JP3399970B2 - Method for producing copper monodisperse particles - Google Patents
Method for producing copper monodisperse particlesInfo
- Publication number
- JP3399970B2 JP3399970B2 JP06151092A JP6151092A JP3399970B2 JP 3399970 B2 JP3399970 B2 JP 3399970B2 JP 06151092 A JP06151092 A JP 06151092A JP 6151092 A JP6151092 A JP 6151092A JP 3399970 B2 JP3399970 B2 JP 3399970B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- copper powder
- particles
- monodisperse particles
- powder
- 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.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は電子回路形成に用いる厚
膜導体用銅ペーストに使用される銅粉の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a copper powder used in a copper paste for thick film conductors used for forming electronic circuits.
【０００２】[0002]
【従来の技術】厚膜導体用ペーストに使用される銅粉
は、微粒子であること、単分散であること、耐酸化性に
優れていることが必要とされる。一般に、かかる銅粉は
凝集体を含まず、５ミクロン以下の粒径を持つものが好
ましいとされているが、微細なパターンの形成や回路部
品の小型化等の理由からより微細なものが求められてき
ている。2. Description of the Related Art Copper powder used in a thick film conductor paste is required to be fine particles, be monodispersed, and have excellent oxidation resistance. In general, it is said that such a copper powder that does not contain agglomerates and has a particle size of 5 microns or less is desired, but a finer one is required for reasons such as formation of a fine pattern and miniaturization of circuit parts. Has been done.
【０００３】銅粉の製造方法としては、いわゆる電解法
が最も一般的である。しかし、この方法で得られる銅粉
は粗大な凝集体となり易い。微細な銅粉を得る方法とし
て、例えば酸化銅をカップリング剤の存在可で湿式還元
する方法（特開平２−３４０８号公報）、塩化物を気相
還元する方法（特開昭６２−６３６０４号公報）、そし
て不均化反応を利用した方法が提案されている。しか
し、これらの方法で得られる銅粉は何れも表面活性が高
く、ペーストとして使用する際に樹脂硬化のための加熱
や半田づけなどにより酸化されたり、有機物の揮散を目
的とする焼成時に雰囲気中にわずかに存在する酸素によ
って酸化されてしまう。このようにして得られた銅粉を
ペーストとして使用すると、銅粉中の酸化物により得ら
れる厚膜の導電性が低下する。又、半田の濡れ性も低下
する。The so-called electrolytic method is the most general method for producing copper powder. However, the copper powder obtained by this method tends to form coarse aggregates. As a method of obtaining fine copper powder, for example, a method of wet-reducing copper oxide in the presence of a coupling agent (Japanese Patent Laid-Open No. 2-3408) and a method of vapor-phase reduction of chloride (Japanese Patent Laid-Open No. 62-63604). And the method utilizing the disproportionation reaction has been proposed. However, all of the copper powders obtained by these methods have high surface activity and are oxidized by heating or soldering for resin curing when used as a paste, or in the atmosphere during firing for the purpose of volatilizing organic substances. It will be oxidized by the oxygen that is slightly present in. When the copper powder thus obtained is used as a paste, the conductivity of the thick film obtained by the oxide in the copper powder decreases. Moreover, the wettability of the solder is also reduced.
【０００４】これを防止すべく表面処理により銅粉の耐
酸化性の増加を図る方法が提案されている。この例とし
て、ベンゾトリアゾールやクロム酸塩をペースト中に混
入するものや、銅粉をアミンで処理した後ほう素−窒素
複合型分散剤を被覆する方法（特公平１−４００６９号
公報）、有機チタネートや有機アルミネートを被覆する
方法が知られている。しかし、これらの方法では、添加
物による導電性の悪化や、充分な酸化効果が得られなか
ったりするという欠点がある。又、銅微粒子を単結晶と
し、酸化性を付与する試み（特開昭６３−２８８９９０
号公報）もあるが、この方法では生産性が低い。In order to prevent this, a method of increasing the oxidation resistance of copper powder by surface treatment has been proposed. Examples of this include mixing benzotriazole or chromate in a paste, a method of coating copper powder with an amine and then coating a boron-nitrogen composite dispersant (Japanese Patent Publication No. 1-40069), organic A method of coating a titanate or an organic aluminate is known. However, these methods have the drawbacks that the conductivity is deteriorated by the additive and a sufficient oxidation effect is not obtained. In addition, an attempt to impart oxidizing properties by forming fine copper particles into a single crystal (JP-A-63-288990)
However, this method has low productivity.
