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WO2010073420A1 - Particules d'argent contenant du cuivre, procédé de production de ces particules, et dispersion utilisant ces particules - Google Patents

Particules d'argent contenant du cuivre, procédé de production de ces particules, et dispersion utilisant ces particules Download PDF

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Publication number
WO2010073420A1
WO2010073420A1 PCT/JP2009/002873 JP2009002873W WO2010073420A1 WO 2010073420 A1 WO2010073420 A1 WO 2010073420A1 JP 2009002873 W JP2009002873 W JP 2009002873W WO 2010073420 A1 WO2010073420 A1 WO 2010073420A1
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Prior art keywords
silver
copper
reaction
solution
protective agent
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English (en)
Japanese (ja)
Inventor
金田秀治
本村公一
苅安達也
久枝穣
伊波興祐
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Dowa Electronics Materials Co Ltd
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Dowa Electronics Materials Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • the present invention relates to a silver particle, a silver particle-containing dispersion, and a method for producing the silver particle that can be suitably used for wiring and electrodes of electronic devices.
  • particles having a nano-order particle size have unique properties compared to particles of micron-order or larger, and studies have been made on how to use them.
  • studies are being made on forming fine wiring on a substrate taking advantage of the size of nanoparticles and low-temperature sintering.
  • the nanoparticles are being studied for use in a wide variety of applications other than those exemplified, but their production methods are roughly classified into two patterns, a gas phase method and a liquid phase method. Since manufacturing by a vapor phase method is generally often performed under vacuum conditions, it has been cited as a disadvantage that the initial investment cost of an apparatus or the like is high and it is not suitable for mass production. In the case of the liquid phase method, it is suitable for mass production, but the particle size obtained from factors such as the difference in liquidity at the beginning and near the end of the reaction, and the variation in liquidity in the reaction tank, or Since the shape may vary, there is a problem that the particle size distribution tends to become wide as a result.
  • the reaction is often started by directly contacting a silver salt solution and a reducing agent solution.
  • the reaction occurs abruptly, and therefore the time until the reaction is completed may be in seconds when it is extreme.
  • the reaction may proceed locally from the portion where the liquid is added. In that case, it can be said that it is difficult to make the shape of the obtained particles uniform.
  • the reaction state is highly controlled, or a relatively slow reducing agent is selected, and the reaction rate is reduced, thereby achieving uniformity. Attempts have been made.
  • Nanoparticles have the problem of particle aggregation. Nanoparticles are characterized by their fine particle size, and their cohesion between particles is larger than conventionally known micron-order and sub-micron-order particles, and the particles themselves are highly reactive. Therefore, there is a case where particles are aggregated and bonded at the same time, so that a so-called coagulation state occurs, and if such a state is reached, the properties expected as nanoparticles may no longer be exhibited.
  • JP 2004-068072 A Japanese Patent Application Laid-Open No. 2007-146279
  • Patent Documents 1 and 2 both satisfy the expected problem of uniform particle diameter because nanoparticles having a uniform particle size are obtained.
  • the part inferior in terms of production management may occur.
  • problems may occur due to various factors. In such a case, it is difficult to grasp the cause of abnormality in the case of continuous reaction.
  • the particles are nano-order, it is difficult to confirm the defect in-situ.
  • continuous production is performed under defective conditions, and many products may be disposed of such as disposal.
  • the batch reaction is preferable from the viewpoint of reducing the loss as much as possible when a failure occurs.
  • the present invention provides a production method suitable for simple and mass production of nanoparticles having a uniform particle diameter, silver particles produced by the production method, and powder that is an aggregate thereof. Aimed.
  • the present inventors have found that the above object can be achieved if a reduction reaction is performed in a state where a small amount of copper component is present in the reaction solution.
  • the invention has been completed.
  • the method for producing silver particles of the present invention is a method for producing silver particles in which a silver compound solution, a protective agent, and a reducing agent solution are mixed and reduced in a reaction tank. And one or more substances (copper component) selected from the group consisting of copper ions.
  • the suitable form of the manufacturing method of the silver particle of this invention is a pre-copper component, a silver compound solution, a protective agent, a reducing agent solution, a mixed solution of a silver compound solution and a protective agent, and a mixing of a reducing agent solution and a protective agent. It is added to at least one selected from the group consisting of solutions.
  • the total addition amount of one or more selected from the group consisting of the copper, the copper compound and the copper ions is 1 to 1 in terms of copper with respect to silver in the reaction solution. It is characterized by being carried out in a state of containing 2000 ppm.
