WO2014077043A1 - Silver powder - Google Patents

Silver powder Download PDF

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Publication number
WO2014077043A1
WO2014077043A1 PCT/JP2013/076687 JP2013076687W WO2014077043A1 WO 2014077043 A1 WO2014077043 A1 WO 2014077043A1 JP 2013076687 W JP2013076687 W JP 2013076687W WO 2014077043 A1 WO2014077043 A1 WO 2014077043A1
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WO
WIPO (PCT)
Prior art keywords
silver
silver powder
particles
powder
spherical
Prior art date
Application number
PCT/JP2013/076687
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French (fr)
Japanese (ja)
Inventor
啓祐 宮之原
松山　敏和
Original Assignee
三井金属鉱業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by 三井金属鉱業株式会社 filed Critical 三井金属鉱業株式会社
Priority to KR1020147036880A priority Critical patent/KR20150028970A/en
Priority to CN201380041950.2A priority patent/CN104520031A/en
Publication of WO2014077043A1 publication Critical patent/WO2014077043A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver

Definitions

  • the present invention relates to a silver powder that can be suitably used for a sintered conductive paste.
  • the conductive paste is a fluid composition in which a conductive filler is dispersed in a vehicle composed of a resin binder and a solvent, and is widely used for forming an electric circuit, an external electrode of a ceramic capacitor, and the like.
  • This type of conductive paste includes a resin-curing type in which conductive fillers are pressure-bonded by curing the resin to ensure conduction, and sintering in which organic components are volatilized by high-temperature firing to sinter the conductive filler to ensure conduction. There is a type.
  • the sintered conductive paste is generally a paste-like composition in which a conductive filler (metal powder) and glass frit are dispersed in an organic vehicle.
  • the vehicle is volatilized and the conductive filler is sintered to ensure conductivity.
  • the glass frit has a function of adhering the conductive film to the substrate, and the organic vehicle functions as an organic liquid medium for enabling printing of the metal powder and the glass frit.
  • Patent Document 1 Japanese Patent Laid-Open No. 2005-48237
  • an alkali or complexing agent is added to a silver salt-containing aqueous solution to form a silver complex-containing aqueous solution, and then a polyvalent such as hydroquinone is used as the reducing agent.
  • a polyvalent such as hydroquinone
  • phenol By adding phenol, by reducing and precipitating highly dispersible spherical silver powder with a particle size of 0.6 ⁇ m or less, it is a fine silver powder and has a dispersibility closer to monodispersion with less aggregation of the powder grains.
  • a method for obtaining the fine silver powder provided is disclosed.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2007-2915173
  • the shape is non-granular and the center particle size (D50) is 0.05 ⁇ m to 3 ⁇ m.
  • Silver particles having a diameter of 0.0 ⁇ m and a carbon content of 0.03 to 3% by mass are disclosed.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2010-202910 discloses silver nanoparticles having an average particle diameter of 10 to 100 nm, and includes a core part made of silver particles and all or part of the surface of the core part. A silver nanoparticle characterized by having a film portion formed of silver oxide or silver hydroxide is disclosed.
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2011-21271 discloses, as a production method suitable for mass production of nanoparticles having a uniform particle diameter, a protective agent composed of an organic substance and copper having a content of 1 to 1000 ppm based on the amount of silver. There is disclosed a production method characterized by performing an operation of reducing silver in a silver solution containing components.
  • the present invention relates to a silver powder containing silver nanoparticles having a particle size on the order of nanometers, and intends to provide a new silver powder having excellent low-temperature sinterability.
  • D50 obtained by image analysis of a scanning electron microscope (SEM) image is 60 nm to 150 nm, and the amount of carbon (C) measured by a carbon quantification method of a metal material is less than 0.40 wt%.
  • the present invention proposes silver powder containing spherical or nearly spherical silver powder particles.
  • the conventional silver nanoparticles are fine and excellent in dispersibility, and are manufactured by adding a protective agent containing an organic substance to facilitate recovery of the produced fine silver powder. Therefore, carbon (C) It contained a relatively large amount. For this reason, when fired, the organic substance that is a protective agent inhibits combustion, and although it is extremely fine, the low-temperature sinterability may not be so excellent. Expected. Therefore, when the amount of carbon (C) was reduced to less than 0.40 wt%, the low temperature sintering property could be improved.
  • the silver powder proposed by the present invention can be suitably used for a sintered conductive paste.
  • the silver powder of the present invention can be sintered at 175 ° C. or lower, it can be sintered on a film substrate such as polyethylene terephthalate (PET). is there.
  • the silver powder according to this embodiment (hereinafter referred to as “main silver powder”) has a D50 obtained by image analysis of a scanning electron microscope (SEM) image of 60 nm to 150 nm, and is measured by a carbon quantification method for metal materials.
  • the amount of carbon (C) is less than 0.40 wt%, and it is a silver powder containing true or nearly spherical silver powder particles.
  • the present silver powder includes both wet silver powder produced by a wet method and silver powder produced by a dry method. Among these, wet silver powder is preferable.
  • a feature of wet silver powder is that small crystallites gather to form one particle, and therefore tend to be sintered at a lower temperature than silver powder produced by a dry method.
  • One of the features of the present silver powder is that many silver powder particles have a true spherical shape or a substantially true spherical shape when observed with an electron microscope (for example, 85,000 times). Thus, if it is silver powder containing a spherical or nearly spherical silver powder particle, particularly excellent dispersibility can be obtained.
  • “contains true spherical or substantially spherical silver powder particles” means that at least 60% by number of silver particles constituting the present silver powder, particularly 80% by number or more, of which 90% by number or more (100 (Including number%) means that spherical or nearly spherical silver powder particles occupy. Further, “substantially spherical” means a shape that is not completely spherical but can be recognized as spherical.
  • D50 One feature of the present silver powder is that D50 obtained by image analysis of a scanning electron microscope (SEM) image is 60 nm to 150 nm.
  • SEM scanning electron microscope
  • D50 of the present silver powder is particularly preferably 73 nm or more and 134 nm or less, and more preferably 85 nm or more or 134 nm or less.
  • the amount of carbon (C) measured by the carbon determination method for metallic materials is less than 0.40 wt%. If the amount of carbon (C) in the present silver powder is less than 0.40 wt%, the low-temperature sinterability can be improved without significantly impairing the dispersibility of the particles. However, strong agglomeration may occur when the amount of carbon (C) is significantly reduced. From this point of view, the amount of carbon (C) in the present silver powder is particularly preferably 0.20 wt% or more or 0.38 wt% or less, and more preferably 0.24 wt% or more or 0.32 wt% or less.
  • BET specific surface area of the silver powder is as long as 4.20m 2 /g ⁇ 6.20m 2 / g, without significantly impairing the dispersibility of the particles, it is possible to improve the low-temperature sinterability. From this viewpoint, it is more preferably 4.33 m 2 / g or more or 6.01 m 2 / g or less, and particularly preferably 4.33 m 2 / g or more or 5.58 m 2 / g or less.
  • the present silver powder has a relatively large particle size and a uniform particle size, and prepares a spherical or nearly spherical wet silver powder.
  • This silver powder particle is used as a base particle and has a small particle size on its surface.
  • the silver powder particles can be obtained by depositing silver powder particles and then separating the silver powder particles having a small particle size from the base particles. However, it is not limited to this manufacturing method.
  • the silver powder particles serving as the base particles are preferably produced as follows. Silver powder is produced by a wet method as in the prior art, and after removing coarse particles from the silver powder using a sieve, fine particles are removed by air classification, so that the particle size is relatively large and the particle size is uniform. In addition, a spherical or nearly spherical wet silver powder can be obtained.
  • the base particles are charged and uniformly dispersed in a reducing agent solution, and further the reducing agent is dispersed. Can be reduced and deposited on the surface of the base particles.
  • the difference in particle size can be obtained by applying ultrasonic waves in a liquid such as water or an organic solvent, or by dry crushing with an airflow crusher. Can be separated relatively easily. The separated base particles can be used again as base particles.
  • a silver complex solution is prepared by adding a complexing agent to a silver aqueous solution such as silver nitrate, and if necessary, a stearic acid salt such as Na or K stearate or an amine-based dispersant is added and stirred to obtain a reducing agent solution. Is added to the silver complex solution and reduced and precipitated to produce silver particles. By classifying the obtained silver particles by sieving to remove coarse particles, fine particles and coarse particles are further removed by airflow classification to obtain a homogeneous silver powder as a base.
