WO2017115462A1 - Silver alloy powder and method for producing same - Google Patents

Silver alloy powder and method for producing same Download PDF

Info

Publication number
WO2017115462A1
WO2017115462A1 PCT/JP2016/005220 JP2016005220W WO2017115462A1 WO 2017115462 A1 WO2017115462 A1 WO 2017115462A1 JP 2016005220 W JP2016005220 W JP 2016005220W WO 2017115462 A1 WO2017115462 A1 WO 2017115462A1
Authority
WO
WIPO (PCT)
Prior art keywords
alloy powder
silver alloy
silver
mass
temperature
Prior art date
Application number
PCT/JP2016/005220
Other languages
French (fr)
Japanese (ja)
Inventor
吉田　昌弘
良幸 道明
井上　健一
Original Assignee
Ｄｏｗａエレクトロニクス株式会社
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
Priority claimed from JP2016247325A external-priority patent/JP6804286B2/en
Application filed by Ｄｏｗａエレクトロニクス株式会社 filed Critical Ｄｏｗａエレクトロニクス株式会社
Priority to KR1020187019850A priority Critical patent/KR102574302B1/en
Priority to CN201680076654.XA priority patent/CN108430671B/en
Priority to EP16881442.4A priority patent/EP3395474A4/en
Priority to US16/065,834 priority patent/US20190009341A1/en
Publication of WO2017115462A1 publication Critical patent/WO2017115462A1/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C11/00—Alloys based on lead
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • 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

