JP2011202245A - Method of manufacturing copper alloy fine particle and copper alloy fine particle provided by the manufacturing method - Google Patents
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本発明は、銅−亜鉛合金微粒子の製造方法、及び該製造方法により得られる銅合金微粒子に関するものである。 The present invention relates to a method for producing copper-zinc alloy fine particles and copper alloy fine particles obtained by the production method.
ナノメートルサイズ（μｍ未満のサイズをいう。以下同じ）の金属微粒子は、比表面積が大きく、粒子径が小さくなるにつれて融点が除々に低下する性質を有し、新しい形態の物質として近年注目されつつある。このナノメートルサイズの金属微粒子は、粒子の種類によって、樹脂との複合化のための微粒子表面修飾、薄膜化技術・粒子の配列、機能素子向けの研究開発が行われ、回路配線、インターコネクター、触媒、電池電極、光機能素子、可視光ＬＥＤ素子などへの応用も検討されている。これらの金属微粒子の製造法として、気相合成法、液相合成法が知られている。 Nanometer-sized (referred to below μm size, hereinafter the same) metal fine particles have a large specific surface area, and have a property of gradually decreasing the melting point as the particle diameter decreases. is there. This nanometer-sized metal fine particle is subjected to fine particle surface modification for compounding with resin, thin film technology / particle arrangement, research and development for functional elements, depending on the type of particle, circuit wiring, interconnector, Applications to catalysts, battery electrodes, optical functional elements, visible light LED elements, and the like are also being studied. Gas phase synthesis methods and liquid phase synthesis methods are known as methods for producing these metal fine particles.
これらの微粒子の中でも銅−亜鉛合金微粒子は、バルク状態でも融点が低いので、ナノメートルサイズの該合金微粒子が商業的に得られれば電気・電子部品等に使用される焼結導電体として有望である。銅−亜鉛合金微粒子の気相合成法としては、例えば銅の塩化物及び合金化すべき元素の塩化物をそれぞれ加熱して蒸発させ、これらの蒸気を混合し水素ガスによって還元して平均粒子径が０．１〜１μｍの銅５０〜９５重量％、亜鉛５〜５０重量％からなる導電ペースト用銅合金粉が開示されている（特許文献１）。また液相合成法として、水アトマイズ法によって製造された体積平均径がいずれも３．０〜４．０μｍの、銅合金粉における亜鉛の含有量が０．０２〜１．２質量％の合金が開示されている（特許文献２）。又、還元溶液中の金属イオンを還元法により金属微粒子として析出させる際に、還元溶液中にハロゲンイオン又はアルカリ金属イオンと、有機分散剤とを散在させると、デンドライト化が防止できることが開示されている（特許文献３、特許文献４）。 Among these fine particles, the copper-zinc alloy fine particles have a low melting point even in the bulk state, so if nanometer-sized fine alloy particles can be obtained commercially, they are promising as sintered conductors used in electrical and electronic parts. is there. As a vapor phase synthesis method of copper-zinc alloy fine particles, for example, copper chloride and chloride of an element to be alloyed are heated and evaporated, these vapors are mixed, reduced by hydrogen gas, and the average particle size is reduced. A copper alloy powder for conductive paste made of 50 to 95% by weight of 0.1 to 1 μm copper and 5 to 50% by weight of zinc is disclosed (Patent Document 1). Further, as a liquid phase synthesis method, an alloy having a volume average diameter of 3.0 to 4.0 μm and a zinc content in a copper alloy powder of 0.02 to 1.2% by mass produced by a water atomization method. It is disclosed (Patent Document 2). Further, it is disclosed that when metal ions in a reducing solution are precipitated as metal fine particles by a reduction method, dendrites can be prevented by dispersing halogen ions or alkali metal ions and an organic dispersant in the reducing solution. (Patent Literature 3, Patent Literature 4).
しかし、特許文献１には、積層セラミックコンデンサ外部電極用銅−亜鉛合金粉をペーストにして高温（焼成完了温度：６３３〜７７０℃程度）で焼結して電気比抵抗（μΩ・ｃｍ）が評価されているが、焼成温度はいずれも極めて高温である。特許文献２には、回路導体形成用や積層セラミックコンデンサ外部電極用に使用される導電材ペーストとして、亜鉛の含有量を０．０２〜１．２質量％とし、かつリン０．００５〜０．０５質量％と共存させることにより、耐食耐酸化性を著しく向上できることが開示されている。特許文献３、４には、還元反応水溶液中の銅イオンを還元して、銅微粒子を析出させる際にハロゲンイオン又はアルカリ金属イオンと、有機分散剤とを存在させて、析出する銅微粒子のデンドライト状の凝集を防止しているが、銅−亜鉛からなる銅合金微粒子を析出させること、及び低温で焼結が可能となる微粒子分散溶液いついては記載されていない。電子部品や半導体などの実装接続に用いられるペーストやインクにおいて、多く用いられる金属粒子は、粒子サイズを小さくすると、低温における加熱でも粒子同士の相互焼結が起こり、金属的な導電性が得られるため、実用的にも金属微粒子が用いられるようになってきているが、より低温でのプロセスに適用するためには、粒子の融点が低くなるような合金化を行うことが必要になる。本発明は、電解還元を行うことにより、デンドライト化が抑制された球状でかつ粒子径がナノメータサイズの銅−亜鉛合金微粒子の製造方法、及びこれらの製造により得られる銅合金微粒子を提供することを目的とする。 However, Patent Document 1 evaluates electrical resistivity (μΩ · cm) by using a copper-zinc alloy powder for multilayer ceramic capacitor external electrode as a paste and sintering it at a high temperature (firing completion temperature: about 633 to 770 ° C.). However, all of the firing temperatures are extremely high. In Patent Document 2, as a conductive material paste used for forming a circuit conductor or a multilayer ceramic capacitor external electrode, the zinc content is 0.02 to 1.2 mass%, and phosphorus is 0.005 to 0.005. It is disclosed that the corrosion resistance and oxidation resistance can be remarkably improved by coexisting with 05% by mass. Patent Documents 3 and 4 describe that dendrites of copper fine particles deposited by reducing the copper ions in the reduction reaction aqueous solution and precipitating copper fine particles in the presence of halogen ions or alkali metal ions and an organic dispersant. However, there is no description of a fine particle dispersion solution that can precipitate copper alloy fine particles made of copper-zinc and that can be sintered at a low temperature. In pastes and inks used for mounting and connection of electronic parts and semiconductors, metal particles that are often used can reduce the particle size and cause mutual sintering of particles even when heated at low temperatures, resulting in metallic conductivity. For this reason, metal fine particles have been used practically, but in order to apply to a process at a lower temperature, it is necessary to perform alloying that lowers the melting point of the particles. The present invention provides a method for producing copper-zinc alloy fine particles having a spherical shape and a nanometer size with suppressed dendrite, and copper alloy fine particles obtained by the production thereof, by performing electrolytic reduction. Objective.
本発明者らは、液相において従来行われていた電解還元を行う際に、通常使用される光沢剤や光沢補助剤を用いることなく、銅−亜鉛合金微粒子が析出可能とする特定の成分である金属塩、有機分散剤、及び無機分散剤を電解還元反応水溶液に添加して、電解還元を行うとデンドライト化が抑制された、平均一次粒子径がナノメートルサイズの銅−亜鉛からなる銅合金微粒子が効率よく製造できることを見出し、本発明を完成するに至った。 The inventors of the present invention have a specific component that allows copper-zinc alloy fine particles to be deposited without using a normally used brightener or gloss auxiliary when performing electrolytic reduction conventionally performed in a liquid phase. A copper alloy composed of copper-zinc with an average primary particle size of nanometer size, in which dendriticization is suppressed by adding a certain metal salt, organic dispersant, and inorganic dispersant to the electrolytic reduction reaction aqueous solution and performing electrolytic reduction. The inventors have found that fine particles can be produced efficiently, and have completed the present invention.
