200911417 九、發明說明 【發明所屬之技術領域】 本發明係關於使用高濃度之銀離子溶液，安定且有效 率製造微細銀粒子的方法、和其銀微粒子。又，本發明係 關於經由銀離子的還原製造銀粒子的技術中，安定且有效 率製造微細銀粒子的技術。更詳言之，本發明係關於安定 且有效率製造適合作爲電子裝置之配線材料和電極材料之 基質成分之微細高分散性銀粒子的方法、製造裝置、及其 銀微粒子。 本案，係對於2 0 0 7年3月3 0日所申請之日本專利申 請第2007-095 6 5 7號、日本專利申請第2007-095 65 8號、 日本專利申請第2007-095659號、日本專利申請第2007- 095660號主張優先權，並且其內容於此處延用。 【先前技術】 近年來，爲了圖謀電子機器的高機能化，乃要求電子 裝置的小型化和高密度化，爲了達成配線及電極的精細化 ，對於形成彼等之基質材料所使用的銀微粒子，亦要求更 微細且高分散性的微粒子。 先前’電子機器材料所使用之銀微粒子的製造方法已 知爲將銀鹽的氨錯合物還原令銀微粒子沈澱，並且將其洗 淨乾燥得平均粒徑爲數μηι左右之銀微粒子的方法（專利文 獻1 ~3)。例如，於專利文獻1中，記載將銀氨錯合物還 原析出銀微粒子時，將還原時的液溫調整至25〜6〇。(：，_ 200911417 造微細銀粒子之方法。又，於專利文獻3中’記載將硝酸 銀溶液和氨水混合所得之銀氨錯合物溶液、與還原劑’於 添加時間20秒鐘以內混合’析出BET比表面積〇.2 5 m2/g 以上之微細銀粒子的方法。但是’於此等製造方法中’因 爲析出之銀粒子的粒度分佈廣，且粒子易凝集’故具有難 以製造粒徑爲均爲且粒徑爲0.2 ~2·5 μιη和Ιμΐη以下之微細 銀微粒子的問題。 於是，已知於銀氨錯合物水溶液流動之流路途中令有 機還原劑溶液合流，則可於管路內將銀還原並製造結晶粒 徑小之銀微粒子的方法（專利文獻4、5)。然而，此製造方 法因於管路內進行銀氨錯合物的還原，故經由銀的析出令 流路變窄，並且於管壁析出的銀片剝離，具有混入粗大粒 子等之問題。又，於取得微細之銀粒子上，因爲使用銀濃 度非常薄的銀氨錯合物水溶液，故不僅製造效率低’且流 量發生大量，回收時的流失亦變多並且效率亦低。 [專利文獻1 ]特開平8 - 1 3 4 5 1 3號公報 [專利文獻2]特開平8_：176620號公報 [專利文獻3 ]特開2 0 0 1 - 1 0 7 1 0 1號公報 [專利文獻4]特開2005 -4 8236號公報 [專利文獻5]特開2005-48237號公報 【發明內容】 (發明所欲解決之課題） 本發明爲提供解決先前製造方法中之上述問題的銀微 -6 - 200911417 粒子製造方法、製造裝置、及銀微粒子，提供使用高濃度 之銀離子溶液安定且有效率製造分散性優良之微細銀粒子 的方法、製造裝置、及銀微粒子。 (解決課題之手段） 本發明之銀微粒子爲於銀微粒子中，令鹵素相對於銀 含有5_Οχ1〇-8〜ι.5χ10-3的莫耳比。 本發明之銀微粒子中，該鹵素爲相對於該銀含有5.Οχ ΗΓ8〜1·8χ1〇_6之莫耳比，且平均粒徑爲15〜〇_5μηι亦可。 該鹵素爲相對於該銀含有大於UxiO-6且3.0x10-5以 下之莫耳比，且平均粒徑爲〇.5〜〇.丨5 μιη亦可。 該鹵素爲相對於該銀含有大於3. Οχ 10·5且1.5x1 〇-3以 下之莫耳比，且平均粒徑爲〇.15~0.08μιη亦可。 本發明之銀微粒子之製造方法爲具有於銀離子溶液中 添加還原劑將銀離子還原並析出銀微粒子的步驟，並且於 作爲銀微粒子核之形成核物質的存在下將銀離子還原，則 可析出該銀微粒子。 本發明之銀微粒子之製造方法的第1形態爲於鹵化物 離子之存在下將該銀離子還原，並生成鹵化銀作爲該形成 核物質，令該銀微粒子析出。 於銀微粒子之製造方法的第1形態中，經由調整相對 對於銀濃度之鹵化物濃度，控制析出之該銀微粒子的粒徑 亦可。 該銀離子溶液爲使用加入氨水的硝酸銀溶液，且該還 200911417 原劑爲使用對苯二酚液，該具有鹵化物離子之化合物爲使 用氯化銨（NH4C1)、溴化銨（NH4Br)、碘化銨（NH4I)、氯化 鉀（KC1)、溴化鉀（KBr)、碘化鉀（KI)、氯化鈉（NaCl)、溴 化鈉（NaBr)、或換化鈉（Nal)亦可。 使用碘離子作爲該鹵化物離子，將該銀離子還原時， ⑴將相對於銀之碘的莫耳比（銀碘莫耳比、I/Ag)調整成 5·0χ1(Γ8〜1·8χ10_6令平均粒徑1.5〜0.5μπι的銀微粒子析出 ，或（ii)將該銀碘莫耳比調整成大於1.8xl(T6且3.0χ10_5 以下令平均粒徑0.5〜0.15 μηι的銀微粒子析出，或（iii)將 該銀碘莫耳比調整成大於3.0xl(T5且1.5xl(T3以下令平均 粒徑0 . 1 5〜0.0 8 μηι的銀微粒子析出亦可。 該銀離子溶液爲使用加入氨水之銀濃度5 Og/L以上的 硝酸銀溶液，該還原劑爲使用對苯二酚液，該齒化物離子 爲使用碘離子，且相對於銀之碘的莫耳比（I/Ag)調整爲5.0x 1(Γ8〜1 .5x1 (Γ3，令平均粒徑1 .5~0·08μηι之銀微粒子的產 率爲9 9 %以上亦可。 本發明之銀微粒子之製造方法的第2形態爲倂用主還 原劑，和比主還原劑之還原力更強的副還原劑，並於該銀 離子溶液中在少量之該副還原劑存在下加入該主還原劑， 生成作爲該形成核物質之膠體的銀微粒子，令該銀微粒子 析出。 本發明之銀微粒子之製造方法的第2形態中，經由調 整該副還原劑的添加量，控制析出之該銀微粒子的粒徑亦 可 ° -8- 200911417 將相對於銀濃度之副還原劑的莫耳比（銀副還原劑比） 控制於2.5xl0·7〜5.0X10-1且，令平均粒徑1.5〜0.05μπι之 銀微粒子析出亦可。 (i)將該銀副還原劑比調整至2.5χ1〇-7〜3.0χ10·5令平 均粒徑1.5〜0·5μιη的銀微粒子析出’或，（ii)將該銀副還 原劑比調整成大於3·0χ10_5且4_2xl0_2以下令平均粒徑 0.5〜Ο.ίμηι之銀微粒子析出，或（iii)將該銀副還原劑比調 整成大於4.2x10 ·2且5.0x10“以下令平均粒徑0.1〜0.05μηι 之銀微粒子析出亦可。 該銀離子溶液爲使用加入氨水的硝酸銀溶液，該主還 原劑爲使用對苯二酚液，且該副還原劑爲使用聯氨亦可。 使用於該主還原劑之對苯二酚液中混合少量該副還原 劑之聯氨液的溶液，或者，於該銀離子溶液中添加少量該 副還原劑之聯氨液後立即添加該主還原劑的對苯二酚液亦 可〇 本發明之銀微粒子之製造方法的第3形態爲於該銀離 子溶液中添加銀奈米粒子作爲該形成核物質’並於此銀奈 米粒子存在下將該銀離子還原，則可令該銀微粒子析出。 銀微粒子之製造方法的第3形態中’經由調整相對於 銀濃度之該銀奈米粒子的添加量，控制析出之該銀微粒子 的粒徑亦可。 該銀離子溶液爲使用加入氨水的硝酸銀溶液’且該還 原劑爲使用對苯二酚液，並且添加平均粒徑5 0nm以下的 銀奈米粒子亦可。 -9 - 200911417 (υ相對於該銀離子溶液中所含之銀離子個數，將該銀 奈米粒子的個數比（銀離子銀奈米粒子比）調整爲5.〇xl〇_7 〜3.0xl(T6令平均粒徑1.5〜0·5μιη之銀微粒子析出，或， (ii) 將該銀離子銀奈米粒子比調整成大於3.0xl(T6且2·5Χ 1(Γ5以下令平均粒徑0.5〜0.1 μηι的銀微粒子析出，或’ (iii) 將該銀離子銀奈米粒子比調整成大於2.5χ1(Γ5且1·5Χ 10 _4以下令平均粒徑〇. 1〜0.02 μηι之銀微粒子析出亦可。 該銀奈米粒子亦可使用於檸檬酸蘇打存在下，於硝酸 銀溶液中添加硫酸亞鐵將銀離子還原所生成之平均粒徑 20nm以下的銀奈米粒子。 本發明之銀微粒子之製造方法的第4形態爲於該銀離 子溶液中添加氨，並於該氨添加後20秒鐘以內添加該還 原劑，則可生成氫氧化銀或氧化銀作爲該形成核物質，並 且析出該銀微粒子。 銀微粒子之製造方法的第4形態中，經由調整該氨之 添加直到該還原劑之添加爲止的時間，控制析出之銀微粒 子的粒徑亦可。 關於該氨之添加直到該還原劑之添加爲止的時間（經 過時間），（i)該經過時間爲〇.3〜0.5秒鐘以內令平均粒徑 0.2〜0.5μηι的銀微粒子析出，或（ii)該經過時間爲長於0.5 秒鐘且爲2秒鐘以內令平均粒徑0.5 μιη〜1 . 5 μιη的銀微粒子 析出，或（iii)該經過時間爲長於2秒鐘且爲5秒鐘以內令 平均粒徑1·5μηι〜2·0μιη的銀微粒子析出，或（iv)該經過時 間爲長於 5 秒鐘且爲 20 秒鐘以內令平均粒徑 -10- 200911417 2.0μιη〜2.5μιη的銀微粒子析出亦可。 本發明之銀微粒子的製造裝置爲於銀離子溶液中添加 氨和還原劑，將銀離子還原析出銀微粒子的製造裝置，具 有銀離子溶液槽，接續至該銀離子溶液槽的第1管路、氨 水溶液槽、接續至該氨水溶液槽的第2管路、還原液槽、 接續至該還原液槽的第3管路、和由該第1管路與該第2 管路之交叉部伸出的第4管路，並將來自該第3管路之還 原液與來自該第4管路之銀離子與氨溶液的混合液予以混 合。 於本發明之銀微粒子的製造裝置中，該第3管路與該 第4管路爲令其管路端部之開口部彼此些微分離且相對向 般設置，且由該第1管路與該第2管路之交叉部直到該第 4管路端部爲止的流路長度亦可調整。 (發明之效果） 本發明之銀微粒子爲在鹵化物離子的存在下將銀離子 還原所製造的銀微粒子，鹵素爲相對於銀含有5.0 X 1 0 _8 〜1 . 5 Οχ 1 0_3的莫耳比，爲微細分散性良好的銀微粒子。 本發明之第1形態之銀微粒子的製造方法爲在鹵化物 離子的存在下將銀離子還原，製造微細分散性良好之銀微 粒子的方法，可安定且有效率製造此銀微粒子。若根據本 發明之第1形態之銀微粒子的製造方法，則於銀離子還原 時’鹵化銀爲優先生成，且其作爲形成核物質並形成核。 其後以鹵化銀作爲核並形銀的結晶性初級粒子，此初級粒 -11 - 200911417 子彼此凝集形成銀微粒子。與鹵化物離子不存在的情況相 比較，可以小能量而輕易且確實形成初期核，又，可增多 其初期核數，且亦可增多初級粒子的凝集中心點數。因此 ，可安定且有效率析出微細的銀微粒子。 又，若根據本發明之第1形態之銀微粒子的製造方法 ，經由調整相對於銀濃度之鹵化物離子濃度，則可控制析 出之銀微粒子的粒徑。因此，經由調整上述鹵素濃度，例 如，可有效率安定取得平均粒徑1 _ 5〜0.5 μηι之銀微粒子、 平均粒徑 〇.5〜0.15 μιη 之銀微粒子、或平均粒徑 0.1 5〜0·08μηι之銀微粒子等根據用途之粒徑的銀微粒子。 更且，若根據本發明之第1形態之製造方法，使用高 濃度之銀離子溶液，則可有效率製造微細的銀微粒子。具 體而言，例如，使用加入氨水之銀濃度50g/L以上的硝酸 銀溶液，則可在 9 9 %以上之產率下取得平均粒徑 1 .5〜0.0 8 μιη的銀微粒子。 又’本發明之第1形態之銀微粒子的製造方法爲在鹵 化物離子存在下將銀離子還原，故若與還原液共同添加鹵 化物離子源（具有鹵化物離子之化合物）即可，並不需要於 管路內注入還原液的特殊裝置構造，故可輕易實施。 本發明之第2形態之銀微粒子的製造方法爲倂用主還 原劑和比此主還原劑還原力更強之副還原劑，並於銀離子 溶液中於少量副還原劑存在下加入主還原劑，令銀微粒子 析出。經由還原力強的副還原劑最初生成許多膠體狀的微 細銀微粒子。其後以膠體狀的微細銀微粒子作爲核並形成 -12- 200911417 銀的結晶性初級粒子，且此初級粒子彼此間凝集形成銀微 粒子。與未存在比主還原劑還原更強之副還原劑的情況相 比較，以較小之能量可輕易且確實形成初期核’又’可增 多此初期核數，且亦可增多初級粒子之凝集中心點數。因 此，可安定且有效率取得微細的銀微粒子。 又，若根據本發明之第2形態之銀微粒子的製造方法 ，調整副還原劑的添加量，則可控制析出之銀微粒子的粒 徑，例如，可有效率且安定製造平均粒徑1.5〜0.5 μιη的銀 微粒子、平均粒徑0.5〜0.1 μιη的銀微粒子，或平均粒徑 0.1~0.05μπι的銀微粒子等 更且，若根據本發明之第2形態之銀微粒子的製造方 法，使用高濃度之銀離子溶液則可有效率製造微細的銀微 粒子。具體而言，例如，使用加入氨水之銀濃度5 Og/L以 上的硝酸銀溶液，則可在99 %以上之產率下取得平均粒徑 1.5〜0.05μιη的銀微粒子。 又，本發明之第2形態之銀微粒子的製造方法爲倂用 主還原劑和副還原劑，於副還原劑之存在下加入主還原劑 即可，不需要於管路內注入還原液之特殊的裝置構造，故 可輕易實施。 本發明之第3形態之銀微粒子的製造方法爲具有還原 銀離子製造銀微粒子的步驟，並添加銀奈米粒子，於此銀 奈米粒子的存在下將銀離子還原的方法，可安定且有效率 製造微細的銀微粒子。於本發明之第3形態之銀微粒子的 製造方法中，於銀離子還原時在液中存在許多微細的銀奈 -13- 200911417 米粒子，且將其作爲形成核物質並形成核。其次 粒子作爲核並形成銀的結晶性初級粒子，且此初 此凝集形成銀微粒子。相比於未存在銀奈米粒子 初期核己形成，又，可任意增多此初期核數，且 初級粒子的凝集中心點數。因此，可安定且有效 細的銀微粒子。 又，若根據本發明之第3形態之銀微粒子的 ，調整所添加之銀奈米粒子份量則控制析出之銀 徑，例如，可有效率且安定取得平均粒徑1.5〜0. 微粒子、平均粒徑0.5〜0.1 μηι的銀微粒子，或 0.1〜0_ 02 μπι的銀微粒子等根據用途之粒徑的銀微 更且，若根據本發明之第3形態之銀微粒子 法，使用高濃度之銀離子溶液則可有效率製造微 粒子。具體而言，例如，使用加入氨水之銀濃度 上的硝酸銀溶液，則可在9 9 %以上之產率下取得 1·5μηι以下的銀微粒子。 又，本發明之第3形態之銀微粒子的製造方 加銀奈米粒子即可，且銀離子溶液與還原液的添 無限制，故不需要於管路內注入還原液之特殊的 ’可輕易實施。 本發明之第4形態之銀微粒子的製造方法中 後2 0秒鐘以內添加還原劑，於形成氨錯合物前 的氫氧化銀（AgOH)或氧化銀（Ag20)作爲形成核 形成核。其後以氫氧化銀或氧化銀作爲核，形成 ，銀奈米 級粒子彼 之情況， 亦可增多 率析出微 製造方法 微粒子粒 5 μ m的銀 平均粒徑 粒子。 的製造方 細的銀微 50g/L 以 平均粒徑 法，若添 加方法並 裝置構造 ，添加氨 暫時生成 物質並且 結晶粒大 -14- 200911417 小爲25nm〜1 5 0nm之銀的結晶性初級粒子， 彼此凝集形成銀微粒子。若核的生成多，且 心點數多則銀微粒子的大小變小。因此，作 銀及氧化銀爲存在許多且若於氨添加2 0秒 原劑’則可安定且有效率取得微細的銀微粒 ，例如，可在9 9 %以上的效率下取得平均粒 的微細銀粒子。另一方面，若添加氨後直到 止的時間長’則於混合初期生成的氮氧化銀 全量變化或銀氨錯合物，故無法作用爲核， 成數。因此，無法令所合成之銀微粒子的粒 又，若根據本發明之第4形態之銀微粒 ，經由調製氨添加後直到添加還原劑爲止的 可製造平均粒徑0.2μηι〜2_5μιη的銀微粒子。 又，本發明之製造裝置中，由於來自第 液與來自第4管路之銀離子溶液與氨溶液的 故可輕易實施上述第4形態之銀微粒子的製 本發明之製造裝置中，經由可變更第1管路 交叉部直到第4管路端部爲止的流路長度， 氨添加後直到添加還原劑爲止的經過時間。 【實施方式】 以下，具體說明本發明及實施例。 (第1實施形態） 且此初級粒子 伴隨之凝集中 爲核之氫氧化 鐘以內添加還 子。具體而言 徑2.5 μ m以下 還原劑添加爲 或氧化銀幾乎 無法控制核生 徑安定。 子的製造方法 經過時間，則 3管路之還原 混合液混合， 造方法。又， 與第2管路之 則可輕易調整 -15- 200911417 本發明之銀微粒子爲在鹵化物離子之存在下將銀離子 還原所製造的銀微粒子，鹵化物爲相對於銀含有5 . Ox 1 0_8 ~1. 5 xl(T3的莫耳比，爲微細分散性良好的銀微粒子。 本發明之銀微粒子爲於銀離子溶液中添加還原劑將銀 離子還原令銀微粒子析出的方法中，在鹵化物離子的存在 下將銀離子還原則可製造。又，於此製造方法中，經由調 整相對於銀濃度之鹵化物離子濃度，即可控制析出之銀微 粒子的粒徑。 銀離子溶液可使用加入氨水的硝酸銀溶液等。經由氨 的存在形成銀氨錯合物，並且經由添加還原劑令銀還原析 出。 還原液可使用對苯二酚液、焦掊酚液、3,4-二羥基甲 苯般具有酚基的有機還原劑溶液等。還原劑的添加量爲令 液中之銀離子充分還原並且析出銀微粒子的份量爲佳。 鹵化物離子源（具有鹵化物離子的化合物）可使用氯化 銨（NH4C1)、溴化銨（NH4Br)、碘化銨（ΝΗ4Ι)、氯化鉀（KC1) 、溴化鉀（KBr)、碘化鉀（ΚΙ)、氯化鈉（NaCl)、溴化鈉 (NaBr)、或碘化鈉（Nal)等。另外，碘、溴、氯依序有微 細化效果強之傾向。 經由存在鹵化物離子，於銀離子還原時，優先生成鹵 化銀，並以其作爲形成核物質且形成核。其後，以鹵化銀 作爲核並形成銀的結晶性初級粒子，此初級粒子彼此凝集 形成銀微粒子。與鹵化物離子未存在的情形相比較，可以 較小之能量而輕易且確實形成初期核，又，可增多其初期 -16- 200911417 核數，且亦可增多初期粒子的凝集中心點數。因此，可安 定且有效率析出微細的銀微粒子。 若未存在鹵化物離子，則經由銀離子還原形成銀團簇 核時’在核的生成上需要大能量，無法輕易形成初期核。 因此，初期核數變少，初級粒子的凝集中心點數亦變少， 故難取得微細的銀微粒子。 鹵化物離子的濃度，例如，於硝酸銀溶液中加入氨水 的溶液中，添加對苯二酚液將銀離子還原時，相對於銀之 碘的莫耳比（銀碘莫耳比、I/Ag)爲5·0χ10·8以上爲適當， 可取得平均粒徑1 .6 μιη以下的銀微粒子。又，相對於銀之 碘的莫耳比愈高則愈可取得微細的銀微粒子。具體而言， 相對於銀之碘的莫耳比爲1 . 0 X 1 (Γ7以上之範圍中，例如， 使用銀濃度50g/L以上的硝酸銀溶液，則可在99%以上之 產率下，取得平均粒徑1·5μιη~0.08μηι的銀微粒子。 另一方面，若鹵化物的添加量過多，則銀微粒子的形 狀難變或球形，或者易凝集。因此，相對於銀之鹵化物離 子的莫耳比爲1 .5x1 (Γ3以下爲適當。 第1實施形態之銀微粒子的製造方法中，經由調整相 對於銀濃度之鹵素濃度，則可控制析出之銀微粒子的粒徑 。例如，於加入氨水之硝酸銀溶液中添加對苯二酚液將銀 離子還原並且析出銀微粒子時，將相對於銀之碘的莫耳比 (I/Ag)如下調整，則可取得平均粒徑 0.08μιη〜1 .5μιη的銀 微粒子。 (i)將銀碘莫耳比（I/Ag)調整至5.0xl(T8〜1.8xl(T6 ’則 -17- 200911417 可析出平均粒徑1 . 5 ~0.5 μιη的銀微粒子。 (Π)將該銀碘莫耳比調整成大於1.8χ10·6且3.0Χ10·5 以下，可析出平均粒徑0.5 ~0.1 5 μιη的銀微粒子。 (iii)將上述銀碘莫耳比調整成大於3·0χ10·5且l.5x W3以下，則可析出平均粒徑0·15~0·08μηι的銀微粒子。 本發明之第1實施形態之銀微粒子的製造方法爲對於 析出銀微粒子的粒徑控制性優良，且析出之銀微粒子的粒 徑爲以相同之銀鹵化物莫耳比，試驗1 〇次求出之平均粒 徑的-10%〜10%範圍內。又，根據第1實施形態之銀微粒 子之製造方法所調製的藥液爲經時安定性優良，調製後9 小時以內所合成之銀微粒子的粒徑變化爲-1 0 %〜1 0 %以內 〇 弟1貫施形氣之銀微粒子的製造方法爲於銀離子還原 時存在鹵化物離子，故析出的銀微粒子爲含有鹵化物，銀 離子爲被還原析出銀微粒子且逐漸成長，故鹵素被含於銀 微粒子的內部。因此，鹵素難被溶出，使用銀微粒子時幾 乎不受鹵素影響。 (第2實施形態） 第2實施形態之銀微粒子的製造方法爲具有於銀離子 溶液中添加還原劑，將銀離子還原令銀微粒子析出的步驟 ，併用主還原劑、和比主還原劑更強還原力的副還原劑， 並於銀離子溶液中在少量副還原劑的存在下加入主還原劑 ，令微細的銀微粒子析出。經由調整副還原劑的添加量， -18- 200911417 則可控制析出的銀微粒子的粒徑。 銀離子溶液可使用加入氨水的硝酸銀溶液等。此溶液 中形成銀氨錯合物，且經由添加還原劑令銀還原析出。 第2實施形態之銀微粒子的製造方法中，倂用主還原 劑、和比此主還原劑更強還原力的副還原劑。主還原劑若 使用對苯二酚液（OH(C6H4)OH)、焦桔酚液、3,4-二羥基甲 苯液般具有酚基的有機還原劑溶液即可。副還原劑可使用 聯氨液（N2H4)、硼氫化鈉（NaBH4)、二甲基胺硼院（BH3 · HN(CH3)2)等，及還原力強的聯氨爲佳。 倂用主還原劑和比此主還原劑更強還原力的副還原劑 ，並於銀離子溶液中在副還原劑的存在下添加主還原劑， 最初經由速原力強的副速原劑將銀®原，可在較小能量下· 輕易且確實形成初期核，又，可增多此初期核數，且亦可 增多初級粒子的凝集中心點數。因此，例如可安定且有效 率取得平均粒徑〇 . 5 μηι以下的微細銀微粒子。 另外，若未存在副還原劑’以還原力弱的主還原劑將 銀離子還原則生成銀團簇核。此時，於生成核上需要大肯g 量，無法輕易形成初期核。因此初期核數變少，初級粒子 的凝集中心點數亦變少，故難以取得微細的銀微粒子。 主還原劑的份量，若爲充分還原銀離子溶液之銀離子 的份量即可。副還原劑的份量，若爲最初生成充分份量之 膠體狀銀微粒子的份量即可。副還原劑的份量若過多，則 銀微粒子變成凝集體，難以取得分散性良好的微細銀微粒 子。具體而言，相對於銀濃度之副還原劑的莫耳比（銀副 -19- 200911417 還原劑比：[副還原劑]/[Ag])控制成2.5 xlO·7〜5.0x1 (Γ1， 則可製造平均粒徑1 · 5〜0.0 5 μπι的銀微粒子。 例如，使用加入氨水的硝酸銀溶液，且主還原劑爲使 用對苯二酚液、副還原劑爲使用聯氨時，相對於銀濃度之 聯氨的莫耳比（銀聯氨比：N2H4/Ag)爲 2.5χ10·7〜5.0Χ10·1 的份量爲適當，以此添加量之範圍，則可在99%以上之產 率下取得平均粒徑1.5〜0_05μπι的銀微粒子。 又，若添加主還原劑後隔一般時間添加副還原劑，則 無法取得上述效果。因此，於主還原劑中添加使用少量之 副還原劑，或於添加少量副還原劑後立即添加主還原劑爲 佳。 第2實施形態之銀微粒子的製造方法中，經由調整銀 副還原劑比，則可控制析出之銀微粒子的粒徑。例如，於 加入氨水的硝酸銀溶液中添加含聯氨之對苯二酚液，令銀 離子還原析出銀微粒子時，將銀聯氨比（N2H4/Ag)如下調 整則可取得平均粒徑1 _ 5〜0.0 5 μ m的銀微粒子。 (i) 將銀聯氨比調整成2.5 X 1 0·7 ~ 3 · 0 X 1 〇_5 ,則可取得 平均粒徑1.5〜5.Ομιη的銀微粒子。 (ii) 將銀聯氨比調整成大於3·Οχ1〇-5且4.2xl(T2以下 ’則可取得平均粒徑0 · 5 ~ 0 · 1 μ m的銀微粒子。 (i i i)將銀聯氨比調整成大於4.2 X 1 0 _2且5 _ 〇 X 1 〇 ·1以下 ，則可取得平均粒徑0.1〜0 · 0 5 μιη的銀微粒子。 (第3實施形態） -20- 200911417 第3實施形態之銀微粒子的製造方法爲具有於銀離子 溶液中添加還原劑，將銀離子還原析出銀微粒子的步驟， 經由添加銀奈米粒子並在此銀奈米粒子存在下將銀離子還 原，則可析出微細的銀微粒子。經由調整相對於銀濃度之 銀奈米粒子的添加量，則可控制析出之銀微粒子的粒徑。 銀離子溶液可使用加入氨水的硝酸銀溶液等。此溶液 中形成銀氨錯合物，經由添加還原劑令銀還原析出。還原 液可使用對苯二酚液、焦掊酚液、3,4-二羥基甲苯般具有 酚基的有機還原劑溶液。 銀奈米粒子爲奈米大小的銀粒子（銀膠體粒子），若於 銀離子溶液中添加即可。所使用之銀奈米粒子爲平均粒徑 50nm以下者爲佳，且以平均粒徑2.5nm~20nm者爲適當 〇 銀奈米粒子爲於檸檬酸蘇打存在下於硝酸銀溶液中添 加硫酸亞鐵，將銀離子還原，使用生成之平均粒徑20nm 以下的銀奈米粒子即可。將硫酸亞鐵與檸檬酸蘇打預先混 合，於室溫下，於此混合溶液中投入硝酸銀溶液’將硝酸 銀還原即可。硝酸銀溶液之銀濃度爲1〜2 00g/L爲適當’ 硫酸亞鐵之份量若爲可充分還原硝酸銀的份量即可。又’ 檸檬酸蘇打之份量爲銀莫耳數的2倍〜7倍爲適當。硝酸 銀溶液與硫酸亞鐵溶液的混合爲對一個供給管嘴投入 5~20mL/min爲佳。混合後，攪拌令其均勻反應。經由此 反應還原銀，取得含有粒徑爲奈米大小之銀超微粒子（銀 奈米粒子）的銀膠體液。將此銀膠體液固液分離’並將分 -21 - 200911417 離的固形成分以檸檬酸蘇打洗淨，取得銀奈米粒子分散的 銀膠體液。 於銀離子溶液中添加銀奈米粒子，以此銀奈米粒子爲 核並形成銀的結晶性初級粒子，此初級粒子彼此凝集形成 銀微粒子。相比於未存在銀奈米粒子的情形，已形成初期 核，又’可任意增多此初期核數’且亦可增多初級粒子的 凝集中心點數。因此，成爲微細的銀微粒子，例如，可安 定且有效率取得平均粒徑1 . 5 μηι以下的微細銀微粒子。另 外’若未存在銀奈米粒子，則經由銀離子的還原令銀圍簇 爲以初期核形式形成，但在生成核上必須有大能量，無法 輕易形成初期核。因此，初期核數變少，初級粒子的凝集 中心點數亦變少，故難取得微細的銀微粒子。 例如，於加入氨水之硝酸銀溶液中添加對苯二酚液將 銀離子還原時，銀奈米粒子的添加量，相對於銀離子個數 之銀奈米粒子的個數比爲5_0χ10·7〜1.5Χ10·4爲佳。於此添 加量之範圍中，例如使用銀濃度50g/L以上的硝酸銀溶液 ，則可在99%以上之產率下取得平均粒徑1.5 μπι以下的銀 微粒子。 又，第3實施形態之銀微粒子的製造方法中，經由調 整相對於銀濃度之銀奈米粒子的添加量，則可控制析出之 銀微粒子的粒徑。例如，於加入氨水之硝酸銀溶液中添加 對苯二酚液，令銀離子還原析出銀微粒子時’將液中之相 對於銀離子個收之銀奈米粒子個數比（以下，稱爲銀離子 銀奈米粒子比率）如下調整，則可取得平均粒徑 -22- 200911417 1 _5~0_02μπι的銀微粒子。 (i)將銀離子銀奈米粒子比率調整成5·0χ10·7 ~3·0χ1(Γ6， 則析出平均粒徑1 . 5〜0.5 μηι的銀微粒子。 (Π)將該銀離子銀奈米粒子比率調整成大於3·0χ1(Γ6 且2.5x1 0_5以下，析出平均粒徑0.5〜0.1 μιη的銀微粒子。 (iii)將該銀離子銀奈米粒子比率調整成大於2·5χ10_5 且1·5χ1(Τ4以下，析出平均粒徑0.1〜〇·〇2μιη的銀微粒子 (第4實施形態） 第4實施形態之銀微粒子的製造方法爲具有於銀離子 溶液中添加氨和還原劑，將銀離子還原令銀微粒子析出的 步驟，於氨添加後20秒鐘以內添加還原劑，則可令微細 的銀微粒子析出。 銀離子溶液可使用硝酸銀溶液等。若於硝酸銀溶液中 添加氨則形成銀氨錯合物，將其還原則析出銀。還原劑可 使用對苯二酚液（oh(c6h4)oh，以下簡稱爲H2Q)等。氨 的添加量爲令液中未殘留未形成氨錯合物之銀離子的份量 爲佳，其份量相對於銀1莫耳之氨爲2〜3莫耳的份量。還 原劑的添加量以液中未殘留未反應之銀氨錯合物的份量爲 佳，其份量於還原劑使用對苯二酚時，相對於1莫耳之對 苯二酚爲0.3〜1.0莫耳之份量。 第4實施形態之銀微粒子的製造方法爲於銀離子溶液 中添加氨後2 0秒鐘以內添加還原劑。氨添加後之短時間 -23- 200911417 中添加還原劑’則可在形成銀氨錯合物前暫時生成的氫氧 化銀（AgOH)或氧化銀（Ag20)作爲形成核物質並且形成核 。其次以氫氧化銀或氧化銀作爲核並且形成銀的結晶性初 級粒子’且此初級粒子彼此凝集形成銀微粒子。若氨添加 後2 0秒鐘以內’殘留許多未形成氨錯合物的氫氧化銀或 氧化銀則其變成核。因此，比還原銀生成銀圍簇核之情形 ，更可增多初期核數，且亦可增多初級粒子的凝集中心點 數，故例如成爲平均粒徑2.5 μηι以下的微細銀微粒子。另 一方面，氨添加後經過長於2 0秒鐘之情形，初期生成的 氫氧化銀及氧化銀變成銀氨錯合物，無法以氫氧化銀及氧 化銀之初期核型式形成結晶性初級粒子。銀離子還原所造 成之銀圍簇核的初期核生成數變爲少量，且初級粒子的凝 集中心點數亦變爲少量，故難取微細的銀微粒子。 第4實施形態之銀微粒子的製造方法中，於銀離子溶 液中添加氨後2 0秒鐘以內添加還原劑’故於銀離子溶液 中預先添加氨並形成銀氨錯合物者’和在銀離子溶液中先 添加還原劑者並無法使用。 第4實施形態之銀微粒子的製造方法中’於氨添加後 2 〇秒鐘以內之範圍中，經由調整氨添加後直到添加還原 劑爲止的經過時間，則可控制析出的銀微粒子粒徑。具體 而言，如下的經過時間即可控制銀微粒子的粒徑。 (i )將上述經過時間調整成0 · 3秒鐘〜0.5秒鐘以內’則 可析出平均粒徑0.2 μηι〜0.5 μιη的銀微粒子。 (ii)將上述經過時間調整成長於0·5秒鐘且爲2秒鐘 -24- 200911417 以內，則可析出平均粒徑0.5 μπι〜1.5 μπι的銀微粒子。 (iii) 將上述經過時間調整成長於2秒鐘且爲5秒鐘以 內，則可析出平均粒徑1 · 5 μπι ~2.0 μιη的銀微粒子。 (iv) 將上述經過時間調整成長於5秒鐘且爲20秒鐘以 內，則可析出平均粒徑2.0μιη~2.50μϊη的銀微粒子。 本實施形態之銀微粒子的製造裝置，係於銀離子溶液 中添加氨和還原劑將銀離子還原並且析出銀微粒子的製造 裝置。此製造裝置的一例示於圖24。如圖示般，本實施 形態之銀微粒子的製造裝置爲具有銀離子溶液槽1 〇、於 銀離子溶液槽1 〇 —端接續的第1管路1 3、氨水溶液槽1 1 、於氨水溶液槽U —般接續的第2管路1 4、還原液槽1 2 、於還原液槽1 2 —端接續的第3管路1 5、和由第1管路 第2管路之交叉部伸出的第4管路16。