JP5305789B2 - Silver powder manufacturing method - Google Patents
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- JP5305789B2 JP5305789B2 JP2008219899A JP2008219899A JP5305789B2 JP 5305789 B2 JP5305789 B2 JP 5305789B2 JP 2008219899 A JP2008219899 A JP 2008219899A JP 2008219899 A JP2008219899 A JP 2008219899A JP 5305789 B2 JP5305789 B2 JP 5305789B2
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 278
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 60
- 229910052709 silver Inorganic materials 0.000 claims abstract description 99
- 239000004332 silver Substances 0.000 claims abstract description 99
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 36
- 150000001412 amines Chemical class 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- -1 silver ions Chemical class 0.000 claims abstract description 23
- 150000003141 primary amines Chemical class 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 150000003335 secondary amines Chemical class 0.000 claims abstract 2
- 239000002245 particle Substances 0.000 claims description 159
- 239000007864 aqueous solution Substances 0.000 claims description 34
- 229920000642 polymer Polymers 0.000 claims description 26
- 229920002873 Polyethylenimine Polymers 0.000 claims description 22
- 230000005587 bubbling Effects 0.000 claims description 20
- 229920000083 poly(allylamine) Polymers 0.000 claims description 5
- 108010039918 Polylysine Proteins 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 4
- 229920000656 polylysine Polymers 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 40
- 239000006185 dispersion Substances 0.000 abstract description 5
- 230000002829 reductive effect Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 description 106
- 238000005259 measurement Methods 0.000 description 71
- 230000000052 comparative effect Effects 0.000 description 55
- 102220043159 rs587780996 Human genes 0.000 description 27
- 238000000034 method Methods 0.000 description 23
- 238000004065 wastewater treatment Methods 0.000 description 22
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 18
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 16
- 239000002002 slurry Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 10
- 229910001961 silver nitrate Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 5
- 229910001923 silver oxide Inorganic materials 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 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 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000019766 L-Lysine Nutrition 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 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
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
本発明は、銀粉の製造方法に関し、積層コンデンサの内部電極や回路基板の導体パターン、プラズマディスプレイパネル用基板の電極や回路などの電子部品に使用する導電性ペースト用に好適な銀粉の製造方法に関する。 The present invention relates to a method for producing silver powder, and more particularly to a method for producing silver powder suitable for conductive pastes used for electronic components such as internal electrodes of multilayer capacitors, conductor patterns of circuit boards, electrodes of plasma display panel boards, and circuits. .
積層コンデンサの内部電極、回路基板の導体パターン、太陽電池やプラズマディスプレイパネル（ＰＤＰ）用基板の電極や回路などの電子部品に使用する導電性ペーストとして、銀粉をガラスフリットとともに有機ビヒクル中に加えて混練することによって製造される導電性ペーストが使用されている。当該導電性ペースト用の銀粉は、電子部品の小型化、導体パターンの高密度化、ファインライン化などに対応するため、粒径が適度に小さく、粒度が揃い、高い分散性を有することが要求されている。導体パターンの形成方法としては、スクリーン印刷方式、感光方式、オフセット方式等あるが、中でも、ＰＤＰに使用される導電性ペーストにおいては、感光性の樹脂を使用した導電ペーストに紫外線を照射させて感光させることにより配線パターンを形成する感光方式が主流である。このため、当該導電ペーストに使用される銀粉は、紫外線を乱反射させないよう、特に表面が滑らかな球状の銀粉が要求される。 Silver powder is added to an organic vehicle together with glass frit as a conductive paste for use in electronic components such as internal electrodes of multilayer capacitors, conductor patterns of circuit boards, and electrodes and circuits of substrates for solar cells and plasma display panels (PDP). A conductive paste produced by kneading is used. Silver powder for the conductive paste is required to have a reasonably small particle size, uniform particle size, and high dispersibility in order to cope with downsizing of electronic components, high density of conductor patterns, fine line formation, etc. Has been. As a method for forming a conductor pattern, there are a screen printing method, a photosensitive method, an offset method, etc. Among them, in a conductive paste used for PDP, a conductive paste using a photosensitive resin is irradiated with ultraviolet rays to be exposed. The photosensitive method of forming the wiring pattern by making it is the mainstream. For this reason, the silver powder used for the said electrically conductive paste is requested | required of spherical silver powder with especially smooth surface so that an ultraviolet-ray may not be irregularly reflected.
このような導電性ペースト用の銀粉を製造する方法としては、銀塩含有水溶液へ、アルカリまたは錯化剤を添加して、酸化銀含有スラリーまたは銀錯体含有水溶液を生成させた後、還元剤としてヒドロキノン等の多価フェノールを添加することにより、銀粉を還元析出させて、その後に乾燥させる方法が知られている(特許文献１、非特許文献１)。 As a method for producing such silver powder for conductive paste, an alkali or complexing agent is added to a silver salt-containing aqueous solution to form a silver oxide-containing slurry or a silver complex-containing aqueous solution, and then as a reducing agent. A method is known in which silver powder is reduced and precipitated by adding a polyhydric phenol such as hydroquinone and then dried (Patent Document 1, Non-Patent Document 1).
また、銀塩含有水溶液にアルカリまたは錯化剤を添加して、酸化銀含有スラリーまたは銀錯体含有水溶液を生成した後、還元剤としてアスコルビン酸等を加えることにより、球状の銀粉を製造する方法も知られている（特許文献２、非特許文献２）。 Also, a method of producing spherical silver powder by adding an alkali or complexing agent to a silver salt-containing aqueous solution to produce a silver oxide-containing slurry or a silver complex-containing aqueous solution and then adding ascorbic acid or the like as a reducing agent. Known (Patent Document 2, Non-Patent Document 2).
一方で、ヒドラジンを還元剤とした銀粉の製法についても知られている。ヒドラジンを還元剤とした銀粉の製法は、ヒドラジンの分解性が良いため、排水処理は比較的容易である。しかし、製造される銀粉は凝集したサブミクロン粒子や、角ばったミクロンサイズ粒子の混合物となり易い。そこで、製造される銀粉の粒径制御性や分散性を向上させる目的で、ビニル系高分子化合物を添加する銀微粉末を製造方法が知られている(特許文献３)。 On the other hand, a method for producing silver powder using hydrazine as a reducing agent is also known. The method for producing silver powder using hydrazine as a reducing agent is relatively easy to treat waste water because hydrazine is easily decomposed. However, the silver powder produced tends to be a mixture of aggregated submicron particles and angular micron-sized particles. Therefore, a method for producing a fine silver powder to which a vinyl polymer compound is added is known for the purpose of improving the particle size controllability and dispersibility of the produced silver powder (Patent Document 3).
また、レドックス還元法を用い、還元剤として３価のチタニウムイオンを使用することで還元剤を再利用することが出来る銀粉の製造方法についても知られている（特許文献４）。 Moreover, the manufacturing method of the silver powder which can reuse a reducing agent by using a redox reduction method and using trivalent titanium ion as a reducing agent is also known (patent document 4).
しかし、本発明者らの検討によると、特許文献１、非特許文献１に記載された、銀塩含有水溶液へアルカリ等を添加し、酸化銀含有スラリー等を生成させた後、還元剤としてヒドロキノン等の多価フェノールを添加して銀粉を還元析出させる方法では、分散性に優れた球状の銀粉を生成させることができるものの、ヒドロキノン等を含む排水が生成してしまい、排水処理が課題となることに想到した。つまり、ヒドロキノン等の多価フェノールを含む排水は難分解性であり、排水処理設備が大掛かりになる等の課題が生まれ、排水処理コストが高くなる。 However, according to the study by the present inventors, after adding alkali or the like to the silver salt-containing aqueous solution described in Patent Document 1 or Non-Patent Document 1 to produce a silver oxide-containing slurry or the like, hydroquinone as a reducing agent In the method of reducing and precipitating silver powder by adding polyhydric phenols and the like, although spherical silver powder having excellent dispersibility can be generated, wastewater containing hydroquinone or the like is generated, and wastewater treatment becomes a problem. I thought of that. That is, wastewater containing polyhydric phenols such as hydroquinone is hardly decomposable, resulting in problems such as large wastewater treatment facilities, and wastewater treatment costs increase.
また、特許文献２、非特許文献２に記載された、銀塩含有水溶液にアルカリ等を添加し、酸化銀含有スラリー等を生成した後、還元剤としてアスコルビン酸等を添加して球状の銀粉を製造する方法では、排水としてアスコルビン酸の分解物を含む褐色の難処理排水が発生する。この場合も、排水処理設備が大掛かりになる等の課題が生まれ、排水処理コストが高くなる。
すなわち、球状で表面が滑らかな銀粉を製造できるいずれの方法を採っても、排水処理設備が大掛かりになる為、銀粉の生産性を上げる際の障害になる上、高価な排水処理コストが、銀粉の製造コストアップに結びつくことが課題であった。
Moreover, after adding alkali etc. to silver salt containing aqueous solution described in patent document 2 and nonpatent literature 2, and producing | generating a silver oxide containing slurry etc., ascorbic acid etc. are added as a reducing agent, and spherical silver powder is made. In the manufacturing method, brown difficult-to-treat wastewater containing a decomposition product of ascorbic acid is generated as wastewater. In this case as well, problems such as a large wastewater treatment facility arise, and the wastewater treatment cost increases.
In other words, any method that can produce spherical and smooth surfaced silver powder requires a large amount of wastewater treatment equipment, which is an obstacle to increasing the productivity of silver powder. It was a problem to lead to an increase in manufacturing costs.
一方で、特許文献３に記載されたヒドラジンを還元剤とした銀粉の製法でも、球状で表面が滑らかな銀粉を得ることはできていない。
また、特許文献４に記載された還元剤に３価のチタニウムイオンを使用することで還元剤を再利用することができるレドックス還元法は、還元剤を再利用可能なため排水処理の負荷は低減され、粒径が数１０〜１００ｎｍの微粒子を作成することができる。さらに、特許文献４には、分散剤としてポリエチレンイミンを使用することが開示されている。しかしながら、この方法で得られる銀粉の形状は球状ではなく、形状が球状で表面が滑らかな銀粉を得ることはできていない。
On the other hand, the silver powder manufacturing method described in Patent Document 3 using hydrazine as a reducing agent cannot obtain a silver powder having a spherical shape and a smooth surface.
In addition, the redox reduction method in which the reducing agent can be reused by using trivalent titanium ions as the reducing agent described in Patent Document 4 reduces the wastewater treatment load because the reducing agent can be reused. Thus, fine particles having a particle diameter of several tens to 100 nm can be produced. Furthermore, Patent Document 4 discloses the use of polyethyleneimine as a dispersant. However, the silver powder obtained by this method is not spherical, and silver powder having a spherical shape and a smooth surface cannot be obtained.