即ち、本発明は、以下の〈１〉〜〈１１〉に記載する発明を要旨とする。
〈１〉電解還元反応による、銅−亜鉛からなる銅合金微粒子の製造方法であって、
（ｉ）少なくとも硫酸銅、硫酸亜鉛、錯化剤（ａ）、有機分散剤、及び無機分散剤を含む還元反応水溶液（還元反応水溶液１）、
(ii)少なくとも塩化第一銅、水溶性亜鉛化合物、錯化剤（ｂ）、有機分散剤、及び無機分散剤を含む還元反応水溶液（還元反応水溶液２）、
(iii)少なくとも酒石酸銅、酸化亜鉛、有機分散剤、及び無機分散剤を含む還元反応水溶液（還元反応水溶液３）、又は
(iv)少なくとも酢酸銅、酢酸亜鉛、有機分散剤、及び無機分散剤を含む還元反応水溶液（還元反応水溶液４）、
でｐＨが４．５〜１３である還元反応水溶液から、電解還元反応により銅−亜鉛からなる合金微粒子を析出させることを特徴とする、銅合金微粒子の製造方法（以下、第一の態様ということがある）。
〈２〉前記還元反応水溶液１における錯化剤（ａ）がグリセリン、トリエタノールアミン、エタノールアミン、シュウ酸ナトリウム、ピロリン酸カリウム、ピロリン酸ナトリウム、及びグルコヘプトン酸ナトリウムから選択される１種又は２種以上であることを特徴とする、前記〈１〉に記載の銅合金微粒子の製造方法。
〈３〉前記還元反応水溶液２における水溶性亜鉛化合物が塩化亜鉛又は硫酸亜鉛であり、錯化剤（ｂ）がチオ硫酸ナトリウムであることを特徴とする、前記〈１〉に記載の銅合金微粒子の製造方法。
〈４〉前記有機分散剤が水溶性高分子からなる有機分散剤であって、ポリエチレンイミン、ポリビニルピロリドン、ポリアクリル酸、カルボキシメチルセルロース、ポリアクリルアミド、ポリビニルアルコール、ポリエチレンオキシド、デンプン、及びゼラチンから選択される１種又は２種以上であることを特徴とする、前記〈１〉ないし〈３〉のいずれかに記載の銅合金微粒子の製造方法。
〈５〉前記還元反応水溶液中における無機分散剤の濃度が無機分散剤と銅原子及び亜鉛原子のモル比（無機分散剤／（銅＋亜鉛））で０．０１〜２０であることを特徴とする、前記〈１〉ないし〈４〉のいずれかに記載の銅合金微粒子の製造方法。
That is, the gist of the present invention is the invention described in the following <1> to <11>.
<1> A method for producing copper alloy fine particles comprising copper-zinc by electrolytic reduction reaction,
(I) Reduction reaction aqueous solution (reduction reaction aqueous solution 1) containing at least copper sulfate, zinc sulfate, complexing agent (a), organic dispersant, and inorganic dispersant,
(ii) A reduction reaction aqueous solution (reduction reaction aqueous solution 2) containing at least cuprous chloride, a water-soluble zinc compound, a complexing agent (b), an organic dispersant, and an inorganic dispersant,
(iii) Reduction reaction aqueous solution (reduction reaction aqueous solution 3) containing at least copper tartrate, zinc oxide, an organic dispersant, and an inorganic dispersant, or
(iv) a reduction reaction aqueous solution (reduction reaction aqueous solution 4) containing at least copper acetate, zinc acetate, an organic dispersant, and an inorganic dispersant;
A method for producing copper alloy fine particles (hereinafter referred to as a first aspect), characterized in that an alloy fine particle comprising copper-zinc is precipitated by electrolytic reduction reaction from a reduction reaction aqueous solution having a pH of 4.5 to 13. There).
<2> One or two complexing agents (a) in the reduction reaction aqueous solution 1 are selected from glycerin, triethanolamine, ethanolamine, sodium oxalate, potassium pyrophosphate, sodium pyrophosphate, and sodium glucoheptonate It is the above, The manufacturing method of the copper alloy fine particle as described in said <1>.
<3> The copper alloy fine particles according to <1>, wherein the water-soluble zinc compound in the aqueous reduction reaction solution 2 is zinc chloride or zinc sulfate, and the complexing agent (b) is sodium thiosulfate. Manufacturing method.
<4> The organic dispersant is an organic dispersant composed of a water-soluble polymer, and is selected from polyethyleneimine, polyvinylpyrrolidone, polyacrylic acid, carboxymethylcellulose, polyacrylamide, polyvinyl alcohol, polyethylene oxide, starch, and gelatin. The method for producing copper alloy fine particles according to any one of <1> to <3>, wherein the method is one or more types.
<5> The concentration of the inorganic dispersant in the reduction reaction aqueous solution is 0.01 to 20 in terms of a molar ratio of the inorganic dispersant to copper atoms and zinc atoms (inorganic dispersant / (copper + zinc)). The method for producing fine copper alloy particles according to any one of <1> to <4>.
〈６〉前記無機分散剤がハロゲンイオン、アルカリ金属イオン、及びアルカリ土類金属イオンから選択される１種又は２種以上であることを特徴とする、前記〈１〉ないし〈５〉のいずれかに記載の銅合金微粒子の製造方法。
〈７〉前記ハロゲンイオンの供給源が塩化水素、塩化カリウム、塩化ナトリウム、塩化アンモニウム、臭化水素、臭化カリウム、臭化ナトリウム、臭化アンモニウム、沃化水素、沃化カリウム、沃化ナトリウム、沃化アンモニウム、フッ化水素、フッ化カリウム、フッ化ナトリウム、及び弗化アンモニウムから選択される１種又は２種以上であり、
前記アルカリ金属イオンの供給源が水酸化ナトリウム、水酸化カリウム、硫酸ナトリウム、硫酸カリウム、酒石酸ナトリウム、酒石酸カリウム、酢酸ナトリウム、及び酢酸カリウムから選択される１種又は２種以上であり、
前記アルカリ土類金属イオンの供給源が臭化カルシウム、臭化バリウム、塩化カルシウム、塩化バリウム、沃化カルシウム、及び沃化バリウムから選択される１種又は２種以上であることを特徴とする、前記〈６〉に記載の銅合金微粒子の製造方法。
<6> Any of the above <1> to <5>, wherein the inorganic dispersant is one or more selected from halogen ions, alkali metal ions, and alkaline earth metal ions The manufacturing method of copper alloy fine particles as described in 2.
<7> The source of the halogen ion is hydrogen chloride, potassium chloride, sodium chloride, ammonium chloride, hydrogen bromide, potassium bromide, sodium bromide, ammonium bromide, hydrogen iodide, potassium iodide, sodium iodide, One or more selected from ammonium iodide, hydrogen fluoride, potassium fluoride, sodium fluoride, and ammonium fluoride,
The alkali metal ion source is one or more selected from sodium hydroxide, potassium hydroxide, sodium sulfate, potassium sulfate, sodium tartrate, potassium tartrate, sodium acetate, and potassium acetate;
The source of the alkaline earth metal ions is one or more selected from calcium bromide, barium bromide, calcium chloride, barium chloride, calcium iodide, and barium iodide, The method for producing copper alloy fine particles according to <6>.
〈８〉前記還元反応水溶液中における無機分散剤の濃度が無機分散剤と銅原子及び亜鉛原子の質量比（無機分散剤／（銅＋亜鉛））で０．０１〜２０であることを特徴とする、前記〈６〉に記載の銅合金微粒子の製造方法。
〈９〉前記還元反応水溶液中の銅原子濃度が０．０１〜４モル／リットルであり、亜鉛原子濃度が前記銅原子濃度の０．０１〜１モル倍であることを特徴とする、前記〈１〉ないし〈８〉のいずれかに記載の銅合金微粒子の製造方法。
〈１０〉前記還元反応水溶液中に設けられたアノード（陽極）とカソード（陰極）間に電圧を印加して還元反応を行うことによりカソード表面付近に銅−亜鉛からなる銅合金微粒子を析出させることを特徴とする、前記〈１〉ないし〈９〉のいずれかに記載の銅合金微粒子の製造方法。
〈１１〉前記〈１〉ないし〈１０〉のいずれかに記載の還元反応により製造された、銅−亜鉛からなる銅合金微粒子の平均一次粒子径が１〜８０ｎｍの範囲であり、かつ平均アスペクト比が１０以下である銅合金微粒子（以下、第二の態様ということがある）。
<8> The concentration of the inorganic dispersant in the reduction reaction aqueous solution is 0.01 to 20 in terms of a mass ratio of the inorganic dispersant to the copper atom and the zinc atom (inorganic dispersant / (copper + zinc)). The manufacturing method of the copper alloy fine particles according to <6>.
<9> The copper atom concentration in the reduction reaction aqueous solution is 0.01 to 4 mol / liter, and the zinc atom concentration is 0.01 to 1 mol times the copper atom concentration. 1> thru | or the manufacturing method of the copper alloy fine particle in any one of <8>.
<10> Depositing copper alloy fine particles composed of copper-zinc in the vicinity of the cathode surface by applying a voltage between the anode (anode) and the cathode (cathode) provided in the aqueous solution of the reduction reaction to perform a reduction reaction. The method for producing fine copper alloy particles according to any one of <1> to <9>.
<11> The average primary particle diameter of copper alloy fine particles made of copper-zinc produced by the reduction reaction according to any one of <1> to <10> is in the range of 1 to 80 nm, and the average aspect ratio Copper alloy fine particles having an A of 10 or less (hereinafter sometimes referred to as a second embodiment).
