TWI331059B - Method for making fine silver powder and silver particles dispersion liquid - Google Patents

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1331059 九、發明說明： 【發明所屬之技術領域】 本發明是有關微細銀粒子粉末之製造方 法進行之微細配線描州 案相使用之銀糊膏所適用之銀微粉之製造方法。另外 本發:是有關該銀微粉分散而成之分散液。本發明 【先前技術】 未）早位之銀粒子所構成之粉末。 非常：體二之大小f4nm單位時’因其比表面積會變得 ㈣子才能具有的特性。其中，以銀奈==二 二就能進行溶結’所以對於耐熱性低之材料： 進:材枓早就受到重視。特別是隨著最近之奈米科技之 展太=製造簡單的奈米級之粒子也變得能簡便進行？ 不未早位之銀粒子粉末之製造方法，可大 及液相法。廣如法、s a 為氨相法 專刺w 氣體中之蒸為主，例如 j文獻1中揭示錢m氣料 X _ 左右之錢下使銀蒸發之方法 0.5乾（T〇rr) 9 , A 夜相去有關者，例如專制 獻2中，揭不在水相中用胺還原銀離子 相移到有機溶劑相（例如高分子量 斤出 之古# 里之分散劑）而獲得銀脒妒 =方法。又，專利文獻3中’也記载在溶劑中使銀勝體 金屬氫硼酸鹽或氫化硼酸 遇原刎（鹼 在下還原齒化銀之方法。）在^系之保護材料的存 最近，更有因應工業規槎攻吝从者 系現輕生產的貫用性奈米粒子之製 319〇〇6 5 1331059 造技術的提案。例如專利文獻4中揭示，以氧化銀為出 原料使用胺化物而大量合成銀奈米粒子之方法，又，專^ 文獻5中揭示，混合胺及銀化合物原料，藉由炫融而人： 銀奈米粒子之方法。非專利文獻丨中，尚介紹使用^ 粒子製造銀糊膏之技術。 ；、 專利文獻1 :日本專利特開2001_35255號公報， 專利文獻2 :日本專利特開平1 1-31 9538號公報， 專利文獻3 :日本專利特開2〇〇3_25331 1號公報， 專利文獻4 :日本專利特開2006-219693號公報， 專利文獻5 :國際公開第04/012884號小冊子， crt?:中許昌美等人，「銀奈米粒子在導電糊 175Γ頁子工業，化學工業社’2005年10月刊，749 (發明欲解決之課題） 用印u途為喷墨法中所使用微細配線描晝 直接二 喷墨法由於可形成微細配線，並且可以 銀=配線本體（不需要钱刻），所以不會浪費昂貴之 銀。同吩也不需要光罩、蝕- 蕤由非Α， 蝕x丨液等。但疋，由於噴墨法係 糟由非吊微小的點重疊而形成 地獲得適合實用之㈣β 力泛戶斤以有效率 重要要件。另一= 銀濃度高之分散液(印墨)為 者’為達成上述S的，=為高濃度之銀分散 利。 °周衣銀浪度高之分散液較為有 劑 然而，已往技術t，存在於銀分散液令之界面活化 319006 6 1331059 成為提高銀濃度時阻礙分散性之原因。換言之，欲提高銀 •分散液中之銀濃度，粒子就凝聚而難形成均一之分散=。 '如果能解決這個問題，銀微粉之應用可行性可望飛躍地成 長。 . 本發明是有鑑於上述現況，其目的在更能提高液狀媒 體中之粒子之分散性以高生產性製造銀微粉，提供適用於 工業生產之銀微粉之製造技術。 【發明内容】 黪 ^為了達成上述目的，本發明提供銀微粉之製造法，其 係在醇中，使用溶劑之醇類及不具有不飽和結合之胺所構 成還原助劑做為還原劑，以具有不飽和結合之分子量為 100至1000之有機化合物（例如i級胺）所構成之有機保護 •材料的存在下還原處理銀化合物，使銀粒子析出而得銀微 粉之製造方法。本發明中，醇類意指一種以上之一元醇及 多70醇（聚醇）之意.。還原助劑以使用2級胺以上之胺，即 籲以2級胺及3級胺之一種以上較佳。銀粒子之平均粒徑例 如以下述Dtem為50nm以下。 本發明提供由下列步驟所構成之銀微粉之製造方法， 即，進行上述還原處理之步驟，將含有析出銀粒子之漿液 加以固液分離，藉由構成有機保護材料之有機化合物被覆 之銀粒子以固形物回收之步驟，將上述以有機化合物被覆 之銀粒子分散於非極性或極性小之液狀溶劑中之步驟，或 再將此分散液施以離心分離處理之後，回收分散有銀粒子 之上澄液之步驟所構成。此處所述「非極性或極性小」乃 7 319006 1331059 指25°C下之電容率為以下者。 ,i述之還原處理係溶劑之_每 ，20莫耳來進行。又，可在有機保護材料/銀 •綱至20下進行，還原尊銀之莫在革 .20下可進行還原處理。 你u· 至 再者，本發明尚可提供具有下列性狀之銀粒子之 液。即’平均粒徑dte„為5GnniWT之銀粒子粉末分散於低 機溶劑而成銀粒子之分散液中，具備酸驗⑽ f 分散液中之銀濃度為5至90質量％，黏度 為50mPa· 3以下’表面張力為8()mN/m以下等牛頓流體性 狀之銀粒子分散液。該分散液具備優異之分散性，例如可 通過具有液中之銀粒子的平均粒徑+2〇11111孔徑之膜過減哭 (membrane filter)程度之分散性。 又，本發明提供在1級胺中，與2級胺或3級胺之任 -種或兩種之共存下，在80至2⑽。c溫度範圍下，還原處 籲理銀鹽而成銀微粉之製造方法。 本發明所得銀微粉由於為奈米粒子，所以在低極性之 液狀溶劑中呈現極為優良之分散性。因此，調製成高濃度 之銀分散液也能防止粒子之凝聚•沈澱，所以甚適用於微 細配線描晝用印墨或銀糊膏。又，本發明之製造方法由於 銀粒子之還原率或分散效率優異，且適合大量生產，所以 有助於分散性極佳之銀微粉之工業普及。 【實施方式】 (實施發明之最佳形態） 319006 8 1331059 依照本發明，如下 步驟」、「分散步驟」可得：，，里由「還原步驟」、「固液分離 •經由「分級步驟」可得：：：於液狀溶劑中之銀微粉。更 •劑中之銀微粉。之後 極良之銀粒子分散在液狀溶 ，狀溶劑中以高濃度分散有:：由二調整步驟」可得所定液 驟之間必要時可插人散液（例如印墨❸。各步 心驟專。以下就各步驟說明之。 洛解銀化物於具有還历 粒子析出之步驟。劑、=劑2以還原，使銀 醇可使銀化物之银還原而析出金屬之銀。此；夺藉 機保護材料之存在下進行還原反應時，可合成構^ 材料之化合物所覆蓋之粒徑整齊球狀之銀微粒子。 惟本發明之特徵，係還原劑除了溶劑的醇以外，更使 2劑。該還原助劑是由比醇類還原力強之物質所構成。 藉由使用還原助劑使醇無法還原之銀被還原，而可提 之還原率。據本發明人等之研究檢討結果’雖然’增加若 干有機保護材料之使用量對於提升分散效率（參照下文）有 利’但有機㈣材料之使用量增多，還料有下降之傾向。 然而，即使使用還原助劑時，有機保護材料之使用量增多 時’也能獲得高還原率，結果在製造分散性極佳之銀粒子 所構成之銀微粉之際，能大幅度提升銀之良率。 還原處理之順序例如只要如下述即可。首先，於醇中 混合有機保護材料，於該溶液中添加銀化物使之溶解。之 後，在備有迴流設備之容器中，加溫而開始還原反應。在 319006 9 1331059 迴流狀態下進行反應時，其效率較佳。起初僅藉醇之還原 .力使銀粒子析出為理想。當藉由醇進行還原反應之際，雖 —可添加一部分或全部之還原助劑，但藉由醇之還原反應大 致終了之際，添加還原助劑’將尚未還原而殘留之銀化物 加以還原為較佳。 、還原反應溫度以50至20(TC範圍内為佳。當反應溫度 過低，醇類之還原作用無法發揮，不但反應難於進展，同 時有發生還原不良之危險。相反地，反應溫度過高時，還 肩過度，粒子之粗大化或粒經之分散有過大之危險。就喷 墨用途而s，以形成平均粒徑Dtem(參照下文）為⑽以下 之銀微粒子為理想。該時，反應溫度以50至範圍較 佳，其中，以60至140。(：範圍為更佳。在8〇至13代範圍 官理時，更容易獲得優異之結果。 又如視情況，還原可分為多段實施。~，還原急激進 你，/子之成長會過於顯著°為了有效控制粒徑，首先 产下行還原反應，之後轉為高溫，或以慢慢提升溫 :生顯此：’；差過大時在粒度分布上會有 。。以内為理相…以最低溫度及最高溫度之差以20 内為更佳。心以嚴密控制在15°c以内，特別是lot:以 醇類 本發明中做為 或多元醇）。藉此， 在迴流狀態下進行 主要還原劑之溶劑是使用醇類（一元醇 可合成雜質混入少之銀奈米粒子。反應 ，其效率較佳。因此，醇類之沸點以較 319006 10 1331059 低者為佳，其中以30(rc以下為宜，以2〇〇。〇以下較佳，以 • 15 0 C以下更佳。具體而言，使用一元醇時，沸點在8 〇至 _ 200°C範圍内，使用多元醇時沸點在15〇至3〇〇t>c範圍内為 佳。儘可能醇類以碳鏈長者就還原性之觀點而言，較佳。 •例如可使用異丁醇、卜丁醇、2_丙醇、卜己醇、乙醇等。 銀化物 供應銀離子來源的銀化物，可使用可溶於醇類溶劑中 之氯化銀、硝酸銀、氧化銀、碳酸銀等，其中以工業上容 易取得且比較廉價之硝酸銀較為適用。銀化合物之使用 ^，以溶劑之醇㈣lkg，設定在Q 2 i 2()莫耳左右之銀 里為理想。在上述範圍内，相對於有機保護材料或還原助 劑’銀量比率設在後述適#範圍内之銀化合之用量為佳。 就溶液中之銀的莫耳濃度而言，大概以銀濃度在〇 〇5至 5. 0莫耳/l左右為準就可以。 直機保謨姑料 進仃還原反應之際，溶劑中共存有有機 =件:構成該有機保護材料之有機化合物是有 . 曼柯枓之功月匕。作為有機保護.材 類，雖可列舉如軸或脂㈣，㈣具有不飽和结 口者為適當。依據本發明人之 自溶解有銀鹽之均一性高 仏本還原步驟裡’ 如果使用不具有不飽和結合之：析出銀之方法’ 二;=二，達成銀微粉之合成。相對於此， 有不飽和結合之有機化合物時，可知能合成其表面 319006 測藉由有機化= 。其原因尚多不詳處，目前推 表面吸著”：：二具有不飽和結合之影響，所析出銀之 程度以：=: 有機化合物使銀之還原在某種 1之粒成護材料之機能，其結果， 確知即使有該不飽和銀粒子。另外，也 溶劑之分散性。 尚能充分確保對於有機 祇要iLtr月人之研究所知，該時之不飽和結合數目， 夠。因择加；：Γ:分子中至少具有一個不飽和結合就足 保護材^中之石山Γ。5數目’就能調整覆蓋銀粒子表面之 同之有機t物所以視需求可添加不飽和結合數目不 物，2保護材料可使用分子量為m至麵之有機化合 中Μ为子量為1〇〇至4〇〇之有機化合物較佳。當分 ‘t滿粒子之凝聚抑制效果低。當分子量超過 有機二雖然凝聚抑制力大，但沸點也變高，所以使用該 口力被覆之銀粒子做為印墨或糊膏使用時，塗布該 :土或^後之燒結時，該保護材料不容易引起揮散。因 ☆所仔銀塗膜會含較多雜質。又，特別是印墨中，存在 Γ銀粒子表面之保護材料之量增多，對於製得高銀濃度之 印墨上不利。 還原反應時， 成保護材料之有機 有機保護材料/銀 溶劑中共存之有機保護材料之量，以構 化合物及銀化物中之銀的莫耳比率即， 之莫耳比率可為〇. 05至20,其中以1. 〇 319006 12 丄丄u；)y 5為車乂佳u 2. 〇至i 〇為更佳。#有㈣ 2過少時，覆蓋銀粒子表面之有機化合物吏 Ή，不能充分確保在溶液中之分散性。相反地，過多時， 卩，中之銀含量之相對比率降低，同時增加有機保護材料 之成本，從工業生產觀點而言不佳。具體而言，例如使用 油胺作為有機保護材料時，設定有機保護材料/銀之莫耳 比率在5±3範圍較為有效。 罄▲構成有機保護材料之有機化合物之例，以脂肪酸而 "’例如两稀酸 '油酸、亞·油酸、花生四晞酸、神經酸、 桐酸、異油酸、亞麻酸等。 /_而言，例如三烯丙胺、油胺等。其中，以！級 ^為1st佳’尤以油胺（C9Hi8=G9Hi7_NH2)對於銀粒子表面之附 者力因不會太強，所以粒子表面之保護材料從油胺變為更 低分子量之有機化物之操作比較容易，獲得燒結溫度較低 之銀微粉上極為有利。這些做為有機保護材料，可單獨使 _用亦可2種以上併用。 還原助劑 還原助劑係僅藉由醇類之還原力無法還原之銀化物， 再進行還原用之還原劑’在為了提升銀之還原率上極為重 要在本發明中疋使用胺，以分子量為50至1000之範圍 為么。還原助劑用之胺類，可使用丨級胺或2級胺以上之 各種胺類。但是使用1級胺時，跟有機保護材料不同，選 用不具有不飽和結合之化合物。胺類中，以使用還原力高 之2級胺或3級胺較佳。即使使用1級胺也能提升還原率， 319006 13 1331059 考慮使用有機保護材料量變動時，分散效率（參照下文 .之^定性等，α 2級胺或3級胺較為有效。還原助劑之使 -用里，使構成還原助劑之胺及銀化合物中之銀間的莫耳比 率，即:還原助劑/銀之莫耳比率以〇1至2〇為理想。:隹 然，此等可添加多些也無妨，惟在上述範圍内，對於* 之效果以及對於之後之分散效果，容易在其平衡上卿^ 利。還原助劑/銀之莫耳比率以較佳 ^兩 至10更佳。 ·ϋ[Technical Field] The present invention relates to a method for producing a silver fine powder to which a silver paste for use in a micro-wiring method is used in the production method of a fine silver particle powder. In addition, the present invention is a dispersion in which the silver fine powder is dispersed. The present invention [Prior Art] A powder composed of silver particles in the early position. Very: When the size of the body 2 is f4nm, the characteristic of the sub-surface will become (4). Among them, it is possible to carry out the dissolution by using Yinnai == two. Therefore, the material having low heat resistance has been paid attention to. In particular, with the recent nanotechnology exhibition too, it is easy to make simple nano-particles. The method for producing the silver particle powder which is not in the early position can be larger than the liquid phase method. Wide as the law, sa is the ammonia phase method specializes in the steam in the gas, for example, j document 1 reveals the money m gas X _ around the money to make the silver evaporation method 0.5 dry (T〇rr) 9 , A The night phase goes to the relevant person, for example, in the special system 2, to remove the silver phase in the aqueous phase by amine reduction to the organic solvent phase (for example, the dispersing agent in the high molecular weight of the ancient #) to obtain the silver 脒妒 = method. Further, in Patent Document 3, it is also described that in the solvent, the silver-rich metal borohydride or the hydroborated acid is used as the raw material (the method of lowering the toothed silver in the base). In response to the industrial regulations, the 319 〇〇 6 5 1331059 manufacturing technology proposal was adopted for the light-produced nano particles. For example, Patent Document 4 discloses a method of synthesizing a large amount of silver nanoparticles using an amination product using silver oxide as a raw material, and further discloses that a mixed amine and a silver compound raw material are blended by a person of silver: silver The method of nanoparticle. In the non-patent literature, a technique for producing a silver paste using ^ particles is also described. Patent Document 1: Japanese Laid-Open Patent Publication No. 2001-35255, Patent