第4管路16與第 3管路1 5爲令其管路的另一端端部開口部爲相互稍微分 離且相對向般設置。 於上述裝置構造中，由銀離子溶液槽10朝向第1管 路1 3的另一端流過銀離子溶液。由氨水溶液槽Η朝向第 2管路1 4的另一端流過氨水溶液。由還原液槽1 2朝向第 3管路15的另一端流過還原液。於第1管路13與第2管 路1 4的交叉部，令銀離子溶液與氨水溶液混合。此交叉 部爲銀離子溶液與氨水溶液的混合位置Α。其次，由第4 管路16與第3管路15之各個端部的開口部吐出銀離子溶 液與氨水溶液的混合液和還原液，並於管路的外側交會混 合。此第4管路1 6與第3管路1 5之端部的開口部間成爲 -25- 200911417 銀離子溶液與氨水溶液的混合液與還原液的混合位置B ° 由銀離子溶液槽10流出的銀離子溶液’首先於第1 管路13與第2管路14的交叉部（混合位置A)與氨水溶液 混合。其次，銀離子溶液與氨水溶液的混合液爲朝向第4 管路1 6之另一端的端部流動’並由另一端端部的開口部 吐出至外部。其後’銀離子溶液與氨水溶液的混合液’與 來自第3管路15之另一端端部開口部所吐出的速原液’ 在管路外側之混合位置B交會混合。氨添加後直到還原液 添加爲止之時間，係根據混合位置A與混合位置B的管 路長（流路長）L(第1管路13與第2管路14之交叉部直到 第4管路16之另一端爲止的距離、或第4管路16的管路 長）而決定，以氨添加後2 0秒鐘以內添加還原液般設定管 路長（流路長）L。 混合位置B所混合的混合液，例如經由混合位置B 下方所設置之混合液捕集槽所捕集。將捕集的混合液過濾 取得銀微粒子。 於上述裝置構造中，混合位置B的第4管路16與第 3管路1 5爲以其管路端部之開口部爲相互些微分離且相 對向設置。經由管路端部之開口部爲相互分離且相對向設 置，則可令通過第4管路1 6流動的添加氨銀離子溶液、 與通過第3管路1 5流動的還原爲在管路的外側混合’並 且於管路外之開放空間形成銀微粒子的析出場所。因此’ 於管路內壁不會附著銀微粒子，不會產生混入粗大之剝離 粒子的問題，故可取得均勻粒徑的銀微粒子。 -26- 200911417 另外’令第1管路13與第2管路14之交叉部（混合 位置A)以可移動般形成，或者令混合位置a至混合位置 B的管路（第4管路1 6)以可伸縮般形成，則可使得混合位 置A至混合位置B的管路長（流路長）L以可調整般形成， 並且可調整氨添加後直到還原液添加爲止的經過時間。 又’令第4管路16的另一端與第3管路15的另一端 接續，且交叉部的一部分爲開口，混合液爲由開口部迅速 吐出至管路外的構造亦可。此時，第4管路1 6與第3管 路1 5的接續部分成爲銀離子溶液與還原液的混合位置b [實施例] 以下’根據實施例具體示出本發明。另外，粒徑之測 定爲根據雷射散亂/繞射法，以個數基準演算求出。 (實施例1) 於加入氨水之硝酸銀溶液中，添加加入碘化銨液的對 苯二酚溶液，將銀離子還原並析出銀微粒子。氨水、硝酸 銀溶液、對苯二酚溶液之組成示於表1。又，碘化銨溶液 的使用量，相對於銀之碘的莫耳比爲示於表2。析出之銀 微粒子的平均粒徑 '產率、碘含量示於表2。更且，關於 —部分之試料，粒子的SEM照片示於圖3〜圖6。另外， 表2中’試料a 1〜A 1 1爲本發明試料。未添加碘化銨液者 以比較試料1 a表示，碘添加量比較佳範圍更爲過剩之例 -27- 200911417 以比較§式料1 b表示。Ag微粒子的粒徑控制爲示出相對於 平均粒徑之變動範圍[μητ]，產率爲以百分率[%]表示。 ΝΗ4 I水浴液濃度於試料a丨〜試料a 7爲〇 _ 〇 2 %，於試料 A8〜試料All 卜 b較試料1 b爲2 %。又，相對於碘添加量 之銀微粒子的平均粒彳孩 一 之上下棒爲示出以1〇 ^ _化示於圖1。圖中之測定値所示 -> μ下括戌、二…… β試驗之測定値的偏差範圍 [表1]BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing fine silver particles by using a high concentration silver ion solution, which is stable and effective, and silver fine particles thereof. Further, the present invention relates to a technique for producing fine silver particles in a stable and effective manner in a technique for producing silver particles by reduction of silver ions. More specifically, the present invention relates to a method, a manufacturing apparatus, and a silver fine particle for stably and efficiently producing finely and highly dispersible silver particles suitable as a matrix component of a wiring material and an electrode material of an electronic device. Japanese Patent Application No. 2007-095 6 5, Japanese Patent Application No. 2007-09565, Japanese Patent Application No. 2007-095659, Japanese Patent Application No. 2007-095659, filed on March 30, 2007 Patent Application No. 2007-095660 claims priority and its content is hereby incorporated by reference. [Prior Art] In recent years, in order to improve the high performance of electronic devices, it is required to reduce the size and density of electronic devices. In order to achieve wiring and electrode refinement, silver fine particles used for forming the matrix materials thereof are required. More fine and highly dispersible microparticles are also required. The method for producing silver microparticles used in the prior art is known as a method of reducing an ammonia complex of a silver salt to precipitate silver fine particles, and washing and drying the silver fine particles having an average particle diameter of about several μηι ( Patent Documents 1 to 3). For example, in Patent Document 1, it is described that when the silver ammonia complex is further precipitated as silver fine particles, the liquid temperature at the time of reduction is adjusted to 25 to 6 Torr. (:, _200911417 A method of producing fine silver particles. Further, in Patent Document 3, 'the silver ammonia complex solution obtained by mixing a silver nitrate solution and ammonia water, and a reducing agent' are mixed within 20 seconds of addition time' precipitation. BET specific surface area 〇. A method of fine silver particles of 2 5 m 2 /g or more. However, in the "manufacturing method", since the precipitated silver particles have a wide particle size distribution and the particles are easily aggregated, it is difficult to produce a particle size of all and a particle diameter of 0. The problem of fine silver particles below 2 ~ 2 · 5 μιη and Ιμΐη. Then, it is known that a method in which an organic reducing agent solution is combined in a flow path in which a silver ammonia complex aqueous solution flows, and silver can be reduced in a piping to produce silver fine particles having a small crystal grain size (Patent Documents 4 and 5) . However, this production method is because the silver ammonia complex is reduced in the pipe, so that the flow path is narrowed by the precipitation of silver, and the silver flakes deposited on the pipe wall are peeled off, and there is a problem that coarse particles are mixed. Further, since fine silver particles are used, since a silver ammonia complex aqueous solution having a very small silver concentration is used, not only is the production efficiency low, but also a large amount of flow occurs, and the loss at the time of recovery is also increased and the efficiency is also low. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] JP-A-2005-48237 (Patent Document 5) JP-A-2005-48237 SUMMARY OF INVENTION Technical Problem The present invention provides a silver which solves the above problems in the prior manufacturing method. Micro-6 - 200911417 The particle production method, the manufacturing apparatus, and the silver fine particles provide a method, a manufacturing apparatus, and silver fine particles which are stable and efficiently produced by using a high-concentration silver ion solution to produce fine silver particles having excellent dispersibility. (Means for Solving the Problem) The silver fine particles of the present invention are in the silver fine particles, and the halogen contains 5_Οχ1〇-8~ι with respect to silver. 5χ10-3 Moerby. In the silver fine particles of the present invention, the halogen is contained in an amount of 5. 莫 ΗΓ 8~1·8χ1〇_6 molar ratio, and the average particle size is 15~〇_5μηι. The halogen contains greater than UxiO-6 and 3. Mox ratio below 0x10-5, and the average particle size is 〇. 5 ~ 〇. 丨 5 μιη can also. The halogen contains more than 3. relative to the silver. Οχ 10·5 and 1. 5x1 〇-3 below the molar ratio, and the average particle size is 〇. 15~0. 08μιη is also available. The method for producing silver fine particles of the present invention is a step of reducing silver ions and depositing silver fine particles by adding a reducing agent to a silver ion solution, and reducing silver ions in the presence of a core material as a silver fine particle core, thereby precipitating The silver particles. In the first aspect of the method for producing silver fine particles of the present invention, the silver ions are reduced in the presence of a halide ion, and silver halide is formed as the core forming material, and the silver fine particles are precipitated. In the first aspect of the method for producing silver fine particles, the particle size of the precipitated silver fine particles may be controlled by adjusting the halide concentration with respect to the silver concentration. The silver ion solution is a silver nitrate solution using ammonia water, and the 200911417 raw agent is a hydroquinone solution, and the halide ion-containing compound is ammonium chloride (NH4C1), ammonium bromide (NH4Br), and iodine. Ammonium (NH4I), potassium chloride (KC1), potassium bromide (KBr), potassium iodide (KI), sodium chloride (NaCl), sodium bromide (NaBr), or sodium (Nal) may also be used. When iodide ions are used as the halide ions and the silver ions are reduced, (1) the molar ratio (silver iodine molar ratio, I/Ag) relative to silver iodine is adjusted to 5·0χ1 (Γ8~1·8χ10_6 order) Average particle size 1. 5~0. 5 μπι of silver microparticles are precipitated, or (ii) the silver iodide molar ratio is adjusted to be greater than 1. 8xl (T6 and 3. 0χ10_5 The following order makes the average particle size 0. 5~0. 15 μηι of silver particles are precipitated, or (iii) the silver iodide molar ratio is adjusted to be greater than 3. 0xl (T5 and 1. 5xl (average particle size 0 below T3). 1 5~0. The silver fine particles of 0 8 μηι can also be precipitated. The silver ion solution is a silver nitrate solution containing a silver concentration of 5 Og/L or more added with ammonia water, the reducing agent is a hydroquinone solution, and the tooth ion is a molar ratio using iodide ions and iodine relative to silver. (I/Ag) is adjusted to 5. 0x 1 (Γ8~1. 5x1 (Γ3, the average particle size is 1 . The yield of silver fine particles of 5~0·08μηι may be 99% or more. A second aspect of the method for producing silver fine particles of the present invention is a primary reducing agent for hydrazine and a secondary reducing agent having a stronger reducing power than the primary reducing agent, and in the presence of a small amount of the secondary reducing agent in the silver ion solution The main reducing agent is added to form silver fine particles as the colloid forming the nuclear material, and the silver fine particles are precipitated. In the second aspect of the method for producing silver fine particles of the present invention, by adjusting the amount of the sub-reducing agent added, the particle size of the precipitated silver fine particles can be controlled to be -8-200911417, and the secondary reducing agent relative to the silver concentration. Moerby (silver secondary reductant ratio) is controlled at 2. 5xl0·7~5. 0X10-1 and, let the average particle size 1. 5~0. The silver microparticles of 05 μπι can also be precipitated. (i) adjusting the silver secondary reducing agent ratio to 2. 5χ1〇-7~3. 0χ10·5 order average particle size 1. 5~0·5μιη of silver fine particles are precipitated' or (ii) the silver secondary reducing agent ratio is adjusted to be greater than 3·0χ10_5 and 4_2xl0_2 or less to give an average particle diameter of 0. 5 ~ Ο. The silver particles of ίμηι are precipitated, or (iii) the silver secondary reducing agent ratio is adjusted to be greater than 4. 2x10 · 2 and 5. 0x10" The following order average particle size 0. 1~0. The silver particles of 05μηι can also be precipitated. The silver ion solution is a silver nitrate solution to which ammonia water is added, the main reducing agent is a hydroquinone solution, and the secondary reducing agent may be hydrazine. a solution for mixing a small amount of the hydrazine solution of the secondary reducing agent in the hydroquinone solution of the main reducing agent, or adding a small amount of the hydrazine solution of the secondary reducing agent to the silver ion solution, and immediately adding the primary reducing solution The hydroquinone liquid may also be used in the third aspect of the method for producing silver fine particles of the present invention, wherein silver nanoparticle is added to the silver ion solution as the core material, and in the presence of the silver nanoparticles When the silver ions are reduced, the silver fine particles can be precipitated. In the third aspect of the method for producing silver fine particles, the particle diameter of the precipitated silver fine particles may be controlled by adjusting the amount of the silver nanoparticles to be added to the silver concentration. The silver ion solution may be a silver nitrate solution to which aqueous ammonia is added, and the reducing agent may be a hydroquinone solution, and a silver nanoparticle having an average particle diameter of 50 nm or less may be added. -9 - 200911417 (υ The ratio of the number of silver ions contained in the silver ion solution is adjusted to 5. The ratio of the silver nanoparticles to silver ions. 〇xl〇_7 ~3. 0xl (T6 makes the average particle size 1. 5~0·5μιη silver particles are precipitated, or (ii) the silver ion silver nanoparticle ratio is adjusted to be greater than 3. 0xl (T6 and 2·5Χ 1 (Γ5 below the average particle size of 0. 5~0. 1 μηι of silver particles are precipitated, or '(iii) the silver ion silver nanoparticle ratio is adjusted to be greater than 2. 5χ1 (Γ5 and 1·5Χ 10 _4 or less to make the average particle size 〇. 1~0. 