本発明の還元反応水溶液に、特定の銅と亜鉛の金属塩（又は錯体）を組み合わせた還元反応水溶液とし、且つ有機分散剤を添加することにより、電解還元反応で析出する金属微粒子を平均一次粒子径がナノメータサイズの合金微粒子として析出させる可能となる。又、該還元反応水溶液に無機分散剤が添加されていることにより、合金微粒子が析出する際にデンドライト状の凝集が抑制された銅−亜鉛からなる銅合金微粒子が形成される。 A reduction reaction aqueous solution in which a specific copper and zinc metal salt (or complex) is combined with the reduction reaction aqueous solution of the present invention, and by adding an organic dispersant, the fine metal particles precipitated in the electrolytic reduction reaction are average primary particles. It is possible to deposit as nanometer-sized alloy fine particles. In addition, by adding an inorganic dispersant to the reduction reaction aqueous solution, copper alloy fine particles composed of copper-zinc in which dendritic aggregation is suppressed when alloy fine particles are precipitated are formed.
以下、本発明について詳述する。
〔１〕銅合金微粒子の製造方法
本発明の「銅合金微粒子の製造方法」は、電解還元反応による、銅−亜鉛からなる銅合金微粒子の製造方法であって、
（ｉ）少なくとも硫酸銅、硫酸亜鉛、錯化剤（ａ）、有機分散剤、及び無機分散剤を含む還元反応水溶液（還元反応水溶液１）、
(ii)少なくとも塩化第一銅、水溶性亜鉛化合物、錯化剤（ｂ）、有機分散剤、及び無機分散剤を含む還元反応水溶液（還元反応水溶液２）、
(iii)少なくとも酒石酸銅、酸化亜鉛、有機分散剤、及び無機分散剤を含む還元反応水溶液（還元反応水溶液３）、又は
(iv)少なくとも酢酸銅、酢酸亜鉛、有機分散剤、及び無機分散剤を含む還元反応水溶液（還元反応水溶液４）、
でｐＨが４．５〜１３である還元反応水溶液から、電解還元反応により銅−亜鉛からなる銅合金微粒子を析出させることを特徴とする。
Hereinafter, the present invention will be described in detail.
[1] Method for producing copper alloy fine particles “The method for producing copper alloy fine particles” of the present invention is a method for producing copper alloy fine particles comprising copper-zinc by electrolytic reduction reaction,
(I) Reduction reaction aqueous solution (reduction reaction aqueous solution 1) containing at least copper sulfate, zinc sulfate, complexing agent (a), organic dispersant, and inorganic dispersant,
(ii) A reduction reaction aqueous solution (reduction reaction aqueous solution 2) containing at least cuprous chloride, a water-soluble zinc compound, a complexing agent (b), an organic dispersant, and an inorganic dispersant,
(iii) Reduction reaction aqueous solution (reduction reaction aqueous solution 3) containing at least copper tartrate, zinc oxide, an organic dispersant, and an inorganic dispersant, or
(iv) a reduction reaction aqueous solution (reduction reaction aqueous solution 4) containing at least copper acetate, zinc acetate, an organic dispersant, and an inorganic dispersant;
Then, copper alloy fine particles made of copper-zinc are deposited from an aqueous reduction reaction solution having a pH of 4.5 to 13 by electrolytic reduction reaction.
以下に本発明の還元反応水溶液１〜４について記載する。
（１）有機分散剤
本発明における有機分散剤の作用のメカニズムは定かではないが、還元反応水溶液中において還元反応による銅合金微粒子の結晶核の生成を助長し、更に生成した結晶を分散させる作用を有するものと推定される。有機分散剤として、水溶性の高分子化合物を使用することができる、このような水溶性の高分子化合物としてポリエチレンイミン、ポリビニルピロリドン等のアミン系の高分子；ポリアクリル酸、カルボキシメチルセルロース等のカルボン酸基を有する炭化水素系高分子；ポリアクリルアミド等のアクリルアミド；ポリビニルアルコール、ポリエチレンオキシド、更にはデンプン、ゼラチン等が例示できる。
The reduction reaction aqueous solutions 1 to 4 of the present invention are described below.
(1) Organic dispersant The mechanism of the action of the organic dispersant in the present invention is not clear, but it promotes the formation of crystal nuclei of the copper alloy fine particles by the reduction reaction in the aqueous reduction reaction solution, and further disperses the generated crystals. It is estimated that A water-soluble polymer compound can be used as the organic dispersant. As such a water-soluble polymer compound, an amine polymer such as polyethyleneimine or polyvinylpyrrolidone; a carboxyl such as polyacrylic acid or carboxymethylcellulose can be used. Examples include hydrocarbon polymers having acid groups; acrylamides such as polyacrylamide; polyvinyl alcohol, polyethylene oxide, and starch and gelatin.
上記例示した水溶性の高分子化合物の具体例として、ポリエチレンイミン（平均分子量：１００〜１００，０００）、ポリビニルピロリドン（平均分子量：１０００〜５００、０００）、カルボキシメチルセルロース（ヒドロキシル基Ｎａ塩のカルボキシメチル基への置換度：０．４以上、平均分子量：１０００〜１００，０００）、ポリアクリル酸（平均分子量：１０００〜１００００）、ポリアクリルアミド（平均分子量：１００〜６，０００，０００）、ポリビニルアルコール（分子量：１０００〜１００，０００）、ポリエチレングリコール（平均分子量：１００〜５０，０００）、ポリエチレンオキシド（平均分子量：５０，０００〜９００，０００）、ゼラチン（平均分子量：６１，０００〜６７，０００）、水溶性のデンプン等が挙げられる。 Specific examples of the water-soluble polymer compounds exemplified above include polyethyleneimine (average molecular weight: 100 to 100,000), polyvinylpyrrolidone (average molecular weight: 1000 to 500,000), carboxymethyl cellulose (carboxymethyl of hydroxyl group Na salt) Substitution degree: 0.4 or more, average molecular weight: 1000 to 100,000), polyacrylic acid (average molecular weight: 1000 to 10,000), polyacrylamide (average molecular weight: 100 to 6,000,000), polyvinyl alcohol (Molecular weight: 1000 to 100,000), polyethylene glycol (average molecular weight: 100 to 50,000), polyethylene oxide (average molecular weight: 50,000 to 900,000), gelatin (average molecular weight: 61,000 to 67,000) ), Water-soluble starch And the like.
上記かっこ内に示す範囲にある平均分子量の高分子化合物は水溶性を有するので、本発明の有機分散剤として好適に使用できる。尚、これらの有機分散剤は、２種以上を混合して使用することもできる。前記還元反応水溶液中における有機分散剤の濃度は、有機分散剤と、銅原子及び亜鉛原子の質量比（有機分散剤／（銅＋亜鉛））で０．０１〜３０が好ましく、０．５〜１０がより好ましい。該比が前記０．０１未満では還元反応が著しく遅くなり、前記３０を超えると添加効果がなくなるおそれがある。 Since the polymer compound having an average molecular weight in the range shown in the parentheses is water-soluble, it can be suitably used as the organic dispersant of the present invention. In addition, these organic dispersing agents can also be used in mixture of 2 or more types. The concentration of the organic dispersant in the reduction reaction aqueous solution is preferably 0.01 to 30, preferably 0.5 to 0.5 by mass ratio of the organic dispersant and the copper atom and the zinc atom (organic dispersant / (copper + zinc)). 10 is more preferable. When the ratio is less than 0.01, the reduction reaction is remarkably slow, and when it exceeds 30, the effect of addition may be lost.
（２）無機分散剤
本発明における無機分散剤は、ハロゲンイオン、アルカリ金属イオン、及びアルカリ土類金属イオンから選択される１種又は２種以上であることが望ましい。本発明における無機分散剤の作用についてのメカニズムは明らかではないが、還元反応水溶液中に好適な濃度範囲で存在していると、銅合金の結晶核の生成を促進すると共に、還元反応により銅合金微粒子の結晶が結晶核から成長する際にデンドライト状の凝集を抑制して、結晶が略球状に成長していくのを助長しているものと推定される。一方、還元反応水溶液中に無機分散剤を存在させずに、銅イオン、亜鉛イオン、及び有機分散剤が溶解している水溶液から電解還元により銅−亜鉛合金微粒子を析出させた場合には、析出した結晶中に原料の銅化合物と亜鉛化合物の混入、及びこれらの化合物の結晶面を介して結晶がデンドライト状に成長していく。特許文献４において無機分散剤は、還元反応水溶液中でデンドライト状の凝集を抑制して、粒子が略球状に成長するのを助長していることが電子顕微鏡等で確認されている。
(2) Inorganic dispersant The inorganic dispersant in the present invention is preferably one or more selected from halogen ions, alkali metal ions, and alkaline earth metal ions. The mechanism of the action of the inorganic dispersant in the present invention is not clear, but when it exists in a suitable concentration range in the reduction reaction aqueous solution, the formation of crystal nuclei of the copper alloy is promoted and the copper alloy is reduced by the reduction reaction. It is presumed that dendritic agglomeration is suppressed when the fine crystal grows from the crystal nucleus, and that the crystal grows into a substantially spherical shape. On the other hand, when copper-zinc alloy fine particles are precipitated by electrolytic reduction from an aqueous solution in which copper ions, zinc ions, and organic dispersants are dissolved without the presence of an inorganic dispersant in the reduction reaction aqueous solution, precipitation occurs. The crystal grows in a dendrite shape through mixing of the raw material copper compound and zinc compound and the crystal planes of these compounds. In Patent Document 4, it has been confirmed with an electron microscope or the like that the inorganic dispersant suppresses dendrite-like aggregation in the reduction reaction aqueous solution and promotes the growth of particles into a substantially spherical shape.
