TWI295666B

TWI295666B -

Info

Publication number: TWI295666B
Application number: TW093118758A
Authority: TW
Original assignee: Mitsui Mining & Smelting Co
Priority date: 2003-07-29
Filing date: 2004-06-28
Publication date: 2008-04-11
Also published as: JP2005048237A; KR20060040712A; CN1826198A; CN100500333C; WO2005009652A1; CA2534108A1; JP4489389B2; DE112004001403T5; TW200503961A; US20070079665A1; KR101132283B1

Description

12956661295666

五、發明說明（1) 【發明所屬之技術領域】銀粉之製造方銀粉為目的之本發明疋有關於一種微粒銀粉及該微粒法，特別是一種以提供不純物含量低之微粒微粒銀粉及該微粒銀粉之製造方法。【先前技術】習知銀粉多採用溼式還原製程來製造，根號所揭露，渔式還原製程係本先專以利有：還Γΐϋΐ製備銀氨錯合物水溶液’再於其中添加原y之方法。近年來，銀粉主要應用於曰電黎顯示器面板等之電極與電路的形成。 '日日70 、因此’該電極與電路中所形成之電路盥化f求曰益增高，而隨著配線的高密度化1 =精：可靠度的要求也日趨嚴袼。回精度化，高 j而，以習知方法所獲得之銀粉的之平均敖你Π 、S A 1 W 其一次粒子仏Du通吊超過〇 . 6 ，以雷射〜得之平均粒㈣5。超過h“m，其凝聚二'二佈」則定法所化之電4:等⑽mi並不適用於目前微間距另-κ .是製品產率大幅降低的主要原因。方面，由銀粉之使用方法來看，屮拐τ 丁 η 碭。。一直以來，於使用銀膠之電路形成中，二問 3 0 0 °C以下的非隐从 > 中’以加熱溫度於為了传到低結晶性之銀粉，於製造條件上不得低、，w緙^〜非燒結、或低溫燒結型的用途較多，為了於社恤又侍向的燒結性能，一般認，、、、；V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) Technical Field of the Invention The present invention relates to a particulate silver powder and the microparticle method, and more particularly to a microparticle silver powder which provides a low impurity content and the microparticles. The method of manufacturing silver powder. [Prior Art] Conventional silver powder is mostly manufactured by a wet reduction process. As revealed by the root number, the fish-type reduction process system is exclusively used for the purpose of: preparing a silver ammonia complex aqueous solution and adding the original y method. In recent years, silver powder has been mainly used for the formation of electrodes and circuits such as 曰Electronic display panels. 'Day 70, therefore, the circuit formed in the electrode and the circuit is increased, and the density is increased with the high density of the wiring. 1 = Fine: The requirements for reliability are becoming increasingly severe. Back to the precision, high j, the average of the silver powder obtained by the conventional method 敖, S A 1 W, its primary particle 仏Du hangs more than 〇. 6 , with the laser ~ get the average grain (four) 5. More than h "m, its condensed two 'two cloth" is determined by the law of electricity 4: et al. (10) mi is not suitable for the current micro-pitch another - κ. It is the main reason for the significant reduction in product yield. In terms of the use of silver powder, the τ τ η η 砀. . For a long time, in the formation of a circuit using silver paste, the second non-implicit condition of less than 300 °C is used to heat the temperature to the silver powder for low crystallinity, and the manufacturing conditions must not be low, w缂^~ non-sintering, or low-temperature sintering type has many uses, in order to meet the sinter performance of social and service, generally recognize,,,;

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不採用還原快速之反應類，只能獲得凝聚顯著的銀粉。因此，提供習知所沒有聚少之單分散的分散性、以粉，即是目前的重要課題。此外，減少銀粉中不純即，銀粉係採用上述渥式還用之還原劑等容易殘留於銀採用習知之製造方法，此即當銀粉中之不純物含量增加氣阻抗也會隨之增加。 &果雖然得到低結晶性，但卻的銀粉、且具備更接近粉粒凝及具有良好低溫燒結性的銀物含量之需求也日益增加。亦原製程來製造，該製程中所使卷之粉粒表面上。因此，既然成為不可避免的問題。而且， ’使用銀粉所形成之導體的電因此，業者不僅要求銀粉具有細小微粒、高分散性，而且，減少不純物含量之要求也同時進行。【發明内容】因此，本發明人等以習知混合硝酸銀水溶液與氨水、使其反應以得到銀氨錯合物水溶液，再於其中添加還原劑以還原析出銀粒子’並進行過濾、清洗、乾燥的製造方法為基本，對該製造方法加入新的創意，並進行研究改盖。結果’不僅可製造出以習知方法所無法得到之等級的&粒銀粉，且藉由顯著減少該微粒銀粉之不純物含量，而得到習知所沒有的微粒銀粉。而且，本發明之製造方法亦可提幵微粒銀粉之產率、並能穩定地形成。以下將本發明分為「微粒銀粉」與「製造方法」兩部分來作說明。Instead of using a fast-reacting reaction, only silver powder with a remarkable agglomeration can be obtained. Therefore, it is an important subject at present to provide a monodisperse dispersibility and powder which are not conventionally gathered. Further, the reduction of the impureness in the silver powder, that is, the use of the reducing agent or the like which is also used in the above-mentioned enamel type, is liable to remain in the silver by a conventional manufacturing method, and as the content of the impurities in the silver powder increases, the gas resistance also increases. Although the fruit has low crystallinity, there is an increasing demand for silver powder and a silver content which is closer to powder granulation and has good low-temperature sinterability. It is also manufactured by the original process, which is used to make the powder particles on the surface of the process. Therefore, since it becomes an inevitable problem. Further, the electric power of the conductor formed by using the silver powder requires the silver powder to have fine particles and high dispersibility, and the requirement for reducing the impurity content is simultaneously performed. SUMMARY OF THE INVENTION Therefore, the inventors of the present invention conventionally mix an aqueous solution of silver nitrate with ammonia water to react it to obtain an aqueous solution of silver ammonia complex, and then add a reducing agent to reduce precipitation of silver particles' and perform filtration, washing, and drying. The manufacturing method is basic, adding new ideas to the manufacturing method, and carrying out research and revision. As a result, not only the & granules of silver which are not available in the conventional method can be produced, but by the fact that the content of the impurities of the pulverized silver powder is remarkably reduced, the pulverized silver powder which is conventionally not obtained is obtained. Further, the production method of the present invention can also improve the yield of the fine particle silver powder and can be stably formed. Hereinafter, the present invention will be described by dividing it into "particulate silver powder" and "manufacturing method".

