WO2015060258A1 - Poudre de cuivre recouverte d'argent - Google Patents

Poudre de cuivre recouverte d'argent Download PDF

Info

Publication number
WO2015060258A1
WO2015060258A1 PCT/JP2014/077851 JP2014077851W WO2015060258A1 WO 2015060258 A1 WO2015060258 A1 WO 2015060258A1 JP 2014077851 W JP2014077851 W JP 2014077851W WO 2015060258 A1 WO2015060258 A1 WO 2015060258A1
Authority
WO
WIPO (PCT)
Prior art keywords
silver
copper powder
coated copper
coated
concentration
Prior art date
Application number
PCT/JP2014/077851
Other languages
English (en)
Japanese (ja)
Inventor
卓 藤本
康成 脇森
林　富雄
Original Assignee
三井金属鉱業株式会社
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
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 JP2015538205A priority Critical patent/JP6278969B2/ja
Publication of WO2015060258A1 publication Critical patent/WO2015060258A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—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
    • B22F1/17—Metallic particles coated with 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
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a silver-coated copper powder that can be suitably used as a conductive material such as a conductive paste.
  • the conductive paste is a fluid composition in which conductive powder is dispersed in a vehicle composed of a resin binder and a solvent, and the formation of an electric circuit, the formation of an external electrode of a ceramic capacitor, the formation of an electromagnetic shielding film, Widely used for forming bonding films.
  • This type of conductive paste has a resin-cured type in which conductive powder is pressure-bonded by curing the resin to ensure conduction, and an organic component is volatilized by firing to sinter the conductive powder to ensure conduction. It is classified as a firing mold.
  • the former resin-curable conductive paste is generally a paste-like composition containing conductive powder made of metal powder and an organic binder made of thermosetting resin such as epoxy resin, and applies heat.
  • thermosetting resin is cured and shrunk together with the conductive powder, and the conductive powder is pressed and brought into contact with each other through the resin, thereby ensuring conductivity.
  • This 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 can be used for printed wiring boards, heat-sensitive resin substrates, electromagnetic shielding films, bonding films, etc. Mainly used.
  • the latter fired conductive paste is a paste-like composition in which conductive powder (metal powder) and glass frit are generally dispersed in an organic vehicle, and is fired at 500 to 900 ° C. Conductivity is ensured by volatilization of the organic vehicle and sintering of the conductive powder. At this time, 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.
  • silver Since silver is excellent in conductivity, it is used as a main constituent material of various conductive materials such as anisotropic conductive films, conductive pastes, and conductive adhesives.
  • a silver paste can be mixed with a binder and a solvent to form a conductive paste, and a circuit pattern can be printed on the substrate using this conductive paste and baked to form a printed wiring board or an electric circuit of an electronic component. it can.
  • Patent Document 1 discloses a silver compound-coated copper powder obtained by coating the surface of silver-coated copper particles as a core material with a silver compound of silver oxide, silver carbonate, and organic acid silver, and SSA (M 3 / g) is 0.1 to 10.0, D50 ( ⁇ m) is 0.5 to 10.0, and a silver compound is adhered to the particle surface at a rate of 1 wt% to 40 wt%.
  • Silver compound-coated copper powder is disclosed.
  • a method of coating the surface of the copper powder particles with silver there can be mentioned two types, a reduction plating coating method and a displacement plating coating.
  • the reduction plating coating method is a method in which fine particles of silver reduced with a reducing agent are densely coated on the surface of copper powder particles.
  • Patent Document 2 discloses metallic copper in an aqueous solution in which a reducing agent is dissolved.
  • a method for producing a silver-coated copper powder in which powder and silver nitrate are reacted is proposed.
  • the displacement plating coating method silver ions exchange electrons with metallic copper at the interface of copper powder particles, silver ions are reduced to metallic silver, and instead metallic copper is oxidized into copper ions. That is, a method in which the surface layer of the copper powder particles is a silver layer.
  • the surface layer of the copper powder particles is a silver layer.
  • Patent Document 3 silver is exchanged between silver ions and metallic copper in an organic solvent-containing solution in which silver ions are present. A method for producing silver-coated copper powder for coating the surface of copper particles is described.
  • Patent Document 4 a dendrite-like conductive powder having a silver layer on the surface of the copper powder particles, the silver content being 3.0 to A dendritic conductive powder characterized by 30.0% by mass has been proposed.
  • silver covering copper powder which consists of silver covering copper powder particle which exhibits the dendritic shape by which the copper powder particle surface is coat
  • BET specific surface area measured by the BET single point method to the surface area
  • Patent Document 6 a silver-coated copper powder composed of silver-coated copper powder particles whose surface is coated with silver, and the silver-coated copper powder particles were observed using a scanning electron microscope (SEM). At this time, it is provided with one main shaft, a plurality of branches obliquely branch from the main shaft, exhibiting a dendritic shape grown two-dimensionally or three-dimensionally, and the thickness a of the main shaft is 0.3 ⁇ m.
  • Silver powder characterized by containing silver-coated copper powder particles having a dendrite shape with a length b of the longest branch extending from the main axis of 0.6 to 10.0 ⁇ m. Coated copper powder has been proposed.
  • the present invention relates to a silver-coated copper powder composed of silver-coated copper powder particles having a structure in which the surface of the copper powder particles obtained by the electrolytic method is coated with silver or a silver alloy. It is intended to provide a new silver-coated copper powder that can enhance the properties.
  • the present invention is a silver-coated copper powder containing silver-coated copper powder particles having a structure in which the surface of copper powder particles obtained by an electrolytic method is coated with silver or a silver alloy, and the concentration of chlorine is 5 wtppm to Ratio of total Cu concentration ( ⁇ Cu) and silver concentration ( ⁇ Ag) of Cu, CuO and Cu 2 O on the surface of the silver-coated copper powder particles, which is 250 wtppm and measured by X-ray photoelectron spectroscopy
  • a silver-coated copper powder characterized in that ( ⁇ Cu / ⁇ Ag) is 0.12 or less is proposed.
  • the silver-coated copper powder proposed by the present invention is a silver-coated copper powder containing silver-coated copper powder particles having a structure in which the surface of the copper powder particles obtained by the electrolytic method is coated with silver or a silver alloy.
