Method for producing metal powder by reduction of metallic salt.

Abstract: Method for producing metal powder, comprising the steps at least partially dissolving of: an alkaline hydroxide, hydrazine or a hydrazine hydrate, and a metallic salt in a solvent comprising an alcohol, and precipitating metal powder comprising a metal contained in the metallic salt by reducing the metallic salt with the hydrazine or the hydrazine hydrate. By the above method, metal powder having a particle size of 100 nm or less can be obtained and the metal powder is not contaminated with impurities originating from the reducing agent.

Description: The present invention relates to a method for producing metal powder. More particularly, the invention relates a method for producing a metal powder useable in conductive paste, for example, which is advantageously used for forming internal conductors of monolithic ceramic electronic components. Conductive paste is used for forming internal conductors of monolithic ceramic electronic components, such as monolithic ceramic capacitors. The conductive paste contains metal powder as a conducting component. As the metal powder, currently, nickel powder is much used. In such monolithic ceramic electronic components, as the size and thickness thereof are decreasing, the particle size of the metal powder contained in the internal conductor must be decreased. As a method for advantageously producing metal powder having a small particle size, for example, a vapor phase process is referred to. However, in the vapor phase process, the production cost of metal powder is high. On the other hand, a method for producing metal powder having a small particle size by a liquid phase process is disclosed, for example, in Japanese Examined Patent Publication No. 6-99143. The patent publication discloses a method for producing nickel powder, in which nickel powder having a small particle size is obtained by a step of subjecting a nickel salt solution to liquid-phase reduction using a reducing agent solution of a boron hydroxide such as sodium boron hydroxide. In accordance with this method, however, since boron precipitates as alloys or impurities in nickel powder, the resultant nickel powder is not always suitable as a conductive component for conductive paste. A method for producing metal powder by a liquid phase process is also disclosed in Japanese Unexamined Patent Publication No. 5-43921. The patent publication discloses a method for producing nickel powder, in which a solution containing basic nickel carbonate is reduced and hydrazine is used as a reducing agent. In accordance with the method, since hydrazine is used as a reducing agent, nickel powder will not be contaminated with impurities. However, the resultant nickel powder has a particle size of more than 100 nm, thus being undesirable as a conductive component to be contained in conductive paste for forming internal conductors in which the thickness thereof must be decreased. CS 275 580 B discloses a method for recovery of platinum describing a reducing agent solution comprising an alkaline hydroxide and hydrazine in a solvent comprising an alcohol. Patent Abstracts of Japan volume 012, No. 374 (M-749), 6 October 1988 (1988-10-06) JP-A-63125605 disclose a metallic salt solution comprising a metallic salt in a solvent comprising alcohol. It is the object of the present invention to provide an improved method for producing metal powder, which serves to overcome the above-described problems. These objects are achieved with a method having the features of Claim 1. Preferable embodiments form the subject matter of the sub-claims. The present invention provides a method for producing metal powder by a liquid phase process in which metal powder having a particle size of 100 nm or less can be obtained, and the mixture of impurities originating from a reducing agent does not occur. The metal powder is not contaminated with impurities originating from a reducing agent. Metal powder produced with the inventive method can be used for conductive paste which can be advantageously used for forming internal conductors with the aim of decreasing the thickness of monolithic ceramic electronic components. In an inventive method for producing metal powder, a hydrazine or a hydrazine hydrate (hereinafter maybe referred to simply as "hydrazine" including the both) does not greatly precipitate impurities in the metal that has been reduced therewith. When hydrazine or a hydrazine hydrate reduces a metal, hydroxide ions must be supplied, and such hydroxide ions are supplied by an alkaline hydroxide. As the alkalinity increases, the rate of reduction reaction is increased, resulting in a smaller size of the resultant metal powder. Therefore, by changing alkaline strength, that is, by changing the concentration of the alkaline hydroxide in the reducing agent solution or the type of alkaline hydroxides, the particle size of the precipitated metal powder can be controlled. When a solvent composed of an alcohol only is used, the reduction reaction of hydrazine does not proceed unless an alkaline hydroxide is present. In a method for producing metal powder in accordance with the present invention, a solvent containing an alcohol is used instead of water as the solvent for dissolving hydrazine or the metallic salt. In such a case, as the solvent containing an alcohol, an alcohol only may be used, or a mixture of an alcohol and water may be used. By using the solvent containing an alcohol as the solvent, instead of water only, the solubility of metallic ions can be decreased, thus enabling an increase in the precipitation rate of the metal and a decrease in the particle size of the precipitated metal powder, in comparison with a case of using water only as the solvent. Therefore, by changing the alcohol concentration in the mixture of