201202447 、 六、發明說明： 【發明所屬之技術領域】 '本發明係關於導電性膏（Paste)用銅粉及使用該銅粉 之導，性膏。詳細而言，係關於可適用於電路的形成或陶 瓷電谷器（ceramic capaci t〇r)的外部電極的形成等方面 之導電性膏’特別關於可適用於作為燒成型導電性膏之導 電填充劑（filler)。 【先前技術】 導電性膏係在由樹酯系黏合劑（b i n d e r )與溶媒所構成 之媒液（vehicle)中分散有導電填充劑μ之流動性組成 物’其廣泛地使用於電路的軸或喊電容器之外部電極 的形成等方面。 此種導電性膏分為下述2類型：藉由樹脂的硬化而壓 口導電性填充劑以確保導通之樹脂硬化型、以及藉由燒成 而將有機成分揮發並燒結導電性填充劑以確保導通之燒成 型。 前者之樹脂硬化型導電性膏，一般為含有由金屬粉末 所構成之導電填充劑與由環氧樹脂等熱硬化樹脂所構成之 有機黏合劑的膏狀組成物，藉加熱而使熱硬化樹脂與導電 填充劑一同硬化收縮，並經由樹脂而使導電填充劑彼此壓 口且形成接觸狀態’以確保導通性。此樹脂硬化型導電膏 可在loot：到最高200°C等較低溫的區域做處理，因熱傷害 較少’故主要使用於印刷配線基板及不耐熱之樹脂基板等。 另一方面，後者之燒成型導電性膏，一般為使導電填 3 323054 201202447 充劑（金屬粉末）與玻璃介質（glass frit)分散於有機媒液 中所形成之膏狀組成物’藉由在500至900°C燒成而將有 機媒液揮發，復使導電填充劑燒結以確保導通性。此時， 玻璃介質具有使此導電膜接著於基板的作用，有機媒液係 以作為用以使金屬粉末及玻璃介質變成可印刷者之有機液 體媒質而發揮作用。 燒成型導電膏因其燒成溫度高，故不可使用於印刷配 線基板及樹脂材料，但因經燒結而使金屬成為一體化，故 可達成低電阻化，而使用於例如積層陶瓷電容器 (laminated ceramic capacitor)之外部電極等。201202447, VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a copper powder for conductive paste and a conductive paste using the same. More specifically, it relates to a conductive paste which is applicable to formation of a circuit or formation of an external electrode of a ceramic electric ceramic device, and the like, and particularly relates to a conductive material which can be applied as a conductive paste for baking. Filler. [Prior Art] The conductive paste is a fluid composition in which a conductive filler μ is dispersed in a vehicle composed of a resin adhesive and a solvent, and is widely used in a shaft or shout of a circuit. The formation of external electrodes of the capacitor and the like. Such a conductive paste is classified into two types: a resin-hardened filler which is pressed by a resin to ensure conduction, and an organic filler is volatilized by firing and a conductive filler is sintered to ensure that the conductive paste is cured. Conductive molding. The resin-curable conductive paste of the former is generally a paste-like composition containing an electrically conductive filler composed of a metal powder and an organic binder composed of a thermosetting resin such as an epoxy resin, and the thermosetting resin is heated by heating. The conductive filler hardens and shrinks together, and the conductive fillers are pressed against each other via the resin to form a contact state to ensure conductivity. This resin-curable conductive paste can be processed in a lower temperature region such as loot: up to 200 °C, and is less likely to be damaged by heat. Therefore, it is mainly used for printed wiring