JP2014105365A - Nickel nanoparticles, its manufacturing method and nickel paste - Google Patents
Nickel nanoparticles, its manufacturing method and nickel paste Download PDFInfo
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本発明は、主にエレクトロニクスの分野において使用されるニッケルナノ粒子とその製造方法、およびニッケルペーストに関する。 The present invention relates to nickel nanoparticles mainly used in the field of electronics, a method for producing the same, and nickel paste.
近年、エレクトロニクスの分野では電子機器の小型化・高性能化に伴い、使用される金属材料も微小化が求められている。例えば、積層セラミックコンデンサーの内部電極層に使用されているニッケル粒子の粒径は、現状では２００〜４００ｎｍ程度であるが、内部電極層の薄膜化に伴いより微小化し、将来的には粒径が１００ｎｍ以下のニッケル粒子が使用されると考えられる。
従来の技術において、粒径１００ｎｍ以下のニッケル粒子については、以下のような製造方法が提案されている。
In recent years, in the field of electronics, with the miniaturization and high performance of electronic devices, metal materials used are also required to be miniaturized. For example, the particle size of nickel particles used in the internal electrode layer of a multilayer ceramic capacitor is about 200 to 400 nm at present, but the particle size becomes smaller as the internal electrode layer becomes thinner, and in the future the particle size will become smaller. It is thought that nickel particles of 100 nm or less are used.
In the prior art, the following manufacturing methods have been proposed for nickel particles having a particle size of 100 nm or less.
特許文献１には、ニッケル塩を高温で気化させた後、当該気化したニッケル塩を気相中においてＨ２ガスにより還元する方法が記載されている。そして、平均粒径５０〜３００ｎｍの一次粒子が得られた旨の記載がある。 Patent Document 1 describes a method in which a nickel salt is vaporized at a high temperature and then the vaporized nickel salt is reduced with H 2 gas in a gas phase. There is a description that primary particles having an average particle diameter of 50 to 300 nm were obtained.
特許文献２には、水、エタノール、トルエンなどのエマルジョン液相中に、ニッケル塩とポリビニルピロリドン（ＰＶＰ）などの保護剤・添加剤と呼ばれる有機物とを添加した後、ヒドラジンを添加してニッケル−ヒドラジン錯体を生成させ、この錯体を含む溶液にＮａＢＨ４を添加し、錯体を還元させることで、ポリマー保護ニッケル超微粒子を作製する方法が記載されている。そして、平均粒子径１００ｎｍ以下のニッケル微粒子が得られた旨の記載がある。 In Patent Document 2, a nickel salt and an organic substance called a protective agent / additive such as polyvinylpyrrolidone (PVP) are added to an emulsion liquid phase such as water, ethanol, toluene, etc., and then hydrazine is added to add nickel- It describes a method for producing polymer-protected nickel ultrafine particles by forming a hydrazine complex, adding NaBH 4 to a solution containing the complex, and reducing the complex. There is a description that nickel fine particles having an average particle diameter of 100 nm or less were obtained.
特許文献３には、ギ酸ニッケル二水和物と、脂肪族アミンなどのルイス塩基と、溶媒とを含む溶液を加熱することにより、微粒子ニッケル粉を作製する方法が記載されている。そして、平均粒子径１００ｎｍ以下で、かつ、粒子径の分布の狭い均一なニッケル粒子が得られた旨の記載がある。 Patent Document 3 describes a method of producing fine nickel powder by heating a solution containing nickel formate dihydrate, a Lewis base such as an aliphatic amine, and a solvent. There is a description that uniform nickel particles having an average particle size of 100 nm or less and a narrow particle size distribution were obtained.
しかしながら、本発明者らの検討によれば、特許文献１に記載の方法は、気相法による製造法であるため、特別な製造装置が必要となり製造コストが高くなるという問題がある。さらに、気相法による製造方法においては１，０００℃以上の高温条件による還元工程があるため、粒径１００ｎｍ以下の粒子を製造する為には分級工程が必要である。この為、粒径１００ｎｍ以下の粒子製造においては、歩留まりが非常に悪くなり不向きである。 However, according to the study by the present inventors, the method described in Patent Document 1 is a manufacturing method by a gas phase method, and thus there is a problem that a special manufacturing apparatus is required and the manufacturing cost increases. Furthermore, in the production method by the vapor phase method, there is a reduction step under a high temperature condition of 1,000 ° C. or higher, and therefore a classification step is necessary to produce particles having a particle size of 100 nm or less. For this reason, in the production of particles having a particle size of 100 nm or less, the yield is very poor and is not suitable.
また、特許文献２に記載の方法は、ニッケル−ヒドラジン錯体からニッケル粉を作成するものである。そして、製造するニッケル粒子の粒径を制御するため、保護剤または分散剤としてポリビニルピロリドン（ＰＶＰ）などの有機物を使用することが必須となっており、製造された粒子には３〜１０質量％程度の有機物が付着している。この為、後工程において、当該有機物（保護剤または分散剤）を除去するための有機洗浄工程が必要となり、製造コストが高くなるという問題がある。また製造した粒子をペーストやインクの原料として使用する際、焼成時に有機物の分解による体積収縮が大きくなると同時に、有機物が残留した際には電気抵抗率を悪化させる要因となってしまう。 Moreover, the method of patent document 2 produces nickel powder from a nickel-hydrazine complex. And in order to control the particle diameter of the nickel particle to manufacture, it is essential to use organic substances, such as polyvinylpyrrolidone (PVP), as a protective agent or a dispersing agent, and 3-10 mass% is manufactured to the manufactured particle. Some organic matter is attached. For this reason, an organic washing process for removing the said organic substance (protective agent or dispersing agent) is needed in a post process, and there exists a problem that manufacturing cost becomes high. In addition, when the produced particles are used as a raw material for pastes and inks, volume shrinkage due to decomposition of the organic matter is increased during firing, and at the same time, when the organic matter remains, the electrical resistivity is deteriorated.
また、特許文献３に記載の方法も特許文献２と同様に、製造するニッケル粉の粒径を制御するため、表面修飾剤として有機物を使用することが必須となっており、特許文献２と同様の課題がある。さらに、反応温度の制御方法として、マイクロ波の照射を行うため、バッチアップ製造が出来にくく、生産性が低い製造方法となっている。 In addition, the method described in Patent Document 3 also requires the use of an organic substance as a surface modifier in order to control the particle size of the nickel powder to be manufactured, as in Patent Document 2, and is similar to Patent Document 2. There is a problem. Furthermore, as a method for controlling the reaction temperature, since microwave irradiation is performed, it is difficult to perform batch-up production and the production method is low.
