WO2025249331A1 - Poudre d'argent sphérique, procédé de production de poudre d'argent sphérique et pâte électroconductrice - Google Patents

Poudre d'argent sphérique, procédé de production de poudre d'argent sphérique et pâte électroconductrice

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Publication number
WO2025249331A1
WO2025249331A1 PCT/JP2025/018811 JP2025018811W WO2025249331A1 WO 2025249331 A1 WO2025249331 A1 WO 2025249331A1 JP 2025018811 W JP2025018811 W JP 2025018811W WO 2025249331 A1 WO2025249331 A1 WO 2025249331A1
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WIPO (PCT)
Prior art keywords
silver powder
silver
spherical silver
mass
spherical
Prior art date
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Pending
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PCT/JP2025/018811
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English (en)
Japanese (ja)
Inventor
廉 中嶋
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Dowa Electronics Materials Co Ltd
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Dowa Electronics Materials Co Ltd
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Filing date
Publication date
Priority claimed from JP2025085713A external-priority patent/JP2025179028A/ja
Application filed by Dowa Electronics Materials Co Ltd filed Critical Dowa Electronics Materials Co Ltd
Publication of WO2025249331A1 publication Critical patent/WO2025249331A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • 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
    • 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
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles
    • 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
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • 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
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • 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
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form

Definitions

  • the present invention relates to spherical silver powder, a method for producing spherical silver powder, and a conductive paste.
  • conductive films such as electrodes and electrical wiring by applying or printing a conductive paste containing conductive metal powder onto a substrate such as a film, board, or electronic component, and then heating it to dry, harden, or bake it, has been widely used for some time.
  • a conductive paste containing conductive metal powder onto a substrate such as a film, board, or electronic component, and then heating it to dry, harden, or bake it.
  • conductive films formed using conductive pastes are required to have lower resistance, and these requirements are becoming stricter every year.
  • Patent Document 1 proposes a silver powder that has a lower volume resistivity than conventional silver powders when used as a conductive paste, the silver powder having an apparent density of 8.2 g/cm or more and 9.2 g /cm or less, and a ratio of the length of the outer periphery line in the cross section of the silver particle to the length of the line circumscribing the periphery of the cross section of the particle of 1.1 or more and 1.4 or less.
  • the gist of the present invention to solve the above-mentioned problems is as follows:
  • [10] A method for producing spherical silver powder according to any one of [7] to [9], in which a surface treatment agent is added to the slurry containing the precipitated silver particles after the reduction step.
  • the present invention it is possible to provide a spherical silver powder that can impart excellent low-temperature sintering properties to a conductive paste. Furthermore, the present invention can provide a method for producing spherical silver powder that can impart excellent low-temperature sintering properties to a conductive paste. Furthermore, according to the present invention, a conductive paste having excellent low-temperature sintering properties can be provided.
  • FIG. 2 is an enlarged graph of an XRD analysis of the spherical silver powder according to Example 1.
  • FIG. 1 is an enlarged graph of an XRD analysis of the spherical silver powder according to Example 2.
  • FIG. 10 is an enlarged graph of an XRD analysis of the spherical silver powder according to Example 3.
  • FIG. 10 is an enlarged graph of an XRD analysis of the spherical silver powder according to Example 4.
  • FIG. 10 is an enlarged graph of an XRD analysis of the spherical silver powder according to Example 5.
  • FIG. 2 is an enlarged graph of an XRD analysis of the spherical silver powder according to Comparative Example 1.
  • FIG. 1 is an enlarged graph of an XRD analysis of the spherical silver powder according to Example 2.
  • FIG. 10 is an enlarged graph of an XRD analysis of the spherical silver powder according to Example 3.
  • FIG. 10 is an enlarged graph of an XRD analysis of the spher
  • FIG. 1 is an enlarged graph of an XRD analysis of a spherical silver powder according to Comparative Example 2.
  • FIG. 10 is an enlarged graph of an XRD analysis of the spherical silver powder according to Comparative Example 3.
  • FIG. 2 is a graph showing the XRD analysis of the spherical silver powders according to Examples 1 to 5 and Comparative Examples 1 to 3.
  • 1 is a 50,000-magnification SEM image of spherical silver powder after crushing in the separation step of Example 1.
  • 1 is a 50,000x SEM image of spherical silver powder after crushing in the separation step of Comparative Example 1.
  • 1 is a 50,000x SEM image of spherical silver powder after crushing in the separation step of Comparative Example 2.
  • the spherical silver powder of the present invention is suitable as a conductive filler for conductive pastes.
  • Conductive pastes using the spherical silver powder of the present invention can be used to form conductive patterns on substrates, or to form or bond electrodes.
  • Conductive pastes using the spherical silver powder of the present invention can be printed on substrates by, for example, screen printing, offset printing, photolithography, etc., to form conductive patterns, conductive films such as electrodes, etc.
  • components can be bonded via the paste printed on the substrate.
  • spherical silver powder means silver powder in which the average shape factor of 100 or more particles observed by image analysis based on scanning electron microscope (SEM) images is in the range of 1.0 to less than 1.7.