前記ハロゲンイオンの供給源として、塩化水素、塩化カリウム、塩化ナトリウム、塩化アンモニウム、臭化水素、臭化カリウム、臭化ナトリウム、臭化アンモニウム、沃化水素、沃化カリウム、沃化ナトリウム、沃化アンモニウム、フッ化水素、フッ化カリウム、フッ化ナトリウム、及び弗化アンモニウム等から選択される１種又は２種以上が例示でき、前記アルカリ金属イオンの供給源として、水酸化ナトリウム、水酸化カリウム、硫酸ナトリウム、硫酸カリウム、酒石酸ナトリウム、酒石酸カリウム、酢酸ナトリウム、及び酢酸カリウム等から選択される１種又は２種以上が例示でき、前記アルカリ土類金属イオンの供給源として、臭化カルシウム、臭化バリウム、塩化カルシウム、塩化バリウム、沃化カルシウム、及び沃化バリウムから選択される１種又は２種以上が例示できる。銅−亜鉛合金微粒子を電解析出させる場合、前記還元反応水溶液中における無機分散剤と、銅原子及び亜鉛原子のモル比（［無機分散剤／（銅＋亜鉛）］）は好ましくは０．０１〜２０、より好ましくは０．０５〜１０である。該モル比が前記２０を超えると還元反応が遅くなり、一方前記０．０１未満では、添加効果が十分に発揮されない。 As the source of halogen ions, hydrogen chloride, potassium chloride, sodium chloride, ammonium chloride, hydrogen bromide, potassium bromide, sodium bromide, ammonium bromide, hydrogen iodide, potassium iodide, sodium iodide, iodide Examples thereof include one or more selected from ammonium, hydrogen fluoride, potassium fluoride, sodium fluoride, ammonium fluoride, and the like. Examples of the alkali metal ion supply source include sodium hydroxide, potassium hydroxide, Examples thereof include one or more selected from sodium sulfate, potassium sulfate, sodium tartrate, potassium tartrate, sodium acetate, and potassium acetate. Examples of the alkaline earth metal ion source include calcium bromide, bromide Barium, calcium chloride, barium chloride, calcium iodide and barium iodide One or more kinds selected can be exemplified. When electrolytically depositing copper-zinc alloy fine particles, the molar ratio of the inorganic dispersant to the copper atom and zinc atom ([inorganic dispersant / (copper + zinc)]) in the reduction reaction aqueous solution is preferably 0.01. -20, more preferably 0.05-10. When the molar ratio exceeds 20, the reduction reaction becomes slow. On the other hand, when the molar ratio is less than 0.01, the effect of addition is not sufficiently exhibited.
（３）還元反応水溶液中の金属塩
（イ）還元反応水溶液１
還元反応水溶液１は、少なくとも硫酸銅、硫酸亜鉛、錯化剤（ａ）、有機分散剤、及び無機分散剤を含む還元反応水溶液である。還元反応水溶液中における硫酸銅の濃度は、０．０１〜４．０モル／リットルが好ましい。該濃度が０．０１モル／リットル未満では、銅−亜鉛合金微粒子の生成量が低減し反応相からの銅−亜鉛合金微粒子の収率が低下するという不都合を生じ、一方、４．０モル／リットルを超えると生成される粒子間での粗大な凝集がおこるおそれがある。よリ好ましい硫酸銅の濃度は、０．０５〜０．５モル／リットルである。硫酸亜鉛の濃度は、前記硫酸銅の濃度の０．０１〜１モル倍（モル倍はモル濃度の比を示す。以下同じ。）が好ましく、０．１〜０．５モル倍がより好ましい。該濃度が０．０１モル倍未満では、還元される亜鉛量が低下するおそれがあり、一方、１モル倍を超えると銅と亜鉛の金属間化合物からなる微粒子を析出するおそれがある。錯化剤（ａ）は、グリセリン、トリエタノールアミン、エタノールアミン、シュウ酸ナトリウム、ピロリン酸カリウム、ピロリン酸ナトリウム、及びグルコヘプトン酸ナトリウムから選択される１種又は２種以上が好ましい。錯化剤（ａ）の使用量は、前記硫酸銅の濃度の２〜６０モル倍が好ましく、５〜３０モル倍がより好ましい。該濃度が２モル倍未満では、銅と亜鉛の共析が困難となるおそれがあり、一方、６０モル倍を超えると金属の還元反応が遅くなるおそれがある。
(3) Metal salt in reduction aqueous solution (a) Reduction reaction aqueous solution 1
The reduction reaction aqueous solution 1 is a reduction reaction aqueous solution containing at least copper sulfate, zinc sulfate, a complexing agent (a), an organic dispersant, and an inorganic dispersant. The concentration of copper sulfate in the reduction reaction aqueous solution is preferably 0.01 to 4.0 mol / liter. When the concentration is less than 0.01 mol / liter, the production amount of copper-zinc alloy fine particles is reduced, resulting in a disadvantage that the yield of copper-zinc alloy fine particles from the reaction phase is lowered, while 4.0 mol / liter If it exceeds 1 liter, coarse agglomeration may occur between the produced particles. A more preferable concentration of copper sulfate is 0.05 to 0.5 mol / liter. The concentration of zinc sulfate is preferably 0.01 to 1 mol times the molar concentration of copper sulfate (mole times indicate a molar concentration ratio; the same shall apply hereinafter), and more preferably 0.1 to 0.5 mol times. If the concentration is less than 0.01 mol times, the amount of zinc to be reduced may be reduced, whereas if it exceeds 1 mol times, fine particles composed of an intermetallic compound of copper and zinc may be precipitated. The complexing agent (a) is preferably one or more selected from glycerin, triethanolamine, ethanolamine, sodium oxalate, potassium pyrophosphate, sodium pyrophosphate, and sodium glucoheptonate. The amount of the complexing agent (a) used is preferably 2 to 60 mol times, more preferably 5 to 30 mol times the concentration of the copper sulfate. If the concentration is less than 2 mol times, the eutectoid of copper and zinc may be difficult. On the other hand, if it exceeds 60 mol times, the metal reduction reaction may be delayed.
（ロ）還元反応水溶液２
還元反応水溶液２は、少なくとも塩化第一銅、水溶性亜鉛化合物、錯化剤（ｂ）、有機分散剤、及び無機分散剤を含む還元反応水溶液である。還元反応水溶液中における塩化第一銅の濃度は、０．０１〜４．０モル／リットルが好ましい。該濃度が０．０１モル／リットル未満では、銅−亜鉛合金微粒子の生成量が低減し反応相からの銅−亜鉛合金微粒子の収率が低下するという不都合を生じ、一方、４．０モル／リットルを超えると生成される粒子間での粗大な凝集がおこるおそれがある。より好ましい塩化第一銅の濃度は、０．０５〜０．５モル／リットルである。水溶性亜鉛化合物としては、塩化亜鉛又は硫酸亜鉛が好ましく、錯化剤（ｂ）はチオ硫酸ナトリウムが好ましい。好ましい水溶性亜鉛化合物の濃度は、前記塩化第一銅の濃度の０．０１〜１モル倍が好ましく、０．１〜０．５モル倍がより好ましい。該濃度が０．０１モル倍未満では、還元される亜鉛量が低下するおそれがあり、一方、１モル倍を超えると銅と亜鉛の金属間化合物からなる微粒子が析出するおっそれがある。錯化剤（ｂ）の使用量は、前記塩化第一銅の濃度の５〜３０モル倍が好ましく、７〜１０モル倍がより好ましい。該濃度が５モル倍未満では、銅と亜鉛の共析が困難となるおそれがあり、一方、３０モル倍を超えると金属の還元反応が遅くなるおそれがある。
(B) Reduction reaction aqueous solution 2
The reduction reaction aqueous solution 2 is a reduction reaction aqueous solution containing at least cuprous chloride, a water-soluble zinc compound, a complexing agent (b), an organic dispersant, and an inorganic dispersant. The concentration of cuprous chloride in the reduction reaction aqueous solution is preferably 0.01 to 4.0 mol / liter. When the concentration is less than 0.01 mol / liter, the production amount of copper-zinc alloy fine particles is reduced, resulting in a disadvantage that the yield of copper-zinc alloy fine particles from the reaction phase is lowered, while 4.0 mol / liter If it exceeds 1 liter, coarse agglomeration may occur between the produced particles. The concentration of cuprous chloride is more preferably 0.05 to 0.5 mol / liter. The water-soluble zinc compound is preferably zinc chloride or zinc sulfate, and the complexing agent (b) is preferably sodium thiosulfate. A preferable concentration of the water-soluble zinc compound is preferably 0.01 to 1 mol times, more preferably 0.1 to 0.5 mol times the concentration of the cuprous chloride. If the concentration is less than 0.01 mol times, the amount of zinc to be reduced may be reduced. On the other hand, if it exceeds 1 mol times, fine particles composed of an intermetallic compound of copper and zinc may be deposited. The amount of the complexing agent (b) used is preferably 5 to 30 mol times, more preferably 7 to 10 mol times the concentration of the cuprous chloride. If the concentration is less than 5 mol times, the eutectoid of copper and zinc may be difficult, whereas if it exceeds 30 mol times, the reduction reaction of the metal may be delayed.
