WO2008059789A1 - Fine poudre de cuivre plaquée argent, pâte conductrice produite à partir d'une fine poudre de cuivre plaquée argent, et procédé pour produire une fine poudre de cuivre plaquée argent - Google Patents

Fine poudre de cuivre plaquée argent, pâte conductrice produite à partir d'une fine poudre de cuivre plaquée argent, et procédé pour produire une fine poudre de cuivre plaquée argent Download PDF

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Publication number
WO2008059789A1
WO2008059789A1 PCT/JP2007/071907 JP2007071907W WO2008059789A1 WO 2008059789 A1 WO2008059789 A1 WO 2008059789A1 JP 2007071907 W JP2007071907 W JP 2007071907W WO 2008059789 A1 WO2008059789 A1 WO 2008059789A1
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Prior art keywords
silver
fine powder
copper fine
plated copper
fine copper
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PCT/JP2007/071907
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English (en)
Japanese (ja)
Inventor
Takahiro Haga
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Nippon Mining & Metals Co., Ltd.
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Priority to JP2008544126A priority Critical patent/JPWO2008059789A1/ja
Publication of WO2008059789A1 publication Critical patent/WO2008059789A1/fr

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    • 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
    • H01B1/023—Alloys based on aluminium
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/166—Process features with two steps starting with addition of reducing agent followed by metal deposition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C23C18/1692—Heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder

Definitions

  • Silver-plated copper fine powder conductive paste produced using silver-plated copper fine powder, and method for producing silver-plated copper fine powder
  • the present invention relates to a silver-plated copper fine powder, a conductive paste produced using the silver-plated copper fine powder, and a method for producing the silver-plated copper fine powder, and is particularly excellent in conductivity and reproducibility during the silver-plated reaction.
  • the present invention relates to a silver-plated copper fine powder having a tap density comparable to that of the raw material copper fine powder.
  • Conductive pastes are widely used from experimental purposes to applications in the electronics industry because of their ease of contact.
  • silver-plated copper fine powder with a silver layer coated on its surface is processed into a conductive paste and applied to circuit formation of printed wiring boards using a screen printing method, various electrical contact portions, etc. It has been used as a material for ensuring electrical continuity.
  • the silver-plated copper fine powder is more excellent in electrical conductivity than the copper fine powder when compared with normal copper fine powder that does not cover the surface with a silver layer.
  • silver powder alone is expensive, but if silver is attached to copper, the conductive powder as a whole will be inexpensive and the production cost can be greatly reduced. Therefore, a conductive paste made of fine copper powder coated with silver, which is superior in conductive properties, has a great advantage if a low-resistance conductor can be manufactured at low cost.
  • Patent Document 1 describes a method of substituting and depositing silver on the surface of metallic copper powder using a silver complex solution of silver nitrate, ammonium carbonate, and ethylenediamine tetraacetate.
  • Patent Document 2 discloses a method in which copper powder is dispersed in a chelating agent solution, a silver nitrate solution is added to the copper powder dispersion, a reducing agent is added in the next step, and a silver film is deposited on the surface of the copper powder. Is disclosed. Furthermore, in Patent Document 3, a chelating agent is added to a copper powder dispersion to prepare a copper powder slurry, and a buffer is added thereto to adjust pH, and then silver ions are added to this for a substitution reaction. A technique for making silver-coated copper powder is disclosed.
  • the silver-plated copper fine powder obtained by these production methods is excellent in electrical conductivity and moisture resistance, and has been used as a suitable material as a conductive paste material.
  • the silver-plated copper fine powders obtained by these manufacturing methods have variations in the color tone after the silver-plated reaction due to the oxidation state of the copper fine powder before the silver-plated, and the tap density is reduced by the silver-plated, etc. I had a problem.
  • Patent Document 1 JP-A-57-59283
  • Patent Document 2 JP-A-2-46641
  • Patent Document 2 JP 2004-52044 A
  • the present invention aims to solve the above-described problems, and is a silver-plated copper fine powder having excellent conductivity and reproducibility during a silver-plated reaction, and having a tap density similar to that of the raw copper fine powder, and a method for producing the same. Provide law.