boards and heat-resistant resin substrates. On the other hand, the latter calcined conductive paste is generally a paste-like composition formed by dispersing a conductive filler (metal powder) and a glass frit in an organic vehicle liquid. The organic vehicle liquid is volatilized at 500 to 900 ° C to anneal the conductive filler to ensure conductivity. At this time, the glass medium functions to adhere the conductive film to the substrate, and the organic medium functions as an organic liquid medium for making the metal powder and the glass medium into a printable person. Since the fired molding paste has a high firing temperature, it cannot be used for a printed wiring board or a resin material. However, since the metal is integrated by sintering, it is possible to achieve a low resistance and is used, for example, in a laminated ceramic capacitor (laminated). External electrode of ceramic capacitor, etc.
不論樹脂硬化型導電膏及高溫燒成型導電膏，其中之 導電填充劑在以往係多使用銀粉，但以使用銅粉者較為便 宜，且難以發生遷移（migration)，耐焊接性亦佳，故使用 銅粉之導電性膏係持續在泛用化中。但是，銅粉容易於空 氣中氧化，故有銅粉表面之氧化膜造成接續電阻增大的課 題。 L 在此，有關於導電性膏用銅粉，至今已提出各種防止 銅粉表面氧化的方法。 例如專利文獻1提出在導電性膏内調配具有還原作用 之物質，以抑制銅表面的氧化。 此外，專利文獻2提出以具有耐氧化性的銀塗佈於粒 子表面，專利文獻3提出以無機氧化物塗佈。 專利文獻4提案一種導電材膏用銅合金，其係在主成 分之銅中添加Zn與Sn中之至少一者而進行合金化的銅合 4 323054 201202447 金粉，該銅合金粉中之Zn及/或Sn之含量為0. 02至1. 2 質量％，且該銅合金粉含有0. 005至0. 05質量％的P。 此外，專利文獻5提案一種導電性膏用銅粉，其係粒 子細微且不損及其耐氧化性及導電性之平衡的導電性膏用 銅粉，其特徵為在粒子内部含有0. 07原子％至10原子％的 A1。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開平8-73780號公報 [專利文獻2]曰本特開平10-152630號公報 [專利文獻3]日本特開2005-129424號公報 [專利文獻4]日本特開2009-99443號公報 [專利文獻5]日本特開2009-235556號公報 【發明内容】 (發明欲解決之課題） 如前述，至今有藉由在銅中添加各種金屬元素而提高 銅粉的耐氧化性之各種提案，但若添加不純物 (impurity)，則相較於未添加之銅粉，有導電性降低的課 題。 在此，本發明欲提供一種新穎的導電性膏用銅粉，其 能維持耐氧化性且可得到良好的導電性。 (解決課題之方法） 本發明提案一種導電性膏用銅粉，其為含有AK鋁）及 P(磷）之導電性膏用銅粉，其中，A1濃度係高於10. Oatm% 5 323054 201202447 且在65. Oatm%以下。 本發明之導電性膏用銅粉，其能維持耐氧化性且可 到良好的導電性。 于 在專利文獻5(日本特開2009-235556號，申請人：二 井金屬礦業股份公司）提出申請時，本發明者們認為若於銅 粉中添加超過10. Oatm%量的M，則不僅會損及導電性，且 因耐氧化性過強，而無法在大氣中燒成。但是，實際混合 於膏中並進行燒成的結果，發現含有範圍在高於1〇 〇的祕 且在65.〇atm°/Q以下之A1的摻有磷之銅粉，可在大氣中以 800 C至900 C左右燒成，且即使在如此之高·溫中亦可維持 耐氧化性，導電性亦優異。相較於r在銅中添加越多不純 物’則越會導致導電性降低」之技術常識，此結果實為令 人吃驚。 7 【實施方式】 其次，依據實施的型態例來說明本發明，但本發明並 不只限定於接下來所說明之實施型態。 〈導電性膏用銅粉〉 本實施形態之導電性膏用銅粉（以下稱為「本銅粉」） 係含有A1(铭）及P(轉）之導電性膏用銅粉。由於只要是含 有A1及p組成之銅粉即可，故亦可含有A1及p以外的金 屬元素，但典型上為Cu-P-Al型銅粉。 