本発明は、上述の状況の下で為されたものであり、その解決しようとする課題は、気相法を採ることなく、また粒径制御を目的とした保護剤または分散剤や、表面修飾剤を使用することなく、平均粒径１００ｎｍ以下のニッケル粒子粉を低コストで高い生産性を保ちながら製造出来る、ニッケルナノ粒子とその製造方法、および当該ニッケルナノ粒子を用いたニッケルペーストを提供することである。 The present invention has been made under the above-mentioned circumstances, and the problem to be solved is a protective agent or a dispersant for the purpose of controlling the particle size without adopting a gas phase method, and surface modification. Provided is a nickel nanoparticle, a method for producing the same, and a nickel paste using the nickel nanoparticle, which can produce nickel particle powder having an average particle size of 100 nm or less at a low cost without using an agent. That is.
上述の課題を解決する為、本発明者等は研究を重ねた結果、まずニッケル化合物とヒドラジン化合物とからニッケル−ヒドラジン錯体を製造し、製造された錯体を固液分離し、洗浄と乾燥工程を行って、製造された錯体に残留する未反応のヒドラジンを除去した後、当該ニッケル−ヒドラジン錯体を含む液へ、アルカリ溶液を添加することによってニッケルナノ粒子を作る製造方法に想到し、本発明を完成した。 In order to solve the above-mentioned problems, the present inventors have made researches. As a result, first, a nickel-hydrazine complex is produced from a nickel compound and a hydrazine compound, the produced complex is solid-liquid separated, and washing and drying steps are performed. And removing the unreacted hydrazine remaining in the produced complex, and then conceiving a production method for producing nickel nanoparticles by adding an alkaline solution to a liquid containing the nickel-hydrazine complex. completed.
即ち、上述の課題を解決するための第１の発明は、
ニッケル化合物溶液とヒドラジン化合物溶液とから、ニッケル−ヒドラジン錯体を生成する工程と、
前記ニッケル−ヒドラジン錯体を溶液から固液分離し、得られたニッケル−ヒドラジン錯体を洗浄する工程と、
前記洗浄したニッケル−ヒドラジン錯体にアルカリを添加して、ニッケルナノ粒子を製造する工程を有することを特徴とするニッケルナノ粒子の製造方法である。
第２の発明は、
前記ニッケル−ヒドラジン錯体を溶液から固液分離し、得られたニッケル−ヒドラジン錯体を洗浄する際、
洗浄液として純水を用い、洗浄後における洗浄液の酸化還元電位が−７００ｍＶ以上となるまで、純水を通過させることで洗浄を行うことを特徴とする、第１の発明に記載のニッケルナノ粒子の製造方法である。
第３の発明は、
前記ニッケル−ヒドラジン錯体を溶液から固液分離し、得られたニッケル−ヒドラジン錯体を洗浄し、前記アルカリを添加する前に、得られたニッケル−ヒドラジン錯体を乾燥させる工程を有し、
前記ニッケル−ヒドラジン錯体を乾燥させる工程において、ニッケル−ヒドラジン錯体の水分量が２質量％以下になるまで、乾燥させることを特徴とする、第１の発明に記載のニッケルナノ粒子の製造方法である。
第４の発明は、
前記洗浄したニッケル−ヒドラジン錯体を溶媒に分散して分散体とし、得られた分散体へアルカリを添加することを特徴とする、第１の発明に記載のニッケルナノ粒子の製造方法である。
第５の発明は
前記ヒドラジン化合物として、ヒドラジン、ヒドラジン水和物、ヒドラジン塩化物から選択される１種以上を用いることを特徴とする、第１から第４の発明のいずれかに記載のニッケルナノ粒子の製造方法である。
第６の発明は、
前記ニッケル化合物として、塩化ニッケル、硫酸ニッケル、酢酸ニッケルから選択される１種以上を用いることを特徴とする、第１から第５の発明のいずれかに記載のニッケルナノ粒子の製造方法である。
第７の発明は、
第１から第６の発明のいずれかに記載のニッケルナノ粒子の製造方法により製造されたことを特徴とするニッケルナノ粒子である。
第８の発明は、
平均粒径が１００ｎｍ以下であり、粒径における変動係数が２０％以下であることを特徴とするニッケルナノ粒子である。
第９の発明は、
第８の発明に記載のニッケルナノ粒子を含むことを特徴とするニッケルペーストである。
That is, the first invention for solving the above-described problem is
Forming a nickel-hydrazine complex from the nickel compound solution and the hydrazine compound solution;
Solid-liquid separation of the nickel-hydrazine complex from the solution and washing the resulting nickel-hydrazine complex;
A method for producing nickel nanoparticles, comprising the step of producing nickel nanoparticles by adding an alkali to the washed nickel-hydrazine complex.
The second invention is
When the nickel-hydrazine complex is solid-liquid separated from the solution and the resulting nickel-hydrazine complex is washed,
Pure water is used as a cleaning liquid, and cleaning is performed by passing pure water until the oxidation-reduction potential of the cleaning liquid after cleaning becomes −700 mV or more. It is a manufacturing method.
The third invention is
Solid-liquid separation of the nickel-hydrazine complex from the solution, washing the resulting nickel-hydrazine complex, and drying the obtained nickel-hydrazine complex before adding the alkali,
In the step of drying the nickel-hydrazine complex, the nickel-hydrazine complex is dried until the moisture content is 2% by mass or less. .
The fourth invention is:
The method for producing nickel nanoparticles according to the first invention, wherein the washed nickel-hydrazine complex is dispersed in a solvent to form a dispersion, and an alkali is added to the obtained dispersion.
5th invention uses 1 or more types selected from hydrazine, hydrazine hydrate, and hydrazine chloride as said hydrazine compound, The nickel nano of any one of 1st to 4th invention characterized by the above-mentioned. A method for producing particles.
The sixth invention is:
The method for producing nickel nanoparticles according to any one of the first to fifth inventions, wherein one or more selected from nickel chloride, nickel sulfate, and nickel acetate is used as the nickel compound.
The seventh invention
Nickel nanoparticles produced by the method for producing nickel nanoparticles according to any one of the first to sixth inventions.
The eighth invention
Nickel nanoparticles having an average particle size of 100 nm or less and a coefficient of variation in particle size of 20% or less.
The ninth invention
A nickel paste comprising the nickel nanoparticles described in the eighth invention.
本発明に係るニッケルナノ粒子の製造方法によれば、粒径制御を目的とした分散剤や表面修飾剤を使用することなく、液相反応によって平均粒径１００ｎｍ以下のニッケルナノ粒子粉を、低コストで高い生産性を保ちながら製造出来る。製造されたニッケルナノ粒子は、エレクトロニクス用途のニッケルペーストに適した性状・特性を有している。 According to the method for producing nickel nanoparticles according to the present invention, a nickel nanoparticle powder having an average particle size of 100 nm or less is reduced by a liquid phase reaction without using a dispersant or a surface modifier for particle size control. It can be manufactured while maintaining high productivity at a low cost. The manufactured nickel nanoparticles have properties and characteristics suitable for nickel pastes for electronics applications.