  • a complexing agent such as silver nitrate
  • a stearic acid salt such as Na or K stearate or an amine-based dispersant
  • the silver complex solution prepared as described above was prepared with the base particles uniformly dispersed. Add and react gently without stirring to reduce and precipitate silver powder particles with a small particle size on the surface of the silver powder particles (base particles). Then, silver powder is obtained by filtering, washing and drying. Then, the silver powder obtained in this manner is put into a liquid such as water or an organic solvent and subjected to ultrasonic waves, or dry pulverized with an airflow type pulverizer, etc. This silver powder can be obtained by separating and classifying the silver powder particles.
  • silver powder particles that are extremely fine have a uniform particle size and shape (true spherical shape), and have a small amount of carbon (C) can be obtained.
  • the particle diameters are uniform, an effect that the loss is extremely small can be obtained.
  • an aqueous solution containing silver nitrate, a silver salt complex, and a silver intermediate or a slurry can be used as the aqueous silver solution such as silver nitrate.
  • complexing agents include ammonia water, ammonium salts, chelate compounds and the like.
  • ascorbic acid, sulfite, alkanolamine, hydrogen peroxide formic acid, ammonium formate, sodium formate, glyoxal, tartaric acid, sodium hypophosphite, borohydride metal salt, dimethylamine borane, hydrazine, hydrazine compound And aqueous solutions containing hydroquinone, pyrogallol, glucose, gallic acid, formalin, anhydrous sodium sulfite, Rongalite and the like.
  • the dispersant include fatty acids, fatty acid salts, surfactants, organic metals, chelating agents, protective colloids and the like.
  • the present silver powder can be used as it is, it can also be used after the present silver powder has been processed into a shape.
  • a true spherical particle powder (powder consisting of 80% or more of true spherical particles) is mechanically processed into non-spherical particle powders such as flakes, scales, and flat plates (80% or more of non-spherical particles).
  • a fatty acid such as stearic acid or an auxiliary agent such as a surfactant.
  • an auxiliary agent such as a surfactant.
  • the present silver powder has a uniform particle size, a medium suitable for the particle size can be effectively selected, so that even flake powder can obtain uniform flake powder particles.
  • a mixed powder of spherical powder and flake powder may be used.
  • the silver powder is suitable as a silver powder for a conductive paste, particularly for a sintered conductive paste.
  • a conductive paste particularly for a sintered conductive paste.
  • sintering at 175 ° C. or lower it can be applied on a resin film substrate.
  • sintering at 150 ° C. or lower sintering on a polyethylene terephthalate (PET) film substrate is also possible.
  • PET polyethylene terephthalate
  • the sintered conductive paste can be prepared, for example, by mixing the present silver powder together with glass frit in an organic vehicle.
  • the glass frit include lead-free glass such as lead borosilicate glass and zinc borosilicate.
  • a resin binder arbitrary resin binders can be used, for example. For example, it is desirable to employ a composition containing at least one selected from an epoxy resin, a polyester resin, a silicon resin, a urea resin, an acrylic resin, and a cellulose resin.
  • D50 image analysis
  • SEM scanning electron microscope
  • XL30 manufactured by PHILIPS
  • SEM three-field scanning electron microscope
  • the image is taken in with A image, an integrated application of IP-1000PC manufactured by Asahi Engineering Co., Ltd., and circular particle analysis is performed with a circularity threshold of 50 and an overlap of 30. Image analysis without manual correction D50 obtained by this was measured.
  • BET specific surface area Using a specific surface area measuring device (Monosorb MS-18) manufactured by QUANTACHROME, JIS R 1626: 1996 (Method for measuring specific surface area of fine ceramic powder by gas adsorption BET method), .5) Single point method ", BET specific surface area (SSA) was measured. At that time, a mixed gas of helium as a carrier gas and nitrogen as an adsorbate gas was used.
  • Carbon (C) amount Carbon analysis was performed using a carbon analyzer (EMIA-221V2) manufactured by HORIBA Ltd. in accordance with JIS Z 2615 (General rules for carbon quantification of metal materials).
  • a silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring. Next, 6 mL of a 1% strength amine-based dispersant (average molecular weight 10,000) aqueous solution is added to the silver ammine complex aqueous solution and stirred, and 1 L of a hydrazine aqueous solution having a concentration of 9.0 g / L is added and reacted without stirring. The base silver particles were reduced and precipitated.
  • the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 ⁇ S / cm or less, and then dried in a dryer at 80 ° C. for 1 hour to obtain silver powder.
  • the obtained silver particles were substantially spherical.
  • coarse particles of 25 ⁇ m or more are removed, and then fine particles and coarse particles are further removed by airflow classification to form a homogeneous silver powder (D10: 2. 26 ⁇ m, D50: 3.10 ⁇ m, D90: 4.63 ⁇ m).
  • the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 ⁇ S / cm or less, and then dried in a dryer at 80 ° C. for 1 hour to obtain silver powder.
  • the obtained silver powder particles are dispersed in methanol, the base particles and the adhered particles are separated by ultrasonic waves, and the slurry of the adhered particles is recovered as a filtrate by filtering with a syringe filter having a pore diameter of 0.8 ⁇ m.
  • This silver powder was obtained by drying for 16 hours in a dryer.
  • the silver powder thus obtained consisted of substantially spherical and homogeneous silver particles.
  • Example 2 Silver powder was obtained in the same manner as in Example 1 except that the addition amount of pure water in the complex solution and the reducing solution used for reducing and precipitating fine silver particles was 1.10 L.
  • Example 3 Silver powder was obtained in the same manner as in Example 1 except that the addition amount of the silver nitrate aqueous solution used for reducing and precipitating fine silver particles was 25 mL, and the addition amount of pure water in the complex solution and the reduction solution was 0.90 L. It was.
  • Example 4 Silver powder was obtained in the same manner as in Example 1 except that the addition amount of the silver nitrate aqueous solution used for reducing and precipitating fine silver particles was 23 mL, and the addition amount of pure water in the complex solution and the reduction solution was 0.90 L. It was.
  • Example 5 Silver powder was obtained in the same manner as in Example 1 except that the addition amount of the aqueous silver nitrate solution used for reducing and precipitating fine silver particles was 25 mL, and the addition amount of pure water in the complex solution and the reduction solution was 0.70 L. It was.
  • Example 6 A silver powder was obtained in the same manner as in Example 1 except that the amount of pure water in the complex solution and the reducing solution used for reducing and precipitating fine silver particles was 0.80 L.
  • Example 7 Silver powder was obtained in the same manner as in Example 1 except that the amount of pure water in the complex solution and the reducing solution used for reducing and precipitating fine silver particles was 0.90 L.
  • Example 8 Silver powder was obtained in the same manner as in Example 1 except that the addition amount of pure water in the complex solution and the reducing solution used for reducing and precipitating the fine silver particles was 0.70 L.
  • Example 9 A silver powder is obtained in the same manner as in Example 1 except that 1 mL of an amine-based dispersant (average molecular weight 10,000) aqueous solution of 1% concentration is added to the complex solution prepared for reduction precipitation of fine silver particles and stirred. It was.
  • an amine-based dispersant average molecular weight 10,000
  • Example 10 Complex used for reducing and precipitating fine silver particles 2 mL of a 1% strength amine-based dispersant (average molecular weight 10,000) aqueous solution was added to the complex solution prepared for reducing and precipitating fine silver particles and stirred. Silver powder was obtained in the same manner as in Example 1 except that the addition amount of pure water in the solution and the reducing solution was changed to 1.10 L.
  • a 1% strength amine-based dispersant average molecular weight 10,000
  • a silver nitrate aqueous solution was obtained by dissolving 20 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water to prepare a silver nitrate aqueous solution, adding 24 mL of 25% by mass ammonia water, and stirring. Next, 6 mL of a 1% strength amine-based dispersant (average molecular weight 10,000) aqueous solution was added to the silver ammine complex aqueous solution and stirred, and then silver in a reduced solution in which 20 g of hydroquinone and 5 mL of hydrazine were dissolved in 1 L of pure water.