  • a preferred embodiment of the method for producing the silver particles is characterized in that the reduction reaction is performed at 40 to 80 ° C.
  • a preferred embodiment of the method for producing the silver particles is characterized in that the protective agent is one or more containing at least one of carbon, nitrogen, and oxygen.
  • a preferred embodiment of the method for producing silver particles is characterized in that the protective agent has a boiling point of 250 ° C. or lower.
  • a preferred embodiment of the method for producing the silver particles is characterized in that the functional group of the protective agent is one or more selected from the group consisting of a carboxyl group and an amino group.
  • the powder composed of the silver particles of the present invention (the term “powder” in this specification is used when a numerical value given when measuring physical properties is given as an average value of a plurality of particles), 1 to 1000 ppm of copper, the arithmetic average value of the particle diameter measured from the TEM image is 1 to 100 nm, and the powder has a specific surface area of 5 to 40 m 2 / g measured by the BET method.
  • the preferred form of the silver particles is characterized in that the coefficient of variation of the particle diameter measurement value is less than 30%.
  • a preferred form of the silver particles is characterized in that the protective agent has a boiling point of 250 ° C. or lower.
  • the preferred form of the silver particles is characterized by the presence of a protective agent containing at least one of carbon, nitrogen, and oxygen.
  • the protective agent is made of an organic carboxylic acid or a derivative thereof and has 3 to 8 carbon atoms.
  • the dispersion of the present invention is characterized by containing the silver particles of the present invention.
  • FIG. 4 is a TEM image obtained by photographing the particles produced in Example 1 at 174,000 times.
  • 4 is a TEM image obtained by photographing the particles produced in Example 8 at 174,000 times.
  • 4 is a TEM image obtained by photographing the particles produced in Example 11 at 174,000 times.
  • the method for producing silver particles of the present invention is characterized in that copper is present in the reaction system in a method for producing silver particles in which a silver compound solution, a protective agent, and a reducing agent solution are mixed and reduced in a reaction vessel.
  • a copper component means that any one or more of copper, a copper compound, and a copper ion exist.
  • the step of causing the copper component to exist in the mixed solution before the silver in the solution is reduced to silver by the reaction with the reducing agent is referred to as a copper addition step.
  • the copper addition step may include, for example, an operation of increasing the liquid temperature of the reaction solution containing copper after copper is present in the reaction system.
  • the reduction reaction is performed in a state where the copper component is present in the reaction solution, the effect is exhibited. In order to ensure uniformity, it is preferable that it be present before the reduction reaction.
  • the form of addition is not particularly limited, but it is more preferable that copper acting in the liquid is in an ionic state.
  • the copper component is added at the stage of the raw material solution before the reduction reaction such as a silver compound solution, a protective agent, a reducing agent solution, a mixed solution of the silver compound solution and the protective agent, and a mixed solution of the reducing agent solution and the protective agent. It may be added to one or more of the raw material solutions, or may be from the start of the reduction reaction after mixing the raw material solutions to the end thereof. However, in some cases, the reduction reaction may be completed in a short time of several minutes. Therefore, when adding during the reduction reaction, it is recommended to select a substance having a weak reducing power. In the present invention, the completion of the reaction means the time when the unreduced silver reaction does not occur when the reducing agent is added to the solution sampled from the reaction solution.
  • the form of added copper is not limited at all.
  • any form of powder, foil, or lump may be used under the condition that copper is eluted as ions.
  • the amount of the copper component added varies depending on the reaction scale, but the effect is saturated when it exceeds a certain amount. Therefore, the upper limit of the addition amount of the copper component is not particularly determined. Therefore, the presence of copper is not required more than necessary, and at most, it should be less than 2000 ppm, preferably less than 1000 ppm with respect to the entire liquid.
  • the silver particle concerning this invention can also be provided as a powder form through a drying process. Therefore, the silver particle in this specification includes the meaning of the powder when it is made into a dry form.
  • Copper contained in the silver powder formed by the method according to the present application is in the range of 1 to 1000 ppm. If it is less than 1 ppm, it can be said that it is not produced by the method according to the present invention, but if it is prepared by a wet method, the particle size becomes non-uniform. On the other hand, if it exceeds 1000 ppm, it indicates that the substitution of copper and silver in the liquid is insufficient, and even if the particle size is uniform, it may adversely affect the conductivity, which is preferable. Absent. In order to obtain pure silver, it is necessary that sufficient substitution is performed. Therefore, the remaining copper content is 1 to 1000 ppm, preferably 1 to 500 ppm, more preferably 1 to 300 ppm.
