JP2005330529A - Spherical silver powder and its production method - Google Patents

Spherical silver powder and its production method Download PDF

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JP2005330529A
JP2005330529A JP2004149068A JP2004149068A JP2005330529A JP 2005330529 A JP2005330529 A JP 2005330529A JP 2004149068 A JP2004149068 A JP 2004149068A JP 2004149068 A JP2004149068 A JP 2004149068A JP 2005330529 A JP2005330529 A JP 2005330529A
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silver powder
silver
spherical silver
spherical
powder according
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JP2005330529A5 (en
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Kozo Ogi
孝造 尾木
Takeaki Fujino
剛聡 藤野
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Dowa Holdings Co Ltd
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Dowa Mining Co Ltd
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Priority to JP2004149068A priority Critical patent/JP2005330529A/en
Priority to US11/132,980 priority patent/US20050257643A1/en
Priority to TW094116087A priority patent/TW200603922A/en
Priority to CN200510074647XA priority patent/CN1700360B/en
Priority to KR1020050041948A priority patent/KR20060046103A/en
Publication of JP2005330529A publication Critical patent/JP2005330529A/en
Publication of JP2005330529A5 publication Critical patent/JP2005330529A5/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles
    • 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
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • 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
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks

Abstract

<P>PROBLEM TO BE SOLVED: To provide spherical silver powder having satisfactory dispersibility and further capable of obtaining satisfactory sinterability even in the case of forming a conductor by being used for paste and fired at a low temperature of ≤600°C, and to provide its production method. <P>SOLUTION: A reducing agent-containing aqueous solution is added to a silver ion-containing water-base reaction system to reductively precipitate silver particles, thus the spherical silver powder in which the ratio (Dx/BET) of the crystallite diameter Dx(nm) to the BET (Brunauer-Emett-Teller) specific surface area (m<SP>2</SP>/g) is 5 to 200, the crystallite diameter is ≤40 nm, the average particle diameter is ≤5 μm, the tap density is ≥2g/cm<SP>3</SP>, and the BET specific surface area is ≤5 m<SP>2</SP>/g is produced. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、球状銀粉およびその製造方法に関し、特に、電子部品の端子電極や回路基板パターンなどを形成するために用いられる球状銀粉およびその製造方法に関する。   The present invention relates to a spherical silver powder and a method for producing the same, and more particularly to a spherical silver powder used for forming a terminal electrode or a circuit board pattern of an electronic component and a method for producing the same.

従来、電子部品などの電極や回路を形成するために、銀粉を有機成分中に分散させた導電性ペーストが使用されている。一般に、導電性ペーストは、熱処理温度により焼成型ペーストと樹脂型ペーストに分類され、それぞれ用途や構成要素などが異なっている。   Conventionally, a conductive paste in which silver powder is dispersed in an organic component has been used to form electrodes and circuits such as electronic components. In general, the conductive paste is classified into a fired paste and a resin paste depending on the heat treatment temperature, and uses and components are different from each other.

焼成型ペーストは、構成要素として、銀粉、エチルセルロースやアクリル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、有機溶剤、分散剤などを含み、ディッピングや印刷などにより所定のパターンに形成された後、焼成されて導体を形成する。このような焼成型ペーストは、ハイブリッドＩＣ、積層セラミックコンデンサ、チップ抵抗器などの電極に使用されている。   The fired paste contains, as constituent elements, silver powder, a vehicle in which ethyl cellulose or acrylic resin is dissolved in an organic solvent, glass frit, an inorganic oxide, an organic solvent, a dispersant, etc., and is formed into a predetermined pattern by dipping or printing. And then fired to form a conductor. Such fired paste is used for electrodes of hybrid ICs, multilayer ceramic capacitors, chip resistors and the like.

焼成型ペーストの焼成温度は用途によって異なるが、ハイブリッドＩＣに用いられるアルミナ基板やガラスセラミック基板のような耐熱性のセラミック基板上において焼成型ペーストを高温で焼成することにより導体を形成する場合と、耐熱性が低い基板上において焼成型ペーストを低温で焼成することにより導体を形成する場合がある。   The firing temperature of the firing paste varies depending on the application, and when a conductor is formed by firing the firing paste at a high temperature on a heat-resistant ceramic substrate such as an alumina substrate or a glass ceramic substrate used in a hybrid IC, In some cases, a conductor is formed by baking a baking paste at a low temperature on a substrate having low heat resistance.

銀の融点は９５０℃であり、その融点以下の可能な限り高温で焼成すれば、銀の焼結体の抵抗値が下がるが、焼成温度に適した銀粉を使用しなければ、様々な不具合が生じる。例えば、セラミック基板上において高温で焼成する場合には、銀の焼結体とセラミック基板との収縮差によってクラックやデラミネーション（積層剥離）などの不具合が生じることがあり、このような不具合を解決するために、高結晶の銀粉が提案されている（例えば、特許文献１、特許文献２参照）。   The melting point of silver is 950 ° C., and if it is fired at the highest possible temperature below that melting point, the resistance of the silver sintered body will decrease, but if silver powder suitable for the firing temperature is not used, various problems will occur. Arise. For example, when firing at a high temperature on a ceramic substrate, defects such as cracks and delamination (lamination delamination) may occur due to the difference in shrinkage between the sintered silver body and the ceramic substrate. In order to do so, highly crystalline silver powder has been proposed (see, for example, Patent Document 1 and Patent Document 2).