  • the shape factor in this specification is the ratio of the area of a virtual circle whose diameter is the average maximum length of 100 or more particles observed by the image analysis to the average particle area of the silver particles obtained by tracing the outline of the particles, and is the value obtained by dividing the area of the virtual circle by the average particle area.
  • the shape factor is calculated by ⁇ (average maximum length/2) 2 /average particle area.
  • X-ray diffraction (XRD) analysis was performed using an X-ray diffractometer (SmartLab manufactured by Rigaku Corporation) under the following measurement conditions.
  • Target material Cu
  • Target voltage 45 kV
  • Target current 200mA
  • Measurement method ⁇ -2 ⁇
  • Scan speed 1 deg/min
  • Scan step 0.02 deg Scan range: 30° ⁇ 2 ⁇ 50°
  • the "intensity of the cubic Ag peak” refers to the numerical value (count number) of the intensity of the peak top of the cubic Ag peak. In this specification, the numerical value of the intensity at 38.14° is used.
  • a point where the difference between the baseline and the X-ray diffraction intensity profile is maximized when a straight line is drawn between the intensity at 35.60° and the intensity at 36.40° and the baseline is used as the baseline is also considered to be a hexagonal Ag peak.
  • hexagonal Ag peak intensity refers to the difference between the numerical value (count number) of the hexagonal Ag peak intensity and the count number of the baseline at the 2 ⁇ position of the peak top of the hexagonal Ag peak when a straight line is drawn between the intensity at 35.60° and the intensity at 36.40° and the baseline is used as the baseline.
  • the intensity of the hexagonal Ag peak will be specifically explained using an enlarged graph ( FIG. 1 ) of the XRD analysis of the spherical silver powder according to Example 1, which will be described later.
  • Example 1 is the straight line (baseline) connecting the intensities at 35.60° and 36.40°, and the intensity of the hexagonal Ag peak is in the range indicated by the arrow in FIG. 1 where the 2 ⁇ value is 36.00°.
  • the intensities of the hexagonal Ag peaks in Examples 1 to 4 were calculated using a 2 ⁇ position of 36.00°.
  • the intensity of the hexagonal Ag peak in Example 5 was calculated using a 2 ⁇ position of 35.92°
  • the intensity of the hexagonal Ag peak in Comparative Example 3 was calculated using a 2 ⁇ position of 36.04°.
  • the "BET specific surface area” was measured using a specific surface area measuring device employing the BET method (Macsorb HM-model 1210, manufactured by MOUNTECH Corp.) by placing 3 g of spherical silver powder in a measurement cell, passing a carrier gas mixture of 70 vol % He gas and 30 vol % nitrogen gas through the measurement cell at 25 mL/min, and degassing the cell at 60°C for 10 minutes, followed by measurement by the BET single-point method.
  • BET method Macsorb HM-model 1210, manufactured by MOUNTECH Corp.
  • the volume-based cumulative 10% particle diameter D 10 , cumulative 50% particle diameter D 50 , cumulative 90% particle diameter D 90 , and cumulative 100% particle diameter D MAX of the spherical silver powder were measured using a laser diffraction/scattering particle size distribution analyzer (Microtrac MT-3300 EXII, manufactured by Microtrac-Bell Co., Ltd.). For the measurements, 0.1 g of sample (spherical silver powder) was added to 40 mL of isopropyl alcohol (IPA) and dispersed.
  • IPA isopropyl alcohol
  • An ultrasonic homogenizer manufactured by Nippon Seiki Seisakusho, device name: US-150T; 19.5 kHz, tip diameter 18 mm
  • the dispersion time was 2 minutes.
  • the dispersed sample was subjected to the above-mentioned apparatus, and the particle size distribution was determined using the attached analysis software.
  • an SDC device was used as the circulator of the laser diffraction/scattering particle size distribution analyzer, and the "flow rate (%)" setting of the circulator was set to 60.
  • the post-measurement calculation mode used for the MT-3300 EXII was HRA mode.
  • volume-based cumulative 10% particle diameter D 10 cumulative 50% particle diameter D 50 , cumulative 90% particle diameter D 90 , and cumulative 100% particle diameter D MAX determined by the laser diffraction method may be simply referred to as "D 10 ,”"D 50 ,””D 90 ,” and “D MAX ,” respectively.
  • Ignition loss (Ig-loss) value refers to the amount of change in mass when heated from room temperature to 800°C, and specifically serves as an index of the amount of components other than silver contained in the spherical silver powder, and indicates the amount of components remaining in the spherical silver powder, such as processing agents and additives used in the manufacturing process of the spherical silver powder.
  • D hkl means the size of the crystallite diameter (the size of the crystallite in the direction perpendicular to hkl) (unit: nm)
  • ⁇ means the wavelength of the measured X-ray (0.15405 nm when using a Cu target)
  • ⁇ means the broadening of the diffraction line due to the size of the crystallite (rad) (expressed using half-width)
  • ⁇ means the Bragg angle of the diffraction angle (rad) (the angle when the angle of incidence and the angle of reflection are equal, the angle of the peak top is used)
  • the spherical silver powder of the present invention has a cubic Ag peak at 2 ⁇ of approximately 38.14° and a hexagonal Ag peak at 2 ⁇ of approximately 36.00°, and the ratio of the intensity of the hexagonal Ag peak to the intensity of the cubic Ag peak (hexagonal Ag peak intensity/cubic Ag peak intensity ⁇ 100[%]) is 0.5% or more.
