200425166 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種例如適合作爲積層陶瓷電容器之內 部電極所使用的導電糊用之超微粉鎳粉分散體，特別是形 成導電糊時具有優異分散性之鎳粉分散體。而且，本發明 係有關該超微粉分散體之調製方法及使用該粉末分散體之 導電糊的調製方法。 【先前技術】 具有鎳、銅、銀、白金等之導電性的金屬粉末，於電 子電路的導體形成時被廣泛使用，特別是對積層陶瓷電容 器之內部電極形成極爲有用。積層陶瓷電容器藉由積層鈦 酸鋇、鈦酸緦等之陶瓷糊、與具有導電性之金屬粉末糊後 f以燒結，使陶瓷之介電體層與金屬微粉末之內部電極層 交互形成者。於上述具有鎳、銀、白金等之導電性的金屬 粉末中，由於鎳粉低價、在還原性氣氛中可燒成等之用途 受到注重。 一般而言，上述積層陶瓷電容器藉由下述方法製造。 換言之，使鈦酸鋇等之介電體粉末與有機黏合劑混合、懸 '浮’藉由刮刀法使該物形成片板狀，製作介電體生片。另 外’使內部電極用鎳粉與有機溶劑、可塑劑、有機黏合劑 '糊料形成用分散劑等混合、分散以形成鎳粉糊，且使該 物以篩網印刷法印刷於上述生片上。然後，實施乾燥、積 ®及壓熔，進行加熱處理以除去有機成分後，在約13〇〇°C ^以上之溫度下燒成，再於介電體陶瓷層兩端上燒附外部 200425166 電極，製得積層陶瓷電容器。 上述之積層陶瓷電容器，近年來企求小型化、大容量 化，伴隨於此強烈企求內部電極薄層化、低電阻化。一般 的內部電極之一層厚度爲1〜2μιη,今後可能更爲要求薄膜 化者。 有鑑於該要求，特別開發有關內部電極薄膜化之各種 技術。然而，於製造內部電極用之鎳糊時，存在有較內部 電極之一層厚度1〜2μιη爲厚的平均粒徑大之鎳粉時，或存 在有因分散性低時鎳粒子凝聚、較內部電極之一層厚度爲 厚的平均粒徑大之二次粒子時，恐會於電極層表面上產生 凹凸現象。使用該存在有粗粉或凝聚粉之糊料形成積層陶 瓷電容器時，容易產生短路現象、且無法使用作爲製品。 而且，於形成糊料時鎳粉之分散性低時，不僅於印刷於生 片上時電極膜厚不均勻，造成產生短路的原因，且於燒成 時容易產生離層或斷裂等內部缺陷的問題。 爲解決該問題時，提案有積層陶瓷電容器用內部電極 之薄膜化方法、表面平坦化方法、或改善鎳糊之分散性的 方法。例如，揭示在由導電性粉末、有機載色劑所成的導 電性組成物中添加陰離子性界面活性劑的方法（例如參照特 開平1 0-92226號公報（專利文獻1))。另外，揭示在由導電 性粉末、有機載色劑所成之導電性糊中添加陰離子性高分 子力ώ μ!Ι，另爲防止該陰離子性高分子分散劑之過剩吸附 側與數個粒子形成三次元交聯、凝膠化時添加胺系界面活 性劑的方法（例如參照特開200 1 _6346號公報（專利文獻2)) 200425166 。此外，揭示以吸油量爲5〜25ml/100g之鎳粉作爲分散性 優異的導電性糊用鎳粉（例如參照特開200 1 -266645號公報（ 專利文獻3 ))。 然而，於上述專利文獻1中記載的技術，僅記載由於 內部電極之表面粗度小，可使內部電極薄膜化，惟沒有記 載有關鎳粉之分散性。 此外，於上述專利文獻2中記載的技術，僅記載提高 分散性，防止糊料凝膠化，惟沒有記載有關提高分散性之 數據。 籲 另外，於上述專利文獻3中記載的技術，係爲藉由進 行緩和習知技術製造的鎳粉凝聚之解粒處理以控制吸油量， 且提高於形成糊料時之分散性者。藉由該方法製得的鎳糊， 雖具有提高分散性之效果5惟該效果於形成鎳粉導電糊時· 鎳粉爲不充分者。 【發明內容】 因此，本發明係以提供形成導電糊時具有優異的分散 性，結果於製作積層陶瓷電容器時可防止因內部電極表面 鲁 之凹凸造成短路現象，或防止產生離層等內部缺陷的鎳粉 分散體爲目的。而且，本·發明亦以提供使該鎳粉充分分散 的微粉錬分散體之調製方法及使用該粉末分散體之導電 糊爲目的。 本發明人等爲達成上述目的再三深入硏究的結果，發 現在由超微粉鎳粉與水溶劑所成的水分散體中添加有機溶 劑後’添加胺系分散劑，然後藉由解碎處理所得的鎳粉分 200425166 散體，於形成糊料時具有極高的鎳粉分散性，特別是適合 積層陶瓷電容器等使用的導電糊用。本發明係爲有鑑於該 見解所成者。 換言之，本發明之鎳粉分散體，其特徵爲在由平均粒 徑1 μηι以下之超微粉鎳粉與水溶劑所成的水分散體中添加 有機溶劑，且使至少部分該水溶劑以上述有機溶劑取代後， 添加胺系分散劑，然後進行解碎處理所成。 本發明所使用的鎳粉爲平均粒徑爲1 μπι以下之超微粉， 較佳者爲〇·〇1〜Ιμηι、更佳者爲〇·1〜〇·6μηι、最佳者爲0.15 鲁 〜0.4 μηι。若平均粒徑大於1 μηι時，爲燒結性降低、或積 層陶瓷電容器之內部電極表面上產生凹凸的原因，結果容 易產生短路等之構造缺陷。此外，若平均粒徑過小時，於 調製導電性糊時鎳粉間容易產生凝聚情形，結果因二次粒 子產生造成電極層表面上產生凹凸，導致構造缺陷。而且， 本發明所使用的鎳粉爲提高燒結特性、分散性時，藉由Β Ε Τ 法之比表面積以1〜20m2/g較佳，該粒子形狀以球形較佳 而且，本發明之鎳粉分散體5爲在鎳粉之水分散體中 添加有機溶劑，至少取代部分水溶劑，添加胺系分散劑後， 製得較高的分散性時，以使僅存於鎳粉分散體中的鎳粉之 凝聚情形緩和爲目的進行解碎處理。該解碎處理只要是可 使分散體中之鎳粉的凝聚情形緩和者即可，可使用利用切 變作用或磨碎作用的解碎處理、攪拌式解碎裝置等之習知 解碎裝置進行。具體而言可使用輥磨、槌磨、震動磨、噴 200425166 射磨、球磨、流星型球磨、珠磨、砂磨、三條輥磨等之解 碎裝置。本發明之解碎處理藉由使用球磨進行解碎處理，極 具效果。 如上述所示，本發明藉由使用分散性良好的鎳粉分散 體、在該分散體中添加胺系分散體、及作爲最終處理的使 鎳粉分散體進行解碎處理，可提供於形成導電糊時具有優 異分散性，結果製作積層陶瓷電容器時可防止因內部電極 表面之凹凸而產生短路或離層等之內部缺陷的鎳粉分散體 〇 於該鎳粉分散體中，以上述胺系分散劑至少一種爲烷 胺及聚竣酸之胺鹽較佳。此等胺系分散劑可使用溶解於醇 類、苯酚類、醚類、酮類、脂肪族烴、燈油、輕油、甲苯 、二甲苯等之芳香族烴等有機溶劑中的溶液狀態者。而且， 上述胺系分散劑亦可使用市售品。 此等胺系分散劑之添加量對1 〇 〇重量份分散體中之鎳 粉而言，胺系分散劑成分以〇 · 〇 5〜5.0重量份較佳、更佳者 爲0 · 2〜2 · 0重量份。胺系分散劑成分之添加量小於〇 . 〇 5重 量份時，無法得到充分的作爲分散劑之效果。而且，胺系 分散劑之添加量大於5 · 0重量份時，於製造積層陶瓷電容 器時以除去有機溶劑爲目的之加熱處理時會產生斷裂情形， 或於形成積層陶瓷電容器時會有電氣特性降低等情形。此 外，胺系分散劑之添加可於進行下述解碎處理前添加，亦 可以於使鎳粉分散體解碎處理時，於解碎處理時同時添加 冬 200425166 其次，該鎳粉分散體以添加上述有機溶劑時在上述水 溶劑中存在有界面活性劑較佳，上述界面活性劑可使用聚 氧乙烯苯醚與其磷酸鹽之混合物。 另外，上述鎳粉分散體之有機溶劑濃度以5〜2 0 0重量 %較佳。此外，上述鎳粉以藉由氯化鎳氣體與還原性氣體接 觸反應的氣相還原法、或使熱分解性鎳化合物之溶液噴霧 予以熱分解的噴霧熱分解法所得者較佳。 上述所示之鎳粉分散體，由於如上述於形成上述導電 糊時具有優異分散性，結果於製作積層陶瓷電容器時可防 止因內部電極表面之凹凸而產生短路、或離層等內部缺陷， 故適合使用於導電糊用、特別是積層陶瓷電容器之內部電 極用。 其次，本發明鎳粉分散體之調整方法，係爲於適合調 製上述鎳粉分散體的方法中，其特徵爲使藉由使氯化鎳氣 體與還原性氣體接觸反應的氣相還原法、或使熱分解性鎳 化合物之溶液噴霧熱分解的噴霧熱分解法所得的平均粒徑 1 μηι以下之超微粉鎳粉水洗，添加純水以形成鎳粉分散體， 且在上述鎳粉分散體中添加有機溶劑，使至少部分水溶劑 以上述有機溶劑取代，使有機溶劑濃度爲5〜2 00重量％， 然後添加胺系分散劑後進行解碎處理。 本發明藉由使用分散性良好的鎳粉分散體，在該分散 體中添加胺系分散劑，及作爲最終處理之使鎳粉分散體解 碎處理，可緩和分散體中僅存在的鎳粉凝聚粉之凝聚情形 。因此，藉由本發明之調整方法，可提供於形成導電糊時 -10- 200425166 具有優異分散性，結果於製作積層陶瓷電容器時可防止因 內部電極表面凹凸產生短路、或產生離層等內部缺陷之鎳 粉分散體。而且，添加上述胺系分散劑，於解碎處理時可 達成防止鎳粉間之凝聚效果。 於該鎳粉分散體之調製方法中，如上所述上述胺系分 散劑爲至少一種烷胺及聚羧酸之胺鹽。 而且，於該鎳粉分散體之調製方法中，可在上述鎳粉 水分散體中添加界面活性劑，或可在上述有機溶劑中預先 混合界面活性劑，或可在添加有機溶劑後添加界面活性劑，鲁 上述界面活性劑可以爲聚氧乙嫌苯釀與其憐酸鹽之混合物 〇 另外，本發明之導電糊的製法，係於利用上述鎳粉分 散體的方法中，其特徵爲在本發明之鎳粉分散體中加A由 有機溶劑或有機黏合劑所成的有機載色劑予以混練。而且， 於調製導電糊時視其所需可添加可塑劑、糊料形成用分散 劑等。 【實施方式】 ® 發明之實施形態 於下述中說明本發羽之實施形態。而且，本發明之I桌 粉分散體的調製方法係除調製鎳粉外，可使用於調製銅1、 銀、白金等之導電糊塡充物、鈦材等之複合材、或觸媒等 各種用途之金屬粉末，另外，可使用於調製鋁、欽、_、 錳、鐵、鈷、鉍等之金屬粉末。 1)鎳粉之製造 -11- 200425166 本發明使用的鎳粉可藉由氣相還原法、噴霧熱分解法 '或液相法等習知方法製造。其中以藉由使氯化鎳氣體與 還原性氣體接觸還原、製得鎳粉之氣相還原法，或使熱分 M t生ϋ化合物之溶液噴霧熱分解的噴霧熱分解法較佳。藉 @該方法可容易控制生成的鎳粉之粒徑、且可以高效率製 h球狀錬粒子。 Μ上述氣相還原法中使氣化的氯化鎳氣體與氫等之還 原性氣體接觸、反應以製得鎳粉。此時，氯化鎳氣體可藉 ή習知方法產生。例如採用使固體氯化鎳加熱蒸發產生氯馨 ft鎳氣體的方法、或使金屬鎳與氯氣接觸連續產生氯化鎳 氣體的方法。 於此等方法中使固體氯化鎳加熱蒸發的方法，由於必 須藉由加熱蒸發進行昇華操作，故不易安定地產生氯化鎳 蒸氣。而且，就考慮防止氯化鎳氧化或吸濕、或能量效率 ^而言，以使金屬鎳與氯氣接觸連續產生氯化鎳氣體的方 法較佳。 藉由該氣相還原反應之鎳微粉末的製造過程，係在使 _ 氯化鎳氣體與還原性氣體接觸的瞬間生成鎳原子，藉由鎳 原子間之衝突、凝聚，使超微粒生成、成長。然後，視還· 原過程之氯化鎳氣體之分壓或溫度等條件而定，控制生成 的鎳微粉末之粒徑。 換言之，藉由上述鎳微粉末之製法，由於產生視氯氣 之供應量而定量之氯化鎳氣體，藉由控制氯氣之供應量可 調整供應給還原工程之氯化鎳氣體的量。因此，可適當控 -12- 200425166 制生成的鎳微粉末之粒徑。 此外，於氣相還原法中，由於使氯氣與金屬反應產生 金屬氯化物氣體，故與使固體金屬氯化物加熱蒸發產生金 屬氯化物氣體時不同，不僅可使載體氣體使用減少，且視 製造條件而定可不使用載體氣體。而且，採用氣相還原反 應時藉由減低載體氣體之使用量、與減低伴隨之加熱能量， 故可以減低製造成本。 而且，藉由使在氯化工程產生的氯化鎳氣體中混合惰 性氣體，可控制還原工程之氯化鎳氣體的分壓。如此藉由 控制氯氣之供應量或供應給還原工程之氯化鎳氣體的分壓， 可控制鎳粉之粒徑。因此，可使鎳微粉末之粒徑安定，且 可任意設定粒徑。. 藉由上述氣相還原法之鎳微粉末的製造條件，可使粉 末之平均粒徑在1 μπι以下任意設定。例如，出發原料之金 屬鎳的粒徑以約5〜20mm之粒狀、塊狀、板狀等較佳，且 該純度以約99· 5 %以上較佳。200425166 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to, for example, an ultra-fine powdered nickel powder dispersion suitable for conductive pastes used as internal electrodes of multilayer ceramic capacitors, and particularly has excellent dispersion when forming conductive pastes Dispersion of nickel powder. Further, the present invention relates to a method for preparing the ultrafine powder dispersion and a method for preparing a conductive paste using the powder dispersion. [Prior art] Metal powders having conductivity such as nickel, copper, silver, platinum, etc., are widely used in the formation of conductors of electronic circuits, and are particularly useful for the formation of internal electrodes of multilayer ceramic capacitors. Laminated ceramic capacitors are formed by laminating ceramic pastes such as barium titanate and gadolinium titanate with conductive metal powder f to sinter, so that the dielectric layer of the ceramic and the internal electrode layer of the fine metal powder are formed alternately. Among the above-mentioned conductive metal powders having nickel, silver, platinum, and the like, the use of nickel powder is low, and it can be fired in a reducing atmosphere. Generally, the multilayer ceramic capacitor is manufactured by the following method. In other words, a dielectric powder such as barium titanate is mixed with an organic binder, and suspended, and then 'floated' to form the material into a sheet shape by a doctor blade method to produce a dielectric green sheet. In addition, the nickel powder for internal electrodes is mixed and dispersed with an organic solvent, a plasticizer, an organic binder, a dispersant for paste formation, and the like to form a nickel powder paste, and this is printed on the green sheet by a screen printing method. Then, dry, build-up and pressure melting are performed, followed by heat treatment to remove the organic components, and then firing at a temperature of about 13,000 ° C ^ or more, and then externally bonding the 2004200466 electrode to both ends of the dielectric ceramic layer. To obtain a multilayer ceramic capacitor. In recent years, the multilayer ceramic capacitors have been required to be miniaturized and increased in capacity, and there has been a strong demand for thinner layers and lower resistance of internal electrodes. One layer of a common internal electrode has a thickness of 1 to 2 μm, and a thin film may be required in the future. In view of this demand, various technologies for thinning the internal electrodes have been developed. However, in the production of nickel paste for internal electrodes, there are nickel powders with a larger average particle diameter than the thickness of one layer of the internal electrode, which is 1 to 2 μm thick, or there are nickel particles aggregated due to low dispersibility, which is higher than the internal electrode When one layer is thick and has secondary particles having a large average particle diameter, unevenness may occur on the surface of the electrode layer. When a multilayer ceramic capacitor is formed by using the paste containing coarse powder or agglomerated powder, a short-circuit phenomenon easily occurs, and it cannot be used as a product. In addition, when the dispersibility of nickel powder is low when forming a paste, not only the electrode film thickness is uneven when printing on a green sheet, which causes short circuits, but also causes internal defects such as delamination or fracture during firing. . To solve this problem, a method of thinning an internal electrode for a multilayer ceramic capacitor, a method of planarizing a surface, or a method of improving the dispersibility of a nickel paste has been proposed. For example, a method of adding an anionic surfactant to a conductive composition made of a conductive powder and an organic vehicle is disclosed (for example, refer to