400 ° C. for 4 hours to dehydrogenate the niobium hydride. Furthermore, it heated for 5 hours at 200 degreeC in presence of air, and obtained the niobium monoxide powder of 0.9 micrometer of average particle diameters. The composition of the produced niobium monoxide powder was NbO _0.88 .
[244] 830 g of this niobium monoxide powder and 400 g of toluene were placed in a niobium pot, and 170 g of barium oxide having an average particle diameter of 1 µm was added. In addition, zirconia balls were added and mixed in a vibration mixer for 1 hour. The mixture from which the zirconia ball was removed was placed in a niobium batt and dried under the condition of 1 × 10 ² Pa and 50 ° C.
[245] Subsequently, the dried mixture was sintered at 1200 ° C. for 3 hours under reduced pressure of 4 × 10 ⁻³ Pa. After cooling until the product temperature was 30 ° C. or less, the sintered niobium monoxide sintered barium oxide mixture was pulverized with a roll granulator to obtain niobium monoxide pulverized powder having a barium oxide mixture having an average particle diameter of 95 μm.
[246] 500 g of niobium monoxide pulverized powder and 1000 g of ion-exchanged water of this barium oxide mixture were placed in a polytetrafluoroethylene vessel and cooled to 15 ° C. or lower. Separately from this, an aqueous solution prepared by mixing 600 g of 60% nitric acid, 150 g of 30% hydrogen peroxide, and 750 g of ion-exchanged water, cooled to 15 ° C. or lower, was prepared and oxidized so that the water temperature did not exceed 20 ° C. while stirring 1000 g of this aqueous solution. It was dripped at the niobium-monoxide disintegration powder suspension aqueous solution of barium mixing. After completion of the dropwise addition, stirring was continued for 1 hour, and after standing still for 30 minutes, the supernatant was separated. 2000 g of ion-exchanged water was added, the mixture was left still for 30 minutes after stirring for 30 minutes, and then the supernatant was separated. This operation was repeated five times, and the niobium monoxide pulverized powder was placed in a Teflon column and washed with water for 4 hours while flowing ion-exchanged water. The electrical conductivity of the wash water at this time was 0.9 µS / cm.
[247] The niobium monoxide pulverized powder after washing with water was dried at 50 ° C. under reduced pressure to obtain about 400 g of niobium monoxide powder.
[248] Table 1 shows the tapping density, average particle diameter, angle of repose, BET specific surface area, and pore diameter peak top of the niobium monoxide powder.
[249] The niobium monoxide powder (about 0.lg) obtained in this manner was put in a hopper of a tantalum element automatic molding machine (TAP-2R manufactured by Seiken Co., Ltd.), and automatically molded with a niobium wire of 0.3 mm Φ, and the size was about 0.3 cm x 0.18 cm. The molded object was produced so that it might become * 0.45 cm. Table 1 shows the appearance of the molded body and the variation in mass.
[250] Next, these molded bodies were left to stand at 1400 degreeC for 30 minutes under reduced pressure of 4x10 <^-3> Pa, and the sintered compact was obtained. 100 of these sintered bodies were prepared and electrolytically formed for 200 minutes using the aqueous 0.1% phosphoric acid solution at the voltage of 20V, and the dielectric oxide film was formed in the surface.
[251] Subsequently, an equivalent mixture of a 10% aqueous solution of ammonium persulfate and a 0.5% aqueous solution of anthraquinonesulfonic acid was brought into contact with the dielectric oxide film, and then a contact of pyrrole vapor was carried out at least five times to form a counter electrode (a counter electrode) made of polypyrrole. Formed.
[252] Then, the carbon layer and the silver paste layer were laminated | stacked on it in order. Next, after loading the lead frame, the whole was sealed with an epoxy resin to produce a chip capacitor. Table 1 shows the capacity appearance rate of this capacitor, and the average (n = 100) of the capacity and LC value of this chip capacitor.
[253] Examples 3-10:
[254] The average particle diameter and the addition amount of polymethyl methacrylate butyl ester were changed using the same method as Example 1, and the average particle diameter and the addition amount of barium oxide were changed using the same method as Example 2, and the niobium monoxide powder, A molded article, a sintered compact and a capacitor were produced. Table 1 shows the physical properties of the niobium monoxide powder, the appearance of the molded body, the variation in mass, the capacity of the capacitor, and the LC.
[255] Examples 11-22:
[256] Examples 11-14 and 16-18 use the same method as Example 1, and Examples 15 and 19-22 use the same method as Example 2, respectively, of polymethyl methacrylate butyl ester or barium oxide. Instead, the niobium monoxide powder, the molded body, and the sintered body were produced using the activator shown in Table 1. Table 1 shows the physical properties of the niobium monoxide powder, the appearance of the molded body, and the variation in mass.
[257] Next, these molded bodies were left to stand at l400 degreeC for 30 minutes under reduced pressure of 4x10 <^-3> Pa, and the sintered compact was obtained. 100 of these sintered bodies were prepared, and electrolytically formed for 200 minutes using the aqueous 0.1% phosphoric acid solution at the voltage of 20V, and the dielectric oxide film was formed in the surface.
[258] Subsequently, after immersing in the aqueous solution (solution 1) containing 25 mass% of ammonium persulfate, it pulled up and dried at 80 degreeC for 30 minutes, and then 18 mass% of 3, 4- ethylene dioxythiophenes in which the dielectric material was formed. It was immersed in an isopropanol solution (solution 2) containing and then pulled up, and oxidation polymerization was performed by leaving it to stand at 60 degreeC atmosphere for 10 minutes. This was immersed in solution 1 again, and it processed similarly to the above. After repeating the operation from the immersion in the solution 1 to the oxidative polymerization eight times, washing was performed for 10 minutes with hot water at 50 ° C., followed by drying at 100 ° C. for 30 minutes, thereby conducting the conductive poly (3,4- A counter electrode (counter electrode) made of ethylenedioxythiophene) was formed.