本発明に係るニッケルナノ粒子の製造方法は、ニッケル−ヒドラジン錯体の製造工程、ニッケル−ヒドラジン錯体の分離工程、ニッケル−ヒドラジン錯体の洗浄工程、ニッケル−ヒドラジン錯体の乾燥工程、ニッケル−ヒドラジン錯体の再分散工程、ニッケルナノ粒子の製造工程を有する。
以下、前記各工程、および、製造されたニッケルナノ粒子の性状・特性について説明する。
The method for producing nickel nanoparticles according to the present invention includes a nickel-hydrazine complex production process, a nickel-hydrazine complex separation process, a nickel-hydrazine complex washing process, a nickel-hydrazine complex drying process, and a nickel-hydrazine complex re-treatment. It has a dispersion | distribution process and the manufacturing process of nickel nanoparticle.
Hereinafter, the above-mentioned steps and the properties and characteristics of the manufactured nickel nanoparticles will be described.
（ニッケル−ヒドラジン錯体の製造工程）
ニッケル−ヒドラジン錯体を製造する工程である。
まず、ニッケル塩の水溶液を準備する。ニッケル塩としては、塩化ニッケル、硫酸ニッケル、酢酸ニッケルなどから選択される１種類以上用いることが出来るが、原料コストや作業性の観点から塩化ニッケルまたは硫酸ニッケルが好ましい。
ニッケル塩水溶液の濃度は、０．１〜３．０モル／Ｌが好ましい。０．１モル／Ｌ以上であれば生産性が良く、３．０モル／Ｌ以下であれば、製造した錯体の凝集が回避出来る。
(Nickel-hydrazine complex production process)
This is a process for producing a nickel-hydrazine complex.
First, an aqueous solution of nickel salt is prepared. As the nickel salt, one or more selected from nickel chloride, nickel sulfate, nickel acetate and the like can be used, but nickel chloride or nickel sulfate is preferred from the viewpoint of raw material cost and workability.
The concentration of the nickel salt aqueous solution is preferably 0.1 to 3.0 mol / L. If it is 0.1 mol / L or more, productivity is good, and if it is 3.0 mol / L or less, aggregation of the produced complex can be avoided.
他方、ニッケル−ヒドラジン錯体形成の為の溶媒を準備する。
溶媒として、濃度が４０〜８０質量％のヒドラジン水溶液を準備する。ヒドラジン水溶液の濃度が４０質量％以上であれば反応が効率良く進行し、８０質量％以下であれば操作上の安全面から好ましいからである。
ヒドラジン原料としては、ヒドラジン、ヒドラジン水和物（８０質量％）、ヒドラジン塩化物を用いることが出来るが、安全面の観点からヒドラジン水和物が好ましい。
溶媒へのヒドラジンの添加量は、当該ヒドラジン水溶液に添加されるニッケル１モルに対して、当量を超えた過剰量である２．０〜１２モル、好ましくは２．５〜１２モルとする。当該ヒドラジン水溶液中に、ニッケル１モルに対してヒドラジンが２．０モル以上であれば、未反応のニッケルが生ぜず、ヒドラジンが１２モル以下であれば効率が保てるからである。
準備した溶媒を、大気下、Ｎ２、Ａｒなどの不活性ガス雰囲気下、好ましくはＮ２雰囲気下に置き、撹拌羽を用いて７００ｒｐｍ以下で撹拌しながら３０〜６０℃、好ましくは４０℃〜６０℃に加温する。
On the other hand, a solvent for forming a nickel-hydrazine complex is prepared.
A hydrazine aqueous solution having a concentration of 40 to 80% by mass is prepared as a solvent. This is because the reaction proceeds efficiently when the concentration of the hydrazine aqueous solution is 40% by mass or more, and preferably 80% by mass or less from the viewpoint of operational safety.
As the hydrazine raw material, hydrazine, hydrazine hydrate (80% by mass), and hydrazine chloride can be used, but hydrazine hydrate is preferable from the viewpoint of safety.
The amount of hydrazine added to the solvent is 2.0 to 12 mol, preferably 2.5 to 12 mol, which is an excess amount exceeding the equivalent with respect to 1 mol of nickel added to the hydrazine aqueous solution. This is because in the hydrazine aqueous solution, if hydrazine is 2.0 mol or more with respect to 1 mol of nickel, no unreacted nickel is produced, and if hydrazine is 12 mol or less, efficiency can be maintained.
The prepared solvent is placed in the atmosphere, under an inert gas atmosphere such as N 2 or Ar, preferably in an N 2 atmosphere, and is stirred at 700 rpm or less using a stirring blade at 30 to 60 ° C., preferably 40 ° C. to Warm to 60 ° C.
前記調温された溶媒へ、前記ニッケル塩水溶液を１ｇ／ｍｉｎ以上の添加速度で連続添加する。尚、当該添加時間が３０分間〜１時間以内になる添加速度で添加するのが好ましい。尚、当該添加方法は、上述したように、ヒドラジン水溶液へニッケル塩水溶液を連続添加する方法が好ましいが、ニッケル塩水溶液へヒドラジン水溶液を連続添加することも出来る。
当該添加中の溶媒の液温は２０〜６０℃、好ましくは２０〜３０℃とする。
生成するニッケル−ヒドラジン錯体は［Ｎｉ（Ｎ２Ｈ４）３］Ｃｌ２、［Ｎｉ（Ｎ２Ｈ４）２］Ｃｌ２と考えられる。ニッケル−ヒドラジン錯体の形状は殆ど球状となるが、楕円状、針状でもよい。
The nickel salt aqueous solution is continuously added to the temperature-controlled solvent at an addition rate of 1 g / min or more. In addition, it is preferable to add at the addition speed | rate which the said addition time will be within 30 minutes-1 hour. As described above, the addition method is preferably a method in which the nickel salt aqueous solution is continuously added to the hydrazine aqueous solution, but the hydrazine aqueous solution can also be continuously added to the nickel salt aqueous solution.
The liquid temperature of the solvent during the addition is 20 to 60 ° C, preferably 20 to 30 ° C.
The produced nickel-hydrazine complex is considered to be [Ni (N 2 H 4 ) 3 ] Cl 2 , [Ni (N 2 H 4 ) 2 ] Cl 2 . The shape of the nickel-hydrazine complex is almost spherical, but may be oval or needle-shaped.
（ニッケル−ヒドラジン錯体の分離工程）
製造したニッケル−ヒドラジン錯体を、溶液から固液分離する。
具体的には、製造したニッケル−ヒドラジン錯体を、加圧ろ過、吸引ろ過、フィルタープレス等を用いて溶液から分離する。この際、分離された固形物（ニッケル−ヒドラジン錯体）の厚みがあることが望ましい。洗浄において通水する際に短時間でも保水させ、ヒドラジンを分散、分離するためである。例えば、最も薄い箇所でも１ｍｍ以上、最も厚い箇所でも３０ｍｍ以下となるように分離装置、または錯体量を調整することが好ましい。後工程のニッケル−ヒドラジン錯体の洗浄工程において、保水性と通水性とのバランスが図れることで固形物内部のヒドラジンの残留をなくすことができるからである。
(Nickel-hydrazine complex separation step)
The produced nickel-hydrazine complex is solid-liquid separated from the solution.
