JPH04333504A - Continuous production of monodisperse fine silver powder - Google Patents
Continuous production of monodisperse fine silver powderInfo
- Publication number
- JPH04333504A JPH04333504A JP10567091A JP10567091A JPH04333504A JP H04333504 A JPH04333504 A JP H04333504A JP 10567091 A JP10567091 A JP 10567091A JP 10567091 A JP10567091 A JP 10567091A JP H04333504 A JPH04333504 A JP H04333504A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- reducing agent
- reaction tube
- solution
- monodisperse
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000010946 fine silver Substances 0.000 title claims abstract description 8
- 238000010924 continuous production Methods 0.000 title description 2
- 229910052709 silver Inorganic materials 0.000 claims abstract description 45
- 239000004332 silver Substances 0.000 claims abstract description 45
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003518 caustics Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000000967 suction filtration Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 230000032683 aging Effects 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- XNRABACJWNCNEQ-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.[Ag+].[O-][N+]([O-])=O XNRABACJWNCNEQ-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- JNKQKOKSOYJQIZ-UHFFFAOYSA-O azanium;silver;dinitrate Chemical compound [NH4+].[Ag+].[O-][N+]([O-])=O.[O-][N+]([O-])=O JNKQKOKSOYJQIZ-UHFFFAOYSA-O 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010130 dispersion processing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、微細な単分散銀粒子を
均質且つ連続的に製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for homogeneously and continuously producing fine monodisperse silver particles.
【０００２】0002
【従来の技術】微細銀粉は、ペーストとして電子部品の
電極材料等に多用されているが、電子デバイスの小型化
，薄型化に伴い、より均質で薄い焼成銀面が得られるよ
うな銀粉が求められている。[Prior Art] Fine silver powder is often used as a paste in electrode materials for electronic components, but as electronic devices become smaller and thinner, there is a demand for silver powder that can produce a more homogeneous and thinner baked silver surface. It is being
【０００３】従来、かかる銀微粉の製造方法としては、
銀溶液を攪拌しながら還元剤を滴下するか、又は還元剤
中に銀溶液を滴下するかして、得られた銀粉を三本ロー
ルミルで処理する方法が採られていた。Conventionally, methods for producing such fine silver powder include:
A method has been adopted in which a reducing agent is added dropwise to the silver solution while stirring, or the silver solution is added dropwise into the reducing agent, and the resulting silver powder is processed in a three-roll mill.
【０００４】0004
【発明が解決しようとする課題】ところで、上記従来の
方法では、銀粉を三本ロールミルで処理してペースト化
する場合、高度な分散処理技術が必要とされ、しかも得
られた銀ペーストの銀電極としての評価は劣るものであ
った。[Problems to be Solved by the Invention] However, in the conventional method described above, when processing silver powder with a three-roll mill to form a paste, advanced dispersion processing technology is required, and furthermore, the silver electrodes of the obtained silver paste are The evaluation was poor.
【０００５】本発明は、従来の技術の有するこのような
問題点に鑑みなされたものであり、その目的とするとこ
ろは、単分散銀粒子を均質且つ連続的に簡単に得ること
のできる製造方法を提供しようとするものである。The present invention has been made in view of the above-mentioned problems of the conventional technology, and its purpose is to provide a manufacturing method that can easily and homogeneously obtain monodisperse silver particles. This is what we are trying to provide.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
に、本発明による単分散銀微粉の連続製造方法は、銀溶
液と還元剤溶液を細長い反応管の上部から連続添加して
攪拌し、還元された銀微粒子を反応管の下部から連続的
に取り出すようにしたものである。攪拌には反応管の周
囲に取付けられた超音波振動子による超音波振動が併用
され得る。[Means for Solving the Problems] In order to achieve the above object, the continuous production method of monodispersed silver fine powder according to the present invention includes continuously adding a silver solution and a reducing agent solution from the upper part of an elongated reaction tube and stirring them. The reduced silver particles are continuously taken out from the bottom of the reaction tube. Ultrasonic vibration by an ultrasonic vibrator attached around the reaction tube may be used for stirring.