  • the present inventors have introduced a surface treatment step before and after the silver plating reaction in the conventional silver plating copper fine powder, and electroless substitution plating and reduction type.
  • a silver layer on the surface of the copper fine powder by plating it was found that the silver-plated copper fine powder was excellent in reproducibility during the production of silver plating and had a tap density similar to that of the raw copper powder.
  • Silver-plated copper fine powder with average particle size ! ⁇ 30 111, tap density 2.4 g / cm 3 or more, specific surface area 0.9 m 2 / g or less
  • Silver-plated copper fine powder with an average particle size of 3 to 20 111, tap density of 3. Og / cm 3 or more, and specific surface area of 0.6 mg or less
  • the present invention also provides
  • the silver-plated copper fine powder manufacturing method that forms a silver layer on the surface of the copper fine powder, remove the copper fine powder from the organic matter on the surface of the copper fine powder in an alkaline solution. After pickling and washing the product, a reducing agent is added to the acidic solution in which the copper fine powder is dispersed to adjust the pH to create a copper fine powder slurry, and a silver ion solution is continuously added to the copper fine powder slurry.
  • the silver plating copper fine powder is immersed in an alcohol solution containing a fatty acid, and the surface of the silver plating copper fine powder is coated with 0.01 to 5.0 wt% of fatty acid.
  • the silver plating copper fine powder is immersed in an alcohol solution containing a fatty acid, and the surface of the silver plating copper fine powder is coated with 0.;! To 1.0% by weight of fatty acid.
  • a method for producing a silver-plated copper fine powder is
  • the surface of the copper fine powder is uniformly coated by introducing a surface treatment step before and after the silver plating reaction and forming a silver layer on the surface of the copper fine powder by electroless substitution plating and reduction type plating.
  • a surface treatment step before and after the silver plating reaction
  • a silver layer on the surface of the copper fine powder by electroless substitution plating and reduction type plating.
  • it has excellent conductivity and reproducibility at the time of silver plating reaction, resulting in silver plating copper fine powder with tap density comparable to that of raw copper fine powder, which is stable when used in conductive paste.
  • it has an excellent effect that high filling can be achieved.
  • the copper hydroxide may be re-precipitated when taken out as a powder.
  • the silver ion solution was charged all together during the substitution reaction, it was considered that the silver ion concentration became non-uniform around the copper powder, and silver-plated copper fine powder with poor silver coating was formed.
  • the present invention removes the organic matter on the surface of the copper fine powder by dispersing the copper fine powder in the alkaline solution, and removes the oxide on the surface of the copper fine powder by dispersing the copper fine powder in the acidic solution.
  • the pH is adjusted so that the copper ions complexed by the agent can be maintained in a stable state, and the silver ion solution is continuously added so that the substitution reaction with silver ions proceeds uniformly.
  • the silver layer can be coated extremely uniformly on the surface of the copper fine powder.
  • Sodium hydroxide, potassium hydroxide, or the like is used as the alkaline solution.
  • An alkaline solution that can reliably remove the organic matter on the surface of the copper fine powder before the substitution reaction is preferred, but potassium hydroxide is preferred.
  • an acidic solution sulfuric acid, hydrochloric acid, phosphoric acid or the like is used. It is preferable to use sulfuric acid, and it should be an acidic solution that can reliably remove the copper oxide on the surface of the copper fine powder before the substitution reaction. The selected type and concentration should not excessively dissolve the copper fine copper itself. there is a need force s to.
  • the pH of this acidic solution is preferably in the acidic range of 2 ⁇ 0 to 5 ⁇ 0. When ⁇ exceeds 5.0, oxides of copper fine powder cannot be sufficiently dissolved and removed, and when pH is lower than 2.0, copper powder dissolves and the copper fine powder itself tends to aggregate. More preferably, it is an acidic region of ⁇ 3.5 to 4.5.
  • the chelating agent can use EDTA, ammonia, or the like.
  • the chelating agent used in the present invention is not particularly limited as long as the effects of the present invention are exhibited, but is preferably ammonia.
  • polycarboxylic acid polyvalent carboxylates, formaldehyde and the like can be used as the reducing agent.