  • the spherical silver powder described above can impart excellent low-temperature sinterability to a conductive paste. The reason for this is presumably due to the possibility of a transition from a hexagonal crystal structure to a cubic crystal structure occurring during sintering at low temperatures, but the reason for this is not entirely clear.
  • the results of the following examples and comparative examples clearly show that spherical silver powders that satisfy the above requirements can impart excellent low-temperature sinterability to a conductive paste.
  • the spherical silver powder of the present invention can be obtained by the method for producing the spherical silver powder of the present invention described below.
  • the ratio of the intensity of the hexagonal Ag peak to the intensity of the cubic Ag peak is 0.5% or more, preferably 0.8% or more, and more preferably 1% or more.
  • the ratio of the hexagonal Ag peak intensity to the cubic Ag peak intensity may be, for example, 30% or less, 15% or less, or 9% or less.
  • the BET specific surface area of the spherical silver powder is preferably 0.1 m 2 /g or more, more preferably 0.2 m 2 /g or more, and is preferably 1.8 m 2 /g or less, more preferably 1.5 m 2 /g or less. If the BET specific surface area of the spherical silver powder is 0.1 m 2 /g or more, the low-temperature sintering property can be improved. On the other hand, if the BET specific surface area of the spherical silver powder is 1.8 m 2 /g or less, when the spherical silver powder is used in a conductive paste or the like, the viscosity of the resulting conductive paste or the like can be effectively reduced.
  • the D10 of the spherical silver powder is preferably 0.2 ⁇ m or more, more preferably 0.5 ⁇ m or more, and is preferably 3 ⁇ m or less, more preferably 2 ⁇ m or less.
  • the D50 of the spherical silver powder is preferably 0.5 ⁇ m or more, more preferably 0.8 ⁇ m or more, and is preferably 6 ⁇ m or less, more preferably 3 ⁇ m or less.
  • the D90 of the spherical silver powder is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and is preferably 8 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the D MAX of the spherical silver powder is preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more, and is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the viscosity of the resulting conductive paste or the like can be effectively reduced when the spherical silver powder is used in a conductive paste or the like.
  • the D10, D50 , D90 and DMAX of the spherical silver powder are each not more than the above upper limit, the particle size of the spherical silver powder will be favorable, and the low-temperature sintering property can be improved.
  • the volume-based cumulative 10% particle diameter D 10 , cumulative 50% particle diameter D 50 , and cumulative 90% particle diameter D 90 determined by the laser diffraction method are calculated using the following formula (1): 0.5 ⁇ (D 90 ⁇ D 10 )/D 50 ⁇ 2.5 (1) It is preferable that the following relationship is satisfied. If (D 90 - D 10 )/D 50 is within the above range, when the spherical silver powder is used in a conductive paste or the like, the stability of the resulting conductive paste can be improved.
  • the ( D90 - D10 )/ D50 of the spherical silver powder is more preferably 2.0 or less, and even more preferably 1.5 or less. If ( D90 - D10 )/ D50 is 2.5 or less, the uniformity of the silver particles is high, and when a conductive paste is prepared using the spherical silver powder, the conductive paste can be easily adjusted.
  • the ignition loss (Ig-loss) value of the spherical silver powder is preferably 0.05% by mass or more, more preferably 0.2% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less. If the ignition loss value of the spherical silver powder is 0.05% by mass or more, when the spherical silver powder is used in a conductive paste or the like, aggregation of the spherical silver powder in the conductive paste can be effectively suppressed.
  • the ignition loss value of the spherical silver powder is 10 mass% or less, the impurities are low, so when a conductive film is obtained using a conductive paste containing the spherical silver powder, an increase in the resistance value of the obtained conductive film can be effectively suppressed.
  • the spherical silver powder of the present invention preferably contains a surface treatment agent.
  • the surface treatment agent is not particularly limited as long as the spherical silver powder satisfies the above-mentioned predetermined requirements, but examples thereof include fatty acids, compounds having an azole structure, fatty acid salts, surfactants, organometallic chelating agents, protective colloids, etc.
  • the surface treatment agent is preferably one or more surface treatment agents selected from the group consisting of fatty acids, compounds having an azole structure, and fatty acid salts, from the viewpoint of being able to adhere uniformly to the surface of the spherical silver powder and obtaining high dispersibility.
  • fatty acids examples include behenic acid, stearic acid, palmitic acid, myristic acid, lauric acid, ricinoleic acid, oleic acid, linoleic acid, linolenic acid, etc. These may be used alone or in combination of two or more.
  • fatty acid salts include salts of the fatty acids listed above, such as sodium salts and potassium salts.
  • Examples of compounds having an azole structure include benzotriazole, sodium salts of benzotriazole, and potassium salts of benzotriazole. These may be used alone or in combination of two or more.