Japanese Patent Application Laid-Open No. 10-92226 (Patent Document 1)). In addition, it was revealed that an anionic polymer was added to a conductive paste made of a conductive powder and an organic vehicle, and to prevent the excessive adsorption side of the anionic polymer dispersant from forming with several particles. Method for adding an amine-based surfactant during three-dimensional crosslinking and gelation (for example, refer to Japanese Patent Application Laid-Open No. 2001-6346 (Patent Document 2)) 200425166. In addition, nickel powder having an oil absorption of 5 to 25 ml / 100 g is disclosed as a nickel powder for conductive pastes having excellent dispersibility (for example, refer to Japanese Patent Application Laid-Open No. 2001-266645 (Patent Document 3)). However, the technique described in the above-mentioned Patent Document 1 only describes that the internal electrode can be made into a thin film because the surface roughness of the internal electrode is small, but it does not describe the dispersibility of the nickel powder. In addition, the technique described in the above-mentioned Patent Document 2 only describes improving dispersibility and preventing gelation of the paste, but does not describe data on improving dispersibility. In addition, the technology described in Patent Document 3 mentioned above is a method for reducing the amount of oil absorbed by improving the disintegration treatment of nickel powder agglomeration produced by conventional techniques, and improving the dispersibility when forming a paste. Although the nickel paste produced by this method has the effect of improving the dispersibility5, when the nickel powder is used to form a conductive paste of nickel powder, the nickel powder is insufficient. [Summary of the Invention] Therefore, the present invention is to provide an excellent dispersibility when forming a conductive paste. As a result, when manufacturing a multilayer ceramic capacitor, it is possible to prevent short circuit caused by unevenness of the internal electrode surface or prevent internal defects such as delamination. A nickel powder dispersion is intended. The present invention also aims to provide a method for preparing a fine powder rhenium dispersion in which the nickel powder is sufficiently dispersed, and to provide a conductive paste using the powder dispersion. As a result of intensive research to achieve the above-mentioned object, the present inventors have found that an organic solvent is added to an aqueous dispersion of ultrafine powdered nickel powder and an aqueous solvent, and an amine-based dispersant is added, and then obtained by disintegration treatment The nickel powder has a dispersion of 200425166, which has extremely high nickel powder dispersibility when forming a paste, and is particularly suitable for conductive pastes used in multilayer ceramic capacitors and the like. The present invention has been made in light of this knowledge. In other words, the nickel powder dispersion of the present invention is characterized in that an organic solvent is added to an aqueous dispersion of ultrafine powdered nickel powder having an average particle diameter of 1 μm or less and an aqueous solvent, and at least a part of the aqueous solvent is based on the organic After the solvent is substituted, an amine-based dispersant is added, followed by pulverization treatment. The nickel powder used in the present invention is an ultrafine powder having an average particle size of 1 μm or less, preferably 0.01 to 1 μm, more preferably 0.1 to 0.6 μm, and most preferably 0.15 to 0.4. μηι. If the average particle diameter is larger than 1 μm, it may be caused by a reduction in sinterability or unevenness on the internal electrode surface of the multilayer ceramic capacitor, and as a result, structural defects such as short circuits are likely to occur. In addition, if the average particle diameter is too small, agglomeration may easily occur between the nickel powders when the conductive paste is prepared. As a result, irregularities are generated on the surface of the electrode layer due to the generation of secondary particles, resulting in structural defects. In addition, when the nickel powder used in the present invention is to improve the sintering characteristics and dispersibility, the specific surface area by the B ET method is preferably 1 to 20 m 2 / g, and the particle shape is preferably spherical. Furthermore, the nickel powder of the present invention Dispersion 5 is to add an organic solvent to an aqueous dispersion of nickel powder, to replace at least a part of the aqueous solvent, and to add an amine-based dispersant to obtain a high dispersibility so that nickel remaining only in the nickel powder dispersion The coagulation of the powder is reduced for the purpose of easing the aggregation of the powder. The disintegration treatment may be performed so long as it can reduce the aggregation of the nickel powder in the dispersion, and can be performed using a conventional disintegration device such as a disintegration treatment using a shearing effect or a grinding effect, a stirring disintegration device, and the like. . Specifically, a crushing device such as a roll mill, a mallet mill, a vibration mill, a spray mill, a ball mill, a ball mill, a meteor ball mill, a bead mill, a sand mill, and a three-roll mill can be used. The disintegration treatment of the present invention is extremely effective by performing a disintegration treatment using a ball mill. As described above, the present invention can provide a conductive nickel powder dispersion by using a nickel powder dispersion having good dispersibility, adding an amine dispersion to the dispersion, and subjecting the nickel powder dispersion to a final treatment. Dispersion of nickel powder with excellent dispersibility. As a result, when producing multilayer ceramic capacitors, internal defects such as short circuits or delamination due to unevenness on the internal electrode surface can be prevented. Nickel powder dispersion is dispersed in the nickel powder dispersion with the above amine system. Preferably, at least one of the agents is an amine salt of an alkylamine and a polycarboxylic acid. These amine-based dispersants can be used in a solution state in organic solvents such as alcohols, phenols, ethers, ketones, aliphatic hydrocarbons, kerosene, light oil, toluene, xylene and other aromatic solvents. Moreover, you may use a commercial item as said amine-type dispersing agent. The addition amount of these amine-based dispersants is preferably 0.005 to 5.0 parts by weight for the amine-based dispersant component for the nickel powder in the 1000 parts by weight of the dispersion, and more preferably 0. 2 to 2 · 0 parts by weight. When the addition amount of the amine-based dispersant component is less than 0.05 parts by weight, a sufficient effect as a dispersant cannot be obtained. In addition, when the amount of the amine-based dispersant is more than 5.0 parts by weight, cracks may occur during the heat treatment for the purpose of removing organic solvents when manufacturing multilayer ceramic capacitors, or the electrical characteristics may decrease when forming multilayer ceramic capacitors. And so on. In addition, the addition of the amine-based dispersant can be added before the following disintegration treatment, and can also be added during the disintegration treatment of the nickel powder dispersion during the disintegration treatment. Next, the nickel powder dispersion can be added by When the organic solvent is used, a surfactant is preferably present in the aqueous solvent. As the surfactant, a mixture of polyoxyethylene phenyl ether and its phosphate can be used. The organic solvent concentration of the nickel powder dispersion is preferably 5 to 200% by weight. The nickel powder is preferably obtained by a gas phase reduction method in which a nickel chloride gas is brought into contact with a reducing gas, or a spray thermal decomposition method in which a solution of a thermally decomposable nickel compound is sprayed and thermally decomposed. The nickel powder dispersion shown above has excellent dispersibility when forming the conductive paste as described above. As a result, when producing a multilayer ceramic capacitor, internal defects such as short circuits or delamination due to unevenness on the surface of the internal electrode can be prevented. Suitable for conductive pastes, especially for internal electrodes of multilayer ceramic capacitors. Next, the method for adjusting the nickel powder dispersion of the present invention is a method suitable for preparing the above-mentioned nickel powder dispersion, and is characterized by a gas-phase reduction method by contacting and reacting a nickel chloride gas with a reducing