Document 2: Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei. Japanese Patent Laid-Open Publication No. 2006-219693, Patent Document 5: International Publication No. 04/012884 pamphlet, crt?: Zhong Xuchangmei et al., "Silver Nanoparticles in Conductive Paste 175ΓPage Industry, Chemical Industry Society' 2005 October issue, 749 (problem to be solved by the invention) The use of the micro-wiring method used in the inkjet method to describe the direct two-ink method can form fine wiring, and can be silver=wiring body (no need for money), Therefore, it is not a waste of expensive silver. The same actor does not need a mask, eclipse - 蕤 by non-Α, 丨x 丨 liquid, etc., but 疋, because the inkjet method is formed by the overlap of non-hanging tiny dots. Practical (4) Beta force is an important factor for efficiency. Another = dispersion with high silver concentration (ink) is 'for the above S, = high concentration of silver dispersion. ° Zhouyi silver wave High dispersion is more potent, however, it has been The operation of t is present in the silver dispersion to activate the interface 319006 6 1331059. This is the reason for hindering the dispersion when the concentration of silver is increased. In other words, in order to increase the concentration of silver in the silver dispersion, the particles aggregate and it is difficult to form a uniform dispersion =. 'If this problem can be solved, the application feasibility of silver micropowder is expected to grow rapidly. The present invention is based on the above-mentioned situation, and its purpose is to improve the dispersibility of particles in a liquid medium to produce silver micropowder with high productivity. In order to achieve the above object, the present invention provides a method for producing a silver fine powder which is used in an alcohol, a solvent using an alcohol and having no unsaturated bond. The reducing aid constituting the amine is used as a reducing agent, and the silver compound is reduced in the presence of an organic protective material composed of an organic compound having an unsaturatedly bonded molecular weight of 100 to 1000 (for example, an i-type amine) to cause silver particles. The method for producing silver micropowder is precipitated. In the present invention, the alcohol means more than one of the monohydric alcohol and the polyhydric alcohol (polyol). The auxiliary agent is preferably one or more amines of a secondary amine or higher, that is, one or more amines and a tertiary amine. The average particle diameter of the silver particles is, for example, 50 nm or less in the following Dtem. The present invention provides the following steps. A method for producing a silver fine powder, that is, a step of performing the reduction treatment, a step of solid-liquid separating a slurry containing precipitated silver particles, and recovering the silver particles coated with the organic compound constituting the organic protective material as a solid matter The step of dispersing the organic compound-coated silver particles in a non-polar or polar liquid solvent, or subjecting the dispersion to a centrifugal separation process, and recovering the dispersion of the silver particles. As used herein, "non-polar or small polarity" is 7 319006 1331059 which means that the permittivity at 25 ° C is the following. The reducing treatment solvent described in i is carried out at 20 moles per liter. In addition, it can be carried out under the organic protective material/silver to 20, and the reduction of the silver can be carried out under the 20th. Further, the present invention can provide a liquid of silver particles having the following traits. That is, the average particle diameter dte is a dispersion of silver particles of 5GnniWT dispersed in a low-methanol solvent, and has a silver concentration of 5 to 90% by mass and a viscosity of 50 mPa·3 in the acid test (10) f dispersion. The following silver particle dispersion having a Newton fluid property such as a surface tension of 8 () mN/m or less. The dispersion has excellent dispersibility, for example, by having an average particle diameter of silver particles in liquid + 2 〇 11111 pore diameter. The degree of dispersibility of the degree of membrane filter. Further, the present invention provides a temperature of 80 to 2 (10) c in a first-grade amine in the presence of either or both of a secondary amine or a tertiary amine. In the range, the method for producing a silver fine powder by the reduction of the silver salt is used. Since the silver fine powder obtained by the present invention is a nanoparticle, it exhibits excellent dispersibility in a liquid solvent of low polarity. The silver dispersion can also prevent the aggregation and precipitation of particles, so it is suitable for inks or silver pastes for fine wiring. Moreover, the manufacturing method of the present invention is excellent in reduction rate or dispersion efficiency of silver particles, and is suitable for mass production. So helpful The industrial fineness of silver fine powder is excellent. [Embodiment] (Best mode for carrying out the invention) 319006 8 1331059 According to the present invention, the following steps and the "dispersion step" are obtained by: "reduction step", "Solid-liquid separation: via the "grading step"::: Silver fine powder in a liquid solvent. More silver powder in the agent. After that, the excellent silver particles are dispersed in a liquid solution, and the solvent is dispersed at a high concentration: by two adjustment steps, a liquid can be inserted between the predetermined liquid steps (for example, ink sputum. The following is a description of each step. The solution of the silver solution has the step of precipitating the particles. The agent, the agent 2, is reduced, so that the silver alcohol can reduce the silver of the silver and precipitate the silver of the metal. When the reduction reaction is carried out in the presence of the protective material, the silver particles having a uniform particle size covered by the compound of the material can be synthesized. However, the present invention is characterized in that the reducing agent is two more than the solvent alcohol. The reducing agent is composed of a substance having a stronger reducing power than the alcohol. The reduction of the silver which can be reduced by the use of a reducing aid can be reduced, and the reduction rate can be improved. Increasing the amount of organic protective material used is beneficial to improve the dispersion efficiency (see below), but the use of organic (four) materials is increasing, and there is a tendency to decrease. However, even when using reducing auxiliaries, organic protection When the amount of the material used is increased, a high reduction ratio can be obtained, and as a result, when the silver fine powder composed of silver particles having excellent dispersibility is produced, the yield of silver can be greatly improved. For example, the order of the reduction treatment is as follows First, an organic protective material is mixed with an alcohol, and a silver compound is added to the solution to dissolve it. Thereafter, the reduction reaction is started by heating in a vessel equipped with a reflux apparatus. The reaction is carried out under reflux at 319006 9 1331059. At the same time, the efficiency is better. At first, only the reduction of the alcohol is used to force the silver particles to precipitate. When the reduction reaction is carried out by the alcohol, although some or all of the reduction aids may be added, the reduction by the