201209850 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種導電膏用之銅粉及使用該銅粉之導 電膏，特別是，有關一種銅粉及使用該銅粉之導電膏，該 銅粉係適於藉由網版印刷加成法（screen printing additive process)而形成導體電路用、或積層陶兗電容器 之外部電極用等各種電接點（electrical con tact)構件用 之導電膏之導電材料等。 【先前技術】 銅粉係因其處理之容易性，所以至今廣泛利用做為藉 由網版印刷加成法而形成導體電路用、或積層陶瓷電容器 之外部電極用等各種電接點構件用之導電膏之導電材料 等。 上述導電膏可經由例如在銅粉中調配環氧樹脂等樹脂 及其硬化劑等各種添加劑並進行混練而得到。此時所使用 之銅粉可藉由下述方法製造：藉由還原劑從包含銅鹽之溶 液等析出之濕式還原法、加熱使銅鹽氣化後在氣相中還原 之氣相還原法、或以惰性氣體或水等冷媒將熔融之銅原料 金屬急速冷卻並粉末化之霧化（atomizing)法等。 在如上述之銅粉之製造方法中，霧化法係具有下述優 點：相較於一般廣泛利用之濕式還原法，可更加降低所得 銅粉中之雜質之殘留濃度，並且可更加減少所得銅粉之粒 子之從表面至内部之細孔。因此，當使用於導電膏之導電 材料時，藉由霧化法製得之銅粉係具有下述優點：可減少 3 322226 201209850 導電膏硬化時之氣體產生量，並且可大幅抑制氧化進行。 然而，銅粉係因其導電性高，故適於導電膏之導電材 料，但有隨著粒度變微小，其耐氧化性會變得不良之問題-， 為了改善此問題，至今一直採用下述方法：以具有耐氧化 性之銀塗佈粒子表面（參照專利文獻υ、以無機氧化物進 行塗佈（參照專利文獻2)等。 〔先前技術文獻〕 〔專利文獻〕 〔專利文獻1〕日本特開平10-152630號公報 〔專利文獻2〕日本特開2005-129424號公報 【發明内容】 (發明欲解決的課題） 近年來’在藉由導電膏等而形成電路時要求更加微小 而必然地也要求導電膏所用之導電粉之粒度亦微小 ^同時’也要求其必須為確保導電膏特性之安定性、可 生三並且形狀和粒度之變異小，且導電性未受損者。而 右僅欲獲得耐氧化性改善，則可以專利文獻1或2等 之技術予以對應。 而定…、，專利文獻1或2等之技術係由於依據被覆技術 也會故不僅需要許多銅以外之會損害導電性之成分，且 減少=生彳欠做為芯材之銅粉粒子剝離之問題。此外，期望 和粒度之變異，並且也期望構成之粒子一致為均 令人滿!!含氧濃度，但關於如此之銅粉，目前尚未發現可 两忍者。 4 322226 ，、 201209850 本奄明之目的為提供一種導電膏用之銅粉，其係雖粒 度微小但耐氧化性、導電性之平衡仍皆未受損之銅粉，並 且其形狀和粒度之變異小且為低含氧濃度。 (解決課題的手段） 本發明人專為了解決上述課題而致力進行研究後結果 發現，若使銅粉之粒子内部包含特定量之Bi，則可解決上 述課題，遂完成本發明。 換言之，本發明之導電膏用之銅粉係在粒子内部包含 0. 05atm%至 lOatm%之 Bi。 並且’可在粒子内部包含〇.〇1&1：111%至〇.如加^之p (磷），且以Bi/P(atm比）為4至200為佳。 此外’可在粒子内部包含〇. latjjj%至之Ag，可 在粒子内部包含0. latm%至lOatm%之Si，可在粒子内部包 含 0. latm%至 lOatm%之 In。 而且’以藉由霧化法製得者為佳。 此外，以在240t：及600°C之重量變化率（Tg(%))/比 表面積（SSA)之差為l°/0/m2/cm3至30%/m2/cm3為佳。 本發明之其他態樣為一種導電膏，其係包含上述導電 膏用之銅粉者。 (發明的效果） 本發明之導電膏用之銅粉雖粒度微小但耐氧化性仍 良，且也取得導電性之平衡。並且，由於形狀和粒度之^ 異小’且為低含氧濃度，故可極為良好地使用於藉 印刷加成法而形成導體電路用、或積層陶究電容哭之外部 5 322226 201209850 電極用等各種電接點構件用之導電膏之導電材料等。 【實施方式】 說明本發明之導電膏用之銅粉的實施形態，但本發明 並非限定於以下之實施形態。 本發明之導電膏用之銅粉的特徵係在粒子内部包含 0. 05atm%至 lOatm%之 Bi。 在此，重要的是.並非單純僅包含Bi，而是在粒子内 部包含特定量。 換言之，上述專利文獻等具代表性的習知技術中所揭 示之在做為芯材之銅粉粒子之表面被覆或附著有導電性較 銅更不良的各種物質或化合物之銅粉，雖具有改善耐氧化 性之效果，但無法得到本發明所尋求之不會損害導電性並 且粒度微小且耐氧化性優良的銅粉。 再者，本發明之導電膏用之銅粉中所含之Bi成分，係 多被觀察到存在於Cu之晶粒界（grain boundary)、特別是 粒子表面之晶粒界，也推測其與粒子之微小化具有相關性。 此外，本發明之導電膏用之銅粉之Bi含量為〇.〇5atm〇/0 至 lOatm%’且以 0.5atm%至 5atm%為佳、以 〇.5atm%至 3atm% 較佳。若此含量未達0. 05atm% ’則無法期待本發明所尋求 之效果。此外，當超過lOatm%時，不僅導電性會受損，也 無法得到與該添加相襯的效果。 此外’本發明之導電膏用之銅粉可藉由將個數平均粒 經設為0.5//in至50 而適於微小的前述形成導體電路 用之導電膏之導電材料等。 ％ 322226 6 201209850 當使B i成分含於銅粉粒子中時，使粒子微小化之效果 尤其顯著。例如：若令Bi含量為0. 05atm%至3. Oatm%左右， 則可使藉由氣體霧化法所得之銅粉之D5。成為5 /z m至2 5 # m 左右。此外，可使藉由水霧化法所得之銅粉之D50成為1 /z m 至5#111左右。若為如此之Bi含量之銅粉，則如後述，也 不會損害使用時之導電性。再者，D5Q為藉由雷射繞射散射 式粒度分布測定裝置等所測得之體積累積粒徑。 此外，本發明之導電膏用之銅粉較佳係不僅在使粒子 微小化之方面有效果，而且也具有其為狹窄的粒度分布、 粗粒少等之特徵。 具體而言，粒度分布可為使由D5〇及標準偏差值SD所 •求得之變異係數（SD/D5〇)成為0. 2至0. 6左右。若為如此 之銅粉，則當使用於導電膏之導電材料等時，可提高在導 電貧中之分散性，故為非常佳。此外，就粗粒而言，當藉 由氣體霧化法所得之銅粉之Dso為5 /z m至25 // m左右時， 可使Dg。成為10 // m至40 /z m左右。此外，當藉由水霧化法 所得之銅粉之Dsd為1 /z m至5 /z m左右時，可使D9G成為5 至10//m左右。若為如此之銅粉，則當使用於導電膏 之導電材料等時，微小電路之可靠性優良，故為非常佳。 此外，本發明之導電膏用之銅粉中，除了 Bi以外，也 宜在粒子内部包含較佳為O.Olatm%至0.3atm%、更佳為 0. 02atm%至0. latm%之P(磷）。若Bi及P在銅粉中共存， 且為在如此之特定量之範圍内，則不但粒度微小、具有耐 氧化性且不會損害導電性，並且形狀和粒度之變異小且為 7 322226 201209850 低含氧濃度之特徵也更顯著。再者，p係以均勻地分布於 粒子内部之金屬相中為佳。 此外，本發明之導電膏用之鋼粉的比）以4 至200為佳、以黯100較佳。若Μ/P之比在如此之範 圍内，則容易取得粒度微小、耐氧化性、S導電性、形狀 和粒度之變異小、為低含氧濃度之特徵之平衡。 此外’本發明之導電膏用之鋼粉宜在粒子内部包含較 佳為0. la«至10a械、更佳為〇. 5at· 5atm%、最佳為 〇. 5a城至3_%之Ag。若為在如此之特定量之範_，則 可在維持導電膏狀銅粉為耐氧化之狀態下更加提高導電 性’且也降低成本。再者’ Ag以均勻地分布於粒子内部之 金屬相中為佳。 此外，本發明之導電膏用之銅粉宜在粒子内部包含較 佳為0. latm%至l〇atm%、更佳為〇· 5_至5_%、最佳為 〇. 5a滅至3atm%之Si。若為在如此之特定量之範圍内則 可更加提高銅粉之财氧化性。再者，Si以均勻地分布於粒 子内部之金屬相中為佳。 而且’本發明之導電膏用之鋼粉宜在粒子内部包含較 佳為0. lat龜更佳為〇 2謎至8滅、最佳為 la城至3㈣之In。若為在如此之特定量之範圍内，則可 更加提高銅粉之耐氧化性H心分布於粒子内部之 金屬相中為佳。 而且，當包含^^以哼及匕全部日^可成為雖 粒度微小但形狀和减之變異仍小，且耐氧化性明顯地更 322226 8 201209850 優良，並且導電性也更優良的導電膏用之銅粉。 此外，雖然本發明之導電膏用之銅粉即使為藉由濕式 還原法所得者，仍可期待其有所效果，但若考慮到粒子形 狀勻稱且在做為導電膏使用時氣體產生少等優點，則以藉 由霧化法製得者為佳。 霧化法有氣體霧化法及水霧化法，但若欲謀求粒子形 狀之勻稱化，則選擇氣體霧化法即可，若欲謀求粒子之微 小化，則選擇水霧化法即可。此外，在霧化法之中，以藉 由高壓霧化法製得者為佳。如此之藉由高壓霧化法製得之 銅粉係粒子更勻稱、或更微小，而為佳。順帶一提，所謂 高壓霧化法，在水霧化法中係指以50MPa至150MPa左右之 水壓力進行霧化之方法，在氣體霧化法中係指以1. 5MPa至 3MPa左右之氣體壓力進行霧化之方法。 此外，本發明之導電膏用之銅粉，以由熱重量/示差 熱分析裝置所測得之在240°C及600°C之重量變化率（Tg (%))/比表面積（SSA)之差（以下稱為△ (TG/SSA))為1°/。/ m2/cm3 至 30%/m2/cm3 為佳、以 l%/m2/cm3 至 25%/m2/ cm3較佳。 根據此Δ(Τ6/58Α)之特性值，可觀察銅粉之耐氧化 性。此外，240°C至600°C之溫度區域為使用例如陶瓷電容 器之外部電極煅燒用導電膏等主流之導電膏時的加熱溫度 區域，在此區域中具有耐氧化性係非常重要。若此Δ (Τϋ /SSA)在上述之較佳範圍内，則會充分發揮耐氧化性，且 也適宜確保南導電性。 S, 9 322226 201209850 此外，本發明之導電膏用之銅粉，可經由再加入Ni、 A1、Ti、Fe、Co、Cr、Μη、Mo、W、Ta、Zr、Mb、B、Ge、 Sn、Zn等中之至少一種以上之元素成分，而提昇例如使以 降低融點而提昇燒結性等為首之導電膏所要求之各種特性 提高的效果。此等元素相對於銅之添加量，係從對應所添 加之元素之種類的導電特性或其他各種特性等來適當設 定，但通常為0.001質量％至2質量％左右。 此外，本發明之導電膏用之銅粉的形狀係以呈粒狀為 佳，特別是以呈球狀為更佳。在此，所謂「粒狀」係指縱 橫比（aspect rat i〇，平均長徑除以平均短徑而得之值）為 1至1. 25左右且一致之形狀，而縱橫比為1至1. 1左右且 一致之形狀係特別稱為「球狀」。再者，形狀不一致之狀態 係指不定形狀。呈如此之粒狀之銅粉係相互纏繞較少，而 當使用於導電膏之導電材料等時，在導電膏中之分散性提 高，故非常佳。 此外，本發明之導電膏用之銅粉，可經由令含氧濃度 為30ppm至2500ppm，而確實地確保導電性，而成為適於 導電膏之導電材料等者。 其次，說明本發明之導電膏用之銅粉的較佳的具體製 造方法。 本發明之導電膏用之銅粉，可藉由在溶融之銅中以母 合金或化合物等之形態添加預定量之Bi成分後，以預定之 霧化法進行粉體化而製造。 根據上述製造方法，可製造一種銅粉，其係雖粒度微 10 322226 201209850 小但耐氧化性、導電性之平衡仍皆未受損之銅粉，並且其 形狀和粒度之變異小且為低含氧濃度。 其理由尚不明確，但推測為：在熔融之銅或銅合金中 所添加之Bi係在不損害導電性之程度内捕捉生成銅粉粒 子中之氧而抑制氧化。 並且推測為：除了加入Bi成分以外，若再加入P成分， 則可降低霧化時之熔融金屬之表面張力，而可有效地進行 粒子形狀之勻稱化和熔融金屬中之脫氧化。P成分之添加 係與Bi成分同樣地，只要在熔融之銅中以母合金或化合物 等之形態添加預定量之P成分即可。 此外，經由除了 Bi成分以外再含有Ag成分，即可確 保銅粉之财乳化性’並且更加提南導電性。 此外，經由除了 B i成分以外再含有S i成分和I η成 分，即可更加提高銅粉之耐氧化性。 此外，在上述製造方法中，因先前所說明之理由，以 採用高壓霧化法為佳。惟，相較於氣體霧化法，水霧化法 中有時其銅以外之添加成分之含有良率較低，故必須相對 於目標之銅粉中之淨重量，該成分為Bi時則添加1至10 倍量，該成分為P時則添加1至100倍量，該成分為Ag時 則添加1至10倍量，該成分為Si時則添加1至10倍量， 該成分為In時則添加1至10倍量。 