Definitions

  • the present invention relates to a silver alloy powder and a method for producing the same, and more particularly, to a silver alloy powder suitable for use as a material for a fired conductive paste and a method for producing the same.
  • an electrode of a solar cell an internal electrode of an electronic component using a low-temperature fired ceramic (LTCC), a multilayer ceramic electronic component such as a multilayer ceramic inductor (MLCI), an external electrode such as a multilayer ceramic capacitor or a multilayer ceramic inductor, etc. are formed.
  • LTCC low-temperature fired ceramic
  • MLCI multilayer ceramic inductor
  • MLCI multilayer ceramic inductor
  • An external electrode such as a multilayer ceramic capacitor or a multilayer ceramic inductor, etc.
  • Metal powder such as silver powder is used as a material for the fired conductive paste.
  • the melting point of silver is as high as 961 ° C., and when used as a fired conductive paste that sinters silver powder at a relatively low temperature, there is a risk that sintering does not proceed sufficiently and desired electrical characteristics cannot be obtained. is there. Moreover, silver powder is expensive and it is desired to use a metal powder that is cheaper.
  • the main component is one or more selected from the group consisting of silver and Sn, Sb, Zn, Bi, and has a melting point of 600 ° C. or lower.
  • a brazing material made of a thin plate-like molten metal quenching material, a fine wire material, and a fine particle material has been proposed (for example, see Patent Document 1).
  • the brazing material of Patent Document 1 is not a metal powder having a small particle diameter, the sintering temperature cannot be lowered sufficiently and good conductivity cannot be obtained.
  • an object of the present invention is to provide an inexpensive silver alloy powder having a low sintering temperature and a method for producing the same.
  • the present inventors have determined that the average particle size of an alloy powder of one kind of metal selected from the group consisting of tin, zinc, lead and indium and silver is 0.5. It was found that a silver alloy powder having a low sintering temperature and a low cost can be produced by adjusting the temperature at a shrinkage rate of 0.5% in a thermomechanical analysis to 300 ° C. or less in a thermomechanical analysis. It came to complete.
  • the silver alloy powder according to the present invention is an alloy powder of one kind of metal selected from the group consisting of tin, zinc, lead and indium and silver, and has an average particle size of 0.5 to 20 ⁇ m and is thermomechanical.
  • the temperature when the shrinkage rate is 0.5% is 300 ° C. or less.
  • the silver alloy powder preferably has a temperature at a shrinkage rate of 1.0% in a thermomechanical analysis of 400 ° C. or less, and preferably has a temperature at a shrinkage rate of 1.5% of 450 ° C. or less. .
  • the oxygen content in the silver alloy powder is preferably 6% by mass or less, and the carbon content is preferably 0.5% by mass or less.
  • the BET specific surface area of the silver alloy powder is preferably 0.1 to 3.5 m 2 / g, and the tap density is preferably 2.5 g / cm 3 or more.
  • the content of tin is preferably 65 to 75% by mass.
  • the method for producing a silver alloy powder according to the present invention includes spraying high-pressure water while dropping a molten metal in which one metal selected from the group consisting of tin, zinc, lead and indium and silver are dissolved in a nitrogen atmosphere. It is characterized by rapid solidification.
  • the high-pressure water is preferably pure water or alkaline water, and the high-pressure water is preferably sprayed in the air or in a nitrogen atmosphere.
  • the conductive paste according to the present invention is characterized in that the silver alloy powder is dispersed in an organic component.
  • This conductive paste is preferably a fired conductive paste.
  • the method for producing a conductive film according to the present invention is characterized in that the fired conductive paste is applied onto a substrate and then fired to produce a conductive film.
  • the “average particle diameter” refers to a volume-based cumulative 50% particle diameter (D 50 diameter) measured by a laser diffraction particle size distribution measuring apparatus (by the Helos method).
  • an inexpensive silver alloy powder having a low sintering temperature and a method for producing the same can be provided.
  • thermomechanical analysis TMA
  • XPS X-ray photoelectron spectrometer
  • the average particle diameter of the alloy powder of one metal selected from the group consisting of tin, zinc, lead and indium and silver is 0.5 to 20 ⁇ m (preferably 0.5 to 15 ⁇ m, more preferably 0.5 to 10 ⁇ m), and in the thermomechanical analysis, the temperature when the shrinkage rate is 0.5% is 300 ° C. or less (preferably 290 ° C. or less).
  • the silver alloy powder preferably has a temperature at a shrinkage rate of 1.0% of 400 ° C. or less (more preferably 360 ° C. or less), and a temperature at a shrinkage rate of 1.5%. Preferably it is 450 degrees C or less (more preferably 420 degrees C or less).
  • the oxygen content in the silver alloy powder is preferably 6% by mass or less so that good conductivity can be obtained when the silver alloy powder is used as a material for the fired conductive paste. % Or less is more preferable, and 2% by mass or less is most preferable.
  • the carbon content in the silver alloy powder is preferably 0.5% by mass or less, and more preferably 0.2% by mass or less.
  • the carbon content in the silver alloy powder is low, when used as a material for the firing type conductive paste, the generation of gas during firing of the conductive paste is suppressed, and the adhesion of the conductive film to the substrate is reduced. While suppressing a fall, it can suppress that a crack arises in an electrically conductive film.
  • the BET specific surface area of the silver alloy powder is preferably from 0.1 to 3.5 m 2 / g, more preferably from 1 to 3.5 m 2 / g.
  • the tap density of the silver alloy powder is preferably 2.5 g / cm 3 or more, and more preferably 3 to 5 g / cm 3 .
  • the content of tin in the silver alloy powder is preferably 45% by mass or more. It is preferable that the content of tin in the silver alloy powder is 80% by mass or less so that good conductivity can be obtained when the silver alloy powder is used as a material for the fired conductive paste.
  • the oxygen content in the silver alloy powder made of an alloy of silver and tin is preferably 2% by mass or less, but the thickness of the oxide film on the surface of the silver alloy powder is 45 to 100 nm. preferable. If a surface oxide film having such a thickness is formed, the surface oxide film may lower the sintering temperature as a sintering aid.
  • the thickness of the surface oxide film is a portion where the oxygen atom concentration on the surface of the silver alloy powder exceeds 9% in the element distribution spectrum of the silver alloy powder by an X-ray photoelectron spectrometer (XPS).
  • XPS X-ray photoelectron spectrometer
  • the shape of the silver alloy powder may be any of various granular shapes such as a spherical shape and a flake shape, or may be an indefinite shape in which the shapes are not uniform.
  • the embodiment of the silver alloy powder described above can be manufactured by the embodiment of the method for manufacturing a silver alloy powder according to the present invention.
  • a molten metal in which one metal selected from the group consisting of tin, zinc, lead and indium and silver is dissolved in a nitrogen atmosphere (preferably Then, it is rapidly solidified by spraying with high-pressure water (which is pure water or alkaline water at a water pressure of 30 to 200 MPa in air or nitrogen atmosphere).
  • high-pressure water which is pure water or alkaline water at a water pressure of 30 to 200 MPa in air or nitrogen atmosphere.
  • silver alloy powder is produced by the so-called water atomization method, in which high-pressure water is sprayed, a silver alloy powder having a small particle diameter can be obtained. Therefore, when silver alloy powder is used as a material for a fired conductive paste, sintering is performed. The temperature becomes low, for example, it can be sufficiently sintered even at a low temperature of about 500 ° C., and good conductivity can be obtained. On the other hand, tin, zinc, lead, and indium are more easily oxidized than silver. Therefore, when dissolved together with silver in an atmosphere where oxygen is present, the oxygen content in the silver alloy powder produced by the water atomization method tends to increase.
  • the embodiment of the silver alloy powder according to the present invention can be used as a material for a conductive paste (in which a silver alloy powder is dispersed in an organic component).
  • the embodiment of the silver alloy powder according to the present invention has a low sintering temperature and thus a low firing temperature (preferably fired at a low temperature of about 300 to 800 ° C., more preferably about 400 to 700 ° C.). It is preferable to use it as a material for the type conductive paste.
  • the embodiment of the silver alloy powder according to the present invention can be used as a material of a calcination type conductive paste having a low calcination temperature, it is heated at a temperature lower than the calcination temperature of a conventional calcination type conductive paste. It may be used as a material for a resin-curing conductive paste (forming a conductive film). Further, as a material of the conductive paste, two or more kinds of Ag—Sn alloy powder, Ag—In alloy powder, Ag—Zn alloy powder and Ag—Pb alloy powder which are embodiments of the silver alloy powder according to the present invention are mixed. The embodiment of the silver alloy powder according to the present invention may be used by mixing with other metal powders having different shapes and particle sizes.
  • a conductive paste such as a fired conductive paste
  • a silver alloy powder and (saturated aliphatic hydrocarbons)
  • Organic solvents such as unsaturated aliphatic hydrocarbons, ketones, aromatic hydrocarbons, glycol ethers, esters, alcohols, etc.
  • a vehicle in which a binder resin (such as ethyl cellulose or acrylic resin) is dissolved in an organic solvent, glass frit, an inorganic oxide, a dispersant, and the like may be included.
  • the content of the silver alloy powder in the conductive paste is preferably 5 to 98% by mass, more preferably 70 to 95% by mass, from the viewpoint of the conductivity of the conductive paste and the manufacturing cost.
  • the silver alloy powder in the conductive paste may be used by mixing with one or more other metal powders (such as silver powder, silver-tin alloy powder, tin powder).
  • This metal powder may be a metal powder having a different shape and particle size from the embodiment of the silver alloy powder according to the present invention.
  • the average particle size of the metal powder is preferably 0.5 to 20 ⁇ m in order to fire the conductive paste at a low temperature.
  • the content of the metal powder in the conductive paste is preferably 1 to 94% by mass, and more preferably 4 to 29% by mass.
  • the total content of the silver alloy powder and the metal powder in the conductive paste is preferably 60 to 98% by mass.
  • the content of the binder resin in the conductive paste is preferably 0.1 to 10% by mass from the viewpoint of the dispersibility of the silver alloy powder in the conductive paste and the conductivity of the conductive paste. More preferably, it is 1 to 6% by mass. Two or more types of vehicles in which this binder resin is dissolved in an organic solvent may be mixed and used.
  • the glass frit content in the conductive paste is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, from the viewpoint of sinterability of the conductive paste. preferable. Two or more kinds of the glass frit may be mixed and used.
  • the content of the organic solvent in the conductive paste depends on the dispersibility and conductivity of the silver alloy powder in the conductive paste. In consideration of the appropriate viscosity of the paste, it is preferably 0.8 to 20% by mass, and more preferably 0.8 to 15% by mass. Two or more organic solvents may be mixed and used.
  • Such a conductive paste is prepared, for example, by weighing each component into a predetermined container, pre-kneading using a raking machine, universal stirrer, kneader, etc., and then carrying out main kneading with three rolls. can do. Further, if necessary, the viscosity may be adjusted by adding an organic solvent thereafter. Alternatively, after only kneading glass frit or inorganic oxide and vehicle to reduce the particle size, silver alloy powder may be added and finally kneaded.
  • the conductive paste can be applied to the substrate in a predetermined pattern shape by dipping or printing (such as metal mask printing, screen printing, and ink jet printing) and then baked to form a conductive film.
  • dipping or printing such as metal mask printing, screen printing, and ink jet printing
  • the substrate is dipped into the conductive paste to form a coating film, and unnecessary portions of the coating film are removed by photolithography using a resist, etc.
  • a coating film having a predetermined pattern shape can be formed.
  • the baking of the conductive paste applied on the substrate may be performed in an air atmosphere or in a non-oxidizing atmosphere such as nitrogen, argon, hydrogen, carbon monoxide.
  • a non-oxidizing atmosphere such as nitrogen, argon, hydrogen, carbon monoxide.
  • the firing temperature of the conductive paste is low (preferably about 300 to 700 ° C., more preferably about 400 to 600 ° C.). can do.
  • the firing temperature of the conductive paste may be a general firing temperature (about 700 to 900 ° C.).
  • Example 1 While dropping molten metal from 7.5 kg of shot silver and 2.5 kg of shot tin heated to 1100 ° C. in a nitrogen atmosphere from the bottom of the tundish, the water atomizer uses a water pressure of 150 MPa and a water volume of 160 L / min. Water was sprayed and rapidly solidified, and the resulting slurry was subjected to solid-liquid separation. The solid was washed with water, dried, crushed, and classified by air to obtain a silver alloy powder (Ag—Sn alloy powder). As high-pressure water, an alkaline aqueous solution (pH 10.26) in which 157.55 g of caustic soda was added to 21.6 m 3 of pure water was used.
  • the BET specific surface area, the tap density, the oxygen content, the carbon content and the particle size distribution were determined, and the alloy composition analysis was performed and the thermomechanical analysis (TMA) was performed.
  • the BET specific surface area was degassed by flowing nitrogen gas at 105 ° C. for 20 minutes in a measuring instrument using a BET specific surface area measuring instrument (4 Sorb US made by Yuasa Ionics Co., Ltd.), While flowing a mixed gas (N 2 : 30% by volume, He: 70% by volume), the BET one-point method was used for measurement. As a result, the BET specific surface area was 0.92 m 2 / g.
  • the tap density (TAP) is obtained by filling a silver alloy powder into a bottomed cylindrical die having an inner diameter of 6 mm to form a silver alloy powder layer in the same manner as in the method described in JP-A-2007-263860. After uniformly applying a pressure of 0.160 N / m 2 on the upper surface of the alloy powder layer, the height of the silver alloy powder layer is measured, and the measured value of the height of the silver alloy powder layer and the filled silver alloy From the weight of the powder, the density of the silver alloy powder was determined and used as the tap density of the silver alloy powder. As a result, the tap density was 3.6 g / cm 3 .
  • the oxygen content was measured with an oxygen / nitrogen / hydrogen analyzer (EMGA-920 manufactured by Horiba, Ltd.). As a result, the oxygen content was 0.32% by mass.
  • Carbon content was measured by a carbon / sulfur analyzer (EMIA-220V manufactured by Horiba, Ltd.). As a result, the carbon content was 0.01% by mass.
  • the particle size distribution was measured at a dispersion pressure of 5 bar using a laser diffraction particle size distribution measuring device (Heros particle size distribution measuring device (HELOS & RODOS (airflow drying module) manufactured by SYMPATEC)).
  • HELOS & RODOS airflow drying module manufactured by SYMPATEC
  • the cumulative 10% particle diameter (D 10 ) was 0.9 ⁇ m
  • the cumulative 50% particle diameter (D 50 ) was 2.2 ⁇ m
  • the cumulative 90% particle diameter (D 90 ) was 4.2 ⁇ m.
  • the alloy composition analysis was performed using an inductively coupled plasma (ICP) emission spectrometer (SPS3520V manufactured by Hitachi High-Tech Science Co., Ltd.). As a result, the Ag content in the silver alloy powder was 74% by mass, and the Sn content was 24% by mass.
  • ICP inductively coupled plasma
  • thermomechanical analysis (TMA) of the silver alloy powder is performed by using a thermomechanical analysis (TMA) apparatus (TMA / SS6200 manufactured by Seiko Instruments Inc.) packed in an alumina pan having a diameter of 5 mm and a height of 3 mm.
  • TMA thermomechanical analysis
  • a load was applied at a measurement load of 980 mN while flowing nitrogen gas at a flow rate of 200 mL / min. The temperature was raised from normal temperature to 500 ° C.
  • Example 2 Silver alloy powder (Ag ⁇ ) was prepared in the same manner as in Example 1 except that pure water (pH 5.8) was used as high-pressure water, and the amounts of shot silver and shot tin were 6.5 kg and 3.5 kg, respectively. Sn alloy powder) was obtained.
  • the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and the alloy composition analysis was performed. Analysis (TMA) was performed.
  • the silver alloy powder has a BET specific surface area of 1.14 m 2 / g, a tap density of 3.5 g / cm 3 , an oxygen content of 0.57% by mass, and a carbon content of 0.01% by mass,
  • the cumulative 10% particle diameter (D 10 ) was 0.8 ⁇ m
  • the cumulative 50% particle diameter (D 50 ) was 1.9 ⁇ m
  • the cumulative 90% particle diameter (D 90 ) was 4.0 ⁇ m.
  • Ag content in a silver alloy powder was 63 mass%, and Sn content was 36 mass%.
  • the temperature at a shrinkage rate of 0.5% was 142 ° C.
  • the temperature at a shrinkage rate of 1.0% was 194 ° C.
  • the temperature at a shrinkage rate of 1.5% was 216 ° C.
  • the thickness of the oxide film on the surface of the silver alloy powder was measured.
  • the surface oxide film was measured with an X-ray photoelectron spectroscopic analyzer (ESCA5800 manufactured by ULBAC-PHI) using monochromated Al as the X-ray source and using K ⁇ rays to measure the surface of the silver alloy powder sample. The test was performed on a region having a diameter of 800 ⁇ m.
  • the sputtering rate of the sample was 1 nm / min in terms of SiO 2 , and in the obtained elemental analysis spectrum in the depth direction, the thickness of the surface where the oxygen atom concentration on the surface of the silver alloy powder exceeds 9% is the thickness of the surface oxide film Say it. As a result, the thickness of the surface oxide film was 18 nm.
  • Example 3 A silver alloy powder (Ag—Sn alloy powder) was obtained in the same manner as in Example 1 except that the amounts of shot silver and shot tin were 1.35 kg and 1.65 kg, respectively.
  • the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and alloy composition analysis and thermomechanical analysis ( TMA) was performed, and the thickness of the surface oxide film was measured by the same method as in Example 2.
  • the silver alloy powder has a BET specific surface area of 1.63 m 2 / g, a tap density of 3.3 g / cm 3 , an oxygen content of 0.76% by mass, and a carbon content of 0.01% by mass,
  • the cumulative 10% particle size (D 10 ) was 0.7 ⁇ m
  • the cumulative 50% particle size (D 50 ) was 1.8 ⁇ m
  • the cumulative 90% particle size (D 90 ) was 4.0 ⁇ m.
  • the Ag content in the silver alloy powder was 45% by mass, and the Sn content was 55% by mass.
  • FIG. 2 shows an elemental analysis spectrum of the silver alloy powder with respect to the depth direction by an X-ray optical spectrometer (XPS).
  • XPS X-ray optical spectrometer
  • Example 4 While dropping 1.35 kg of shot silver and 1.65 kg of shot tin to 1430 ° C. in a nitrogen atmosphere and dropping the molten metal from the lower part of the tundish, a water atomizing device is used in a nitrogen atmosphere at a water pressure of 150 MPa and a water amount of 160 L / min. High pressure water was sprayed to cool and solidify, and the resulting slurry was separated into solid and liquid, and the solid was washed with water, dried, crushed, and classified by air to obtain a silver alloy powder (Ag—Sn alloy powder). .
  • a high pressure water using an alkali aqueous solution prepared by adding sodium hydroxide 157.55g against pure 21.6m 3 (pH10.26).
  • the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and alloy composition analysis and thermomechanical analysis ( TMA) was performed, and the thickness of the surface oxide film was measured by the same method as in Example 2.
  • BET specific surface area of the silver alloy powder 1.37 m 2 / g, a tap density of 3.1 g / cm 3, oxygen content 0.61 wt%, the carbon content was 0.01 wt%,
  • the cumulative 10% particle diameter (D 10 ) was 0.5 ⁇ m
  • the cumulative 50% particle diameter (D 50 ) was 1.3 ⁇ m
  • the cumulative 90% particle diameter (D 90 ) was 2.4 ⁇ m.
  • the Ag content in the silver alloy powder was 45% by mass, and the Sn content was 55% by mass.
  • the temperature when the shrinkage rate was 0.5% was 121 ° C.
  • the temperature when the shrinkage rate was 1.0% was 172 ° C.
  • the temperature when the shrinkage rate was 1.5% was 205 ° C.
  • the thickness of the surface oxide film was 65 nm.
  • Example 5 A silver alloy powder (Ag—Sn alloy powder) was obtained in the same manner as in Example 4 except that high-pressure water was sprayed in the atmosphere.
  • the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and alloy composition analysis and thermomechanical analysis ( TMA) was performed, and the thickness of the surface oxide film was measured by the same method as in Example 2.
  • BET specific surface area of the silver alloy powder 3.30m 2 / g, a tap density of 3.4 g / cm 3, oxygen content 1.44 wt%, the carbon content was 0.01 wt%
  • the cumulative 10% particle size (D 10 ) was 0.5 ⁇ m
  • the cumulative 50% particle size (D 50 ) was 1.0 ⁇ m
  • the cumulative 90% particle size (D 90 ) was 1.9 ⁇ m.
  • Ag content in a silver alloy powder was 44 mass%, and Sn content was 55 mass%.
  • the temperature when the shrinkage rate was 0.5% was 106 ° C.
  • the temperature when the shrinkage rate was 1.0% was 155 ° C.
  • the temperature when the shrinkage rate was 1.5% was 196 ° C.
  • the thickness of the surface oxide film was 55 nm.
  • Example 6 A silver alloy powder (Ag—Sn alloy powder) was obtained in the same manner as in Example 2, except that the heating temperature was 1200 ° C. and the amounts of shot silver and shot tin were 2.01 kg and 4.69 kg, respectively. .
  • the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and the alloy composition analysis was performed. Analysis (TMA) was performed.
  • the BET specific surface area of the silver alloy powder is 1.48 m 2 / g
  • the tap density is 3.3 g / cm 3
  • the oxygen content is 1.11% by mass
  • the carbon content is 0.01% by mass
  • the cumulative 10% particle size (D 10 ) was 0.6 ⁇ m
  • the cumulative 50% particle size (D 50 ) was 1.5 ⁇ m
  • the cumulative 90% particle size (D 90 ) was 3.4 ⁇ m.
  • the Ag content in the silver alloy powder was 30% by mass, and the Sn content was 70% by mass.
  • the temperature at a shrinkage rate of 0.5% was 158 ° C.
  • the temperature at a shrinkage rate of 1.0% was 195 ° C.
  • the temperature at a shrinkage rate of 1.5% was 206 ° C.
  • Example 7 While dropping 2 kg of shot silver and 2 kg of indium by heating to 1100 ° C. in a nitrogen atmosphere from the lower part of the tundish, high pressure water (pH 5.8) at a water pressure of 150 MPa and an amount of water of 160 L / min. The obtained slurry is solidified by solid-liquid separation, the solid is washed with water, dried, crushed, and air-classified to produce silver alloy powder (Ag-In alloy powder). Obtained.
  • the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and the alloy composition analysis was performed. Analysis (TMA) was performed.
  • the silver alloy powder has a BET specific surface area of 1.17 m 2 / g, a tap density of 3.5 g / cm 3 , an oxygen content of 1.06% by mass, and a carbon content of 0.02% by mass,
  • the cumulative 10% particle diameter (D 10 ) was 0.7 ⁇ m
  • the cumulative 50% particle diameter (D 50 ) was 1.8 ⁇ m
  • the cumulative 90% particle diameter (D 90 ) was 3.5 ⁇ m.
  • Ag content in silver alloy powder was 47 mass%, and In content was 52 mass%.
  • the temperature at a shrinkage rate of 0.5% was 141 ° C.
  • the temperature at a shrinkage rate of 1.0% was 166 ° C.
  • the temperature at a shrinkage rate of 1.5% was 178 ° C.
  • Example 8 While dropping 1.5 kg of shot silver and 3.5 kg of zinc heated to 1000 ° C. in a nitrogen atmosphere from the lower part of the tundish, high-pressure water at a water pressure of 150 MPa and a water volume of 160 L / min. (Pure water of pH 5.8) is sprayed to cool and solidify, the resulting slurry is solid-liquid separated, the solid is washed with water, dried, crushed, air-classified, and silver alloy powder (Ag—Zn) Alloy powder) was obtained.
  • the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and the alloy composition analysis was performed. Analysis (TMA) was performed.
  • the silver alloy powder has a BET specific surface area of 1.77 m 2 / g, a tap density of 3.3 g / cm 3 , an oxygen content of 0.84 mass%, and a carbon content of 0.02 mass%.
  • cumulative 10% particle diameter (D 10) is 1.0 .mu.m
  • cumulative 50% particle diameter (D 50) is 2.3 .mu.m
  • cumulative 90% particle diameter (D 90) was 4.6 .mu.m.
  • Ag content in a silver alloy powder was 57 mass%, and Zn content was 43 mass%.
  • the temperature at a shrinkage rate of 0.5% was 283 ° C.
  • the temperature at a shrinkage rate of 1.0% was 356 ° C.
  • the temperature at a shrinkage rate of 1.5% was 419 ° C.
  • Example 9 250g of carbon powder is added as a reducing agent to molten metal obtained by heating 3.5kg of shot silver and 1.5kg of shot lead to 1100 ° C in a nitrogen atmosphere, and the molten metal to which this reducing agent has been added falls from the bottom of the tundish. Then, high pressure water (alkaline water having the same pH of 10.26 as in Example 3) was sprayed and rapidly solidified in the atmosphere at a water pressure of 150 MPa and a water volume of 160 L / min by a water atomizer, and the resulting slurry was solid-liquid separated. The solid was washed with water, dried, crushed, and classified by air to obtain a silver alloy powder (Ag—Pb alloy powder).
  • the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and the alloy composition analysis was performed. Analysis (TMA) was performed.
  • the silver alloy powder has a BET specific surface area of 2.14 m 2 / g, a tap density of 3.1 g / cm 3 , an oxygen content of 1.87% by mass, and a carbon content of 0.10% by mass,
  • the cumulative 10% particle diameter (D 10 ) was 0.7 ⁇ m
  • the cumulative 50% particle diameter (D 50 ) was 1.8 ⁇ m
  • the cumulative 90% particle diameter (D 90 ) was 3.6 ⁇ m.
  • Ag content in a silver alloy powder was 70 mass%, and Pb content was 27 mass%.
  • the temperature at a shrinkage rate of 0.5% was 133 ° C.
  • the temperature at a shrinkage rate of 1.0% was 152 ° C.
  • the temperature at a shrinkage rate of 1.5% was 166 ° C.
  • Example 10 A silver alloy powder (Ag—Pb alloy powder) was obtained in the same manner as in Example 9, except that the amounts of shot silver and shot lead were 1.5 kg and 3.5 kg, respectively.
  • the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and the alloy composition analysis was performed. Analysis (TMA) was performed.
  • BET specific surface area of the silver alloy powder 2.41m 2 / g, a tap density of 3.0 g / cm 3, the oxygen content is 5.56 mass%, the carbon content was 0.13 wt%, The cumulative 10% particle diameter (D 10 ) was 0.6 ⁇ m, the cumulative 50% particle diameter (D 50 ) was 1.6 ⁇ m, and the cumulative 90% particle diameter (D 90 ) was 3.5 ⁇ m.
  • the Ag content in the silver alloy powder was 30% by mass, and the Pb content was 64% by mass.
  • the temperature at a shrinkage rate of 0.5% was 200 ° C.
  • the temperature at a shrinkage rate of 1.0% was 229 ° C.
  • the temperature at a shrinkage rate of 1.5% was 245 ° C.
  • the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution are determined by the same method as in Example 1, and the alloy composition analysis is performed, and the thermomechanical analysis is performed. (TMA) was performed.
  • the BET specific surface area of the silver powder was 0.47 m 2 / g
  • the tap density was 5.1 g / cm 3
  • the oxygen content was 0.07 mass%
  • the carbon content was 0.01 mass%
  • The% particle size (D 10 ) was 0.7 ⁇ m
  • the cumulative 50% particle size (D 50 ) was 2.1 ⁇ m
  • the cumulative 90% particle size (D 90 ) was 4.1 ⁇ m.
  • the Ag content in the silver powder was 100% by mass.
  • the temperature when the shrinkage rate was 0.5% was 479 ° C.
  • the temperature when the shrinkage rate was 1.0% was 490 ° C.
  • the temperature when the shrinkage rate was 1.5% was 500 ° C.
  • Tables 1 to 3 show the production conditions and characteristics of the silver alloy powders of these examples and the silver powder of the comparative example. Further, FIG. 1 shows the relationship of the expansion coefficient with respect to temperature in the thermomechanical analysis (TMA) of the silver alloy powders of Examples 1 to 10 and the silver powder of the comparative example.
  • TMA thermomechanical analysis
  • the film was baked at a peak temperature of 780 ° C. and 820 ° C. (In-Out 21 seconds) in a high-speed baking IR furnace (a high-speed baking test 4-chamber furnace manufactured by NGK Co., Ltd.) to prepare a conductive film.
  • a high-speed baking IR furnace a high-speed baking test 4-chamber furnace manufactured by NGK Co., Ltd.
  • the silver powder of the comparative example had a film thickness of 23.4 ⁇ m and an electrical resistance of 1.39 ⁇ 10 ⁇ 1.
  • the volume resistivity of 4.35 ⁇ 10 -6 ⁇ ⁇ cm, in the silver alloy powder of example 2 the film thickness 27.5, the electrical resistance 4.00 ⁇ 10 5 ⁇ , the volume resistivity of 1.47 ⁇ 10 1
  • the film thickness was 28.6 ⁇ m
  • the electric resistance was 4.39 ⁇ 10 3 ⁇
  • the volume resistivity was 1.69 ⁇ 10 ⁇ 1 ⁇ ⁇ cm
  • the silver alloy powder of Example 6 Then, the film thickness is 31.0 ⁇ m, the electric resistance is 4.04 ⁇ 10 1 ⁇ , the volume resistivity is 1.67 ⁇ 10 ⁇ 3 ⁇ ⁇ cm, and the tin powder is 20.7 ⁇ m in thickness and the electric resistance is 2.28 ⁇ 10 6.
  • the silver alloy powder of Example 2 has a film thickness of 28.5 ⁇ m, electric resistance 5.40 ⁇ 10 4 ⁇ , volume resistivity 2.05 ⁇ 10 0 ⁇ ⁇ cm, silver alloy powder of Example 3, film thickness 29.0 ⁇ m, electrical resistance 1.40 ⁇ 10 4 ⁇ , volume resistivity 5.39 ⁇ 10 -1 ⁇ ⁇ cm, film thickness 30.6 ⁇ m, electric resistance 3.93 ⁇ 10 1 ⁇ , volume resistivity 1.61 ⁇ 10 ⁇ 3 ⁇ ⁇ cm for the silver alloy powder of Example 6, film for tin powder The thickness was 19.7 ⁇ m, the electric resistance was 4.78 ⁇ 10 6 ⁇ , and the volume resistivity was 1.26 ⁇ 10 2 ⁇ ⁇ cm.
  • the volume resistivity with respect to the content of tin in the metal powder used in these conductive films is shown in FIG.
  • the silver alloy powder of Example 6 including 70% by mass of tin
  • the silver alloy powder of Example 2 including 35% by mass of tin
  • the volume resistivity is extremely low despite containing a large amount of tin (which has a lower electrical resistance than silver). Yes. From this result, it is understood that a conductive film having a low volume resistivity can be obtained by using a conductive paste containing an Ag—Sn alloy powder containing 65 to 75% by mass of tin.
  • Silver alloy powders according to the present invention include electrodes for solar cells, internal electrodes for multilayer ceramic electronic components such as electronic components and multilayer ceramic inductors using low temperature fired ceramics (LTCC), and external electrodes for multilayer ceramic capacitors and multilayer ceramic inductors, etc. Can be used as a material for a fired conductive paste that is sintered at a low temperature.
  • LTCC low temperature fired ceramics

