WO2019065341A1 - 銀粉およびその製造方法 - Google Patents

銀粉およびその製造方法 Download PDF

Info

Publication number
WO2019065341A1
WO2019065341A1 PCT/JP2018/034336 JP2018034336W WO2019065341A1 WO 2019065341 A1 WO2019065341 A1 WO 2019065341A1 JP 2018034336 W JP2018034336 W JP 2018034336W WO 2019065341 A1 WO2019065341 A1 WO 2019065341A1
Authority
WO
WIPO (PCT)
Prior art keywords
silver powder
diameter
particle diameter
sem
copper
Prior art date
Application number
PCT/JP2018/034336
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
良幸 道明
吉田　昌弘
井上　健一
Original Assignee
Ｄｏｗａエレクトロニクス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2018162411A external-priority patent/JP7090511B2/ja
Application filed by Ｄｏｗａエレクトロニクス株式会社 filed Critical Ｄｏｗａエレクトロニクス株式会社
Priority to US16/648,423 priority Critical patent/US11420256B2/en
Priority to SG11202001993XA priority patent/SG11202001993XA/en
Priority to EP18863425.7A priority patent/EP3670028A4/en
Priority to KR1020207011932A priority patent/KR102430857B1/ko
Priority to CN201880061178.3A priority patent/CN111132777B/zh
Publication of WO2019065341A1 publication Critical patent/WO2019065341A1/ja

Links

Images

Classifications

    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
    • B22F1/0003—
    • 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
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C22C5/08—Alloys based on silver with copper as the next major constituent
    • 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
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F2009/0804—Dispersion in or on liquid, other than with sieves
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/0824—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid
    • B22F2009/0828—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid with water
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/10—Copper
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
    • B22F2301/255—Silver or gold
    • 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
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0466—Alloys based on noble metals

