WO2014115614A1 - 銅粉 - Google Patents

銅粉 Download PDF

Info

Publication number
WO2014115614A1
WO2014115614A1 PCT/JP2014/050539 JP2014050539W WO2014115614A1 WO 2014115614 A1 WO2014115614 A1 WO 2014115614A1 JP 2014050539 W JP2014050539 W JP 2014050539W WO 2014115614 A1 WO2014115614 A1 WO 2014115614A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper powder
copper
electrolytic
particles
concentration
Prior art date
Application number
PCT/JP2014/050539
Other languages
English (en)
French (fr)
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 CN201480005241.3A priority Critical patent/CN104918732A/zh
Priority to JP2014549264A priority patent/JP5711435B2/ja
Priority to KR1020157018007A priority patent/KR101613601B1/ko
Publication of WO2014115614A1 publication Critical patent/WO2014115614A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of 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
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions

Definitions

  • the present invention relates to a copper powder that can be suitably used as a conductive filler contained in a conductive paste or the like.
  • a conductive paste is a fluid composition in which a conductive filler is dispersed in a vehicle composed of a resin binder and a solvent.
  • a conductive filler is dispersed in a vehicle composed of a resin binder and a solvent.
  • Dendritic copper powder particles obtained by the electrolytic method have a larger number of contacts between the particles than spherical copper powder particles, so when used as a conductive material for conductive paste, the amount of conductive material is reduced. Even if it has an advantage that a conductive characteristic can be improved. Therefore, for example, in the case where the wiring connection hole is embedded with a conductive paste or the like in the manufacture of a semiconductor device, it is sufficient that the electrical signal can be transmitted, so that even a smaller amount can be obtained. Dendritic copper powder particles are particularly useful.
  • a copper powder for a conductive paint that can be soldered is a rod shape obtained by pulverizing a dendritic copper powder having a particle shape, and has an oil absorption amount.
  • a copper powder characterized by (JIS K5101) of 20 ml / 100 g or less, a maximum particle size of 44 ⁇ m or less, an average particle size of 10 ⁇ m or less, and a hydrogen reduction weight loss of 0.5% or less is disclosed.
  • Patent Document 3 and Patent Document 4 disclose electrolytic copper powder particles having a dendritic shape as a heat pipe constituent raw material.
  • Patent Document 5 describes that a method for electrolysis by adding chlorine to an electrolytic solution is known as a production method for adjusting the dendrite form of the electrolytic copper powder with respect to the method for producing the dendritic electrolytic copper powder. Yes.
  • Japanese Patent Laid-Open No. 06-158103 Japanese Patent Laid-Open No. 2000-80408 JP 2008-122030 A JP 2009-047383 A Japanese Patent Laid-Open No. 1-224784
  • Patent Document 5 it is known that when copper powder is produced by an electrolysis method, copper powder particles can be atomized while maintaining a dendritic particle shape by adding chlorine to the electrolytic solution. It has been. However, when adding chlorine to the electrolyte and conducting electrolysis, the conductivity of the obtained copper powder is less than expected due to the influence of residual chlorine, or when the copper powder particles are coated with silver. It has been found that there are problems such as difficulty in coating to a uniform thickness. It has also been found that the copper powder obtained in this way, that is, the copper powder containing dendritic copper powder particles, is significantly deteriorated over time such as oxidation and corrosion.
  • the present invention relates to a copper powder containing dendritic copper powder particles, and provides a new copper powder that suppresses the influence of residual chlorine and improves the property of being easily oxidized.
  • the present invention is a copper powder containing dendritic copper powder particles having a dendritic shape, the concentration of chlorine contained in the copper powder is 5 wtppm to 250 wtppm, and conforms to JIS K 5101-17-2
  • a copper powder (referred to as “the copper powder of the present invention”) characterized in that the pH of the copper powder measured in this way is 5 to 9 is proposed.
  • the copper powder of the present invention is a copper powder containing dendritic copper powder particles, the number of contacts between the particles is larger than that of a copper powder made of spherical copper powder particles.
  • the conductive characteristics can be improved even if the amount of the conductive material is reduced.
  • the concentration of chlorine contained in the copper powder of the present invention to 5 wtppm to 250 wtppm, it is possible to effectively suppress the adverse effects due to residual chlorine.
  • the copper powder particles are coated with silver, a uniform thickness is achieved. Can be coated.
  • the copper powder of the present invention has also succeeded in improving oxidative and corrosive deterioration over time by setting the pH of the copper powder to 5-9.
  • the copper powder according to the present embodiment is a copper powder containing dendritic copper powder particles (referred to as “present copper powder particles”).
