JPS6357703A - Production of fine metallic powder - Google Patents
Production of fine metallic powderInfo
- Publication number
- JPS6357703A JPS6357703A JP20133086A JP20133086A JPS6357703A JP S6357703 A JPS6357703 A JP S6357703A JP 20133086 A JP20133086 A JP 20133086A JP 20133086 A JP20133086 A JP 20133086A JP S6357703 A JPS6357703 A JP S6357703A
- Authority
- JP
- Japan
- Prior art keywords
- metal salt
- water
- metal powder
- reducing agent
- metal
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 55
- 239000002184 metal Substances 0.000 claims abstract description 55
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract 2
- 229910001111 Fine metal Inorganic materials 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052699 polonium Inorganic materials 0.000 claims description 2
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- 230000010355 oscillation Effects 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- -1 ethyl ether Chemical compound 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は湿式法を適用した金属微粉末の製造法に関し、
さらに詳しくは、粉末粒径が１μ調以下の均一な金属微
粉末を容易かつ安価に製造する方法に関する。[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a method for producing fine metal powder using a wet method.
More specifically, the present invention relates to a method for easily and inexpensively producing uniform fine metal powder having a powder particle size of 1 μm or less.
（従来の技術）
近年、金属微粉末は粉末冶金分野で用いられるのみなら
ず、例えば導電性ペースト、導電性塗料、帯電防止材料
、電磁波シールド材料などの電子材料分野においてもそ
の需要が高まっている。(Prior art) In recent years, fine metal powders are not only used in the field of powder metallurgy, but also have increased demand in the field of electronic materials, such as conductive pastes, conductive paints, antistatic materials, and electromagnetic shielding materials. .
このような電子材料として使用される金属微粉末は、従
来の粉末冶金用のものに比べて粉末粒径がより小さなも
のが求められており、その製造法としては、（１）ボー
ルミルをはじめとする機械的粉砕法、炙２）溶融金属を
水、ガス、遠心力を用いて飛散させる噴霧法、（３）真
空あるいは不活性ガス中で加熱気化した金属をａ集させ
るガス中蒸発法、（４）活性水素中でアークもしくはプ
ラズマなどにより金属粉を粉塵として得る水素活性プラ
ズマ法、（５）電解法および化学的還元法などがあげら
れる。Fine metal powder used as such electronic materials is required to have a smaller powder particle size than that used in conventional powder metallurgy, and manufacturing methods include (1) ball milling and other methods. 2) Spraying method, in which molten metal is dispersed using water, gas, or centrifugal force; (3) Evaporation method in gas, in which metal heated and vaporized in a vacuum or inert gas is collected. 4) Hydrogen activated plasma method in which metal powder is obtained as dust by arc or plasma in active hydrogen; (5) Electrolytic method and chemical reduction method.
（問題点を解決するための問題点）
上記（１）および（２）の方法は従来より粉末冶金分野
において広く利用されているものであるが、得られる金
属粉末の平均粒径は１０μｍ以上と大きく、また粒度分
布幅も広く、形状も均一でないため電子材料用には全く
適さない。一方、（３）および（４）の方法によると、
粒径がＬｐｍ以下の金属微粉末が容易に得られるという
利点がある。しかし、これらの方法は温１度、圧力など
の条件の制（ＴＤが煩雑であったり、装置が複雑・大型
化して！！ｌ！造コストコストするなどの不都合がある
。さらに（５）の方法は、比較的小規模な設備で金属粉
末を安価に製造し得るという利点はあるものの、得られ
た粉末の粒度分布は０．１〜２００μＩと極めて広く、
機械的粉砕工程やふるい分けなどが必要とされていた。(Problems for solving problems) The methods (1) and (2) above have been widely used in the field of powder metallurgy, but the average particle size of the obtained metal powder is 10 μm or more. It is large, has a wide particle size distribution, and is not uniform in shape, so it is completely unsuitable for electronic materials. On the other hand, according to methods (3) and (4),
There is an advantage that fine metal powder having a particle size of Lpm or less can be easily obtained. However, these methods have disadvantages such as restrictions on conditions such as temperature and pressure (TD is complicated, the equipment is complicated and large, and manufacturing costs are increased.In addition, (5) Although this method has the advantage of being able to manufacture metal powder at low cost using relatively small-scale equipment, the particle size distribution of the obtained powder is extremely wide, ranging from 0.1 to 200 μI;
Mechanical crushing processes and sieving were required.
