US20180096747A1 - Spherical silver powder and method for producing same - Google Patents
Spherical silver powder and method for producing same Download PDFInfo
- Publication number
- US20180096747A1 US20180096747A1 US15/831,696 US201715831696A US2018096747A1 US 20180096747 A1 US20180096747 A1 US 20180096747A1 US 201715831696 A US201715831696 A US 201715831696A US 2018096747 A1 US2018096747 A1 US 2018096747A1
- Authority
- US
- United States
- Prior art keywords
- silver powder
- ppm
- silver
- particles
- spherical silver
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 202
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000002245 particle Substances 0.000 claims abstract description 128
- 229910052709 silver Inorganic materials 0.000 claims abstract description 98
- 239000004332 silver Substances 0.000 claims abstract description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- -1 silver ions Chemical class 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 25
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 38
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- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 8
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 3
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Images
Classifications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0549—Hollow particles, including tubes and shells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
- B22F1/0655—Hollow particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
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- 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
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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
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- B22F2001/0029—
-
- 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
- B22F2202/00—Treatment under specific physical conditions
- B22F2202/01—Use of vibrations
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2202/00—Treatment under specific physical conditions
- B22F2202/11—Use of irradiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
Definitions
- the present invention relates generally to a spherical silver powder and a method for producing the same. More specifically, the invention relates to a spherical silver powder for a conductive paste for use in electronic parts, such as internal electrodes of laminated capacitors, conductive patterns of circuit boards, and electrodes and circuits of substrates for plasma display panels and solar cells, and a method for producing the same.
- cermet type conductive paste As a conventional method for forming internal electrodes of laminated capacitors, conductive patterns of circuit boards, electrodes and circuits of substrates for solar cells and plasma display panels (PDPs), there is widely used a method for forming a cermet type conductive paste, which is produced by kneading a mixture obtained by adding a silver powder and a glass frit to an organic vehicle, in a predetermined pattern on a substrate, and thereafter, heating the paste at a temperature of not lower than 500° C. to remove organic components to sinter silver particles with each other to form a conductive film.
- a silver powder for a conductive paste for use in such a method has a reasonably small particle size and a reasonably narrow range of the particle size in order to form small electronic parts and conductive patterns having a high density and fine lines.
- a spherical silver powder having a particle size which is substantially equal to that of a spherical silver powder produced by a conventional wet reducing method, is used for forming a cermet type conductive paste, even if the paste is heated at a temperature of about 600° C., there are some cases where it is not possible to sufficiently sinter silver particles with each other, so that it is not possible to form a good conductive film.
- a spherical silver powder which has a particle size being substantially equal to that of a spherical silver powder produced by a conventional wet reducing method and which is capable of being fired at a lower temperature, if silver particles are deposited by reduction by mixing a reducing agent containing solution, which contains an aldehyde as a reducing agent, with a water reaction system containing silver ions while causing cavitation in the water reaction system.
- a reducing agent containing solution which contains an aldehyde as a reducing agent
- a method for producing a spherical silver powder comprising the steps of: preparing a water reaction system containing silver ions; preparing a reducing agent containing solution which contains an aldehyde as a reducing agent; and depositing silver particles by reduction by mixing the reducing agent containing solution with the water reaction system while causing cavitation in the water reaction system.
- the cavitation is caused by irradiating the water reaction system containing silver ions with ultrasonic waves.
- the water reaction system containing silver ions is preferably an aqueous solution containing a silver ammonia complex.
- the reducing agent containing solution is preferably a solution containing formaldehyde or acetaldehyde.
- the method may further comprise steps of carrying out the solid-liquid separation of the silver particles deposited by reduction; washing the separated silver particles; and drying the washed silver particles at a temperature of not higher than 100° C.
- the spherical silver powder preferably has a closed cavity in each particle thereof.
- a spherical silver powder which has a closed cavity in each particle thereof.
- This spherical silver powder preferably has a mean particle size D 50 of 0.1 to 10 ⁇ m when the particle size is obtained by a laser diffraction method.
- the spherical silver powder preferably has a true specific gravity of not greater than 9.8 g/cm 3 .
- the content of each of impurities, except for carbon, nitrogen, oxygen and hydrogen, contained in the spherical silver powder is preferably less than 100 ppm.
- a conductive paste using the above-described spherical silver powder as a conductor.
- a spherical silver powder which has a particle size being substantially equal to that of a spherical silver powder produced by a conventional wet reducing method and which is capable of being fired at a lower temperature, by depositing silver particles by reduction by mixing a reducing agent containing solution, which contains an aldehyde as a reducing agent, with a water reaction system containing silver ions while causing cavitation in the water reaction system.
- FIG. 1 is a field emission-scanning electron micrograph (FE-SEM image) of a cross section of a spherical silver powder obtained in Example 1;
- FIG. 2 is an FE-SEM image of a cross section of a spherical silver powder obtained in Example 2;
- FIG. 3 is an FE-SEM image of a cross section of a spherical silver powder obtained in Example 3.
- FIG. 4 is an FE-SEM image of a cross section of a spherical silver powder obtained in Comparative Example 1.
- silver particles are deposited by reduction by mixing a reducing agent containing solution, which contains an aldehyde as a reducing agent, with a water reaction system containing silver ions while causing cavitation in the water reaction system.
- the cavitation is a physical phenomenon in which the generation and extinction of bubbles occur in a short time by a local pressure difference caused in a liquid.
- the cavitation can be produced by the irradiation with ultrasonic waves, a homogenizer for emulsion treatment or the like.
- the cavitation is preferably produced by irradiating the water reaction system containing silver ions with ultrasonic waves.
- the oscillating frequency of the irradiated ultrasonic waves may be an oscillating frequency capable of causing cavitation, and is preferably in the range of from 28 kHz to 40 kHz.
- the output of the ultrasonic waves may be set in accordance with the amount of liquid used for causing the deposition reaction of silver particles by reduction.
- the irradiation with the ultrasonic waves may be carried out when the reducing agent containing solution is added for depositing the silver particles by reduction, or it may be carried out before or after the reducing agent containing solution is added for depositing the silver particles by reduction.
- an aqueous solution or slurry containing silver nitrate, a silver salt complex or a silver intermediate may be used as the water reaction system containing silver ions.
- the aqueous solution containing a silver salt complex may be produced by adding aqueous ammonia or an ammonia salt to an aqueous silver nitrate solution or a suspension of silver oxide.
- an aqueous solution of silver ammine complex obtained by adding aqueous ammonia to an aqueous silver nitrate solution is preferably used in order to produce a silver powder having an appropriate particle size and a spherical shape.
- the coordination number of ammonia in the silver ammine complex is 2, so that 2 moles or more of ammonia per 1 mole of silver is added. If the amount of ammonia to be added is too large, the complex is too stable, so that it is difficult to proceed reduction. Therefore, the amount of ammonia to be added is preferably not larger than 8 moles per 1 mole of silver. Furthermore, if adjustment is carried out by increasing the amount of ammonia to be added or the like, even if the amount of ammonia to be added exceeds 8 moles, it is possible to obtain a spherical silver powder having an appropriate particle size.
- a compound having an aldehyde group may be used, and formaldehyde or acetaldehyde is preferably used.
- the aldehyde may be used alone, or aldehyde compounds may be combined to be used.
- a mixture of water or alcohol with an aldehyde, such as formalin may be used. If the cavitation is caused when a reducing agent containing solution, which contains an aldehyde as the reducing agent, is added to deposit silver particles by reduction, it is possible to obtain a spherical silver powder having a closed cavity in the interior of each particle thereof.
- the amount of the reducing agent to be added may be an excessive amount with respect to the water reaction system containing silver ions.
- the amount of the reducing agent required to cause the amount of unreduced silver ions to be 10 ppm or less may be added.
- a pH adjusting agent may be added to the water reaction system containing silver ions.
- a general acid or base may be used.
- nitric acid, sodium hydroxide or the like may be used.
- a surface treating agent may be added to the water reaction system containing silver ions.
- the surface treating agent there may be used any one or more of fatty acids, fatty acid salts, surface active agents, organometallic compounds, chelating agents, high-polymer dispersing agents and so forth.
