JP2004027347A - Metal colloid organosol and method for manufacturing the same - Google Patents
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Abstract
Description
【０００１】
【産業上の利用分野】
本発明は、高濃度であって、且つ、ナノオーダーのサイズの金属コロイド粒子の粒度分布が狭い金属コロイドオルガノゾルを提供する。
【０００２】
【従来の技術】
Ａｕ、Ａｇ、Ｐｔ等の貴金属及びＦｅ、Ｃｏ、Ｎｉ等の遷移金属からなる金属コロイド粒子は触媒用材料、磁気記録用材料、着色顔料等に用いられている。
【０００３】
特に、平均粒子径が数ｎｍ程度であるナノオーダーサイズの金属コロイド粒子は、触媒用材料として用いる場合には触媒活性が高いこと、磁気記録用材料として用いる場合には単分散であること、着色顔料として用いる場合には単分散であって、しかも、高濃度であることが強く要求されている。
【０００４】
しかしながら、ナノオーダーサイズの金属コロイドオルガノゾルは、高濃度にすると凝集が生じやすく、粒度分布の広いものとなる。さらに、粒度分布の狭いナノオーダーサイズの金属コロイド粒子の作製には、特殊な装置、高度な技術が必要であり、高濃度及び粒度分布の狭い金属コロイドナノ粒子を経済的、工業的に有利に得ることは現在最も要求されているところである。
【０００５】
従来、金属ナノ粒子を製造する方法としては、溶媒中に金属塩とアミンを溶解した溶液を還元し、さらにチオールを添加し表面を保護する方法（特開平１０−１９５５０５号公報）、貴金属化合物を溶媒に溶解し、高分子量の顔料分散剤を加えた後、還元する方法（特開平１１−８０６４７号公報）、金属前駆体溶液に界面活性剤を加えた後還元する方法（特開２０００−５４０１２号公報）及び塩化金酸と保護高分子とを加熱混合する方法（特開２０００−１６０２１０号公報）等が知られている。
【０００６】
【発明が解決しようとする課題】
ナノオーダーサイズの金属コロイド粒子が高濃度であって、しかも、粒度分布の狭い金属コロイドオルガノゾルは現在最も要求されているところであるが、未だそのような金属コロイドオルガノゾルは得られていない。
【０００７】
即ち、前出特開平１０−１９５５０５号公報には、チオールを添加することによって金属超微粒子を得る方法が記載されているが、チオールを添加して金属超微粒子の粒子表面を保護する必要があり、また、得られる金属超微粒子の濃度は十分に高いものとは言い難い。
【０００８】
また、前出特開平１１−８０６４７号公報記載の方法は１０ｍｍｏｌ／ｋｇ以上の高濃度のオルガノゾルを得ることができるが、特殊な高分子量顔料分散剤を必要とするものであるため工業的、経済的に製造できるとは言い難い。
【０００９】
また、前出特開２０００−５４０１２号公報記載の方法は単分散ナノ粒子が作製できるが、１００〜３００℃の温度範囲で加熱することが必要であり、また、原料が高価であり工業的、経済的に製造できるとは言い難い。
【００１０】
また、前出特開２０００−１６０２１０号公報記載の方法は、５０ｍｍｏｌ／ｋｇ以上の高濃度の保護高分子中に分散させた、金微粒子が作製できるが、この方法はＡｕ以外の元素には適用できない。
【００１１】
そこで、本発明は、１０ｍｍｏｌ／ｋｇ以上の高濃度であって、且つ、ナノオーダーサイズの金属コロイド粒子であって、粒度分布の狭い金属コロイドオルガノゾルを特殊な材料や装置を用いることなく工業的、経済的に有利に得ることを技術的課題とする。
【００１２】
【課題を解決する為の手段】
前記技術的課題は、以下の通りの本発明により達成することができる。
【００１３】
本発明は、金属コロイド粒子と脂肪族アミンとを有機溶剤に分散した金属コロイドオルガノゾルであって、前記金属コロイド粒子が下記式
金属コロイド粒子の変換係数＝σ／ｘ×１００（％）
（式中、σは金属コロイド粒子の粒度分布の標準偏差を示し、ｘは金属コロイド粒子の平均粒径（ｎｍ）を示す。）から算出される金属コロイド粒子の変換係数が２０％以下であって金属濃度が１０ｍｍｏｌ／ｋｇ以上であり、前記有機溶剤のＨａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒが２０ＭＰａ１／２以下であることを特徴とする金属コロイドオルガノゾルである（本発明１）。
【００１４】
また、本発明は、金属コロイド粒子、脂肪族アミン及び脂肪酸を有機溶剤に分散した金属コロイドオルガノゾルであって、前記金属コロイド粒子が下記式
