JPS63186803A - Production of fine copper particles - Google Patents
Production of fine copper particlesInfo
- Publication number
- JPS63186803A JPS63186803A JP1706487A JP1706487A JPS63186803A JP S63186803 A JPS63186803 A JP S63186803A JP 1706487 A JP1706487 A JP 1706487A JP 1706487 A JP1706487 A JP 1706487A JP S63186803 A JPS63186803 A JP S63186803A
- Authority
- JP
- Japan
- Prior art keywords
- particle size
- copper
- 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 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 39
- 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 30
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 15
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000002211 L-ascorbic acid Substances 0.000 claims abstract description 13
- 235000000069 L-ascorbic acid Nutrition 0.000 claims abstract description 13
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 150000000996 L-ascorbic acids Chemical class 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 claims 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 8
- 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
- 239000010419 fine particle Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 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
- 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
- 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
- 150000000994 L-ascorbates Chemical class 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
- 239000002244 precipitate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 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）
本発明は硫酸銅水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 an aqueous copper sulfate solution. This method is characterized by obtaining dispersed copper 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１を用いる理由は、これら
の酸化還元電位が硫酸銅水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 why L-ascorbic acid or L-ascorbate 1 is used in the production method of the present invention is that the redox potential thereof is suitable for reducing the aqueous copper sulfate solution, and at the same time, the reason is that L-ascorbic acid or L-ascorbate 1 is used. 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、硫酸銅水溶液のｐＨは０．３よ
りも低いと反応が遅くなり、５よりも高いと銅の水酸化
物の沈殿が生成するので、０．３〜５の範囲がより好ま
しく、Ｌ−アスコルビン酸のｐ Ｈ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１０℃より低いと反応が遅く
、１００℃を超えると銅微粒子が凝集してくるので、１
０〜１００℃の範囲がより好ましい。Furthermore, in the present invention, if the pH of the copper sulfate aqueous solution is lower than 0.3, the reaction will be slow, and if it is higher than 5, copper hydroxide will precipitate, so it is more preferably in the range of 0.3 to 5. If the pH of L-ascorbic acid is lower than 0.5, the reaction will be extremely slow, so a pH of 0.5 or higher is more preferable, and if the reaction temperature is lower than 10°C, the reaction will be slow; If the copper particles exceed 1, the copper particles will aggregate.
The range of 0 to 100°C is more preferable.
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１１の水溶液とした後
、希硫酸を加えてｐ Ｈ＝ １に調整する。(Example 1) After dissolving 197 g of copper sulfate crystals in water to make an aqueous solution of No. 11, dilute sulfuric acid was added to adjust the pH to 1.
また、Ｌ−アスコルビン酸２００ｇを水に溶解し１２の
水溶液とした後、水酸化ナトリウムを加えてｐＨ＝７に
調整する。ここで、この２液の温度を３０℃にし、硫酸
銅水溶液を攪拌しなからＬ−アスコルビン酸溶液を添加
し、５分間反応させる。Further, 200 g of L-ascorbic acid was dissolved in water to form an aqueous solution of No. 12, and then sodium hydroxide was added to adjust the pH to 7. Here, the temperature of these two liquids is set to 30° C., and while stirring the copper sulfate aqueous solution, the L-ascorbic acid solution is added, and the mixture is allowed to react for 5 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．
２．ｕ ｍ、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 almost spherical and had an average particle size of 1.
2. The particle size distribution was sharp with 70% falling within 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、Ｈの水溶液とした後
、希硫酸を加えてｐＨ＝３に調整する。(Example 2) After dissolving 126 g of copper sulfate crystals in water to make an aqueous solution of H, dilute sulfuric acid is added to adjust the pH to 3.
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、水酸化ナトリウムを加えてｐ Ｈ＝
５に調整する。ここで、この２液の温度を７０℃にし、
硫酸銅水溶液を攪拌しながらＬ−アスコルビン酸溶液を
添加し、３分間反応させる。Further, 128 g of L-ascorbic acid was dissolved in water to make an aqueous solution of 11, and sodium hydroxide was added to adjust the pH=
Adjust to 5. Here, the temperature of these two liquids is set to 70℃,
The L-ascorbic acid solution is added to the copper sulfate aqueous solution while stirring, and the mixture is allowed to react for 3 minutes.
得られたＦ４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 F4 fine particles were filtered and 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１．８μ
ｍ、粒度分布は１．５〜２．５μｍ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 1.8 μm.
m, the particle size distribution was sharp with 70% falling between 1.5 and 2.5 μm.