Specifically, the produced nickel-hydrazine complex is separated from the solution using pressure filtration, suction filtration, filter press, or the like. At this time, it is desirable that the separated solid (nickel-hydrazine complex) has a thickness. This is because the hydrazine is dispersed and separated by allowing water to be retained even for a short time when passing water in the washing. For example, it is preferable to adjust the separation device or the complex amount so that the thinnest portion is 1 mm or more and the thickest portion is 30 mm or less. This is because in the subsequent step of washing the nickel-hydrazine complex, the balance between water retention and water permeability can be achieved, so that hydrazine residue in the solid can be eliminated.
（ニッケル−ヒドラジン錯体の洗浄工程）
固液分離した固形物（ニッケル−ヒドラジン錯体）を洗浄する。
具体的には、上記固液分離して得られた２ｍｍ〜５ｍｍの厚みを有する固形物へ、洗浄溶媒を通過させることで洗浄するのが好ましい。洗浄溶媒には純水、エタノール、イソプロピルアルコール、アセトン、またはこれらの混合溶媒を用いることができるが、コスト、生産性の観点から純水が最も好ましい。
このように固形物（ニッケル−ヒドラジン錯体）を定置し、通水することで固形物内にある未反応ヒドラジンを好適に洗い出すことができる。
(Nickel-hydrazine complex washing process)
The solid substance (nickel-hydrazine complex) separated by solid-liquid separation is washed.
Specifically, it is preferable to perform washing by passing a washing solvent through a solid material having a thickness of 2 mm to 5 mm obtained by solid-liquid separation. As the cleaning solvent, pure water, ethanol, isopropyl alcohol, acetone, or a mixed solvent thereof can be used, but pure water is most preferable from the viewpoint of cost and productivity.
In this way, the unreacted hydrazine in the solid can be suitably washed out by placing the solid (nickel-hydrazine complex) and passing water.
前記洗浄により、固形物（ニッケル−ヒドラジン錯体）中に残留する未反応ヒドラジンを除去することができる。しかし、固形物中に残留する未反応ヒドラジンの量は、直接、分析することができない。本発明者らは、洗浄後の洗浄液の酸化還元電位をパラメーターとして、固形物中に残留する未反応ヒドラジンの量を推定することに想到した。具体的には、洗浄後の洗浄液の酸化還元電位が低い（マイナス数字が大きい）ほど、固形物中に残留する未反応ヒドラジン量が多いこととなる。 The unreacted hydrazine remaining in the solid (nickel-hydrazine complex) can be removed by the washing. However, the amount of unreacted hydrazine remaining in the solid cannot be analyzed directly. The present inventors have conceived that the amount of unreacted hydrazine remaining in the solid matter is estimated using the oxidation-reduction potential of the washing solution after washing as a parameter. Specifically, the lower the redox potential of the cleaning liquid after cleaning (the larger the negative number), the greater the amount of unreacted hydrazine remaining in the solid.
一方、固形物（ニッケル−ヒドラジン錯体）を洗浄する洗浄溶媒量は、固形分量に対して２〜３倍量を用いることが好ましい。これは、洗浄溶媒量が固形分量の３倍量以下であれば、当該洗浄に伴うニッケル−ヒドラジン錯体の分解を最小限にすることができるからである。 On the other hand, the amount of the washing solvent for washing the solid (nickel-hydrazine complex) is preferably 2 to 3 times the solid content. This is because if the amount of the washing solvent is not more than 3 times the amount of the solid content, the decomposition of the nickel-hydrazine complex accompanying the washing can be minimized.
所定量の洗浄溶媒で固形物（ニッケル−ヒドラジン錯体）を洗浄した後、固形物に５００ｍＬの純水を通過させ、その通過水の酸化還元電位を測定する。このとき、通過水の酸化還元電位が−７００ｍＶ以上、好ましくは−６５０ｍＶ以上（尚、純水の酸化還元電位は+２００ｍＶである。）であることが好ましい。通過水の酸化還元電位が−７００ｍＶ未満の場合は、固形物中に未反応のヒドラジンが残留していると考えられる。当該洗浄は、通過水の酸化還元電位が−７００ｍＶ以上、好ましくは−６５０ｍＶ以上となる迄、継続する。 After washing the solid (nickel-hydrazine complex) with a predetermined amount of washing solvent, 500 mL of pure water is passed through the solid and the redox potential of the passing water is measured. At this time, the redox potential of the passing water is −700 mV or higher, preferably −650 mV or higher (note that the redox potential of pure water is +200 mV). When the redox potential of the passing water is less than −700 mV, it is considered that unreacted hydrazine remains in the solid. The washing is continued until the redox potential of the passing water becomes −700 mV or more, preferably −650 mV or more.
（ニッケル−ヒドラジン錯体の乾燥工程）
洗浄を終了した固形物（ニッケル−ヒドラジン錯体）を乾燥させる。
具体的には、上記洗浄を終了した固形物を回収し、乾燥装置にて乾燥させる。乾燥装置はＮ２雰囲気下の乾燥機、減圧乾燥機が使用できるが、減圧乾燥機が好ましい。乾燥させる際には固形物をできるだけ細かく粉砕し、その厚みが、できるだけ薄くなるように広げておくことが好ましい。こうすることで水分が蒸発しやすくなる。固形物の乾燥条件は、乾燥温度は３０℃以下、減圧度は０．０５ＭＰａ以下が好ましい。減圧時にはＮ２ガスを流して乾燥を促進させることも可能である。乾燥させた固形物中の水分量が２%以下となる迄、実施することが望ましい。固形物中の水分量が２％以下であれば、ニッケル−ヒドラジン錯体の凝集が起こらないと同時に、ニッケル−ヒドラジン錯体の分解も抑制することが可能である。
(Drying process of nickel-hydrazine complex)
The solid matter (nickel-hydrazine complex) that has been washed is dried.
Specifically, the solid matter that has been washed is collected and dried by a drying device. As the drying apparatus, a dryer under a N 2 atmosphere or a vacuum dryer can be used, but a vacuum dryer is preferable. When drying, it is preferable to pulverize the solid as finely as possible and spread it so that its thickness is as thin as possible. By doing so, moisture easily evaporates. As for the drying conditions of the solid material, the drying temperature is preferably 30 ° C. or lower, and the degree of vacuum is preferably 0.05 MPa or lower. It is also possible to promote drying by flowing N 2 gas during decompression. It is desirable to carry out until the moisture content in the dried solid is 2% or less. If the water content in the solid is 2% or less, the aggregation of the nickel-hydrazine complex does not occur, and at the same time, the decomposition of the nickel-hydrazine complex can be suppressed.