  • “dendritic copper powder particles” are provided with one main axis as shown in FIG. 1 when observed with an electron microscope (500 to 20,000 times).
  • the main axis refers to a rod-like portion that is a group from which a plurality of branches are branched.
  • the present copper powder particles are observed with an electron microscope (500 to 20,000 times), it is particularly preferable to exhibit a dendrite shape having the following predetermined characteristics.
  • the thickness a of the main axis is preferably 0.3 ⁇ m to 5.0 ⁇ m, more preferably 0.4 ⁇ m or more and 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 of dendrites is 0.3 ⁇ m or less, the main axis may not be solid, so branches may be difficult to grow. On the other hand, if the thickness is larger than 5.0 ⁇ m, the particles tend to aggregate and form a pinecone There is a possibility of becoming.
  • 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 0.8 ⁇ m to 12.0 ⁇ m. Among these, 1.0 ⁇ m or more or 10.0 ⁇ m or less is preferable, and among them, 1.2 ⁇ m or more or 8.0 ⁇ m or less is more preferable. If the branch length b is less than 0.8 ⁇ m, it cannot be said that the dendrite has grown sufficiently. On the other hand, if the branch length b exceeds 12.0 ⁇ m, the fluidity of the copper powder may be lowered and handling may be difficult.
  • 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 dendritic particles as described above may be mixed even if particles of other shapes are mixed.
  • the effect similar to the copper powder which consists only of can be acquired. Therefore, from this point of view, when the present copper powder is observed with an electron microscope (500 to 20,000 times), the dendrite-like copper powder particles are 80% by number or more, preferably 90% by number of the total copper powder particles. As long as it occupies the above, non-dendritic copper powder particles that are not recognized as dendritic may be contained.
  • the present copper powder preferably has a concentration of chlorine contained in the copper powder, that is, a contained chlorine concentration of 5 wtppm to 250 wtppm, of which 10 wtppm or more or 220 wtppm or less, of which 20 wtppm or more or 200 wtppm or less, of which 30 wtppm or more. More preferably, it is 180 wtppm or less. If the concentration of chlorine contained in the copper powder is 250 wtppm or less, adverse effects due to residual chlorine can be effectively suppressed. For example, the copper powder particles can be coated with a uniform thickness when coated with silver. . In addition, although the content chlorine concentration of this copper powder may be less than 5 wtppm, about 5 wtppm is a detection limit of a content chlorine concentration.
  • the chlorine concentration in the copper powder is set to 5 wtppm to 250 wtppm by removing even the inside of the particles, and at least the chlorine in the vicinity of the surface, which has an adverse effect, so that the residual chlorine depends on the residual chlorine.
  • An adverse effect can be effectively suppressed, and for example, when silver is coated on copper powder particles, it can be coated with a uniform thickness.
  • the chlorine concentration in the copper powder cannot be made 5 wtppm to 250 wtppm.
  • the powder pH (measured in accordance with JIS K 5101-17-2) of the present copper powder is preferably 5 to 9, especially 5.5 or more and 8 or less, especially 6 or 7.5 or less. More preferably.
  • the powder pH of the present copper powder is 5 to 9, deterioration over time due to oxidation and corrosion of the copper powder surface can be effectively suppressed.
  • Examples of the method for adjusting the powder pH of the present copper powder to 5 to 9 include a method in which the copper powder immediately after electrolysis is alkali-treated as described above.
  • the D50 of the present copper powder that is, the volume cumulative particle size D50 measured by a laser diffraction / scattering particle size distribution measuring device is preferably 3 ⁇ m to 30 ⁇ m, more preferably 5 ⁇ m or more or 25 ⁇ m or less, especially 7 ⁇ m or more or 20 ⁇ m or less.
  • the thickness is particularly preferably 15 ⁇ m or less. If D50 is 3 ⁇ m or more, the viscosity can be easily adjusted. On the other hand, if D50 is 30 ⁇ m or less, it can be applied to various conductive pastes, which is preferable.
  • the specific surface area of the copper powder measured by the BET single point method is preferably 0.30 to 1.50 m 2 / g. If it is remarkably smaller than 0.30 m 2 / g, the branch does not develop and it becomes close to a pinecone to a sphere, so that it is difficult to obtain the effect of the dendritic copper powder. On the other hand, if it is significantly larger than 1.50 m 2 / g, the dendrite branch becomes too thin, and there is a possibility that the branch breaks in the paste processing step, which may hinder the conductivity.
  • the specific surface area as measured by single point method BET of the copper powder is 0.30 ⁇ 1.50m 2 / g at and even good properly, inter alia 0.40 m 2 / g or more or 1.40 m 2 / g or less, Among these, it is more preferable that it is 1.00 m ⁇ 2 > / g or less especially.
  • the oxygen concentration of this copper powder is 0.20 mass% or less. If the oxygen concentration of the present copper powder is 0.20% by mass or less, the conductivity can be further improved. From this viewpoint, the oxygen concentration of the present copper powder is more preferably 0.18% by mass or less, and particularly preferably 0.15% by mass or less.