此外，在上述製造方法中，在霧化後也可進行還原處 理。藉由此還原處理，即可更加減少容易進行氧化之銅粉 之表面之氧濃度。在此，從作業性之觀點來看，上述還原 S： 11 322226 201209850 處理以藉由氣體而進行還原為佳。此還原處理用氣體係益 特別較，可舉例如：氫氣、氨氣、丁㈣等。 … 並且，上述還原處理以在15(rCl3()(rc之溫度進行為 佳^別是以在17代至21代之溫度進行較佳。其原因 為：若上述溫度未達150ΐ，則還原速度緩慢，而無法充 分顯現處理效果；若上述溫度超過30(TC，則有導致銅粉 之凝聚和燒結之虞；若上述溫度為17(^至21代，則可一 面謀求效率良好地降低氧濃度，一面確實地抑制銅粉之凝 聚和燒結。 此外’在上述製造方法巾，在粉魏後，崎行分級 為佳。此分級可經由以使目標之粒度成為中心之方式，使 用適當的分級裝置將粗粉和微粉從所得之鋼粉中分離出， 而容易地實施。在此，以使先前所說明之變異係數⑽Α。) 成為〇· 2至〇· 6之方式進行分級為佳。 在如以上所說明之銅粉中調配例如環氧樹脂 其硬化劑等各種添加劑並進行混練等而製得之含有本^明 之導電膏用之銅粉的導電膏，係由於該鋼粉雖粒度微小但 仍取得耐氧化性、導電性之平衡，並且形狀之變異小且含 氧濃度低，故可極為良好地使用於藉由網版印刷加成法而 形成導體電路用、或積層陶瓷電容器之外部電極用等各種 電接點構件用之導電膏之導電材料等。 此外，本發明之導電膏用之銅粉也可使用於：積層陶 瓷電容器之内部電極、電感器（inductor)或暫存ρ (register)等晶片零件；單板電容器電極、鈕電容器電極、 322226 12 201209850 知十月曰多層基板、陶瓷（LTCC，Low Temperature Cofired Ceramics ’低溫共燒陶瓷）多層基板、可撓性印刷基板 (FPC)、天線開關模組（antenna switch module)、PA(Power Amplifier ’功率放大器）模組或高頻主動式濾波器等模 、组；PDP前面板及背面板或PDP濾色片（color niter)用 電磁遮蔽膜、結晶型太陽電池表面電極及背面抽出電極、 V電性接著劑、emi(Electromagnetic Interference ，電 磁干擾）屏蔽、RF-ID(Radio Frequency-Identification ， …、線射頻辨識）、及PC鍵盤等薄膜開關（membrane SWltch)、異向性導電膜（ACF/ACP)等。 以下’依據下述實施例及比較例而更詳述本發明。 (實施例1) · . 將氣體霧化裝置（日新技研（股）製，NEVA —GP2型）之 反應室（chamber)及原料溶解室内以氮氣填充後，以位於溶 解室内之碳坩堝將原料加熱溶解而製成熔融物（在溶有電 解銅之熔融金屬中添加金屬鉍2. 62g，製成8〇〇g之熔融金 屬，並充分攪拌混合）。然後，從口徑015麵之喷嘴將熔 融金屬以1250Ϊ、3.〇MPa進行喷霧.，而得到在粒子内部包 二叙之銅粉。然後，使用53#m試驗_ (⑽t h㈣）進行 筛k後以_出物做為最後的銅粉。所得之銅粉之特徵如 表2所示。 (實施例2至4) 一除了按照表1所示變更金屬叙添加量以外，其餘進行 與貫施例1同樣之操作，而得到銅粉。201209850 VI. Description of the Invention: [Technical Field] The present invention relates to a copper powder for a conductive paste and a conductive paste using the copper powder, and more particularly to a copper powder and a conductive paste using the copper powder, The copper powder is suitable for forming a conductive paste for various electrical contacting members such as a conductor circuit or an external electrode for laminating a ceramic capacitor by a screen printing additive process. Conductive materials, etc. [Prior Art] Copper powder is widely used as a variety of electrical contact members for forming a conductor circuit or an external electrode for a multilayer ceramic capacitor by a screen printing additive method because of its ease of handling. Conductive material of conductive paste, etc. The conductive paste can be obtained by, for example, mixing various additives such as a resin such as an epoxy resin and a curing agent in copper powder. The copper powder used at this time can be produced by a wet reduction method in which a reducing agent is precipitated from a solution containing a copper salt or the like, and a vapor phase reduction method in which a copper salt is vaporized and then reduced in a gas phase by heating. Or an atomizing method in which a molten copper raw material metal is rapidly cooled and powdered by a refrigerant such as an inert gas or water. In the method for producing copper powder as described above, the atomization method has the advantage that the residual concentration of impurities in the obtained copper powder can be further reduced and the yield can be further reduced as compared with the wet reduction method which is generally widely used. The pores of the particles of copper powder from the surface to the inside. Therefore, when used for a conductive material of a conductive paste, the copper powder obtained by the atomization method has the following advantages: the amount of gas generated when the conductive paste is hardened by 3,322,226, 201209850 can be reduced, and oxidation can be greatly suppressed. However, copper powder is suitable for a conductive material of a conductive paste because of its high conductivity, but it has a problem that its oxidation resistance becomes poor as the particle size becomes small. In order to improve this problem, the following has been used so far. Method: Coating the surface of a silver-coated particle with oxidation resistance (refer to the patent document υ, coating with an inorganic oxide (refer to Patent Document 2), etc. [Prior Art Document] [Patent Document] [Patent Document 1] [Problems to be Solved by the Invention] In recent years, when a circuit is formed by a conductive paste or the like, it is required to be smaller and inevitably The particle size of the conductive powder used for the conductive paste is also small. At the same time, it is required to ensure the stability of the conductive paste, the third property, and the small variation in shape and particle size, and the conductivity is not impaired. When the oxidation resistance is improved, the technique of Patent Document 1 or 2 can be used. The technology of Patent Document 1 or 2 is not only required depending on the coating technique. Many components other than copper can damage the conductivity, and reduce the problem of the peeling of the copper powder particles that are not used as the core material. In addition, it is desirable to have variations in particle size, and it is also expected that the constituent particles are consistently full! Oxygen concentration, but for such copper powder, no two ninjas have been found. 4 322226 , , 201209850 The purpose of this invention is to provide a copper powder for conductive paste, which is small in particle size but resistant to oxidation and conductivity. The copper powder which is still undamaged in balance, and has a small variation in shape and particle size and a low oxygen concentration. (Means for Solving the Problem) The present inventors have made efforts to solve the above problems and found that if The copper powder of the conductive paste of the present invention contains 0. 