- fatty acids include propionic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, acrylic acid, oleic acid, linolic acid, and arachidonic acid.
- fatty acid salts include salts formed by fatty acids and metals, such as lithium, sodium, potassium, barium, magnesium, calcium, aluminum, iron, cobalt, manganese, lead, zinc, tin, strontium, zirconium, silver or copper.
- surface active agents include: anionic surface active agents, such as alkyl benzene sulfonates and polyoxyethylene alkyl ether phosphates; cationic surface active agents, such as aliphatic quaternary ammonium salts; amphoteric surface active agents, such as imidazolinium betaine; and nonionic surface active agents, such as polyoxyethylene alkyl ethers and polyoxyethylene fatty acid esters.
- organometallic compounds include acetylacetone tributoxyzirconium, magnesium citrate, diethylzinc, dibutyltin oxide, dimethylzinc, tetra-n-butoxyzirconium, triethyl indium, triethyl gallium, trimethyl indium, trimethyl gallium, monobutyl tin oxide, tetraisocyanate silane, tetramethyl silane, tetramethoxy silane, polymethoxy siloxane, monomethyl triisocyanate silane, silane coupling agent, titanate coupling agents, and aluminum coupling agents.
- chelating agents include imidazole, oxazole, triazole, selenazole, pyrazole, isoxazole, isothiazole, 1H-1,2,3-triazole, 2H-1,2,3-triazole, 1H-1,2,4-triazole, 4H-1,2,4-triazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1H-1,2,3,4-tetrazole, 1,2,3,4-oxatriazole, 1,2,3,4-thiatriazole, 2H-1,2,3,4-tetrazole, 1,2,3,5-oxatriazole, 1,2,3,5-thiatriazole, indazole, benzoimidazole, benzotriazo
- the silver particles are washed with water.
- a solid cake which contains 1 to 200 wt % of water with respect to silver and which is hardly fluid.
- water in the cake may be replaced with a lower alcohol or the like.
- a dried silver powder by drying the cake by means of a drier, such as a forced circulation air drier, a vacuum drier or a flash drier (pneumatic conveying drier).
- the temperature of drying is preferably not higher than 100° C. in order to maintain a closed cavity in the interior of each particle of the silver powder.
- the obtained silver powder may be subjected to a dry-crushing and/or classification process.
- the silver powder may be subjected to a surface smoothing process for smoothing the irregularities and angular portions on the surface of the particles of the silver powder by mechanically causing the particles of the silver powder to collide with each other by putting the silver powder into an apparatus capable of mechanically fluidizing particles.
- a classification process may be carried out.
- the drying, crushing and classification processes may be carried out by an integrated apparatus capable of carrying out the drying, crushing and classification processes (DRY MASTER produced by Hosokawa Micron Corporation, Micron Drier or the like).
- the process for forming a conductive film by firing a cermet type conductive paste using a silver powder generally comprises: (1) Evaporation of Diluent Solvent, (2) Combustion of Organic Components (surface treating agent and resin), (3) Softening of Glass Frit serving as Sintering Additive, and (4) Liquid-Phase Sintering of Silver Particles.
- Evaporation of Diluent Solvent (2) Combustion of Organic Components (surface treating agent and resin), (3) Softening of Glass Frit serving as Sintering Additive, and (4) Liquid-Phase Sintering of Silver Particles.
- a method for producing a silver powder having cavities in particles thereof there is considered a method for using particles of a metal, which is loss nobler than silver, as particles of a base material to deposit silver on the surface of the particles of the metal by a substitution reaction to dissolve and remove the particles of the base material.
- a substitution reaction to dissolve and remove the particles of the base material.
- the cavities in particles thereof are closed cavities, the metal component of the particles of the base material remains. For that reason, there is the possibility of deteriorating the conductivity of the silver powder and the reliability of the silver powder due to oxidation, so that it is required to cause the cavities in particles thereof to be cavities which are open to the outside.
- the content of each of the impurity elements is preferably less than 100 ppm.
- the true specific gravity of the spherical silver powder having the closed cavities in particles thereof is preferably not greater than 9.8 g/cm 3 . Since the true specific gravity of bulk silver is 10.5 g/cm 3 , the true specific gravity of not greater than 9.8 g/cm 3 is lower than that of bulk silver by 7% or more. If the true specific gravity is greater than 9.8 g/cm 3 , the size or number of the cavities is too small, or the cavities are open to the outside, so that there are some cases where the effect of promoting sintering by the expansion of substances in the particles thereof and the combustion of the substances may be insufficient.
- the mean particle size D 50 of the spherical silver powder having the closed cavities in particles thereof is preferably 0.1 to 10 ⁇ m when the particle size is obtained by a laser diffraction method.
- the mean particle size is more preferably not greater than 5 ⁇ m.
- the mean particle size of the spherical silver powder is preferably not smaller than 0.1 ⁇ m.
- the above-described spherical silver powder may be used as a conductor for producing a conductive paste.
- a conductive paste may be produced by mixing the above-described spherical silver powder with a resin.
- the resin include epoxy resins, acrylic resins, polyester resins, polyimide resins, polyurethane resins, phenoxy resins, silicone resins, and ethyl cellulose. These resins may be used alone, or two or more of these resins may be combined to be used.
- the conductive paste may be printed on a substrate by the screen printing, offset printing, photolithography method, or the like.
- the viscosity of the conductive paste is preferably 30 to 100 Pa ⁇ s at 25° C. If the viscosity of the conductive paste is less than 30 Pa ⁇ s, “bleeding” may occur during the printing, and if the viscosity of the conductive paste exceeds 100 Pa ⁇ s, the lack of print uniformity may be caused.
- the slurry containing silver particles was filtrated and washed with water.
- the cake thus obtained was dried at 75° C. for 10 hours by means of a vacuum drier.
- the silver powder thus dried was crushed for 30 seconds by means of a coffee mill to obtain a spherical silver powder.
- the particle size distribution based on the laser diffraction method, BET specific surface area and true specific gravity thereof were measured, and the cross section of particles thereof was observed.
- the contents of impurity elements, silver and organic components were obtained.
- the particle size distribution based on the laser diffraction method was measured by means of a micro-track particle size distribution measuring apparatus (9320 HAR (X-100) produced by Haneywell-Nikkiso Co., Ltd.) after dispersing 0.3 g of the spherical silver powder, which was put in 30 mL of isopropyl alcohol, for 5 minutes by an ultrasonic cleaning apparatus having an output of 50 W.
- the BET specific surface area was measured, by the single point BET method based on adsorption of nitrogen, using a specific surface area measuring apparatus (Monosorb produced by Quanta Chrome Ltd.) after the spherical silver powder was degassed at 60° C. for 10 minutes. As a result, the BET specific surface area was 0.35 m 2 /g.
- the true specific gravity was measured using 10 g of the spherical silver powder, isopropyl alcohol serving as a liquid for immersion, and a pycnometer having a volume of 50 mL. As a result, the true specific gravity was 9.6 g/cm 3 , so that it was conformed that the true specific gravity was decreased by 9% with respect to the true specific gravity of bulk silver being 10.5 g/cm 3 .
- the observation of the cross section of particles was carried out by observing the cross section of the spherical silver powder by a field emission scanning microscope (FE-SEM) (JSM-6700F produced by JEOL Ltd.), the cross section of the spherical silver powder being obtained by cutting the silver powder by a focused ion beam (FIB) system (JEM-9310FIB produced by JEOL Ltd.). As a result, it was confirmed that closed cavities exist in the particles of the spherical silver powder as shown in the FE-SEM image of FIG. 1 .
- FE-SEM field emission scanning microscope
- FIB focused ion beam
- the area of all particles of the spherical silver powder on the FE-SEM image was 13.7 ⁇ m 2 , and the area of particles having the closed cavities was 0.56 ⁇ m 2 , so that the percentage of the area of particles having the closed cavities with respect to the area of all particles of the spherical silver powder was 4.1%.
- the mean cavity size evaluated from the FE-SEM image was 0.07 ⁇ m corresponding to 2.4% with respect to the mean particle size D 50 , the evaluated mean cavity size being a sufficient cavity size.