金属コロイド粒子の変換係数＝σ／ｘ×１００（％）
（式中、σは金属コロイド粒子の粒度分布の標準偏差を示し、ｘは金属コロイド粒子の平均粒径（ｎｍ）を示す。）から算出される金属コロイド粒子の変換係数が２０％以下であって金属濃度が１０ｍｍｏｌ／ｋｇ以上であり、前記有機溶剤のＨａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒが２０ＭＰａ１／２以下であることを特徴とする金属コロイドオルガノゾルである（本発明２）。
【００１５】
また、本発明は、Ｈａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒが２０ＭＰａ１／２以下である有機溶媒中に金属塩と脂肪族アミンとを混合・攪拌した後、還元することを特徴とする請求項１記載の金属コロイドオルガノゾルの製造法である（本発明３）。
【００１６】
また、本発明は、Ｈａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒが２０ＭＰａ１／２以下である有機溶媒中に、金属塩、脂肪族アミン及び脂肪酸を混合・攪拌した後、還元することを特徴とする請求項２記載の金属コロイドオルガノゾルの製造法である（本発明４）。
【００１７】
本発明の構成を詳しく説明すれば、次の通りである。
【００１８】
先ず、本発明に係る金属コロイドオルガノゾルについて述べる。
【００１９】
本発明に係る金属コロイドオルガノゾルは、Ａｕ、Ｐｔ、Ａｇ、Ｒｈ、Ｒｕ及びＰｄ等の貴金属、Ｃｒ、Ｆｅ、Ｃｏ、Ｎｉ及びＣｕ等の遷移金属から選ばれる１種又は２種以上からなる金属コロイド粒子を含有する。
【００２０】
本発明に係る金属コロイドオルガノゾル中の金属コロイド粒子は、変換係数が２０％以下である。変換係数が２０％を越える場合には、粗大粒子が存在するため経済的ではなく、触媒材料用に用いる場合には、触媒活性が低下する。また磁気記録材料として用いる場合には、基板上にナノ粒子が均一な間隔で配置しない。好ましくは５〜１９％である。
【００２１】
本発明に係る金属コロイドオルガノゾル中の金属濃度は１０ｍｍｏｌ／ｋｇ以上である。上限値は１０００ｍｍｏｌ／ｋｇである。
【００２２】
本発明に係る金属オルガノゾル中の金属コロイドナノ粒子の平均粒子径は１．０〜１０ｎｍが好ましい。
【００２３】
本発明における脂肪族アミンとしては、下記表１に示す各脂肪族アミンである。
【００２４】
【表１】
本発明に係る金属コロイドオルガノゾル中の脂肪族アミンの含有量は、金属に対してモル比で０．０５を超える量が好ましい。０．０５未満の場合には、金属塩と脂肪族アミンの結合が不十分となり、粒度分布に優れた金属コロイド粒子が得られない。上限値は１０モル倍である。より好ましくは０．２〜５モル倍である。
【００２６】
本発明における有機溶媒としてはＨａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒが２０ＭＰａ１／２以下のものを使用する。有機溶媒のＨａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒが２０ＭＰａ１／２を越える場合には、粒度分布の狭い金属コロイドナノ粒子を得ることが困難となる。
【００２７】
本発明における有機溶媒としては、例えば、ヘキサン（Ｈａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒ：１４．９ＭＰａ１／２）、オクタン（１５．６ＭＰａ１／２）、シクロヘキサン（１６．８ＭＰａ１／２）、ベンゼン（１８．６ＭＰａ１／２）、トルエン（１８．２ＭＰａ１／２）及びキシレン（１８．０ＭＰａ１／２）等の炭化水素が使用できる。前記有機溶媒は単独で使用しても二種類以上を併用して使用しても良い。
【００２８】
本発明においては、金属コロイドオルガノゾルに対して脂肪酸を含有させることによって、分散安定性が向上する。脂肪酸の含有量は金属に対してモル比で０．０５〜１０が好ましい。
【００２９】
脂肪酸としては、１０〜２２の炭素原子を有する高級脂肪酸を使用することができる。例えば、オレイン酸、ステアリン酸、エルカ酸、リノール酸、ペンタデカン酸、リノレン酸を使用することができる。
【００３０】
次に、本発明に係る金属コロイドオルガノゾルの製造法について述べる。
【００３１】
本発明における金属塩は、特に限定されることはないが、例えば、Ａｕ、Ｐｔ、Ａｇ、Ｒｈ、Ｒｕ及びＰｄ等の貴金属の金属塩、Ｃｒ、Ｆｅ、Ｃｏ、Ｎｉ及びＣｕ等の遷移金属の金属塩から選ばれる１種又は２種以上からなる。
