JPH04325608A - Production of copper powder - Google Patents
Production of copper powderInfo
- Publication number
- JPH04325608A JPH04325608A JP3122634A JP12263491A JPH04325608A JP H04325608 A JPH04325608 A JP H04325608A JP 3122634 A JP3122634 A JP 3122634A JP 12263491 A JP12263491 A JP 12263491A JP H04325608 A JPH04325608 A JP H04325608A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- reducing
- copper oxide
- copper powder
- liter
- 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 36
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000005751 Copper oxide Substances 0.000 claims abstract description 26
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000013081 microcrystal Substances 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 239000010410 layer Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- PLFLRQISROSEIJ-UHFFFAOYSA-N methylborane Chemical compound CB PLFLRQISROSEIJ-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- -1 sheets Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、長さ或いは長辺が〜数
μmで直径或いは厚さがサブミクロン以下である新規な
銅粉の製造法であり、導電性塗料、粉末冶金、防かび、
その他種々の用途に好適に使用可能なものである。[Industrial Application Field] The present invention is a novel method for producing copper powder having a length or long side of ~ several μm and a diameter or thickness of submicron or less, and is used in conductive coatings, powder metallurgy, and anti-fungal applications. ,
It can be suitably used for various other uses.
【0002】0002
【従来の技術】従来、銅粉の製造法としては、電解法、
アトマイズ法、機械的粉砕などが知られ、主に粉末冶金
などの用途に用いられている。これら方法による銅粉は
、粒子径が大きく、製造条件の制御や分別によってより
微細な銅粉も得られるように成ってきているが、生産性
が悪く、微細化にも自ずと限度があるものであった。
また、導電性塗料などの分野において、鱗片状或いは針
状などの高アスペクト比を有するものを通常の粉末と併
用して使用されているが、銅粉には高アスペクト比のも
のがなく、銀粉などのような良好な導電性塗料を製造す
ることが困難であった。[Prior Art] Conventionally, methods for producing copper powder include electrolytic method,
Atomization methods, mechanical pulverization, etc. are known and are mainly used for applications such as powder metallurgy. Copper powder produced by these methods has a large particle size, and although it has become possible to obtain finer copper powder by controlling manufacturing conditions and sorting, the productivity is low and there is a limit to miniaturization. there were. In addition, in fields such as conductive paints, powders with high aspect ratios such as scales or needles are used in combination with regular powders, but copper powders do not have high aspect ratios, and silver powders It has been difficult to produce good electrically conductive paints such as these.
【0003】0003
【発明が解決しようとする課題】本発明者は、先に、多
層プリント配線板の内層板の層間接着力の向上のために
内層銅箔表面を化学的に酸化して、微細な針、クサビ、
斧などの形状の凹凸を形成し、これを気相還元してこの
凹凸を実質的に保持した金属銅とすることにより、スル
ーホールメッキ工程における「ハロー」や「ピンクリン
グ」のない多層板を製造する方法を見いだした。さらに
、この方法について検討したところ、この方法は、微細
な針、クサビ、斧などの形状の銅粉の製造に適用できる
ことを発見し、本発明に至った。[Problems to be Solved by the Invention] The present inventor first attempted to chemically oxidize the surface of the inner layer copper foil in order to improve the interlayer adhesion of the inner layer board of a multilayer printed wiring board, thereby eliminating fine needles and wedges. ,
By forming irregularities in the shape of an axe, etc., and reducing them in a vapor phase to produce metallic copper that substantially retains these irregularities, we can create multilayer boards without "halos" or "pink rings" during the through-hole plating process. I found a way to manufacture it. Furthermore, upon studying this method, it was discovered that this method could be applied to the production of copper powder in the shape of fine needles, wedges, axes, etc., leading to the present invention.
【0004】0004
【課題を解決するための手段】すなわち、本発明は、銅
を酸化して針、クサビ、或いは斧状の酸化銅微細結晶と
し該酸化銅微細結晶を還元性ガス存在雰囲気で該酸化銅
微細結晶の形状を実質的に保持して気相還元することを
特徴とする銅粉の製造法であり、該還元性ガスが、水素
、一酸化炭素又はこれらの混合物であること、該還元性
ガスが、還元性の化合物ガスであることからなる銅粉の
製造法である。[Means for Solving the Problems] That is, the present invention oxidizes copper to form needle-, wedge-, or ax-shaped copper oxide microcrystals, and converts the copper oxide microcrystals into copper oxide microcrystals in an atmosphere in the presence of a reducing gas. A method for producing copper powder, which is characterized in that the reducing gas is hydrogen, carbon monoxide, or a mixture thereof, and the reducing gas is hydrogen, carbon monoxide, or a mixture thereof. , is a method for producing copper powder using a reducing compound gas.