[259] Then, the carbon layer and the silver paste layer were laminated | stacked on it in order. Next, after loading the lead frame, the whole was sealed with an epoxy resin to produce a chip capacitor. Table 1 shows the capacity appearance rate of this capacitor, and the average (n = 100) of the capacity and LC value of this chip capacitor.
[260] Example 23:
[261] In the same manner as in Example 1, niobium monoxide having an average particle diameter of 0.9 µm was obtained. The composition of this niobium monoxide powder was NbO _1.02 . 200g of niobium monoxide powder was put into the container made from alumina, and it heated at 300 degreeC under nitrogen atmosphere for 2 hours. The amount of nitrogen contained in the obtained raw material niobium monoxide powder was 2100 mass ppm. Barium oxide was used as an activator, and niobium monoxide pulverized powder containing nitrogen having an average particle diameter of 130 µm was obtained in the same manner as in Example 2, and a molded body and a sintered body were produced. Table 1 shows the physical properties of the niobium monoxide powder, the appearance of the molded body, and the variation in mass. Subsequently, a chip capacitor was produced in the same manner as in Example 22. Table 1 shows the capacity appearance rate of this capacitor, and the average (n = 100) of the capacity and LC value of this chip capacitor.
[262] Example 24:
[263] In the same manner as in Example 1, niobium monoxide having an average particle diameter of 0.9 µm was obtained. The composition of this niobium monoxide powder was NbO _1.02 . 200 g of niobium monoxide powder and 5 g of sulfur powder were mixed well and placed in a container made of platinum. After argon substitution in the reactor, the mixture was heated at 250 ° C. for 2 hours. The amount of sulfur contained in the obtained raw material niobium monoxide powder was 2500 mass ppm. Barium oxide was used as an activator, and niobium monoxide pulverized powder containing sulfur having an average particle diameter of 200 µm was obtained in the same manner as in Example 2, whereby a molded body and a sintered body were produced. Table 1 shows the physical properties of the niobium monoxide powder, the appearance of the molded body, and the variation in mass. Subsequently, a chip capacitor was produced in the same manner as in Example 22. Table 1 shows the capacity appearance rate of this capacitor, and the average (n = 100) of the capacity and LC value of this chip capacitor.
[264] Example 25:
[265] Using the boron powder in the same manner as in Example 24, a raw material niobium monoxide powder containing boron was obtained. The amount of boron contained in the obtained raw material niobium monoxide powder was 1200 mass ppm. Using a barium oxide as an activator, niobium monoxide pulverized powder containing boron having an average diameter of 80 µm was obtained in the same manner as in Example 2, to form a molded body and a sintered body. Table 1 shows the physical properties of the niobium monoxide powder, the appearance of the molded body, and the variation in mass. Subsequently, a chip capacitor was produced in the same manner as in Example 22. Table 1 shows the capacity appearance rate of this capacitor, and the average (n = 100) of the capacity and LC value of this chip capacitor.
[266] Examples 26-29:
[267] Using the same method as in Example 2, the starting material was a niobium hydride-neodymium alloy powder in Example 26, a niobium hydride-antimony alloy powder in Example 27, a niobium hydride- ytterbium-boron alloy powder in Example 28, and an example In 29, a niobium hydride powder was obtained using a niobium hydride-zinc-zinc alloy powder. Each composition was niobium monoxide powder containing an ellipsoid which is NbO _{0.94 in} Example 26, NbO _{0.96 in} Example 27, NbO _{1.12 in} Example 28, and NbO _1.08 in Example 29. Further, using the same activator and method as in Example 2, a niobium monoxide powder containing an ellipsoid having an average particle diameter of 70 to 250 µm was obtained to obtain a molded body and a sintered body. Table 1 shows the physical properties of the niobium monoxide powder, the appearance of the molded body, and the variation in mass. Subsequently, a chip capacitor was produced in the same manner as in Example 2. Table 1 shows the capacity appearance rate of this capacitor, and the average (n = 100) of the capacity and LC value of this chip capacitor.
[268] Comparative Examples 1-3:
[269] A cylindrical stainless steel container having an inner diameter of 150 mm and an inner volume of 5 L was prepared from a sheet of tantalum. The vessel was provided with an argon gas supply and discharge pipe, a powder material feeder, a stirrer, a temperature controller, a heater, and a cooler. 400 g of shaved metal magnesium was placed in a cylindrical container, flashed with argon, and heated to 750 ° C. (reduction temperature). After maintaining this temperature for 15 minutes to melt the metal magnesium, the stirrer was started. About 10 g of Nb ₂ O ₅ powder (using an average particle diameter of 2 to 10 탆) was introduced into the powder feeder. The temperature in the reactor rose about 30 ° C. After waiting until the temperature in the reactor reached the reduction temperature, about 10 g of Nb ₂ O ₅ powder was added to the powder feeder again. This operation was repeated until the addition of the total amount of 350g of the Nb ₂ O ₅ powder. After the addition was completed, stirring was continued at a reduction temperature of 30 minutes. Next, the reactor was cooled down to 10 ° C. or lower, and flashing of argon was stopped. After reducing pressure, air was slowly added so that the temperature in the reactor did not exceed 50 ° C. The reaction product was taken out and washed alternately with a mixed aqueous solution of hydrogen peroxide and nitric acid and ion exchanged water. The composition of the produced niobium monoxide powder was NbO _1.01 , and the average particle diameter was 1.3-7 micrometers.
[270] Table 1 shows physical properties such as tapping density, average particle diameter, angle of repose, BET specific surface area, and average pore diameter of the niobium monoxide powder.
[271] The niobium monoxide powder (about 0.lg) obtained in this way was put into the hopper of a tantalum element automatic molding machine (TAP-2R by Seiken Co., Ltd.), and automatic molding was attempted with a niobium wire of 0.3 mm phi, but it could not be molded.
[272] Comparative Examples 4-9:
[273] The addition amount of barium oxide having an average particle diameter of 1 mu m was changed, and niobium monoxide powder having a tapping density of 0.2 to 0.4 g / ml and 2.6 to 3.3 g / ml was obtained in the same manner as in Example 2. Its physical properties are shown in Table 1.
[274] The niobium monoxide powder (about 0.lg) obtained in this manner was put in a hopper of a tantalum element automatic molding machine (TAP-2R manufactured by Seiken Co., Ltd.), and automatically molded with a niobium wire of 0.3 mm Φ, and the size was about 0.3 cm x 0.18 cm. The molded object was produced so that it might become * 0.45 cm. Table 1 shows the appearance of the molded body and the variation in mass.
[275] Next, these molded bodies were left to stand at 140 degreeC under vacuum of 4x10 <^-3> Pa for 30 minutes, and the sintered compact was obtained. 100 of these sintered bodies were prepared and electrolytically formed for 200 minutes using 0.1% phosphoric acid aqueous solution at a voltage of 20V to form a dielectric oxide film on the surface.
[276] Subsequently, an equivalent mixture of a 10% aqueous solution of ammonium persulfate and a 0.5% aqueous solution of anthraquinonesulfonic acid was brought into contact with the dielectric oxide film, followed by at least five operations of contacting pyrrole vapor with a counter electrode made of polypyrrole. Formed.
[277] Then, the carbon layer and the silver paste layer were laminated | stacked on it in order. Next, after loading the lead frame, the whole was sealed with an epoxy resin to produce a chip capacitor. Table 1 shows the capacity appearance rate of this capacitor and the average (n = 100) of the capacity and LC value of this chip capacitor.
[278] Example 30:
[279] In the same manner as in Example 2, niobium monoxide powder was obtained. The average particle diameter of this niobium monoxide powder was 0.6 micrometers, and the composition was NbO _0.95 . Acetone anhydride was added so that a slurry concentration might be 60 mass%, and it suspended well. This slurry was placed in a pot made of niobium, and 15% by mass and 10% by mass of barium oxide having an average particle diameter of 1.4 µm and 23 µm were added to niobium monoxide, respectively. In addition, zirconia balls were added and mixed in a vibration mixer for 1 hour. The mixture from which the zirconia ball was removed was put into a niobium batt, and dried under the conditions of 1 × 10 ² Pa and 50 ° C.
[280] In the same manner as in Example 2, a sintered niobium monoxide sintered barium oxide mixture and a niobium monoxide crushed powder were obtained.
[281] 500 g of niobium monoxide pulverized powder of this barium oxide mixture was added to 1000 g of ion-exchanged water cooled to 15 ° C. or lower, so that the water temperature did not exceed 20 ° C. After the addition was completed, stirring was continued for 1 hour, and after allowing to stand for 30 minutes, the supernatant was separated. 2000 g of ion-exchanged water was added, after stirring for 30 minutes, the mixture was left for 30 minutes and the supernatant was separated. This operation was repeated five times, and the niobium monoxide pulverized powder was put in a Teflon column and washed with water for 4 hours while flowing ion exchanged water. The electrical conductivity of the wash water at this time was 0.5 µS / cm.
[282] The niobium monoxide pulverized powder after washing with water was dried at 50 ° C. under reduced pressure to obtain about 350 g of niobium monoxide powder.
[283] Table 1 shows physical properties such as tapping density, average particle diameter, angle of repose, BET specific surface area, and average pore diameter of the niobium monoxide powder.
[284] In the same manner as in Example 2, a molded body and a sintered body were created. Table 1 shows the appearance of the sintered compact and the variation in mass.
[285] After the dielectric film was formed in the same manner as in Example 2, an electrode was formed immediately, and a carbon layer and a silver paste layer were laminated. Next, after loading the lead frame, the whole was sealed with an epoxy resin to produce a chip capacitor. Table 1 shows the capacity appearance rate of this capacitor, and the average (n = 100) of the capacity and LC value of this chip capacitor.
[286] Examples 31 to 37:
[287] In the same manner as in Example 30, the niobium monoxide pulverized powder of the activator mixture was obtained by changing the kind of the activator to be added, the average particle diameter of the two kinds to be mixed and the amount of addition. The solvent for eluting the activator is selected from a solution containing water, an acid, an alkali, an ion exchange resin, an ammonium nitrate solution, and an solution containing ethylenediamine tetraacetic acid, and the activator is eluted in the same manner as in Example 30. Niobium monoxide powder was obtained. The physical properties are shown in Table 1.
[288] In the same manner as in Example 30, a molded body and a sintered body were created, and a chip capacitor was prepared. Table 1 shows the appearance of the molded product, the variation in mass, the capacity of the capacitor and the average of LC.
[289] Examples 38-40:
[290] The same method as in Example 30 was used, and as a starting material, in Example 38, a niobium hydride-tin alloy powder, Example 39 used a niobium-tungsten alloy powder, and Example 40 used a niobium-tantalum alloy powder, respectively, A niobium monoxide powder containing was obtained. The physical properties are shown in Table 1.
[291] In the same manner as in Example 30, a molded body and a sintered body were created, and a chip capacitor was prepared. Table 1 shows the appearance of the molded product, the variation in mass, the capacity of the capacitor and the average of LC.
[292] Examples 41 to 51:
[293] The niobium monoxide sintered compact was produced by the method similar to Example 2 using the niobium monoxide powder created in Examples 30-40. Table 2 shows the pore diameter distribution of the sintered compact.
[294] Examples 52-62:
[295] 100 niobium monoxide sintered bodies produced in Examples 41 to 51 were each produced, and each sintered body was formed at 80 ° C. for 100 minutes and 20 V in 0.1% aqueous phosphoric acid solution to form a dielectric oxide film layer on the surface of the sintered body. Next, ammonium persulfate and anthraquinonesulfonic acid are attached to this chemically sintered compact, and then the operation of performing gas phase polymerization with pyrrole vapor is repeated to impregnate polypyrrole of a negative electrode agent (hereinafter referred to as negative electrode agent by A method). After that, carbon paste and silver paste were laminated in order, and then sealed with an epoxy resin to prepare a chip capacitor. Table 3 shows the capacity appearance rate and ESR of the produced capacitor.