【００３２】
具体的には硝酸銀、塩化金酸、塩化白金酸、塩化ロジウム、塩化ルテニウム、塩化パラジューム、塩化銅、塩化ニッケル、塩化コバルト、塩化クロム、硫酸鉄、酢酸銅、酢酸ニッケル等の硝酸塩、塩化物、硫酸塩、酢酸塩を使用することができる。
【００３３】
本発明における脂肪族アミンの添加量は、金属に対してモル比で０．０５を超える量である。０．０５未満の場合には、金属塩と脂肪族アミンの結合が不十分となり、粒度分布に優れた金属コロイド粒子が得られない。上限値は１０モル倍である。好ましくは、０．２〜５モル倍である。
【００３４】
本発明における有機溶媒としては前記Ｈａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒが２０ＭＰａ１／２以下の有機溶媒を使用する。
【００３５】
金属濃度は１０ｍｍｏｌ／ｋｇ以上が好ましく、より好ましくは１００ｍｍｏｌ／ｋｇ以上である。その上限は１０００ｍｍｏｌ／ｋｇである。１０００ｍｍｏｌ／ｋｇ以上では粘性が高くなり、取り扱いが困難になる。
【００３６】
前記金属塩、脂肪族アミン及び有機溶媒の混合・攪拌は、十分に分散させることが出来る装置・条件であれば特に限定されないが、例えば、マグネッチクスターラ、ボールミル、超音波分散機等が使用できる。
【００３７】
還元は、化学還元法又は光照射法のいずれかを使用することができ、特に限定されない。例えば、化学還元法に用いる還元剤は、水素化ホウ素ナトリウム、ヒドラジン、ヒドラジン一水和物、クエン酸ナトリウム及びコハク酸などであり、光照射法は高圧水銀灯を用いる方法などを挙げることができる。
【００３８】
還元剤の濃度下限は金属塩に対して２モル倍、上限は５０モル倍である。より好ましくは３〜３０モル倍量である。
【００３９】
得られた金属コロイドオルガノゾルは、用途によっては水洗してもよい。
【００４０】
また、本発明に係る金属コロイドオルガノゾルは、金属塩と脂肪族アミンとの混合溶液に対して、更に、前記脂肪酸を添加して混合・攪拌してもよい。脂肪酸を添加することによって分散性を向上させることができる。
【００４１】
脂肪酸の添加量は、金属に対してモル比で０．０５〜１０が好ましい。
【００４２】
【発明の実施の形態】
本発明の代表的な実施の形態は、次の通りである。
【００４３】
平均粒子径は、電子顕微鏡観察で撮影した画像の粒子に対して統計解析（グラッテク株式会社製 デジタイザＫＤ４６２０）から求めた。
【００４４】
粒子サイズの標準偏差σは、電子顕微鏡観察で撮影した画像の粒子に対して統計解析（グラフテック株式会社製 デジタイザＫＤ４６２０）から求めた。
【００４５】
金属コロイド粒子の変換係数は前記平均粒子径ｘ（ｎｍ）と前記標準偏差σとから下記式に従って算出した。
金属コロイド粒子の変換係数＝σ／ｘ×１００（％）
【００４６】
＜Ｐｔコロイドオルガノゾルの合成（本発明３による製造）＞
白金の金属化合物Ｈ２ＰｔＣｌ６・６Ｈ２Ｏ １．００ｇとＮ−牛脂アルキル−１，３−ジアミノプロパン（商品名：デュオミンＴ、ライオン・アクゾ株式会社製） ０．６０ｇと有機溶媒シクロヘキサン（Ｈａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒ：１６．８ＭＰａ１／２）１７．７１ｇとをフラスコに採取し、室温で２４時間、ボールミルで攪拌混合し金属コロイドオルガノゾル用材料を得た。還元剤としてＮａＢＨ４ ０．３７ｇを前記貴金属コロイドオルガノゾル用材料に室温で加え、マグネッチクスターラで１２時間攪拌混合して黒褐色の白金コロイドオルガノゾルを得た。
【００４７】
ここに得た金属コロイドオルガノゾルは金属濃度が９８ｍｍｏｌ／ｋｇであって金属コロイド粒子の平均粒径が６．６ｎｍ、変換係数が１８％の粒子である粒度分布の狭い白金コロイドオルガノゾルであった。
【００４８】
【作用】
本発明において最も重要な点は、金属塩と脂肪族アミンとをＨａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒが２０ＭＰａ１／２以下の有機溶媒中に含有させて還元することによって、得られる金属コロイドナノ粒子が高濃度で得られ、粒度分布に優れているという点である。
【００４９】
本発明において粒度分布に優れる金属コロイドナノ粒子が得られる理由として、本発明者は、還元前に脂肪族アミンを存在させることによって、溶媒中で金属塩と脂肪族アミンが錯体を形成した後、還元することによって、脂肪族アミンがナノ粒子保護剤として働き、凝集を生じることなく金属コロイドナノ粒子を作製できることによるものと推定している。