alcohol is obtained. At the end of the reaction, the reduction aid is added to reduce the remaining silver halide to be reduced. Preferably, the reduction temperature is 50 to 20 (the range of TC is preferred. When the reaction temperature is too low, the reduction of the alcohol The effect cannot be exerted, not only the reaction is difficult to progress, but also the risk of reductive failure occurs. Conversely, when the reaction temperature is too high, the shoulder is excessive, and the particles are coarsened or grained. There is a danger of being too large. In terms of ink jet use, it is preferable to form silver fine particles having an average particle diameter Dtem (refer to the following) of (10) or less. In this case, the reaction temperature is preferably in the range of 50 to 60, and in the range of 60 to 140. (: The range is better. In the 8th to 13th generation range, it is easier to get excellent results. Also, depending on the situation, the restoration can be divided into multiple implementations. ~, restore radicals into you, / son growth To be too significant. In order to effectively control the particle size, firstly, the reduction reaction is produced, and then the temperature is changed to high temperature, or the temperature is slowly raised: the growth is: '; when the difference is too large, there will be a particle size distribution. The difference between the lowest temperature and the highest temperature is preferably within 20. The core is tightly controlled within 15 ° C, especially in the case of alcohol: in the present invention or as a polyol). The solvent of the reducing agent is an alcohol (the monovalent alcohol can be synthesized by mixing impurities with less silver nanoparticles. The reaction is more efficient. Therefore, the boiling point of the alcohol is preferably lower than 319006 10 1331059, wherein 30 (the following is preferably rc, preferably 2 〇〇. 〇 is preferably below, preferably 1500 ° C or less. Specifically, one yuan is used. In the case of alcohol, the boiling point is in the range of 8 〇 to _ 200 ° C, and the boiling point in the range of 15 〇 to 3 〇〇 t > c is preferably used when the alcohol is used. As far as possible, the alcohol is based on the reduction of the carbon chain. Preferably, for example, isobutanol, butanol, 2-propanol, dihexyl alcohol, ethanol, etc. can be used. The silver compound supplies a silver ion-derived silver compound, and can be used in a solvent soluble in an alcohol solvent. Silver, silver nitrate, silver oxide, silver carbonate, etc., among which silver nitrate which is industrially easy to obtain and relatively inexpensive is suitable. Silver compound is used, and the alcohol (4) lkg of the solvent is set to the silver of Q 2 i 2 () In the above range, the amount of silver combined with the organic protective material or the reducing aid 'the silver amount ratio is preferably within the range of the later description. In terms of the molar concentration of silver in the solution, The silver concentration is 〇〇5 to 5.0 m/l or so. When the machine is protected, the organic solvent is coexisted in the solvent. The organic compound constituting the organic protective material is Manke's work. As an organic protection material, it can be enumerated as The shaft or fat (4), (4) is suitable for having an unsaturated junction. According to the present inventors, the homogenization of the self-dissolving silver salt is high. In the present reduction step, 'If the use does not have an unsaturated bond: the method of depositing silver' ; = two, to achieve the synthesis of silver micro-powder. In contrast, when there is an organic compound that is unsaturatedly combined, it can be known that the surface can be synthesized 319,006 by organication =. The reason is still unknown, and the current surface is sucked": : The effect of the unsaturation of the two, the degree of the precipitated silver is: =: The function of the organic compound to reduce the silver in a certain particle forming material, and as a result, it is known that even the unsaturated silver particles are present. Also the dispersibility of the solvent. It is still sufficient to ensure that for the organic as long as iLtr Yueren's research, the number of unsaturated bonds at that time is sufficient. Because of the addition;: Γ: at least one unsaturated bond in the molecule The protective material ^ stone stone Γ. 5 number 'can adjust the surface of the same silver particles covering the surface of the silver particles, so the number of unsaturated bonds can be added depending on the demand, 2 protective materials can be used in the molecular weight m to the surface of the organic compound It is preferred that the quinone is an organic compound having a particle size of from 1 Å to 4 Å. When the molecular weight exceeds that of the organic component, the aggregation resistance is large, but the boiling point is also high, so the use is When the silver-coated particles are used as ink or paste, the protective material is not likely to cause volatilization when the material is coated with the soil or the solder. The silver coating film contains a lot of impurities. In particular, in the ink, the amount of the protective material on the surface of the silver particles is increased, which is disadvantageous for the ink having a high silver concentration. In the reduction reaction, the amount of the organic protective material coexisting in the organic organic protective material/silver solvent of the protective material, the molar ratio of the silver in the structuring compound and the silver compound, that is, the molar ratio may be 〇. 05 to 20 Among them, 1. 〇319006 12 丄丄u;) y 5 is the car 乂u u 2. 〇 to i 〇 is better. #有(四) 2 When the amount is too small, the organic compound 吏 覆盖 covering the surface of the silver particles cannot sufficiently ensure the dispersibility in the solution. On the contrary, when the amount is too large, the relative ratio of the silver content in the crucible is lowered, and the cost of the organic protective material is increased, which is not preferable from the viewpoint of industrial production. Specifically, for example, when oleylamine is used as the organic protective material, it is effective to set the organic protective material/silver molar ratio in the range of 5 ± 3.罄 ▲ An example of an organic compound constituting an organic protective material, such as a fatty acid, such as oleic acid, linoleic acid, arachidonic acid, nervonic acid, tungstic acid, isooleic acid, linolenic acid, and the like. In terms of /_, for example, triallylamine, oleylamine, and the like. Among them, to! The level ^ is better than 1st good', especially oleylamine (C9Hi8=G9Hi7_NH2). The effect on the surface of the silver particles is not too strong, so the operation of the protective material on the surface of the particles from oleylamine to lower molecular weight is easier. It is extremely advantageous to obtain a silver fine powder having a lower sintering temperature. These are organic protective materials, and they can be used alone or in combination of two or more. The reduction aid reduction aid is a silver compound which cannot be reduced only by the reducing power of the alcohol, and the reducing agent for reduction is extremely important in order to increase the reduction ratio of silver. In the present invention, an amine is used, and the molecular weight is What is the range of 50 to 1000? As the amine for the reducing aid, various amines such as a guanamine or a quaternary amine can be used. However, when a primary amine is used, unlike an organic protective material, a compound which does not have an unsaturated bond is selected. Among the amines, a secondary amine or a tertiary amine having a high reducing power is preferably used. Even if a grade 1 amine is used, the reduction rate can be increased. 319006 13 1331059 Considering the use of an organic protective material, the dispersion efficiency (see the following paragraphs, etc., α 2 or 3 amines are more effective. - In the use, the ratio of the molar ratio between the silver in the amine and the silver compound constituting the reducing aid, that is, the molar ratio of the reducing aid/silver is preferably 〇1 to 2〇.: 隹然, these may It is also possible to add more, but within the above range, it is easy to balance the effect of * and the dispersion effect afterwards. The ratio of reduction aid/silver molar ratio is preferably better than two to ten. ·ϋ