  • the said silver compound solution means what melt
  • the functional groups constituting the particles according to the present invention those having a so-called high affinity property that is easily compatible with the surface of the silver particles are preferably used.
  • Specific examples include a carboxyl group and an amino group.
  • the silver particles according to the present invention can be used as a conductive dispersion liquid or a paste mixed in a solvent or the like. At this time, in order to achieve high conductivity, it is preferable to have a high purity with as few impurities as possible.
  • the surfactant constituting the surface has a low boiling point. Specifically, it is preferably 250 ° C. or lower, more preferably 200 ° C. or lower, and still more preferably 150 ° C. or lower.
  • the protective agent in the present invention is not particularly limited as long as it has the above characteristics, but examples include butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, sorbic acid, lactic acid, succinic acid, hexyl. Examples include amine, octylamine, hexamethylenediamine and the like.
  • the addition amount of the protective agent is preferably 0.1 to 4.0 in terms of a molar ratio to silver (number of moles of protective agent molecule / number of moles of silver). If it is less than 0.1, the amount of the protective agent is too small with respect to silver, so that a large number of particles may be condensed.
  • the ratio of the addition amount of the protective agent / silver is preferably in the range of 0.5 to 3.0, more preferably 1.0 to 2.0.
  • the reducing agent is not particularly limited as long as it can reduce silver ions to silver, and sodium borohydride, hydrazine, L-ascorbic acid, hydroquinone, gallic acid, formalin, phosphine, which have been widely used conventionally. Gluconic acid and derivatives thereof can be used.
  • the amount of the reducing agent added is preferably in the range of 1.0 to 9.0 in terms of equivalent to silver. If it is less than 1.0, there is a possibility that unreduction occurs, and if it exceeds 9.0, the amount of the reducing agent is too large and the reaction becomes excessively fast, so that the condensed particles increase and finally the particle size is increased. This is not preferable because the variation may increase.
  • the reducing agent solution may further contain a protective agent solubilizer.
  • a protective agent solubilizer This is for dissolving the protective agent when the protective agent that can be used in the production method of the present invention has poor solubility in a solvent.
  • the protective agent does not dissolve in the reducing agent solution and exists non-uniformly, the reaction may become non-uniform. Therefore, it is preferable to add the protective agent dissolving agent to dissolve the protective agent.
  • the type of the protective agent solubilizer varies depending on the type of the protective agent, but when the protective agent is an acid, ammonia or the like can be used. Further, the minimum amount necessary for dissolving the protective agent is sufficient.
  • the method for producing the silver particles is preferably performed within a range of 40 to 80 ° C.
  • the temperature is lower than 40 ° C.
  • the degree of supersaturation of silver increases, so that excessive nucleation occurs and primary particles become excessively fine.
  • the primary particle size is small, the cohesive force becomes strong, and the coagulation of the particles proceeds, leading to variations in the particle size.
  • the reduction is insufficient to cause reduction, and thus unreduction may occur.
  • the temperature exceeds 80 ° C. the reaction is too early, so that the particles may be fused together before being sufficiently protected by the protective agent, resulting in an increase in aggregated particles and accompanying particle size variation.
  • the reduction reaction is carried out at 40 to 80 ° C.” means that each of the solutions to be introduced into the reaction vessel may be heated to 40 to 80 ° C., or the solution is first brought to 40 to 80 ° C. in the reaction vessel. A method of heating and putting another solution at 40 to 80 ° C. may be performed.
  • the particle diameter of silver particles means the primary particle diameter measured by a measurement method described later from a TEM image.
  • the silver particles according to the present invention preferably have an average primary particle diameter in the range of 1 to 100 nm. When the average value of the primary particle diameters is less than 1 nm, it is difficult to prevent the occurrence of particle aggregation because the cohesive force of the particles is too strong. Further, when it exceeds 100 nm, the low-temperature sinterability deteriorates, so that it may be unsuitable for metal wiring applications where the silver particles of the present invention are expected to be used.
  • the specific surface area of the silver particle powder of the present invention measured by the BET method is 5 to 40 m 2 / g, preferably 15 to 40 m 2 / g, more preferably 20 to 30 m 2 / g.
  • the specific surface area of the silver particles produced by the production method of the present invention is remarkably increased by adding a copper component during production. Although the cause of this is unknown, it was found that the reaction rate was remarkably increased by comparing the reaction with and without the addition of copper. This suggests the possibility of acting as a catalyst.