本銅粉除了含有A1(銘）及P(鱗）以外，亦可含有例如Regardless of the resin-curable conductive paste and the high-temperature fired conductive paste, among the conductive fillers, silver powder is often used in the past, but copper powder is cheaper, migration is difficult, and solder resistance is good. Conductive pastes using copper powder continue to be used in generalization. However, the copper powder is easily oxidized in the air, so that the oxide film on the surface of the copper powder causes an increase in the connection resistance. L Here, regarding copper powder for conductive paste, various methods for preventing surface oxidation of copper powder have been proposed so far. For example, Patent Document 1 proposes to mix a substance having a reducing action in a conductive paste to suppress oxidation of the copper surface. Further, Patent Document 2 proposes coating silver on a surface of a particle with oxidation resistance, and Patent Document 3 proposes coating with an inorganic oxide. Patent Document 4 proposes a copper alloy for a conductive material paste which is a copper alloy 4 323054 201202447 gold powder which is alloyed with at least one of Zn and Sn in copper of a main component, and Zn and/or in the copper alloy powder. 005至0. 05质量百分比的的。 P. The mass of the copper alloy is 0. 005 to 0. 05% by mass of P. Further, the patent document 5 proposes a copper powder for a conductive paste, which is a copper powder for a conductive paste which is fine and does not impair the balance between its oxidation resistance and electrical conductivity, and is characterized in that it contains 0.07 atom in the particle. % to 10 atom% of A1. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. 2009-235556 (Patent Document 5) JP-A-2009-235556 SUMMARY OF INVENTION [Problems to be Solved by the Invention] As described above, various metal elements have been added to copper by the present. There are various proposals for improving the oxidation resistance of copper powder. However, when an impurity is added, there is a problem that the conductivity is lowered as compared with the copper powder which is not added. Here, the present invention is intended to provide a novel copper powder for conductive paste which can maintain oxidation resistance and can obtain good electrical conductivity. The method of the present invention is a copper powder for a conductive paste, which is a copper powder for a conductive paste containing AK aluminum) and P (phosphorus), wherein the A1 concentration is higher than 10. Oatm% 5 323054 201202447 And below 65. Oatm%. The copper powder for conductive paste of the present invention can maintain oxidation resistance and can have good electrical conductivity. In the