  • the method for producing spherical silver powder of the present invention comprises a silver complex formation step of adding ammonia and a first chelating agent consisting of ethylenediaminetetraacetic acid to a silver-containing aqueous solution to obtain a silver complex aqueous solution, and a reduction step of adding a reducing agent to the silver complex aqueous solution to reduce and precipitate silver particles, wherein the amount of the first chelating agent added is 3 parts by mass or more and 40 parts by mass or less per 100 parts by mass of silver (Ag) in the silver-containing aqueous solution.
  • the above-described production method makes it possible to obtain the spherical silver powder of the present invention, which can impart excellent low-temperature sintering properties to a conductive paste.
  • the production method of the present invention may optionally include steps other than the silver complex formation step and the reduction step (hereinafter, these steps may be referred to as "other steps"). Examples of other steps include a pH adjuster addition step of adding a pH adjuster to the aqueous silver complex solution before reduction, a surface treatment agent addition step of adding a surface treatment agent to a mixed solution containing precipitated silver particles, and a separation step of separating and drying the silver particles or the surface treatment agent-coated silver particles (silver particles coated with a surface treatment agent) obtained in the surface treatment agent addition step.
  • ⁇ Silver complex formation process> ammonia and a first chelating agent consisting of ethylenediaminetetraacetic acid are added to a silver-containing aqueous solution to obtain a silver complex aqueous solution.
  • the order of adding ammonia and the first chelating agent to the silver-containing aqueous solution may be ammonia first, or the first chelating agent may be added first, or ammonia and the first chelating agent may be added simultaneously to the silver-containing aqueous solution. Both ammonia and the first chelating agent can form a complex with silver, but it is preferable to stir and mix them until they are complexed.
  • a second chelating agent consisting of a polymer may be further added to the silver-containing aqueous solution or the silver complex aqueous solution.
  • the timing of adding the second chelating agent is not particularly limited; it may be added before the addition of ammonia, before the addition of the first chelating agent, after the addition of ammonia, after the addition of the first chelating agent, or simultaneously with the ammonia and the first chelating agent.
  • the silver-containing aqueous solution is not particularly limited, but may be a silver nitrate aqueous solution, a silver oxide aqueous solution, or the like. Of these, a silver nitrate aqueous solution is preferred.
  • ammonia to be added to the silver-containing aqueous solution examples include aqueous ammonia and ammonium salts.
  • the amount of ammonia added is not particularly limited as long as a silver ammine complex is obtained as the complex that constitutes the silver complex aqueous solution, but it is preferably 38 parts by mass or more, more preferably 47 parts by mass or more, and preferably 78 parts by mass or less, more preferably 62 parts by mass or less, per 100 parts by mass of silver in the silver-containing aqueous solution.
  • the first chelating agent added to the silver-containing aqueous solution is ethylenediaminetetraacetic acid.
  • Ethylenediaminetetraacetic acid includes ethylenediaminetetraacetic acid in the form of an alkali metal salt. That is, ethylenediaminetetraacetic acid may have some or all of its four carboxylic acids in the form of alkali metal salts. From the standpoint of solubility in the silver-containing aqueous solution, it is preferable to use ethylenediaminetetraacetic acid in the form of an alkali metal salt. Ethylenediaminetetraacetic acid in the form of an alkali metal salt may also be in the form of a hydrate.
  • Examples of ethylenediaminetetraacetic acid in the form of an alkali metal salt include disodium ethylenediaminetetraacetic acid, trisodium ethylenediaminetetraacetic acid, tetrasodium ethylenediaminetetraacetic acid, dipotassium ethylenediaminetetraacetic acid, tripotassium ethylenediaminetetraacetic acid, and tetrapotassium ethylenediaminetetraacetic acid. Of these, disodium ethylenediaminetetraacetic acid is preferred.
  • the above ethylenediaminetetraacetic acids may be used alone or in combination of two or more.
  • the amount of the first chelating agent added is 3 parts by mass or more, preferably 3.5 parts by mass or more, and 40 parts by mass or less, preferably 36 parts by mass or less, per 100 parts by mass of silver in the silver-containing aqueous solution. If the amount of the first chelating agent added is less than 3 parts by mass, the resulting silver powder will have a very low proportion of hexagonal Ag, which may not achieve the effects of the present invention. However, if the amount is within the above range, it is possible to easily obtain silver powder in which the ratio of the hexagonal Ag peak intensity to the cubic Ag peak intensity falls within the range of the present invention.
  • the amount of the first chelating agent added is preferably 5 parts by mass or more, more preferably 6 parts by mass or more, and is preferably 70 parts by mass or less, more preferably 65 parts by mass or less, relative to 100 parts by mass of ammonia in the silver-containing aqueous solution.
  • the second chelating agent added to the silver-containing aqueous solution consists of a polymer.
  • a second chelating agent consisting of a polymer can effectively suppress the aggregation of silver particles obtained in the reduction process.
  • preferred second chelating agents include amino compounds and imine compounds.
  • polyethyleneimine (PEI) is preferred.