一方、樹脂型ペーストは、スルーホールやメンブレンなどの配線材や導電性接着剤などに使用されている。このような樹脂型ペーストは、構成要素として、銀粉、エポキシ樹脂やウレタン樹脂などの熱硬化性樹脂、硬化剤、有機溶剤、分散剤などを含み、ディスペンスや印刷などにより所定の導体パターンに形成され、室温から２５０℃程度の温度で硬化し、残存する樹脂の硬化収縮による銀粒子同士の接触により導電性が得られる。したがって、銀粒子同士の接触面積を増大するために、通常、銀粉を機械的に鱗辺状に加工したフレーク銀粉が使用されている。なお、３００℃以上の温度では、樹脂が劣化して導体の抵抗や接着強度が悪化する。   On the other hand, resin paste is used for wiring materials such as through holes and membranes, and conductive adhesives. Such resin-type paste contains silver powder, thermosetting resin such as epoxy resin and urethane resin, curing agent, organic solvent, dispersant, etc. as a component, and is formed into a predetermined conductor pattern by dispensing or printing. The resin is cured at a temperature from room temperature to about 250 ° C., and conductivity is obtained by contact between silver particles due to curing shrinkage of the remaining resin. Therefore, in order to increase the contact area between the silver particles, flaky silver powder obtained by mechanically processing silver powder into a scale shape is usually used. Note that, at a temperature of 300 ° C. or higher, the resin deteriorates and the resistance and adhesive strength of the conductor deteriorate.

特開２０００−１０７６号公報（段落番号０００８−０００９）JP 2000-1076 A (paragraph numbers 0008-0009) 特開２０００−１０７７号公報（段落番号００１２−００１３）JP 2000-1077 A (paragraph number 0012-0013)

しかし、例えば、プラズマディスプレイパネル（ＰＤＰ）基板の場合には、基板の材料であるガラスの耐熱性が低いため、セラミック基板の場合と異なり、７５０〜９００℃程度の高温で焼成することができない。したがって、より低い温度で焼成することが必要になり、基板の耐熱性との関係で６００℃以下の温度、実際には５００〜６００℃の低温で焼成することにより導体を形成する必要があるが、導体の抵抗値を低くするのが困難になる。   However, for example, in the case of a plasma display panel (PDP) substrate, since the heat resistance of glass as a substrate material is low, unlike a ceramic substrate, it cannot be fired at a high temperature of about 750 to 900 ° C. Therefore, it is necessary to fire at a lower temperature, and it is necessary to form a conductor by firing at a temperature of 600 ° C. or lower, in fact, at a low temperature of 500 to 600 ° C. in relation to the heat resistance of the substrate. It becomes difficult to reduce the resistance value of the conductor.

低温で焼成する場合、焼成温度より低い軟化点のガラスフリットを添加して焼結を促進させることにより導体の抵抗値を下げることができる。しかし、繰り返し焼成を行うＰＤＰ基板の場合には、必要以上に低い軟化点のガラスフリットを使用することは、導体の抵抗値の変動の原因になるので好ましくない。   When firing at a low temperature, the resistance value of the conductor can be lowered by adding glass frit having a softening point lower than the firing temperature to promote sintering. However, in the case of a PDP substrate that is repeatedly fired, it is not preferable to use a glass frit having a softening point that is lower than necessary because it causes fluctuations in the resistance value of the conductor.

また、銀粉を感光性ペーストに使用する場合には、銀粉の形状が不定形やフレーク状であると、紫外線の散乱や反射が起こり、パターニング不良の原因になる。   Moreover, when using silver powder for the photosensitive paste, when the shape of the silver powder is indefinite or flaky, scattering or reflection of ultraviolet rays occurs, resulting in patterning failure.

さらに、その他の方法、例えば、印刷法や転写法により導体パターンを形成する場合にも、スクリーン版の抜け性や転写性の観点から、銀粉の形状が不定形やフレーク状であると、良好な導体パターンを形成することができない。   Furthermore, when a conductor pattern is formed by other methods, for example, a printing method or a transfer method, it is preferable that the shape of the silver powder is indefinite or flaky from the viewpoint of the detachability and transferability of the screen plate. A conductor pattern cannot be formed.

したがって、本発明は、このような従来の問題点に鑑み、ペーストに使用して６００℃以下の低温で焼成することにより導体を形成する場合にも良好な焼結性を得ることができる、球状銀粉およびその製造方法を提供することを目的とする。また、本発明は、良好な分散性を有する球状銀粉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 a conventional problem, the present invention can obtain a good sinterability even when a conductor is formed by firing at a low temperature of 600 ° C. or lower using a paste. It aims at providing silver powder and its manufacturing method. Moreover, an object of this invention is to provide the spherical silver powder which has favorable dispersibility, and its manufacturing method.

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、ＢＥＴ比表面積（ｍ２／ｇ）に対する結晶子径Ｄｘ（ｎｍ）の比（Ｄｘ／ＢＥＴ）が５〜２００の球状の銀粉、好ましくは結晶子径が４０ｎｍ以下で平均粒径が５μｍ以下の球状の銀粉をペーストに使用して焼成することにより導体を形成すれば、焼成温度が６００℃以下の低温でも良好な焼結性を得ることができ、また、タップ密度が２ｇ／ｃｍ３以上、ＢＥＴ比表面積５ｍ２／ｇ以下の分散性が良好な球状銀粉を使用したペーストから、感光性ペースト法、印刷法または転写法により良好な導体パターンを得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 intensive studies to solve the above problems, the inventors of the present invention have obtained a spherical silver powder having a ratio (Dx / BET) of crystallite diameter Dx (nm) to BET specific surface area (m 2 / g) of 5 to 200. Preferably, if a conductor is formed by using spherical silver powder having a crystallite diameter of 40 nm or less and an average particle diameter of 5 μm or less as a paste to form a conductor, good sinterability even at a low temperature of 600 ° C. or less From a paste using spherical silver powder having good dispersibility with a tap density of 2 g / cm 3 or more and a BET specific surface area of 5 m 2 / g or less, by a photosensitive paste method, a printing method or a transfer method. The present inventors have found that a good conductor pattern can be obtained and have completed the present invention.

すなわち、本発明による球状銀粉は、ＢＥＴ比表面積（ｍ２／ｇ）に対する結晶子径Ｄｘ（ｎｍ）の比（Ｄｘ／ＢＥＴ）が５〜２００であることを特徴とする。この球状銀粉は、結晶子径が４０ｎｍ以下、平均粒径が５μｍ以下、タップ密度が２ｇ／ｃｍ３以上、ＢＥＴ比表面積が５ｍ２／ｇ以下であるのが好ましい。 That is, the spherical silver powder according to the present invention is characterized in that the ratio (Dx / BET) of the crystallite diameter Dx (nm) to the BET specific surface area (m 2 / g) is 5 to 200 . The spherical silver powder preferably has a crystallite size of 40 nm or less, an average particle size of 5 μm or less, a tap density of 2 g / cm 3 or more, and a BET specific surface area of 5 m 2 / g or less.