02 μηι silver particles can also be precipitated. The silver nanoparticles may be used in the presence of citric acid soda, and silver nitrate particles having an average particle diameter of 20 nm or less formed by reducing silver ions by adding ferrous sulfate to a silver nitrate solution. In a fourth aspect of the method for producing silver fine particles of the present invention, ammonia is added to the silver ion solution, and the reducing agent is added within 20 seconds after the ammonia is added, whereby silver hydroxide or silver oxide can be formed as the core. The substance, and the silver fine particles are precipitated. In the fourth aspect of the method for producing silver fine particles, the particle diameter of the precipitated silver fine particles may be controlled by adjusting the time until the addition of the ammonia until the addition of the reducing agent. Regarding the time until the addition of the ammonia until the addition of the reducing agent (time), (i) the elapsed time is 〇. 3~0. The average particle size is within 5 seconds. 2~0. 5 μηι of silver particles are precipitated, or (ii) the elapsed time is longer than 0. 5 seconds and 2 seconds to achieve an average particle size of 0. 5 μιη~1 . 5 μηη of silver fine particles are precipitated, or (iii) the silver fine particles having an average particle diameter of 1·5 μηι 2 to 0·0η are precipitated for a period of time longer than 2 seconds and 5 seconds or (iv) the elapsed time is longer than 5 seconds and 20 seconds to make the average particle size -10- 200911417 2. 0μιη~2. It is also possible to precipitate 5 μm of silver fine particles. The apparatus for producing silver fine particles of the present invention is a manufacturing apparatus for adding silver and a reducing agent to a silver ion solution, and reducing silver ions to precipitate silver fine particles, having a silver ion solution tank, and continuing to the first line of the silver ion solution tank, An ammonia solution tank, a second line connected to the ammonia solution tank, a reducing liquid tank, a third line connected to the reducing liquid tank, and an intersection of the first line and the second line The fourth conduit mixes the reducing liquid from the third conduit with the mixture of silver ions and ammonia solution from the fourth conduit. In the apparatus for producing silver fine particles according to the present invention, the third conduit and the fourth conduit are arranged such that the opening portions of the end portions of the conduits are slightly separated from each other, and the first conduit and the first conduit are The length of the flow path up to the end of the fourth conduit at the intersection of the second conduit can also be adjusted. (Effects of the Invention) The silver fine particles of the present invention are silver fine particles produced by reducing silver ions in the presence of halide ions, and the halogen is contained in 5. 0 X 1 0 _8 ~1 . The molar ratio of 5 Οχ 1 0_3 is finely dispersed silver fine particles. In the method for producing silver fine particles according to the first aspect of the present invention, silver ions are reduced in the presence of halide ions to produce silver fine particles having excellent fine dispersibility, and the silver fine particles can be produced stably and efficiently. According to the method for producing silver fine particles according to the first aspect of the present invention, silver halide is preferentially formed during silver ion reduction, and forms a core material to form a core. Thereafter, silver halide is used as a crystalline primary particle of a core-shaped silver, and the primary particles -11 - 200911417 are agglomerated with each other to form silver fine particles. Compared with the case where halide ions are not present, the initial nucleus can be formed easily and surely with a small amount of energy, and the initial number of nucleuses can be increased, and the number of agglomerated center points of the primary particles can be increased. Therefore, fine silver fine particles can be precipitated stably and efficiently. Further, according to the method for producing silver fine particles according to the first aspect of the present invention, the particle diameter of the precipitated silver fine particles can be controlled by adjusting the halide ion concentration with respect to the silver concentration. Therefore, by adjusting the above halogen concentration, for example, the average particle diameter of 1 _ 5~0 can be obtained with high efficiency. 5 μηι silver particles, average particle size 〇. 5~0. 15 μιη silver particles, or an average particle size of 0. Silver fine particles having a particle diameter of 1 5 to 0·08 μηι, such as silver particles. Further, according to the production method of the first aspect of the present invention, by using a silver ion solution having a high concentration, fine silver fine particles can be efficiently produced. Specifically, for example, a silver nitrate solution having a silver concentration of 50 g/L or more added to aqueous ammonia can be used to obtain an average particle diameter of 1 9 % or more. 5~0. 0 8 μιη silver particles. Further, in the method for producing silver fine particles according to the first aspect of the present invention, since silver ions are reduced in the presence of halide ions, a halide ion source (a compound having a halide ion) may be added together with the reducing solution, and A special device structure for injecting a reducing liquid into the pipeline is required, so that it can be easily implemented. In the method for producing silver fine particles according to the second aspect of the present invention, the primary reducing agent and the secondary reducing agent having a stronger reducing power than the primary reducing agent are added, and the primary reducing agent is added to the silver ion solution in the presence of a small amount of the secondary reducing agent. , the silver particles are precipitated. A plurality of colloidal fine silver fine particles are initially formed by a reducing agent having a strong reducing power. Thereafter, colloidal fine silver fine particles are used as nuclei to form crystalline primary particles of -12-200911417 silver, and the primary particles are agglomerated with each other to form silver fine particles. Compared with the case where there is no secondary reducing agent which is stronger than the reduction of the main reducing agent, the initial nuclear nucleus can be easily and surely formed with a small energy, and the initial nuclear number can be increased, and the agglomerating center of the primary particles can also be increased. Points. Therefore, fine silver fine particles can be obtained stably and efficiently. Further, according to the method for producing silver fine particles according to the second aspect of the present invention, by adjusting the amount of the sub-reducing agent added, the particle diameter of the precipitated silver fine particles can be controlled, and for example, the average particle diameter can be efficiently and stably produced. 5~0. 5 μιη silver microparticles, average particle size 0. 5~0. 1 μηη silver microparticles, or an average particle size of 0. 1~0. Further, in the silver microparticles according to the second aspect of the present invention, fine silver microparticles can be efficiently produced by using a silver ion solution having a high concentration. Specifically, for example, using a silver nitrate solution having a silver concentration of 5 Og/L or more added with ammonia water, an average particle diameter can be obtained at a yield of 99% or more. 5~0. 05μιη silver particles. Further, in the method for producing silver fine particles according to the second aspect of the present invention, the main reducing agent and the sub-reducing agent are used, and the main reducing agent may be added in the presence of the sub-reducing agent, and it is not necessary to inject the reducing liquid into the piping. The device structure is easy to implement. The method for producing silver fine particles according to the third aspect of the present invention is a step of producing silver fine particles by reducing silver ions, adding silver nanoparticles, and reducing silver ions in the presence of the silver nanoparticles, which is stable and has Efficiency produces fine silver particles. In the method for producing silver fine particles according to the third aspect of the present invention, a large number of fine silver natriene-13-200911417 particles are present in the liquid at the time of silver ion reduction, and this is formed as a nuclear material to form a core. Next, the particles act as nuclei and form crystalline primary particles of silver, and this initially aggregates to form silver fine particles. Compared with the absence of silver nanoparticles, the initial nuclear formation is increased, and the initial number of cores and the number of agglomerated centers of the primary particles can be arbitrarily increased. Therefore, silver fine particles can be stabilized and effectively fine. Further, according to the silver fine particles of the third aspect of the present invention, the amount of the silver nanoparticles to be added is adjusted to control the silver diameter of the precipitate, and for example, the average particle diameter can be obtained efficiently and stably. 5~0. Microparticles, average particle size 0. 5~0. 1 μηι of silver particles, or 0. Further, according to the silver fine particle method of the third aspect of the present invention, silver fine particles having a particle diameter of 1 to 0_02 μπι can be efficiently produced by using a high-concentration silver ion solution according to the silver fine particle method of the third aspect of the present invention. Specifically, for example, by using a silver nitrate solution added to the silver concentration of ammonia water, silver fine particles of 1·5 μη or less can be obtained at a yield of 99% or more. Further, in the silver microparticles of the third aspect of the present invention, silver nanoparticles may be added, and the addition of the silver ion solution and the reducing solution is not limited, so that it is not necessary to inject a special reducing liquid into the pipeline. Implementation. In the method for producing silver fine particles according to the fourth aspect of the present invention, a reducing agent is added within 20 seconds, and silver hydroxide (AgOH) or silver oxide (Ag20) before the formation of the ammonia complex is used as a nucleation forming nucleus. Thereafter, silver hydroxide or silver oxide is used as a core to form silver nanoparticles, and the rate of micro-particles is 5 μm. The fine silver fine 50g/L is produced by the average particle diameter method. If the method is added and the structure is added, the ammonia is temporarily added to the material and the crystal grain is large -14-200911417 is a crystalline primary particle of 25 nm to 150 nm. , agglutinating each other to form silver particles. If the number of cores is large and the number of heart points is large, the size of the silver particles becomes small. Therefore, silver and silver oxide are present in many cases, and if 20 seconds of the original agent is added to ammonia, fine silver particles can be obtained stably and efficiently. For example, fine silver having an average particle size can be obtained at an efficiency of 99% or more. particle. On the other hand, if the time until the addition of ammonia is long, the total amount of silver oxynitride produced in the initial stage of mixing changes or the silver ammonia complex, and therefore it cannot function as a nucleus. Therefore, the particles of the silver fine particles to be synthesized cannot be produced. According to the silver fine particles of the fourth aspect of the present invention, the average particle diameter can be produced by adding the reducing agent until the addition of the reducing agent. Silver microparticles of 2μηι~2_5μιη. Further, in the manufacturing apparatus of the present invention, the silver microparticles of the fourth aspect can be easily produced from the liquid electrolyte solution and the ammonia solution from the fourth conduit, and the silver microparticles of the fourth aspect can be easily changed. 