  • a method of controlling the oxygen concentration and drying temperature in a dry atmosphere or performing an alkali treatment as described above can be mentioned. . However, it is not limited to this method.
  • This copper powder can be manufactured by a predetermined 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.
  • chlorine to the electrolytic solution to adjust the chlorine concentration of the electrolytic solution to 3 to 300 mg / L, particularly 5 to 200 mg / L.
  • the copper ions in the electrolytic solution are consumed as copper is deposited, so the copper ion concentration in the electrolytic solution near the electrode plate is reduced, and the electrolytic efficiency is reduced as it is. Resulting in. Therefore, it is usually preferable to circulate the electrolytic solution in the electrolytic cell so that the copper ion concentration of the electrolytic solution between the electrodes does not become thin in order to increase the electrolytic efficiency.
  • the size of the electrolytic cell, the number of electrodes, the distance between the electrodes, and the circulation amount of the electrolytic solution are adjusted, and the copper ion concentration of the electrolytic solution near the electrodes is adjusted to be 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 10 g / L
  • the current density may be 100 A / m 2 to 3000 A / m 2
  • the electrolysis time may be 3 minutes to 3 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.
  • this copper powder has excellent conductive properties, it is used as a main constituent material of various conductive materials such as conductive pastes and conductive adhesives, and conductive paints. It can be used suitably. Moreover, other copper powder can be mixed with this copper powder, and it can also be used as main constituent materials of various conductive materials, such as conductive resin compositions, such as a conductive paste and a conductive adhesive.
  • the copper powder in order to produce a conductive paste, 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 a circuit pattern on a substrate to form various electric circuits.
  • 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.
  • the copper powder particles of the present copper powder have particularly developed dendrites, the number of contacts between the particles is increased, and excellent conductive properties can be obtained even if the content of the conductive powder is reduced. It is suitable as a conductive paste material used for the purpose of embedding the inside of a wiring connection hole when manufacturing a semiconductor device.
  • the present copper powder particles as a core material, a part or all of these surfaces can be covered with a different conductive material such as gold, silver, nickel, tin and the like.
  • a different conductive material such as gold, silver, nickel, tin and the like.
  • 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.
  • the copper deposited on the cathode surface was mechanically scraped and collected, and then washed to obtain a hydrated copper powder cake equivalent to 1 kg of copper powder.
  • 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.
  • 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.
  • an electrolytic copper powder (sample)
  • SEM scanning electron microscope
  • Example 2 In the alkali treatment of Example 1, instead of performing an alkali treatment by adding an ammonium carbonate solution until a pH of 9, in Example 2, an aqueous ammonia was added and an alkali treatment was conducted until a pH of 11 was reached. Then, alkali treatment was performed by adding caustic soda until the pH reached 14. Except for this point, an electrolytic copper powder (sample) was obtained in the same manner as in Example 1. When the electrolytic copper powder (sample) obtained in this way was observed using a scanning electron microscope (SEM), at least 90% or more of the copper powder particles had one main axis, and a plurality of the main parts were separated from the main axis. It was confirmed that the branches had a dendrite shape that grew vertically and diagonally and grew three-dimensionally.
  • SEM scanning electron microscope
  • 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 copper deposited on the cathode surface was mechanically scraped and collected, and then washed to obtain a hydrated copper powder cake equivalent to 1 kg of copper powder.
  • 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.
  • 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.
  • an electrolytic copper powder (sample)
  • SEM scanning electron microscope
  • 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 until the pH reached 14. Except for this point, an electrolytic copper powder (sample) was obtained in the same manner as in Example 4. When the electrolytic copper powder (sample) obtained in this way was observed using a scanning electron microscope (SEM), at least 90% or more of the copper powder particles had one main axis, and a plurality of the main parts were separated from the main axis. It was confirmed that the branches had a dendrite shape that grew vertically and diagonally and grew three-dimensionally.
  • SEM scanning electron microscope
  • 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 Cu concentration of the electrolyte to be circulated was adjusted to 20 g / L