Definitions

  • the present invention relates to silver powder and a method for producing the same, and more particularly to silver powder suitable for a material of a conductive paste and a method for producing the same.
  • the electrodes of solar cells the internal electrodes of multilayer ceramic electronic components such as electronic components using low-temperature fired ceramic (LTCC) and multilayer ceramic inductors (MLCI), and the external electrodes such as multilayer ceramic capacitors and multilayer ceramic inductors are formed.
  • LTCC low-temperature fired ceramic
  • MLCI multilayer ceramic inductors
  • the external electrodes such as multilayer ceramic capacitors and multilayer ceramic inductors
  • metal powder such as silver powder is used as silver powder.
  • a reducing agent is added to an aqueous reaction system containing silver ions in the presence of seed particles such as copper to reduce and deposit silver particles.
  • a manufacturing method has been proposed (see, for example, Patent Document 1).
  • silver powder produced by the conventional method of producing silver powder by water atomization is likely to agglomerate and the secondary particle diameter tends to be large, and the surface is smooth when the silver powder thus agglomerated is used as a material of the conductive paste It becomes difficult to form a thin conductive film.
  • silver powder with a small particle diameter is required as silver powder used for conductive paste in recent years due to miniaturization of internal electrodes of electronic components such as multilayer ceramic inductors (MLCI), but the particle diameter of silver powder is small. Then, the silver powder tends to aggregate.
  • MLCI multilayer ceramic inductors
  • the inventors of the present invention found that 40 ppm or more of copper can be obtained by rapidly solidifying by spraying high pressure water while dropping a molten metal in which silver containing 40 ppm or more of copper is dissolved. It has been found that silver powder containing and having a carbon content of 0.1% by mass or less can be produced to produce a silver powder having a low carbon content and which is difficult to aggregate, and the present invention has been completed.
  • the silver powder according to the present invention is characterized by containing 40 ppm or more of copper and having a carbon content of 0.1 mass% or less.
  • the content of copper in this silver powder is preferably 40 to 10000 ppm.
  • the silver powder preferably has a volume-based 50% cumulative particle diameter (D 50 diameter) of 1 to 15 ⁇ m as measured by a laser diffraction particle size distribution analyzer, and the cumulative 50% particle diameter of the silver powder (D 50)
  • the ratio (SEM diameter / D 50 diameter) of the average particle diameter (SEM diameter) of single particles observed by a field emission scanning electron microscope to the diameter) is preferably 0.3 to 1.0. Further, it is preferable that a ratio of tap density (tap density / D 50 diameter) to a cumulative 50% particle diameter (D 50 diameter) of this silver powder is 0.45 to 3.0 g / (cm 3 ⁇ ⁇ m).
  • the oxygen content in silver dust is 0.1 mass% or less.
  • the BET specific surface area of the silver powder is preferably 0.1 to 1.0 m 2 / g, and the tap density is preferably 2 to 6 g / cm 3 .
  • the method for producing silver powder according to the present invention is characterized in that high-pressure water is sprayed to rapidly solidify while dropping a molten metal in which silver containing 40 ppm or more of copper is dissolved.
  • the content of copper in the molten metal is preferably 40 to 10000 ppm.
  • the conductive paste according to the present invention is characterized in that the silver powder is dispersed in the organic component.
  • the method for producing a conductive film according to the present invention is characterized in that the above-mentioned conductive paste is applied onto a substrate and then fired to produce a conductive film.
  • the copper content is 40 ppm or more and the carbon content is 0.1 mass% or less.
  • the content of copper in the silver powder is 40 ppm or more (from the viewpoint of preventing aggregation of the silver powder), and from the viewpoint of improving the oxidation resistance and conductivity of the silver powder, the content is preferably 40 to 10000 ppm. It is more preferably 2000 ppm, particularly preferably 40 to 800 ppm, and most preferably 230 to 750 ppm.
  • the carbon content in the silver powder is 0.1% by mass or less, preferably 0.03% by mass or less, and more preferably 0.007% by mass or less.
  • the oxygen content in the silver powder is preferably 0.1% by mass or less, and more preferably 0.01 to 0.07% by mass. Thus, if the oxygen content in silver powder is low, it can fully sinter and can form a highly conductive conductive film.
  • the volume-based 50% cumulative particle diameter (D 50 diameter) of this silver powder (by the Heros method) measured by a laser diffraction particle size distribution analyzer is preferably 1 to 15 ⁇ m, and the electronic component is further miniaturized silver powder
  • the thickness is more preferably 1 to 8 ⁇ m, and most preferably 1.2 to 7 ⁇ m.
  • the average particle diameter (SEM diameter) of single particles observed by field emission scanning electron microscope (SEM) of this silver powder is used as a material of conductive paste for forming internal electrodes of electronic components obtained by further miniaturizing silver powder.
  • the ratio (SEM diameter / D 50 diameter) of the average particle diameter (SEM diameter) of single particles observed by a field emission scanning electron microscope to the cumulative 50% particle diameter (D 50 diameter) of this silver powder is 0. It is preferably 3 to 1.0, more preferably 0.35 to 1.0, still more preferably 0.5 to 1.0, and 0.65 to 1.0. Is most preferred. As the ratio (SEM diameter / D 50 diameter) (primary particle diameter / secondary particle diameter) is larger, it can be said that aggregation of silver powder is less.
