WO2015122251A1 - 銅粉 - Google Patents

銅粉 Download PDF

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Publication number
WO2015122251A1
WO2015122251A1 PCT/JP2015/051512 JP2015051512W WO2015122251A1 WO 2015122251 A1 WO2015122251 A1 WO 2015122251A1 JP 2015051512 W JP2015051512 W JP 2015051512W WO 2015122251 A1 WO2015122251 A1 WO 2015122251A1
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WIPO (PCT)
Prior art keywords
copper powder
plasma
powder
copper
flow rate
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PCT/JP2015/051512
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English (en)
French (fr)
Japanese (ja)
Inventor
晃祐 織田
隆 障子口
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三井金属鉱業株式会社
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=53799999&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2015122251(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 三井金属鉱業株式会社 filed Critical 三井金属鉱業株式会社
Priority to JP2015515066A priority Critical patent/JP5826435B1/ja
Priority to CN201580002507.3A priority patent/CN105705276B/zh
Priority to KR1020167009321A priority patent/KR101671324B1/ko
Publication of WO2015122251A1 publication Critical patent/WO2015122251A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • 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
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/12—Making metallic powder or suspensions thereof using physical processes starting from gaseous material
    • 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
    • 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
    • B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates to a copper powder that can be used as a conductive material for various applications, for example, a copper powder that can be used as a conductive filler in a conductive paste used for forming an electric circuit or forming an external electrode of a ceramic capacitor.
  • a conductive paste in which copper powder, which is a conductive material, is dispersed in a paste is printed on a substrate, the paste is baked or cured to form a circuit.
  • This type of conductive paste is a fluid composition in which a conductive filler is dispersed in a vehicle composed of a resin binder and a solvent, and is widely used for the formation of electric circuits and the formation of external electrodes for ceramic capacitors. Yes.
  • This type of conductive paste includes a resin-curing mold that ensures electrical conduction when a conductive filler is pressed by curing the resin, and a firing mold that ensures electrical conduction when the organic component is volatilized by firing and the conductive filler is sintered. There is.
  • the former resin-curable conductive paste is generally a paste-like composition containing a conductive filler made of metal powder and an organic binder made of a thermosetting resin such as an epoxy resin, and is applied with heat. As a result, the thermosetting resin is cured and shrunk together with the conductive filler, and the conductive fillers are pressure-bonded through the resin so as to be in contact with each other, thereby ensuring conductivity.
  • a resin curable conductive paste can be processed in a relatively low temperature range from 100 ° C. to 200 ° C. and has little thermal damage, so it is used for printed wiring boards and heat-sensitive resin substrates. .
  • the latter fired conductive paste is a paste-like composition in which a conductive filler made of metal powder and glass frit are dispersed in an organic vehicle.
  • the organic vehicle Volatilizes and the conductive filler is sintered to ensure conductivity.
  • the glass frit has a function of adhering the conductive film to the substrate, and the organic vehicle functions as an organic liquid medium for enabling printing of the metal powder and the glass frit.
  • Firing-type conductive paste cannot be used for printed wiring boards or resin materials because of its high firing temperature, but it can be reduced in resistance because it is sintered and the metal is integrated. It is used for external electrodes.
  • copper powder has been frequently used as the conductive filler in both the resin curable conductive paste and the high-temperature fired conductive paste. Since copper powder is inexpensive, migration is unlikely to occur, and solder resistance is excellent, conductive paste using copper powder is being widely used. In recent years, as fine pitches have been advanced in electric circuits and the like, copper powder for conductive paste has been required to be finely divided.
  • Patent Document 1 when reducing copper hydroxide in a liquid to metal copper particles using a reducing agent, hydrazine or a hydrazine compound is used as the reducing agent, and the reduction is performed.
  • a method is disclosed in which the reaction is carried out in the presence of an antifoaming agent, and further, by adding a surface treatment agent before, after or during the reduction reaction, fine copper powder having a minor axis and a major axis both less than 100 nm is obtained. ing.
  • Patent Document 2 as a method for producing fine and uniform copper powder by a wet reduction method, a copper hydroxide slurry obtained by reacting a copper ion-containing aqueous solution and an alkali solution is obtained, and the copper hydroxide slurry is obtained.
  • a first reducing treatment is performed by adding a reducing agent to make a cuprous oxide slurry, the cuprous oxide slurry is allowed to stand to precipitate cuprous oxide particles, the supernatant is removed, and water is added to add sublimation.
  • the first reduction treatment comprises hydroxylation
  • a method for producing copper powder characterized in that a hydrazine as a reducing agent and an aqueous ammonia solution as a pH adjuster are added to a copper slurry in combination.