【００５０】
また、Ｈａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒが２０ＭＰａ１／２以下の有機溶媒を用いることによって、脂肪族アミンによって保護された大きさが均一な反応場ができるため、容易に粒度分布に優れた金属コロイドナノ粒子を得ることができる。
【００５１】
さらに、本発明において脂肪酸を添加することにより、分散安定性が向上する。
【００５２】
【実施例】
次に、実施例並びに比較例を挙げる。
【００５３】
実施例１〜７
金属化合物の種類及び添加量、脂肪族アミンの種類及び添加量、有機溶媒の種類及び添加量、還元剤の種類及び添加量を種々変化させた以外は前記発明の実施の形態と同様にして金属オルガノゾル用材料を得た。
【００５４】
このときの金属コロイドオルガノゾルの製造条件を表２に、得られた金属コロイドオルガノゾルの諸特性を表４に示す。
【００５５】
実施例８＜Ｐｔコロイドオルガノゾルの合成（本発明４による製造）＞
白金の金属化合物Ｈ２ＰｔＣｌ６・６Ｈ２Ｏ １．００ｇとＮ−牛脂アルキル−１，３−ジアミノプロパン（商品名：デュオミンＴ、ライオン・アクゾ株式会社製）０．６０ｇと有機溶媒シクロヘキサン（Ｈａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒ：１６．８ＭＰａ１／２）１８５．００ｇとオレイン酸０．５５ｇをフラスコに採取し、室温で２４時間、ボールミルで攪拌混合し金属コロイドオルガノゾル用材料を得た。還元剤としてＮ２Ｈ４・Ｈ２Ｏ ０．９７ｇを前記貴金属コロイドオルガノゾル用材料に室温で加え、マグネッチクスターラで１２時間攪拌混合して黒褐色の白金コロイドオルガノゾルを得た。
【００５６】
ここに得た金属コロイドオルガノゾルは金属濃度が１０ｍｍｏｌであって金属コロイド粒子の平均粒径が８．８ｎｍ、変換係数が１５％の粒子である粒度分布の狭いコロイドオルガノゾルであった。
【００５７】
実施例９〜１７
金属化合物の種類及び添加量、脂肪族アミンの種類及び添加量、有機溶媒の種類及び添加量、脂肪酸の種類及び添加量、還元剤の種類及び添加量を種々変化させた以外は前記発明の実施の形態と同様にして金属オルガノゾル用材料を得た。
【００５８】
このときの金属コロイドオルガノゾルの製造条件を表３に、得られた金属コロイドオルガノゾルの諸特性を表４に示す。なお、アミンとして、Ｎ−牛脂アルキル−１，３−ジアミノプロパン（商品名：デュオミンＴ、ライオン・アクゾ株式会社製）、Ｎ−オレイル１，３−ジアミノプロパン（商品名：デュオミンＯＸ、ライオン・アクゾ株式会社製）を使用した。
【００５９】
比較例１〜３
比較例１では、有機溶媒としてメタノール（Ｈａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒ：２９．７ＭＰａ１／２）を用いた以外は、前記発明の実施の形態と同様にして製造したが、２層に分離し金属ナノ粒子は得られなかった。比較例２では、アミンとしてアニリン（芳香族アミン）を用いた以外は、前記発明の実施の形態と同様にして製造したが、Ｈ２ＰｔＣｌ６・６Ｈ２Ｏがシクロヘキサンに分散しなかったため、製造することができなかった。比較例３では、アミンとしてアニリン（芳香族アミン）を用いて、有機溶媒としてメタノール（Ｈａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒ：２９．７ＭＰａ１／２）を用いた以外は、前記発明の実施の形態と同様にして製造したが、２層に分離し金属コロイドナノ粒子は得られなかった。
【００６０】
【表２】
【表３】
【表４】
【発明の効果】
本発明の製造方法によれば、簡単な製造装置と一般市販の原料を用いて、高濃度であって、且つ、ナノオーダーのサイズであって粒度分布の狭い金属ナノ粒子を得ることができるので、触媒用材料、磁気記録材料等として好適である。[0001]
[Industrial applications]
The present invention provides a metal colloid organosol having a high concentration and a narrow particle size distribution of metal colloid particles having a nano-order size.