【０００７】生成される銀粒子の単分散化（ばらばらの
状態にすること）と球状化を図るために、還元剤溶液に
は、ポリビニールピロリドン，ゼラチン，アラビアゴム
，カルボキシメチルセルローズ，ポリアクリル酸及びデ
キストリンの如き水溶性の高分子物質が添加されてもよ
い。又、銀微粒子の粒径を制御するために、銀溶液中に
アンモニア水を、そして還元剤溶液中にアンモニア水，
トリエタノールアミン，グリセリン，炭酸アルカリ及び
苛性アルカリが夫々添加されてＰＨ値が調整される。尚
、還元剤としては、ナトリウムボロハイドライド，ホル
ムアルデヒドに、ハイドロキノン，メトール，フエニド
ン及びｌ−アスコビル酸又はこれらと亜硫酸塩，酸性亜
硫酸塩との混合物を加えたものが使用される。[0007] In order to make the produced silver particles monodisperse (individual state) and spherical, the reducing agent solution contains polyvinyl pyrrolidone, gelatin, gum arabic, carboxymethyl cellulose, polyacrylic acid. A water-soluble polymeric substance such as dextrin may also be added. In addition, in order to control the particle size of silver fine particles, ammonia water was added to the silver solution, and ammonia water was added to the reducing agent solution.
Triethanolamine, glycerin, alkali carbonate and caustic alkali are respectively added to adjust the pH value. As the reducing agent, a mixture of sodium borohydride, formaldehyde, hydroquinone, metol, phenidone, l-ascobylic acid, or a mixture of these and a sulfite or acidic sulfite is used.
【０００８】[0008]
【作用】還元剤溶液中に硝酸銀アンモニウム錯塩溶液を
添加還元する場合は、その添加時間を長くすればする程
、得られる銀粒子は成長凝集して大きくなり、逆に短け
れば短い程単分散化し、微粒子となる。多量の銀溶液を
一度に還元剤溶液中に投入すると、両溶液の相互拡散均
質化までに時間が掛り、粒径のばらつきが増大する。
還元剤がナトリウムボロハイドライド，ｌ−アスコルビ
ン酸及びハイドロキノンの場合には、還元終了までに要
する時間は４〜５分である。従って、反応管として両溶
液の滞留時間が１０分間となるようなものを設計するこ
とにより、下部から連続的に均質な単分散銀微粉を得る
ことができる。[Effect] When adding and reducing a silver ammonium nitrate complex salt solution to a reducing agent solution, the longer the addition time, the larger the resulting silver particles will grow and agglomerate; , and become fine particles. When a large amount of silver solution is added to the reducing agent solution at once, it takes time for both solutions to become homogenized through mutual diffusion, which increases the variation in particle size. When the reducing agent is sodium borohydride, l-ascorbic acid, and hydroquinone, the time required to complete the reduction is 4 to 5 minutes. Therefore, by designing the reaction tube so that the residence time of both solutions is 10 minutes, it is possible to continuously obtain homogeneous monodispersed silver fine powder from the lower part.