  • sodium potassium tartrate Rossiel salt
  • glucose glucose
  • this reducing agent exhibits weak reducing power and reduces only the oxides (CuO, Cu 0, AgO, Ag O) that are produced as a by-product of the substitution reaction.
  • a silver nitrate solution is used as the silver ion solution in the present invention.
  • the silver ion solution used in the present invention is not particularly limited as long as the effects of the present invention are exhibited.
  • the silver nitrate solution has a silver nitrate concentration of 20 to 300 g / L, preferably 50 to 100 g / L.
  • the rate of the silver ion solution added to the copper fine powder slurry is 200 mL / min or less, preferably lOOmL / min or less.
  • Decantation treatment is also called the gradient method.
  • the solution is allowed to stand to settle copper fine powder or silver-plated copper fine powder, and then the supernatant is gently tilted. Operation to separate and collect. This In this case, since the copper fine powder or silver-plated copper fine powder does not come into contact with the atmosphere, it is possible to proceed to the next step in a state in which re-oxidation of the copper fine powder or silver-plated copper fine powder is prevented.
  • One method of post-treatment used in the production method of the present invention is 150 to 220 in a reducing atmosphere under a hydrogen stream.
  • C heat treatment for 30-90 minutes.
  • C heat treatment is carried out for 20 to 40 minutes, and by this heat treatment, the interface between the copper fine powder and the silver layer is partially alloyed, so that the bond strength at the interface can be increased.
  • the silver-plated copper fine powder is kneaded with a resin or solvent when it is made into a conductive paste.
  • a resin or solvent when it is made into a conductive paste.
  • the silver layer will peel off when subjected to mechanical friction. Therefore, heat treatment at a low temperature in a short time is effective.
  • heat treatment is carried out at a very high temperature or for a long time, silver may completely diffuse into copper.
  • the second method of post-treatment used in the production method of the present invention is to immerse silver-plated copper fine powder in an alcohol solution containing 0.01 to 5.0% by weight of a fatty acid, and filter after stirring for about 30 minutes. , dry. Preferably, 0.;! ⁇ 1.0 Silver silver fine copper powder is immersed in an alcohol solution containing 10% by weight of fatty acid, filtered and dried after stirring for about 30 minutes. Stearic acid is used as the fatty acid. Fatty acid coating is achieved by the fact that the fatty acid is coated on the surface of the silver-plated copper fine powder to make the surface smooth, and that the fatty acid itself acts as a lubricant to increase the filling ability of the silver-plated copper fine powder. It has an excellent effect.
  • the silver-plated copper fine powder and the copper fine powder used in the production method shown above are obtained from ordinary electrolytic methods, reduction methods, atomization methods, mechanical pulverization, etc. with no particular restrictions on the type and production method. It is possible to use the copper fine powder that is used. Further, the shape of the copper powder may be a spherical shape, a flake shape, a needle shape, or a resin shape.
  • silver-plated copper fine powder having an average particle size of 1 to 30111, a tap density of 2.4 g / cm 3 or more, and a specific surface area of 0.9 m 2 / g or less can be obtained.
  • This silver-plated copper fine powder can further achieve an average particle size of 3 to 20 m, a tap density of 3. Og / cm 3 or more, and a specific surface area of 0.6 m 2 / g or less.
  • the silver-plated copper fine powder can be made into a silver-plated copper fine powder having a structure covered with 0.01 to 5.0% by weight of fatty acid by the above treatment. Further, the silver-plated copper fine powder may have a structure coated with 0.;! To 1.0% by weight of fatty acid.
  • These silver-plated copper fine powders are useful as conductive pastes.
  • the present invention includes a conductive paste manufactured using these copper powders.
  • Example 1 electrolytic copper powder obtained by a method called a so-called electrolytic process was used, and copper fine powder obtained by further pulverizing with a jet mill was used.
  • This copper fine powder had a weight cumulative particle size D of 6.2 111 as measured by a laser diffraction scattering particle size distribution measurement method.
  • a dilute sulfuric acid or potassium hydroxide solution was added to the copper slurry to adjust the pH of the copper slurry to 3.5 to 4.5.
