JPS63186804A - Production of fine copper particles - Google Patents
Production of fine copper particlesInfo
- Publication number
- JPS63186804A JPS63186804A JP1706587A JP1706587A JPS63186804A JP S63186804 A JPS63186804 A JP S63186804A JP 1706587 A JP1706587 A JP 1706587A JP 1706587 A JP1706587 A JP 1706587A JP S63186804 A JPS63186804 A JP S63186804A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- particle size
- ascorbic acid
- soln
- particles
- 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.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 21
- 239000010949 copper Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000002245 particle Substances 0.000 title abstract description 40
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 28
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 14
- 239000002211 L-ascorbic acid Substances 0.000 claims abstract description 12
- 235000000069 L-ascorbic acid Nutrition 0.000 claims abstract description 12
- ZURAKLKIKYCUJU-UHFFFAOYSA-N copper;azane Chemical compound N.[Cu+2] ZURAKLKIKYCUJU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 15
- 239000010419 fine particle Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 6
- 150000000994 L-ascorbates Chemical class 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 239000011859 microparticle Substances 0.000 claims 2
- 238000009826 distribution Methods 0.000 abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001431 copper ion Inorganic materials 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 3
- 238000001914 filtration Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000000203 mixture Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 150000000996 L-ascorbic acids Chemical class 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 2
- 235000019187 sodium-L-ascorbate Nutrition 0.000 description 2
- 239000011755 sodium-L-ascorbate Substances 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001956 copper hydroxide 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
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
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Ｌ−
アスコルビン酸又はＬ−アスコルビン酸塩類を用いるこ
とによって単分散した！ＰＩ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 fine copper particles by reducing copper ions in a copper ammonium complex solution.
Monodispersed by using ascorbic acid or L-ascorbates! This method is characterized by obtaining PI fine particles.
而して本発明の製造方法において、Ｌ−アスコルビン酸
又は、Ｌ−アスコルビン酸塩類を用いる理由は、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。The reason for using L-ascorbic acid or L-ascorbic acid salts in the production method of the present invention is that their redox potential is suitable for reducing the copper ammonium complex solution, and at the same time, it prevents the aggregation of particles. This is because it works to prevent
また、本発明の請求範囲においてＬ−アスコルビン酸及
びＬ−アスコルビン酸塩類としては、ナトリウム塩、カ
リウム塩、アンモニウム塩等を問わない。In addition, in the scope of the present invention, L-ascorbic acid and L-ascorbate salts include sodium salts, potassium salts, ammonium salts, and the like.
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精製し、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、Ｌ
−アスコルビン酸のｐＨは０．５よりも低いと反応が極
端に遅くなるので、０．５以上がより好ましく、また、
反応時の温度は３０℃より低いと反応が遅く、１００°
Ｃを超えると銅微粒子が凝集して（るので、３０〜１０
０℃の範囲がより好ましい。Furthermore, in the present invention, the pH of the copper ammonium complex solution
is lower than 7.5, the precipitation of copper hydroxide is purified, and 1
If it is higher than 3, ammonia gas will be generated more and the reaction will be slow, so the range of 7.5 to 13 is more preferable.
- If the pH of ascorbic acid is lower than 0.5, the reaction will be extremely slow, so it is more preferably 0.5 or higher, and
If the reaction temperature is lower than 30°C, the reaction will be slow;
If the temperature exceeds C, copper fine particles will aggregate (so 30 to 10
A range of 0°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１９７ｇを水に溶解し１ｉの水溶液とした後
、２８％のアンモニア水を力■えて銅アンモニウム錯体
溶液と、そのｐＨを９に調整する。(Example 1) After dissolving 197 g of copper sulfate crystals in water to make a 1i aqueous solution, 28% ammonia water was added to prepare a copper ammonium complex solution and its pH was adjusted to 9.
また、Ｌ−アスコルビン酸２００ｇを水に溶解し１１の
水溶液とした後、水酸化ナトリウムを加えてｐＨ＝２．
５に調整する。ここで、この２液の温度を３０℃にし、
銅アンモニウム錯体溶液を攪拌しながらＬ−アスコルビ
ン酸溶液を添加し、３０分間反応させる。Further, 200 g of L-ascorbic acid was dissolved in water to make an aqueous solution of No. 11, and sodium hydroxide was added to the solution to pH=2.
Adjust to 5. Here, the temperature of these two liquids is set to 30℃,
The L-ascorbic acid 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、この銅微粒子はほぼ球状で、平均粒径が１．
０μｍ、粒度分布は０．８〜１．３μｍに７０％が入る
シャープなものであった。As a result, the copper fine particles were almost spherical and had an average particle size of 1.