  • a silver ammine complex aqueous solution was obtained by dissolving 7 ml of an aqueous silver nitrate solution having a silver concentration of 400 g / L in 0.98 L of pure water to prepare an aqueous silver nitrate solution, adding 12 ml of ammonia water having a concentration of 25% by mass and stirring. Subsequently, silver particles were reduced and precipitated by mixing 1.0 L of a hydroquinone aqueous solution having a concentration of 1.5 g / L with this silver ammine complex aqueous solution at 20 ° C. Next, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 ⁇ S / cm or less, and then dried in a dryer at 80 ° C. for 1 hour to obtain silver powder.
  • a silver ammine complex aqueous solution was obtained by dissolving 35 ml of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water to prepare a silver nitrate aqueous solution, adding 60 ml of ammonia water having a concentration of 25% by mass and stirring. Next, at 20 ° C., the silver ammine complex aqueous solution was mixed with 1.2 L of a hydroquinone aqueous solution having a concentration of 6 g / L to reduce and precipitate silver particles. Next, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 ⁇ S / cm or less, and then dried in a dryer at 80 ° C. for 1 hour to obtain silver powder.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
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  • Non-Insulated Conductors (AREA)

Abstract

The present invention relates to a silver powder comprising silver nanoparticles each having a particle diameter of the nano-meter order (1 to 100 nm), and provides a novel silver powder having an excellent low-temperature sintering property. Proposed is a silver powder having a D50 value of 60 to 150 nm as determined by the image analysis of a scanning electron microscope (SEM) image, having a carbon (C) content of less than 0.40 wt% as determined in accordance with JIS Z 2615 (a method for quantitating carbon in a metallic material - general), and comprising truly-spherical or almost-spherical silver powder particles.

Description

銀粉Silver powder
　本発明は、焼結型導電性ペーストに好適に用いることができる銀粉に関する。 The present invention relates to a silver powder that can be suitably used for a sintered conductive paste.
　導電性ペーストは、樹脂系バインダーと溶媒からなるビヒクル中に導電フィラーを分散させた流動性組成物であり、電気回路の形成や、セラミックコンデンサの外部電極の形成などに広く用いられている。この種の導電性ペーストには、樹脂の硬化によって導電性フィラーが圧着され導通を確保する樹脂硬化型と、高温焼成によって有機成分が揮発し導電性フィラーが焼結して導通を確保する焼結型とがある。 The conductive paste is a fluid composition in which a conductive filler is dispersed in a vehicle composed of a resin binder and a solvent, and is widely used for forming an electric circuit, an external electrode of a ceramic capacitor, and the like. This type of conductive paste includes a resin-curing type in which conductive fillers are pressure-bonded by curing the resin to ensure conduction, and sintering in which organic components are volatilized by high-temperature firing to sinter the conductive filler to ensure conduction. There is a type.
　このうちの焼結型導電性ペーストは、一般に導電フィラー（金属粉末）とガラスフリットとを有機ビヒクル中に分散させてなるペースト状組成物であり、４００～８００℃にて焼成することにより、有機ビヒクルが揮発し、さらに導電フィラーが焼結することによって導通性を確保するものである。この際、ガラスフリットは、この導電膜を基板に接着させる作用を有し、有機ビヒクルは、金属粉末およびガラスフリットを印刷可能にするための有機液体媒体として作用する。 Of these, the sintered conductive paste is generally a paste-like composition in which a conductive filler (metal powder) and glass frit are dispersed in an organic vehicle. The vehicle is volatilized and the conductive filler is sintered to ensure conductivity. At this time, the glass frit has a function of adhering the conductive film to the substrate, and the organic vehicle functions as an organic liquid medium for enabling printing of the metal powder and the glass frit.
　このような焼結型導電性ペーストに用いる銀粉については、従来、電極や回路のファインライン化に対応すべく、微粒な銀粉が一般的に求められるため、それに対応した新たな技術が提案されている。 As for silver powder used in such sintered conductive pastes, fine silver powder is generally required in order to cope with fine lines of electrodes and circuits. Therefore, a new technology corresponding to that has been proposed. Yes.
　例えば特許文献１（特開２００５－４８２３７号公報）には、銀塩含有水溶液へ、アルカリまたは錯化剤を添加して、銀錯体含有水溶液を生成させた後、還元剤としてヒドロキノン等の多価フェノールを添加することで、０．６μｍ以下の微粒子化した高分散性の球状の銀粉を還元析出させることにより、微粒の銀粉であって、しかも粉粒の凝集の少ない単分散により近い分散性を備える微粒銀粉を得る方法が開示されている。 For example, in Patent Document 1 (Japanese Patent Laid-Open No. 2005-48237), an alkali or complexing agent is added to a silver salt-containing aqueous solution to form a silver complex-containing aqueous solution, and then a polyvalent such as hydroquinone is used as the reducing agent. By adding phenol, by reducing and precipitating highly dispersible spherical silver powder with a particle size of 0.6 μm or less, it is a fine silver powder and has a dispersibility closer to monodispersion with less aggregation of the powder grains. A method for obtaining the fine silver powder provided is disclosed.
　特許文献２（特開２００７－２９１５１３号公報）には、溶液に分散させた後に沈降しない特性に優れた銀粒子として、形状が非粒状であり、中心粒径（Ｄ５０）が０．０５μｍ～３．０μｍであり、且つ、カーボン含有量が０．０３～３質量％である銀粒子が開示されている。 In Patent Document 2 (Japanese Patent Application Laid-Open No. 2007-291513), as silver particles having excellent properties that do not settle after being dispersed in a solution, the shape is non-granular and the center particle size (D50) is 0.05 μm to 3 μm. Silver particles having a diameter of 0.0 μm and a carbon content of 0.03 to 3% by mass are disclosed.
　特許文献３（特開２０１０－２０２９１０号公報）には、平均粒径が１０～１００ｎｍである銀ナノ粒子であって、銀粒子からなるコア部と、前記コア部の表面の全部又は一部に形成され酸化銀又は水酸化銀からなる膜部とを有することを特徴とする銀ナノ粒子が開示されている。 Patent Document 3 (Japanese Patent Application Laid-Open No. 2010-202910) discloses silver nanoparticles having an average particle diameter of 10 to 100 nm, and includes a core part made of silver particles and all or part of the surface of the core part. A silver nanoparticle characterized by having a film portion formed of silver oxide or silver hydroxide is disclosed.
　また、特許文献４（特開２０１１－２１２７１号公報）には、粒子径の均整なナノ粒子の大量生産に適した製法として、有機物からなる保護剤と、銀量に対して１～１０００ｐｐｍの銅成分とが存在する銀溶液中で銀を還元する操作を行うことを特徴とする製法が開示されている。 Patent Document 4 (Japanese Patent Application Laid-Open No. 2011-21271) discloses, as a production method suitable for mass production of nanoparticles having a uniform particle diameter, a protective agent composed of an organic substance and copper having a content of 1 to 1000 ppm based on the amount of silver. There is disclosed a production method characterized by performing an operation of reducing silver in a silver solution containing components.
特開２００５－４８２３７号公報JP 2005-48237 A 特開２００７－２９１５１３号公報JP 2007-291513 A 特開２０１０－２０２９１０号公報JP 2010-202910 A 特開２０１１－２１２７１号公報JP 2011-21271 A
　前述のように、最近では、ナノメートルオーダー（１～１００ｎｍ）の粒径を有する銀ナノ粒子が開発され、提案されている。しかしながら、従来提案されていた銀ナノ粒子の多くは、粒径が極めて小さいにもかかわらず、粒径の割には低温焼結性が優れたものではなかった。低温焼結性に関しては、１７５℃以下での焼結が可能であればフィルム基板上などで使用ができ、用途をさらに広げることができる。さらに１５０℃以下での焼結が可能であると、ポリエチレンテレフタレート（ＰＥＴ）フィルム基板上で焼結させることも可能になる。 As described above, recently, silver nanoparticles having a particle size of nanometer order (1 to 100 nm) have been developed and proposed. However, many of the silver nanoparticles that have been proposed in the past have not been excellent in low-temperature sinterability with respect to the particle size, despite the extremely small particle size. Regarding the low temperature sintering property, if it can be sintered at 175 ° C. or lower, it can be used on a film substrate or the like, and the application can be further expanded. Furthermore, if sintering at 150 ° C. or lower is possible, sintering on a polyethylene terephthalate (PET) film substrate is also possible.