- the content of each of the impurity elements in the spherical silver powder was obtained by a quantitative analysis using an inductively coupled plasma (ICP) analyzer (iCAP 6300 produced by Thermo Scientific, Inc.) after the following procedures were carried out. That is, after 1.0 g of the spherical silver powder was dissolved in 10 mL of (1+1) nitric acid, 5 mL of (1+1) hydrochloric acid was added thereto to deposit silver chloride. Then, after the solution containing the deposited silver chloride was filtrated to obtain a filtrate, pure water was added to the obtained filtrate to cause the filtrate to have a constant volume. Thereafter, the filtrate thus obtained was used for obtaining the content of each of the impurity elements.
- ICP inductively coupled plasma
- the content of silver in the spherical silver powder was obtained by measuring the weight of dried silver chloride obtained by drying silver chloride obtained by the filtration. As a result, the content of silver was 99.37 wt %.
- the content of each of organic components (carbon, nitrogen, oxygen and hydrogen) in the spherical silver powder was obtained as follows.
- the content of carbon was obtained by determining the quantity of carbon at a heating temperature of 1350° C. by means of a carbon/sulfur analyzer (EMIA-U510 produced by HORIBA, Ltd.). As a result, the content of carbon was 1700 ppm.
- the content of each of nitrogen, oxygen and hydrogen was obtained by determining the quantity of each of nitrogen, oxygen and hydrogen by means of a nitrogen/oxygen /hydrogen analyzer (ONH836 produced LECO, Ltd.). As a result, the contents of nitrogen, oxygen and hydrogen were 745 ppm, 3020 ppm and 800 ppm, respectively.
- the conductive paste thus obtained was printed on each of two 96% alumina substrates at an attack pressure of squeegee of 0.3 MPa by the screen printing using a screen printing machine (produced by Micro-tech Co., Ltd.) so as to form a rectangular film having a size of 8 mm ⁇ 10 mm, and was dried at 200° C. for 20 minutes by means of an atmospheric circulation type drier. Thereafter, a box furnace was used for heating each of the substrates at 400° C. and 700° C. for 10 minutes, respectively, to prepare a conductive film.
- the slurry containing silver particles was filtrated and washed with water.
- the cake thus obtained was dried at 75° C. for 10 hours by means of a vacuum drier.
- the silver powder thus dried was crushed for 30 seconds by means of a coffee mill to obtain a spherical silver powder.
- the particle size distribution based on the laser diffraction method, BET specific surface area and true specific gravity thereof were measured by the same methods as those in Example 1, and the cross section of particles thereof was observed by the same method as that in Example 1.
- the contents of impurity elements, silver and organic components were obtained by the same methods as those in Example 1.
- the true specific gravity was 9.7 g/cm 3 , so that it was confirmed that the true specific gravity was decreased by 8% with respect to the true specific gravity of bulk silver being 10.5 g/cm 3 .
- the area of all particles of the spherical silver powder on the FE-SEM image was 11.8 ⁇ m 2 , and the area of particles having the closed cavities was 0.34 ⁇ m 2 , so that the percentage of the area of particles having the closed cavities with respect to the area of all particles of the spherical silver powder was 2.9%.
- the mean cavity size obtained by the FE-SEM image is 0.05 ⁇ m which corresponds to 1.7% with respect to the mean particle size D 50 and which is a sufficient cavity size.
- the spherical silver powder thus obtained was used for preparing a conductive film from a conductive paste by the same methods as those in Example 1, and the volume resistivity thereof was derived by the same method as that in Example 1.
- the volume resistivity of the conductive film fired at 400° C. was 5.7 ⁇ 10 ⁇ 6 ⁇ cm
- the volume resistivity of the conductive film fired at 700 0 C was 2.4 ⁇ 10 ⁇ 6 ⁇ cm.
- the conductivity in an order of 10 ⁇ 6 ⁇ cm was ensured even if the conductive film was obtained by firing at 400° C.
- the slurry containing silver particles was filtrated and washed with water.
- the cake thus obtained was dried at 75° C. for 10 hours by means of a vacuum drier.
- the silver powder thus dried was crushed for 30 seconds by means of a coffee mill to obtain a spherical silver powder.
- the particle size distribution based on the laser diffraction method, BET specific surface area and true specific gravity thereof were measured by the same methods as those in Example 1, and the cross section of particles thereof was observed by the same method as that in Example 1.
- the contents of impurity elements, silver and organic components were obtained by the same methods as those in Example
- the true specific gravity was 9.3 g/cm 3 , so that it was confirmed that the true specific gravity was decreased by 11% with respect to the true specific gravity of bulk silver being 10.5 g/cm 3 .
- the mean cavity size obtained by the FE-SEM image is 0.11 ⁇ m which corresponds to 8.5% with respect to the mean particle size D 50 and which is a sufficient cavity size.
- the spherical silver powder thus obtained was used for preparing a conductive film from a conductive paste by the same methods as those in Example 1, and the volume resistivity thereof was derived by the same method as that in Example 1.
- the volume resistivity of the conductive film fired at 400° C. was 4.5 ⁇ 10 ⁇ 6 ⁇ cm
- the volume resistivity of the conductive film fired at 700° C. was 2.3 ⁇ 10 ⁇ 6 ⁇ cm.
- the conductivity in an order of 10 ⁇ 6 ⁇ cm was ensured even if the conductive film was obtained by firing at 400° C.
- the slurry containing silver particles was filtrated and washed with water.
- the cake thus obtained was dried at 75° C. for 10 hours by means of a vacuum drier.
- the silver powder thus dried was crushed for 30 seconds by means of a coffee mill to obtain a spherical silver powder.
- the particle size distribution based on the laser diffraction method, BET specific surface area and true specific gravity thereof were measured by the same methods as those in Example 1, and the cross section of particles thereof was observed by the same method as that in Example 1.
- the contents of impurity elements, silver and organic components were obtained by the same methods as those in Example
- the true specific gravity was 10.3 g/cm 3 , so that it was confirmed that the true specific gravity was decreased by only 2% with respect to the true specific gravity of bulk silver being 10.5 g/cm 3 .
- the spherical silver powder thus obtained was used for preparing a conductive film from a conductive paste by the same methods as those in Example 1, and the volume resistivity thereof was derived by the same method as that in Example 1.
- the volume resistivity of the conductive film fired at 400° C. was 1.1 ⁇ 10 ⁇ 5 ⁇ cm
- the volume resistivity of the conductive film fired at 700° C. was 3.0 ⁇ 10 ⁇ 6 ⁇ cm.
- the volume resistivity of the conductive film fired at 400° C. was in an order of 10 ⁇ 5 ⁇ cm, so that the conductivity was inferior to that in Examples 1 through 3.
- the particle size distribution based on the laser diffraction method, BET specific surface area and true specific gravity thereof are shown in Table 1, and the results of the observation of the cross section of particles thereof are shown in Table 2.
- the volume resistivity of the conductive film obtained in each of these examples and comparative examples is shown in Table 3.
- the spherical silver powder can be utilized for preparing a conductive paste as a spherical silver powder which has a particle size being substantially equal to that of a spherical silver powder produced by a conventional wet reducing method and which is capable of being fired at a lower temperature.
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Abstract
Description
- The present invention relates generally to a spherical silver powder and a method for producing the same. More specifically, the invention relates to a spherical silver powder for a conductive paste for use in electronic parts, such as internal electrodes of laminated capacitors, conductive patterns of circuit boards, and electrodes and circuits of substrates for plasma display panels and solar cells, and a method for producing the same.
- As a conventional method for forming internal electrodes of laminated capacitors, conductive patterns of circuit boards, electrodes and circuits of substrates for solar cells and plasma display panels (PDPs), there is widely used a method for forming a cermet type conductive paste, which is produced by kneading a mixture obtained by adding a silver powder and a glass frit to an organic vehicle, in a predetermined pattern on a substrate, and thereafter, heating the paste at a temperature of not lower than 500° C. to remove organic components to sinter silver particles with each other to form a conductive film.