  • Patent Document 3 discloses a copper powder for conductive paste containing Al (aluminum) and P (phosphorus) as a copper powder capable of adjusting the sintering start temperature even if it is fine,
  • the Al concentration is 0.01 atm% or more and less than 0.80 atm%, and the D50 based on the volume-based particle size distribution measured by the laser diffraction / scattering particle size distribution measurement method is 0.1 ⁇ m to 10 ⁇ m.
  • a copper powder is disclosed.
  • Patent Document 4 a raw material powder (metal powder) is put into a high-frequency plasma flame to evaporate, and surface treatment is performed in the middle of manufacture, whereby the dispersion of copper powder in the solution is achieved by surface treatment with this thermal plasma.
  • a method for improving the properties and obtaining copper powder having a particle size of several nanometers to several tens of nanometers is disclosed.
  • the present invention intends to provide a new copper powder that can ensure excellent electrical conductivity even if it is a fine copper powder.
  • the volume cumulative particle diameter D50 measured by a laser diffraction / scattering particle size distribution analyzer is 0.20 ⁇ m to 0.70 ⁇ m, and the ratio of crystallite diameter to D50 (crystallite diameter / D50) is A copper powder characterized by 0.15 to 0.60 ( ⁇ m / ⁇ m) is proposed.
  • the copper powder proposed by the present invention is a fine copper powder having a D50 of 0.20 ⁇ m to 0.70 ⁇ m, the ratio of the crystallite diameter to the D50 (crystallite diameter / D50) is 0.15. It has a feature that the crystallite diameter is large as ⁇ 0.60 ( ⁇ m / ⁇ m). Thereby, even if the copper powder proposed by the present invention is a fine copper powder, the powder resistance is excellent with low dust resistance, and the coating film formed with the conductive paste using this copper powder is also the same. Excellent conductivity can be obtained. Furthermore, the copper powder proposed by the present invention has excellent dispersibility, and the coating film of the conductive paste using the copper powder of the present invention has excellent smoothness. Therefore, the copper powder proposed by the present invention can be favorably applied as a copper powder for conductive paste used for, for example, a conductor circuit of a printed wiring board, an electrode of a multilayer ceramic capacitor, or the like.
  • the copper powder according to the present embodiment (hereinafter referred to as “the present copper powder”) has a volume cumulative particle diameter D50 measured by a laser diffraction / scattering particle size distribution measuring device of 0.20 ⁇ m to 0.70 ⁇ m, and A copper powder characterized in that the ratio of crystallite diameter to D50 (crystallite diameter / D50) is 0.15 to 0.60 ( ⁇ m / ⁇ m).
  • the D50 of the copper powder that is, the D50 based on the volume-based particle size distribution obtained by measurement by the laser diffraction / scattering particle size distribution measuring method is preferably 0.20 ⁇ m to 0.70 ⁇ m as described above. If the D50 of this copper powder is 0.70 ⁇ m or less, it is possible to easily form fine lines when printing a paste, and if it is 0.20 ⁇ m or more, high aspect printing can be easily performed. It is. Therefore, from this point of view, the D50 of the present copper powder is preferably 0.20 ⁇ m to 0.70 ⁇ m, more preferably 0.21 ⁇ m or more or 0.65 ⁇ m or less, and more preferably 0.22 ⁇ m or more or 0.55 ⁇ m or less. In particular, the thickness is more preferably 0.25 ⁇ m or more or 0.40 ⁇ m or less.
  • the copper powder preferably has a D90 of 0.35 ⁇ m to 12.0 ⁇ m, that is, a volume cumulative particle size D90 measured by a laser diffraction / scattering particle size distribution analyzer. If D90 of this copper powder is 0.35 ⁇ m or more, it is easy to prevent agglomeration when it is made into a paste because the influence of the particle surface energy is small. The dust resistance can be lowered.
  • the D90 of the present copper powder is preferably 0.35 ⁇ m to 12.0 ⁇ m, more preferably 0.38 ⁇ m or more and 9.00 ⁇ m or less, particularly 0.40 ⁇ m or more or 2.00 ⁇ m or less, In particular, the thickness is more preferably 0.50 ⁇ m or more or 0.70 ⁇ m or less.
  • the copper powder preferably has a D10, that is, a volume cumulative particle size D10 measured by a laser diffraction / scattering particle size distribution analyzer of 0.08 ⁇ m to 0.30 ⁇ m.
  • D10 of the present copper powder is 0.08 ⁇ m or more, it is possible to prevent agglomeration of fine particles when kneaded as a conductive paste, and when it is 0.30 ⁇ m or less, the conductive paste has a high particle filling property and low resistance. Can be obtained.
  • the D10 of the present copper powder is preferably 0.08 ⁇ m to 0.30 ⁇ m, more preferably 0.09 ⁇ m or more or 0.28 ⁇ m or less, especially 0.10 ⁇ m or more or 0.26 ⁇ m or less,
  • the thickness is more preferably 0.12 ⁇ m or more or 0.20 ⁇ m or less.