  • the BET specific surface area of silver powder is preferably 0.1 to 1.0 m 2 / g, more preferably 0.2 to 0.8 m 2 / g, and 0.3 to 0.5 m 2. It is most preferable that it is / g.
  • the tap density of silver powder is 2 to 6 g / g to enhance the filling property of silver powder and form a conductive film having good conductivity when silver powder is used as a material of the conductive paste to form a conductive film. It is preferably cm 3, and more preferably from 2.5 ⁇ 5.5g / cm 3, is most preferable 3.5 ⁇ 5.5g / cm 3.
  • the cumulative 50% particle diameter of silver powder (D 50 to increase the filling property of silver powder and form a conductive film having good conductivity)
  • the ratio of tap density to diameter) is preferably 0.45 to 3.0 g / (cm 3 ⁇ ⁇ m), and 0.8 to 2.8 g / (cm 3 ⁇ ⁇ m) More preferably 1.1 to 2.5 g / (cm 3 ⁇ ⁇ m).
  • the shape of said silver powder may be any shape of various granular shapes, such as spherical shape and flake shape, and the shape may not be uniform.
  • the embodiment of the silver powder described above can be manufactured by the embodiment of the method for manufacturing silver powder according to the present invention.
  • copper of 40 ppm or more is preferably added to silver.
  • a very small amount (40 ppm or more, preferably 40 to 10000 ppm, more preferably 40 to 2000 ppm, particularly preferably 40 to 800 ppm, most preferably 230 to 750 ppm) of copper is added to silver by so-called water atomizing method of spraying high pressure water.
  • water atomizing method of spraying high pressure water When silver powder is produced from a molten metal, it is possible to obtain silver powder which has a small particle size, a small carbon content and is difficult to aggregate.
  • the average particle diameter of silver powder can be adjusted by adjusting the temperature of a molten metal, and the pressure of high pressure water.
  • the average particle diameter of the silver powder can be reduced by increasing the temperature of the molten metal or the pressure of high pressure water.
  • the solid obtained by solid-liquid separation may be washed with water before drying, or after drying, the particle size may be adjusted by crushing or classification.
  • this silver powder (saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons, ketones, etc.
  • a conductive paste can be produced by dispersing in organic components such as aromatic hydrocarbons, glycol ethers, esters, alcohols and the like organic solvents and binder resins (such as ethyl cellulose and acrylic resin) and the like.
  • organic components such as aromatic hydrocarbons, glycol ethers, esters, alcohols and the like organic solvents and binder resins (such as ethyl cellulose and acrylic resin) and the like.
  • the content of silver powder in the conductive paste is preferably 5 to 98% by mass, and more preferably 70 to 95% by mass, from the viewpoint of the production cost of the conductive paste and the conductivity of the conductive film.
  • the silver powder in the conductive paste may be used by mixing with one or more other metal powders (alloy powder of silver and tin, metal powder such as tin powder).
  • the metal powder may be a metal powder having a shape or particle size different from that of the silver powder according to the present invention.
  • the cumulative 50% particle diameter (D 50 diameter) based on volume measured by laser diffraction type particle size distribution measuring device of this metal powder is 0.5 to 20 ⁇ m in order to form a thin conductive film by firing the conductive paste. Is preferred.
  • the content of the metal powder in the conductive paste is preferably 1 to 94% by mass, and more preferably 4 to 29% by mass.
  • the total content of silver powder and metal powder in the conductive paste is preferably 60 to 99% by mass.
  • the content of the organic solvent in the conductive paste is preferably 0.8 to 20% by mass in consideration of the dispersibility of silver powder in the conductive paste and the appropriate viscosity of the conductive paste, More preferably, it is 8 to 15% by mass.
  • the organic solvent may be used as a mixture of two or more.
  • the content of the binder resin in the conductive paste is preferably 0.1 to 10% by mass from the viewpoint of the dispersibility of silver powder in the conductive paste and the conductivity of the conductive paste. It is more preferable that the content be 6% by mass.
  • the binder resin may be used as a mixture of two or more. Further, the content of the glass frit in the conductive paste is preferably 0.1 to 20% by mass from the viewpoint of the sinterability of the conductive paste, and further preferably 0.1 to 10% by mass. preferable. You may use this glass frit in mixture of 2 or more types.
  • Such a conductive paste is prepared, for example, by weighing each component and putting it in a predetermined container, prekneading it using a grinder, a universal stirrer, a kneader or the like, and then carrying out main kneading with a triple roll. can do. Further, if necessary, an organic solvent may be added thereafter to adjust the viscosity. In addition, after the glass frit or the inorganic oxide and the organic solvent or the binder resin are kneaded to reduce the particle size, silver powder may be finally added and this kneading may be performed.
  • This conductive paste is applied in a predetermined pattern on a substrate (such as a ceramic substrate or dielectric layer) by dipping or printing (such as metal mask printing, screen printing, or inkjet printing), and then fired to form a conductive film. can do.
  • a substrate such as a ceramic substrate or dielectric layer
  • dipping or printing such as metal mask printing, screen printing, or inkjet printing
  • the conductive paste is applied by dipping, the substrate is dipped in the conductive paste to form a coating film, and the unnecessary portion of the conductive film obtained by firing the coating film is removed to obtain a substrate.
  • a conductive film having a predetermined pattern shape can be formed thereon.