  • the conductivity can be effectively increased even if chlorine is contained. Became. Therefore, the silver-coated copper powder proposed by the present invention can be used particularly effectively as a material such as a conductive paste.
  • Silver-coated copper powder according to the present embodiment is a silver-coated copper powder particle having a structure in which the surface of a copper powder particle as a core material is coated with silver or a silver alloy ( (Referred to as “silver-coated copper powder particles”).
  • the copper powder particles as the core material may be copper powder particles obtained by an electrolytic method.
  • spherical copper powder particles are also included.
  • the core material particles are preferably copper powder particles exhibiting a dendrite shape.
  • the shape of the silver-coated copper powder particles is not particularly limited.
  • various shapes such as a spherical shape, a substantially spherical shape, an elliptical granular shape, a substantially elliptical spherical shape, a prismatic shape, a bowl shape, a plate shape, a flake shape, a needle shape, and a dendrite shape may be used.
  • the silver-coated copper powder particles have a dendritic shape, the number of contacts between the particles is large, and excellent conductivity can be obtained.
  • the conductive powder particles contained in the conductive paste have a dendritic shape
  • the number of contact points between the particles is larger than that of the spherical particles, so that even if the amount of the conductive powder is reduced, the conductive powder particles are conductive.
  • the characteristics can be enhanced. Therefore, it is preferable that the silver-coated copper powder particles have a dendrite shape.
  • the “dendritic shape” is provided with a single main axis when observed with an electron microscope (500 to 20,000 times), and a plurality of main axes from the main axis.
  • the branches are vertically or obliquely branched to form a shape grown two-dimensionally or three-dimensionally.
  • the main axis refers to a rod-like portion that is a group from which a plurality of branches are branched.
  • the thickness a of the main axis is preferably 0.3 ⁇ m to 5.0 ⁇ m, more preferably 0.4 ⁇ m or more or 4.5 ⁇ m or less, and particularly preferably 0.5 ⁇ m or more or 4.0 ⁇ m or less. If the thickness a of the main axis in the dendrite is 0.3 ⁇ m or more, the main axis is firm and the branches are likely to grow. On the other hand, if the thickness is 5.0 ⁇ m or less, the particles are not likely to aggregate. Can be prevented.
  • the longest branch length b (referred to as “branch length b”) among the branches extending from the main axis indicates the degree of dendrite growth, and is preferably 0.7 ⁇ m to 12.0 ⁇ m. 0.0 ⁇ m or more or 10.0 ⁇ m or less, more preferably 1.2 ⁇ m or more or 8.0 ⁇ m or less. If the branch length b is 0.7 ⁇ m or more, the dendrite is sufficiently grown, and it is possible to enjoy the effect that the conductivity can be increased with a small amount. On the other hand, if the branch length b is 12.0 ⁇ m or less, the present Since the fluidity
  • the number of branches with respect to the major axis L of the main axis indicates the number of dendrite branches, and is preferably 0.5 / ⁇ m to 4.0 / ⁇ m. .6 / ⁇ m or more or 3.5 / ⁇ m or less, more preferably 0.8 / ⁇ m or more or 3.0 / ⁇ m or less. If the number of branches / major axis L is 0.5 / ⁇ m or more, the number of branches is sufficiently large and sufficient contact can be secured, while if the number of branches / major axis L is 4.0 / ⁇ m or less, It can prevent that the fluidity
  • the silver-coated copper powder particles as described above are preferably 80% by number or more of the total copper powder particles, preferably As long as it occupies 90% by number or more, it may contain non-dendritic silver-coated copper powder particles that are not recognized as dendritic.
  • the average value of the main axis thickness a in the particles recognized as dendritic particles is preferably 0.5 ⁇ m to 4.0 ⁇ m, and more preferably 1.0 ⁇ m or more. Alternatively, it is preferably 3.0 ⁇ m or less, more preferably 1.2 ⁇ m or more or 2.0 ⁇ m or less.
  • the average branch length b in the particles recognized as dendrite-like particles is preferably 0.7 ⁇ m to 8.0 ⁇ m, and more preferably 3.0 ⁇ m or more or 6.0 ⁇ m.
  • the thickness is particularly preferably 2.0 ⁇ m or more and 4.0 ⁇ m or less.
  • the average value of the number of branches / major axis length L is preferably 1.0 to 4.0 / ⁇ m, and more preferably 1.5 / ⁇ m or more or 3.0 / ⁇ m or less. More preferably, it is 7 pieces / ⁇ m or more or 2.5 pieces / ⁇ m or less.
  • a method for obtaining the average value it is necessary to arbitrarily measure 50 or more dendrite-like particles among the copper powder particles constituting the copper powder and obtain the average value.
  • the core material of the present silver-coated copper powder particles that is, In the production of copper powder, it is preferable to perform electrolysis by adding chlorine to the electrolyte under predetermined electrolysis conditions using an electrolysis apparatus described later.
  • the chlorine concentration of the silver-coated copper powder that is, the contained chlorine concentration is preferably 5 wtppm to 250 wtppm. More preferably, it is 50 wtppm or more. If the concentration of chlorine contained in the present silver-coated copper powder is 250 wtppm or less, adverse effects due to residual chlorine can be effectively suppressed. For example, when silver is coated on copper powder particles, it can be uniformly coated to a uniform thickness.
  • the chlorine concentration contained in the present silver-coated copper powder is about 5 wtppm, which is the detection limit.
  • the chlorine concentration in the copper powder as a core material and further the silver-coated copper powder is reduced to 5 wtppm by removing even the chlorine inside the particles, at least the adverse effect of the vicinity of the surface.
  • silver when silver is coated on copper powder particles, it can be coated with a uniform thickness.
  • the concentration of chlorine contained in the core copper powder and the silver-coated copper powder cannot be made 5 wtppm to 250 wtppm. It has been confirmed.
  • the oxygen concentration of the present silver-coated copper powder is preferably 0.20% by mass or less. If the oxygen concentration of the present silver-coated copper powder is 0.20% by mass or less, the conductivity can be further improved. From this viewpoint, the oxygen concentration of the present silver-coated copper powder is more preferably 0.18% by mass or less, and particularly preferably 0.15% by mass or less. In order to set the oxygen concentration of the present silver-coated copper powder to 0.20% by mass or less, when producing copper powder as a core material, the oxygen concentration and drying temperature in a dry atmosphere are controlled, or after electrolysis The method of carrying out alkali treatment of copper powder can be mentioned. However, it is not limited to this method.