the alcohol and water as the solvent, the particle size of the precipitated metal powder may also be controlled. In order to make an alkaline hydroxide, hydrazine or a hydrazine hydrate, and a metallic salt exist in the solvent as described above, a reducing agent solution, which is obtained by dissolving an alkaline hydroxide and hydrazine or a hydrazine hydrate in a solvent containing at least an alcohol, is prepared. At the same time, a metallic salt solution, which is obtained by dissolving a metallic salt in a solvent containing at least an alcohol, is prepared, and the reducing agent solution and the metallic salt solution are mixed. The concentration of the alcohol contained in the solvent described above is in the range of from 10% to 100% by volume. If the concentration is less than 10% by volume, the particle size of the metal powder will not substantially differ from that of metal powder which has been produced by reduction in water by a conventional method. The concentration of the alkaline hydroxide contained in the reducing agent solution is in the range of from four times the concentration of the hydrazine or hydrazine hydrate used to 10 moles/liter. If the concentration is less than four times the concentration of the hydrazine or hydrazine hydrate, the reduction reaction does not finish. On the other hand, if the concentration is more than 10 moles/liter, the alkaline hydroxide is not dissolved in the solvent. The concentration of the hydrazine or hydrazine hydrate contained in the reducing agent solution is in the range of from the amount stoichiometrically required for reducing the metallic salt to 20 moles/liter. If the concentration is less than the amount stoichiometrically required for reducing the metallic salt, the reduction reaction does not finish. On the other hand, if the concentration is more than 20 moles/liter, the effect of using an alcohol as the solvent is lessened because hydrazine is a liquid at room temperature. The concentration of the metallic salt contained in the metallic salt solution is 10 moles/liter or less. If the concentration exceeds 10 moles/liter, the metallic salt is not dissolved in the solvent. Preferably, the metal powder produced has a particle size of 100 nm or less. Preferably, conductive paste containing metal powder produced with the inventive method is used for forming internal conductors of monolithic ceramic electronic components. When metal powder is produced in accordance with a preferred embodiment of the present invention, firstly, a reducing agent solution, which is obtained by dissolving an alkaline hydroxide and hydrazine or a hydrazine hydrate in a solvent containing at least an alcohol, is prepared. As the alcohol, preferably, at least one monovalent alcohol selected from the group consisting of methanol, ethanol, and propanol is used. As the alkaline hydroxide, for example, at least one selected form the group consisting of potassium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, and ammonium hydroxide is used. In a more specifically preferred embodiment, ethanol alone is used as the solvent, and as the alkaline hydroxide, sodium hydroxide alone is used. In order to obtain a reducing agent solution, sodium hydroxide is dissolved in ethanol at a molarity of 0.5 to 5.0 moles/liter, and hydrazine or a hydrazine hydrate is dissolved in the range of from the amount stoichiometrically required for reducing a metallic salt to 15 times the required amount. On the other hand, a metallic salt solution, which is obtained by dissolving a metallic salt in a solvent containing at least an alcohol, is prepared. As the alcohol, the same as in the reducing agent solution described above, preferably, at least one monovalent alcohol such as methanol, ethanol, and propanol is used. In general, the monovalent alcohol has a higher capacity of dissolving a metallic salt than that of a polyhydric alcohol, and thus the productivity of metal powder can be increased. As the metallic salt, depending on the type of metal powder to be obtained, a metallic salt containing at least one metallic element selected from the group consisting of Au, Ag, Pd, Cu, Ni, Co, Fe, and Mn is used. The metallic salt containing the metallic element described can precipitate a specific metal alone or as an alloy by being reduced with hydrazine, and the metallic element contained in the metallic salt demonstrates conductivity, thus enabling a use for a conductive material, such as a conductive paste, for electronic components. The metallic salt is, for example, at least one salt selected from the group consisting of a chloride, a sulfate, and a nitrate. Preferably, the metallic salt is satisfactorily dissolved in a solvent comprising an alcohol or a mixture of an alcohol and water. In a more specifically preferred embodiment, ethanol alone is used as the solvent, and as the metallic salt, a chloride containing at least one metallic element selected from the group consisting of Au, Ag, Pd, Cu, Ni, Co, Fe, and Mn is used alone. In order to obtain a metallic salt solution, the chloride is dissolved in ethanol at a molarity of 1.0 x 10 -2 to 1.0 mole/liter. Next, the reducing agent solution and the metallic salt solution obtained as described above are mixed. Preferably, the temperatures of the reducing agent solution and the metallic salt solution are controlled in the range of from 20°C to 60°C. When mixing is performed, preferably, the metallic salt solution is added dropwise to the reducing agent solution that is being stirred. By mixing the reducing agent solution and the metallic salt solution as described above, the metallic salt contained in the metallic salt solution is reduced with the hydrazine or hydrazine hydrate. Thus, particulate metal powder having a particle size of 15 nm to 100 nm and having a uniform particle size is