1 The length of the flow path from the pipe intersection to the end of the fourth pipe, and the elapsed time until the addition of the reducing agent after the addition of ammonia. [Embodiment] Hereinafter, the present invention and examples will be specifically described. (First Embodiment) The conjugation of the primary particles is added to the inside of the hydrogen hydroxide of the core. Specifically, the diameter is 2. Addition of 5 μm or less The addition of reducing agent to or silver oxide has little control over nuclear growth stability. Sub-manufacturing method After the elapsed time, the three-line reduction mixed liquid mixture is mixed. Further, the second pipe can be easily adjusted. -15-200911417 The silver fine particles of the present invention are silver fine particles produced by reducing silver ions in the presence of halide ions, and the halide contains 5 with respect to silver. Ox 1 0_8 ~1. 5 xl (the molar ratio of T3 is a fine fine particle of silver fine particles. The silver fine particles of the present invention are a method of adding a reducing agent to a silver ion solution to reduce silver ions to precipitate silver fine particles, in the presence of halide ions Silver ions can also be produced in principle. In this manufacturing method, the particle size of the precipitated silver particles can be controlled by adjusting the concentration of the halide ions relative to the concentration of silver. The silver ion solution can be a silver nitrate solution added with aqueous ammonia. Etc. A silver ammonia complex is formed via the presence of ammonia, and silver is reduced and precipitated by adding a reducing agent. The reducing solution can be a hydroquinone solution, a pyrogallol solution, or a 3,4-dihydroxytoluene-like phenol group. An organic reducing agent solution, etc. The amount of the reducing agent added is preferably such that the silver ions in the liquid are sufficiently reduced and the silver fine particles are precipitated. The halide ion source (a compound having a halide ion) may be ammonium chloride (NH4C1). Ammonium bromide (NH4Br), ammonium iodide (ΝΗ4Ι), potassium chloride (KC1), potassium bromide (KBr), potassium iodide (ΚΙ), sodium chloride (NaCl), sodium bromide (NaBr), or iodinated Sodium (Nal In addition, iodine, bromine, and chlorine tend to have a finer refining effect. By the presence of a halide ion, silver halide is preferentially formed during the reduction of silver ions, and a nuclear material is formed as a core to form a core. a silver halide crystallized primary particle formed by silver halide as a core, and the primary particles agglomerate to each other to form silver fine particles. Compared with the case where the halide ion is not present, the initial core can be easily and surely formed with a small amount of energy. The number of cores of the initial-16-200911417 can be increased, and the number of agglomeration centers of the initial particles can be increased. Therefore, fine silver particles can be precipitated stably and efficiently. If halide ions are not present, silver groups are formed by silver ion reduction. In the case of a cluster nucleus, it requires a large amount of energy in the formation of a nucleus, and it is not easy to form an initial nucleus. Therefore, the initial number of nucleuses decreases, and the number of agglomerated center points of the primary particles also decreases, so that it is difficult to obtain fine silver granules. Concentration, for example, in a solution in which ammonia water is added to a silver nitrate solution, and when the hydroquinone solution is added to reduce silver ions, the molar relative to the silver iodine The ratio (silver iodine molar ratio, I/Ag) is suitably 5.0·10·8·8 or more, and an average particle diameter of 1 can be obtained. Silver particles below 6 μηη. Further, the higher the molar ratio of iodine relative to silver, the finer the silver fine particles can be obtained. Specifically, the molar ratio to iodine relative to silver is 1. 0 X 1 (In the range of Γ7 or more, for example, using a silver nitrate solution having a silver concentration of 50 g/L or more, an average particle diameter of 1·5 μmη~0 can be obtained at a yield of 99% or more. Silver particles of 08μηι. On the other hand, if the amount of the halide added is too large, the shape of the silver fine particles is hard to change or spherical, or it is easy to aggregate. Therefore, the molar ratio to the halide of silver is 1 . In the method for producing silver fine particles according to the first embodiment, the particle size of the precipitated silver fine particles can be controlled by adjusting the halogen concentration with respect to the silver concentration. For example, it is added to the silver nitrate solution to which aqueous ammonia is added. When the hydroquinone solution reduces silver ions and precipitates silver fine particles, the molar ratio (I/Ag) relative to silver iodine is adjusted as follows, and an average particle diameter of 0 can be obtained. 08μιη~1 . 5 μιη silver microparticles. (i) Adjust the silver iodide ratio (I/Ag) to 5. 0xl (T8~1. 8xl (T6 </ /> -17- 200911417 can precipitate an average particle size of 1 . 5 ~0. 5 μιη silver particles. (Π) adjust the silver iodine molar ratio to be greater than 1. 8χ10·6 and 3. Below 0Χ10·5, the average particle diameter can be precipitated. 5 ~0. 1 5 μιη silver particles. (iii) adjusting the above silver iodide molar ratio to be greater than 3·0χ10·5 and l. Below 5x W3, silver fine particles having an average particle diameter of 0·15 to 0·08 μm can be precipitated. In the method for producing silver fine particles according to the first embodiment of the present invention, the particle size controllability of the precipitated silver fine particles is excellent, and the particle size of the precipitated silver fine particles is the same silver halide molar ratio, and the test 1 is obtained one after another. The average particle size ranges from -10% to 10%. Further, the chemical solution prepared by the method for producing silver fine particles according to the first embodiment is excellent in stability over time, and the particle diameter of the silver fine particles synthesized within 9 hours after preparation is changed to within -10% to 1%. The method for producing silver particles in the form of a gas is that halide ions are present during the reduction of silver ions, so that the precipitated silver particles contain a halide, and the silver ions are reduced to precipitate silver particles and gradually grow, so that the halogen is contained in The interior of the silver particles. Therefore, halogen is hardly eluted, and silver fine particles are hardly affected by halogen. (Second Embodiment) The method for producing silver fine particles according to the second embodiment is a step of adding a reducing agent to a silver ion solution, and reducing silver ions to precipitate silver fine particles, and using a main reducing agent and being stronger than the main reducing agent. A reducing agent for reducing power, and a main reducing agent is added to the silver ion solution in the presence of a small amount of a sub-reducing agent to precipitate fine silver particles. By adjusting the amount of the sub-reducing agent added, -18-200911417 can control the particle size of the precipitated silver fine particles. As the silver ion solution, a silver nitrate solution to which ammonia water is added or the like can be used. A silver ammonia complex is formed in this solution, and silver is reduced and precipitated by adding a reducing agent. In the method for producing silver fine particles according to the second embodiment, a primary reducing agent and a secondary reducing agent having a stronger reducing power than the primary reducing agent are used. The main reducing agent may be an organic reducing agent solution having a phenol group like a hydroquinone solution (OH(C6H4)OH), a caroline phenol solution or a 3,4-dihydroxytoluene solution. As the secondary reducing agent, hydrazine solution (N2H4), sodium borohydride (NaBH4), dimethylamine boron (BH3.HN(CH3)2), or the like, and hydrazine having a strong reducing power can be used. Using a primary reducing agent and a secondary reducing agent having a greater reducing power than the primary reducing agent, and adding a primary reducing agent in the presence of a secondary reducing agent in the silver ion solution, initially via a prosthetic Silver® can easily and accurately form the initial nucleus at a lower energy. It can increase the initial number of cores and increase the number of agglomerated center points of the primary particles. Therefore, for example, the average particle diameter 〇 can be obtained stably and efficiently. Fine silver particles of 5 μηι or less. Further, if the primary reducing agent having a weak reducing power is present in the absence of the secondary reducing agent, silver ions are also formed in principle to form a cluster core. At this time, a large amount of g is required on the generation core, and the initial core cannot be easily formed. Therefore, the number of initial nuclei is small, and the number of agglomerated center points of the primary particles is also small, so that it is difficult to obtain fine silver fine particles. The amount of the main reducing agent is sufficient to sufficiently reduce the amount of silver ions in the silver ion solution. The amount of the by-reduction agent may be a part of the amount of colloidal silver fine particles which is initially produced in a sufficient amount. When the amount of the by-reduction agent is too large, the silver fine particles become aggregates, and it is difficult to obtain fine silver fine particles having good dispersibility. Specifically, the molar ratio of the secondary reducing agent relative to the silver concentration (silver pair -19-200911417 reducing agent ratio: [sub-reducing agent] / [Ag]) is controlled to 2. 5 xlO·7~5. 0x1 (Γ1, the average particle size can be made 1 · 5~0. 0 5 μπι silver particles. For example, a silver nitrate solution containing ammonia water is used, and the main reducing agent is a molar ratio of hydrazine to the silver concentration when the hydroquinone solution and the secondary reducing agent are used as hydrazine (the silver-linked ammonia ratio: N2H4/Ag). For 2. 5χ10·7~5. The amount of 0Χ10·1 is appropriate, and the range of the added amount can be obtained at an average particle diameter of 99% or more. Silver particles of 5~0_05μπι. Further, when the primary reducing agent is added and the secondary reducing agent is added every other time, the above effects cannot be obtained. Therefore, it is preferred to add a small amount of a secondary reducing agent to the main reducing agent, or to add a primary reducing agent immediately after adding a small amount of the secondary reducing agent. In the method for producing silver fine particles according to the second embodiment, the particle size of the precipitated silver fine particles can be controlled by adjusting the ratio of the silver-based reducing agent. For example, when a hydroquinone-containing hydroquinone solution is added to a silver nitrate solution containing ammonia, and silver ions are reduced to precipitate silver fine particles, the silver-linked ammonia ratio (N2H4/Ag) is adjusted as follows to obtain an average particle diameter of 1 _ 5~ 0. 0 5 μ m of silver particles. (i) Adjust the UnionPay ammonia ratio to 2. 5 X 1 0·7 ~ 3 · 0 X 1 〇_5 , the average particle size can be obtained. 5~5. Ομιη silver particles. (ii) Adjusting the Union's ammonia ratio to greater than 3·Οχ1〇-5 and 4. 2xl (below T2) can obtain silver fine particles with an average particle diameter of 0 · 5 ~ 0 · 1 μ m. (i i i) Adjust the silver-linked ammonia ratio to be greater than 4. 