JP2749863B2 - Preparation method of noble metal fine particles - Google Patents
Preparation method of noble metal fine particlesInfo
- Publication number
- JP2749863B2 JP2749863B2 JP1099767A JP9976789A JP2749863B2 JP 2749863 B2 JP2749863 B2 JP 2749863B2 JP 1099767 A JP1099767 A JP 1099767A JP 9976789 A JP9976789 A JP 9976789A JP 2749863 B2 JP2749863 B2 JP 2749863B2
- Authority
- JP
- Japan
- Prior art keywords
- noble metal
- fine particles
- metal fine
- organic
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、触媒、各種ペースト、プリントの材料、そ
の他電気材料分野に利用される貴金属微粒子を球状の単
分散した状態で貴金属微粒子の粒径を調製する方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention relates to a precious metal fine particle having a spherical and monodispersed state, which is used in the field of catalysts, various pastes, printing materials and other electric materials. And methods for preparing
（従来技術とその問題点） 従来貴金属微粒子の利用として、貴金属を含有するペ
ースト、インキの原料や、触媒、機能膜等に貴金属を担
持、あるいは被膜を形成する等、その利用範囲は多く、
しかも高価な貴金属を有効に活用するため、粒子径が用
途に合った大きさで、粒子径の揃ったもので、サブミク
ロン以下のものの開発が強く望まれている。(Prior art and its problems) Conventionally, noble metal fine particles are used in a wide range of applications, such as supporting a noble metal on a paste or ink containing noble metal, a catalyst, a functional film, etc., or forming a film.
In addition, in order to effectively use expensive noble metals, it is strongly desired to develop a material having a particle size suitable for the intended use, having a uniform particle size and a submicron size or less.
しかし、従来法は貴金属塩化物が多く用いられ、該塩
化物を水に溶解し高分子の界面活性剤等を加えて貴金属
を還元して貴金属微粒子を得る方法が用いられている。However, in the conventional method, a noble metal chloride is often used, and a method in which the noble metal is reduced by dissolving the noble metal in water and adding a polymeric surfactant or the like to reduce the noble metal is used.
上記、従来法の欠点は粒子径が0.3μ程度が限界であ
り、しかも、貴金属微粒子を高分子の界面活性剤等の不
純物と分離するのが極めてむずかしく、微粒子が洗浄中
に凝集したりして粒子径の分布範囲が広くなりやすくな
るという欠点があった。The disadvantages of the above conventional methods are that the particle size is limited to about 0.3μ, and it is extremely difficult to separate the noble metal fine particles from impurities such as high molecular surfactants, and the fine particles aggregate during washing. There is a disadvantage that the distribution range of the particle diameter is likely to be widened.
（発明の目的） 本発明は、上記従来法の欠点を解決するためになされ
たもので、貴金属微粒子の粒子径が0.05〜0.3μのもの
を任意に調製し、しかも球状で粒径分布の範囲が狭い貴
金属微粒子を調製する方法を提供するものである。(Object of the Invention) The present invention has been made in order to solve the above-mentioned drawbacks of the conventional method, and arbitrarily prepares noble metal fine particles having a particle size of 0.05 to 0.3 μm and has a spherical particle size distribution range. And a method of preparing noble metal fine particles having a narrow particle size.
（問題点を解決するための手段） 本発明は、有機貴金属化合物を有機溶媒に溶解した溶
液を加熱分解して球状の単分散した貴金属微粒子を調製
することを特徴とする貴金属微粒子の調製方法であり、
有機貴金属化合物の貴金属は金、銀、白金、パラジウ
ム、ロジウム、イリジウム、ルテニウムで、有機貴金属
化合物がトリスまたはビス（アセチルアセトナト）貴金
属化合物、貴金属酢酸化合物、アセチルアセトン貴金属
化合物、および貴金属樹脂酸塩より選択した１種または
２種以上からなり、有機溶媒がキシレン、ブロモベンゼ
ン、メチルイソブチルケトン、酢酸イソアミル、ジメチ
ルスルフォキシドより選択した１種または２種以上から
成ることと、加熱分解が還流器付き反応容器内で撹拌下
溶液の沸点で行われることを特徴とする貴金属微粒子の
調製方法である。(Means for Solving the Problems) The present invention relates to a method for preparing noble metal fine particles, which comprises thermally decomposing a solution of an organic noble metal compound in an organic solvent to prepare spherical monodispersed noble metal fine particles. Yes,
The noble metals of organic noble metal compounds are gold, silver, platinum, palladium, rhodium, iridium, ruthenium, and the organic noble metal compounds are tris or bis (acetylacetonato) noble metal compounds, noble metal acetate compounds, acetylacetone noble metal compounds, and noble metal resinates. It consists of one or more selected, and the organic solvent consists of one or more selected from xylene, bromobenzene, methyl isobutyl ketone, isoamyl acetate, and dimethyl sulfoxide. This is a method for preparing noble metal fine particles, which is carried out at the boiling point of a solution under stirring in a reaction vessel.