produced by precipitation. Since the metal powder is precipitated as a loose (that is, easily shredded) aggregate during the reduction reaction described above, recovery is easy in the subsequent step, thus enabling excellent productivity. Since hydrazine is used as the reducing agent, the metal powder is not contaminated with impurities originating from the reducing agent. Even if the aggregation is insufficient, recovery may be performed easily by separately adding an additive. Next, the metal powder is cleaned, followed by drying. Thus, desired metal powder can be obtained. By dispersing the resultant metal powder into an appropriate vehicle, a conductive paste can be obtained. The conductive paste is used for forming internal conductors of monolithic ceramic electronic components, such as internal electrodes of monolithic ceramic capacitors. The metal powder contained in the conductive paste is an excellent conductive component because it is not contaminated with impurities originating from a reducing agent. Since the metal powder has a particle size of 100 nm or less, by using the conductive paste containing the metal powder for forming internal conductors of monolithic ceramic electronic components, a decrease in the thickness of the ceramic electronic components can be advantageously achieved. In the embodiment described above, the reducing agent solution and the metallic salt solution are prepared separately, and the reducing agent solution and the metallic salt solution are mixed so that the reduction reaction of the metallic salt with hydrazine occurs. However, the invention is not limited to this. For example, a solution for dissolving an alkaline hydroxide, a solution for dissolving hydrazine, and a solution for dissolving a metallic salt may be prepared separately, and in order to generate a reduction reaction, these three solutions may be mixed. Alternatively, as a solution, the reducing agent solution described above alone may be prepared, and a metallic salt may be added thereto directly, or the metallic salt solution described above alone may be prepared, and an alkaline hydroxide and hydrazine may be added thereto. As described above, although various modifications may be made, in short, in order to generate the desired reduction reaction in which metal powder comprising a metal contained in a metallic salt is precipitated by reducing the metallic salt with hydrazine, a method for producing metal powder must include a step of making an alkaline hydroxide, hydrazine or a hydrazine hydrate, and a metallic salt exist in a solvent containing at least an alcohol, at least a portion each thereof being dissolved. With respect to a method for producing metal powder, preferred examples and comparative examples in accordance with the present invention will be described below. [Example 1] A reducing agent solution was prepared by dissolving 2 g of sodium hydroxide and 5 g of 80% hydrazine hydrate in 100 ml of ethanol. On the other hand, 5 g of nickel chloride was dissolved in 100 ml of ethanol to prepare a metallic salt solution. Next, with the temperatures of both solutions being kept at 60°C, the metallic salt solution was introduced into the reducing agent solution. Thus, after nickel powder was precipitated, the nickel powder was separated and recovered, followed by cleaning with pure water and acetone in that order. Drying was then performed in an oven. The resultant nickel powder was observed with a scanning electron microscope, and it was confirmed that spherical nickel powder of 40 to 60 nm had been obtained. [Example 2] A reducing agent solution was prepared by dissolving 7.5 g of potassium hydroxide and 40 g of 80% hydrazine hydrate in 100 ml of methanol. On the other hand, 10 g of copper nitrate was dissolved in a mixture of 100 ml of methanol and 10 ml of pure water to prepare a metallic salt solution. Next, with the temperatures of both solutions being kept at 50°C, the metallic salt solution was introduced into the reducing agent solution that was being stirred. Thus, after copper powder was precipitated, the copper powder was separated and recovered, followed by cleaning with pure water and acetone in that order. Next, drying was performed at room temperature. The resultant copper powder was observed with a scanning electron microscope, and it was confirmed that spherical copper powder of 60 to 80 nm had been obtained. [Comparative Example 1] Except that sodium hydroxide as an alkaline hydroxide was not used, under the same conditions as in example 1, an operation was performed in order to obtain nickel powder. A reduction reaction did not occur and nickel powder was not precipitated. This is because of the fact that the reduction reaction with hydrazine does not proceed in the absence of an alkaline hydroxide. [Comparative Example 2] Except that ion-exchanged water only was used as a solvent instead of ethanol, under the same conditions as in example 1, an operation was performed in order to obtain nickel powder. The resultant nickel powder was observed with a scanning electron microscope, and it was confirmed that spherical nickel powder having a particle size of 400 to 500 nm, which was larger than that in example 1, had been obtained. This is because of the fact that when water only is used as a solvent for reaction, the solubility of nickel ions increases, resulting in a decrease in the precipitation rate of nikkel. In a method for producing metal powder in accordance with the present invention, an alkaline hydroxide, hydrazine or a hydrazine hydrate, and a metallic salt are made to exist in a solvent containing at least an alcohol, at least a portion each thereof being dissolved. In this state, while hydroxide ions from the alkaline hydroxide are being supplied, the metallic salt is reduced with the hydrazine or hydrazine hydrate, and thus