• _構成還原助劑之胺之例子如Ν，Ν_二乙基乙酵胺H -曱基乙醇胺、Ν-(2_胺乙基）乙醇胺、卜甲基二乙醇胺、 .二丁基乙醇胺、Ν_甲基乙醇胺、二異丙胺、二乙烯三 胺、二乙醇胺、雙（2-氰乙基）胺、亞胺基雙（丙胺）、 .丁基苯胺、二苯胺、雙-2-乙基己胺、二辛胺、三甲胺、二 曱基乙胺、Ν-亞硝基二曱胺、三乙胺、四甲基乙稀二胺、 乙基乙醇胺、曱基二乙醇胺、三丙烯胺、Ν_甲基一 φ亞胺基雙（丙胺）、三乙醇胺、3_(二丁胺基）丙胺、Ν_亞硝 基二苯胺、三苯胺、三正辛基胺等。其中，就工業上較容 2取传’胺類中還原力較強之二乙醇胺或三乙醇胺為適 宜。做為還原助劑之該胺化物可單獨使用亦可2種以上併 用。 五_類製法 製造銀微粉之另類方法係在1級胺中，將銀鹽與2級 胺或3級胺之單一或雙方之共存下，且在8〇至2〇〇t之溫 度範圍下還原處理可以製成。此時，替代上述醇類使用丄 319006 14 1331059 級胺做為銀離子之反應溶劑兼還原劑之用途，所以使用之 •〗級胺、2級胺及3級胺之種類可如同前述。 - 依據本發明方法，皆可製得平均粒徑Dtem為50nm以下 之銀微粉。結晶粒徑仏為50nm以下，單結晶化度（Dtem/Dx) 以2. 0以下為佳。 _固液分離步驟 遇原反應終了後之漿液中，存在有構成有機保護材料 罄之有機化合物（保護材）所被覆之銀粒子。將該漿液進行固 液分離，而回收固形物之銀微粉。該固液分離操作可配合 洗淨操作重複進行數次較為有效。例如可按照下述[丨]至[4] 之順序重複進行。 [1] 將還原反應後H藉傾析法或離^分離機進行 固液分離，去除上澄液。 [2] 添加甲醇於上述經固液分離所得固形物（即，生成 物）’加以超音波分散處理，洗除附著於生成物表面之雜質。 []t[l] [2]項之操作重複進行數次，盡可能 表面之雜質。 ’、云 物 [4]最後再行U]項之操作，廢棄上澄液 而採取固形 重複3次[1]至[4]項之步 下記實施例中 所產生銀微粉量（包含存在於粒子表面之 可按照下列順序求得。 何抖里）• Examples of amines constituting a reduction aid such as hydrazine, hydrazine-diethylethylamine H-mercaptoethanolamine, hydrazine-(2-aminoethyl)ethanolamine, methyldiethanolamine, dibutylethanolamine, hydrazine _ Methylethanolamine, diisopropylamine, diethylenetriamine, diethanolamine, bis(2-cyanoethyl)amine, iminobis(propylamine), .butylaniline, diphenylamine, bis-2-ethylhexylamine , dioctylamine, trimethylamine, dimercaptoethylamine, hydrazine-nitrosodiamine, triethylamine, tetramethylethylenediamine, ethylethanolamine, mercaptodiethanolamine, triacrylamide, hydrazine Methyl-φimino bis(propylamine), triethanolamine, 3-(dibutylamino)propylamine, hydrazine-nitrosodiphenylamine, triphenylamine, tri-n-octylamine, and the like. Among them, industrially, it is suitable to take the diethanolamine or triethanolamine which has a strong reducing power in the amine. The amination product as a reducing aid may be used singly or in combination of two or more. The fifth method of making silver micropowder is a method in which a silver salt is coexisted with a single or both of a grade 2 amine or a grade 3 amine in a grade 1 amine, and is reduced at a temperature range of 8 Torr to 2 Torr. Processing can be made. In this case, instead of using the above alcohol, 丄 319006 14 1331059 amine is used as a reaction solvent and a reducing agent for silver ions, so the types of the amine, the second amine and the tertiary amine which are used may be as described above. - According to the method of the present invention, silver fine powder having an average particle diameter Dtem of 50 nm or less can be obtained. The crystal grain size 仏 is 50 nm or less, and the single crystallinity (Dtem/Dx) is preferably 2.0 or less. _ Solid-liquid separation step In the slurry after the end of the original reaction, silver particles coated with an organic compound (protective material) constituting the organic protective material are present. The slurry was subjected to solid-liquid separation, and the silver fine powder of the solid matter was recovered. This solid-liquid separation operation can be repeated several times in conjunction with the washing operation. For example, it can be repeated in the order of [丨] to [4] below. [1] After the reduction reaction, H is subjected to solid-liquid separation by decantation or separation, and the supernatant is removed. [2] Methanol is added to the solid matter (i.e., product) obtained by solid-liquid separation as described above, and subjected to ultrasonic dispersion treatment to remove impurities adhering to the surface of the product. The operation of []t[l] [2] is repeated several times, as much as possible on the surface. ', cloud material [4] finally re-run U], discard the liquid and repeat the solid three times [1] to [4], the amount of silver powder produced in the example (including the presence of particles) The surface can be obtained in the following order.

質量^)。測定提供上述[1]項前之反應後之漿液質量做為A 319006 15 為液分取得樣品(例如氣)，測定其質量做 -4〇ml ? /物，放入已知質量之容器中之後，在 乾燥12小時。敎所得乾燥物質量做為U量值。— i = V)所產纽微粉之量D(包含存在於粒子表面之保 4材料1 )，可藉由下式算出。 ’、 d=Cx(A/B) 本發U月書中’還原反應之成功率之指標所用的 原率」’可由反應開始前之銀化合物所含銀質量e，及上 之比率而算出。即，還原率（％)可藉下式求得。 還原率（％)=D/Exl00 該2原率之數值因表示做為反應生成物所回收之 ^人完全還原時，銀微粉之質量包括其表面具有有 口勿^保護材料）所構成值，也可能出現高於⑽％之還 銀微於^為止，依據本發明人所知，按照本發明方法， 銀微叔之逛原率確知大約在85至12〇%範圍。 分散步驟 [1]上述固液分離步驟後所得固形物，添加到下 液狀溶劑中。 ’、 液狀溶 有機化合物為主體之非極性或極性低之液狀溶劑，具 體而言，為在25。〇下之電容率為15以下之液狀溶^。例 319006 16 1331059 如異辛烧、正癸燒、正十—烧、正十四燒 :燒、已烧、庚燒等之脂肪族烴、苯等之芳香二:;之; == 適用。該液狀溶劑在能維持上述低^ 内亦了添加胺類等之其他分散助劑。 中。⑵其次’施以超音波分散’使固形物分散在液狀溶劑 分級步驟 步驟所得銀粒子之分散液，由於保護材料附 ::::Γ等，混合有分散性極良之銀粒子及分散性稍 因此，從這些銀粒子中僅萃取分散性極良之 為有# 分散液，在麵性能良好之印墨或糊膏上極 為有：。/刀級步驟乃獲得上述分散液之步驟。 :級操作可使轉心機來進行。離心機之操作條件隨 規模或目的之分散性之水準而多少有異，舉例而 :训八散步驟所得分餘，以離心機在300一下操 八π鐘’分離為上澄液及沈降物f。據此所得上澄液中 有刀散1·生極為良好之銀粒子。因此，回收該上澄液可 付由分散性極為良好之銀粒子所構成之銀微粉。 分散效率 广述所传上澄液中所含有銀量及沈降物質量之比率稱 之為[分散效率]，其定義如下： 、刀政效率（％)=([固液分離步驟所產生銀微粉之質量 (上述D)]-[離心後’附著於容器壁面之物質之質量])/ [口液刀離步驟所產生銀微粉之質量（上述D)]xl00 319006 17 1331059 此處，上迷附著於容器壁面之物質之質量， 收f登液後，在2〇(rC下真空乾燥6小時而測定之。分散 效虿愈南表不粒子做為分散膠體之分散性愈高 _以上為宜，其中以7〇%以上較佳，以更 收率 又住 在最後的分級步驟後所得分散液中，作為表示回收多 少銀之指標，而規定「收率」。收率之定義如下： 测收率（％>([還原率（％)]/1GG)x([分散效率⑻]/⑽） 胃收率高時，乃表示相對於原料所使用之銀化合物中的 銀量，分散性極為良好之銀微粉之收率高之意。 調整步驟 ^ ㈣t在分級步驟所得銀粒子分散液（上澄液），藉真空乾 各機浪縮至看不到液體。再分散該濃縮㈣ 而形成調整為適當銀濃度之八吟π ^ ^ ^ 所旦田跟/辰度之刀散液。銀濃度可能高達90 φ f4%左右°分散液中之銀漠度可藉ICP分析分散液而求 得。 上述步驟中所得分散液，係擴大其規模也難發生標度 因子’而具有安定特性之銀奈米粒子狀谬體液。Quality ^). The mass of the slurry after the reaction before the above [1] is determined as A 319006 15 A sample (for example, gas) is obtained as a liquid, and the mass is determined to be -4 〇ml? / after being placed in a container of known quality. , dried for 12 hours. The dry matter quality obtained by 敎 is taken as the U value. — i = V) The amount D of the powder produced (including the material 1 present on the surface of the particle) can be calculated by the following formula. ', d = Cx (A / B) The original rate used in the index of the success rate of the reduction reaction in the U-month book is calculated from the silver mass e of the silver compound before the start of the reaction, and the ratio of the above. That is, the reduction rate (%) can be obtained by the following formula. Reduction rate (%)=D/Exl00 The value of the 2 original rate is a value represented by the mass of the silver fine powder including the surface of the powder, which is recovered by the reaction product. It is also possible that more than (10)% of the repayment of silver is less than ^, and according to the inventors' knowledge, according to the method of the present invention, the silver micro-uncle's stroll rate is known to be in the range of about 85 to 12%. Dispersion step [1] The solid matter obtained after the above solid-liquid separation step is added to the lower liquid solvent. The liquid soluble organic compound is a non-polar or low-polarity liquid solvent of the main body, specifically, at 25. The submersible has a permittivity of 15 or