- It is required that a silver powder for a conductive paste for use in such a method has a reasonably small particle size and a reasonably narrow range of the particle size in order to form small electronic parts and conductive patterns having a high density and fine lines.
- As a method for producing such a silver powder for a conductive paste, there is known a wet reducing method for adding a reducing agent to a water reaction system containing silver ions to deposit a spherical silver powder by reduction (see, e.g., Japanese Patent Laid-Open No. 8-176620).
- However, if a spherical silver powder having a particle size, which is substantially equal to that of a spherical silver powder produced by a conventional wet reducing method, is used for forming a cermet type conductive paste, even if the paste is heated at a temperature of about 600° C., there are some cases where it is not possible to sufficiently sinter silver particles with each other, so that it is not possible to form a good conductive film.
- It is therefore an object of the present invention to eliminate the aforementioned conventional problems and to provide a spherical silver powder, which has a particle size being substantially equal to that of a spherical silver powder produced by a conventional wet reducing method and which is capable of being fired at a lower temperature, and a method for producing the same.
- In order to accomplish the aforementioned and other objects, the inventors have diligently studied and found that it is possible to produce a spherical silver powder, which has a particle size being substantially equal to that of a spherical silver powder produced by a conventional wet reducing method and which is capable of being fired at a lower temperature, if silver particles are deposited by reduction by mixing a reducing agent containing solution, which contains an aldehyde as a reducing agent, with a water reaction system containing silver ions while causing cavitation in the water reaction system. Thus, the inventors have made the present invention.
- According to the present invention, there is provided a method for producing a spherical silver powder, the method comprising the steps of: preparing a water reaction system containing silver ions; preparing a reducing agent containing solution which contains an aldehyde as a reducing agent; and depositing silver particles by reduction by mixing the reducing agent containing solution with the water reaction system while causing cavitation in the water reaction system. In this method for producing a spherical silver powder, the cavitation is caused by irradiating the water reaction system containing silver ions with ultrasonic waves. The water reaction system containing silver ions is preferably an aqueous solution containing a silver ammonia complex. The reducing agent containing solution is preferably a solution containing formaldehyde or acetaldehyde. The method may further comprise steps of carrying out the solid-liquid separation of the silver particles deposited by reduction; washing the separated silver particles; and drying the washed silver particles at a temperature of not higher than 100° C. The spherical silver powder preferably has a closed cavity in each particle thereof.
- According to the present invention, there is provided a spherical silver powder which has a closed cavity in each particle thereof. This spherical silver powder preferably has a mean particle size D50 of 0.1 to 10 μm when the particle size is obtained by a laser diffraction method. The spherical silver powder preferably has a true specific gravity of not greater than 9.8 g/cm3. The content of each of impurities, except for carbon, nitrogen, oxygen and hydrogen, contained in the spherical silver powder is preferably less than 100 ppm.
- According to the present invention, there is provided a conductive paste using the above-described spherical silver powder as a conductor.
- According to the present invention, it is possible to produce a spherical silver powder, which has a particle size being substantially equal to that of a spherical silver powder produced by a conventional wet reducing method and which is capable of being fired at a lower temperature, by depositing silver particles by reduction by mixing a reducing agent containing solution, which contains an aldehyde as a reducing agent, with a water reaction system containing silver ions while causing cavitation in the water reaction system.
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FIG. 1 is a field emission-scanning electron micrograph (FE-SEM image) of a cross section of a spherical silver powder obtained in Example 1; -
FIG. 2 is an FE-SEM image of a cross section of a spherical silver powder obtained in Example 2; -
FIG. 3 is an FE-SEM image of a cross section of a spherical silver powder obtained in Example 3; and -
FIG. 4 is an FE-SEM image of a cross section of a spherical silver powder obtained in Comparative Example 1. - In a preferred embodiment of a method for producing a spherical silver powder according to the present invention, silver particles are deposited by reduction by mixing a reducing agent containing solution, which contains an aldehyde as a reducing agent, with a water reaction system containing silver ions while causing cavitation in the water reaction system.
- The cavitation is a physical phenomenon in which the generation and extinction of bubbles occur in a short time by a local pressure difference caused in a liquid. The cavitation can be produced by the irradiation with ultrasonic waves, a homogenizer for emulsion treatment or the like. In order to cause cavitation in the whole water reaction system containing silver ions, the cavitation is preferably produced by irradiating the water reaction system containing silver ions with ultrasonic waves. The oscillating frequency of the irradiated ultrasonic waves may be an oscillating frequency capable of causing cavitation, and is preferably in the range of from 28 kHz to 40 kHz. The output of the ultrasonic waves may be set in accordance with the amount of liquid used for causing the deposition reaction of silver particles by reduction. The irradiation with the ultrasonic waves may be carried out when the reducing agent containing solution is added for depositing the silver particles by reduction, or it may be carried out before or after the reducing agent containing solution is added for depositing the silver particles by reduction.
- As the water reaction system containing silver ions, an aqueous solution or slurry containing silver nitrate, a silver salt complex or a silver intermediate may be used. The aqueous solution containing a silver salt complex may be produced by adding aqueous ammonia or an ammonia salt to an aqueous silver nitrate solution or a suspension of silver oxide. Among them, an aqueous solution of silver ammine complex obtained by adding aqueous ammonia to an aqueous silver nitrate solution is preferably used in order to produce a silver powder having an appropriate particle size and a spherical shape. The coordination number of ammonia in the silver ammine complex is 2, so that 2 moles or more of ammonia per 1 mole of silver is added. If the amount of ammonia to be added is too large, the complex is too stable, so that it is difficult to proceed reduction. Therefore, the amount of ammonia to be added is preferably not larger than 8 moles per 1 mole of silver. Furthermore, if adjustment is carried out by increasing the amount of ammonia to be added or the like, even if the amount of ammonia to be added exceeds 8 moles, it is possible to obtain a spherical silver powder having an appropriate particle size.
- As the reducing agent, a compound having an aldehyde group may be used, and formaldehyde or acetaldehyde is preferably used. The aldehyde may be used alone, or aldehyde compounds may be combined to be used. Alternatively, a mixture of water or alcohol with an aldehyde, such as formalin, may be used. If the cavitation is caused when a reducing agent containing solution, which contains an aldehyde as the reducing agent, is added to deposit silver particles by reduction, it is possible to obtain a spherical silver powder having a closed cavity in the interior of each particle thereof. The amount of the reducing agent to be added may be an excessive amount with respect to the water reaction system containing silver ions. In order to decrease the amount of silver ions remaining in the water reaction system containing silver ions to suppress the loss of silver being a noble metal, the amount of the reducing agent required to cause the amount of unreduced silver ions to be 10 ppm or less may be added.
- To the water reaction system containing silver ions, a pH adjusting agent may be added. As the pH adjusting agent, a general acid or base may be used. For example, nitric acid, sodium hydroxide or the like may be used.
- To the water reaction system containing silver ions, a surface treating agent may be added. As the surface treating agent, there may be used any one or more of fatty acids, fatty acid salts, surface active agents, organometallic compounds, chelating agents, high-polymer dispersing agents and so forth. Examples of fatty acids include propionic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, acrylic acid, oleic acid, linolic acid, and arachidonic acid. Examples of fatty acid salts include salts formed by fatty acids and metals, such as lithium, sodium, potassium, barium, magnesium, calcium, aluminum, iron, cobalt, manganese, lead, zinc, tin, strontium, zirconium, silver or copper. Examples of surface active agents include: anionic surface active agents, such as alkyl benzene sulfonates and polyoxyethylene alkyl ether phosphates; cationic surface active agents, such as aliphatic quaternary ammonium salts; amphoteric surface active agents, such as imidazolinium betaine; and nonionic surface active agents, such as polyoxyethylene alkyl ethers and polyoxyethylene fatty acid esters. Examples of organometallic compounds include acetylacetone tributoxyzirconium, magnesium citrate, diethylzinc, dibutyltin oxide, dimethylzinc, tetra-n-butoxyzirconium, triethyl indium, triethyl gallium, trimethyl indium, trimethyl gallium, monobutyl tin oxide, tetraisocyanate silane, tetramethyl silane, tetramethoxy silane, polymethoxy siloxane, monomethyl triisocyanate silane, silane coupling agent, titanate coupling agents, and aluminum coupling agents. Examples of chelating agents include imidazole, oxazole, triazole, selenazole, pyrazole, isoxazole, isothiazole, 1H-1,2,3-triazole, 2H-1,2,3-triazole, 1H-1,2,4-triazole, 4H-1,2,4-triazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1H-1,2,3,4-tetrazole, 1,2,3,4-oxatriazole, 1,2,3,4-thiatriazole, 2H-1,2,3,4-tetrazole, 1,2,3,5-oxatriazole, 1,2,3,5-thiatriazole, indazole, benzoimidazole, benzotriazole and salts thereof, and oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, didodecanoic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, glycolic acid, lactic acid, hydroxybutyricacid, glyceric acid, tartaric acid, malic acid, tartronic acid, hydracrylic acid, mandelic acid, citric acid and ascorbic acid. Examples of high-polymer dispersing agents include peptide, gelatin, collagen peptide, albumin, gum arabic, protarbic acid and lysalbic acid. These surface active agents may be used alone, or they may be combined to be used.