  • the specific surface area of the silver particle powder can be adjusted by the amount of copper component added during production.
  • the viscosity is adjusted to suit the application and printing method.
  • the viscosity of the dispersion is greatly influenced by the specific surface area of the particle powder.
  • the specific surface area of the particle powder is large, the amount of solvent in contact with the particle surface increases, so that the amount of solvent not in contact with the particle surface decreases and the viscosity increases.
  • the surface area of the particle powder is small, the amount of the solvent in contact with the particle surface decreases, so that the amount of free solvent increases and the viscosity decreases.
  • the production method for easily obtaining silver particle powders having various specific surface areas as in the present invention has an advantage that it can easily cope with the adjustment of the dispersion viscosity suitable for various applications.
  • the specific surface area of the particle powder can be adjusted by a conventional method such as adjustment of the reducing agent amount and reaction temperature without using the production method of the present invention.
  • a dry silver particle powder having a specific surface area of 5 m 2 / g or more was not obtained even by such a change in reaction conditions.
  • it becomes an undesirable silver particle such as changing to the shape, or depending on the reaction conditions there is a risk of bumping, and it is necessary to take countermeasures each time, so changing the reaction conditions It is better to keep fine adjustments.
  • a coefficient of variation which is a value obtained by dividing the standard deviation value of the primary average particle diameter generally measured from the TEM image by the average value, is used as an index.
  • the coefficient of variation is less than 35%. If this value is 35% or more, it indicates that the variation in particle diameter is large, which is not preferable. Preferably it is less than 30%.
  • the silver particles according to the present invention by adopting the above-described configuration, the silver particles exhibit excellent properties at low temperature sintering.
  • the bulk resistance value of silver is 1.6 ⁇ ⁇ cm
  • the use of the particles according to the present invention makes it possible to take a resistance value approximate to this value even when the firing temperature is about 250 ° C.
  • the dispersion liquid of the present invention refers to a liquid in which the silver particles of the present invention are dispersed in a solvent.
  • the powder can be redispersed in various solvents.
  • the dispersion solvent that can be used in this case include water, alcohol, polyol, glycol ether, 1-methylpyrrolidinone, pyridine, terpineol, butyl carbitol, butyl carbitol acetate, texanol, and phenoxypropanol.
  • the binder is a necessary element for imparting dispersion independence to the particles, it is necessary to have at least an affinity for the solvent and the particles. Further, no matter how high the dispersibility is, it does not meet the object of the present invention unless it is discharged out of the system during sintering. That is, the decomposition or volatilization temperature is more preferably selected to be 250 ° C. or lower. If it has at least the above-mentioned property, it can be suitably used regardless of whether it is commercially available organic or inorganic. Moreover, you may use together not only a single kind.
  • organic binder acrylic resin, polyester resin, epoxy resin, phenol resin, phenoxy resin, DAP resin, urethane resin, fluororesin, polyimide resin, polyamide resin, silicone resin, polyolefin resin, ethyl cellulose and polyvinyl Alcohol or the like can be added, and silica sol, alumina sol, zirconia sol, titania sol, or the like can be used as the inorganic binder.
  • acrylic resins include BR-102, BR-105, BR-117, BR-118, BR-1122, MB-3058 (manufactured by Mitsubishi Rayon Co., Ltd.), Alflon UC-3000, Alflon UG-4010, Alflon UG-4070.
  • any commercially available one may be used as long as it has an affinity for the particle surface and also has an affinity for the dispersion medium. Moreover, you may use together not only a single kind.
  • Dispersants include fatty acid salts (soap), ⁇ -sulfo fatty acid ester salts (MES), alkylbenzene sulfonates (ABS), linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkyl ether sulfates Low molecular weight anionic (anionic) compounds such as salt (AES) and alkyl sulfate triethanol, fatty acid ethanolamide, polyoxyethylene alkyl ether (AE), polyoxyethylene alkylphenyl ether (APE), sorbitol, sorbitan Nonionic compounds, low molecular weight cationic (cationic) compounds such as alkyltrimethylammonium salts, dialkyldimethylammonium chlorides, alkylpyridinium chlorides, alkylcarboxyl betaines, sulfobetas Low molecular amphoteric compounds such as styrene and lecithin
  • Florene DOPA-15B Florene DOPA-17 (manufactured by Kyoeisha Chemical Co., Ltd.), Solplus AX5, Solplus TX5, Solsperse 9000, Solsperse 12000, Solsperse 17000, Solsperse 20000, Solsperse 21000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 35100, Solsperse 54000, Sol Six 250, (manufactured by Nippon Lubrizol Corporation), EFKA4008, EFKA4009, EFKA4010, EFKA4015, EFKA4046, EFKA4047, EFKA4060, EFKA7440E, EFKA7440E , EFKA4400, EFKA4401, EFKA4402, EFKA4403, EFKA4300, EFKA4330, EFKA4340, EFKA6220
  • any known method can be employed under the condition that the mechanical dispersion treatment does not involve significant modification of particles.