（ニッケル−ヒドラジン錯体の再分散工程）
乾燥させたニッケル−ヒドラジン錯体を溶媒中に分散させ、分散液を得る。
具体的には、乾燥させたニッケル−ヒドラジン錯体を純水中に添加し、超音波処理やミキサーなどによって攪拌してニッケル−ヒドラジン錯体を純水中に分散させ、分散液を得る。当該分散は、次のニッケルナノ粒子の製造工程において、アルカリの添加と同時に行っても良い。尤も、より分散性の高いニッケルナノ粒子を得るためには、予め、ニッケル−ヒドラジン錯体を溶媒等の液に分散させる構成が好ましい。
(Redispersion step of nickel-hydrazine complex)
The dried nickel-hydrazine complex is dispersed in a solvent to obtain a dispersion.
Specifically, the dried nickel-hydrazine complex is added to pure water and stirred by ultrasonic treatment or a mixer to disperse the nickel-hydrazine complex in pure water to obtain a dispersion. The dispersion may be performed simultaneously with the addition of alkali in the next nickel nanoparticle production process. However, in order to obtain nickel nanoparticles with higher dispersibility, a configuration in which a nickel-hydrazine complex is dispersed in a liquid such as a solvent in advance is preferable.
（ニッケルナノ粒子の製造工程）
水中に分散したニッケル−ヒドラジン錯体から、ニッケルナノ粒子を製造する工程である。
得られた分散液を攪拌しながら２０〜６０℃、好ましくは４０〜５０℃まで昇温してからアルカリを添加する。分散液が６０℃以下なら、ニッケル−ヒドラジン錯体が安定だからである。
(Manufacturing process of nickel nanoparticles)
This is a process for producing nickel nanoparticles from a nickel-hydrazine complex dispersed in water.
While stirring the obtained dispersion, the temperature is raised to 20 to 60 ° C., preferably 40 to 50 ° C., and then an alkali is added. This is because the nickel-hydrazine complex is stable when the dispersion is 60 ° C. or lower.
分散液の昇温時間は、例えば４０℃〜６０℃まで昇温するなら、６０分間以内が良く、好ましくは３０分間以内であり、１５分間以内がさらに好ましい。分散液における４０℃〜６０℃までの昇温時間が６０分間以内なら、ニッケル−ヒドラジン錯体が安定だからである。
前記アルカリとしては、ＮａＯＨ水溶液、ＫＯＨ水溶液等が使用できる。これらアルカリ水溶液の濃度は、５０質量％以下であると水溶液の粘度が上昇せず、作業性に優れる。
加温された分散液へのアルカリの添加量は、分散液に含まれるニッケル−ヒドラジン錯体中のニッケル１モルに対して、３〜１８モル、好ましくは６〜１２モル、最も好ましくは１２モルである。
分散液への、アルカリの添加方法は、一挙に添加することが好ましく、添加時間１０秒以内で加圧添加することも好ましい。アルカリの添加時の雰囲気は、大気下、Ｎ２雰囲気下、Ａｒなどの不活性ガス雰囲気下とするのが好ましい、中でもＮ２雰囲気下が好ましい。
当該アルカリの添加後、分散液を３０分間〜３時間、好ましくは３０分間〜２時間、熟成させてニッケルナノ粒子を製造する。
The temperature rise time of the dispersion is, for example, within 60 minutes, preferably within 30 minutes, more preferably within 15 minutes if the temperature is raised to 40 ° C to 60 ° C. This is because the nickel-hydrazine complex is stable when the temperature rise time from 40 ° C. to 60 ° C. in the dispersion is within 60 minutes.
As said alkali, NaOH aqueous solution, KOH aqueous solution, etc. can be used. When the concentration of these alkaline aqueous solutions is 50% by mass or less, the viscosity of the aqueous solution does not increase and the workability is excellent.
The amount of alkali added to the heated dispersion is 3 to 18 mol, preferably 6 to 12 mol, and most preferably 12 mol, relative to 1 mol of nickel in the nickel-hydrazine complex contained in the dispersion. is there.
As a method of adding alkali to the dispersion, it is preferable to add at once, and it is also preferable to add under pressure within 10 seconds. The atmosphere at the time of addition of alkali is preferably air, N 2 atmosphere, or an inert gas atmosphere such as Ar, and N 2 atmosphere is particularly preferable.
After the addition of the alkali, the dispersion is aged for 30 minutes to 3 hours, preferably 30 minutes to 2 hours to produce nickel nanoparticles.
製造したニッケルナノ粒子を固液分離によって分散液から回収し、洗浄した後、乾燥を行ってニッケルナノ粒子を得た。
固液分離および洗浄方法としては、加圧ろ過、吸引ろ過、フィルタープレス等が使用できる。洗浄水は、製造したニッケルナノ粒子の重量の１０倍以下が好ましく、さらには５〜７倍が好ましい。
乾燥は低温乾燥が好ましいので、真空乾燥機、Ｎ２、Ａｒなどの不活性ガス流通下での乾燥が好ましい。具体的には、２０℃〜５０℃、好ましくは３０℃〜５０℃、Ｎ２雰囲気下、６時間以上が好ましい。
The manufactured nickel nanoparticles were recovered from the dispersion by solid-liquid separation, washed, and then dried to obtain nickel nanoparticles.
As the solid-liquid separation and washing method, pressure filtration, suction filtration, filter press and the like can be used. The washing water is preferably 10 times or less, more preferably 5 to 7 times the weight of the produced nickel nanoparticles.
Since drying is preferably performed at a low temperature, drying under a circulation of an inert gas such as a vacuum dryer, N 2 , or Ar is preferable. Specifically, 20 ° C. to 50 ° C., preferably 30 ° C. to 50 ° C., and preferably 6 hours or longer under N 2 atmosphere.
以上、説明した液相反応を用いた製造方法により、粒径制御用等の有機剤や分散剤を使用することなく、平均粒径１００ｎｍ以下であって、粒径における変動係数が２０％以下であるニッケルナノ粒子（粒子粉）を、低コストで高い生産性をもって製造することが出来た。
そして、本発明に係る平均粒径１００ｎｍ以下であって、粒径における変動係数が２０％以下であるニッケルナノ粒子を用いることで、例えば、ニッケルナノ粒子に、所定量のテルピネオールおよび所定量のエチルセルロースを加えて３本ロールで混練するといった公知の方法で、容易に、高特性のニッケルペーストを製造することが出来た。
As described above, by the production method using the liquid phase reaction described above, the average particle size is 100 nm or less and the coefficient of variation in the particle size is 20% or less without using an organic agent or dispersant for controlling the particle size. A certain nickel nanoparticle (particle powder) could be manufactured at low cost and high productivity.
Then, by using nickel nanoparticles having an average particle size of 100 nm or less and a coefficient of variation in particle size of 20% or less according to the present invention, for example, a predetermined amount of terpineol and a predetermined amount of ethyl cellulose are used as the nickel nanoparticles. In addition, a nickel paste having high characteristics could be easily produced by a known method of kneading with three rolls.