- After the solid-liquid separation of the silver containing slurry obtained by depositing the silver particles by reduction is carried out, the silver particles are washed with water. Thus, there is obtained a solid cake which contains 1 to 200 wt % of water with respect to silver and which is hardly fluid. In order to rapidly dry the cake, water in the cake may be replaced with a lower alcohol or the like. It is possible to obtain a dried silver powder by drying the cake by means of a drier, such as a forced circulation air drier, a vacuum drier or a flash drier (pneumatic conveying drier). The temperature of drying is preferably not higher than 100° C. in order to maintain a closed cavity in the interior of each particle of the silver powder.
- The obtained silver powder may be subjected to a dry-crushing and/or classification process. In place of the crushing, the silver powder may be subjected to a surface smoothing process for smoothing the irregularities and angular portions on the surface of the particles of the silver powder by mechanically causing the particles of the silver powder to collide with each other by putting the silver powder into an apparatus capable of mechanically fluidizing particles. After the crushing or surface smoothing process is carried out, a classification process may be carried out. The drying, crushing and classification processes may be carried out by an integrated apparatus capable of carrying out the drying, crushing and classification processes (DRY MASTER produced by Hosokawa Micron Corporation, Micron Drier or the like).
- By the above-described method for producing a spherical silver powder, it is possible to produce a spherical silver powder having a plurality of closed cavities (closed pores) in particles thereof. The process for forming a conductive film by firing a cermet type conductive paste using a silver powder, generally comprises: (1) Evaporation of Diluent Solvent, (2) Combustion of Organic Components (surface treating agent and resin), (3) Softening of Glass Frit serving as Sintering Additive, and (4) Liquid-Phase Sintering of Silver Particles. In order to form the wiring of the conductive film at a lower temperature, it is required to lower the temperature for the above-described (2) through (4). When a usual spherical silver powder is used, the combustion of organic components in the above-described (2) occurs only on the surface of the silver particles, so that the influence of the combustion of organic components on the combustion of the silver particles is limited. However, when a spherical silver powder having cavities in particles thereof is used, it is considered that the expansion of substances in the cavities and the energy of the combustion thereof in addition to the combustion of the organic components on the surface of the silver particles advantageously contribute to the combustion of the silver particles. On the other hand, in the case of a spherical silver powder wherein the cavities in particles thereof are open to the outside, the extinction of the substances in the particles is caused during the washing and drying in the production of the spherical silver powder. Therefore, the expansion and combustion of the substances in the cavities are not caused during combustion, substantially similar to those in the usual spherical silver powder. Furthermore, as a method for producing a silver powder having cavities in particles thereof, there is considered a method for using particles of a metal, which is loss nobler than silver, as particles of a base material to deposit silver on the surface of the particles of the metal by a substitution reaction to dissolve and remove the particles of the base material. However, in this method, if the cavities in particles thereof are closed cavities, the metal component of the particles of the base material remains. For that reason, there is the possibility of deteriorating the conductivity of the silver powder and the reliability of the silver powder due to oxidation, so that it is required to cause the cavities in particles thereof to be cavities which are open to the outside.
- In order to prevent the rise of electric resistance and the deterioration of reliability due to oxidation in the spherical silver powder having closed cavities in the particles thereof, the content of each of the impurity elements, such as transition metals, alkali earth metals, alkali metals, aluminum and magnesium, as impurities (contained therein by catching the reaction mother liquor during reduction) is preferably less than 100 ppm.
- The true specific gravity of the spherical silver powder having the closed cavities in particles thereof is preferably not greater than 9.8 g/cm3. Since the true specific gravity of bulk silver is 10.5 g/cm3, the true specific gravity of not greater than 9.8 g/cm3 is lower than that of bulk silver by 7% or more. If the true specific gravity is greater than 9.8 g/cm3, the size or number of the cavities is too small, or the cavities are open to the outside, so that there are some cases where the effect of promoting sintering by the expansion of substances in the particles thereof and the combustion of the substances may be insufficient.
- The mean particle size D50 of the spherical silver powder having the closed cavities in particles thereof is preferably 0.1 to 10 μm when the particle size is obtained by a laser diffraction method. In order to use the spherical silver powder for forming a thinner conductive film, the mean particle size is more preferably not greater than 5 μm. On the other hand, if the particle size of the spherical silver powder is too small, the specific surface area thereof increases. For that reason, if such a spherical silver powder is used for forming a conductive paste, the viscosity thereof increase, and if such a spherical silver powder is used for forming a photosensitive paste, the transmission of ultraviolet rays is easy to be insufficient. Therefore, the mean particle size of the spherical silver powder is preferably not smaller than 0.1 μm.
- The above-described spherical silver powder may be used as a conductor for producing a conductive paste. For example, a conductive paste may be produced by mixing the above-described spherical silver powder with a resin. Furthermore, examples of the resin include epoxy resins, acrylic resins, polyester resins, polyimide resins, polyurethane resins, phenoxy resins, silicone resins, and ethyl cellulose. These resins may be used alone, or two or more of these resins may be combined to be used. The conductive paste may be printed on a substrate by the screen printing, offset printing, photolithography method, or the like.
- In the case of the screen printing, the viscosity of the conductive paste is preferably 30 to 100 Pa·s at 25° C. If the viscosity of the conductive paste is less than 30 Pa·s, “bleeding” may occur during the printing, and if the viscosity of the conductive paste exceeds 100 Pa·s, the lack of print uniformity may be caused.
- Examples of a spherical silver powder and a method for producing the same according to the present invention will be described below in detail.
- First, 753 g of an aqueous silver nitrate solution containing 8.63 g of silver was distributed into a 1 L beaker. Then, the beaker was put in an ultrasonic washing machine (Cleaner USD-4R produced by AS ONE CORPORATION, Output 160 W) containing water having a temperature of 35° C. therein. Then, the solution in the beaker was started to be irradiated with ultrasonic waves at an oscillating frequency of 40 kHz and to be stirred.
- Then, 29.1 g of an aqueous solution containing 28 wt % of ammonia (the equivalent thereof corresponding to 3.0 with respect to silver) was added to the aqueous silver nitrate solution in the beaker to form a silver ammine complex. After 30 seconds from the addition of the aqueous ammonia, 0.48 g of an aqueous solution containing 20 wt % of sodium hydroxide was added thereto. After 20 minutes from the addition of the aqueous ammonia, 48.7 g of an aqueous solution containing 27.4 wt % of formaldehyde (the equivalent thereof corresponding to 11.1 with respect to silver) prepared by diluting formalin with pure water was added thereto. After 30 seconds from the addition of the aqueous formaldehyde solution, 0.86 g of an ethanol solution containing 1.2 wt % of stearic acid was added thereto to form a slurry containing silver particles.
- Then, after the irradiation with ultrasonic waves was completed, the slurry containing silver particles was filtrated and washed with water. The cake thus obtained was dried at 75° C. for 10 hours by means of a vacuum drier. The silver powder thus dried was crushed for 30 seconds by means of a coffee mill to obtain a spherical silver powder.