[0002]
[Prior art]
Metal colloid particles made of a noble metal such as Au, Ag, and Pt and a transition metal such as Fe, Co, and Ni are used as a catalyst material, a magnetic recording material, a coloring pigment, and the like.
[0003]
In particular, metal colloid particles having a nano-order size having an average particle diameter of about several nanometers have high catalytic activity when used as a material for a catalyst, are monodispersed when used as a material for magnetic recording, and are colored. When used as a pigment, it is strongly required that the pigment be monodispersed and have a high concentration.
[0004]
However, when the metal colloid organosol having a nano-order size is made to have a high concentration, aggregation tends to occur and the particle size distribution becomes broad. Furthermore, the production of nano-order size metal colloid particles having a narrow particle size distribution requires special equipment and advanced technology, and the metal colloid nanoparticles having a high concentration and a narrow particle size distribution are economically and industrially advantageous. Gaining is currently the most demanding.
[0005]
Conventionally, as a method for producing metal nanoparticles, a method in which a solution in which a metal salt and an amine are dissolved in a solvent is reduced, and a thiol is further added to protect the surface (Japanese Patent Application Laid-Open No. 10-195505). A method of dissolving in a solvent, adding a high molecular weight pigment dispersant, and then reducing (JP-A-11-80647), and a method of adding a surfactant to a metal precursor solution and reducing the same (JP-A-2000-54012) And a method of heating and mixing chloroauric acid and a protective polymer (Japanese Patent Laid-Open No. 2000-160210).
[0006]
[Problems to be solved by the invention]
At present, a metal colloid organosol having a high concentration of nano-order size metal colloid particles and a narrow particle size distribution is most demanded, but such a metal colloid organosol has not yet been obtained.
[0007]
That is, Japanese Patent Application Laid-Open No. H10-195505 describes a method of obtaining ultrafine metal particles by adding thiol. However, it is necessary to protect the surface of ultrafine metal particles by adding thiol. In addition, the concentration of the obtained ultrafine metal particles is not sufficiently high.
[0008]
The method described in Japanese Patent Application Laid-Open No. 11-80647 can obtain an organosol having a high concentration of 10 mmol / kg or more, but requires a special high-molecular-weight pigment dispersant, so that it can be used industrially and economically. It is hard to say that it can be manufactured in a special way.
[0009]
In addition, the method described in JP-A-2000-54012 can produce monodispersed nanoparticles, but requires heating in a temperature range of 100 to 300 ° C., and the raw materials are expensive and industrial, It is hard to say that it can be manufactured economically.
[0010]
The method described in Japanese Patent Application Laid-Open No. 2000-160210 can produce gold fine particles dispersed in a protective polymer having a high concentration of 50 mmol / kg or more, but this method is applicable to elements other than Au. Can not.
[0011]
Thus, the present invention provides a method for producing metal colloid particles having a high concentration of 10 mmol / kg or more and having a nano-order size by using a metal colloid organosol having a narrow particle size distribution without using special materials or equipment. It is a technical task to obtain an economic advantage.
[0012]
[Means for solving the problem]
The technical problem can be achieved by the present invention as described below.
[0013]
The present invention is a metal colloid organosol in which metal colloid particles and an aliphatic amine are dispersed in an organic solvent, wherein the metal colloid particles have a conversion coefficient of metal colloid particles represented by the following formula: σ / x × 100 (%)
(In the formula, σ indicates the standard deviation of the particle size distribution of the metal colloid particles, and x indicates the average particle size (nm) of the metal colloid particles.) The conversion coefficient of the metal colloid particles is 20% or less. The metal colloid organosol is characterized in that the metal concentration is 10 mmol / kg or more and the Hansen Solubility Parameter of the organic solvent is 20 MPa 1/2 or less (the present invention 1).
[0014]
Further, the present invention is a metal colloid organosol in which metal colloid particles, an aliphatic amine and a fatty acid are dispersed in an organic solvent, wherein the metal colloid particles have a conversion coefficient of the following formula: σ / x × 100 (% )
(In the formula, σ indicates the standard deviation of the particle size distribution of the metal colloid particles, and x indicates the average particle size (nm) of the metal colloid particles.) The conversion coefficient of the metal colloid particles is 20% or less. The metal colloid organosol is characterized in that the metal concentration is 10 mmol / kg or more, and the Hansen Solubility Parameter of the organic solvent is 20 MPa 1/2 or less (the present invention 2).
[0015]
The metal colloid organo according to claim 1, wherein the metal salt and the aliphatic amine are reduced after mixing and stirring the metal salt and the aliphatic amine in an organic solvent having a Hansen Solubility Parameter of 20 MPa 1/2 or less. This is a method for producing a sol (the present invention 3).