case of the application of the patent document 5 (Japanese Patent Laid-Open No. 2009-235556, the applicant: the company, the company, the company, the company), the inventors believe that if the amount of M of more than 10. Oatm% is added to the copper powder, not only will it be It is inferior in conductivity and is too resistant to oxidation and cannot be fired in the atmosphere. However, as a result of actually mixing in the paste and firing, it was found that the phosphorus-doped copper powder containing A1 in the range of more than 1 秘 and below 65. 〇 atm ° / Q can be in the atmosphere. It is fired at around 800 C to 900 C, and oxidation resistance is maintained even at such high temperatures and temperatures, and electrical conductivity is also excellent. This result is surprisingly compared to the technical common sense that the more impurities added to the copper in r are, the more the conductivity is reduced. [Embodiment] Next, the present invention will be described based on an embodiment of the embodiment, but the present invention is not limited to the embodiment described below. <Copper powder for conductive paste> The copper powder for conductive paste of the present embodiment (hereinafter referred to as "the present copper powder") contains copper powder for conductive paste of A1 (Ming) and P (Turn). As long as it is a copper powder containing a composition of A1 and p, it may contain a metal element other than A1 and p, but is typically a Cu-P-Al type copper powder. The copper powder may contain, for example, A1 (Ming) and P (Scale).
Ni、Ti、Fe、Co、Cr、Mg、Mn、Mo、W、Ta、In、Zr、Nb、 B Λ Ge、Sn、Zn、Bi等中之一種或由兩種以上之組合所構 323054 6 201202447 成之元素成分。 藉由添加此等元素，可調整導電性膏所要求之諸特 性，例如可降低熔點並使燒結性提昇等。 (A1濃度） 本銅粉的構絲子（町料「本銅餘子」）之Μ濃 度係高於10.0a城且在65. 0at祕以下，此特點為相當重 要0 若A1濃度高於！〇·〇_，即可有效地提升導電性。 具體而言，若由體積電阻值來看，可降低到低於ι 〇χΐ〇2 Ω .cm’特別是可降低到低於2 〇χ1(Γ3Ω .⑽。由於可如 此般地降減積電崎，故*需過度Μ地填充 保導通。 另一方面，若Α1濃度超過7〇. 〇_%，則可見溶點降 低’失去在高溫下之耐氧化效果，所以，在65鳥％以下 係相當重要。 如此，從降低體積電阻值的效果與維持在高溫下的耐 氧化性的觀點來看，本崎粒子之A1濃度較佳為 以上，其中更佳為3G.Gatm%以上，或是較佳為⑽〇atm% 以下’其中更佳為50. 〇atm%以下。 (P濃度） 本銅粉粒子之P(磷）濃度並無特別限定，較佳為含有 0.01至G.3Gatm%，特佳為utm%以上或〇.1Qatm%以下， 其中又以含有G· G2atm%以上或〇. Q6atm%以下的比例為佳。 若P(磷）含量在此範圍中，可達到粒度微細、具有耐 323054 201202447 氧化性、不損及導電性、使性狀與粒度的不一致性小、降 低氧濃度。 (D50) 本銅粉之D50,亦即以雷射繞射散射式粒度分布測定 法所測得之體積粒度分布之D50’從因微距化 等而有之微粉化之要求與因降低比電阻（sPecif ic resistance)之要求而進行南密度燒成的觀點來看，較佳為 〇. l//m至10/zra，特別是〇.3em以上或5.〇vm以下，其 中更佳為0. 5/im以上或3. 〇Μπι以下。 (粒子形狀） 本銅粉粒子可為昱粗狀，特別是球狀者，亦可為將球 狀粒子予以形狀加工者。 在此，「粒狀」係指縱橫比（asPect ratio，將平均長 直徑除以平均短直徑而抑的值）一致在1至1.25左右之形 狀’其中，縱橫比一致為1至丨.1左右之形狀特別稱為「球 狀」。