五、發明說明（3) <微粒銀粉〉首先，針對本發明之微粒銀粉來作說明。本發明之微粒銀粉之主要特徵在於具備有下列a.〜d•之粉體特^性。在此舉出的這些粉體特性，係目前粉體測量技術中最容易突顯，發明之微粒銀粉之特徵、且同時成立的特性。以下針對每個特性來作說明。 a.特性係指以掃描電子顯微鏡照相圖作影像分析所得之一次粒子之平均粒徑Du為〇6#m以下。在此，以電子顯微鏡照相圖作影像分析所得之一次粒子‘平均二象'm f用掃描電子顯微鏡(S E M )所觀察之銀粉作影像分析所得之平均粒徑。本說明書 =1?鏡⑽)所觀察之微粒銀粉的影像解析，係：用Asahi Englneering股份有限公司所製之 ’、木以圓度閥值為10、重疊度為2〇來進行圓I ，並 J平均粒徑dia。由於藉由對微觀” :求夠確實地捕捉一次粒子之平均粒徑。依接，析而传’故能察，本發明中所述之微粒銀粉 '落=人的觀 //in之範圍内，但是實1A成干洛於0·01 //in〜〇·6 此此處不敢斷定其下限值。13 、、、田微粒控的粒子，因 b ·特性係指由於本發明之 :具有的高分散性，故以「凝聚度；= 標。」术作為此分散性之指本說明書中所述之凝聚度係指以上述平均粒徑〜、與 1295666 五、發明說明（4) 雷射粒徑分佈測定法所得值。在此，D孫蚀田兩Γ 5Q所表示的D5G/Du 為5 0。/味+ a 5Q係使用雷射粒徑分佈測定法所得之重量累籍為50/。時之粒徑，此平均粒里累積粒子是”Λ平：粒：。這是因為實際的銀粉粉粒的每個的凝聚狀態少，平均粒徑Ds。值小至粉且右“為·25//ΙΠ〜0·80_，此微粒銀外了本戈明：中2 : f所無法得到之平均粒徑^範圍。此卜本°兒明書中之雷射粒徑分佈測定法係將0 t# 粉與離子交換水混合，以超立、㈣曾二將士0.2g之被粒銀所製之USinnTH / 質機（日本精機製作所測定儀ir τ二5 /刀鐘的分散後，再以雷射粒徑分佈司製)進Π 量'a。RA 932°-X1°° 型(UedS+ N〇rthrup 公 r夕Π :謂、:以掃描電子顯微鏡照相圖作影像分析所 (Lmt'均粒徑、」係指對使用掃描電子顯微鏡 (S E Μ)所観察之銀粉的影像作影像分析所得之平均粒徑，不需考慮其凝聚狀態，可確實地捕捉―次粒子徑。 -結果，本發明人等以雷射粒徑分佈測定法所得之平均粒徑D5。、與影像分析所得之平均粒徑〜所求出值作為凝聚度。亦即，假設同一批之微粒銀粉能以同一精度來測里D5。與D1A值’根據上述理論，於測量值中反應凝聚狀第10頁 2213-6406-PF(N2).ptd 1295666V. INSTRUCTION DESCRIPTION (3) <Particulate Silver Powder> First, the particulate silver powder of the present invention will be described. The main feature of the fine silver powder of the present invention is that it has the following powder characteristics of a. to d. The powder characteristics mentioned here are the characteristics that are most easily highlighted in the current powder measuring technique, and the characteristics of the inventive particulate silver powder are simultaneously established. The following is a description of each feature. a. Characteristics means that the average particle diameter Du of the primary particles obtained by image analysis by scanning electron micrograph is 〇6#m or less. Here, the average particle diameter of the primary particle 'average two image' m f obtained by image analysis using an electron micrograph is analyzed by image analysis of silver powder observed by a scanning electron microscope (S E M ). The image analysis of the particulate silver powder observed in this specification = 1 (mirror (10)) is: using the 'sahi Englneering Co., Ltd.', the wood has a roundness threshold of 10 and an overlap of 2 〇 for the circle I, and J average particle diameter dia. By relying on the microscopic": to surely capture the average particle size of the primary particles. According to the analysis, it can be observed that the particulate silver powder described in the present invention falls within the range of the human view / /in , but the real 1A into the dry Luo at 0·01 //in~〇·6 This is not the case here to determine the lower limit. 13, particles, particles controlled by the particle, because the characteristics of the invention refers to: Has a high degree of dispersibility, so the "cohesion degree; = standard." as the meaning of this dispersibility as described in the specification refers to the above average particle size ~, and 1295666 five, invention description (4) Lei The value obtained by the particle size distribution measurement method. Here, the D5G/Du represented by DQ Γ5Γ5Q is 50. /flavor + a 5Q is a weight of 50/ using a laser particle size distribution method. The particle size of the time, the cumulative particle in the average particle is "Λ平:粒:. This is because the actual state of the silver powder particles is less, the average particle size Ds. The value is small to the powder and the right "for · 25 / / ΙΠ ~ 0 · 80 _, this particle silver outside the Ben Ge Ming: 2: f can not get the average particle size ^ range. The laser particle size distribution method in this book is to mix 0 t# powder with ion-exchanged water, and to use the USinnTH / mass machine made of granules of 0.2g. After the dispersion of the ir τ 2 / 5 knives of the Japan Seiki Co., Ltd., the amount of ' ' is measured by the laser particle size distribution. RA 932°-X1°° type (UedS+ N〇rthrup public Π Π : ::, using a scanning electron microscope photographic image for image analysis (Lmt 'average particle size, ― refers to the use of scanning electron microscope (SE Μ) The average particle diameter of the image of the observed silver powder for image analysis does not need to consider the state of aggregation, and the "secondary particle diameter" can be surely captured. - As a result, the average particle obtained by the inventors of the present invention by laser particle size distribution measurement method The diameter D5., and the average particle diameter obtained by image analysis~ the obtained value is used as the degree of cohesion. That is, it is assumed that the same batch of particulate silver powder can measure D5 with the same precision. The value of D1A is measured according to the above theory. Medium Reaction Aggregate Page 10 2213-6406-PF(N2).ptd 1295666

五、發明說明（5) 態之D5。值應比dia值還大。此時，D5。值幾乎呈現無微粒之粉粒狀態、無限地接近DIA值，故凝聚度H1A值接近於％ 1。當凝聚度等於1時’可說是完全無粉粒之凝聚單分散粉。早於粒銀粉體表面由此可微粒銀度於1. 之表面狀態愈密度愈此值。— 故，理真球，疋，本發明人等探究了凝聚度、與以各凝聚度之所製造之微粒銀粉漿料的黏度、燒結加工所得之暮平滑性等之間的關係。結果得知其關係相當密切。知，若能控制微粒銀粉之凝聚度，則可任意地控粉所製造之微粒銀粉漿料的黏度。而且，若使凝铲 5以下，則可使微粒銀粉漿料之黏度、燒結加工後^ 平滑性等的變動縮小至狹窄的範圍中。此^卜，凝聚 ^，則對該氧化微粒銀粉進行燒結所得之導體的= 咼，進而降低所形成之燒結導體的電氣阻抗。外，試著求出實際的凝聚度，有時會得到未滿i的般認為這是因為將計算凝聚度之DIA假設為真球之緣一上雖然不會出現未滿1的值，但由於實際上並非故可獲得未滿1之值的凝聚度。 C.特性係晶粒粒徑於丨0nm以下，此晶粒粒徑與燒結起始溫度間有相當密切之關係。亦即，以平均粒徑相當之銀粉來比較，晶粒粒徑小者可於低溫進行燒結。因此，由於如本發明之微粒銀粉般小的微粒，所以表面能量大，且具有1 Onm以下之小的晶粒粒徑，因而可使燒結起始溫度低溫化。在此並無設定晶粒粒徑之下限值，這是因為測量裝置、測量條件等會產生一定的測量誤差之緣故。此外，要V. Description of the invention (5) State D5. The value should be larger than the dia value. At this time, D5. The value is almost in the form of a particle-free particle and infinitely close to the DIA value, so the degree of aggregation H1A is close to %1. When the degree of cohesion is equal to 1, it can be said that it is a completely powder-free agglomerated monodisperse powder. It is earlier than the surface of the grain silver powder, so that the surface density of the particles is higher than 1. Therefore, the inventors of the present invention have studied the relationship between the degree of aggregation, the viscosity of the fine particle silver powder slurry produced by each degree of aggregation, and the smoothness obtained by the sintering process. It turns out that the relationship is quite close. It is known that if the degree of aggregation of the particulate silver powder can be controlled, the viscosity of the particulate silver powder slurry produced can be arbitrarily controlled. Further, when the shovel 5 or less is used, the viscosity of the fine particle silver powder slurry and the smoothness after the sintering process can be reduced to a narrow range. In this case, the condensed ^, the conductor of the oxidized fine particle silver powder is sintered = 咼, thereby reducing the electrical impedance of the sintered conductor formed. In addition, try to find the actual degree of cohesion, and sometimes I think that it is less than i. This is because the DIA that calculates the degree of cohesion is assumed to be the edge of the true ball, although the value of less than 1 does not appear, but because In fact, it is not possible to obtain a degree of cohesion of a value less than one. C. The characteristic grain size is below 丨0 nm, and the grain size is closely related to the sintering starting temperature. That is, in comparison with the silver powder having an average particle diameter, the grain size is small and the sintering can be performed at a low temperature. Therefore, since the particles are as small as the fine particles of the silver powder of the present invention, the surface energy is large and the crystal grain size of 1 Onm or less is small, so that the sintering initiation temperature can be lowered. The lower limit of the grain size is not set here because the measurement device, measurement conditions, etc., cause a certain measurement error. In addition, to