  • ((D90-D10) / D50) is an index indicating the sharpness of the particle size distribution, so if it is in the range of 1.0 to 7.0, the particle size distribution is sufficiently sharp and the conductive paste is printed. Since the variation in dimensions can be controlled when a circuit is formed, it is possible to enjoy benefits such as obtaining a wiring board with excellent impedance control.
  • ((D90-D10) / D50) in the present copper powder is preferably 1.0 to 7.0, more preferably 1.1 or more and 6.0 or less, and particularly preferably 1.2 or more. 3.0 or less, more preferably 1.3 or more or 2.0 or less.
  • DC plasma direct current thermal plasma
  • the ratio of crystallite diameter to D50 is preferably 0.15 to 0.60 ( ⁇ m / ⁇ m). If the crystallite diameter / D50 of the present copper powder is 0.15 ( ⁇ m / ⁇ m) or more, the dust resistance can be further reduced, and if it is 0.60 ( ⁇ m / ⁇ m) or less, the particle shape Can maintain a substantially spherical shape. Therefore, from this viewpoint, the crystallite diameter / D50 of the present copper powder is preferably 0.15 to 0.60 ( ⁇ m / ⁇ m), and more preferably 0.20 ( ⁇ m / ⁇ m) or more, or 0.58 ( ⁇ m).
  • crystallite diameter means an average of crystallite diameters obtained by analyzing a diffraction pattern obtained by powder X-ray diffraction and calculated from a half-value width of a diffraction angle peak on a crystal plane, which is calculated by Scherrer's equation. The value.
  • the copper powder preferably has a ratio of crystallite diameter to average particle diameter (Dsem) of primary particles (crystallite diameter / Dsem) of 0.10 to 0.70 ( ⁇ m / ⁇ m). If the crystallite diameter / Dsem of the present copper powder is 0.10 ( ⁇ m / ⁇ m) or more, the dust resistance can be further reduced, and if it is 0.70 ( ⁇ m / ⁇ m) or less, the particle shape Can maintain a substantially spherical shape. Therefore, from this point of view, the crystallite diameter / Dsem of the present copper powder is preferably 0.10 to 0.70 ( ⁇ m / ⁇ m), especially 0.15 ( ⁇ m / ⁇ m) or more or 0.60 ( ⁇ m).
  • the “average particle size of primary particles” means that copper powder is photographed with a scanning electron microscope (magnification 10,000 times or 30,000 times), and the primary particle size of each particle is measured in terms of a sphere, It means the average value of the obtained sphere-converted primary particle diameter.
  • DC plasma direct current thermal plasma
  • a mixed gas of argon and nitrogen may be used as the gas, and a method of adjusting the plasma flame to be thick and long in a laminar flow state may be employed.
  • a method of adjusting the plasma flame to be thick and long in a laminar flow state may be employed.
  • it is not limited to such a manufacturing method.
  • the crystallite size decreases.
  • the crystallite size can be increased if prepared as described above.
  • the ratio of the oxygen amount (O amount) to the specific surface area (SSA) is preferably 0.10 to 0.40 (wt% ⁇ g / m 2 ). If the ratio of the oxygen amount (O amount) to the specific surface area is 0.10 (wt% ⁇ g / m 2 ) or more, the particle shape can be kept substantially spherical, while 0.40 (wt% ⁇ g / M 2 ) or less, since the oxygen concentration on the particle surface can be lowered, the dust resistance can be kept even lower.
  • the ratio of the oxygen amount (O amount) to the specific surface area of the copper powder is preferably 0.10 to 0.40 (wt% ⁇ g / m 2 ), more preferably 0.15 (wt % ⁇ G / m 2 ) or more or 0.35 (wt% ⁇ g / m 2 ) or less, among which 0.17 (wt% ⁇ g / m 2 ) or more or 0.30 (wt% ⁇ g / m 2) It is even more preferable that:
  • the ratio of the oxygen amount (O amount) to the specific surface area within the above range in order to adjust the ratio of the oxygen amount (O amount) to the specific surface area within the above range, as described above, when the raw copper powder is heated and jetted using a DC plasma device, as a plasma gas, A mixed gas of argon and nitrogen may be used, and the plasma flame may be adjusted to be thick and long in a laminar flow state. However, it is not limited to such a manufacturing method.
  • the particle shape is not particularly limited. However, from the viewpoint of dispersibility, a spherical shape or a substantially spherical shape is preferable. For example, when this copper powder is observed with an electron microscope (for example, 85,000 times), it is preferable that many copper powder particles have a true spherical shape or a substantially true spherical shape. More specifically, 50% by number or more of the copper powder particles constituting the copper powder, especially 80% by number or more, of which 90% by number or more, and of which 95% by number or more (including 100% by number) are spherical or substantially It is preferably spherical.
  • substantially spherical means a shape that is not completely spherical but can be recognized as a sphere.