【０００９】[0009]
【実施例】図１は本発明方法を実施するために使用され
る反応管装置を示しており、１は上部にガス抜き孔１ａ
を下端小径部にコック１ｂを有する内径１０ｃｍ，長さ
１２０ｃｍの反応管、２は反応管１の周囲に付設されて
いて温度調整を行うためのジャケット、３は反応管１の
周囲に設置されていて得られる銀微粉粒子の均質化を図
るための複数の超音波振動子、４は反応管１の下部に設
置された銀イオン濃度計、５は銀溶液貯溜槽、６は還元
剤溶液貯留槽、７及び８は貯溜槽６と反応管１を結ぶパ
イプライン中に設けられたコック及び流量計、９及び１
０は貯留槽６と反応管１を結ぶパイプライン中に設けら
れたコック及び流量計、１１は反応管１中に設置された
攪拌機１２を駆動するためのモータ、１３は熟成槽、１
４は熟成槽中に設けられた攪拌機、１５は反応管１の下
端と熟成槽１３とを結ぶパイプライン中に設けられたコ
ック、１６は遠心分離法又は吸引濾過法により銀微粉を
取り出すための分取装置、１７は反応管１の下端と分取
装置１６とを結ぶパイプライン中に設けられたコック、
１８は熟成槽１３と分取装置１６とを結ぶパイプライン
中に設けられたコックである。[Example] Fig. 1 shows a reaction tube apparatus used for carrying out the method of the present invention, and 1 indicates a gas vent hole 1a in the upper part.
A reaction tube with an inner diameter of 10 cm and a length of 120 cm has a cock 1b at the small diameter part of the lower end, 2 is a jacket attached around the reaction tube 1 to adjust the temperature, and 3 is installed around the reaction tube 1. 4 is a silver ion concentration meter installed at the bottom of the reaction tube 1, 5 is a silver solution storage tank, and 6 is a reducing agent solution storage tank. , 7 and 8 are cocks and flow meters installed in the pipeline connecting the storage tank 6 and the reaction tube 1, 9 and 1
0 is a cock and a flow meter installed in the pipeline connecting the storage tank 6 and the reaction tube 1, 11 is a motor for driving the stirrer 12 installed in the reaction tube 1, 13 is an aging tank, 1
4 is a stirrer installed in the aging tank; 15 is a cock installed in the pipeline connecting the lower end of the reaction tube 1 and the aging tank 13; and 16 is a cock for removing fine silver powder by centrifugation or suction filtration. A separation device 17 is a cock provided in the pipeline connecting the lower end of the reaction tube 1 and the separation device 16;
18 is a cock provided in the pipeline connecting the aging tank 13 and the fractionating device 16.
【００１０】実施例１
貯留槽５に、硝酸銀１７００ｇ，アンモニア水（Ｓ．Ｇ
．０．９）１５００ｍｌ及び純水から成る硝酸銀アンモ
ニア錯塩水溶液５０００ｍｌを、又貯留槽６に、亜硫酸
カリウム１４００ｇ，ハイドロキノン４００ｇ，炭酸ナ
トリウム４００ｇ，ゼラチン１００ｇ及び純水から成る
還元剤溶液４５０００ｍｌを夫々用意した。両溶液を夫
々１０℃に保ち、先づコック９を開いて反応管１を還元
剤溶液で満たし、次に、コック７を開いて銀溶液を毎分
５０ｍｌの割合で、又還元剤溶液を毎分４５０ｍｌの割
合で、反応管１内へ同時に滴下しながら攪拌した。同時
にコック１ｂ，１７を開き、毎分５００ｍｌの割合で銀
粉スラリーを分取装置１６へ流出させた。分取装置１６
において、この銀粉スラリーは連続的に母液と分離され
、洗滌，乾燥することにより、真球状の銀粒子１０７５
ｇを得た。反応は約１１０分で終了し、銀粒子の平均粒
径は１．８μｍ，シグマは０．３μｍであった。Example 1 In the storage tank 5, 1700 g of silver nitrate and aqueous ammonia (S.G.
．． 0.9) 5,000 ml of a silver nitrate ammonia complex aqueous solution consisting of 1,500 ml and pure water, and 45,000 ml of a reducing agent solution consisting of 1,400 g of potassium sulfite, 400 g of hydroquinone, 400 g of sodium carbonate, 100 g of gelatin and pure water were prepared in storage tank 6. Both solutions were kept at 10°C, and first the cock 9 was opened to fill the reaction tube 1 with the reducing agent solution, and then the cock 7 was opened to add the silver solution at a rate of 50 ml per minute and the reducing agent solution every minute. The mixture was simultaneously dropped into the reaction tube 1 at a rate of 450 ml and stirred. At the same time, the cocks 1b and 17 were opened, and the silver powder slurry was flowed out to the fractionator 16 at a rate of 500 ml per minute. Preparation device 16
In the process, this silver powder slurry is continuously separated from the mother liquor, washed and dried to form truly spherical silver particles 1075.