1295666 五、發明說明（6) —-- 粒粒，小於10⑽之範圍的測量值具有高可靠性是相當 + α的，右一定要設定下限值的話，根據本發明人等研究之結果，其約為2nm。 v d.特性係指有機不純物含量以含碳量換算於〇. 25wt0/〇 H1在此，使用碳之含量作為有機不純物含量之指標， ^為附著於銀粉粉粒之不純物量之基準。此時含碳量之 ^則定係使用堀場製作所之EMU —32〇v，並將微粒銀粉1295666 V. Description of the invention (6) —-- The measured value of the particle range of less than 10 (10) has a high reliability of +α, and if the lower limit is set to the right, according to the results of research by the present inventors, It is about 2 nm. v d. Characteristics means that the content of organic impurities is converted to 〇. 25wt0/〇 H1. Here, the content of carbon is used as an index of the content of organic impurities, and ^ is the basis of the amount of impurities attached to the particles of silver powder. At this time, the amount of carbon contained in the market is determined by the use of EMU-32〇v from Horiba, and the powder silver powder

中g、鶴粉1 · 5g與錫粉〇· 3g進行混合，其後將其置入坩堝丄以燃燒-紅外線吸收法來進行測量。以習知製造方法所知之銀粉之含碳量不管如何加強清洗，仍〇· 25wt0/〇〇、Z為本發明之微粒銀粉具有上述a·〜d.之粉體特性，故為4知所沒有的銀粉。而且，由燒結起始溫度之特性來看ί發明之微粒銀粉，其可說是可於240 °c以下進行燒結 : 之微粒銀粉。另外，此處並無對此燒結起始溫度之下限值_ 作特別的規範，但依照本發明人等所進行之研究與一般的技術常識，幾乎不可能獲得低於17 0°C之燒結起始溫度，故可將其視為下限值。 ^ 再者’具備上述粉體特性之效果包括本發明之微粒銀 < 粉之，實填充密度可高達4· Og/cm3以上。在此所述之振實 1 填充密度係先精秤微粒銀粉20 0g，將其置入15〇cm3的量筒中’於行程（stroke)40mm處反覆進行1 00 0次的落下、輕敲之後’對微粒銀粉進行測量所得。此振實填充密度係如同理論上具有微小的粒徑、且粉粒間無凝聚之高分散性之狀Medium g, crane powder 1 · 5g was mixed with tin powder · 3g, and then placed in 坩埚进行 by combustion-infrared absorption method for measurement. The carbon content of the silver powder known by the conventional manufacturing method is 〇·25wt0/〇〇, Z is the powdery silver powder of the present invention having the above-mentioned a·~d. powder characteristics, so it is 4 knowledge centers. No silver powder. Further, from the characteristics of the sintering initiation temperature, the fine particle silver powder of the invention can be said to be sintered at a temperature of 240 ° C or less: fine particle silver powder. In addition, there is no specific specification for the lower limit of the sintering initiation temperature, but it is almost impossible to obtain a sintering of less than 170 °C according to the research conducted by the present inventors and the general technical knowledge. The starting temperature, so it can be regarded as the lower limit. Further, the effect of having the above-mentioned powder characteristics includes the particulate silver < powder of the present invention, and the solid packing density can be as high as 4·Og/cm3 or more. The tapping density of the tapping 1 described here is 20 g of the fine-grained fine-grained silver powder, which is placed in a measuring cylinder of 15 〇cm3, and then repeated at 1000 mm at a stroke of 40 mm, after tapping and tapping. The particle silver powder was measured. This tapped packing density is like a theoretically small particle size and a high degree of dispersion without aggregation between the particles.

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態般高的數值。比起振實填充密度未滿4. 〇g/cm3之習知銀叙，本發明之微粒銀粉非常地微細，且呈有良好的分散性。八五、發明說明（7) 〈微粒銀粉之製造方法> 本毛月之製造方法之主要特徵係於混合端酸銀水溶液與^水、使其反應以得到銀氨錯合物水溶液，再將其與有機還原劑接觸，使其反應以還原析出銀粒子，並進行過 f、凊洗、乾燥來製造銀粉之方法中，使用添加後成稀薄浪度之還原劑量、硝酸銀量、氨水量。習知還原劑溶液盘銀氨錯合物水溶液係於同一槽中進行混合，因此由於銀濃度一般設定為10g/l以上，若添加多量的硝酸銀、還原劑與氨水，則無法確保獲得對應設備規模的生產性。本發明之製造方法之第1特徵在於銀氨錯合物水溶液與有機還原劑接觸產生反應後的有機還原劑濃度低少吸附殘留於生成之銀粉粉粒表面上、或於粉粒成2 中進入粉粒内部的有機還原材料。因此，此混合後 ^ :’相對於lg/卜6g/1的銀濃度，有機還原劑好合：持於lg/Ι〜3g/l。取野維在此，銀的濃度與還原劑量間成比例關係，者度愈高，可獲得愈多的銀粉。然而，若此處之銀銀浪 6g/l的話，所析出之銀粒子會呈現大顆粒的傾向/辰度超過與習知銀粉相同之粒徑，因而無法得到本發明所述而形成高分散性的微粒銀粉。相對地，若此處之銀濃度^之具有的話’雖然獲得非常細小之微粒銀粉，但因高1 g /1 q双過於細小使A state of high value. The fine particle silver powder of the present invention is very fine and has good dispersibility compared to the conventional silver having a tapping packing density of less than .g/cm3. Eighth Five, Invention Description (7) <Method for Producing Particulate Silver Powder> The main feature of the manufacturing method of this Maoyue is that the aqueous solution of mixed acid silver is reacted with water to react to obtain an aqueous solution of silver ammonia complex, and then The method of bringing it into contact with an organic reducing agent, reacting it to reduce precipitation of silver particles, and performing f, washing, and drying to produce silver powder uses a reducing dose, a silver nitrate amount, and an ammonia amount which are added to a lean wave. Conventional reducing agent solution tray silver ammonia complex aqueous solution is mixed in the same tank, so the silver concentration is generally set to 10g / l or more, if a large amount of silver nitrate, reducing agent and ammonia water are added, it is impossible to ensure the corresponding equipment scale Productive. The first feature of the production method of the present invention is that the concentration of the organic reducing agent after the reaction of the aqueous solution of the silver ammonia complex with the organic reducing agent is low, and the adsorption remains on the surface of the generated silver powder particles, or enters into the powder particles 2 An organic reducing material inside the powder. Therefore, after this mixing, ^ : ' is relative to the silver concentration of lg / b 6g / 1, the organic reducing agent is good: holding lg / Ι ~ 3g / l. Take the wild dimension Here, the concentration of silver is proportional to the amount of reducing dose. The higher the degree, the more silver powder can be obtained. However, if the silver-silver wave here is 6 g/l, the precipitated silver particles tend to exhibit large particles with a tendency to exceed the same particle size as the conventional silver powder, and thus the high-dispersibility cannot be obtained as described in the present invention. Particle silver powder. In contrast, if the silver concentration here has 'very small particle silver powder, the height is 1 g / 1 q double is too small

