JPH0459904A - Manufacture of silver fine powder - Google Patents
Manufacture of silver fine powderInfo
- Publication number
- JPH0459904A JPH0459904A JP16838490A JP16838490A JPH0459904A JP H0459904 A JPH0459904 A JP H0459904A JP 16838490 A JP16838490 A JP 16838490A JP 16838490 A JP16838490 A JP 16838490A JP H0459904 A JPH0459904 A JP H0459904A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- alkali
- salt
- powder
- reducing agent
- 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 62
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 33
- 239000004332 silver Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 title abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 17
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 150000001447 alkali salts Chemical class 0.000 claims abstract description 4
- 239000010946 fine silver Substances 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 8
- -1 silver ions Chemical class 0.000 claims description 7
- 239000010419 fine particle Substances 0.000 claims description 4
- 150000003378 silver Chemical class 0.000 claims description 2
- 159000000011 group IA salts Chemical class 0.000 claims 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002245 particle Substances 0.000 abstract description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001961 silver nitrate Inorganic materials 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 abstract description 2
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 abstract description 2
- 229940041616 menthol Drugs 0.000 abstract description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910001923 silver oxide Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 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
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 2
- 229910001958 silver carbonate Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 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
- 239000000919 ceramic Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はセラミックコンデンサー、セラミックバリスタ
、セラミックバリスタ、圧電素子、サーブイブ、旧Ｏ等
の電子部品の電極形成に用いられる微細な銀粉末の製造
方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a method for producing fine silver powder used for forming electrodes of electronic components such as ceramic capacitors, ceramic varistors, piezoelectric elements, Surveve, and old O. It is related to.
従来の銀粉末の製造方法としては、硝酸銀水溶液に水酸
化ナトリウムを加えて酸化銀を作り、これをヒドラジン
、ホルムアルデヒド或いは、ナトリウムボロンバイトラ
ンド等の還元剤で還元して銀粉末を得るのが一般的な方
法であるが、この方法では、不完全な球状あるいは不定
形状の粒子が多く生成し、しかも粒子は単粒子ではなく
単粒子が凝集した粒子が多く含まれた銀粉末ができ、微
細な球状の単分散銀粉末あるいは微細な樹枝状の銀粉末
が得られなかった。又、古くから銀に関連があるものと
して、写真技術の写真現像に有機還元剤が利用されてお
り、例えば、−船釣に現像主薬として、メトール、ヒド
ロキノン系或いはフェニドン−ヒドロキノン系の還元剤
が広（利用されている。この方法ではフィルム上のゼラ
チン層中に分布するハロゲン化銀結晶をこれら現像主薬
の還元により超微細な黒い繊維状の凝集体として還元銀
が形成され、これが黒い写真画像となっているのが知ら
れている。The conventional method for producing silver powder is to add sodium hydroxide to an aqueous solution of silver nitrate to produce silver oxide, and then reduce this with a reducing agent such as hydrazine, formaldehyde, or sodium boron bitland to obtain silver powder. However, in this method, many imperfectly spherical or irregularly shaped particles are produced, and moreover, the particles are not single particles but silver powder that contains many aggregated particles of single particles, resulting in fine particles. A spherical monodisperse silver powder or a fine dendritic silver powder was not obtained. In addition, organic reducing agents have been used in photographic development in photographic technology since ancient times, as they have been associated with silver.For example, metol, hydroquinone-based, or phenidone-hydroquinone-based reducing agents have been used as developing agents in boat fishing. In this method, silver halide crystals distributed in the gelatin layer on the film are reduced by these developing agents to form reduced silver as ultrafine black fibrous aggregates, which form black photographic images. It is known that
本発明の目的は上記問題を解消するために、有機還元剤
を利用した、微細な球状銀粉末及び樹枝状あるいは棒状
の銀粉末等、従来になかった形状の銀粉末の製造方法を
提供するものである。An object of the present invention is to provide a method for producing silver powder in shapes that have not been seen before, such as fine spherical silver powder, dendritic or rod-shaped silver powder, etc., using an organic reducing agent, in order to solve the above problems. It is.