（ハ）還元反応水溶液３
還元反応水溶液３は、少なくとも酒石酸銅、酸化亜鉛、有機分散剤、及び無機分散剤を含む還元反応水溶液である。この還元反応水溶液３において、酒石酸銅は錯イオンを形成しているので新に錯化剤の添加は不要である。還元反応水溶液中における酒石酸銅の濃度は、０．０１〜４．０モル／リットルが好ましい。該濃度が０．０１モル／リットル未満では、銅−亜鉛合金微粒子の生成量が低減し反応相からの銅−亜鉛合金微粒子の収率が低下するという不都合を生じ、一方、４．０モル／リットルを超えると生成される粒子間での粗大な凝集がおこるおそれがある。より好ましい酒石酸銅の濃度は、０．０５〜０．５モル／リットルである。好ましい酸化亜鉛の濃度は、前記酒石酸銅の濃度の０．０１〜１モル倍が好ましく、０．１〜０．５モル倍がより好ましい。該濃度が０．０１モル倍未満では、還元される亜鉛量が低下するおそれがあり、一方、１モル倍を超えると銅と亜鉛の金属間化合物からなる微粒子を析出するおそれがある。
(C) Reduction reaction aqueous solution 3
The reduction reaction aqueous solution 3 is a reduction reaction aqueous solution containing at least copper tartrate, zinc oxide, an organic dispersant, and an inorganic dispersant. In this reduction reaction aqueous solution 3, copper tartrate forms complex ions, so that it is not necessary to newly add a complexing agent. The concentration of copper tartrate in the reduction reaction aqueous solution is preferably 0.01 to 4.0 mol / liter. When the concentration is less than 0.01 mol / liter, the production amount of copper-zinc alloy fine particles is reduced, resulting in a disadvantage that the yield of copper-zinc alloy fine particles from the reaction phase is lowered, while 4.0 mol / liter If it exceeds 1 liter, coarse agglomeration may occur between the produced particles. A more preferable concentration of copper tartrate is 0.05 to 0.5 mol / liter. The preferable zinc oxide concentration is preferably 0.01 to 1 mol times, more preferably 0.1 to 0.5 mol times the concentration of the copper tartrate. If the concentration is less than 0.01 mol times, the amount of zinc to be reduced may be reduced, whereas if it exceeds 1 mol times, fine particles composed of an intermetallic compound of copper and zinc may be precipitated.
（ニ）還元反応水溶液４
還元反応水溶液４は、少なくとも酢酸銅、酢酸亜鉛、有機分散剤、及び無機分散剤を含む還元反応水溶液である。還元反応水溶液中における酢酸銅の濃度は、０．０１〜４．０モル／リットルが好ましい。該濃度が０．０１モル／リットル未満では、銅−亜鉛合金微粒子の生成量が低減し反応相からの銅−亜鉛合金微粒子の収率が低下するという不都合を生じ、一方、４．０モル／リットルを超えると生成される粒子間での粗大な凝集がおこるおそれがある。よリ好ましい酢酸銅の濃度は、０．０５〜０．５モル／リットルである。好ましい酢酸亜鉛の濃度は、前記酢酸銅の濃度の０．０１〜１モル倍が好ましく、０．０１〜０．５モル倍がより好ましい。該濃度が０．０１モル倍未満では、還元される亜鉛量が低下するおそれがあり、一方、１モル倍を超えると銅と亜鉛の金属間化合物からなる微粒子を析出するおそれがある。
(D) Reduction reaction aqueous solution 4
The reduction reaction aqueous solution 4 is a reduction reaction aqueous solution containing at least copper acetate, zinc acetate, an organic dispersant, and an inorganic dispersant. The concentration of copper acetate in the reduction reaction aqueous solution is preferably 0.01 to 4.0 mol / liter. When the concentration is less than 0.01 mol / liter, the production amount of copper-zinc alloy fine particles is reduced, resulting in a disadvantage that the yield of copper-zinc alloy fine particles from the reaction phase is lowered, while 4.0 mol / liter If it exceeds 1 liter, coarse agglomeration may occur between the produced particles. A more preferable copper acetate concentration is 0.05 to 0.5 mol / liter. The preferable concentration of zinc acetate is preferably 0.01 to 1 mol times, more preferably 0.01 to 0.5 mol times the concentration of copper acetate. If the concentration is less than 0.01 mol times, the amount of zinc to be reduced may be reduced, whereas if it exceeds 1 mol times, fine particles composed of an intermetallic compound of copper and zinc may be precipitated.
（４）電解還元について
（イ）電極（陽極と陰極）材料等
陰極は、白金、カーボン等が好ましく、陽極は、銅、銅−亜鉛合金、カーボン、白金等が好ましい。尚、陰極表面付近に析出した粒子を脱離、回収するために陰極に超音波振動等の揺動を与えることが可能な構造とすることもできる。
（ロ）電解還元反応
電解還元反応のｐＨは４．５〜１３の範囲に調整する。ｐＨが４．５未満だと錯化剤の効果が低下するなどの悪影響を与える場合があり、ｐＨが１３を超えると電流密度範囲が狭くなり、電流効率が低下する場合がある。尚、ｐＨの調整は次亜リン酸アルカリ金属塩等の添加により行うことができる。電流密度は好ましくは０．３〜２０Ａ／ｄｍ２、より好ましくは５〜１５Ａ／ｄｍ２程度である。還元温度は、０〜７０℃が好ましく、高温になるほど還元反応速度は速くなり、低温になるほど析出する粒子の粒径は小さくなる傾向がある。
(4) Electroreduction (a) Electrode (Anode and Cathode) Materials, etc. The cathode is preferably platinum, carbon or the like, and the anode is preferably copper, copper-zinc alloy, carbon, platinum or the like. In addition, in order to desorb and collect particles deposited in the vicinity of the cathode surface, it is possible to adopt a structure capable of imparting oscillation such as ultrasonic vibration to the cathode.
(B) Electrolytic reduction reaction The pH of the electrolytic reduction reaction is adjusted to a range of 4.5-13. If the pH is less than 4.5, the effect of the complexing agent may be adversely affected. If the pH exceeds 13, the current density range may be narrowed, and the current efficiency may be reduced. The pH can be adjusted by adding an alkali metal hypophosphite or the like. The current density is preferably about 0.3 to 20 A / dm 2 , more preferably about 5 to 15 A / dm 2 . The reduction temperature is preferably 0 to 70 ° C., the higher the temperature, the faster the reduction reaction rate, and the lower the temperature, the smaller the particle size of the precipitated particles.
（ハ）電解溶液からの銅合金微粒子の回収
電解還元反応終了後に、電極の洗浄等により電極表面に付着した銅合金微粒子を回収する。回収方法としては、電極に逆電流を流し、電極表面に付着した微粒子を脱離させ、沈殿物を回収することも可能である。また上記したように、陰極に超音波振動等の揺動を与える回収を行うこともできる。かくして得られる銅合金微粒子は、平均一次粒子径が１〜８０ｎｍの範囲であり、かつ平均アスペクト比が１０以下の比較的小さい略球状である。尚、前記平均一次粒子径と平均アスペクト比は、透過型電子顕微鏡（ＴＥＭ）で観察し、ＪＩＳ Ｚ８８２７−１に規定される解析方法によって求めることができる。本発明において平均一次粒子径は透過型電子顕微鏡で観察可能な粒子の数平均粒子径である。
(C) Recovery of copper alloy fine particles from the electrolytic solution After completion of the electrolytic reduction reaction, the copper alloy fine particles adhering to the electrode surface are recovered by washing the electrode or the like. As a recovery method, it is possible to apply a reverse current to the electrode, desorb the fine particles adhering to the electrode surface, and recover the precipitate. Further, as described above, it is possible to carry out recovery by giving a swing such as ultrasonic vibration to the cathode. The copper alloy fine particles thus obtained have a relatively small spherical shape having an average primary particle diameter in the range of 1 to 80 nm and an average aspect ratio of 10 or less. The average primary particle diameter and the average aspect ratio can be obtained by an observation method with a transmission electron microscope (TEM) and an analysis method defined in JIS Z8827-1. In the present invention, the average primary particle diameter is the number average particle diameter of particles observable with a transmission electron microscope.