  • the present silver-coated copper powder is a ratio of the total Cu concentration ( ⁇ Cu) and silver concentration ( ⁇ Ag) of Cu, CuO and Cu 2 O on the surface of the silver-coated copper powder particles measured by X-ray photoelectron spectroscopy. It is important that ( ⁇ Cu / ⁇ Ag) is 0.12 or less. If the ratio ( ⁇ Cu / ⁇ Ag) of the total Cu concentration ( ⁇ Cu) and silver concentration ( ⁇ Ag) of Cu, CuO and Cu 2 O on the surface of the silver-coated copper powder particles is 0.12 or less, chlorine is included. Also, the conductivity can be effectively increased.
  • the ratio ( ⁇ Cu / ⁇ Ag) of the total Cu concentration ( ⁇ Cu) and the silver concentration ( ⁇ Ag) of Cu, CuO and Cu 2 O on the surface of the silver-coated copper powder particles is 0.12 or less. Is important, and among them, it is preferably 0.10 or less, more preferably 0.08 or less, and particularly preferably 0.06 or less. In consideration of analysis accuracy and the like, the lower limit value of ⁇ Cu / ⁇ Ag is estimated to be about 0.01.
  • the core material In the present silver-coated copper powder, in order to reduce the copper ratio on the particle surface in this way, in other words, in order to uniformly coat silver on the copper powder particles as the core material, as described above, the core material
  • an alkali treatment in which chlorine is added to the electrolytic solution, and the copper powder immediately after electrolysis is brought into contact with an alkaline solution having a pH of 8 or more.
  • the silver content is preferably 0.5 to 35.0 mass% with respect to the total silver-coated copper powder. If the silver content occupies 0.5% by mass or more of the total silver-coated copper powder, the particles on the surface of the silver-coated copper powder will be in contact with each other when the particles composing the silver-coated copper powder overlap. Can be increased. On the other hand, when it exceeds 35.0 mass%, it will be uneconomical because it coats silver more than necessary. In other words, if it is 35.0% by mass or less, although it depends on the production method, it is preferable because it is economically superior to silver particles.
  • the silver content is preferably 0.5 to 35.0% by mass of the total silver-coated copper powder, and more preferably 3.0% by mass or more and 25.0% by mass or less. Of these, 5.0% by mass or more or 20.0% by mass or less is more preferable.
  • the central particle size (D50) of the present silver-coated copper powder that is, the volume cumulative particle size D50 measured by a laser diffraction / scattering particle size distribution analyzer is preferably 1.0 ⁇ m to 30.0 ⁇ m. If the particles are large as the conductive particles, the conductive particle network in the paste is reduced, which may reduce the conductive performance. On the other hand, if the particle diameter is too small, it is necessary to increase the silver content in order to eliminate unevenness in the silver coating, which is economically wasteful.
  • the central particle diameter (D50) of the present silver-coated copper powder is preferably 1.0 ⁇ m to 30.0 ⁇ m, more preferably 2.0 ⁇ m or more or 25.0 ⁇ m or less, and particularly preferably 3.0 ⁇ m or more or 20.0 ⁇ m. More preferably, it is as follows.
  • the silver-coated copper powder preferably has a BET specific surface area (SSA) of, for example, 0.30 to 2.00 m 2 / g. If it is remarkably smaller than 0.30 m 2 / g, the branches are not developed, and it becomes close to a pinecone or a sphere, so that the dendrite shape defined by the present invention cannot be exhibited. On the other hand, if it is significantly larger than 2.00 m 2 / g, the dendrite branch becomes too thin and it becomes difficult to disperse without breaking the dendrite branch when it is made into a paste. It is not preferable because a problem may occur and the target conductivity may not be ensured.
  • SSA BET specific surface area
  • the specific surface area as measured by single point method BET of the silver-coated copper powder is 0.30 ⁇ 2.00m 2 / g at and even good properly, inter alia 0.40 m 2 / g or more or 1.80 m 2 / g In particular, among these, it is more preferable to be 1.50 m 2 / g or less.
  • the tap bulk density of the present silver-coated copper powder is preferably 0.5 to 2.0 g / cm 3 .
  • the tap bulk density of the present silver-coated copper powder depends on the degree of development of the dendrite shape. Since the silver-coated copper powder particles have a dendrite shape, the tap bulk density is low and can be 2.0 g / cm 3 or less. On the other hand, if the tap bulk density is 0.5 g / cm 3 or more, not only the handling at the time of preparing the paste becomes easy, but also higher conductivity can be obtained.
  • the tap bulk density of the present silver-coated copper powder is preferably 0.5 to 2.0 g / cm 3 , particularly 0.7 g / cm 3 or more or 1.8 g / cm 3 or less, More preferably, it is 0.9 g / cm 3 or more or 1.6 g / cm 3 or less.
  • the present silver-coated copper powder is prepared by dispersing desired copper powder as a core material in water, adding a chelating agent as necessary, and then adding a water-soluble silver salt to cause a substitution reaction.
  • the surface layer can be replaced with silver, and the obtained silver-coated copper powder can be taken out of the solution, washed with a chelating agent as necessary, and then dried.
  • it is not limited to this manufacturing method.
  • the shape of the copper powder particles used as the core material is almost directly converted to the particle shape of the silver-coated copper powder. be able to.
  • the copper powder used as the core material it is preferable to use a copper powder obtained by an electrolysis method, and in particular, an electrolytic copper powder exhibiting a dendritic shape with sufficiently developed branches.
  • the electrolytic copper powder having a dendritic shape with sufficiently developed branches as described above can be produced by the following electrolytic method.
  • an electrolysis method for example, an anode and a cathode are immersed in a sulfuric acid electrolytic solution containing copper ions, and a direct current is passed through the electrolyte to conduct electrolysis.
  • An example is a method of producing electrolytic copper powder by scraping and collecting by an electric method, washing, drying, and passing through a sieving step as necessary.
  • the electrolytic solution in the electrolytic cell is circulated so that the copper ion concentration of the electrolytic solution between the electrodes does not become thin.
  • the copper ion concentration in the electrolyte solution near the electrode is low.
  • conditions may be set as appropriate based on common general technical knowledge within the range of the above conditions.
  • the copper concentration is preferably set to a relatively high concentration within the above preferred range, and the current density is relatively low within the above preferred range.
  • the density is preferably set, and the electrolysis time is preferably set to a relatively long time within the above preferable range.
  • the respective conditions based on the opposite concept.
  • the copper concentration may be 1 g / L to 30 g / L
  • the current density may be 100 A / m 2 to 4000 A / m 2
  • the electrolysis time may be 3 minutes to 8 hours.