less. Example 319006 16 1331059 Such as isooctane, simmering, simmering, burning, burning, burning, smoldering, etc., aliphatic hydrocarbons, benzene, etc. Aroma 2:;;; = apply. The liquid solvent may be added with other dispersing aids such as amines while maintaining the above-mentioned low level. in. (2) Next, 'Ultra-sonic dispersion' is used to disperse the solid matter in the dispersion step of the silver particles obtained in the liquid solvent fractionation step, and the silver-containing particles with excellent dispersibility are mixed due to the protective material::::Γ, etc. Therefore, it is possible to extract only the dispersing liquid from these silver particles, and it is extremely excellent in the ink or paste having good surface properties. The / knife step is the step of obtaining the above dispersion. : Level operation can be performed by the rotary machine. The operating conditions of the centrifuge vary with the scale of the scale or purpose. For example: the score of the training step is divided into the upper liquid and the sediment by the centrifuge at 300 rpm. . According to this, there is a silver particle in the upper liquid which is very good. Therefore, the supernatant liquid can be recovered by paying silver fine powder composed of silver particles having extremely excellent dispersibility. Dispersion efficiency The ratio of the amount of silver contained in the liquid to the sediment and the mass of the sediment is called [dispersion efficiency], which is defined as follows: Knife efficiency (%) = ([Silver powder produced by solid-liquid separation step] The mass (the above D)] - [the quality of the substance attached to the wall surface of the container after centrifugation]) / [The quality of the silver micropowder produced by the liquid knife away from the step (above D)] xl00 319006 17 1331059 Here, the attachment The quality of the material on the wall surface of the container is measured by vacuum drying at 2 Torr (rC for 6 hours). The dispersion effect is higher. The higher the dispersion of the particles as the dispersed colloid, the higher the dispersion. Among them, it is preferably 7 % by weight or more, and in the dispersion obtained after the final classification step in a more yield, the "yield" is defined as an index indicating how much silver is recovered. The yield is defined as follows: (% > ([reduction rate (%)] / 1GG) x ([dispersion efficiency (8)] / (10)) When the gastric yield is high, it means that the dispersibility is extremely good with respect to the amount of silver in the silver compound used for the raw material. The yield of silver micropowder is high. Adjustment step ^ (4) t Dispersion of silver particles obtained in the classification step (Shangcheng liquid), by vacuum drying each machine to reduce the liquid to see no liquid. Then disperse the concentration (4) to form a suitable concentration of silver in the eight 吟 π ^ ^ ^ dantian / Chen degree knife liquid. The silver concentration may be as high as 90 φ f4%. The silver infiltration in the dispersion can be obtained by analyzing the dispersion by ICP. The dispersion obtained in the above step is difficult to scale and has a stable property. Silver nanoparticle sputum body fluid.

依據本發明之銀微粉之平均粒徑〜^可按照下列方法 求得。 i^A#_DTEM 本發明中，銀粒子之平均粒徑採用透過型電子顯微鏡 319006 上331059 (TEM)所求仔之平均粒徑Dtem。即，藉透過型電子顯微鏡以 、600, 000倍之倍率所觀察之粒子中，測量未重疊之期個 粒子之粒徑而計算其平均粒徑值。本發明中可得為 • 50nro以下之銀微粉。微細配線用途以D為2〇咖以下者 較適用，=15mn以下者更為適用，以1〇mn以下者最為適 用。下述貫施例中，透過型電子顯微鏡（TEM)是採用日本電 子公司製品之JEM-2010型。 本發明所得分散液之物性說明如下。 卜黏廑 依據本發明可得低黏度之銀奈米印墨。實施例中，黏 度係藉由在東機產業公司製品之R55〇型黏度計re55〇l上 安裝錐形轉子G.8> 25ΐ之條件下測定而得。此時，適於 使用喷墨法形成配線，印墨之黏度以5〇mPa · s以下為宜， 其中以40mPa · s以下較佳。例如調整在〇. i至4〇mpa · s 耗圍’只要調整在〇. ；!至2〇mPa· s範圍就可以。使用黏度 調整在該範圍内之銀奈米印墨時，不容易發生喷嘴阻塞現 象，可順利地形成液滴。黏度之下限隨用途而可規範在 ImPa · s 以上。 表面張力 本發明之銀粒子分散液在25。〇下之表面張力為 80mN/m以下。因此’適合作為於喷墨法中之配線形成用材 料。表面張力大之分散液，在噴嘴先端之彎月形（meniscus) 之形狀不穩定’所以吐出量或吐出時機之調控困難，基板 上著落之液滴的沾濕性不佳，而產生配線平坦性不良之結 319006 19 1331059 杲。然而，本發明之銀粒子分散液，因其表面張力在8〇mN/m ^以下，所以不會發生上述問題，可獲得品質良好之配線。 該表面張力乃使用協和界面科學公司製品之型儀 器’在25°C之恆溫下測得。 •膜濾之孔姆 本發明之銀粒子分散液是要通過具有銀粒子粉末之平 •均粒徑（DTE«) + 2()nro之孔徑之膜濾。由於要通過只比銀粒子 之平均粒徑（D™)大20mn之孔徑，所以分散液中之銀粒子 不致於凝聚，為各個粒子在液中能流動之狀態，即，幾乎 完全以單分散而存在。此亦指本發明之銀粒子之分散液極 -適合於由喷墨法之配線形成用材料。倘若粒子有凝聚部分 存在時，不僅容易發生噴嘴之阻塞，所形成之配線之填充 .性變差，在锻燒時會產生孔洞而成為高電阻化或斷路之原 因，但在本發明之分散液可回避上述問題。膜滤筛過試驗 二尚可使用Whatman公司製品之An〇t〇ppius 25注射濾 •器（20nm孔徑）做為孔徑最小之濾器。 酸驗值 本發明之銀粒子分散液之酸驗值（pH，^離子濃度）在 6.5以上。因此，做為配線形成用材料時，有不會使電路 基板上之銅治腐钱，另外在配線間難發生移動之特徵。該 分散液之P H值是使用堀場公司製品之酸驗測定儀D - 5 5 T =’低導電性水-非水溶顧pH電極㈣卜丨⑽進行測定。 路St測二之分散液PH值未滿6. 5時，由酸成分引起電 路基板上之銅羯腐韻，又容易發生佈線間之移動，而降低 319006 20 1331059 電路之可靠性。 【實施方式】 feAi列 1 選擇異丁醇（和光純藥公司製品，特級試藥）做為具有 」二力之醇類〉谷劑’混合做為有機保護材料以油胺（和光純 2二製二？級試藥)。該混合液中添加硝酸銀結晶(關 予么5製品，特級試藥）做為銀化合物，藉磁力攪拌器 ^，使硝酸銀溶解。所❹之各物質質量，分別為石肖酸 = .59g、異丁醇96.叫、油胺165爲。此時有機保護 材料/銀之莫耳比率相當於5.〇。 移該液到具有迴流器之3〇〇ml容器内，放置在油浴 ，中’容器中—面以彻ml/min之流量導人惰性氣體之氮 2，-面以l_rpm磁力攪拌器之攪拌下加熱，升溫速度 為2c/min，升溫至液溫10『C。在loot下呈迴流狀離， =溫度下迴流300分鐘進行反應。本反應中不添加還原助 劑，迴流300分鐘後停止加熱，使反應終止。 就反應終了後之聚液，實施上述之「㈣㈣㈣」、 分散步驟」、「分級步驟」而得分散性高之銀微粉。該固 液分離步驟中，上述[1]之步驟中，使用日立工機公司势口 之離心機謂型，以3_rpm離心分離3〇分鐘。分散； 驟吏用煤油作為液狀溶劑。分級步驟中使用上述離心機 以300〇rpro離心分離30分鐘，回收分散有銀粒子之上澄 液。藉上述方法求得還原率，分散效率及收率。苴釺 於表1中（下文中’比較例2、3亦相同）。 319006 21 、3 丄丄υ：)9 、3 丄丄υ：)9 粉 表 以古匕較例1中，除了改變有機保護材料之油胺之使用量 機保護材料/銀之莫耳比率’為3 〇(比較例2)、2.〇 又例3)之外，其他皆按照比較例丨相同條件製得銀微 還原助劑/ 銀莫耳比 -還原率 (%) 分散效率 (%) 收率 (%) 59. 0¾ 75. 8% 44. 3% 66. 5% ^77. 8% 51. 7% 86. 2% 52. 8% 45. 6% 比較例 有機保護材料 還原助劑 種類 有機保護材料 /銀莫耳比 種類The average particle diameter of the silver fine powder according to the present invention can be obtained by the following method. i^A#_DTEM In the present invention, the average particle diameter of the silver particles is the average particle diameter Dtem obtained by a transmission electron microscope 319006 on 331059 (TEM). Namely, the average particle diameter value of the particles which were not overlapped was measured by a transmission electron microscope at a magnification of 600,000 times. In the present invention, silver fine powder of 50 nro or less can be obtained. For fine wiring applications, those with a D of 2 〇 or less are more suitable, and those of = 15 mn or less are more suitable, and those of 1 〇 or less are most suitable. In the following examples, the transmission electron microscope (TEM) is a JEM-2010 type manufactured by JEOL. The physical properties of the dispersion obtained in the present invention are explained below. According to the invention, a low viscosity silver nano ink can be obtained. In the examples, the viscosity was measured by mounting a conical rotor G.8 > 25 上 on a R55 黏 type viscometer re55 〇l of the Toki Sangyo Co., Ltd. product. In this case, it is suitable to form wiring by the ink-jet method, and the viscosity of the ink is preferably 5 〇 mPa · s or less, and more preferably 40 mPa · s or less. For example, adjust the range from 〇. i to 4〇mpa · s ‘just adjust it to 〇. ;! to 2〇mPa· s range. When the silver nano ink in this range is adjusted by using the viscosity, nozzle clogging is less likely to occur, and droplets can be formed smoothly. The lower limit of viscosity can be specified above ImPa · s depending on the application. Surface tension The silver particle dispersion of the present invention is at 25. The surface tension under the armpit is 80 mN/m or less. Therefore, it is suitable as a material for wiring formation in the ink jet method. The dispersion having a large surface tension is unstable in the shape of the meniscus at the tip end of the nozzle. Therefore, the discharge amount or the timing of the discharge is difficult to control, and the wettability of the droplets on the substrate is poor, and the wiring flatness is generated. Bad knot 319006 19 1331059 杲. However, since