  • the baking of the conductive paste applied on the substrate may be performed in a non-oxidizing atmosphere such as nitrogen, argon, hydrogen or carbon monoxide, but since silver powder is difficult to oxidize, it is performed in the air because of cost. Is preferred.
  • the firing temperature of the conductive paste is preferably about 600 to 1000 ° C., and more preferably about 700 to 900 ° C.
  • volatile components such as an organic solvent in the conductive paste may be removed by preliminary drying by vacuum drying or the like.
  • the conductive paste contains a binder resin, it is preferable to heat the conductive paste at a low temperature of 250 to 400 ° C. as a binder removal step for reducing the content of the binder resin before firing.
  • Example 1 Molten metal (silver containing 46 ppm copper) dissolved by heating 23.96 kg of shot silver having a purity of 99.99% by mass and 6.04 kg of Ag-Cu alloy (containing 228 ppm copper) at 1600 ° C. in the atmosphere. while dropping the melt) from the lower tundish, pressure by the water atomizing device in an air atmosphere 150 MPa, the amount of water 160L / min with alkaline water (aqueous alkaline solution prepared by adding sodium hydroxide 157.55g against pure water 21.6 m 3 (pH 10 .7)) was sprayed to quench and solidify, the obtained slurry was solid-liquid separated, the solid was washed with water and dried to obtain silver powder (containing a trace amount of copper).
  • alkaline water aqueous alkaline solution prepared by adding sodium hydroxide 157.55g against pure water 21.6 m 3 (pH 10 .7)
  • the particle size (primary particle size) of the silver powder thus obtained is a single particle observed at a magnification of 5000 with a field emission scanning electron microscope (SEM) (S-4700 manufactured by Hitachi High-Technologies Corporation)
  • SEM field emission scanning electron microscope
  • the average particle diameter (SEM diameter) was determined from the average value of Feret diameters of 30 arbitrary particles.
  • the SEM diameter (primary particle diameter) of the silver powder was 2.35 ⁇ m.
  • dispersion is performed using a laser diffraction type particle size distribution measuring apparatus (Hyros particle size distribution measuring apparatus (HELOS & RODOS (air flow type dispersing module) made by SYMPATEC)).
  • HELOS & RODOS air flow type dispersing module
  • the content of copper in silver powder is ⁇ 10% of the content of copper in molten metal within the range of
  • the carbon content in the silver powder is measured by a carbon / sulfur analyzer (EMIA-920V2 manufactured by Horiba, Ltd.), the carbon content is 0.004 mass%, and the oxygen content is oxygen / nitrogen / The oxygen content was 0.040% by mass as measured by a hydrogen analyzer (EMGA-920 manufactured by Horiba, Ltd.).
  • the BET specific surface area of silver powder is degassed by flowing nitrogen gas at 105 ° C. for 20 minutes in the measuring device using a BET specific surface area measuring device (Macsorb manufactured by Mounttech Co., Ltd.), and then mixing nitrogen and helium
  • the BET specific surface area was 0.34 m 2 / g as measured by the BET one-point method while flowing a gas (N 2 : 30 vol%, He: 70 vol%).
  • the tap density (TAP) of silver powder silver powder is used up to 80% of the volume in a bottomed cylindrical die with an inner diameter of 6 mm and a height of 11.9 mm, similarly to the method described in JP-A-2007-263860.
  • Fill to form a silver powder layer uniformly apply a pressure of 0.160 N / m 2 to the upper surface of the silver powder layer, and compress the silver powder until the silver powder is no longer densely packed at this pressure, and then the silver powder layer
  • the density of the silver powder was determined from the measured value of the height of the silver powder layer and the weight of the filled silver powder. As a result, the tap density was 3.0 g / cm 3 .
  • the ratio (TAP / D 50 diameter) of tap density (TAP) to the 50% cumulative particle diameter (D 50 diameter) of silver powder was calculated to be 0.50 g / (cm 3 ⁇ ⁇ m).
  • Example 2 A small amount of copper was used in the same manner as in Example 1 except that a molten metal (a molten metal of silver containing 218 ppm of copper) in which 25 kg of shot silver and 15 kg of Ag—Cu alloy (containing 581 ppm of copper) were dissolved was used. ) Containing silver powder.
  • a molten metal a molten metal of silver containing 218 ppm of copper
  • Ag—Cu alloy containing 581 ppm of copper
  • the SEM diameter (primary particle diameter) is calculated, the cumulative 50% particle diameter (D 50 diameter) (secondary particle diameter) is measured, and the cumulative 50% particle diameter (D 50 diameter)
  • the SEM diameter (primary particle diameter) of the silver powder is The cumulative 50% particle diameter (D 50 diameter) was 4.1 ⁇ m, and the SEM diameter / D 50 diameter (primary particle diameter / secondary particle diameter) was 0.57.
  • composition analysis of silver powder is carried out by the same method as in Example 1, carbon content and oxygen content in silver powder are measured, BET specific surface area and tap density (TAP) of silver powder are determined, and accumulation of silver powder 50 %
  • TAP tap density
  • D 50 diameter particle size
  • the content of copper in silver powder is within ⁇ 10% of the content of copper in molten metal
  • the carbon content is 0.002% by mass
  • the oxygen content is 0.041% by mass
  • the BET specific surface area is 0.36 m 2 / g
  • the tap density is 4.1 g / cm 3
  • 50 of the silver powder is accumulated.
  • % ratio of tap density to particle diameter (D 50 diameter) (tAP) (tAP / D 50 diameter) was 1.00g / (cm 3 ⁇ ⁇ m) .
  • Example 3 A small amount of copper was used in the same manner as in Example 1 except that a molten metal (a molten metal of silver containing 238 ppm of copper) in which 24 kg of shot silver and 16 kg of Ag—Cu alloy (containing 595 ppm of copper) were dissolved was used. ) Containing silver powder.
  • the SEM diameter (primary particle diameter) is calculated, the cumulative 50% particle diameter (D 50 diameter) (secondary particle diameter) is measured, and the cumulative 50% particle diameter (D 50 diameter)