【0005】以下、本発明について説明する。本発明の
銅は、製造する銅粉の純度を考慮した場合、より高純度
のものが好適であるまた、その形態は特に限定されず、
シート、箔、粉末、線材など種々のものが使用でき、主
に針、クサビ、或いは斧状の酸化銅結晶の製造方法との
関係を考慮して最適なものを選択する。特に、粉末とし
てμmオーダーのものを使用して、完全に酸化させ、全
て酸化銅の結晶とする方法は、生産性が高く好ましい。The present invention will be explained below. Considering the purity of the copper powder to be produced, the copper of the present invention is preferably of higher purity, and its form is not particularly limited,
Various materials such as sheets, foils, powders, and wires can be used, and the most suitable one is selected mainly in consideration of the relationship with the manufacturing method of needle-, wedge-, or ax-shaped copper oxide crystals. In particular, a method of using powder on the order of μm and completely oxidizing it to form all copper oxide crystals is highly productive and preferred.
【0006】銅を酸化して、酸化銅結晶に変換する方法
も公知であり、種々の方法が選択可能であるが、得られ
た酸化銅結晶の形態の点から、多層板の内層銅箔を酸化
処理してその表面に微細凹凸を形成するために使用され
ているものが高アスペクト比の酸化銅を得るものとして
好適に使用できる。これらとしては具体的には下記の如
きものが例示されるが、これらに限定されるものではな
く、公知方法が使用できる。
■. 水酸化ナトリウム(NaOH(15g/リットル
))/次亜塩素酸ナトリウム(NaClO2(31g/
リットル))/リン酸ナトリウム(15g/リットル)
、70〜100 ℃、 0.5〜10分間。
■. 硫酸銅(50g/リットル)/塩化ナトリウム(
200g/リットル)、40〜80℃、 3〜15分間
。
■. 酢酸(20g/リットル)/塩化アンモニウム(
20g/リットル)/酢酸銅(10g/リットル)、3
0〜80℃、 1〜10分間。
■. 酢酸銅(10g/リットル)/硫酸銅(24g/
リットル)/硫化バリウム(24g/リットル)/塩化
アンモニウム(24g/リットル)、40〜50℃、
1〜10分間。
■. 硫酸銅(25g/リットル)/硫酸ニッケル(2
5g/リットル)/塩素酸カリウム(25g/リットル
)、70〜90℃、1〜10分間。
■. 過硫酸カリウム(20g/リットル)/水酸化ナ
トリウム(50g/リットル)、50〜80℃、 1〜
3 分間。[0006] A method of oxidizing copper to convert it into copper oxide crystals is also known, and various methods can be selected, but from the viewpoint of the morphology of the obtained copper oxide crystals, it is difficult to use the inner layer copper foil of the multilayer board. Those used to form fine irregularities on the surface by oxidation treatment can be suitably used to obtain copper oxide with a high aspect ratio. Specific examples of these include, but are not limited to, the following, and known methods can be used. ■. Sodium hydroxide (NaOH (15g/liter))/sodium hypochlorite (NaClO2 (31g/liter))
liter))/sodium phosphate (15g/liter)
, 70-100°C, 0.5-10 minutes. ■. Copper sulfate (50g/liter)/sodium chloride (
200g/liter), 40-80℃, 3-15 minutes. ■. Acetic acid (20g/liter)/Ammonium chloride (
20g/liter)/copper acetate (10g/liter), 3
0-80℃, 1-10 minutes. ■. Copper acetate (10g/liter)/Copper sulfate (24g/liter)
liter)/barium sulfide (24g/liter)/ammonium chloride (24g/liter), 40-50℃,
1 to 10 minutes. ■. Copper sulfate (25g/liter)/Nickel sulfate (2
5g/liter)/potassium chlorate (25g/liter), 70-90°C, 1-10 minutes. ■. Potassium persulfate (20g/liter)/sodium hydroxide (50g/liter), 50-80℃, 1-
3 minutes.