Abstract

This silver alloy powder is produced by melting silver and one kind of metal selected from the group consisting of tin, zinc, lead and indium in a nitrogen atmosphere to obtain a molten metal, and then while dropping the molten metal, rapidly cooling and solidifying the molten metal by spraying high-pressure water (preferably, pure water or alkaline water) onto the molten metal in the air or in a nitrogen atmosphere. The silver alloy powder is composed of silver and one kind of metal selected from the group consisting of tin, zinc, lead and indium, and has an average particle size of 0.5-20 µm. During thermomechanical analysis, the temperature of the silver alloy powder is 300°C or lower at a shrinkage rate of 0.5%, 400°C or lower at a shrinkage rate of 1.0%, and 450°C or lower at a shrinkage rate of 1.5%.

Description

銀合金粉末およびその製造方法Silver alloy powder and method for producing the same
　本発明は、銀合金粉末およびその製造方法に関し、特に、焼成型導電性ペーストの材料として使用するのに適した銀合金粉末およびその製造方法に関する。 The present invention relates to a silver alloy powder and a method for producing the same, and more particularly, to a silver alloy powder suitable for use as a material for a fired conductive paste and a method for producing the same.
　従来、太陽電池の電極、低温焼成セラミック（ＬＴＣＣ）を使用した電子部品や積層セラミックインダクタ（ＭＬＣＩ）などの積層セラミック電子部品の内部電極、積層セラミックコンデンサや積層セラミックインダクタなどの外部電極などを形成する焼成型導電性ペーストの材料として、銀粉などの金属粉末が使用されている。 Conventionally, an electrode of a solar cell, an internal electrode of an electronic component using a low-temperature fired ceramic (LTCC), a multilayer ceramic electronic component such as a multilayer ceramic inductor (MLCI), an external electrode such as a multilayer ceramic capacitor or a multilayer ceramic inductor, etc. are formed. Metal powder such as silver powder is used as a material for the fired conductive paste.
　しかし、銀の融点は９６１℃と高く、銀粉を比較的低温で焼結する焼成型導電性ペーストに使用する場合には、十分に焼結が進まず、所望の電気特性が得られないおそれがある。また、銀粉は高価であり、さらに安価な金属粉末を使用することが望まれている。 However, the melting point of silver is as high as 961 ° C., and when used as a fired conductive paste that sinters silver powder at a relatively low temperature, there is a risk that sintering does not proceed sufficiently and desired electrical characteristics cannot be obtained. is there. Moreover, silver powder is expensive and it is desired to use a metal powder that is cheaper.
　銀よりも焼結温度が低く且つ安価な金属として、銀およびＳｎ、Ｓｂ、Ｚｎ、Ｂｉよりなる群から選ばれた１種または２種以上を主成分とし、かつ６００℃以下の融点を有する、薄板状の溶湯急冷材、細線材、微粒材からなるろう材が提案されている（例えば、特許文献１参照）。 As a metal having a sintering temperature lower than silver and inexpensive, the main component is one or more selected from the group consisting of silver and Sn, Sb, Zn, Bi, and has a melting point of 600 ° C. or lower. A brazing material made of a thin plate-like molten metal quenching material, a fine wire material, and a fine particle material has been proposed (for example, see Patent Document 1).
特開昭５８－６７９３号公報（第２頁）JP 58-6793 (page 2)
　しかし、特許文献１のろう材では、粒子径が小さい金属粉末でないため、焼結温度を十分に低下させることができず、良好な導電性を得ることができない。 However, since the brazing material of Patent Document 1 is not a metal powder having a small particle diameter, the sintering temperature cannot be lowered sufficiently and good conductivity cannot be obtained.
　したがって、本発明は、このような従来の問題点に鑑み、焼結温度が低く且つ安価な銀合金粉末およびその製造方法を提供することを目的とする。 Therefore, in view of such conventional problems, an object of the present invention is to provide an inexpensive silver alloy powder having a low sintering temperature and a method for producing the same.
　本発明者らは、上記課題を解決するために鋭意研究した結果、錫、亜鉛、鉛およびインジウムからなる群から選ばれる１種の金属と銀との合金粉末において、平均粒径を０．５～２０μｍとし、熱機械的分析において収縮率０．５％のときの温度を３００℃以下にすることにより、焼結温度が低く且つ安価な銀合金粉末を製造することができることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors have determined that the average particle size of an alloy powder of one kind of metal selected from the group consisting of tin, zinc, lead and indium and silver is 0.5. It was found that a silver alloy powder having a low sintering temperature and a low cost can be produced by adjusting the temperature at a shrinkage rate of 0.5% in a thermomechanical analysis to 300 ° C. or less in a thermomechanical analysis. It came to complete.
　すなわち、本発明による銀合金粉末は、錫、亜鉛、鉛およびインジウムからなる群から選ばれる１種の金属と銀との合金粉末において、平均粒径が０．５～２０μｍであり、熱機械的分析において収縮率０．５％のときの温度が３００℃以下であることを特徴とする。 That is, the silver alloy powder according to the present invention is an alloy powder of one kind of metal selected from the group consisting of tin, zinc, lead and indium and silver, and has an average particle size of 0.5 to 20 μm and is thermomechanical. In the analysis, the temperature when the shrinkage rate is 0.5% is 300 ° C. or less.
　この銀合金粉末は、熱機械的分析において収縮率１．０％のときの温度が４００℃以下であるのが好ましく、収縮率１．５％のときの温度が４５０℃以下であるのが好ましい。また、銀合金粉末中の酸素含有量が６質量％以下であるのが好ましく、炭素含有量が０．５質量％以下であるのが好ましい。また、銀合金粉末のＢＥＴ比表面積が０．１～３．５ｍ２／ｇであるのが好ましく、タップ密度が２．５ｇ／ｃｍ３以上であるのが好ましい。また、銀合金粉末が錫と銀の合金粉末である場合、錫の含有量が６５～７５質量％であるのが好ましい。 The silver alloy powder preferably has a temperature at a shrinkage rate of 1.0% in a thermomechanical analysis of 400 ° C. or less, and preferably has a temperature at a shrinkage rate of 1.5% of 450 ° C. or less. . Further, the oxygen content in the silver alloy powder is preferably 6% by mass or less, and the carbon content is preferably 0.5% by mass or less. The BET specific surface area of the silver alloy powder is preferably 0.1 to 3.5 m 2 / g, and the tap density is preferably 2.5 g / cm 3 or more. Further, when the silver alloy powder is an alloy powder of tin and silver, the content of tin is preferably 65 to 75% by mass.
　また、本発明による銀合金粉末の製造方法は、錫、亜鉛、鉛およびインジウムからなる群から選ばれる１種の金属と銀を窒素雰囲気中において溶解した溶湯を落下させながら、高圧水を吹き付けて急冷凝固させることを特徴とする。 The method for producing a silver alloy powder according to the present invention includes spraying high-pressure water while dropping a molten metal in which one metal selected from the group consisting of tin, zinc, lead and indium and silver are dissolved in a nitrogen atmosphere. It is characterized by rapid solidification.
　この銀合金粉末の製造方法において、高圧水が純水またはアルカリ水であるのが好ましく、高圧水が大気中または窒素雰囲気中において吹き付けられるのが好ましい。 In this silver alloy powder production method, the high-pressure water is preferably pure water or alkaline water, and the high-pressure water is preferably sprayed in the air or in a nitrogen atmosphere.
　また、本発明による導電性ペーストは、上記の銀合金粉末が有機成分中に分散していることを特徴とする。この導電性ペーストは、焼成型導電性ペーストであるのが好ましい。 The conductive paste according to the present invention is characterized in that the silver alloy powder is dispersed in an organic component. This conductive paste is preferably a fired conductive paste.
　さらに、本発明による導電膜の製造方法は、上記の焼成型導電性ペーストを基板上に塗布した後に焼成して導電膜を製造することを特徴とする。 Furthermore, the method for producing a conductive film according to the present invention is characterized in that the fired conductive paste is applied onto a substrate and then fired to produce a conductive film.
　なお、本明細書中において、「平均粒径」とは、（ヘロス法によって）レーザー回折式粒度分布測定装置により測定した体積基準の累積５０％粒子径（Ｄ５０径）をいう。 In the present specification, the “average particle diameter” refers to a volume-based cumulative 50% particle diameter (D 50 diameter) measured by a laser diffraction particle size distribution measuring apparatus (by the Helos method).
　本発明によれば、焼結温度が低く且つ安価な銀合金粉末およびその製造方法を提供することができる。 According to the present invention, an inexpensive silver alloy powder having a low sintering temperature and a method for producing the same can be provided.
実施例１～１０の銀合金粉末と比較例の銀粉の熱機械的分析（ＴＭＡ）における温度に対する膨張率の関係を示す図である。It is a figure which shows the relationship of the expansion coefficient with respect to the temperature in the thermomechanical analysis (TMA) of the silver alloy powder of Examples 1-10 and the silver powder of a comparative example. 実施例３の銀合金粉末のＸ線光電子分光分析装置（ＸＰＳ）による深さ方向に対する元素分析スペクトルを示す図である。It is a figure which shows the elemental analysis spectrum with respect to the depth direction by the X-ray photoelectron spectrometer (XPS) of the silver alloy powder of Example 3. FIG. 実施例２、３および６の銀合金粉末と、比較例の銀粉と、錫粉とをそれぞれ使用して作製した導電性ペーストを７８０℃と８２０℃で焼成して得られた導電膜の体積抵抗率を示す図である。Volume resistance of conductive films obtained by firing conductive pastes produced using the silver alloy powders of Examples 2, 3 and 6 and the silver powders of comparative examples and tin powder at 780 ° C. and 820 ° C., respectively. It is a figure which shows a rate.
　本発明による銀合金粉末の実施の形態では、錫、亜鉛、鉛およびインジウムからなる群から選ばれる１種の金属と銀との合金の粉末において、平均粒径が０．５～２０μｍ（好ましくは０．５～１５μｍ、さらに好ましくは０．５～１０μｍ）であり、熱機械的分析において、収縮率０．５％のときの温度が３００℃以下（好ましくは２９０℃以下）である。 In the embodiment of the silver alloy powder according to the present invention, the average particle diameter of the alloy powder of one metal selected from the group consisting of tin, zinc, lead and indium and silver is 0.5 to 20 μm (preferably 0.5 to 15 μm, more preferably 0.5 to 10 μm), and in the thermomechanical analysis, the temperature when the shrinkage rate is 0.5% is 300 ° C. or less (preferably 290 ° C. or less).
　この銀合金粉末は、熱機械的分析において、収縮率１．０％のときの温度が好ましくは４００℃以下（さらに好ましくは３６０℃以下）であり、収縮率１．５％のときの温度が好ましくは４５０℃以下（さらに好ましくは４２０℃以下）である。 In the thermomechanical analysis, the silver alloy powder preferably has a temperature at a shrinkage rate of 1.0% of 400 ° C. or less (more preferably 360 ° C. or less), and a temperature at a shrinkage rate of 1.5%. Preferably it is 450 degrees C or less (more preferably 420 degrees C or less).
　銀合金粉末中の酸素含有量は、銀合金粉末を焼成型導電性ペーストの材料に使用した場合に良好な導電性を得ることができるように、６質量％以下であるのが好ましく、４質量％以下であるのがさらに好ましく、２質量％以下であるのが最も好ましい。 The oxygen content in the silver alloy powder is preferably 6% by mass or less so that good conductivity can be obtained when the silver alloy powder is used as a material for the fired conductive paste. % Or less is more preferable, and 2% by mass or less is most preferable.
　銀合金粉末中の炭素含有量は、０．５質量％以下であるのが好ましく、０．２質量％以下であるのがさらに好ましい。なお、銀合金粉末中の炭素含有量が低いと、焼成型導電性ペーストの材料として使用した場合に、導電性ペーストの焼成時にガスの発生を抑制して、導電膜の基板との密着性の低下を抑制するとともに、導電膜にクラックが生じるのを抑制することができる。 The carbon content in the silver alloy powder is preferably 0.5% by mass or less, and more preferably 0.2% by mass or less. In addition, when the carbon content in the silver alloy powder is low, when used as a material for the firing type conductive paste, the generation of gas during firing of the conductive paste is suppressed, and the adhesion of the conductive film to the substrate is reduced. While suppressing a fall, it can suppress that a crack arises in an electrically conductive film.
　銀合金粉末のＢＥＴ比表面積は、０．１～３．５ｍ２／ｇであるのが好ましく、１～３．５ｍ２／ｇであるのがさらに好ましい。 The BET specific surface area of the silver alloy powder is preferably from 0.1 to 3.5 m 2 / g, more preferably from 1 to 3.5 m 2 / g.
　銀合金粉末のタップ密度は、２．５ｇ／ｃｍ３以上であるのが好ましく、３～５ｇ／ｃｍ３であるのがさらに好ましい。 The tap density of the silver alloy powder is preferably 2.5 g / cm 3 or more, and more preferably 3 to 5 g / cm 3 .
　なお、銀合金粉末が銀と錫の合金である場合には、高価な銀の含有量を少なくするために、、銀合金粉末中の錫の含有量を４５質量％以上にするのが好ましいが、銀合金粉末を焼成型導電性ペーストの材料に使用した場合に良好な導電性を得ることができるように、銀合金粉末中の錫の含有量を８０質量％以下にするのが好ましい。また、銀と錫の合金からなる銀合金粉末中の酸素含有量は、２質量％以下であるのが好ましいが、銀合金粉末の表面の酸化膜の厚さは、４５～１００ｎｍであるのが好ましい。このような厚さの表面酸化膜が形成されていれば、表面酸化膜が焼結助剤として焼結温度を低下させる可能性がある。なお、本明細書中において、表面酸化膜の厚さは、Ｘ線光電子分光分析装置（ＸＰＳ）による銀合金粉末の元素分布スペクトルにおいて、銀合金粉末の表面の酸素原子濃度が９％を超える部分の厚さをいう。 In addition, when the silver alloy powder is an alloy of silver and tin, in order to reduce the content of expensive silver, the content of tin in the silver alloy powder is preferably 45% by mass or more. It is preferable that the content of tin in the silver alloy powder is 80% by mass or less so that good conductivity can be obtained when the silver alloy powder is used as a material for the fired conductive paste. Further, the oxygen content in the silver alloy powder made of an alloy of silver and tin is preferably 2% by mass or less, but the thickness of the oxide film on the surface of the silver alloy powder is 45 to 100 nm. preferable. If a surface oxide film having such a thickness is formed, the surface oxide film may lower the sintering temperature as a sintering aid. In the present specification, the thickness of the surface oxide film is a portion where the oxygen atom concentration on the surface of the silver alloy powder exceeds 9% in the element distribution spectrum of the silver alloy powder by an X-ray photoelectron spectrometer (XPS). The thickness of
　また、銀合金粉末の形状は、球状やフレーク状などの様々な粒状の形状のいずれの形状でもよく、形状が揃っていない不定形状でもよい。 Further, the shape of the silver alloy powder may be any of various granular shapes such as a spherical shape and a flake shape, or may be an indefinite shape in which the shapes are not uniform.
　上述した銀合金粉末の実施の形態は、本発明による銀合金粉末の製造方法の実施の形態により製造することができる。 The embodiment of the silver alloy powder described above can be manufactured by the embodiment of the method for manufacturing a silver alloy powder according to the present invention.
　本発明による銀合金粉末の製造方法の実施の形態では、錫、亜鉛、鉛およびインジウムからなる群から選ばれる１種の金属と銀を窒素雰囲気中において溶解した溶湯を落下させながら、（好ましくは、大気中または窒素雰囲気中において水圧３０～２００ＭＰａで純水またはアルカリ水である）高圧水を吹き付けて急冷凝固させる。 In the embodiment of the method for producing silver alloy powder according to the present invention, while dropping a molten metal in which one metal selected from the group consisting of tin, zinc, lead and indium and silver is dissolved in a nitrogen atmosphere (preferably Then, it is rapidly solidified by spraying with high-pressure water (which is pure water or alkaline water at a water pressure of 30 to 200 MPa in air or nitrogen atmosphere).