  • the sulfuric acid (H 2 SO 4 ) concentration was set to 80 g / L
  • the chlorine concentration was adjusted to 20 mg / L
  • the current density was adjusted to 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 copper deposited on the cathode surface was mechanically scraped and collected, and then washed to obtain a hydrated copper powder cake equivalent to 1 kg of copper powder.
  • 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.
  • 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.
  • an electrolytic copper powder (sample)
  • SEM scanning electron microscope
  • Example 8 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 8, an alkali treatment was performed by adding an ammonium carbonate solution until a pH of 8.5, In Example 9, an alkali treatment was performed by adding an ammonium carbonate solution until the pH reached 8.0. Except for this point, an electrolytic copper powder (sample) was obtained in the same manner as in Example 1. When the electrolytic copper powder (sample) obtained in this way was observed using a scanning electron microscope (SEM), at least 90% or more of the copper powder particles had one main axis, and a plurality of the main parts were separated from the main axis. It was confirmed that the branches had a dendrite shape that grew vertically and diagonally and grew three-dimensionally.
  • SEM scanning electron microscope
  • Example 1 In 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 washed with pure water to remove impurities, 1 L of an industrial gelatin (Nitta Gelatin Co., Ltd.) 10 g / L aqueous solution was added and stirred, and then 80 80 under reduced pressure (1 ⁇ 10 ⁇ 3 Pa). It was made to dry at 5 degreeC for 6 hours, and the electrolytic copper powder (sample) was obtained. The other points were manufactured in the same manner as in Example 1.
  • an industrial gelatin Nita Gelatin Co., Ltd.
  • the electrolytic copper powder (sample) obtained in this way was observed using a scanning electron microscope (SEM), at least 90% or more of the copper powder particles had one main axis, and a plurality of the main parts were separated from the main axis. It was confirmed that the branches had a dendrite shape that grew vertically and diagonally and grew three-dimensionally.
  • 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 washed with pure water to remove impurities, 1 L of an industrial gelatin (Nitta Gelatin Co., Ltd.) 10 g / L aqueous solution was added and stirred, and then 80 80 under reduced pressure (1 ⁇ 10 ⁇ 3 Pa). It was made to dry at 5 degreeC for 6 hours, and the electrolytic copper powder (sample) was obtained.
  • the other points were manufactured in the same manner as in Example 4.
  • the electrolytic copper powder (sample) obtained in this way was observed using a scanning electron microscope (SEM), at least 90% or more of the copper powder particles had one main axis, and a plurality of the main parts were separated from the main axis. It was confirmed that the branches had a dendrite-like shape that was obliquely branched and grew three-dimensionally.
  • ⁇ Particle size measurement> Take a measurement sample (copper powder) in a small amount of beaker, add a few drops of 3% Triton X solution (manufactured by Kanto Chemical Co., Ltd.), and blend with the powder. Then, 0.1% SN Dispersant 41 solution (San Nopco) 50 mL was added, and then a measurement sample was prepared by dispersing for 2 minutes using an ultrasonic disperser TIP ⁇ 20 (manufactured by Nippon Seiki Seisakusho). This sample for measurement was measured for volume accumulation standard D50 using a laser diffraction / scattering particle size distribution measuring device MT3300 (manufactured by Nikkiso), and is shown in Table 1.
  • the specific surface area was measured by a BET one-point method using a monosorb manufactured by Mountec Co., Ltd., and is shown in Table 1 as BET.
  • the slurry is washed with a solution of 1200 g of EDTA (ethylenediaminetetraacetic acid) in 12 L of pure water, and subsequently 6.0 L.
  • the residual EDTA was washed with pure water. Then, it dried at 120 degreeC for 3 hours, and obtained silver covering copper powder. Then, the surface of the silver-coated copper powder thus obtained was observed with an Auger electron spectrometer, and it was evaluated whether silver was coated to a uniform thickness. In this case, the case where the silver is entirely covered and the copper exposed part is not recognized is evaluated as “uniform”, the silver is not covered and the copper exposed part is recognized Was evaluated as "non-uniform".
  • the electrolytic copper powder obtained in the examples and comparative examples was evaluated for oxidative deterioration and corrosive deterioration in a high temperature and high humidity test at 85 ° C. and 85 RH% for 100 hours. Thereby, it can be evaluated whether it is easy to oxidize or corrode with time.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Nanotechnology (AREA)
  • Mechanical Engineering (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Powder Metallurgy (AREA)
  • Non-Insulated Conductors (AREA)
PCT/JP2014/050539 2013-01-24 2014-01-15 銅粉 WO2014115614A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201480005241.3A CN104918732A (zh) 2013-01-24 2014-01-15 铜粉
JP2014549264A JP5711435B2 (ja) 2013-01-24 2014-01-15 銅粉
KR1020157018007A KR101613601B1 (ko) 2013-01-24 2014-01-15 구리분