2 X 1 0 _2 and 5 _ 〇 X 1 〇 ·1 or less, the average particle diameter of 0 can be obtained. Silver particles of 1 to 0 · 0 5 μηη. (Third Embodiment) -20-200911417 The method for producing silver fine particles according to the third embodiment is a step of adding a reducing agent to a silver ion solution and reducing silver ions by silver ions, and adding silver nanoparticles thereto. When silver ions are reduced in the presence of silver nanoparticles, fine silver fine particles can be precipitated. By adjusting the amount of silver nanoparticle added to the silver concentration, the particle size of the precipitated silver fine particles can be controlled. As the silver ion solution, a silver nitrate solution to which ammonia water is added or the like can be used. A silver ammonia complex is formed in this solution, and silver is reduced and precipitated by adding a reducing agent. As the reducing liquid, an organic reducing agent solution having a phenol group such as hydroquinone solution, pyrogallol solution or 3,4-dihydroxytoluene can be used. The silver nanoparticle is a nanometer-sized silver particle (silver colloidal particle), and may be added to a silver ion solution. The silver nanoparticles used are preferably an average particle diameter of 50 nm or less, and have an average particle diameter of 2. Suitable for 5 nm to 20 nm 〇 Silver nanoparticles are obtained by adding ferrous sulfate to a silver nitrate solution in the presence of citric acid soda, and reducing silver ions to form silver nanoparticles having an average particle diameter of 20 nm or less. The ferrous sulfate and the citric acid soda are premixed, and the silver nitrate solution is put into the mixed solution at room temperature to reduce the silver nitrate. The silver concentration of the silver nitrate solution is suitably 1 to 2 00 g/L. The amount of the ferrous sulfate is sufficient to sufficiently reduce the amount of silver nitrate. Further, the amount of citric acid soda is 2 to 7 times the number of silver moles. The mixing of the silver nitrate solution and the ferrous sulfate solution is preferably carried out by adding 5 to 20 mL/min to one supply nozzle. After mixing, stir to homogenize the reaction. Silver was reduced by this reaction to obtain a silver colloidal liquid containing silver ultrafine particles (silver nanoparticles) having a particle size of nanometer. The silver colloidal liquid was solid-liquid separated and the solid component separated from -21 - 200911417 was washed with citric acid soda to obtain a silver colloidal liquid in which silver nanoparticles were dispersed. Silver nanoparticles are added to the silver ion solution, and the silver nanoparticles are used as a core to form crystalline primary particles of silver, and the primary particles are agglomerated with each other to form silver fine particles. In the case where silver nanoparticles are not present, an initial nucleus is formed, and the initial number of nucleus can be arbitrarily increased, and the number of aggregation center points of the primary particles can be increased. Therefore, it becomes fine silver fine particles, and for example, the average particle diameter 1 can be obtained stably and efficiently. Fine silver particles of 5 μηι or less. In addition, if silver nanoparticles are not present, the silver clusters are formed in the form of initial nucleus by reduction of silver ions, but there is a large amount of energy in the formation nucleus, and the initial nucleus cannot be easily formed. Therefore, the initial number of cores is reduced, and the number of points of aggregation of the primary particles is also small, so that it is difficult to obtain fine silver particles. For example, when a hydroquinone solution is added to a silver nitrate solution containing ammonia water to reduce silver ions, the amount of silver nanoparticles added is 5_0χ10·7~1 with respect to the number of silver nanoparticles. . 5Χ10·4 is better. In the range of the amount of addition, for example, a silver nitrate solution having a silver concentration of 50 g/L or more is used, and an average particle diameter of 1.7% can be obtained at a yield of 99% or more. Silver microparticles below 5 μπι. Further, in the method for producing silver fine particles according to the third embodiment, the particle diameter of the precipitated silver fine particles can be controlled by adjusting the amount of silver nanoparticle added to the silver concentration. For example, when a hydroquinone solution is added to a silver nitrate solution to which ammonia is added, when the silver ions are reduced to precipitate silver fine particles, the ratio of the silver nanoparticles to the silver ions is measured (hereinafter, referred to as silver ions). The silver nanoparticle ratio is adjusted as follows, and silver fine particles having an average particle diameter of -22-200911417 1 _5~0_02 μπι can be obtained. (i) The ratio of silver ion silver nanoparticles is adjusted to 5·0χ10·7 ~3·0χ1 (Γ6, the average particle size is 1). 5~0. 5 μηι of silver particles. (Π) The silver ion silver nanoparticle ratio is adjusted to be greater than 3·0χ1 (Γ6 and 2. 5x1 0_5 or less, the average particle diameter is 0. 5~0. 1 μηη silver particles. (iii) adjusting the silver ion silver nanoparticle ratio to be greater than 2·5χ10_5 and 1. 5χ1 (Τ4 or less, and an average particle diameter of 0. Silver fine particles of 1 to 〇2〇ιη (Fourth Embodiment) The method for producing silver fine particles according to the fourth embodiment is a step of adding ammonia and a reducing agent to a silver ion solution, and reducing silver ions to precipitate silver fine particles. When a reducing agent is added within 20 seconds after the addition of ammonia, fine silver fine particles can be precipitated. A silver nitrate solution or the like can be used as the silver ion solution. If ammonia is added to the silver nitrate solution, a silver ammonia complex is formed, and silver is also precipitated in principle. As the reducing agent, hydroquinone solution (oh(c6h4)oh, hereinafter abbreviated as H2Q) or the like can be used. The amount of ammonia added is preferably such that the amount of silver ions in which no ammonia complex is formed remains in the liquid, and the amount thereof is 2 to 3 moles with respect to the ammonia of silver. The amount of the reducing agent added is preferably such that the amount of the unreacted silver ammonia complex remains in the liquid, and the amount is 0. Compared with the 1 mol of hydroquinone when the reducing agent is used in the hydroquinone. 3~1. 0 moles of the amount. In the method for producing silver fine particles according to the fourth embodiment, a reducing agent is added within 20 seconds after the addition of ammonia to the silver ion solution. A short time after the addition of ammonia -23-200911417, a reducing agent is added to form a nuclear material and form a core by forming silver hydroxide (AgOH) or silver oxide (Ag20) temporarily formed before the formation of the silver ammonia complex. Next, silver hydroxide or silver oxide is used as a core and silver-forming crystalline primary particles ' are formed and the primary particles are agglomerated with each other to form silver fine particles. If a large amount of silver hydroxide or silver oxide which does not form an ammonia complex is left within 20 seconds after the addition of ammonia, it becomes a nucleus. Therefore, in the case of reducing silver to form a silver-clad cluster core, the initial number of cores can be increased, and the number of agglomeration centers of the primary particles can be increased, so that, for example, the average particle diameter is 2. Fine silver particles of 5 μηι or less. On the other hand, when the ammonia is added for more than 20 seconds, the initially formed silver hydroxide and silver oxide become a silver ammonia complex, and the crystalline primary particles cannot be formed in the initial nucleation form of silver hydroxide and silver oxide. The initial nucleation number of the silver-clad cluster nucleus caused by the reduction of silver ions becomes a small amount, and the number of aggregation center points of the primary particles also becomes small, so that it is difficult to take fine silver fine particles. In the method for producing silver fine particles according to the fourth embodiment, after the addition of ammonia to the silver ion solution, the reducing agent is added within 20 seconds, so that ammonia is added to the silver ion solution to form a silver ammonia complex, and silver is formed. Those who add the reducing agent first in the ionic solution cannot use it. In the method for producing silver fine particles according to the fourth embodiment, the particle diameter of the precipitated silver fine particles can be controlled by adjusting the period of time after the addition of ammonia until the addition of the reducing agent in the range of 2 seconds or less after the addition of ammonia. Specifically, the particle size of the silver fine particles can be controlled by the elapsed time as follows. (i) adjust the above elapsed time to 0 · 3 seconds ~ 0. Within 5 seconds, the average particle size can be precipitated. 2 μηι~0. 5 μιη silver particles. (ii) If the above elapsed time is adjusted to be longer than 0.5 seconds and is 2 seconds -24-200911417, the average particle diameter of 0 can be precipitated. 5 μπι~1. 5 μπι silver particles. (iii) If the above elapsed time is adjusted to be longer than 2 seconds and within 5 seconds, the average particle size of 1 · 5 μπι ~2 can be precipitated. 0 μιη silver particles. (iv) If the above elapsed time is adjusted to be longer than 5 seconds and within 20 seconds, the average particle diameter can be precipitated. 0μιη~2. 50 μϊη of silver particles. The apparatus for producing silver fine particles according to the present embodiment is a manufacturing apparatus for reducing silver ions and depositing silver fine particles by adding ammonia and a reducing agent to a silver ion solution. An example of such a manufacturing apparatus is shown in FIG. As shown in the figure, the apparatus for producing silver fine particles of the present embodiment has a silver ion solution tank 1 〇, a first line 13 connected to the silver ion solution tank 1 端 end, an ammonia solution tank 1 1 , and an ammonia solution. The second line 14 of the groove U is connected, the reducing liquid tank 1 2 , the third line 15 connected to the end of the reducing liquid tank 1 2 , and the intersection of the second line of the first line and the second line The fourth line 16 is discharged. The fourth conduit 16 and the third conduit 15 are such that the other end portions of the conduits are slightly spaced apart from each other and disposed opposite each other. In the above device configuration, the silver ion solution is flowed from the silver ion solution tank 10 toward the other end of the first pipe 13 . An aqueous ammonia solution flows through the aqueous ammonia solution tank toward the other end of the second conduit 14. The reducing liquid flows from the reducing liquid tank 12 toward the other end of the third line 15. At the intersection of the first conduit 13 and the second conduit 14, the silver ion solution is mixed with the aqueous ammonia solution. This intersection is the mixing position of the silver ion solution and the aqueous ammonia solution. Then, a mixed liquid of a silver ion solution and an aqueous ammonia solution and a reducing liquid are discharged from the openings of the respective ends of the fourth conduit 16 and the third conduit 15, and are mixed and mixed on the outside of the conduit. Between the opening of the fourth conduit 16 and the end of the third conduit 15 is -25-200911417. The mixing position of the mixture of the silver ion solution and the aqueous ammonia solution and the reducing solution B° flows out of the silver ion solution tank 10. The silver ion solution 'firstly mixes with the aqueous ammonia solution at the intersection (mixing position A) of the first line 13 and the second line 14 . Then, the mixed solution of the silver ion solution and the aqueous ammonia solution flows toward the end portion of the other end of the fourth conduit 16 and is discharged to the outside through the opening of the other end portion. Thereafter, the mixed liquid of the silver ion solution and the aqueous ammonia solution and the fast liquid solution e discharged from the opening of the other end portion of the third line 15 are mixed and mixed at the mixing position B outside the pipe. The time until the addition of the reducing solution after the addition of ammonia is based on the length of the line (flow path length) L of the mixing position A and the mixing position B (the intersection of the first line 13 and the second line 14 until the fourth line) The distance from the other end of the 16 or the length of the pipe of the fourth line 16 is determined, and the length of the pipe (flow path length) L is set by adding a reducing liquid within 20 seconds after the addition of ammonia. The mixed liquid mixed in the mixing position B is collected, for example, via the mixed liquid collecting tank provided below