JPH01225706A - Production of fine copper particles - Google Patents
Production of fine copper particlesInfo
- Publication number
- JPH01225706A JPH01225706A JP5029888A JP5029888A JPH01225706A JP H01225706 A JPH01225706 A JP H01225706A JP 5029888 A JP5029888 A JP 5029888A JP 5029888 A JP5029888 A JP 5029888A JP H01225706 A JPH01225706 A JP H01225706A
- Authority
- JP
- Japan
- Prior art keywords
- particle size
- copper
- fine particles
- particles
- size distribution
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 23
- 239000010949 copper Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000002245 particle Substances 0.000 title abstract description 38
- ZURAKLKIKYCUJU-UHFFFAOYSA-N copper;azane Chemical compound N.[Cu+2] ZURAKLKIKYCUJU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 239000010419 fine particle Substances 0.000 claims description 15
- 150000001491 aromatic compounds Chemical class 0.000 claims description 6
- 239000000243 solution Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は微細な銅粒子の製造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 method for producing fine copper particles.
（従来技術とその問題点）
従来、銅微粒子の製造方法としては、酸化銅粒子を水性
媒体中でヒドラジンなどの還元剤を用いて還元する方法
が用いられてきた。(Prior art and its problems) Conventionally, as a method for producing copper fine particles, a method has been used in which copper oxide particles are reduced in an aqueous medium using a reducing agent such as hydrazine.
ところが、この方法では、還元された粒子の粒径が酸化
物の粒径に依存するために粒径のコントロールが難しく
、かつ還元された粒子同士が引き寄せ合うために凝集し
た粒度分布の幅の広い銅粒子しか得られないという欠点
を有していた。However, with this method, it is difficult to control the particle size because the particle size of the reduced particles depends on the particle size of the oxide, and the reduced particles attract each other, resulting in agglomerated particles with a wide range of particle size distribution. It had the disadvantage that only copper particles could be obtained.
本発明は上記の欠点を解消せんがためになされたもので
あり、分散した、粒度分布の幅の狭い微細な銅粒子の粒
径コントロール可能な製造方法を提供せんとするもので
ある。The present invention has been made to solve the above-mentioned drawbacks, and aims to provide a method for producing dispersed fine copper particles having a narrow particle size distribution, in which the particle size can be controlled.
（問題点を解決するための手段）
本発明は銅アンモニウム錯体溶液中の銅イオンを還元し
て銅微粒子を製造する方法において、還元剤としてヒド
ロキシル（−ＯＨ）基を１個もしくは数個含む芳香族化
合物を用いることによって単分散した銅微粒子を得るこ
とを特徴とするものである。(Means for Solving the Problems) The present invention provides a method for producing copper fine particles by reducing copper ions in a copper ammonium complex solution, in which an aromatic compound containing one or several hydroxyl (-OH) groups is used as a reducing agent. The method is characterized in that monodisperse copper fine particles are obtained by using a group compound.
而して本発明の製造方法において、ヒドロキシル（−Ｏ
Ｈ）基を１個もしくは数個含む芳香族化合物を用いる理
由は、これらの酸化還元電位が銅アンモニウム錯体溶液
を還元するのに適当であると同時に粒子同士の凝集を防
ぐ働きがあるためである。Therefore, in the production method of the present invention, hydroxyl (-O
The reason for using aromatic compounds containing one or several H) groups is that their redox potential is appropriate for reducing the cupric ammonium complex solution, and at the same time, they have the ability to prevent particles from aggregating with each other. .
さらに本発明において、銅アンモニウム錯体溶液のｐＨ
は７．５よりも低いと銅の水酸化物の沈殿が生成し、１
３より高いとアンモニアガスの発生が多くなり、反応が
遅くなるので、７．５〜１３の範囲がより好ましく、還
元剤としてヒドロキシル基を１個もしくは数個を含む芳
香族化合物水溶液のｐＨは０．５よりも低いと反応が極
端に遅くなるので、０．５以上がより好ましい。また、
反応時の温度は３０°Ｃより低いと反応が遅く、 １０
０°Ｃを超えると銅微粒子が凝集してくるので、３０〜
１００°Ｃの範囲がより好ましい。Furthermore, in the present invention, the pH of the copper ammonium complex solution
If the value is lower than 7.5, copper hydroxide precipitates will form, and 1
If the pH is higher than 3, the generation of ammonia gas will increase and the reaction will be slow, so the range of 7.5 to 13 is more preferable, and the pH of the aqueous solution of an aromatic compound containing one or several hydroxyl groups as a reducing agent is 0. If it is lower than .5, the reaction will be extremely slow, so it is more preferably 0.5 or more. Also,
If the reaction temperature is lower than 30°C, the reaction will be slow.