  • a mixed gas of argon and nitrogen is used as the plasma gas when the raw copper powder is heated and jetted using the DC plasma apparatus.
  • a method of adjusting the plasma flame to be thick and long in a laminar flow state may be employed. However, it is not limited to such a manufacturing method.
  • the copper powder is preferably a flaky particle obtained by processing the spherical particle or the substantially spherical particle, and the spherical or substantially spherical particle and the flaky particle.
  • a mixed product is also preferred.
  • this copper powder is made of Si, P, Ni, Ti, Fe, Co, Cr, Mg, Mn, Mo, W, Ta, In, Zr, Nb, B, Ge, Sn, Zn, Bi, etc. You may contain the element component of at least 1 or more types of them. By containing these, various properties required for the conductive paste can be adjusted, for example, by improving the sinterability by lowering the melting point.
  • the compacting resistance of the copper powder is 1.0 ⁇ 10 ⁇ 1 ⁇ ⁇ cm or less, especially 5.0 ⁇ 10 ⁇ 2 ⁇ ⁇ cm or less, and more preferably 1.0 ⁇ 10 ⁇ 2 ⁇ ⁇ cm or less. preferable. Since the contact resistance between particles can be kept low as long as the powder resistance of the present copper powder is within the range, it can be made excellent in conductivity when made into a conductive paste.
  • the plasma flame may be adjusted to be thick and long in a laminar flow state. However, it is not limited to such a manufacturing method.
  • This copper powder is adjusted so that the plasma flame becomes thick and long in a laminar flow state while using a mixed gas of argon and nitrogen as a plasma gas when the raw copper powder is heated and jetted using a DC plasma apparatus.
  • a mixed gas of argon and nitrogen as a plasma gas when the raw copper powder is heated and jetted using a DC plasma apparatus.
  • it can be manufactured. However, it is not limited to such a manufacturing method.
  • the aspect ratio of the frame length to the frame width (hereinafter referred to as the frame aspect ratio). ) Is 3 or more. If the frame aspect ratio is 3 or more, a laminar flow state can be determined.
  • a plasma device including a powder supply device 2, a chamber 3, a DC plasma torch 4, a recovery pot 5, a powder supply nozzle 6, a gas supply device 7, and a pressure adjustment device 8. 1 can be mentioned.
  • the raw material powder passes through the DC plasma torch 4 from the powder supply apparatus 2 through the powder supply nozzle 6.
  • the plasma torch 4 is supplied with a mixed gas of argon and nitrogen from the gas supply device 7 to generate a plasma flame. Further, in the plasma flame generated by the DC plasma torch 4, the raw material powder is gasified, released into the chamber 3, cooled, and then accumulated and collected in the collection pot 5 as a fine powder.
  • the interior of the chamber 3 is controlled by the pressure adjusting device 8 so as to maintain a negative pressure relative to the powder supply nozzle 6 and has a structure that stably generates a plasma flame.
  • this is an example of a DC plasma apparatus, and is not limited to such an apparatus.
  • the raw material copper powder is not particularly limited.
  • the particle size (D50) of the raw material copper powder is preferably 3.0 ⁇ m to 30 ⁇ m, and more preferably 5.0 ⁇ m or more or 15 ⁇ m or less.
  • the shape of the raw material copper powder is not particularly limited, such as a dendritic shape, a rod shape, a flake shape, a cubic shape, or a spherical shape or a substantially spherical shape.
  • it is preferably spherical or substantially spherical.
  • the raw material copper powder can be instantly evaporated in the plasma flame and supply sufficient energy in the plasma flame, so that nucleation and aggregation toward the plasma tail flame part
  • condensation occurs to form fine particles, in particular, submicron order fine particles.
  • the plasma output of the direct-current thermal plasma apparatus is preferably 2 kW to 30 kW, and more preferably 4 kW or more or 15 kW or less.
  • the gas flow rate of the plasma gas is preferably 0.1 L / min to 20 L / min from the above viewpoint, and more preferably 0.5 L / min or more or 18 L / min or less.
  • the above-described plasma output and gas flow rate ranges are maintained, and the Ar gas flow rate (B) and the N 2 gas flow rate (C) with respect to the plasma output (A).
  • the value calculated by the formula (B + C) / A (unit: L / (min ⁇ kW)) is more preferably 0.50 or more and 2.00 or less.
  • the (B + C) / A value is preferably 0.50 or more, and 2.00 or less in order to keep the plasma flame stable in a laminar flow. Is preferable. From this additional point, it is particularly preferable that (B + C) / A is adjusted to be 0.70 or more or 1.70 or less, and among them, adjustment is made to be 0.75 or more or 1.50 or less. Further preferred.
  • a mixed gas of argon and nitrogen as the working gas for generating the thermal plasma.