　高圧水を吹き付ける、所謂水アトマイズ法により銀合金粉末を製造すると、粒子径が小さい銀合金粉末を得ることができるので、銀合金粉末を焼成型導電性ペーストの材料に使用した場合に、焼結温度が低くなり、例えば５００℃程度の低温でも十分に焼結して、良好な導電性を得ることができる。一方、錫、亜鉛、鉛およびインジウムは、銀に比べて酸化し易いため、酸素が存在する雰囲気中で銀とともに溶解すると、水アトマイズ法により製造した銀合金粉末中の酸素含有量が高くなり易く、焼結温度が高くなって、導電性が低下し易いという問題があるが、窒素雰囲気中において錫、亜鉛、鉛またはインジウムを銀とともに溶解して水アトマイズ法により銀合金粉末を製造することによって、酸素含有量を低下させることができる。 When silver alloy powder is produced by the so-called water atomization method, in which high-pressure water is sprayed, a silver alloy powder having a small particle diameter can be obtained. Therefore, when silver alloy powder is used as a material for a fired conductive paste, sintering is performed. The temperature becomes low, for example, it can be sufficiently sintered even at a low temperature of about 500 ° C., and good conductivity can be obtained. On the other hand, tin, zinc, lead, and indium are more easily oxidized than silver. Therefore, when dissolved together with silver in an atmosphere where oxygen is present, the oxygen content in the silver alloy powder produced by the water atomization method tends to increase. However, there is a problem that the electrical conductivity tends to decrease because the sintering temperature becomes high, but by dissolving tin, zinc, lead or indium together with silver in a nitrogen atmosphere to produce silver alloy powder by the water atomization method , The oxygen content can be reduced.
　本発明による銀合金粉末の実施の形態は、（銀合金粉末を有機成分中に分散させた）導電性ペーストの材料などに使用することができる。特に、本発明による銀合金粉末の実施の形態は、焼結温度が低いことから、焼成温度が低い（好ましくは３００～８００℃程度、さらに好ましくは４００～７００℃程度の低温で焼成する）焼成型導電性ペーストの材料として使用するのが好ましい。なお、本発明による銀合金粉末の実施の形態は、焼成温度が低い焼成型導電性ペーストの材料として使用することができるので、（従来の焼成型導電性ペーストの焼成温度より低温で加熱して導電膜を形成する）樹脂硬化型導電性ペーストの材料として使用してもよい。また、導電性ペーストの材料として、本発明による銀合金粉末の実施の形態であるＡｇ－Ｓｎ合金粉末、Ａｇ－Ｉｎ合金粉末、Ａｇ－Ｚｎ合金粉末およびＡｇ－Ｐｂ合金粉末から２種以上を混合して使用してもよく、本発明による銀合金粉末の実施の形態を形状や粒径が異なる他の金属粉末と混合して使用してもよい。 The embodiment of the silver alloy powder according to the present invention can be used as a material for a conductive paste (in which a silver alloy powder is dispersed in an organic component). In particular, the embodiment of the silver alloy powder according to the present invention has a low sintering temperature and thus a low firing temperature (preferably fired at a low temperature of about 300 to 800 ° C., more preferably about 400 to 700 ° C.). It is preferable to use it as a material for the type conductive paste. In addition, since the embodiment of the silver alloy powder according to the present invention can be used as a material of a calcination type conductive paste having a low calcination temperature, it is heated at a temperature lower than the calcination temperature of a conventional calcination type conductive paste. It may be used as a material for a resin-curing conductive paste (forming a conductive film). Further, as a material of the conductive paste, two or more kinds of Ag—Sn alloy powder, Ag—In alloy powder, Ag—Zn alloy powder and Ag—Pb alloy powder which are embodiments of the silver alloy powder according to the present invention are mixed. The embodiment of the silver alloy powder according to the present invention may be used by mixing with other metal powders having different shapes and particle sizes.
　本発明による銀合金粉末の実施の形態を（焼成型導電性ペーストなどの）導電性ペーストの材料として使用する場合、導電性ペーストの構成要素として、銀合金粉末と、（飽和脂肪族炭化水素類、不飽和脂肪族炭化水素類、ケトン類、芳香族炭化水素類、グリコールエーテル類、エステル類、アルコール類などの）有機溶剤が含まれる。また、必要に応じて、（エチルセルロースやアクリル樹脂などの）バインダ樹脂を有機溶剤に溶解したビヒクル、ガラスフリット、無機酸化物、分散剤などを含んでもよい。 When the embodiment of the silver alloy powder according to the present invention is used as a material of a conductive paste (such as a fired conductive paste), as a constituent of the conductive paste, a silver alloy powder and (saturated aliphatic hydrocarbons) Organic solvents (such as unsaturated aliphatic hydrocarbons, ketones, aromatic hydrocarbons, glycol ethers, esters, alcohols, etc.). Further, if necessary, a vehicle in which a binder resin (such as ethyl cellulose or acrylic resin) is dissolved in an organic solvent, glass frit, an inorganic oxide, a dispersant, and the like may be included.
　導電性ペースト中の銀合金粉末の含有量は、導電性ペーストの導電性および製造コストの観点から、５～９８質量％であるのが好ましく、７０～９５質量％であるのがさらに好ましい。また、導電性ペースト中の銀合金粉末は、（銀粉、銀と錫の合金粉末、錫粉などの）１種以上の他の金属粉末と混合して使用してもよい。この金属粉末は、本発明による銀合金粉末の実施の形態と形状や粒径が異なる金属粉末でもよい。この金属粉末の平均粒径は、導電性ペーストを低温で焼成するために、０．５～２０μｍであるのが好ましい。また、この金属粉末の導電性ペースト中の含有量は、１～９４質量％であるのが好ましく、４～２９質量％であるのがさらに好ましい。なお、導電性ペースト中の銀合金粉末と金属粉末の含有量の合計は、６０～９８質量％であるのが好ましい。また、導電性ペースト中のバインダ樹脂の含有量は、導電性ペースト中の銀合金粉末の分散性や導電性ペーストの導電性の観点から、０．１～１０質量％であるのが好ましく、０．１～６質量％であるのがさらに好ましい。このバインダ樹脂を有機溶剤に溶解したビヒクルは、２種以上を混合して使用してもよい。また、導電性ペースト中のガラスフリットの含有量は、導電性ペーストの焼結性の観点から、０．１～２０質量％であるのが好ましく、０．１～１０質量％であるのがさらに好ましい。このガラスフリットは、２種以上を混合して使用してもよい。また、導電性ペースト中の有機溶剤の含有量（導電性ペースト中にビヒクルが含まれる場合は、ビヒクルの有機溶剤を含む含有量）は、導電性ペースト中の銀合金粉末の分散性や導電性ペーストの適切な粘度を考慮して、０．８～２０質量％であるのが好ましく、０．８～１５質量％であるのがさらに好ましい。この有機溶剤は、２種以上を混合して使用してもよい。 The content of the silver alloy powder in the conductive paste is preferably 5 to 98% by mass, more preferably 70 to 95% by mass, from the viewpoint of the conductivity of the conductive paste and the manufacturing cost. The silver alloy powder in the conductive paste may be used by mixing with one or more other metal powders (such as silver powder, silver-tin alloy powder, tin powder). This metal powder may be a metal powder having a different shape and particle size from the embodiment of the silver alloy powder according to the present invention. The average particle size of the metal powder is preferably 0.5 to 20 μm in order to fire the conductive paste at a low temperature. In addition, the content of the metal powder in the conductive paste is preferably 1 to 94% by mass, and more preferably 4 to 29% by mass. The total content of the silver alloy powder and the metal powder in the conductive paste is preferably 60 to 98% by mass. The content of the binder resin in the conductive paste is preferably 0.1 to 10% by mass from the viewpoint of the dispersibility of the silver alloy powder in the conductive paste and the conductivity of the conductive paste. More preferably, it is 1 to 6% by mass. Two or more types of vehicles in which this binder resin is dissolved in an organic solvent may be mixed and used. In addition, the glass frit content in the conductive paste is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, from the viewpoint of sinterability of the conductive paste. preferable. Two or more kinds of the glass frit may be mixed and used. In addition, the content of the organic solvent in the conductive paste (the content including the organic solvent in the vehicle when the vehicle is included in the conductive paste) depends on the dispersibility and conductivity of the silver alloy powder in the conductive paste. In consideration of the appropriate viscosity of the paste, it is preferably 0.8 to 20% by mass, and more preferably 0.8 to 15% by mass. Two or more organic solvents may be mixed and used.
　このような導電性ペーストは、例えば、各構成要素を計量して所定の容器に入れ、らいかい機、万能攪拌機、ニーダーなどを用いて予備混練した後、３本ロールで本混練することによって作製することができる。また、必要に応じて、その後、有機溶剤を添加して、粘度調整を行ってもよい。また、ガラスフリットや無機酸化物とビヒクルのみを本混練して粒度を下げた後、最後に銀合金粉末を追加して本混練してもよい。 Such a conductive paste is prepared, for example, by weighing each component into a predetermined container, pre-kneading using a raking machine, universal stirrer, kneader, etc., and then carrying out main kneading with three rolls. can do. Further, if necessary, the viscosity may be adjusted by adding an organic solvent thereafter. Alternatively, after only kneading glass frit or inorganic oxide and vehicle to reduce the particle size, silver alloy powder may be added and finally kneaded.
　この導電性ペーストをディッピングや（メタルマスク印刷、スクリーン印刷、インクジェット印刷などの）印刷などにより基板上に所定パターン形状に塗布した後に焼成して導電膜を形成することができる。導電性ペーストをディッピングにより塗布する場合には、導電性ペースト中に基板をディッピングして塗膜を形成し、レジストを利用したフォトリソグラフィなどにより塗膜の不要な部分を除去することによって、基板上に所定パターン形状の塗膜を形成することができる。 The conductive paste can be applied to the substrate in a predetermined pattern shape by dipping or printing (such as metal mask printing, screen printing, and ink jet printing) and then baked to form a conductive film. When applying conductive paste by dipping, the substrate is dipped into the conductive paste to form a coating film, and unnecessary portions of the coating film are removed by photolithography using a resist, etc. A coating film having a predetermined pattern shape can be formed.
　基板上に塗布した導電性ペーストの焼成は、大気雰囲気下で行ってもよいし、窒素、アルゴン、水素、一酸化炭素などの非酸化性雰囲気下で行ってもよい。なお、本発明による銀合金粉末の実施の形態は、焼結温度が低いため、導電性ペーストの焼成温度を低く（好ましくは３００～７００℃程度、さらに好ましくは４００～６００℃程度の低温に）することができる。なお、導電性ペーストの焼成温度を一般的な焼成温度（７００～９００℃程度）にしてもよい。また、導電性ペーストの焼成の前に、真空乾燥などにより予備乾燥を行うことにより、導電性ペースト中の有機溶剤などの揮発成分を除去してもよい。 The baking of the conductive paste applied on the substrate may be performed in an air atmosphere or in a non-oxidizing atmosphere such as nitrogen, argon, hydrogen, carbon monoxide. In the embodiment of the silver alloy powder according to the present invention, since the sintering temperature is low, the firing temperature of the conductive paste is low (preferably about 300 to 700 ° C., more preferably about 400 to 600 ° C.). can do. Note that the firing temperature of the conductive paste may be a general firing temperature (about 700 to 900 ° C.). Moreover, you may remove volatile components, such as the organic solvent in an electrically conductive paste, by performing preliminary drying by vacuum drying etc. before baking of an electrically conductive paste.
　以下、本発明による銀合金粉末およびその製造方法の実施例について詳細に説明する。 Hereinafter, examples of the silver alloy powder and the manufacturing method thereof according to the present invention will be described in detail.
［実施例１］
　ショット銀７．５ｋｇとショット錫２．５ｋｇを窒素雰囲気中において１１００℃に加熱して溶解した溶湯をタンディッシュ下部から落下させながら、水アトマイズ装置により大気中において水圧１５０ＭＰａ、水量１６０Ｌ／分で高圧水を吹き付けて急冷凝固させ、得られたスラリーを固液分離し、固形物を水洗し、乾燥し、解砕し、風力分級して、銀合金粉末（Ａｇ－Ｓｎ合金粉末）を得た。なお、高圧水として、純水２１．６ｍ３に対して苛性ソーダ１５７．５５ｇを添加したアルカリ水溶液（ｐＨ１０．２６）を使用した。 [Example 1]
While dropping molten metal from 7.5 kg of shot silver and 2.5 kg of shot tin heated to 1100 ° C. in a nitrogen atmosphere from the bottom of the tundish, the water atomizer uses a water pressure of 150 MPa and a water volume of 160 L / min. Water was sprayed and rapidly solidified, and the resulting slurry was subjected to solid-liquid separation. The solid was washed with water, dried, crushed, and classified by air to obtain a silver alloy powder (Ag—Sn alloy powder). As high-pressure water, an alkaline aqueous solution (pH 10.26) in which 157.55 g of caustic soda was added to 21.6 m 3 of pure water was used.
　このようにして得られた銀合金粉末について、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求め、合金組成分析を行うとともに、熱機械的分析（ＴＭＡ）を行った。 For the silver alloy powder thus obtained, the BET specific surface area, the tap density, the oxygen content, the carbon content and the particle size distribution were determined, and the alloy composition analysis was performed and the thermomechanical analysis (TMA) was performed.
　ＢＥＴ比表面積は、ＢＥＴ比表面積測定器（ユアサアイオニクス株式会社製の４ソーブＵＳ）を使用して、測定器内に１０５℃で２０分間窒素ガスを流して脱気した後、窒素とヘリウムの混合ガス（Ｎ２：３０体積％、Ｈｅ：７０体積％）を流しながら、ＢＥＴ１点法により測定した。
その結果、ＢＥＴ比表面積は０．９２ｍ２／ｇであった。 The BET specific surface area was degassed by flowing nitrogen gas at 105 ° C. for 20 minutes in a measuring instrument using a BET specific surface area measuring instrument (4 Sorb US made by Yuasa Ionics Co., Ltd.), While flowing a mixed gas (N 2 : 30% by volume, He: 70% by volume), the BET one-point method was used for measurement.
As a result, the BET specific surface area was 0.92 m 2 / g.
　タップ密度（ＴＡＰ）は、特開２００７－２６３８６０号公報に記載された方法と同様に、銀合金粉末を内径６ｍｍの有底円筒形のダイに充填して銀合金粉末層を形成し、この銀合金粉末層の上面に０．１６０Ｎ／ｍ２の圧力を均一に加えた後、銀合金粉末層の高さを測定し、この銀合金粉末層の高さの測定値と、充填された銀合金粉末の重量とから、銀合金粉末の密度を求めて、銀合金粉末のタップ密度とした。その結果、タップ密度は３．６ｇ／ｃｍ３であった。 The tap density (TAP) is obtained by filling a silver alloy powder into a bottomed cylindrical die having an inner diameter of 6 mm to form a silver alloy powder layer in the same manner as in the method described in JP-A-2007-263860. After uniformly applying a pressure of 0.160 N / m 2 on the upper surface of the alloy powder layer, the height of the silver alloy powder layer is measured, and the measured value of the height of the silver alloy powder layer and the filled silver alloy From the weight of the powder, the density of the silver alloy powder was determined and used as the tap density of the silver alloy powder. As a result, the tap density was 3.6 g / cm 3 .
　酸素含有量は、酸素・窒素・水素分析装置（株式会社堀場製作所製のＥＭＧＡ－９２０）により測定した。その結果、酸素含有量は０．３２質量％であった。 The oxygen content was measured with an oxygen / nitrogen / hydrogen analyzer (EMGA-920 manufactured by Horiba, Ltd.). As a result, the oxygen content was 0.32% by mass.
　炭素含有量は、炭素・硫黄分析装置（堀場製作所製のＥＭＩＡ－２２０Ｖ）により測定した。その結果、炭素含有量は０．０１質量％であった。 Carbon content was measured by a carbon / sulfur analyzer (EMIA-220V manufactured by Horiba, Ltd.). As a result, the carbon content was 0.01% by mass.
　粒度分布は、レーザー回折式粒度分布測定装置（ＳＹＭＰＡＴＥＣ社製のへロス粒度分布測定装置（ＨＥＬＯＳ＆ＲＯＤＯＳ（気流式の乾燥モジュール）））を使用して、分散圧５ｂａｒで測定した。その結果、累積１０％粒子径（Ｄ１０）は０．９μｍ、累積５０％粒子径（Ｄ５０）は２．２μｍ、累積９０％粒子径（Ｄ９０）は４．２μｍであった。 The particle size distribution was measured at a dispersion pressure of 5 bar using a laser diffraction particle size distribution measuring device (Heros particle size distribution measuring device (HELOS & RODOS (airflow drying module) manufactured by SYMPATEC)). As a result, the cumulative 10% particle diameter (D 10 ) was 0.9 μm, the cumulative 50% particle diameter (D 50 ) was 2.2 μm, and the cumulative 90% particle diameter (D 90 ) was 4.2 μm.
　合金組成分析は、誘導結合プラズマ（ＩＣＰ）発光分析装置（株式会社日立ハイテクサイエンス製のＳＰＳ３５２０Ｖ）によって行った。その結果、銀合金粉末中のＡｇ含有量は７４質量％、Ｓｎ含有量は２４質量％であった。 The alloy composition analysis was performed using an inductively coupled plasma (ICP) emission spectrometer (SPS3520V manufactured by Hitachi High-Tech Science Co., Ltd.). As a result, the Ag content in the silver alloy powder was 74% by mass, and the Sn content was 24% by mass.