【0007】上記の褐色或いは黒色の酸化銅微細凹凸皮
膜を形成する方法のなかで、実用化されている方法は得
られた酸化銅膜自体、またはこれを液相で還元処理した
ものを積層成形した場合に強い接着力を示す好適な条件
である。しかし、本発明は、これらの酸化銅膜を用いる
ものではなく、これを銅から分離した微細酸化銅結晶を
用い、気相還元して銅粉とする。従って、酸化処理膜と
しての接着強度など無関係であり、より高いアスペクト
比の分離容易な酸化銅とする条件、すなわち、より凹凸
度の大きく、剥離の容易な酸化銅結晶が生成する条件を
選択するのが好ましく、通常、より高温、より長時間な
どのより厳しい条件側を選択するのが好ましい。[0007] Among the methods for forming the brown or black finely uneven copper oxide film described above, the method that has been put into practical use involves lamination molding of the obtained copper oxide film itself or a product that has been reduced in a liquid phase. This is a suitable condition that shows strong adhesive strength when However, the present invention does not use these copper oxide films, but uses fine copper oxide crystals separated from copper, and performs vapor phase reduction to obtain copper powder. Therefore, the adhesion strength as an oxidized film is irrelevant, and conditions are selected that produce copper oxide crystals with a higher aspect ratio that are easier to separate, that is, conditions that produce copper oxide crystals that have greater unevenness and are easier to peel off. Usually, it is preferable to select harsher conditions such as higher temperature and longer time.
【0008】上記で得た酸化銅結晶を通常、必要に応じ
て水洗などして精製し、乾燥した後本発明の気相還元を
する。本発明の還元性ガス雰囲気は、■.水素、一酸化
炭素などの還元性ガス、■.ヒドラジン、その他のガス
化可能な還元性の化合物、又は■.■と■とを同時に含
む気相雰囲気である。まず、これら還元性ガスを供給す
る方法は、特に限定されるものではなく、例えば、上記
■のガスをボンベにて供給する方法、電気分解、触媒熱
分解することにより上記■のガスを供給する方法、さら
に、非酸化性或いは還元性の気体により還元性化合物の
気化を促進させて化合物ガスを供給することなどにより
行うことが可能である。The copper oxide crystals obtained above are usually purified by washing with water if necessary, dried, and then subjected to the gas phase reduction of the present invention. The reducing gas atmosphere of the present invention is: (1). Reducing gases such as hydrogen and carbon monoxide, ■. Hydrazine, other gasifiable reducing compounds, or ■. This is a gaseous atmosphere that simultaneously contains (1) and (2). First, the method of supplying these reducing gases is not particularly limited, and for example, the method of supplying the above gas (①) in a cylinder, the method of supplying the above gas (②) by electrolysis, catalytic pyrolysis, etc. Further, it is possible to carry out the method by supplying a compound gas by promoting the vaporization of a reducing compound with a non-oxidizing or reducing gas.
【0009】ここに、水素や一酸化炭素などの還元性ガ
スを触媒熱分解により発生させるために使用しうる化合
物としては、メタノール、エタノール、プロパノール、
ブタノールなどの低級アルコール類;ホルムアルデヒド
、パラホルムアルデヒド、トリオキサンなどのアルデヒ
ド或いはその誘導体;蟻酸、蟻酸エステル、酢酸などの
低級カルボン酸;アンモニア、ヒドラジン;メチルアミ
ン、エチルアミン、ジエチルアミン、メチルヒドラジン
、その他の窒素含有の低級のアミン類やヒドラジン誘導
体;カルシウムハイドライト、ボロンハイドライト、メ
チルボロンなどの金属の水素化物や有機金属化合物など
が例示され、本発明の用途においては特に限定されない
ものである。これらの中で、取り扱いの容易さ、安全性
、廃棄物の有無、価格などから低級アルコール類、低級
カルボン酸、アンモニアなどが好適である。また、還元
性化合物のガスを供給するために好適に使用しうる化合
物としては、ヒドラジン、メチルヒドラジンなどのヒド
ラジン類;蟻酸や熱分解して蟻酸を発生する化合物が挙
げられ、蟻酸ガスは酸化銅や金属銅と接触することによ
り水素と二酸化炭素に分解されるものであり有効に使用
できるものである。Compounds that can be used to generate reducing gases such as hydrogen and carbon monoxide through catalytic thermal decomposition include methanol, ethanol, propanol,
Lower alcohols such as butanol; aldehydes or their derivatives such as formaldehyde, paraformaldehyde, and trioxane; lower carboxylic acids such as formic acid, formic acid esters, and acetic acid; ammonia, hydrazine; methylamine, ethylamine, diethylamine, methylhydrazine, and other nitrogen-containing Examples include lower amines and hydrazine derivatives; metal hydrides and organometallic compounds such as calcium hydrite, boron hydrite, and methyl boron, and are not particularly limited in use in the present invention. Among these, lower alcohols, lower carboxylic acids, ammonia and the like are preferred from the viewpoint of ease of handling, safety, presence or absence of waste, price, etc. Compounds that can be suitably used to supply reducing compound gas include hydrazines such as hydrazine and methylhydrazine; formic acid and compounds that generate formic acid by thermal decomposition, and formic acid gas is copper oxide. It decomposes into hydrogen and carbon dioxide when it comes into contact with copper or metal, so it can be used effectively.