gas, or Ultrafine nickel powder having an average particle diameter of 1 μm or less obtained by spray thermal decomposition of a solution of thermally decomposable nickel compound by spray thermal decomposition is washed with water, and pure water is added to form a nickel powder dispersion, and added to the above nickel powder dispersion For the organic solvent, at least a part of the aqueous solvent is replaced with the above-mentioned organic solvent so that the concentration of the organic solvent is 5 to 200% by weight, and then an amine-based dispersant is added, and then the disintegration treatment is performed. In the present invention, by using a nickel powder dispersion having good dispersibility, adding an amine-based dispersant to the dispersion, and pulverizing the nickel powder dispersion as a final treatment, the nickel powder dispersion existing only in the dispersion can be alleviated. Condensation of powder. Therefore, with the adjustment method of the present invention, it can provide excellent dispersibility when forming a conductive paste -10- 200425166. As a result, when producing a multilayer ceramic capacitor, it is possible to prevent internal defects such as short circuits due to unevenness on the surface of the internal electrode or delamination. Nickel powder dispersion. In addition, by adding the amine-based dispersant, the effect of preventing aggregation between nickel powders can be achieved during the disintegration treatment. In the method for preparing the nickel powder dispersion, the amine-based dispersant is at least one alkylamine and an amine salt of a polycarboxylic acid as described above. Moreover, in the method for preparing the nickel powder dispersion, a surfactant may be added to the above-mentioned nickel powder aqueous dispersion, or the surfactant may be mixed in the organic solvent in advance, or the interface activity may be added after the organic solvent is added. The above surfactant may be a mixture of polyoxyethylbenzene and its phosphonate. In addition, the method for producing the conductive paste of the present invention is based on the method using the above-mentioned nickel powder dispersion, and is characterized in that the present invention The nickel powder dispersion is mixed with an organic vehicle formed by an organic solvent or an organic binder. Moreover, when preparing the conductive paste, a plasticizer, a dispersant for forming a paste, and the like may be added as necessary. [Embodiment] ® Embodiments of the invention Embodiments of the hair feather will be described below. In addition, the method for preparing the I table powder dispersion of the present invention can be used to prepare various conductive materials such as copper, silver, platinum, etc., composite materials such as titanium, or catalysts, in addition to nickel powder. In addition, the metal powder can be used to prepare metal powders such as aluminum, zinc, manganese, iron, cobalt, and bismuth. 1) Production of nickel powder -11- 200425166 The nickel powder used in the present invention can be produced by conventional methods such as a gas phase reduction method, a spray thermal decomposition method, or a liquid phase method. Among them, a vapor phase reduction method in which nickel powder is produced by contact reduction with a nickel chloride gas and a reducing gas, or a spray thermal decomposition method in which a solution of thermally separated Mt compounds are sprayed and thermally decomposed. By this method, the particle diameter of the nickel powder can be easily controlled, and h spherical rhenium particles can be produced with high efficiency. In the gas phase reduction method described above, the vaporized nickel chloride gas is brought into contact with a reducing gas such as hydrogen and reacted to obtain nickel powder. At this time, nickel chloride gas can be generated by a conventional method. For example, a method in which solid nickel chloride is heated to evaporate to produce chlorin ft nickel gas, or a method in which metallic nickel is brought into contact with chlorine gas to continuously produce nickel chloride gas. Among these methods, the method of heating and evaporating solid nickel chloride requires a sublimation operation by heating and evaporation, so that it is difficult to stably generate nickel chloride vapor. Further, in consideration of preventing oxidation or moisture absorption of nickel chloride, or energy efficiency, a method of continuously generating nickel chloride gas by contacting metallic nickel with chlorine gas is preferred. The manufacturing process of the nickel fine powder by this gas phase reduction reaction is to generate nickel atoms at the moment when the nickel chloride gas is brought into contact with the reducing gas, and the ultra fine particles are generated and grown by the collision and aggregation of the nickel atoms. . Then, depending on the conditions such as the partial pressure or temperature of the nickel chloride gas in the reduction and recovery process, the particle size of the nickel fine powder to be produced is controlled. In other words, by the above-mentioned method for producing nickel fine powder, nickel chloride gas is quantified due to the supply amount of chlorine gas, and the amount of nickel chloride gas supplied to the reduction process can be adjusted by controlling the supply amount of chlorine gas. Therefore, the particle size of nickel fine powder produced by -12-200425166 can be appropriately controlled. In addition, in the gas-phase reduction method, since chlorine gas is reacted with a metal to generate a metal chloride gas, it is different from the case of heating and evaporating a solid metal chloride to generate a metal chloride gas, which not only reduces the use of a carrier gas, but also depends on manufacturing conditions It is not necessary to use a carrier gas. In addition, when the gas-phase reduction reaction is adopted, the use amount of the carrier gas and the accompanying heating energy are reduced, so that the manufacturing cost can be reduced. Furthermore, by mixing an inert gas with the nickel chloride gas generated in the chlorination process, the partial pressure of the nickel chloride gas in the reduction process can be controlled. In this way, the particle size of the nickel powder can be controlled by controlling the amount of chlorine gas supplied or the partial pressure of the nickel chloride gas supplied to the reduction process. Therefore, the particle diameter of the nickel fine powder can be stabilized, and the particle diameter can be arbitrarily set. The average particle diameter of the powder can be arbitrarily set to 1 μm or less by the manufacturing conditions of the nickel fine powder of the gas phase reduction method described above. For example, the particle diameter of the metallic nickel as the starting material is preferably in the form of granules, lumps, plates, etc. of about 5 to 20 mm, and the purity is preferably about 99.5% or more.
使該金屬鎳先與氯氣反應以生成氯化鎳氣體。此時之 溫度爲充分促進反應時爲8 0 0 t：以上，且鎳之熔點爲1 4 5 3 °C 以下。考慮反應速度與氯化爐之耐久性雙方時，實用上以 900 〜1100〇C 較佳。 其次，將該氯化鎳氣體直接供應給還原工程，且使氫 氣等之還原性氣體接觸反應。此時，對氯化鎳氣體而言混 合1〜30莫耳％氮氣或氬氣等之惰性氣體，且可使該混合氣 體導入還原工程。另外，可使氯化鎳氣體同時或獨立將氯 -13- 200425166 氣供應給還原工程。藉由將氯氣供應給還原工程，可調整 氯化鎳氣體之分壓，且可控制生成的鎳粉粒徑。還原反應 之溫度只要是可使反應完成的充分溫度以上即可，由於生 成固體狀鎳粉者容易處理，故以鎳之熔點以下較佳。而且， 就考慮經濟性時實用上爲9 0 0〜1 1 0 0 °c。 進行該還原反應生成鎳微粉末後，使生成鎳粉冷卻。 冷卻時爲防止因生成鎳之一次粒子間凝聚致使二次粒子生 成，製得企求粒徑的鎳粉時，在完成還原反應之1 00 0 °c附 近的氣流下吹入氮氣等惰性氣體，急速冷卻至約400〜 · 8 0 0 °C爲宜。 然後，使生成的鎳粉例如藉由袋濾器等分離、回收。 分離回收前或後，視其所需可使生成的鎳微粉末以水、碳 數1〜4之一元醇等之溶劑洗淨。 2)鎳粉水分散體之調製 本發明係在上述所得的鎳粉中添加純水，形成鎳粉水 分散體。該鎳粉水分散體係在水溶劑濃度爲1 0重量％以上 、較佳者爲5〜3 00重量％、更佳者爲10〜100重量％之水 ® 溶劑中使鎳粉分散者。此處之水溶劑濃度係表示對分散體 之鎳粉重量而言水的重量％。總之，鎳粉水分散體對100重 量份鎳粉而言水爲1重量份以上、較佳者爲5〜3 00重量份 、更佳者爲1 〇〜1 00重量份漿料狀混合物。 在鎳粉表面上吸附氫氧化物時，藉由該OH基之極性 以吸附粉末，且親水性（懸浮性）降低。因此，推測爲鎳粉容 易凝聚，降低分散性。因此，本發明於形成鎳粉水分散體 -14- 200425166 時，以碳酸水溶液處理較佳。如此藉由以碳酸水溶液處理， 不僅鎳粉表面上附著的殘留氯化物可更爲充分除去，且可 除去鎳粉表面上附著的氫氧化鎳等之氫氧化物，結果可更 爲提高分散性。 上述藉由碳酸水溶液之處理，可藉由使生成的鎳粉以 純水洗淨時該洗淨以碳酸水溶液進行的方法、純水洗淨後 在純水中殘留有鎳粉之水漿料中吹入碳酸氣體的方法、或 在上述水漿料中添加碳酸水溶液之處理方法等進行。以氣 相還原法生成鎳粉時，於純水洗淨途中或之後，以水漿料 · 的狀態下與碳酸水溶液接觸予以處理的方法。 藉由該碳酸水溶液之處理中，ρ Η値以5.5〜6.5之範圍 較佳、更佳者爲5.5〜6.0。藉由碳酸水溶液之處理在ΡΗ値 小於5.5下進行時5在鎳粉表面上生成不均勻的氧化皮膜， 使鎳粉之燒結性降低。另外，使該處理在ρ Η値大於6.0下 進行時，無法除去鎳粉表面上吸附的氫氧化物，使該鎳粉 乾燥時表面之氫氧化物氧化，形成不均勻的氧化皮膜。而 且，碳酸水溶液之溫度爲〇〜loot：、較佳者爲10〜5〇°c、 ® 更佳者爲1 〇〜3 5它。 .而且，藉由碳酸水溶液之處理方法例如在使鎳粉懸浮 於純水的漿料中吹入碳酸氣體且使碳酸氣體溶存於漿料中， 同時使漿料對流予以處理的方法，或在碳酸水溶液中使鎳 粉懸浮的漿料攪拌予以處理的方法。另外，以碳酸水溶液 處理前、或處理中，爲除去附著於鎳粉之氯化鎳等時予以 水洗，視其所需藉由液體旋風器等濕式分級機除去粗粉， -15- 200425166 調整鎳粉之粒度較佳。 如上所述，以碳酸水溶液處理後，視其所需以純水取 代或洗淨以形成鎳粉水分散體。於習知鎳粉分散體之調製 方法中，使上述鎳粉生成後，同樣地洗淨。然而，爲使鎳 粉作爲製品時，使繼後的鎳粉分離及乾燥，形成不含水之’ 粉末狀態。 對此而言，本發明鎳粉分散體之調製方法係使上述鎳 粉以碳酸水溶液處理調製水分散體後，進行鎳粉之乾燥。 具體而言，不使水溶劑濃度小於1重量％下，可提高最終鎳 · 粉之分散性。總之，先藉由氯化鎳氣體與氫氣等之還原性 氣體接觸的氣相還原法等，以生成鎳粉。然後，水洗且以 碳酸水溶液處理以使鎳粉沉澱，藉由離層以除去上層澄淸 液。然後，在不使鎳粉乾燥下，調製水溶劑濃度爲〗重量％ 以上之水分散體。 此外，本發明以上述方法調製的鎳粉之水分散體中添 加界面活性劑爲較佳形態之一。