JPS63186806A - Production of fine copper particles - Google Patents
Production of fine copper particlesInfo
- Publication number
- JPS63186806A JPS63186806A JP1706787A JP1706787A JPS63186806A JP S63186806 A JPS63186806 A JP S63186806A JP 1706787 A JP1706787 A JP 1706787A JP 1706787 A JP1706787 A JP 1706787A JP S63186806 A JPS63186806 A JP S63186806A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- particle size
- soln
- erythorbic acid
- 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.)
- 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 9
- 239000002245 particle Substances 0.000 title abstract description 42
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims abstract description 17
- ZURAKLKIKYCUJU-UHFFFAOYSA-N copper;azane Chemical compound N.[Cu+2] ZURAKLKIKYCUJU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract 4
- 239000010419 fine particle Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 5
- 229940026231 erythorbate Drugs 0.000 claims description 3
- 235000010350 erythorbic acid Nutrition 0.000 claims description 3
- 239000011859 microparticle Substances 0.000 claims 2
- 238000009826 distribution Methods 0.000 abstract description 13
- 238000003756 stirring Methods 0.000 abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 5
- 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
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 7
- 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
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007788 liquid Substances 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
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 239000004318 erythorbic acid Substances 0.000 description 2
- 229940026239 isoascorbic acid Drugs 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium 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
- 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
- 238000001556 precipitation Methods 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Ｄ−
エリソルビン酸又はＤ−エリソ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 fine copper particles by reducing copper ions in a copper ammonium complex solution.
It is characterized in that monodispersed copper fine particles are obtained by using erythorbic acid or D-erythorbic acid salts.
而して本発明の製造方法において、Ｄ−エリソルビン酸
又は、Ｄ−エリソ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 why D-erythorbic acid or D-erythorbic acid salts are used 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Ｄ−エリソルビン酸及
びＤ−エリソ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。Further, in the scope of the present invention, D-erythorbic acid and D-erythorbic acid 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か生成し、１
３よりも高いとアンモニアガスが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、Ｄ
−エリソルビン酸の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℃よりも低いと反応が遅く、１００
℃を超えると銅微粒子が凝集してくるので、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
If the value is lower than 7.5, precipitation of copper hydroxide will occur, and 1
If it is higher than 3, ammonia gas will be generated more and the reaction will be slower, so the range of 7.5 to 13 is more preferable.
- If the pH of erythorbic 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, and
If the temperature exceeds 30 to 10℃, the copper particles will aggregate.
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ｐ）ｌを９．５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, 28% ammonia water was added to make a copper ammonium complex solution, and its p)l was adjusted to 9.5.
また、Ｄ−エリソルビン酸２００ｇを水に溶解し１βの
水溶液とした後、２８％のアンモニア水を加えてｐＨ＝
３に調整する。ここで、この２液の温度を９０℃にし、
銅アンモニウム錯体溶液を攪拌しながらＤ−エリソルビ
ン酸溶液を添加し、３０分間反応させる。In addition, after dissolving 200 g of D-erythorbic acid in water to make a 1β aqueous solution, 28% aqueous ammonia was added to pH=
Adjust to 3. Here, the temperature of these two liquids is set to 90℃,
The D-erythorbic 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゜
５μｍ、粒度分布は１．１〜１，８μｍに７０％が入る
シャープなものであった。As a result, the copper fine particles were found to be approximately spherical, with an average particle size of 1.5 μm, and a sharp particle size distribution with 70% of the particles falling between 1.1 and 1.8 μm.
（実施例２）
硫酸銅結晶１２６ｇを水に溶解し１β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１工に調整する。(Example 2) After dissolving 126 g of copper sulfate crystals in water to obtain a 1β aqueous solution, 28% ammonia water is added to obtain a copper ammonium complex solution, and the pH thereof is adjusted to 1β.
また、Ｄ−エリソルビン酸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＝
４．５に調整する。ここで、この２液の温度を７０℃に
し、銅アンモニウム錯体溶液を攪拌しなからＤ−エリソ
ルビン酸溶液を添加し、４０分間反応させる。In addition, after dissolving 128 g of D-erythorbic acid in water to make an aqueous solution of 11, 28% aqueous ammonia was added to pH=
Adjust to 4.5. Here, the temperature of these two liquids is set to 70°C, and the D-erythorbic acid solution is added while stirring the copper ammonium complex solution, and the mixture is allowed to react for 40 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１．８μ
ｍ１粒度分布は１．５〜２．０μｍ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 1.8 μm.
The m1 particle size distribution was sharp with 70% falling between 1.5 and 2.0 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７．５に調整する。(Example 3) After dissolving 197 g of copper sulfate crystals in water to make an aqueous solution of No. 12, 28% ammonia water is added to make a copper ammonium complex solution, and the pH thereof is adjusted to 7.5.
また、Ｄ−エリソ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６０
℃にし、銅アンモニウム錯体容器を攪拌しなからＤ−エ
リソルビン酸ナトリウムを添加し６０分間反応させる。Further, 200 g of sodium D-erythorbate was dissolved in water to form an aqueous solution of No. 11. Here, the temperature of these two liquids is 60
℃, and while stirring the copper ammonium complex container, sodium D-erythorbate was added and allowed to react for 60 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ｍａ粒子はほぼ球状で平均粒径が０．９
μｍ、粒度分布は０．６〜１．４μｍに７０％が入るシ
ャープなものであった。As a result, the ma particles were almost spherical and had an average particle size of 0.9.
The particle size distribution was sharp with 70% falling within the range of 0.6 to 1.4 μm.
（従来例）
水１，０ＯＯｎｊ！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 1,0OOnj! While stirring, 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。Further, the temperature of this liquid was raised to 70℃ while stirring, and 80%
After adding 200 ml of hydrazine hydrate aqueous solution of
The mixture was stirred for 2 hours.
得られた銅微粒子は濾過、洗浄して粒度分布側。The obtained copper fine particles are filtered and washed to obtain a particle size distribution side.
定及び電子顕微鏡観察を行った。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Ｄ−エリソルビン酸又はＤ−エリ
ソ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 D-erythorbic acid or D-erythorbic 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Ｄ−エリソルビン酸又はＤ
−エリソ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, D-erythorbic acid or D
- A method for producing copper microparticles, which comprises obtaining monodispersed copper microparticles by using erythorbate salts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1706787A JPS63186806A (en) | 1987-01-27 | 1987-01-27 | Production of fine copper particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1706787A JPS63186806A (en) | 1987-01-27 | 1987-01-27 | Production of fine copper particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63186806A true JPS63186806A (en) | 1988-08-02 |
Family
ID=11933640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1706787A Pending JPS63186806A (en) | 1987-01-27 | 1987-01-27 | Production of fine copper particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63186806A (en) |
-
1987
- 1987-01-27 JP JP1706787A patent/JPS63186806A/en active Pending
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