　銀合金粉末の熱機械的分析（ＴＭＡ）は、銀合金粉末を直径５ｍｍ、高さ３ｍｍのアルミナパンに詰めて、熱機械的分析（ＴＭＡ）装置（セイコーインスツルメンツ株式会社製のＴＭＡ／ＳＳ６２００）の試料ホルダ（シリンダ）にセットし、測定プローブにより荷重０．１４７Ｎで１分間押し固めて作製した測定試料について、２００ｍＬ／分の流量で窒素ガスを流入しながら、測定荷重９８０ｍＮで荷重を付与して、常温から昇温速度１０℃／分で５００℃まで昇温し、測定試料の収縮率（常温のときの測定試料の長さに対する収縮率）を測定した。その結果、収縮率０．５％（膨張率－０．５％）のときの温度は１６２℃、収縮率１．０％（膨張率－１．０％）のときの温度は２６８℃、収縮率１．５％（膨張率－１．５％）のときの温度は３３５℃であった。 The thermomechanical analysis (TMA) of the silver alloy powder is performed by using a thermomechanical analysis (TMA) apparatus (TMA / SS6200 manufactured by Seiko Instruments Inc.) packed in an alumina pan having a diameter of 5 mm and a height of 3 mm. For a measurement sample that was set in a sample holder (cylinder) and pressed and solidified with a measurement probe at a load of 0.147 N for 1 minute, a load was applied at a measurement load of 980 mN while flowing nitrogen gas at a flow rate of 200 mL / min. The temperature was raised from normal temperature to 500 ° C. at a temperature increase rate of 10 ° C./min, and the shrinkage rate of the measurement sample (shrinkage rate relative to the length of the measurement sample at normal temperature) was measured. As a result, the temperature when the shrinkage rate was 0.5% (expansion rate−0.5%) was 162 ° C., the temperature when the shrinkage rate was 1.0% (expansion rate−1.0%), and the temperature was 268 ° C. The temperature at a rate of 1.5% (expansion rate—1.5%) was 335 ° C.
［実施例２］
　高圧水として純水（ｐＨ５．８）を使用し、ショット銀およびショット錫の量をそれぞれ６．５ｋｇおよび３．５ｋｇとした以外は、実施例１と同様の方法により、銀合金粉末（Ａｇ－Ｓｎ合金粉末）を得た。 [Example 2]
Silver alloy powder (Ag−) was prepared in the same manner as in Example 1 except that pure water (pH 5.8) was used as high-pressure water, and the amounts of shot silver and shot tin were 6.5 kg and 3.5 kg, respectively. Sn alloy powder) was obtained.
　このようにして得られた銀合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求め、合金組成分析を行うとともに、熱機械的分析（ＴＭＡ）を行った。 For the silver alloy powder thus obtained, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and the alloy composition analysis was performed. Analysis (TMA) was performed.
　その結果、銀合金粉末のＢＥＴ比表面積は１．１４ｍ２／ｇ、タップ密度は３．５ｇ／ｃｍ３、酸素含有量は０．５７質量％、炭素含有量は０．０１質量％であり、累積１０％粒子径（Ｄ１０）は０．８μｍ、累積５０％粒子径（Ｄ５０）は１．９μｍ、累積９０％粒子径（Ｄ９０）は４．０μｍであった。銀合金粉末中のＡｇ含有量は６３質量％、Ｓｎ含有量は３６質量％であった。また、収縮率０．５％のときの温度は１４２℃、収縮率１．０％のときの温度は１９４℃、収縮率１．５％のときの温度は２１６℃であった。 As a result, the silver alloy powder has a BET specific surface area of 1.14 m 2 / g, a tap density of 3.5 g / cm 3 , an oxygen content of 0.57% by mass, and a carbon content of 0.01% by mass, The cumulative 10% particle diameter (D 10 ) was 0.8 μm, the cumulative 50% particle diameter (D 50 ) was 1.9 μm, and the cumulative 90% particle diameter (D 90 ) was 4.0 μm. Ag content in a silver alloy powder was 63 mass%, and Sn content was 36 mass%. The temperature at a shrinkage rate of 0.5% was 142 ° C., the temperature at a shrinkage rate of 1.0% was 194 ° C., and the temperature at a shrinkage rate of 1.5% was 216 ° C.
　また、銀合金粉末の表面の酸化膜の厚さを測定した。この表面酸化膜の測定は、Ｘ線光電子分光分析装置（ＵＬＢＡＣ－ＰＨＩ社製のＥＳＣＡ５８００）により、Ｘ線源として単色化Ａｌを使用し、Ｋα線を使用して、銀合金粉末の試料の表面の直径８００μｍの領域について行った。試料のスパッタリングレートをＳｉＯ２換算で１ｎｍ／分とし、得られた深さ方向の元素分析スペクトルにおいて、銀合金粉末の表面の酸素原子濃度が９％を超える部分の厚さを表面酸化膜の厚さとした。その結果、表面酸化膜の厚さは１８ｎｍであった。 Further, the thickness of the oxide film on the surface of the silver alloy powder was measured. The surface oxide film was measured with an X-ray photoelectron spectroscopic analyzer (ESCA5800 manufactured by ULBAC-PHI) using monochromated Al as the X-ray source and using Kα rays to measure the surface of the silver alloy powder sample. The test was performed on a region having a diameter of 800 μm. The sputtering rate of the sample was 1 nm / min in terms of SiO 2 , and in the obtained elemental analysis spectrum in the depth direction, the thickness of the surface where the oxygen atom concentration on the surface of the silver alloy powder exceeds 9% is the thickness of the surface oxide film Say it. As a result, the thickness of the surface oxide film was 18 nm.
［実施例３］
　ショット銀およびショット錫の量をそれぞれ１．３５ｋｇおよび１．６５ｋｇとした以外は、実施例１と同様の方法により、銀合金粉末（Ａｇ－Ｓｎ合金粉末）を得た。 [Example 3]
A silver alloy powder (Ag—Sn alloy powder) was obtained in the same manner as in Example 1 except that the amounts of shot silver and shot tin were 1.35 kg and 1.65 kg, respectively.
　このようにして得られた銀合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求め、合金組成分析および熱機械的分析（ＴＭＡ）を行うとともに、実施例２と同様の方法により、表面酸化膜の厚さを測定した。 For the silver alloy powder thus obtained, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and alloy composition analysis and thermomechanical analysis ( TMA) was performed, and the thickness of the surface oxide film was measured by the same method as in Example 2.
　その結果、銀合金粉末のＢＥＴ比表面積は１．６３ｍ２／ｇ、タップ密度は３．３ｇ／ｃｍ３、酸素含有量は０．７６質量％、炭素含有量は０．０１質量％であり、累積１０％粒子径（Ｄ１０）は０．７μｍ、累積５０％粒子径（Ｄ５０）は１．８μｍ、累積９０％粒子径（Ｄ９０）は４．０μｍであった。銀合金粉末中のＡｇ含有量は４５質量％、Ｓｎ含有量は５５質量％であった。また、収縮率０．５％のときの温度は１６４℃、収縮率１．０％のときの温度は２０２℃、収縮率１．５％のときの温度は２１０℃であった。また、表面酸化膜の厚さは、５０ｎｍであった。この銀合金粉末のＸ線光分光分析装置（ＸＰＳ）による深さ方向に対する元素分析スペクトルを図２に示す。図２において、スパッタ時間が０～５０分の範囲では、酸素原子濃度が９％を超えて、ＡｇとＳｎとＯが存在しており、このスパッタ時間０～５０分の範囲が深さ０～５０ｎｍに相当し、この深さ０～５０ｎｍの範囲が表面酸化膜である。 As a result, the silver alloy powder has a BET specific surface area of 1.63 m 2 / g, a tap density of 3.3 g / cm 3 , an oxygen content of 0.76% by mass, and a carbon content of 0.01% by mass, The cumulative 10% particle size (D 10 ) was 0.7 μm, the cumulative 50% particle size (D 50 ) was 1.8 μm, and the cumulative 90% particle size (D 90 ) was 4.0 μm. The Ag content in the silver alloy powder was 45% by mass, and the Sn content was 55% by mass. The temperature when the shrinkage rate was 0.5% was 164 ° C., the temperature when the shrinkage rate was 1.0% was 202 ° C., and the temperature when the shrinkage rate was 1.5% was 210 ° C. The thickness of the surface oxide film was 50 nm. FIG. 2 shows an elemental analysis spectrum of the silver alloy powder with respect to the depth direction by an X-ray optical spectrometer (XPS). In FIG. 2, when the sputtering time is in the range of 0 to 50 minutes, the oxygen atom concentration exceeds 9%, and Ag, Sn, and O are present. The surface oxide film corresponds to 50 nm and this depth range of 0 to 50 nm is the surface oxide film.
［実施例４］
　ショット銀１．３５ｋｇとショット錫１．６５ｋｇを窒素雰囲気中において１４３０℃に加熱して溶解した溶湯をタンディッシュ下部から落下させながら、水アトマイズ装置により窒素雰囲気中において水圧１５０ＭＰａ、水量１６０Ｌ／分で高圧水を吹き付けて急冷凝固させ、得られたスラリーを固液分離し、固形物を水洗し、乾燥し、解砕し、風力分級して、銀合金粉末（Ａｇ－Ｓｎ合金粉末）を得た。なお、高圧水として、純水２１．６ｍ３に対して苛性ソーダ１５７．５５ｇを添加したアルカリ水溶液（ｐＨ１０．２６）を使用した。 [Example 4]
While dropping 1.35 kg of shot silver and 1.65 kg of shot tin to 1430 ° C. in a nitrogen atmosphere and dropping the molten metal from the lower part of the tundish, a water atomizing device is used in a nitrogen atmosphere at a water pressure of 150 MPa and a water amount of 160 L / min. High pressure water was sprayed to cool and solidify, and the resulting slurry was separated into solid and liquid, and the solid was washed with water, dried, crushed, and classified by air to obtain a silver alloy powder (Ag—Sn alloy powder). . Incidentally, as a high pressure water, using an alkali aqueous solution prepared by adding sodium hydroxide 157.55g against pure 21.6m 3 (pH10.26).
　このようにして得られた銀合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求め、合金組成分析および熱機械的分析（ＴＭＡ）を行うとともに、実施例２と同様の方法により、表面酸化膜の厚さを測定した。 For the silver alloy powder thus obtained, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and alloy composition analysis and thermomechanical analysis ( TMA) was performed, and the thickness of the surface oxide film was measured by the same method as in Example 2.
　その結果、銀合金粉末のＢＥＴ比表面積は１．３７ｍ２／ｇ、タップ密度は３．１ｇ／ｃｍ３、酸素含有量は０．６１質量％、炭素含有量は０．０１質量％であり、累積１０％粒子径（Ｄ１０）は０．５μｍ、累積５０％粒子径（Ｄ５０）は１．３μｍ、累積９０％粒子径（Ｄ９０）は２．４μｍであった。銀合金粉末中のＡｇ含有量は４５質量％、Ｓｎ含有量は５５質量％であった。また、収縮率０．５％のときの温度は１２１℃、収縮率１．０％のときの温度は１７２℃、収縮率１．５％のときの温度は２０５℃であった。また、表面酸化膜の厚さは、６５ｎｍであった。 As a result, BET specific surface area of the silver alloy powder 1.37 m 2 / g, a tap density of 3.1 g / cm 3, oxygen content 0.61 wt%, the carbon content was 0.01 wt%, The cumulative 10% particle diameter (D 10 ) was 0.5 μm, the cumulative 50% particle diameter (D 50 ) was 1.3 μm, and the cumulative 90% particle diameter (D 90 ) was 2.4 μm. The Ag content in the silver alloy powder was 45% by mass, and the Sn content was 55% by mass. The temperature when the shrinkage rate was 0.5% was 121 ° C., the temperature when the shrinkage rate was 1.0% was 172 ° C., and the temperature when the shrinkage rate was 1.5% was 205 ° C. The thickness of the surface oxide film was 65 nm.
［実施例５］
　大気中において高圧水を吹き付けた以外は、実施例４と同様の方法により、銀合金粉末（Ａｇ－Ｓｎ合金粉末）を得た。 [Example 5]
A silver alloy powder (Ag—Sn alloy powder) was obtained in the same manner as in Example 4 except that high-pressure water was sprayed in the atmosphere.
　このようにして得られた銀合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求め、合金組成分析および熱機械的分析（ＴＭＡ）を行うとともに、実施例２と同様の方法により、表面酸化膜の厚さを測定した。 For the silver alloy powder thus obtained, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and alloy composition analysis and thermomechanical analysis ( TMA) was performed, and the thickness of the surface oxide film was measured by the same method as in Example 2.
　その結果、銀合金粉末のＢＥＴ比表面積は３．３０ｍ２／ｇ、タップ密度は３．４ｇ／ｃｍ３、酸素含有量は１．４４質量％、炭素含有量は０．０１質量％であり、累積１０％粒子径（Ｄ１０）は０．５μｍ、累積５０％粒子径（Ｄ５０）は１．０μｍ、累積９０％粒子径（Ｄ９０）は１．９μｍであった。銀合金粉末中のＡｇ含有量は４４質量％、Ｓｎ含有量は５５質量％であった。また、収縮率０．５％のときの温度は１０６℃、収縮率１．０％のときの温度は１５５℃、収縮率１．５％のときの温度は１９６℃であった。また、表面酸化膜の厚さは、５５ｎｍであった。 As a result, BET specific surface area of the silver alloy powder 3.30m 2 / g, a tap density of 3.4 g / cm 3, oxygen content 1.44 wt%, the carbon content was 0.01 wt%, The cumulative 10% particle size (D 10 ) was 0.5 μm, the cumulative 50% particle size (D 50 ) was 1.0 μm, and the cumulative 90% particle size (D 90 ) was 1.9 μm. Ag content in a silver alloy powder was 44 mass%, and Sn content was 55 mass%. The temperature when the shrinkage rate was 0.5% was 106 ° C., the temperature when the shrinkage rate was 1.0% was 155 ° C., and the temperature when the shrinkage rate was 1.5% was 196 ° C. The thickness of the surface oxide film was 55 nm.
［実施例６］
　加熱温度を１２００℃とし、ショット銀およびショット錫の量をそれぞれ２．０１ｋｇおよび４．６９ｋｇとした以外は、実施例２と同様の方法により、銀合金粉末（Ａｇ－Ｓｎ合金粉末）を得た。 [Example 6]
A silver alloy powder (Ag—Sn alloy powder) was obtained in the same manner as in Example 2, except that the heating temperature was 1200 ° C. and the amounts of shot silver and shot tin were 2.01 kg and 4.69 kg, respectively. .
　このようにして得られた銀合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求め、合金組成分析を行うとともに、熱機械的分析（ＴＭＡ）を行った。 For the silver alloy powder thus obtained, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and the alloy composition analysis was performed. Analysis (TMA) was performed.
　その結果、銀合金粉末のＢＥＴ比表面積は１．４８ｍ２／ｇ、タップ密度は３．３ｇ／ｃｍ３、酸素含有量は１．１１質量％、炭素含有量は０．０１質量％であり、累積１０％粒子径（Ｄ１０）は０．６μｍ、累積５０％粒子径（Ｄ５０）は１．５μｍ、累積９０％粒子径（Ｄ９０）は３．４μｍであった。銀合金粉末中のＡｇ含有量は３０質量％、Ｓｎ含有量は７０質量％であった。また、収縮率０．５％のときの温度は１５８℃、収縮率１．０％のときの温度は１９５℃、収縮率１．５％のときの温度は２０６℃であった。 As a result, the BET specific surface area of the silver alloy powder is 1.48 m 2 / g, the tap density is 3.3 g / cm 3 , the oxygen content is 1.11% by mass, and the carbon content is 0.01% by mass, The cumulative 10% particle size (D 10 ) was 0.6 μm, the cumulative 50% particle size (D 50 ) was 1.5 μm, and the cumulative 90% particle size (D 90 ) was 3.4 μm. The Ag content in the silver alloy powder was 30% by mass, and the Sn content was 70% by mass. The temperature at a shrinkage rate of 0.5% was 158 ° C., the temperature at a shrinkage rate of 1.0% was 195 ° C., and the temperature at a shrinkage rate of 1.5% was 206 ° C.
［実施例７］
　ショット銀２ｋｇとインジウム２ｋｇを窒素雰囲気中において１１００℃に加熱して溶解した溶湯をタンディッシュ下部から落下させながら、水アトマイズ装置により大気中において水圧１５０ＭＰａ、水量１６０Ｌ／分で高圧水（ｐＨ５．８の純水）を吹き付けて急冷凝固させ、得られたスラリーを固液分離し、固形物を水洗し、乾燥し、解砕し、風力分級して、銀合金粉末（Ａｇ－Ｉｎ合金粉末）を得た。 [Example 7]
While dropping 2 kg of shot silver and 2 kg of indium by heating to 1100 ° C. in a nitrogen atmosphere from the lower part of the tundish, high pressure water (pH 5.8) at a water pressure of 150 MPa and an amount of water of 160 L / min. The obtained slurry is solidified by solid-liquid separation, the solid is washed with water, dried, crushed, and air-classified to produce silver alloy powder (Ag-In alloy powder). Obtained.
　このようにして得られた銀合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求め、合金組成分析を行うとともに、熱機械的分析（ＴＭＡ）を行った。 For the silver alloy powder thus obtained, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and the alloy composition analysis was performed. Analysis (TMA) was performed.
　その結果、銀合金粉末のＢＥＴ比表面積は１．１７ｍ２／ｇ、タップ密度は３．５ｇ／ｃｍ３、酸素含有量は１．０６質量％、炭素含有量は０．０２質量％であり、累積１０％粒子径（Ｄ１０）は０．７μｍ、累積５０％粒子径（Ｄ５０）は１．８μｍ、累積９０％粒子径（Ｄ９０）は３．５μｍであった。銀合金粉末中のＡｇ含有量は４７質量％、Ｉｎ含有量は５２質量％であった。また、収縮率０．５％のときの温度は１４１℃、収縮率１．０％のときの温度は１６６℃、収縮率１．５％のときの温度は１７８℃であった。 As a result, the silver alloy powder has a BET specific surface area of 1.17 m 2 / g, a tap density of 3.5 g / cm 3 , an oxygen content of 1.06% by mass, and a carbon content of 0.02% by mass, The cumulative 10% particle diameter (D 10 ) was 0.7 μm, the cumulative 50% particle diameter (D 50 ) was 1.8 μm, and the cumulative 90% particle diameter (D 90 ) was 3.5 μm. Ag content in silver alloy powder was 47 mass%, and In content was 52 mass%. The temperature at a shrinkage rate of 0.5% was 141 ° C., the temperature at a shrinkage rate of 1.0% was 166 ° C., and the temperature at a shrinkage rate of 1.5% was 178 ° C.
［実施例８］
　ショット銀１．５ｋｇと亜鉛３．５ｋｇを窒素雰囲気中において１０００℃に加熱して溶解した溶湯をタンディッシュ下部から落下させながら、水アトマイズ装置により大気中において水圧１５０ＭＰａ、水量１６０Ｌ／分で高圧水（ｐＨ５．８の純水）を吹き付けて急冷凝固させ、得られたスラリーを固液分離し、固形物を水洗し、乾燥し、解砕し、風力分級して、銀合金粉末（Ａｇ－Ｚｎ合金粉末）を得た。 [Example 8]