  • the electrolytically deposited copper powder is washed with water as necessary, and then mixed with water to form a slurry, or a copper powder cake, and then an alkaline solution having a pH of 8 or more is added. It is preferable to reduce the concentration of chlorine contained in the copper powder by mixing, stirring as necessary, performing an alkali treatment for bringing the copper powder into contact with the alkaline solution, and washing with water or the like.
  • the pH of the slurry or copper powder cake after electrolytic copper powder deposition is preferably adjusted to 8 or more, particularly 9 or more, or 12 or less, and more preferably 10 or more or 11 or less.
  • the alkali agent used for such alkali treatment include ammonium carbonate solution, caustic soda solution, sodium bicarbonate, potassium hydroxide, and aqueous ammonia.
  • the surface of the electrolytic copper powder particles may be subjected to an oxidation resistance treatment using an organic material as necessary to form an organic material layer on the surface of the copper powder particles. It is not always necessary to form the organic layer, but it is more preferable that the organic layer is formed in consideration of the change over time due to oxidation of the copper powder particle surface.
  • the organic substance used for this oxidation resistance treatment is not particularly limited, and examples thereof include glue, gelatin, organic fatty acid, and a coupling agent.
  • the oxidation-resistant treatment method that is, the organic layer forming method may be a dry method or a wet method.
  • a method of mixing an organic substance and copper powder particles with a V-type mixer or the like in the case of a wet method, a method of adding an organic substance to a water-copper powder particle slurry and adsorbing it on the surface can be mentioned.
  • a method of adding an organic substance to a water-copper powder particle slurry and adsorbing it on the surface can be mentioned.
  • the method of mixing the copper powder cake and the aqueous solution containing the desired organic substance, and the organic solvent, and making an organic substance adhere to the copper powder surface is a preferable example.
  • a reducing agent such as hydrazine is added and stirred and mixed to react. At this time, it is preferable that the added reducing agent is sufficiently washed and removed from the core material.
  • the displacement plating coating method can more uniformly coat the surface of the core material (copper powder particles) with silver or a silver alloy, and can also suppress aggregation of particles after coating. Furthermore, it has a feature that it can be manufactured at a lower cost. Therefore, it is preferable to employ a displacement plating coating method.
  • the hydrophobic organic substance layer is formed in the copper powder particle surface as mentioned above, when coat
  • the degreasing treatment is preferably performed in a non-stirred state such as soaking.
  • a hydrophilic surface treatment agent such as gelatin to make them hydrophilic, it is not necessary to degrease, so from the viewpoint of maintaining the shape of the copper powder particles, Is preferable.
  • chelating agent examples include ethylenediaminetetraacetic acid salt (hereinafter referred to as “EDTA”), aminocarboxylic acid-based chelating agents such as diethylenetriaminepentaacetic acid and iminodiacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid), 1 , 3-propanediaminetetraacetic acid, one or two or more selected from propanediaminetetraacetic acid can be mentioned, and among these, EDTA is preferably used.
  • EDTA ethylenediaminetetraacetic acid salt
  • aminocarboxylic acid-based chelating agents such as diethylenetriaminepentaacetic acid and iminodiacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid), 1 , 3-propanediaminetetraacetic acid, one or two or more selected from propanediaminetetraace
  • the pH of the solution that is, the pH of the solution during the substitution reaction is preferably adjusted to 3-4.
  • Silver salts soluble in water that is, Ag ion sources include silver nitrate, silver perchlorate, silver acetate, silver oxalate, silver chlorate, silver hexafluorophosphate, and boron tetrafluoride.
  • One or more selected from acid silver, silver hexafluoroarsenate, and silver sulfate can be mentioned.
  • the addition amount of the silver salt is preferably equal to or greater than the theoretical equivalent, for example, when copper is used as the core material, the silver salt is added in an amount of 2 mol or more, particularly 2.1 mol or more with respect to 1 mol of copper. When the amount is less than 2 mol, the substitution is insufficient and a large amount of copper remains in the silver powder particles. However, it is not economical to add 2.5 mol or more.
  • the silver content in the present silver-coated copper powder can be adjusted by the amount of silver salt added, the reaction time, the reaction rate, the amount of chelating agent added, and the like. After completion of the substitution reaction, the silver powder particles are preferably thoroughly washed and dried.
  • the silver-coated copper powder Since the silver-coated copper powder has excellent conductive properties, the silver-coated copper powder can be used for various conductive materials such as conductive resin compositions such as conductive pastes and conductive adhesives, and conductive paints. It can be suitably used as a main constituent material.
  • the present silver-coated copper powder can be mixed with a binder and a solvent, and further, if necessary, a curing agent, a coupling agent, a corrosion inhibitor, etc. to produce a conductive paste.
  • the binder include liquid epoxy resins, phenol resins, unsaturated polyester resins, and the like, but are not limited thereto.
  • the solvent include terpineol, ethyl carbitol, carbitol acetate, butyl cellosolve and the like.
  • the curing agent include 2-ethyl 4-methylimidazole.
  • the corrosion inhibitor include benzothiazole and benzimidazole.
  • the conductive paste can be used to form various electrical circuits by forming a circuit pattern on the substrate.
  • a printed wiring board an electric circuit of various electronic components, external electrodes, and the like by applying or printing on a fired substrate or an unfired substrate, heating, pressurizing and baking as necessary.
  • it can utilize also for formation of an electromagnetic wave shield film, a bonding film, etc.
  • Table 1 also shows that the thickness a is in the range of 0.3 ⁇ m to 5.0 ⁇ m, the length b is in the range of 0.7 ⁇ m to 12.0 ⁇ m, and the number of branches / major axis L is 0.1.
  • Table 1 shows the number ratio of dendrite-like copper powder particles (referred to as “special dendrites”) of 5 to 4.0 particles / ⁇ m in the total copper powder particles as “number ratio of special dendrite in all particles”. It was shown to. Further, the thickness a is in the range of 0.3 ⁇ m to 5.0 ⁇ m, the length b is in the range of 0.7 ⁇ m to 12.0 ⁇ m, and the number of branches / major axis L is 0.5 to 4.0.
  • Table 1 shows the number ratio of the dendrite-like copper powder particles (referred to as “special dendrites”) / ⁇ m in the dendrite-like copper powder particles as “number ratio of special dendrite in dendrites”.