本発明は、銀塩または銀アミン錯体中の銀イオンを還元
して銀微粒子を製造する方法において、有機還元剤であ
るヒドロキノン、メントール、フェニドン等の還元剤を
単品あるいは二種類以上の組み合わせと亜硫酸塩及びア
ルカリ、アルカリ塩の溶液を用いて効率良く銀微粉末を
得ることを特徴したものである。The present invention is a method for producing silver fine particles by reducing silver ions in a silver salt or a silver amine complex, in which organic reducing agents such as hydroquinone, menthol, and phenidone are used singly or in combination of two or more and sulfur dioxide. This method is characterized by efficiently obtaining fine silver powder using a salt, an alkali, and a solution of an alkali salt.
本発明における有機還元剤を用いると、不溶性の酸化生
成物と銀粉末とが温存生成する。When the organic reducing agent of the present invention is used, insoluble oxidation products and silver powder are produced while being preserved.
例えば、ヒドロキノン、Ｉｍｏｌは、銀２ｍｏｌを還元
し、Ｉｍｏｌの難溶性キノンが生成する。この系に亜硫
酸塩、重亜硫酸塩、異性亜硫酸塩等を添加することによ
り還元剤の酸化生成物が亜硫酸塩と反応して、水溶性化
合物となり、銀微粉末との分離が容昌になる。For example, Imol of hydroquinone reduces 2 mol of silver to produce Imol of poorly soluble quinone. By adding sulfite, bisulfite, isomeric sulfite, etc. to this system, the oxidation product of the reducing agent reacts with the sulfite and becomes a water-soluble compound, which can be easily separated from fine silver powder.
５０３２−添加により、水性スルフォン酸塩となって、
系外に除去されるばかりでなく、ヒドロキノンＩ ｌｌ
１ｏｌ 当たりの当量を迩かに越える４、４ｍｏｌの銀
粉末が得られた。5032-addition results in an aqueous sulfonate,
In addition to being removed from the system, hydroquinone Ill
4.4 mol of silver powder was obtained, which far exceeded the equivalent amount per 1 ol.
この反応系に、水素イオン濃度も重要な役割を持ってお
り、ｐＨ７〜１３が望ましくｐｉ（７未満では、還元反
応が遅くなり非能率的であり、ｐＨ１３を越える分では
生成した銀粒子が粗大となり目的の微粒粉末が得られな
い。Hydrogen ion concentration also plays an important role in this reaction system, and a pH of 7 to 13 is desirable (pi below 7, the reduction reaction becomes slow and inefficient; above pH 13, the produced silver particles become coarse). As a result, the desired fine powder cannot be obtained.
アルカリとして水酸化ナトリウム、炭酸ナトリウム、重
炭酸ナトリウム、アンモニア水、トリエタノールアミン
、硼砂等を含むが、亜硫酸塩やアルカリ類を含めて、ナ
トリウムイオン以外にカリウムイオンやアンモニアイオ
ンも含まれる。Alkali include sodium hydroxide, sodium carbonate, sodium bicarbonate, aqueous ammonia, triethanolamine, borax, etc., but also includes sulfites and alkalis, and in addition to sodium ions, potassium ions and ammonia ions are also included.
この有機還元剤の還元系に、水溶性高分子化合物である
ゼラチン、デキストリン、アラビアゴム、ポリビニール
アルコール、ポリビニールピロリドン、カルボキシメチ
ルセルロース、ポリアクリル酸及び、酸化数２００以上
のロジン誘導体等の添加により、銀粒子サイズをコント
ロールし、特に微細なサブミクロンの銀微粉末を製造す
ることをも含むものである。By adding water-soluble polymer compounds such as gelatin, dextrin, gum arabic, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, polyacrylic acid, and rosin derivatives with an oxidation number of 200 or more to the reducing system of this organic reducing agent, , control of silver particle size and production of particularly fine submicron silver powder.
銀化合物としては、可溶性の硫酸銀、硝酸銀アミン錯塩
の他に、酸化銀、炭酸銀、ハロゲン化銀等を含むもので
ある。Silver compounds include silver oxide, silver carbonate, silver halide, etc. in addition to soluble silver sulfate and silver amine nitrate complex salts.