While dropping 1.5 kg of shot silver and 3.5 kg of zinc heated to 1000 ° C. in a nitrogen atmosphere from the lower part of the tundish, high-pressure water at a water pressure of 150 MPa and a water volume of 160 L / min. (Pure water of pH 5.8) is sprayed to cool and solidify, the resulting slurry is solid-liquid separated, the solid is washed with water, dried, crushed, air-classified, and silver alloy powder (Ag—Zn) Alloy powder) was obtained.
　このようにして得られた銀合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求め、合金組成分析を行うとともに、熱機械的分析（ＴＭＡ）を行った。 For the silver alloy powder thus obtained, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and the alloy composition analysis was performed. Analysis (TMA) was performed.
　その結果、銀合金粉末のＢＥＴ比表面積は１．７７ｍ２／ｇ、タップ密度は３．３ｇ／ｃｍ３、酸素含有量は０．８４質量％、炭素含有量は０．０２質量％であり、累積１０％粒子径（Ｄ１０）は１．０μｍ、累積５０％粒子径（Ｄ５０）は２．３μｍ、累積９０％粒子径（Ｄ９０）は４．６μｍであった。銀合金粉末中のＡｇ含有量は５７質量％、Ｚｎ含有量は４３質量％であった。また、収縮率０．５％のときの温度は２８３℃、収縮率１．０％のときの温度は３５６℃、収縮率１．５％のときの温度は４１９℃であった。 As a result, the silver alloy powder has a BET specific surface area of 1.77 m 2 / g, a tap density of 3.3 g / cm 3 , an oxygen content of 0.84 mass%, and a carbon content of 0.02 mass%. cumulative 10% particle diameter (D 10) is 1.0 .mu.m, cumulative 50% particle diameter (D 50) is 2.3 .mu.m, cumulative 90% particle diameter (D 90) was 4.6 .mu.m. Ag content in a silver alloy powder was 57 mass%, and Zn content was 43 mass%. The temperature at a shrinkage rate of 0.5% was 283 ° C., the temperature at a shrinkage rate of 1.0% was 356 ° C., and the temperature at a shrinkage rate of 1.5% was 419 ° C.
［実施例９］
　ショット銀３．５ｋｇとショット鉛１．５ｋｇを窒素雰囲気中において１１００℃に加熱して溶解した溶湯に還元剤としてカーボン粉２５０ｇを添加し、この還元剤が添加された溶湯をタンディッシュ下部から落下させながら、水アトマイズ装置により大気中において水圧１５０ＭＰａ、水量１６０Ｌ／分で高圧水（実施例３と同様のｐＨ１０．２６のアルカリ水）を吹き付けて急冷凝固させ、得られたスラリーを固液分離し、固形物を水洗し、乾燥し、解砕し、風力分級して、銀合金粉末（Ａｇ－Ｐｂ合金粉末）を得た。 [Example 9]
250g of carbon powder is added as a reducing agent to molten metal obtained by heating 3.5kg of shot silver and 1.5kg of shot lead to 1100 ° C in a nitrogen atmosphere, and the molten metal to which this reducing agent has been added falls from the bottom of the tundish. Then, high pressure water (alkaline water having the same pH of 10.26 as in Example 3) was sprayed and rapidly solidified in the atmosphere at a water pressure of 150 MPa and a water volume of 160 L / min by a water atomizer, and the resulting slurry was solid-liquid separated. The solid was washed with water, dried, crushed, and classified by air to obtain a silver alloy powder (Ag—Pb alloy powder).
　このようにして得られた銀合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求め、合金組成分析を行うとともに、熱機械的分析（ＴＭＡ）を行った。 For the silver alloy powder thus obtained, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and the alloy composition analysis was performed. Analysis (TMA) was performed.
　その結果、銀合金粉末のＢＥＴ比表面積は２．１４ｍ２／ｇ、タップ密度は３．１ｇ／ｃｍ３、酸素含有量は１．８７質量％、炭素含有量は０．１０質量％であり、累積１０％粒子径（Ｄ１０）は０．７μｍ、累積５０％粒子径（Ｄ５０）は１．８μｍ、累積９０％粒子径（Ｄ９０）は３．６μｍであった。銀合金粉末中のＡｇ含有量は７０質量％、Ｐｂ含有量は２７質量％であった。また、収縮率０．５％のときの温度は１３３℃、収縮率１．０％のときの温度は１５２℃、収縮率１．５％のときの温度は１６６℃であった。 As a result, the silver alloy powder has a BET specific surface area of 2.14 m 2 / g, a tap density of 3.1 g / cm 3 , an oxygen content of 1.87% by mass, and a carbon content of 0.10% by mass, The cumulative 10% particle diameter (D 10 ) was 0.7 μm, the cumulative 50% particle diameter (D 50 ) was 1.8 μm, and the cumulative 90% particle diameter (D 90 ) was 3.6 μm. Ag content in a silver alloy powder was 70 mass%, and Pb content was 27 mass%. The temperature at a shrinkage rate of 0.5% was 133 ° C., the temperature at a shrinkage rate of 1.0% was 152 ° C., and the temperature at a shrinkage rate of 1.5% was 166 ° C.
［実施例１０］
　ショット銀およびショット鉛の量をそれぞれ１．５ｋｇおよび３．５ｋｇとした以外は、実施例９と同様の方法により、銀合金粉末（Ａｇ－Ｐｂ合金粉末）を得た。 [Example 10]
A silver alloy powder (Ag—Pb alloy powder) was obtained in the same manner as in Example 9, except that the amounts of shot silver and shot lead were 1.5 kg and 3.5 kg, respectively.
　このようにして得られた銀合金粉末について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求め、合金組成分析を行うとともに、熱機械的分析（ＴＭＡ）を行った。 For the silver alloy powder thus obtained, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution were determined by the same method as in Example 1, and the alloy composition analysis was performed. Analysis (TMA) was performed.
　その結果、銀合金粉末のＢＥＴ比表面積は２．４１ｍ２／ｇ、タップ密度は３．０ｇ／ｃｍ３、酸素含有量は５．５６質量％、炭素含有量は０．１３質量％であり、累積１０％粒子径（Ｄ１０）は０．６μｍ、累積５０％粒子径（Ｄ５０）は１．６μｍ、累積９０％粒子径（Ｄ９０）は３．５μｍであった。銀合金粉末中のＡｇ含有量は３０質量％、Ｐｂ含有量は６４質量％であった。また、収縮率０．５％のときの温度は２００℃、収縮率１．０％のときの温度は２２９℃、収縮率１．５％のときの温度は２４５℃であった。 As a result, BET specific surface area of the silver alloy powder 2.41m 2 / g, a tap density of 3.0 g / cm 3, the oxygen content is 5.56 mass%, the carbon content was 0.13 wt%, The cumulative 10% particle diameter (D 10 ) was 0.6 μm, the cumulative 50% particle diameter (D 50 ) was 1.6 μm, and the cumulative 90% particle diameter (D 90 ) was 3.5 μm. The Ag content in the silver alloy powder was 30% by mass, and the Pb content was 64% by mass. The temperature at a shrinkage rate of 0.5% was 200 ° C., the temperature at a shrinkage rate of 1.0% was 229 ° C., and the temperature at a shrinkage rate of 1.5% was 245 ° C.
［比較例］
　ショット銀１３ｋｇを窒素雰囲気中において１６００℃に加熱して溶解した溶湯をタンディッシュ下部から落下させながら、水アトマイズ装置により大気中において水圧１５０ＭＰａ、水量１６０Ｌ／分で高圧水（ｐＨ５．８の純水）を吹き付けて急冷凝固させ、得られたスラリーを固液分離し、固形物を水洗し、乾燥し、解砕し、風力分級して、銀粉を得た。 [Comparative example]
While dropping 13 kg of shot silver heated to 1600 ° C. in a nitrogen atmosphere from the lower part of the tundish, high pressure water (pure water of pH 5.8) at a water pressure of 150 MPa and a water volume of 160 L / min. ) Was sprayed and solidified rapidly, and the resulting slurry was solid-liquid separated, the solid was washed with water, dried, crushed, and air-classified to obtain silver powder.
　このようにして得られた銀粉について、実施例１と同様の方法により、ＢＥＴ比表面積、タップ密度、酸素含有量、炭素含有量および粒度分布を求め、合金組成分析を行うとともに、熱機械的分析（ＴＭＡ）を行った。 For the silver powder thus obtained, the BET specific surface area, tap density, oxygen content, carbon content and particle size distribution are determined by the same method as in Example 1, and the alloy composition analysis is performed, and the thermomechanical analysis is performed. (TMA) was performed.
　その結果、銀粉のＢＥＴ比表面積は０．４７ｍ２／ｇ、タップ密度は５．１ｇ／ｃｍ３、酸素含有量は０．０７質量％、炭素含有量は０．０１質量％であり、累積１０％粒子径（Ｄ１０）は０．７μｍ、累積５０％粒子径（Ｄ５０）は２．１μｍ、累積９０％粒子径（Ｄ９０）は４．１μｍであった。銀粉中のＡｇ含有量は１００質量％であった。また、収縮率０．５％のときの温度は４７９℃、収縮率１．０％のときの温度は４９０℃、収縮率１．５％のときの温度は５００℃であった。 As a result, the BET specific surface area of the silver powder was 0.47 m 2 / g, the tap density was 5.1 g / cm 3 , the oxygen content was 0.07 mass%, the carbon content was 0.01 mass%, and the cumulative 10 The% particle size (D 10 ) was 0.7 μm, the cumulative 50% particle size (D 50 ) was 2.1 μm, and the cumulative 90% particle size (D 90 ) was 4.1 μm. The Ag content in the silver powder was 100% by mass. The temperature when the shrinkage rate was 0.5% was 479 ° C., the temperature when the shrinkage rate was 1.0% was 490 ° C., and the temperature when the shrinkage rate was 1.5% was 500 ° C.
　これらの実施例の銀合金粉末および比較例の銀粉の製造条件および特性を表１～表３に示す。また、実施例１～１０の銀合金粉末および比較例の銀粉の熱機械的分析（ＴＭＡ）における温度に対する膨張率の関係を図１に示す。 Tables 1 to 3 show the production conditions and characteristics of the silver alloy powders of these examples and the silver powder of the comparative example. Further, FIG. 1 shows the relationship of the expansion coefficient with respect to temperature in the thermomechanical analysis (TMA) of the silver alloy powders of Examples 1 to 10 and the silver powder of the comparative example.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１～表３および図１からわかるように、実施例１～１０では、比較例の銀粉と比べて低い温度で焼結する銀合金粉末を製造することができる。 As can be seen from Tables 1 to 3 and FIG. 1, in Examples 1 to 10, it is possible to produce a silver alloy powder that is sintered at a lower temperature than the silver powder of the comparative example.
　また、金属粉末として、（原料中のＡｇを６５質量％、Ｓｎを３５質量％とした）実施例２の銀合金粉末と、（原料中のＡｇを４５質量％、Ｓｎを５５質量％とした）実施例３の銀合金粉末と、（原料中のＡｇを３０質量％、Ｓｎを７０質量％とした）実施例６の銀合金粉末と、（原料中のＡｇを１００質量％とした）比較例の銀粉と、錫粉（累積５０％粒子径（Ｄ５０）＝１．８μｍ）とを用意し、これらの金属粉末の各々を８９．２質量％と、添加剤としてガラスフリット（ＺｎＯ系）１．６質量％とＴｅＯ２４．０質量％と、樹脂としてエチルセルロースを１．２質量％と、溶剤としてテキサノール２．０質量％およびブチルカルビトールアセテート（ＢＣＡ）２．０質量％とを自公転式真空攪拌脱泡装置（株式会社シンキー製のあわとり練太郎）により予備混練した後、三本ロール（ＥＸＡＫＴ社製の８０Ｓ）により金属粉末を分散させて導電性ペーストを作製した。これらの導電性ペーストの各々をスクリーン印刷機（マイクロテック株式会社製のＭＴ－３２０）によりシリコンウエハ上に５００μｍ×３７．５ｍｍのラインに印刷し、熱風式乾燥機により２００℃で１０分間加熱した後、高速焼成ＩＲ炉（日本ガイシ株式会社製の高速焼成試験４室炉）により、それぞれピーク温度を７８０℃および８２０℃として（Ｉｎ－Ｏｕｔ２１秒間）焼成して導電膜を作製した。 Further, as the metal powder, the silver alloy powder of Example 2 (Ag in the raw material was 65% by mass and Sn was 35% by mass), and the Ag in the raw material was 45% by mass and Sn was 55% by mass. ) Comparison with the silver alloy powder of Example 3 and the silver alloy powder of Example 6 (30% by mass of Ag in the raw material and 70% by mass of Sn) and 100% by mass of Ag in the raw material) Example silver powder and tin powder (cumulative 50% particle diameter (D 50 ) = 1.8 μm) were prepared, 89.2% by mass of each of these metal powders, and glass frit (ZnO-based) as an additive. 1.6% by mass, 4.0% by mass of TeO 2 , 1.2% by mass of ethyl cellulose as a resin, 2.0% by mass of texanol and 2.0% by mass of butyl carbitol acetate (BCA) as solvents Revolving-type vacuum stirring deaerator (made by Shinky Co., Ltd. After pre-kneaded by taking Rentaro), to prepare a conductive paste by dispersing metal powder by a three-roll (EXAKT Co. 80S). Each of these conductive pastes was printed on a silicon wafer on a 500 μm × 37.5 mm line by a screen printer (MT-320 manufactured by Microtech Co., Ltd.) and heated at 200 ° C. for 10 minutes by a hot air dryer. Thereafter, the film was baked at a peak temperature of 780 ° C. and 820 ° C. (In-Out 21 seconds) in a high-speed baking IR furnace (a high-speed baking test 4-chamber furnace manufactured by NGK Co., Ltd.) to prepare a conductive film.
　これらの導電膜の膜厚および電気抵抗を測定し、体積抵抗率を求めたところ、７８０℃で焼成した場合、比較例の銀粉では、膜厚２３．４μｍ、電気抵抗１．３９×１０－１Ω、体積抵抗率４．３５×１０－６Ω・ｃｍ、実施例２の銀合金粉末では、膜厚２７．５μｍ、電気抵抗４．００×１０５Ω、体積抵抗率１．４７×１０１Ω・ｃｍ、実施例３の銀合金粉末では、膜厚２８．６μｍ、電気抵抗４．３９×１０３Ω、体積抵抗率１．６９×１０－１Ω・ｃｍ、実施例６の銀合金粉末では、膜厚３１．０μｍ、電気抵抗４．０４×１０１Ω、体積抵抗率１．６７×１０－３Ω・ｃｍ、錫粉では、膜厚２０．７μｍ、電気抵抗２．２８×１０６Ω、体積抵抗率６．３３×１０１Ω・ｃｍであり、８２０℃で焼成した場合、比較例の銀粉では、膜厚２３．１μｍ、電気抵抗１．３９×１０－１Ω、体積抵抗率４．２６×１０－６Ω・ｃｍ、実施例２の銀合金粉末では、膜厚２８．５μｍ、電気抵抗５．４０×１０４Ω、体積抵抗率２．０５×１００Ω・ｃｍ、実施例３の銀合金粉末では、膜厚２９．０μｍ、電気抵抗１．４０×１０４Ω、体積抵抗率５．３９×１０－１Ω・ｃｍ、実施例６の銀合金粉末では、膜厚３０．６μｍ、電気抵抗３．９３×１０１Ω、体積抵抗率１．６１×１０－３Ω・ｃｍ、錫粉では、膜厚１９．７μｍ、電気抵抗４．７８×１０６Ω、体積抵抗率１．２６×１０２Ω・ｃｍであった。 The film thickness and electrical resistance of these conductive films were measured and the volume resistivity was determined. When fired at 780 ° C., the silver powder of the comparative example had a film thickness of 23.4 μm and an electrical resistance of 1.39 × 10 −1. Omega, the volume resistivity of 4.35 × 10 -6 Ω · cm, in the silver alloy powder of example 2, the film thickness 27.5, the electrical resistance 4.00 × 10 5 Ω, the volume resistivity of 1.47 × 10 1 In the silver alloy powder of Example 3, the film thickness was 28.6 μm, the electric resistance was 4.39 × 10 3 Ω, the volume resistivity was 1.69 × 10 −1 Ω · cm, and the silver alloy powder of Example 6 Then, the film thickness is 31.0 μm, the electric resistance is 4.04 × 10 1 Ω, the volume resistivity is 1.67 × 10 −3 Ω · cm, and the tin powder is 20.7 μm in thickness and the electric resistance is 2.28 × 10 6. Ω, volume resistivity 6.33 × 10 1 Ω · cm, and when fired at 820 ° C. 23.1 μm, electric resistance 1.39 × 10 −1 Ω, volume resistivity 4.26 × 10 −6 Ω · cm, the silver alloy powder of Example 2 has a film thickness of 28.5 μm, electric resistance 5.40 × 10 4 Ω, volume resistivity 2.05 × 10 0 Ω · cm, silver alloy powder of Example 3, film thickness 29.0 μm, electrical resistance 1.40 × 10 4 Ω, volume resistivity 5.39 × 10 -1 Ω · cm, film thickness 30.6 μm, electric resistance 3.93 × 10 1 Ω, volume resistivity 1.61 × 10 −3 Ω · cm for the silver alloy powder of Example 6, film for tin powder The thickness was 19.7 μm, the electric resistance was 4.78 × 10 6 Ω, and the volume resistivity was 1.26 × 10 2 Ω · cm.
　これらの導電膜で使用した金属粉末中の錫の含有量に対する体積抵抗率を図３に示す。図３からわかるように、（７０質量％の錫を含む）実施例６の銀合金粉末を使用した導電膜では、（３５質量％の錫を含む）実施例２の銀合金粉末や（５５質量％の錫を含む）実施例３の銀合金粉末を使用した導電膜と比べて、（銀よりも電気抵抗が低い）錫を多く含んでいるにもかかわらず、体積抵抗率が極めて低くなっている。この結果から、６５～７５質量％の錫を含むＡｇ－Ｓｎ合金粉末を含む導電性ペーストを使用すれば、安価で且つ体積抵抗率が低い導電膜を得ることができることがわかる。 The volume resistivity with respect to the content of tin in the metal powder used in these conductive films is shown in FIG. As can be seen from FIG. 3, in the conductive film using the silver alloy powder of Example 6 (including 70% by mass of tin), the silver alloy powder of Example 2 (including 35% by mass of tin) and (55% by mass) Compared to the conductive film using the silver alloy powder of Example 3 (including tin), the volume resistivity is extremely low despite containing a large amount of tin (which has a lower electrical resistance than silver). Yes. From this result, it is understood that a conductive film having a low volume resistivity can be obtained by using a conductive paste containing an Ag—Sn alloy powder containing 65 to 75% by mass of tin.
　本発明による銀合金粉末は、太陽電池の電極、低温焼成セラミック（ＬＴＣＣ）を使用した電子部品や積層セラミックインダクタなどの積層セラミック電子部品の内部電極、積層セラミックコンデンサや積層セラミックインダクタなどの外部電極などを形成するために、低温で焼結する焼成型導電性ペーストの材料として利用することができる。 Silver alloy powders according to the present invention include electrodes for solar cells, internal electrodes for multilayer ceramic electronic components such as electronic components and multilayer ceramic inductors using low temperature fired ceramics (LTCC), and external electrodes for multilayer ceramic capacitors and multilayer ceramic inductors, etc. Can be used as a material for a fired conductive paste that is sintered at a low temperature.