05atm% to 10at% of Bi in the particle, and the copper particle of the copper powder contains a specific amount of Bi. It can contain 〇.〇1&1:111% to 〇 inside the particle, such as adding p (phosphorus), and Bi/P (atm ratio) is preferably 4 to 200. In addition, ' can contain 〇 inside the particle .latjjj% to Ag, can Included in the inside of the particle is 0. latm% to lOatm% of Si, and may contain 0. latm% to lOatm% of In. and 'made by atomization method. Also, at 240t: and 600 The difference in weight change rate (Tg (%)) / specific surface area (SSA) of ° C is preferably from 1 ° / 0 / m 2 / cm 3 to 30% / m 2 / cm 3 . Other aspects of the invention are a conductive paste, The copper powder for the above-mentioned conductive paste is used. (Effect of the invention) The copper powder for the conductive paste of the present invention has a small particle size, but the oxidation resistance is good, and the balance of conductivity is also obtained. Moreover, due to the shape and particle size. It is a low-oxygen concentration, so it can be used very well in the formation of a conductor circuit by a printing additive method, or an external layer of a ceramic capacitor. 5 322226 201209850 Various electrical contact members for electrodes The conductive material of the conductive paste, and the like. [Embodiment] An embodiment of the copper powder for a conductive paste of the present invention will be described, but the present invention is not limited to the following embodiments. The copper powder for the conductive paste of the present invention is characterized in that it contains 0. 05 atm% to 10 atm% of Bi inside the particles. Here, it is important that not only Bi is included, but a specific amount is contained inside the particle. In other words, the copper powder which is coated on the surface of the copper powder particles as the core material or which adheres to various substances or compounds which are less conductive than copper, which are disclosed in the above-mentioned patent documents, has improved. Although it has an effect of oxidation resistance, it is not possible to obtain a copper powder which is not damaged by the present invention and which has a small particle size and excellent oxidation resistance. Further, the Bi component contained in the copper powder for the conductive paste of the present invention is mostly observed in the grain boundary of Cu, particularly the grain boundary of the particle surface, and is also presumed to be associated with the particle. The miniaturization is relevant. Further, the copper powder for the conductive paste of the present invention has a Bi content of 〇. 5 atm 〇 /0 to 10 atm% and preferably 0.5 atm% to 5 atm%, preferably 〇5 atm% to 3 atm%. If the content is less than 0.05 atm%, the effects sought by the present invention cannot be expected. Further, when it exceeds 10 atm%, not only the conductivity is impaired, but also the effect of the phase contrast is not obtained. Further, the copper powder for the conductive paste of the present invention can be suitably used for the above-mentioned conductive material for forming a conductive paste for a conductor circuit by setting the number average particle diameter to 0.5//in to 50. % 322226 6 201209850 When the component B i is contained in the copper powder particles, the effect of miniaturizing the particles is particularly remarkable. For example, if the Bi content is from about 0.05 atm% to about 3. Oatm%, D5 of the copper powder obtained by the gas atomization method can be obtained. Become 5 / z m to 2 5 # m or so. Further, the D50 of the copper powder obtained by the water atomization method can be made from about 1 /z m to about 5 #111. If it is such a Bi content copper powder, as will be described later, the conductivity at the time of use is not impaired. Further, D5Q is a volume cumulative particle diameter measured by a laser diffraction scattering type particle size distribution measuring apparatus or the like. Further, the copper powder for the conductive paste of the present invention is preferably not only effective in miniaturizing the particles but also in characteristics of a narrow particle size distribution and a small amount of coarse particles. 5至左右。 The particle size distribution, the coefficient of variation (SD / D5 〇) obtained by D5 〇 and the standard deviation value SD is 0. 