1295666 五、發明說明（8) 吸油量增大，造成漿料黏度增加，因此必須增加有機載體的塁’因而導致最終形成之燒結導體的膜密度降低、電氣阻抗增加。而且，也無法滿足所需的工業生產性。相對於上述lg/Ι〜6g/l的銀濃度，有機還原劑濃度維持於lg/Ι〜3g/l，這是提升本發明之微粒銀粉的產率之最佳條件。在此，將有機還原劑濃度設定為lg/1〜3g/l，是因為此範圍是與銀氨錯合物水溶液之銀濃度間的關係中最適合得到微粒銀粉之範圍。若有機還原劑濃度超過3 g / 1的 U舌’雖然對銀氣錯合物水》谷液添加之還原劑液量變少，但疋還原析出之銀粉粉粒開始顯著地凝聚，包含於粉粒之不純物量（於本說明書中不純物量係指含碳量）也開始急遽增多。若有機還原劑濃度未滿1 g / 1的話，使用之還原劑的總液量增加，廢水處理量也增大，因而無法滿足工業上之經濟效益。在此所述之「有機還原劑」係指對笨二齡、於驗酸、葡萄糖等。其中，最好於有機還原劑中選擇性地使用對笨二酚。於本發明中，對苯二酚比其他有機還原劑具有較佳之反應性，可說是具備有最適於得到晶粒粒徑小之低結曰性銀粉的反應速度。 " 此外，還可於與上述有機還原劑之組合中使用其他的添加劑。在此所述之添加劑最好使用明膠等之膠類、胺類高分子劑、纖維素等能使銀粉之還原析出製程穩定、且同時能達到一定之分散劑之功能者，亦可因應有機還原劑、製程種類等來作適當的選擇。1295666 V. INSTRUCTION DESCRIPTION (8) As the oil absorption increases, the viscosity of the slurry increases, so it is necessary to increase the 塁' of the organic carrier, thereby causing a decrease in the film density of the sintered conductor finally formed and an increase in electrical resistance. Moreover, it does not meet the required industrial productivity. The organic reducing agent concentration is maintained at lg/Ι 3 g/l with respect to the above silver concentration of lg/Ι to 6 g/l, which is the optimum condition for increasing the yield of the particulate silver powder of the present invention. Here, the organic reducing agent concentration is set to lg/1 to 3 g/l because this range is the range most suitable for obtaining the particulate silver powder in the relationship with the silver concentration of the aqueous solution of the silver ammonia complex. If the U-head of the organic reducing agent concentration exceeds 3 g / 1 , although the amount of the reducing agent added to the silver gas complex water solution is small, the silver powder particles which are precipitated and precipitated are initially coagulated, and are contained in the powder. The amount of impurities (in the present specification, the amount of impurities refers to the amount of carbon) also began to increase rapidly. If the concentration of the organic reducing agent is less than 1 g / 1, the total amount of the reducing agent used is increased, and the amount of wastewater treatment is also increased, so that the industrial economic benefit cannot be satisfied. The term "organic reducing agent" as used herein refers to a second generation of acid, acid test, glucose, and the like. Among them, it is preferable to selectively use p-diphenol in an organic reducing agent. In the present invention, hydroquinone has better reactivity with other organic reducing agents, and it can be said that it has a reaction rate which is most suitable for obtaining a low-cracking silver powder having a small crystal grain size. " In addition, other additives may be used in combination with the above organic reducing agent. The additive described herein preferably uses gelatin such as gelatin, amine polymer agent, cellulose, etc., which can stabilize the precipitation process of the silver powder and at the same time achieve a certain dispersant function, and can also be organically reduced. Agents, process types, etc. to make appropriate choices.

1295666 五、發明說明（9) ------ #丨μ i發明於使上述方法所得之銀氨錯合物水溶液與還原背發生反應以還原析出微粒銀粉的方法中，最好採用t第1圖所不之方法，其係將銀氨錯合物水溶液S1以特定奴徑（以上與以下將此稱為「第一流徑」）進行流動，於此第一流徑a中途設置匯流之第二流徑b，藉由此第二流徑 b j吏有機還原劑與因應需要而使用之添加劑s 2流入第一流徑a，於第一流徑a與第二流徑b之匯流點1}1進行接觸、混合，以還原析出銀粒子（以下將此方法稱為「匯流混合方才木用此匯流混合方式因為可於最短時間内將2個溶液此合，且系統於均勻狀態下進行反應，故可形成具有均勻 f狀之粉粒。而且，以混合後整個溶液來看，有機還原劑量低，其表示吸附殘留於還原析出之微粒銀粉之粉粒表面上的有機還原劑量減少。如此，可降低過濾、乾燥後所得之微粒銀粉的不純物附著。又由於此微粒銀粉之附著不純量降低，故可降低以銀膠所形成之燒結導體的電氣阻抗”。再者，當銀氨錯合物水溶液與氨水接觸、產生反應以生成銀氨錯合物水溶液時，最好使用硝酸銀濃度為 2· 6g/l〜48gn的硝酸銀水溶液，以獲得銀濃度為 2g/l〜12gM之銀氨錯合物水溶液。在此，規範硝酸銀水、☆ 液之濃度與規範硝酸銀水溶液之液量是同義的，將銀氨二合物水溶液之銀濃度設定為Zg/uggM，則於其中添加^ 氨水的濃度與液量也自然地確定。雖然現階段尚無法給明確之技術上的理由，但藉由此處所述之硝酸銀濃度為21295666 V. INSTRUCTION DESCRIPTION (9) ------ #丨μ i Invented in the method of reacting the aqueous solution of silver ammonia complex obtained by the above method with a reducing back to reduce the precipitation of fine silver powder, it is preferable to adopt t In the method of Fig. 1, the silver ammonia complex aqueous solution S1 is flowed by a specific slave diameter (hereinafter referred to as "first flow path" hereinafter), and the second flow path is set in the middle of the first flow path a. The flow path b is caused by the second flow path bj 吏 the organic reducing agent and the additive s 2 used as needed to flow into the first flow path a, and the first flow path a is contacted with the confluent point 1}1 of the second flow path b And mixing to reduce the precipitation of silver particles (hereinafter, this method is called "the confluent mixing method". This method can be formed because the two solutions can be combined in the shortest time and the system is reacted in a uniform state. The powder having a uniform f shape, and the organic reducing amount is low in view of the entire solution after mixing, which means that the amount of organic reducing agent adsorbed on the surface of the fine particles of the precipitated silver powder is reduced, thereby reducing filtration, After drying The impure substance of the obtained silver powder is attached, and the electrical imperfection of the sintered conductor formed by the silver paste can be reduced due to the reduced impure amount of the silver powder. Further, when the silver ammonia complex aqueous solution is in contact with ammonia water, When reacting to form an aqueous solution of silver ammonia complex, it is preferred to use a silver nitrate aqueous solution having a silver nitrate concentration of 2·6 g/l to 48 gn to obtain an aqueous solution of silver ammonia complex having a silver concentration of 2 g/l to 12 gM. The concentration of silver nitrate water and ☆ liquid is synonymous with the liquid amount of the standard silver nitrate aqueous solution. When the silver concentration of the silver ammonia dihydrate aqueous solution is set to Zg/uggM, the concentration and liquid amount of the aqueous ammonia added thereto are also naturally determined. Although it is not possible to give a clear technical reason at this stage, the concentration of silver nitrate described here is 2