  • ⁇ Particle size measurement> Take the silver-coated copper powder (sample) obtained in Examples and Comparative Examples in a small amount of beaker, add a few drops of 3% Triton X solution (manufactured by Kanto Chemical Co., Inc.), blend into the powder, and then add 0.1% SN Dispersant 41 solution (manufactured by San Nopco) (50 mL) was added, and thereafter a dispersion sample was dispersed for 2 minutes using an ultrasonic disperser TIP ⁇ 20 (manufactured by Nippon Seiki Seisakusho) to prepare a measurement sample. The volume accumulation standard D50 of this measurement sample was measured using a laser diffraction / scattering particle size distribution measuring device MT3300 (manufactured by Nikkiso).
  • the silver-coated copper powder (sample) obtained in Examples and Comparative Examples was quantitatively analyzed for Ag and Cu components at a depth from the particle surface to about 5 nm.
  • Table 1 shows the total Ag concentration ( ⁇ Ag) of Ag on the particle surface as “Ag (wt%)” or “Ag (atomic%)”, Cu, CuO (Cu concentration conversion) and Cu 2 O on the particle surface.
  • the total Cu concentration ( ⁇ Cu) in terms of Cu concentration is shown as “Cu (atomic%)”, and the ratio of the total Cu concentration ( ⁇ Cu) of Cu, CuO and Cu 2 O to the Ag concentration ( ⁇ Ag) on the particle surface is It was shown as “ ⁇ Cu / ⁇ Ag”.
  • TD Tip bulk density
  • Example 1 In an electrolytic cell having a size of 2.5 m ⁇ 1.1 m ⁇ 1.5 m (about 4 m 3 ), 9 SUS cathode plates and insoluble anode plates (DSE) each having a size (1.0 m ⁇ 1.0 m). (Permelec Electrode Co., Ltd.)) is suspended so that the distance between the electrodes is 5 cm, and a copper sulfate solution as an electrolytic solution is circulated at 30 L / min, and an anode and a cathode are immersed in the electrolytic solution. Electrolysis was performed by applying a direct current, and powdered copper was deposited on the cathode surface.
  • the Cu concentration of the electrolyte to be circulated is adjusted to 10 g / L
  • the sulfuric acid (H 2 SO 4 ) concentration is set to 100 g / L
  • the chlorine concentration is set to 50 mg / L
  • the current density is adjusted to 800 A / m 2 to 30.
  • Electrolysis was performed for a minute. The pH of the solution at this time was 1.
  • the copper ion concentration of the electrolyte solution between the electrodes was always kept lower than the copper ion concentration of the electrolyte solution at the bottom of the electrolytic cell.
  • Residual EDTA was washed with water. Then, it was made to dry at 120 degreeC for 3 hours, and dendritic silver covering copper powder (sample) was obtained. The silver coating amount was 10.8% by mass of the total silver-coated copper powder.
  • the obtained dendrite-like silver-coated copper powder (sample) was observed using a scanning electron microscope (SEM), at least 90% by number of silver-coated copper powder particles had one main axis, It has a dendritic shape in which a plurality of branches are obliquely branched from the main axis and grown three-dimensionally, and the main axis thickness a is in the range of 0.3 ⁇ m to 5.0 ⁇ m, and the length of the longest branch It was confirmed that b was in the range of 0.7 ⁇ m to 12.0 ⁇ m, and the number of branches (the number of branches / major axis L) was 0.5 to 4.0 / ⁇ m with respect to the major axis L of the main shaft. Moreover, when the electroconductivity of this silver covering copper powder was measured as shown in Table 1, the favorable value was shown.
  • Example 2 In Example 1, “Alkali treatment”, instead of adding an ammonium carbonate solution until pH 9 and performing an alkali treatment, in Example 2, an aqueous ammonia was added until pH 11 and an alkali treatment was performed. In Example 3, caustic soda was added to pH 14 to perform alkali treatment, and silver coating treatment was performed. Except this point, a silver-coated copper powder (sample) was obtained in the same manner as in Example 1.
  • the obtained silver-coated copper powder (sample) was observed using a scanning electron microscope (SEM), at least 90% by number or more of the silver-coated copper powder particles had one main axis, and the main axis A plurality of branches obliquely branch to form a dendritic shape that grows three-dimensionally, the main axis thickness a is in the range of 0.3 ⁇ m to 5.0 ⁇ m, and the longest branch length b is It was within the range of 0.7 ⁇ m to 12.0 ⁇ m, and it was confirmed that the number of branches with respect to the major axis L of the main shaft (the number of branches / major axis L) was 0.5 to 4.0 / ⁇ m. Moreover, when the electroconductivity of this silver covering copper powder was measured as shown in Table 1, the favorable value was shown.
  • Example 4 In an electrolytic cell having a size of 2.5 m ⁇ 1.1 m ⁇ 1.5 m (about 4 m 3 ), 9 SUS cathode plates and insoluble anode plates (DSE) each having a size (1.0 m ⁇ 1.0 m). (Permelec Electrode Co., Ltd.)) is suspended so that the distance between the electrodes is 5 cm, and a copper sulfate solution as an electrolytic solution is circulated at 30 L / min, and an anode and a cathode are immersed in the electrolytic solution. Electrolysis was performed by applying a direct current, and powdered copper was deposited on the cathode surface.
  • the Cu concentration of the electrolyte to be circulated is adjusted to 5 g / L
  • the sulfuric acid (H 2 SO 4 ) concentration is set to 80 g / L
  • the chlorine concentration is set to 100 mg / L
  • the current density is adjusted to 1200 A / m 2 to 10.
  • Electrolysis was performed for a minute. The pH of the solution at this time was 1.
  • the copper ion concentration of the electrolyte solution between the electrodes was always kept lower than the copper ion concentration of the electrolyte solution at the bottom of the electrolytic cell.
  • the silver-coated copper powder (sample) obtained in this way was observed using a scanning electron microscope (SEM), at least 90% by number or more of the silver-coated copper powder particles had one main axis, It has a dendritic shape in which a plurality of branches obliquely branch from the main axis and grows three-dimensionally, the main axis thickness a is in the range of 0.3 ⁇ m to 5.0 ⁇ m, and the longest branch length b was within the range of 0.7 ⁇ m to 12.0 ⁇ m, and the number of branches (number of branches / major axis L) with respect to the major axis L of the main shaft was confirmed to be 0.5 to 4.0 / ⁇ m. Moreover, when the electroconductivity of this silver covering copper powder was measured as shown in Table 1, the favorable value was shown.
  • Example 5 In the alkali treatment of Example 4, instead of performing an alkali treatment by adding an ammonium carbonate solution until the pH reached 9, in Example 5, an aqueous ammonia was added until the pH reached 11, and the alkali treatment was performed. Then, alkali treatment was performed by adding caustic soda to pH14. Except this point, it carried out similarly to Example 4, and obtained the silver covering copper powder (sample).