  • the SEM diameter (primary particle diameter) of the silver powder is The cumulative 50% particle diameter (D 50 diameter) was 2.9 ⁇ m, and the SEM diameter / D 50 diameter (primary particle diameter / secondary particle diameter) was 0.75.
  • composition analysis of silver powder is carried out by the same method as in Example 1, carbon content and oxygen content in silver powder are measured, BET specific surface area and tap density (TAP) of silver powder are determined, and accumulation of silver powder 50 %
  • TEP tap density
  • D 50 diameter particle size
  • the content of copper in silver powder is within ⁇ 10% of the content of copper in molten metal
  • the carbon content is 0.004% by mass
  • the oxygen content is 0.051% by mass
  • the BET specific surface area is 0.42 m 2 / g
  • the tap density is 4.2 g / cm 3
  • 50 of the silver powder is accumulated.
  • the ratio of tap density (TAP) to% particle diameter (D 50 diameter) (TAP / D 50 diameter) was 1.45 g / (cm 3 ⁇ ⁇ m).
  • Example 4 A small amount of copper was used in the same manner as in Example 1 except that a molten metal (a molten metal of silver containing 253 ppm of copper) in which 25 kg of shot silver and 15 kg of Ag—Cu alloy (containing 675 ppm of copper) were dissolved was used. ) Containing silver powder.
  • a molten metal a molten metal of silver containing 253 ppm of copper
  • Ag—Cu alloy containing 675 ppm of copper
  • the SEM diameter (primary particle diameter) is calculated, the cumulative 50% particle diameter (D 50 diameter) (secondary particle diameter) is measured, and the cumulative 50% particle diameter (D 50 diameter)
  • the SEM diameter (primary particle diameter) of the silver powder is The cumulative 50% particle diameter (D 50 diameter) was 3.1 ⁇ m, and the SEM diameter / D 50 diameter (primary particle diameter / secondary particle diameter) was 0.81.
  • composition analysis of silver powder is carried out by the same method as in Example 1, carbon content and oxygen content in silver powder are measured, BET specific surface area and tap density (TAP) of silver powder are determined, and accumulation of silver powder 50 %
  • TAP tap density
  • D 50 diameter particle size
  • the content of copper in silver powder is within ⁇ 10% of the content of copper in molten metal
  • the carbon content is 0.003% by mass
  • the oxygen content is 0.036% by mass
  • the BET specific surface area is 0.36 m 2 / g
  • the tap density is 5.0 g / cm 3
  • 50 of the silver powder is accumulated.
  • % ratio of tap density to particle diameter (D 50 diameter) (tAP) (tAP / D 50 diameter) was 1.61g / (cm 3 ⁇ ⁇ m) .
  • Example 5 By the same method as Example 1, except that a molten metal (a molten metal of silver containing 370 ppm of copper) in which 18.62 kg of shot silver and 11.38 kg of Ag-Cu alloy (containing 975 ppm of copper) were dissolved was used. Silver powder (containing a small amount of copper) was obtained.
  • a molten metal a molten metal of silver containing 370 ppm of copper
  • Ag-Cu alloy containing 975 ppm of copper
  • the SEM diameter (primary particle diameter) is calculated, the cumulative 50% particle diameter (D 50 diameter) (secondary particle diameter) is measured, and the cumulative 50% particle diameter (D 50 diameter)
  • the SEM diameter (primary particle diameter) of the silver powder is The cumulative 50% particle diameter (D 50 diameter) was 2.8 ⁇ m, and the SEM diameter / D 50 diameter (primary particle diameter / secondary particle diameter) was 0.90.
  • composition analysis of silver powder is carried out by the same method as in Example 1, carbon content and oxygen content in silver powder are measured, BET specific surface area and tap density (TAP) of silver powder are determined, and accumulation of silver powder 50 %
  • TAP tap density
  • D 50 diameter particle size
  • accumulation of silver powder 50 % When the ratio of tap density (TAP) to particle size (D 50 diameter) (TAP / D 50 diameter) was calculated, the content of copper in silver powder is within ⁇ 10% of the content of copper in molten metal
  • the carbon content is 0.004% by mass
  • the oxygen content is 0.049% by mass
  • the BET specific surface area is 0.37 m 2 / g
  • the tap density is 4.7 g / cm 3.
  • % ratio of tap density to particle diameter (D 50 diameter) (tAP) (tAP / D 50 diameter) was 1.68g / (cm 3 ⁇ ⁇ m) .
  • Example 6 By the same method as in Example 1, except that a molten metal (a molten metal of silver containing 375 ppm of copper) in which 6.27 kg of shot silver and 2.43 kg of an Ag—Cu alloy (containing 1343 ppm of copper) were dissolved was used Silver powder (containing a small amount of copper) was obtained.
  • a molten metal a molten metal of silver containing 375 ppm of copper
  • Ag—Cu alloy containing 1343 ppm of copper
  • the SEM diameter (primary particle diameter) is calculated, the cumulative 50% particle diameter (D 50 diameter) (secondary particle diameter) is measured, and the cumulative 50% particle diameter (D 50 diameter)
  • the SEM diameter (primary particle diameter) of the silver powder is The cumulative 50% particle diameter (D 50 diameter) was 3.1 ⁇ m, and the SEM diameter / D 50 diameter (primary particle diameter / secondary particle diameter) was 0.91.
  • composition analysis of silver powder is carried out by the same method as in Example 1, carbon content and oxygen content in silver powder are measured, BET specific surface area and tap density (TAP) of silver powder are determined, and accumulation of silver powder 50 %
  • TAP tap density
  • D 50 diameter particle size
  • accumulation of silver powder 50 % When the ratio of tap density (TAP) to particle size (D 50 diameter) (TAP / D 50 diameter) was calculated, the content of copper in silver powder is within ⁇ 10% of the content of copper in molten metal
  • the carbon content is 0.006% by mass
  • the oxygen content is 0.069% by mass
  • the BET specific surface area is 0.35 m 2 / g
  • the tap density is 4.7 g / cm 3
  • the accumulated 50 of silver powder is % ratio of tap density to particle diameter (D 50 diameter) (tAP) (tAP / D 50 diameter) was 1.52g / (cm 3 ⁇ ⁇ m) .