[296] Examples 63-68:
[297] In the same manner as in Example 2, niobium monoxide primary particles having an average particle diameter of 0.8 µm were obtained. The primary particles were calcined and pulverized to obtain granular powder of niobium monoxide. This granular powder 0.lg was put into a mold (4.0 mm x 3.5 mm x 1.8 mm) with a length of 10 mm and a 0.3 mm thick niobium wire separately prepared, and a tantalum element automatic molding machine (TAP-2R manufactured by Seiken Co., Ltd.) As shown in Table 4, it weighted and produced the molded object. Next, it sintered at 1400 degreeC for 30 minutes, and the target sintered compact was obtained. By adjusting the weight of the molding machine, a sintered compact having a pore diameter distribution shown in Table 4 was created. The size, specific surface area, and CV value of the sintered compact of Example 63 were 24.7 kPa, 1.1 m <2> / g, and 86000 micro FV / g, respectively, respectively, and the numerical value of another example was also within +/- 2% of Example 63.
[298] Examples 69-71:
[299] By classifying the primary particles, the sintered compact was obtained in the same manner as in Examples 63 to 65 except that the average particle diameter of the primary particles was 0.5 μm. The size, specific surface area, and CV value of the sintered compact of Example 69 were 24.9 kPa, l.5 m <2> / g, and 126000 micro FV / g, respectively, respectively, and the numerical value of another example was also less than +/- 1% of Example 69. Table 4 shows the pore diameter distribution of the produced sintered compact.
[300] Example 72:
[301] A sintered compact was obtained in the same manner as in Example 68 using a niobium monoxide powder obtained in the same manner as in Example 4 instead of the granulated powder. The size, specific surface area, and CV value of the sintered compact of Example 72 were 24.8 kPa, 1.2 m <2> / g, and 79000 micro FV / 9 in order, respectively. Table 4 shows the pore diameter distribution of the produced sintered compact.
[302] Comparative Examples 10-12:
[303] A sintered compact was produced in the same manner as in Examples 63 to 65 except that the niobium monoxide powder obtained by reducing niobium pentoxide with magnesium was heat treated at 1200 ° C. instead of the niobium monoxide granular powder used in Examples 63 to 65. Made. The size, specific surface area, and CV value of the produced sintered compact of the comparative example 10 were 24.3 kPa, 0.8 m <2> / g, and 85000 micro FV / g, respectively, and all the numerical values of another Example were also within +/- 2% of the comparative example 10. Table 4 shows the pore diameter distribution of the produced sintered compact.
[304] Example 73:
[305] In Example 30 and Examples 63-72, the same sintered compact was produced 60 pieces each, and each sintered compact was formed at 80 degreeC, 1000 minutes, and 20V in 0.1% phosphoric acid aqueous solution, and a dielectric material was formed on the surface of the sintered compact. An oxide film layer was formed. Subsequently, the chemically completed sintered bodies are divided into 30 pieces, and the operation of immersing the polypyrrole negative electrode agent or the mixed liquid of lead acetate and ammonium persulfate according to the method A in Examples 52 to 62 is repeated in each of 30 sets of sintered bodies. After impregnating a negative electrode agent (hereinafter referred to as a negative electrode agent by the B method) composed of a mixture of lead dioxide and lead sulfate (98% by mass of lead dioxide), carbon paste and silver paste are laminated in this order, and an epoxy resin It sealed with and produced the chip | tip capacitor | condenser. Table 5 shows the capacity expression rate and moisture resistance of the manufactured capacitor.
[306] Comparative Example 13:
[307] In the method of manufacturing the sintered bodies in Comparative Examples 9 to 12, 60 identical sintered bodies were produced, and each sintered body was formed at 80 ° C., 1000 minutes, and 20 V in 0.1% aqueous phosphoric acid solution to form a dielectric oxide film layer on the surface of the sintered body. did. Subsequently, 30 pieces of each of these chemically completed sintered bodies were separated, and each of the 30 sets of sintered bodies was impregnated with the polypyrrole negative electrode agent according to the method A described in Examples 52 to 62, and carbon paste and silver paste were laminated in this order. The chip capacitor was produced by sealing with epoxy resin. Table 5 shows the capacity expression rate and moisture resistance of the manufactured capacitor.
[308] Comparative Examples 14-17:
[309] 100 niobium monoxide sintered bodies produced in Comparative Examples 9 to 12 were each produced, and each sintered body was formed at 80 ° C., 1000 minutes, and 20 V in 0.1% aqueous phosphoric acid solution to form a dielectric oxide film layer on the surface of the sintered body. Next, the chemically sintered compact was impregnated with the polypyrrole negative electrode according to the method A described in Examples 52 to 62, and carbon paste and silver paste were laminated in this order, sealed with epoxy resin, and a chip capacitor was produced. Table 3 shows the capacity appearance rate and ESR of the produced capacitor.
[310]
[311]
[312]
[313]
[314]
[315]
[316] Formula: NbOx (x = 0.8-1.2), the tapping density is 0.5-2.5 g / ml, the average particle diameter is 10-1000 micrometers, the angle of repose is 10-60 degree, BET specific surface area is 0.5-40 m <2> / g The niobium monoxide powder for capacitors of the present invention, which has good flowability, is capable of continuous molding, and has a pore diameter peak top within the range of 0.01 µm to 500 µm obtained by sintering the niobium powder, and preferably, a plurality of pores By using a niobium sintered body having a pore distribution with a diameter peak top for a capacitor electrode, a high capacity expression rate can be obtained, a low equivalent series resistance (ESR), and a capacitor having good leakage current characteristics and moisture resistance can be produced.