2 to 0.6 or so. In the case of such a copper powder, when it is used for a conductive material of a conductive paste or the like, the dispersibility in conductivity depletion can be improved, which is very preferable. Further, in the case of coarse particles, when the Dso of the copper powder obtained by the gas atomization method is about 5 /z m to 25 // m, Dg can be obtained. Become around 10 // m to 40 /z m. Further, when the Dsd of the copper powder obtained by the water atomization method is from about 1 /z m to about 5 /z m, D9G can be made to be about 5 to 10 / / m. In the case of such a copper powder, when it is used for a conductive material of a conductive paste or the like, the reliability of the microcircuit is excellent, which is very preferable. In addition, the copper powder for the conductive paste of the present invention, in addition to Bi, preferably contains O. Olatm% to 0.3 atm%, more preferably 0.02 atm% to 0. latm% of P ( phosphorus). If Bi and P coexist in the copper powder and are within such a specific amount, not only the particle size is small, the oxidation resistance is not impaired, and the variation in shape and particle size is small and is 7 322226 201209850 low. The characteristics of the oxygen concentration are also more pronounced. Further, p is preferably a metal phase uniformly distributed inside the particles. Further, the ratio of the steel powder for the conductive paste of the present invention is preferably 4 to 200, more preferably 黯100. If the ratio of Μ/P is within such a range, it is easy to obtain a balance of small particle size, oxidation resistance, S conductivity, small variation in shape and particle size, and low oxygen concentration. Further, the steel powder for the conductive paste of the present invention preferably contains 0. la« to 10a, more preferably at. 5at· 5 atm%, most preferably 5. 5a to 3% of Ag. If it is such a specific amount, it is possible to further improve the conductivity while maintaining the conductive paste-like copper powder in an oxidation-resistant state, and also to reduce the cost. Further, 'Ag is preferably a metal phase uniformly distributed inside the particles. In addition, the copper powder for the conductive paste of the present invention preferably contains from 0. latm% to l〇atm%, more preferably 〇·5_ to 5_%, most preferably 〇. 5a to 3 atm%. Si. If it is within such a specific amount, the oxidation of copper powder can be further improved. Further, Si is preferably distributed in a metal phase uniformly distributed inside the particles. Further, the steel powder for the conductive paste of the present invention preferably contains preferably 0. lat turtle is preferably 〇 2 mystery to 8 annihilation, preferably la to 3 (four) In. If it is within such a specific amount, it is preferable to further improve the oxidation resistance of the copper powder. The H-core is preferably distributed in the metal phase inside the particles. Moreover, when the total amount of yttrium and yttrium is contained, it can be used as a conductive paste which is small in particle size, small in shape and reduced in variation, and which is excellent in oxidation resistance and more excellent in 322226 8 201209850 and more excellent in electrical conductivity. Copper powder. Further, although the copper powder for the conductive paste of the present invention can be expected to have an effect even if it is obtained by a wet reduction method, it is considered that the particle shape is uniform and the gas generation is small when used as a conductive paste. The advantage is preferably made by the atomization method. The atomization method includes a gas atomization method and a water atomization method. However, if the particle shape is to be uniformized, the gas atomization method may be selected. If the particle size is to be miniaturized, the water atomization method may be selected. Further, among the atomization methods, those obtained by a high pressure atomization method are preferred. It is preferable that the copper powder particles obtained by the high pressure atomization method are more uniform or smaller. The gas pressure of about 1. 5MPa to 3MPa is used in the gas atomization method, and the gas pressure is about 1.5 MPa to 3 MPa. The method of atomization. Further, the copper powder for the conductive paste of the present invention has a weight change rate (Tg (%)) / specific surface area (SSA) at 240 ° C and 600 ° C as measured by a thermogravimetric / differential thermal analyzer. The difference (hereinafter referred to as Δ (TG/SSA)) is 1°/. It is preferably from m/cm3 to 30%/m2/cm3, preferably from 1%/m2/cm3 to 25%/m2/cm3. According to the characteristic value of Δ(Τ6/58Α), the oxidation resistance of the copper powder can be observed. Further, the temperature region of 240 ° C to 600 ° C is a heating temperature region when a mainstream conductive paste such as a conductive paste for external electrode firing of a ceramic capacitor is used, and oxidation resistance is important in this region. When Δ (Τϋ / SSA) is within the above preferred range, the oxidation resistance is sufficiently exhibited, and the south conductivity is also suitably ensured. S, 9 322226 201209850 In addition, the copper powder for the conductive paste of the present invention may further contain Ni, Al, Ti, Fe, Co, Cr, Μη, Mo, W, Ta, Zr, Mb, B, Ge, Sn. In addition, at least one or more of the elemental components of Zn and the like enhance the effects of various characteristics required for the conductive paste, such as a reduction in melting point and a improvement in sinterability. The amount of addition of these elements to copper is appropriately set depending on the conductivity characteristics or other various characteristics of the elements to be added, but is usually about 0.001% by mass to about 2% by mass. Further, the shape of the copper powder for the conductive paste of the present invention is preferably in the form of