  • PEI which is an imine compound, has a network structure containing both a primary amine (—NH 2 ) and a secondary amine ( ⁇ NH) in the molecule, and provides preferred results in the present invention.
  • the second chelating agent preferably has a weight-average molecular weight of 600 or less, and more preferably 145 or more and 600 or less. This is because a weight-average molecular weight of 145 or more of the second chelating agent has the effect of producing highly dispersible silver particles. On the other hand, a weight-average molecular weight of 600 or less of the polymeric amine ensures the water solubility of the polymeric amine, and it is believed that the polymeric amine hardly remains on the surface or inside of the produced silver particles.
  • the weight average molecular weight of the second chelating agent can be measured by GPC-MALS.
  • the amount of the second chelating agent added is preferably 0.1 parts by mass or more, and more preferably 0.3 parts by mass or more, per 100 parts by mass of silver in the silver-containing aqueous solution. It is presumed that if the amount of the second chelating agent added is 0.1 parts by mass or more relative to 100 parts by mass of silver in the silver-containing aqueous solution, the silver particles will grow uniformly and spherically, and aggregation can be effectively suppressed. Although there is no particular upper limit to the amount added, if an excessive amount is added, the growth of silver will be significantly inhibited, so it is, for example, 10 parts by mass or less, and preferably 3 parts by mass or less.
  • the temperature of the aqueous silver complex solution is preferably 5°C or higher, more preferably 20°C or higher, and is preferably 50°C or lower, more preferably 40°C or lower. If the temperature of the aqueous silver complex solution is 5° C. or higher, the reduction reaction can proceed effectively. On the other hand, if the temperature of the aqueous silver complex solution is 50°C or less, the reaction rate of the reduction reaction described below can be effectively prevented from becoming excessive, and the variation in particle size of the silver particles can be effectively suppressed. Furthermore, if the temperature of the aqueous silver complex solution is within the above range, an increase in energy costs can be effectively suppressed.
  • a pH adjuster may be added to the aqueous silver complex solution before the addition of the reducing agent. Adding a pH adjuster to the aqueous silver complex solution before reduction allows for easy adjustment of the particle size of the resulting silver powder.
  • Common acids or bases may be used as pH adjusters, such as nitric acid and sodium hydroxide.
  • the amount of pH adjuster added can be adjusted appropriately depending on the amount of aqueous silver nitrate solution used and the particle size of the silver powder to be obtained. Examples of methods for this adjustment include conducting a level test of the particle size of the silver powder depending on the amount of pH adjuster added and adjusting the amount added.
  • a reducing agent is added to the stirred aqueous silver complex solution to reduce and precipitate silver particles, thereby obtaining a slurry in which silver particles are dispersed, which is a mixture containing silver particles.
  • the reducing agent to be added to the aqueous silver complex solution is not particularly limited, but examples include hydrazine, formalin, sodium borohydride, glucose, hypophosphorous acid, etc. Among these, hydrazine is preferred.
  • the amount of reducing agent added should preferably be at least 1 equivalent relative to the silver of the reducing agent being reacted.
  • equivalent here refers to the molar equivalent, which represents the quantitative relationship in the chemical reaction between silver and the reducing agent. For example, in the case of hydrazine reduction, 1 equivalent of hydrazine per mole of silver is 0.25 moles.
  • reducing agents with weak reducing power such as formalin or glucose
  • 2 equivalents or more relative to the silver are preferred, and 10 to 20 equivalents are even more preferred.
  • ⁇ Surface treatment agent addition step When the surface treatment agent addition step is performed, the surface treatment agent is added to the mixture containing the silver particles precipitated in the reduction step, thereby obtaining silver particles coated with the surface treatment agent.
  • the mixed liquid containing silver particles coated with a surface treatment agent is usually a slurry in which silver particles coated with a surface treatment agent are dispersed.
  • Examples of surface treatment agents that can be added to the mixture containing precipitated silver particles include fatty acids, compounds having an azole structure, fatty acid salts, surfactants, organometallic chelating agents, and protective colloids.
  • the surface treatment agent is preferably one or more surface treatment agents selected from the group consisting of fatty acids, compounds having an azole structure, and fatty acid salts, from the viewpoint of being easily and uniformly attached to the silver powder surface.
  • fatty acids examples include behenic acid, stearic acid, palmitic acid, myristic acid, lauric acid, ricinoleic acid, oleic acid, linoleic acid, linolenic acid, etc. These may be used alone or in combination of two or more.
  • fatty acid salts include salts of the fatty acids listed above, such as sodium salts and potassium salts.
  • Examples of compounds having an azole structure include benzotriazole, sodium salts of benzotriazole, and potassium salts of benzotriazole. These may be used alone or in combination of two or more.
  • the amount of the surface treatment agent added to the mixed solution containing silver particles is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and is preferably 3 parts by mass or less, more preferably 1 part by mass or less, relative to 100 parts by mass of silver in the silver-containing aqueous solution.
  • the amount of the surface treatment agent added is 0.05 parts by mass or more per 100 parts by mass of silver in the silver-containing aqueous solution, the dispersibility of the silver particles can be improved.