权利要求:
Claims (65)
[1" claim-type="Currently amended] A niobium monoxide powder for a capacitor, represented by NbOx (x = 0.8 to 1.2), and having a tapping density of 0.5 to 2.5 g / ml.
[2" claim-type="Currently amended] The process of claim 1 further comprising magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, ruthetium, titanium, zirconium , Hafnium, vanadium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium, carbon, silicon Niobium monoxide powder containing at least one ellipsoid selected from the group consisting of, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, sulfur, selenium and tellurium.
[3" claim-type="Currently amended] The niobium monoxide powder according to claim 1 or 2, wherein the ellipsoid forms a composite oxide with niobium.
[4" claim-type="Currently amended] The niobium monoxide powder according to claim 2 or 3, wherein the content of the ellipsoid is 50 to 200,000 ppm.
[5" claim-type="Currently amended] The niobium monoxide powder according to any one of claims 1 to 4, wherein the average particle diameter is 10 to 1000 µm.
[6" claim-type="Currently amended] The niobium monoxide powder according to any one of claims 1 to 5, wherein the angle of repose is 10 to 60 degrees.
[7" claim-type="Currently amended] The niobium monoxide powder according to any one of claims 1 to 6, wherein the BET specific surface area is 0.5 to 40 m 2 / g.
[8" claim-type="Currently amended] The niobium monoxide powder according to any one of claims 1 to 7, which has a pore distribution having a pore diameter peak top within a range of 0.01 µm to 500 µm.
[9" claim-type="Currently amended] The niobium monoxide powder according to claim 8, wherein the pore distribution has a plurality of pore diameter peak tops.
[10" claim-type="Currently amended] The niobium monoxide powder according to claim 8 or 9, wherein all of the pore diameter peak tops are in the range of 0.5 to 100 µm.
[11" claim-type="Currently amended] The niobium monoxide powder as described in any one of Claims 1-10 was used, The sintered compact characterized by the above-mentioned.
[12" claim-type="Currently amended] The sintered compact according to claim 11, wherein the sintered compact has a pore distribution having a pore diameter peak top within a range of 0.01 µm to 500 µm.
[13" claim-type="Currently amended] A niobium monoxide sintered compact for capacitor electrodes, wherein the pore distribution of the niobium monoxide sintered compact has a plurality of pore diameter peak tops.
[14" claim-type="Currently amended] The niobium monoxide sintered compact according to any one of claims 11 to 13, wherein the pore distribution consists of two pore diameter peak saws.
[15" claim-type="Currently amended] 15. The monoxide of claim 13 or 14, wherein the peak tops of the two peaks having the largest relative strengths among the plurality of pore diameter peak tops are in the range of 0.2 to 0.7 µm and 0.7 to 3 µm, respectively. Niobium sintered body.
[16" claim-type="Currently amended] The niobium monoxide sintered compact according to claim 13, wherein the peak top of the peak having the largest relative strength is in the larger diameter side than the peak top of the next largest relative strength among the plurality of pore diameter peak saws.
[17" claim-type="Currently amended] The niobium monoxide sintered compact according to any one of claims 11 to 16, wherein the sintered compact has a volume of 10 GPa or more, including the pore pore volume.
[18" claim-type="Currently amended] The niobium monoxide sintered compact according to any one of claims 11 to 17, wherein the sintered compact has a specific surface area of 0.2 to 7 m 2 / g.
[19" claim-type="Currently amended] A niobium monoxide sintered compact according to any one of claims 11 to 18, wherein a part of the sintered compact is nitrided.
[20" claim-type="Currently amended] The niobium monoxide according to any one of claims 11 to 19, wherein the sintered body is a sintered body obtained from a niobium monoxide formed body which gives a sintered body having a CV value of 40000 to 200000 µFV / g when sintered at 1400 ° C. Sintered body.
[21" claim-type="Currently amended] The capacitor | condenser comprised from the niobium-oxide monoxide sintered compact in any one of Claims 11-20 as one electrode, and consists of a dielectric material interposed between the counter electrode.
[22" claim-type="Currently amended] The capacitor as claimed in claim 21, wherein the main component of the dielectric is dinitrogen pentaoxide.
[23" claim-type="Currently amended] A capacitor according to claim 21, wherein the counter electrode is at least one material selected from the group consisting of an electrolyte, an organic semiconductor, and an inorganic semiconductor.
[24" claim-type="Currently amended] 24. The main electrode according to claim 23, wherein the counter electrode is an organic semiconductor, and the organic semiconductor is an organic semiconductor consisting of benzopyrroline tetramer and chloranyl, an organic semiconductor mainly composed of tetrathiotetracene, and tetracyanoquinomimethane. At least one material selected from the group consisting of organic semiconductors and conductive polymers
[25" claim-type="Currently amended] The capacitor according to claim 24, wherein the conductive polymer is at least one selected from polypyrrole, polythiophene, polyaniline, and substituted derivatives thereof.
[26" claim-type="Currently amended] The conductive polymer according to claim 24, wherein the conductive polymer is represented by the following General Formula (1) or (2).