0 μm, and the particle size distribution was sharp with 70% falling between 0.8 and 1.3 μm.
（実施例２）
硫酸銅結晶１２６ｇ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１２に調整する。(Example 2) After dissolving 126 g of copper sulfate crystals in water to make an aqueous solution of 11, 28% ammonia water is added to make a copper ammonium complex solution, and the pH thereof is adjusted to 12.
また、Ｌ−アスコルビン酸１２８ｇ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＝
５に調整する。ここで、この２液の温度を６０℃にし、
渭アンモニウム錯体溶液を攪拌しながらＬ−アスコルビ
ン酸溶液を添加し、３０分間反応させる。In addition, after dissolving 128 g of L-ascorbic acid in water to make an aqueous solution of 11, 28% aqueous ammonia was added to pH=
Adjust to 5. Here, the temperature of these two liquids is set to 60℃,
The L-ascorbic acid solution was added to the Wei ammonium complex solution while stirring, and the mixture was allowed to react for 30 minutes.
得られたｍｅ粉粒子濾過、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 me powder 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１．７μ
ｍ、粒度分布は１．３〜２．０μｍ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 1.7 μm.
m, the particle size distribution was sharp with 70% falling in the range of 1.3 to 2.0 μm.
（実施例３）
硫酸銅結晶１９７ｇを水に溶解し１！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) 197g of copper sulfate crystals was dissolved in water and 1! After making an aqueous solution, 28% aqueous ammonia is added to make a copper ammonium complex solution, and its pH is adjusted to 8.
また、Ｌ−アスコルビン酸ナトリウム２００ｇを水に溶
解し１ｊ２の水溶液にする。ここでこの２液の温度を５
０℃にし銅アンモニウム錯体溶液を攪拌しながらＬ−ア
スコルビン酸ナトリウムを添加し５０分間反応させる。Further, 200 g of sodium L-ascorbate was dissolved in water to make an aqueous solution of 1j2. Here, the temperature of these two liquids is 5
While stirring the copper ammonium complex solution at 0° C., sodium L-ascorbate is added and 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ｆＩ微粒子は多面体で平均粒径が０．８
μｍ１粒度分布は０．５〜１．２μｍに７０％が入るシ
ャープなものであった。As a result, the fI fine particles were polyhedral and had an average particle size of 0.8.
The μm1 particle size distribution was sharp with 70% falling between 0.5 and 1.2 μm.
（従来例）
水１，０００＋＋ｖを攪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 ++v of water with stirring.
さらにこの液を攪拌しながら７０℃まで昇温し、８０％
の抱水ヒドラジン水溶液２００ｍ ！！を添加後、７０
℃で２時間攪拌した。Furthermore, the temperature of this liquid was raised to 70℃ while stirring, and the temperature was increased to 80%.
200m of hydrazine hydrate solution! ! After adding 70
The mixture was stirred at ℃ 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Ｌ−アスコルビン酸又はＬ−アス
コルビン酸塩類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 uses L-ascorbic acid or L-ascorbic acid salts as a reducing agent in the method of producing copper fine particles by reducing a copper ammonium complex solution. As a result, it is possible to produce fine copper particles with a narrow particle size distribution that is monodisperse, which could not be obtained using conventional methods, by controlling the particle size, so it can be said to be an epoch-making method that can replace conventional production methods. .
Claims (1)
方法において、還元剤としてＬ−アスコルビン酸又はＬ
−アスコルビン酸塩類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 the method of producing copper fine particles by reducing a copper ammonium complex solution, L-ascorbic acid or L-ascorbic acid is used as a reducing agent.
- A method for producing copper microparticles, which comprises obtaining monodispersed copper microparticles by using ascorbates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1706587A JPH07107169B2 (en) | 1987-01-27 | 1987-01-27 | Method for producing fine copper particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1706587A JPH07107169B2 (en) | 1987-01-27 | 1987-01-27 | Method for producing fine copper particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63186804A true JPS63186804A (en) | 1988-08-02 |
| JPH07107169B2 JPH07107169B2 (en) | 1995-11-15 |
Family
ID=11933582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1706587A Expired - Lifetime JPH07107169B2 (en) | 1987-01-27 | 1987-01-27 | Method for producing fine copper particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07107169B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315604C (en) * | 2003-11-08 | 2007-05-16 | 桂林工学院 | Chemical Preparation for sheet superfine copper powder |
-
1987
- 1987-01-27 JP JP1706587A patent/JPH07107169B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315604C (en) * | 2003-11-08 | 2007-05-16 | 桂林工学院 | Chemical Preparation for sheet superfine copper powder |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07107169B2 (en) | 1995-11-15 |
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