  • the amount of the surface treatment agent added is 3 parts by mass or less per 100 parts by mass of silver in the silver-containing aqueous solution, the risk of a decrease in low-temperature sinterability can be effectively suppressed.
  • the surface treatment agent is preferably added to the mixed solution containing silver particles a specific time after the reducing agent has been added to the aqueous silver complex solution.
  • the addition of the surface treatment agent stops the grain growth of the silver particles, so the timing of addition can be determined as long as it allows the silver in the mixed solution to be sufficiently precipitated as silver particles.
  • the separation step the silver particles are separated from the mixed solution containing the silver particles or the silver particles coated with the surface treatment agent.
  • a washing and recovery step can be carried out, or the drying step can be carried out without going through the washing and recovery step.
  • washing and recovery process for example, the cake-like aggregate of separated silver particles or silver particles coated with a surface treatment agent is washed.
  • Washing in the washing and recovery process may be carried out using, for example, pure water.
  • Dehydration in the washing and recovery process may be carried out using, for example, decantation or a filter press.
  • the end point of washing may be determined using the electrical conductivity of the washing water. Specifically, the end of washing may be determined when the electrical conductivity of the washing water falls to a predetermined value or below.
  • the silver particles or silver particles coated with a surface treatment agent may be subjected to a drying process in a cake-like aggregated state, etc.
  • the drying process aggregates of silver particles that contain moisture and are in an agglomerated state or silver particles coated with a surface treatment agent are dried.
  • the drying process may be performed using vacuum drying or an airflow dryer.
  • a high-pressure air flow may be blown onto the aggregates of silver particles or silver particles coated with a surface treatment agent, or the cake or spherical silver powder in the drying process may be placed in a mixer with a stirring rotor and stirred, thereby applying a dispersing force to the cake or spherical silver powder in the drying process and promoting dispersion and drying.
  • the temperature of the spherical silver powder is not particularly limited as long as the conditions are such that the aggregates of silver particles are sufficiently dried, but it is preferably 40°C or higher, more preferably 70°C or higher, and is preferably 120°C or lower, more preferably 100°C or lower. If the temperature of the spherical silver powder is 40° C. or higher, the drying efficiency can be improved. On the other hand, if the temperature of the spherical silver powder is 120°C or less, the transition from the hexagonal crystal structure to the cubic crystal structure in the silver particles or silver particles coated with a surface treatment agent can be effectively suppressed.
  • the spherical silver powder may be in the form of clumps after drying, it is preferable to carry out a dry crushing process or classification operation simultaneously with or after the drying process in order to improve the handleability of the spherical silver powder.
  • improving the handleability of the spherical silver powder means, for example, ensuring a level of fluidity that does not interfere with the supply operation into the equipment, or loosening the spherical silver powder to an appropriate degree so that processing in the equipment proceeds efficiently.
  • a crusher that rotates agitator blades to crush the material and fluidize the spherical silver powder; for example, a sample mill, blender, coffee mill, etc. may be used.
  • the conductive paste of the present invention contains the spherical silver powder of the present invention as a conductive filler.
  • the conductive paste preferably contains a solvent and a binder, and may further contain other components as necessary.
  • the solvent, binder, etc. may be selected appropriately depending on the application mode.
  • Example 1 ⁇ Silver complex formation process> First, 3436 g of a silver nitrate aqueous solution containing 50.84 g of silver was stirred at 174 rpm, and 103.2 g of 28% by weight aqueous ammonia (manufactured by Junsei Chemical Co., Ltd.) was added.
  • ⁇ Surface treatment agent addition step> stirring was stopped once after 5 seconds of stirring after the addition of hydrazine to the obtained slurry containing silver particles, and then stirring was resumed 130 seconds after the addition of hydrazine.
  • 5.12 g of a 1.55% stearic acid emulsion (amount of stearic acid added per 100 parts by mass of silver: 0.16 parts by mass) was added as a surface treatment agent, and stirring was continued for an additional 75 seconds to obtain a slurry containing silver particles coated with a surface treatment agent.
  • a baffled reaction chamber and a two-stage turbine blade were used for the reaction.
  • the spherical silver powder thus obtained was used to measure or calculate the following: XRD analysis, cubic Ag peak intensity, hexagonal Ag peak intensity, ratio of hexagonal Ag peak intensity to cubic Ag peak intensity, BET specific surface area, particle size distribution, ignition loss (Ig-loss), and crystallite diameter Dx.
  • Table 2 An enlarged graph of the XRD analysis of the spherical silver powder according to Example 1 in the 2 ⁇ range of 35.00° to 37.00° is shown in Figure 1, a graph of the XRD analysis in the 2 ⁇ range of 35.00 to 40.00° is shown in Figure 9, and an SEM image of the spherical silver powder after crushing in the separation step at 50,000 times magnification is shown in Figure 10.