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013011393 2013-01-24
JP2013-011393 2013-01-24

Publications (1)

Publication Number Publication Date
WO2014115614A1 true WO2014115614A1 (ja) 2014-07-31

Family

ID=51227406

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/050539 WO2014115614A1 (ja) 2013-01-24 2014-01-15 銅粉

Country Status (5)

Country Link
JP (1) JP5711435B2 (ko)
KR (1) KR101613601B1 (ko)
CN (1) CN104918732A (ko)
TW (1) TW201439377A (ko)
WO (1) WO2014115614A1 (ko)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017039988A (ja) * 2015-08-21 2017-02-23 古河電気工業株式会社 金属粒子の分散溶液および接合構造体ならびにそれらの製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6350475B2 (ja) * 2015-09-29 2018-07-04 住友金属鉱山株式会社 銅粉の製造方法、及びそれを用いた導電性ペーストの製造方法

Citations (3)

* 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
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

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6036839A (en) * 1998-02-04 2000-03-14 Electrocopper Products Limited Low density high surface area copper powder and electrodeposition process for making same
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
JP5720693B2 (ja) * 2010-10-06 2015-05-20 旭硝子株式会社 導電性銅粒子の製造方法
JP5320442B2 (ja) * 2011-07-13 2013-10-23 三井金属鉱業株式会社 デンドライト状銅粉

Patent Citations (3)

* 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
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017039988A (ja) * 2015-08-21 2017-02-23 古河電気工業株式会社 金属粒子の分散溶液および接合構造体ならびにそれらの製造方法

Also Published As

Publication number Publication date
JPWO2014115614A1 (ja) 2017-01-26
JP5711435B2 (ja) 2015-04-30
KR20150090256A (ko) 2015-08-05
KR101613601B1 (ko) 2016-04-19
TW201439377A (zh) 2014-10-16
CN104918732A (zh) 2015-09-16

Similar Documents

Publication Publication Date Title
JP5320442B2 (ja) デンドライト状銅粉
JP5631910B2 (ja) 銀被覆銅粉
JP2013053347A (ja) デンドライト状銅粉
JP5631841B2 (ja) 銀被覆銅粉
JP5876971B2 (ja) 銅粉
JP6166012B2 (ja) 導電性粉末及び導電性ペースト
JP6165399B1 (ja) 銀被覆銅粉
JP5701695B2 (ja) 銀被覆銅粉及びその製造方法
JP6278969B2 (ja) 銀被覆銅粉
JP2013136818A (ja) 銅粉
JP2013168375A (ja) デンドライト状銅粉
JP4881013B2 (ja) 導電性粉末、導電性ペーストおよび電気回路
JP6938986B2 (ja) 粒子形状の評価方法
JP2014159646A (ja) 銀被覆銅粉
JP5711435B2 (ja) 銅粉
JP6225711B2 (ja) 硫化銅被覆銅粉、導電ペースト及びこれら製造方法
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

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: 14743070

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014549264

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20157018007

Country of ref document: KR

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: 14743070

Country of ref document: EP

Kind code of ref document: A1