【０００５】これらの欠点のないものとして、酸化銅を
ポリオール中で還元する方法が開示されている（特開昭
５９−１７３２０６号公報）。これによれば、確かに耐
酸化性の優れた銅粉が得られる。しかし、この方法に
は、使用する原料酸化銅の差により得られる銅粉の粒
径、形状、分散性に著しい差異が生じ、粒状で単分散性
に優れた銅粉を安定的に得ることは難しい。As a method without these drawbacks, a method of reducing copper oxide in a polyol has been disclosed (JP-A-59-173206). According to this, copper powder having excellent oxidation resistance can be obtained. However, in this method, there is a significant difference in the particle size, shape, and dispersibility of the copper powder obtained due to the difference in the raw material copper oxide used, and it is possible to stably obtain a granular copper powder having excellent monodispersity. difficult.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記ポリオ
ールを用いる銅粉の製造方法の改良に関し、安定的に所
望の粒系の単分散性に優れた銅粉を得ることを可能とす
る方法の提供を目的とする。DISCLOSURE OF THE INVENTION The present invention relates to an improvement in a method for producing a copper powder using the above-mentioned polyol, and a method which makes it possible to stably obtain a copper powder having a desired grain system and excellent monodispersity. For the purpose of providing.
【０００７】[0007]
【課題を解決するための手段】上記課題を達成する本発
明の方法は、酸化銅又はその含水物をポリオール中に懸
濁させ、２００℃以上に加熱して銅粉を得る方法におい
て、原料としてニッケル品位が１０ｐｐｍ未満で且つ水
分率が１０％以下の酸化銅粉及び／又はその含水物を用
いることにより、この原料の酸化銅の全量がＣｕ２Ｏの
超微粒子となった後、Ｃｕ２ＯからＣｕに還元されて均
一なＣｕ微粒子となることを特徴とするものである。好
ましくはポリオールとして、トリエチレングリコール、
テトラエチレングリコールのいずれか、又はこれらの混
合物を用いる。The method of the present invention for achieving the above-mentioned object is a method of suspending copper oxide or a water-containing material thereof in a polyol and heating it to 200 ° C. or higher to obtain copper powder. by using the nickel grade copper oxide powder and water content below 10% in less than 10ppm and / or its hydrate, after which the total amount of copper oxide of the raw material was the ultrafine particles Cu 2 O, Cu 2 O Is reduced to Cu to form uniform Cu fine particles. Preferably, as the polyol, triethylene glycol,
Either tetraethylene glycol or a mixture thereof is used.
【０００８】[0008]
【作用】ポリオール中で酸化銅が還元される機構につい
ては、未だ完全な解明はなされていない。しかしなが
ら、本発明者らは、反応生成物を経時的にサンプリング
し、ＳＥＭとＸ線回折とを用いて調査することにより、
本発明方法においては原料酸化銅が一度均一なＣｕ２Ｏ
の超微粒子となり、原料酸化銅の全量がＣｕ２Ｏの超微
粒子となった後、Ｃｕ２ＯからＣｕへの還元が開始さ
れ、生成したＣｕ超微粒子が凝集し、均一なＣｕ微粒子
となることを見いだした。[Function] The mechanism of reduction of copper oxide in polyol has not yet been completely elucidated. But Naga
Et al., By sampling the reaction products over time and investigating using SEM and X-ray diffraction,
In the method of the present invention, the raw material copper oxide is once uniform Cu 2 O.
Of become ultrafine particles, after the whole amount of the starting copper oxide became ultrafine particles Cu 2 O, reduction of Cu 2 O to Cu is started, resulting Cu ultrafine particles are aggregated, be a homogeneous Cu particles I found it.