  • the silver-coated copper powder (sample) obtained in this way was observed using a scanning electron microscope (SEM), at least 90% by number or more of the silver-coated copper powder particles had one main axis, It has a dendritic shape in which a plurality of branches obliquely branch from the main axis and grows three-dimensionally, the main axis thickness a is in the range of 0.3 ⁇ m to 5.0 ⁇ m, and the longest branch length b was within the range of 0.7 ⁇ m to 12.0 ⁇ m, and the number of branches (number of branches / major axis L) with respect to the major axis L of the main shaft was confirmed to be 0.5 to 4.0 / ⁇ m. Moreover, when the electroconductivity of this silver covering copper powder was measured as shown in Table 1, the favorable value was shown.
  • Example 7 In an electrolytic cell having a size of 2.5 m ⁇ 1.1 m ⁇ 1.5 m (about 4 m 3 ), 9 SUS cathode plates and insoluble anode plates (DSE) each having a size (1.0 m ⁇ 1.0 m). (Permelec Electrode Co., Ltd.)) is suspended so that the distance between the electrodes is 5 cm, and a copper sulfate solution as an electrolytic solution is circulated at 30 L / min, and an anode and a cathode are immersed in the electrolytic solution. Electrolysis was performed by applying a direct current, and powdered copper was deposited on the cathode surface.
  • the electrolytic solution to be circulated was adjusted to a Cu concentration of 20 g / L, a sulfuric acid (H 2 SO 4 ) concentration of 80 g / L, a chlorine concentration of 20 mg / L, and a current density of 500 A / m 2 to 10 Electrolysis was performed for a minute.
  • the pH of the solution at this time was 1.
  • the copper ion concentration of the electrolyte solution between the electrodes was always kept lower than the copper ion concentration of the electrolyte solution at the bottom of the electrolytic cell.
  • the silver-coated copper powder (sample) obtained in this way was observed using a scanning electron microscope (SEM), at least 90% by number or more of the silver-coated copper powder particles had one main axis, It has a dendritic shape in which a plurality of branches obliquely branch from the main axis and grows three-dimensionally, the main axis thickness a is in the range of 0.3 ⁇ m to 5.0 ⁇ m, and the longest branch length b was within the range of 0.7 ⁇ m to 12.0 ⁇ m, and the number of branches (number of branches / major axis L) with respect to the major axis L of the main shaft was confirmed to be 0.5 to 4.0 / ⁇ m. Moreover, when the electroconductivity of this silver covering copper powder was measured as shown in Table 1, the favorable value was shown.
  • Example 8 A silver-coated copper powder (sample) was obtained in the same manner as in Example 4 except that the “current density” in Example 4 was set to 3000 A / m 2 and the “chlorine concentration” was set to 30 mg / L.
  • the obtained silver-coated copper powder (sample) was observed using a scanning electron microscope (SEM), at least 90% by number or more of the silver-coated copper powder particles had one main axis, and the main axis A plurality of branches obliquely branch to form a dendritic shape that grows three-dimensionally, the main axis thickness a is in the range of 0.3 ⁇ m to 5.0 ⁇ m, and the longest branch length b is It was within the range of 0.7 ⁇ m to 12.0 ⁇ m, and it was confirmed that the number of branches with respect to the major axis L of the main shaft (the number of branches / major axis L) was 0.5 to 4.0 / ⁇ m. Moreover, when the electroconductivity of this silver covering copper powder was measured as shown in Table 1, the favorable value was shown.
  • Example 1 (Comparative Example 1)
  • the copper deposited on the cathode surface was mechanically scraped and collected, and then washed to obtain a hydrous copper powder cake equivalent to 1 kg of copper powder.
  • the cake was dispersed in 3 L of water, 1 L of an aqueous solution of 10 g / L of industrial gelatin (manufactured by Nitta Gelatin) was added, and then washed with pure water. Next, it was dried at 80 ° C. for 6 hours under reduced pressure (1 ⁇ 10 ⁇ 3 Pa) to obtain electrolytic copper powder. Otherwise, silver-coated copper powder (sample) was obtained in the same manner as in Example 1.
  • Example 2 (Comparative Example 2)
  • the copper deposited on the cathode surface was mechanically scraped off and collected, and then washed to obtain a hydrous copper powder cake equivalent to 1 kg of copper powder.
  • the cake was dispersed in 3 L of water, 1 L of an aqueous solution of 10 g / L of industrial gelatin (manufactured by Nitta Gelatin) was added, and then washed with pure water. Next, it was dried at 80 ° C. for 6 hours under reduced pressure (1 ⁇ 10 ⁇ 3 Pa) to obtain electrolytic copper powder. Otherwise, silver-coated copper powder (sample) was obtained in the same manner as in Example 1.
  • the silver-coated copper powder (sample) obtained in this way was observed using a scanning electron microscope (SEM), at least 90% by number or more of the silver-coated copper powder particles had one main axis, It was confirmed that a plurality of branches from the main axis were obliquely branched to form a dendritic shape that grew three-dimensionally.
  • SEM scanning electron microscope
  • Powdered copper was deposited on the cathode surface, and the copper deposited on the cathode surface was mechanically scraped and collected, and then washed to obtain a hydrous copper powder cake equivalent to 1 kg of copper powder.
  • the electrolytic solution to be circulated was adjusted to a Cu concentration of 80 g / L, a sulfuric acid (H 2 SO 4 ) concentration of 200 g / L, and a current density of 90 A / m 2 for electrolysis for 6 hours.
  • This cake was dispersed in 3 L of water to make a slurry, and an ammonium carbonate solution was added until pH 9 was obtained, followed by stirring to perform alkalinization treatment. Thereafter, the impurities were removed by washing with pure water.
  • Example 1 L of an industrial gelatin (Nitta Gelatin) 10 g / L aqueous solution was added and stirred, and then dried under reduced pressure (1 ⁇ 10 ⁇ 3 Pa) at 80 ° C. for 6 hours to obtain electrolytic copper powder. It was.
  • the electrolytic copper powder thus obtained was subjected to a silver coating step in the same manner as in Example 1 to obtain a silver-coated copper powder (sample).
  • the particle shape of the obtained electrolytic copper powder was pinecone-like, and the main shaft thickness, branch length, number of branches / long diameter L could not be measured.
  • the coated copper powder obtained in the examples using a scanning electron microscope (SEM) As a result of observing the coated copper powder obtained in the examples using a scanning electron microscope (SEM), it is provided with one main axis, and a plurality of branches branch obliquely from the main axis, It has a dendritic shape that grows three-dimensionally, has a main axis thickness a of 0.3 ⁇ m to 5.0 ⁇ m, and the longest branch length b of the branches extending from the main axis is 0.7 ⁇ m to 12 ⁇ m. It was confirmed that the dendrite-like silver-coated copper powder particles having a dendrite shape of 0.0 ⁇ m (referred to as “special dendritic shape”) accounted for 80% by number or more of the total silver-coated copper powder particles.
  • SEM scanning electron microscope
  • the dendrite-like silver-coated copper powder particles exhibiting the above-mentioned special dendritic shape are among the dendrite-like silver-coated copper powder particles. It was confirmed that it occupied 90% by number or more.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Powder Metallurgy (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