結局、球状で表面が滑らかな銀粉を製造可能な方法では、高価な排水処理コストが銀粉の製造コストを高いものにしていた。他方、排水処理コストを抑制できる製造方法の場合は、球状で表面が平滑な銀粉を製造することができない。即ち、球状で表面が滑らかな銀粉を得ること、排水処理コストを抑制して当該銀粉の製造コストを抑制すること、の両立ができないという問題があった。 After all, in a method capable of producing a silver powder having a spherical surface and a smooth surface, the expensive wastewater treatment cost increases the production cost of the silver powder. On the other hand, in the case of a production method capable of suppressing wastewater treatment costs, it is impossible to produce a silver powder having a spherical shape and a smooth surface. That is, there is a problem that it is impossible to achieve both of obtaining a spherical silver powder having a smooth surface and suppressing the wastewater treatment cost and the production cost of the silver powder.
本発明は、このような状況の下でなされた発明であり、上述したＰＤＰ用途にも使用可能な表面が滑らかで球状を有する導電性ペースト用の銀粉を、難処理排水を生成することなく製造することの出来る製造方法を提供することを目的とする。 The present invention is an invention made under such circumstances, and produces silver powder for a conductive paste having a smooth and spherical surface that can also be used for the above-mentioned PDP applications without generating difficult-to-treat wastewater. It aims at providing the manufacturing method which can do.
本発明者らは、上記課題を解決するため鋭意研究した結果、銀イオンを含有する水性反応系に還元剤を添加して銀粒子を還元析出させる反応において、当該銀粒子の還元析出前または還元析出中に、予め、高分子アミンを存在させることで、還元剤としてはエアーのバブリングで分解可能なものを用いても、表面が滑らかな球状で、なおかつ高分散で粒径の揃った導電性ペーストに適した銀粉を製造することができることを見出し、本発明を完成するに至った。
尚、本発明において、硝酸銀、銀錯体または銀中間体を含有する水溶液等の銀イオンを含有する水溶液、および、当該銀イオンを含有する水溶液であって、さらに含銀スラリーを含むもののことを、「銀イオンを含有する水性反応系」と記載する場合がある。
As a result of diligent research to solve the above-mentioned problems, the present inventors have conducted a reaction in which silver particles are reduced and precipitated by adding a reducing agent to an aqueous reaction system containing silver ions. Pre-deposition of high molecular amine during precipitation, so even if a reducing agent that can be decomposed by air bubbling is used, the surface has a smooth spherical shape, high dispersion, and uniform conductivity. The inventors have found that silver powder suitable for a paste can be produced, and have completed the present invention.
In the present invention, an aqueous solution containing silver ions, such as an aqueous solution containing silver nitrate, a silver complex or a silver intermediate, and an aqueous solution containing the silver ions, further containing a silver-containing slurry, It may be described as “aqueous reaction system containing silver ions”.
即ち、上述の課題を解決するための第１の手段は、
銀イオンを含有する水性反応系へ、還元剤を添加して銀粒子を還元析出させる銀粉の製
造方法であって、
前記還元剤として、エアーのバブリングで分解可能なものを用い、
前記銀粒子の還元析出前または還元析出中に、第一アミンおよび／または第二アミンを有する高分子アミンを添加することを特徴とする銀粉の製造方法である。
That is, the first means for solving the above-described problem is:
A method for producing silver powder, wherein a reducing agent is added to an aqueous reaction system containing silver ions to reduce and precipitate silver particles,
As the reducing agent, one that can be decomposed by bubbling air,
A method for producing silver powder comprising adding a polymer amine having a primary amine and / or a secondary amine before or during the reduction precipitation of the silver particles.
第２の手段は、
前記還元剤が、ヒドラジンであることを特徴とする第１の手段に記載の銀粉の製造方法である。
The second means is
The method for producing silver powder according to the first means, wherein the reducing agent is hydrazine.
第３の手段は、
前記高分子アミンが、イミン化合物であることを特徴とする第１または第２の手段に記載の銀粉の製造方法である。
The third means is
The method for producing silver powder according to the first or second means, wherein the polymer amine is an imine compound.
第４の手段は、
前記高分子アミンが、ポリエチレンイミンであることを特徴とする第１または第２の手段に記載の銀粉の製造方法である。
The fourth means is
The method for producing silver powder according to the first or second means, wherein the polymer amine is polyethyleneimine.
第５の手段は、
前記高分子アミンが、ポリアリルアミンであることを特徴とする第１または第２の手段に記載の銀粉の製造方法である。
The fifth means is
The method for producing silver powder according to the first or second means, wherein the polymer amine is polyallylamine.
第６の手段は、
前記高分子アミンが、ポリリジンであることを特徴とする第１または第２の手段に記載の銀粉の製造方法である。
The sixth means is
The method for producing silver powder according to the first or second means, wherein the polymer amine is polylysine.
第７の手段は、
前記高分子アミンの分子量が１０００以上であることを特徴とする第１から第６の手段のいずれかに記載の銀粉の製造方法である。
The seventh means is
The silver powder production method according to any one of the first to sixth means, wherein the molecular weight of the high molecular amine is 1000 or more.
第８の手段は、
前記高分子アミンの添加量が、銀の仕込量に対して、０．２質量％以上であることを特徴とする第１から第７の手段のいずれかに記載の銀粉の製造方法である。
The eighth means is
The method for producing silver powder according to any one of the first to seventh means, wherein the addition amount of the polymer amine is 0.2% by mass or more based on the amount of silver charged.
第９の手段は、
前記銀イオンを含有する水性反応系が、銀のアンミン錯体を含有する水溶液であることを特徴とする第１から第８の手段のいずれかに記載の銀粉の製造方法である。
The ninth means is
The silver powder production method according to any one of the first to eighth means, wherein the aqueous reaction system containing silver ions is an aqueous solution containing a silver ammine complex.
本発明によれば、表面が滑らかな球状の導電性ペースト用の銀粉を、難処理排水を発生させることなく製造することができる。 According to the present invention, a silver powder for a spherical conductive paste having a smooth surface can be produced without generating difficult-to-treat waste water.
本発明に係る銀粉の製造方法について、１．銀イオンを含有する水性反応系、２．還元剤、３．高分子アミン、４．銀イオンを含有する水性反応系への還元剤および高分子アミンの添加方法、５．効果、の順に説明する。 About the manufacturing method of the silver powder which concerns on this invention. 1. an aqueous reaction system containing silver ions; 2. reducing agent; High molecular amine, 4. 4. Addition method of reducing agent and polymer amine to aqueous reaction system containing silver ion The effect will be described in this order.
〈１．銀イオンを含有する水性反応系〉
銀イオンを含有する水性反応系とは、上述したように、硝酸銀、銀錯体または銀中間体を含有する水溶液等の銀イオンを含有する水溶液、および、当該銀イオンを含有する水溶液のことをいう。そして、本発明においては、これらの銀イオンを含有する水性反応系を
銀の供給元として用いることが出来る。
<1. Aqueous reaction system containing silver ions>
As described above, the aqueous reaction system containing silver ions refers to an aqueous solution containing silver ions such as an aqueous solution containing silver nitrate, a silver complex or a silver intermediate, and an aqueous solution containing the silver ions. . In the present invention, an aqueous reaction system containing these silver ions can be used as a silver supplier.
具体例として、銀錯体を含有する水溶液は、アンモニア水、アンモニウム塩を硝酸銀水溶液もしくは酸化銀懸濁液に添加することにより生成することができる。中でも、硝酸銀水溶液にアンモニア水を添加して得られる銀アンミン錯体水溶液は、生成する銀粉が適当な粒径と球形状とを有するので、好ましい構成である。尚、当該銀アンミン錯体中におけるアンモニアの配位数は２であるため、銀１モル当たりアンモニア２モル以上を添加することが望ましい。アンモニアの添加量の上限については特に限定されないが、添加量を増やすにつれ原料のコストアップとなる。当該原料コストの観点からは、得ようとする銀粉の粒径に応じた銀アンミン錯体の適度な安定性を得るために、必要な量を添加すれば良い。例えば、銀１モル当たりアンモニア４モルを添加すれば、必要な銀アンミン錯体の安定性を得ることができる。 As a specific example, an aqueous solution containing a silver complex can be produced by adding aqueous ammonia or ammonium salt to an aqueous silver nitrate solution or a silver oxide suspension. Among them, a silver ammine complex aqueous solution obtained by adding aqueous ammonia to a silver nitrate aqueous solution is a preferable configuration because the silver powder to be produced has an appropriate particle size and spherical shape. Since the coordination number of ammonia in the silver ammine complex is 2, it is desirable to add 2 moles or more of ammonia per mole of silver. The upper limit of the amount of ammonia added is not particularly limited, but the cost of the raw material increases as the amount added is increased. From the viewpoint of the raw material cost, a necessary amount may be added in order to obtain an appropriate stability of the silver ammine complex corresponding to the particle size of the silver powder to be obtained. For example, if 4 moles of ammonia per 1 mole of silver is added, the required stability of the silver ammine complex can be obtained.
〈２．還元剤〉
本発明に係る還元剤としては、生成した排水が簡易な設備で処理が可能で、排水処理コストを引き上げることのない還元剤を用いることが肝要である。即ち、エアーのバブリング等の簡便な排水処理で分解可能なものを用いる。好ましい具体例としては、ヒドラジンを挙げることが出来る。尚、銀の反応収率を上げる観点から、還元剤量は、銀に対して１当量以上添加する必要がある。
<2. Reducing agent>
As the reducing agent according to the present invention, it is important to use a reducing agent that can treat the generated wastewater with simple equipment and does not increase wastewater treatment costs. That is, a material that can be decomposed by a simple waste water treatment such as air bubbling is used. A preferred specific example is hydrazine. In addition, from the viewpoint of increasing the reaction yield of silver, it is necessary to add the reducing agent in an amount of 1 equivalent or more with respect to silver.