I got g. The reaction was completed in about 110 minutes, and the average particle size of the silver particles was 1.8 μm, and the sigma was 0.3 μm.
【００１１】実施例２
銀溶液は実施例１と同様のものを同量用意し、還元剤溶
液としては、亜硫酸アンモニウム１２００ｇ，アンモニ
ア水（Ｓ．Ｇ．０．９）２００ｍｌ，ハイドロキノン２
００ｇ，フエニドン（１−フエニール−３−ピラゾリド
ン）４０ｇ及びポリビニールピロリドン４０ｇを純水に
溶解して４５０００ｍｌを用意した。そして、銀溶液を
毎分５０ｍｌの割合で、又還元剤溶液を毎分４５０ｍｌ
の割合で、実施例１と同じ条件で反応させ、銀微粉１０
７０ｇを得た。この銀粉は表面に凹凸のある単分散球状
体であり、平均粒径０．７μｍ、シグマ０．２μｍであ
った。Example 2 The same amount of silver solution as in Example 1 was prepared, and the reducing agent solution was 1200 g of ammonium sulfite, 200 ml of aqueous ammonia (S.G. 0.9), and 2 ml of hydroquinone.
00 g, phenidone (1-phenyl-3-pyrazolidone), 40 g, and polyvinylpyrrolidone, 40 g, were dissolved in pure water to prepare 45,000 ml. Then, the silver solution was added at a rate of 50 ml per minute, and the reducing agent solution was added at a rate of 450 ml per minute.
The reaction was carried out under the same conditions as in Example 1 at a ratio of 10
70g was obtained. This silver powder was a monodisperse spherical body with an uneven surface, and had an average particle size of 0.7 μm and a sigma of 0.2 μm.
【００１２】実施例３
フエニドンの代わりにメトール（Ｐ−メチルアミノフエ
ノール硫酸塩）４０ｇを用いたほかは実施例２と全く同
じものを同じ条件で反応させて、単分散銀微粉１０７２
ｇを得た。平均粒径０．７μｍ，シグマ０．２μｍであ
った。Example 3 The same reaction as in Example 2 was carried out under the same conditions except that 40 g of metol (P-methylaminophenol sulfate) was used instead of phenidone, and 1072 g of monodispersed silver fine powder was obtained.
I got g. The average particle diameter was 0.7 μm, and the sigma was 0.2 μm.
【００１３】実施例４
硝酸銀結晶１７００ｇを純水に溶解して５０００ｍｌの
銀溶液を、又ナトリウムボロハイドライド５５ｇ，カセ
イソーダ３７０ｇを純水に溶解して５５００ｍｌの還元
剤溶液を夫々用意した。先づ反応管１を純水で満たし、
銀溶液と還元剤溶液を夫々毎分３０ｍｌの割合で同時に
滴下した。反応温度は２０℃，ＰＨは９．０±０．１に
保ち、約３時間後に反応は終了し、１０７０ｇの黒灰色
銀粉が得られた。銀粉の平均粒径は０．６μｍ（ＦＳＳ
Ｓ）であった。Example 4 1700 g of silver nitrate crystals were dissolved in pure water to prepare 5000 ml of a silver solution, and 55 g of sodium borohydride and 370 g of caustic soda were dissolved in pure water to prepare 5500 ml of a reducing agent solution. First, fill reaction tube 1 with pure water,
A silver solution and a reducing agent solution were each added dropwise at the same time at a rate of 30 ml per minute. The reaction temperature was maintained at 20° C. and the pH at 9.0±0.1, and the reaction was completed after about 3 hours, yielding 1070 g of black-gray silver powder. The average particle size of silver powder is 0.6 μm (FSS
S).