　そこで本発明は、ナノメートルオーダーの粒径を有する銀ナノ粒子を含有する銀粉に関し、低温焼結性に優れた新たな銀粉を提供せんとするものである。 Therefore, the present invention relates to a silver powder containing silver nanoparticles having a particle size on the order of nanometers, and intends to provide a new silver powder having excellent low-temperature sinterability.
　本発明は、走査型電子顕微鏡（ＳＥＭ）像の画像解析により得られるＤ５０が６０ｎｍ～１５０ｎｍであり、金属材料の炭素定量方法により測定される炭素（Ｃ）量が０．４０ｗｔ％未満であり、真球状又は略真球状の銀粉粒子を含有する銀粉を提案する。 In the present invention, D50 obtained by image analysis of a scanning electron microscope (SEM) image is 60 nm to 150 nm, and the amount of carbon (C) measured by a carbon quantification method of a metal material is less than 0.40 wt%. The present invention proposes silver powder containing spherical or nearly spherical silver powder particles.
　従来の銀ナノ粒子の多くは、微粒で分散性に優れ、且つ、製造した微粒銀粉を回収し易くするために、有機物を含んだ保護剤などを添加して製造していたため、炭素（Ｃ）を比較的多く含むものであった。そのため、焼成した際に、保護剤である有機物に燃焼を阻害されることになり、極めて微粒であるにもかかわらず、低温焼結性がそれほど優れたものにならないのではないかと、本発明者は予想した。そこで、炭素（Ｃ）量を０．４０ｗｔ％未満まで軽減したところ、低温焼結性を高めることができた。これより、本発明が提案する銀粉は、焼結型導電性ペーストに好適に用いることができる。特に後述する実施例でも確認されているように、本発明の銀粉は、１７５℃以下での焼結が可能であるため、ポリエチレンテレフタレート（ＰＥＴ）などのフィルム基板上で焼結させることが可能である。 Many of the conventional silver nanoparticles are fine and excellent in dispersibility, and are manufactured by adding a protective agent containing an organic substance to facilitate recovery of the produced fine silver powder. Therefore, carbon (C) It contained a relatively large amount. For this reason, when fired, the organic substance that is a protective agent inhibits combustion, and although it is extremely fine, the low-temperature sinterability may not be so excellent. Expected. Therefore, when the amount of carbon (C) was reduced to less than 0.40 wt%, the low temperature sintering property could be improved. Thus, the silver powder proposed by the present invention can be suitably used for a sintered conductive paste. In particular, as confirmed in Examples described later, since the silver powder of the present invention can be sintered at 175 ° C. or lower, it can be sintered on a film substrate such as polyethylene terephthalate (PET). is there.
　次に、実施の形態例に基づいて本発明を説明する。但し、本発明が次に説明する実施形態に限定されるものではない。 Next, the present invention will be described based on an embodiment. However, the present invention is not limited to the embodiment described below.
＜本銀粉＞
　本実施形態に係る銀粉（以下、「本銀粉」と称する）は、走査型電子顕微鏡（ＳＥＭ）像の画像解析により得られるＤ５０が６０ｎｍ～１５０ｎｍであり、金属材料の炭素定量方法により測定される炭素（Ｃ）量が０．４０ｗｔ％未満であり、真球状又は略真球状の銀粉粒子を含有する銀粉である。
　以下、本銀粉の特徴について説明する。 <Silver powder>
The silver powder according to this embodiment (hereinafter referred to as “main silver powder”) has a D50 obtained by image analysis of a scanning electron microscope (SEM) image of 60 nm to 150 nm, and is measured by a carbon quantification method for metal materials. The amount of carbon (C) is less than 0.40 wt%, and it is a silver powder containing true or nearly spherical silver powder particles.
Hereinafter, features of the present silver powder will be described.
（湿式銀粉）
　本銀粉は、湿式法で作製される湿式銀粉、乾式法で作製される銀粉のいずれも包含する。中でも、湿式銀粉であるのが好ましい。
　湿式銀粉の特徴は、小さな結晶子が集まって一つの粒子を形成するため、乾式法で作製される銀粉に比べて、低温焼結し易い傾向がある。 (Wet silver powder)
The present silver powder includes both wet silver powder produced by a wet method and silver powder produced by a dry method. Among these, wet silver powder is preferable.
A feature of wet silver powder is that small crystallites gather to form one particle, and therefore tend to be sintered at a lower temperature than silver powder produced by a dry method.
（粒子形状）
　本銀粉の特徴の一つは、電子顕微鏡（例えば８５０００倍）で観察した際に、多くの銀粉粒子が真球状又は略真球状を呈していることにある。このように、真球状又は略真球状の銀粉粒子を含有する銀粉であれば、特に優れた分散性を得ることができる。
　この際、「真球状又は略真球状の銀粉粒子を含有する」とは、本銀粉を構成する銀粒子のうちの少なくとも６０個数％以上、中でも８０個数％以上、その中でも９０個数％以上（１００個数％を含む）が、真球状又は略真球状の銀粉粒子が占めるという意味である。
　また、「略真球状」とは、完全な真球状ではないが、球状として認識可能な形状を意味するものである。 (Particle shape)
One of the features of the present silver powder is that many silver powder particles have a true spherical shape or a substantially true spherical shape when observed with an electron microscope (for example, 85,000 times). Thus, if it is silver powder containing a spherical or nearly spherical silver powder particle, particularly excellent dispersibility can be obtained.
In this case, “contains true spherical or substantially spherical silver powder particles” means that at least 60% by number of silver particles constituting the present silver powder, particularly 80% by number or more, of which 90% by number or more (100 (Including number%) means that spherical or nearly spherical silver powder particles occupy.
Further, “substantially spherical” means a shape that is not completely spherical but can be recognized as spherical.
（Ｄ５０）
　本銀粉においては、走査型電子顕微鏡（ＳＥＭ）像の画像解析により得られるＤ５０が６０ｎｍ～１５０ｎｍであることも特徴の一つである。
　本銀粉のＤ５０が６０ｎｍ～１５０ｎｍ以下であれば、粒子の分散性を大きく損なうことなく、低温焼結性を高めることができる。よって、かかる観点から、本銀粉のＤ５０は、特に７３ｎｍ以上或いは１３４ｎｍ以下、その中でも８５ｎｍ以上或いは１３４ｎｍ以下であるのがより一層好ましい。 (D50)
One feature of the present silver powder is that D50 obtained by image analysis of a scanning electron microscope (SEM) image is 60 nm to 150 nm.
When the D50 of the present silver powder is 60 nm to 150 nm or less, the low-temperature sinterability can be improved without greatly impairing the dispersibility of the particles. Therefore, from this viewpoint, D50 of the present silver powder is particularly preferably 73 nm or more and 134 nm or less, and more preferably 85 nm or more or 134 nm or less.
（炭素（Ｃ）量）
　また、金属材料の炭素定量方法により測定される炭素（Ｃ）量が０．４０ｗｔ％未満である点も本銀粉の特徴の一つである。
　本銀粉の炭素（Ｃ）量が０．４０ｗｔ％未満であれば、粒子の分散性を大きく損なうことなく低温焼結性を高めることができる。但し、炭素（Ｃ）量が著しく少なくなると強い凝集が生じる可能性がある。
　かかる観点から、本銀粉の炭素（Ｃ）量は、特に０．２０ｗｔ％以上或いは０．３８ｗｔ％以下、その中でも０．２４ｗｔ％以上或いは０．３２ｗｔ％以下であるのがより一層好ましい。 (Amount of carbon (C))
Another feature of the present silver powder is that the amount of carbon (C) measured by the carbon determination method for metallic materials is less than 0.40 wt%.
If the amount of carbon (C) in the present silver powder is less than 0.40 wt%, the low-temperature sinterability can be improved without significantly impairing the dispersibility of the particles. However, strong agglomeration may occur when the amount of carbon (C) is significantly reduced.
From this point of view, the amount of carbon (C) in the present silver powder is particularly preferably 0.20 wt% or more or 0.38 wt% or less, and more preferably 0.24 wt% or more or 0.32 wt% or less.
