JPH0657314A - Production of fine palladium powder - Google Patents
Production of fine palladium powderInfo
- Publication number
- JPH0657314A JPH0657314A JP23138292A JP23138292A JPH0657314A JP H0657314 A JPH0657314 A JP H0657314A JP 23138292 A JP23138292 A JP 23138292A JP 23138292 A JP23138292 A JP 23138292A JP H0657314 A JPH0657314 A JP H0657314A
- Authority
- JP
- Japan
- Prior art keywords
- palladium
- silver
- fine
- powder
- chloride
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は導電ペーストの導電材料
として用いるパラジウム微粉末の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing fine palladium powder used as a conductive material for a conductive paste.
【０００２】[0002]
【従来の技術】従来の導電ペースト用のパラジウム微粉
末は、パラジウム塩の水溶液に水酸化ナトリウムなどの
アルカリを加えてｐＨを調整した後、ホルマリン、蟻
酸、ヒドラジン等の還元剤を加えてパラジウム微粉末を
析出させる方法により製造されている。この方法はパラ
ジウム塩の水溶液中のパラジウム濃度、ｐＨ、温度、還
元剤などの調節が難しく、平均粒径が０.１〜１.０μｍ
のパラジウム微粉末を得ることが容易でなく、かつ粒径
の分布の広いものしか得られなかった。2. Description of the Related Art Palladium fine powder for a conventional conductive paste is prepared by adding an alkali such as sodium hydroxide to an aqueous solution of palladium salt to adjust the pH, and then adding a reducing agent such as formalin, formic acid and hydrazine to the palladium fine powder. It is manufactured by the method of depositing powder. In this method, it is difficult to control the palladium concentration in the aqueous solution of palladium salt, pH, temperature, reducing agent, etc., and the average particle size is 0.1 to 1.0 μm.
It was not easy to obtain the palladium fine powder, and only the one having a wide particle size distribution was obtained.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、平均粒径が
０.１〜１.０μｍで粒径の分布の狭いパラジウム微粉末
を容易に製造できる方法を提供することを課題とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for easily producing a fine palladium powder having an average particle size of 0.1 to 1.0 μm and a narrow particle size distribution.
【０００４】[0004]
【課題を解決するための手段】本発明による課題を解決
するための手段は、パラジウム塩化物及び又はパラジウ
ムのクロロ錯体をパラジウムとして１０〜６０ｇ／ｌ
と、塩化パラジウム及び又は銀アンミン錯体を銀として
前記パラジウム量に対して１.８〜５０００ｐｐｍとを
含むｐＨ７〜１１のパラジウム水溶液を、還元剤を含む
水溶液に温度１０〜５０℃で添加しパラジウム微粉末を
析出させることを特徴とするパラジウム微粉末の製造方
法にある。Means for solving the problems according to the present invention include a palladium chloride and / or a chloro complex of palladium as palladium in an amount of 10 to 60 g / l.
And palladium chloride and / or silver ammine complex as silver, and an aqueous palladium solution having a pH of 7 to 11 containing 1.8 to 5000 ppm with respect to the amount of palladium is added to an aqueous solution containing a reducing agent at a temperature of 10 to 50 ° C. A method for producing a fine palladium powder, which comprises depositing the powder.
【０００５】パラジウム源として用いるパラジウム塩化
物としては、塩化パラジウム(II)（ＰｄＣｌ2）、パラ
ジウムのクロロ錯体としては、テトラクロロパラジウム
(II)酸カリ〔Ｋ2（ＰｄＣｌ4）〕、テトラクロロパラジ
ウム(II)酸ナトリウム〔Ｎａ2（ＰｄＣｌ4）〕、ジクロ
ロジアンミンパラジウム(II)〔Ｐｄ（ＮＨ3）2Ｃｌ2〕
の内の少なくとも１種が用いられる。The palladium chloride used as the palladium source is palladium (II) chloride (PdCl 2 ), and the chloro complex of palladium is tetrachloropalladium.
Potassium (II) acid [K 2 (PdCl 4 )], sodium tetrachloropalladium (II) [Na 2 (PdCl 4 )], dichlorodiamminepalladium (II) [Pd (NH 3 ) 2 Cl 2 ]
At least one of the above is used.
【０００６】銀源としては、塩化ジアンミン銀(I)
［〔Ａｇ（ＮＨ3）2〕Ｃｌ］、硫酸ジアンミン銀(I)
［〔Ａｇ（ＮＨ3）2〕2ＳＯ4］、硝酸ジアンミン銀
［〔Ａｇ（ＮＨ3）2〕ＮＯ3］の内の少なくとも１種が
用いられ、還元剤としては、アミジノスルフイン酸、水
素化ホウ素ナトリウム、ヒドラジンの内の少なくとも１
種が用いられる。As a silver source, silver diammine chloride (I)
[[Ag (NH 3 ) 2 ] Cl], silver diammine sulfate (I)
At least one of [[Ag (NH 3 ) 2 ] 2 SO 4 ] and silver diammine nitrate [[Ag (NH 3 ) 2 ] NO 3 ] is used, and the reducing agent is amidinosulfinic acid, hydrogen. At least one of sodium borohydride and hydrazine
Seeds are used.