Claims (14)

  1. 錫、亜鉛、鉛およびインジウムからなる群から選ばれる１種の金属と銀との合金粉末において、平均粒径が０．５～２０μｍであり、熱機械的分析において、収縮率０．５％のときの温度が３００℃以下であることを特徴とする、銀合金粉末。 In an alloy powder of one kind of metal selected from the group consisting of tin, zinc, lead and indium and silver, the average particle size is 0.5 to 20 μm, and in the thermomechanical analysis, the shrinkage rate is 0.5%. Silver alloy powder, characterized in that the temperature is 300 ° C. or less.
  2. 前記熱機械的分析において、収縮率１．０％のときの温度が４００℃以下であることを特徴とする、請求項１に記載の銀合金粉末。 2. The silver alloy powder according to claim 1, wherein in the thermomechanical analysis, the temperature at a shrinkage rate of 1.0% is 400 ° C. or less.
  3. 前記熱機械的分析において、収縮率１．５％のときの温度が４５０℃以下であることを特徴とする、請求項１に記載の銀合金粉末。 2. The silver alloy powder according to claim 1, wherein, in the thermomechanical analysis, a temperature at a shrinkage rate of 1.5% is 450 ° C. or less.
  4. 前記銀合金粉末中の酸素含有量が６質量％以下であることを特徴とする、請求項１に記載の銀合金粉末。 The silver alloy powder according to claim 1, wherein an oxygen content in the silver alloy powder is 6% by mass or less.
  5. 前記銀合金粉末中の炭素含有量が０．５質量％以下であることを特徴とする、請求項１に記載の銀合金粉末。 The silver alloy powder according to claim 1, wherein a carbon content in the silver alloy powder is 0.5 mass% or less.
  6. ＢＥＴ比表面積が０．１～３．５ｍ２／ｇであることを特徴とする、請求項１に記載の銀合金粉末。 The silver alloy powder according to claim 1, wherein the BET specific surface area is 0.1 to 3.5 m 2 / g.
  7. タップ密度が２．５ｇ／ｃｍ３以上であることを特徴とする、請求項１に記載の銀合金粉末。 The silver alloy powder according to claim 1, wherein the tap density is 2.5 g / cm 3 or more.
  8. 前記銀合金粉末が錫と銀の合金粉末であり、錫の含有量が６５～７５質量％であることを特徴とする、請求項１に記載の銀合金粉末。 The silver alloy powder according to claim 1, wherein the silver alloy powder is an alloy powder of tin and silver, and a tin content is 65 to 75 mass%.
  9. 錫、亜鉛、鉛およびインジウムからなる群から選ばれる１種の金属と銀を窒素雰囲気中において溶解した溶湯を落下させながら、高圧水を吹き付けて急冷凝固させることを特徴とする、銀合金粉末の製造方法。 A silver alloy powder characterized by being rapidly solidified by blowing high-pressure water while dropping a molten metal in which a metal selected from the group consisting of tin, zinc, lead and indium is melted in a nitrogen atmosphere. Production method.
  10. 前記高圧水が純水またはアルカリ水であることを特徴とする、請求項９に記載の銀合金粉末の製造方法。 The method for producing a silver alloy powder according to claim 9, wherein the high-pressure water is pure water or alkaline water.
  11. 前記高圧水が大気中または窒素雰囲気中において吹き付けられることを特徴とする、請求項９に記載の銀合金粉末の製造方法。 The method for producing a silver alloy powder according to claim 9, wherein the high-pressure water is sprayed in the air or in a nitrogen atmosphere.
  12. 請求項１に記載の銀合金粉末が有機成分中に分散していることを特徴とする、導電性ペースト。 A conductive paste, wherein the silver alloy powder according to claim 1 is dispersed in an organic component.
  13. 前記導電性ペーストが焼成型導電性ペーストであることを特徴とする、請求項１２に記載の導電性ペースト。 The conductive paste according to claim 12, wherein the conductive paste is a fired conductive paste.
  14. 請求項１３の焼成型導電性ペーストを基板上に塗布した後に焼成して導電膜を製造することを特徴とする、導電膜の製造方法。 A method for producing a conductive film, wherein the fired conductive paste of claim 13 is applied on a substrate and then fired to produce a conductive film.
PCT/JP2016/005220 2015-12-28 2016-12-26 Silver alloy powder and method for producing same WO2017115462A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020187019850A KR102574302B1 (en) 2015-12-28 2016-12-26 Silver alloy powder and manufacturing method thereof
CN201680076654.XA CN108430671B (en) 2015-12-28 2016-12-26 Silver alloy powder and method for producing same
EP16881442.4A EP3395474A4 (en) 2015-12-28 2016-12-26 Silver alloy powder and method for producing same
US16/065,834 US20190009341A1 (en) 2015-12-28 2016-12-26 Silver alloy powder and method for producing same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015-256201 2015-12-28
JP2015256201 2015-12-28
JP2016247325A JP6804286B2 (en) 2015-12-28 2016-12-21 Silver alloy powder and its manufacturing method
JP2016-247325 2016-12-21