particles, and more preferably in the form of a sphere. Here, the term "granular" means that the aspect ratio (the average length is divided by the average short diameter) is from 1 to 1.25 and the shape is uniform, and the aspect ratio is from 1 to 1. The shape of 1 or so is especially called "spherical". Furthermore, the state in which the shapes are inconsistent refers to an indefinite shape. The copper powder in such a granular form is less entangled with each other, and when it is used for a conductive material of a conductive paste or the like, the dispersibility in the conductive paste is improved, which is very preferable. Further, the copper powder for a conductive paste of the present invention can be surely ensured conductivity by setting the oxygen concentration to 30 ppm to 2500 ppm, thereby becoming a conductive material suitable for a conductive paste. Next, a preferred specific manufacturing method of the copper powder for the conductive paste of the present invention will be described. The copper powder for a conductive paste of the present invention can be produced by adding a predetermined amount of a Bi component in the form of a mother alloy or a compound in molten copper, followed by powdering by a predetermined atomization method. According to the above manufacturing method, it is possible to produce a copper powder which is a copper powder having a small particle size of 10 322226 201209850 but which is still undamaged in oxidation resistance and electrical conductivity, and has a small variation in shape and particle size and is low in content. Oxygen concentration. Although the reason for this is not clear, it is presumed that the Bi added to the molten copper or the copper alloy captures oxygen in the copper powder particles to the extent that the conductivity is not impaired, thereby suppressing oxidation. Further, it is presumed that, in addition to the addition of the Bi component, when the P component is further added, the surface tension of the molten metal at the time of atomization can be lowered, and the particle shape can be appropriately stratified and deoxidized in the molten metal. Addition of the P component In the same manner as the Bi component, a predetermined amount of the P component may be added to the molten copper in the form of a master alloy or a compound. Further, by further containing an Ag component in addition to the Bi component, the emulsification of the copper powder can be ensured and the conductivity of the south can be further improved. Further, by further containing the Si component and the I η component in addition to the component B i , the oxidation resistance of the copper powder can be further improved. Further, in the above production method, it is preferred to employ a high pressure atomization method for the reasons explained above. However, compared with the gas atomization method, in the water atomization method, the content of the additive component other than copper may be low, so it is necessary to add it to the target copper powder in the case of Bi. 1 to 10 times the amount is 1 to 100 times when the component is P, 1 to 10 times when the component is Ag, and 1 to 10 times when the component is Si, when the component is In Then add 1 to 10 times the amount. Further, in the above production method, the reduction treatment may be performed after the atomization. By this reduction treatment, the oxygen concentration on the surface of the copper powder which is easily oxidized can be further reduced. Here, from the viewpoint of workability, the above-mentioned reduction S: 11 322226 201209850 treatment is preferably carried out by gas reduction. The gas system for reduction treatment is particularly advantageous, and examples thereof include hydrogen gas, ammonia gas, and butyl (tetra). Further, the above reduction treatment is preferably carried out at a temperature of 15 (rCl3 () (the temperature of rc is preferably from 17 to 21 generations. The reason is: if the above temperature is less than 150 Torr, the reduction rate It is slow and cannot fully express the treatment effect; if the above temperature exceeds 30 (TC, there is a tendency to cause aggregation and sintering of copper powder; if the above temperature is 17 (^ to 21 generations, it is possible to efficiently reduce the oxygen concentration) On the one hand, the aggregation and sintering of the copper powder are surely suppressed. Further, in the above-mentioned manufacturing method, it is preferable to classify the powder after the powder, and the classification can be carried out by using an appropriate classification device in such a manner that the particle size of the target is centered. The coarse powder and the fine powder are separated from the obtained steel powder, and are easily carried out. Here, it is preferable to classify the coefficient of variation (10) 先前 previously described as 〇·2 to 〇·6. The conductive paste containing the copper powder for the conductive paste of the present invention prepared by blending various additives such as an epoxy resin and a curing agent, etc., as described above, is still small in size due to the small size of the steel powder. Obtain It has a small balance between oxidation resistance and electrical conductivity, and has a small