以下、本発明の詳細について説明する。 Hereinafter, details of the present invention will be described.
本発明に用いる有機貴金属化合物として、トリスまた
はビス（アセチルアセトナト）貴金属化合物、貴金属酢
酸塩、アセチルアセトン貴金属化合物、貴金属樹脂酸塩
を選択したのは、入手しやすいと共に合成するのも比較
的簡単にでき、一般的な有機溶媒に溶解するもので、低
い温度で分解して金属となるものであり、貴金属以外の
元素が限られた組成であるため貴金属微粒子と分離がし
やすいからである。As the organic noble metal compounds used in the present invention, tris or bis (acetylacetonato) noble metal compounds, noble metal acetates, acetylacetone noble metal compounds and noble metal resinates are easily available and relatively easy to synthesize. This is because it can be dissolved in a general organic solvent and decomposes at a low temperature to become a metal, and since it has a limited composition of elements other than the noble metal, it can be easily separated from the noble metal fine particles.
有機溶媒としては、キシレン、ブロモベンゼン、メチ
ルイソブチルケトン（MIBK）、酢酸イソアミル、ジメチ
ルスルフォキシドより選択した１種または２種以上を用
いるのは上記有機貴金属化合物を溶解するものを用いて
均一な溶液とすることができ、さらに有機貴金属化合物
を分解するための温度や貴金属微粒子が凝集しないため
の適度の粘性を持たせるためである。As the organic solvent, one or more selected from xylene, bromobenzene, methyl isobutyl ketone (MIBK), isoamyl acetate, and dimethyl sulfoxide is used. This is because the solution can be made into a solution, and further has a temperature for decomposing the organic noble metal compound and an appropriate viscosity for preventing noble metal fine particles from aggregating.
該有機貴金属化合物を有機溶媒に溶解した溶液を加熱
分解する方法は、還流器付きの反応容器を用いて有機貴
金属化合物を有機溶媒に溶解した溶液の沸点で還流する
と貴金属微粒子が生成し、貴金属微粒子の粒子径を調製
するのは、上記溶液の沸点で還流する時間で調節するこ
とができる。The method of thermally decomposing a solution in which the organic noble metal compound is dissolved in an organic solvent is performed by using a reaction vessel equipped with a reflux device and refluxing at the boiling point of the solution in which the organic noble metal compound is dissolved in the organic solvent to generate noble metal fine particles. The particle size of can be adjusted by adjusting the reflux time at the boiling point of the solution.
但し、有機貴金属化合物の有機溶媒中の濃度は１ミリ
モル〜５ミリモルの範囲が好ましい。However, the concentration of the organic noble metal compound in the organic solvent is preferably in the range of 1 mmol to 5 mmol.
上記の条件で還流すると貴金属微粒子の粒子径は0.05
〜0.3μのものが得られ、その粒子径の大きさは還流時
間に比例しており、20分間程度を過ぎると変化せずに一
定の粒子径を保つようになり、その微粒子は単分散した
ものである。When refluxed under the above conditions, the particle size of the noble metal fine particles is 0.05
~ 0.3μ is obtained, the size of the particle size is proportional to the reflux time, and after about 20 minutes, it keeps a constant particle size without changing, and the fine particles are monodispersed Things.
以下、本発明の実施例を記載するが該実施例は本発明
を限定するものではない。Hereinafter, examples of the present invention will be described, but the examples do not limit the present invention.