換言之，藉由添加界面活 性劑，可容易藉由下述有機溶劑取代水溶劑，且可發揮最 _ 終優異的糊特性。界面活性劑可使用至少一種陽離子性界 面活性劑、陰離子性界面活性劑、兩離子性界面活性劑、 非離子性界面活性劑、氟系界面活性劑及反應性界面活性 劑。 具體而言，陽離子性界面活性劑例如脂肪族1〜3級胺 鹽、脂肪族4級錢鹽、；院錢鹽、氯化苯異丙錢鹽、吡淀 鹽、咪唑鐵鹽等。 •16- 200425166 陰離子性界面活性劑例如脂肪酸石鹼、N -醯基胺酸或 其鹽、聚氧乙烯烷醚羧酸鹽等之羧酸鹽、烷基苯磺酸鹽、 烷基萘磺酸鹽、二烷基磺基琥珀酸鹽、磺基琥珀酸烷基二 鹽、烷基楓醋酸鹽等之磺酸鹽、硫酸化油、高級醇硫酸鹽 、聚氧乙烯烷醚硫酸鹽、聚氧乙烯烷基苯醚硫酸鹽、單乙 硫酸鹽等之硫酸鹽、聚氧乙烯烷醚磷酸鹽、聚氧乙烯苯醚 磷酸鹽、烷基磷酸鹽等之磷酸鹽等。 兩離子性界面活性劑例如羧基甜菜鹼型、胺基羧酸鹽 、茚二鏺甜菜鹼、卵磷脂、氧化烷胺等。 · 非離子性界面活性劑例如烷基之碳數1〜1 8的聚氧乙 烯單或二烷醚、聚氧乙烯2級烷醚、聚氧乙烯烷基苯醚、 聚氧乙烯硬脂醇醚、聚氧乙烯含水羊毛脂衍生物等之醚類 、聚氧乙烯丙三醇脂肪酸酯、聚氧乙烯蓖麻油、聚氧乙烯 山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇脂肪酸酯、聚氧 乙烯脂肪酸烷醇醯胺硫酸鹽等之醚酯類、聚乙二醇脂肪酸 酯、乙二醇脂肪酸酯、脂肪酸單丙三醇、聚丙三醇脂肪酸 酯、山梨糖醇酐脂肪酸酯、丙二醇脂肪酸酯、蔗糖脂肪酸 _ 酯等之酯型、脂肪酸烷醇醯胺、聚氧乙烯脂肪酸醯胺、聚 氧乙烯烷胺等之含氮型等。 氟系界面活性劑例如氟化烷基羧酸、過氟化烷基羧酸 、N-過氟辛烷磺醯基谷胺酸二鈉等。 反應性界面活性劑例如聚氧乙烯烯丙基環氧丙基壬基 苯醚、聚氧乙烯丙烯基苯醚等。 上述所示之界面活性劑除單獨使用外，亦可組合2種 -17· 200425166 以上使用。於此等之中以使用 HLB(親水親油平衡性）値通 常爲3〜2 0之非離子性界面活性劑較佳，以η LB値爲1 0〜 2〇之親水性非離子界面活性劑更佳。 具體而言，以使用至少一種壬基苯醚等之聚氧乙烯烷 基苯醚及其磷酸鹽或此等之混合物、聚氧乙烯山梨糖醇單 硬脂酸酯等之聚氧乙烯山梨糖醇酐脂肪酸酯、聚丙三醇硬 脂酸酯等之聚丙三醇脂肪酸酯、山梨糖醇單硬脂酸酯等之 山梨糖醇酐脂肪酸酯更佳。而且，極佳的界面活性劑爲聚 氧乙烯烷基苯醚及其磷酸鹽或此等之混合物。 3 )藉由有機溶劑之水取代 其次，在上述調製的鎳粉之水分散體中添加有機溶劑 。本發明使用的有機溶劑例如醇類、苯酚類、醚類、酮類 、碳數5〜1 8之脂肪族烴、燈油、輕油、甲苯、二甲苯等 之芳香族烴、矽油等。其中以對水而言具有某程度之溶解 度的有機溶劑較佳，具體例如以醇類、醚類、或酮類較佳 〇 有機溶劑之具體例如甲醇、乙醇、丙醇、丁醇、己醇 、2-乙基己醇、2 -甲基-1-丙醇、異丁醇、2_(乙基胺基）乙醇 、2-乙基-卜丁醇、3-乙基_3_戊醇、2-異丙氧基乙醇、2·乙 氧基乙醇、2-丙氧基乙醇、2_甲氧基乙醇、2-乙氧基乙醇、 2-甲氧基乙醇、2-甲氧基乙醇、2-甲氧基甲氧基乙醇、丨-十 八烷醇、η-辛醇、2,3_環氧基丙醇、環己醇、二甲基丁 醇、一甲基丙醇、2，6·二甲基-4-庚醇、2,4 -二甲基-3-戊醇 、1，3 -二甲氧基-2-丙醇、二甲氧基丙醇、卜癸醇、^十二烷 >18- 200425166 醇、三甲基丁醇、3,5,5 -三甲基己醇、壬醇、苯基乙醇、2-甲基-2-丙醇、t_丁醇、甲基丙醇、1-甲氧基-2-丙醇、1-乙 氧基-2-丙醇、1-丁氧基-2-丙醇、十六烷醇、十七烷醇、t-戊醇、甲基環己醇、2 -甲基-卜丁醇、3 -甲基-卜丁醇、3 -甲 基戊醇、3 -甲氧基丁醇、2_(2_ 丁氧基乙氧基）乙醇、苯胺 基乙醇、胺基乙醇、胺基丙醇、胺基丁醇、2-(丁基胺基）乙 醇、2-(甲基胺基）乙醇、2 -胺基-2-乙基-1，3 -丙一醇、2 -胺 基-2-甲基- -丙二醇、二苯基乙二醇、乙二醇、丙三醇、 2_乙基-1，3-己二醇、2-氯-1，3-丙二醇、cis-1，2-環己二醇、 cis-l，4 -環己二醇、3,5-二甲基-1-己炔-3_醇、結品醇、丁二 醇、丁烯醇、丁氧基丙二醇、丙二醇、己二醇、己烯醇、 戊二醇、萜品醇、二乙醚、丙酮、聚合度2之聚氧乙烯醇 '聚氧丙烯二醇、聚氧乙烯醇單酯等。特別是以使用乙醇 系醇類較佳。 此等之有機溶劑可以單獨使用或2種以上組合使用。 該組合例如混合數種不同的醇類者、或組合溶解於水之醇 類與不溶於水之例如飽和烴溶劑等者。另外，不溶於水之 萜品醇的有機溶劑藉由在水分散體或有機溶劑中添加界面 活性劑等之界面活性劑存在下使用，可有效地取代水與有 機溶劑。 上述鎳粉分散體中可殘留有水溶劑。而且，添加上述 有機溶劑後，自分散體除去水、取代有機溶劑較佳。此時 分散體中水之殘留里封为故體中之鎮粉的重量而言以10重 量％以下較佳、更佳者爲5重量％以下、最佳者爲2重量％ 200425166 以下。而且，本發明之鎳粉分散體由鎳粉與上述有機溶劑 所成時，由鎳粉與上述有機溶劑與水所成。 取代方法可採用添加有機溶劑後，藉由數次離層或_ 濾以與鎳粉相同的有機溶劑洗淨、取代的方法、或$力卩w 機溶劑後在加熱或減壓下彳吏水蒸發的方法。藉由該$ #有* 機溶劑、調製導電性糊時，與形成導電糊時使用的有;^幾κ 色劑等之相溶性良好，可防止鎳粉凝聚且可提高分散性。 此處，說明有關上述有機溶劑之濃度。本發明之鎳粉 分散體之有機溶劑的濃度可以任意。惟就考慮調製導電糊 鲁 時之相溶性、或保存性時，有機溶劑之濃度爲5〜200重量 %、較佳者爲10〜100重量％、更佳者爲20〜60重量％。此 處之有機溶劑的濃度爲對分散體中之鎳粉重量而言有機溶 劑的重量％。換言之，本發明之鎳粉分散體對1 0 0重量份鎳 粉而言，有機溶劑爲5〜200重量份、較佳者爲10〜1〇〇重 量份、更佳者爲20〜60重量份之漿料狀混合物。 而且，本發明之鎳粉分散體中可添加與上述相同的界 面活性劑。添加方法例如添加有機溶劑後添加界面活性劑 _ 的方法、或在添加的有機溶劑中預先添加界面活性劑予以 混合，使該混合物添加於鎳粉之水分散體的方法等。 此時，界面活性劑以醇或酮等之上述有機溶劑稀釋， 或混合於有機溶劑予以添加較佳。而且，對1重量份界面 活性劑而言稀釋的有機溶劑爲1〜50重量份、較佳者爲1 0 〜40重量份。藉由添加界面活性劑，具有促進藉由鎳粉分 散體之有機溶劑取代的效果。 -20- 200425166 另外，就考慮界面活性劑之作用效果時，在鎳粉水分 散體中預先添加界面活性劑，且在鎳粉之表面中使界面活 性劑充分分散後，添加有機溶劑予以取代較佳。而且，以 上述氣相還原法等之方法製造的鎳粉以水洗淨，且調製鎳 粉水分散體時，以添加上述界面活性劑時可調製最終分散 性高的鎳粉分散體及導電糊較佳。 而且，有關界面活性劑之量比沒有特別的限制，添加 在鎳粉之粒子表面上形成界面活性劑的單一分子皮膜程度 之量。通常，1 kg鎳粉所使用的界面活性劑之量爲〇 · 〇 〇 〇 1〜 鲁 100g、較佳者爲0.1〜50g、更佳者爲0.5〜25g。 4)鎳粉分散體之解碎處理 使用上述所得的鎳粉分散體調製鎳糊時，可得鎳粉凝 聚情形少、分散性優異的糊。本發明之鎳粉分散體，爲更 爲提高分散性時在上述所得鎳粉分散體中添加胺系分散劑 且另施予解碎處理。換言之，藉由添加胺系分散劑，具有 可更爲提高分散體中鎳粉之分散性、緩和藉由解碎處理僅 存的鎳粉之凝聚情形、發揮最終優異的糊特性。 ® 胺系分散劑以至少一種烷胺及聚羧酸之胺鹽較佳。例 如使聚酯酸、脂肪酸、脂肪酸醯胺、聚羧酸、環氧烷基、 聚環氧烷基、聚氧乙烯脂肪酸酯、聚氧乙烯丙三醇脂肪酸 酯、及此等之衍生物等胺化者。 胺鹽爲醯胺胺鹽、脂肪族胺鹽、芳香族胺鹽、烷醇胺 鹽、多元胺鹽等，例如聚氧乙烯脂肪酸醯胺、聚氧乙烯烷 胺、三丙胺、二乙基胺基乙胺、二甲基胺基丙胺、二乙基 -21- 200425166 胺基丙胺等。 此等胺系分散劑可使用溶解於溶劑成分的溶液狀態者， 亦可使用巾售品。而且，此等胺系分散劑對i 0 0重量份分 散體中之鎳粉而言胺系分散劑成分爲0·05〜50重量份、較 佳者爲0.2〜2.0重量份。 其次，使上述添加有胺系分散劑之鎳粉分散體使用球 磨予以解碎處理。球磨解碎條件視鎳粉分散體之凝聚狀態 而定，可在凝聚情形充分緩和下任意設定。具體而言，粉 碎容器內部之材質可使用氧化鋁、高分子塑膠、耐龍等。· 於本發明中容器之耐久性及對鎳粉之影響而言以使用具有 耐龍製內部材質之粉碎容器較佳。 此處，粉碎球磨可適當選擇氧化銷、碳化鎢、不銹鋼 、氧化銘等，粉碎球徑爲0 · 3〜2 0 m m。使平均粒徑爲1 μ m 之鎳粉的分散體解碎處理時，以使用粉碎容器內部之材質 作爲耐龍且直徑爲3〜1 0mm之氧化鉻球較佳。而且，1次 粉碎處理中投入的鎳粉分散體量對粉碎容器之容量而言爲 2 0〜6 0 %、較佳者爲2 0〜4 0 %。 ® 另外，解碎處理的鎳粉分散體的黏度以 1 5 0 〇 〇〜 3 5 00 0cps較佳、更佳者爲1 8000〜3 0000cpS。而且，粉碎處 理時之溫度以1〇〜4〇°C較佳、更佳者爲20〜30°C。解碎處 理時間與鎳粉分散體之凝聚程度、上述粉碎容器、粉碎球 之材質、粉碎球徑及分散體黏度等有關，一般而言以6〜1 5 小時較佳。此外，本發明之鎳粉分散體的解碎處理除上述 球磨外，亦可使用切變作用或磨碎作用之解碎機進行。 -22- 200425166 如此所得的鎳粉分散體係鎳粉之分散性極佳，使用該 物形成導電性糊時，具有優異的分散性，可防止於形成積 層陶瓷電容器時因電極表面凹凸產生短路、或離層等之內 部缺陷。 5)導電糊之調製 上述所得的鎳粉分散體適合使用於導電糊或電極形成 用糊。該鎳粉分散體係使有機溶劑及黏合劑混練形成糊。 有機溶劑（有機載色劑）可使用習知導電糊所使用者即可，例 如乙基纖維素、乙二醇、甲苯、二甲苯、礦物油、丁基卡 春 必醇、萜品醇、癸醇等之高沸點有機溶劑。黏合劑可使用 有機或無機黏合劑，以使用乙基纖維素等之纖維素樹脂系 高分子黏合劑、或以丁基甲基丙烯酸酯等之丙烯酸樹脂較 佳。 而且，形成糊時視其所需可混合酞酸酯、硬脂酸等之 可塑劑、或鉛系坡璃、鋅系玻璃或矽系玻璃等之玻璃料、 及氧化猛、氧化鍾、氧化鉍等之金屬氧化物塡充物等。藉 由混合此等之添加物，塗覆於陶瓷等之基材上予以燒結、 · 形成電極時，與基材之密接性優異、可形成導電性高的電 極、.且可提高與焊接之濕潤性。 實施例 於下述中藉由實施例具體地說明本發明。而且，鎳粉 之平均粒徑、調製的導電糊中鎳粉之粒度分布及膜密度以 下述方法測定。 •鎳粉之平均粒徑測定 -23- 200425166 藉由電子顯微鏡攝影鎳粉之照片，自該照片測定200 個鎳粉粒子之粒徑，求取平均値。粒徑係爲包圍粒子之最 小圓的直徑。 •導電糊中鎳粉之粒度分布 使用雷射光散射折射法粒度測定機（Coulter LS23 0 :克 魯塔（譯音）公司製），試料爲分散體時使適量的鎳粉分散體 乾燥、懸浮於乙醇中，或試料爲乾燥鎳粉時直接懸浮於乙 醇後，施加超音波予以分散3分鐘，以試料折射率爲1.8 測定鎳粉之粒度，求取體積統計値之粒度分布。而且，於 下述表1之粒度分布中D90、D5〇、D10係表示各以積算粒 度爲 90%、50%、10%時之粒徑（μηι)，特別是D90之値（積 算粒度爲90%之粒徑）愈大時，係表示導電糊形成用分散劑 中鎳粉有凝聚，反之，該値愈小時表示鎳粉爲高分散情形 〇 •膜密度之測定 使萜品醇作爲分散劑，且在萜品醇中添加含有5 5重量 %鎳粉之鎳粉分散體、或乾燥鎳粉所形成的分散體中，添加 1 〇重量％乙基纖維素，然後予以混練作成糊。另外，在表 面平滑的玻璃板上貼合脫模薄膜，使兩端貼合固定於中央 殘留有脫模薄膜面上。在表面均勻下使上述脫模薄膜以薄 膜塗布機印刷於該脫模薄膜上以形成膜。然後，在80〜 200 °C下乾燥，且自乾燥膜剝離脫模薄膜，使膜以圓形模具 穿孔。測定經穿孔膜之重量及體積以求得膜密度。此時膜 之容積係測定圓面積、且以微測器測定數個膜厚度並求取 -24- 200425166 平均値予以求得。 而且，於本發明中分散性優異係指鎳粉粒子之二次粒 子的凝聚情形少，藉由雷射光散射繞射法測定鎳粉之積算 粒度分布時的平均粒徑（D 50)及粗粉側粒徑（D 90)較小，以 及自導電糊形成鎳粉之薄膜時的膜密度較大。 [實施例1] 1)鎳粉之製造 A 氯化工程 在氯化爐中自原料供應管塡充出發原料之平均粒徑 春 5 mm的鎳粉，且藉由加熱方法使爐內氣氛溫度爲1 1 〇 〇 °c。 然後，自氯氣供應管以4Nl/min供應氯氣給氯化爐，使金 屬鎳氯化產生氯化鎳氣體。在氯化爐中自射於氯化爐下側 的惰性氣體供應管供應氯氣供應量之1 0 % (莫耳比）的氮氣， 與該氯化鎳氣體混合。然後，使氯化鎳氣體與氮氣之混合 氣體經由噴嘴導入還原爐內。 B還原工程 其次，使氯化鎳氣體與氮氣之混合氣體自噴嘴以流速 ® 2.3m/秒（ 1 000 °C換算）導入藉由加熱方法形成1 000 °C之爐內 氣氛溫度的還原爐內作爲還原工程。同時，以流速7Nl/min 自設置於還原爐內頂部之還原性氣體供應管將氫氣供應給 氯化爐，使氯化鎳氣體還原，製得金屬鎳粉。 C冷卻工程 使自設置於還原爐下側的冷卻氣體供應管以16.4N1/分 • g供應的氮氣與以上述還原工程生成的鎳粉接觸，以使鎳 -25- 200425166 粉冷卻。然後，使生成的鎳粉與氯氣及鹽酸蒸氣同時經由 噴嘴導入回收爐後，導入袋濾器，使鎳粉分離回收。 2) 鎳粉分散體之調製 使該回收的鎳粉以純水洗淨，最後加入純水形成鎳粉 水分散體，然後，使碳酸氣體吹入分散體中形成ρ Η値爲5.5 之碳酸溶液，且在常溫下使鎳粉以碳酸水溶液處理60分鐘 。然後，使該鎳粉沉澱，藉由離層作用以除去上層澄淸液， 另外加入純水以製得鎳粉水分散體。 此外，在上述鎳粉水分散體中添加對鎳粉而言爲0.1 · 重量％作爲界面活性劑之聚氧乙烯苯醚磷酸鹽80%與聚氧乙 烯苯醚20%之混合物予以攪拌。此時之水溶劑濃度爲6〇重 量％ 〇 採取2.5 kg上述鎳粉水分散體（鎳粉1 .：5kg、水1 .〇kg)，於 其中添加1 kg萜品醇5在室溫下攪拌，使鎳粉分散。然後， 在1 2 0 °C下乾燥1 6小時，另1 〇 〇 °c下乾燥4 8小時，製得鎳 粉分散體。該鎳粉分散體實質上沒有存在殘留水，水之全 量以¢5品醇取代。 · 其次，在上述鎳粉分散體中添加對100重量份鎳粉分 散體而言如表1所示之〇〜4.0重量份作爲分散劑之烷胺（楠 本化成（股）製、品番Ε ϋ 1 1 7、有效成分5 0 %、溶劑成分爲二 甲本）。然而，由於使用的品番E D 1 1 7之有效成分爲5 0 %，故 院胺成分之實質添加量如表1所示爲〇〜2.〇重量份。 另外，使如此所得的鎳粉分散體使用球磨解碎機進行 解碎處理。解碎處理使用日陶科學股份有限公司製之球磨 -26- 200425166 回轉台AN-3S，且使用直徑4〇〇mm之耐龍製壺，使直徑10m Φ之氧化銷球作爲粉碎球，在常溫下以回轉數70rpm、解碎 時間1 2小時進行。 所得鎳粉分散體中鎳粉的平均粒徑、所得鎮粉分散體 之粒度刀布、及使用所得鎳粉分散體調製的導電糊之膜密 度的測疋結果如表1所示。The metallic nickel is first reacted with chlorine gas to generate a nickel chloride gas. At this time, the temperature is 800 ° C when the reaction is sufficiently promoted: above, and the melting point of nickel is below 1 45 3 ° C. In consideration of both the reaction speed and the durability of the chlorination furnace, 900 to 1100 ° C is practically preferred. Next, the nickel chloride gas is directly supplied to a reduction process, and a reducing gas such as hydrogen gas is brought into contact with the reaction. At this time, an inert gas such as 1 to 30 mole% nitrogen or argon is mixed for the nickel chloride gas, and the mixed gas can be introduced into a reduction process. In addition, nickel chloride gas can be supplied to the reduction project simultaneously or independently. By supplying chlorine gas to the reduction process, the partial pressure of the nickel chloride gas can be adjusted, and the particle size of the nickel powder generated can be controlled. The temperature of the reduction reaction may be higher than a sufficient temperature for the completion of the reaction. Since a solid nickel powder is easily handled, it is preferable that the melting point be lower than the melting point of nickel. In consideration of economic efficiency, it is practically 9 0 to 1 1 0 ° C. After the reduction reaction is performed to generate fine nickel powder, the generated nickel powder is cooled. In order to prevent the formation of secondary particles due to the condensation between the primary particles that generate nickel during cooling, when nickel powder with a desired particle size is obtained, an inert gas such as nitrogen is blown under a gas flow near 1 00 ° c after the reduction reaction is completed, and rapidly. It is advisable to cool to about 400 ~ 800 ° C. Then, the produced nickel powder is separated and recovered, for example, by a bag filter or the like. Before or after separation and recovery, the generated nickel fine powder may be washed with a solvent such as water or a monohydric alcohol having 1 to 4 carbon atoms, if necessary. 