variation in shape and a low oxygen concentration. Therefore, it can be used extremely well for forming an external electrode for a conductor circuit or a multilayer ceramic capacitor by a screen printing addition method. The conductive material of the conductive paste for various electrical contact members, etc. In addition, the copper powder for the conductive paste of the present invention can also be used for: internal electrodes of an organic ceramic capacitor, an inductor or a temporary storage ρ (register), etc. Wafer parts; single-plate capacitor electrode, button capacitor electrode, 322226 12 201209850 Know the October multilayer substrate, ceramic (LTCC, Low Temperature Cofired Ceramics 'multi-temperature co-fired ceramic) multilayer substrate, flexible printed circuit board (FPC), antenna switch Modules and groups such as antenna switch module, PA (Power Amplifier 'Power Amplifier) module or high-frequency active filter; electromagnetic shielding film for PDP front and back panels or PDP color niter Crystalline solar cell surface electrode and back extraction electrode, V electrical adhesive, emi (Electromagnetic Interference) shielding, RF-ID (Ra Dio Frequency-Identification, ..., line radio frequency identification), and membrane switch (membrane SWltch) such as PC keyboard, anisotropic conductive film (ACF/ACP), etc. The following 'more details on the following examples and comparative examples (Embodiment 1) The gas chamber of the gas atomizing device (manufactured by Nisshin Kasei Co., Ltd., NEVA-GP2 type) and the raw material dissolution chamber are filled with nitrogen gas to form a carbon crucible located in the dissolution chamber. The raw material was heated and dissolved to obtain a molten product (2.6 g of metal crucible was added to the molten metal in which electrolytic copper was dissolved, and 8 g of molten metal was prepared and stirred well). Then, the molten metal was sprayed at 1,250 Å and 3. MPa from a nozzle having a diameter of 015, and copper powder contained in the inside of the particles was obtained. Then, using the 53#m test _ ((10) t h (four)), the sieve was used, and the _ output was used as the final copper powder. The characteristics of the obtained copper powder are shown in Table 2. (Examples 2 to 4) A copper powder was obtained in the same manner as in Example 1 except that the metal addition amount was changed as shown in Table 1.
S 322226 13 201209850 •(實施例5至11) 除了在金屬鉍以外也按照表1所示添加銅一磷母合金 (磷等級15質量％)以外，其餘進行與實施例1同樣之操作， 而得到銅粉。 (實施例12及13) 除了在金屬鉍和銅一磷母合金以外再按照表1所示添 加電解銀以外，其餘進行與實施例1同樣之操作，而得到 銅粉。 (實施例14) 除了在金屬鉍和銅一磷母合金以外再按照表1所示添 加金屬矽（日本金屬化學工業（股）製NIKSIL)以外，其餘進 行與實施例1同樣之操作，而得到銅粉。 (實施例15) 除了在金屬鉍以外再按照表1所示添加金屬銦以外， 其餘進行與實施例1同樣之操作，而得到銅粉。 (實施例16) 除了按照表1所示添加金屬鉍及/或銅一磷母合金之 添加量以外，其餘進行與實施例1同樣之操作，而得到銅 粉。 14 322226 201209850 [表1 ]S 322226 13 201209850 • (Examples 5 to 11) The same operation as in Example 1 was carried out except that a copper-phosphorus mother alloy (phosphorus grade: 15% by mass) was added as shown in Table 1 except for the metal crucible. Copper powder. (Examples 12 and 13) Copper powder was obtained in the same manner as in Example 1 except that electrolytic silver was added in addition to the metal lanthanum and the copper-phosphorus mother alloy. (Example 14) The same procedure as in Example 1 was carried out except that a metal ruthenium (NIKSIL, manufactured by Nippon Metal Chemical Co., Ltd.) was added in addition to the metal ruthenium and the copper-phosphorus mother alloy. powder. (Example 15) A copper powder was obtained in the same manner as in Example 1 except that metal indium was added in addition to the metal crucible as shown in Table 1. (Example 16) A copper powder was obtained in the same manner as in Example 1 except that the addition amount of the metal ruthenium and/or the copper-phosphorus mother alloy was added as shown in Table 1. 14 322226 201209850 [Table 1]
322226 15 201209850 和In係分別含於粒子内部。 (1) 銀、磷、銀、妙之含量 以酸將樣品溶解後’藉由ICP(Inductively Coupled Plasma，感應輕合電聚）進行分析。 (2) 氧濃度 藉由氧/氮分析裝置（堀場製作所股份有限公司製 「EMGA-520C型號）」）進行分析。結果如表2所示。再者， 為了評估經時性的耐氧化性劣化，也使用山陽精工製之SK —8000，以氣體流量8L/分鐘，分別以分鐘升溫至 200°C，然後保持1小時後’測定樣品之氧濃度。結果如表 5所示。 (3) MTG/SSA) 使用示差熱/熱重量同時測定裝置（TG/DTA)(SII 製，TG/DTA6300高溫型）（升溫速度：i〇〇c/分鐘，氣體 流量：200mL/分鐘）測定在40Ϊ至60(TC之Tg(°/〇，求出 在240°C至600°C之重量變化率之差。另一方面，比表面積 係以由粒度測定裝置（日機裝製，Micr〇trac MT— 300型） 測得之粒度分布所求出，且是以算術之方式從兩者之數值 求出。再者，各溫度之TG/SSA(%/m2/cm3)如表3所示， 將該TG/SSA除以比較例1之純銅粉之TG/SSA(表中記載 為[TG/SSA]cu)的結果係如表4所示。 (4) 粒子形狀 藉由掃描型電子顯微鏡觀察。 (5) Ds〇 ' SD > SD/Dso 16 322226 201209850 將樣品（0.2g)加入純水（lOOmL)中，並照射超音波（3 / 分鐘）使其分散後，藉由粒度分布測定裝置（曰機裝股份有 限公司製「Microtrac」（商品名）FRA(型號）），分別求出體 積累積粒徑D5。及標準偏差值SD以及變異係數（SD/D5。）。 (6)粉體電阻 將樣品15g加入筒狀容器中並以壓力40xl06(408kgf /cm2)進行壓縮成形而形成測定樣品後，藉由Loresta AP 及LorestaPD-41型（皆為三菱化學（股）公司製）進行測定。 17 322226 201209850 CO CO in 00 CO 〇〇 σ» ΙΓ3 05 ς〇 CO Ο) CSJ CM CSJ l£5 〇〇 05 CO σ> oo CO =1 ai CO s CO CO 00 CO CO CvJ CO — CO 卜· ΙΛ CO cd CVJ Γ-* cr> 〇> CVJ od CO σ> LO σ> 却 C*3 ΙΛ ΙΛ oo LO in s 05 CO m s 写 3 Cvj ΙΛ CO ΪΛ 〇〇 oo g Γϊ CV3 ΙΛ o 〇 o ο 〇 〇 ο o ο 〇 d 〇 ο o ο ο C> Ο o /~s oo oo CO 9.49 CD 03 CO oo co 05 CO oo η ΟΟ Cg s v_^ cj o CO tri 〇 od cd ο c=> ο od ci ύ ?