〈３．高分子アミン〉
本発明に係る高分子アミンは、第一アミン（−ＮＨ２）、第二アミン（＝ＮＨ）のいずれか一つ、または、両者を共に有する高分子のことである。そして、本発明に係る高分子アミンは、還元剤として上述した排水処理が容易なものを用いた場合であっても、生成する銀の粒子形状を球状に制御する効果を発揮する。
本発明に係る高分子アミンによって、球状で分散性の高い銀の粒子が得られる詳細な理由は明らかではないが、当該高分子アミンが有する第一アミンおよび／または第二アミンと、当該高分子アミンの大きな分子長とが、生成する銀の粒子形状を球状に制御するのであると考えられる。具体的には、第一アミンおよび／または第二アミンが、銀イオンと錯体を形成することで当該銀イオンの還元速度を適度に緩和すること、および、高分子アミンの大きな分子長が粒子同士の結合を抑制すること、によると考えられる。
ここで、本発明に係る好ましい高分子アミンの具体例としては、アミノ化合物、イミン化合物が挙げられる。中でもポリエチレンイミン、ポリアリルアミン、ポリリジンが好ましい。特に、イミン化合物であるポリエチレンイミンは、その構造が分子中に第一アミンおよび第二アミンの両者を共に有する網状構造であり、本発明において好ましい結果を与える。
<3. Polymer amine>
The polymer amine according to the present invention is a polymer having either one or both of a primary amine (—NH 2 ) and a secondary amine (═NH). And even if it is a case where the thing which the waste water treatment mentioned above is easy as a reducing agent is used for the polymeric amine which concerns on this invention, the effect which controls the particle shape of the produced | generated silver to spherical shape is exhibited.
Although the detailed reason for obtaining spherical and highly dispersible silver particles by the polymer amine according to the present invention is not clear, the primary amine and / or the secondary amine of the polymer amine and the polymer The large molecular length of the amine is considered to control the shape of the silver particles produced to be spherical. Specifically, the primary amine and / or the secondary amine moderately moderates the reduction rate of the silver ion by forming a complex with the silver ion, and the large molecular length of the polymer amine is It is thought to be due to suppressing the binding of.
Here, specific examples of preferred polymer amines according to the present invention include amino compounds and imine compounds. Of these, polyethyleneimine, polyallylamine, and polylysine are preferable. In particular, polyethyleneimine, which is an imine compound, has a network structure having both a primary amine and a secondary amine in the molecule, and gives favorable results in the present invention.
当該高分子アミンの分子量については、生成する銀粉の粒子形状を球状化し、表面を滑らかにするために、平均分子量１０００以上、１００，０００以下の高分子アミンを用いることが好ましい。高分子アミンの平均分子量が１０００以上あれば、得られる銀粉の形状を球状で表面が滑らかにする効果が十分に得られ、平均分子量１００，０００以下であれば、当該高分子アミンを含有する液の粘性が高くなり過ぎず、取扱いが容易だからである。さらに、当該高分子アミンとしては、平均分子量１０００以上のポリエチレンイミンまたはポリアリルアミンが好ましい。一般に入手可能なポリエチレンイミンの平均分子量の上限値は７０，０００である。そして、当該平均分子量７０，０００のポリエチレンイミンは、銀粉の粒子形状を球状化し表面を滑らかにする効果を発揮すると同時に、当該ポリエチレンイミンを含有する液の粘性が高くなり過ぎることもない。従って、銀イオンを含有する水性反応系に溶解可能な限り、ポリエチレンイミンの平均分子量の上限は、特に限定されない。 Regarding the molecular weight of the high molecular amine, it is preferable to use a high molecular amine having an average molecular weight of 1000 or more and 100,000 or less in order to make the particle shape of the silver powder to be spheroidized and smooth the surface. If the average molecular weight of the polymer amine is 1000 or more, the resulting silver powder has a spherical shape with a smooth surface, and if the average molecular weight is 100,000 or less, a liquid containing the polymer amine is contained. This is because the viscosity of is not too high and handling is easy. Furthermore, as the polymeric amine, polyethyleneimine or polyallylamine having an average molecular weight of 1000 or more is preferable. The upper limit of the average molecular weight of generally available polyethyleneimine is 70,000. The polyethyleneimine having an average molecular weight of 70,000 exhibits the effect of making the particle shape of silver powder spherical and smoothing the surface, and at the same time, the viscosity of the liquid containing the polyethyleneimine does not become too high. Therefore, the upper limit of the average molecular weight of polyethyleneimine is not particularly limited as long as it can be dissolved in an aqueous reaction system containing silver ions.
当該高分子アミンの添加量は、銀の仕込量に対して０．２質量％以上あれば生成する銀の粒子形状を球状に制御することが出来る。一方、銀イオンを含有する水性反応系に溶解可能な限り、特に添加量の上限値は規定されない。尚、銀の仕込量とは、前記銀イオンを含有する水性反応系に投入された、銀化合物中の銀含有量のことである。 If the amount of the polymer amine added is 0.2% by mass or more with respect to the amount of silver charged, the shape of the silver particles produced can be controlled to be spherical. On the other hand, as long as it can be dissolved in an aqueous reaction system containing silver ions, the upper limit of the addition amount is not particularly defined. In addition, the preparation amount of silver is silver content in the silver compound thrown into the aqueous reaction system containing the said silver ion.
〈４．銀イオンを含有する水性反応系への還元剤および高分子アミンの添加方法〉
銀イオンを含有する水性反応系への還元剤の添加方法については、生成する銀粉の粒径を揃え、かつ凝集を防ぐために、１当量／ｍｉｎ以上の速度で添加することが好ましい。当該添加速度が効果を発揮する理由は明確ではないが、還元剤を短時間で投入することで銀粉粒子の還元析出が一挙に生じ、短時間で還元反応が終了するため、発生した銀粉粒子の核同士の凝集が生じ難くなり、分散性が向上するのではないかと考えられる。したがって、還元剤の添加速度は速いほど好ましく、例えば１００当量／ｍｉｎ以上の速度であっても良い。また、還元の際には、より短時間で反応を終了させる観点から反応液を攪拌することが好ましい。
<4. Method of adding reducing agent and polymer amine to aqueous reaction system containing silver ion>
Regarding the method of adding the reducing agent to the aqueous reaction system containing silver ions, it is preferable to add at a rate of 1 equivalent / min or more in order to make the particle diameter of the silver powder to be produced uniform and prevent aggregation. The reason why the addition rate is effective is not clear, but by introducing the reducing agent in a short time, reduction precipitation of the silver powder particles occurs at once, and the reduction reaction is completed in a short time. It is thought that aggregation between nuclei hardly occurs and dispersibility is improved. Therefore, the addition rate of the reducing agent is preferably as high as possible, and may be, for example, a rate of 100 equivalent / min or more. In the reduction, it is preferable to stir the reaction solution from the viewpoint of completing the reaction in a shorter time.
銀イオンを含有する水性反応系への高分子アミンの添加方法としては、上述した還元剤による還元前に銀イオンを含有する水性反応系へ予め添加していても良いし、高分子アミンと還元剤とを予め混合しておき、当該混合物を銀イオン含有水性反応系へ添加しても良く、特に限定されない。 As a method for adding a polymer amine to an aqueous reaction system containing silver ions, it may be added in advance to an aqueous reaction system containing silver ions before reduction with the reducing agent described above, The agent may be mixed in advance, and the mixture may be added to the silver ion-containing aqueous reaction system, and is not particularly limited.
また、必要に応じて、表面処理剤を併用することも好ましい構成である。表面処理剤としては、脂肪酸、脂肪酸塩、界面活性剤、有機金属、キレート剤、高分子分散剤等を使用することができる。 Moreover, it is also a preferable structure to use a surface treating agent together as necessary. As the surface treatment agent, fatty acid, fatty acid salt, surfactant, organic metal, chelating agent, polymer dispersing agent and the like can be used.
〈５．効果〉
銀イオンを含有する水性反応系への、還元剤および高分子アミンの添加により得られた銀粉含有スラリーを、濾過、水洗することによって、銀に対して１〜２００質量％の水を含み、流動性がほとんどない塊状のケーキが得られる。尚、当該ケーキの乾燥を早めるために、ケーキ中の水分を低級アルコール等で置換してもよい。当該ケーキを、強制循環式大気乾燥機、真空乾燥機、気流乾燥装置等の乾燥機で乾燥することにより本発明に係る銀粉が得られる。また、必要に応じて、乾式解砕処理や、特開２００５−２４００９２号公報に記載されているような分級処理を行ってもよい。なお、乾燥、解砕および分級を行なうことができる一体型の装置（（株）ホソカワミクロン製のドライマイスタや、ミクロンドライヤなど）を用いて乾燥、粉砕、分級を行なってもよい。
<5. effect>
A silver powder-containing slurry obtained by adding a reducing agent and a polymer amine to an aqueous reaction system containing silver ions is filtered, washed with water, thereby containing 1 to 200% by mass of water with respect to silver, and flowing. A lump cake with little nature is obtained. In order to accelerate the drying of the cake, the moisture in the cake may be replaced with a lower alcohol or the like. Silver powder according to the present invention is obtained by drying the cake with a dryer such as a forced circulation air dryer, a vacuum dryer, or an airflow dryer. Moreover, you may perform a dry crushing process and the classification process as described in Unexamined-Japanese-Patent No. 2005-240092 as needed. In addition, drying, pulverization, and classification may be performed using an integrated apparatus that can perform drying, pulverization, and classification (a dry meister manufactured by Hosokawa Micron Corporation, a micron dryer, or the like).
上述の操作を行って得られた銀粉は、表面が滑らかな球状であり、感光性方式をはじめとしたＰＤＰ用途に使用する導電性ペースト用の銀粉として適したものであった。
そして、上述の銀粉含有スラリーを、濾過、水洗することによって生成した排水は、流量１〜１０Ｌ／ｍｉｎ程度のエアーのバブリングを１〜５時間程度行うことで、ヒドラジン濃度が１ｐｐｍ以下となり、容易に分解可能あった。なお、ヒドラジンの分解を促進させるため、エアレーション時のアルカリ調整や加温も有効である。
The silver powder obtained by performing the above-mentioned operation has a smooth spherical shape, and was suitable as a silver powder for conductive paste used for PDP applications including a photosensitive system.
And the waste_water | drain produced | generated by filtering and washing with water the above-mentioned silver powder containing slurry performs the bubbling of air with a flow rate of about 1 to 10 L / min for about 1 to 5 hours, the hydrazine concentration becomes 1 ppm or less, and easily Decomposable. In addition, in order to accelerate | stimulate decomposition | disassembly of hydrazine, the alkali adjustment and heating at the time of aeration are also effective.
以下、本発明について、実施例を参照しながら詳細に説明する。
（実施例１）
銀を５．４ｇ含む硝酸銀水溶液３９４０ｇに、２８質量％のアンモニア水１２．２ｇ（銀に対して２．０当量相当）を添加し、銀アンミン錯塩水溶液を得た。
この銀アンミン錯塩水溶液の液温を２５℃とし、含有される銀の質量に対して０．５質量％のポリエチレンイミン（和光純薬製試薬、平均分子量１０，０００）を添加した後で、７．７質量％のヒドラジン水溶液を８．８ｇ（銀に対して１．２当量相当）加えて、銀
粒子を含有するスラリーを析出させた。当該製造条件を表１に示す。
以下同様に、実施例２〜９、比較例１〜６においても製造条件を表１に示す。
Hereinafter, the present invention will be described in detail with reference to examples.