また、本発明による球状銀粉の製造方法は、銀イオンを含有する水性反応系に還元剤含有水溶液を添加して銀粒子を還元析出させることにより、上記の球状銀粉を製造することを特徴とする。この球状銀粉の製造方法において、銀粒子の還元析出前または還元析出後のスラリー状の反応系に分散剤を添加するのが好ましい。この分散剤は、脂肪酸、脂肪酸塩、界面活性剤、有機金属、キレート形成剤および保護コロイドからなる群から選ばれる１種以上の分散剤であるのが好ましい。還元剤含有水溶液に含まれる還元剤は、アスコルビン酸、アルカノールアミン、ヒドロキノン、ヒドラジンおよびホルマリンからなる群から選ばれる１種以上の還元剤であるのが好ましい。還元剤含有水溶液は、銀イオンを含有する水性反応系中の銀の含有量に対して１当量／分以上の速度で添加するのが好ましい。また、得られた球状銀粉に、粒子同士を機械的に衝突させる表面平滑化処理を施すのが好ましく、表面平滑化処理を施した後に、分級により銀の凝集体を除去するのが好ましい。   The method for producing spherical silver powder according to the present invention is characterized in that the above spherical silver powder is produced by adding a reducing agent-containing aqueous solution to an aqueous reaction system containing silver ions to reduce and precipitate silver particles. . In this method for producing spherical silver powder, it is preferable to add a dispersant to the slurry-like reaction system before or after the reduction precipitation of silver particles. This dispersant is preferably one or more dispersants selected from the group consisting of fatty acids, fatty acid salts, surfactants, organometallics, chelating agents, and protective colloids. The reducing agent contained in the reducing agent-containing aqueous solution is preferably one or more reducing agents selected from the group consisting of ascorbic acid, alkanolamine, hydroquinone, hydrazine and formalin. The reducing agent-containing aqueous solution is preferably added at a rate of 1 equivalent / minute or more with respect to the silver content in the aqueous reaction system containing silver ions. The obtained spherical silver powder is preferably subjected to a surface smoothing treatment that causes particles to mechanically collide with each other. After the surface smoothing treatment, it is preferable to remove silver aggregates by classification.

本発明によれば、良好な分散性を有するとともに、ペーストに使用して６００℃以下の低温で焼成することにより導体を形成する場合にも良好な焼結性を得ることができる、球状銀粉を製造することができる。   According to the present invention, there is provided a spherical silver powder that has good dispersibility and can obtain good sinterability even when a conductor is formed by firing at a low temperature of 600 ° C. or lower when used in a paste. Can be manufactured.

本発明による球状銀粉の実施の形態では、ＢＥＴ比表面積（ｍ２／ｇ）に対する結晶子径Ｄｘ（ｎｍ）の比（Ｄｘ／ＢＥＴ）が５〜２００であり、好ましくは、結晶子径が４０ｎｍ以下、平均粒径が５μｍ以下である。このような銀粉は、ペーストに使用して６００℃以下の低温で焼成しても良好な焼結性を得ることができるため、形成された導体の抵抗値を低くすることができる。 In the embodiment of the spherical silver powder according to the present invention, the ratio (Dx / BET) of the crystallite diameter Dx (nm) to the BET specific surface area (m 2 / g) is 5 to 200 , preferably the crystallite diameter is 40 nm. Hereinafter, the average particle size is 5 μm or less. Since such silver powder can be used in a paste and can obtain good sinterability even when fired at a low temperature of 600 ° C. or lower, the resistance value of the formed conductor can be lowered.

また、銀粉の形状を球状にすることにより、感光性ペースト法に使用するのに適した銀粉になる。銀粉の形状が不定形やフレーク状の場合には、紫外線の乱反射や散乱が起こるために感光特性が劣り、不具合が生じるが、銀粉の形状が球状であれば、印刷法や転写法に使用するのにも適している。   Moreover, it becomes silver powder suitable for using for the photosensitive paste method by making the shape of silver powder spherical. When the shape of the silver powder is irregular or flakes, the ultraviolet light diffuses or scatters, resulting in inferior photosensitivity and problems. However, if the silver powder has a spherical shape, it is used for printing and transfer methods. Also suitable for.

また、本発明による球状銀粉の実施の形態では、タップ密度が２ｇ／ｃｍ３以上、ＢＥＴ比表面積５ｍ２／ｇ以下であるのが好ましい。タップ密度が２ｇ／ｃｍ３より小さいと、銀粒子同士の凝集が激しく、上記のいずれの方法に使用した場合も、ファインライン化への対応が難しく、また、ＢＥＴ比表面積が５ｍ２／ｇより大きいと、ペーストの粘度が高過ぎて作業性に劣るからである。 In the embodiment of the spherical silver powder according to the present invention, it is preferable that the tap density is 2 g / cm 3 or more and the BET specific surface area is 5 m 2 / g or less. When the tap density is less than 2 g / cm 3 , the silver particles agglomerate strongly, and when used in any of the above methods, it is difficult to cope with fine lines, and the BET specific surface area is less than 5 m 2 / g. This is because if it is large, the viscosity of the paste is too high and the workability is poor.

本発明による球状銀粉の製造方法の実施の形態では、銀イオンを含有する水性反応系に還元剤含有水溶液を添加して銀粒子を還元析出させる。この銀粒子の還元析出前または還元析出後のスラリー状の反応系に分散剤を添加するのが好ましい。   In the embodiment of the method for producing spherical silver powder according to the present invention, a reducing agent-containing aqueous solution is added to an aqueous reaction system containing silver ions to reduce and precipitate silver particles. It is preferable to add a dispersant to the slurry-like reaction system before or after the reduction precipitation of the silver particles.