（比表面積）
　本銀粉のＢＥＴ比表面積（ＳＳＡ）は４．２０ｍ2／ｇ～６．２０ｍ2／ｇであれば、粒子の分散性を大きく損なうことなく、低温焼結性を高めることができる。
　かかる観点から、より好ましくは４．３３ｍ２／ｇ以上或いは６．０１ｍ２／ｇ以下、その中でも特に４．３３ｍ２／ｇ以上或いは５．５８ｍ２／ｇ以下であるのがさらに好ましい。 (Specific surface area)
BET specific surface area of the silver powder (SSA) is as long as 4.20m 2 /g~6.20m 2 / g, without significantly impairing the dispersibility of the particles, it is possible to improve the low-temperature sinterability.
From this viewpoint, it is more preferably 4.33 m 2 / g or more or 6.01 m 2 / g or less, and particularly preferably 4.33 m 2 / g or more or 5.58 m 2 / g or less.
＜製法＞
　次に、本銀粉の好ましい製造方法として、湿式法による具体的な製造方法について説明する。但し、上述のように湿式法に限定するものではない。 <Production method>
Next, a specific manufacturing method by a wet method will be described as a preferable manufacturing method of the present silver powder. However, it is not limited to the wet method as described above.
　本銀粉は、先ず、粒径が比較的大きく、且つ粒径が揃っており、且つ真球状若しくは略真球状の湿式銀粉を用意し、この銀粉粒子を母体粒子として、その表面に小粒径の銀粉粒子を付着形成させ、その後、母体粒子から小粒径の銀粉粒子を分離することで、本銀粉粒子を得ることができる。但し、この製法に限定するものではない。 First, the present silver powder has a relatively large particle size and a uniform particle size, and prepares a spherical or nearly spherical wet silver powder. This silver powder particle is used as a base particle and has a small particle size on its surface. The silver powder particles can be obtained by depositing silver powder particles and then separating the silver powder particles having a small particle size from the base particles. However, it is not limited to this manufacturing method.
（母体粒子の製法）
　母体粒子となる銀粉粒子は、次のように製造するのが好ましい。
　従来同様に湿式法により銀粉を製造し、この銀粉を篩を用いて粗粒を除去した後、気流分級により微粉を除去することにより、粒径が比較的大きく、且つ粒径が揃っており、且つ真球状若しくは略真球状の湿式銀粉を得ることができる。 (Manufacturing method of base particles)
The silver powder particles serving as the base particles are preferably produced as follows.
Silver powder is produced by a wet method as in the prior art, and after removing coarse particles from the silver powder using a sieve, fine particles are removed by air classification, so that the particle size is relatively large and the particle size is uniform. In addition, a spherical or nearly spherical wet silver powder can be obtained.
（小粒径の銀粉粒子の製法）
　上記の如く作製した銀粉粒子を母体粒子として、その表面に小粒径の銀粉粒子を形成させる方法としては、例えば、還元剤溶液中に母体粒子を投入して一様に分散させ、さらに還元剤を加えて反応させることで、母体粒子の表面に小粒径の銀粉粒子を還元析出させることができる。
　母体粒子から小粒径の銀粉粒子を分離するには、水や有機溶媒のような液中で超音波をかけたり、或いは気流式粉砕機などで乾式解砕したりすれば、粒径の差を利用して比較的容易に分離することができる。なお、分離した母体粒子は、再度母体粒子として使用することができる。 (Manufacturing method of silver powder particles with small particle size)
As a method for forming silver powder particles having a small particle diameter on the surface of the silver powder particles produced as described above, for example, the base particles are charged and uniformly dispersed in a reducing agent solution, and further the reducing agent is dispersed. Can be reduced and deposited on the surface of the base particles.
In order to separate silver powder particles with a small particle size from the base particles, the difference in particle size can be obtained by applying ultrasonic waves in a liquid such as water or an organic solvent, or by dry crushing with an airflow crusher. Can be separated relatively easily. The separated base particles can be used again as base particles.
（具体的な製法）
　次に、具体的な一例について説明する。
　先ず、硝酸銀などの銀水溶液に錯化剤を加えて銀錯体溶液を調製し、必要に応じてステアリン酸ＮａやＫなどのステアリン酸塩やアミン系の分散剤を加えて撹拌し、還元剤溶液を前記銀錯体溶液に添加して還元析出させて銀粒子を作製する。
　得られた銀粒子をふるいで分級することにより、粗粒を除去した後、さらに、気流分級にて微粒と粗粒を除去し、母体となる均質な銀粉を得る。
　次に、上記同様の還元剤溶液中に、前記のように作製した銀粒子を添加して撹拌した後、母体粒子を一様に分散させた状態で、前記のように調製した銀錯体溶液を添加して撹拌することなく静かに反応させ、銀粉粒子（母体粒子）の表面に小粒径の銀粉粒子を還元析出させる。その後、ろ過、洗浄、乾燥させて銀粉を得る。そして、このようにして得た銀粉を水や有機溶媒のような液中に投入して超音波をかけたり、或いは気流式粉砕機などで乾式解砕したりして、母体粒子から小粒径の銀粉粒子を分離して分級することで、本銀粉を得ることができる。
　このように製造すれば、極めて微粒で、かつ粒径と形状（真球状）が揃っており、炭素（Ｃ）量が少ない銀粉粒子を得ることができる。しかも、粒径が揃っているため、ロスが極めて少ないという効果も得ることができる。 (Specific manufacturing method)
Next, a specific example will be described.
First, a silver complex solution is prepared by adding a complexing agent to a silver aqueous solution such as silver nitrate, and if necessary, a stearic acid salt such as Na or K stearate or an amine-based dispersant is added and stirred to obtain a reducing agent solution. Is added to the silver complex solution and reduced and precipitated to produce silver particles.
By classifying the obtained silver particles by sieving to remove coarse particles, fine particles and coarse particles are further removed by airflow classification to obtain a homogeneous silver powder as a base.
Next, after adding and stirring the silver particles prepared as described above in the same reducing agent solution as described above, the silver complex solution prepared as described above was prepared with the base particles uniformly dispersed. Add and react gently without stirring to reduce and precipitate silver powder particles with a small particle size on the surface of the silver powder particles (base particles). Then, silver powder is obtained by filtering, washing and drying. Then, the silver powder obtained in this manner is put into a liquid such as water or an organic solvent and subjected to ultrasonic waves, or dry pulverized with an airflow type pulverizer, etc. This silver powder can be obtained by separating and classifying the silver powder particles.
If manufactured in this way, silver powder particles that are extremely fine, have a uniform particle size and shape (true spherical shape), and have a small amount of carbon (C) can be obtained. In addition, since the particle diameters are uniform, an effect that the loss is extremely small can be obtained.
　上記の製法において、硝酸銀などの銀水溶液は、硝酸銀、銀塩錯体、及び銀中間体のいずれかを含有する水溶液、又はスラリーを使用することができる。
　また、錯化剤としては、例えばアンモニア水、アンモニウム塩、キレート化合物等を挙げることができる。
　還元剤としては、アスコルビン酸、亜硫酸塩、アルカノールアミン、過酸化水素水、ギ酸、ギ酸アンモニウム、ギ酸ナトリウム、グリオキサール、酒石酸、次亜燐酸ナトリウム、水素化ホウ素金属塩、ジメチルアミンボラン、ヒドラジン、ヒドラジン化合物、ヒドロキノン、ピロガロール、ぶどう糖、没食子酸、ホルマリン、無水亜硫酸ナトリウム、ロンガリットなどを含む水溶液を挙げることができる。
　分散剤としては、脂肪酸、脂肪酸塩、界面活性剤、有機金属、キレート剤、保護コロイド等を挙げることができる。 In the above production method, an aqueous solution containing silver nitrate, a silver salt complex, and a silver intermediate or a slurry can be used as the aqueous silver solution such as silver nitrate.
Examples of complexing agents include ammonia water, ammonium salts, chelate compounds and the like.
As reducing agents, ascorbic acid, sulfite, alkanolamine, hydrogen peroxide, formic acid, ammonium formate, sodium formate, glyoxal, tartaric acid, sodium hypophosphite, borohydride metal salt, dimethylamine borane, hydrazine, hydrazine compound And aqueous solutions containing hydroquinone, pyrogallol, glucose, gallic acid, formalin, anhydrous sodium sulfite, Rongalite and the like.