Wherein R ¹ to R ⁴ each independently represent a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group, or a halogen atom, a nitro group, a cyano group, or a primary And a monovalent group selected from the group consisting of secondary or tertiary amino groups, CF ₃ groups, phenyl groups and substituted phenyl groups, wherein the hydrocarbon chains of R ¹ and R ² and R ³ and R ⁴ are bonded to each other at arbitrary positions, You may form a bivalent chain which forms the cyclic structure of one or more 3-7 membered saturated or unsaturated hydrocarbons with the carbon atom substituted by such group. In the said cyclic bond chain, carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, may already contain the combination of the furnace at any position. X represents an oxygen, sulfur or nitrogen atom, R ⁵ is present only when X is a nitrogen source to be Giles, independent Or C 1 represents an alkyl group of a saturated or unsaturated straight-chain or branched and 10.) A polymer comprising a repeating unit represented by the condenser, characterized in that the conductive polymer doped with a dopant.
[27" claim-type="Currently amended] The conductive polymer according to claim 26, wherein 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 any position and contains two oxygen elements; The substituent refers to a substituent forming a cyclic structure of one or more 5- to 7-membered saturated hydrocarbons, wherein the cyclic structure includes a vinylene bond which may be substituted or a phenylene structure which may be substituted. A capacitor characterized in that it is a conductive polymer comprising a repeating unit represented by.
[28" claim-type="Currently amended] The capacitor as claimed in claim 27, wherein the conductive polymer is a conductive polymer obtained by doping a poly (3,4-ethylenedioxythiophene) with a dopant.
[29" claim-type="Currently amended] The capacitor as claimed in claim 21, wherein the counter electrode is made of a material having at least a part of a layer structure.
[30" claim-type="Currently amended] 22. The capacitor as claimed in claim 21, wherein the counter electrode is a material containing a eutectic acid anion as a dopant.
[31" claim-type="Currently amended] A method for producing the niobium monoxide powder according to any one of claims 1 to 10, wherein the niobium monoxide or niobium monoxide compound is activated to produce a niobium monoxide powder.
[32" claim-type="Currently amended] The method for producing niobium monoxide powder according to claim 31, wherein the activation treatment of niobium monoxide or niobium monoxide compound is carried out in at least one step selected from the group consisting of a sintering step and a pulverization step.
[33" claim-type="Currently amended] 33. The method for producing a niobium monoxide powder according to claim 31 or 32, wherein the activation treatment of the niobium monoxide or niobium monoxide compound is performed using a mixture containing the niobium monoxide or niobium monoxide compound and an activator.
[34" claim-type="Currently amended] 34. The method for producing a niobium monoxide powder according to any one of claims 31 to 33, wherein the average particle diameter of the niobium monoxide or niobium monoxide compound to be activated is 0.01 µm to 10 µm.
[35" claim-type="Currently amended] 35. The method according to any one of claims 31 to 34, wherein the niobium monoxide or niobium monoxide compound is magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, Dysprosium, holmium, erbium, thulium, ytterbium, ruthetium, titanium, zirconium, hafnium, vanadium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, At least one element selected from the group consisting of mercury, boron, aluminum, gallium, indium, thallium, carbon, silicon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, sulfur, selenium and tellurium. A process for producing niobium monoxide powder, characterized in that it contains ˜200,000 ppm.
[36" claim-type="Currently amended] 36. The method for producing a niobium monoxide powder according to claim 35, wherein the ellipsoid contained in the niobium monoxide or niobium monoxide compound forms a complex oxide with niobium.
[37" claim-type="Currently amended] The method for producing niobium monoxide powder according to claim 33, wherein the mixture containing niobium monoxide or niobium monoxide compound and an activator is mixed using a solvent.
[38" claim-type="Currently amended] The niobium monoxide powder according to claim 37, wherein the solvent is at least one solvent selected from the group consisting of water, alcohols, ethers, cellulsolves, ketones, aliphatic hydrocarbons, aromatic hydrocarbons and halogenated hydrocarbons. Manufacturing method.
[39" claim-type="Currently amended] The method for producing niobium monoxide powder according to claim 33, wherein the activator is used in an amount of 1 to 40% by mass based on the total amount of niobium monoxide or niobium monoxide compound.
[40" claim-type="Currently amended] 40. The method for producing niobium monoxide powder according to claim 33 or 39, wherein the average particle diameter of the activator is 0.01 to 500 mu m.
[41" claim-type="Currently amended] 41. The method for producing niobium monoxide powder according to any one of claims 33, 37, 39, and 40, wherein the particle diameter peak top of the activator is plural.
[42" claim-type="Currently amended] 42. The method for producing niobium monoxide powder according to any one of claims 33, 37 and 39 to 41, wherein the activator is a substance which is removed as a gas at 2000 ° C or lower.
[43" claim-type="Currently amended] 43. The method of claim 42, wherein the activator is naphthalene, anthracene, quinone, camphor, polyacrylic acid, polyacrylic acid ester, polyacrylamide, polymethacrylic acid, polymethacrylic acid ester, polymethacrylamide, polyvinyl alcohol, NH ₄ Cl , ZnO, WO ₂ , SnO ₂ , MnO _{3 The} method for producing niobium monoxide powder, characterized in that at least one selected from the group consisting of.