  • Example 1 500 g of silver-plated copper fine powder prepared in Example 1 was dispersed in 750 ml of a 0.5% ethanolic stearate solution and stirred for 30 minutes. Then, the solution was separated from the stearic acid-coated silver-plated copper metal powder by filtration washing and suction dehydration, and the stearic acid-coated silver-plated copper metal powder was dried at a temperature of 90 ° C. for 2 hours.
  • Example 1 500 g of the silver-plated copper fine powder prepared in Example 1 was placed in a tubular furnace and heat-treated at 200 ° C. for 30 minutes in a reducing atmosphere under a hydrogen stream (3.0 to 3.51 / min). The heat treated silver powdered copper fine powder was pulverized in a mortar.
  • Example 3 500 g of silver-plated copper fine powder prepared in Example 3 was dispersed in 750 ml of 0.5% ethanol stearate solution and stirred for 30 minutes. Then, the solution was separated from the stearic acid-coated silver-plated copper metal powder by filtration washing and suction dehydration, and the stearic acid-coated silver-plated copper metal powder was dried at a temperature of 90 ° C. for 2 hours.
  • Example 1 500 g of the copper fine powder used in Example 1 was added to 2500 ml of 1% sodium potassium tartrate solution and stirred for several minutes. Next, dilute sulfuric acid or potassium hydroxide solution was added to the copper slurry to adjust the pH of the copper slurry to 3.5-5.
  • decantation treatment was performed, 3500 ml of pure water was added, and the mixture was stirred for several minutes. After further decantation treatment, 3500 ml of pure water was added and stirred for several minutes. And filtration The silver-plated copper fine powder and the solution were separated by washing and dehydrating by suction, and the silver-plated copper fine powder was dried at a temperature of 90 ° C. for 2 hours.
  • the average particle size, specific surface area, apparent density, and tap density of the silver-plated copper fine powder according to the above-described examples were measured.
  • the average particle size was determined by the laser diffraction scattering particle size distribution measurement method, and the value of weight cumulative particle size D was adopted.
  • the specific surface area was measured by the BET method. Apparent
  • the density was measured according to JISZ2504.
  • the tap density was measured according to JISZ2512. The results are shown in Table 1.
  • Example 1 an average particle diameter of 9.4 ⁇ 111, specific surface area 0. 33m 2 / g, a tap density of 3. 92 g / cm 3, the resistivity became 1 ⁇ 3X 10- 4 ⁇ 'cm .
  • Example 2 an average particle diameter of 11. 7 m, specific surface area 0. 24m 2 / g, a tap density of 4. 76 g / cm 3, specific resistance 7. ivy Do and 1 X 10- 5 ⁇ 'cm.
  • the average particle size is 13. 8Mie, specific surface area 0. 19 m 2 / g, a tap density of 3. 99 g / cm 3, the resistivity became 1. 1 X 10- 4 ⁇ 'cm .
  • Example 4 the average particle size was 13.3 ⁇ m, the specific surface area was 0.16 m 2 / g, the tap density was 4.95 g / cm 3 , and the specific resistance was 6.5 ⁇ 10 ⁇ 5 ⁇ ′cm. .
  • the silver-plated copper fine powder of the present invention having an average particle size of 1 to 30 111, a tap density of 2.4 g / cm 3 or more, and a specific surface area of 0.9 m 2 / g or less.
  • the specific resistance is 1 becomes less 5 X 10- 4 ⁇ 'cm, as compared with the comparative example of the raw material powder and below, and shows the good conductivity.
  • Example 2 11.7 0.24 3.93 4.76 7.1X10-5
  • Example 3 13.8 0.19 2.79 3.99 1.lXlO- 4
  • Example 4 13.3 0.16 4.34 4.95 6.5X10-5 Comparative Example 8.7 0.44 2.87 4.00
  • the average particle size of Comparative Example 1 is 8.7 m
  • the tap density is 4,000 gg / cm 3
  • the force specific surface area is 0.44 m 2 / g, compared with the other examples.
  • the silver-plated copper fine powder surface has many irregularities, the color tone of the silver-plated surface is poor, and the conductivity is lowered, so that the object of the present invention cannot be achieved, resulting in an undesirable result.