【０００９】しかし、原料酸化銅中のＮｉ品位が高い場
合には、Ｃｕ２Ｏが形成される段階で、Ｃｕ２Ｏ超微粒
子に混ざって該超微粒子より数倍大きなＮｉＯと思われ
る粒子が存在し、一部の銅がこれらの粒子表面に析出す
るため、得られるＣｕ粒子の一部が大きくなり、粒径が
不揃いとなる。Ｎｉ品位が１０ｐｐｍ未満の原料酸化銅
粉末を用いれば上記現象は生ぜず、均質な銅微粒子が得
られる。However, when the Ni quality in the raw material copper oxide is high, there are particles which are mixed with the Cu 2 O ultrafine particles and are several times larger than the NiO particles when Cu 2 O is formed. However, since a part of copper is deposited on the surface of these particles, a part of the obtained Cu particles becomes large and the particle diameters become uneven. If the raw material copper oxide powder having a Ni quality of less than 10 ppm is used, the above phenomenon does not occur and uniform copper fine particles can be obtained.
【００１０】また、系内に水が存在すると、ポリオール
の酸化が進行してアルデヒドが生成するため、ＣｕＯの
全量がＣｕ ２ Ｏとなる前に、生成したアルデヒドにより
銅粉の生成が開始される。この結果、均質な銅微粒子が
得られなくなるので、原料酸化銅中の水は少ないほどよ
く、具体的には１０％以下の水分率であることが必要で
ある。In addition, when water is present in the system, the oxidation of the polyol proceeds to form an aldehyde, so that CuO
Before the total amount becomes Cu 2 O,
Generation of copper powder is started . As a result, homogeneous copper particles
Since the amount of water in the raw material copper oxide is smaller, it is more preferable that the water content be 10% or less.
【００１１】更に、原料中に０．５μm以上のＣｕ2Ｏが
含有されている場合にも均質な粒子の成長が進行し難い
ので、原料中のＣｕ2Ｏは可能な限り少ないことが望ま
れる。Further, even if the raw material contains Cu 2 O of 0.5 μm or more, it is difficult for the uniform grain growth to proceed. Therefore, Cu 2 O in the raw material should be as small as possible. .
【００１２】[0012]
【実施例】次に本発明の実施例について述べる
（実施例１）トリエチレングリコール６．６Ｋｇに住友
金属鉱山製の酸化銅（Ｎｉ ＜１０ｐｐｍ、水分 ５．
１ ％）２Ｋｇを懸濁し、２３５℃に加熱し、２時間攪
はんしつつそのその温度に保持した後、生成した銅粉を
遠心分離し、洗浄し、乾燥した。得られた銅粉をＳＥＭ
観察したところ０．５μmの粒径を持つ単分散粒子であ
ることがわかった。EXAMPLES Next, examples of the present invention will be described (Example 1). Triethylene glycol 6.6 kg was added with copper oxide (Ni <10 ppm, water content 5. manufactured by Sumitomo Metal Mining Co., Ltd.).
(1%) 2 Kg was suspended, heated to 235 ° C. and kept at that temperature for 2 hours while stirring, then the produced copper powder was centrifuged, washed and dried. SEM of the obtained copper powder
Observation revealed that the particles were monodisperse particles having a particle size of 0.5 μm.
【００１３】（実施例２）加熱温度２５５℃とし、保持
時間を１時間とした以外は実施例１と同様にして銅粉を
得た。得られた銅粉をＳＥＭ観察したところ０．３μm
の粒径を持つ単分散粒子であることがわかった。Example 2 A copper powder was obtained in the same manner as in Example 1 except that the heating temperature was 255 ° C. and the holding time was 1 hour. SEM observation of the obtained copper powder gave 0.3 μm.
It was found to be monodisperse particles having a particle size of.
【００１４】（実施例３）加熱温度２２５℃とし、保持
時間を３時間とした以外は実施例１と同様にして銅粉を
得た。得られた銅粉をＳＥＭ観察したところ１μmの粒
径を持つ単分散粒子であることがわかった。Example 3 A copper powder was obtained in the same manner as in Example 1 except that the heating temperature was 225 ° C. and the holding time was 3 hours. The obtained copper powder was observed by SEM and found to be monodisperse particles having a particle size of 1 μm.