Examples of the dispersant include fatty acids, fatty acid salts, surfactants, organic metals, chelating agents, protective colloids and the like.
（形状加工）
　本銀粉は、そのまま利用することも可能であるが、本銀粉を形状加工処理した上で、利用することもできる。
　例えば、真球状粒子粉末（：８０％以上が真球状粒子からなる粉末）を、機械的に形状加工して、フレーク状、鱗片状、平板状などの非球状粒子粉末（：８０％以上が非球状粒子からなる粉末）に加工することができる。
　より具体的には、ビーズミル、ボールミル、アトライター、振動ミルなどを用いて機械的に偏平化加工（圧伸延または展伸）することにより、フレーク状粒子粉末（：８０％以上がフレーク状粒子からなる粉末）に形状加工することができる。この際、粒子同士の凝集や結合を防止しながら各粒子を独立した状態で加工するために、例えばステアリン酸などの脂肪酸や、界面活性剤などの助剤を添加するのが好ましい。
　そして、このような形状加工処理した銀粉を利用することもできるし、また、形状加工しない元粉とこれとを混合して利用することもできる。 (Shape processing)
Although the present silver powder can be used as it is, it can also be used after the present silver powder has been processed into a shape.
For example, a true spherical particle powder (powder consisting of 80% or more of true spherical particles) is mechanically processed into non-spherical particle powders such as flakes, scales, and flat plates (80% or more of non-spherical particles). A powder composed of spherical particles).
More specifically, flaky particle powder (: 80% or more from flaky particles) is mechanically flattened (rolled or stretched) using a bead mill, ball mill, attritor, vibration mill or the like. Shape powder). At this time, in order to process each particle independently while preventing aggregation and bonding of the particles, it is preferable to add a fatty acid such as stearic acid or an auxiliary agent such as a surfactant.
And the silver powder which carried out such shape processing can also be utilized, and the original powder which is not shape-processed and this can also be mixed and utilized.
　本銀粉は、粒径がきれいに揃っているため、粒径に適したメディアを効果的に選択できるため、フレーク粉としても、均質なフレーク粉粒子を得ることができる。
　球形粉とフレーク粉の混合粉でもよい。 Since the present silver powder has a uniform particle size, a medium suitable for the particle size can be effectively selected, so that even flake powder can obtain uniform flake powder particles.
A mixed powder of spherical powder and flake powder may be used.
＜用途＞
　本銀粉は、導電ペースト用、特に焼結型導電性ペースト用の銀粉として好適である。例えば１７５℃以下での焼結が可能であるため樹脂フィルム基板上などに適用することも可能である。特に、１５０℃以下での焼結が可能であると、ポリエチレンテレフタレート（ＰＥＴ）フィルム基板上で焼結させることも可能になる。 <Application>
The silver powder is suitable as a silver powder for a conductive paste, particularly for a sintered conductive paste. For example, since sintering at 175 ° C. or lower is possible, it can be applied on a resin film substrate. In particular, if sintering at 150 ° C. or lower is possible, sintering on a polyethylene terephthalate (PET) film substrate is also possible.
　焼結型導電性ペーストは、例えば有機ビヒクル中に、本銀粉をガラスフリットと共に混合することで調製することができる。
　この際、ガラスフリットとしては、例えば、鉛ボロシリケートガラスや、ジンクボロシリケート等の無鉛ガラスも挙げることができる。
　また、樹脂バインダーとしては、例えば任意の樹脂バインダーを使用することができる。例えばエポキシ樹脂、ポリエステル樹脂、ケイ素樹脂、ユリア樹脂、アクリル樹脂、セルロース樹脂から選ばれる１種以上を含む組成を採用するのが望ましい。 The sintered conductive paste can be prepared, for example, by mixing the present silver powder together with glass frit in an organic vehicle.
In this case, examples of the glass frit include lead-free glass such as lead borosilicate glass and zinc borosilicate.
Moreover, as a resin binder, arbitrary resin binders can be used, for example. For example, it is desirable to employ a composition containing at least one selected from an epoxy resin, a polyester resin, a silicon resin, a urea resin, an acrylic resin, and a cellulose resin.
＜語句の説明＞
　本明細書において「Ｘ～Ｙ」（Ｘ，Ｙは任意の数字）と表現する場合、特にことわらない限り「Ｘ以上Ｙ以下」の意と共に、「好ましくはＸより大きい」或いは「好ましくはＹより小さい」の意も包含する。
　また、「Ｘ以上」（Ｘは任意の数字）或いは「Ｙ以下」（Ｙは任意の数字）と表現した場合、「Ｘより大きいことが好ましい」或いは「Ｙ未満であることが好ましい」旨の意図も包含する。 <Explanation of words>
In the present specification, when expressed as “X to Y” (X and Y are arbitrary numbers), “X is preferably greater than X” or “preferably Y”, with the meaning of “X to Y” unless otherwise specified. It also includes the meaning of “smaller”.
In addition, when expressed as “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), it is “preferably greater than X” or “preferably less than Y”. Includes intentions.
　以下、本発明を下記実施例及び比較例に基づいてさらに詳述する。
　実施例および比較例で得られた銀粉に関して、以下に示す方法で諸特性を評価した。 Hereinafter, the present invention will be further described in detail based on the following examples and comparative examples.
With respect to the silver powder obtained in Examples and Comparative Examples, various characteristics were evaluated by the following methods.
（１）Ｄ５０（画像解析）
　走査型電子顕微鏡（ＳＥＭ）（ＰＨＩＬＩＰＳ社製 ＸＬ３０）を用いて標本数１５０～３５０となるよう１３０００～８５０００倍程度で適宜撮影した任意の３視野の走査型電子顕微鏡（ＳＥＭ）像を、ＢＭＰファイルに変換し、旭エンジニアリング株式会社製のＩＰ－１０００ＰＣの統合アプリケーションであるＡ像くんで取り込み、円度しきい値５０、重なり度３０として円形粒子解析を行ない、手動補正をかけることなく、画像解析により得られるＤ５０を計測した。 (1) D50 (image analysis)
Using a scanning electron microscope (SEM) (XL30 manufactured by PHILIPS), an arbitrary three-field scanning electron microscope (SEM) image captured appropriately at a magnification of about 13000 to 85000 times to obtain a specimen number of 150 to 350 is a BMP file. The image is taken in with A image, an integrated application of IP-1000PC manufactured by Asahi Engineering Co., Ltd., and circular particle analysis is performed with a circularity threshold of 50 and an overlap of 30. Image analysis without manual correction D50 obtained by this was measured.
（２）ＢＥＴ比表面積（ＳＳＡ）
　ＱＵＡＮＴＡＣＨＲＯＭＥ社製の比表面積測定装置（モノソーブＭＳ－１８）を用いて、ＪＩＳ　Ｒ　１６２６：１９９６（ファインセラミックス粉体の気体吸着ＢＥＴ法による比表面積の測定方法）の「６．２流動法の（３．５）一点法」に準拠して、ＢＥＴ比表面積（ＳＳＡ）の測定を行った。その際、キャリアガスであるヘリウムと、吸着質ガスである窒素の混合ガスを使用した。 (2) BET specific surface area (SSA)
Using a specific surface area measuring device (Monosorb MS-18) manufactured by QUANTACHROME, JIS R 1626: 1996 (Method for measuring specific surface area of fine ceramic powder by gas adsorption BET method), .5) Single point method ", BET specific surface area (SSA) was measured. At that time, a mixed gas of helium as a carrier gas and nitrogen as an adsorbate gas was used.
（３）炭素（Ｃ）量
　ＨＯＲＩＢＡ製作所社製の炭素分析装置（ＥＭＩＡ－２２１Ｖ２）を用いて、ＪＩＳ　Ｚ　２６１５（金属材料の炭素定量方法通則）に準拠して炭素分析を行なった。 (3) Carbon (C) amount Carbon analysis was performed using a carbon analyzer (EMIA-221V2) manufactured by HORIBA Ltd. in accordance with JIS Z 2615 (General rules for carbon quantification of metal materials).