mm

2213-6406-PF(N2).ptd 第15頁2213-6406-PF(N2).ptd第15页

1295666 6g/l〜48g/l的硝酸銀水溶液，可獲得具有最優良之製造穩定性、且品質穩定的微粒銀粉。本發明之製造方法之第2特徵係於最後進行非常重要的清洗^驟。此時之清洗步驟可使用水清洗與乙醇清洗之組合，亦可僅使用乙醇清洗，主要是加強以乙醇進行清洗時的清洗。亦即，對還原析出4 0 g之微粒銀粉’一般係以約1 0 Om 1的純水來清洗，其後再以約5 Om 1的乙醇進行乙醇清洗。而本發明於進行乙醇清洗時，以2 〇〇 m 1以上的乙醇，亦即相當於對1 kg的微粒銀粉以5L以上之過量的乙醇來進行清洗。一藉由=強清洗以降低不純物，亦是因為於銀氨錯合物 ίt Ϊ:原劑接觸反應而得到微粒銀粉之製程中，採用原劑量的方法之緣故。口傻您正個，合液的有機還〈發明之效果〉本發明之微粒銀粉係習知精由上述製造方法，率 / 散性高，且為習知之銀粉$ 形成之微粒，不僅分 ϋ cb μ #制、4 ' +存在之微細粉粒。而且，提升本發明之微粒録之生產效【實施方式】以下同時比較對態。评細說明本發明之最佳實施形【實施例1】 2213-6406-PF(N2).ptd 第16頁 1295666 五、發明說明（11) 本實施例中，對以上述製造方法體特性進行測定。並且使用微粒銀粉製成銀;“立2的粉測试電路，以進行導體阻抗與燒結起始溫度之測定-成首先將63.3g之硝酸銀溶解於9·7升的純水中，以 =銀水，液’=其中添加濃度為2^%之氨水235mi2 撥拌’而付到銀氣錯合物水溶液。门其後，將此銀氨錯合物水溶液以15〇〇ml/sec的流入第1圖所示之内徑為13_的第一流徑a 導 ! 5咖/咖的流量導入於第二流徑b，並使兩€/於^1295666 6g/l to 48g/l of a silver nitrate aqueous solution can obtain fine particle silver powder having the most excellent manufacturing stability and stable quality. The second feature of the manufacturing method of the present invention is that a very important cleaning step is performed at the end. In this case, the washing step can be carried out by using a combination of water washing and ethanol washing, or by using only ethanol washing, mainly to enhance the cleaning when washing with ethanol. Namely, the fine silver powder for the precipitation of 40 g is usually washed with pure water of about 10 OM 1 , and then washed with ethanol of about 5 OM 1 . On the other hand, in the present invention, when ethanol washing is carried out, ethanol of 2 〇〇 m 1 or more, that is, equivalent to 1 kg of fine particle silver powder, is washed with an excess of 5 L or more of ethanol. One is to reduce the impurities by strong cleaning, and also because the method of using the original dosage is used in the process of obtaining the silver powder by the silver ammonia complex ίt Ϊ: the original agent is in contact with the reaction. The mouth is stupid, and the organic matter of the liquid is also the effect of the invention. The fine particle silver powder of the present invention is a fine particle/dispersion by the above-mentioned manufacturing method, and is a fine particle formed by the conventional silver powder, not only the cb μ #制, 4 ' + fine powder present. Further, the production efficiency of the microparticle recording of the present invention is improved. [Embodiment] The following comparisons are made at the same time. BEST MODE FOR CARRYING OUT THE INVENTION [Embodiment 1] 2213-6406-PF(N2).ptd Page 16 1295666 V. Description of Invention (11) In the present embodiment, the physical properties of the above manufacturing method were measured. . And using silver powder to make silver; "Liquid 2 powder test circuit to measure the conductor impedance and the sintering start temperature - first dissolve 63.3g of silver nitrate in 9·7 liters of pure water, to = silver Water, liquid '=In which a concentration of 2% by weight of ammonia water 235mi2 is added and mixed, and the silver gas complex aqueous solution is added. After that, the aqueous solution of the silver ammonia complex is infused with 15〇〇ml/sec. 1 shows the first flow path a with an inner diameter of 13_ a! The flow of 5 coffee/coffee is introduced into the second flow path b, and two €/in ^

於匯流點m產生接觸，以還原析出微粒銀粉。此時之還原劑係採用以21g之對苯二酚溶解於丨〇升純水中備之對苯二酚水溶液。因此，於混合結束時對苯二衣* 度約為1· 〇4g/l，係非常稀薄的濃度。激、、為了分離上述所得之4〇g的微粒銀粉，使用漏斗進行，濾，並以100ml的水與6〇〇ml的甲醇來清洗，然後進行小時的乾燥，以得到微粒銀粉。第2圖即為上述所得之微粒銀粉之掃描電子顯微鏡照相圖。上述所得之微粒銀粉之粉體特性，與實施例2及對照例中所得之銀粉的粉體特性一同列於表格1中。因此，在此補充上述測定方法等說明中不清楚之部分。表格丨之燒結起始溫度之測定係以天平精秤〇· 5g的微粒銀粉，以 21 /、c m的壓力進行1分鐘的重壓，以形成板狀，然後使用型號為TMA/SS6000之Seiko Instruments公司所製的熱機械分析裝置（TMA裝置），以空氣流量為2〇〇cc/分、升溫速度Contact is made at the confluence point m to reduce the precipitation of the particulate silver powder. The reducing agent at this time was an aqueous solution of hydroquinone prepared by dissolving 21 g of hydroquinone in soared pure water. Therefore, at the end of the mixing, the benzoic acid* degree is about 1·4 g/l, which is a very thin concentration. The fine silver powder of 4 〇g obtained by the above was separated, filtered using a funnel, washed with 100 ml of water and 6 ml of methanol, and then dried for a while to obtain fine silver powder. Fig. 2 is a scanning electron micrograph of the above-obtained fine particle silver powder. The powder characteristics of the above-mentioned fine particle silver powder are shown in Table 1 together with the powder characteristics of the silver powder obtained in Example 2 and the comparative example. Therefore, it is hereby supplemented with the unclear part of the above description of the measurement method and the like. The sintering initiation temperature of the table is measured by a micronized silver powder of a balance of 5 g, and subjected to a pressure of 21 /, cm for 1 minute to form a plate, and then Seiko Instruments of the type TMA/SS6000 is used. The thermomechanical analysis device (TMA device) manufactured by the company has an air flow rate of 2 〇〇cc/min and a heating rate.