If the temperature exceeds 0°C, copper fine particles will aggregate, so
A range of 100°C is more preferred.
ここで本発明の実施例について説明する。Examples of the present invention will now be described.
（実施例１）
硫酸銅結晶１９．７ｇを水に溶解し１１の水溶液とした
後、２８％のアンモニア水を加えて銅アンモニウム錯体
溶液とし、そのｐＨを９に調整する。(Example 1) After dissolving 19.7 g of copper sulfate crystals in water to make an aqueous solution of No. 11, 28% aqueous ammonia is added to make a copper ammonium complex solution, and the pH thereof is adjusted to 9.
また、ヒドロキノン１５０ｇを水に溶解し１１の水溶液
とした後、２８％のアンモニア水を加えてｐＨ＝３．０
に調整する。ここで、この２液の温度を４０°Ｃにし、
銅アンモニウム錯体溶液を撹拌しながらヒドロキノン水
溶液を添加し、３０分間反応させる。In addition, after dissolving 150 g of hydroquinone in water to make an aqueous solution of 11, 28% aqueous ammonia was added to make the pH = 3.0.
Adjust to. Now, set the temperature of these two liquids to 40°C,
An aqueous hydroquinone solution is added to the copper ammonium complex solution while stirring, and the mixture is allowed to react for 30 minutes.
得られた銅微粒子は濾過、洗浄して、粒度分布測定及び
電子顕微鏡観察を行った。The obtained copper fine particles were filtered, washed, and subjected to particle size distribution measurement and electron microscope observation.
その結果、この銅微粒子は多面体で、平均粒径が１．１
μｍ、粒度分布は０．８〜１．５μｍに７０％が入るシ
ャープなものであった。As a result, the copper fine particles were polyhedral and had an average particle size of 1.1.
The particle size distribution was sharp with 70% falling in the range of 0.8 to 1.5 μm.
（実施例２）
硫酸銅結晶１２６ｇを水に溶解し１２の水溶液とした後
、２８％のアンモニア水を加えて銅アンモニウム錯体溶
液とし、そのｐＨを１２に調整する。(Example 2) After dissolving 126 g of copper sulfate crystals in water to make an aqueous solution of 12, 28% ammonia water is added to make a copper ammonium complex solution, and the pH thereof is adjusted to 12.
また、ヒドロキノン１００ｇを水に溶解し１２の水溶液
とした後、２８％のアンモニア水を加えてｐＨ−５に調
整する。ここで、この２液の温度を７０°Ｃにし、銅ア
ンモニウム錯体溶液を撹拌しながらヒドロキノン水溶液
を添加し、３０分間反応させる。Moreover, after dissolving 100 g of hydroquinone in water to make an aqueous solution of 12, 28% aqueous ammonia was added to adjust the pH to -5. Here, the temperature of these two liquids is set to 70°C, and the hydroquinone aqueous solution is added while stirring the copper ammonium complex solution, and the mixture is allowed to react for 30 minutes.
得られた銅微粒子は濾過、洗浄して、粒度分布測定及び
電子顕微鏡観察を行った。The obtained copper fine particles were filtered, washed, and subjected to particle size distribution measurement and electron microscope observation.
その結果、この銅微粒子は多面体で平均粒径が１．５μ
ｍ、粒度分布は１．２〜１．８μｍに７０％が入るシャ
ープなものであった。As a result, the copper fine particles were polyhedral and had an average particle size of 1.5 μm.
m, the particle size distribution was sharp with 70% falling in the range of 1.2 to 1.8 μm.
（実施例３）
硫酸銅結晶１９７ｇを水に溶解し１２の水溶液とした後
、２８％のアン、モニア水を加えて銅アンモニウム錯体
溶液とし、そのｐＨを８に調整する。(Example 3) After dissolving 197 g of copper sulfate crystals in water to make an aqueous solution of 12, 28% aqueous ammonium and monium was added to make a copper ammonium complex solution, and its pH was adjusted to 8.
また、ピロガロール１００ｇを水に溶解し１１の水溶液
とした後、２８％のアンモニア水を加えてｐＨ＝４．０
に調整する。ここでこの２液の温度を５０°Ｃにし銅ア
ンモニウム錯体溶液を撹拌しながらピロガロール水溶液
を添加し５０分間反応させる。In addition, 100 g of pyrogallol was dissolved in water to make an aqueous solution of 11, and then 28% ammonia water was added to the solution to pH = 4.0.
Adjust to. Here, the temperature of these two liquids is set to 50°C, and the aqueous pyrogallol solution is added while stirring the copper ammonium complex solution, and the mixture is allowed to react for 50 minutes.
得られた銅微粒子は濾過、洗浄して、粒度分布測定及び
電子顕微鏡観察を行った。The obtained copper fine particles were filtered, washed, and subjected to particle size distribution measurement and electron microscope observation.