銀イオンを含有する水性反応系としては、硝酸銀、銀塩錯体または銀中間体を含有する水溶液またはスラリーを使用することができる。銀塩錯体は、アンモニア水、アンモニア塩、キレート化合物などの添加により生成することができる。また、銀中間体は、水酸化ナトリウム、塩化ナトリウム、炭酸ナトリウムなどの添加により生成することができる。これらの中で、銀粉が適当な粒径と球状の形状を有するようにするためには、硝酸銀水溶液にアンモニア水を添加して得られるアンミン錯体を使用するのが好ましい。アンミン錯体の配位数は２であるため、銀１モル当たりアンモニアを２モル以上添加する。   As an aqueous reaction system containing silver ions, an aqueous solution or slurry containing silver nitrate, a silver salt complex or a silver intermediate can be used. A silver salt complex can be produced by adding ammonia water, an ammonia salt, a chelate compound, or the like. The silver intermediate can be produced by adding sodium hydroxide, sodium chloride, sodium carbonate or the like. Among these, it is preferable to use an ammine complex obtained by adding aqueous ammonia to an aqueous silver nitrate solution so that the silver powder has an appropriate particle size and spherical shape. Since the coordination number of the ammine complex is 2, 2 moles or more of ammonia is added per mole of silver.

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、次亜りん酸ナトリウム、水素化ほう素ナトリウム、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使用することができる。これらの中で、アスコルビン酸、アルカノールアミン、ヒドロキノン、ヒドラジンおよびホルマリンからなる群から選ばれる１種以上を使用するのが好ましい。これらの還元剤を使用すれば、適当な結晶性と適当な粒径の銀粒子を得ることができる。   As the reducing agent, ascorbic acid, sulfite, alkanolamine, hydrogen peroxide solution, formic acid, ammonium formate, sodium formate, glyoxal, tartaric acid, sodium hypophosphite, sodium borohydride, hydrazine, hydrazine compound, hydroquinone, Pyrogallol, glucose, gallic acid, formalin, anhydrous sodium sulfite, Rongalite and the like can be used. Among these, it is preferable to use one or more selected from the group consisting of ascorbic acid, alkanolamine, hydroquinone, hydrazine and formalin. If these reducing agents are used, silver particles having an appropriate crystallinity and an appropriate particle size can be obtained.

また、還元剤の添加方法については、銀粉の凝集を防ぐために、１当量／分以上の速さで添加するのが好ましい。この理由は明確ではないが、還元剤を短時間で投入することで、銀粒子の還元析出が一挙に生じて、短時間で還元反応が終了し、発生した核同士の凝集が生じ難いため、分散性が向上すると考えられる。また、還元の際には、より短時間で反応が終了するように反応液を攪拌するのが好ましい。   Moreover, about the addition method of a reducing agent, in order to prevent aggregation of silver powder, it is preferable to add at a speed | rate of 1 equivalent / min or more. The reason for this is not clear, but by introducing the reducing agent in a short time, reduction precipitation of silver particles occurs at once, the reduction reaction is completed in a short time, and aggregation of the generated nuclei is difficult to occur, It is thought that dispersibility is improved. In the reduction, the reaction solution is preferably stirred so that the reaction is completed in a shorter time.

分散剤としては、脂肪酸、脂肪酸塩、界面活性剤、有機金属、キレート形成剤および保護コロイドからなる群から選ばれる１種以上を使用するのが好ましい。脂肪酸の例として、プロピオン酸、カプリル酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、アクリル酸、オレイン酸、リノール酸、アラキドン酸などを挙げることができる。脂肪酸塩の例として、リチウム、ナトリウム、カリウム、バリウム、マグネシウム、カルシウム、アルミニウム、鉄、コバルト、マンガン、鉛、亜鉛、スズ、ストロンチウム、ジルコニウム、銀、銅などの金属と脂肪酸が塩を形成したものを挙げることができる。界面活性剤の例として、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテルリン酸塩のような陰イオン界面活性剤、脂肪族４級アンモニウム塩のような陽イオン界面活性剤、イミダゾリニウムベタインのような両性界面活性剤、ポリオキシエチレンアルキルエーテル、ポリオキシエチレン脂肪酸エステルのような非イオン界面活性剤などを挙げることができる。有機金属の例として、アセチルアセトントリブトキシジルコニウム、クエン酸マグネシウム、ジエチル亜鉛、ジブチルスズオキサイド、ジメチル亜鉛、テトラ−ｎ−ブトキシジルコニウム、トリエチルインジウム、トリエチルガリウム、トリメチルインジイウム、トリメチルガリウム、モノブチルスズオキサイド、テトライソシアネートシラン、テトラメチルシラン、テトラメトキシシラン、ポリメトキシシロキサン、モノメチルトリイソシアネートシラン、シランカップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤などを挙げることができる。キレート形成剤の例として、イミダゾール、オキサゾール、チアゾール、セレナゾール、ピラゾール、イソオキサゾール、イソチアゾール、１Ｈ−１，２，３−トリアゾール、２Ｈ−１，２，３−トリアゾール、１Ｈ−１，２，４−トリアゾール、４Ｈ−１，２，４−トリアゾール、１，２，３−オキサジアゾール、１，２，４−オキサジアゾール、１，２，５−オキサジアゾール、１，３，４−オキサジアゾール、１，２，３−チアジアゾール、１，２，４−チアジアゾール、１，２，５−チアジアゾール、１，３，４−チアジアゾール、１Ｈ−１，２，３，４−テトラゾール、１，２，３，４−オキサトリアゾール、１，２，３，４−チアトリアゾール、２Ｈ−１，２，３，４−テトラゾール、１，２，３，５−オキサトリアゾール、１，２，３，５−チアトリアゾール、インダゾール、ベンゾイミダゾールおよびベンゾトリアゾールとこれらの塩、あるいは、シュウ酸、コハク酸、マロン酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸、マレイン酸、フマル酸、フタル酸、イソフタル酸、テレフタル酸、グリコール酸、乳酸、オキシ酪酸、グリセリン酸、酒石酸、リンゴ酸、タルトロン酸、ヒドロアクリル酸、マンデル酸、クエン酸、アスコルビン酸などを挙げることができる。保護コロイドの例として、ゼラチン、アルブミン、アラビアゴム、プロタルビン酸、リサルビン酸などを挙げることができる。   As the dispersant, it is preferable to use one or more selected from the group consisting of fatty acids, fatty acid salts, surfactants, organic metals, chelating agents, and protective colloids. Examples of fatty acids include propionic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, acrylic acid, oleic acid, linoleic acid, arachidonic acid and the like. Examples of fatty acid salts are salts of fatty acids and metals such as lithium, sodium, potassium, barium, magnesium, calcium, aluminum, iron, cobalt, manganese, lead, zinc, tin, strontium, zirconium, silver, and copper Can be mentioned. Examples of surfactants include anionic surfactants such as alkyl benzene sulfonates and polyoxyethylene alkyl ether phosphates, cationic surfactants such as aliphatic quaternary ammonium salts, and imidazolinium betaines. Nonionic surfactants such as amphoteric surfactants, polyoxyethylene alkyl ethers, and polyoxyethylene fatty acid esters. Examples of organometals include acetylacetone tributoxyzirconium, magnesium citrate, diethylzinc, dibutyltin oxide, dimethylzinc, tetra-n-butoxyzirconium, triethylindium, triethylgallium, trimethylindiium, trimethylgallium, monobutyltin oxide, tetra Examples include isocyanate silane, tetramethylsilane, tetramethoxysilane, polymethoxysiloxane, monomethyltriisocyanate silane, silane coupling agent, titanate coupling agent, aluminum coupling agent and the like. Examples of chelating agents include imidazole, oxazole, thiazole, selenazole, pyrazole, isoxazole, isothiazole, 1H-1,2,3-triazole, 2H-1,2,3-triazole, 1H-1,2,4. -Triazole, 4H-1,2,4-triazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxa Diazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1H-1,2,3,4-tetrazole, 1,2 , 3,4-oxatriazole, 1,2,3,4-thiatriazole, 2H-1,2,3,4-tetrazole, 1,2,3,5-oxatriazole, 1 2,3,5-thiatriazole, indazole, benzimidazole and benzotriazole and their salts, or oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Dodecanedioic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, glycolic acid, lactic acid, oxybutyric acid, glyceric acid, tartaric acid, malic acid, tartronic acid, hydroacrylic acid, mandelic acid, citric acid, ascorbic acid And so on. Examples of protective colloids include gelatin, albumin, gum arabic, protalbic acid, lysalbic acid and the like.