1295666 五、發明說明（12) 為2 °C /分、停滯時間為〇分鐘的條件，於常溫〜9〇〇它的範圍中進行測量。表格1中所列之導體阻抗的測定係先以各銀粉製成銀膠，於陶瓷基板上形成電路，並利用於 1 8 0〜2 5 0 C的溫度中進行燒結加工所得之1 mm寬度的電路來進行量測。此外，銀膠之組成為微粒銀粉85wt%、乙基纖維素0.75wt%、與松烯醇14.25% 〇FIB分析係測量析出結晶粒之大小，用於晶粒粒徑的測定。【實施例2】本實施例係對使用不同於實施例1之製造條件所製造而得之微粒銀粉，進行粉體特性的測定。並且使用微粒銀粉製成銀膠，進而形成測試電路，以進行導體阻抗與燒結起始溫度之測定。首先將63· 3g之硝酸銀溶解於3· !升的純水中，以製備硝酸銀水溶液，於其中添加濃度為25wt%之氨水235mi 一同稅拌’而得到銀氨錯合物水溶液。 +其後，-將此銀氨錯合物水溶液以15〇〇1111/3^的流量導入第1圖所示之内徑為13_的第一流徑a，將還原劑以 15〇〇ml/sec的流量導入於第二流徑b，並使兩者於2〇。〇下於，流點'產生接觸，以還原析出微粒銀粉。此時所使用之還原j係採用以2 1 g之對苯二酚溶解於3 · 4升純水中所製 2之對苯二酚水溶液。因此，於混合結束時對苯二酚之‘ 度約為3· 〇g/1，係非常稀薄的濃度。、# 一 t ϋ實知例1，將上述所得之40g的微粒銀粉使用漏斗灯a L，並以l〇〇ml的水與6〇〇ml的甲醇來清洗，然後進1295666 V. Description of invention (12) For the condition of 2 °C / min and the stagnation time is 〇 min, it is measured in the range of normal temperature ~ 9 。. The conductor impedances listed in Table 1 were determined by making silver paste from each silver powder, forming a circuit on the ceramic substrate, and using a 1 mm width obtained by sintering at a temperature of 180 to 250 ° C. The circuit is used for measurement. Further, the composition of the silver paste was 85 wt% of the fine particle silver powder, 0.75 wt% of the ethyl cellulose, and 14.25% of the terpene alcohol. The FIB analysis system measures the size of the precipitated crystal grains for the measurement of the crystal grain size. [Embodiment 2] In the present embodiment, the measurement of the powder characteristics was carried out by using the fine particle silver powder produced by the production conditions different from those of the first embodiment. Further, silver paste was used to form a silver paste, thereby forming a test circuit for measuring the conductor resistance and the sintering initiation temperature. First, 63 g of silver nitrate was dissolved in 3 liters of pure water to prepare an aqueous solution of silver nitrate, and 235 mi of ammonia water having a concentration of 25 wt% was added thereto to form a silver ammonia complex aqueous solution. + Thereafter, the aqueous solution of the silver ammonia complex is introduced into the first flow path a having an inner diameter of 13 _ shown in Fig. 1 at a flow rate of 15 〇〇 111 1/3 ,, and the reducing agent is 15 〇〇 ml / The traffic of sec is introduced into the second flow path b, and the two are at 2 〇. Under the squat, the flow point 'produces contact to reduce the precipitation of particulate silver powder. The reduction j used at this time was an aqueous solution of hydroquinone prepared by dissolving 2 1 g of hydroquinone in 3 4 liters of pure water. Therefore, the degree of hydroquinone at the end of the mixing is about 3·〇g/1, which is a very thin concentration. , #一 t ϋ 知 1 , , , , 知 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40

1295666 五、發明說明（13) __ 行7 0 C x5小時的乾燥，以得到微粒銀粉。第 … 所得之微粒銀粉之掃描電子顯微鏡照相圖。w p為上述粒銀粉之粉體特性，與實施例丨及對照例中达所得之微粉體特性一同列於表格1中。 f之銀粉的【對照例1】本對照例中僅改變實施例丨之清洗條複說明，在此僅說明清洗條件。為了避免重將實施例1中所得之微粒銀粉4 〇g使用漏斗並以10〇ml的水與50ml的甲醇來清洗，然後' 過^慮，時的乾燥，以得到微粒銀粉。第2圖即為上述=〇Cx5小銀粉之掃描電子顯微鏡照相圖。上述之所侍之微粒體特性，與其他實施例及對照例中所得之==粉一同列於表格1中。 m私的粉體特性【對照例2】本對照例中僅改變實施例2之清洗條複說明’在此僅說明清洗條件。 ’、為了避免重將實施例2中所得之微粒並以1 0〇ml的水與50ιη1的甲 2，使秋用漏斗進行過濾’ 時的乾燥，以得到微粒銀粉。 =彳進仃70 °Cx5小銀粉之掃描電子顯微鏡照相圖马上述所得之微粒體特性’與其他實施例及對；例戶微粒銀粉之粉一同列於表格1中。、斤件之銀粉的粉體特性【對照例3】本對照例係對使用下列所示之製造方法所製造而得之1295666 V. INSTRUCTIONS (13) __ Row 7 0 C x 5 hours drying to obtain particulate silver powder. A scanning electron microscope photograph of the particulate silver powder obtained in the first. Wp is the powder property of the above-mentioned granulated silver powder, and is shown in Table 1 together with the micropowder characteristics obtained in the examples 对照 and the comparative examples. Silver powder of f [Comparative Example 1] In the present comparative example, only the cleaning strip of the example was changed, and only the washing conditions will be described here. In order to avoid the use of the funnel silver powder 4 〇g obtained in Example 1 was washed with a funnel and washed with 10 ml of water and 50 ml of methanol, and then dried, to obtain fine silver powder. Fig. 2 is a scanning electron micrograph of the above = 〇Cx5 small silver powder. The above-mentioned particulate characteristics are listed in Table 1 together with the == powder obtained in the other examples and the comparative examples. m powder characteristics [Comparative Example 2] In the present comparative example, only the cleaning strip of Example 2 was changed. In order to avoid the heavy particles obtained in Example 2 and drying with 10 〇ml of water and 50 ηη1 of forging, the autumn funnel was filtered to obtain fine silver powder. = 彳仃 70 ° C x 5 small scanning electron micrograph of silver powder The microparticle properties obtained by the above-mentioned horses are shown in Table 1 together with other examples and pairs; Powder characteristics of silver powder of the powder [Comparative Example 3] This comparative example was produced by using the production method shown below.

12956661295666

五、發明說明（14) 微粒銀粉，進行粉體特性的測定。並且使用微粒銀粉製成銀膠，進而形成測試電路，以進行導體阻抗與燒結起二、、w 度之測定。首先將6 3 · 3 g之硝酸銀溶解於1升的純水中，以製備确酸銀水溶液，於其中添加濃度為25wt%之氨水235ml —同授摔’而得到銀氣錯合物水溶液。其後，將此銀氨錯合物溶液置入反應槽中，此時一同添加以對苯二酚2 1 g溶解於1 · 3升的純水、作為還原劑之對苯二紛水溶液，將溶液溫度維持於2 〇 X：進行攪拌、使其發生反應，以還原析出銀粉。於混合結束時對苯二酚之^ ^ 約為14· 5g/l，係高濃度溶液。 /又如同實施例1，將上述所得之微粒銀粉使用漏斗過濾，並以100ml的水與5〇ml的甲醇來清洗，然後 Cx5小時的乾燥，以得到微粒銀粉。第4圖即為上之微粒銀粉之掃描電子顯微鏡照相圖。斤仔粉之粉體特性，盥卜a每a , ^ ^行< Μ粒銀的e转I π與上述實施例及第2對照例中所得之銀粉的叔體特性一同列於表格】中。、跟物【對照例4】微粒銀粉，進;^ :：歹:所：之製造方法所製造而得之銀膠，進而形成測試電0、測疋。並且使用微粒銀粉製成度之測定。以電路’以進行導體阻抗與燒結起始溫盲先將6 3 · 3 g之石肖酸夺、々硝酸銀水溶液，於豆中六X/谷解於3 00nU的純水中，以製有、八中添加濃度為25wt%之氨水2351]11一同V. INSTRUCTIONS (14) Fine silver powder for the determination of powder properties. Further, silver powder is used to form silver paste, thereby forming a test circuit for measuring the impedance and sintering of the conductor and the degree of w. First, 6 3 · 3 g of silver nitrate was dissolved in 1 liter of pure water to prepare an aqueous solution of silver acetate, and 235 ml of ammonia water having a concentration of 25 wt% was added thereto to give a silver gas complex aqueous solution. Thereafter, the silver ammonia complex solution is placed in the reaction tank, and at this time, the hydroquinone 2 1 g is dissolved in 1.3 liters of pure water, and the aqueous solution of benzodiazepine as a reducing agent is added. The solution temperature was maintained at 2 〇X: stirring was carried out to cause a reaction to reduce the precipitation of silver powder. At the end of the mixing, the hydroquinone was about 14.5 g/l, which was a high concentration solution. Further, as in Example 1, the above-obtained fine particle silver powder was filtered using a funnel, washed with 100 ml of water and 5 ml of methanol, and then Cx dried for 5 hours to obtain a fine particle silver powder. Figure 4 is a scanning electron micrograph of the upper particulate silver powder. The powder characteristics of the powder, the a per ^, ^ ^ row < the e-trans I π of the silver of the silver and the uncharacteristics of the silver powder obtained in the above examples and the second comparative example are listed in the table] . [Comparative Example 4] Fine silver powder, into; ^ ::歹: The silver gel produced by the manufacturing method, and then formed test 0, test. And the determination of the degree of manufacture of the particulate silver powder is used. In order to conduct the conductor impedance and the sintering initiation temperature, the 6 3 · 3 g of the sulphuric acid and the silver nitrate aqueous solution are dissolved in the pure water of 300 N U in the bean to prepare Adding a concentration of 25wt% ammonia water 2351]11