【０００７】[0007]
【作用】本発明はパラジウム水溶液中に銀錯イオンを存
在させ、還元反応時に結晶となる微細な核を多量に発生
させ、粒子数を増加させることにより、結晶の成長を防
止し、得られるパラジウム微粉末の平均粒径が０.１〜
１.０μｍで、かつ粒径の分布が狭くなるようにしたも
のである。パラジウム源として、パラジウム塩化物及び
又はパラジウムのクロロ錯体を用いるのは溶解度が非常
に良いからであり、銀源としてジアンミン銀錯体を用い
るのは、銀が〔Ａｇ（ＮＨ3）2〕-として水溶液中に存
在し、この銀錯体イオンがそれぞれ還元されることによ
り微小な結晶核を生成し、次いで、この核の上にパラジ
ウムが析出するため平均粒径が０.１〜１.０μｍで、粒
度分布の狭いパラジウム微粉末が得ることができるもの
と考えられる。The present invention prevents the growth of crystals by allowing silver complex ions to be present in an aqueous palladium solution to generate a large amount of fine nuclei that become crystals during the reduction reaction, thereby increasing the number of particles, thereby preventing the growth of palladium. The average particle size of the fine powder is 0.1-
It is 1.0 μm and has a narrow particle size distribution. The reason why the palladium chloride and / or the chloro complex of palladium is used as the palladium source is that the solubility is very good, and the reason why the diammine silver complex is used as the silver source is that silver is an aqueous solution as [Ag (NH 3 ) 2 ] −. Which are present in the core, and each of these silver complex ions is reduced to generate a fine crystal nucleus, and then palladium is deposited on the nucleus, so that the average particle diameter is 0.1 to 1.0 μm and the particle diameter is It is considered that a fine palladium powder having a narrow distribution can be obtained.
【０００８】水溶液中のパラジウムの濃度を１０〜６０
ｇ／ｌとするのは、１０ｇ／ｌ未満では、析出するパラ
ジウムの平均粒径が０.１μｍ以下となり、６０ｇ／ｌ
を超えると、平均粒径が１.０μｍより大きくなり、凝
集して２次粒子を形成し分散性が悪くなるためである。The concentration of palladium in the aqueous solution is 10-60.
When the amount is less than 10 g / l, the average particle diameter of precipitated palladium is 0.1 μm or less, and the g / l is 60 g / l.
If it exceeds, the average particle diameter becomes larger than 1.0 μm and aggregates to form secondary particles, resulting in poor dispersibility.
【０００９】銀をパラジウムに対して１.８〜５０００
ｐｐｍとするのは、１.８ｐｐｍ未満では析出するパラ
ジウムの平均粒径が１.０μｍを超えるようになると同
時に、粒度分布が広くなるからである。５０００ｐｐｍ
を超えても平均粒径は０.１μｍより小さくならず、多
量に添加する必要を認めないからである。Silver to palladium is 1.8 to 5000
When the content is less than 1.8 ppm, the average particle size of the precipitated palladium exceeds 1.0 μm and the particle size distribution is broadened. 5000ppm
Even if it exceeds, the average particle size does not become smaller than 0.1 μm, and it is not necessary to add a large amount.
【００１０】パラジウム水溶液のｐＨを７〜１１とする
のは、ｐＨが７未満の水溶液を用いると、粒子の成長速
度が遅く、平均粒径０.１μｍ未満の微粒子しか得られ
ず、ｐＨが１１を超えると、核生成速度が粒子の成長速
度より速くなり、平均粒径０.１μｍ未満の微粒子しか
得られなくなるからである。The pH of the aqueous palladium solution is set to 7 to 11 because when an aqueous solution having a pH of less than 7 is used, the growth rate of the particles is slow and only fine particles having an average particle size of less than 0.1 μm can be obtained. If it exceeds, the nucleation rate becomes faster than the growth rate of particles, and only fine particles having an average particle size of less than 0.1 μm can be obtained.
【００１１】反応温度は１０℃より低いと、反応速度が
遅く単位時間当たりのパラジウムの析出量が減少し、経
済性が成り立たず、５０℃より高いと、反応速度が速く
なり過ぎて得られるパラジウム微粉末の粒度分布が広く
なる。このため反応温度は１０〜５０℃の範囲とする。If the reaction temperature is lower than 10 ° C., the reaction rate is slow and the amount of palladium deposited per unit time is reduced, so that economic efficiency is not realized. If it is higher than 50 ° C., the reaction rate becomes too fast to obtain palladium. The particle size distribution of the fine powder becomes wider. Therefore, the reaction temperature is in the range of 10 to 50 ° C.