La présente invention concerne une poudre de cuivre recouverte d'argent, qui est composée de particules de poudre de cuivre recouverte d'argent, dont chacune a une configuration dans laquelle la surface d'une particule de poudre de cuivre obtenue par électrolyse est recouverte de l'argent ou d'un alliage d'argent, et la présente invention concerne une nouvelle poudre de cuivre recouverte d'argent qui a une conductivité électrique augmentée de façon efficace même si elle contient du chlore en son sein. L'invention concerne une poudre de cuivre recouverte d'argent, qui est caractérisée par le fait que la concentration de chlore est de 5-250 ppm en poids et que le rapport de la concentration Cu totale (ρCu) de Cu, CuO et Cu2O à la concentration d'argent (ρAg) dans les surfaces de particules de poudre de cuivre recouverte d'argent, déterminée par une analyse de spectroscopie de photoélectrons à rayons X, c'est-à-dire ρCu/ρAg, est de 0,12 ou moins.
PCT/JP2014/077851 2013-10-24 2014-10-20 Poudre de cuivre recouverte d'argent WO2015060258A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015538205A JP6278969B2 (ja) 2013-10-24 2014-10-20 銀被覆銅粉

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013220786 2013-10-24
JP2013-220786 2013-10-24

Publications (1)

Publication Number Publication Date
WO2015060258A1 true WO2015060258A1 (fr) 2015-04-30

Family

ID=52992853

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/077851 WO2015060258A1 (fr) 2013-10-24 2014-10-20 Poudre de cuivre recouverte d'argent

Country Status (2)

Country Link
JP (2) JP6278969B2 (fr)
WO (1) WO2015060258A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5907301B1 (ja) * 2015-05-15 2016-04-26 住友金属鉱山株式会社 銀コート銅粉及びそれを用いた銅ペースト、導電性塗料、導電性シート、並びに銀コート銅粉の製造方法
CN109773179A (zh) * 2019-03-23 2019-05-21 昆明理工大学 一种外加电磁场高致密度银包铜粉的制备方法
US10695830B2 (en) 2015-05-15 2020-06-30 Sumitomo Metal Mining Co., Ltd. Copper powder, copper paste using same, conductive coating material, conductive sheet, and method for producing copper powder

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6938986B2 (ja) * 2017-03-15 2021-09-22 住友金属鉱山株式会社 粒子形状の評価方法
KR102301256B1 (ko) * 2017-09-29 2021-09-10 제이엑스금속주식회사 금속 적층 조형용 금속분 및 그 금속분을 사용하여 제조한 조형물

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0257623A (ja) * 1988-08-24 1990-02-27 Kawasaki Steel Corp 銅微粉の製造方法
JP2008019475A (ja) * 2006-07-12 2008-01-31 Sumitomo Metal Mining Co Ltd 電着銅の脱塩素方法
JP2009191321A (ja) * 2008-02-15 2009-08-27 Sumitomo Metal Mining Co Ltd 電解採取した銅粉から塩素の除去方法
WO2012046666A1 (fr) * 2010-10-06 2012-04-12 旭硝子株式会社 Particules de cuivre électroconductrices, procédé de production de particules de cuivre électroconductrices, composition permettant de former un corps électroconducteur et base présentant un corps électroconducteur fixé à celle-ci
JP2012153967A (ja) * 2011-01-28 2012-08-16 Mitsui Mining & Smelting Co Ltd 導電性粉末及び導電性ペースト
JP2013001917A (ja) * 2011-06-13 2013-01-07 Mitsui Mining & Smelting Co Ltd 銀被覆銅粉及びその製造方法
JP2013100592A (ja) * 2011-10-21 2013-05-23 Mitsui Mining & Smelting Co Ltd 銀被覆銅粉