  • the silver-plated copper fine powder in which the silver layer is uniformly coated on the surface of the copper fine powder according to the present invention has excellent conductivity.

Abstract

L'invention concerne un procédé pour produire une fine poudre de cuivre plaquée argent, qui est caractérisé par le traitement d'une fine poudre de cuivre par une solution alcaline pour éliminer des substances organiques présentes sur la surface de la fine poudre de cuivre, le lavage de la poudre avec de l'eau, le lavage d'un oxyde présent sur la surface de la fine poudre de cuivre avec une solution acide, le lavage de la poudre avec de l'eau, l'addition ultérieure d'un agent réducteur à une solution acide contenant cette fine poudre de cuivre dispersée dans celle-ci pour produire une suspension de la fine poudre de cuivre, la régulation du pH de la suspension, puis l'addition en continu à cette suspension de fine poudre de cuivre d'une solution d'ions argent complexés par un agent complexant pour former de cette façon une couche d'argent sur la surface de la fine poudre de cuivre par placage par déplacement chimique et placage par réduction. Ce procédé élimine les problèmes trouvés dans de fines poudres de cuivre plaquées argent classiques, tels que, par exemple, les différence de ton de couleur des fines poudres de cuivre obtenues par une réaction de placage d'argent selon l'état d'oxydation de celles-ci avant le placage d'argent, et la diminution de la masse volumique après tassement amenée par le placage d'argent. La fine poudre de cuivre plaquée argent présente d'excellentes caractéristiques de conductivité de l'électricité et de reproductibilité de la réaction de placage d'argent et possède presque la même densité volumique après tassement que la fine poudre de cuivre brute.
PCT/JP2007/071907 2006-11-17 2007-11-12 Fine poudre de cuivre plaquée argent, pâte conductrice produite à partir d'une fine poudre de cuivre plaquée argent, et procédé pour produire une fine poudre de cuivre plaquée argent WO2008059789A1 (fr)

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JP2011028985A (ja) * 2009-07-24 2011-02-10 Fujikura Kasei Co Ltd 導電性ペーストの製造方法および導電性ペースト
WO2011125556A1 (fr) * 2010-03-31 2011-10-13 Jx日鉱日石金属株式会社 Fine poudre de cuivre plaquée à l'argent et procédé pour sa production
JP2012092376A (ja) * 2010-10-25 2012-05-17 Ishihara Chem Co Ltd スズめっき銅粉の製造方法
JP2012180563A (ja) * 2011-03-01 2012-09-20 Mitsui Mining & Smelting Co Ltd 銅粒子
CN102773475A (zh) * 2012-07-31 2012-11-14 东南大学 一种导电浆料用抗氧化铜银复合粉及其制备方法
CN103752842A (zh) * 2013-11-11 2014-04-30 南京工业大学 置换与化学沉积复合法制备纳米银包铜粉末
JP2014208908A (ja) * 2013-03-29 2014-11-06 Ｄｏｗａエレクトロニクス株式会社 銀コート銅粉、銀コート銅粉の製造方法および樹脂硬化型導電性ペースト