（実施例１） 酢酸パラジウムをメチルイソブチルケトンに溶解し
て、２ミリモルの溶液とし、これを撹拌しながら、還流
器付きフラスコ内で溶液の沸点で１時間還流したとこ
ろ、平均粒径0.27μの球状の単分散したパラジウムの微
粒子が得られた。(Example 1) Palladium acetate was dissolved in methyl isobutyl ketone to form a 2 mmol solution, which was refluxed for 1 hour at the boiling point of the solution in a flask equipped with a reflux device with stirring. Spherical monodispersed fine particles of palladium were obtained.
（実施例２） 酢酸パラジウムをメチルイソブチルケトンに溶解し
て、２ミリモルの溶液とし、これを撹拌しながら、還流
器付きフラスコ内で溶液の沸点で還流時間を２分、５
分、10分、15分、20分、30分、40分の７段階に分けて行
ったところ、平均粒径は、２分では0.05μ、５分では0.
1μ、10分では0.15μ、15分では0.21μ、20分では0.27
μ、30分では0.26μ、40分では0.27μで、それぞれ球状
の単分散したパラジウムの微粒子が得られた。(Example 2) Palladium acetate was dissolved in methyl isobutyl ketone to form a 2 mmol solution. While stirring the solution, the reflux time was 2 minutes at the boiling point of the solution in a flask equipped with a reflux condenser.
Minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, and 40 steps, the average particle size was 0.05 μm for 2 minutes and 0,0 for 5 minutes.
1μ, 0.15μ at 10 minutes, 0.21μ at 15 minutes, 0.27 at 20 minutes
Spherical monodispersed fine particles of palladium were obtained at 0.26 μm for μ and 30 minutes and 0.27 μ for 40 minutes, respectively.
（実施例３） 酢酸パラジウムを有機溶媒として、メチルイソブチル
ケトンを用いて0.5〜4.0ミリモル／の濃度で段階的に
溶解した溶液を実施例１と同様に沸点でそれぞれ40分間
還流して生成したパラジウムの微粒子の粒子径を測定し
たところ下記の表−１のような結果であった。(Example 3) Palladium produced by refluxing a solution in which palladium acetate was used as an organic solvent in a stepwise manner at a concentration of 0.5 to 4.0 mmol / with methyl isobutyl ketone at a boiling point of 40 minutes in the same manner as in Example 1 When the particle diameter of the fine particles was measured, the results were as shown in Table 1 below.
（実施例４） 酢酸パラジウムを有機溶媒として、ブロモベンゼン、
オルトキシレン、ジメチルスルファキシドを用いて0.1
〜3.0ミリモル／の濃度で段階的に溶解した溶液を実
施例１と同様に沸点でそれぞれ40分間還流して生成した
パラジウムの微粒子の粒子径を測定したところ下記の表
−２、表−３、表−４のような結果であった。 (Example 4) Using palladium acetate as an organic solvent, bromobenzene,
0.1 using ortho-xylene and dimethyl sulfoxide
A solution obtained by gradually dissolving the solution at a concentration of ~ 3.0 mmol / was refluxed at the boiling point for 40 minutes in the same manner as in Example 1 to measure the particle size of the fine particles of palladium. The results were as shown in Table-4.
尚、上記実施例では１種類の有機貴金属化合物につい
て記載されているが、必要に応じて（例えば複合微粒子
を作る場合など）２種類以上の有機貴金属化合物を使用
するようにしてもよいものである。 In the above embodiment, one kind of organic noble metal compound is described. However, two or more kinds of organic noble metal compounds may be used as needed (for example, when making composite fine particles). .
（発明の効果） 本発明は、従来例では得られなかったサブミクロン以
下の貴金属微粒子を任意の粒子径に調製することがで
き、しかも単分散して球状の粒径分布の幅の狭い安定し
たものを調製することが可能となり、触媒、ペースト、
薄膜形成材料等、化学工業、電気工業、電子工業等に於
ける貴金属微粒子の利用分野の拡大に貢献できるもので
ある。(Effects of the Invention) According to the present invention, it is possible to prepare noble metal fine particles of submicron size or less, which cannot be obtained in the conventional example, to have an arbitrary particle size, and furthermore, it is monodispersed and has a stable and narrow spherical particle size distribution. Things can be prepared, catalysts, pastes,
It can contribute to the expansion of the application field of noble metal fine particles in the chemical industry, electric industry, electronic industry, etc., such as thin film forming materials.