  • Specific examples include ultrasonic dispersion, a disper, a three-roll mill, a ball mill, a bead mill, a twin-screw kneader, and a self-revolving stirrer, and these can be used alone or in combination.
  • image analysis software (A Image-kun (registered trademark) manufactured by Asahi Kasei Engineering Co., Ltd.) was used. This image analysis software identifies individual particles by color shading. For a 174,000 times TEM image, the “particle brightness” is “dark”, the “noise removal filter” is “present”, “ The primary particle average diameter was measured by performing circular particle analysis under the conditions of “20” for the “round threshold” and “50” for the “overlap degree”. In addition, when there were many condensed particles and irregular shaped particles in the TEM image, it was determined that measurement was impossible.
  • Hydrochloric acid is added to a solution that is free from cloudiness and suspended matter to produce silver chloride. Thereafter, the mixture was separated into solid and liquid by filtration to separate the silver chloride and the filtrate, and the filtrate was analyzed for the amount of copper using ICP-MS (AGILENT 7500i manufactured by Agilent Technologies).
  • TAP density measurement The measurement was performed using the measurement method described in JP-A-2007-263860.
  • the silver particle powder was pasted and coated on a glass substrate.
  • the coated glass substrate was baked with a dryer (manufactured by Yamato Scientific Co., Ltd.) at the temperatures and times shown in the examples and comparative examples.
  • the volume resistance value per 1 ⁇ m thickness of the fired film was measured using a resistivity meter (Loresta GP manufactured by Mitsubishi Chemical Analytech Co., Ltd.), and the film thickness was measured by a surface roughness meter (Surfcom 1500D manufactured by Tokyo Seimitsu Co., Ltd.). ) was used to calculate the volume resistance value of the film.
  • Example 1 In Examples 1 to 7, a 5 L reaction vessel was used as the reaction vessel. In addition, a stirring bar with a blade was installed at the center of the reaction tank for stirring. A thermometer for monitoring the temperature was installed in the reaction tank, and a nozzle was provided so that nitrogen could be supplied to the solution from the bottom.
  • hexanoic acid manufactured by Wako Pure Chemical Industries, Ltd.
  • a protective agent corresponding to a molar ratio of 1.98 with respect to silver
  • 23.9 g (corresponding to 4.82 equivalents of silver) of a 50% by mass hydrazine hydrate (manufactured by Otsuka Chemical Co., Ltd.) aqueous solution as a reducing agent was added to obtain a reducing agent solution.
  • an aqueous silver nitrate solution prepared by dissolving 33.8 g of silver nitrate crystals (manufactured by Wako Pure Chemical Industries, Ltd.) in 180 g of water was prepared, and this was used as an aqueous silver salt solution.
  • copper nitrate trihydrate manufactured by Wako Pure Chemical Industries, Ltd.
  • the addition of copper nitrate trihydrate is adjusted by preparing a copper nitrate trihydrate aqueous solution having a known concentration in advance and adding a diluted solution thereof. Further, the temperature of the silver salt aqueous solution was adjusted to 60 ° C., the same as the reducing agent solution in the reaction vessel.
  • an aqueous silver salt solution was added to the reducing agent solution by mixing at once and a reduction reaction was started. At this time, the color of the slurry immediately changed from the end of the addition. Stirring was performed continuously and aged for 10 minutes in that state. Then, stirring is stopped, solid-liquid separation is performed by suction filtration, and after washing with pure water until the electrical conductivity of the washing waste liquid is less than 2.0 ⁇ S / cm, by drying at 40 ° C. for 12 hours, A fine silver particle powder was obtained. In addition, since the powder obtained has high sensitivity to heat, drying at a temperature higher than this temperature may result in massive silver.
  • Example 2 Example 1 was repeated except that the copper nitrate trihydrate aqueous solution added to the silver salt aqueous solution was changed to an amount of 5 ppm based on silver in terms of copper.