  • argon gas and nitrogen gas are mixed
  • larger vibration energy (thermal energy) can be imparted to the copper powder particles by the nitrogen (diatomic molecule) gas, and the aggregation state can be made uniform. Therefore, nanoparticles with a sharper particle size distribution can be obtained.
  • the content of nitrogen is too large, the plasma flame is reduced, and a powder having a sharp particle size distribution cannot be obtained.
  • the ratio of argon and nitrogen in the plasma gas is preferably 99: 1 to 10:90 in terms of flow ratio, particularly 95: 5 to 60:40, and more preferably 95: 5 to 80:20. Is more preferable.
  • the ratio of argon to nitrogen is 99: 1 to 50:50 in flow rate ratio, and particularly 95: 5. It is preferable to adjust within a ratio in which the flow rate of argon is larger than that of nitrogen, such as ⁇ 50: 50.
  • the copper powder obtained as described above can be used as it is, but it is more desirable to classify it in order to remove coarse agglomerated particles and foreign substances present as contamination.
  • coarse powder and fine powder may be separated using an appropriate classifier so that the target particle size becomes the center.
  • this copper powder can be used as it is, it can also be used after the copper powder is subjected to shape processing.
  • a spherical particle powder (powder consisting of 80% or more of spherical particles) is mechanically processed into non-spherical particle powders such as flakes, scales, and flat plates (: 80% or more of non-spherical particles) Powder).
  • flaky particle powder (: 80% or more from flaky particles) is mechanically flattened (rolled or stretched) using a bead mill, ball mill, attritor, vibration mill or the like. Shape powder).
  • a fatty acid such as stearic acid or an auxiliary agent such as a surfactant.
  • an auxiliary agent such as a surfactant.
  • the copper powder which carried out such shape processing can also be utilized, and the original powder which is not shape-processed and this can also be mixed and utilized.
  • the present copper powder is suitable as a conductive filler used alone or in combination with other copper powder such as flake powder, for example, in either a resin-cured conductive paste or a fired conductive paste. Moreover, if a coating film is produced from the paste using this copper powder, a coating film having high conductivity and high smoothness can be produced. This is thought to be due to the fact that the present copper powder has very high crystallinity, so that there are few crystal grain boundaries that can be an inhibitor of electrical conduction or an inducer of oxidative aggregation.
  • this copper powder alone or mixed with other copper powder such as this copper powder and flake powder, and blended with an organic binder made of a thermosetting resin such as epoxy resin, for example, to give a resin-curable conductive paste It can also be prepared.
  • the present copper powder alone or mixed with other copper powder such as the present copper powder and flake powder and blended in an organic vehicle to prepare a fired conductive paste.
  • the conductive paste using the present copper powder or mixed powder containing the present copper powder as a conductive filler is, for example, various electrical contact members for forming a conductive circuit by a screen printing additive method or for an external electrode of a multilayer ceramic capacitor. It can be suitably used as a conductive paste.
  • this copper powder or mixed powder containing this copper powder is used for internal electrodes of multilayer ceramic capacitors, electrodes of chip components such as inductors and resistors, single plate capacitor electrodes, tantalum capacitor electrodes, conductor circuits of resin multilayer boards, ceramics (LTCC) Conductor circuit of multilayer substrate, flexible printed circuit board (FPC) conductor circuit, antenna switch module circuit, module circuit such as PA module circuit and high frequency active filter, electromagnetic wave for PDP front and back plates and PDP color filter Shielding film, crystalline solar cell surface electrode and back surface extraction electrode, conductive adhesive, EMI shield, RF-ID, membrane switch such as PC keyboard, anisotropic conductive film (ACF / ACP), electronic component and semiconductor Conductive materials such as bonding materials and circuit repair paste It is possible to use.
  • LTCC ceramics
  • FPC flexible printed circuit board
  • antenna switch module circuit module circuit such as PA module circuit and high frequency active filter
  • electromagnetic wave for PDP front and back plates and PDP color filter Shielding film electromagnetic wave for PDP front and
  • copper powder was produced according to the following using a DC plasma fine powder production apparatus. Copper powder (particle size: 10 ⁇ m, spherical particles) is introduced as a raw material powder from the raw material powder supply port, and at a raw material supply rate of 10 g / min, an Ar flow rate of 13.0 L / min and an N 2 flow rate of 0.7 L / min Plasma gas was supplied to the inside of the plasma flame (in other words, plasma flame). At this time, the ratio of the Ar flow rate (B) to the N 2 flow rate (C) was 95: 5.
  • the copper powder thus obtained was accumulated in a collection pot, and after the production batch was gently opened to the atmosphere, the copper powder (sample) was collected.
  • the plasma frame is photographed from the side where the frame width is observed to be the thickest, binarized, and the aspect ratio of the frame length to the frame width (Frame aspect ratio) was measured (the same applies to Examples and Comparative Examples described later. As a result, it was confirmed that the generated plasma flame had a frame aspect ratio of 4 and was laminar.