このようにして得られた球状銀粉に、粒子同士を機械的に衝突させる表面平滑化処理を施した後に、分級により銀の凝集体を除去して感光性ペーストに使用すると、感度が良好になり、得られるパターンの直線性も極めて良好になり、ファインパターン化への対応が可能になる。また、このようにして得られた銀粉は、印刷法に用いた場合に版抜け性に優れ、転写法に用いた場合に転写性に優れ、各種の方法への使用に適している。   The spherical silver powder thus obtained is subjected to a surface smoothing treatment that mechanically collides particles, and then the silver aggregates are removed by classification and used in a photosensitive paste, so that the sensitivity is improved. Also, the linearity of the obtained pattern becomes very good, and it becomes possible to cope with fine patterning. Further, the silver powder obtained in this way is excellent in plate slippage when used in a printing method and excellent in transferability when used in a transfer method, and is suitable for use in various methods.

以下、本発明による球状銀粉およびその製造方法の実施例について詳細に説明する。   Examples of the spherical silver powder and its production method according to the present invention will be described in detail below.

［実施例１］
銀イオンとして１２ｇ／Ｌの硝酸銀溶液３６００ｍＬに、工業用のアンモニア３００ｍＬを加えて、銀のアンミン錯体溶液を生成した。この銀のアンミン錯体溶液に水酸化ナトリウム６０ｇを加えてｐＨを調整した後、還元剤として工業用のホルマリン９０ｍＬを１０秒で加えた。その直後に、ステアリン酸エマルジョン０．５ｇを加えて銀のスラリーを得た。この銀のスラリーをろ過、水洗した後、乾燥して銀粉を得た。この銀粉に高速攪拌機で表面平滑化処理を施した後、分級により８μｍより大きい銀の凝集体を除去した。 [Example 1]
300 mL of industrial ammonia was added to 3600 mL of a 12 g / L silver nitrate solution as silver ions to form a silver ammine complex solution. After adjusting the pH by adding 60 g of sodium hydroxide to the silver ammine complex solution, 90 mL of industrial formalin was added as a reducing agent in 10 seconds. Immediately thereafter, 0.5 g of stearic acid emulsion was added to obtain a silver slurry. The silver slurry was filtered, washed with water, and dried to obtain silver powder. The silver powder was subjected to a surface smoothing treatment with a high-speed stirrer, and then silver aggregates larger than 8 μm were removed by classification.

このようにして得られた銀粉について、結晶子径を算出し、ＢＥＴ比表面積、タップ密度および平均粒径Ｄ５０を測定し、導電性を評価した。なお、本実施例および以下の実施例、比較例において得られた銀粉が球状銀粉であることを走査型電子顕微鏡（ＳＥＭ）により確認した。 The silver powder thus obtained, to calculate the crystallite size, BET specific surface area, tap density and mean particle diameter D 50 was measured to evaluate the conductivity. In addition, it confirmed with the scanning electron microscope (SEM) that the silver powder obtained in the present Example and the following Examples and Comparative Examples was spherical silver powder.