metal powder comprising a metal contained in the metallic salt is precipitated. As described above, in the method for producing metal powder in accordance with the present invention, since hydrazine or a hydrazine hydrate is used as a reducing agent, metal powder which is not contaminated with impurities originating from the reducing agent can be obtained. Since a solvent containing an alcohol is used as a solvent for dissolving the hydrazine or hydrazine hydrate and the metallic salt described above, the solubility of the metallic ions can be decreased in comparison with a case when water only is used as a solvent, and thus the precipitation rate of the metal can be increased, resulting in a decrease in the particle size of precipitated metal powder. Metal powder having a particle size of 100 nm or less and having a small variation in the particle size can be obtained. In the method for producing metal powder in accordance with the present invention, by preparing a reducing agent solution obtained by dissolving an alkaline hydroxide and hydrazine or a hydrazine hydrate in a solvent containing at least an alcohol, by preparing a metallic salt solution obtained by dissolving a metallic salt in a solvent containing at least an alcohol, and by mixing the reducing agent solution and the metallic salt solution, an operation for obtaining a state in which the alkaline hydroxide, the hydrazine or hydrazine hydrate, and the metallic salt exist in the solvent described above can be facilitated. When the reducing agent solution and the metallic salt solution is mixed as described above, if the metallic salt solution is added dropwise to the reducing agent solution, control for stably generating a reduction reaction can be facilitated, and thus metal powder with stable quality can be easily produced. When the reducing agent solution is prepared as described above, by changing the concentration and/or type of the alkaline hydroxide in the reducing agent solution, the particle size of the precipitated metal powder can be controlled. Thus, the particle size of metal powder to be obtained can be relatively easily controlled. In the method for producing metal powder in accordance with the present invention, by using a mixture of an alcohol and water as the solvent, the particle size of metal powder to be precipitated can be controlled. Thus, the particle size of metal powder to be obtained can also be relatively easily controlled. Metal powder obtained in the producing method as described above is not contaminated with impurities originating from the reducing agent and the metal powder has a particle size of 100 nm or less. By providing conductive paste containing such metal powder for forming internal conductors of monolithic ceramic electronic components, the thickness of the monolithic ceramic electronic components can be advantageously decreased.

Claims: A method for producing metal powder, comprising the steps of: preparing a reducing agent solution obtained by dissolving hydrazine or a hydrazine hydrate and an alkaline hydroxide in a solvent comprising an alcohol; preparing a metallic salt solution obtained by dissolving a metallic salt in a solvent comprising an alcohol; mixing the reducing agent solution and the metallic salt solution; whereby at least a portion of each of hydrazine or a hydrazine hydrate, alkaline hydroxide, and metallic salt is dissolved in said solvent, wherein metal powder comprising a metal contained in the metallic salt is precipitated by reducing the metallic salt with the hydrazine or the hydrazine hydrate, the metallic element contained in the metallic salt being at least one element selected from the group consisting of Au, Ag, Pd, Cu, Ni, Co, Fe, and Mn, the concentration of the alcohol contained in the solvent being in the range of from 10 % to 100 % by volume; the concentration of the hydrazine or the hydrazine hydrate contained in the reducing agent solution being in the range of from the amount stoichiometrically required for reducing the metallic salt to 20 moles/liter; the concentration of the alkaline hydroxide contained in the reducing agent solution being in the range of from four times the concentration of the hydrazine or a hydrazine hydrate to 10 moles/liter, and the concentration of the metallic salt contained in the metallic salt solution being 10 moles/liter or less. The method according to Claim 1, wherein the step of mixing the reducing agent solution and the metallic salt solution comprises a step of adding dropwise the metallic salt solution to the reducing agent solution. The method for producing metal powder according to one of the Claims 1 or 2, further comprising a step of controlling the particle size of the precipitated metal powder by changing the concentration and/or type of the alkaline hydroxide in the reducing agent solution. The method according to any one of Claims 1 to 3, wherein the solvent comprises a mixture of the alcohol and water. The method according to Claim 4, further comprising a step of controlling the particle size of the precipitated metal powder by changing the alcohol concentration in the mixture of the alcohol and water. The method according to any one of Claims 1 to 5, wherein the metallic salt is at least one selected from the group consisting of a chloride, a sulfate, and a nitrate. The method according to any one of Claims 1 to 6, wherein the alcohol is a monovalent alcohol. The method according to any one of Claims 1 to 7, wherein the alkaline hydroxide is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, and ammonium hydroxide.

Inventors: HOSOKURA TADASU, HOSOKURA, TADASU, Hosokura, Tadasu, (A170) Intellectual Prop. Dept.
Applicants: MURATA MANUFACTURING CO, MURATA MANUFACTURING CO., LTD.
Application year: 1999
Main classification: B22F9
IPC codes: C22B5, H01G4, H05K1, B22F9, H01B1, B22F1