  • Table 2 an SEM image of the spherical silver powder after crushing in the separation step at 50,000 times magnification
  • a mixture was obtained by mixing 93.01 parts by mass of the spherical silver powder obtained above, 0.25 parts by mass of ethyl cellulose, 1.59 parts by mass of Texanol, 3.86 parts by mass of butyl carbitol acetate, 0.26 parts by mass of tributyl citrate, 0.25 parts by mass of oleic acid, 0.26 parts by mass of triacetin, and 0.51 parts by mass of methylphenylpolysiloxane (KF96-100).
  • the resulting mixture was then premixed using a planetary mixer (revolution 1000 rpm), and then kneaded using a three-roll mill (manufactured by EXAKT) with a roll gap ranging from 100 ⁇ m to 20 ⁇ m, to obtain a conductive paste.
  • the conductive paste obtained above was used to print a linear shape by screen printing.
  • the linear shape had a design line width of 500 ⁇ m and a linear length of 128 mm.
  • a Microtec printer was used for printing, and printing was performed at a squeegee speed of 80 mm/sec.
  • a silicon substrate for solar cell applications, textured and with SiNx film already formed with a thickness of approximately 170 ⁇ m was used for printing.
  • the conductive film was dried for 10 minutes in a dryer set at 100°C to form a conductive film.
  • the conductive film was measured for its resistance (unit: ⁇ ) over time from room temperature to 300°C at a temperature increase rate of 10°C/min using a high-temperature microscope (manufactured by Yonekura Seisakusho Co., Ltd.).
  • the resistance values at 100°C, 140°C, 160°C, 180°C, 190°C, 195°C, and 200°C are shown in Table 3. The lower the resistance value shown in Table 3, the better the conductive paste's low-temperature sintering properties.
  • Example 2 to 4 Spherical silver powders according to Examples 2 to 4 were obtained in the same manner as in Example 1, except that the amounts of the first chelating agent and the second chelating agent added were as shown in Table 1.
  • the spherical silver powder thus obtained was subjected to XRD analysis, and measurements or calculations of BET specific surface area, particle size distribution, ignition loss (Ig-loss), and crystallite diameter Dx were performed. The results are shown in Table 2.
  • the spherical silver powder was also subjected to resistance measurement, and the results are shown in Table 3.
  • enlarged graphs of XRD analysis of the spherical silver powders according to Examples 2 to 4 in the 2 ⁇ range of 35.00° to 37.00° are shown in FIGS. 2 to 4, and a graph of XRD analysis in the 2 ⁇ range of 35.00° to 40.00° is shown in FIG. 9.
  • Example 5 The spherical silver powder of Example 5 was obtained in the same manner as Example 1, except that 50 g of silver was added to the dried silver powder obtained and crushed twice for 30 seconds using a coffee mill (manufactured by Melitta Japan Co., Ltd.). The spherical silver powder thus obtained was subjected to XRD analysis, and measurements or calculations of BET specific surface area, particle size distribution, ignition loss (Ig-loss), and crystallite diameter Dx were performed. The results are shown in Table 2. The spherical silver powder was also subjected to resistance measurement, and the results are shown in Table 3.
  • FIG. 5 an enlarged graph of the XRD analysis of the spherical silver powder according to Example 5 in the 2 ⁇ range of 35.00° to 37.00° is shown in FIG. 5, and a graph of the XRD analysis in the 2 ⁇ range of 35.00° to 40.00° is shown in FIG. 5.
  • ⁇ Surface treatment agent addition step> 15 seconds after the addition of the reducing agent, 6.13 g of a 1.55% stearic acid emulsion (0.18 parts by mass of stearic acid added per 100 parts by mass of silver) was added as a surface treatment agent to the resulting slurry containing silver particles, and the mixture was stirred for an additional 180 seconds to obtain a slurry containing silver particles coated with the surface treatment agent. Note that a baffled reaction chamber and a two-stage turbine blade were used for the reaction.
  • the spherical silver powder thus obtained was subjected to XRD analysis, and measurements or calculations of BET specific surface area, particle size distribution, ignition loss (Ig-loss), and crystallite diameter Dx were performed. The results are shown in Table 2.
  • the spherical silver powder was then subjected to resistance measurement, and the results are shown in Table 3.
  • an enlarged graph of the XRD analysis of the spherical silver powder according to Comparative Example 1 in the 2 ⁇ range of 35.00° to 37.00° is shown in FIG. 6
  • a graph of the XRD analysis in the 2 ⁇ range of 35.00° to 40.00° is shown in FIG. 9
  • a 50,000x SEM image of the spherical silver powder after crushing in the separation step is shown in FIG. 11.
  • ⁇ Surface treatment agent addition step> 15 seconds after the addition of the reducing agent, 5.12 g of a 1.55% stearic acid emulsion (0.16 parts by mass of stearic acid added per 100 parts by mass of silver) was added as a surface treatment agent to the resulting slurry containing silver particles, and the mixture was stirred for an additional 180 seconds to obtain a slurry containing silver particles coated with the surface treatment agent. Note that a baffled reaction chamber and a two-stage turbine blade were used for the reaction.
  • the spherical silver powder thus obtained was subjected to XRD analysis, and measurements or calculations of BET specific surface area, particle size distribution, ignition loss (Ig-loss), and crystallite diameter Dx were performed. The results are shown in Table 2.