【００１２】還元剤は一般の使用量に従い１〜２当量を
用いる。又、還元剤水溶液中にパラジウム水溶液を添加
する際の速度は、あまり速いと、生成したパラジウム粒
子の凝集を生じ、反対に長すぎると単位時間当たりの生
産量が低下する。添加中添加量が均一となるようにして
連続的に６０分以上１２０分の範囲で添加するのがよ
い。The reducing agent is used in an amount of 1 to 2 equivalents according to the general amount used. When the rate of addition of the palladium aqueous solution to the reducing agent aqueous solution is too high, the generated palladium particles agglomerate. On the contrary, when the rate is too long, the production amount per unit time decreases. It is advisable to add continuously for 60 minutes or more and 120 minutes so that the addition amount becomes uniform during addition.
【００１３】[0013]
【実施例】パラジウム量で２００ｇのジクロロジアンミ
ンパラジウム(II)を含む水溶液４ｌを、アンモニア水と
塩酸とでｐＨ１０に調整し、Ａｇを種々の量含む塩化ジ
アンミン銀(I)水溶液１.４ｍｌ添加し、充分に撹拌し完
全に溶解させ液温を１５℃とした。ヒドラジン９０ｇ
（１.９当量）純水に溶解して２ｌとし液温を１５℃と
した。ヒドラジンの水溶液にパラジウム含有水溶液を毎
分３６ｍｌの割合で約１１０分かけて連続的に添加し
た。[Examples] 4 l of an aqueous solution containing 200 g of dichlorodiamminepalladium (II) in a palladium amount was adjusted to pH 10 with aqueous ammonia and hydrochloric acid, and 1.4 ml of an aqueous solution of silver diammine chloride (I) containing various amounts of Ag was added. The solution temperature was set to 15 ° C. by thoroughly stirring and completely dissolving. 90 g of hydrazine
(1.9 equivalents) It was dissolved in pure water to make 2 liters and the liquid temperature was set to 15 ° C. The palladium-containing aqueous solution was continuously added to the hydrazine aqueous solution at a rate of 36 ml / min over about 110 minutes.
【００１４】添加終了後、吸引濾過により、パラジウム
微粉末を水溶液と分離し、純水にて洗浄した後、真空乾
燥機を用いて乾燥した。このパラジウム微粉末を電子顕
微鏡で観察したところ、形状はほぼ球状で、凝集部分の
ない単分散のものであった。パラジウム量に対する銀の
添加割合と、これに対するパラジウム微粉末の平均粒径
及び粒径の標準偏差を表１に示す。After the addition was completed, the fine palladium powder was separated from the aqueous solution by suction filtration, washed with pure water, and then dried using a vacuum dryer. When this fine palladium powder was observed with an electron microscope, it was found to be almost spherical in shape and monodispersed with no agglomerated portions. Table 1 shows the addition ratio of silver to the amount of palladium, the average particle diameter of the palladium fine powder and the standard deviation of the particle diameter.
【００１５】[0015]
【表１】 銀量 パラジウム微粉末の パラジウム微粉末の （ｐｐｍ) 平均粒径（μｍ） 粒径の標準偏差（μｍ） ０.０ １.１２ ０.６８ １.８ １.００ ０.２７ ５ ０.７８ ０.２１ ２５ ０.４９ ０.１３ １３０ ０.３２ ０.０９ ３０００ ０.１５ ０.０４ ５０００ ０.１０ ０.０３[Table 1] Silver amount Palladium fine powder Palladium fine powder (ppm) Average particle size (μm) Standard deviation of particle size (μm) 0.0 1.12 0.68 1.8 1.8 1.00 0.275 0.78 0.21 25 0.49 0.13 130 0.32 0.09 3000 0.15 0.04 5000 5000 0.10 0.03
【００１６】表１より銀の含有量が１.８〜５０００ｐ
ｐｍでパラジウムとして平均粒径が１.０〜０.１μｍで
粒度分布の狭い微粉末が得られることが分かる。又、銀
を含有しない場合には、平均粒径が１.０μｍ以下とな
らず、標準偏差も大きくなることが分かる。From Table 1, the silver content is 1.8 to 5000 p.
It can be seen that a fine powder having a narrow particle size distribution is obtained with an average particle size of 1.0 to 0.1 μm as palladium in pm. Further, it is understood that when silver is not contained, the average particle size does not become 1.0 μm or less and the standard deviation becomes large.
【００１７】[0017]
【発明の効果】本発明方法によれば、平均粒径が１〜
０.１μｍで、粒度分布の狭いパラジウム微粉末が得ら
れ、導電ペーストの用途にそれぞれ適したパラジウム微
粉末を提供することができる。According to the method of the present invention, the average particle diameter is 1 to
Palladium fine powder having a narrow particle size distribution of 0.1 μm can be obtained, and the palladium fine powder suitable for each application of the conductive paste can be provided.