  • Example 2 In Example 1, the plasma output (A), the Ar flow rate (B), and the N 2 flow rate (C) were adjusted as shown in Table 1, respectively, and the gas ratio between the Ar flow rate (B) and the N 2 flow rate (C) was adjusted. Was changed to 90:10, and copper powder (sample) was obtained in the same manner as in Example 1. At this time, the generated plasma flame had a flame aspect ratio of 5 and was a laminar flow.
  • Example 3 In Example 1, the plasma output (A), the Ar flow rate (B), and the N 2 flow rate (C) were adjusted as shown in Table 1, respectively, and the gas ratio between the Ar flow rate (B) and the N 2 flow rate (C) was adjusted.
  • a copper powder (sample) was obtained in the same manner as in Example 1 except that the ratio was 85:15. At this time, the generated plasma flame had a flame aspect ratio of 7, and was a laminar flow.
  • Example 4 In Example 1, the plasma output (A), the Ar flow rate (B), and the N 2 flow rate (C) were adjusted as shown in Table 1, respectively, and the gas ratio between the Ar flow rate (B) and the N 2 flow rate (C) was adjusted.
  • a copper powder (sample) was obtained in the same manner as in Example 1 except that the ratio was 80:20. At this time, the generated plasma flame had a flame aspect ratio of 8 and was a laminar flow.
  • Example 5 In Example 1, the plasma output (A), the Ar flow rate (B), and the N 2 flow rate (C) were adjusted as shown in Table 1, respectively, and the gas ratio between the Ar flow rate (B) and the N 2 flow rate (C) was adjusted.
  • a copper powder (sample) was obtained in the same manner as in Example 1 except that the ratio was set to 70:30. At this time, the generated plasma flame had a flame aspect ratio of 7, and was a laminar flow.
  • Example 6 In Example 1, the plasma output (A), the Ar flow rate (B), and the N 2 flow rate (C) were adjusted as shown in Table 1, respectively, and the gas ratio between the Ar flow rate (B) and the N 2 flow rate (C) was adjusted.
  • a copper powder (sample) was obtained in the same manner as in Example 1 except that the ratio was set to 60:40. At this time, the generated plasma flame had a flame aspect ratio of 6 and was a laminar flow.
  • Example 7 In Example 1, the plasma output (A), the Ar flow rate (B), and the N 2 flow rate (C) were adjusted as shown in Table 1, respectively, and the gas ratio between the Ar flow rate (B) and the N 2 flow rate (C) was adjusted.
  • a copper powder (sample) was obtained in the same manner as in Example 1 except that the ratio was 40:60. At this time, the generated plasma flame had a flame aspect ratio of 4 and was a laminar flow.
  • Example 8 In Example 1, the plasma output (A), the Ar flow rate (B), and the N 2 flow rate (C) were adjusted as shown in Table 1, respectively, and the gas ratio between the Ar flow rate (B) and the N 2 flow rate (C) was adjusted.
  • a copper powder (sample) was obtained in the same manner as in Example 1 except that the ratio was 10:90. At this time, the generated plasma flame had a flame aspect ratio of 3 and was a laminar flow.
  • Example 1 ⁇ Comparative Example 1>
  • the plasma output (A), the Ar flow rate (B), and the N 2 flow rate (C) were adjusted as shown in Table 1, respectively, and the gas ratio between the Ar flow rate (B) and the N 2 flow rate (C).
  • a copper powder (sample) was obtained in the same manner as in Example 1 except that was changed to 100: 0. At this time, the generated plasma flame was turbulent and was in an unstable state in which the flame shook from side to side.
  • Copper powder (sample) was obtained by the wet reduction method as follows. To 6.5 L of pure water at 65 ° C., copper sulfate pentahydrate was added and stirred so that the concentration of copper was 3.7 mol / L, and then 0.61 mmol of pyrophosphoric acid with respect to 1 mol of copper. Sodium was added and stirring was continued for 30 minutes to obtain a copper-containing aqueous solution. While stirring this aqueous solution, 0.88 mol of ammonia water with respect to 1 mol of copper and 0.87 mol of sodium hydroxide with respect to 1 mol of copper were simultaneously added to the aqueous solution, and cupric oxide was added to the solution. Generated.
  • BET specific surface area Using monosorb (trade name) manufactured by Yuasa Ionics Co., Ltd., “6.2 Flow Method (3.5)” in JIS R1626-1996 (Method for Measuring Specific Surface Area by Gas Adsorption BET Method of Fine Ceramics Powder)
  • the BET specific surface area (SSA) was measured according to “one-point method”. At that time, a mixed gas of helium as a carrier gas and nitrogen as an adsorbate gas was used.