（実施例３）
硫酸銅結晶１９７ｇを水に溶解し１βの水溶液とした後
、希硫酸を加えてｐ Ｈ＝ １に調整する。(Example 3) After dissolving 197 g of copper sulfate crystals in water to obtain a 1β aqueous solution, dilute sulfuric acid was added to adjust the pH to 1.
また、Ｌ−アスコルビン酸ナトリウム２００ｇを水に溶
解し１１の水溶液にする。ここでこの２液の温度を２０
°Ｃにし硫酸銅水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５分間反応させる。Further, 200 g of sodium L-ascorbate was dissolved in water to form an aqueous solution of No. 11. Here, the temperature of these two liquids is 20
While stirring the aqueous copper sulfate solution, add sodium L-ascorbate and allow to react for 5 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１．０
μｍ、粒度分布は０．７〜１．３μｍ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.
The particle size distribution was sharp with 70% falling in the range of 0.7 to 1.3 μm.
（従来例）
水１．ＯＯＯｍＡ’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) Water 1. While stirring OOOmA', 50 g of cupric oxide having an average particle size of 5 μm is dispersed and suspended.
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 ｌ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%.
After adding 200ml of hydrazine hydrate aqueous solution of
The mixture was stirred 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硫酸銅
水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 an aqueous copper sulfate solution. By using this method, it is possible to manufacture monodisperse fine copper particles with a narrow particle size distribution, which cannot 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 manufacturing methods.
Claims (1)
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。A method for producing copper microparticles by reducing an aqueous copper sulfate solution, the method comprising obtaining monodispersed copper microparticles by using L-ascorbic acid or L-ascorbic acid salts as a reducing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1706487A JPH07107168B2 (en) | 1987-01-27 | 1987-01-27 | Method for producing fine copper particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1706487A JPH07107168B2 (en) | 1987-01-27 | 1987-01-27 | Method for producing fine copper particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63186803A true JPS63186803A (en) | 1988-08-02 |
| JPH07107168B2 JPH07107168B2 (en) | 1995-11-15 |
Family
ID=11933551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1706487A Expired - Lifetime JPH07107168B2 (en) | 1987-01-27 | 1987-01-27 | Method for producing fine copper particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07107168B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050003164A (en) * | 2003-06-30 | 2005-01-10 | 나노솔루션주식회사 | Method for manufacturing copper powder |
| CN1300381C (en) * | 2003-06-16 | 2007-02-14 | 昆明理工恒达科技有限公司 | Preparing method for conductive composite bronze powder and composite bronze conductive sizing agent |
| JP2010018880A (en) * | 2008-04-01 | 2010-01-28 | Dowa Electronics Materials Co Ltd | Copper powder for conductive paste, and method for producing the same |
| WO2012043267A1 (en) | 2010-09-30 | 2012-04-05 | Ｄｏｗａエレクトロニクス株式会社 | Copper powder for conductive paste and method for manufacturing same |
| CN102601383A (en) * | 2012-03-30 | 2012-07-25 | 电子科技大学 | Method for preparing ultrafine copper powder at room temperature |
| JP2014118589A (en) * | 2012-12-14 | 2014-06-30 | Unitika Ltd | Coated fibrous copper fine particle aggregate |
| JP2014118590A (en) * | 2012-12-14 | 2014-06-30 | Unitika Ltd | Fibrous silver fine particle aggregate |
-
1987
- 1987-01-27 JP JP1706487A patent/JPH07107168B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300381C (en) * | 2003-06-16 | 2007-02-14 | 昆明理工恒达科技有限公司 | Preparing method for conductive composite bronze powder and composite bronze conductive sizing agent |
| KR20050003164A (en) * | 2003-06-30 | 2005-01-10 | 나노솔루션주식회사 | Method for manufacturing copper powder |
| JP2010018880A (en) * | 2008-04-01 | 2010-01-28 | Dowa Electronics Materials Co Ltd | Copper powder for conductive paste, and method for producing the same |
| WO2012043267A1 (en) | 2010-09-30 | 2012-04-05 | Ｄｏｗａエレクトロニクス株式会社 | Copper powder for conductive paste and method for manufacturing same |
| US9248504B2 (en) | 2010-09-30 | 2016-02-02 | Dowa Electronics Materials Co., Ltd. | Copper powder for conductive paste and method for producing same |
| CN102601383A (en) * | 2012-03-30 | 2012-07-25 | 电子科技大学 | Method for preparing ultrafine copper powder at room temperature |
| JP2014118589A (en) * | 2012-12-14 | 2014-06-30 | Unitika Ltd | Coated fibrous copper fine particle aggregate |
| JP2014118590A (en) * | 2012-12-14 | 2014-06-30 | Unitika Ltd | Fibrous silver fine particle aggregate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07107168B2 (en) | 1995-11-15 |
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