the surface dispersion of the silver particle dispersion of the present invention is 8 〇mN/m ^ or less, the above problem does not occur, and a wiring having good quality can be obtained. The surface tension was measured at a constant temperature of 25 ° C using a type instrument of the product of Concord Interface Science. • Membrane filter The silver particle dispersion of the present invention is passed through a membrane filter having a pore diameter of a uniform particle diameter (DTE «) + 2 () nro of a silver particle powder. Since it is only 20 nm larger than the average particle diameter (DTM) of the silver particles, the silver particles in the dispersion do not agglomerate, and the particles can flow in the liquid, that is, almost completely monodisperse. presence. This also refers to the dispersion liquid of the silver particles of the present invention - which is suitable for the wiring forming material by the ink jet method. When the particles have agglomerated portions, not only the clogging of the nozzles is likely to occur, but also the filling properties of the formed wiring are deteriorated, and holes are formed during calcination to cause high resistance or open circuit, but the dispersion of the present invention Can avoid the above problems. Membrane Screening Test Two Anman's An〇t〇ppius 25 syringe filter (20 nm pore size) can be used as the smallest pore size filter. Acid test value The acid particle value (pH, ion concentration) of the silver particle dispersion of the present invention is 6.5 or more. Therefore, when it is used as a material for wiring formation, there is a feature that the copper on the circuit board is not rotted and the wiring is hard to move. The P H value of the dispersion was measured using an acid tester D - 5 5 T = 'low conductivity water-non-aqueous solution pH electrode (4) dip (10). When the pH value of the dispersion of the road St is not more than 6.5, the copper component on the circuit board caused by the acid component is rotted, and the movement between the wirings is prone to occur, and the reliability of the circuit of 319006 20 1331059 is lowered. [Embodiment] feAi column 1 selects isobutanol (Wako Pure Chemical Co., Ltd., special grade drug) as a mixture of "two alcohols" and "valley" as an organic protective material with oleylamine (and pure light 2 Second-level reagents). To the mixed solution, silver nitrate crystals (manufactured by the product 5, a special grade test) were added as a silver compound, and the silver nitrate was dissolved by a magnetic stirrer ^. The quality of each substance was as follows: oxalic acid = .59g, isobutanol 96. oleylamine 165. At this time, the organic protective material/silver molar ratio is equivalent to 5. 〇. The liquid was transferred to a 3 〇〇ml container with a reflux device, placed in an oil bath, and the inside of the container was introduced into the nitrogen gas of the inert gas at a flow rate of ml/min, and the surface was stirred by a magnetic stirrer at a l_rpm. The heating was carried out, the heating rate was 2 c/min, and the temperature was raised to a liquid temperature of 10 『C. The reaction was carried out under reflux at a loot, and refluxed at a temperature of 300 minutes. In the present reaction, no reducing aid was added, and after refluxing for 300 minutes, the heating was stopped to terminate the reaction. The silver fine powder having high dispersibility is obtained by performing the above-mentioned "(4) (4) (4)", "dispersion step", and "gradation step" for the liquid liquid after the completion of the reaction. In the solid-liquid separation step, the above-mentioned step [1] was centrifuged at 3 rpm for 3 minutes using a centrifuge of the Hitachi Machinery Co., Ltd. Disperse; use kerosene as a liquid solvent. In the classification step, the above centrifuge was used to carry out centrifugation at 300 Torr for 30 minutes, and the supernatant was dispersed in the silver particles. The reduction rate, dispersion efficiency and yield were obtained by the above method.苴釺 In Table 1 (hereinafter, 'Comparative Examples 2 and 3 are the same). 319006 21, 3 丄丄υ:)9,3 丄丄υ:)9 The powder table is the same as in the case of Example 1, except that the amount of oleylamine used to change the organic protective material is used to protect the material/silver molar ratio' 3 〇 (Comparative Example 2), 2. 〇 and Example 3), other silver fulminating aids were obtained according to the same conditions of the comparative example 银 silver molar ratio - reduction ratio (%) dispersion efficiency (%) Rate (%) 59. 03⁄4 75. 8% 44. 3% 66. 5% ^77. 8% 51. 7% 86. 2% 52. 8% 45. 6% Comparative organic protective materials Protective material / silver molar ratio

艾施例1 比較例1中，進行300分鐘之迴流後，除了添加二乙 =胺（和光純藥公司製品，特級試藥）12為之2級胺做為 遇原助劑，維持上述迴流狀態下保持1小時並進行反應， #然後停止加熱之外，其餘皆按照比較例}相同條件製得實 施例1之銀微粉。此時，還原助劑/銀之莫耳比率相當= 1 · 0。依S?、上述方法求得還原率、分散效率及收率。其妗果 示於表2中（下文中’實施例2及3亦相同）。 、。 貫施例2、3 實施例1中，除了有機保護材料之油胺之使用量，、 有機保護材料/銀之莫耳比率計，分別改變為4 、 Λ、 . . · U、錢施例 2)、2.0(貫施例3)之外，其餘皆按照實施例i相同停 得銀微粉。 *千衣 319〇〇6 22 1331059 表 實施例 有機保護材料 種類 有機保護材料 /銀莫耳比 1 油胺 5.0 2 油胺 4.0 3 油胺 2. 0 二Ai Shi Example 1 In Comparative Example 1, after refluxing for 300 minutes, in addition to adding diethylamine (Wako Pure Chemical Co., Ltd., special grade reagent) 12, the second-grade amine was used as an auxiliary agent to maintain the above-mentioned reflux state. The silver fine powder of Example 1 was prepared under the same conditions as in Comparative Example} while maintaining the reaction for 1 hour and carrying out the reaction, #, then stopping the heating. At this time, the reduction aid/silver molar ratio is equivalent to = 1 · 0. According to S?, the above method was used to determine the reduction rate, dispersion efficiency and yield. The results are shown in Table 2 (hereinafter, Examples 2 and 3 are also the same). ,. In Examples 1 and 3, in Example 1, except for the amount of oleylamine used in the organic protective material, the organic protective material/silver molar ratio meter was changed to 4, Λ, . . . U, Qian Shi 2 Except for 2.0 and (Example 3), the silver fine powder was stopped in the same manner as in Example i. *Thousands of clothes 319〇〇6 22 1331059 Table Examples Organic protective materials Type Organic protective material / Silver molar ratio 1 Oil amine 5.0 2 Oil amine 4.0 3 Oil amine 2. 0 Two

94^ δδΤδί 62. 〇% 尤：施例1至3及比較例1至3,所得有機保護材料 /銀之莫耳比率與分散效率之關係表示於第 ^銀之莫耳比率與還原率之關係表示於第j機： 中，籲標緣表示實施例，△標纷表示比較例 =可，加還原助劑之2級胺可改善分散效= 當未添加還原助劑時’隨有機保護材料/ .艮之莫耳比率之提高^有降低還原之傾向， =皁=材料/銀之莫耳比率變動，也=高 材料/銀之笪f 效率隨有機保護 、 莫耳比平之增尚而提升（參昭第] =!'助劑之添加’而在高的有機保護材料/银:二t 顯著地二:現，生率(還原率及分散效率之積) 時，就生產產l *大里生產分散性優異之銀微粉 極為，士率之提升’生產成本之降低等觀點而言，罝有 極為重大之意義。 。八百 :乙1%例1至3中，除了分別將還原助劍改為3級胺之 -乙醇胺之外，其餘皆按照實施例…相同條件而製得 319006 23 1331059 銀微粉 其結果示上述方法求得還原率’分散效率及收率 表3 有機保護材料 實施例 種類 有機保護材料 /銀莫耳比 ◊丁、初閉 還原率 (%) 分散效率 (%) 種類 還原助劑/ j^a 'it -ο-. 收率 4 油胺 5.0 三乙醇胺 耳比 5 油胺 广4. 0 三乙气1 三乙醇胺 ___jL 0 97. 4% 94.1% 92. 2% ~Γ~ 油胺 " To 98. 3% 72. 1% 70. 9% —1 1· 0 ---- 98. 5% 56. 0¾ 55. 2% 就實施例4至6及比較例〗$。 ^ ^ ^ 至3 ’有機保護材料/銀 之莫耳比率及分散效率之關传# 斜/相+钴π七 係表不於第3圖，有機保護材 料/銀之莫耳比率及還原率 赢挪仏* —— 千<關係表不於第4圖。圖中， 国~Γ Λ 比較例。由第3圖及第4 圖可知添加3級胺作為還原助 弟 Ψ ^ ^ L ^ ^不官有機保護材料/ 銀之莫耳比率之變動，皆可維掊古 艾利Tt/ 之期待。 ，准持-遇原率，可實現高收率94^ δδΤδί 62. 〇% Especially: In Examples 1 to 3 and Comparative Examples 1 to 3, the relationship between the organic protective material/silver molar ratio and the dispersion efficiency is expressed in the relationship between the molar ratio of the silver and the reduction ratio. Expressed in the jth machine: in the middle, the standard edge indicates the example, the △ mark indicates the comparative example = can, the addition of the second aid of the reducing aid can improve the dispersion efficiency = when the reducing aid is not added 'with the organic protective material / The increase in the molar ratio of ^ has a tendency to reduce the reduction, = soap = material / silver molar ratio change, also = high material / silver 笪 f efficiency with the increase in organic protection, Mobibite (See the quotation] =! 