  • Dust Resistance A dust resistance value was measured using a dust resistance measurement system (PD-41 manufactured by Mitsubishi Chemical Analytic Co., Ltd.) and a resistivity meter (MCP-T600 manufactured by Mitsubishi Chemical Analytic Co., Ltd.). 5 g of copper powder (sample) was put into the probe cylinder, and the probe unit was set on PD-41. The resistance value when a load of 18 kN was applied by a hydraulic jack was measured using a resistivity meter. From the measured resistance value and sample thickness, the volume resistivity (dust resistance) was calculated.
  • PD-41 dust resistance measurement system
  • MCP-T600 manufactured by Mitsubishi Chemical Analytic Co., Ltd.
  • ethyl cellulose polymer Etocel manufactured by Nisshin Kasei Co., Ltd.
  • ARE-500 manufactured by Sinky Corporation
  • Conductivity evaluation coating film formation The paste A thus prepared was applied onto a slide glass substrate with an gap of 35 ⁇ m using an applicator. Then, after heat-drying at 150 degreeC for 10 minute (s) in nitrogen oven, it further baked at 300 degreeC for 1 hour in nitrogen oven, and produced the coating film.
  • Coating film smoothness evaluation The same method as the paste A was adopted except that 20 g of copper powder, 1.9 g of ethyl cellulose polymer (Ethcel, manufactured by Nisshin Kasei Co., Ltd.) and 11.7 g of terpineol were weighed. (The paste thus obtained is referred to as paste B.)
  • the copper powder of the examples has a ratio of crystallite diameter to D50 (crystallite diameter / D50) of 0.15 to 0.60 ( ⁇ m / Even if fine copper powder with a large crystallite diameter such as D50 of 0.20 ⁇ m to 0.70 ⁇ m has a large crystallite diameter, conductive pastes using these copper powders are It turned out that it is excellent in electroconductivity and smoothness.

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  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017122252A (ja) * 2016-01-05 2017-07-13 Ｄｏｗａエレクトロニクス株式会社 表面処理銅粉およびその製造方法
JP2017179428A (ja) * 2016-03-29 2017-10-05 Ｄｏｗａエレクトロニクス株式会社 導電性材料、導電膜の形成方法、回路基板、半導体装置及び半導体装置の製造方法
JP2019065390A (ja) * 2017-10-03 2019-04-25 三井金属鉱業株式会社 粒子の製造方法
KR20190132351A (ko) 2017-03-31 2019-11-27 미쓰이금속광업주식회사 구리 입자 및 그 제조 방법
WO2021060126A1 (ja) * 2019-09-25 2021-04-01 Ｄｏｗａエレクトロニクス株式会社 接合材、接合材の製造方法、接合方法及び半導体装置
WO2021100595A1 (ja) * 2019-11-22 2021-05-27 東邦チタニウム株式会社 銅粉体とその製造方法
WO2021199512A1 (ja) 2020-03-31 2021-10-07 三井金属鉱業株式会社 銅粒子及びその製造方法
WO2022185600A1 (ja) * 2021-03-02 2022-09-09 三井金属鉱業株式会社 導電性組成物、導電性部材及びその製造方法
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WO2020027874A2 (en) * 2018-03-05 2020-02-06 Global Advanced Metals Usa, Inc. Spherical tantalum powder, products containing the same, and methods of making the same
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005154861A (ja) * 2003-11-27 2005-06-16 Mitsui Mining & Smelting Co Ltd 二層コート銅粉及びその二層コート銅粉の製造方法並びにその二層コート銅粉を用いた導電性ペースト
JP2005314755A (ja) * 2004-04-28 2005-11-10 Mitsui Mining & Smelting Co Ltd フレーク銅粉及びその製造方法並びに導電性ペースト
JP2006169559A (ja) * 2004-12-14 2006-06-29 Sumitomo Metal Mining Co Ltd 銅合金微粒子とその製造方法