本発明は上記問題点を解決するためになされたもので、
湿式法、即ち化学的還元法により平均粒径１μｍ以下で
、均一な形状を有し、しかも−次粒子の状態を保持する
金属微粉末を容易且つ安価に製造する方法を提供するこ
とを目的とする。The present invention has been made to solve the above problems,
The purpose of the present invention is to provide a method for easily and inexpensively producing fine metal powder having an average particle size of 1 μm or less, a uniform shape, and maintaining the state of secondary particles by a wet method, that is, a chemical reduction method. do.
（問題点を解決するための手段および作用）上記目的を
達成するために本発明によれば、金属塩を水または／お
よび水に可溶の有機溶媒中に溶解し、この金属塩溶液中
に、そのままでは金属を析出せしめない濃度の還元剤水
溶液を徐々に添加混合し、得られた混合溶液に振動を与
えて金属塩を還元し、微少な一次粒子として析出させる
構成としたものである。(Means and effects for solving the problems) In order to achieve the above object, according to the present invention, a metal salt is dissolved in water and/or an organic solvent soluble in water, and in this metal salt solution, The structure is such that an aqueous reducing agent solution with a concentration that does not precipitate metal is gradually added and mixed, and the resulting mixed solution is vibrated to reduce the metal salt and precipitate it as fine primary particles.
本発明の製造法において、まず、出発物資として使用す
る金属塩としては、とくに限定されるものではないが、
例えば、銅（Ｃｕ） 、恨（Ａｇ） 、金（Ａｕ） 、
ルテニウム（Ｒｕ） 、オスミウム（Ｏ３）、ロジウム
（Ｒｈ）、イリジウム（Ｉｒ）、パラジウム（Ｐｄ）、
白金（Ｐｔ）、セレン（Ｓｓ）、テルル（Ｔｅ）、ポロ
ニウム（Ｐａ）、アンチモン（Ｓｂ）、ビスマス（Ｂｉ
）の塩化物、硫酸塩、硝酸塩などを好適なものとしてあ
げることができ、このうち１種もしくは、２種以上を使
用することができる。In the production method of the present invention, metal salts used as starting materials are not particularly limited, but include:
For example, copper (Cu), grudge (Ag), gold (Au),
Ruthenium (Ru), osmium (O3), rhodium (Rh), iridium (Ir), palladium (Pd),
Platinum (Pt), selenium (Ss), tellurium (Te), polonium (Pa), antimony (Sb), bismuth (Bi
) are preferable, such as chlorides, sulfates, and nitrates, and one or more of these can be used.
本発明の製造法においては、まず、上記した金属塩を水
または／および水に可溶の有機溶媒中に溶解させる。こ
の水に可溶の有機溶媒としては、例えば、メタノール、
エタノール、プロパツールなどの一価アルコール、エチ
レングリコール、グリセロールなどの多価アルコール、
ジエチルアミン、ピリジンなどのアミン類、エチルエー
テルなどのエーテル類、アセトン、メチルエチルケトン
などのケトン類などをあげることができ、このうち１種
または２種以上を混合して使用する。なお、金属塩が水
または水と水に可溶の有機溶媒との混合溶媒に溶解しに
くい場合は、加温するか、または酸もしくはアルカリを
加えて溶解させてもよい。In the production method of the present invention, first, the metal salt described above is dissolved in water and/or an organic solvent soluble in water. Examples of the water-soluble organic solvent include methanol,
Monohydric alcohols such as ethanol and propatool; polyhydric alcohols such as ethylene glycol and glycerol;
Examples include amines such as diethylamine and pyridine, ethers such as ethyl ether, and ketones such as acetone and methyl ethyl ketone, among which one type or a mixture of two or more types may be used. If the metal salt is difficult to dissolve in water or a mixed solvent of water and a water-soluble organic solvent, it may be dissolved by heating or by adding an acid or alkali.