【００１４】実施例５
銀溶液として、硝酸銀結晶１７００ｇ，アンモニア水（
Ｓ．Ｇ．０．９）１４５０ｍｌ及び純水から成る硝酸銀
アンモニア錯塩水溶液６０００ｍｌを、又還元剤溶液と
して、ｌ−アスコルビン酸６００ｇ，亜硫酸アンモニウ
ム４００ｇ，ポリビニールピロリドン１００ｇを純水に
溶解したもの６００００ｍｌを夫々用意した。両溶液共
１５℃に保ち、銀溶液を毎分６０ｍｌ，還元剤溶液を毎
分６００ｍｌの割合で同時に滴下し、反応させた。反応
管１からは毎分６６０ｍｌの割合で分取装置１６へ取り
出し、ここで直接遠心分離機にかけ、水洗乾燥して、１
０７４ｇの真球状の銀微粉を得た。反応は１１０分で終
了し、平均粒径は０．３μｍであった。Example 5 As a silver solution, 1700 g of silver nitrate crystals and aqueous ammonia (
S. G. 0.9) 6000 ml of a silver nitrate ammonia complex aqueous solution consisting of 1450 ml and pure water, and 60000 ml of a reducing agent solution in which 600 g of l-ascorbic acid, 400 g of ammonium sulfite, and 100 g of polyvinyl pyrrolidone were dissolved in pure water were prepared. Both solutions were kept at 15° C., and the silver solution and the reducing agent solution were simultaneously added dropwise at a rate of 60 ml per minute and 600 ml per minute, respectively, to cause a reaction. The reaction tube 1 is taken out at a rate of 660 ml per minute to the fractionator 16, where it is directly centrifuged, washed with water, and dried.
074 g of perfectly spherical fine silver powder was obtained. The reaction was completed in 110 minutes, and the average particle size was 0.3 μm.
【００１５】上記各実施例では、反応後の銀粉スラリー
を直接分取装置１６へ流出させて銀粉を得るようにした
が、それに代えてコック１５を開き、銀粉スラリーを一
旦熟成槽１３へ流出させ、ここで攪拌機１４により熟成
させた後分取装置１６へ送るようにしてもよい。In each of the above embodiments, the silver powder slurry after the reaction was directly flowed to the fractionator 16 to obtain silver powder, but instead, the cock 15 was opened and the silver powder slurry was temporarily flowed to the ripening tank 13. Here, the mixture may be aged using the stirrer 14 and then sent to the fractionating device 16.
【００１６】次に、比較例として従来方法を用いた場合
の実験例について説明する。銀溶液として、純水２ｌ，
亜硫酸カリウム１００ｇ，ハイドロキノン１５ｇ，ゼラ
チン２．０ｇから成る水溶液を、又還元剤溶液として、
硝酸銀結晶８５ｇ，アンモニア水７４ｍｌを純水に溶解
したもの５００ｍｌを夫々用意した。銀溶液を２０℃に
保ちながら攪拌しておき、これに上記還元剤溶液を滴下
して銀粉を生成したが、その滴下時間と生成された銀粒
子との関係は次の通りであった。
還元剤溶液の滴下時間
銀粒子の状態 １８００秒
粒径１〜１０μｍ
の凝集粒子
３０秒 粒径
０．５〜３μｍの凝集粒子
１０秒
粒径０．６μｍの単分散球状粒子Next, as a comparative example, an experimental example using the conventional method will be explained. As a silver solution, 2 liters of pure water,
An aqueous solution consisting of 100 g of potassium sulfite, 15 g of hydroquinone, and 2.0 g of gelatin was also used as a reducing agent solution.