［実施例１］
（ニッケル−ヒドラジン錯体の製造）
塩化ニッケル・六水和物（和光純薬工業製）１５．２１ｇを、純水２７．６７ｇに溶解させた塩化ニッケル水溶液を準備した。
一方、８０質量％ヒドラジン・一水和物（昭和化学製）４７．８９ｇを攪拌し、１５分間かけて、温度６０℃に調温してヒドラジン水溶液を準備した。
当該ヒドラジン水溶液へ、前記塩化ニッケル水溶液を１ｇ／ｍｉｎの速度で連続的に添加し、ニッケル−ヒドラジン錯体を製造した。
[Example 1]
(Production of nickel-hydrazine complex)
A nickel chloride aqueous solution in which 15.21 g of nickel chloride hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 27.67 g of pure water was prepared.
Meanwhile, 47.89 g of 80% by mass hydrazine monohydrate (manufactured by Showa Chemical) was stirred and adjusted to a temperature of 60 ° C. over 15 minutes to prepare an aqueous hydrazine solution.
The nickel chloride aqueous solution was continuously added to the hydrazine aqueous solution at a rate of 1 g / min to produce a nickel-hydrazine complex.
（ニッケル−ヒドラジン錯体の回収、洗浄・乾燥）
ニッケル−ヒドラジン錯体が生成した液を、加圧ろ過器（ＫＳＴ−１４２、東洋濾紙会社製）を使用し、固形物（ニッケル−ヒドラジン錯体）を回収した。濾紙は孔径１．０μｍのＰＴＦＥ濾紙（Ｈ１００Ａ１４２Ｃ、東洋濾紙会社製）を用いた。
回収された固形物（ニッケル−ヒドラジン錯体）をＰＴＦＥ濾紙上に、厚みが最も薄い箇所で２ｍｍ以上、最も厚い箇所で５ｍｍ以下となるように設置し、純水１００ｍＬで洗浄を行った。この時、洗浄水の酸化還元電位は−６２９ｍＶであった。
洗浄した固形物を減圧乾燥機内に装填し、窒素ガスを流しながら、室温で１２時間以上減圧乾燥を行った。この時、固形物中の水分量は１．３％であった。
(Recovery, washing and drying of nickel-hydrazine complex)
The liquid in which the nickel-hydrazine complex was produced was collected using a pressure filter (KST-142, manufactured by Toyo Roshi Kaisha Co., Ltd.) to recover a solid (nickel-hydrazine complex). As the filter paper, PTFE filter paper (H100A142C, manufactured by Toyo Filter Paper Co., Ltd.) having a pore size of 1.0 μm was used.
The collected solid (nickel-hydrazine complex) was placed on a PTFE filter paper so that the thickness was 2 mm or more at the thinnest part and 5 mm or less at the thickest part, and washed with 100 mL of pure water. At this time, the oxidation-reduction potential of the washing water was −629 mV.
The washed solid was loaded into a vacuum dryer and dried under reduced pressure for 12 hours or more at room temperature while flowing nitrogen gas. At this time, the water content in the solid was 1.3%.
（錯体の分散、ニッケルナノ粒子の製造）
乾燥した固形物（ニッケル−ヒドラジン錯体）１２ｇを純水１７ｇと混合し、超音波処理をしながら１０分程度攪拌を行い、分散液を得た。
当該分散液を攪拌しながら１５分間で５０℃まで昇温し、濃度５０質量％のＮａＯＨ溶液（和光純薬工業製）を６３．２１ｇ添加した。当該ＮａＯＨ溶液添加後、当該分散液を１時間熟成し、ニッケルナノ粒子を製造した。
(Dispersion of complex, production of nickel nanoparticles)
12 g of the dried solid (nickel-hydrazine complex) was mixed with 17 g of pure water and stirred for about 10 minutes while performing ultrasonic treatment to obtain a dispersion.
While stirring the dispersion, the temperature was raised to 50 ° C. over 15 minutes, and 63.21 g of a 50 mass% NaOH solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After the NaOH solution was added, the dispersion was aged for 1 hour to produce nickel nanoparticles.
（ニッケルナノ粒子の回収）
生成した固形物（ニッケルナノ粒子）を加圧ろ過器によって回収し、純水１Ｌで洗浄した。その後、固形物（ニッケルナノ粒子）を減圧乾燥機内に装填し、窒素ガスを流しながら、室温で１２時間減圧乾燥を行って実施例１に係るニッケルナノ粒子を得た。
(Recovery of nickel nanoparticles)
The produced solid (nickel nanoparticles) was collected by a pressure filter and washed with 1 L of pure water. Thereafter, solid matter (nickel nanoparticles) was loaded into a vacuum dryer, and dried under reduced pressure at room temperature for 12 hours while flowing nitrogen gas to obtain nickel nanoparticles according to Example 1.
（ニッケルナノ粒子の性状、特性）
〈粒子径測定〉
実施例１に係るニッケルナノ粒子の粒子径を、走査型電子顕微鏡（株式会社日立製作所製、Ｓ−４７００）を用いて測定した。具体的には、当該走査型電子顕微鏡により得られたＳＥＭ写真を用い、粒子径測定用ソフトウェア（ホーザン株式会社製のＭｏｔｉｃ Ｉｍａｇｅｓ Ｐｌｕｓ）により、１１万倍率（一部５０万倍率）の画像よりニッケルナノ粒子の一次粒子径を算出した。
算出する粒子数は信頼性の観点より、２００個以上の粒子から算出した。算出した粒子径の値を計算ソフトにてヒストグラム解析をすることで、Ｄ５０粒子径、および標準偏差（σＤ）を算出した。
一方、粒子径分布の広さを示す変動係数は以下の（１式）を用いて算出した。
変動係数（％）＝σＤ／Ｄ５０（ＳＥＭ）・・・・・（１式）
ここで「Ｄ５０（ＳＥＭ）」はヒストグラム解析をした頻度分布における５０％粒子径であり、σＤは測定対象とした個々の粒子の粒子径についての標準偏差である。
得られた実施例１に係るニッケルナノ粒子は、略球状の形をしていた。そして、一次粒子径のＤ５０粒径は６８ｎｍ、変動係数は、１３．６％であった。
実施例１に係るニッケルナノ粒子の５万倍率のＳＥＭ写真を、図１に示す。
(Characteristics and properties of nickel nanoparticles)
<Particle size measurement>
The particle diameter of the nickel nanoparticles according to Example 1 was measured using a scanning electron microscope (manufactured by Hitachi, Ltd., S-4700). Specifically, using the SEM photograph obtained by the scanning electron microscope, the particle size measurement software (Motic Images Plus manufactured by Hozan Co., Ltd.) was used to extract nickel from an image of 110,000 magnification (partially 500,000 magnification). The primary particle size of the nanoparticles was calculated.