'Addition of additives' and in the high organic protective material / silver: two t significant two: now, the birth rate (product of reduction rate and dispersion efficiency), the production of l * Dali It is extremely important to produce silver micropowder with excellent dispersibility and the increase in the rate of production. The production cost is extremely significant. Eight hundred: B1% of cases 1 to 3, except for the reduction of the auxiliary swords Except for the 3-grade amine-ethanolamine, the others were prepared according to the same conditions of the example... 319006 23 1331059 Silver micro The results show that the above method can be used to determine the reduction rate 'dispersion efficiency and yield. Table 3 Organic protective material Example Organic protective material / Silver molar ratio 、, initial closure reduction rate (%) Dispersion efficiency (%) Type reduction aid / j^a 'it -ο-. Yield 4 Oleamine 5.0 Triethanolamine Ear Ratio 5 Oil Amine Wide 4. 0 Triethylene 1 Triethanolamine ___jL 0 97. 4% 94.1% 92. 2% ~Γ~ Oil Amine " To 98. 3% 72. 1% 70. 9% -1 1· 0 ---- 98. 5% 56. 03⁄4 55. 2% For Examples 4 to 6 and Comparative Example 〗 〖. ^ ^ ^ to 3 'Organic protective material / silver molar ratio and dispersion efficiency of the pass # oblique / phase + cobalt π seven series is not in Figure 3, organic protective material / silver molar ratio and reduction rate wins * —— Thousands < Relational Table is not in Figure 4. In the figure, the country ~ Γ Λ Comparative example. From Figure 3 and Figure 4, it can be seen that the addition of a tertiary amine as a reduction aid Ψ ^ ^ L ^ ^ The change of the protective material / silver molar ratio can be expected by the Victorian Avery Tt/.

U包例7至Q 實施例1至3中，除了還原 乙醆脍夕从甘从〜 月J之1級胺分別改用單 粉。並依昭上述方法$ 3相同條件獲得銀微 表示於表4 ΐ _ ’分散效率及㈣。結果 319006 24U package examples 7 to Q In Examples 1 to 3, in addition to the reduction of the acetaminophen, the amines from the sulphate were replaced with the mono- succinates. According to the above method, the same condition as the above is obtained by the silver micro micrometer shown in Table 4 ΐ _ 'Dispersion efficiency and (4). Results 319006 24

及分散效率之而δ ’有機保護材料/銀之莫耳比率 耳比率及5圖’有機保護材料，銀之莫 有機保護材料/銀之莫耳：：第6圖。此時，分散效率在 5圖）m / 耳率低時有降低《傾向（參照第 古信’、：'有機保護材料，銀之莫耳比率變動也呈現 阿值(參照第6圖）。所以為了猶〜^ 千-動也呈現 級胺以上之脸… 疋之高收率，使用2 為… 還原助劑較為有利，使用1級胺作 又二齊’J時，較之僅使用醇類還原，可能實現高收率。 用1級胺作為還原助料，有機賴材料/銀之莫 耳比率提高至4以上較為有利。 實施例1Π 使用異丁醇（和光純藥公司製品，特級試藥η4^作 為反應溶劑兼還原劑，其中，添加油胺（和光純藥公司製 口口 Mw 267)185. 33ml作為有機保護材料，及硝酸銀結晶 (關東化干a司製品）19· 2叫作為銀化物。藉由磁力搜拌 機擾拌使硝酸銀溶解。 該溶液移至備有迴流器之反應容器中，放置油浴上， 容器中以4〇Qml/min之流量導入惰性氣體之氮氣，藉由磁 319006 25 1331059 力攪拌器以lOOrpm之旋轉速度攪拌下加熱。以2t：/min V 之升溫速度加溫至loot：。 w 在100°C下迴流5小時後，添加2級胺之二乙醇胺（和 光純藥公司製品’Mw=105. 64)12. 01g(對於銀之莫耳比率為 1. 〇)做為還原助劑。然後，保持1小時而終止反應。 針對終止反應之漿液，按照比較例1相同方法實施「固 液分離步驟」、「分散步驟」、「分級步驟」而得分散性高之 銀微粉。其結果，還原率為、分散效率為89·⑽、收 •率為 89. 8%。 實施例1] • 除了替代2級胺之二乙醇胺，改用3級胺之三乙醇胺 (和光純藥公司製品，Mw=149· 2)17. 05g(對銀之莫耳比率為 1 · 〇 )做為還原助劑之外，其餘重複進行實施例1 〇。 就終止反應之液漿，按照比較例1相同方法，實施「固 液分離步驟」、「分散步驟」、「分級步驟」，而得分散性高之 φ銀微粉。其結果’還原率為97. 4%、分散效率為94. 7%、收 率為92. 2%。 比較例4 除了不添加還原助劑以外，其餘重複實施例1 (^但是 由於不添加還原助劑，所以在i〇〇t下迴流5小時而終止 反應。 就終止反應後之液漿，按照比較例1相同方法，實施 「固液分離步驟」、「分散步驟」、「分级步驟」而得分散性 咼之銀微粉。其結果，還原率為7〇. 1%、分散效率為83. 5%、 319006 26 1331059 收率為58. 5%。較之實施例1 〇及11，1 丹遇原率倍 率也稍低’所以結果收率也低。 -’为散效 【圖式簡單說明】 表示其有 圖中，鲁 ’表示其有 圖中，_表 第1圖針對實施例1至3及比較例丨至3 機保護材料/銀莫耳比率及分散效率之關係固 表示實施例，△表示比較例。And dispersion efficiency of δ 'organic protective material / silver molar ratio ear ratio and 5 map 'organic protective material, silver Mo organic protective material / silver Moer:: Figure 6. At this time, when the dispersion efficiency is 5 (m) m / when the ear rate is low, the tendency is lowered (refer to the first ancient letter, : 'organic protective material, and the change in the molar ratio of silver also exhibits an A value (see Fig. 6). For the sake of ~~ thousand-moving, it also shows the face above the amine. The high yield of 疋, using 2 is... The reduction aid is more advantageous. When using the amine of the first grade, it is more efficient than using only alcohol. It is possible to achieve high yield. It is advantageous to use a grade 1 amine as a reduction aid, and it is advantageous to increase the molar ratio of the organic lysate/silver to 4 or more. Example 1 Π Use of isobutanol (Wako Pure Chemical Co., Ltd., special grade η4) ^ As a reaction solvent and a reducing agent, 185. 33 ml of oleylamine (Mk 267, manufactured by Wako Pure Chemical Industries, Ltd.) was added as an organic protective material, and silver nitrate crystals (products of Kanto Chemical Co., Ltd.) 19·2 were called silver compounds. The silver nitrate was dissolved by a magnetic stirrer. The solution was transferred to a reaction vessel equipped with a reflux device, placed on an oil bath, and a nitrogen gas of an inert gas was introduced into the vessel at a flow rate of 4 〇Qml/min. 319006 25 1331059 Force agitator rotating at 100 rpm Heating at a speed of stirring, heating to a loot at a temperature increase rate of 2t:/min V. w After refluxing at 100 ° C for 5 hours, adding a second-grade amine diethanolamine (Wako Pure Chemicals Co., Ltd. 'Mw=105.64 12.1g (the molar ratio of silver to 1. 〇) was used as a reducing aid. Then, the reaction was terminated by holding for 1 hour. The solid-liquid separation step was carried out in the same manner as in Comparative Example 1 for the slurry to terminate the reaction. In the "dispersion step" and the "staged step", the silver fine powder having a high dispersibility is obtained. As a result, the reduction ratio and the dispersion efficiency are 89·(10), and the yield is 89.8%. Example 1] • In addition to the substitution 2 The diamine of the amine is changed to the triethanolamine of the tertiary amine (product of Wako Pure Chemical Industries Co., Ltd., Mw=149·2) 17. 05g (the ratio of silver to silver is 1 · 〇) as a reducing aid. In the same manner as in Comparative Example 1, the "solid-liquid separation step", the "dispersion step", and the "staged step" were carried out to obtain a high-dispersion φ silver fine powder. 2%。 The result of the reduction rate of 97.4%, the dispersion efficiency of 94.7%, the yield of 92.2%. Comparative Example 4 The procedure of Example 1 was repeated except that no reducing aid was added. However, since no reducing aid was added, the reaction was terminated by refluxing for 5 hours at i〇〇t. The liquid slurry after the termination of the reaction was compared. In the same manner as in Example 1, the "solid-liquid separation step", the "dispersion step", and the "staged step" were carried out to obtain a silver fine powder having a dispersive enthalpy. The reduction ratio was 7 〇. 1%, and the dispersion efficiency was 83.5%. 319006 26 1331059 The yield was 58.5%. Compared with Example 1 and 11,1, the rate of the original rate was slightly lower, so the yield was also low. - 'for the effect of the effect [simplified description of the figure] means that it has a picture, Lu ' means that it has a picture, _ table of the first picture for the examples 1 to 3 and the comparative example to 3 machine protection material / silver molar ratio The relationship between the dispersion efficiency and the embodiment is shown in the figure, and Δ indicates a comparative example.