Claims (2)
クロロ錯体をパラジウムとして１０〜６０ｇ／ｌと、銀
アンミン錯体を銀として前記パラジウム量に対して１.
８〜５０００ｐｐｍとを含むｐＨ７〜１１のパラジウム
水溶液を、還元剤を含む水溶液に温度１０〜５０℃で添
加しパラジウム微粉末を析出させることを特徴とするパ
ラジウム微粉末の製造方法。1. A palladium chloride and / or a chloro complex of palladium is used as palladium in an amount of 10 to 60 g / l, and a silver ammine complex is used as silver with respect to the amount of palladium.
A method for producing a fine palladium powder, which comprises adding an aqueous palladium solution having a pH of 7 to 11 containing 8 to 5000 ppm to an aqueous solution containing a reducing agent at a temperature of 10 to 50 ° C. to precipitate fine palladium powder.
（ＰｄＣｌ2）、パラジウムのクロロ錯体がテトラクロ
ロパラジウム(II)酸カリ〔Ｋ2（ＰｄＣｌ4）〕、テトラ
クロロパラジウム(II)酸ナトリウム〔Ｎａ2（ＰｄＣ
ｌ4）〕、ジクロロジアンミンパラジウム(II)〔Ｐｄ
（ＮＨ3）2Ｃｌ2〕の内の少なくとも１種であり、銀イ
オンが塩化ジアンミン銀(I)［〔Ａｇ（ＮＨ3）2〕Ｃ
ｌ］、硫酸ジアンミン銀(I)［〔Ａｇ（ＮＨ3）2〕2ＳＯ
4］、硝酸ジアンミン銀［〔Ａｇ（ＮＨ3）2〕ＮＯ3］の
内の少なくとも１種であり、還元剤がアミジノスルフイ
ン酸、水素化ホウ素ナトリウム、ヒドラジンの内の少な
くとも１種である請求項１に記載のパラジウム微粉末の
製造方法。2. The palladium chloride is palladium (II) chloride.
(PdCl 2 ), chloro complex of palladium is potassium tetrachloropalladium (II) acid [K 2 (PdCl 4 )], sodium tetrachloropalladium (II) acid [Na 2 (PdC
l 4 )], dichlorodiamminepalladium (II) [Pd
(NH 3 ) 2 Cl 2 ], and the silver ion is diammine silver chloride (I) [[Ag (NH 3 ) 2 ] C
l], diammine silver sulfate (I) [[Ag (NH 3 ) 2 ] 2 SO
4 ] and at least one of silver diammine nitrate [[Ag (NH 3 ) 2 ] NO 3 ] and the reducing agent is at least one of amidinosulfinic acid, sodium borohydride, and hydrazine. Item 2. A method for producing a palladium fine powder according to Item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23138292A JPH0657314A (en) | 1992-08-06 | 1992-08-06 | Production of fine palladium powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23138292A JPH0657314A (en) | 1992-08-06 | 1992-08-06 | Production of fine palladium powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0657314A true JPH0657314A (en) | 1994-03-01 |
Family
ID=16922743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23138292A Pending JPH0657314A (en) | 1992-08-06 | 1992-08-06 | Production of fine palladium powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0657314A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004216544A (en) * | 2002-12-25 | 2004-08-05 | Fuji Photo Film Co Ltd | Nanoparticle and method of producing nanoparticle |
| CN105537614A (en) * | 2015-12-28 | 2016-05-04 | 重庆文理学院 | Method for preparing hollow precious metal nano material with cuprous oxide as template |
| CN105689734A (en) * | 2016-02-02 | 2016-06-22 | 重庆文理学院 | Preparing method for Cu-doped Pt hollow nanometer material |
| CN112809015A (en) * | 2020-12-29 | 2021-05-18 | 有研亿金新材料有限公司 | Preparation method of low-apparent-density micron palladium powder |
-
1992
- 1992-08-06 JP JP23138292A patent/JPH0657314A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004216544A (en) * | 2002-12-25 | 2004-08-05 | Fuji Photo Film Co Ltd | Nanoparticle and method of producing nanoparticle |
| CN105537614A (en) * | 2015-12-28 | 2016-05-04 | 重庆文理学院 | Method for preparing hollow precious metal nano material with cuprous oxide as template |
| CN105689734A (en) * | 2016-02-02 | 2016-06-22 | 重庆文理学院 | Preparing method for Cu-doped Pt hollow nanometer material |
| CN112809015A (en) * | 2020-12-29 | 2021-05-18 | 有研亿金新材料有限公司 | Preparation method of low-apparent-density micron palladium powder |
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