Publications (1)

Publication Number Publication Date
WO2017115462A1 true WO2017115462A1 (en) 2017-07-06

Family

ID=59225389

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/005220 WO2017115462A1 (en) 2015-12-28 2016-12-26 Silver alloy powder and method for producing same

Country Status (1)

Country Link
WO (1) WO2017115462A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3670701A1 (en) * 2018-12-19 2020-06-24 Paris Sciences et Lettres - Quartier Latin Method for converting carbon dioxide (co2) into co by an electrolysis reaction

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS586793A (en) 1981-07-03 1983-01-14 Hitachi Ltd Brazing filter metal
JPS63125583A (en) * 1987-10-09 1988-05-28 Matsushita Electric Ind Co Ltd Conductive paint
JP2007084906A (en) * 2005-09-26 2007-04-05 Fukuda Metal Foil & Powder Co Ltd Ag-BASED METAL POWDER, Cu-BASED METAL POWDER, AND METHOD FOR PRODUCING THE SAME
WO2007072894A1 (en) * 2005-12-22 2007-06-28 Namics Corporation Thermosetting conductive paste and multilayer ceramic component having external electrode which is formed by using such thermosetting conductive paste
JP2007263860A (en) 2006-03-29 2007-10-11 Dowa Holdings Co Ltd Tap density measuring method and device of powder
WO2008111615A1 (en) * 2007-03-12 2008-09-18 Senju Metal Industry Co., Ltd. Anisotropic electroconductive material
WO2009098938A1 (en) * 2008-02-06 2009-08-13 Namics Corporation Thermosetting conductive paste and laminated ceramic electronic component possessing external electrodes formed using same.
JP2013107132A (en) * 2011-11-17 2013-06-06 Samsung Electro-Mechanics Co Ltd Lead-free solder alloy and method for manufacturing the same
WO2013084683A1 (en) * 2011-12-07 2013-06-13 三井金属鉱業株式会社 Silver powder for sintered electrically conductive paste
JP2014213337A (en) * 2013-04-24 2014-11-17 三井金属鉱業株式会社 Solder alloy
WO2015083332A1 (en) * 2013-12-04 2015-06-11 京都エレックス株式会社 Heat-cured conductive paste composition

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS586793A (en) 1981-07-03 1983-01-14 Hitachi Ltd Brazing filter metal
JPS63125583A (en) * 1987-10-09 1988-05-28 Matsushita Electric Ind Co Ltd Conductive paint
JP2007084906A (en) * 2005-09-26 2007-04-05 Fukuda Metal Foil & Powder Co Ltd Ag-BASED METAL POWDER, Cu-BASED METAL POWDER, AND METHOD FOR PRODUCING THE SAME
WO2007072894A1 (en) * 2005-12-22 2007-06-28 Namics Corporation Thermosetting conductive paste and multilayer ceramic component having external electrode which is formed by using such thermosetting conductive paste
JP2007263860A (en) 2006-03-29 2007-10-11 Dowa Holdings Co Ltd Tap density measuring method and device of powder
WO2008111615A1 (en) * 2007-03-12 2008-09-18 Senju Metal Industry Co., Ltd. Anisotropic electroconductive material
WO2009098938A1 (en) * 2008-02-06 2009-08-13 Namics Corporation Thermosetting conductive paste and laminated ceramic electronic component possessing external electrodes formed using same.
JP2013107132A (en) * 2011-11-17 2013-06-06 Samsung Electro-Mechanics Co Ltd Lead-free solder alloy and method for manufacturing the same
WO2013084683A1 (en) * 2011-12-07 2013-06-13 三井金属鉱業株式会社 Silver powder for sintered electrically conductive paste
JP2014213337A (en) * 2013-04-24 2014-11-17 三井金属鉱業株式会社 Solder alloy
WO2015083332A1 (en) * 2013-12-04 2015-06-11 京都エレックス株式会社 Heat-cured conductive paste composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3395474A4

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3670701A1 (en) * 2018-12-19 2020-06-24 Paris Sciences et Lettres - Quartier Latin Method for converting carbon dioxide (co2) into co by an electrolysis reaction
WO2020127821A1 (en) * 2018-12-19 2020-06-25 Paris Sciences Et Lettres - Quartier Latin Method for converting carbon dioxide (co2) into co by an electrolysis reaction

Similar Documents

Publication Publication Date Title
JP7039126B2 (en) Copper powder and its manufacturing method
TWI635051B (en) Silver-bismuth powder, electroconductive paste, and electroconductive film
JP6804286B2 (en) Silver alloy powder and its manufacturing method
US11420256B2 (en) Silver powder and method for producing same
US20230279523A1 (en) Copper powder and method for producing same
JP7272834B2 (en) Silver powder and its manufacturing method
JP7084730B2 (en) Silver alloy powder and its manufacturing method
JP6899275B2 (en) Silver alloy powder and its manufacturing method
WO2017115462A1 (en) Silver alloy powder and method for producing same
TWI755565B (en) Silver powder and method for producing same
JP6303022B2 (en) Copper powder
JP7136970B2 (en) Silver powder containing phosphorus and conductive paste containing the silver powder

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: 16881442

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20187019850

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2016881442

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2016881442

Country of ref document: EP

Effective date: 20180725