還元反応温度は、１０〜５０℃が望ましく、１０℃未満
では、塩類が析出しやすく、銀の生成速度も遅いので非
能率的であり、５０℃を越える分には、銀粒子が粗大と
なり目的の微粉末が得られない。The reduction reaction temperature is preferably 10 to 50°C. If it is less than 10°C, salts tend to precipitate and the rate of silver production is slow, making it inefficient. If it exceeds 50°C, the silver particles become coarse and cannot be used for the purpose. fine powder cannot be obtained.
〔実施例−１〕
無水亜硫酸カリウム３０ｇ５炭酸ナトリウム１０ｇ及び
ヒドロキノン２０ｇを純水１５００−に熔解し、これに
硝酸銀８５ｇを純水５００Ｍ１１に溶解したものを２０
℃で添加攪拌する。還元反応は４〜５分間で完結し、銀
の沈殿物を生成させた、この銀の沈殿物を口過・乾燥し
銀粉末を得た。[Example-1] 30 g of anhydrous potassium sulfite, 10 g of sodium carbonate, and 20 g of hydroquinone were dissolved in 1500 M of pure water, and 85 g of silver nitrate was dissolved in 500 M of pure water.
Add and stir at °C. The reduction reaction was completed in 4 to 5 minutes, producing a silver precipitate. This silver precipitate was filtered and dried to obtain a silver powder.
重量は約５４ｇであった。The weight was approximately 54g.
この微粉末を電子顕微鏡で観察した結果、サブミクロン
サイズの樹枝状の銀微粉末であった。When this fine powder was observed under an electron microscope, it was found to be submicron-sized dendritic fine silver powder.
〔実施例−２〕
水酸化ナトリウム２２ｇを含む水溶液３００Ｍ１と、硝
酸銀８５ｇを含む水溶液２００−を純水１０００−に添
加攪拌し、酸化銀の沈殿物を生成させてティカンテイジ
ョンにより沈殿物を水洗いする。[Example-2] 300 M1 of an aqueous solution containing 22 g of sodium hydroxide and 200 M1 of an aqueous solution containing 85 g of silver nitrate were added to 1000 M of pure water and stirred to form a silver oxide precipitate, and the precipitate was washed with water using a ticantision. do.
これに亜硫酸ナトリウム３０ｇとヒドロキノン１５ｇを
純水５００ｄに溶解した還元剤を添加攪拌して２５ｇで
反応させ、やや黒色帯びた銀の沈殿物を生成させて、口
過・乾燥を行ない約５４ｇの銀粉末を得た。この銀粉末
を電子顕微鏡で観察した結果、約０．３μｍ棒状の単分
散銀微粉末であった。A reducing agent prepared by dissolving 30 g of sodium sulfite and 15 g of hydroquinone in 500 d of pure water was added and stirred to react with 25 g to form a slightly blackish silver precipitate, which was then filtered and dried to yield about 54 g of silver. A powder was obtained. As a result of observing this silver powder with an electron microscope, it was found to be a monodisperse fine silver powder having a rod shape of about 0.3 μm.
（実施例−３〕
炭酸アンモニウム６０ｇを純水１０００−に溶解し、酸
化銀８５ｇを含む水溶液２００ｗ１１を添加撹拌して、
炭酸銀の黄色い沈殿物を得た。(Example-3) 60g of ammonium carbonate was dissolved in 1000ml of pure water, and 200w11 of an aqueous solution containing 85g of silver oxide was added and stirred.
A yellow precipitate of silver carbonate was obtained.
これに亜硫酸アンモン５０ｇとヒドロキノン２０ｇを純
水５００ｄに溶解せしめた還元剤を、２０℃で添加攪拌
すると、１０分間で反応は完結し、銀の沈殿物を生成さ
せて、口過・乾燥を行ない銀粉末が約５４ｇが得られた
。When a reducing agent made by dissolving 50 g of ammonium sulfite and 20 g of hydroquinone in 500 d of pure water is added and stirred at 20°C, the reaction is completed in 10 minutes, forming a silver precipitate, which is then filtered and dried. Approximately 54 g of silver powder was obtained.