2) Preparation of nickel powder water dispersion The present invention is to add pure water to the nickel powder obtained above to form a nickel powder water dispersion. This nickel powder water dispersion system disperses nickel powder in a water ® solvent having a water solvent concentration of 10% by weight or more, preferably 5 to 300% by weight, and more preferably 10 to 100% by weight. The water solvent concentration herein means the weight% of water with respect to the weight of the nickel powder of the dispersion. In short, the aqueous nickel powder dispersion is 1 part by weight or more of water, preferably 5 to 300 parts by weight, and more preferably 100 to 100 parts by weight of a slurry-like mixture for 100 parts by weight of nickel powder. When the hydroxide is adsorbed on the surface of the nickel powder, the polarity of the OH group is used to adsorb the powder, and the hydrophilicity (suspensibility) is reduced. Therefore, it is presumed that the nickel powder is likely to aggregate and reduce dispersibility. Therefore, when the nickel powder aqueous dispersion -14-200425166 is formed in the present invention, it is preferably treated with an aqueous solution of carbonic acid. By treating with a carbonic acid aqueous solution in this way, not only the residual chlorides adhering to the surface of the nickel powder can be removed more sufficiently, but also hydroxides such as nickel hydroxide adhering to the surface of the nickel powder can be removed. As a result, dispersibility can be further improved. The above-mentioned treatment with an aqueous solution of carbonic acid can be carried out by washing the generated nickel powder with pure water. The method of washing with an aqueous solution of carbonic acid can be performed in an aqueous slurry of nickel powder remaining in pure water after washing with pure water. A method of blowing carbon dioxide gas, a method of adding a carbonic acid aqueous solution to the water slurry, and the like are performed. When the nickel powder is produced by the gas phase reduction method, it is treated by contacting with a carbonic acid aqueous solution in the state of an aqueous slurry · during or after washing with pure water. In the treatment with the carbonic acid aqueous solution, ρ Η 値 is preferably in the range of 5.5 to 6.5, and more preferably 5.5 to 6.0. When the treatment with a carbonic acid aqueous solution is performed at a pH of less than 5.5, 5 a non-uniform oxide film is formed on the surface of the nickel powder, thereby reducing the sinterability of the nickel powder. In addition, when this treatment is performed at ρ Η 値 greater than 6.0, the hydroxide adsorbed on the surface of the nickel powder cannot be removed, and the hydroxide on the surface is oxidized when the nickel powder is dried to form a non-uniform oxide film. In addition, the temperature of the carbonic acid aqueous solution is 0 ~ loot :, preferably 10 ~ 50 ° C, and more preferably 10 ~ 35 ° C. Also, by a method of treating a carbonic acid aqueous solution, for example, a method in which carbon dioxide gas is blown into a slurry in which nickel powder is suspended in pure water and the carbonic acid gas is dissolved in the slurry, and the slurry is treated by convection, or in carbonic acid A method in which a slurry in which nickel powder is suspended in an aqueous solution is stirred and treated. In addition, before or during the treatment with a carbonic acid aqueous solution, in order to remove the nickel chloride adhering to the nickel powder, etc., it is washed with water. If necessary, the coarse powder is removed by a wet classifier such as a liquid cyclone. -15- 200425166 adjustment The particle size of nickel powder is better. As described above, after treatment with a carbonic acid aqueous solution, it may be replaced with pure water or washed as necessary to form an aqueous nickel powder dispersion. In the conventional method for preparing a nickel powder dispersion, the nickel powder is generated and then washed in the same manner. However, when nickel powder is used as a product, subsequent nickel powders are separated and dried to form a water-free powder state. In this regard, the method for preparing the nickel powder dispersion of the present invention is a method in which the nickel powder is treated with a carbonic acid aqueous solution to prepare the aqueous dispersion, and then the nickel powder is dried. Specifically, the dispersibility of the final nickel powder can be improved without making the concentration of the water solvent less than 1% by weight. In short, the nickel powder is first produced by a gas phase reduction method in which nickel chloride gas is brought into contact with a reducing gas such as hydrogen. Then, it was washed with water and treated with an aqueous solution of carbonic acid to precipitate nickel powder, and the upper layer was removed by delamination. Then, without drying the nickel powder, an aqueous dispersion having a water solvent concentration of ≧ wt% is prepared. In addition, the addition of a surfactant to the aqueous dispersion of the nickel powder prepared by the above method of the present invention is one of the preferred forms. In other words, by adding a surfactant, it is possible to easily replace the water solvent with the organic solvent described below, and it is possible to exert excellent final paste characteristics. As the surfactant, at least one of a cationic surfactant, an anionic surfactant, a diionic surfactant, a nonionic surfactant, a fluorine-based surfactant, and a reactive surfactant can be used. Specifically, the cationic surfactants are, for example, aliphatic 1-3 grade amine salts, aliphatic quaternary grade salts, diamine salts, phenylisopropyl chloride salts, pyridonium salts, and imidazole iron salts. • 16- 200425166 Anionic surfactants such as carboxylic acid salts of fatty acid alkaloids, N-fluorenylamino acids or their salts, polyoxyethylene alkyl ether carboxylates, alkylbenzenesulfonates, alkylnaphthalenesulfonic acids Salt, dialkyl sulfosuccinate, alkyl sulfosuccinate, alkyl maple acetate, etc. sulfonates, sulfated oils, higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxylates Sulfates such as ethylene alkyl phenyl ether sulfate, monoethyl sulfate, and other phosphates such as polyoxyethylene alkyl ether phosphate, polyoxyethylene phenyl ether phosphate, and alkyl phosphate. Examples of the ionic surfactant include carboxybetaine type, aminocarboxylate, indinadiol betaine, lecithin, alkylamine, and the like. Non-ionic surfactants such as polyoxyethylene mono- or dialkyl ethers of 1 to 18 carbons in alkyl groups, polyoxyethylene secondary alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene stearyl alcohol ethers , Ethers such as polyoxyethylene hydrolanolin derivatives, polyoxyethylene glycerol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters , Ether esters such as polyoxyethylene fatty acid alkanolamine sulfate, polyethylene glycol fatty acid ester, ethylene glycol fatty acid ester, fatty acid monoglycerol, polyglycerol fatty acid ester, sorbitan fatty acid Ester types such as esters, propylene glycol fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamines, polyoxyethylene fatty acid amines, polyoxyethylene alkylamines, and other nitrogen-containing types. Examples of the fluorine-based surfactant include fluorinated alkylcarboxylic acid, perfluorinated alkylcarboxylic acid, and disodium N-perfluorooctanesulfonylglutamate. Examples of the reactive surfactant include polyoxyethylene allyl epoxy nonyl phenyl ether, polyoxyethylene allyl phenyl ether, and the like. In addition to the surfactants shown above, they can also be used in combination with two or more -17 · 200425166 or more. Among these, a non-ionic surfactant with HLB (hydrophilic-lipophilic balance) 値 usually 3 to 20 is preferred, and a hydrophilic non-ionic surfactant with η LB 値 10 to 20 is preferred. Better. Specifically, at least one kind of polyoxyethylene alkyl phenyl ethers such as nonylphenyl ether and its phosphates, or mixtures thereof, polyoxyethylene sorbitol monostearate, and the like are used. Polyglycerol fatty acid esters such as anhydride fatty acid esters, polyglycerol stearate, and sorbitan fatty acid esters such as sorbitol monostearate are more preferred. Moreover, excellent surfactants are polyoxyethylene alkylphenyl ethers and their phosphates or mixtures thereof. 