また、銀粉の結晶子径は、以下のＳｃｈｅｒｒｅｒの式によって求めた。
Ｄｈｋｌ＝Ｋλ／βｃｏｓθ
ここで、Ｄｈｋｌは結晶子径の大きさ（ｈｋｌに垂直な方向の結晶子の大きさ）（オングストローム）、λは測定Ｘ線の波長（オングストローム）（Ｃｕターゲット使用時１．５４０５オングストローム）、βは結晶子の大きさによる回折線の広がり（ｒａｄ）（半価幅を用いて表す）、θは回折角のブラッグ角（ｒａｄ）（入射角と反射角が等しいときの角度であり、ピークトップの角度を使用する）、ＫはＳｃｈｅｒｒｅｒ定数（Ｄやβの定義により異なり、βに半価幅を用いる場合にはＫ＝０．９４）である。なお、測定には粉末Ｘ線回折装置を使用し、計算には（２００）面のピークデータを使用した。 The crystallite diameter of the silver powder was determined by the following Scherrer equation.
Dhkl = Kλ / βcosθ
Here, Dhkl is the size of the crystallite (the size of the crystallite in the direction perpendicular to hkl) (angstrom), λ is the wavelength of the measured X-ray (angstrom) (1.5405 angstrom when using the Cu target), β Is the broadening of the diffraction line depending on the size of the crystallite (rad) (expressed using the half width), and θ is the Bragg angle (rad) of the diffraction angle (the angle when the incident angle and the reflection angle are equal, and the peak top) K is a Scherrer constant (depending on the definition of D or β, and K = 0.94 when using a half-value width for β). Note that a powder X-ray diffractometer was used for the measurement, and peak data on the (200) plane was used for the calculation.

また、導電性の評価については、６５重量部の銀粉と、１４重量部のアクリル樹脂（三菱レイヨン（株）製のＢＲ−１０５）と、２１重量部の有機溶剤（ジエチレングリコールモノエチルエーテルアセテート（試薬））と、１重量部のガラスフリット（日本電気硝子（株）製のＧＡ−８）とを計量し、３本ロールで混錬してペーストを作製した後、このペーストを市販のソーダガラス基板上に印刷し、５５０℃で１０分間焼成し、得られた焼結体の導電性を評価した。この抵抗値が３×１０−６Ω以下で安定している場合を良好とし、３×１０−６Ω以上または安定しない場合を良好でないとして評価した。 In addition, regarding the evaluation of conductivity, 65 parts by weight of silver powder, 14 parts by weight of acrylic resin (BR-105 manufactured by Mitsubishi Rayon Co., Ltd.), and 21 parts by weight of an organic solvent (diethylene glycol monoethyl ether acetate (reagent) )) And 1 part by weight of glass frit (GA-8 manufactured by Nippon Electric Glass Co., Ltd.), and kneaded with three rolls to prepare a paste. It was printed on and fired at 550 ° C. for 10 minutes, and the conductivity of the obtained sintered body was evaluated. The case where the resistance value was stable at 3 × 10 −6 Ω or less was evaluated as good, and the case where the resistance value was 3 × 10 −6 Ω or higher or not stable was evaluated as not good.

その結果、結晶子径は３２．４ｎｍ、ＢＥＴ比表面積は０．７５ｍ２／ｇ、タップ密度は５．０ｇ／ｃｍ３、平均粒径Ｄ５０は１．４μｍであり、導電性は良好であった。また、ＢＥＴ比表面積（ｍ２／ｇ）に対する結晶子径Ｄｘ（ｎｍ）の比（Ｄｘ／ＢＥＴ）は４３であった。 As a result, the crystallite diameter was 32.4 nm, the BET specific surface area was 0.75 m 2 / g, the tap density was 5.0 g / cm 3 , the average particle diameter D 50 was 1.4 μm, and the conductivity was good. It was. Further, the ratio (Dx / BET) of the crystallite diameter Dx (nm) to the BET specific surface area (m 2 / g) was 43.

［実施例２］
銀イオンとして１２ｇ／Ｌの硝酸銀溶液３６００ｍＬに、工業用のアンモニア１８０ｍＬを加えて、銀のアンミン錯体溶液を生成した。この銀のアンミン錯体溶液に水酸化ナトリウム７ｇを加えてｐＨを調整した後、還元剤として工業用のホルマリン１９２ｍＬを１０秒で加えた。その直後に、オレイン酸０．１ｇを加えて銀のスラリーを得た。この銀のスラリーをろ過、水洗した後、乾燥して銀粉を得た。この銀粉をフードミキサーで解砕した。 [Example 2]
180 mL of industrial ammonia was added to 3600 mL of a 12 g / L silver nitrate solution as silver ions to form a silver ammine complex solution. After adding sodium hydroxide 7g to this silver ammine complex solution and adjusting pH, 192 mL of industrial formalin was added in 10 seconds as a reducing agent. Immediately thereafter, 0.1 g of oleic acid was added to obtain a silver slurry. The silver slurry was filtered, washed with water, and dried to obtain silver powder. This silver powder was crushed with a food mixer.

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、結晶子径を算出し、ＢＥＴ比表面積、タップ密度および平均粒径Ｄ５０を測定し、導電性を評価した。その結果、結晶子径は２９．６ｎｍ、ＢＥＴ比表面積は０．４６ｍ２／ｇ、タップ密度は４．７ｇ／ｃｍ３、平均粒径Ｄ５０は２．１μｍであり、導電性は良好であった。また、ＢＥＴ比表面積（ｍ２／ｇ）に対する結晶子径Ｄｘ（ｎｍ）の比（Ｄｘ／ＢＥＴ）は６４であった。 The silver powder thus obtained, in the same manner as in Example 1, to calculate the crystallite size, BET specific surface area, tap density and mean particle diameter D 50 was measured to evaluate the conductivity. As a result, the crystallite diameter was 29.6 nm, the BET specific surface area was 0.46 m 2 / g, the tap density was 4.7 g / cm 3 , the average particle diameter D 50 was 2.1 μm, and the conductivity was good. It was. Moreover, the ratio (Dx / BET) of the crystallite diameter Dx (nm) to the BET specific surface area (m 2 / g) was 64.