酸としては、金属塩が塩化物の場合は塩酸、硫酸塩の場
合は硫酸、硝酸塩の場合は硝酸をそれぞれ２Ｎ程度の濃
度で、また、アルカリとしてはアンモニア水を使用する
ことができる。As the acid, hydrochloric acid can be used if the metal salt is a chloride, sulfuric acid can be used if the metal salt is a sulfate, and nitric acid can be used if the metal salt is a nitrate, each at a concentration of about 2N, and aqueous ammonia can be used as the alkali.
次いで、この金属塩溶液に還元剤水溶液を徐々に添加混
合する。使用する還元剤としては、とくに限定されるも
のではないが、例えば、ヒドラジン、水素化ホウ素ナト
リウム、ジメチルアミンボラン、ホルマリン、ギ酸、次
亜リン酸ナトリウム、過酸化水素などが好ましく、この
うち１種もしくは２種以上を用いることができる。そし
て、この還元剤水溶液の濃度はそのままでは、すなわち
、前記金属塩溶液に単に加えただけでは、金属を析出せ
しめないような濃度にする必要があり、好ましくは金属
を析出せしめない最大の濃度（飽和状態）を選択する。Next, an aqueous reducing agent solution is gradually added to and mixed with the metal salt solution. The reducing agent to be used is not particularly limited, but preferably includes hydrazine, sodium borohydride, dimethylamine borane, formalin, formic acid, sodium hypophosphite, hydrogen peroxide, etc. Alternatively, two or more types can be used. The concentration of this reducing agent aqueous solution needs to be such that the metal will not be precipitated as it is, that is, if it is simply added to the metal salt solution, preferably the maximum concentration that does not cause the metal to be precipitated ( saturation).
この加えただけで金属を析出セしない濃度は還元剤の種
類によって、あるいは還元剤と金属の組合せによって異
なるので一概に決められないが、例えば、金属塩溶液中
の金属に対する還元剤のモル比がｌＸｌ０−’〜１０の
範囲にあることが好ましい。The concentration at which the metal does not precipitate even when the metal is added cannot be determined unconditionally because it varies depending on the type of reducing agent or the combination of reducing agent and metal, but for example, the molar ratio of the reducing agent to the metal in the metal salt solution is It is preferably in the range of lXl0-' to 10.
しかるのち、この金属塩・還元剤混合溶液に振動を与え
ることにより反応系を刺激し、金属塩と還元剤との反応
を促進させることにより金属塩を還元して金属を微小粉
末として析出させる。このとき、混合溶液に振動を与え
る手段としては、超音波による振動、機械的手段による
振動などがあげられるが、とくに超音波によるものは効
果的である。この混合溶液に微少振動を与えても還元反
応が進行しにくい場合は、上述した如き、酸もしくはア
ルカリを、言わば還元反応触媒として添加してもよいし
、溶媒の沸点以下に加熱してもよい。Thereafter, the reaction system is stimulated by applying vibration to this metal salt/reducing agent mixed solution to promote the reaction between the metal salt and the reducing agent, thereby reducing the metal salt and depositing the metal as a fine powder. At this time, means for imparting vibration to the mixed solution include vibrations by ultrasonic waves, vibrations by mechanical means, etc., and vibrations by ultrasonic waves are particularly effective. If the reduction reaction does not proceed easily even when slight vibrations are applied to this mixed solution, an acid or alkali as described above may be added as a catalyst for the reduction reaction, or the solution may be heated to a temperature below the boiling point of the solvent. .
なお、析出した金属微粉末は、ただちに溶媒中に分散さ
れ、−次粒子の状態で保持され、二次凝集や薄膜化が生
ずることが有効に防止される。The precipitated fine metal powder is immediately dispersed in the solvent and maintained in the state of secondary particles, thereby effectively preventing secondary aggregation and thinning.