- With respect to the spherical silver powder thus obtained, the particle size distribution based on the laser diffraction method, BET specific surface area and true specific gravity thereof were measured, and the cross section of particles thereof was observed. In addition, the contents of impurity elements, silver and organic components (carbon, nitrogen, oxygen and hydrogen) were obtained.
- The particle size distribution based on the laser diffraction method was measured by means of a micro-track particle size distribution measuring apparatus (9320 HAR (X-100) produced by Haneywell-Nikkiso Co., Ltd.) after dispersing 0.3 g of the spherical silver powder, which was put in 30 mL of isopropyl alcohol, for 5 minutes by an ultrasonic cleaning apparatus having an output of 50 W. As a result, the particle size distribution was D10=1.6 μm, D50=3.0 μm and D90=5.3 μm.
- The BET specific surface area was measured, by the single point BET method based on adsorption of nitrogen, using a specific surface area measuring apparatus (Monosorb produced by Quanta Chrome Ltd.) after the spherical silver powder was degassed at 60° C. for 10 minutes. As a result, the BET specific surface area was 0.35 m2/g.
- The true specific gravity was measured using 10 g of the spherical silver powder, isopropyl alcohol serving as a liquid for immersion, and a pycnometer having a volume of 50 mL. As a result, the true specific gravity was 9.6 g/cm3, so that it was conformed that the true specific gravity was decreased by 9% with respect to the true specific gravity of bulk silver being 10.5 g/cm3.
- The observation of the cross section of particles was carried out by observing the cross section of the spherical silver powder by a field emission scanning microscope (FE-SEM) (JSM-6700F produced by JEOL Ltd.), the cross section of the spherical silver powder being obtained by cutting the silver powder by a focused ion beam (FIB) system (JEM-9310FIB produced by JEOL Ltd.). As a result, it was confirmed that closed cavities exist in the particles of the spherical silver powder as shown in the FE-SEM image of
FIG. 1 . The area of all particles of the spherical silver powder on the FE-SEM image was 13.7 μm2, and the area of particles having the closed cavities was 0.56 μm2, so that the percentage of the area of particles having the closed cavities with respect to the area of all particles of the spherical silver powder was 4.1%. Considering that it is not always that the cross section of the observed particles of the spherical silver powder passes through the center of each of the particles, it is considered that the cavities exist in most of the particles of the spherical silver powder. It was also confirmed that the mean cavity size evaluated from the FE-SEM image was 0.07 μm corresponding to 2.4% with respect to the mean particle size D50, the evaluated mean cavity size being a sufficient cavity size. - The content of each of the impurity elements in the spherical silver powder was obtained by a quantitative analysis using an inductively coupled plasma (ICP) analyzer (iCAP 6300 produced by Thermo Scientific, Inc.) after the following procedures were carried out. That is, after 1.0 g of the spherical silver powder was dissolved in 10 mL of (1+1) nitric acid, 5 mL of (1+1) hydrochloric acid was added thereto to deposit silver chloride. Then, after the solution containing the deposited silver chloride was filtrated to obtain a filtrate, pure water was added to the obtained filtrate to cause the filtrate to have a constant volume. Thereafter, the filtrate thus obtained was used for obtaining the content of each of the impurity elements. As a result, it was confirmed that Cr=1 ppm, Mn <1 ppm, Fe=7 ppm, Co<5 ppm, Ni<5 ppm, Cu<1 ppm, Zn<5 ppm, Cd<1 ppm, Pb<5 ppm, Sn<10 ppm, Ca<1 ppm, Mg<1 ppm, S<50 ppm, Zr<1 ppm, Bi<10 ppm, Al<10 ppm, Sr<1 ppm, Ba<1 ppm, Li<100 ppm, Na<100 ppm, K<100 ppm, Rb<100 ppm and Cs<100 ppm, so that the content of each of the impurity elements was less than 100 ppm.
- The content of silver in the spherical silver powder was obtained by measuring the weight of dried silver chloride obtained by drying silver chloride obtained by the filtration. As a result, the content of silver was 99.37 wt %.
- The content of each of organic components (carbon, nitrogen, oxygen and hydrogen) in the spherical silver powder was obtained as follows. The content of carbon was obtained by determining the quantity of carbon at a heating temperature of 1350° C. by means of a carbon/sulfur analyzer (EMIA-U510 produced by HORIBA, Ltd.). As a result, the content of carbon was 1700 ppm. The content of each of nitrogen, oxygen and hydrogen was obtained by determining the quantity of each of nitrogen, oxygen and hydrogen by means of a nitrogen/oxygen /hydrogen analyzer (ONH836 produced LECO, Ltd.). As a result, the contents of nitrogen, oxygen and hydrogen were 745 ppm, 3020 ppm and 800 ppm, respectively.
- Then, after the operation for mixing 83.4 wt % of the spherical silver powder thus obtained, 1.2 wt % of a resin (ethyl cellulose produced by Wako Pure Chemical Industries, Ltd., 100 cps) and 15.4 wt % of a solvent (terpineol produced by Wako Pure Chemical Industries, Ltd.) for 30 seconds was carried out twice by means of a propellerless planetary centrifugal stirring/degassing apparatus (AR250 produced by Thinky Corporation), the mixture thus obtained was caused to pass through a triple roll mill (EXAKT80S produced by Otto-Harmann, Ltd.) at a roll gap of 100 μm to 20 μm to be kneaded to obtain a conductive paste.
- Then, the conductive paste thus obtained was printed on each of two 96% alumina substrates at an attack pressure of squeegee of 0.3 MPa by the screen printing using a screen printing machine (produced by Micro-tech Co., Ltd.) so as to form a rectangular film having a size of 8 mm×10 mm, and was dried at 200° C. for 20 minutes by means of an atmospheric circulation type drier. Thereafter, a box furnace was used for heating each of the substrates at 400° C. and 700° C. for 10 minutes, respectively, to prepare a conductive film.
- With respect to the conductive film thus obtained, the thickness thereof was obtained by measuring the difference in level between the surface of the conductive film on the alumina substrate and a portion on the alumina substrate, in which the conductive film was not printed, by means of a surface roughness tester (Surfcoder SE-30D produced by Kosaka Laboratory Ltd.), and the surface resistivity thereof was measured by the four-point probe method using a resistivity measuring apparatus (MCP-T410 produced by Mitsubishi Chemical Corporation). Then, the volume resistivity of the conductive film was derived from the surface resistivity and the volume of the conductive film (=Width×Length×Thickness). As a result, the volume resistivity of the conductive film fired at 400° C. was 5.2×10−6 Ω·cm, and the volume resistivity of the conductive film fired at 700° C. was 2.6×10−6 Ω·cm. Thus, the conductivity in an order of 10−6 Ω·cm was ensured even if the conductive film was obtained by firing at 400° C.
- First, 753 g of an aqueous silver nitrate solution containing 8.63 g of silver was distributed into a 1 L beaker. Then, the beaker was put in an ultrasonic washing machine (Cleaner USD-4R produced by AS ONE CORPORATION, Output 160 W) containing water having a temperature of 20° C. therein, and the solution in the beaker was started to be stirred.
- Then, 26.2 g of an aqueous solution containing 28 wt % of ammonia (the equivalent thereof corresponding to 2.7 with respect to silver) was added to the aqueous silver nitrate solution in the beaker to form a silver ammine complex. After 19 minutes from the addition of the aqueous ammonia, the solution in the beaker was started to be irradiated with ultrasonic waves at an oscillating frequency of 40 kHz. After 1 minute from the irradiation, 54.4 g of an aqueous solution containing 27.4 wt % of formaldehyde (the equivalent thereof corresponding to 12.4 with respect to silver) prepared by diluting formalin with pure water was added thereto. After 15 seconds from the addition of the aqueous formaldehyde solution, 1.06 g of an ethanol solution containing 2.1 wt % of benzotriazole was added thereto to form a slurry containing silver particles.