〔２〕第２の態様
前記第１の態様に記載の還元反応により製造された、銅−亜鉛からなる合金微粒子は、平均一次粒子径が１〜８０ｎｍの範囲であり、かつ平均アスペクト比が１０以下である。上記第１の態様に記載の製造方法により得られる銅合金微粒子は、有機分散剤と無機分散剤の存在下に還元反応がおこなわれる結果、デンドライト化が抑制されて平均一次粒子径が好ましくは１〜８０ｎｍの範囲、より好ましくは１〜５０ｎｍの範囲であり、平均アスペクト比が好ましくは１０以下、より好ましくは５以下、特に好ましくは２以下の略球状のものである。
[2] Second Aspect The alloy fine particles made of copper-zinc produced by the reduction reaction according to the first aspect have an average primary particle diameter in the range of 1 to 80 nm and an average aspect ratio of 10 It is as follows. The copper alloy fine particles obtained by the production method described in the first aspect are preferably reduced in dendrite as a result of a reduction reaction in the presence of an organic dispersant and an inorganic dispersant, and the average primary particle size is preferably 1. It is in the range of ˜80 nm, more preferably in the range of 1˜50 nm, and the average aspect ratio is preferably 10 or less, more preferably 5 or less, and particularly preferably 2 or less.
以下本発明を実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではない。電解還元反応により銅−亜鉛からなる銅合金微粒子を調製して、得られた微粒子の評価を行った。
［実施例１］
（１）銅合金微粒子の調製
まず、銅イオンとして硫酸銅０．１モル／Ｌ、亜鉛イオンとして硫酸亜鉛０．０２モル／Ｌ、錯化剤としてエタノールアミン５．７モル／Ｌ、無機分散剤として硫酸ナトリウム０．０１モル／Ｌ、有機分散剤としてポリビニルピロリドン（数平均分子量：３５００）５ｇ／Ｌを含有する１０００ｍｌの還元反応水溶液を調製した。ｐＨは約５．０であった。
次にこの溶液中で２ｃｍ四方の銅シートからなる陽極（アノード電極）と白金基板からなる陰極（カソード電極）間を浴温２５℃で、電流密度１０Ａ／ｄｍ２で３０分間通電を行った。得られたコロイド溶液を、カーボン支持膜をとりつけたアルミメッシュ上に採取し、溶媒を乾燥除去して、銅合金微粒子を得た。
（２）生成した銅合金微粒子の評価
得られた銅合金微粒子について、透過電子顕微鏡（ＴＥＭ）による観測結果、粒子の９０％以上の一次粒子径は５〜５０ｎｍの範囲で、平均アスペクト比は１．５であった。また、エネルギー分散型Ｘ線分析装置（ＥＤＳ）による分析結果、合金組成は、銅９０質量％、亜鉛１０質量％の合金であった。
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples. Copper alloy fine particles comprising copper-zinc were prepared by electrolytic reduction reaction, and the obtained fine particles were evaluated.
[Example 1]
(1) Preparation of copper alloy fine particles First, copper sulfate 0.1 mol / L as copper ions, zinc sulfate 0.02 mol / L as zinc ions, ethanolamine 5.7 mol / L as complexing agent, inorganic dispersant As an organic dispersant, 1000 ml of a reduction reaction aqueous solution containing 0.01 g / L of polyvinyl pyrrolidone (number average molecular weight: 3500) was prepared. The pH was about 5.0.
Next, in this solution, an electric current was applied between an anode (anode electrode) made of a 2 cm square copper sheet and a cathode (cathode electrode) made of a platinum substrate at a bath temperature of 25 ° C. and a current density of 10 A / dm 2 for 30 minutes. The obtained colloid solution was collected on an aluminum mesh to which a carbon support film was attached, and the solvent was removed by drying to obtain copper alloy fine particles.
(2) Evaluation of produced copper alloy fine particles The obtained copper alloy fine particles were observed with a transmission electron microscope (TEM). As a result, the primary particle diameter of 90% or more of the particles was in the range of 5 to 50 nm, and the average aspect ratio was 1. .5. As a result of analysis by an energy dispersive X-ray analyzer (EDS), the alloy composition was an alloy of 90% by mass of copper and 10% by mass of zinc.
［実施例２］
（１）銅合金微粒子の調製
まず、銅イオンとして塩化第一銅０．１モル／Ｌ、亜鉛イオンとして塩化亜鉛０．０１モル／Ｌ、錯化剤としてチオ硫酸ナトリウム０．８モル／Ｌ、無機分散剤として塩化アンモニウム１．５モル／Ｌ、有機分散剤としてポリビニルピロリドン（数平均分子量：３５００）５ｇ／Ｌを含有する１０００ｍｌの還元反応水溶液を調製した。ｐＨは約５．０であった。
次にこの溶液中で２ｃｍ四方の銅シートからなる陽極（アノード電極）と、白金基板からなる陰極（カソード電極）間を浴温２５℃で、白金基板からなる陽極（アノード電極）と陰極（カソード電極）を用いて陰極電流密度１０Ａ／ｄｍ２で３０分間通電を行った。得られたコロイド溶液を、カーボン支持膜をとりつけたアルミメッシュ上に採取し、溶媒を乾燥除去して、銅合金微粒子を得た。
（２）生成した銅合金微粒子の評価
得られた銅合金微粒子について、透過電子顕微鏡（ＴＥＭ）による観測結果、粒子の９０％以上の一次粒子径は５〜５０ｎｍの範囲で、平均アスペクト比は１．５であった。また、エネルギー分散型Ｘ線分析装置（ＥＤＳ）による分析結果、合金組成は、銅９８質量％、亜鉛２質量％の合金であった。
[Example 2]
(1) Preparation of copper alloy fine particles First, cuprous chloride 0.1 mol / L as copper ions, zinc chloride 0.01 mol / L as zinc ions, sodium thiosulfate 0.8 mol / L as complexing agent, A 1000 ml aqueous reduction reaction solution containing 1.5 mol / L of ammonium chloride as an inorganic dispersant and 5 g / L of polyvinylpyrrolidone (number average molecular weight: 3500) as an organic dispersant was prepared. The pH was about 5.0.
Next, an anode (anode electrode) composed of a 2 cm square copper sheet and a cathode (cathode electrode) composed of a platinum substrate in this solution at a bath temperature of 25 ° C., and an anode (anode electrode) composed of a platinum substrate and a cathode (cathode) Electrode) was used for 30 minutes at a cathode current density of 10 A / dm 2 . The obtained colloid solution was collected on an aluminum mesh to which a carbon support film was attached, and the solvent was removed by drying to obtain copper alloy fine particles.
(2) Evaluation of produced copper alloy fine particles The obtained copper alloy fine particles were observed with a transmission electron microscope (TEM). As a result, the primary particle diameter of 90% or more of the particles was in the range of 5 to 50 nm, and the average aspect ratio was 1. .5. As a result of analysis by an energy dispersive X-ray analyzer (EDS), the alloy composition was an alloy of 98 mass% copper and 2 mass% zinc.
［実施例３］
（１）銅合金微粒子の調製
まず、銅イオンとして酒石酸銅０．０９６モル／Ｌ、亜鉛イオンとして酸化亜鉛０．０３２モル／Ｌ、無機分散剤として水酸化ナトリウム２．５モル／Ｌ、有機分散剤としてポリビニルピロリドン（数平均分子量：３５００）５ｇ／Ｌを含有する１０００ｍｌの還元反応水溶液を調製した。ｐＨは約５．０であった。
次にこの溶液中で２ｃｍ四方の銅シートからなる陽極（アノード電極）と、白金基板からなる陰極（カソード電極）間を浴温２５℃で、白金基板からなる陽極（アノード電極）と陰極（カソード電極）を用いて陰極電流密度１０Ａ／ｄｍ２で３０分間通電を行った。得られたコロイド溶液を、カーボン支持膜をとりつけたアルミメッシュ上に採取し、溶媒を乾燥除去して、銅合金微粒子を得た。
（２）生成した銅合金微粒子の評価
銅合金微粒子について、透過電子顕微鏡（ＴＥＭ）による観測結果、粒子の９０％以上の一次粒子径は５〜５０ｎｍの範囲で、平均アスペクト比は１．５であった。また、エネルギー分散型Ｘ線分析装置（ＥＤＳ）による分析結果、合金組成は、銅８０質量％、亜鉛２０質量％の合金であった。
[Example 3]
(1) Preparation of copper alloy fine particles First, copper tartrate 0.096 mol / L as copper ions, zinc oxide 0.032 mol / L as zinc ions, sodium hydroxide 2.5 mol / L as inorganic dispersant, organic dispersion As an agent, 1000 ml of an aqueous reduction reaction solution containing 5 g / L of polyvinylpyrrolidone (number average molecular weight: 3500) was prepared. The pH was about 5.0.