1295666 五、發明說明（15) 擾拌’而得到銀氨錯合物水溶液。其後’將此銀氨錯合物溶液置入添加以明膠3g溶解於200ml的純水所應槽^中’此時一同對苯二酚21g溶解於700ml的純水、、之溶液、以及以水溶液，將溶液溫度維持於2G t進.f原剤之對苯二酚應，以還原析出銀粉。於混合結束二使其發生反 14· 5g/l，係高濃度溶液。、本一酚之濃度約為如同實施例1，將上述所得之微粒銀過濾，並以100ml的水與50roi的甲醇々使用漏斗進行 °Cx5小時的乾燥，以得到微粒銀粉 ^ =進行70 之微粒銀粉之掃描電子顯微鏡照圖尸為/述所得的粉體特性一同列於表格1中。銀私【對照例5】本對照例係對使用下列所示之製造方法所製 =銀：而开進Γ'體特性之測定。並且使用微粒銀粉ϊί =測J而形成測試電路’以進行導體阻抗與燒結起始】首先將20g之聚乙烯吡咯烷酮溶解於26〇mi 然後使其轉奶Or錢銀，㈣備錢銀切屯水中’ ，其中添加25g的硝酸一同進行授拌，而得 =溶液。於混合結束時於驗酸之濃度約為36 〇之^ 濃度溶液。 1 係鬲另外還原劑之製作係將3 5 · 8 g之菸鹼酸溶解於5 〇〇 m i 第21頁1295666 V. INSTRUCTION DESCRIPTION (15) Agitating the mixture to obtain an aqueous solution of silver ammonia complex. Thereafter, the silver ammonia complex solution was placed in a tank containing 3 g of gelatin dissolved in 200 ml of pure water. At this time, 21 g of hydroquinone was dissolved in 700 ml of pure water, a solution thereof, and In the aqueous solution, the temperature of the solution is maintained at 2 G t to the original hydroquinone to reduce the precipitation of silver powder. At the end of the mixing, the reaction was carried out at a concentration of 7.5 g/l, which was a high concentration solution. The concentration of the present phenol is about the same as in Example 1. The above-obtained fine particles of silver are filtered, and dried with 100 ml of water and 50 roi of methanol in a funnel at ° Cx for 5 hours to obtain a particulate silver powder. The powder characteristics of the silver powder scanning electron microscope are shown in Table 1. Silver Private [Comparative Example 5] This comparative example is a measurement of the physical properties of the silver produced by the following production method. And use the particle silver powder ϊ ί = test J to form the test circuit 'to conduct the conductor impedance and the sintering start. First, dissolve 20g of polyvinylpyrrolidone in 26〇mi and then turn it into milk, silver, (4) reserve money, silver cut water ', wherein 25 g of nitric acid was added for mixing, and the solution was obtained. At the end of the mixing, the concentration of the acid is about 36 ^. 1 system 鬲 Another reducing agent is prepared by dissolving 3 5 · 8 g of nicotinic acid in 5 〇〇 m i Page 21

2213-6406-PF(N2).ptd 1295666 五、發明說明（16) 的純水中，而配製成還原溶液。其後，將此含銀之硝酸颛溶液置入反應同添加上述還原溶液，將溶液溫度維持於2 5此時一使其發生反應，以還原析出銀粉。、進行攪拌、如同實施例1，將上述所得之微粒銀粉使過濾，並以1 0 0 m 1的水與5 0 m 1的甲醇來清洗，然^斗進行。㈤小時的乾燥’以得到微粒銀粉。：述所得？微進= 之粉體特性，與上述實施例及對照例中所得之 = 特性一同列於表格1中。刀曰]物體〈實施例與對照例之比較〉請參照表格1，以進行上述各實施例與對照例的比較。此外，由第2圖〜第5圖之掃描電子顯微鏡照相圖可明確得知粉粒之一次粒子的粒徑。2213-6406-PF(N2).ptd 1295666 5. In pure water of the invention (16), it is formulated into a reducing solution. Thereafter, the silver-containing cerium nitrate solution is placed in the reaction and the above-mentioned reducing solution is added, and the temperature of the solution is maintained at 2 5 to cause a reaction to reduce the precipitation of the silver powder. The mixture was stirred, and the particulate silver powder obtained above was filtered as in Example 1, and washed with 100 ml of water and 50 ml of methanol. (five hours of drying) to obtain particulate silver powder. : What is the income? The powder characteristics of micro-increment = are listed in Table 1 together with the characteristics obtained in the above examples and comparative examples. Knife] object <Comparison of Example and Comparative Example> Referring to Table 1, the comparison between the above examples and the comparative examples was carried out. Further, the scanning electron microscope photographs of Figs. 2 to 5 can clearly show the particle diameter of the primary particles of the particles.

1295666 — 五、發明說明（17) 表辂1 試料粉體特性 _燒結導體 SSA m2/g 振霣塡充密度〇 g/cm Dso Dia D50/ Dia 晶粒粒徑 nm 含碳量 % 導體阻抗 μΩ· cm 燒結起始溫度 °C μιη 賞施例1 2.54 4.2 0.31 0.30 1.03 7 0.15 4.6 160 富施例2 1.68 4.7 0.55 0.49 1.12 7 0.21 5.9 190 對照例1 2.89 4.3 0.29 0.28 1.04 7 0.28 8.5 160 對照例2 0.55 4.0 3.90 2.20 1.77 7 0.32 7.9 190 對照例3 1.18 4.3 1.78 1.02 1.75 9 0.88 無法測量 250 對照例4 0.55 4.0 3.90 2.20 1.77 8 0.89 無法測量 250 對照例5 0.62 4.0 3.03 1.20 2.53 38 0.30 無法測量 350 由表格1可得知，比較各個粉體特性值，上述實施例中所得之微粒銀粉不僅比以習知製造方法所製造之銀粉粉 :二細分散性較高，也降低了不純物含量，係習妒銀 m:; ϊϊ粉所形成之電路不僅膜密度高，真電 :阻抗也降低。而各對照例因導體阻抗高，而無法進行測產業上可利性：本發明之微粒銀粉具有習不僅粉粒之凝聚度低，而且比性。此外，藉由本發明之微粒知銀粉所沒有的微細粉粒，習知銀粉具有更良好的分散銀粉之製造方法，可降低微1295666 — V. INSTRUCTIONS (17) Table 1 Sample powder characteristics _ Sintered conductor SSA m2/g Vibrating density 〇g/cm Dso Dia D50/ Dia Grain size nm Carbon content % Conductor impedance μΩ· Cm Sintering start temperature °C μιη Appreciation Example 1 2.54 4.2 0.31 0.30 1.03 7 0.15 4.6 160 Rich Example 2 1.68 4.7 0.55 0.49 1.12 7 0.21 5.9 190 Comparative Example 1 2.89 4.3 0.29 0.28 1.04 7 0.28 8.5 160 Comparative Example 2 0.55 4.0 3.90 2.20 1.77 7 0.32 7.9 190 Comparative Example 3 1.18 4.3 1.78 1.02 1.75 9 0.88 Unable to measure 250 Comparative Example 4 0.55 4.0 3.90 2.20 1.77 8 0.89 Unable to measure 250 Comparative Example 5 0.62 4.0 3.03 1.20 2.53 38 0.30 Unable to measure 350 by Table 1 It can be seen that, in comparison with the respective powder property values, the particulate silver powder obtained in the above examples is not only higher in fine dispersion than the silver powder produced by the conventional manufacturing method, but also has a low impurity content, and is also reduced in the amount of impurities. :; The circuit formed by the powder is not only high in film density, but also in real electric power: impedance is also reduced. On the other hand, each of the comparative examples was incapable of performing measurement because of high conductor resistance. Industrially, the particulate silver powder of the present invention has a low degree of cohesion and a specificity. Further, by the fine particles of the present invention which are not known to the silver powder, the conventional silver powder has a better method for producing the dispersed silver powder, which can reduce the micro-particles.