WO2015008628A1 (fr) * 2013-07-16 2015-01-22 Ｄｏｗａエレクトロニクス株式会社 Poudre d'alliage de cuivre recouverte d'argent et procédé de fabrication de cette dernière
CN104797360A (zh) * 2012-10-03 2015-07-22 户田工业株式会社 银混合铜粉及其制造方法、含有该银混合铜粉的导电性膏、导电性粘合剂、导电性膜和电气回路
JP2015183291A (ja) * 2014-03-26 2015-10-22 三井金属鉱業株式会社 銀被覆銅粉及びこれを用いた導電性ペースト
CN105903980A (zh) * 2016-05-16 2016-08-31 深圳市微纳集成电路与系统应用研究院 铜纳米粉及其制备方法，银包铜粉末及其制备方法
JP2016176093A (ja) * 2015-03-19 2016-10-06 Ｄｏｗａエレクトロニクス株式会社 銀被覆金属粉末およびその製造方法
JP2017514020A (ja) * 2014-04-23 2017-06-01 アルファ・アセンブリー・ソリューションズ・インコーポレイテッドＡｌｐｈａ Ａｓｓｅｍｂｌｙ Ｓｏｌｕｔｉｏｎｓ Ｉｎｃ． 金属粉末を製造するための方法
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CN111872376A (zh) * 2020-07-21 2020-11-03 云南铜业科技发展股份有限公司 一种抗氧化性高的银包覆微合金化铜粉制备方法

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JP2011028985A (ja) * 2009-07-24 2011-02-10 Fujikura Kasei Co Ltd 導電性ペーストの製造方法および導電性ペースト
WO2011125556A1 (fr) * 2010-03-31 2011-10-13 Jx日鉱日石金属株式会社 Fine poudre de cuivre plaquée à l'argent et procédé pour sa production
CN102811830A (zh) * 2010-03-31 2012-12-05 Jx日矿日石金属株式会社 镀银铜微粉及其制备方法
JP2012092376A (ja) * 2010-10-25 2012-05-17 Ishihara Chem Co Ltd スズめっき銅粉の製造方法
JP2012180563A (ja) * 2011-03-01 2012-09-20 Mitsui Mining & Smelting Co Ltd 銅粒子
CN102773475A (zh) * 2012-07-31 2012-11-14 东南大学 一种导电浆料用抗氧化铜银复合粉及其制备方法
CN102773475B (zh) * 2012-07-31 2014-06-11 东南大学 一种导电浆料用抗氧化铜银复合粉及其制备方法
CN104797360A (zh) * 2012-10-03 2015-07-22 户田工业株式会社 银混合铜粉及其制造方法、含有该银混合铜粉的导电性膏、导电性粘合剂、导电性膜和电气回路
JP2014208908A (ja) * 2013-03-29 2014-11-06 Ｄｏｗａエレクトロニクス株式会社 銀コート銅粉、銀コート銅粉の製造方法および樹脂硬化型導電性ペースト
JP2015021137A (ja) * 2013-07-16 2015-02-02 Ｄｏｗａエレクトロニクス株式会社 銀被覆銅合金粉末およびその製造方法
WO2015008628A1 (fr) * 2013-07-16 2015-01-22 Ｄｏｗａエレクトロニクス株式会社 Poudre d'alliage de cuivre recouverte d'argent et procédé de fabrication de cette dernière
CN103752842A (zh) * 2013-11-11 2014-04-30 南京工业大学 置换与化学沉积复合法制备纳米银包铜粉末
JP2015183291A (ja) * 2014-03-26 2015-10-22 三井金属鉱業株式会社 銀被覆銅粉及びこれを用いた導電性ペースト
JP2017514020A (ja) * 2014-04-23 2017-06-01 アルファ・アセンブリー・ソリューションズ・インコーポレイテッドＡｌｐｈａ Ａｓｓｅｍｂｌｙ Ｓｏｌｕｔｉｏｎｓ Ｉｎｃ． 金属粉末を製造するための方法
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JP2021113358A (ja) * 2015-03-19 2021-08-05 Ｄｏｗａエレクトロニクス株式会社 銀被覆金属粉末およびその製造方法
JP2016176093A (ja) * 2015-03-19 2016-10-06 Ｄｏｗａエレクトロニクス株式会社 銀被覆金属粉末およびその製造方法
JP7042945B2 (ja) 2015-03-19 2022-03-28 Ｄｏｗａエレクトロニクス株式会社 銀被覆金属粉末およびその製造方法
CN105903980A (zh) * 2016-05-16 2016-08-31 深圳市微纳集成电路与系统应用研究院 铜纳米粉及其制备方法，银包铜粉末及其制备方法
CN107626917A (zh) * 2017-09-15 2018-01-26 烟台屹海新材料科技有限公司 一种镀银铜粉的制备方法
CN109773212A (zh) * 2019-03-29 2019-05-21 金陵科技学院 一种适用于大功率封装抗氧化镀银铜焊膏的制备方法
CN109773212B (zh) * 2019-03-29 2022-05-20 金陵科技学院 一种适用于大功率封装抗氧化镀银铜焊膏的制备方法
CN111872376A (zh) * 2020-07-21 2020-11-03 云南铜业科技发展股份有限公司 一种抗氧化性高的银包覆微合金化铜粉制备方法

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