【0010】次に、還元温度は、還元により生成した銅
のシンタリング−すなわち、酸化銅としての外観が変化
してより凝集した形態となること−の起きにくい或いは
全くおきない条件であればよく、通常、50℃〜300
℃、好ましくは 80℃〜200 ℃、特に 10
0〜150 ℃の範囲から選択され、処理時間 1分間
〜12時間、好ましくは2〜60分間の範囲から選択す
るのが連続生産の面から好ましい。特に、還元性化合物
ガスとしてヒドラジンを使用した場合、この化合物は常
温でも酸化銅を金属銅に還元する能力を有するものであ
ることから還元速度が大きくなりすぎることが生じやす
い。還元速度が速すぎたりすると、発熱により銅の凝縮
が起こりやすく、また、生成水が極めて微細な薄膜を形
成し、その中で還元反応が進行する場合が生じる。この
場合、酸化銅結晶の形態が破壊されるので、ヒドラジン
の濃度を低くするなど還元するのが好ましい。[0010] Next, the reduction temperature may be selected as long as it does not cause sintering of the copper produced by the reduction, that is, the appearance of copper oxide changes and becomes more aggregated, or does not occur at all. , usually 50℃~300℃
°C, preferably 80 °C to 200 °C, especially 10 °C
From the viewpoint of continuous production, the temperature is preferably selected from the range of 0 to 150° C., and the processing time is preferably selected from the range of 1 minute to 12 hours, preferably 2 to 60 minutes. In particular, when hydrazine is used as the reducing compound gas, the reduction rate tends to become too high because this compound has the ability to reduce copper oxide to metallic copper even at room temperature. If the reduction rate is too fast, copper tends to condense due to heat generation, and the produced water may form an extremely fine thin film in which the reduction reaction may proceed. In this case, since the morphology of the copper oxide crystal is destroyed, it is preferable to reduce the concentration of hydrazine.
【0011】[0011]
【実施例】以下、実施例などによって本発明をさらに具
体的に説明する。
実施例1
厚み70μmの圧延銅箔を用い、これを NaOH(
15g/リットル)/次亜塩素酸ナトリウム(31g/
リットル)/リン酸ナトリウム(15g/リットル)の
水溶液で90℃、10分間処理し、水洗して両面黒色酸
化処理銅箔とし、 200℃にて乾燥した。ついで、表
面をヘラでかきとり、最大の長さ或いは幅は、約3μm
の酸化銅結晶粉末を得た。この酸化銅結晶粉末を真空吸
引可能な乾燥機中に投入し温度を上げながら乾燥機内を
減圧吸引し、窒素ガスを投入し、再び、真空吸引した後
、水素ガス 5%を含む窒素ガスを導入し 160℃、
30分間の還元を行った。この後、乾燥機内を真空吸引
し、微量の酸素を含む窒素ガスを導入して徐酸化した後
、冷却し乾燥機から還元された銅粉を取り出した。この
銅粉はやや薄い黒色であり、酸素含有量 2.7%であ
り、その形は最大の長さ或いは幅が約2μmの針、クサ
ビ、斧、鱗片などの形態の混合物からなる微細銅粉であ
った。[Examples] The present invention will be explained in more detail below with reference to Examples. Example 1 A rolled copper foil with a thickness of 70 μm was used, and this was treated with NaOH (
15g/liter)/sodium hypochlorite (31g/liter)
The foil was treated with an aqueous solution of sodium phosphate (15 g/liter) at 90°C for 10 minutes, washed with water to obtain a double-sided black oxidized copper foil, and dried at 200°C. Next, scrape the surface with a spatula, and the maximum length or width is about 3 μm.