〇 - /—s CO o σ> 05 m CO 节 ΟΟ LTi ΙΛ CN3 CvJ 廿 s CO cn C^J oo oo 卜 oo CM CO CO CO m 05 s^· CO s CO ο ?0 od Ο S LT5 s CvJ CO CO od CM esa CO Vf <D K-<D 屮 资 资 怼 背 资 /**N CO CNJ σ> 卜 1Λ ΙΛ 卜 ο CM 卜 卜 Ο CO 〇〇 σ> iri kS E Qi CO 令 σ> 〇> CM CO S Ο CO CNJ cvi ΙΟ CVJ od ΟΟ CO — cd CO σό CO CM OO fM Tji uo oo CO (Μ 03 兮 CO 〇〇 g /-N S CO CO in LT> e=> (Ν» 〇〇 ΟΟ C*3 呀 os CO ΙΛ 05 05 LTD CSJ ιΛ 却 Γ ΟΟ 05 CO t— ΙΛ Ο CO 〇> CO 05 CO o o ws CO CM ο CM oi ο CM CS3 CO Ο OJ (Μ 卜· CSJ CO ΟΟ ir> CN3 CO Cvi s CO Cvl 05 CO CM CO CO CO < Bi/P /-~N CD Ο 〇0 CO Ο Ο CM 卜 vS 1 1 1 <=ί § od cn σ> ΙΛ g CN3 g eg ΟΟ 1 o 1 1 〇 1 1 1 1 1 1 l 1 1 ιΛ OJ ο 1 1 l 1 Ίλ 1 I 1 I 1 1 1 1 1 i 1 分 ο 1 1 t ί 1 含量（atm% b〇 1 1 1 t 1 i 1 1 i Lf3 o in O 1 1 1 t 1 tr— o O σ> 却 ο 03 03 ιΛ 05 σ> m ο 寸 s ο CO CO σί ο Ln ο 05 〇) 05 〇 03 o (Μ in CO o 1 1 Ο ο o o Qu 1 i 1 〇〇 ο ο ο m ο ο 03 o o e<j 1Γ3 G> 〇 m ο ο ο C3 ο 05 ς=> ο ο 1 oo o o c- 寸 Ο Ο 1 1 ο m ο ο 1 t- o o C-J cr> ΙΛ CO r- oo 05 ο 二 Csl CO in 一 Cv3 CO τ τ 4£) «5· 运 4£) 运 Λΰ « 18 322226 201209850 [表3] TG/SSA(%/m7cm3) 200°C 240〇C 300°C 400°C 500°C 600°C 實施例1 0. 205 0. 405 1. 408 4. 901 9. 681 23.726 實施例2 0. 178 0. 329 1. 048 3. 783 8. 460 20. 880 實施例3 0. 292 0. 644 1. 907 6. 478 12. 471 21.739 實施例4 0. 269 0. 726 2. 492 6. 440 10.834 13. 542 實施例5 0. 197 0. 535 1. 710 4. 958 10.281 21. 916 實施例6 0. 230 0. 646 1. 958 5. 531 11.641 21. 582 實施例7 0. 291 0. 727 2. 187 6. 756 13.290 23. 288 實施例8 0. 300 0. 716 2. 154 7. 127 13.244 21.705 實施例9 0. 303 0. 851 2. 330 6. 689 10.635 12.998 實施例10 0. 375 0. 764 2. 065 7. 311 15.237 28.280 實施例11 0. 349 0. 656 1. 872 6. 441 12.806 23. 795 實施例12 0. 333 0. 568 1. 524 4. 885 11.181 26.442 實施例13 0. 290 0. 638 1. 705 5. 152 11.707 27. 032 實施例14 0. 359 0. 545 1. 096 4. 305 11.676 20. 717 實施例15 • 0.165 0. 434 1. 488 4. 017 9. 075 22. 486 比較例1 0. 239 0. 926 4. 324 15.838 28. 166 39.854 比較例2 0. 560 1. 173 2. 093 4. 644 11.582 33.811 比較例3 0. 521 1. 254 4. 693 15. 810 23.853 32. 439 比較例4 0. 631 1. 228 2. 103 4. 718 12.233 32.255 19 322226 201209850 [表4] [TG/SSA]/[TG/SSA]c„ 200°C 240 °C 300°C 400°C 500°C 600°C 實施例1 0. 850 0. 437 0. 323 0. 309 0. 344 0. 594 實施例2 0. 732 0. 354 0. 241 0. 239 0. 300 0. 525 實施例3 0. 213 0. 694 0. 437 0. 408 0. 443 0. 545 實施例4 0. 751 0. 790 0. 706 0. 445 0. 400 0. 354 實施例5 0. 827 0. 586 0. 394 0. 313 0. 364 0. 549 實施例6 0. 965 0. 707 0. 451 0. 349 0. 413 0. 541 實施例7 1. 222 0. 796 0. 504 0. 426 0. 471 0. 583 實施例8 1. 260 0. 784 0. 496 0. 449 0. 469 0. 544 實施例9 0. 847 0. 927 0. 660 0. 463 0. 393 0. 339 實施例10 1. 574 0. 837 0. 476 0. 461 0. 540 0. 708 實施例11 1. 465 0. 719 0. 431 0. 406 0. 454 0. 596 實施例12 1. 398 0. 622 0. 351 0. 308 0. 396 0. 662 實施例13 1. 216 0. 698 0. 393 0. 325 0. 415 0. 677 實施例14 1. 504 0. 596 0. 254 0. 272 0. 415 0. 519 實施例15 0. 689 0. 475 0. 344 0. 254 0. 322 .0. 564 比較例1 1 1 1 1 1 1 比較例2 2. 347 1. 166 0. 484 0. 293 0. 411 0. 848 比較例3 2. 125 1. 326 1. 081 0. 991 0. 847 0. 811 比較例4 2. 589 1. 319 0. 485 0. 296 0. 433 0. 807 由表2至4所示得知，與不含鉍、或不含鉍及磷之比 較例相比，實施例之銅粉之财氧化性較優良，特別是在240 °C至600°C之溫度區域中為優良。 並且，如表2所示，實施例之銅粉係形狀為球狀且形 狀無變異者，並且其尺寸也為微小。特別是，鉍之含量越 20 322226 201209850 多則所得之銅粉越微粒化。 氧化之環境 經時性的耐 [表5]322226 15 201209850 and In are contained inside the particles, respectively. (1) Silver, phosphorus, silver, and wonderful content After the sample was dissolved with an acid, it was analyzed by ICP (Inductively Coupled Plasma). (2) Oxygen concentration The analysis was carried out by an oxygen/nitrogen analyzer ("EMGA-520C model" manufactured by Horiba, Ltd.). The results are shown in Table 2. In addition, in order to evaluate the deterioration of oxidation resistance over time, SK-8000 manufactured by Sanyo Seiko Co., Ltd. was used to measure the oxygen of the sample after heating to 200 ° C in minutes at a gas flow rate of 8 L/min. concentration. The results are shown in Table 5. (3) MTG/SSA) Measured by differential heat/thermal weight simultaneous measurement device (TG/DTA) (SII system, TG/DTA6300 high temperature type) (heating rate: i〇〇c/min, gas flow rate: 200 mL/min) From 40 Ϊ to 60 (Tg of TC (°/〇, the difference in weight change rate between 240 ° C and 600 ° C is determined. On the other hand, the specific surface area is determined by the particle size measuring device (daily machine, Micr〇) Trac MT—300 type) The measured particle size distribution is obtained by arithmetic calculation from the values of the two. Furthermore, the TG/SSA (%/m2/cm3) of each temperature is shown in Table 3. The TG/SSA was divided by the TG/SSA of the pure copper powder of Comparative Example 1 (described as [TG/SSA] cu in the table) as shown in Table 4. (4) Particle shape by scanning electron microscope (5) Ds〇' SD > SD/Dso 16 322226 201209850 The sample (0.2g) was added to pure water (100 mL) and irradiated with ultrasonic waves (3 / min) to disperse and determined by particle size distribution. The device (Microtrac (trade name) FRA (model) manufactured by Seiko Co., Ltd.) was used to obtain a volume cumulative particle diameter D5, a standard deviation value SD, and a coefficient of variation (SD/D5). (6) Powder resistance 15 g of the sample was placed in a cylindrical container and compression-molded at a pressure of 40×10 6 (408 kgf /cm 2 ) to form a measurement sample, which was obtained by Loresta AP and Loresta PD-41 (all of which are Mitsubishi Chemical Corporation). Manufactured by the company. 17 322226 201209850 CO CO in 00 CO 〇〇σ» ΙΓ3 05 ς〇CO Ο) CSJ CM CSJ l£5 〇〇05 CO σ> oo CO =1 ai CO s CO CO 00 CO CO CvJ CO — CO 卜· ΙΛ CO cd CVJ Γ-* cr>〇> CVJ od CO σ> LO σ> but C*3 ΙΛ ΙΛ oo LO in s 05 CO ms Write 3 Cvj ΙΛ CO ΪΛ 〇〇oo g Γϊ CV3 ΙΛ o 〇o ο 〇〇ο o ο 〇d 〇ο o ο ο C> Ο o /~s oo oo CO 9.49 CD 03 CO oo co 05 CO oo η ΟΟ Cg s v_^ cj o CO tri 〇od cd ο c=> ο od ci ύ ?