the mixing position B. The trapped mixture was filtered to obtain silver fine particles. In the above-described apparatus configuration, the fourth line 16 and the third line 15 of the mixing position B are slightly separated from each other and are disposed opposite to each other with the opening of the end portion of the line. When the openings of the end portions of the pipelines are separated from each other and are disposed opposite each other, the ammonia silver ion solution added through the fourth conduit 16 and the reduction through the third conduit 15 can be reduced in the pipeline. The outer side is mixed' and the deposition space of the silver fine particles is formed in the open space outside the pipeline. Therefore, silver fine particles are not adhered to the inner wall of the pipe, and the problem of mixing coarse particles is not caused, so that silver fine particles having a uniform particle diameter can be obtained. -26- 200911417 In addition, the intersection of the first line 13 and the second line 14 (mixing position A) is formed so as to be movable, or the line from the mixing position a to the mixing position B (the fourth line 1) 6) The tube length (flow path length) L of the mixing position A to the mixing position B can be formed in an adjustable manner, and the elapsed time from the addition of ammonia until the addition of the reducing liquid can be adjusted. Further, the other end of the fourth conduit 16 is connected to the other end of the third conduit 15, and a part of the intersection is an opening, and the mixed liquid may be configured to be quickly discharged from the opening to the outside of the conduit. At this time, the connection portion between the fourth conduit 16 and the third conduit 15 becomes a mixing position b of the silver ion solution and the reducing solution. [Examples] Hereinafter, the present invention is specifically shown by way of examples. Further, the measurement of the particle diameter is carried out based on the laser scattering/dipping method and calculated on the basis of the number. (Example 1) A hydroquinone solution containing ammonium iodide solution was added to a silver nitrate solution to which ammonia water was added to reduce silver ions and precipitate silver fine particles. The compositions of ammonia water, silver nitrate solution, and hydroquinone solution are shown in Table 1. Further, the amount of use of the ammonium iodide solution relative to the molar ratio of silver to iodine is shown in Table 2. The average particle diameter of the precipitated silver microparticles 'the yield and the iodine content are shown in Table 2. Further, regarding the sample of the portion, the SEM photograph of the particles is shown in Fig. 3 to Fig. 6. Further, in Table 2, samples a 1 to A 1 1 were samples of the present invention. If the ammonium iodide solution is not added, the comparison sample 1 a indicates that the iodine addition amount is more than the better range. -27- 200911417 is expressed by comparing § formula 1 b. The particle diameter of the Ag fine particles is controlled to show a range of variation [μητ] with respect to the average particle diameter, and the yield is expressed by a percentage [%]. ΝΗ4 I water bath concentration in the sample a丨~sample a 7 is 〇 _ 〇 2 %, and the sample A8 ~ sample All b b is 2% than the sample 1 b. Further, the average particle size of the silver fine particles with respect to the amount of iodine added is shown in Fig. 1 as 1 〇 ^ _. The measurement in the figure is shown in the figure -> μ 下 戌 戌 二 二 β β β β β β β β β β β β β β β β β
-28- 200911417 [表2] nh4i 液量(g) 碘添加 量(g) I/Ag 莫耳比 Ag微粒子 SEM像 粒徑 (μπι) 粒徑控 制(μπι) 碘素 (ppm) 產率 (%) 比較試 料la 0.000 0 0 1.67 >0.50 0 99.0 圖3 試料A1 0.033 5.78xl0'6 4.91xl〇·8 1.45 <0.15 0.06 99.6 試料A2 0.330 5·78χ10·5 4.91χ1〇·7 1.40 <0.14 0.6 99.5 圖4 試料A3 0.750 1.31Χ10-4 1_12χ10·6 0.75 <0.08 1.3 99.4 - 試料A4 1.200 2.10Χ10-4 1.79x10-6 0.50 <0.05 2.1 99.6 - 試料A5 1.650 2.89Χ10·4 2.46x10'6 0.40 <0.04 2.9 99.8 圖5 試料A6 4.000 7.00x1 Ο·4 5.95x10'6 0.30 <0.03 7 99.5 - 試料A7 8.200 1.44x1 Ο·3 1.22x10'5 0.22 <0.02 14 99.3 圖6 試料A8 0.200 3.50x10° 2.98x10'5 0.16 <0.02 35 99.5 - 試料A9 0.500 8.76x103 7.44x105 0.13 <0.01 88 99.7 - um A10 2.500 4.38χ10'2 3.72χ10'4 0.10 <0.01 438 99.6 _ 試料 All 10.000 1.75x10] 1.49x10'3 0.08 <0.01 1751 99.4 - 比較試 料lb 20.000 3.50x1ο-1 2.98χ10'3 0.15 >0.05 3500 99.2 - 如表2及圖1所示般，未添加碘化銨的比較試料中析 出平均粒徑1 · 5 μιη以上的銀微粒子，但若存在碘化物離子 則銀微粒子變爲微細，根據碘化物離子量令銀微粒子的平 均粒徑變化。具體而言，（i)銀碘莫耳比（I/Ag)爲5.0x10· 8〜1.8χ10·6之範圍，析出平均粒徑！·5〜〇.5μιη的銀微粒子 ’（ii)銀碘莫耳比爲大於1.8xl0·6且3·〇χ1〇.5以下範圍， 析出平均粒徑0.5〜1_5μηι的銀微粒子，（iii)銀碘莫耳比爲 大於3_0xl0-5且15χ1〇-3以下之範圍，析出平均粒徑 〇· 1 5〜〇.〇8μηι的銀微粒子。 -29- 200911417 又，如表2及圖1所示般，本發明之銀微粒子爲粒徑 的控制性良好，且實施例之銀微粒子的粒徑均爲試驗1 〇 次求出之平均粒徑的-10%〜10%範圍內（表2的粒徑控制） 。更且，本發明所用之藥液爲經時安定性亦優良，調製後 9小時以內所合成之銀微粒子的粒徑亦收在-1 0 %〜1 0 %的範 圍。 (實施例2) 於加入氨水之硝酸銀溶液中，添加預先加入鹵化銨溶 液的對苯二酚液（鹵化物的莫耳數·· 2.8 2 X 1 0·5 )，將銀離子 還原並析出銀微粒子。硝酸銀溶液，對苯二酚液、銨液爲 使用表1中所示者。鹵素之種類爲如表3所示般，使用 NH4C1、NH4Br、NH4I。測定析出之銀微粒子的平均粒徑 。平均粒徑的測定方法爲同實施例丨。其結果示於表3及 圖7〜圖10。另外，表3中，試料B1〜試料B3爲本發明試 料。未添加鹵化銨液者以比較試料2表示。又，鹵化物鹽 液爲0 · 1 Μ水溶液’銀溶液及還原液爲同表1。如表3及 圖7~圖1 0所示般’以碘、溴、氯之順序對於銀粒子的微 細化效果漸強。 -30- 200911417 [表3] 鹵素之種類 試料B1 試料Β2 試料B3 NH4C1 NH4Br NH4I 液量(μι) 0 300 300 300 鹵素量(g) 0 1.06xl〇-3 2.39xl〇·3 3.80xl0'3 對Ag莫耳比㈠ Ag 粒徑(μιη) 0 -----— 3.23x1 Ο·5 3.23xl〇-5 3.23xl〇·5 ___ 0.40 0.20 0.12 SEM像 ____B 7 - ---- 圖8 圖9 圖10 (實施例3 ) 除了使用表4所示之鹵化鹽水溶液代替實施例2之鹵 化鞍 '液以外’以實施例2相同條件將銀離子還原且析出銀 微粒子’並且測定析出之銀微粒子的平均粒徑。平均粒徑 的測定方法爲同實施例1。其結果示於表4。另外，表4 中’試料C 1〜試料C3爲本發明試料。未添加鹵化鹽水溶 液者以比較試料3表示。又，鹵化物鹽液爲〇 . 1 Μ水溶液 ’銀溶液及3s原 仪爲同表1。如表4所示般，鹵化物離子 的相對離子即使改變亦不會令本發明的效果改變。 [表4] 比較 試料3 試料 C1-1 試料 C1-2 試料 C1-3 試料|試料 C2-1 C2-2 試料 C2-3 試料 C3-1 試料 C3-2 試料 C3-3 鹵 化 物 鹽 液 鹵素種 - C1 Br I 抗衡種 nh4 Na K nh4 Na K nh4 Na K 液量(μΡ 0 300 300 300 鹵素量(g) 0 1.06x10'3 2.39xlO'3 3.80xl0'3 對Ag莫 耳比㈠ 0 3.23χ10'5 3.23x10'5 3.23xl〇-5 Ag 粒徑(μιη) 1.71 0.41 0.39 0.40 0.20 0.19 0.20 0.13 0.13 0.13 -31 - 200911417 (比較例1) 使用表5 (比較5式料4 )及表6 (比較試料$ )所示之加入 氨水的硝酸銀溶液’並於此溶液中添加對苯二酚液，將銀 離子還原並析出銀微粒子，測定析出之銀微粒子的平均粒 徑。平均粒徑的測定方法爲同實施例1。其結果示於表7 。於還原液中未預先添加鹵化物離子的情形中’亦可在減 薄銀濃度下取得平均粒徑爲〇·5 〇μιη以下的銀微粒子，但 因回收困難故產率低於99% ° [表5] 銀溶液 還ϋ 灵液 0.6%AgN〇3 液 995JE. 對苯二酚 2.〇4s 28%NH3 液 4.85g 純水 998.0ε [表6] J —— 銀溶液__ 還H 艮液 l_6%AgN03 液 987.9g 對苯二酚 . 5.10g 28%NH3 液 I2.12g _ 純水 994.9ε [表7] 比較試料4 比較試料5 Ag 粒子(μιη) 0.35 0.47 產率(％) 96.7 97.9 (實施例4) -32- 200911417 使用表8所示加入氨水的硝酸銀溶液，主還原劑爲使 用對苯二酣液’副還原劑A爲使用聯氨液，並將預先添 加副還原劑液之對苯二酚液加入硝酸銀溶液，將銀離子還 原並析出銀微粒子。副還原劑液的添加量爲調整至表9所 示之濃度，並以雷射散亂/繞射法測定析出之銀微粒子的 平均粒徑。所得之結果示於表9。另外，表9中，試料 D 1〜D 1 1爲本發明試料，未添加副還原劑者以比較試料表 示。又，銀微粒子的狀態，未凝集之情形以Ο K表示，有 凝集之情形以NG表示。又，相對於聯氨添加量之銀微粒 子的平均粒徑變化示於圖U。圖中之測定値所示之上τ 棒爲表示1 0次試驗之測定値的偏差範圍。關於一部分的 試料示出粒子狀態的電子顯微鏡照片示於圖1 3〜圖1 7。 _ 銀溶液 還原液 __16%AgN03 液 977g 對苯二酚 "*--- 51g _ 28%NH3 液 121g 純水 ----- 973g ------- 副還原劑 表9〜表11 -33- 200911417 [表9]-28- 200911417 [Table 2] nh4i liquid amount (g) iodine addition amount (g) I/Ag molar ratio Ag microparticle SEM image size (μπι) particle size control (μπι) iodine (ppm) yield (% Comparative sample la 0.000 0 0 1.67 >0.50 0 99.0 Figure 3 Sample A1 0.033 5.78xl0'6 4.91xl〇·8 1.45 <0.15 0.06 99.6 Sample A2 0.330 5·78χ10·5 4.91χ1〇·7 1.40 <0.14 0.6 99.5 Figure 4 Sample A3 0.750 1.31Χ10-4 1_12χ10·6 0.75 <0.08 1.3 99.4 - Sample A4 1.200 2.10Χ10-4 1.79x10-6 0.50 <0.05 2.1 99.6 - Sample A5 1.650 2.89Χ10·4 2.46x10'6 0.40 <0.04 2.9 99.8 Figure 5 Sample A6 4.000 7.00x1 Ο·4 5.95x10'6 0.30 <0.03 7 99.5 - Sample A7 8.200 1.44x1 Ο·3 1.22x10'5 0.22 <0.02 14 99.3 Figure 6 Sample A8 0.200 3.50x10° 2.98x10'5 0.16 <0.02 35 99.5 - Sample A9 0.500 8.76x103 7.44x105 0.13 <0.01 88 99.7 - um A10 2.500 4.38χ10'2 3.72χ10'4 0.10 <0.01 438 99.6 _ Sample All 10.000 1.75 X10] 1.49x10'3 0.08 <0.01 1751 99.4 - Comparative sample lb 20.000 3.50x1ο-1 2.98χ10'3 0.15 >0.05 3500 99.2 - As shown in Table 2 and Figure 1, In the comparative sample in which ammonium iodide is not added, silver fine particles having an average particle diameter of 1 · 5 μm or more are precipitated. However, if iodide ions are present, the silver fine particles are fine, and the average particle diameter of the silver fine particles is changed depending on the amount of iodide ions. Specifically, (i) the silver iodide molar ratio (I/Ag) is in the range of 5.0×10·8 to 1.8χ10·6, and the average particle diameter is precipitated! · Silver microparticles of 5~〇.5μιη' (ii) Silver iodide molar ratio is greater than 1.8xl0·6 and 3·〇χ1〇.5 or less, silver fine particles having an average particle diameter of 0.5~1_5μηι are precipitated, (iii) silver The iodomol ratio is a range of more than 3_0xl0-5 and 15χ1〇-3 or less, and silver fine particles having an average particle diameter of 〇·1 5~〇.〇8μηι are precipitated. -29- 200911417 Further, as shown in Table 2 and Fig. 1, the silver fine particles of the present invention have good controllability of the particle diameter, and the particle diameter of the silver fine particles of the examples is the average particle diameter obtained by the test 1 time. The range of -10% to 10% (table diameter control of Table 2). Further, the chemical solution used in the present invention is excellent in stability over time, and the particle size of the silver fine particles synthesized within 9 hours after preparation is also in the range of -10% to 100%. (Example 2) In a silver nitrate solution to which aqueous ammonia was added, a hydroquinone solution (halogen number of a halide · 2.8 2 X 1 0·5 ) in which an ammonium halide solution was previously added was added to reduce silver ions and precipitate silver. Microparticles. The silver nitrate solution, the hydroquinone solution, and the ammonium solution were as shown in Table 1. The types of halogens were as shown in Table 3, and NH4C1, NH4Br, and NH4I were used. The average particle diameter of the precipitated silver fine particles was measured. The method for measuring the average particle diameter is the same as in the examples. The results are shown in Table 3 and Figures 7 to 10. Further, in Table 3, Samples B1 to B3 were samples of the present invention. The case where the ammonium halide solution was not added was represented by Comparative Sample 2. Further, the halide salt solution was a 0. 1 hydrazine aqueous solution, and the silver solution and the reducing solution were the same as in Table 1. As shown in Table 3 and Fig. 7 to Fig. 10, the effect of refining silver particles in the order of iodine, bromine and chlorine is gradually enhanced. -30- 200911417 [Table 3] Halogen type sample B1 sample Β 2 sample B3 NH4C1 NH4Br NH4I liquid amount (μι) 0 300 300 300 halogen amount (g) 0 1.06xl〇-3 2.39xl〇·3 3.80xl0'3 pair Ag Mobi ratio (1) Ag particle size (μιη) 0 ------ 3.23x1 Ο·5 3.23xl〇-5 3.23xl〇·5 ___ 0.40 0.20 0.12 SEM image ____B 7 - ---- Figure 8 9 (Example 3) In addition to using the halogenated salt aqueous solution shown in Table 4 instead of the halogenated saddle liquid of Example 2, silver ions were reduced and silver fine particles were precipitated under the same conditions as in Example 2, and precipitated silver fine particles were measured. Average particle size. The method for measuring the average particle diameter is the same as in Example 1. The results are shown in Table 4. Further, in Table 4, the sample C 1 to the sample C3 were samples of the present invention. The case where the halogenated salt solution was not added was shown by Comparative Sample 3. Further, the halide salt solution is 〇. 1 Μ aqueous solution 'silver solution and 3s original instrument are the same as Table 1. As shown in Table 4, the relative ions of the halide ions did not change the effects of the present invention even if they were changed. [Table 4] Comparative Sample 3 Sample C1-1 Sample C1-2 Sample C1-3 Sample | Sample C2-1 C2-2 Sample C2-3 Sample C3-1 Sample C3-2 Sample C3-3 Halide Salt Halogen - C1 Br I Counterbalance species nh4 Na K nh4 Na K nh4 Na K Liquid volume (μΡ 0 300 300 300 Halogen amount (g) 0 1.06x10'3 2.39xlO'3 3.80xl0'3 Pair Ag molar ratio (1) 0 3.23χ10 '5 3.23x10'5 3.23xl〇-5 Ag Particle size (μιη) 1.71 0.41 0.39 0.40 0.20 0.19 0.20 0.13 0.13 0.13 -31 - 200911417 (Comparative Example 1) Using Table 5 (Comparative 5) 4 and Table 6 ( Comparing the silver nitrate solution of the ammonia water shown in the sample $) and adding a hydroquinone solution to the solution, reducing the silver ions and depositing the silver fine particles, and measuring the average particle diameter of the precipitated silver fine particles. The results are the same as those in the first embodiment. The results are shown in Table 7. In the case where the halide ions are not previously added to the reducing solution, silver fine particles having an average particle diameter of 〇·5 〇μηη or less can be obtained at a reduced silver concentration. However, the yield is less than 99% due to difficulty in recovery [Table 5] Silver solution is also ϋ 灵 0.6 0.6 0.6% 〇 995 995 995 995 995 995 995 995 995 995 995 995 995 995 995 995 s s s s NH3 solution 4.85g pure water 998.0ε [Table 6] J —— Silver solution __ Also H 艮 liquid l_6% AgN03 liquid 987.9g hydroquinone. 