3) Replacement with water by organic solvent Next, an organic solvent is added to the aqueous dispersion of the nickel powder prepared as described above. The organic solvents used in the present invention are, for example, alcohols, phenols, ethers, ketones, aliphatic hydrocarbons having 5 to 18 carbons, kerosene, light oil, aromatic hydrocarbons such as toluene, xylene, and silicone oil. Among them, organic solvents having a certain degree of solubility in water are preferred, and specific examples include alcohols, ethers, or ketones. Specific examples of organic solvents include methanol, ethanol, propanol, butanol, hexanol, 2-ethylhexanol, 2-methyl-1-propanol, isobutanol, 2- (ethylamino) ethanol, 2-ethyl-butanol, 3-ethyl-3-pentanol, 2 -Isopropoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-methoxyethanol, 2-methoxyethanol, 2 -Methoxymethoxyethanol, octadecanol, η-octanol, 2,3-epoxypropanol, cyclohexanol, dimethylbutanol, monomethylpropanol, 2,6 Dimethyl-4-heptanol, 2,4-dimethyl-3-pentanol, 1,3-dimethoxy-2-propanol, dimethoxypropanol, butanol, decyl Dioxane> 18- 200425166 alcohol, trimethylbutanol, 3,5,5-trimethylhexanol, nonanol, phenylethanol, 2-methyl-2-propanol, t-butanol, methyl alcohol Propylpropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, cetyl alcohol, heptadecanol, t-pentyl Alcohol, methylcyclohexanol, 2-methyl -Butanol, 3-methyl-butanol, 3-methylpentanol, 3-methoxybutanol, 2- (2-butoxyethoxy) ethanol, aniline ethanol, aminoethanol, amine Propanol, aminobutanol, 2- (butylamino) ethanol, 2- (methylamino) ethanol, 2-amino-2-ethyl-1,3-propanol, 2-amine 2-methyl-propanediol, diphenylethylene glycol, ethylene glycol, glycerol, 2-ethyl-1,3-hexanediol, 2-chloro-1,3-propanediol, cis- 1,2-cyclohexanediol, cis-l, 4-cyclohexanediol, 3,5-dimethyl-1-hexyne-3-ol, ceanol, butanediol, butenol, butane Oxypropylene glycol, propylene glycol, hexanediol, hexenol, pentyl glycol, terpineol, diethyl ether, acetone, polyoxyethylene alcohol 'polyoxypropylene glycol with a degree of polymerization of 2, polyoxyethylene alcohol monoester, and the like. In particular, ethanol-based alcohols are preferably used. These organic solvents can be used alone or in combination of two or more. The combination is, for example, a mixture of several different alcohols, or a combination of a water-soluble alcohol and a water-insoluble saturated hydrocarbon solvent. In addition, terpineol-insoluble organic solvents can effectively replace water and organic solvents by using a surfactant such as a surfactant in an aqueous dispersion or organic solvent. An aqueous solvent may remain in the nickel powder dispersion. Furthermore, after adding the above-mentioned organic solvent, it is preferable to remove water from the dispersion and replace the organic solvent. At this time, the residual content of water in the dispersion is preferably 10% by weight or less, more preferably 5% by weight or less, and most preferably 2% by weight or less, 25,825,166. When the nickel powder dispersion of the present invention is made of nickel powder and the organic solvent, the nickel powder dispersion is made of nickel powder and the organic solvent and water. The replacement method can be the method of washing and replacing with organic solvent, which is the same as nickel powder, by delamination or filtration several times after adding an organic solvent, or using organic solvents under heating or decompression. Method of evaporation. With this organic solvent and the preparation of conductive paste, it has good compatibility with those used in the formation of conductive paste, which can prevent the agglomeration of nickel powder and improve the dispersibility. Here, the concentration of the organic solvent will be described. The concentration of the organic solvent of the nickel powder dispersion of the present invention may be arbitrary. However, when considering the compatibility or storage stability of the conductive paste, the concentration of the organic solvent is 5 to 200% by weight, preferably 10 to 100% by weight, and more preferably 20 to 60% by weight. The concentration of the organic solvent here is the weight% of the organic solvent with respect to the weight of the nickel powder in the dispersion. In other words, for the nickel powder dispersion of the present invention, for 100 parts by weight of the nickel powder, the organic solvent is 5 to 200 parts by weight, preferably 10 to 100 parts by weight, and more preferably 20 to 60 parts by weight. A slurry-like mixture. Moreover, the same surfactant as described above can be added to the nickel powder dispersion of the present invention. The method of addition is, for example, a method of adding a surfactant _ after adding an organic solvent, or a method of adding a surfactant in advance to the added organic solvent and mixing them, and adding the mixture to an aqueous dispersion of nickel powder. In this case, the surfactant is preferably diluted with the above-mentioned organic solvent such as alcohol or ketone, or mixed with the organic solvent and added. The diluted organic solvent is 1 to 50 parts by weight, preferably 10 to 40 parts by weight, for 1 part by weight of the surfactant. By adding a surfactant, it has the effect of promoting substitution by an organic solvent of a nickel powder dispersion. -20- 200425166 In addition, when considering the effect of the surfactant, add the surfactant in the nickel powder aqueous dispersion in advance, and after the surfactant is sufficiently dispersed in the surface of the nickel powder, add an organic solvent to replace it. good. In addition, the nickel powder produced by the above-mentioned gas phase reduction method is washed with water, and when the nickel powder aqueous dispersion is prepared, the nickel powder dispersion and conductive paste with high final dispersibility can be prepared when the above-mentioned surfactant is added. Better. In addition, there is no particular limitation on the amount ratio of the surfactant, and the amount is such that the single molecular film of the surfactant is formed on the surface of the nickel powder particles. Generally, the amount of the surfactant used for 1 kg of nickel powder is 100 g, preferably 0.1 to 50 g, and more preferably 0.5 to 25 g. 4) Disintegration treatment of nickel powder dispersion When a nickel paste is prepared by using the nickel powder dispersion obtained above, a paste with less aggregation of nickel powder and excellent dispersibility can be obtained. In order to further improve the dispersibility of the nickel powder dispersion of the present invention, an amine-based dispersant is added to the nickel powder dispersion obtained above and subjected to a disintegration treatment. In other words, by adding an amine-based dispersant, it is possible to further improve the dispersibility of the nickel powder in the dispersion, ease the agglomeration of the remaining nickel powder by the disintegration treatment, and exert the ultimate excellent paste characteristics. ® The amine-based dispersant is preferably an amine salt of at least one alkylamine and polycarboxylic acid. For example, polyester acids, fatty acids, fatty acid amines, polycarboxylic acids, alkylene oxides, polyalkylene oxides, polyoxyethylene fatty acid esters, polyoxyethylene glycerol fatty acid esters, and derivatives thereof Wait for the aminated person. The amine salts are ammonium amine salts, aliphatic amine salts, aromatic amine salts, alkanolamine salts, polyamine salts, and the like, such as polyoxyethylene fatty acid amidine, polyoxyethylene alkylamine, tripropylamine, and diethylamine groups. Ethylamine, dimethylaminopropylamine, diethyl-21-200425166 aminopropylamine, etc. These amine-based dispersants may be used in a solution state dissolved in a solvent component, or may be a towel product. These amine-based dispersants have an amine-based dispersant component of 0.05 to 50 parts by weight, and more preferably 0.2 to 2.0 parts by weight, for nickel powder in i 0 0 parts by weight of the dispersion. Next, the nickel powder dispersion to which the amine-based dispersant was added was pulverized using a ball mill. The ball milling and disintegration conditions depend on the agglomeration state of the nickel powder dispersion, and can be arbitrarily set with the agglomeration situation sufficiently relaxed. Specifically, the material inside the crushing container may be alumina, high-molecular plastic, or dragon resistant. · For the durability of the container and the effect on nickel powder in the present invention, it is preferable to use a pulverized container with a dragon-resistant internal material. Here, the pulverizing ball mill can be appropriately selected from oxidized pins, tungsten carbide, stainless steel, oxidized metal, and the like, and the diameter of the pulverized balls is 0.3 to 20 mm. When the dispersion of the nickel powder having an average particle diameter of 1 μm is pulverized, it is preferable to use a chrome oxide ball having a diameter of 3 to 10 mm as the material resistant to the inside of the pulverization container. In addition, the amount of the nickel powder dispersion charged in one pulverization process is 20 to 60%, and more preferably 20 to 40% of the capacity of the pulverization container. ® In addition, the viscosity of the pulverized nickel powder dispersion is preferably 15 000 to 3 500 cps, and more preferably 1 8000 to 3 0000 cpS. The temperature during the pulverization treatment is preferably 10 to 40 ° C, and more preferably 20 to 30 ° C. The disintegration processing time is related to the degree of agglomeration of the nickel powder dispersion, the material of the above crushing container, the crushing ball, the diameter of the crushing ball, and the viscosity of the dispersion. Generally, it is preferably 6 to 15 hours. In addition, the disintegration treatment of the nickel powder dispersion of the present invention may be performed by using a disintegrator having a shearing effect or a grinding effect in addition to the above-mentioned ball milling. -22- 200425166 The nickel powder dispersion system thus obtained has excellent dispersibility. When it is used to form a conductive paste, it has excellent dispersibility, which can prevent short circuits due to unevenness of the electrode surface when forming a multilayer ceramic capacitor, or Internal defects such as separation. 