  • Example 7 By the same method as Example 1, except that a molten metal (a molten metal of silver containing 385 ppm of copper) in which 29.79 kg of shot silver and 10.21 kg of an Ag—Cu alloy (containing 1508 ppm of copper) were dissolved was used Silver powder (containing a small amount of copper) was obtained.
  • a molten metal a molten metal of silver containing 385 ppm of copper
  • an Ag—Cu alloy containing 1508 ppm of copper
  • the SEM diameter (primary particle diameter) is calculated, the cumulative 50% particle diameter (D 50 diameter) (secondary particle diameter) is measured, and the cumulative 50% particle diameter (D 50 diameter)
  • the SEM diameter (primary particle diameter) of the silver powder is The cumulative 50% particle diameter (D 50 diameter) was 2.9 ⁇ m, and the SEM diameter / D 50 diameter (primary particle diameter / secondary particle diameter) was 0.89.
  • composition analysis of silver powder is carried out by the same method as in Example 1, carbon content and oxygen content in silver powder are measured, BET specific surface area and tap density (TAP) of silver powder are determined, and accumulation of silver powder 50 %
  • TEP tap density
  • D 50 diameter particle size
  • the content of copper in silver powder is within ⁇ 10% of the content of copper in molten metal
  • the carbon content is 0.002% by mass
  • the oxygen content is 0.046% by mass
  • the BET specific surface area is 0.36 m 2 / g
  • the tap density is 4.3 g / cm 3
  • 50 of the silver powder is accumulated.
  • the ratio of tap density (TAP) to the% particle size (D 50 diameter) (TAP / D 50 diameter) was 1.48 g / (cm 3 ⁇ ⁇ m).
  • Example 8 The same method as in Example 1 except that a molten metal (a molten metal of silver containing 218 ppm of copper) in which 39.97 kg of shot silver and 0.031 kg of an Ag—Cu alloy (containing 28 mass% of copper) were dissolved was used. Thus, silver powder (containing 220 ppm of copper) was obtained.
  • a molten metal a molten metal of silver containing 218 ppm of copper
  • an Ag—Cu alloy containing 28 mass% of copper
  • the SEM diameter (primary particle diameter) is calculated, the cumulative 50% particle diameter (D 50 diameter) (secondary particle diameter) is measured, and the cumulative 50% particle diameter (D 50 diameter)
  • the SEM diameter (primary particle diameter) of the silver powder is The cumulative 50% particle diameter (D 50 diameter) was 4.3 ⁇ m, and the SEM diameter / D 50 diameter (primary particle diameter / secondary particle diameter) was 0.54.
  • composition analysis of silver powder is carried out by the same method as in Example 1, carbon content and oxygen content in silver powder are measured, BET specific surface area and tap density (TAP) of silver powder are determined, and accumulation of silver powder 50 % was calculated the ratio of tap density to particle diameter (D 50 diameter) (tAP) (tAP / D 50 diameter), the content of copper in the silver powder is 220 ppm, the carbon content is 0.005 wt%, The oxygen content is 0.046% by mass, the BET specific surface area is 0.34 m 2 / g, the tap density is 3.7 g / cm 3 , and the tap density (TAP) relative to the 50% cumulative particle diameter (D 50 diameter) of silver powder The ratio of (TAP / D 50 diameter) was 0.84 g / (cm 3 ⁇ ⁇ m).
  • Example 9 By the same method as Example 1, except that a molten metal (a molten metal of silver containing 257 ppm of copper) in which 31.79 kg of shot silver and 8.21 kg of an Ag—Cu alloy (containing 1252 ppm of copper) were dissolved was used Silver powder (containing 270 ppm copper) was obtained.
  • a molten metal a molten metal of silver containing 257 ppm of copper
  • an Ag—Cu alloy containing 1252 ppm of copper
  • the SEM diameter (primary particle diameter) is calculated, the cumulative 50% particle diameter (D 50 diameter) (secondary particle diameter) is measured, and the cumulative 50% particle diameter (D 50 diameter)
  • the SEM diameter (primary particle diameter) of the silver powder is The cumulative 50% particle diameter (D 50 diameter) was 2.9 ⁇ m, and the SEM diameter / D 50 diameter (primary particle diameter / secondary particle diameter) was 0.89.
  • composition analysis of silver powder is carried out by the same method as in Example 1, carbon content and oxygen content in silver powder are measured, BET specific surface area and tap density (TAP) of silver powder are determined, and accumulation of silver powder 50 % was calculated the ratio of tap density to particle diameter (D 50 diameter) (tAP) (tAP / D 50 diameter), the content of copper in the silver powder is 270 ppm, the carbon content is 0.001 wt%, The oxygen content is 0.042% by mass, the BET specific surface area is 0.37 m 2 / g, the tap density is 4.7 g / cm 3 , and the tap density (TAP) relative to the cumulative 50% particle diameter (D 50 diameter) of silver powder Ratio (TAP / D 50 diameter) was 1.60 g / (cm 3 ⁇ ⁇ m).
  • Example 10 By the same method as in Example 1, except that a molten metal (a molten metal of silver containing 303 ppm of copper) in which 48.00 kg of shot silver and 32.00 kg of an Ag—Cu alloy (containing 757 ppm of copper) were dissolved was used. Silver powder (containing 310 ppm copper) was obtained.
  • a molten metal a molten metal of silver containing 303 ppm of copper
  • an Ag—Cu alloy containing 757 ppm of copper
  • the SEM diameter (primary particle diameter) is calculated, the cumulative 50% particle diameter (D 50 diameter) (secondary particle diameter) is measured, and the cumulative 50% particle diameter (D 50 diameter)
  • the SEM diameter (primary particle diameter) of the silver powder is The cumulative 50% particle diameter (D 50 diameter) was 3.6 ⁇ m, and the SEM diameter / D 50 diameter (primary particle diameter / secondary particle diameter) was 0.76.