2213-6406-PF(N2).ptd 第23頁 1295666 五、發明說明（18) 粒銀粉上所殘留的有機物，雖為微粒銀粉，但與原來的膜密度之高度重疊、作用，因而有助於降低最終所獲得之導體的電氣阻抗。2213-6406-PF(N2).ptd Page 23 1295666 V. DESCRIPTION OF THE INVENTION (18) The organic matter remaining on the granular silver powder is a fine particle silver powder, but it overlaps with the original film density and thus contributes to Reduce the electrical impedance of the resulting conductor.

2213-6406-PF(N2).ptd 第24頁 1295666 圖式簡單說明第1圖繪示銀氨錯合物水溶液與還原劑混合之示意圖。第2圖與第3圖係本發明之微粒銀粉之掃描電子顯微鏡照相圖。第4圖與第5圖係以習知方法所得到之微粒銀粉之掃描電子顯微鏡照相圖。符號說明： 51 :銀氨錯合物水溶液 52 ··添加劑 a :第一流徑 b :第二流徑 m :匯流點2213-6406-PF(N2).ptd Page 24 1295666 Brief Description of the Drawing Figure 1 is a schematic diagram showing the mixing of an aqueous solution of silver ammonia complex with a reducing agent. Fig. 2 and Fig. 3 are scanning electron microscope photographs of the particulate silver powder of the present invention. Fig. 4 and Fig. 5 are scanning electron micrographs of the fine particle silver powder obtained by a conventional method. DESCRIPTION OF SYMBOLS 51: Aqueous solution of silver ammonia complex 52 ··Additive a : First flow path b : Second flow path m : Confluence point

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Claims

9311875893118758

1 · 一種微粒銀粉，粉粒凝聚性低之銀粉包括下列a ·〜d ·之粉體特性： a·以掃描電子顯微鏡照相圖作影像分析所得之〜子之平均粒徑Du為〇· 6 μιη以下；次极 b •以上述平均粒徑DIA、與雷射粒徑分佈測定法戶平均粒徑I所表示之凝聚度D5q/Dia為丨，5以下；得之 C .晶粒粒徑為1 Q nm以下·，及 d·有機不純物含量以含碳量換算於〇· 25以％以下。 2·如申請專利範圍第i項所述之微粒銀榼起始溫度為2 40 t：以下。、甲^結 & 3· —種微粒銀粉之製造方法，由混合硝酸銀水溶液與 i ^，使ΐ反應得到銀氨錯合物水溶液，再於其中添加對本一酚以還原析出銀粒子，並進行過濾、清洗、乾燥，其特徵在於： ' 使對苯一酞與上述銀氨錯合物水溶液進行接觸、混 :输且仏合後〉谷液中之銀濃度為1 g/ 1〜6g/ 1、對苯二酚濃 ς :持於1 g/ 1 3 g/ 1，以還原析出銀粒子，並對該銀粒子進仃過濾、水清洗、及過量的乙醇溶液清洗。1 · A kind of fine-grained silver powder, the silver powder with low cohesiveness of the powder includes the following powder characteristics of a · ~ d · a: The average particle diameter of the sub-substituent of the image obtained by scanning electron micrographs is 〇· 6 μιη Hereinafter, the secondary electrode b: the average particle diameter DIA, and the aggregation degree D5q/Dia expressed by the average particle diameter I of the laser particle size distribution method is 丨, 5 or less; C. The grain size is 1 The Q nm or less and the d·organic impurity content are converted to 〇·25% or less in terms of carbon content. 2. The particle size of silver 榼 as described in item i of the patent application range is 2 40 t: or less. A method for producing a particulate silver powder by mixing an aqueous solution of silver nitrate with i^, reacting hydrazine to obtain an aqueous solution of silver ammonia complex, and then adding a phenol to the present phenol to reduce and precipitate silver particles, and performing Filtration, washing and drying, characterized in that: 'After contacting and mixing the benzoquinone with the aqueous solution of the silver ammonia complex, the silver concentration in the gluten solution is 1 g / 1 to 6 g / 1 Hydroquinone concentration: held at 1 g / 13 g / 1, to reduce the precipitation of silver particles, and the silver particles are filtered, washed with water, and washed with an excess of ethanol solution.

4.如申請專利範圍第3項所述之微粒銀粉之製造方 ^1中當對苯二酚與上述銀氨錯合物水溶液進行接觸、 4，上述銀氨錯合物水溶液以特定流經（以下稱為、古，一流徑」Ο流動，於該第一流徑中途設置匯流之第二版=，错由該第二流徑使對苯二酚流入，於第一流徑與第一 k徑之匯流點進行接觸、混合。4. In the manufacturing method of the particulate silver powder according to claim 3, when hydroquinone is contacted with the aqueous solution of the above silver ammonia complex, 4, the aqueous solution of the silver ammonia complex is specifically flowed through ( The following is called "ancient, first-class diameter" Ο flow, and the second version of the confluence is set in the middle of the first flow path. The second flow path causes the hydroquinone to flow in the first flow path and the first k-path. Confluence points are contacted and mixed.

第26頁 1295666 案號 93Π8758 修正六、申請專利範圍 5. 如申請專利範圍第3項所述之微粒銀粉之製造方法，其中使用硝酸銀濃度為2. 6 g / 1〜4 8 g / 1之硝酸銀水溶液與氨水進行混合、反應、且銀濃度為2 g / 1〜1 2 g / 1之銀氨錯合物水溶液。 6. 如申請專利範圍第3項所述之微粒銀粉之製造方法，其中使用之對苯二驗中包含分散劑。 7. 如申請專利範圍第3項所述之微粒銀粉之製造方法，其中乙醇係使用相當於對1 k g之銀粒子使用5 L以上之乙醇的量來進行。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 An aqueous solution of a silver ammonia complex in which an aqueous solution is mixed with ammonia water, reacted, and has a silver concentration of 2 g / 1 to 1 2 g / 1. 6. The method for producing a particulate silver powder according to claim 3, wherein the para-benzoic test used comprises a dispersant. 7. The method for producing a particulate silver powder according to the third aspect of the invention, wherein the ethanol is used in an amount equivalent to 5 L or more of ethanol for 1 k g of silver particles.

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