  • Example 3 Example 1 was repeated except that the copper nitrate trihydrate aqueous solution added to the silver salt aqueous solution was changed to an amount of 10 ppm with respect to silver in terms of copper.
  • the prepared silver particle-containing dispersion was coated on a slide glass using an applicator. Then, it baked for 30 minutes at 150 degreeC using the dryer (made by Yamato Scientific Co., Ltd.). Moreover, the sample baked for 30 minutes at 200 degreeC was also produced, and each volume resistance value was measured.
  • Example 4 The silver particle production process of Example 3 was repeated except that the copper source added to the aqueous silver salt solution was changed to cuprous oxide.
  • Example 5 Example 1 was repeated except that the copper nitrate trihydrate aqueous solution added to the silver salt aqueous solution was changed to an amount of 100 ppm with respect to silver in terms of copper.
  • Example 6 Example 5 was repeated except that the copper source added to the aqueous silver salt solution was changed to copper powder.
  • Example 7 Example 1 was repeated except that the copper nitrate trihydrate aqueous solution added to the silver salt aqueous solution was changed to an amount of 1000 ppm with respect to silver in terms of copper.
  • Example 8 In Examples 8 to 13, a 200 L reaction vessel was used as the reaction vessel. A stir bar, a thermometer, and a nitrogen nozzle were installed in the same manner as the 5 L reaction tank. First, 137 kg of water was put into the reaction tank, and nitrogen was passed from the lower part at a rate of 20 L / min for 600 seconds in order to remove the remaining oxygen. Thereafter, nitrogen was supplied from the upper part of the reaction tank at a rate of 20 L / min to make the inside of the reaction tank a nitrogen atmosphere. And temperature was adjusted, stirring so that the solution temperature in a reaction tank might be 60 degreeC. Then, 282.3 g of ammonia water containing 28% by mass as ammonia was added to the reaction vessel, and then stirred for 1 minute to make the solution uniform.
  • an aqueous silver nitrate solution in which 1350.3 g of silver nitrate crystals (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 7200 g of water was prepared, and this was used as an aqueous silver salt solution.
  • 0.0325 g of copper nitrate trihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) (corresponding to 10 ppm of silver in terms of copper) was added.
  • the temperature of the silver salt aqueous solution was adjusted to 60 ° C., the same as the reducing agent solution in the reaction vessel.
  • the silver salt aqueous solution was added to the reducing agent solution at once and mixed to start the reduction reaction. Stirring was performed continuously and aged for 10 minutes in that state. Thereafter, stirring is stopped, solid-liquid separation by a filter press, washing with pure water until the electric conductivity of the washing liquid becomes less than 2.0 ⁇ S / cm, and after drying at 40 ° C. for 12 hours or more, fine silver Particle powder was obtained.
  • the obtained fine silver particle powder was added to a solvent or the like to prepare a dispersion.
  • 1.0 g of fine silver particle powder, 10.0 g of butyl carbitol acetate (manufactured by Wako Pure Chemical Industries, Ltd.), and 0.1 g of DisperBYK2020 (manufactured by Big Chemie Japan) as a dispersant were weighed. They were mixed in a test tube and dispersed with an ultrasonic disperser for 10 minutes. As a result, it was uniformly dispersed and no precipitate was observed on the bottom of the test tube. In addition, no precipitate was seen on the bottom of the test tube after standing for 24 hours, and the redispersibility was good.
  • Example 9 Example 8 was repeated except that the amount of copper nitrate trihydrate added to the aqueous silver salt solution was changed to an amount of 20 ppm based on silver in terms of copper.
  • Example 10 Example 8 was repeated except that the amount of copper nitrate trihydrate added to the aqueous silver salt solution was changed to an amount of 50 ppm based on silver in terms of copper.
  • Example 11 Example 8 was repeated except that the amount of copper nitrate trihydrate added to the aqueous silver salt solution was changed to an amount of 100 ppm based on silver in terms of copper.
  • Example 12 Example 8 was repeated except that the amount of copper nitrate trihydrate added to the aqueous silver salt solution was changed to an amount of 300 ppm based on silver in terms of copper.
  • Example 13 Example 8 was repeated except that the amount of copper nitrate trihydrate added to the aqueous silver salt solution was changed to an amount of 500 ppm based on silver in terms of copper.
  • Example 1 Example 1 was repeated except that copper nitrate trihydrate was not added to the aqueous silver salt solution. The change of the color of the reaction slurry was completed about 30 seconds after the addition was completed.