Example 1
To 3940 g of a silver nitrate aqueous solution containing 5.4 g of silver, 12.2 g of 28% by mass of ammonia water (corresponding to 2.0 equivalents with respect to silver) was added to obtain a silver ammine complex salt aqueous solution.
After the liquid temperature of this silver ammine complex salt aqueous solution was set to 25 ° C. and 0.5% by mass of polyethyleneimine (reagent manufactured by Wako Pure Chemical Industries, average molecular weight 10,000) was added to the mass of silver contained, 7 8.8 g (corresponding to 1.2 equivalents of silver) of a 0.7 mass% hydrazine aqueous solution was added to precipitate a slurry containing silver particles. The production conditions are shown in Table 1.
Similarly, Table 1 shows the production conditions in Examples 2 to 9 and Comparative Examples 1 to 6.
このようにして得られた銀含有スラリーを濾過、水洗し、ケーキを得た。ケーキより銀粉を少量サンプリングし、走査型電子顕微鏡（ＳＥＭ）を用い、銀粉形状として表面の平滑性の測定と粒子形状との観察を行うと伴に、湿式のレーザー回折式粒度分布の評価を行った。
一方、得られたケーキを７５℃の真空乾燥機で１０時間乾燥させ、乾燥した銀粉を得た。当該乾燥銀粉に対し、ＢＥＴ比表面積測定および乾式レーザー回折式粒度分布測定を行った。
The silver-containing slurry thus obtained was filtered and washed with water to obtain a cake. A small amount of silver powder is sampled from the cake, and the surface smoothness measurement and particle shape observation are performed using a scanning electron microscope (SEM) to evaluate the wet laser diffraction particle size distribution. It was.
On the other hand, the obtained cake was dried with a vacuum dryer at 75 ° C. for 10 hours to obtain dried silver powder. A BET specific surface area measurement and a dry laser diffraction particle size distribution measurement were performed on the dry silver powder.
ここで、表面の平滑性の測定と粒子形状の観察は、ＳＥＭ（日本電子製ＪＳＭ−６１００）を使用し、１００００倍にて観察を行った。当該ＳＥＭ写真を図１に示す。そして、当該ＳＥＭ観察の結果を、後述する比較例２と比較しながら評価した。以下、実施例２〜９、比較例１〜６においても同様である。 Here, the measurement of the smoothness of the surface and the observation of the particle shape were performed using a SEM (JSM-6100 manufactured by JEOL Ltd.) at a magnification of 10,000. The SEM photograph is shown in FIG. And the result of the said SEM observation was evaluated comparing with the comparative example 2 mentioned later. The same applies to Examples 2 to 9 and Comparative Examples 1 to 6 below.
湿式レーザー回折式の粒度分布測定は、銀粉０．３ｇをイソプロピルアルコール３０ｍＬに入れ、出力５０Ｗの超音波洗浄器により５分間分散させ、マイクロトラック粒度分布測定装置（ハネウエル（Ｈａｎｅｙｗｅｌｌ）−日機装製９３２０ＨＲＡ（Ｘ−１００））を用いて測定した。当該測定結果を図２に示す。図２は、横軸に粒径、縦軸に頻度（％）と累積（％）とをとったグラフであり、棒グラフで頻度を示し、折れ線グラフで累積を示した。そして、累積１０質量％粒径をＤ１０、累積５０質量％粒径をＤ５０、累積９０質量％粒径をＤ９０と表記したものである。
以下、実施例２〜９、比較例１〜５においても同様である。
In the wet laser diffraction type particle size distribution measurement, 0.3 g of silver powder is placed in 30 mL of isopropyl alcohol, and dispersed for 5 minutes by an ultrasonic cleaner with an output of 50 W. A microtrack particle size distribution measuring device (Honeywell-Nikkiso 9320HRA ( X-100)). The measurement results are shown in FIG. FIG. 2 is a graph in which the horizontal axis indicates the particle size, and the vertical axis indicates the frequency (%) and the accumulation (%), the frequency is indicated by a bar graph, and the accumulation is indicated by a line graph. The cumulative 10 mass% particle size is represented as D10, the cumulative 50 mass% particle size as D50, and the cumulative 90 mass% particle size as D90.
The same applies to Examples 2 to 9 and Comparative Examples 1 to 5 below.
ＢＥＴ比表面積は、モノソーブ（カウンタクローム（Ｑｕａｎｔａ Ｃｈｒｏｍｅ）社製）を用いて窒素吸着によるＢＥＴ１点法で測定した。尚、当該ＢＥＴ比表面積測定において、測定前の脱気条件は６０℃、１０分間とした。以下、実施例２〜９、比較例１〜５においても同様である。 The BET specific surface area was measured by a BET one-point method by nitrogen adsorption using monosorb (manufactured by Quanta Chrome). In the measurement of the BET specific surface area, the deaeration conditions before the measurement were 60 ° C. and 10 minutes. The same applies to Examples 2 to 9 and Comparative Examples 1 to 5 below.
乾式レーザー回折式の粒度分布測定は、粒度分布測定装置（Ｓｙｍｐａｔｅｃ−日本レーザー製、Ｈｅｌｏｓ＆Ｒｏｄｏｓ）を使用し、分散圧４ｂａｒ、測定レンズＲ１にて測定した。当該測定結果を図３に示す。図３は、横軸に粒径、縦軸に頻度分布をとったグラフである。以下、実施例２〜９、比較例１〜５においても同様である。 The dry laser diffraction particle size distribution measurement was performed using a particle size distribution measuring device (Sympatec—manufactured by Nippon Laser, Helos & Rodos) with a dispersion pressure of 4 bar and a measuring lens R1. The measurement results are shown in FIG. FIG. 3 is a graph in which the horizontal axis represents the particle size and the vertical axis represents the frequency distribution. The same applies to Examples 2 to 9 and Comparative Examples 1 to 5 below.
評価、測定結果について説明する。
ＳＥＭ写真（図１）より、ケーキを構成する銀粉の表面の平滑性と粒子形状は、表面が滑らかで、粒径の揃った球状であり、高分散の銀粉が生成していることが確認できた。
湿式の粒度分布測定結果（図２）より、Ｄ１０＝０．７３μｍ、Ｄ５０＝１．１０μｍ、Ｄ９０＝１．９５μｍであった。このことから、粒度分布のバラツキを表す（Ｄ９０−Ｄ１０）／Ｄ５０は１．１であり、粒度分布が非常にシャープであること（粒径が揃っていること）が確認できた。
ＢＥＴ比表面積は０．５６ｍ２／ｇであった。
乾式の粒度分布（図３）より、乾燥後の銀粉において、Ｄ１０＝０．３１μｍ、Ｄ５０＝１．１９μｍ、Ｄ９０＝１．９３μｍであった。このことから、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．３６であり、乾燥後の銀粉においても、粒度分布がシャープであることが確認できた。
Evaluation and measurement results will be described.
From the SEM photograph (Fig. 1), it can be confirmed that the surface smoothness and particle shape of the silver powder constituting the cake are spherical with a smooth surface and a uniform particle size, and highly dispersed silver powder is produced. It was.
From the wet particle size distribution measurement result (FIG. 2), D10 = 0.73 μm, D50 = 1.10 μm, and D90 = 1.95 μm. From this, (D90-D10) / D50 representing the variation in the particle size distribution was 1.1, and it was confirmed that the particle size distribution was very sharp (the particle size was uniform).
The BET specific surface area was 0.56 m 2 / g.
From the dry particle size distribution (FIG. 3), the dried silver powder had D10 = 0.31 μm, D50 = 1.19 μm, and D90 = 1.93 μm. From this, (D90−D10) /D50=1.36, and it was confirmed that the particle size distribution was sharp even in the dried silver powder.
上述の銀粉製造に際して、生成した排水は無色透明であった。当該排水を４０℃とし、攪拌しながら５Ｌ／ｍｉｎ．のエアーを用いて２時間バブリングすることにより、当該排
水中のヒドラジンが分解され、濃度１ｐｍｍ以下まで低下することを確認した。
尚、ヒドラジンの定量分析は、塩酸酸性下、ｐ−ジメチルアミノベンズアルデヒド溶液と混合し、吸光光度法（波長４５８ｎｍ）により行った。
以上より、実施例１によれば、優れた特性を有する銀粉が製造できると伴に、排水処理に関し大がかりな装置、複雑な操作が不要で、容易かつ簡便で低コストであることが確認された。
当該評価結果を表２に示す。以下、実施例２〜９、比較例１〜６においても同様に評価結果を表２に示す。
In the above silver powder production, the generated waste water was colorless and transparent. The waste water was set to 40 ° C. and stirred at 5 L / min. It was confirmed that hydrazine in the waste water was decomposed by bubbling for 2 hours using the air, and the concentration decreased to 1 pmm or less.
In addition, the quantitative analysis of hydrazine was carried out by absorptiometry (wavelength 458 nm) by mixing with p-dimethylaminobenzaldehyde solution under hydrochloric acid acidity.
As described above, according to Example 1, it was confirmed that a silver powder having excellent characteristics can be produced, and that a large-scale apparatus and complicated operation for wastewater treatment are not required, and that it is easy, simple, and low-cost. .
The evaluation results are shown in Table 2. Hereinafter, the evaluation results are also shown in Table 2 for Examples 2 to 9 and Comparative Examples 1 to 6.
（実施例２）
銀を４３．２ｇ含む硝酸銀水溶液３９５０ｇに、２８質量％のアンモニア水９７．３ｇ（銀に対して２．０当量相当）を添加し、銀アンミン錯塩水溶液を得た。
この銀アンミン錯塩水溶液の液温を２５℃とし、含有される銀の量に対して０．５質量％のポリエチレンイミン（和光純薬製試薬、平均分子量１０，０００）を添加した後で、７．７質量％のヒドラジン水溶液を７８．１ｇ（銀に対して１．２当量相当）加えて、銀粒子を析出させた。
(Example 2)
To 3950 g of silver nitrate aqueous solution containing 43.2 g of silver, 97.3 g of 28 mass% ammonia water (corresponding to 2.0 equivalents with respect to silver) was added to obtain a silver ammine complex salt aqueous solution.