5) Preparation of conductive paste The nickel powder dispersion obtained above is suitable for use as a conductive paste or a paste for electrode formation. The nickel powder dispersion system kneads the organic solvent and the binder to form a paste. Organic solvents (organic vehicles) can be used by users of conventional conductive pastes, such as ethyl cellulose, ethylene glycol, toluene, xylene, mineral oil, butyl carbinol, terpineol, decyl High boiling organic solvents such as alcohols. As the binder, an organic or inorganic binder can be used, and a cellulose resin-based polymer binder such as ethyl cellulose or an acrylic resin such as butyl methacrylate is preferred. In addition, when forming a paste, plasticizers such as phthalic acid esters and stearic acid, or glass frits such as lead-based slope glass, zinc-based glass, or silicon-based glass, and oxides, bell oxides, and bismuth oxides can be mixed as needed. And other metal oxides. By mixing these additives, coating and sintering on a substrate such as ceramics. When forming an electrode, it has excellent adhesion to the substrate, can form an electrode with high conductivity, and can improve the wettability with soldering. Sex. Examples The present invention will be specifically described below by way of examples. The average particle diameter of the nickel powder, the particle size distribution of the nickel powder in the prepared conductive paste, and the film density were measured by the following methods. • Measurement of the average particle size of nickel powder -23- 200425166 Take a picture of nickel powder with an electron microscope, measure the particle size of 200 nickel powder particles from the picture, and obtain the average 値. The particle size is the diameter of the smallest circle surrounding the particles. • The particle size distribution of nickel powder in the conductive paste uses a laser light scattering refraction method particle size measuring machine (Coulter LS23 0: manufactured by Kruta). When the sample is a dispersion, an appropriate amount of nickel powder dispersion is dried and suspended in ethanol. After the sample is directly suspended in ethanol when it is a dry nickel powder, the ultrasonic wave is applied to disperse it for 3 minutes. The particle size of the nickel powder is measured with the refractive index of the sample to be 1.8, and the particle size distribution of volume statistics is calculated. Moreover, in the particle size distribution of Table 1 below, D90, D50, and D10 represent the particle size (μηι) at the cumulative particle size of 90%, 50%, and 10%, in particular, 値 of D90 (the cumulative particle size is 90) The larger the particle diameter (%), it means that the nickel powder is agglomerated in the dispersant for conductive paste formation. Conversely, the smaller the value is, the higher the dispersion of nickel powder is. The measurement of film density uses terpineol as a dispersant. In addition, a nickel powder dispersion containing 55% by weight of nickel powder or a dried nickel powder was added to terpineol, and 10% by weight of ethyl cellulose was added, followed by kneading to form a paste. In addition, a release film was bonded to a smooth glass plate, and both ends were bonded and fixed to the surface where the release film remained in the center. The release film was printed on the release film with a film coater to form a film with a uniform surface. Then, it is dried at 80 to 200 ° C, and the release film is peeled from the dried film, so that the film is perforated with a circular mold. The weight and volume of the perforated film were measured to determine the film density. At this time, the volume of the film is determined by measuring the circular area, and measuring the thickness of several films with a micrometer, and averaging -24-200425166. In addition, in the present invention, excellent dispersibility means that the secondary particles of the nickel powder particles have less agglomeration, and the average particle diameter (D 50) and coarse powder when measuring the cumulative particle size distribution of the nickel powder by laser light scattering diffraction method. The side particle diameter (D 90) is small, and the film density is large when a thin film of nickel powder is formed from the conductive paste. [Example 1] 1) Manufacture of nickel powder A Chlorination process In a chlorination furnace, a nickel powder having an average particle diameter of 5 mm from a raw material supply pipe was charged, and the temperature of the atmosphere in the furnace was set by a heating method. 1 1 0 ° C. Then, chlorine gas was supplied from the chlorine gas supply pipe to the chlorination furnace at 4 Nl / min to chlorinate the metal nickel to produce nickel chloride gas. In the chlorination furnace, an inert gas supply pipe radiating from the lower side of the chlorination furnace was supplied with 10% (mole ratio) of nitrogen gas, and was mixed with the nickel chloride gas. Then, a mixed gas of nickel chloride gas and nitrogen gas is introduced into the reduction furnace through a nozzle. B reduction project Secondly, the mixed gas of nickel chloride gas and nitrogen was introduced from the nozzle into the reduction furnace that formed an atmosphere temperature of 1 000 ° C by a heating method at a flow rate of 2.3 m / s (converted to 1 000 ° C). As a restoration project. At the same time, hydrogen was supplied to the chlorination furnace from a reducing gas supply pipe provided at the top of the reduction furnace at a flow rate of 7 Nl / min, and the nickel chloride gas was reduced to obtain metallic nickel powder. C. Cooling process The nitrogen gas supplied from the cooling gas supply pipe provided at the lower side of the reduction furnace at 16.4 N1 / min • g was brought into contact with the nickel powder generated by the above reduction process to cool the nickel -25- 200425166 powder. Then, the generated nickel powder was introduced into a recovery furnace simultaneously with chlorine gas and hydrochloric acid vapor through a nozzle, and then introduced into a bag filter to separate and recover the nickel powder. 2) Preparation of nickel powder dispersion. The recovered nickel powder was washed with pure water. Finally, pure water was added to form a nickel powder water dispersion. Then, carbon dioxide gas was blown into the dispersion to form a carbonic acid solution with a ρ Η 値 of 5.5. , And the nickel powder was treated with a carbonic acid aqueous solution at normal temperature for 60 minutes. Then, the nickel powder was precipitated, and the upper layer liquid was removed by delamination, and pure water was additionally added to prepare a nickel powder aqueous dispersion. In addition, to the above nickel powder aqueous dispersion, a mixture of 80% of polyoxyethylene phenylene ether phosphate and 20% of polyoxyethylene phenylene ether as a surfactant was added to the nickel powder as a surfactant, and the mixture was stirred. At this time, the concentration of the water solvent was 60% by weight. 2.5 kg of the above-mentioned nickel powder aqueous dispersion (nickel powder 1: 5kg, water 1.0kg) was taken, and 1 kg of terpineol 5 was added thereto and stirred at room temperature. Disperse the nickel powder. Then, it was dried at 120 ° C for 16 hours and at 1000 ° C for 48 hours to obtain a nickel powder dispersion. The nickel powder dispersion was substantially free of residual water, and the entire amount of water was replaced with? 5 pinol. · Next, to the above-mentioned nickel powder dispersion, 100 to 4.0 parts by weight of nickel powder dispersion as shown in Table 1 is added as a dispersant of alkylamine (made by Kusumoto Kasei Co., Ltd., product number 1). 1) Active ingredient 50%, solvent component is dimethyl form). However, since the effective content of the used product E D 1 1 7 is 50%, the substantial addition amount of the amine component shown in Table 1 is 0 to 2.0 parts by weight. The nickel powder dispersion thus obtained was subjected to a pulverization process using a ball mill pulverizer. For the disintegration process, a ball mill-26-200425166 made by NITTO SCIENCE CO., LTD. Was used, AN-3S, and a 400mm diameter pot made of Nylon was used. The oxidation pin ball with a diameter of 10m Φ was used as a crushing ball. The rotation was performed at 70 rpm and the disintegration time was 12 hours. Table 1 shows the measurement results of the average particle diameter of the nickel powder in the obtained nickel powder dispersion, the particle size of the obtained ballast dispersion, and the film density of the conductive paste prepared using the obtained nickel powder dispersion.