  • Example 8 was repeated except that copper nitrate trihydrate was not added to the aqueous silver salt solution.
  • Example 3 (Comparative Example 3) Example 1 was repeated except that the amount of copper nitrate trihydrate aqueous solution added to the silver salt aqueous solution was changed to an amount of 6000 ppm based on silver in terms of copper.
  • Example 1 (Comparative Example 4) Example 1 was repeated except that the amount of copper nitrate trihydrate aqueous solution added to the aqueous silver salt solution was changed to an amount of 60000 ppm based on silver in terms of copper.
  • Example 1 Example 1 was repeated except that nickel nitrate hexahydrate aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added instead of copper nitrate trihydrate to add an amount of 100 ppm in terms of nickel.
  • nickel nitrate hexahydrate aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 6 (Comparative Example 6) Example 1 was repeated except that an iron (III) nitrate nonahydrate aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added instead of copper nitrate trihydrate to add an amount of 100 ppm in terms of iron. It was.
  • an iron (III) nitrate nonahydrate aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.
  • Comparative Example 7 After completion of the reduction reaction of Comparative Example 1, an aqueous solution of copper nitrate trihydrate was added to the reaction slurry in an amount of 3000 ppm with respect to silver in terms of copper, and stirring was continued for 5 minutes. Thereafter, stirring was stopped and filtration and washing were performed.
  • Comparative Example 8 Comparative Example 1 was repeated except that the amount of hydrazine hydrate of the reducing agent was changed to an amount that was 9.6 equivalents with respect to silver. Immediately after the start of the reduction reaction, the color change of the reaction slurry was completed, and it was confirmed that the reaction was complete.
  • Reaction scales of Examples and Comparative Examples additives added at the time of production and their addition amount, Cu content contained in the silver particle powder after the reaction, BET specific surface area of the dried silver particle powder, TAP density, Table 1 shows the TEM diameter, the coefficient of variation, and the volume resistance value of the silver film.
  • 1 to 3 show TEM images of Examples 1, 3 and 5, and
  • FIG. 4 shows a TEM image of Comparative Example 1. The magnification of all TEM photographs is 174,000 times. Note that the arrows on the lower right of the photographs in FIGS. 1 to 9 all represent 100 nm.
  • FIG. 10 is a graph showing the relationship between the amount of added Cu and BET for the examples and comparative examples separately for the 5L reaction and the 200L reaction.
  • Example 1 Comparative Example 1 and FIG. 10 in Table 1.
  • the vertical axis represents BET and the horizontal axis represents the amount of Cu added to Ag.
  • White circles and white triangles represent the results of Examples prepared in 5 L and 200 L reaction vessels, respectively.
  • the black circles and black triangles are comparative examples in 5 L and 200 L reaction tanks, respectively. Specifically, the black circle mark is Comparative Example 1 and the black triangle mark is Comparative Example 2.
  • Example 1 Even in Example 1 in which 1 ppm of Cu was added, the BET was 7 m 2 / g or more higher than the comparative example in which Cu was not added. In other words, it can be seen that the BET of the silver particle powder is increased when the comparative example Cu is added to the example and reacted. Moreover, since the same effect was acquired also by addition of copper powder (Example 6) and cuprous oxide (Example 4), it turns out that the effect of this invention is acquired irrespective of the form of the copper component to add. . Moreover, the effect appeared notably from the addition of 1 ppm of Cu, and was saturated around 10 ppm.
  • the relationship between the amount of copper component added and BET has a gentler slope than that in the case of 5 L reaction. This is very preferable from a manufacturing point of view. That is, as described above, when the silver particle powder having a desired BET is prepared by controlling the amount of copper component added, the control range of the amount of copper component added is widened in the 200L reaction. It is considered possible to obtain silver particles.
  • Comparative Examples 3 and 4 were obtained by adding 6000 ppm (0.6% by mass) and 60000 ppm (6% by mass), respectively, of the copper component. In the silver particles thus obtained, the amount of copper contained in the silver particles was It has become very much. When the silver particles of Comparative Examples 3 and 4 are made into a silver film, it is considered that this is because the resistance value is deteriorated.
  • Comparative Examples 5 and 6 a nickel component and an iron component were added instead of the copper component, respectively, but the effect as in the present invention was not obtained. It turns out that it is necessary to add a copper component in the manufacturing method concerning this invention.