［実施例３］
銀イオンとして１２ｇ／Ｌの硝酸銀溶液３６００ｍＬに、工業用のアンモニア１８０ｍＬを加えて、銀のアンミン錯体溶液を生成した。この銀のアンミン錯体溶液に水酸化ナトリウム１ｇを加えてｐＨ調整した後、還元剤として工業用のホルマリン１９２ｍＬを１５秒で加えた。その直後に、ステアリン酸０．１ｇを加えて銀のスラリーを得た。この銀のスラリーをろ過、水洗した後、乾燥して銀粉を得た。この銀粉に高速攪拌機で表面平滑化処理を施した後、分級により１１μｍより大きい銀の凝集体を除去した。 [Example 3]
180 mL of industrial ammonia was added to 3600 mL of a 12 g / L silver nitrate solution as silver ions to form a silver ammine complex solution. After adjusting the pH by adding 1 g of sodium hydroxide to the silver ammine complex solution, 192 mL of industrial formalin was added as a reducing agent in 15 seconds. Immediately thereafter, 0.1 g of stearic acid was added to obtain a silver slurry. The silver slurry was filtered, washed with water, and dried to obtain silver powder. The silver powder was subjected to a surface smoothing treatment with a high-speed stirrer, and then silver aggregates larger than 11 μm were removed by classification.

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、結晶子径を算出し、ＢＥＴ比表面積、タップ密度および平均粒径Ｄ５０を測定し、導電性を評価した。その結果、結晶子径は３３．３ｎｍ、ＢＥＴ比表面積は０．２８ｍ２／ｇ、タップ密度は５．４ｇ／ｃｍ３、平均粒径Ｄ５０は３．１μｍであり、導電性は良好であった。また、ＢＥＴ比表面積（ｍ２／ｇ）に対する結晶子径Ｄｘ（ｎｍ）の比（Ｄｘ／ＢＥＴ）は１１９であった。 The silver powder thus obtained, in the same manner as in Example 1, to calculate the crystallite size, BET specific surface area, tap density and mean particle diameter D 50 was measured to evaluate the conductivity. As a result, the crystallite diameter was 33.3 nm, the BET specific surface area was 0.28 m 2 / g, the tap density was 5.4 g / cm 3 , the average particle diameter D 50 was 3.1 μm, and the conductivity was good. It was. The ratio (Dx / BET) of the crystallite diameter Dx (nm) to the BET specific surface area (m 2 / g) was 119.

［実施例４］
銀イオンとして１２ｇ／Ｌの硝酸銀溶液３６００ｍＬに、工業用のアンモニア１５０ｍＬを加えて、銀のアンミン錯体溶液を生成した。この銀のアンミン錯体溶液に還元剤として工業用のヒドラジン１３ｍＬを２秒で加えた。その直後に、オレイン酸０．２ｇを加えて銀のスラリーを得た。この銀のスラリーをろ過、水洗した後、乾燥して銀粉を得た。この銀粉に高速攪拌機で表面平滑化処理を施した。 [Example 4]
150 mL of industrial ammonia was added to 3600 mL of a 12 g / L silver nitrate solution as silver ions to form a silver ammine complex solution. To this silver ammine complex solution, 13 mL of industrial hydrazine was added in 2 seconds as a reducing agent. Immediately thereafter, 0.2 g of oleic acid was added to obtain a silver slurry. The silver slurry was filtered, washed with water, and dried to obtain silver powder. The silver powder was subjected to a surface smoothing treatment with a high-speed stirrer.

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、結晶子径を算出し、ＢＥＴ比表面積、タップ密度および平均粒径Ｄ５０を測定し、導電性を評価した。その結果、結晶子径は３４．０ｎｍ、ＢＥＴ比表面積は０．８６ｍ２／ｇ、タップ密度は４．０ｇ／ｃｍ３、平均粒径Ｄ５０は１．７μｍであり、導電性は良好であった。また、ＢＥＴ比表面積（ｍ２／ｇ）に対する結晶子径Ｄｘ（ｎｍ）の比（Ｄｘ／ＢＥＴ）は３９であった。 The silver powder thus obtained, in the same manner as in Example 1, to calculate the crystallite size, BET specific surface area, tap density and mean particle diameter D 50 was measured to evaluate the conductivity. As a result, the crystallite diameter was 34.0 nm, the BET specific surface area was 0.86 m 2 / g, the tap density was 4.0 g / cm 3 , the average particle diameter D 50 was 1.7 μm, and the conductivity was good. It was. Moreover, the ratio (Dx / BET) of the crystallite diameter Dx (nm) to the BET specific surface area (m 2 / g) was 39.

［比較例１］
銀イオンとして６ｇ／Ｌの硝酸銀溶液３６００ｍＬに、工業用のアンモニア５０ｍＬを加えて、銀のアンミン錯体溶液を生成した。この銀のアンミン錯体溶液に還元剤として工業用の過酸化水素水６０ｍＬを１５秒で加えた。その直後に、ステアリン酸ソーダ０．１ｇを加えて銀のスラリーを得た。この銀のスラリーをろ過、水洗した後、乾燥して銀粉を得た。 [Comparative Example 1]
To 3600 mL of a 6 g / L silver nitrate solution as silver ions, 50 mL of industrial ammonia was added to produce a silver ammine complex solution. To this silver ammine complex solution, 60 mL of industrial hydrogen peroxide solution was added as a reducing agent in 15 seconds. Immediately thereafter, 0.1 g of sodium stearate was added to obtain a silver slurry. The silver slurry was filtered, washed with water, and dried 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、結晶子径を算出し、ＢＥＴ比表面積、タップ密度および平均粒径Ｄ５０を測定し、導電性を評価した。その結果、結晶子径は４７．８ｎｍ、ＢＥＴ比表面積は０．１５ｍ２／ｇ、タップ密度は５．０ｇ／ｃｍ３、平均粒径Ｄ５０は６．５μｍであり、導電性は良好ではなかった。また、ＢＥＴ比表面積（ｍ２／ｇ）に対する結晶子径Ｄｘ（ｎｍ）の比（Ｄｘ／ＢＥＴ）は３１８であった。 The silver powder thus obtained, in the same manner as in Example 1, to calculate the crystallite size, BET specific surface area, tap density and mean particle diameter D 50 was measured to evaluate the conductivity. As a result, the crystallite diameter was 47.8 nm, the BET specific surface area was 0.15 m 2 / g, the tap density was 5.0 g / cm 3 , the average particle diameter D 50 was 6.5 μm, and the conductivity was not good. It was. The ratio (Dx / BET) of the crystallite diameter Dx (nm) to the BET specific surface area (m 2 / g) was 318.