その結果、この銅微粒子は多面体で平均粒径が０．７μ
ｍ、粒度分布は０．５〜１．０μｍに７０％が入るシャ
ープなものであった。As a result, the copper fine particles were polyhedral and had an average particle size of 0.7 μm.
m, the particle size distribution was sharp with 70% falling in the range of 0.5 to 1.0 μm.
（従来例）
水１．０００ｍＩｌを撹拌しながら平均粒径５μｍの酸
化第２銅５０ｇを分散懸濁させる。(Conventional example) 50 g of cupric oxide having an average particle size of 5 μm is dispersed and suspended in 1.000 ml of water while stirring.
さらにこの液を撹拌しながら７０’Ｃまで昇温し、８０
％の抱水ヒドラジン水溶液２００ｍ ｌを添加後、７０
゛Ｃで２時間撹拌した。Further, the temperature of this liquid was raised to 70'C while stirring, and the temperature was raised to 80'C.
After adding 200 ml of hydrazine hydrate aqueous solution of 70%
The mixture was stirred at °C for 2 hours.
得られた銅微粒子は濾過、洗浄して粒度分布測定及び電
子顕微鏡観察をおこなった。The obtained copper fine particles were filtered, washed, and subjected to particle size distribution measurement and electron microscope observation.
その結果、この銅微粒子は不定形で、平均粒径が３．５
μｍ、粒度分布は０．５〜１０μｍと幅が広く、凝集し
たものであった。As a result, the copper particles were irregularly shaped and had an average particle size of 3.5.
The particle size distribution was wide, ranging from 0.5 to 10 μm, and was agglomerated.
（発明の効果）
上記の説明で明らかなように本発明の製造方法は銅アン
モニウム錯体溶液を還元して銅微粒子を製造する方法に
おいて、還元剤としてヒドロキシル（−０Ｈ）基を１個
もしくは数個含む芳香族化合物を用いることにより、従
来法では得られなかった単分散した粒度分布の幅の狭い
微細な銅粒子を粒径をコントロールして製造できるので
、従来の製造方法にとって代わることのできる画期的な
ものと言える。(Effects of the Invention) As is clear from the above explanation, the production method of the present invention is a method for producing copper fine particles by reducing a copper ammonium complex solution, in which one or several hydroxyl (-0H) groups are used as a reducing agent. By using aromatic compounds containing aromatic compounds, it is possible to produce monodispersed fine copper particles with a narrow particle size distribution, which could not be obtained using conventional methods, by controlling the particle size. It can be said that it is temporary.
出願人 田中貴金属工業株式会社 永井忠雄Applicant: Tanaka Kikinzoku Kogyo Co., Ltd. Tadao Nagai
Claims (1)
る方法において、還元剤としてヒドロキシル（−ＯＨ）
基を１個もしくは数個含む芳香族化合物を用いることに
よって単分散した銅微粒子を得ることを特徴とする銅微
粒子の製造方法。In a method for producing copper fine particles by reducing a copper ammonium complex solution, hydroxyl (-OH) is used as a reducing agent.
A method for producing copper fine particles, which comprises obtaining monodispersed copper fine particles by using an aromatic compound containing one or several groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5029888A JPH01225706A (en) | 1988-03-03 | 1988-03-03 | Production of fine copper particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5029888A JPH01225706A (en) | 1988-03-03 | 1988-03-03 | Production of fine copper particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01225706A true JPH01225706A (en) | 1989-09-08 |
Family
ID=12854990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5029888A Pending JPH01225706A (en) | 1988-03-03 | 1988-03-03 | Production of fine copper particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01225706A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003141948A (en) * | 2001-11-06 | 2003-05-16 | Sumitomo Electric Ind Ltd | Forming method of micro metal structural body and ceramic package, multi-chip substrate, and substrate for plasma display panel using the same |
| CN111530636A (en) * | 2020-05-09 | 2020-08-14 | 昆明理工大学 | Method for enhanced sulfuration flotation recovery of copper oxide ore by copper ammonia complex gradient activation |
-
1988
- 1988-03-03 JP JP5029888A patent/JPH01225706A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003141948A (en) * | 2001-11-06 | 2003-05-16 | Sumitomo Electric Ind Ltd | Forming method of micro metal structural body and ceramic package, multi-chip substrate, and substrate for plasma display panel using the same |
| CN111530636A (en) * | 2020-05-09 | 2020-08-14 | 昆明理工大学 | Method for enhanced sulfuration flotation recovery of copper oxide ore by copper ammonia complex gradient activation |
| CN111530636B (en) * | 2020-05-09 | 2021-03-23 | 昆明理工大学 | Method for enhanced sulfuration flotation recovery of copper oxide ore by copper ammonia complex gradient activation |
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