[44" claim-type="Currently amended] 42. The method according to any one of claims 33, 37 and 39-41, wherein the activator forms a water-soluble substance, an organic solvent soluble substance, an acid solution soluble substance, an alkaline solution soluble substance, and a complex to form these soluble substances. A process for producing a niobium monoxide powder, characterized in that at least one selected from the group consisting of a substance and a soluble substance at 2000 ° C. or lower.
[45" claim-type="Currently amended] 45. The compound of claim 44, wherein the activator is a compound of the metal with carbonic acid, sulfuric acid, sulfurous acid, halogens, perhalogenic acid, hypohalogenic acid, nitric acid, nitrous acid, phosphoric acid, acetic acid, oxalic acid or boric acid, or metals, metal hydroxides and metals. A method for producing niobium monoxide powder, characterized in that at least one selected from the group consisting of oxides.
[46" claim-type="Currently amended] 46. The method for producing niobium monoxide powder according to claim 45, wherein the activator is at least one selected from the group consisting of metal carbonates, metal carbonates, metal hydroxides and metal oxides.
[47" claim-type="Currently amended] The niobium monoxide powder according to claim 46, wherein the activator is at least one selected from the group consisting of metal carbonates, metal carbonates, metal hydroxides and metal oxides, and has a melting point higher than the temperature in the sintering step. Manufacturing method.
[48" claim-type="Currently amended] 45. The method of claim 44, wherein the activator is lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, Terbium, dysprosium, holmium, erbium, thulium, ytterbium, ruthetium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, 1 type selected from the group consisting of silver, gold, zinc, cadmium, boron, aluminum, gallium, indium, thallium, carbon, silicon, germanium, tin, lead, arsenic, antimony, bismuth, selenium, tellurium, polonium and these compounds The manufacturing method of niobium monoxide powder characterized by the above.
[49" claim-type="Currently amended] 34. The niobium monoxide powder according to any one of claims 31 to 33, wherein the activation treatment is a treatment for removing the activator by heating and / or depressurization before or during the sintering step. Manufacturing method.
[50" claim-type="Currently amended] 34. The activating treatment according to any one of claims 31 to 33, wherein the activation treatment is a treatment for removing an activator component by contacting a solvent with the sintered or crushed product after the sintering step, during the crushing step, or after the crushing step. Process for producing niobium monoxide powder.
[51" claim-type="Currently amended] The method for producing niobium monoxide powder according to claim 50, wherein the solvent is at least one selected from the group consisting of water, an organic solvent, an acidic solution, an alkaline solution, and a solution containing a ligand to form a soluble complex.
[52" claim-type="Currently amended] The method of claim 51, wherein the acidic solution is at least one solution selected from the group consisting of nitric acid, sulfuric acid, hydrofluoric acid and hydrochloric acid.
[53" claim-type="Currently amended] The method of claim 51, wherein the alkaline solution contains at least one member selected from the group consisting of hydroxides of alkali metals and ammonia.
[54" claim-type="Currently amended] The method of claim 51, wherein the ligand is at least one member selected from the group consisting of ammonia, glycine and ethylenediamine tetraacetic acid.
[55" claim-type="Currently amended] The niobium monoxide powder according to any one of claims 1 to 10 is treated by at least one method selected from the group consisting of liquid nitriding, ion nitriding and gas nitriding. Method for preparing niobium powder.
[56" claim-type="Currently amended] The niobium monoxide powder according to any one of claims 1 to 10 is treated by at least one method selected from the group consisting of solid phase carbonization and liquid carbonization. Manufacturing method.
[57" claim-type="Currently amended] The niobium monoxide powder according to any one of claims 1 to 10 is treated by at least one method selected from the group consisting of gas boronation and solid phase boronation. Method for preparing the powder.
[58" claim-type="Currently amended] The niobium monoxide powder according to any one of claims 1 to 10 is treated by at least one method selected from the group consisting of gas sulfidation, ion sulfidation and solid phase sulfiding. Method for preparing niobium powder.
[59" claim-type="Currently amended] A niobium monoxide powder obtained by the production method according to any one of claims 31 to 58.
[60" claim-type="Currently amended] The niobium monoxide powder as described in any one of Claims 1-10 and 59 is used, The manufacturing method of the niobium monoxide sintered compact characterized by the above-mentioned.
[61" claim-type="Currently amended] A niobium monoxide sintered body as one electrode, and a method for producing a capacitor comprising a dielectric formed on the surface of the sintered body and a counter electrode formed on the dielectric. A method for producing a capacitor, characterized by sintering the niobium monoxide powder according to any one of claims 1 to 9.
[62" claim-type="Currently amended] 62. The method of claim 61, wherein the dielectric is formed by electrolytic oxidation.
[63" claim-type="Currently amended] 21. A niobium monoxide sintered body is the manufacturing method of a capacitor comprising a niobium monoxide sintered body as one electrode and a dielectric formed on the surface of the sintered body and a counter electrode formed on the dielectric. It is a niobium monoxide sintered compact as described in the manufacturing method of the capacitor characterized by the above-mentioned.
[64" claim-type="Currently amended] An electronic circuit comprising the capacitor according to any one of claims 21 to 30.
[65" claim-type="Currently amended] An electronic device comprising the capacitor according to any one of claims 21 to 30.