After the liquid temperature of this silver ammine complex salt aqueous solution was 25 ° C. and 0.5% by mass of polyethyleneimine (Wako Pure Chemical Industries, average molecular weight 10,000) was added to the amount of silver contained, 78.1 g (corresponding to 1.2 equivalents of silver) of a 7 mass% hydrazine aqueous solution was added to precipitate silver particles.
このようにして得られた銀含有スラリーを濾過、水洗し、ケーキを得た。ケーキより銀粉を少量サンプリングし、走査型電子顕微鏡（ＳＥＭ）を用い、銀粉形状として表面の平滑性の測定と粒子形状との観察を行った。
一方、得られたケーキを７５℃の真空乾燥機で１０時間乾燥させ、乾燥した銀粉を得た。乾燥した銀粉をコーヒーミルにて解砕し、当該乾燥銀粉に対し、ＢＥＴ比表面積測定、湿式のレーザー回折式粒度分布測定および乾式レーザー回折式粒度分布測定を行った。
The silver-containing slurry thus obtained was filtered and washed with water to obtain a cake. A small amount of silver powder was sampled from the cake, and using a scanning electron microscope (SEM), the surface smoothness was measured and the particle shape was observed as the silver powder shape.
On the other hand, the obtained cake was dried with a vacuum dryer at 75 ° C. for 10 hours to obtain dried silver powder. The dried silver powder was crushed with a coffee mill, and BET specific surface area measurement, wet laser diffraction particle size distribution measurement, and dry laser diffraction particle size distribution measurement were performed on the dry silver powder.
得られた実施例２に係る銀粉の１００００倍のＳＥＭ写真を図４、湿式粒度分布を図５、乾式粒度分布を図６に示す。
ＳＥＭ写真より、実施例２に係る銀粉は、形状は球状で表面が非常に滑らかであり高分散であることが確認できた。当該銀粉のＢＥＴ比表面積は０．２５ｍ２／ｇであり、湿式粒度分布は、Ｄ１０＝２．４８μｍ、Ｄ５０＝４．４９μｍ、Ｄ９０＝８．３５μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．３１であり、乾式粒度分布は、Ｄ１０＝２．０９μｍ、Ｄ５０＝４．３６μｍ、Ｄ９０＝６．９８μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．１２であった。この結果、実施例２に係る銀粉は、粒度分布がシャープであることが確認できた。
FIG. 4 shows a 10,000 times SEM photograph of the obtained silver powder according to Example 2, FIG. 5 shows the wet particle size distribution, and FIG. 6 shows the dry particle size distribution.
From the SEM photograph, it was confirmed that the silver powder according to Example 2 had a spherical shape, a very smooth surface, and high dispersion. The silver powder has a BET specific surface area of 0.25 m 2 / g and wet particle size distributions of D10 = 2.48 μm, D50 = 4.49 μm, D90 = 8.35 μm, (D90−D10) /D50=1.31. The dry particle size distribution was D10 = 2.09 μm, D50 = 4.36 μm, D90 = 6.98 μm, (D90−D10) /D50=1.12. As a result, it was confirmed that the silver powder according to Example 2 had a sharp particle size distribution.
実施例２に係る銀粉の製造により生成する排水は、実施例１に係る排水と同様に無色透明で、エアーのバブリングによりヒドラジンを分解できることを確認した。
以上より、実施例２に係る製造方法で製造された銀粉の特性が優れ、かつ生成する排水処理も容易で、低コストであることが確認された。
The waste water produced | generated by manufacture of the silver powder which concerns on Example 2 was colorless and transparent similarly to the waste water which concerns on Example 1, and it confirmed that hydrazine could be decomposed | disassembled by bubbling of air.
From the above, it was confirmed that the characteristics of the silver powder produced by the production method according to Example 2 were excellent, the waste water treatment to be produced was easy, and the cost was low.
（実施例３）
ポリエチレンイミン量を、含有される銀の質量に対して１．０質量％とした以外は、実施例２と同様の操作を行った。
得られた実施例３に係る銀粉の１００００倍のＳＥＭ写真を図７、湿式粒度分布を図８、乾式粒度分布を図９に示す。
ＳＥＭ写真より、実施例３に係る銀粉は、粒子同士が若干凝集しているが、形状は球状で表面が非常に滑らかであることが確認できた。当該銀粉のＢＥＴ比表面積は０．１７ｍ２／ｇであり、湿式粒度分布は、Ｄ１０＝３．４２μｍ、Ｄ５０＝８．７５μｍ、Ｄ９０＝１９．４μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．８２であり、乾式粒度分布は、Ｄ１０＝２．６４μｍ、Ｄ５０＝７．８８μｍ、Ｄ９０＝１６．０μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．７０であった。この結果、実施例３に係る銀粉は、実施例２より若干凝集
傾向があるものの、粒度分布はシャープであることが確認できた。
(Example 3)
The same operation as in Example 2 was performed except that the amount of polyethyleneimine was 1.0% by mass with respect to the mass of silver contained.
FIG. 7 shows a 10,000 times SEM photograph of the obtained silver powder according to Example 3, FIG. 8 shows the wet particle size distribution, and FIG. 9 shows the dry particle size distribution.
From the SEM photograph, it was confirmed that the silver powder according to Example 3 was slightly agglomerated, but the shape was spherical and the surface was very smooth. The silver powder has a BET specific surface area of 0.17 m 2 / g and a wet particle size distribution of D10 = 3.42 μm, D50 = 8.75 μm, D90 = 19.4 μm, (D90−D10) /D50=1.82. The dry particle size distribution was D10 = 2.64 μm, D50 = 7.88 μm, D90 = 16.0 μm, (D90−D10) /D50=1.70. As a result, although the silver powder according to Example 3 has a tendency to agglomerate slightly from Example 2, it was confirmed that the particle size distribution was sharp.
実施例３に係る銀粉の製造により生成する排水は、実施例１に係る排水と同様に無色透明で、エアーのバブリングによりヒドラジンを分解できることを確認した。
以上より、実施例３に係る製造方法で製造された銀粉の特性が優れ、かつ生成する排水処理も容易で、低コストであることが確認された。
The waste water produced | generated by manufacture of the silver powder which concerns on Example 3 was colorless and transparent similarly to the waste water which concerns on Example 1, and it confirmed that hydrazine could be decomposed | disassembled by bubbling of air.
From the above, it was confirmed that the characteristics of the silver powder produced by the production method according to Example 3 were excellent, the waste water treatment to be produced was easy, and the cost was low.
（実施例４）
ポリエチレンイミンとして、平均分子量が７０，０００(和光純薬試薬)のものを用いた以外は、実施例２と同様の操作を行った。
得られた実施例４に係る銀粉の１００００倍のＳＥＭ写真を図１０、湿式粒度分布を図１１、乾式粒度分布を図１２に示す。
ＳＥＭ写真より、実施例４に係る銀粉は、粒子同士が若干凝集しているが、形状は球状で表面が滑らかであることが確認できた。当該銀粉のＢＥＴ比表面積は０．２６ｍ２／ｇであり、湿式粒度分布は、Ｄ１０＝１．８４μｍ、Ｄ５０＝４．４９μｍ、Ｄ９０＝８．２４μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．４３であり、乾式粒度分布は、Ｄ１０＝１．６３μｍ、Ｄ５０＝４．５７μｍ、Ｄ９０＝７．９８μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．３９であった。この結果、実施例４に係る銀粉は、実施例２より若干凝集傾向があるものの、粒度分布はシャープであることが確認できた。
Example 4
The same operation as in Example 2 was performed except that polyethyleneimine having an average molecular weight of 70,000 (Wako Pure Chemical Reagent) was used.
FIG. 10 shows a 10,000 times SEM photograph of the obtained silver powder according to Example 4, FIG. 11 shows the wet particle size distribution, and FIG. 12 shows the dry particle size distribution.
From the SEM photograph, it was confirmed that the silver powder according to Example 4 was slightly agglomerated, but the shape was spherical and the surface was smooth. The silver powder has a BET specific surface area of 0.26 m 2 / g, and wet particle size distributions are D10 = 1.84 μm, D50 = 4.49 μm, D90 = 8.24 μm, (D90−D10) /D50=1.43. The dry particle size distribution was D10 = 1.63 μm, D50 = 4.57 μm, D90 = 7.98 μm, (D90−D10) /D50=1.39. As a result, the silver powder according to Example 4 was confirmed to have a sharp particle size distribution although it had a tendency to agglomerate slightly from Example 2.
実施例４に係る銀粉の製造により生成する排水は、実施例１に係る排水と同様に無色透明で、エアーのバブリングによりヒドラジンを分解できることを確認した。
以上より、実施例４に係る製造方法で製造された銀粉の特性が優れ、かつ生成する排水処理も容易で、低コストであることが確認された。
The waste water produced | generated by manufacture of the silver powder which concerns on Example 4 was colorless and transparent similarly to the waste water which concerns on Example 1, and it confirmed that hydrazine could be decomposed | disassembled by bubbling of air.
From the above, it was confirmed that the characteristics of the silver powder produced by the production method according to Example 4 were excellent, the waste water treatment to be produced was easy, and the cost was low.
（実施例５）
銀を５．４ｇ含む硝酸銀水溶液１８．０ｇに、２８質量％のアンモニア水１２．２ｇ（前記銀に対して２．０当量相当）を添加し、銀アンミン錯塩水溶液を得た。
一方、０．０２質量％のヒドラジン水溶液３９４０ｇ（前記銀に対して１．２当量相当）へ、前記銀の質量に対して０．５質量％のポリエチレンイミン（和光純薬試薬、平均分子量１００００）を添加し、液温を４０℃とした。
このヒドラジン−ポリエチレンイミン水溶液に、前記銀アンミン錯塩水溶液を添加することで、銀粒子を含むスラリーを析出させた。このようにして得られた銀含有スラリーを濾過、水洗し、ケーキを得た。乾燥・評価については、実施例１と同様に行った。
(Example 5)
To 18.0 g of a silver nitrate aqueous solution containing 5.4 g of silver, 12.2 g of 28% by mass of ammonia water (corresponding to 2.0 equivalents with respect to the silver) was added to obtain a silver ammine complex salt aqueous solution.
On the other hand, to 3940 g of 0.02% by mass of hydrazine aqueous solution (corresponding to 1.2 equivalents relative to the silver), 0.5% by mass of polyethyleneimine (Wako Pure Chemical Industries, average molecular weight 10,000) with respect to the mass of the silver Was added to bring the liquid temperature to 40 ° C.
A slurry containing silver particles was precipitated by adding the silver ammine complex salt aqueous solution to the hydrazine-polyethyleneimine aqueous solution. The silver-containing slurry thus obtained was filtered and washed with water to obtain a cake. About drying and evaluation, it carried out similarly to Example 1. FIG.