- Then, after the irradiation with ultrasonic waves was completed, the slurry containing silver particles was filtrated and washed with water. The cake thus obtained was dried at 75° C. for 10 hours by means of a vacuum drier. The silver powder thus dried was crushed for 30 seconds by means of a coffee mill to obtain a spherical silver powder.
- With respect to the spherical silver powder thus obtained, the particle size distribution based on the laser diffraction method, BET specific surface area and true specific gravity thereof were measured by the same methods as those in Example 1, and the cross section of particles thereof was observed by the same method as that in Example 1. In addition, the contents of impurity elements, silver and organic components (carbon, nitrogen, oxygen and hydrogen) were obtained by the same methods as those in Example 1.
- As a result, the particle size distribution was D10=1.5 μm, D50=2.8 μm and D90=4.5 μm, and the BET specific surface area was 0.36 m2/g .
- The true specific gravity was 9.7 g/cm3, so that it was confirmed that the true specific gravity was decreased by 8% with respect to the true specific gravity of bulk silver being 10.5 g/cm3. In the observation of the cross section of the particles of the spherical silver powder, it was confirmed that closed cavities exist in the particles of the spherical silver powder as shown in the FE-SEM image of
FIG. 2 . The area of all particles of the spherical silver powder on the FE-SEM image was 11.8 μm2, and the area of particles having the closed cavities was 0.34 μm2, so that the percentage of the area of particles having the closed cavities with respect to the area of all particles of the spherical silver powder was 2.9%. Considering that it is not always that the cross section of the observed particles of the spherical silver powder passes through the center of each of the particles, it is considered that the cavities exist in most of the particles of the spherical silver powder. It was also confirmed that the mean cavity size obtained by the FE-SEM image is 0.05 μm which corresponds to 1.7% with respect to the mean particle size D50and which is a sufficient cavity size. - With respect to the content of each of the impurity elements in the spherical silver powder, it was confirmed that Cr=1 ppm, Mn<1 ppm, Fe=6 ppm, Co<5 ppm, Ni<5 ppm, Cu<1 ppm, Zn<5 ppm, Cd<1 ppm, Pb<5 ppm, Sn<10 ppm, Ca<1 ppm, Mg<1 ppm, S<50 ppm, Zr<1 ppm, Bi<10 ppm, Al<10 ppm, Sr<1 ppm, Ba<1 ppm, Li<100 ppm, Na<100 ppm, K<100 ppm, Rb<100 ppm and Cs<100 ppm, so that the content of each of the impurity elements was less than 100 ppm. The content of silver in the spherical silver powder was 99.21 wt %. The contents of carbon, nitrogen, oxygen and hydrogen were 2400 ppm, 1710 ppm, 3360 ppm and 650 ppm, respectively.
- The spherical silver powder thus obtained was used for preparing a conductive film from a conductive paste by the same methods as those in Example 1, and the volume resistivity thereof was derived by the same method as that in Example 1. As a result, the volume resistivity of the conductive film fired at 400° C. was 5.7×10−6 Ω·cm, and the volume resistivity of the conductive film fired at 700 0C was 2.4×10−6 Ω·cm. Thus, the conductivity in an order of 10−6 Ω·cm was ensured even if the conductive film was obtained by firing at 400° C.
- First, 688 g of an aqueous silver nitrate solution containing 9.00 g of silver was distributed into a 1 L beaker. Then, the beaker was put in an ultrasonic washing machine (Cleaner USD-4R produced by AS ONE CORPORATION, Output 160 W) containing water having a temperature of 30° C. therein. Then, the solution in the beaker was started to be irradiated with ultrasonic waves at an oscillating frequency of 28 kHz, and to be stirred.
- Then, 27.6 g of an aqueous solution containing 28 wt % of ammonia (the equivalent thereof corresponding to 2.5 with respect to silver) was added to the aqueous silver nitrate solution in the beaker to form a silver ammine complex. After 1minute from the addition of the aqueous ammonia, 2.5 g of an aqueous solution containing 20 wt % of sodium hydroxide was added thereto. After 20 minutes from the addition of the aqueous sodium hydroxide solution, 79.4 g of an aqueous solution containing 27.4 wt % of formaldehyde prepared by diluting formalin with pure water (the equivalent thereof corresponding to 13.0 with respect to silver) was added thereto. After 5 seconds from the addition of the aqueous formaldehyde solution, 2.3 g of an ethanol solution containing 2.5 wt % of stearic acid was added thereto to forma slurry containing silver particles.
- Then, after the irradiation with ultrasonic waves was completed, the slurry containing silver particles was filtrated and washed with water. The cake thus obtained was dried at 75° C. for 10 hours by means of a vacuum drier. The silver powder thus dried was crushed for 30 seconds by means of a coffee mill to obtain a spherical silver powder.
- With respect to the spherical silver powder thus obtained, the particle size distribution based on the laser diffraction method, BET specific surface area and true specific gravity thereof were measured by the same methods as those in Example 1, and the cross section of particles thereof was observed by the same method as that in Example 1. In addition, the contents of impurity elements, silver and organic components (carbon, nitrogen, oxygen and hydrogen) were obtained by the same methods as those in Example
- As a result, the particle size distribution was D10=0.7 μm, D50=1.3 μm and D90=2.3 g m, and the BET specific surface area was 0.77 m2 /g. The true specific gravity was 9.3 g/cm3, so that it was confirmed that the true specific gravity was decreased by 11% with respect to the true specific gravity of bulk silver being 10.5 g/cm3.
- In the observation of the cross section of the particles of the spherical silver powder, it was confirmed that closed cavities exist in the particles of the spherical silver powder as shown in the FE-SEM image of
FIG. 3 . The area of all particles of the spherical silver powder on the FE-SEM image was 2.08 μm2, and the area of particles having the closed cavities was 0.21 μm2, so that the percentage of the area of particles having the closed cavities with respect to the area of all particles of the spherical silver powder was 10% . Considering that it is not always that the cross section of the observed particles of the spherical silver powder passes through the center of each of the particles, it is considered that the cavities exist in most of the particles of the spherical silver powder. It was also confirmed that the mean cavity size obtained by the FE-SEM image is 0.11 μm which corresponds to 8.5% with respect to the mean particle size D50 and which is a sufficient cavity size. - With respect to the content of each of the impurity elements in the spherical silver powder, it was confirmed that Cr=1 ppm, Mn<1 ppm, Fe=8 ppm, Co<5 ppm, Ni<5 ppm, Cu<1 ppm, Zn<5 ppm, Cd<1 ppm, Pb<5 ppm, Sn<10 ppm, Ca<1 ppm, Mg<1 ppm, S<50 ppm, Zr<1 ppm, Bi<10 ppm, Al<10 ppm, Sr<1 ppm, Ba<1 ppm, Li<100 ppm, Na<100 ppm, K<100 ppm, Rb<100 ppm and Cs<100 ppm, so that the content of each of the impurity elements was less than 100 ppm. The content of silver in the spherical silver powder was 99.00 wt %. The contents of carbon, nitrogen, oxygen and hydrogen were 3700 ppm, 575 ppm, 3955 ppm and 1300 ppm, respectively.
- The spherical silver powder thus obtained was used for preparing a conductive film from a conductive paste by the same methods as those in Example 1, and the volume resistivity thereof was derived by the same method as that in Example 1. As a result, the volume resistivity of the conductive film fired at 400° C. was 4.5×10−6 Ω·cm, and the volume resistivity of the conductive film fired at 700° C. was 2.3×10−6 Ω·cm. Thus, the conductivity in an order of 10−6 Ω·cm was ensured even if the conductive film was obtained by firing at 400° C.
- First, 28.6 g of an aqueous silver nitrate solution containing 8.63 g of silver was distributed into a 1 L beaker. Then, the beaker was put in an ultrasonic washing machine (Cleaner USD-4R produced by AS ONE CORPORATION, Output 160 W) containing water having a temperature of 35° C. therein. Then, the solution in the beaker was started to be irradiated with ultrasonic waves at an oscillating frequency of 40 kHz, and to be stirred.