Next, an anode (anode electrode) composed of a 2 cm square copper sheet and a cathode (cathode electrode) composed of a platinum substrate in this solution at a bath temperature of 25 ° C., and an anode (anode electrode) composed of a platinum substrate and a cathode (cathode) Electrode) was used for 30 minutes at a cathode current density of 10 A / dm 2 . The obtained colloid solution was collected on an aluminum mesh to which a carbon support film was attached, and the solvent was removed by drying to obtain copper alloy fine particles.
(2) Evaluation of produced copper alloy fine particles As for the copper alloy fine particles, observation results by transmission electron microscope (TEM) show that the primary particle diameter of 90% or more of the particles is in the range of 5 to 50 nm and the average aspect ratio is 1.5. there were. As a result of analysis by an energy dispersive X-ray analyzer (EDS), the alloy composition was an alloy of 80% by mass of copper and 20% by mass of zinc.
［実施例４］
（１）銅合金微粒子の調製
まず、銅イオンとして酢酸銅０．１モル／Ｌ、亜鉛イオンとして酢酸亜鉛０．０１モル／Ｌ、無機分散剤として酢酸ナトリウム０．０１モル／Ｌ、有機分散剤としてポリビニルピロリドン（数平均分子量：３５００）５ｇ／Ｌを含有する１０００ｍｌの還元反応水溶液を調製した。ｐＨは約５．０であった。次にこの溶液中で２ｃｍ四方の銅シートからなる陽極（アノード電極）と白金基板からなる陰極（カソード電極）間を浴温２５℃で、電流密度１５Ａ／ｄｍ２で３０分間通電を行った。得られたコロイド溶液を、カーボン支持膜をとりつけたアルミメッシュ上に採取し、溶媒を乾燥除去して、銅合金微粒子を得た。
（２）生成した銅合金微粒子の評価
得られた銅合金微粒子について、透過電子顕微鏡（ＴＥＭ）による観測結果、粒子の９０％以上の一次粒子径は５〜５０ｎｍの範囲で、平均アスペクト比は１．５であった。また、エネルギー分散型Ｘ線分析装置（ＥＤＳ）による分析結果、合金組成は、銅９５質量％、亜鉛５質量％の合金であった。
[Example 4]
(1) Preparation of copper alloy fine particles First, copper acetate 0.1 mol / L, zinc ion 0.01 mol / L as zinc ion, sodium acetate 0.01 mol / L as inorganic dispersant, organic dispersant As a solution, 1000 ml of a reduction reaction aqueous solution containing 5 g / L of polyvinylpyrrolidone (number average molecular weight: 3500) was prepared. The pH was about 5.0. Next, in this solution, a current was applied between an anode (anode electrode) made of a 2 cm square copper sheet and a cathode (cathode electrode) made of a platinum substrate at a bath temperature of 25 ° C. and a current density of 15 A / dm 2 for 30 minutes. The obtained colloid solution was collected on an aluminum mesh to which a carbon support film was attached, and the solvent was removed by drying to obtain copper alloy fine particles.
(2) Evaluation of produced copper alloy fine particles The obtained copper alloy fine particles were observed with a transmission electron microscope (TEM). As a result, the primary particle diameter of 90% or more of the particles was in the range of 5 to 50 nm, and the average aspect ratio was 1. .5. As a result of analysis by an energy dispersive X-ray analyzer (EDS), the alloy composition was an alloy of 95% by mass of copper and 5% by mass of zinc.
［比較例１］
還元反応水溶液中の無機分散剤濃度を０モル／Ｌとして、電解還元反応により銅合金微粒子を調製して、得られた微粒子の評価を行った。
（１）銅合金微粒子の調製
酢酸ナトリウム濃度を０モル／Ｌとした以外は実施例４と同様に、還元反応水溶液を調製し、電解還元反応を行った。得られたコロイド溶液を、カーボン支持膜をとりつけたアルミメッシュ上に採取し、溶媒を乾燥除去して、銅合金微粒子を得た。
（２）生成した銅合金微粒子の評価
銅合金微粒子について、透過電子顕微鏡（ＴＥＭ）により観測した結果、粒子の９０％以上の一次粒子径は５〜３００ｎｍの範囲で、結晶形状はデンドライト状に凝集して、１〜１０μｍの凝集体になっていることが観察された。また、エネルギー分散型Ｘ線分析装置（ＥＤＳ）による分析結果、合金組成は、銅９５質量％、亜鉛５質量％の合金であった。
[Comparative Example 1]
Copper alloy fine particles were prepared by electrolytic reduction reaction with the inorganic dispersant concentration in the reduction reaction aqueous solution being 0 mol / L, and the obtained fine particles were evaluated.
(1) Preparation of copper alloy fine particles A reduction reaction aqueous solution was prepared and subjected to an electrolytic reduction reaction in the same manner as in Example 4 except that the sodium acetate concentration was 0 mol / L. The obtained colloid solution was collected on an aluminum mesh to which a carbon support film was attached, and the solvent was removed by drying to obtain copper alloy fine particles.
(2) Evaluation of generated copper alloy fine particles As a result of observing the copper alloy fine particles with a transmission electron microscope (TEM), the primary particle diameter of 90% or more of the particles is in the range of 5 to 300 nm, and the crystal shape is aggregated in a dendrite shape And it was observed that it became an aggregate of 1-10 micrometers. As a result of analysis by an energy dispersive X-ray analyzer (EDS), the alloy composition was an alloy of 95% by mass of copper and 5% by mass of zinc.
［比較例２］
（１）銅合金微粒子の調製
硫酸ナトリウム濃度を０モル／Ｌとした以外は実施例１と同様に、還元反応水溶液を調製し、電解還元反応を行った。得られたコロイド溶液を、カーボン支持膜をとりつけたアルミメッシュ上に採取し、溶媒を乾燥除去して、銅合金微粒子を得た。
（２）生成した銅合金微粒子の評価
得られた銅合金微粒子について、透過電子顕微鏡（ＴＥＭ）により観測した結果、粒子の９０％以上の一次粒子径は５〜３００ｎｍの範囲で、結晶形状はデンドライト状に凝集して、１〜１０μｍの凝集体になっていることが観察された。また、エネルギー分散型Ｘ線分析装置（ＥＤＳ）による分析結果、合金組成は、銅９０質量％、亜鉛１０質量％の合金であった。
[Comparative Example 2]
(1) Preparation of copper alloy fine particles A reduction reaction aqueous solution was prepared and subjected to an electrolytic reduction reaction in the same manner as in Example 1 except that the sodium sulfate concentration was 0 mol / L. The obtained colloid solution was collected on an aluminum mesh to which a carbon support film was attached, and the solvent was removed by drying to obtain copper alloy fine particles.
(2) Evaluation of the produced copper alloy fine particles The obtained copper alloy fine particles were observed with a transmission electron microscope (TEM). It was observed that the agglomerates were 1 to 10 μm. As a result of analysis by an energy dispersive X-ray analyzer (EDS), the alloy composition was an alloy of 90% by mass of copper and 10% by mass of zinc.