另一方面，形狀不/致的狀態稱為「不定形狀」。 「粒狀」之銅粉的相互的集結為較少’當使用在導電 性膏之導電材料等時，因可提昇膏中的分散性，故為較佳。 (比表面積） 本銅粉粒子之BET比表面積（SSA)，從將燒結之開始溫 度予以適當調整的觀點來看，較佳為〇 4〇m7g至〇 75m〇 g，特別是0.45mVg以上或〇 7〇mVg以下，其中特佳 0. 50m /g 以上或 〇· 65m2/g 以下。 (氧濃度） 323054 8 201202447 一本銅叙之（最初）氧濃度較佳為800ppm至5000ppm。若 氧濃度在該範圍中，可使作為導電性膏之導電材料的導電 性及耐氧化性變更良好。 從該觀點來看，本鋼粉之（最初）氧濃度較佳為800ppm 至5000ppm，特別是1〇〇〇ppm以上或4〇〇〇ppm以下其中 更佳是1200ppm以上或3000ppm以下。 (ΔΤΟ 熱重量/不差熱分析裝置之預定溫度區域中的重量變 化率ΔΤ6(/〇，係表示在該溫度區域中的銅粉的耐氧化性 之指標。 本銅私因其耐氧化性優異，故可使在4〇至綱。c間之 △ TG成為7.0%以下，特別是4 〇%以下，其中更可達& 〇% 以下。 〈製法〉 其次’說明㈣於本銅粉較就具㈣造方法。 本銅粉可藉由在熔融銅中以母合金或化合物的形態添 力預疋量之Α1成》及其他的添加元素成分後，依據預定之 粉化法（atomizing)進行粉體化而製造之。 此種銅粉可藉由以下方法製造：從含鋼鹽之溶液等以 還原劑析出之濕式縣法、將銅鹽加減化並在氣相中還 原之氣相還原法、絲_塊則錄氣體或水等冷媒急冷 而粉末化之粉化法。在此等方法中，相較於H乏利用 之濕式還原法，粉化法具有可使所得銅粉中的不純物殘留 /農度降低、且同時可使從所得鋼粉的粒子表面至内部的細 323054 9 201202447 孔變少之優點。κ ^ 性膏之導電性材料 $化去所製造之銅粉使用於導電 少，化時氣 由進行水粉化，；:3水粉化法(—心。蚪2他)。藉 而使溶於水中的氧會謀^匈田微化。藉由進行水翁化f = 化法可使粒子徑變成較氣體粉化法為〆 且均較佳為高壓粉化法’以其方法可製，細 间壓私化去係指在水粉化法中，以通％至⑽卿左 右的水壓力進行粉化之方法。 法所得之銅粉亦可經還原處理。藉由還原處 ，° 、一步降低容易進行氧化之銅粉表面的氧濃声。 如此之還原處理，以作業性的觀點來看，較佳^ 體進行之還原。此還原處理狀氣魅祕職定 出例如氫氣、氨氣、氣體丁烧等。 上述還原處理較佳為在15〇至3〇(rc的溫度進行， 佳是在1M至2耽的溫度進行。其原因為：若上述溫户 未達15GC則還原速度較慢，無法充分表現處理的致果， 若上述溫度超過3GGt則有引起銅粉之凝集或燒結之虞， 若上述溫度為170至21(TC則可圖謀氧濃度之效率更加降 低，同時亦可確實地抑制銅粉之凝集或燒結。 粉體化後的銅粉係以進行分級為佳。 201202447 此分級可藉由使用適當的分級裝置，以使目的之粒度 成為中心之方式’將粗粉與微粉予以分離而容易地實施之二 (形狀加工） 可直接利用本鋼粉，亦可將本銅粉做形狀加工處理後 再利用。 例如，可將球狀粒子粉末（：_以上為由球狀粒子所 構成的粉末）以機械方式進行形狀加工，而加工成薄片 (flake)狀、鱗片狀、平板狀等之非球狀粒子粉末（：80% 以上為由非球狀粒子所構成的粉末）。 更具體而言，可藉由使用珠磨機（beads mill)、球磨 機、磨碎機（attritor)、振動磨機们."）等以 機械方式進行扁平化加工（壓延伸或伸展），而加工成薄片 狀的粒子粉末（：80%以上為由薄片狀粒子所構成的粉末）。 此時，為了防止粒子彼此之凝集或結合並同時使各粒子在 獨立的狀態下加工，較佳係添加例如硬脂酸等脂肪酸或界 面活性劑等助劑。 並且，可利用經如此之形狀加工處理後的銅粉，此外， 亦可將其與未經形狀加工的原粉混合使用。 〈用途〉 由於本鋼粉可依基板、用途、膏的調配組成等而控制 燒結溫度特性，故作為導電性膏用銅粉，特別是作為在500 至900 C之高溫下燒成之導電性膏用銅粉係相當優異。可 非常良好地適用於作為例如以網版印刷加成法（additive process)形成導體電路時所用、或積層陶瓷電容器之外部 11 323054 201202447 電極用等各種電性接點構件用之導電性膏之導電材料等。 本銅粉適合作為例如燒成型導電性膏所使用之導電填 充劑。因此，例如亦可在有機媒液中調配本鋼粉而調製燒 成型導電性膏。 使用本銅粉作為導電填充劑而成之導電性膏用銅粉， 係可適合用於例如以網版印刷加成法形成導體電路時所 用、或積層陶瓷電容器之外部電極用等各種電性接點構件 用之導電性膏。 另外，本發明之導電性膏用銅粉亦可使用於積層陶瓷 電容器之内部電运、感應器（induct or)及記錄器（register) 等之晶片零件、單層電容器電極、钽電容器電極、樹脂多 層基板、陶瓷（LTCC)多層基板、撓性印刷基板（FPC)、天線 開關模組（antenna switch module)、PA模組與高頻率主 動濾波器（active filter)等模組、PDP前面板及背面板或 PDP濾色器用電磁遮蔽膜、結晶性太陽能電池表面電極及 背面提取電極（extraction electrodes)、導電性接著劑、 電磁波阻隔材（EMI shielding)、無線射頻識別（RF-ID)及 PC鍵盤等膜片開關、異方性導電膜（ACF/ACP)等。 〈語句的說明〉 在本發明中，以「X至Y」（X，Y為任意數字）表現時， 在並無特別限定之情況下，即表示「X以上γ以下」之意， 同時亦包含「較佳為大於X」或「較佳為小於Y」的意思。 此外，以「X以上」（X為任意數字）或「Y以下」（Y為 任思數子）表現時’亦包含意指「較佳為大於X」或「較佳 12 323054 201202447 為未達γ」之意。 [實施例] 以下，根據下述實施例及比較例而更進一步詳述本發 明。 關於實施例以及比較例所得之銅粉，依以下所示方法 評價各特性。 (1) 元素濃度 將試料溶於酸中，以ICP分析之。 (2) 氧濃度（〇2濃度） 使用氧/氮分析裝置（堀場製作所股份有限公司製 「EMGA-520C型號）」）分析銅粉（樣品）的氧濃度（亦稱為最 初氧濃度）。 (3) 粒度分布 將銅粉（樣品）0. 2 g放入純水10 0 in 1中並以超音波照射 (3分鐘）而分散後，以粒度分布測定裝置（日機裝股份有限 公司製（Microtrac(商品名）FRA(型號）））測定體積累積粒 徑 D50。 (4) BET比表面積（SSA) 使用Yuasa Ionics(股）製之Monosorb(商品名），以 JISR1626-1996C精密陶瓷粉體的依據氣體吸附BET法之比 表面積之測定方法）之「6.2流動法之（3. 5) —點法」為基 準，進行BET比表面積（SSA)的測定。此時，使用作為載送 氣體（carrier gas)之氦氣與作為吸附質氣體之氮氣的混 合氣體。 13 323054 201202447 (ATG) 使用示差熱熱重量同時測定裝置（TG/DTA)(Seiko Instruments Inc公司製，TG/DTA6300高溫型）（升溫速度： l〇°C/分鐘，空氣流量：200mL/分鐘），測定銅粉（樣品）在 40°C至800°C的TG(%)，以40°C時之TG(%)為基準值，求得 此基準值與800°C的重量變化率（TG(W)之差（ATG)。 (粉體電阻） 將銅粉（樣品）放入15g筒狀容器中，以40xl06Pa (408kgf/cm2)之加壓壓力而形成經壓縮成型之測定樣品， 並以Loresta Ap及Loresta PD-41型（皆為三菱化學股份 有限公司製）測定體積電阻率（Ω · cm)。 (7)燒結性的評價 使用Seiko Instruments Inc公司製之熱機器分析裝 置（TMA裝置）TMA/SS600，在氮氣環境中測定燒結開始溫 度，依以下之基準進行評價。 ◎:燒結開始溫度在600°C以上，且在8501以下。 〇：燒結開始溫度高於850°C，且在900°C以下。 X :燒結開始溫度超過900°C，或未達600Ϊ，或是沒 有燒結。 〈樣品的調製：實施例1至4及比較例1〉 在將電氣精煉銅（銅純度：Cu99. 95%)予以炫解而成的 熔湯（1350°C)中，分別僅添加適宜量之作為純金屬的A1以 及銅-磷的母合金（P15wt%)，充分攪拌混合而製作丨〇〇kg的 熔湯。 323054 14 201202447 其次’在水粉化裝置的傲槽（tundish)中注入上述熔湯 100kg(保持溫度1350 C )後’ 邊從顧·槽底部的喷嘴（口徑 5mm)流下熔湯（流量5kg/分鐘），一邊對於上述熔湯，從全 錐型（full cone)之噴嘴（口徑26mm)之噴射孔將水以成為 逆圓錐狀之水流形狀之方式進行喷射（水壓1〇〇MPa、水量 350L/分鐘），藉由進行水粉化而製造銅粉。 繼而，將所得之銅粉以分級裝置（日清工程股份有限公 司製「TURBOCLASSFIER(商品名）TC-25C型號）」）進行分級 而得到鋼粉（樣品）。 此外，比較例1並未添加A1。 〈比較例2〉 以日本特開2009-235556之實施例1為基準，依如下 方式製作銅粉。 在氣體粉化裝置（日新技研股份有限公司製，NEVA-GP2 型）之機室（chamber)及原料熔解室内充填氬氣後，以位於 溶解室内之碳坩堝將原料加熱熔解，而製成熔融物（在將電 氣精煉銅予以熔解而成的溶湯中添加金屬鋁l.74g 、銅-麟 的母合金（P15wt%)，製成800g之熔湯，並充分攪拌混合）。 之後’將熔湯從口徑φ 1. 5mm之喷嘴以1250。(：、3. OMPa進 行喷霧’而得到粒子内部含有鋁之銅粉。然後，以m 之試驗篩（testing sieve)過篩’而以過篩品之形式得到最 後的銅粉（樣品）。 15 323054 201202447 〔r—Η玺 燒結性 ◎ ◎ 〇 〇 X X 體積電阻率 Β 〇 • G 1.3x1 O'3 2.4x1 O'3 4. 5x10-3 1_ 9. 5x1 O'3 1 2·2x10-1 1.0x1 O'3 △ TG 2.50 2.83 3.30 m ζό 24.95 CO 〇2濃度 ppm 2298 2317 1628 1885 1955 185.1 00 bO eg ε CD 〇· 0. 58 0.55 CO in <=> 寸 c=> 〇 S m 2.82 〇〇 oi 2.78 2. 73 CO 寸 c<i 1 25. 39 Α1濃度 atm% 49. 76 37.12 20.73 〇 〇· 0. 00 69.30 Ρ濃度 atm% CO ltd o 〇· 0.049 0. 050 1 1 LO 〇 ◦· CO ltd <〇 <=» 〇〇 <=> o 組成 Cu-0.053P-49.76A1 Cu-0.049P-37.12A1 Cu-0.050P-20.73A1 Cu-0.051P-10.10A1 Cu-O. 053P Cu-0. 048P-69. 30A1 實施例1 實施例2 實施例3 實施例4 比較例1 比較例2 16 323054 201202447 以電子顯微鏡等觀察實施例所得之銅粉並分析的結 果，幾乎皆為球狀粒子。 此外，將實施例1至4所得之銅粉與膏混合燒成之結 果，可在大氣中以800°C至900°C左右燒成。 檢討實施例、比較例以及至此之試驗結果，可明白若 A1濃度高於lO.Oatm%且在65.0atm%以下時，即可提高導 電性，特別是可顯著地使體積電阻率降低。 此外，亦確認到此等效果不會受到P(磷）濃度的影響。 P(磷）濃度係因會影響微粒子化與耐氧化性，故可認為較佳 的P(磷）含量為含有0. 01至0. 3atm%的比例。 