こうして得られた金属微粉末は、混合溶液の振動を停止
後ただちにろ過することにより回収することが好ましい
、なお、金属塩を水のみに溶解したものを用いた場合は
、金属微粉末析出後に溶液の振動を停止するとただちに
二次凝集が起きるので、分散剤として例えばエタノール
などを加えて再び超音波などにかけ微粉末を分散させて
からろ過することが好ましい。It is preferable to recover the metal fine powder obtained in this way by filtering it immediately after stopping the vibration of the mixed solution.In addition, if a metal salt dissolved only in water is used, the metal fine powder is precipitated and then dissolved. Since secondary aggregation occurs immediately when the vibration is stopped, it is preferable to add a dispersant such as ethanol and apply ultrasonic waves again to disperse the fine powder before filtering.
（実施例）
１立■工
硝酸銀（Ａ ｇ Ｎｏｔ） １７０ ｇを水１ｊｌに溶
解させＩＭのＡｇＮ０．水溶液を調製した。この水溶液
に５ｘｌＯ−”Ｍのヒドラジン水溶液１１を徐々に添加
したところ、溶液には全く変化は見られなかった。つい
で、この混合溶液を超音波により振動させると無色の溶
液が３０秒後に灰色に変化し、３０分後に反応が終了し
、微粉末が析出した。超音波による振動を停止し、分散
剤としてエタノールをｌ！加えて再度超音波により微粉
末を分散させて、ただちに、ろ過した。得られた微粉末
を水：エタノール（１： １）混合溶液で洗浄後、アセ
トンで水分を除去して風乾した。(Example) IM AgN0. An aqueous solution was prepared. When hydrazine aqueous solution 11 of 5xlO-''M was gradually added to this aqueous solution, no change was observed in the solution.Next, when this mixed solution was vibrated by ultrasonic waves, the colorless solution turned gray after 30 seconds. After 30 minutes, the reaction was completed and a fine powder was precipitated.The ultrasonic vibration was stopped, 1 liter of ethanol was added as a dispersant, the fine powder was dispersed again by ultrasonic waves, and immediately filtered. The obtained fine powder was washed with a water:ethanol (1:1) mixed solution, water was removed with acetone, and air-dried.
このようにして得られた微粉末は、Ｘ線回折パターンか
らＡｇ結晶であることが確かめられ、また、走査電子ｗ
４微鏡で観察したところ、粒径範囲が０．１〜０．３
μｍと非常にせまく、はぼ球形の極めて均一な粉末であ
ることが、確認された。尚、純度は９９．８％、比表面
積は６゜５５ｓｚ／ｇであった。The fine powder thus obtained was confirmed to be Ag crystal from the X-ray diffraction pattern, and the scanning electron w
4 When observed with a microscope, the particle size range was 0.1 to 0.3.
It was confirmed that the powder was extremely narrow, micrometer-sized, and very spherical and extremely uniform. The purity was 99.8% and the specific surface area was 6.55 sz/g.
失施Ｎ２
ＡｇＮＯｓ ８５ ｇを水５００ｔａｌに溶解し、これ
にエタノール５００Ｉ１１を加えた。こめ溶液に５ ｘ
１０−”Ｍのヒドラジン水溶液５００ｔａ Ｉｔを添
加したところ変化は生じなかった。ついで、この混合溶
液を超音波により振動させると無色の溶液が数分後に灰
色に変化し、１時間後には反応が終了して微粉末が析出
した。振動を停止し、１晩放置しても得られた粉末の分
散状態は良好であった。しかるのち、上記実施例１と同
様にろ過を行いＡｇ微粉末を得た。この微粉末の特性は
実施例１と同様であった。85 g of untreated N2 AgNOs was dissolved in 500 tal of water, and 500 I11 of ethanol was added thereto. 5 x in rice solution
When 500 ta It of a 10-"M hydrazine aqueous solution was added, no change occurred. Next, when this mixed solution was vibrated by ultrasonic waves, the colorless solution turned gray after a few minutes, and the reaction was completed after 1 hour. A fine powder was precipitated.The dispersion state of the obtained powder was good even when the vibration was stopped and the mixture was left overnight.Thereafter, filtration was carried out in the same manner as in Example 1 above to obtain a fine Ag powder. The characteristics of this fine powder were similar to those of Example 1.