〇- /-s CO o σ> 05 m CO throttling LTi ΙΛ CN3 CvJ 廿s CO cn C^J oo oo oo CM CO CO CO m 05 s^· CO s CO ο ?0 od Ο S LT5 s CvJ CO CO od CM esa CO Vf <D K-<D 屮 屮背资/**N CO CNJ σ> 卜1Λ 卜 οο CM Bu Bu Ο CO 〇〇σ> iri kS E Qi CO σ gt> 〇> CM CO S Ο CO CNJ cvi ΙΟ CVJ od ΟΟ CO — cd CO ό ό CO CM OO fM Tji uo oo CO (Μ 03 兮CO 〇〇g /-NS CO CO in LT>e=> (Ν» 〇〇ΟΟ C*3 呀 os CO ΙΛ 05 05 LTD CSJ ιΛ Γ Γ ΟΟ 05 CO t— ΙΛ Ο CO 〇> CO 05 CO oo ws CO CM ο CM oi ο CM CS3 CO Ο OJ (Μ Bu· CSJ CO ΟΟ ir> CN3 CO Cvi s CO Cvl 05 CO CM CO CO CO < Bi /P /-~N CD Ο 〇0 CO Ο Ο CM 卜 vS 1 1 1 <=ί § od cn σ> ΙΛ g CN3 g eg ΟΟ 1 o 1 1 〇1 1 1 1 1 1 l 1 1 ιΛ OJ ο 1 1 l 1 Ίλ 1 I 1 I 1 1 1 1 1 i 1 分 ο 1 1 t ί 1 Content (atm% b〇1 1 1 t 1 i 1 1 i Lf3 o in O 1 1 1 t 1 tr— o O σ> but ο 03 03 ιΛ 05 σ> m ο inch s ο CO CO σί ο Ln ο 05 〇) 05 〇03 o (Μ in CO o 1 1 Ο ο oo Qu 1 i 1 〇〇ο ο ο m ο ο 03 oo e<j 1Γ3 G> 〇m ο ο ο C3 ο 05 ς=> ο ο 1 oo oo c- inch Ο Ο 1 1 ο m ο ο 1 t- oo CJ cr> ΙΛ CO r- oo 05 ο II Csl CO in a Cv3 CO τ τ 4£) «5· 运4£) Λΰ « 18 322226 201209850 [Table 3] TG/SSA (%/m7cm3) 200°C 240〇C 300°C 400°C 500°C 600°C Implementation Example 1 0. 205 0. 405 1. 408 4. 901 9. 681 23.726 Example 2 0. 178 0. 329 1. 048 3. 783 8. 460 20. 880 Example 3 0. 292 0. 644 1. 907 6. 478 12. 471 21.739 Example 4 0. 269 0. 726 2. 492 6. 440 10.834 13. 542 Example 5 0. 197 0. 535 1. 710 4. 958 10.281 21. 916 Example 6 0 230 0. 646 1. 958 5. 531 11.641 21. 582 Example 7 0. 291 0. 727 2. 187 6. 756 13.290 23. 288 Example 8 0. 300 0. 716 2. 154 7. 127 13.244 21.705 Example 9 0. 303 0. 851 2. 330 6. 689 10.635 12.998 Example 10 0. 375 0. 764 2. 065 7. 311 15.237 28.280 Example 11 0. 349 0. 656 1. 872 6. 441 12.806 23. 795 Example 12 0. 333 0. 568 1. 524 4. 885 11.181 26.442 Example 13 0. 290 0. 638 1 705 5. 152 11.707 27. 032 Example 14 0. 359 0. 545 1. 096 4. 305 11.676 20. 717 Example 15 • 0.165 0. 434 1. 488 4. 017 9. 075 22. 486 Comparative example 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 439 Comparative Example 4 0. 631 1. 228 2. 103 4. 718 12.233 32.255 19 322226 201209850 [Table 4] [TG/SSA]/[TG/SSA]c„ 200°C 240 °C 300°C 400°C 500 ° C 600 ° C Example 1 0. 850 0. 437 0. 323 0. 309 0. 344 0. 594 Example 2 0. 732 0. 354 0. 241 0. 239 0. 300 0. 525 Example 3 0 。 。 。 。 。 。 。 。 394 0. 313 0. 364 0. 549 Example 6 0. 965 0. 707 0. 451 0. 349 0. 413 0. 541 Example 7 1. 222 0. 796 0. 504 0. 426 0. 471 0. 583 Example 8 1. 260 0. 784 0. 496 0. 449 0. 469 0. 544 Example 9 0. 847 0. 927 0. 660 0. 463 0. 393 0. 339 Example 10 1. 574 0. 837 0. 476 0. 461 0. 540 0. 708 Real Example 11 1. 465 0. 719 0. 431 0. 406 0. 454 0. 596 Example 12 1. 398 0. 622 0. 351 0. 308 0. 396 0. 662 Example 13 1. 216 0. 698 0. 393 0. 325 0. 415 0. 677 Example 14 1. 504 0. 596 0. 254 0. 272 0. 415 0. 519 Example 15 0. 689 0. 475 0. 344 0. 254 0 322 .0. 564 Comparative Example 1 1 1 1 1 1 1 Comparative Example 2 2. 347 1. 166 0. 484 0. 293 0. 411 0. 848 Comparative Example 3 2. 125 1. 326 1. 081 0. 991 0. 847 0. 811 Comparative Example 4 2. 589 1. 319 0. 485 0. 296 0. 433 0. 807 As shown in Tables 2 to 4, with or without antimony and phosphorus In comparison with the comparative examples, the copper powder of the examples was excellent in oxidation property, and particularly excellent in a temperature range of 240 ° C to 600 ° C. Further, as shown in Table 2, the copper powder of the example has a spherical shape and a shape without variation, and its size is also small. In particular, the more the content of bismuth is 20 322226 201209850, the more the copper powder obtained is more micronized. Oxidation environment Time-dependent resistance [Table 5]
此外，如表5所示，當長時間保持在容易 夺/、比較例之鋼粉相比，實施例之鋼粉之 氧化性為顯著地較優良。 如表6所示’與比較例之銅粉相比’實施例之 銅粉係未觀致 白H音A到體積電阻率有太大的變化，而確認其具有 良好的導電性。 21 322226 201209850 [表6] 含量（atm%) 體積電阻率（Ω . cm) P Bi Ag Si In 實施例2 — 0. 51 一 一 — 2. lxlO"3 實施例5 0. 048 0. 49 — — — 3. OxlO'3 實施例12 一 0. 49 0. 51 — — 1·4x10—3 實施例13 0. 048 0. 49 0. 51 — - 2.OxlO3 實施例14 0. 047 1. 02 -' 2. 04 - 4_ OxlO-3 實施例15 一 0. 25 — - 0. 25 3. 5xl0'3 比較例1 — — — — — 0. 9xl0'3 比較例2 0. 050 — - — — 0. 9xl0'3 【圖式簡單說明】 第1圖係表示實施例2之SEM觀察結果之照片。 【主要元件符號說明】 無。 22 322226Further, as shown in Table 5, the oxidizing property of the steel powder of the example was remarkably excellent as compared with the steel powder of the comparative example which was easily retained for a long period of time. As shown in Table 6, 'Compared with the copper powder of the comparative example', the copper powder of the Example showed no significant change in the volume resistivity, and it was confirmed that it had good conductivity. 21 322226 201209850 [Table 6] Content (atm%) Volume resistivity (Ω. cm) P Bi Ag Si In Example 2 - 0. 51 One-one - 2. lxlO"3 Example 5 0. 048 0. 49 — — — 3. OxlO′3 Example 12 A 0. 49 0. 51 — — 1·4×10—3 Example 13 0. 048 0. 49 0. 51 — — 2.OxlO3 Example 14 0. 047 1. 02 -' 2. 04 - 4_ OxlO-3 Example 15 A 0. 25 — - 0. 25 3. 5xl0'3 Comparative Example 1 — — — — — 0. 9xl0'3 Comparative Example 2 0. 050 — — — — 0. 9xl0'3 [Simplified description of the drawings] Fig. 1 is a photograph showing the results of SEM observation of Example 2. [Main component symbol description] None. 22 322226