此外，比較例2的銅粉在燒結性評價試驗中並未燒 結。推察其原因為粒徑過大。 若分析實施例1至4所得之銅粉，則Cu與A1之合金 結晶係偏析於粒子表面，未確認到A1在粒子表面濃化的傾 向，因此，可認為Cu與A1是在粒子内部進行合金化。因 此，認為本發明的銅粉亦可稱為鋁-銅合金粉。 【圖式簡單說明】 無。 【主要元件符號說明】 無。 17 323054One of Ni, Ti, Fe, Co, Cr, Mg, Mn, Mo, W, Ta, In, Zr, Nb, B Λ Ge, Sn, Zn, Bi, or the like, or a combination of two or more types 323054 6 201202447 Elemental composition. By adding these elements, the characteristics required for the conductive paste can be adjusted, for example, the melting point can be lowered and the sinterability can be improved. (A1 concentration) The concentration of the copper powder is higher than 10.0a and below 65. 0at. This feature is quite important. 0 If the A1 concentration is higher than! 〇·〇_, can effectively improve the conductivity. Specifically, if it is considered by the volume resistance value, it can be lowered to less than ι 〇χΐ〇 2 Ω .cm', especially to less than 2 〇χ 1 (Γ3 Ω . (10). Since the power can be reduced as such Saki, so * need to overfill the Baotong. On the other hand, if the concentration of Α1 exceeds 7〇. 〇_%, the melting point is reduced, and the oxidation resistance at high temperature is lost. Therefore, it is less than 65%. Therefore, from the viewpoint of the effect of lowering the volume resistance value and maintaining the oxidation resistance at a high temperature, the A1 concentration of the Benzaki particles is preferably at least, and more preferably 3 G. Gatm% or more. Preferably, the amount of P (phosphorus) of the copper powder particles is not particularly limited, and preferably contains 0.01 to G.3 Gatm%. Preferably, it is utm% or more or 〇.1Qatm% or less, and preferably contains a ratio of G·G2atm% or more or Q. Q6atm% or less. If the P (phosphorus) content is in this range, the particle size is fine and resistant. 323054 201202447 Oxidation, non-destructive and electrical conductivity, small inconsistency between traits and particle size, reduced oxygen concentration (D50) The D50 of the copper powder, that is, the D50' of the volume particle size distribution measured by the laser diffraction scattering particle size distribution measurement, the micronization requirement and the reduction ratio due to the macroization From the viewpoint of the resistance of the sPecic ic resistance and the south density firing, it is preferably 〇. l//m to 10/zra, particularly 〇.3em or more or 5.〇vm or less, more preferably 0. 5/im or more or 3. 