The number of particles to be calculated was calculated from 200 or more particles from the viewpoint of reliability. The calculated value of the particle size calculated by the histogram analysis with software, to calculate D 50 particle size, and the standard deviation (σ D).
On the other hand, the coefficient of variation indicating the breadth of the particle size distribution was calculated using the following (formula 1).
Coefficient of variation (%) = σ D / D 50 (SEM) (1 formula)
Here, “D 50 (SEM)” is a 50% particle size in the frequency distribution obtained by histogram analysis, and σ D is a standard deviation of the particle size of each particle to be measured.
The obtained nickel nanoparticles according to Example 1 had a substantially spherical shape. Then, D 50 particle size of the primary particle size 68 nm, coefficient of variation was 13.6%.
An SEM photograph at a magnification of 50,000 of the nickel nanoparticles according to Example 1 is shown in FIG.
［実施例２〜４］
実施例１と同様の製造方法であるが、固形物（ニッケル−ヒドラジン錯体）製造後の洗浄水量を、実施例２では５００ｍＬ、実施例３では１．０Ｌ、実施例４では１．５Ｌにて行った。この時、錯体分離時の洗浄水の酸化還元電位は実施例１と同程度で−６５０ｍＶ以上であった。固形物（ニッケル−ヒドラジン錯体）乾燥時の固形物中の水分量は１．５質量％以下であった。
その結果、実施例２〜４の全てにおいてニッケルナノ粒子が得られた。
得られた実施例２〜４に係るニッケルナノ粒子の特性を表１に示す。
実施例２〜４に係るニッケルナノ粒子の５万倍率のＳＥＭ写真を、図２〜４に示す。
[Examples 2 to 4]
Although it is the same manufacturing method as Example 1, the amount of washing water after manufacturing a solid (nickel-hydrazine complex) is 500 mL in Example 2, 1.0 L in Example 3, and 1.5 L in Example 4. went. At this time, the oxidation-reduction potential of the washing water at the time of complex separation was about 650 mV or more, similar to that in Example 1. The amount of water in the solid when the solid (nickel-hydrazine complex) was dried was 1.5% by mass or less.
As a result, nickel nanoparticles were obtained in all of Examples 2 to 4.
The characteristics of the obtained nickel nanoparticles according to Examples 2 to 4 are shown in Table 1.
SEM photographs at 50,000 magnifications of the nickel nanoparticles according to Examples 2 to 4 are shown in FIGS.
［実施例５〜８］
実施例１と同様の製造方法であるが、ニッケルナノ粒子を製造する際の分散液の液温を、実施例５では６０℃、実施例６では５５℃、実施例７では４５℃、実施例８では４０℃に設定して行った。この時、固形物（ニッケル−ヒドラジン錯体）の固液分離後の洗浄における洗浄水の酸化還元電位は、実施例１と同程度で−６５０ｍＶ以上であり、乾燥時の固形物中の水分量は１．５質量％以下であった。
その結果、実施例５〜８の全てにおいてニッケルナノ粒子が得られた。
得られた実施例５〜８に係るニッケルナノ粒子の特性を表１に示す。
実施例５〜８に係るニッケルナノ粒子の５万倍率のＳＥＭ写真を、図５〜８に示す。
[Examples 5 to 8]
The manufacturing method is the same as in Example 1, but the temperature of the dispersion liquid when manufacturing nickel nanoparticles is 60 ° C. in Example 5, 55 ° C. in Example 6, 45 ° C. in Example 7, and Example No. 8 was set at 40 ° C. At this time, the oxidation-reduction potential of the washing water in the washing after solid-liquid separation of the solid (nickel-hydrazine complex) is about -650 mV, which is the same as in Example 1, and the amount of water in the solid at the time of drying is It was 1.5 mass% or less.
As a result, nickel nanoparticles were obtained in all of Examples 5 to 8.
Table 1 shows the characteristics of the obtained nickel nanoparticles according to Examples 5 to 8.
The SEM photograph of 50,000 magnifications of the nickel nanoparticles according to Examples 5 to 8 is shown in FIGS.
［実施例９］
ニッケル原料を、塩化ニッケル・６水和物から、硫酸ニッケル・６水和物（和光純薬工業製）に変更した以外は、実施例１と同様の操作を行なって、実施例６に係るニッケルナノ粒子を得た。この時、固形物（ニッケル−ヒドラジン錯体）の固液分離後の洗浄における洗浄水の酸化還元電位は、実施例１と同程度で−６５０ｍＶ以上であり、乾燥時の固形物中の水分量は１．５質量％以下であった。
得られた実施例９に係るニッケルナノ粒子の特性を表１に示す。
実施例９に係るニッケルナノ粒子の５万倍率のＳＥＭ写真を、図９に示す。
[Example 9]
Nickel according to Example 6 was obtained by performing the same operation as in Example 1 except that the nickel raw material was changed from nickel chloride hexahydrate to nickel sulfate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.). Nanoparticles were obtained. At this time, the oxidation-reduction potential of the washing water in the washing after solid-liquid separation of the solid (nickel-hydrazine complex) is about -650 mV, which is the same as in Example 1, and the amount of water in the solid at the time of drying is It was 1.5 mass% or less.
Table 1 shows the characteristics of the obtained nickel nanoparticles according to Example 9.
An SEM photograph at a magnification of 50,000 of the nickel nanoparticles according to Example 9 is shown in FIG.
［比較例１］
実施例１と同様の工程であるが、固形物（ニッケル−ヒドラジン錯体）を製造した後、溶液からの固形物の固液分離、洗浄および乾燥工程を行なわずに、比較例１に係るニッケルナノ粒子を製造した。尚、ニッケル−ヒドラジン錯体製造時の溶液の酸化還元電位は−８８３ｍＶ以下であった。
得られた比較例１に係るニッケル粒子の一次粒子径のＤ５０粒径は２３３ｎｍであり、変動係数は２２．１％であった。尚、比較例１に係るニッケルナノ粒子の形状は歪であった。
得られた比較例１に係るニッケルナノ粒子の特性を表１に示す。
比較例１に係るニッケルナノ粒子の５万倍率のＳＥＭ写真を、図１０に示す。
[Comparative Example 1]
Although it is the process similar to Example 1, after manufacturing a solid substance (nickel-hydrazine complex), solid-liquid separation of the solid substance from a solution, washing | cleaning, and a drying process are not performed, but the nickel nanometer which concerns on the comparative example 1 Particles were produced. The oxidation-reduction potential of the solution at the time of producing the nickel-hydrazine complex was −883 mV or less.
The D 50 particle diameter of the primary particle diameter of the nickel particles according to Comparative Example 1 obtained was 233 nm, and the coefficient of variation was 22.1%. In addition, the shape of the nickel nanoparticle which concerns on the comparative example 1 was distortion.
The characteristics of the obtained nickel nanoparticles according to Comparative Example 1 are shown in Table 1.
A SEM photograph of nickel nanoparticles according to Comparative Example 1 at a magnification of 50,000 is shown in FIG.