[0016]
The metal according to claim 2, wherein the metal salt, the aliphatic amine, and the fatty acid are mixed and stirred in an organic solvent having a Hansen Solubility Parameter of 20 MPa 1/2 or less, and then reduced, wherein the metal is reduced. This is a method for producing a colloid organosol (Invention 4).
[0017]
The configuration of the present invention will be described in detail as follows.
[0018]
First, the metal colloid organosol according to the present invention will be described.
[0019]
The metal colloid organosol according to the present invention is a metal composed of one or more selected from noble metals such as Au, Pt, Ag, Rh, Ru and Pd, and transition metals such as Cr, Fe, Co, Ni and Cu. Contains colloidal particles.
[0020]
The conversion coefficient of the metal colloid particles in the metal colloid organosol according to the present invention is 20% or less. When the conversion coefficient exceeds 20%, it is not economical due to the presence of coarse particles, and when used for a catalyst material, the catalytic activity decreases. When used as a magnetic recording material, nanoparticles are not arranged at uniform intervals on the substrate. Preferably it is 5 to 19%.
[0021]
The metal concentration in the metal colloid organosol according to the present invention is 10 mmol / kg or more. The upper limit is 1000 mmol / kg.
[0022]
The average particle diameter of the metal colloid nanoparticles in the metal organosol according to the present invention is preferably 1.0 to 10 nm.
[0023]
The aliphatic amine in the present invention is each aliphatic amine shown in Table 1 below.
[0024]
[Table 1]
The content of the aliphatic amine in the metal colloid organosol according to the present invention is preferably more than 0.05 in a molar ratio to the metal. If it is less than 0.05, the bond between the metal salt and the aliphatic amine becomes insufficient, and metal colloid particles having an excellent particle size distribution cannot be obtained. The upper limit is 10 mol times. More preferably, the molar ratio is 0.2 to 5 times.
[0026]
As the organic solvent in the present invention, a solvent having a Hansen Solubility Parameter of 20 MPa 1/2 or less is used. If the Hansen Solubility Parameter of the organic solvent exceeds 20 MPa 1/2 , it becomes difficult to obtain metal colloid nanoparticles having a narrow particle size distribution.
[0027]
Examples of the organic solvent in the present invention include hexane (Hansen Solubility Parameter: 14.9 MPa 1/2 ), octane (15.6 MPa 1/2 ), cyclohexane (16.8 MPa 1/2 ), and benzene (18.6 MPa 1 ). / 2 ), toluene (18.2 MPa 1/2 ) and xylene (18.0 MPa 1/2 ). The organic solvents may be used alone or in combination of two or more.
[0028]
In the present invention, the dispersion stability is improved by adding a fatty acid to the metal colloid organosol. The content of the fatty acid is preferably 0.05 to 10 in a molar ratio to the metal.
[0029]
As fatty acids, higher fatty acids having 10 to 22 carbon atoms can be used. For example, oleic acid, stearic acid, erucic acid, linoleic acid, pentadecanoic acid, linolenic acid can be used.
[0030]
Next, a method for producing the metal colloid organosol according to the present invention will be described.
[0031]
The metal salt in the present invention is not particularly limited. For example, metal salts of noble metals such as Au, Pt, Ag, Rh, Ru and Pd, and transition metals such as Cr, Fe, Co, Ni and Cu One or more selected from metal salts.
[0032]
Specifically, nitrates, chlorides such as silver nitrate, chloroauric acid, chloroplatinic acid, rhodium chloride, ruthenium chloride, palladium chloride, copper chloride, nickel chloride, cobalt chloride, chromium chloride, iron sulfate, copper acetate, nickel acetate, etc. Sulfates and acetates can be used.
[0033]
The amount of the aliphatic amine to be added in the present invention is an amount exceeding 0.05 in a molar ratio to the metal. If it is less than 0.05, the bond between the metal salt and the aliphatic amine becomes insufficient, and metal colloid particles having an excellent particle size distribution cannot be obtained. The upper limit is 10 mol times. Preferably, it is 0.2 to 5 mole times.
[0034]
As the organic solvent in the present invention, an organic solvent having the Hansen Solubility Parameter of 20 MPa 1/2 or less is used.
[0035]
The metal concentration is preferably at least 10 mmol / kg, more preferably at least 100 mmol / kg. The upper limit is 1000 mmol / kg. If it is more than 1000 mmol / kg, the viscosity becomes high and handling becomes difficult.
[0036]
The mixing and stirring of the metal salt, the aliphatic amine and the organic solvent are not particularly limited as long as they can be sufficiently dispersed, but, for example, a magnetic stirrer, a ball mill, an ultrasonic disperser and the like can be used. .