第2圖針對實施例1至3及比較例i至 機保護材料/銀莫耳比率及還原率之關係圖 示實施例，△表示比較例。 第3圖針對實施例4至6及比較例丨至3， 機保護材料/銀莫耳比率及分散效率之關其: 表示實施例’ △表示比較例。 ° ’ · 第4圖針對實施例4至6及比較例j至3，夺厂 機保護材料/銀莫耳比率及還原率之_圖。 示貫施例’ △表示比較例。 、 第5圖針對實施例7至9，表示其有機保護_ 莫耳比率及分散效率之關係圖。 #第6圖針對實施例7至9,表示其有機保護材料/銀 莫耳比率及還原率之關係圖。 319006 27Fig. 2 is a view showing the relationship between the examples 1 to 3 and the comparative example i to the protective material/silver molar ratio and the reduction ratio, and Δ indicates a comparative example. Fig. 3 is directed to Examples 4 to 6 and Comparative Examples 丨 to 3, and the mechanical protective material/silver molar ratio and dispersion efficiency are as follows: Illustrative Example Δ indicates a comparative example. ° ' Figure 4 is a graph of the factory protection material/silver molar ratio and reduction rate for Examples 4 to 6 and Comparative Examples j to 3. The example shown in the figure Δ indicates a comparative example. Fig. 5 is a graph showing the relationship between the organic protection _ molar ratio and the dispersion efficiency for Examples 7 to 9. Fig. 6 is a graph showing the relationship between the organic protective material/silver molar ratio and the reduction ratio for Examples 7 to 9. 319006 27

Claims (1)

1331059 ζ 961〇5883號專利申請案 ^99年3月12日） i tm «ι ι·>· m . 十、申請專利範圍：Ί L =種銀微粉之製造方法，其特徵為：在醇類中，使用醇 ，作為溶劑及由2級胺或3級胺所構成之還原助劑做為 •還原劑’在由具有不飽和結合之分子量為1〇〇至1〇〇〇 之1級胺所構成之有機保護材料的存在下，還原處理銀 化物使平均粒徑DTEMg 5〇nm以下之銀粒子析出之銀 粉的製造方法。 2. 如申請專利範圍第1項之銀微粉之製造方法，其係進行 申請專利範圍第丨項之還原處理之步驟，再具備將含有 :斤出之銀粒子的漿液加以固液分離，而將由構成有機保 護材料之有機化合物被覆之銀粒子以固形物回收之步 驟’以非極性或極性小之液狀溶劑分散上述二 物被覆之銀粒子之步驟。 〇 3. 如申請專利範圍第1項之銀微粉之製造方法，i係進Γ ::專利範圍第i項之還原處理之步驟，再具備將含有丁 護材之漿液加以固液分離’而將由構成有機保 ’、有機化合物被覆之銀粒子以固形物回收之牛 =被以非極性或極性小之液狀溶劑分散上述由有機“ 覆之銀粒子之步驟’對該分散液施加離心分離操作 έ回收分散有銀粒子之上澄液之步驟。 4. 如申請專利範圍第1項之銀微粉之製造方法，其中，一 處理係對作為溶劑之醇類每lkg以銀量 『 莫耳來進行。 勺K至20 5·如申請專利範園第1項之銀微粉之製造方法，其中，還 (修正本)319006 28 ''Ί i331059 第96105883號專利申請案 (99年3月12日 吁年3月 片虛掙在 + 士，"!―"—( 9 9 年 3 月 1 2 日二 μ 有機保護材料/銀之莫耳比率為U5至2〇 之條件下進行。 6.如申請專利範圍第1項之銀微粉之製造方法，1中，還 f處理係在還原助劑/銀之莫耳比率為〇1纟2〇 ’ 件下進行。 ” 7· 一種銀粒子分散液，係將平均粒#卜為I以下之 銀粒子粉末分散於極性低之液狀有機溶劑中之銀粒子 分散液’其特徵為具備下列做為牛頓流體特性之銀粒子 分散液： 酸驗（pH)值在6.5以上， 分散液中之銀濃度為5至90質量％， 黏度為50mPa · s以下， 表面張力為80mN/m以下。 8. 如申請專利範圍第7項之銀粒子分散液，其係通過且有 液中之銀粒子之平均粒徑+20nm之孔徑之膜過遽器之 分散液。 9. 一種銀微粉之製造方法，其特徵為於丨級胺中，將銀_ 在2級胺或3級胺之-者或二者之共存在下且在8〇 至200t溫度範圍内進行還原處理。 (修正本)319006 291331059 专利 Patent Application No. 961〇5883 ^March 12, 1999) i tm «ι ι·>· m. X. Patent application scope: Ί L = manufacturing method of silver micropowder, characterized by: alcohol In the class, an alcohol is used as a solvent and a reducing aid composed of a secondary amine or a tertiary amine is used as a reducing agent in the first-order amine having a molecular weight of 1 〇〇 to 1 不 having an unsaturated bond. A method for producing silver powder in which silver particles having an average particle diameter DTEMg of 5 〇 nm or less are precipitated by reduction treatment of silver compounds in the presence of the organic protective material. 2. The method for manufacturing a silver micropowder according to the scope of claim 1 is to carry out the step of reducing the treatment of the scope of the patent application, and further comprises solid-liquid separation of the slurry containing the silver particles: The step of recovering the above-mentioned two-coated silver particles in a non-polar or less-polar liquid solvent in the step of recovering the organic compound-coated silver particles constituting the organic protective material. 〇3. For the manufacturing method of silver micropowder in the scope of patent application No. 1, i is in the process of reduction: the step of reduction treatment of the i-th item of the patent scope, and then the solid-liquid separation of the slurry containing the butyl material is to be The bovine which is composed of the organic compound and the organic compound-coated silver particles recovered as a solid substance is dispersed in a liquid solvent having a non-polar or a small polarity, and the centrifugal separation operation is applied to the dispersion by the organic "step of coating the silver particles". The method of producing a silver fine powder in which the silver particles are dispersed. 4. The method for producing a silver fine powder according to the first aspect of the invention, wherein the treatment is carried out by using a molar amount of alcohol per lkg of the alcohol as a solvent. Spoon K to 20 5 · For example, the manufacturing method of the silver micropowder of the patent application Fan Park No. 1, among which, (Revised) 319006 28 ''Ί i331059 Patent No. 96105883 (Announcement of March 12, 1999) The monthly film is earned in + 士, "!―"—(Mr. March 12, 2nd, 2μ organic protective material / silver molar ratio is U5 to 2〇. 6. If applying for a patent The manufacturing method of silver micropowder in the first item of the range, 1 Further, the f treatment is carried out under the condition that the reduction aid/silver molar ratio is 〇1纟2〇'. 7. A silver particle dispersion is obtained by dispersing a silver particle powder having an average particle size of 1 or less in a polar group. The silver particle dispersion in the low liquid organic solvent is characterized by having the following silver particle dispersion as a Newtonian fluid property: the acid value (pH) is 6.5 or more, and the silver concentration in the dispersion is 5 to 90 mass. %, the viscosity is 50 mPa · s or less, and the surface tension is 80 mN/m or less. 8. The silver particle dispersion according to claim 7 is passed through and has an average particle diameter of silver particles in the liquid + 20 nm. a dispersion of a film-passing device. 9. A method for producing a silver fine powder, characterized in that in a hydrazine amine, silver _ in the presence of a 2- or amine-amine or a combination of both Reduction treatment in the temperature range of 8 〇 to 200 t. (Revised) 319006 29