（４）焼結開始温度
　銀粉（サンプル）０．２ｇを用い、４９３ｋｇの加重をかけてφ３．８ｍｍの円柱状に成形した。この成形体の縦方向の線収縮率（％）を、セイコーインスツルメンツ社製の熱機械分析装置（ＴＭＡ）（ＥＸＳＴＡＲ６０００ＴＭＡ／ＳＳ６２００）を用い、９８ｍＮの加重をかけながらＡｉｒ雰囲気中２℃／分の昇温速度で測定し、熱収縮率の値が正から負へ転じた最低温度（℃）を焼結開始温度として求めた。但し、熱収縮率の値が正から負へ転じた際の収縮率の差が、前記成形体の初期の長さ（１００％）に対して０．０１％未満の場合は、有効な変動ではないと判断して無視することとした。 (4) Sintering start temperature Using 0.2 g of silver powder (sample), a weight of 493 kg was applied and molded into a cylindrical shape of φ3.8 mm. Using a thermomechanical analyzer (TMA) manufactured by Seiko Instruments Inc. (EXSTAR6000TMA / SS6200), the linear shrinkage rate (%) in the vertical direction of this molded body was increased by 2 ° C./min in an Air atmosphere while applying a load of 98 mN. The temperature was measured at a temperature rate, and the lowest temperature (° C.) at which the value of the heat shrinkage rate changed from positive to negative was determined as the sintering start temperature. However, in the case where the difference in shrinkage rate when the value of heat shrinkage rate changes from positive to negative is less than 0.01% with respect to the initial length (100%) of the molded body, effective fluctuation is not possible. I decided to ignore it and decided to ignore it.
＜実施例１＞
　銀濃度４００ｇ／Ｌの硝酸銀水溶液５０ｍＬを純水１Ｌに溶解させて硝酸銀水溶液を調製し、濃度２５質量％のアンモニア水６０ｍＬを添加して攪拌することにより、銀アンミン錯体水溶液を得た。
　次いで、銀アンミン錯体水溶液に、１％濃度のアミン系の分散剤（平均分子量１００００）水溶液６ｍＬを添加して攪拌し、濃度９．０ｇ／Ｌのヒドラジン水溶液１Ｌを添加し、撹拌することなく反応させて母体となる銀粒子を還元析出させた。
　次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、８０℃の乾燥機中で１時間乾燥させることにより銀粉を得た。得られた銀粒子は略真球状であった。
　得られた銀粒子を２５μｍのふるいで分級することにより、２５μｍ以上の粗粒を除去した後、さらに、気流分級にて微粒と粗粒を除去し、母体となる均質な銀粉（Ｄ１０：２．２６μｍ、Ｄ５０：３．１０μｍ、Ｄ９０：４．６３μｍ）を得た。 <Example 1>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring.
Next, 6 mL of a 1% strength amine-based dispersant (average molecular weight 10,000) aqueous solution is added to the silver ammine complex aqueous solution and stirred, and 1 L of a hydrazine aqueous solution having a concentration of 9.0 g / L is added and reacted without stirring. The base silver particles were reduced and precipitated.
Next, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and then dried in a dryer at 80 ° C. for 1 hour to obtain silver powder. The obtained silver particles were substantially spherical.
By classifying the obtained silver particles with a sieve of 25 μm, coarse particles of 25 μm or more are removed, and then fine particles and coarse particles are further removed by airflow classification to form a homogeneous silver powder (D10: 2. 26 μm, D50: 3.10 μm, D90: 4.63 μm).
　次に、銀濃度４００ｇ／Ｌの硝酸銀水溶液２０ｍＬを純水１Ｌに溶解させて硝酸銀水溶液を調製し、濃度２５質量％のアンモニア水２４ｍＬを添加して攪拌することにより、銀アンミン錯体水溶液を得た。
　次いで、ヒドロキノン２０ｇおよびヒドラジン５ｍＬを純水１Ｌに溶解させた還元溶液中に、上記で得られた銀粒子を添加、攪拌した後、銀アンミン錯体水溶液を添加し、攪拌することなく反応させて母体となる銀粒子の表面に微粒銀粒子を還元析出させた。
　次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、８０℃の乾燥機中で１時間乾燥させることにより銀粉を得た。
　得られた銀粉粒子をメタノール中に分散させ、超音波により母体粒子と付着粒子を分離し、孔径０．８μｍのシリンジフィルターでろ過することで付着粒子のスラリーをろ液として回収し、６０℃の乾燥機中で１６時間乾燥することにより本銀粉を得た。
　このようにして得た本銀粉は、略真球状の均質な銀粒子からなるものであった。 Next, 20 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L was dissolved in 1 L of pure water to prepare a silver nitrate aqueous solution, and 24 mL of ammonia water having a concentration of 25% by mass was added and stirred to obtain a silver ammine complex aqueous solution. .
Next, after adding and stirring the silver particles obtained above in a reducing solution in which 20 g of hydroquinone and 5 mL of hydrazine are dissolved in 1 L of pure water, an aqueous silver ammine complex solution is added and reacted without stirring. Fine silver particles were reduced and deposited on the surfaces of the silver particles.
Next, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and then dried in a dryer at 80 ° C. for 1 hour to obtain silver powder.
The obtained silver powder particles are dispersed in methanol, the base particles and the adhered particles are separated by ultrasonic waves, and the slurry of the adhered particles is recovered as a filtrate by filtering with a syringe filter having a pore diameter of 0.8 μm. This silver powder was obtained by drying for 16 hours in a dryer.
The silver powder thus obtained consisted of substantially spherical and homogeneous silver particles.
＜実施例２＞
　微粒銀粒子を還元析出させるために使用した、錯体溶液および還元溶液中の純水の添加量を１．１０Ｌにした以外は、実施例１と同様にして銀粉を得た。 <Example 2>
Silver powder was obtained in the same manner as in Example 1 except that the addition amount of pure water in the complex solution and the reducing solution used for reducing and precipitating fine silver particles was 1.10 L.
＜実施例３＞
　微粒銀粒子を還元析出させるために使用した硝酸銀水溶液の添加量を２５ｍＬ、錯体溶液および還元溶液中の純水の添加量を０．９０Ｌにした以外は、実施例１と同様にして銀粉を得た。 <Example 3>
Silver powder was obtained in the same manner as in Example 1 except that the addition amount of the silver nitrate aqueous solution used for reducing and precipitating fine silver particles was 25 mL, and the addition amount of pure water in the complex solution and the reduction solution was 0.90 L. It was.
＜実施例４＞
　微粒銀粒子を還元析出させるために使用した硝酸銀水溶液の添加量を２３ｍＬ、錯体溶液および還元溶液中の純水の添加量を０．９０Ｌにした以外は、実施例１と同様にして銀粉を得た。 <Example 4>
Silver powder was obtained in the same manner as in Example 1 except that the addition amount of the silver nitrate aqueous solution used for reducing and precipitating fine silver particles was 23 mL, and the addition amount of pure water in the complex solution and the reduction solution was 0.90 L. It was.
＜実施例５＞
　微粒銀粒子を還元析出させるために使用した硝酸銀水溶液の添加量を２５ｍＬ、錯体溶液および還元溶液中の純水の添加量を０．７０Ｌにした以外は、実施例１と同様にして銀粉を得た。 <Example 5>
Silver powder was obtained in the same manner as in Example 1 except that the addition amount of the aqueous silver nitrate solution used for reducing and precipitating fine silver particles was 25 mL, and the addition amount of pure water in the complex solution and the reduction solution was 0.70 L. It was.
＜実施例６＞
　微粒銀粒子を還元析出させるために使用した、錯体溶液および還元溶液中の純水の添加量を０．８０Ｌにした以外は、実施例１と同様にして銀粉を得た。 <Example 6>
A silver powder was obtained in the same manner as in Example 1 except that the amount of pure water in the complex solution and the reducing solution used for reducing and precipitating fine silver particles was 0.80 L.
＜実施例７＞
　微粒銀粒子を還元析出させるために使用した、錯体溶液および還元溶液中の純水の添加量を０．９０Ｌにした以外は、実施例１と同様にして銀粉を得た。 <Example 7>
Silver powder was obtained in the same manner as in Example 1 except that the amount of pure water in the complex solution and the reducing solution used for reducing and precipitating fine silver particles was 0.90 L.