  • the spherical silver powder was then subjected to resistance measurement, and the results are shown in Table 3.
  • an enlarged graph of the XRD analysis of the spherical silver powder according to Comparative Example 2 in the 2 ⁇ range of 35.00° to 37.00° is shown in FIG. 7
  • a graph of the XRD analysis in the 2 ⁇ range of 35.00° to 40.00° is shown in FIG. 9
  • a 50,000x SEM image of the spherical silver powder after crushing in the separation step is shown in FIG. 12.
  • Example 3 A spherical silver powder according to Comparative Example 3 was obtained in the same manner as in Example 1, except that the amounts of the first chelating agent and the second chelating agent added were as shown in Table 1.
  • the spherical silver powder thus obtained was subjected to XRD analysis, and measurements or calculations of BET specific surface area, particle size distribution, ignition loss (Ig-loss), and crystallite diameter Dx were performed. The results are shown in Table 2.
  • the spherical silver powder was also subjected to resistance measurement, and the results are shown in Table 3. Furthermore, an enlarged graph of the XRD analysis of the spherical silver powder according to Comparative Example 3 in the 2 ⁇ range of 35.00° to 37.00° is shown in FIG. 8, and a graph of the XRD analysis in the 2 ⁇ range of 35.00° to 40.00° is shown in FIG.
  • the present invention it is possible to provide a spherical silver powder that can impart excellent low-temperature sintering properties to a conductive paste. Furthermore, the present invention can provide a method for producing spherical silver powder that can impart excellent low-temperature sintering properties to a conductive paste. Furthermore, according to the present invention, a conductive paste having excellent low-temperature sintering properties can be provided.

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Abstract

Le but de la présente invention est de fournir une poudre d'argent sphérique qui peut conférer une aptitude au frittage à basse température exceptionnelle à une pâte électroconductrice. La présente invention concerne une poudre d'argent sphérique ayant, lors d'une analyse XRD, un pic Ag cubique et un pic Ag hexagonal, le rapport de l'intensité du pic Ag hexagonal à l'intensité du pic Ag cubique étant supérieur ou égal à 0,5 %.
PCT/JP2025/018811 2024-05-27 2025-05-23 Poudre d'argent sphérique, procédé de production de poudre d'argent sphérique et pâte électroconductrice Pending WO2025249331A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008156720A (ja) * 2006-12-25 2008-07-10 Mitsui Mining & Smelting Co Ltd 銀ナノ粒子の製造方法
WO2017150580A1 (fr) * 2016-03-01 2017-09-08 国立大学法人京都大学 NANOPARTICULES DE Ru ET Cu EN SOLUTION SOLIDE, LEUR PROCÉDÉ DE PRODUCTION, ET CATALYSEUR
WO2018159644A1 (fr) * 2017-03-01 2018-09-07 国立大学法人京都大学 NANOPARTICULES DE SOLUTION SOLIDE DE Pd-Ru, LEUR PROCÉDÉ DE PRODUCTION ET CATALYSEUR ASSOCIÉ, PROCÉDÉ DE RÉGULATION DE LA STRUCTURE CRISTALLINE DE NANOPARTICULES DE SOLUTION SOLIDE DE Pt-Ru, NANOPARTICULES DE SOLUTION SOLIDE Au-Ru, ET LEUR PROCÉDÉ DE FABRICATION
JP2020501013A (ja) * 2016-11-24 2020-01-16 ヴァレオ システム ドゥ コントロール モトゥール Ａｇ−Ｓｎ金属間化合物の合成
WO2020067282A1 (fr) * 2018-09-28 2020-04-02 Ｄｏｗａエレクトロニクス株式会社 Poudre d'argent, son procédé de production et pâte conductrice

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008156720A (ja) * 2006-12-25 2008-07-10 Mitsui Mining & Smelting Co Ltd 銀ナノ粒子の製造方法
WO2017150580A1 (fr) * 2016-03-01 2017-09-08 国立大学法人京都大学 NANOPARTICULES DE Ru ET Cu EN SOLUTION SOLIDE, LEUR PROCÉDÉ DE PRODUCTION, ET CATALYSEUR
JP2020501013A (ja) * 2016-11-24 2020-01-16 ヴァレオ システム ドゥ コントロール モトゥール Ａｇ−Ｓｎ金属間化合物の合成
WO2018159644A1 (fr) * 2017-03-01 2018-09-07 国立大学法人京都大学 NANOPARTICULES DE SOLUTION SOLIDE DE Pd-Ru, LEUR PROCÉDÉ DE PRODUCTION ET CATALYSEUR ASSOCIÉ, PROCÉDÉ DE RÉGULATION DE LA STRUCTURE CRISTALLINE DE NANOPARTICULES DE SOLUTION SOLIDE DE Pt-Ru, NANOPARTICULES DE SOLUTION SOLIDE Au-Ru, ET LEUR PROCÉDÉ DE FABRICATION
WO2020067282A1 (fr) * 2018-09-28 2020-04-02 Ｄｏｗａエレクトロニクス株式会社 Poudre d'argent, son procédé de production et pâte conductrice

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