得られた実施例５に係る銀粉の１００００倍のＳＥＭ写真を図１３、湿式粒度分布を図１４、乾式粒度分布を図１５に示す。
ＳＥＭ写真より、実施例５に係る銀粉は、若干微粒子が存在するが、形状は球状で表面が滑らかであることが確認できた。当該銀粉のＢＥＴ比表面積は０．２９ｍ２／ｇであり、湿式粒度分布は、Ｄ１０＝１．１５μｍ、Ｄ５０＝１．９２μｍ、Ｄ９０＝２．７８μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝０．８５であり、乾式粒度分布は、Ｄ１０＝０．８７μｍ、Ｄ５０＝２．１７μｍ、Ｄ９０＝３．４１μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．１７であった。この結果、実施例５に係る銀粉は、粒度分布が非常にシャープであることが確認できた。
FIG. 13 shows a 10,000 times SEM photograph of the obtained silver powder according to Example 5, FIG. 14 shows the wet particle size distribution, and FIG. 15 shows the dry particle size distribution.
From the SEM photograph, it was confirmed that the silver powder according to Example 5 had some fine particles but had a spherical shape and a smooth surface. The silver powder has a BET specific surface area of 0.29 m 2 / g and a wet particle size distribution of D10 = 1.15 μm, D50 = 1.92 μm, D90 = 2.78 μm, (D90−D10) /D50=0.85. The dry particle size distribution was D10 = 0.87 μm, D50 = 2.17 μm, D90 = 3.41 μm, (D90−D10) /D50=1.17. As a result, it was confirmed that the silver powder according to Example 5 had a very sharp particle size distribution.
実施例５に係る銀粉の製造により生成する排水は、実施例１に係る排水と同様に無色透明で、エアーのバブリングによりヒドラジンを分解できることを確認した。
以上より、実施例５に係る製造方法で製造された銀粉の特性が優れ、かつ生成する排水処理も容易で、低コストであることが確認された。
The waste water produced | generated by manufacture of the silver powder which concerns on Example 5 was colorless and transparent similarly to the waste water which concerns on Example 1, and it confirmed that hydrazine could be decomposed | disassembled by bubbling of air.
From the above, it was confirmed that the characteristics of the silver powder produced by the production method according to Example 5 were excellent, the waste water treatment to be produced was easy, and the cost was low.
（実施例６）
高分子アミンを、平均分子量が１，８００のポリエチレンイミン(和光純薬試薬)とした以外は、実施例２と同様と同様の操作を行った。
(Example 6)
The same operation as in Example 2 was performed, except that the polymeric amine was polyethyleneimine (Wako Pure Chemical Reagent) having an average molecular weight of 1,800.
得られた実施例６に係る銀粉の１００００倍のＳＥＭ写真を図１６、湿式粒度分布を図１７、乾式粒度分布を図１８に示す。
ＳＥＭ写真より、実施例６に係る銀粉は粒子同士が、一部凝集していることが観察された。しかし、銀粉の形状は球状で表面が滑らかであることが確認できた。当該銀粉のＢＥＴ比表面積は０．１２ｍ２／ｇであり、湿式粒度分布は、Ｄ１０＝３．２８μｍ、Ｄ５０＝５．９７μｍ、Ｄ９０＝１０．９８μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．２９であり、乾式粒度分布は、Ｄ１０＝３．０１μｍ、Ｄ５０＝５．６２μｍ、Ｄ９０＝８．９０μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．０５であった。この結果、実施例６に係る銀粉は、実施例２と同様に、シャープな粒度分布を持つことが確認できた。
FIG. 16 shows a 10,000 times SEM photograph of the obtained silver powder according to Example 6, FIG. 17 shows the wet particle size distribution, and FIG. 18 shows the dry particle size distribution.
From the SEM photograph, it was observed that the particles of the silver powder according to Example 6 were partially aggregated. However, it was confirmed that the silver powder had a spherical shape and a smooth surface. The silver powder has a BET specific surface area of 0.12 m 2 / g and a wet particle size distribution of D10 = 3.28 μm, D50 = 5.97 μm, D90 = 10.98 μm, (D90−D10) /D50=1.29. The dry particle size distribution was D10 = 3.01 μm, D50 = 5.62 μm, D90 = 8.90 μm, (D90−D10) /D50=1.05. As a result, it was confirmed that the silver powder according to Example 6 had a sharp particle size distribution as in Example 2.
実施例６に係る銀粉の製造により生成する排水は、実施例１に係る排水と同様に無色透明で、エアーのバブリングによりヒドラジンを分解できることを確認した。
以上より、実施例６に係る製造方法で製造された銀粉の特性が優れ、かつ生成する排水処理も容易で、低コストであることが確認された。
The waste water produced | generated by manufacture of the silver powder which concerns on Example 6 was colorless and transparent similarly to the waste water which concerns on Example 1, and it confirmed that hydrazine could be decomposed | disassembled by bubbling of air.
From the above, it was confirmed that the characteristics of the silver powder produced by the production method according to Example 6 were excellent, the waste water treatment to be produced was easy, and the cost was low.
（実施例７）
ポリエチレンイミン量を、含有される銀の質量に対して０．２質量％とした以外は、実施例４と同様の操作を行った。
得られた実施例７に係る銀粉の１００００倍のＳＥＭ写真を図１９、湿式粒度分布を図２０、乾式粒度分布を図２１に示す。
(Example 7)
The same operation as in Example 4 was performed except that the amount of polyethyleneimine was 0.2% by mass with respect to the mass of silver contained.
FIG. 19 shows a 10,000 times SEM photograph of the obtained silver powder according to Example 7, FIG. 20 shows the wet particle size distribution, and FIG. 21 shows the dry particle size distribution.
ＳＥＭ写真より、実施例７に係る銀粉は、わずかに微粒子が生成してはいるが、形状は球状で表面が滑らかであることが確認できた。当該銀粉のＢＥＴ比表面積は０．３１ｍ２／ｇであり、湿式粒度分布は、Ｄ１０＝１．３６μｍ、Ｄ５０＝２．９２μｍ、Ｄ９０＝５．０４μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．２６であり、乾式粒度分布は、Ｄ１０＝１．１８μｍ、Ｄ５０＝２．８９μｍ、Ｄ９０＝５．００μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．３２であった。この結果、実施例７に係る銀粉は、実施例４と同様に、シャープな粒度分布を持つことが確認できた。 From the SEM photograph, it was confirmed that the silver powder according to Example 7 was slightly formed with fine particles but had a spherical shape and a smooth surface. The silver powder has a BET specific surface area of 0.31 m 2 / g and wet particle size distributions of D10 = 1.36 μm, D50 = 2.92 μm, D90 = 0.04 μm, (D90−D10) /D50=1.26. The dry particle size distribution was D10 = 1.18 μm, D50 = 2.89 μm, D90 = 5.00 μm, (D90−D10) /D50=1.32. As a result, it was confirmed that the silver powder according to Example 7 had a sharp particle size distribution as in Example 4.
実施例７に係る銀粉の製造により生成する排水は、実施例１に係る排水と同様に無色透明で、エアーのバブリングによりヒドラジンを分解できることを確認した。
以上より、実施例７に係る製造方法で製造された銀粉の特性が優れ、かつ生成する排水処理も容易で、低コストであることが確認された。
The waste water produced | generated by manufacture of the silver powder which concerns on Example 7 was colorless and transparent similarly to the waste water which concerns on Example 1, and it confirmed that hydrazine could be decomposed | disassembled by bubbling of air.
From the above, it was confirmed that the characteristics of the silver powder produced by the production method according to Example 7 were excellent, the waste water treatment to be produced was easy, and the cost was low.
（実施例８）
高分子アミンを、平均分子量が８，０００のポリアリルアミン(日東紡製)とした以外は、実施例１と同様の操作を行った。
得られた実施例８に係る銀粉の１００００倍のＳＥＭ写真を図２２、湿式粒度分布を図２３、乾式粒度分布を図２４に示す。
ＳＥＭ写真より、実施例８に係る銀粉は、形状が球状で表面が滑らかであることが確認できた。当該銀粉のＢＥＴ比表面積は０．２２ｍ２／ｇであり、湿式粒度分布は、Ｄ１０＝２．０５μｍ、Ｄ５０＝３．２２μｍ、Ｄ９０＝４．８８μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝０．８８であり、乾式粒度分布は、Ｄ１０＝１．５８μｍ、Ｄ５０＝３．４０μｍ、Ｄ９０＝５．１０μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．０４であった。この結果、実施例６に係る銀粉は、実施例１と同様に、非常にシャープな粒度分布を持つことが確認できた。
実施例８に係る銀粉の製造により生成する排水は、実施例１に係る排水と同様に無色透明で、エアーのバブリングによりヒドラジンを分解できることを確認した。
以上より、実施例８に係る製造方法で製造された銀粉の特性が優れ、かつ生成する排水処理も容易で、低コストであることが確認された。
(Example 8)
The same operation as in Example 1 was performed except that polyallylamine having an average molecular weight of 8,000 (manufactured by Nittobo) was used as the polymer amine.
FIG. 22 shows a 10,000 times SEM photograph of the obtained silver powder according to Example 8, FIG. 23 shows the wet particle size distribution, and FIG. 24 shows the dry particle size distribution.
From the SEM photograph, it was confirmed that the silver powder according to Example 8 had a spherical shape and a smooth surface. The silver powder has a BET specific surface area of 0.22 m 2 / g and a wet particle size distribution of D10 = 2.05 μm, D50 = 3.22 μm, D90 = 4.88 μm, (D90−D10) /D50=0.88. The dry particle size distribution was D10 = 1.58 μm, D50 = 3.40 μm, D90 = 5.10 μm, (D90−D10) /D50=1.04. As a result, it was confirmed that the silver powder according to Example 6 had a very sharp particle size distribution as in Example 1.
The waste water produced | generated by manufacture of the silver powder which concerns on Example 8 was colorless and transparent similarly to the waste water which concerns on Example 1, and it confirmed that hydrazine could be decomposed | disassembled by bubbling of air.
From the above, it was confirmed that the characteristics of the silver powder produced by the production method according to Example 8 were excellent, the waste water treatment to be produced was easy, and the cost was low.