  • Comparative Example 7 a copper component was added after completion of the reduction reaction, but the effect as in the present invention was not obtained. In the manufacturing method concerning this invention, it turns out that it is necessary to add a copper component before completion
  • Comparative Example 8 and FIG. 9 when Comparative Example 8 and FIG. 9 are seen, it can be seen that a large number of coarse particles are generated, although the reduction reaction is accelerated by increasing the amount of the reducing agent. From this, it can be seen that the reduction reaction is not simply accelerated, and the presence of the copper component is necessary for the particle size distribution and dispersibility.
  • the copper component was previously mixed with the silver component and then mixed with the reducing agent solution. Therefore, since the copper component was present in the mixed solution from the time when the reduction reaction was started, the end point of the reduction reaction was judged from the color change of the reaction slurry. However, even if the color change of the reaction slurry is completed, the reduction reaction itself may not be completed yet. Therefore, even when the reduction reaction is performed only with the silver compound solution, the protective agent, and the reducing agent solution, and the color change of the reaction slurry is completed, the effect of the present invention can be obtained by adding the copper component.
  • the production method of the present invention can easily produce silver particles similar to the small scale even in a large scale reaction, it is excellent in mass productivity. Further, the silver particles according to the present invention have a small variation in particle diameter and can be redispersed in various solvents, and therefore are suitable for dispersions used for metal wiring applications.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

L'invention concerne un procédé approprié pour la production de masse simple de nanoparticules ayant une taille de grain uniforme, et des particules d'argent produites par ce procédé de production. Un ou plusieurs éléments sélectionnés dans le groupe consistant en le cuivre, les composés de cuivre et les ions de cuivre sont ajoutés avant la fin de la réaction de réduction pendant la réaction des particules d'argent pendant laquelle une solution de composé d'argent, un protecteur et une solution d'agent de réduction sont mélangés et une réduction est effectuée. En conséquence, indépendamment de l'échelle de la réaction, il est possible de produire des particules ayant une taille de grain uniforme par une réaction pendant laquelle des particules d'argent sont obtenues de sorte que la taille de grain moyenne dans la solution soit de 1 à 100 nm.
PCT/JP2009/002873 2008-12-26 2009-06-23 Particules d'argent contenant du cuivre, procédé de production de ces particules, et dispersion utilisant ces particules Ceased WO2010073420A1 (fr)

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WO2014054550A1 (fr) * 2012-10-01 2014-04-10 Ｄｏｗａエレクトロニクス株式会社 Procédé de production de fines particules d'argent
CN117620193A (zh) * 2023-10-18 2024-03-01 广东聚砺新材料有限责任公司 一种银粉的制备方法
CN119657916A (zh) * 2024-12-16 2025-03-21 安徽省有色金属新材料研究院有限公司 利用钢渣酸浸出液制备银包铜粉的制备方法

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KR101764219B1 (ko) 2015-09-23 2017-08-03 엘에스니꼬동제련 주식회사 은 분말의 제조방법
JP7090511B2 (ja) * 2017-09-29 2022-06-24 Ｄｏｗａエレクトロニクス株式会社 銀粉およびその製造方法
WO2020137329A1 (fr) * 2018-12-26 2020-07-02 昭栄化学工業株式会社 Pâte d'argent
US12100530B2 (en) 2018-12-26 2024-09-24 Shoei Chemical Inc. Silver paste
CN113593772B (zh) * 2021-07-27 2023-04-07 哈尔滨工业大学（深圳） 纳米银铜固溶体及其制备方法和应用
WO2025197747A1 (fr) * 2024-03-21 2025-09-25 日清エンジニアリング株式会社 Particules fines d'argent et procédé de production de particules fines d'argent

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WO2014054550A1 (fr) * 2012-10-01 2014-04-10 Ｄｏｗａエレクトロニクス株式会社 Procédé de production de fines particules d'argent
JP2014070264A (ja) * 2012-10-01 2014-04-21 Dowa Electronics Materials Co Ltd 銀微粒子の製造方法
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CN117620193A (zh) * 2023-10-18 2024-03-01 广东聚砺新材料有限责任公司 一种银粉的制备方法
CN119657916A (zh) * 2024-12-16 2025-03-21 安徽省有色金属新材料研究院有限公司 利用钢渣酸浸出液制备银包铜粉的制备方法
CN119657916B (zh) * 2024-12-16 2025-09-30 安徽省有色金属新材料研究院有限公司 利用钢渣的酸浸出液制备银包铜粉的制备方法

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