A copper oxide crystal powder was obtained. This copper oxide crystal powder is placed in a dryer that can be vacuum-suctioned, and the inside of the dryer is vacuumed while raising the temperature, nitrogen gas is introduced, and after vacuum suction is performed again, nitrogen gas containing 5% hydrogen gas is introduced. 160℃,
Reduction was performed for 30 minutes. Thereafter, the inside of the dryer was vacuum-suctioned, and nitrogen gas containing a trace amount of oxygen was introduced to perform gradual oxidation, and then the reduced copper powder was cooled and taken out from the dryer. This copper powder is a slightly pale black color, has an oxygen content of 2.7%, and its shape is a mixture of needles, wedges, axes, scales, etc. with a maximum length or width of about 2 μm. Met.
【0012】実施例2
実施例1において、還元性ガスとして、ヒドラジンを3
mmHg含む窒素ガスを用い、温度を 120℃、10
分間とする他は同様とした。得られた銅粉はやや薄い黒
色であり、酸素含有量 3.1%であり、その形は最大
の長さ或いは幅が約2μmの針、クサビ、斧、鱗片など
の形態の混合物からなる微細銅粉であった。Example 2 In Example 1, hydrazine was used as the reducing gas.
Using nitrogen gas containing mmHg, the temperature was set to 120℃, 10
It was the same except that it was set to 1 minute. The obtained copper powder has a slightly pale black color, an oxygen content of 3.1%, and a fine shape consisting of a mixture of needles, wedges, axes, scales, etc., with a maximum length or width of about 2 μm. It was copper powder.
【0013】[0013]
【発明の効果】以上、詳細な説明および実施例から本発
明の製造法による銅粉は、従来にないアスペクト比の銅
粉である。そして、この製造方法は、従来公知の方法に
、本発明者らが開発した気相還元を併用することにより
達成されるものであり容易に実施可能であり、その工業
的な意義は極めて高いものである。[Effects of the Invention] From the above detailed description and examples, the copper powder produced by the production method of the present invention has an aspect ratio that is unprecedented. This production method is achieved by combining a conventionally known method with the gas phase reduction developed by the present inventors, and is easily implemented, and has extremely high industrial significance. It is.
Claims (1)
の酸化銅微細結晶とし該酸化銅微細結晶を、還元性ガス
存在雰囲気で該酸化銅微細結晶の形状を実質的に保持し
て気相還元することを特徴とする銅粉の製造法【請求項
2】 該還元性ガスが、水素、一酸化炭素又はこれら
の混合物である請求項1記載の銅粉の製造法【請求項3
】 該還元性ガスが、還元性の化合物ガスである請求
項1記載の銅粉の製造法Claim 1: Copper is oxidized to produce needle-, wedge-, or ax-shaped copper oxide microcrystals, and the copper oxide microcrystals are substantially maintained in the shape of the copper oxide microcrystals in an atmosphere in the presence of a reducing gas. A method for producing copper powder characterized by gas phase reduction.Claim 2. A method for producing copper powder according to claim 1, wherein the reducing gas is hydrogen, carbon monoxide, or a mixture thereof.Claim 3
The method for producing copper powder according to claim 1, wherein the reducing gas is a reducing compound gas.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3122634A JPH04325608A (en) | 1991-04-25 | 1991-04-25 | Production of copper powder |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3122634A JPH04325608A (en) | 1991-04-25 | 1991-04-25 | Production of copper powder |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04325608A true JPH04325608A (en) | 1992-11-16 |
Family
ID=14840829
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3122634A Pending JPH04325608A (en) | 1991-04-25 | 1991-04-25 | Production of copper powder |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04325608A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011202208A (en) * | 2010-03-24 | 2011-10-13 | Tohoku Univ | Method of producing metal fine particles or metal oxide fine particles, metal fine particles or metal oxide fine particles, and metal-containing paste, and metal film or metal oxide film |
CN106424751A (en) * | 2016-11-18 | 2017-02-22 | 南昌大学 | Preparation method of nano copper powder |
-
1991
- 1991-04-25 JP JP3122634A patent/JPH04325608A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011202208A (en) * | 2010-03-24 | 2011-10-13 | Tohoku Univ | Method of producing metal fine particles or metal oxide fine particles, metal fine particles or metal oxide fine particles, and metal-containing paste, and metal film or metal oxide film |
US9309119B2 (en) | 2010-03-24 | 2016-04-12 | Hitachi Metals, Ltd. | Producing method of metal fine particles or metal oxide fine particles, metal fine particles or metal oxide fine particles, and metal-containing paste, and metal film or metal oxide film |
CN106424751A (en) * | 2016-11-18 | 2017-02-22 | 南昌大学 | Preparation method of nano copper powder |
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