[0037]
The reduction can use either a chemical reduction method or a light irradiation method, and is not particularly limited. For example, reducing agents used in the chemical reduction method include sodium borohydride, hydrazine, hydrazine monohydrate, sodium citrate, and succinic acid, and the light irradiation method includes a method using a high-pressure mercury lamp.
[0038]
The lower limit of the concentration of the reducing agent is 2 mol times and the upper limit is 50 mol times of the metal salt. More preferably, it is 3 to 30 times the molar amount.
[0039]
The obtained metal colloid organosol may be washed with water depending on the use.
[0040]
Further, the metal colloid organosol according to the present invention may be further mixed and stirred with the above-mentioned fatty acid added to a mixed solution of a metal salt and an aliphatic amine. Dispersibility can be improved by adding a fatty acid.
[0041]
The amount of the fatty acid added is preferably 0.05 to 10 in a molar ratio to the metal.
[0042]
BEST MODE FOR CARRYING OUT THE INVENTION
A typical embodiment of the present invention is as follows.
[0043]
The average particle diameter was determined by statistical analysis (digitizer KD4620 manufactured by Grattek Co., Ltd.) for the particles of the image photographed by electron microscope observation.
[0044]
The standard deviation σ of the particle size was determined from the statistical analysis (digitizer KD4620, manufactured by Graphtech Co., Ltd.) for the particles of the image photographed by electron microscope observation.
[0045]
The conversion coefficient of the metal colloid particles was calculated from the average particle diameter x (nm) and the standard deviation σ according to the following equation.
Conversion coefficient of metal colloid particles = σ / x × 100 (%)
[0046]
<Synthesis of Pt colloid organosol (production according to the present invention 3)>
Platinum metal compounds H 2 PtCl 6 · 6H 2 O 1.00g and N- tallow-alkyl-1,3-diaminopropane (trade name: Duomeen T, manufactured by Lion Akzo Co., Ltd.) 0.60 g and an organic solvent cyclohexane (Hansen (Solubility Parameter: 16.8 MPa 1/2 ) (17.71 g) was collected in a flask, and stirred and mixed by a ball mill at room temperature for 24 hours to obtain a metal colloid organosol material. 0.37 g of NaBH 4 as a reducing agent was added to the material for a precious metal colloid organosol at room temperature, and the mixture was stirred and mixed with a magnetic stirrer for 12 hours to obtain a black-brown platinum colloid organosol.
[0047]
The metal colloid organosol obtained here was a platinum colloid organosol having a metal concentration of 98 mmol / kg, an average particle diameter of the metal colloid particles of 6.6 nm, and a conversion coefficient of 18% and having a narrow particle size distribution. .
[0048]
[Action]
The most important point in the present invention is that a metal salt and an aliphatic amine are reduced by being contained in an organic solvent having a Hansen Solubility Parameter of 20 MPa 1/2 or less, whereby the obtained metal colloid nanoparticles can be obtained at a high concentration. And is excellent in particle size distribution.
[0049]
The reason why the metal colloid nanoparticles having an excellent particle size distribution are obtained in the present invention is that the present inventors, by the presence of the aliphatic amine before reduction, form a complex between the metal salt and the aliphatic amine in a solvent, It is presumed that, by the reduction, the aliphatic amine functions as a nanoparticle protective agent and metal colloid nanoparticles can be produced without causing aggregation.
[0050]
In addition, by using an organic solvent having a Hansen Solubility Parameter of 20 MPa 1/2 or less, a uniform reaction field protected by an aliphatic amine can be formed, so that metal colloid nanoparticles excellent in particle size distribution can be easily obtained. be able to.
[0051]
Furthermore, the addition of fatty acids in the present invention improves the dispersion stability.
[0052]
【Example】
Next, examples and comparative examples will be described.
[0053]
Examples 1 to 7
Except that the type and amount of the metal compound, the type and amount of the aliphatic amine, the type and amount of the organic solvent, and the type and amount of the reducing agent were changed variously, An organosol material was obtained.
[0054]
Table 2 shows the production conditions of the metal colloid organosol at this time, and Table 4 shows various characteristics of the obtained metal colloid organosol.
[0055]
Example 8 <Synthesis of Pt colloid organosol (production according to the present invention 4)>
Platinum metal compounds H 2 PtCl 6 · 6H 2 O 1.00g and N- tallow-alkyl-1,3-diaminopropane (trade name: Duomeen T, manufactured by Lion Akzo Co., Ltd.) 0.60 g and an organic solvent cyclohexane (Hansen (Solubility Parameter: 16.8 MPa 1/2 ) 185.00 g and oleic acid 0.55 g were collected in a flask and stirred and mixed by a ball mill at room temperature for 24 hours to obtain a material for a metal colloid organosol. 0.97 g of N 2 H 4 .H 2 O as a reducing agent was added to the precious metal colloid organosol material at room temperature, and stirred and mixed with a magnetic stirrer for 12 hours to obtain a black-brown platinum colloid organosol.