この銀粉末を電子顕微鏡で観察した結果、板状のＷ＆微
粉末であった。As a result of observing this silver powder with an electron microscope, it was found to be a plate-shaped W&fine powder.
〔実施例−４〕
実施例−１において、ヒドロキノン２０ｇを、フェニド
ン３ｇ＋ヒドロキノン１５ｇの混合した還元剤に換えて
、これを用い、同様に還元を行ない、銀の沈殿物を生成
させて、口過・乾燥を行ない銀粉末が約５４ｇが得られ
た。[Example 4] In Example 1, 20 g of hydroquinone was replaced with a reducing agent mixed with 3 g of phenidone and 15 g of hydroquinone, and reduction was carried out in the same manner as in Example 1 to generate a silver precipitate. - Approximately 54 g of silver powder was obtained by drying.
この銀粉末を電子顕微鏡で観察した結果、サブミクロン
サイズの板状の銀微粉末であった。When this silver powder was observed under an electron microscope, it was found to be submicron-sized, plate-shaped fine silver powder.
〔実施例−５〕
無水亜硫酸カリウム１００ｇ、炭酸ナトリウム１００ｇ
及びヒドロキノン２０ｇを純水２０００−に溶解し、２
０℃で攪拌しながら、これに硝酸銀８５ｇを純水２００
１１１に溶解し、次いでアンモニア水７０＋＋ｄ！を加
えアミン錯塩溶液にさせたものを添加し、銀の沈殿物を
生成させ、約５分間で還元反応は完結した。この沈殿物
を口過・乾燥を行ない銀粉末が約５４ｇが得られた。[Example-5] 100g of anhydrous potassium sulfite, 100g of sodium carbonate
and 20g of hydroquinone were dissolved in 2000ml of pure water.
While stirring at 0°C, add 85 g of silver nitrate to 200 g of pure water.
111, then aqueous ammonia 70++d! was added to form an amine complex salt solution, a silver precipitate was formed, and the reduction reaction was completed in about 5 minutes. This precipitate was filtered and dried to obtain about 54 g of silver powder.
この銀粉末を電子顕微鏡で観察した結果、平均粒径０．
７μｍの単分散の球状の銀微粉末であった。As a result of observing this silver powder with an electron microscope, the average particle size was 0.
It was a monodisperse spherical fine silver powder with a diameter of 7 μm.
〔実施例−６〕
実ｍ例−５の系の純水２０００−にポリビニールピロト
ン２ｇを溶解した系で、同様に還元反応させ、銀の沈殿
物を生成させ、この沈殿物を口過・乾燥を行ない銀粉末
が約５４ｇが得られた。[Example-6] Using the same system as in Example-5, in which 2 g of polyvinyl pyroton was dissolved in 2000 g of pure water, a reduction reaction was carried out in the same manner to produce a silver precipitate, and this precipitate was passed through a mouth sieve. - Approximately 54 g of silver powder was obtained by drying.
この銀粉末を電子顕微鏡で観察した結果、平均粒径０．
３μｍ単分散の球状の銀微粉末であった。As a result of observing this silver powder with an electron microscope, the average particle size was 0.
It was a spherical fine silver powder with a monodisperse size of 3 μm.
無水炭酸カリウム１００ｇ、ヒドロキノン６０ｇを純水
２０００ｄに溶解し、硝酸銀１７０ｇを純水５００−に
溶解した溶液を２０℃で添加攪拌し、還元反応を行ない
、銀の沈殿物を生成させるが、難溶性のｐ−キノンも多
量に生成した。A solution of 100 g of anhydrous potassium carbonate and 60 g of hydroquinone dissolved in 2000 g of pure water and 170 g of silver nitrate dissolved in 500 g of pure water are added and stirred at 20°C to perform a reduction reaction and form a silver precipitate, but it is hardly soluble. A large amount of p-quinone was also produced.
このため銀粉末とキノンの分離には多量の有機溶剤を必
要とし経済的にも不都合であるばかりでなく、電子顕微
鏡で観察した結果、生成銀粉末は不定形の微粒子と粗大
粒子を含み一部は樹枝状のものであった。For this reason, separation of silver powder and quinone requires a large amount of organic solvent, which is not only economically inconvenient, but also, as a result of observation with an electron microscope, the produced silver powder contains some irregularly shaped fine particles and coarse particles. was dendritic.