叉皇勇主
ＣｕＣｌ＊ ・２Ｔｏ０１７０ｇをエチレングリコール
１２４ｇに加え、徐々に加熱しながら溶解すると緑色の
粘稠な液体が生成される。常温まで冷却した後、この溶
液にホルマリン（３７χＨＣＨＯ）８１ｇを加えたとこ
ろ変化は見られなかった０次いで、この混合溶液を超音
波により振動させたところ１時間経過しても変化が無か
った。そこで、アンモニア水を加えＰＨを１２に高める
と溶液は濃青色に変化し、ここで再度超音波により振動
させると赤褐色の沈澱物が析出した。ただちに母液から
沈澱物を分離し、水及びエタノールで洗浄後、真空乾燥
にて乾燥した。Add 170g of 2To0 to 124g of ethylene glycol and dissolve while gradually heating to produce a green viscous liquid. After cooling to room temperature, 81 g of formalin (37χHCHO) was added to this solution, and no change was observed.Next, this mixed solution was vibrated by ultrasonic waves, and no change was observed even after 1 hour had passed. Then, when aqueous ammonia was added to raise the pH to 12, the solution turned dark blue, and when it was again vibrated by ultrasonic waves, a reddish brown precipitate was deposited. The precipitate was immediately separated from the mother liquor, washed with water and ethanol, and then dried in vacuum.
得られた微粉末は非常に活性なためＡｒに封入して保存
する必要がある。この微粉末をＸ線回折パターンにより
Ｃｕ結晶であることが確かめられ、走査電子顕微鏡で観
察したところ、粒径範囲が０．１〜０．４ μｍでほぼ
球形の粉末であることが確認された。The obtained fine powder is very active and must be stored in Ar. The X-ray diffraction pattern of this fine powder confirmed that it was a Cu crystal, and when it was observed with a scanning electron microscope, it was confirmed that it was a nearly spherical powder with a particle size range of 0.1 to 0.4 μm. .
（発明の効果）
以上説明したように、本発明の製造法によれば、金属塩
を水または／および水に可溶の有機溶媒中に熔解し、こ
の金属塩溶液中に、そのままでは金属を析出せしめない
１度の還元剤水溶液を徐々に添加混合し、得られた混合
溶液に振動を与えて金属塩を還元し、金属微粉末を析出
させることとしたので、得られた金属微粉末は、粒径１
μ請以下の極めて均一なものとなり、さらに、−次粒子
として良好な分散状態で得られ、２次凝集や薄膜化が発
生することがない。それに加えて、設備なども節単であ
るため安価で量産が可能であるなどの利点を有する。(Effects of the Invention) As explained above, according to the production method of the present invention, a metal salt is dissolved in water and/or an organic solvent soluble in water, and the metal is dissolved in the metal salt solution as it is. We decided to gradually add and mix a one-time reducing agent aqueous solution that does not cause precipitation, and give vibration to the obtained mixed solution to reduce the metal salt and precipitate the metal fine powder. , particle size 1
The particles are extremely uniform with a diameter of less than μm, and furthermore, they are obtained as secondary particles in a good dispersed state, and no secondary agglomeration or thinning occurs. In addition, it has the advantage that it can be mass-produced at low cost because the equipment is simple.
Claims (7)
に溶解し、この金属塩溶液中に、そのままでは金属を析
出せしめない濃度の還元剤水溶液を徐々に添加混合し、
得られた混合溶液に振動を与えて金属塩を還元し、金属
微粉末を析出させることを特徴とする金属微粉末の製造
法。(1) A metal salt is dissolved in water or/and an organic solvent soluble in water, and an aqueous reducing agent solution with a concentration that does not precipitate the metal is gradually added and mixed into the metal salt solution,
A method for producing fine metal powder, which comprises applying vibration to the obtained mixed solution to reduce the metal salt and precipitate fine metal powder.