（実施例９）
分子量１０００以上の高分子アミンを、ε−ポリリジン（奥野製薬工業株式会社製）とした以外は、実施例１と同様の操作を行った。
得られた実施例９に係る銀粉の１００００倍のＳＥＭ写真を図２５、湿式粒度分布を図２６、乾式粒度分布を図２７に示す。
ＳＥＭ写真より、実施例９に係る銀粉は、形状が球状で表面が滑らかであることが確認できた。当該銀粉のＢＥＴ比表面積は０．４８ｍ２／ｇであり、湿式粒度分布は、Ｄ１０＝１．０２μｍ、Ｄ５０＝２．２８μｍ、Ｄ９０＝４．２２μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．４０であり、乾式粒度分布は、Ｄ１０＝０．６４μｍ、Ｄ５０＝１．７７μｍ、Ｄ９０＝３．８１μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．７９であった。この結果、実施例９に係る銀粉は、若干微粒子を含むが、分散性が高いことが確認できた。
実施例９に係る銀粉の造により生成する排水は、実施例１に係る排水と同様に無色透明で、エアーのバブリングによりヒドラジンを分解できることを確認した。
以上より、実施例９に係る製造方法で製造された銀粉の特性が優れ、かつ生成する排水処理も容易で、低コストであることが確認された。
Example 9
The same operation as in Example 1 was performed except that ε-polylysine (Okuno Pharmaceutical Co., Ltd.) was used as the polymeric amine having a molecular weight of 1000 or more.
FIG. 25 shows a 10,000 times SEM photograph of the obtained silver powder according to Example 9, FIG. 26 shows the wet particle size distribution, and FIG. 27 shows the dry particle size distribution.
From the SEM photograph, it was confirmed that the silver powder according to Example 9 had a spherical shape and a smooth surface. The silver powder has a BET specific surface area of 0.48 m 2 / g and wet particle size distributions of D10 = 1.02 μm, D50 = 2.28 μm, D90 = 4.22 μm, (D90-D10) /D50=1.40. The dry particle size distribution was D10 = 0.64 μm, D50 = 1.77 μm, D90 = 3.81 μm, (D90−D10) /D50=1.79. As a result, it was confirmed that the silver powder according to Example 9 contained a small amount of fine particles but had high dispersibility.
The waste water produced by the production of silver powder according to Example 9 was colorless and transparent like the waste water according to Example 1, and it was confirmed that hydrazine could be decomposed by bubbling air.
From the above, it was confirmed that the characteristics of the silver powder produced by the production method according to Example 9 were excellent, the waste water treatment to be produced was easy, and the cost was low.
（比較例１）
ポリエチレンイミンを添加しないこと以外は、実施例２と同様の操作を行った。
得られた比較例１に係る銀粉の１００００倍のＳＥＭ写真を図２８、湿式粒度分布を図２９、乾式粒度分布を図３０に示す。
ＳＥＭ写真より、比較例１に係る銀粉は、凝集したサブミクロン粒子が多く存在するとともに、多面体状の角ばったミクロン粒子も混在していることが確認された。
当該銀粉のＢＥＴ比表面積は０．６８ｍ２／ｇであり、湿式粒度分布は、Ｄ１０＝７．９３μｍ、Ｄ５０＝１８．１μｍ、Ｄ９０＝３５．７μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．５４であり、乾式粒度分布は、Ｄ１０＝２．１４μｍ、Ｄ５０＝５．８４μｍ、Ｄ９０＝１０．２μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．３８であった。この結果、比較例１に係る銀粉は、粒度分布形状は比較的シャープであるが、ＳＥＭより観察される一次粒径と比較し、Ｄ５０が明らかに大きくなっており、凝集がひどいことがわかった。
(Comparative Example 1)
The same operation as in Example 2 was performed except that polyethyleneimine was not added.
FIG. 28 shows a 10,000 times SEM photograph of the obtained silver powder according to Comparative Example 1, FIG. 29 shows the wet particle size distribution, and FIG. 30 shows the dry particle size distribution.
From the SEM photograph, it was confirmed that the silver powder according to Comparative Example 1 had many agglomerated submicron particles and was also mixed with polyhedral angular micron particles.
The silver powder has a BET specific surface area of 0.68 m 2 / g and wet particle size distributions of D10 = 7.93 μm, D50 = 18.1 μm, D90 = 35.7 μm, (D90−D10) /D50=1.54. The dry particle size distribution was D10 = 2.14 μm, D50 = 5.84 μm, D90 = 10.2 μm, (D90−D10) /D50=1.38. As a result, the silver powder according to Comparative Example 1 has a relatively sharp particle size distribution shape, but D50 is clearly larger than the primary particle size observed by SEM, indicating that the aggregation is severe. .
比較例１に係る銀粉の製造により生成する排水は、実施例１に係る排水と同様に無色透明で、エアーのバブリングによりヒドラジンを分解できることを確認した。
以上より、比較例１に係る製造方法で製造された銀粉は、粒子形状、粒子バラツキ、分散性のいずれも問題があった。
The waste water produced | generated by manufacture of the silver powder which concerns on the comparative example 1 was colorless and transparent similarly to the waste water which concerns on Example 1, and it confirmed that hydrazine could be decomposed | disassembled by bubbling of air.
As mentioned above, the silver powder manufactured with the manufacturing method which concerns on the comparative example 1 had a problem in all of particle shape, particle variation, and dispersibility.
（比較例２）
還元剤にヒドロキノンを用いたことと、銀アンミン錯体の希釈率を変更したこと以外は、比較例１と同様の操作を行った。
なお、銀アンミン錯体は、銀を４３．２ｇ含む硝酸銀水溶液３６１０ｇに、２８質量％のアンモニア水９７．３ｇ（銀に対して２．０当量相当）を添加し調製したものを使用した。還元剤のヒドロキノン水溶液は、ヒドロキノン（和光純薬製試薬）２３．１ｇを、４６２ｇの純水に溶解させたものを使用した。
(Comparative Example 2)
The same operation as in Comparative Example 1 was performed except that hydroquinone was used as the reducing agent and the dilution rate of the silver ammine complex was changed.
The silver ammine complex used was prepared by adding 97.3 g of 28 mass% ammonia water (equivalent to 2.0 equivalents to silver) to 3610 g of an aqueous silver nitrate solution containing 43.2 g of silver. As the hydroquinone aqueous solution of the reducing agent, a solution obtained by dissolving 23.1 g of hydroquinone (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) in 462 g of pure water was used.
得られた比較例２に係る銀粉の１００００倍のＳＥＭ写真を図３１、湿式粒度分布を図３２、乾式粒度分布を図３３に示す。
ＳＥＭ写真より、比較例２に係る銀粉は、形状は球状で表面が滑らかで高分散であるこ
とが確認できた。
当該銀粉のＢＥＴ比表面積は０．８３ｍ２／ｇであり、湿式粒度分布は、Ｄ１０＝０．８７μｍ、Ｄ５０＝１．５１μｍ、Ｄ９０＝２．９７μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．４０であり、乾式粒度分布は、Ｄ１０＝０．５１μｍ、Ｄ５０＝１．２６μｍ、Ｄ９０＝２．１５μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．３０であった。この結果、比較例２に係る銀粉は、粒度分布形状はシャープであることがわかった。
FIG. 31 shows a 10,000 times SEM photograph of the obtained silver powder according to Comparative Example 2, FIG. 32 shows the wet particle size distribution, and FIG. 33 shows the dry particle size distribution.
From the SEM photograph, it was confirmed that the silver powder according to Comparative Example 2 had a spherical shape, a smooth surface, and high dispersion.
The silver powder has a BET specific surface area of 0.83 m 2 / g and wet particle size distributions of D10 = 0.87 μm, D50 = 1.51 μm, D90 = 2.97 μm, (D90−D10) /D50=1.40. The dry particle size distribution was D10 = 0.51 μm, D50 = 1.26 μm, D90 = 2.15 μm, (D90−D10) /D50=1.30. As a result, the silver powder according to Comparative Example 2 was found to have a sharp particle size distribution shape.
反応で生成した黒色の排水は、エアーのバブリングや、酸化剤等の薬品を使用しても分解することができなかった。そこで、蒸発濃縮を試みたが、燃料コストが高価なだけでなく、濃縮分がタール状となり処理困難となることがわかった。
次に、微生物処理を試みたが、ヒドロキノン自身の有害性が高いため、かなりの低濃度にしないかぎり微生物が死滅し、処理することができなかった。
さらに、焼却処理を試みたところ、排水処理可能であったが、処理コストが高価となり、銀粉製造コストの増加をもたらすと考えられた。
The black wastewater generated by the reaction could not be decomposed even when air bubbling or chemicals such as an oxidant was used. Therefore, evaporative concentration was attempted, but it was found that not only the fuel cost is expensive, but also the concentrated component becomes tar-like and difficult to process.
Next, an attempt was made to treat the microorganism. However, because of the high toxicity of hydroquinone itself, the microorganism was killed and could not be treated unless the concentration was considerably reduced.
Furthermore, when an incineration process was attempted, it was possible to treat the waste water, but it was considered that the processing cost was increased, resulting in an increase in silver powder production cost.
（比較例３）
銀を４３．２ｇ含む硝酸銀水溶液３７５０ｇに、２８質量％のアンモニア水１３６ｇ（銀に対して２．８当量相当）を添加し、銀アンミン錯塩水溶液を得た。
この銀アンミン錯塩水溶液の液温を２０℃とし、２７．４質量％のホルマリン水溶液を３００ｇ（銀に対して１３．７当量相当）加えて、銀粒子を析出させた。次に、析出した銀粒子の凝集を防止するため、前記ホルマリン水溶液を添加してから３０秒後に、エタノール１２．０ｇにラウリン酸０．１５gを溶解させた液を添加して銀粒子の表面処理を行
った。このようにして得られた銀含有スラリーを濾過、水洗し、ケーキを得た。当該ケーキに対して実施例１と同様の操作を行った。
(Comparative Example 3)
To 3750 g of an aqueous silver nitrate solution containing 43.2 g of silver, 136 g of 28% by mass ammonia water (equivalent to 2.8 equivalents with respect to silver) was added to obtain an aqueous silver ammine complex salt solution.
The liquid temperature of this silver ammine complex salt aqueous solution was set to 20 ° C., and 300 g (corresponding to 13.7 equivalents of silver) of a 27.4 mass% formalin aqueous solution was added to precipitate silver particles. Next, in order to prevent aggregation of the precipitated silver particles, 30 seconds after adding the formalin aqueous solution, a solution obtained by dissolving 0.15 g of lauric acid in 12.0 g of ethanol is added to treat the surface of the silver particles. Went. The silver-containing slurry thus obtained was filtered and washed with water to obtain a cake. The same operation as in Example 1 was performed on the cake.