- Then, 52.7 g of an aqueous solution containing 28 wt % of ammonia (the equivalent thereof corresponding to 5.0 with respect to silver) was added to the aqueous silver nitrate solution in the beaker to form a silver ammine complex. After 5 minutes from the addition of the aqueous ammonia, 2.2 g of an aqueous solution containing 0.40 wt % of polyethylene imine (having a molecular weight of 10,000) was added thereto. After 20 minutes from the addition of the aqueous ammonia, 19.4 g of an aqueous solution containing 6.2 wt % of hydrazine hydrate (the equivalent thereof corresponding to 1.2 with respect to silver) was added thereto. After 30 seconds from the addition of the aqueous solution of hydrazine hydrate, 0.77 g of a solution containing 1.3 wt % of stearic acid was added thereto to form a slurry containing silver particles. Furthermore, in this comparative example, polyethylene imine was added for adjusting the particle size which was decreased by the use of hydrazine.
- Then, after the irradiation with ultrasonic waves was completed, the slurry containing silver particles was filtrated and washed with water. The cake thus obtained was dried at 75° C. for 10 hours by means of a vacuum drier. The silver powder thus dried was crushed for 30 seconds by means of a coffee mill to obtain a spherical silver powder.
- With respect to the spherical silver powder thus obtained, the particle size distribution based on the laser diffraction method, BET specific surface area and true specific gravity thereof were measured by the same methods as those in Example 1, and the cross section of particles thereof was observed by the same method as that in Example 1. In addition, the contents of impurity elements, silver and organic components (carbon, nitrogen, oxygen and hydrogen) were obtained by the same methods as those in Example
- As a result, the particle size distribution was D10=1.8 μm, D50=2.9 μm and D90=4.4 μm, and the BET specific surface area was 0.16 m2/g. The true specific gravity was 10.3 g/cm3, so that it was confirmed that the true specific gravity was decreased by only 2% with respect to the true specific gravity of bulk silver being 10.5 g/cm3.
- In the observation of the cross section of the particles of the spherical silver powder, it was confirmed that no closed cavities exist in the particles of the spherical silver powder as shown in the FE-SEM image of
FIG. 4 . - With respect to the content of each of the impurityelementsinthe spherical silver powder, it was confirmed that Cr=1 ppm, Mn<1 ppm, Fe=7 ppm, Co<5 ppm, Ni<5 ppm, Cu<2 ppm, Zn<5 ppm, Cd<1 ppm, Pb<5 ppm, Sn<10 ppm, Ca<1 ppm, Mg<1 ppm, S<50 ppm, Zr<1 ppm, Bi<10 ppm, Al<10 ppm, Sr<1 ppm, Ba<1 ppm, Li<100 ppm, Na<100 ppm, K<100 ppm, Rb<100 ppm and Cs<100 ppm, so that the content of each of the impurity elements was less than 100 ppm. The content of silver in the spherical silver powder was 99.80 wt %. The contents of carbon, nitrogen, oxygen and hydrogen were 900 ppm, 70 ppm, 320 ppm and 200 ppm, respectively.
- The spherical silver powder thus obtained was used for preparing a conductive film from a conductive paste by the same methods as those in Example 1, and the volume resistivity thereof was derived by the same method as that in Example 1. As a result, the volume resistivity of the conductive film fired at 400° C. was 1.1×10−5 Ω·cm, and the volume resistivity of the conductive film fired at 700° C. was 3.0×10−6 Ω·cm. Thus, the volume resistivity of the conductive film fired at 400° C. was in an order of 10−5 Ω·cm, so that the conductivity was inferior to that in Examples 1 through 3.
- With respect to the spherical silver powder obtained in each of these examples and comparative examples, the particle size distribution based on the laser diffraction method, BET specific surface area and true specific gravity thereof are shown in Table 1, and the results of the observation of the cross section of particles thereof are shown in Table 2. In addition, the volume resistivity of the conductive film obtained in each of these examples and comparative examples is shown in Table 3.
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TABLE 1 Particle Size Specific True Distribution Surface Specific D10 D50 D90 Area Gravity (μm) (μm) (μm) (m2/g) (g/cm3) Example 1 1.6 3.0 5.3 0.35 9.6 Example 2 1.5 2.8 4.5 0.36 9.7 Example 3 0.7 1.3 2.4 0.77 9.3 Comp. 1 1.8 2.9 4.4 0.16 10.3 -
TABLE 2 SEM Image Cross- Cross- Sectional Sectional Mean Area of Area of Area Cavity Particles Cavities Ratio Size (μm2) (μm2) (%) (μm) Example 1 13.7 0.56 4.1 0.07 Example 2 11.8 0.34 2.9 0.05 Example 3 2.08 0.21 10 0.11 Comp. 1 — 0 0 — -
TABLE 3 Volume Resistivity (Ω · cm) 400° C. 700° C. Example 1 5.2 × 10−6 2.6 × 10−6 Example 2 5.7 × 10−6 2.4 × 10−6 Example 3 4.5 × 10−6 2.3 × 10−6 Comp. 1 1.1 × 10−5 3.0 × 10−6 - As can be seen from these examples and comparative examples, if silver particles are deposited by reduction by mixing a reducing agent containing solution, which contains an aldehyde, while causing cavitation in a water reaction system containing silver ions, it is possible to produce a spherical silver powder having closed cavities in the particles thereof.
- Since a spherical silver powder according to the present invention has closed cavities in the particles thereof, the spherical silver powder can be utilized for preparing a conductive paste as a spherical silver powder which has a particle size being substantially equal to that of a spherical silver powder produced by a conventional wet reducing method and which is capable of being fired at a lower temperature.
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JP2012-028315 | 2012-02-13 | ||
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JP2012250271A JP5872440B2 (en) | 2012-02-13 | 2012-11-14 | Spherical silver powder and method for producing the same |
US14/377,985 US11424049B2 (en) | 2012-02-13 | 2013-02-12 | Spherical silver powder and method for producing same |
PCT/JP2013/053785 WO2013122244A1 (en) | 2012-02-13 | 2013-02-12 | Spherical silver powder and method for producing same |
US15/831,696 US20180096747A1 (en) | 2012-02-13 | 2017-12-05 | Spherical silver powder and method for producing same |
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PCT/JP2013/053785 Division WO2013122244A1 (en) | 2012-02-13 | 2013-02-12 | Spherical silver powder and method for producing same |
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US15/831,696 Abandoned US20180096747A1 (en) | 2012-02-13 | 2017-12-05 | Spherical silver powder and method for producing same |
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EP (1) | EP2796231B1 (en) |
JP (1) | JP5872440B2 (en) |
KR (3) | KR102014055B1 (en) |
CN (1) | CN104136151B (en) |
MY (1) | MY169336A (en) |
SG (2) | SG10201606633QA (en) |
WO (1) | WO2013122244A1 (en) |
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JP2023164095A (en) * | 2022-04-28 | 2023-11-10 | Dowaエレクトロニクス株式会社 | Spherical silver powder, method for producing spherical silver powder, apparatus for producing spherical silver powder, and conductive paste |
KR20240060587A (en) | 2022-10-27 | 2024-05-08 | 후쿠다 킨조쿠 하쿠훈 코교 가부시키가이샤 | Silver-based metal powder and method for producing the silver-based metal powder |
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Also Published As
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KR20190075150A (en) | 2019-06-28 |
JP5872440B2 (en) | 2016-03-01 |
KR102014055B1 (en) | 2019-08-23 |
US11424049B2 (en) | 2022-08-23 |
JP2013189704A (en) | 2013-09-26 |
EP2796231A4 (en) | 2015-12-16 |
SG10201606633QA (en) | 2016-10-28 |
KR102073531B1 (en) | 2020-02-04 |
WO2013122244A1 (en) | 2013-08-22 |
SG11201404018WA (en) | 2014-10-30 |
EP2796231A1 (en) | 2014-10-29 |
EP2796231B1 (en) | 2020-11-11 |
MY169336A (en) | 2019-03-21 |
KR20190075149A (en) | 2019-06-28 |
CN104136151A (en) | 2014-11-05 |
US20150034883A1 (en) | 2015-02-05 |
CN104136151B (en) | 2016-08-31 |
KR20140125418A (en) | 2014-10-28 |
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