───────────────────────────────────────────────────── フロントページの続き 審査官 刑部 俊 (56)参考文献 特開 昭61−107937（ＪＰ，Ａ) 特開 昭62−121640（ＪＰ，Ａ) 特公 昭36−152（ＪＰ，Ｂ１) 特公 昭50−5996（ＪＰ，Ｂ１) ────────────────────────────────────────────────── ─── Continued on the front page Examiner Shun Kube (56) References JP-A-61-107937 (JP, A) JP-A-62-121640 (JP, A) JP-B-36-152 (JP, B1) JP 50-5996 (JP, B1)
Claims (4)
貴金属化合物、貴金属酢酸化合物、アセチルアセトン貴
金属化合物、貴金属樹脂酸塩より選ばれる１種または２
種以上の有機貴金属化合物を有機溶媒に溶解した溶液
を、加熱分解して球状の単分散した貴金属微粒子を調製
することを特徴とする貴金属微粒子の調製方法。1. Tris or bis (acetylacetonato)
One or two selected from noble metal compounds, noble metal acetate compounds, acetylacetone noble metal compounds, and noble metal resinates
A method for preparing noble metal fine particles, which comprises thermally decomposing a solution in which at least one kind of organic noble metal compound is dissolved in an organic solvent to prepare spherical monodispersed noble metal fine particles.
白金、パラジウム、ロジウム、イリジウム、ルテニウム
であることを特徴とする請求項１記載の貴金属微粒子の
調製方法。2. The method according to claim 2, wherein the noble metal of the organic noble metal compound is gold, silver,
2. The method for preparing fine precious metal particles according to claim 1, wherein the method is platinum, palladium, rhodium, iridium, or ruthenium.
ン、メチルイソブチルケトン、酢酸イソアミル、ジメチ
ルスルフォキシドより選択した１種または２種以上から
成ることを特徴とする請求項１または２記載の貴金属微
粒子の調製方法。3. The noble metal fine particle according to claim 1, wherein the organic solvent comprises one or more selected from xylene, bromobenzene, methyl isobutyl ketone, isoamyl acetate, and dimethyl sulfoxide. Preparation method.
拌下溶液の沸点で行われることを特徴とする請求項１、
２または３記載の貴金属微粒子の調製方法。4. The method according to claim 1, wherein the thermal decomposition is carried out at a boiling point of the solution under stirring in a reaction vessel equipped with a reflux condenser.
4. The method for preparing noble metal fine particles according to 2 or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1099767A JP2749863B2 (en) | 1989-04-19 | 1989-04-19 | Preparation method of noble metal fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1099767A JP2749863B2 (en) | 1989-04-19 | 1989-04-19 | Preparation method of noble metal fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02277706A JPH02277706A (en) | 1990-11-14 |
| JP2749863B2 true JP2749863B2 (en) | 1998-05-13 |
Family
ID=14256123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1099767A Expired - Lifetime JP2749863B2 (en) | 1989-04-19 | 1989-04-19 | Preparation method of noble metal fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2749863B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5250101A (en) * | 1991-04-08 | 1993-10-05 | Mitsubishi Gas Chemical Company, Inc. | Process for the production of fine powder |
| EP3766997A1 (en) * | 2019-07-18 | 2021-01-20 | The Swatch Group Research and Development Ltd | Method for manufacturing precious metal alloys and precious metal alloys thus obtained |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5244478B2 (en) * | 1973-05-21 | 1977-11-08 | ||
| JPS61107937A (en) * | 1984-11-01 | 1986-05-26 | Agency Of Ind Science & Technol | Preparation of noble metal organosol |
| JPS62121640A (en) * | 1985-11-21 | 1987-06-02 | Agency Of Ind Science & Technol | Preparation of noble metal organosol |
-
1989
- 1989-04-19 JP JP1099767A patent/JP2749863B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02277706A (en) | 1990-11-14 |
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