  • composition analysis of silver powder is carried out by the same method as in Example 1, carbon content and oxygen content in silver powder are measured, BET specific surface area and tap density (TAP) of silver powder are determined, and accumulation of silver powder 50 % was calculated the ratio of tap density to particle diameter (D 50 diameter) (tAP) (tAP / D 50 diameter), the content of copper in the silver powder is 310 ppm, the carbon content is 0.003 wt%, The oxygen content is 0.042% by mass, the BET specific surface area is 0.35 m 2 / g, the tap density is 4.1 g / cm 3 , and the tap density (TAP) relative to the 50% cumulative particle diameter (D 50 diameter) of silver powder The ratio of (TAP / D 50 diameter) was 1.14 g / (cm 3 ⁇ ⁇ m).
  • Example 11 By the same method as in Example 1, except that a molten metal (a molten metal of silver containing 349 ppm of copper) in which 20.69 kg of shot silver and 19.31 kg of an Ag—Cu alloy (containing 723 ppm of copper) were dissolved was used Silver powder (containing 360 ppm copper) was obtained.
  • the SEM diameter (primary particle diameter) is calculated, the cumulative 50% particle diameter (D 50 diameter) (secondary particle diameter) is measured, and the cumulative 50% particle diameter (D 50 diameter)
  • the SEM diameter (primary particle diameter) of the silver powder is The cumulative 50% particle diameter (D 50 diameter) was 3.3 ⁇ m, and the SEM diameter / D 50 diameter (primary particle diameter / secondary particle diameter) was 0.97.
  • composition analysis of silver powder is carried out by the same method as in Example 1, carbon content and oxygen content in silver powder are measured, BET specific surface area and tap density (TAP) of silver powder are determined, and accumulation of silver powder 50 % was calculated the ratio of tap density to particle diameter (D 50 diameter) (tAP) (tAP / D 50 diameter), the content of copper in the silver powder is 360 ppm, the carbon content is 0.003 wt%, The oxygen content is 0.043% by mass, the BET specific surface area is 0.38 m 2 / g, the tap density is 3.8 g / cm 3 , and the tap density (TAP) relative to the 50% cumulative particle diameter (D 50 diameter) of silver powder The ratio of (TAP / D 50 diameter) was 1.16 g / (cm 3 ⁇ ⁇ m).
  • Example 12 By the same method as in Example 1, except that a molten metal (a molten metal of silver containing 560 ppm of copper) in which 6.00 kg of shot silver and 14.00 kg of Ag-Cu alloy (containing 800 ppm of copper) were dissolved was used Silver powder (containing 620 ppm copper) was obtained.
  • a molten metal a molten metal of silver containing 560 ppm of copper
  • Ag-Cu alloy containing 800 ppm of copper
  • the SEM diameter (primary particle diameter) is calculated, the cumulative 50% particle diameter (D 50 diameter) (secondary particle diameter) is measured, and the cumulative 50% particle diameter (D 50 diameter)
  • the SEM diameter (primary particle diameter) of the silver powder is The cumulative 50% particle diameter (D 50 diameter) was 2.8 ⁇ m, and the SEM diameter / D 50 diameter (primary particle diameter / secondary particle diameter) was 0.84.
  • composition analysis of silver powder is carried out by the same method as in Example 1, carbon content and oxygen content in silver powder are measured, BET specific surface area and tap density (TAP) of silver powder are determined, and accumulation of silver powder 50 % was calculated the ratio of tap density to particle diameter (D 50 diameter) (tAP) (tAP / D 50 diameter), the content of copper in the silver powder is 620 ppm, the carbon content is 0.003 wt%, The oxygen content is 0.057% by mass, the BET specific surface area is 0.38 m 2 / g, the tap density is 4.4 g / cm 3 , and the tap density (TAP) relative to the 50% cumulative particle diameter (D 50 diameter) of silver powder Ratio (TAP / D 50 diameter) was 1.59 g / (cm 3 ⁇ ⁇ m).
  • the SEM diameter (primary particle diameter) is calculated, the cumulative 50% particle diameter (D 50 diameter) (secondary particle diameter) is measured, and the cumulative 50% particle diameter (D 50 diameter)
  • the SEM diameter (primary particle diameter) of the silver powder is The cumulative 50% particle diameter (D 50 diameter) was 9.6 ⁇ m, and the SEM diameter / D 50 diameter (primary particle diameter / secondary particle diameter) was 0.24.
  • composition analysis of silver powder is carried out by the same method as in Example 1, carbon content and oxygen content in silver powder are measured, BET specific surface area and tap density (TAP) of silver powder are determined, and accumulation of silver powder 50 % was calculated the ratio of tap density to particle diameter (D 50 diameter) (tAP) (tAP / D 50 diameter), resulting silver powder is a silver powder containing no Cu, the carbon content is 0.004 mass%
  • the oxygen content is 0.038% by mass
  • the BET specific surface area is 0.35 m 2 / g
  • the tap density is 2.3 g / cm 3
  • the tap density relative to the 50% cumulative particle size (D 50 diameter) of silver powder The ratio of TAP) (TAP / D 50 diameter) was 0.24 g / (cm 3 ⁇ ⁇ m).
  • the silver powder according to the present invention forms an electrode of a solar cell, an internal electrode of a multilayer ceramic electronic component such as an electronic component using low temperature fired ceramic (LTCC) or a multilayer ceramic inductor, an external electrode such as a multilayer ceramic capacitor or a multilayer ceramic inductor
  • LTCC low temperature fired ceramic
  • a multilayer ceramic inductor an external electrode such as a multilayer ceramic capacitor or a multilayer ceramic inductor
  • a highly conductive conductive film can be obtained by utilizing it as a material of the fired conductive paste.
PCT/JP2018/034336 2017-09-29 2018-09-18 銀粉およびその製造方法 WO2019065341A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US16/648,423 US11420256B2 (en) 2017-09-29 2018-09-18 Silver powder and method for producing same
SG11202001993XA SG11202001993XA (en) 2017-09-29 2018-09-18 Silver powder and method for producing same
EP18863425.7A EP3670028A4 (en) 2017-09-29 2018-09-18 SILVER POWDER AND MANUFACTURING METHOD FOR IT
KR1020207011932A KR102430857B1 (ko) 2017-09-29 2018-09-18 은 분말 및 그의 제조 방법
CN201880061178.3A CN111132777B (zh) 2017-09-29 2018-09-18 银粉及其制造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2017189319 2017-09-29
JP2017-189319 2017-09-29
JP2018162411A JP7090511B2 (ja) 2017-09-29 2018-08-31 銀粉およびその製造方法
JP2018-162411 2018-08-31