JP2010018880A (ja) * 2008-04-01 2010-01-28 Dowa Electronics Materials Co Ltd 導電性ペースト用銅粉およびその製造方法
JP2012126942A (ja) * 2010-12-14 2012-07-05 Jx Nippon Mining & Metals Corp 球状銅微粉及びその製造方法
JP2014001443A (ja) * 2012-06-21 2014-01-09 Kyoritsu Kagaku Sangyo Kk 酸化物被覆銅微粒子及びその製造方法
JP2014034697A (ja) * 2012-08-08 2014-02-24 Furukawa Co Ltd 銅微粒子の製造方法、導電性ペーストおよび導電性ペーストの製造方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6156209A (ja) * 1984-08-27 1986-03-20 Natl Res Inst For Metals 貴金属超微粒子の製造法
JP3254278B2 (ja) * 1992-12-09 2002-02-04 高周波熱錬株式会社 混合／複合超微粒子製造方法及びその製造装置
JP4196500B2 (ja) * 1999-09-20 2008-12-17 堺化学工業株式会社 微細球状金属粉末の製造方法
JP2002220601A (ja) * 2001-01-29 2002-08-09 Hitachi Metals Ltd Ｄｃ熱プラズマ処理による低酸素球状金属粉末の製造方法
JP4204849B2 (ja) 2002-11-12 2009-01-07 Ｄｏｗａエレクトロニクス株式会社 微粒子銅粉の製法
JP4145127B2 (ja) * 2002-11-22 2008-09-03 三井金属鉱業株式会社 フレーク銅粉及びそのフレーク銅粉の製造方法並びにそのフレーク銅粉を用いた導電性ペースト
JP4149353B2 (ja) * 2003-10-28 2008-09-10 三井金属鉱業株式会社 二層コート金属粉及びその二層コート金属粉の製造方法並びにその二層コート金属粉を用いた導電性ペースト
JP5144022B2 (ja) 2006-03-24 2013-02-13 三井金属鉱業株式会社 銅粉の製造方法及びその製造方法で得られた銅粉
JP4687599B2 (ja) * 2006-07-26 2011-05-25 住友金属鉱山株式会社 銅微粉とその製造方法及び導電性ペースト
JP5052291B2 (ja) 2006-11-02 2012-10-17 株式会社日清製粉グループ本社 合金超微粒子、およびその製造方法
JP4697643B2 (ja) * 2009-09-07 2011-06-08 福田金属箔粉工業株式会社 電解銅粉の集合体及び該電解銅粉の製造方法
KR101143890B1 (ko) * 2009-12-18 2012-05-11 인하대학교 산학협력단 이송식 또는 비이송식 플라즈마 장치를 이용한 벌크 구리로부터 구리 나노분말의 제조방법
JP2012067327A (ja) 2010-09-21 2012-04-05 Mitsui Mining & Smelting Co Ltd 導電性ペースト用銅粉及び導電性ペースト
TWI544977B (zh) * 2011-09-09 2016-08-11 同和電子科技有限公司 導電性糊用銅粉及其製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005154861A (ja) * 2003-11-27 2005-06-16 Mitsui Mining & Smelting Co Ltd 二層コート銅粉及びその二層コート銅粉の製造方法並びにその二層コート銅粉を用いた導電性ペースト
JP2005314755A (ja) * 2004-04-28 2005-11-10 Mitsui Mining & Smelting Co Ltd フレーク銅粉及びその製造方法並びに導電性ペースト
JP2006169559A (ja) * 2004-12-14 2006-06-29 Sumitomo Metal Mining Co Ltd 銅合金微粒子とその製造方法
JP2010018880A (ja) * 2008-04-01 2010-01-28 Dowa Electronics Materials Co Ltd 導電性ペースト用銅粉およびその製造方法
JP2012126942A (ja) * 2010-12-14 2012-07-05 Jx Nippon Mining & Metals Corp 球状銅微粉及びその製造方法
JP2014001443A (ja) * 2012-06-21 2014-01-09 Kyoritsu Kagaku Sangyo Kk 酸化物被覆銅微粒子及びその製造方法
JP2014034697A (ja) * 2012-08-08 2014-02-24 Furukawa Co Ltd 銅微粒子の製造方法、導電性ペーストおよび導電性ペーストの製造方法

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017122252A (ja) * 2016-01-05 2017-07-13 Ｄｏｗａエレクトロニクス株式会社 表面処理銅粉およびその製造方法
JP2017179428A (ja) * 2016-03-29 2017-10-05 Ｄｏｗａエレクトロニクス株式会社 導電性材料、導電膜の形成方法、回路基板、半導体装置及び半導体装置の製造方法
KR20190132351A (ko) 2017-03-31 2019-11-27 미쓰이금속광업주식회사 구리 입자 및 그 제조 방법
JP2019065390A (ja) * 2017-10-03 2019-04-25 三井金属鉱業株式会社 粒子の製造方法
JP7194544B2 (ja) 2017-10-03 2022-12-22 三井金属鉱業株式会社 粒子の製造方法
WO2021060126A1 (ja) * 2019-09-25 2021-04-01 Ｄｏｗａエレクトロニクス株式会社 接合材、接合材の製造方法、接合方法及び半導体装置
WO2021100595A1 (ja) * 2019-11-22 2021-05-27 東邦チタニウム株式会社 銅粉体とその製造方法
JP2021080549A (ja) * 2019-11-22 2021-05-27 東邦チタニウム株式会社 銅粉体とその製造方法
WO2021199512A1 (ja) 2020-03-31 2021-10-07 三井金属鉱業株式会社 銅粒子及びその製造方法
WO2022185600A1 (ja) * 2021-03-02 2022-09-09 三井金属鉱業株式会社 導電性組成物、導電性部材及びその製造方法
WO2023074827A1 (ja) * 2021-10-28 2023-05-04 三井金属鉱業株式会社 銅粒子及びその製造方法

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