[0056]
The metal colloid organosol obtained here was a colloidal organosol having a metal concentration of 10 mmol, an average particle diameter of the metal colloid particles of 8.8 nm, and a conversion coefficient of 15% and having a narrow particle size distribution.
[0057]
Examples 9 to 17
Except for changing the kind and addition amount of the metal compound, the kind and addition amount of the aliphatic amine, the kind and addition amount of the organic solvent, the kind and addition amount of the fatty acid, and the kind and addition amount of the reducing agent, the execution of the above-mentioned invention. In the same manner as in the above, a metal organosol material was obtained.
[0058]
Table 3 shows the production conditions of the metal colloid organosol at this time, and Table 4 shows various properties of the obtained metal colloid organosol. As amines, N-tallow alkyl-1,3-diaminopropane (trade name: Duomin T, manufactured by Lion Akzo Co., Ltd.), N-oleyl 1,3-diaminopropane (trade name: Duomin OX, Lion Akzo) Co., Ltd.) was used.
[0059]
Comparative Examples 1-3
Comparative Example 1 was manufactured in the same manner as in the embodiment of the invention except that methanol (Hansen Solubility Parameter: 29.7 MPa 1/2 ) was used as the organic solvent, but the metal nanoparticles were separated into two layers. Could not be obtained. Comparative Example 2 was produced in the same manner as in the embodiment of the invention except that aniline (aromatic amine) was used as the amine, but was produced because H 2 PtCl 6.6H 2 O was not dispersed in cyclohexane. I couldn't do that. Comparative Example 3 was manufactured in the same manner as in the embodiment of the present invention except that aniline (aromatic amine) was used as the amine and methanol (Hansen Solubility Parameter: 29.7 MPa 1/2 ) was used as the organic solvent. However, it was separated into two layers and no metal colloid nanoparticles were obtained.
[0060]
[Table 2]
[Table 3]
[Table 4]
【The invention's effect】
According to the production method of the present invention, it is possible to obtain metal nanoparticles having a high concentration, a size on the order of nanometers, and a narrow particle size distribution using a simple production apparatus and a commercially available raw material. , A catalyst material, a magnetic recording material and the like.
Claims (4)
金属コロイド粒子の変換係数＝σ／ｘ×１００（％）
（式中、σは金属コロイド粒子の粒度分布の標準偏差を示し、ｘは金属コロイド粒子の平均粒子径（ｎｍ）を示す。）から算出される金属コロイド粒子の変換係数が２０％以下であって金属濃度が１０ｍｍｏｌ／ｋｇ以上であり、前記有機溶剤のＨａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒが２０ＭＰａ１／２以下であることを特徴とする金属コロイドオルガノゾル。A metal colloid organosol in which metal colloid particles and an aliphatic amine are dispersed in an organic solvent, wherein the metal colloid particles have the following conversion coefficient of metal colloid particles: σ / x × 100 (%)
(In the formula, σ represents the standard deviation of the particle size distribution of the metal colloid particles, and x represents the average particle diameter (nm) of the metal colloid particles.) The conversion coefficient of the metal colloid particles is 20% or less. A metal concentration of 10 mmol / kg or more, and a Hansen Solubility Parameter of the organic solvent is 20 MPa 1/2 or less.
金属コロイド粒子の変換係数＝σ／ｘ×１００（％）
（式中、σは金属コロイド粒子の粒度分布の標準偏差を示し、ｘは金属コロイド粒子の平均粒子径（ｎｍ）を示す。）から算出される金属コロイド粒子の変換係数が２０％以下であって金属濃度が１０ｍｍｏｌ／ｋｇ以上であり、前記有機溶剤のＨａｎｓｅｎ Ｓｏｌｕｂｉｌｉｔｙ Ｐａｒａｍｅｔｅｒが２０ＭＰａ１／２以下であることを特徴とする金属コロイドオルガノゾル。A metal colloid organosol in which metal colloid particles, an aliphatic amine and a fatty acid are dispersed in an organic solvent, wherein the metal colloid particles have the following conversion coefficient of metal colloid particles = σ / x × 100 (%)
(In the formula, σ represents the standard deviation of the particle size distribution of the metal colloid particles, and x represents the average particle diameter (nm) of the metal colloid particles.) The conversion coefficient of the metal colloid particles is 20% or less. A metal concentration of 10 mmol / kg or more, and a Hansen Solubility Parameter of the organic solvent is 20 MPa 1/2 or less.
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