Claims (11)
（ｉ）少なくとも硫酸銅、硫酸亜鉛、錯化剤（ａ）、有機分散剤、及び無機分散剤を含む還元反応水溶液（還元反応水溶液１）、
(ii)少なくとも塩化第一銅、水溶性亜鉛化合物、錯化剤（ｂ）、有機分散剤、及び無機分散剤を含む還元反応水溶液（還元反応水溶液２）、
(iii)少なくとも酒石酸銅、酸化亜鉛、有機分散剤、及び無機分散剤を含む還元反応水溶液（還元反応水溶液３）、又は
(iv)少なくとも酢酸銅、酢酸亜鉛、有機分散剤、及び無機分散剤を含む還元反応水溶液（還元反応水溶液４）、
でｐＨが４．５〜１３である還元反応水溶液から、電解還元反応により銅−亜鉛からなる合金微粒子を析出させることを特徴とする、銅合金微粒子の製造方法。 A method for producing copper alloy fine particles comprising copper-zinc by electrolytic reduction reaction,
(I) Reduction reaction aqueous solution (reduction reaction aqueous solution 1) containing at least copper sulfate, zinc sulfate, complexing agent (a), organic dispersant, and inorganic dispersant,
(ii) A reduction reaction aqueous solution (reduction reaction aqueous solution 2) containing at least cuprous chloride, a water-soluble zinc compound, a complexing agent (b), an organic dispersant, and an inorganic dispersant,
(iii) Reduction reaction aqueous solution (reduction reaction aqueous solution 3) containing at least copper tartrate, zinc oxide, an organic dispersant, and an inorganic dispersant, or
(iv) a reduction reaction aqueous solution (reduction reaction aqueous solution 4) containing at least copper acetate, zinc acetate, an organic dispersant, and an inorganic dispersant;
A method for producing copper alloy fine particles, comprising depositing alloy fine particles composed of copper-zinc from an aqueous reduction reaction solution having a pH of 4.5 to 13 by electrolytic reduction reaction.
前記アルカリ金属イオンの供給源が水酸化ナトリウム、水酸化カリウム、硫酸ナトリウム、硫酸カリウム、酒石酸ナトリウム、酒石酸カリウム、酢酸ナトリウム、及び酢酸カリウムから選択される１種又は２種以上であり、
前記アルカリ土類金属イオンの供給源が臭化カルシウム、臭化バリウム、塩化カルシウム、塩化バリウム、沃化カルシウム、及び沃化バリウムから選択される１種又は２種以上であることを特徴とする、請求項６に記載の銅合金微粒子の製造方法。 The source of halogen ions is hydrogen chloride, potassium chloride, sodium chloride, ammonium chloride, hydrogen bromide, potassium bromide, sodium bromide, ammonium bromide, hydrogen iodide, potassium iodide, sodium iodide, ammonium iodide , One or more selected from hydrogen fluoride, potassium fluoride, sodium fluoride, and ammonium fluoride,
The alkali metal ion source is one or more selected from sodium hydroxide, potassium hydroxide, sodium sulfate, potassium sulfate, sodium tartrate, potassium tartrate, sodium acetate, and potassium acetate;
The source of the alkaline earth metal ions is one or more selected from calcium bromide, barium bromide, calcium chloride, barium chloride, calcium iodide, and barium iodide, The method for producing copper alloy fine particles according to claim 6.
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| JP2011219862A (en) * | 2010-03-26 | 2011-11-04 | Furukawa Electric Co Ltd:The | Dispersant of fine-particle of copper alloy, method of manufacturing sintering conductive material, sintering conductive material, and conductive connection member |
| CN103510106A (en) * | 2013-09-22 | 2014-01-15 | 中南大学 | Copper electrolysis additive and use method thereof |
| JP2014129583A (en) * | 2012-12-28 | 2014-07-10 | Jx Nippon Mining & Metals Corp | Method for recovering metal or alloy from high-purity metal or alloy scrap |
| JP2015209575A (en) * | 2014-04-28 | 2015-11-24 | 住友電気工業株式会社 | Metal fine particle dispersion, production method of metal fine particle dispersion, production method of metal film and metal film |
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| CN108971513B (en) * | 2018-10-12 | 2021-09-21 | 圣戈莱（北京）科技有限公司 | Nano copper particle and low-cost green and environment-friendly preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS613896A (en) * | 1984-06-15 | 1986-01-09 | Kosaku:Kk | Electroplating bath for forming golden film |
| JPH06287791A (en) * | 1993-02-19 | 1994-10-11 | Learonal Inc | Plating solution of monovalent metal wherein no cyanide is incorporated |
| JP2004076054A (en) * | 2002-08-13 | 2004-03-11 | National Institute For Materials Science | Method for producing copper-zinc alloy powder |
| JP2005314806A (en) * | 2004-03-29 | 2005-11-10 | Nano Gijutsu Kenkyusho:Kk | Powder of nano crystalline copper metal and nano crystalline copper alloy having high hardness and high electric conductivity, bulk material of nano crystalline copper or copper alloy having high hardness, high strength, high electric conductivity and high toughness, and production method thereof |
| JP2007270184A (en) * | 2006-03-30 | 2007-10-18 | Furukawa Electric Co Ltd:The | Electrode, and apparatus and method for manufacturing metallic fine particle |
| JP2008050691A (en) * | 2006-07-28 | 2008-03-06 | Furukawa Electric Co Ltd:The | Method for producing fine particle, fine particle obtained by using the production method, method for producing fine particle dispersion, fine particle dispersion obtained by using the production method, and conductive material |
| JP2008231564A (en) * | 2007-03-23 | 2008-10-02 | Furukawa Electric Co Ltd:The | Method of manufacturing copper fine particle |
| JP2008248267A (en) * | 2007-03-29 | 2008-10-16 | Furukawa Electric Co Ltd:The | Method of manufacturing copper alloy fine particle and copper alloy fine particle obtained by the same method |
| JP2009099443A (en) * | 2007-10-18 | 2009-05-07 | Fukuda Metal Foil & Powder Co Ltd | Cooper alloy powder for conductive material paste |
| JP2009149978A (en) * | 2007-11-26 | 2009-07-09 | Bridgestone Corp | Copper-zinc alloy electroplating bath and plating method using the same |
| JP2009185348A (en) * | 2008-02-07 | 2009-08-20 | Furukawa Electric Co Ltd:The | Method for producing copper fine particle |
-
2010
- 2010-03-26 JP JP2010071734A patent/JP5566743B2/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS613896A (en) * | 1984-06-15 | 1986-01-09 | Kosaku:Kk | Electroplating bath for forming golden film |
| JPH06287791A (en) * | 1993-02-19 | 1994-10-11 | Learonal Inc | Plating solution of monovalent metal wherein no cyanide is incorporated |
| JP2004076054A (en) * | 2002-08-13 | 2004-03-11 | National Institute For Materials Science | Method for producing copper-zinc alloy powder |
| JP2005314806A (en) * | 2004-03-29 | 2005-11-10 | Nano Gijutsu Kenkyusho:Kk | Powder of nano crystalline copper metal and nano crystalline copper alloy having high hardness and high electric conductivity, bulk material of nano crystalline copper or copper alloy having high hardness, high strength, high electric conductivity and high toughness, and production method thereof |
| JP2007270184A (en) * | 2006-03-30 | 2007-10-18 | Furukawa Electric Co Ltd:The | Electrode, and apparatus and method for manufacturing metallic fine particle |
| JP2008050691A (en) * | 2006-07-28 | 2008-03-06 | Furukawa Electric Co Ltd:The | Method for producing fine particle, fine particle obtained by using the production method, method for producing fine particle dispersion, fine particle dispersion obtained by using the production method, and conductive material |
| JP2008231564A (en) * | 2007-03-23 | 2008-10-02 | Furukawa Electric Co Ltd:The | Method of manufacturing copper fine particle |
| JP2008248267A (en) * | 2007-03-29 | 2008-10-16 | Furukawa Electric Co Ltd:The | Method of manufacturing copper alloy fine particle and copper alloy fine particle obtained by the same method |
| JP2009099443A (en) * | 2007-10-18 | 2009-05-07 | Fukuda Metal Foil & Powder Co Ltd | Cooper alloy powder for conductive material paste |
| JP2009149978A (en) * | 2007-11-26 | 2009-07-09 | Bridgestone Corp | Copper-zinc alloy electroplating bath and plating method using the same |
| JP2009185348A (en) * | 2008-02-07 | 2009-08-20 | Furukawa Electric Co Ltd:The | Method for producing copper fine particle |
Non-Patent Citations (1)
| Title |
|---|
| JULIA HAMBROCK 外４名: "Nano-Brass: Bimetallic Copper/Zinc Colloids by a Nonaqueous Organometallic Route Using [Cu(OCH(Me)CH", CHEMISTRY OF MATERIALS, vol. 15, JPN6014009952, 2003, US, pages 4217 - 4222, XP002436830, ISSN: 0002763586, DOI: 10.1021/cm0341383 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011219862A (en) * | 2010-03-26 | 2011-11-04 | Furukawa Electric Co Ltd:The | Dispersant of fine-particle of copper alloy, method of manufacturing sintering conductive material, sintering conductive material, and conductive connection member |
| JP2014129583A (en) * | 2012-12-28 | 2014-07-10 | Jx Nippon Mining & Metals Corp | Method for recovering metal or alloy from high-purity metal or alloy scrap |
| CN103510106A (en) * | 2013-09-22 | 2014-01-15 | 中南大学 | Copper electrolysis additive and use method thereof |
| JP2015209575A (en) * | 2014-04-28 | 2015-11-24 | 住友電気工業株式会社 | Metal fine particle dispersion, production method of metal fine particle dispersion, production method of metal film and metal film |
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