得られた比較例３に係る銀粉の１００００倍のＳＥＭ写真を図３４、湿式粒度分布を図３５、乾式粒度分布を図３６に示す。
ＳＥＭ写真より、比較例３に係る銀粉は、形状はほぼ球状であるが、スジ状の凹凸がある表面性の粗い粒子が生成することがわかった。
当該銀粉のＢＥＴ比表面積は０．８６ｍ２／ｇであり、湿式粒度分布は、Ｄ１０＝０．９７μｍ、Ｄ５０＝１．７８μｍ、Ｄ９０＝２．９７μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．１２であり、乾式粒度分布は、Ｄ１０＝０．７２μｍ、Ｄ５０＝１．５４μｍ、Ｄ９０＝２．４５μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．１２であった。この結果、比較例３に係る銀粉は、粒度分布形状は非常にシャープであることがわかった。
A SEM photograph of 10,000 times the obtained silver powder according to Comparative Example 3 is shown in FIG. 34, the wet particle size distribution is shown in FIG. 35, and the dry particle size distribution is shown in FIG.
From the SEM photograph, it was found that the silver powder according to Comparative Example 3 was roughly spherical in shape, but produced coarse particles with surface properties having streaky irregularities.
The silver powder has a BET specific surface area of 0.86 m 2 / g and a wet particle size distribution of D10 = 0.97 μm, D50 = 1.78 μm, D90 = 2.97 μm, (D90−D10) /D50=1.12. The dry particle size distribution was D10 = 0.72 μm, D50 = 1.54 μm, D90 = 2.45 μm, (D90−D10) /D50=1.12. As a result, the silver powder according to Comparative Example 3 was found to have a very sharp particle size distribution shape.
反応で生成した排水は無色透明であった。しかし、エアーのバブリングや、酸化剤等の薬品を添加しても、ホルマリンを分解することができなかった。 The waste water generated by the reaction was colorless and transparent. However, formalin could not be decomposed even by adding air bubbling or chemicals such as an oxidant.
（比較例４）
ポリエチレンイミンに代えて、ポリビニルアルコール（和光純薬製、平均分子量２２，０００）を、含有される銀の質量に対して１．０質量％添加したこと以外は、実施例２と同様の操作を行った。
得られた比較例４に係る銀粉の４００００倍のＳＥＭ写真および１００００倍のＳＥＭ写真を図３７、湿式粒度分布を図３８、乾式粒度分布を図３９に示す。
(Comparative Example 4)
Instead of polyethyleneimine, the same operation as in Example 2 was performed except that polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, average molecular weight 22,000) was added in an amount of 1.0% by mass based on the mass of silver contained. went.
FIG. 37 shows an SEM photograph of 40000 times and 10,000 times of SEM of the obtained silver powder according to Comparative Example 4, FIG. 38 shows a wet particle size distribution, and FIG. 39 shows a dry particle size distribution.
ＳＥＭ写真より、比較例４に係る銀粉は、粒子同士が癒着して形成された粒子が多く見られ、形状は不定形であった。
当該銀粉のＢＥＴ比表面積は１．６７ｍ２／ｇであり、湿式粒度分布は、Ｄ１０＝１．３１μｍ、Ｄ５０＝３．７２μｍ、Ｄ９０＝７．６０μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．６９であり、乾式粒度分布は、Ｄ１０＝０．３５μｍ、Ｄ５０＝１．１２μｍ、Ｄ９
０＝２．９４μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝２．３１であった。この結果、比較例４に係る銀粉は、粒度分布形状はブロードで、ＳＥＭより観察される一次粒径と比較し、Ｄ５０が明らかに大きくなっており、凝集していることがわかった。
From the SEM photograph, the silver powder according to Comparative Example 4 was found to have many particles formed by adhesion between particles, and the shape was irregular.
The silver powder has a BET specific surface area of 1.67 m 2 / g and wet particle size distributions of D10 = 1.31 μm, D50 = 3.72 μm, D90 = 7.60 μm, (D90−D10) /D50=1.69. The dry particle size distribution is D10 = 0.35 μm, D50 = 1.12 μm, D9
It was 0 = 2.94 μm and (D90−D10) /D50=2.31. As a result, it was found that the silver powder according to Comparative Example 4 had a broad particle size distribution shape, and D50 was clearly increased as compared with the primary particle size observed by SEM, and was agglomerated.
比較例４に係る銀粉の製造により生成する排水は、実施例１に係る排水と同様に無色透明で、エアーのバブリングによりヒドラジンを分解できることを確認した。
以上より、比較例４に係る製造方法で製造された銀粉は、粒子形状が球状ではなく、分散性に問題があることがわかった。
The waste water produced | generated by manufacture of the silver powder concerning the comparative example 4 was colorless and transparent similarly to the waste water concerning Example 1, and it confirmed that hydrazine could be decomposed | disassembled by bubbling of air.
As mentioned above, it turned out that the silver powder manufactured with the manufacturing method which concerns on the comparative example 4 has a problem in a dispersibility rather than a spherical particle shape.
（比較例５）
ポリエチレンイミンに代えて、ポリビニルピロリドン（純正薬品製、平均分子量１０，０００）を、含有される銀の質量に対して１．０質量％添加したこと以外は、実施例２と同様の操作を行った。
得られた比較例５に係る銀粉の１００００倍のＳＥＭ写真を図４０、湿式粒度分布を図４１、乾式粒度分布を図４２に示す。
(Comparative Example 5)
The same operation as in Example 2 was performed except that polyvinyl pyrrolidone (manufactured by Junyaku, average molecular weight 10,000) was added in an amount of 1.0% by mass based on the mass of silver contained instead of polyethyleneimine. It was.
FIG. 40 shows a 10,000 times SEM photograph of the obtained silver powder according to Comparative Example 5, FIG. 41 shows the wet particle size distribution, and FIG. 42 shows the dry particle size distribution.
ＳＥＭ写真より、比較例５に係る銀粉は、凝集した粒径が１μｍ未満の粒子が多く存在するとともに、多面体状の角ばった形状を有し粒径が１μｍ超である粒子も混在していることが確認された。
当該銀粉のＢＥＴ比表面積は０．９１ｍ２／ｇであり、湿式粒度分布は、Ｄ１０＝１．３４μｍ、Ｄ５０＝３．２０μｍ、Ｄ９０＝６．８１μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝１．７１であり、乾式粒度分布は、Ｄ１０＝０．４３μｍ、Ｄ５０＝１．６７μｍ、Ｄ９０＝４．２０μｍ、（Ｄ９０−Ｄ１０）／Ｄ５０＝２．２６であった。この結果、比較例５に係る銀粉は、粒度分布形状がブロードで、ＳＥＭより観察される一次粒径と比較し、Ｄ５０が明らかに大きくなっており、凝集がひどいことがわかった。
From the SEM photograph, the silver powder according to Comparative Example 5 has many particles with an aggregated particle size of less than 1 μm, and also includes particles having a polyhedral angular shape and a particle size exceeding 1 μm. Was confirmed.
The silver powder has a BET specific surface area of 0.91 m 2 / g and wet particle size distributions of D10 = 1.34 μm, D50 = 3.20 μm, D90 = 6.81 μm, (D90−D10) /D50=1.71. The dry particle size distribution was D10 = 0.43 μm, D50 = 1.67 μm, D90 = 4.20 μm, (D90−D10) /D50=2.26. As a result, it was found that the silver powder according to Comparative Example 5 had a broad particle size distribution shape, and D50 was clearly increased as compared with the primary particle size observed by SEM, and the aggregation was severe.
比較例５に係る銀粉の製造により生成する排水は、実施例１に係る排水と同様に無色透明で、エアーのバブリングによりヒドラジンを分解できることを確認した。
以上より、比較例５に係る方法で製造された銀粉は、粒子形状、粒子バラツキ、分散性とも、いずれも問題があった。
The waste water produced | generated by manufacture of the silver powder concerning the comparative example 5 was colorless and transparent similarly to the waste water concerning Example 1, and it confirmed that hydrazine could be decomposed | disassembled by bubbling of air.
From the above, the silver powder produced by the method according to Comparative Example 5 has problems in all of the particle shape, particle variation, and dispersibility.
（比較例６）
ポリエチレンイミンに代えて、Ｌ−リシン（和光純薬製、分子量１４６）を含有される銀の質量に対して０．５質量％添加したこと以外は、実施例１と同様の操作を行った。得られた比較例６に係る銀粉の１００００倍のＳＥＭ写真を図４３に示す。
得られた銀粉は、比較例５と同様に、凝集した粒径が１μｍ未満の粒子が多く存在するとともに、多面体状の角ばった形状を有しており、球状の銀粉は得られなかった。
比較例６に係る銀粉の製造により生成する排水は、実施例１に係る排水と同様に無色透明で、エアーのバブリングによりヒドラジンを分解できることを確認した。
以上より、比較例６に係る製造方法で製造された銀粉は、形状が球状でなく、粒子形状に問題があった。
(Comparative Example 6)
It replaced with polyethyleneimine and performed operation similar to Example 1 except having added 0.5 mass% with respect to the mass of the silver containing L-lysine (made by Wako Pure Chemicals, molecular weight 146). FIG. 43 shows a 10,000 times SEM photograph of the silver powder according to Comparative Example 6 obtained.
Similar to Comparative Example 5, the obtained silver powder had many particles with an aggregated particle size of less than 1 μm and had a polygonal angular shape, and no spherical silver powder was obtained.
The waste water produced | generated by manufacture of the silver powder concerning the comparative example 6 was colorless and transparent similarly to the waste water concerning Example 1, and it confirmed that hydrazine could be decomposed | disassembled by bubbling of air.
From the above, the silver powder produced by the production method according to Comparative Example 6 was not spherical in shape and had a problem in the particle shape.
Claims (6)
前記還元剤として、エアーのバブリングで分解可能なものを用い、
前記銀粒子の還元析出前または還元析出中に、イミン化合物、ポリアリルアミン、ポリリジンから選択される１種以上の、第一アミンおよび／または第二アミンを有する高分子アミンを添加することを特徴とする銀粉の製造方法。 A method for producing silver powder, wherein a reducing agent is added to an aqueous reaction system containing silver ions to reduce and precipitate silver particles,
As the reducing agent, one that can be decomposed by bubbling air,
One or more polymer amines having a primary amine and / or a secondary amine selected from an imine compound, polyallylamine, and polylysine are added before or during the reduction precipitation of the silver particles. To produce silver powder.
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| CN102211206B (en) * | 2011-05-25 | 2013-09-18 | 华东微电子技术研究所合肥圣达实业公司 | Method for preparing superfine spherical silver powder for barium-titanate-based semiconductor ceramic ohmic electrode slurry |
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