Γ -27- 200425166 比較例3 壊 壊 壊 璀 1 1 〇 加熱乾燥 0.49 2.20 1.55 s r-^ 4.55 !乾燥粉 比較例2 壊 壊 1 1 1 璀 加熱乾燥 0.49 2.30 OO V〇 r—H I 1.10 4.05 乾燥粉 比較例1 聚氧乙烯苯醚及其磷酸鹽之混合物添加 _：_1 同左 實施 壊 1 1 壊 顯 0.49 1.77 (N r—t 1 0.62 4.81 同左 實施例2 實施 m^213添加 〇 (Ν f-H 〇 壊 0.49 1.35 0.95 i ；0.54 5.66 萜品醇分散體 〇 Τ—- oo d 〇 壊 0.49 ON 0.95 1 0.54 5.45 m ο 0.24 〇 壊 0.49 寸 Η S T—H 0.57 5.30 r-H d 0.08 〇 壊 0.49 Ο in 1—Η 卜 〇 ! 0,9 5.29 o o 〇 壊 0.49 Ο OO o 0.59 5.26 實施例1 實施 EDI 17添加 o 对· o (N 〇 壊 0.49 1.31 0.90 1 0.52 5.65 萜品醇分散體 o O T—H 〇 壊 0.49 ΟΝ m 0.92 1 0.52 5.47 <N vo o 〇 摧 0.49 Os 寸· 0.95 0.56 5.37 寸 d (N d 〇 壊 0.49 (Ν in o 0.57 5.35 d 0.05 〇 壊 0.49 1.56 o r-H 0.59 5.29 o 〇 〇 壊 0.49 ο νο OO o 0.59 5.26 對鎳粉之水分散體添加界面 活性劑 對鎳粉之水分散體添加有機 溶劑 藉由加熱乾燥除去水分 腾 細 1$〇2 藏 Φ騷 ^ Μ 锲銶 Φ 骤狴 胺系分散劑之添加量 胺系分散劑成分之實質添 加量 解碎處理(球磨解碎）：〇有 解碎處理 糊形成前之加熱乾燥 平均粒徑(μπι) 1粒度分布(μηι) D90 D50 D10 CO B 铂 m 鉍 Rg 1ΪΪ5Β 驩 蜱ϋ 矻》 Η 聲囬 200425166 [實施例2] 在實施例1所得的鎳粉之萜品醇分散體中添加作爲胺 系分散劑之聚羧酸的胺鹽（楠本化成股份有限公司製、品番 E D 2 1 3、有效成分8 0 %、溶劑成分爲二甲苯）。聚羧酸之胺 鹽的添加量如表1所示，對1〇〇重量份鎳粉而言爲〇〜2.0 重量份。然而，由於ED213之有效成分爲80%，分散劑之 實質添加量如表1所示爲0〜1 · 6重量份。最後，與實施例 1相同地進行解碎處理，進行各種評估。結果倂記於表1。 [比較例1 ] 〇 在實施例1所得鎳粉之萜品醇分散體中沒有添加胺系 分散劑，進行解碎處理的狀態下製得鎳粉分散體。有關該 鎳粉分散體，與實施例1相同地進行各種評估。結果倂記 於表1。 [比較例2 ] 對實施例1所得的鎳粉之水分散體而言，沒有添加界 面活性劑且沒有添加有機溶劑，沒有添加胺系分散劑及進 行解碎處理，使鎳粉水分散體加熱乾燥以除去水分，製得 f 鎳粉（乾燥粉）。測定使該鎳粉分散於乙醇時之粒度分布及 使用所得鎳粉（乾燥粉）調整的導電糊之膜密度。結果倂記 於表1。 [比較例3] 對實施例1所得的鎳粉之水分散體而言，沒有添加界 面活性劑且沒有添加有機溶劑，沒有添加胺系分散劑的狀 態下，使該水分散體與實施例1相同地進行球磨解碎處理 -29- 200425166 。然後，使該鎳粉之水分散體過濾後，加熱乾燥製得鎳粉（ 乾燥粉）。有關該鎳粉，與比較例2相同地進行各種評估。 結果倂記於表1。 如表1所示，實施例1、2之鎳粉使用電子顯微鏡觀察， 平均粒徑與比較例1〜3之鎳粉相同。然而，鎳粉之有機溶 劑的分散體於各實施例中藉由在鎳粉分散體中添加胺系分 散劑且另藉由解碎處理，對各比較例而言可知粒度分布 (D90、D50、D10)變小，鎳粉凝聚、粗粉化的二次粒子變小 。另外，添加胺系分散劑且解碎處理的各實施例對各比較 例而言，可知膜密度變大、即提高分散性。此外，各實施 例中胺系分散劑添加量爲〇且僅進行解碎處理時，較添加 有胺系分散劑且解碎者之粒度分布爲大、膜密度爲低。換 言之，藉由添加胺系分散劑與解碎處理，可得較高的分散 性。 另外，特別是比較例2中直接將鎳乾燥粉分散於有機 溶劑中，沒有在鎳粉之水分散體中添加有機溶劑取代水。 因此，可知粒度分布D 9 0、D 5 0、D 1 0與各實施例相比時較 大，導電糊中因鎳粉凝聚致使粒子粗大化，膜密度變小。 此外，比較例3中沒有在鎳粉之水分散體中添加有機 溶劑以取代水，且沒有添加胺系分散劑的狀態下僅進行球 磨解碎處理。由於進行該球磨解碎處理時，與比較例2相 比時可知稍微控制因鎳粉凝聚造成的粗粉化。然而，由於 沒有在鎳粉之水分散體中添加有機溶劑以取代水、及沒有 添加胺系分散劑，與添加有胺系分散劑之各實施例相比時， 可知粒子大、膜密度低，各分散性不佳。 -30-Γ -27- 200425166 Comparative Example 3 壊 壊 壊 1 1 〇 Heating and drying 0.49 2.20 1.55 s r- ^ 4.55! Drying powder Comparative Example 2 壊 壊 1 1 1 加热 Heating and drying 0.49 2.30 OO V〇r—HI 1.10 4.05 Drying Powder Comparative Example 1 Polyoxyethylene phenyl ether and its phosphate mixture added _: _ 1 Same as the left implementation 1 1 壊 0.49 1.77 (N r-t 1 0.62 4.81 Same as the left example 2 implementation m ^ 213 addition 〇 (N fH 〇壊 0.49 1.35 0.95 i; 0.54 5.66 terpineol dispersion 〇Τ—- oo 〇 〇 0.40.4 ON 0.95 1 0.54 5.45 m ο 0.24 〇 0.49 inch Η ST—H 0.57 5.30 rH d 0.08 〇 0.49 〇 in 1—卜 〇! 0,9 5.29 oo 〇 壊 0.49 〇 OO o 0.59 5.26 Example 1 Implementation of EDI 17 addition o o (N 〇 壊 0.49 1.31 0.90 1 0.52 5.65 terpineol dispersion o OT-H 〇0.40.49 〇Ν m 0.92 1 0.52 5.47 < N vo o 〇 Destruction 0.49 Os inch 0.95 0.56 5.37 inch d (N d 〇 壊 0.49 (N in o 0.57 5.35 d 0.05 〇 壊 0.49 1.56 o rH 0.59 5.29 o 〇〇 壊 0.49 ο νο OO o 0.59 5.26 Add surfactant to water dispersion of nickel powder Add an organic solvent to the aqueous dispersion of nickel powder and remove the water by heating and drying. The fineness is 1 $. 2 藏 Φ ^ Μ 锲 銶 锲 銶 狴 The amount of amine-based dispersant is added. The substantial amount of amine-based dispersant component is disintegrated. Treatment (ball milling and disintegration): 〇The average particle size (μπι) of heating and drying before the formation of the disintegrated paste. 1 Particle size distribution (μηι) D90 D50 D10 CO B Platinum m Bismuth Rg 1ΪΪ5B Tick tick Example 2] To the terpineol dispersion of the nickel powder obtained in Example 1 was added an amine salt of a polycarboxylic acid as an amine-based dispersant (produced by Nanben Chemical Co., Ltd., Pinfan ED 2 1 3, active ingredient 8 0 %, The solvent component is xylene). The amount of the amine salt of the polycarboxylic acid is shown in Table 1, and it is 0 to 2.0 parts by weight for 100 parts by weight of the nickel powder. However, since the effective content of ED213 is 80%, the substantial amount of dispersant added is 0 to 1.6 parts by weight as shown in Table 1. Finally, the pulverization process was performed in the same manner as in Example 1, and various evaluations were performed. Results are recorded in Table 1. [Comparative Example 1] ○ A nickel powder dispersion was obtained in a state where the amine-based dispersant was not added to the terpineol dispersion of the nickel powder obtained in Example 1 and the pulverization treatment was performed. Various evaluations were performed on this nickel powder dispersion in the same manner as in Example 1. The results are shown in Table 1. [Comparative Example 2] For the aqueous nickel powder dispersion obtained in Example 1, no surfactant was added, no organic solvent was added, no amine-based dispersant was added, and the disintegration treatment was performed to heat the nickel powder aqueous dispersion. Drying to remove water, f nickel powder (dry powder) was prepared. The particle size distribution when this nickel powder was dispersed in ethanol and the film density of the conductive paste adjusted using the obtained nickel powder (dry powder) were measured. The results are shown in Table 1. [Comparative Example 3] The aqueous dispersion of the nickel powder obtained in Example 1 was added with the surfactant and Example 1 without adding a surfactant, an organic solvent, or an amine-based dispersant. Ball milling and pulverization were performed in the same manner. Then, the aqueous dispersion of the nickel powder was filtered, and then heated and dried to obtain a nickel powder (dry powder). About this nickel powder, various evaluations were performed similarly to the comparative example 2. Results are recorded in Table 1. As shown in Table 1, the nickel powders of Examples 1 and 2 were observed with an electron microscope, and the average particle diameter was the same as that of the nickel powders of Comparative Examples 1 to 3. However, in each example, the dispersion of the organic solvent of the nickel powder was obtained by adding an amine-based dispersant to the nickel powder dispersion and subjecting it to a disintegration treatment. The particle size distribution (D90, D50, D10) becomes smaller, and secondary particles of nickel powder are aggregated and coarsely pulverized. In each of the examples in which the amine-based dispersant was added and the pulverization treatment was performed, it was found that the film density was increased, that is, the dispersibility was improved. In addition, in each example, when the addition amount of the amine-based dispersant was 0 and only the disintegration treatment was performed, the particle size distribution was larger and the film density was lower than those with the amine-based dispersant added and disintegrated. In other words, a higher dispersibility can be obtained by adding an amine-based dispersant and a disintegration treatment. In particular, in Comparative Example 2, the dry nickel powder was directly dispersed in an organic solvent, and no organic solvent was added to the aqueous dispersion of the nickel powder instead of water. Therefore, it can be seen that the particle size distributions D 9 0, D 5 0, and D 1 0 are larger than those in the examples, and the particles in the conductive paste are coarsened due to the aggregation of the nickel powder, and the film density is reduced. In addition, in Comparative Example 3, no organic solvent was added to the aqueous dispersion of nickel powder to replace water, and only the ball milling and pulverizing treatment was performed in the state where no amine-based dispersant was added. When this ball milling and pulverizing treatment was performed, it was found that coarsening due to agglomeration of nickel powder was slightly controlled when compared with Comparative Example 2. However, since no organic solvent was added to the aqueous dispersion of nickel powder to replace water, and no amine-based dispersant was added, it was found that the particles were large and the film density was low when compared with the examples in which the amine-based dispersant was added. The dispersion is poor. -30-