5.10g 28% NH3 liquid I2.12g _ pure water 994.9ε [Table 7] Comparative sample 4 Comparative sample 5 Ag particles (μιη) 0.35 0.47 Yield (%) 96.7 97.9 (Example 4) -32- 200911417 Using a silver nitrate solution added with ammonia as shown in Table 8, the main reducing agent was a terephthalic acid The sputum 'sub-reducing agent A is a hydrazine solution, and the hydroquinone solution of the sub-reducing agent liquid is added to the silver nitrate solution to reduce the silver ions and precipitate the silver fine particles. The amount of the sub-reducing agent liquid is adjusted to The average particle diameter of the precipitated silver fine particles was measured by the laser scattering/diffraction method, and the results obtained are shown in Table 9. In addition, in Table 9, the samples D 1 to D 1 1 were In the sample of the invention, the case where the sub-reducing agent is not added is represented by the comparative sample. Further, the state of the silver microparticles, the case of non-aggregation is represented by Ο K, and the case of agglutination is represented by NG. Further, the amount of silver microparticles added to the amount of hydrazine is added. The average particle size change is shown in Figure U. The measurement in the figure 値 above the τ bar represents 1 The deviation range of the measurement 値 of the 0 test. An electron micrograph showing the state of the particles in a part of the sample is shown in Fig. 13 to Fig. 17. _ Silver solution reducing solution __16% AgN03 liquid 977g hydroquinone "*--- 51g _ 28%NH3 liquid 121g pure water----- 973g ------- Sub-reducing agent table 9~ 11 -33- 200911417 [Table 9]
N2H4 量(g) 銀/聯氨比 Ag微粒子 備註 粒徑(μηι) 產率(％) 狀態 比較試料6 0 0 1.80 _ 0K 圖13 比較試料7 7.43X10'8 2.5χ10-9 1.78 _ 0K 比較試料8 7.43x10’ 2.5xlO'8 1.76 _ 0K 試料D1 7_43xl0-6 2.5χ1〇·7 1.49 99%以上 0K 試料D2 5.94x10'5 2.0χ10'6 0.97 99%以上 0K 圖14 試料D3 2.97xl〇·4 1.0x10'5 0.85 99%以上 0K 試料D4 9.80xl0·4 3.3χ1〇·5 0.49 99%以上 0K 試料D5 5.94x10'3 2.0χ1〇·4 0.30 99%以上 0K 圖15 試料D6 2.97xl〇·2 1.0x10'3 0.20 99%以上 0K 試料D7 1.49x1ο·1 5_0χ10-3 0.18 99%以上 0K 試料D8 5.94Χ10—1 2.0x10'2 0.13 99%以上 0K 圖16 試料D9 1.49x10° 5.0χ1〇·2 0.10 99%以上 0K 圖17 試料D10 3.56x10° 1.2x10'' 0.08 99%以上 0K 試料D11 1.49x10' 5.0x10'* 0.05 99%以上 0K 比較試料9 2.97Χ101 1.0x10° 0.89 _ NG 比較試料10 4.46Χ101 1.5x10° 2.30 NG (實施例5〜實施例6) 副還原劑B爲使用硼氫化鈉溶液（實施例5)、副還原 劑C爲使用二甲基胺硼烷溶液（實施例6)、其他爲同實施 例4處理製造銀微粒子。其結果示於表1 0(實施例5 : E 1〜E 3 )、表1 1 (實施例6 : F 1〜F 3 )。又，圖1 2中示出副還 原劑添加量與Ag粒徑的關係。 -34- 200911417 [表 1 〇ιN2H4 Amount (g) Silver / hydrazine ratio Ag fine particle Remarks Particle size (μηι) Yield (%) State comparison sample 6 0 0 1.80 _ 0K Figure 13 Comparative sample 7 7.43X10'8 2.5χ10-9 1.78 _ 0K Comparative sample 8 7.43x10' 2.5xlO'8 1.76 _ 0K Sample D1 7_43xl0-6 2.5χ1〇·7 1.49 99% or more 0K Sample D2 5.94x10'5 2.0χ10'6 0.97 99% or more 0K Figure 14 Sample D3 2.97xl〇·4 1.0x10'5 0.85 99% or more 0K Sample D4 9.80xl0·4 3.3χ1〇·5 0.49 99% or more 0K Sample D5 5.94x10'3 2.0χ1〇·4 0.30 99% or more 0K Figure 15 Sample D6 2.97xl〇·2 1.0x10'3 0.20 99% or more 0K Sample D7 1.49x1ο·1 5_0χ10-3 0.18 99% or more 0K Sample D8 5.94Χ10-1 2.0x10'2 0.13 99% or more 0K Figure 16 Sample D9 1.49x10° 5.0χ1〇·2 0.10 99% or more 0K Figure 17 Sample D10 3.56x10° 1.2x10'' 0.08 99% or more 0K Sample D11 1.49x10' 5.0x10'* 0.05 99% or more 0K Comparative sample 9 2.97Χ101 1.0x10° 0.89 _ NG Comparative sample 10 4.46 Χ101 1.5x10° 2.30 NG (Examples 5 to 6) The secondary reducing agent B is a sodium borohydride solution (Example 5), and the secondary reducing agent C is dimethylamine borane. Solution (Example 6), other embodiments for the same process in Example 4 for producing fine silver particles. The results are shown in Table 10 (Example 5: E 1 to E 3 ) and Table 1 1 (Example 6: F 1 to F 3 ). Further, Fig. 12 shows the relationship between the amount of the sub-reagent added and the Ag particle diameter. -34- 200911417 [Table 1 〇ι
NaBH4 量 銀副還原劑比 Ag粒徑(Pm) Ag產率(％) 備註 試料E1 7.01xl〇·5 2.0〇xl〇·6 0.99 >99 無凝集 試料E2 7.01 xlO'3 2.00x10"4 0.34 >99 無凝集 試料E3 7·01χΚΓ1 2.00x10'2 0.12 >99 無凝集 [表 1 1] BH3-HN(CH3)2 量 銀副還原劑比 Ag 粒徑(μηι) Ag產率(％) 備註 試料Π 1.09X10'4 2.00χ10'6 1.10 >99 無凝集 試料F2 1.09xl〇·2 2.00ΧΗΓ4 0.40 >99 無凝集 試料F3 1.09x10° 23.00Χ10'2 0.15 >99 無凝集 如表9 ~表1 1及圖1 1〜圖1 2所示般，未添加副還原劑 的比較試料中析出平均粒徑1 . 8 μιη以上的銀微粒子，但若 添加副還原劑則銀微粒子爲微細，根據副還原劑的添加量 令銀微粒子的平均粒徑變化。具體而言，（i)銀聯氨比爲 2.5χ10_7〜3_〇xl 〇_5的範圍中析出平均粒徑1 ·5〜0·5μπι的銀 微粒子，（ii)銀聯氨比爲大於3.OxlO·5且4·2χ1(Γ2以下的 範圍中析出平均粒徑0.5〜0.1 μηι的銀微粒子，（iii)銀聯氨 比爲大於4 · 2 X 1 0 _2且5 · 0 X 1 0 ·1以下的範圍中析出平均粒徑 0 . 1〜0 · 5 μ m的銀微粒子。 又’如圖1 1所示般，本發明之銀微粒子爲粒徑的控 制性良好，且實施例之銀微粒子的粒徑均在-20%〜20%以 內的範圍內。更且’根據本發明所調製之藥液爲經時安定 性亦優良’於調製後3小時以內合成的銀微粒子粒徑均 在- 20%〜2 0%以內的範圍內。 -35- 200911417 (比較例2) 使用表1 2 (比較試料n )及表1 3 (比較試料1 2)所示之 加入氨水的硝酸銀溶液，並於此溶液中添加對苯二酚液， 將銀離子還原並析出銀微粒子，測定析出之銀微粒子的平 均粒徑。平均粒徑的測定方法爲同實施例4。其結果示於 表1 4。於未添加副還原劑的情形中’亦可在減薄銀濃度 下取得平均粒徑爲0 _ 5 0 ^ m以下的銀微粒子’但因回收困 難故產率低於99%。 [表 12] 銀溶液 還原液 0.6%AgN〇3 液 995.2S 對苯二酚 2.048 28%NH3 液 4.85ε 純水 998.0g [表 13] 銀溶液 .__ 還原液 1.6%AgN03 液 987.9ε 對苯二酚 5.10g 28%NH3 液 12.l2g 純水 994.9g [表 14] 比較試料11 比較試料12 Ag 粒子(μιη) 0.35 0.47 產率(％) 96.7 97.9 (實施例7) -36- 200911417 使用表1 5所示之加入氨水的硝酸銀溶液’並於此溶 液中預先加入銀奈米粒子’再添加對苯二酚液將銀離子還 原並析出銀微粒子。銀奈米粒子的粒徑及添加量調整至表 1 6〜表1 7所示之條件。根據雷射散亂法測定析出之銀微粒 子的平均粒徑。又，以S Ε Μ觀察銀微粒子。所得之結果 示於表16〜表17及圖18〜圖23。另外，試料G1~G5、 Η 1 ~ Η 3、J 1〜J 3、K爲本發明試料，未添力Π銀奈米粒子者以 比較試料表示。 如表16〜表17及圖18~圖23所示般，未添加銀奈米 粒子的比較試料中析出平均粒徑1 . 5 μιη以上的銀微粒子， 但若添加銀奈米粒子，則根據銀奈米粒子的粒徑及添加量 令銀微粒子的平均粒徑變化。具體而言，（i)銀離子銀奈米 粒子比率爲 5·0χ10·7〜3.0xl0·6的範圍中，析出平均粒徑 1. 5〜0.5 μηι的銀微粒子。又，（ii)銀離子銀奈米粒子比率爲 大於3_0χ10_6且2·5χ1(Γ5以下的範圍中，析出平均粒徑 0.5〜Ο.ίμιη的銀微粒子。又，（iii)銀離子銀奈米粒子比率 爲大於2.5\1〇-5且UxW4以下的範圍中，析出平均粒徑 0.1〜0·02μιη的銀微粒子。另外，試料g〜J中使用根據檸 檬酸法所製作的銀奈米粒子，試料Κ爲使用未明製法（非 揭示）之5 Onm的銀奈米粒子。 -37- 200911417 m i5]NaBH4 silver secondary reducing agent ratio Ag particle size (Pm) Ag yield (%) Remarks sample E1 7.01xl〇·5 2.0〇xl〇·6 0.99 >99 non-agglutination sample E2 7.01 xlO'3 2.00x10"4 0.34 >99 Non-agglutination sample E3 7·01χΚΓ1 2.00x10'2 0.12 >99 Non-agglutination [Table 1 1] BH3-HN(CH3)2 Silver Sub-reducing agent ratio Ag Particle size (μηι) Ag yield (%) Remarks Π 1.09X10'4 2.00χ10'6 1.10 >99 Non-agglutination sample F2 1.09xl〇·2 2.00ΧΗΓ4 0.40 >99 Non-agglutination sample F3 1.09x10° 23.00Χ10'2 0.15 >99 No agglutination as shown in Table 9 As shown in Table 1 1 and FIG. 1 1 to FIG. 12, silver fine particles having an average particle diameter of 1.8 μm or more are precipitated in the comparative sample to which no by-reducing agent is added, but silver fine particles are fine when a secondary reducing agent is added. The average particle diameter of the silver fine particles is changed in accordance with the amount of the sub-reducing agent added. Specifically, (i) the silver-linked ammonia ratio in the range of 2.5χ10_7~3_〇xl 〇_5 precipitates silver fine particles having an average particle diameter of 1 ·5~0·5μπι, and (ii) the silver-linked ammonia ratio is greater than 3.OxlO ·5 and 4·2χ1 (in the range of Γ2 or less, silver fine particles having an average particle diameter of 0.5 to 0.1 μηι are precipitated, and (iii) the silver-linked ammonia ratio is more than 4 · 2 X 1 0 _2 and 5 · 0 X 1 0 · 1 or less Silver fine particles having an average particle diameter of 0.1 to 0 · 5 μm are precipitated in the range. Further, as shown in Fig. 11, the silver fine particles of the present invention have good controllability of particle diameter, and the particles of the silver fine particles of the examples The diameters are all within the range of -20% to 20%. Moreover, the liquid chemical prepared according to the present invention is excellent in stability over time. The particle size of the silver fine particles synthesized within 3 hours after preparation is -20%. Within the range of ~20%. -35- 200911417 (Comparative Example 2) The solution of silver nitrate added with ammonia shown in Table 1 2 (Comparative Sample n) and Table 13 (Comparative Sample 1 2) was used. The hydroquinone solution is added, the silver ions are reduced and silver fine particles are precipitated, and the average particle diameter of the precipitated silver microparticles is measured. The average particle diameter is determined by the same method. Example 4. The results are shown in Table 14. In the case where no sub-reducing agent is added, 'silver microparticles having an average particle diameter of 0 _ 5 0 ^ m or less can be obtained at a reduced silver concentration', but it is difficult to recover. Therefore, the yield is less than 99%. [Table 12] Silver solution reducing solution 0.6% AgN〇3 liquid 995.2S Hydroquinone 2.048 28% NH3 solution 4.85 ε Pure water 998.0 g [Table 13] Silver solution.__ Reduction solution 1.6 %AgN03 solution 987.9ε hydroquinone 5.10g 28% NH3 solution 12.l2g pure water 994.9g [Table 14] Comparative sample 11 Comparative sample 12 Ag particles (μιη) 0.35 0.47 Yield (%) 96.7 97.9 (Example 7 -36- 200911417 The silver nitrate solution added with ammonia water shown in Table 15 is used, and silver nanoparticles are added to this solution in advance, and then the hydroquinone solution is added to reduce silver ions and precipitate silver fine particles. Silver nanoparticles The particle size and the amount of addition were adjusted to the conditions shown in Tables 1 6 to 17. The average particle diameter of the precipitated silver fine particles was measured by the laser scattering method, and the silver fine particles were observed by S Ε 。. Tables 16 to 17 and Figs. 18 to 23. In addition, samples G1 to G5, Η 1 to Η 3, J 1 to J 3, and K are According to Table 16 to Table 17 and Figure 18 to Figure 23, the average particle size of the comparative sample in which no silver nanoparticles are added is 1.5. Silver fine particles of μιη or more. However, when silver nanoparticles are added, the average particle diameter of the silver fine particles changes depending on the particle diameter and the added amount of the silver nanoparticles. Specifically, in the range of (i) silver ion silver nanoparticle ratio of 5·0χ10·7 to 3.0x10·6, silver fine particles having an average particle diameter of 1.5 to 0.5 μm are precipitated. Further, (ii) the silver ion silver nanoparticle ratio is more than 3_0χ10_6 and 2. 5χ1 (in the range of Γ5 or less, silver fine particles having an average particle diameter of 0.5 to ί.ίμιη are precipitated. Further, (iii) silver ion silver nanoparticles Silver microparticles having an average particle diameter of 0.1 to 0·02 μm were precipitated in a range of more than 2.5\1〇-5 and not more than UxW4. Further, silver nanoparticles prepared by the citric acid method were used in the samples g to J, and the sample was used. Κ is a silver nanoparticle of 5 Onm using an unspecified method (not disclosed) -37- 200911417 m i5]