［比較例２］
市販のアトマイズ銀粉（５μｍ）について、実施例１と同様の方法により、結晶子径を算出し、ＢＥＴ比表面積、タップ密度および平均粒径Ｄ５０を測定し、導電性を評価した。その結果、結晶子径は４２．６ｎｍ、ＢＥＴ比表面積は０．２１ｍ２／ｇ、タップ密度は５．２ｇ／ｃｍ３、平均粒径Ｄ５０は５．３μｍであり、導電性は良好ではなかった。また、ＢＥＴ比表面積（ｍ２／ｇ）に対する結晶子径Ｄｘ（ｎｍ）の比（Ｄｘ／ＢＥＴ）は２０３であった。 [Comparative Example 2]
With respect to commercially available atomized silver powder (5 μm), the crystallite diameter was calculated by the same method as in Example 1, the BET specific surface area, the tap density, and the average particle diameter D 50 were measured, and the conductivity was evaluated. As a result, the crystallite diameter was 42.6 nm, the BET specific surface area was 0.21 m 2 / g, the tap density was 5.2 g / cm 3 , the average particle diameter D 50 was 5.3 μm, and the conductivity was not good. It was. The ratio (Dx / BET) of the crystallite diameter Dx (nm) to the BET specific surface area (m 2 / g) was 203.

これらの結果を表１に示す。なお、表１では、導電性の評価が良好な場合を○、良好でない場合を×で示している。   These results are shown in Table 1. In Table 1, the case where the conductivity evaluation is good is indicated by ◯, and the case where the conductivity is not good is indicated by ×.

Figure 2005330529
Figure 2005330529

Claims (10)

ＢＥＴ比表面積（ｍ２／ｇ）に対する結晶子径Ｄｘ（ｎｍ）の比（Ｄｘ／ＢＥＴ）が５〜２００であることを特徴とする、球状銀粉。 A spherical silver powder having a ratio (Dx / BET) of crystallite diameter Dx (nm) to BET specific surface area (m 2 / g) of 5 to 200 . 前記結晶子径が４０ｎｍ以下であり、平均粒径が５μｍ以下であることを特徴とする、請求項１に記載の球状銀粉。 The spherical silver powder according to claim 1, wherein the crystallite diameter is 40 nm or less and the average particle diameter is 5 μm or less. タップ密度が２ｇ／ｃｍ３以上であり、ＢＥＴ比表面積が５ｍ２／ｇ以下であることを特徴とする、請求項１または２に記載の球状銀粉。 The spherical silver powder according to claim 1 or 2, wherein a tap density is 2 g / cm 3 or more and a BET specific surface area is 5 m 2 / g or less. 銀イオンを含有する水性反応系に還元剤含有水溶液を添加して銀粒子を還元析出させることにより、請求項１乃至３のいずれかに記載の球状銀粉を製造することを特徴とする、球状銀粉の製造方法。 The spherical silver powder according to any one of claims 1 to 3, wherein the spherical silver powder according to any one of claims 1 to 3 is produced by adding a reducing agent-containing aqueous solution to an aqueous reaction system containing silver ions to reduce and precipitate silver particles. Manufacturing method. 前記銀粒子の還元析出前または還元析出後のスラリー状の反応系に分散剤を添加することを特徴とする、請求項４に記載の球状銀粉の製造方法。 The method for producing a spherical silver powder according to claim 4, wherein a dispersing agent is added to the slurry-like reaction system before or after the reduction precipitation of the silver particles. 前記分散剤が、脂肪酸、脂肪酸塩、界面活性剤、有機金属、キレート形成剤および保護コロイドからなる群から選ばれる１種以上の分散剤であることを特徴とする、請求項５に記載の球状銀粉の製造方法。 6. The spherical shape according to claim 5, wherein the dispersant is one or more dispersants selected from the group consisting of fatty acids, fatty acid salts, surfactants, organometallics, chelating agents, and protective colloids. A method for producing silver powder. 前記還元剤含有水溶液に含まれる還元剤が、アスコルビン酸、アルカノールアミン、ヒドロキノン、ヒドラジンおよびホルマリンからなる群から選ばれる１種以上の還元剤であることを特徴とする、請求項４乃至６のいずれかに記載の球状銀粉の製造方法。 The reducing agent contained in the reducing agent-containing aqueous solution is one or more reducing agents selected from the group consisting of ascorbic acid, alkanolamine, hydroquinone, hydrazine, and formalin. A method for producing the spherical silver powder according to claim 1. 前記還元剤含有水溶液を、前記銀イオンを含有する水性反応系中の銀の含有量に対して１当量／分以上の速度で添加することを特徴とする、請求項４乃至７のいずれかに記載の球状銀粉の製造方法。 The reducing agent-containing aqueous solution is added at a rate of 1 equivalent / min or more with respect to the silver content in the aqueous reaction system containing the silver ions. The manufacturing method of spherical silver powder of description. 前記球状銀粉に、粒子同士を機械的に衝突させる表面平滑化処理を施すことを特徴とする、請求項４乃至８のいずれかに記載の球状銀粉の製造方法。 The method for producing a spherical silver powder according to any one of claims 4 to 8, wherein the spherical silver powder is subjected to a surface smoothing treatment in which particles are mechanically collided with each other. 前記表面平滑化処理を施した後、分級により銀の凝集体を除去することを特徴とする、請求項９に記載の球状銀粉の製造方法。

The method for producing spherical silver powder according to claim 9, wherein after the surface smoothing treatment, silver aggregates are removed by classification.

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JP2021501267A (en) * 2017-10-31 2021-01-14 エルエスニッコカッパー インコーポレイテッドＬｓ−Ｎｉｋｋｏ Ｃｏｐｐｅｒ Ｉｎｃ． Method of manufacturing silver powder and conductive paste containing silver powder
JP7069311B2 (en) 2017-10-31 2022-05-17 エルエスニッコカッパー インコーポレイテッド How to make silver powder and conductive paste containing silver powder

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