[比較例２]
実施例１と同様の工程であるが、固形物（ニッケル−ヒドラジン錯体）を製造した後、溶液からの固形物の固液分離を行い、洗浄せずに錯体を乾燥させてニッケル粒子を製造し、比較例２に係るニッケルナノ粒子を製造した。尚、ニッケル−ヒドラジン錯体製造後の、ろ液の酸化還元電位は−８５１ｍＶ以下であった。
得られた比較例２に係るニッケルナノ粒子の一次粒子径のＤ５０粒径は１３０ｎｍであり、変動係数は２５．５％であった。
得られた比較例２に係るニッケルナノ粒子の特性を表１に示す。
比較例２に係るニッケルナノ粒子の５万倍率のＳＥＭ写真を、図１１に示す。
[Comparative Example 2]
Although it is the same process as Example 1, after manufacturing a solid substance (nickel-hydrazine complex), solid-liquid separation of the solid substance from a solution is performed, a complex is dried without washing, and nickel particles are manufactured. The nickel nanoparticles according to Comparative Example 2 were produced. The oxidation-reduction potential of the filtrate after the production of the nickel-hydrazine complex was −851 mV or less.
D 50 particle size of the primary particle size of the nickel nanoparticles of Comparative Example 2 obtained is 130 nm, coefficient of variation was 25.5%.
The characteristics of the obtained nickel nanoparticles according to Comparative Example 2 are shown in Table 1.
An SEM photograph at 50,000 magnifications of the nickel nanoparticles according to Comparative Example 2 is shown in FIG.
［比較例３］
実施例１と同様であるが、ヒドラジン・一水和物水溶液とＮａＯＨとの添加順序を逆にしてニッケルナノ粒子を製造した。即ち、一般的な水酸化物の還元方法によりニッケルナノ粒子を製造した。
その結果、溶液へのＮａＯＨ混合によって、まず水酸化ニッケルが製造し、次にヒドラジンを投入することで還元反応が起こり、比較例３に係るニッケルナノ粒子が得られた。
得られた比較例３に係るニッケルナノ粒子の一次粒子径のＤ５０粒径は７００ｎｍであり、変動係数は２８．５％であった。
得られた比較例３に係るニッケル粒子は表面の凹凸が激しく、形状も球状や楕円状など歪な形状のものが多数確認された。
得られた比較例３に係るニッケルナノ粒子の特性を表１に示す。
比較例３に係るニッケルナノ粒子の５万倍率のＳＥＭ写真を、図１２に示す。
[Comparative Example 3]
Nickel nanoparticles were produced in the same manner as in Example 1, except that the order of addition of the hydrazine monohydrate aqueous solution and NaOH was reversed. That is, nickel nanoparticles were produced by a general hydroxide reduction method.
As a result, nickel hydroxide was first produced by mixing NaOH into the solution, and then hydrazine was added to cause a reduction reaction, whereby nickel nanoparticles according to Comparative Example 3 were obtained.
The D 50 particle diameter of the primary particle diameter of the nickel nanoparticles according to Comparative Example 3 obtained was 700 nm, and the coefficient of variation was 28.5%.
The obtained nickel particles according to Comparative Example 3 were found to have many irregular shapes on the surface and many distorted shapes such as spherical and elliptical shapes.
The characteristics of the obtained nickel nanoparticles according to Comparative Example 3 are shown in Table 1.
An SEM photograph at 50,000 magnifications of the nickel nanoparticles according to Comparative Example 3 is shown in FIG.
［まとめ］
上述した実施例、比較例より以下のことが判明した。
本発明に係るニッケル−ヒドラジン錯体からニッケル粒子を製造する製造方法において、ニッケル−ヒドラジン錯体の洗浄を本発明条件にすること、また乾燥条件においても本発明条件にしてニッケルナノ粒子を製造することで、一次粒子径のＤ５０粒径が１００ｎｍ以下であり、粒径における変動係数が２０％以下であるニッケルナノ粒子を、容易に製造することができた。
これに対し、錯体の洗浄・乾燥工程を行わない製造方法や、従来の技術に係るニッケル化合物とアルカリとから水酸化ニッケルを製造し、ここへヒドラジンを添加してニッケル粒子を得る方法では、一次粒子径のＤ５０粒径が１００ｎｍ以下のニッケルナノ粒子を得ることは困難であった。
[Summary]
From the examples and comparative examples described above, the following was found.
In the production method for producing nickel particles from the nickel-hydrazine complex according to the present invention, the nickel-hydrazine complex is washed under the present invention conditions, and the nickel nanoparticles are produced under the present invention conditions even under dry conditions. , D 50 particle size of the primary particle diameter is not more 100nm or less, variations in grain size coefficient of the nickel nanoparticles is 20% or less, it could be easily manufactured.
On the other hand, in the manufacturing method in which the complex washing / drying process is not performed, or in the method in which nickel hydroxide is manufactured from a nickel compound and an alkali according to the conventional technique and hydrazine is added thereto to obtain nickel particles, D 50 particle size of the particle size was difficult to get the following nickel nanoparticles 100 nm.
Claims (9)
前記ニッケル−ヒドラジン錯体を溶液から固液分離し、得られたニッケル−ヒドラジン錯体を洗浄する工程と、
前記洗浄したニッケル−ヒドラジン錯体にアルカリを添加して、ニッケルナノ粒子を製造する工程を有することを特徴とするニッケルナノ粒子の製造方法。 Forming a nickel-hydrazine complex from the nickel compound solution and the hydrazine compound solution;
Solid-liquid separation of the nickel-hydrazine complex from the solution and washing the resulting nickel-hydrazine complex;
A method for producing nickel nanoparticles, comprising: adding nickel to the washed nickel-hydrazine complex to produce nickel nanoparticles.
洗浄液として純水を用い、洗浄後における洗浄液の酸化還元電位が−７００ｍＶ以上となるまで、純水を通過させることで洗浄を行うことを特徴とする、請求項１に記載のニッケルナノ粒子の製造方法。 When the nickel-hydrazine complex is solid-liquid separated from the solution and the resulting nickel-hydrazine complex is washed,
The production of nickel nanoparticles according to claim 1, wherein pure water is used as a cleaning liquid, and cleaning is performed by passing pure water until the oxidation-reduction potential of the cleaning liquid after cleaning becomes -700 mV or more. Method.
前記ニッケル−ヒドラジン錯体を乾燥させる工程において、ニッケル−ヒドラジン錯体の水分量が２質量％以下になるまで、乾燥させることを特徴とする、請求項１に記載のニッケルナノ粒子の製造方法。 Solid-liquid separation of the nickel-hydrazine complex from the solution, washing the resulting nickel-hydrazine complex, and drying the obtained nickel-hydrazine complex before adding the alkali,
2. The method for producing nickel nanoparticles according to claim 1, wherein in the step of drying the nickel-hydrazine complex, the nickel-hydrazine complex is dried until the water content becomes 2 mass% or less.
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