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同族专利:

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公开号 | 公开日

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US20030218857A1|2003-11-27|

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AU2002308967B2|2007-12-06|

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WO2002092864A3|2003-09-25|

---

RU2300156C2|2007-05-27|

---

CA2420162A1|2003-02-28|

---

KR20030023702A|2003-03-19|

---

EP1388870A4|2006-07-26|

---

EP1402079B1|2014-12-03|

---

AU2002307722B2|2007-10-18|

---

WO2002092864A2|2002-11-21|

---

US6934146B2|2005-08-23|

---

RU2003110959A|2005-01-20|

---

JPWO2002093596A1|2004-09-02|

---

CA2419291A1|2002-11-21|

---

WO2002093596A1|2002-11-21|

---

US20050139037A1|2005-06-30|

---

EP1388870A1|2004-02-11|

---

JP4480943B2|2010-06-16|

---

EP1402079A2|2004-03-31|

---

US7374596B2|2008-05-20|

---

KR100524166B1|2005-10-25|

---

KR100663735B1|2007-01-03|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2001-05-15|Priority to JPJP-P-2001-00145571

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2001-05-15|Priority to JP2001145571

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2001-05-21|Priority to US29192501P

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2001-05-21|Priority to US60/291,925

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2001-11-06|Priority to JPJP-P-2001-00340318

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2001-11-06|Priority to JP2001340318

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2001-11-09|Priority to US33120001P

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2001-11-09|Priority to US60/331,200

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2002-05-14|Application filed by 쇼와 덴코 가부시키가이샤

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2002-05-14|Priority to PCT/JP2002/004646

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2003-03-08|Publication of KR20030020366A

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2005-10-25|Application granted

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2005-10-25|Publication of KR100524166B1

优先权:

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申请号 | 申请日 | 专利标题

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JPJP-P-2001-00145571|2001-05-15|

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JP2001145571|2001-05-15|

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US29192501P| true| 2001-05-21|2001-05-21|

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US60/291,925|2001-05-21|

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JPJP-P-2001-00340318|2001-11-06|

---

JP2001340318|2001-11-06|

---

US33120001P| true| 2001-11-09|2001-11-09|

---

US60/331,200|2001-11-09|

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PCT/JP2002/004646|WO2002093596A1|2001-05-15|2002-05-14|Niobium monoxide powder, niobium monoxide sintered product and capacitor using niobium monoxide sintered product|