上記の発明で明らかなように、本発明の製造方法は、サ
ブミクロンの樹枝状や単分散の真球状等の極めて特徴あ
る銀微粉末が得られる。As is clear from the above invention, the production method of the present invention yields very distinctive silver fine powders such as submicron dendritic shapes and monodisperse true spherical shapes.
有機還元剤とアルカリ及び亜硫酸塩を含むものの製法は
、ｐＨ及び、温度により銀粒子の粒径を容易にコントロ
ール出来るうえ、短時間に効率良く反応を完結させるこ
とが出来、安価で極めて有益な銀微粉末を得ることが出
来る。The manufacturing method containing an organic reducing agent, alkali, and sulfite allows the particle size of silver particles to be easily controlled by adjusting pH and temperature, and the reaction can be completed efficiently in a short time, making it an inexpensive and extremely useful silver product. Fine powder can be obtained.
又、電子部品の電極形成において、特に、樹枝状銀粉末
は電極のエッヂ構成に有効であり、球状銀粉末はペース
ト分散性に優れており、これらは従来技術になく、画期
的なものと言える。In addition, in the formation of electrodes for electronic components, dendritic silver powder is particularly effective in forming the edge structure of electrodes, and spherical silver powder has excellent paste dispersibility. I can say it.
特許出願人 住友金属鉱山株式会社Patent applicant: Sumitomo Metal Mining Co., Ltd.
Claims (1)
を製造する方法において、有機還元剤と亜硫酸塩及びア
ルカリもしくはアルカリ塩でｐＨ７〜１３に調整した溶
液を還元反応温度１０〜５０℃で反応させて、微細な銀
粉末を得ることを特徴とした銀微粉末の製造方法。In a method for producing silver fine particles by reducing silver ions of silver salts or silver amine complexes, a solution adjusted to pH 7 to 13 with an organic reducing agent, sulfite, and alkali or alkaline salt is reacted at a reduction reaction temperature of 10 to 50°C. A method for producing fine silver powder, characterized by obtaining fine silver powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16838490A JPH0459904A (en) | 1990-06-28 | 1990-06-28 | Manufacture of silver fine powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16838490A JPH0459904A (en) | 1990-06-28 | 1990-06-28 | Manufacture of silver fine powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0459904A true JPH0459904A (en) | 1992-02-26 |
Family
ID=15867111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16838490A Pending JPH0459904A (en) | 1990-06-28 | 1990-06-28 | Manufacture of silver fine powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0459904A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06172822A (en) * | 1992-12-07 | 1994-06-21 | Sumitomo Metal Mining Co Ltd | Production of fine silver powder |
| EP0652293A1 (en) * | 1993-07-13 | 1995-05-10 | E.I. Du Pont De Nemours And Company | Process for making finely divided, dense packing, spherical shaped silver particles |
| US6127294A (en) * | 1996-07-02 | 2000-10-03 | Japan Pionics Co., Ltd. | Sheet shaped heat generating body and method of manufacturing same |
| WO2008013274A1 (en) * | 2006-07-28 | 2008-01-31 | Mitsubishi Materials Corporation | Silver fine particles and processes and equipment for the production thereof |
| JP2008031526A (en) * | 2006-07-28 | 2008-02-14 | Mitsubishi Materials Corp | Method for producing silver particulate |
| JP2008050697A (en) * | 2006-07-28 | 2008-03-06 | Mitsubishi Materials Corp | Silver fine particle and method and apparatus for producing the same |
| JP2011511885A (en) * | 2008-01-09 | 2011-04-14 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | Method for producing noble metal nanoparticle dispersion and method for isolating such nanoparticles from said dispersion |
| WO2014119793A1 (en) * | 2013-02-04 | 2014-08-07 | 国立大学法人山形大学 | Metallic silver separation method, coated silver fine particles, and thin, linear, coated metallic silver |