Publications (1)

Publication Number Publication Date
WO2019065341A1 true WO2019065341A1 (ja) 2019-04-04

Family

ID=65903531

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/034336 WO2019065341A1 (ja) 2017-09-29 2018-09-18 銀粉およびその製造方法

Country Status (2)

Country Link
TW (1) TWI755565B (zh)
WO (1) WO2019065341A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020137329A1 (ja) * 2018-12-26 2020-07-02 昭栄化学工業株式会社 銀ペースト

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007263860A (ja) 2006-03-29 2007-10-11 Dowa Holdings Co Ltd 粉体のタップ密度測定方法およびタップ密度測定装置
JP2009235474A (ja) 2008-03-26 2009-10-15 Dowa Electronics Materials Co Ltd 銀粉の製造方法
JP2013014790A (ja) 2011-06-30 2013-01-24 Mitsui Mining & Smelting Co Ltd 焼結型導電性ペースト用銀粉
JP2017172043A (ja) * 2016-03-16 2017-09-28 Ｄｏｗａエレクトロニクス株式会社 Ａｇ−Ｃｕ合金粉末およびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007263860A (ja) 2006-03-29 2007-10-11 Dowa Holdings Co Ltd 粉体のタップ密度測定方法およびタップ密度測定装置
JP2009235474A (ja) 2008-03-26 2009-10-15 Dowa Electronics Materials Co Ltd 銀粉の製造方法
JP2013014790A (ja) 2011-06-30 2013-01-24 Mitsui Mining & Smelting Co Ltd 焼結型導電性ペースト用銀粉
JP2017172043A (ja) * 2016-03-16 2017-09-28 Ｄｏｗａエレクトロニクス株式会社 Ａｇ−Ｃｕ合金粉末およびその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020137329A1 (ja) * 2018-12-26 2020-07-02 昭栄化学工業株式会社 銀ペースト

Also Published As

Publication number Publication date
TWI755565B (zh) 2022-02-21
TW201920697A (zh) 2019-06-01

Similar Documents

Publication Publication Date Title
JP7090511B2 (ja) 銀粉およびその製造方法
JP7039126B2 (ja) 銅粉およびその製造方法
WO2018123809A1 (ja) 銅粉およびその製造方法
KR102574302B1 (ko) 은 합금 분말 및 그의 제조 방법
JP2010013726A (ja) 導電性ペースト用銅粉及び導電性ペースト
JP2010013730A (ja) 導電性ペースト用銅粉及び導電性ペースト
JP6186197B2 (ja) 銀被覆銅合金粉末およびその製造方法
JP7272834B2 (ja) 銀粉およびその製造方法
JP5932638B2 (ja) 導電性ペースト用銅粉及び導電性ペースト
JP2017082327A (ja) 銀粉およびその製造方法
WO2019065341A1 (ja) 銀粉およびその製造方法
JP7084730B2 (ja) 銀合金粉末およびその製造方法
JP6899275B2 (ja) 銀合金粉末およびその製造方法
JP2012067327A (ja) 導電性ペースト用銅粉及び導電性ペースト
WO2017115462A1 (ja) 銀合金粉末およびその製造方法
JP7136970B2 (ja) りんを含有する銀粉および該銀粉を含む導電性ペースト
JP6722495B2 (ja) 銀被覆銅粉およびその製造方法
WO2017073057A1 (ja) 銀粉およびその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18863425

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2018863425

Country of ref document: EP

Effective date: 20200318

ENP Entry into the national phase

Ref document number: 20207011932

Country of ref document: KR

Kind code of ref document: A