【００１５】（比較例１）原料としてＮｉを１４００ｐ
ｐｍ含有し、水分５％の酸化銅（有）高南無機製を用い
た以外は実施例１と同様にして銅粉を得た。得られた銅
粉は不定型の凝集した粒子であった。(Comparative Example 1) Ni as a raw material was 1400 p
A copper powder was obtained in the same manner as in Example 1 except that a copper oxide (containing) Konan inorganic product containing pm and having a water content of 5% was used. The obtained copper powder was atypical and agglomerated particles.
【００１６】（比較例２）原料としてＮｉを１０ｐｐｍ
未満含有し、水分１８％の酸化銅（有）高南無機製を用
いた以外は実施例１と同様にして銅粉を得た。得られた
銅粉は不定型の凝集した粒子であった。(Comparative Example 2) Ni as the raw material at 10 ppm
A copper powder was obtained in the same manner as in Example 1 except that a copper oxide (containing) Konan Mineral containing less than 18% of water was used. The obtained copper powder was atypical and agglomerated particles.
【００１７】（実施例４）比較例２で用いた酸化銅を１
５０℃で乾燥し、この乾燥物を用いて実施例１と同様に
して銅粉を得た。得られた銅粉をＳＥＭ観察したところ
０．５μmの粒径を持つ単分散粒子であることがわかっ
た。Example 4 The copper oxide used in Comparative Example 2 was 1
It dried at 50 degreeC and the copper powder was obtained like Example 1 using this dried material. The obtained copper powder was observed by SEM and found to be monodisperse particles having a particle size of 0.5 μm.
【００１８】[0018]
【発明の効果】本発明の方法によれば、微細で均質な形
状と粒径とを持った銅粉を安定して得ることができる。According to the method of the present invention, a copper powder having a fine and uniform shape and particle size can be stably obtained.
Claims (2)
懸濁させ、２００℃以上に加熱して銅粉を得る方法にお
いて、原料としてニッケル品位が１０ｐｐｍ未満で且つ
水分率が１０％以下の酸化銅粉及び／又はその含水物を
用いることにより、この原料の酸化銅の全量がＣｕ２Ｏ
の超微粒子となった後、Ｃｕ２ＯからＣｕに還元されて
均一なＣｕ微粒子となることを特徴とする銅単分散粒子
の製造方法。1. A method for obtaining copper powder by suspending copper oxide or a water-containing material thereof in a polyol and heating the same to 200 ° C. or higher to obtain a copper powder, the oxidation of which has a nickel grade of less than 10 ppm and a water content of 10% or less. By using copper powder and / or its hydrous material, the total amount of copper oxide of this raw material is Cu 2 O.
The method for producing copper monodisperse particles, wherein the Cu 2 O is reduced to Cu to form uniform Cu fine particles after becoming the ultrafine particles.
ルとしてトリエチレングリコール、テトラエチレングリ
コールのいずれか、又はこれらの混合物を用いることを
特徴とする銅単分散粒子の製造方法。2. The method for producing copper monodisperse particles according to claim 1, wherein one of triethylene glycol and tetraethylene glycol or a mixture thereof is used as the polyol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06151092A JP3399970B2 (en) | 1992-02-17 | 1992-02-17 | Method for producing copper monodisperse particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06151092A JP3399970B2 (en) | 1992-02-17 | 1992-02-17 | Method for producing copper monodisperse particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05222413A JPH05222413A (en) | 1993-08-31 |
| JP3399970B2 true JP3399970B2 (en) | 2003-04-28 |
Family
ID=13173162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06151092A Expired - Lifetime JP3399970B2 (en) | 1992-02-17 | 1992-02-17 | Method for producing copper monodisperse particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3399970B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7674401B2 (en) * | 2001-12-18 | 2010-03-09 | Asahi Kasei Kabushiki Kaisha | Method of producing a thin conductive metal film |
| KR101711601B1 (en) * | 2015-02-17 | 2017-03-03 | 이화이앤지 주식회사 | a manufacturing method of iron oxide modified Cu |
| JP6004034B1 (en) * | 2015-04-21 | 2016-10-05 | 住友金属鉱山株式会社 | Copper powder |
-
1992
- 1992-02-17 JP JP06151092A patent/JP3399970B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05222413A (en) | 1993-08-31 |
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