| JP2015209555A (en) * | 2014-04-24 | 2015-11-24 | 株式会社ノリタケカンパニーリミテド | Silver nanowire and manufacturing method therefor |
| CN109332723A (en) * | 2018-12-10 | 2019-02-15 | 西安宏星电子浆料科技有限责任公司 | A kind of preparation method of low-temperature conductive adhesive silver powder |
| US11008470B2 (en) | 2019-03-28 | 2021-05-18 | Noritake Co., Limited | Core-shell particles and use thereof |
| US11219883B2 (en) | 2018-10-18 | 2022-01-11 | Noritake Co., Limited | Ag—Pd core-shell particle and use thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6077907A (en) * | 1983-10-04 | 1985-05-02 | Sumitomo Metal Mining Co Ltd | Manufacture of silver dust |
| JPS63312906A (en) * | 1987-06-16 | 1988-12-21 | Daido Steel Co Ltd | Production of fine silver alloy powder |
| JPH01287210A (en) * | 1988-05-12 | 1989-11-17 | Tanaka Kikinzoku Kogyo Kk | Manufacture of silver fine particle |
| JPH0211707A (en) * | 1988-06-28 | 1990-01-16 | Tanaka Kikinzoku Kogyo Kk | Production of silver fine particle |
-
1990
- 1990-06-28 JP JP16838490A patent/JPH0459904A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6077907A (en) * | 1983-10-04 | 1985-05-02 | Sumitomo Metal Mining Co Ltd | Manufacture of silver dust |
| JPS63312906A (en) * | 1987-06-16 | 1988-12-21 | Daido Steel Co Ltd | Production of fine silver alloy powder |
| JPH01287210A (en) * | 1988-05-12 | 1989-11-17 | Tanaka Kikinzoku Kogyo Kk | Manufacture of silver fine particle |
| JPH0211707A (en) * | 1988-06-28 | 1990-01-16 | Tanaka Kikinzoku Kogyo Kk | Production of silver fine particle |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06172822A (en) * | 1992-12-07 | 1994-06-21 | Sumitomo Metal Mining Co Ltd | Production of fine silver powder |
| EP0652293A1 (en) * | 1993-07-13 | 1995-05-10 | E.I. Du Pont De Nemours And Company | Process for making finely divided, dense packing, spherical shaped silver particles |
| US6127294A (en) * | 1996-07-02 | 2000-10-03 | Japan Pionics Co., Ltd. | Sheet shaped heat generating body and method of manufacturing same |
| WO2008013274A1 (en) * | 2006-07-28 | 2008-01-31 | Mitsubishi Materials Corporation | Silver fine particles and processes and equipment for the production thereof |
| JP2008031526A (en) * | 2006-07-28 | 2008-02-14 | Mitsubishi Materials Corp | Method for producing silver particulate |
| JP2008050697A (en) * | 2006-07-28 | 2008-03-06 | Mitsubishi Materials Corp | Silver fine particle and method and apparatus for producing the same |
| JP2011511885A (en) * | 2008-01-09 | 2011-04-14 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | Method for producing noble metal nanoparticle dispersion and method for isolating such nanoparticles from said dispersion |
| WO2014119793A1 (en) * | 2013-02-04 | 2014-08-07 | 国立大学法人山形大学 | Metallic silver separation method, coated silver fine particles, and thin, linear, coated metallic silver |
| JP2014152337A (en) * | 2013-02-04 | 2014-08-25 | Yamagata Univ | Precipitation method of metallic silver, coated silver fine particle, thin wire-like coated metallic silver |
| JP2015209555A (en) * | 2014-04-24 | 2015-11-24 | 株式会社ノリタケカンパニーリミテド | Silver nanowire and manufacturing method therefor |
| US11219883B2 (en) | 2018-10-18 | 2022-01-11 | Noritake Co., Limited | Ag—Pd core-shell particle and use thereof |
| CN109332723A (en) * | 2018-12-10 | 2019-02-15 | 西安宏星电子浆料科技有限责任公司 | A kind of preparation method of low-temperature conductive adhesive silver powder |
| US11008470B2 (en) | 2019-03-28 | 2021-05-18 | Noritake Co., Limited | Core-shell particles and use thereof |
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