Ag離子溶液 還原液 AgN03 液 液量(g) 977 對苯_酚液 (H2Q 液） 液量(g) 1024 Ag 量(g) 100 H2Q 量(g) 51 Ag莫耳量(mol) 0.93 對Ag莫耳比㈠ 0.5 Ag離子個數 5.58x1023 銀 奈 米 粒 子 試料G1〜G5 5nm 表16 28%NH3 液 液量(g) 121 試料H1〜H3 2.6mn 表17 NH3 量(g) 34 試料J1〜J3 16.4nm 對Ag莫耳比㈠ 2.15 試料K 50nm im i6] 奈米粒子徑 (nm) 銀離子奈米 粒子比㈠ Ag粒徑 (μηι) Ag產率 (%) 備註 比較試料13 姐 • 1.67 >99 圖20 比較試料14 5 9.38xl〇·8 1.67 >99 比較試料15 5 2.11X10'7 1.66 >99 試料G1 5 4.93xlO'7 1.55 >99 圖21 試料G2 5 3_17xl0·6 0.47 >99 圖22 試料G3 5 6_80xl0-6 0.27 >99 圖23 試料G4 5 2.70xl〇·5 0.09 >99 試料G5 5 1.50x10-4 0.02 >99 比較試料16 5 3.50X10-4 0.02 >99 異形粉 -38- 200911417 m i7] 奈米粒子徑 (nm) 銀離子奈米 粒子比㈠ Ag粒徑 (μηι) Ag產率 (%) 備註 試料Η1 2.6 8_34xl0·7 1.15 >99 試料Η2 2.6 3_34xl0·6 0.45 >99 試料Η3 2.6 2.42xl0-5 0.09 >99 試料J1 16.4 9.31xl〇·7 1.50 >99 試料J2 16.4 2.66x10'6 0.65 >99 試料J3 16.4 1.33xlO-5 0.15 >99 試料Κ 50.0 7.04x10'7 1.50 >99 (比較例3 ) 使用表1 8 (比較試料1 7 )及表1 9 (比較試料1 8 )所示之 加入氨水的硝酸銀溶液，並於此溶液中添加對苯二酚液， 將銀離子還原並析出銀微粒子，測定析出之銀微粒子的平 均粒徑。平均粒徑的測定方法爲同實施例1。其結果示於 表2 0。於未添加銀奈米粒子的情形中，亦可經由減薄銀 濃度而取得平均粒徑爲〇 . 5 0 μηι以下的銀微粒子，但因回 收困難故產率低於9 9 %。 [表 18]Ag ion solution reducing solution AgN03 liquid amount (g) 977 p-benzene phenol liquid (H2Q liquid) liquid amount (g) 1024 Ag amount (g) 100 H2Q amount (g) 51 Ag molar amount (mol) 0.93 for Ag Mohr ratio (1) 0.5 Ag ion number 5.58x1023 Silver nanoparticle sample G1~G5 5nm Table 16 28% NH3 liquid amount (g) 121 Sample H1~H3 2.6mn Table 17 NH3 amount (g) 34 Sample J1~J3 16.4nm vs. Ag Mobi ratio (1) 2.15 Sample K 50nm im i6] Nanoparticle diameter (nm) Silver ion nanoparticle ratio (1) Ag particle size (μηι) Ag yield (%) Remarks comparison sample 13 sister • 1.67 > 99 Figure 20 Comparative sample 14 5 9.38xl〇·8 1.67 >99 Comparative sample 15 5 2.11X10'7 1.66 >99 Sample G1 5 4.93xlO'7 1.55 >99 Figure 21 Sample G2 5 3_17xl0·6 0.47 > 99 Figure 22 Sample G3 5 6_80xl0-6 0.27 >99 Figure 23 Sample G4 5 2.70xl〇·5 0.09 >99 Sample G5 5 1.50x10-4 0.02 >99 Comparative sample 16 5 3.50X10-4 0.02 >99 Shaped powder-38- 200911417 m i7] Nanoparticle diameter (nm) Silver ion nanoparticle ratio (I) Ag particle size (μηι) Ag yield (%) Remarks sample Η1 2.6 8_34xl0·7 1.15 >99 Sample Η2 2.6 3_34xl0 ·6 0.45 >99 sample Η3 2.6 2.42xl0-5 0.09 >99 sample J1 16.4 9.31xl〇·7 1.50 >99 sample J2 16.4 2.66x10'6 0.65 >99 sample J3 16.4 1.33xlO-5 0.15 >99 sample Κ 50.0 7.04x10'7 1.50 >99 (Comparative Example 3) The ammonia nitrate-added silver nitrate solution shown in Table 1 8 (Comparative Sample 1 7) and Table 1 9 (Comparative Sample 1 8) was used and added to the solution. In the hydroquinone solution, silver ions were reduced and silver fine particles were precipitated, and the average particle diameter of the precipitated silver fine particles was measured. The method for measuring the average particle diameter is the same as in Example 1. The results are shown in Table 20. In the case where silver nanoparticles are not added, silver fine particles having an average particle diameter of 〇0.50 μηι or less may be obtained by thinning the silver concentration, but the yield is less than 99% due to difficulty in recovery. [Table 18]
Ag離子溶液 遠原液 AgN03 液 液量(g) 995.2 對苯+酚液 (H2Q 液） 液量(g) 1000.0 Ag 量(g) 4.00 H2Q 量(g) 2.04 Ag莫耳量(mol) 0.037 對Ag莫耳比㈠ 0.5 28%NH3 液 液量(g) 4.85 銀奈米粒子 無添加 丽3量(g) 1.36 對Ag莫耳比㈠ 2.15 -39- 200911417 [表 19]Ag ion solution far solution AgN03 liquid amount (g) 995.2 p-benzene + phenol solution (H2Q solution) liquid amount (g) 1000.0 Ag amount (g) 4.00 H2Q amount (g) 2.04 Ag molar amount (mol) 0.037 for Ag Mo Erbi (1) 0.5 28% NH3 Liquid (g) 4.85 Silver nanoparticles without added Li 3 (g) 1.36 vs. Ag Mobi (1) 2.15 -39- 200911417 [Table 19]
Ag離子溶液 還原液 AgN03 液 液量(g) 987.9 對苯二酚液 (H2Q 液） 液量(g) 1000.0 Ag 量(g) 10.0 H2Q 量(g) 5.10 Ag旲耳量(mol) 0.093 對Ag莫耳比 0.5 28%NH3 液 液量㈤ 12.12 NH3 量(g) 3.39 銀奈米粒子 無添加 對Ag莫耳比㈠ 2.15 [表 20] 比較試料Π 比較試料18 Ag粒徑(μ m ) 0.35 0.47 產率(％) 96.7 97.9 (實施例8及比較例4) 使手表21所示之硝酸銀溶液（AgN03液）和氨水（NH3 水）還原劑爲使用對苯二酚液（〇H(C6H4)OH液），一邊將硝 酸銀溶液中氨水的混合重量比保持於8 · 0〜8.2，一邊於氨 水添加後20秒鐘以內添加還原劑將銀離子還原並析出銀 微粒子。直到添加還原液爲止的經過時間如表22所示般 調整。根據雷射散亂法測定析出之銀微粒子的平均粒徑。 本發明試料 L1-L7的結果示於表 22。比較試料 Μ 1 ~ Μ 5的結果示於表2 3。於硝酸銀溶液中添加氨水後直 到添加還原劑爲止的經過時間與銀粒子粒徑的關係示於圖 25。示出試料L 1〜L5之銀粒子之粒子狀態的電子顯微鏡 照片示於圖26~圖30。 如表2 2及圖2 5所示般，（i)上述經過時間爲0 · 3秒鐘 -40- 200911417 〜0.5秒鐘以內時析出平均粒徑0.2μιη〜0.5μηι的銀微粒子 。（i i)上述經過時間爲長於0.5秒鐘且爲2秒鐘以內時析 出平均粒徑〇.5μηι~1 .5μηι的銀微粒子。（iii)上述經過時間 爲長於 2 秒鐘且爲 5 秒鐘以內時析出平均粒徑 1 . 5 μ m〜2.0 μ m的銀微粒子。（i v )上述經過時間爲長於5秒 鐘且爲2 0秒鐘以內時析出平均粒徑2.0 μηι〜2.5 μπι的銀微 粒子。 [表 21] 硝酸銀(AgN03)液 氨(NH2)7」 對苯二酚(H2Q)液 液量(g) 977 液量(g) 121 液量(g) 1024 Ag 量(g) 100 NH3 量(g) 34 H2Q 量(g) 51 Ag莫耳量(mol) 0.93 對Ag莫耳比㈠ 2.15 對Ag莫耳比㈠ 0.5 [表 22] 試料L1 試料L2 試料L3 試料L4 試料L5 試料L6 試料L7 經過時間(秒） 0.3 0.5 1.4 3 6 10 20 Ag粒徑(μ m ) 0.21 0.47 1.13 1.73 2.13 2.45 2.49 Ag產率(％) >99 >99 >99 >99 >99 >99 >99 備註 圖26 圖27 圖28 圖29 - _ 圖30 [表 23] 比較試料Ml 比較試料M2 比較試料M3 比較試料M4 比較試料M5 經過時間(秒） 0.1 0.2 30 60 300 Ag粒徑(μ m) 無法測定 無法測定 2.39 2.83 1.67 Ag產率(％) 73 89 >99 >99 >99 備註 察見凝集且產率差 粒徑不安定 -41 - 200911417 (產業上之可利用性） 若根據本發明之銀微粒子的製造方法及製造裝置，則 可使用高濃度之銀離子溶液，安定且有效率製造本發明之 分散性優良的微細銀粒子。因此，本發明之銀微粒子可應 用作爲電子裝置之配線材料和作爲電極材料的糊劑成分， 且本發明之銀微粒子的製造方法及製造裝置爲於此銀粒子 的製造步驟中可適當應用。 【圖式簡單說明】 圖1爲示出碘化物離子添加量與Ag粒徑的關係圖。 圖2爲示出鹵素之種類與A g粒徑的關係圖。 圖3爲示出比較試料1之粒子狀態的電子顯微鏡照片 (下端白桿的長度爲Ιμιη)。 圖4爲示出試料Α2之粒子狀態的電子顯微鏡照片（下 端白桿的長度爲ΐμπ〇。 圖5爲示出試料A 5之粒子狀態的電子顯微鏡照片（下 端白桿的長度爲1 μπι)。 圖6爲示出試料A7之粒子狀態的電子顯微鏡照片（下 端白桿的長度爲1 μηι)。 圖7爲示出比較試料2之粒子狀態的電子顯微鏡照片 (下端白桿的長度爲1 μιη)。 圖8爲示出試料Β 1之粒子狀態的電子顯微鏡照片（下 端白桿的長度爲1 μηι)。 -42 - 200911417 圖9爲示出試料B2之粒子狀態的電子顯微鏡照片（下 端白桿的長度爲Ιμιη)。 圖10爲示出試料Β3之粒子狀態的電子顯微鏡照片（ 下端白桿的長度爲Ιμηι)。 圖1 1爲示出Ν2Η4添加量與Ag粒徑的關係圖。 圖1 2爲示出副還原劑添加量與Ag粒徑的關係圖。 圖1 3爲示出比較試料6之粒子狀態的電子顯微鏡照 片（下端白桿的長度爲1 μιη)。 圖1 4爲示出試料D2之粒子狀態的電子顯微鏡照片（ 下端白桿的長度爲Ιμηι)。 圖1 5爲示出試料D5之粒子狀態的電子顯微鏡照片（ 下端白桿的長度爲1 μηι)。 圖1 6爲示出試料D8之粒子狀態的電子顯微鏡照片（ 下端白桿的長度爲1 μηι)。 圖1 7爲示出試料D9之粒子狀態的電子顯微鏡照片（ 下端白桿的長度爲1 μηι)。 圖1 8爲示出Ag奈米粒子數與Ag粒徑的關係圖。 圖19爲不出Ag奈米粒子數與Ag粒徑的關係圖。 圖2 0爲示出比較試料1 3之粒子狀態的電子顯微鏡照 片（下端白桿的長度爲Ιμιη)。 圖2 1爲示出試料G 1之粒子狀態的電子顯微鏡照片（ 下端白桿的長度爲1 μηι)。 圖22爲示出試料G2之粒子狀態的電子顯微鏡照片（ 下端白桿的長度爲1 Pm)。 -43- 200911417 圖23爲示出試料G3之粒子狀態的電子顯微鏡照片（ 下端白桿的長度爲1μΠ1) ° 圖24爲本發明之裝置構造的槪念圖。 圖2 5爲實施例中氨添加後之經過時間與銀微粒子之 平均粒徑圖。 圖2 6爲示出試料L1之銀粒子的粒子狀態的電子顯微 鏡照片。 圖2 7爲示出試料L 2之銀粒子的粒子狀態的電子顯微 鏡照片。 圖2 8爲示出試料L 3之銀粒子的粒子狀態的電子顯微 鏡照片。 圖2 9爲示出試料L4之銀粒子的粒子狀態的電子顯微 鏡照片。 圖30爲示出試料L7之銀粒子的粒子狀態的電子顯微 鏡照片。 【主要元件符號說明】 1 〇 :銀離子溶液槽 1 1 :氨水溶液槽 12 :還原槽 1 3 :第1管路 14 :第2管路 1 5 :第3管路 1 6 :第4管路 -44 - 200911417 A :銀離子溶液與氨水溶液的混合位置 B :銀離子溶液與還原液的混合位置Ag ion solution reducing solution AgN03 liquid amount (g) 987.9 hydroquinone solution (H2Q solution) liquid amount (g) 1000.0 Ag amount (g) 10.0 H2Q amount (g) 5.10 Ag amount (mol) 0.093 for Ag Mohr ratio 0.5 28% NH3 liquid amount (5) 12.12 NH3 amount (g) 3.39 silver nanoparticles without added to Ag molar ratio (1) 2.15 [Table 20] Comparative sample Π Comparative sample 18 Ag particle size (μ m ) 0.35 0.47 Yield (%) 96.7 97.9 (Example 8 and Comparative Example 4) The silver nitrate solution (AgN03 liquid) and the ammonia water (NH3 water) reducing agent shown in the watch 21 were hydroquinone liquid (〇H(C6H4)OH). In the liquid), while maintaining the mixing ratio of the ammonia water in the silver nitrate solution at 8·0 to 8.2, the reducing agent is added within 20 seconds after the addition of the ammonia water to reduce the silver ions and precipitate the silver fine particles. The elapsed time until the addition of the reducing solution was adjusted as shown in Table 22. The average particle diameter of the precipitated silver fine particles was measured according to the laser scattering method. The results of the samples L1-L7 of the present invention are shown in Table 22. The results of the comparative samples Μ 1 ~ Μ 5 are shown in Table 23. The relationship between the elapsed time until the addition of the reducing agent to the silver nitrate solution and the particle diameter of the silver particles is shown in Fig. 25. An electron micrograph showing the state of the particles of the silver particles of the samples L 1 to L5 is shown in Figs. 26 to 30 . As shown in Table 2 2 and Fig. 25, (i) silver fine particles having an average particle diameter of 0.2 μm to 0.5 μm are precipitated when the elapsed time is from 0 to 3 seconds -40 to 200911417 to 0.5 seconds. (i i) Silver fine particles having an average particle diameter of 5.5 μηι to 1.5 μm when the elapsed time is longer than 0.5 seconds and within 2 seconds. (iii) Silver fine particles having an average particle diameter of 1.5 μm to 2.0 μm precipitated when the elapsed time is longer than 2 seconds and within 5 seconds. (i v ) Silver microparticles having an average particle diameter of 2.0 μη to 2.5 μm precipitate when the elapsed time is longer than 5 seconds and within 20 seconds. [Table 21] Silver nitrate (AgN03) liquid ammonia (NH2) 7" hydroquinone (H2Q) liquid amount (g) 977 liquid amount (g) 121 liquid amount (g) 1024 Ag amount (g) 100 NH3 amount ( g) 34 H2Q Amount (g) 51 Ag Molar (mol) 0.93 Ag molar ratio (1) 2.15 Ag molar ratio (1) 0.5 [Table 22] Sample L1 Sample L2 Sample L3 Sample L4 Sample L5 Sample L6 Sample L7 Time (seconds) 0.3 0.5 1.4 3 6 10 20 Ag particle size (μ m ) 0.21 0.47 1.13 1.73 2.13 2.45 2.49 Ag yield (%) >99 >99 >99 >99 >99 >99 > ;99 Remarks Figure 26 Figure 27 Figure 28 Figure 29 - _ Figure 30 [Table 23] Comparative sample Ml Comparison sample M2 Comparison sample M3 Comparison sample M4 Comparison sample M5 Elapsed time (seconds) 0.1 0.2 30 60 300 Ag particle size (μ m Unable to measure 2.39 2.83 1.67 Ag yield (%) 73 89 >99 >99 >99 Remarks to observe agglomeration and poor yield particle size instability -41 - 200911417 (industrial availability) According to the method and apparatus for producing silver fine particles of the present invention, fine silver ions having excellent dispersibility of the present invention can be produced stably and efficiently by using a silver ion solution having a high concentration. Therefore, the silver fine particles of the present invention can be used as a wiring material for an electronic device and a paste component as an electrode material, and the method and apparatus for producing silver fine particles of the present invention can be suitably applied in the production steps of the silver particles. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the relationship between the amount of iodide ion added and the particle size of Ag. Fig. 2 is a graph showing the relationship between the kind of halogen and the particle diameter of A g . Fig. 3 is an electron micrograph showing the state of the particles of Comparative Sample 1 (the length of the lower end white rod is Ιμιη). 4 is an electron micrograph showing the state of the particles of the sample (2 (the length of the lower white rod is ΐμπ〇. Fig. 5 is an electron micrograph showing the state of the particles of the sample A 5 (the length of the lower white rod is 1 μm). Fig. 6 is an electron micrograph showing the state of the particles of the sample A7 (the length of the lower white rod is 1 μηι). Fig. 7 is an electron micrograph showing the state of the particles of the comparative sample 2 (the length of the lower white rod is 1 μm) Fig. 8 is an electron micrograph showing the state of the particles of the sample Β 1 (the length of the lower white rod is 1 μηι). -42 - 200911417 Fig. 9 is an electron micrograph showing the state of the particles of the sample B2 (lower white rod) The length is Ιμηη. Fig. 10 is an electron micrograph showing the state of the particles of the sample Β3 (the length of the lower white rod is Ιμηι). Fig. 1 1 is a graph showing the relationship between the amount of Ν2Η4 added and the particle size of Ag. Fig. 13 is an electron micrograph showing the state of the particles of the comparative sample 6 (the length of the lower white rod is 1 μm). Fig. 14 shows the sample D2. Particle state Electron micrograph (the length of the lower white rod is Ιμηι). Fig. 15 is an electron micrograph showing the state of the particles of the sample D5 (the length of the lower white rod is 1 μηι). Fig. 16 shows the particle state of the sample D8. Electron micrograph (the length of the lower white rod is 1 μηι). Fig. 17 is an electron micrograph showing the state of the particles of the sample D9 (the length of the lower white rod is 1 μηι). Fig. 18 shows the Ag nanometer. Fig. 19 is a graph showing the relationship between the number of Ag nanoparticles and the particle size of Ag. Fig. 20 is an electron micrograph showing the state of the particles of Comparative Sample 13 (lower white rod) Fig. 21 is an electron micrograph showing the state of the particles of the sample G 1 (the length of the lower white rod is 1 μηι). Fig. 22 is an electron micrograph showing the particle state of the sample G2 (lower white rod) The length is 1 Pm). -43- 200911417 Fig. 23 is an electron micrograph showing the state of the particles of the sample G3 (the length of the lower white rod is 1 μΠ1). Fig. 24 is a view of the structure of the apparatus of the present invention. 5 is the addition of ammonia in the examples. The elapsed time and the average particle diameter of the silver particles. Fig. 26 is an electron micrograph showing the particle state of the silver particles of the sample L1. Fig. 27 is an electron micrograph showing the particle state of the silver particles of the sample L 2 . Fig. 28 is an electron micrograph showing the state of the particles of the silver particles of the sample L 3. Fig. 29 is an electron micrograph showing the particle state of the silver particles of the sample L4. Fig. 30 is a view showing the silver particles of the sample L7. Electron micrograph of particle state. [Explanation of main component symbols] 1 〇: Silver ion solution tank 1 1 : Ammonia solution tank 12: Reduction tank 1 3 : First line 14 : 2nd line 1 5 : 3rd line 1 6 : 4th line -44 - 200911417 A : Mixing position of silver ion solution and ammonia solution B: Mixing position of silver ion solution and reducing solution