＜実施例８＞
　微粒銀粒子を還元析出させるために使用した、錯体溶液および還元溶液中の純水の添加量を０．７０Ｌにした以外は、実施例１と同様にして銀粉を得た。 <Example 8>
Silver powder was obtained in the same manner as in Example 1 except that the addition amount of pure water in the complex solution and the reducing solution used for reducing and precipitating the fine silver particles was 0.70 L.
＜実施例９＞
　微粒銀粒子を還元析出させるために作製した錯体溶液に、１％濃度のアミン系の分散剤（平均分子量１００００）水溶液１ｍＬを添加して攪拌した以外は、実施例１と同様にして銀粉を得た。 <Example 9>
A silver powder is obtained in the same manner as in Example 1 except that 1 mL of an amine-based dispersant (average molecular weight 10,000) aqueous solution of 1% concentration is added to the complex solution prepared for reduction precipitation of fine silver particles and stirred. It was.
＜実施例１０＞
　微粒銀粒子を還元析出させるために作製した錯体溶液に、１％濃度のアミン系の分散剤（平均分子量１００００）水溶液２ｍＬを添加して攪拌し、微粒銀粒子を還元析出させるために使用した錯体溶液および還元溶液中の純水の添加量を１．１０Ｌにした以外は、実施例１と同様にして銀粉を得た。 <Example 10>
Complex used for reducing and precipitating fine silver particles 2 mL of a 1% strength amine-based dispersant (average molecular weight 10,000) aqueous solution was added to the complex solution prepared for reducing and precipitating fine silver particles and stirred. Silver powder was obtained in the same manner as in Example 1 except that the addition amount of pure water in the solution and the reducing solution was changed to 1.10 L.
＜比較例１＞
　銀濃度４００ｇ／Ｌの硝酸銀水溶液２０ｍＬを純水１Ｌに溶解させて硝酸銀水溶液を調製し、濃度２５質量％のアンモニア水２４ｍＬを添加して攪拌することにより、銀アンミン錯体水溶液を得た。
　次いで、銀アンミン錯体水溶液に、１％濃度のアミン系の分散剤（平均分子量１００００）水溶液６ｍＬを添加して攪拌し、ヒドロキノン２０ｇおよびヒドラジン５ｍＬを純水１Ｌに溶解させた還元溶液中に、銀アンミン錯体水溶液を添加し、攪拌することなく反応させて微粒銀粒子を還元析出させた。
　次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、８０℃の乾燥機中で１時間乾燥させることにより銀粉を得た。得られた銀粉粒子は略真球状であった。 <Comparative Example 1>
A silver nitrate aqueous solution was obtained by dissolving 20 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water to prepare a silver nitrate aqueous solution, adding 24 mL of 25% by mass ammonia water, and stirring.
Next, 6 mL of a 1% strength amine-based dispersant (average molecular weight 10,000) aqueous solution was added to the silver ammine complex aqueous solution and stirred, and then silver in a reduced solution in which 20 g of hydroquinone and 5 mL of hydrazine were dissolved in 1 L of pure water. An aqueous ammine complex solution was added and reacted without stirring to reduce and precipitate fine silver particles.
Next, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and then dried in a dryer at 80 ° C. for 1 hour to obtain silver powder. The obtained silver powder particles were substantially spherical.
＜比較例２＞
　銀濃度４００ｇ／Ｌの硝酸銀水溶液７ｍｌを純水０．９８Ｌに溶解させ硝酸銀水溶液を調整し、濃度２５質量％のアンモニア水１２ｍｌを添加して攪拌することにより、銀アンミン錯体水溶液を得た。次いで、２０℃で、この銀アンミン錯体水溶液に、濃度１．５ｇ／Ｌのヒドロキノン水溶液１．０Ｌを混合することにより銀粒子を還元析出させた。
　次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、８０℃の乾燥機中で１時間乾燥させることにより銀粉を得た。 <Comparative Example 2>
A silver ammine complex aqueous solution was obtained by dissolving 7 ml of an aqueous silver nitrate solution having a silver concentration of 400 g / L in 0.98 L of pure water to prepare an aqueous silver nitrate solution, adding 12 ml of ammonia water having a concentration of 25% by mass and stirring. Subsequently, silver particles were reduced and precipitated by mixing 1.0 L of a hydroquinone aqueous solution having a concentration of 1.5 g / L with this silver ammine complex aqueous solution at 20 ° C.
Next, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and then dried in a dryer at 80 ° C. for 1 hour to obtain silver powder.
＜比較例３＞
　銀濃度４００ｇ／Ｌの硝酸銀水溶液３５ｍｌを純水１Ｌに溶解させ硝酸銀水溶液を調整し、濃度２５質量％のアンモニア水６０ｍｌを添加して攪拌することにより、銀アンミン錯体水溶液を得た。次いで、２０℃で、この銀アンミン錯体水溶液に、濃度６ｇ／Ｌのヒドロキノン水溶液１．２Ｌを混合することにより銀粒子を還元析出させた。
　次いで、この銀粒子をろ過し、ろ液の伝導率が４０μＳ／ｃｍ以下となるまで水洗後、８０℃の乾燥機中で１時間乾燥させることにより銀粉を得た。 <Comparative Example 3>
A silver ammine complex aqueous solution was obtained by dissolving 35 ml of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water to prepare a silver nitrate aqueous solution, adding 60 ml of ammonia water having a concentration of 25% by mass and stirring. Next, at 20 ° C., the silver ammine complex aqueous solution was mixed with 1.2 L of a hydroquinone aqueous solution having a concentration of 6 g / L to reduce and precipitate silver particles.
Next, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and then dried in a dryer at 80 ° C. for 1 hour to obtain silver powder.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（考察）
　実施例１～１０の製法によれば、粒径が比較的大きな母体粒子の表面に小粒径の銀粉粒子を付着形成させたことで、粒径制御や分散性を維持することができ、必要な有機物の保護剤が少量で済み、従来の銀ナノ粒子よりもＣ量の低い銀粉を得ることができた。
　実施例１～１０で得た銀粉はいずれも、Ｄ５０が６０ｎｍ～１５０ｎｍで、炭素（Ｃ）量が０．４０ｗｔ％未満であり、１７５℃以下での焼結が可能であることが認められた。よって、樹脂フィルム基板上などで焼結させることができる。 (Discussion)
According to the production methods of Examples 1 to 10, small particle size silver powder particles are adhered and formed on the surface of base particles having a relatively large particle size, so that the particle size control and dispersibility can be maintained. A small amount of organic protective agent is required, and silver powder having a lower C content than conventional silver nanoparticles can be obtained.
All of the silver powders obtained in Examples 1 to 10 were found to have a D50 of 60 nm to 150 nm, a carbon (C) amount of less than 0.40 wt%, and could be sintered at 175 ° C. or lower. . Therefore, it can be sintered on a resin film substrate.

Claims (5)

  1. 　走査型電子顕微鏡（ＳＥＭ）像の画像解析により得られるＤ５０が６０ｎｍ～１５０ｎｍであり、ＪＩＳ　Ｚ　２６１５（金属材料の炭素定量方法通則）に準拠して測定される炭素（Ｃ）量が０．４０ｗｔ％未満であり、真球状又は略真球状の銀粉粒子を含有する銀粉。 D50 obtained by image analysis of a scanning electron microscope (SEM) image is 60 nm to 150 nm, and the amount of carbon (C) measured in accordance with JIS Z 2615 (general rules for carbon determination of metal materials) is 0.40 wt. Silver powder containing less than% and containing spherical or nearly spherical silver powder particles.
  2. 　ＢＥＴ法により測定される比表面積が４．２０ｍ2／ｇ～６．２０ｍ2／ｇであることを特徴とする請求項１記載の銀粉。 Silver powder according to claim 1, wherein the specific surface area measured by the BET method is characterized by a 4.20m 2 /g~6.20m 2 / g.
  3. 　湿式反応で作製されたことを特徴とする請求項１又は２記載の銀粉。 The silver powder according to claim 1 or 2, which is prepared by a wet reaction.
  4. 　請求項１～３の何れかに記載の銀粉を形状加工処理してなる銀粉。 Silver powder obtained by shape-processing the silver powder according to any one of claims 1 to 3.
  5. 　請求項１～４の何れかに記載の銀粉を用いてなる焼結型導電性ペースト。
          A sintered conductive paste using the silver powder according to any one of claims 1 to 4.
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