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01247584A (ja) * 1988-03-30 1989-10-03 Nippon Mining Co Ltd 電解銅粉の製造方法
JPH11189813A (ja) * 1997-12-25 1999-07-13 Kawatetsu Mining Co Ltd 金属超微粉の洗浄方法
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
WO2009060803A1 (fr) * 2007-11-05 2009-05-14 Sumitomo Metal Mining Co., Ltd. Fine particule de cuivre, son procédé de production et dispersion de fines particules de cuivre
JP5868752B2 (ja) * 2012-03-26 2016-02-24 富士フイルム株式会社 金属ナノワイヤの製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0257623A (ja) * 1988-08-24 1990-02-27 Kawasaki Steel Corp 銅微粉の製造方法
JP2008019475A (ja) * 2006-07-12 2008-01-31 Sumitomo Metal Mining Co Ltd 電着銅の脱塩素方法
JP2009191321A (ja) * 2008-02-15 2009-08-27 Sumitomo Metal Mining Co Ltd 電解採取した銅粉から塩素の除去方法
WO2012046666A1 (fr) * 2010-10-06 2012-04-12 旭硝子株式会社 Particules de cuivre électroconductrices, procédé de production de particules de cuivre électroconductrices, composition permettant de former un corps électroconducteur et base présentant un corps électroconducteur fixé à celle-ci
JP2012153967A (ja) * 2011-01-28 2012-08-16 Mitsui Mining & Smelting Co Ltd 導電性粉末及び導電性ペースト
JP2013001917A (ja) * 2011-06-13 2013-01-07 Mitsui Mining & Smelting Co Ltd 銀被覆銅粉及びその製造方法
JP2013100592A (ja) * 2011-10-21 2013-05-23 Mitsui Mining & Smelting Co Ltd 銀被覆銅粉

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5907301B1 (ja) * 2015-05-15 2016-04-26 住友金属鉱山株式会社 銀コート銅粉及びそれを用いた銅ペースト、導電性塗料、導電性シート、並びに銀コート銅粉の製造方法
WO2016185628A1 (fr) * 2015-05-15 2016-11-24 住友金属鉱山株式会社 Poudre de cuivre enrobée d'argent, pâte de cuivre la mettant en œuvre, matériau de revêtement conducteur, feuille conductrice, et procédé de fabrication d'une poudre de cuivre enrobée d'argent
JP2016216760A (ja) * 2015-05-15 2016-12-22 住友金属鉱山株式会社 銀コート銅粉及びそれを用いた銅ペースト、導電性塗料、導電性シート、並びに銀コート銅粉の製造方法
US10654101B2 (en) 2015-05-15 2020-05-19 Sumitomo Metal Mining Co., Ltd. Silver-coated copper powder, copper paste using same, conductive coating material, conductive sheet, and method for producing silver-coated copper powder
US10695830B2 (en) 2015-05-15 2020-06-30 Sumitomo Metal Mining Co., Ltd. Copper powder, copper paste using same, conductive coating material, conductive sheet, and method for producing copper powder
CN109773179A (zh) * 2019-03-23 2019-05-21 昆明理工大学 一种外加电磁场高致密度银包铜粉的制备方法

Also Published As

Publication number Publication date
JPWO2015060258A1 (ja) 2017-03-09
JP2017002401A (ja) 2017-01-05
JP6278969B2 (ja) 2018-02-14

Similar Documents

Publication Publication Date Title
JP5631910B2 (ja) 銀被覆銅粉
JP5631841B2 (ja) 銀被覆銅粉
JP6165399B1 (ja) 銀被覆銅粉
JP6166012B2 (ja) 導電性粉末及び導電性ペースト
JP5701695B2 (ja) 銀被覆銅粉及びその製造方法
WO2016038914A1 (fr) Poudre de cuivre revêtue d'argent et pâte conductrice, matériau de revêtement conducteur et feuille conductrice utilisant chacun ladite poudre de cuivre revêtue d'argent
JP6278969B2 (ja) 銀被覆銅粉
JP5907301B1 (ja) 銀コート銅粉及びそれを用いた銅ペースト、導電性塗料、導電性シート、並びに銀コート銅粉の製造方法
WO2016031286A1 (fr) Poudre de cuivre revêtue d'argent, et pâte conductrice, matériau de revêtement conducteur et feuille conductrice, chacun utilisant celle-ci
WO2016151859A1 (fr) Poudre de cuivre revêtue d'argent, et pâte conductrice, matériau conducteur et feuille conductrice la comprenant
JP2013053347A (ja) デンドライト状銅粉
WO2015115139A1 (fr) Poudre de cuivre
JP2016139598A (ja) 銀コート銅粉、及びそれを用いた銅ペースト、導電性塗料、導電性シート
JP2014159646A (ja) 銀被覆銅粉
JP5711435B2 (ja) 銅粉
JP6332125B2 (ja) 銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート
JPWO2016038914A1 (ja) 銀コート銅粉及びそれを用いた導電性ペースト、導電性塗料、導電性シート
JP2017071809A (ja) Ｓｎコート銅粉及びそれを用いた導電性ペースト、並びにＳｎコート銅粉の製造方法
JP2017071820A (ja) Ｓｎコート銅粉及びそれを用いた導電性ペースト、並びにＳｎコート銅粉の製造方法
TWI553661B (zh) Silver powder and its use of conductive paste, conductive paint, conductive film
JP2015183291A (ja) 銀被覆銅粉及びこれを用いた導電性ペースト
JP2017071823A (ja) Ｓｎコート銅粉及びそれを用いた導電性ペースト、並びにＳｎコート銅粉の製造方法
JP2017071822A (ja) Ｓｎコート銅粉及びそれを用いた導電性ペースト、並びにＳｎコート銅粉の製造方法
JP2017071821A (ja) Ｓｎコート銅粉及びそれを用いた導電性ペースト

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: 14855960

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015538205

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14855960

Country of ref document: EP

Kind code of ref document: A1