ウム、ロジウム、イリジウム、パラジウム、白金、セレ
ン、テルル、ポロニウム、アンチモン、ビスマスの塩化
物、硫酸塩、硝酸塩よりなる群から選ばれた少なくとも
１種であることを特徴とする特許請求の範囲第１項記載
の金属微粉末の製造法。(2) The metal salt is selected from the group consisting of chlorides, sulfates, and nitrates of copper, silver, gold, ruthenium, osmium, rhodium, iridium, palladium, platinum, selenium, tellurium, polonium, antimony, and bismuth. The method for producing a fine metal powder according to claim 1, characterized in that at least one type of metal powder is used.
ウム、ジメチルアミンボラン、ホルマリン、ギ酸、次亜
リン酸ナトリウム、過酸化水素よりなる群から選ばれた
少なくとも１種であることを特徴とする特許請求の範囲
第１項記載の金属微粉末の製造法。(3) A patent characterized in that the reducing agent is at least one selected from the group consisting of hydrazine, sodium borohydride, dimethylamine borane, formalin, formic acid, sodium hypophosphite, and hydrogen peroxide. A method for producing fine metal powder according to claim 1.
特徴とする特許請求の範囲第１項記載の金属微粉末の製
造法。(4) The method for producing fine metal powder according to claim 1, characterized in that vibration is applied to the mixed solution by ultrasonic waves.
アルカリを添加することを特徴とする特許請求の範囲第
１項記載の金属微粉末の製造法。(5) The method for producing fine metal powder according to claim 1, characterized in that an acid or an alkali is added to the mixed solution when the mixed solution is vibrated.
金属塩を溶解させることを特徴とする特許請求の範囲第
１項記載の金属微粉末の製造法。(6) The method for producing fine metal powder according to claim 1, characterized in that the water and/or the organic solvent is heated to dissolve the metal salt.
リを添加して前記金属塩を溶解させることを特徴とする
特許請求の範囲第１項記載の金属微粉末の製造法。(7) The method for producing fine metal powder according to claim 1, characterized in that an acid or alkali is added to the water and/or an organic solvent to dissolve the metal salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20133086A JPS6357703A (en) | 1986-08-29 | 1986-08-29 | Production of fine metallic powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20133086A JPS6357703A (en) | 1986-08-29 | 1986-08-29 | Production of fine metallic powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6357703A true JPS6357703A (en) | 1988-03-12 |
Family
ID=16439224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20133086A Pending JPS6357703A (en) | 1986-08-29 | 1986-08-29 | Production of fine metallic powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6357703A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03287707A (en) * | 1990-04-04 | 1991-12-18 | Murata Mfg Co Ltd | Production of copper powder |
| US6620219B1 (en) | 1998-09-11 | 2003-09-16 | Murata Manufacturing Co., Ltd. | Metal powder, method for producing the same, and conductive paste |
| JP2005036316A (en) * | 2003-06-23 | 2005-02-10 | Mitsubishi Materials Corp | Metal particulate and production method therefor |
| CN109732102A (en) * | 2019-03-18 | 2019-05-10 | 湘潭市泽宇新材料科技有限公司 | A kind of monodisperse high conductivity silver powder and preparation method thereof suitable for high and low temperature silver paste |
-
1986
- 1986-08-29 JP JP20133086A patent/JPS6357703A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03287707A (en) * | 1990-04-04 | 1991-12-18 | Murata Mfg Co Ltd | Production of copper powder |
| US6620219B1 (en) | 1998-09-11 | 2003-09-16 | Murata Manufacturing Co., Ltd. | Metal powder, method for producing the same, and conductive paste |
| JP2005036316A (en) * | 2003-06-23 | 2005-02-10 | Mitsubishi Materials Corp | Metal particulate and production method therefor |
| JP4640570B2 (en) * | 2003-06-23 | 2011-03-02 | 三菱マテリアル株式会社 | Metal fine particles and production method thereof |
| CN109732102A (en) * | 2019-03-18 | 2019-05-10 | 湘潭市泽宇新材料科技有限公司 | A kind of monodisperse high conductivity silver powder and preparation method thereof suitable for high and low temperature silver paste |
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