85 g of silver nitrate crystals and 74 ml of ammonia water were dissolved in pure water to prepare 500 ml of each. The silver solution was stirred while being maintained at 20° C., and the reducing agent solution was added dropwise to the silver solution to produce silver powder. The relationship between the dropping time and the produced silver particles was as follows. Dripping time of reducing agent solution
Silver particle state 1800 seconds
Particle size 1-10μm
agglomerated particles of
30 seconds Agglomerated particles with a particle size of 0.5 to 3 μm
10 seconds
Monodisperse spherical particles with a particle size of 0.6 μm
【００１７】[0017]
【発明の効果】上述の如く、本発明によれば、極めて均
質の単分散銀粒子を容易且つ連続的に製造することがで
きる。又、本発明方法により得られた銀粒子は、焼成面
が平滑であって、従来の銀粉に見られる銀焼結面の穴は
全く見られず、特に積層型チップコンデンサの内部電極
用等として極めて有用である。As described above, according to the present invention, extremely homogeneous monodisperse silver particles can be easily and continuously produced. In addition, the silver particles obtained by the method of the present invention have a smooth sintered surface and do not have any holes on the sintered surface that are found in conventional silver powder, and are particularly suitable for internal electrodes of multilayer chip capacitors. Extremely useful.
【図１】本発明方法の実施に用いられる反応管装置の構
成図である。FIG. 1 is a configuration diagram of a reaction tube apparatus used to carry out the method of the present invention.
１ 反応管
３ 超音波振動子
４ 銀イオン濃度計
５ 銀溶液貯留槽
６ 還元剤溶液貯留槽
１ｂ，７，９，１７，１８ コック８，１０
流量計
１２，１４ 攪拌機
１３ 熟成槽
１６ 分取装置1 Reaction tube 3 Ultrasonic vibrator 4 Silver ion concentration meter 5 Silver solution storage tank 6 Reducing agent solution storage tank 1b, 7, 9, 17, 18 Cock 8, 10
Flow meter 12, 14 Stirrer 13 Aging tank 16 Preparation device
Claims (4)
上部から連続添加して攪拌し、還元された銀微粒子を上
記反応管の下部から連続して取り出すようにした、単分
散銀微粉の連続製造方法。1. A monodisperse fine silver powder, in which a silver solution and a reducing agent solution are continuously added from the upper part of a long and narrow reaction tube and stirred, and the reduced silver particles are continuously taken out from the lower part of the reaction tube. Continuous manufacturing method.
加して、生成される銀粒子の単分散化と球状化を図るよ
うにした、請求項１に記載の方法。2. The method according to claim 1, wherein a water-soluble polymeric substance is added to the reducing agent solution to make the produced silver particles monodisperse and spherical.
溶液中にアンモニア水，トリエタノールアミン，グリセ
リン，炭酸アルカリ及び苛性アルカリを夫々添加してＰ
Ｈ値を調整することにより、銀微粒子の粒径を制御する
ようにした、請求項１に記載の方法。Claim 3: Adding ammonia water to the silver solution and adding ammonia water, triethanolamine, glycerin, alkali carbonate and caustic alkali to the reducing agent solution respectively.
The method according to claim 1, wherein the particle size of the silver particles is controlled by adjusting the H value.
て、攪拌と併用するようにした、請求項１乃至３の何れ
かに記載の方法。4. The method according to claim 1, wherein an ultrasonic vibrator is installed around the reaction tube to be used in conjunction with stirring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10567091A JPH04333504A (en) | 1991-05-10 | 1991-05-10 | Continuous production of monodisperse fine silver powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10567091A JPH04333504A (en) | 1991-05-10 | 1991-05-10 | Continuous production of monodisperse fine silver powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04333504A true JPH04333504A (en) | 1992-11-20 |
Family
ID=14413878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10567091A Pending JPH04333504A (en) | 1991-05-10 | 1991-05-10 | Continuous production of monodisperse fine silver powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04333504A (en) |
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