〇Μπι or less. (Particle shape) The copper powder particles may be in the form of upsetting, especially in the shape of a sphere, or may be a shape processing of spherical particles. The shape refers to an aspect ratio (asPect ratio, which is obtained by dividing the average long diameter by the average short diameter) in a shape of about 1 to 1.25. The shape in which the aspect ratio is uniform from 1 to 丨.1 is particularly called "Spherical". On the other hand, the shape of the shape is not "indefinite shape". The "granular" copper powder is less aggregated when used in the conductive material of the conductive paste, etc. It is preferable to improve the dispersibility in the paste. (Specific surface area) BET specific surface area of the copper powder particles (SS The abbreviated from 0. 50m / g, from 观点4〇m7g to 〇75m〇g, especially 0.45mVg or more or 〇7〇mVg or less. The above or 〇·65m2/g or less. (Oxygen concentration) 323054 8 201202447 A copper (initial) oxygen concentration is preferably 800ppm to 5000ppm. If the oxygen concentration is in this range, it can be used as a conductive material for conductive paste. The conductivity and oxidation resistance were changed well. From this point of view, the (initial) oxygen concentration of the present steel powder is preferably from 800 ppm to 5,000 ppm, particularly preferably from 1 〇〇〇 ppm or more to 4 〇〇〇 ppm or less, more preferably from 1200 ppm or more to 3,000 ppm or less. (The weight change rate ΔΤ6 (/〇 in the predetermined temperature region of the ΔΤΟ thermal weight/inferior thermal analyzer) is an index indicating the oxidation resistance of the copper powder in the temperature region. The copper is excellent in oxidation resistance. Therefore, the Δ TG between 4 〇 and 。 c can be 7.0% or less, especially 4 〇% or less, and more preferably & 〇% or less. <Preparation method> Next 'Description (4) Compared with the copper powder (4) The method of the present invention. The copper powder can be powdered according to a predetermined atomization method by adding a pre-measured amount of Α1" and other additive element components in the form of a master alloy or a compound in molten copper. The copper powder can be produced by the following method: a wet county method in which a reducing agent is precipitated from a solution containing a steel salt, a gas phase reduction method in which a copper salt is added and subtracted and reduced in a gas phase. The silk_block is a pulverization method in which a refrigerant such as a gas or water is quenched and powdered. In these methods, the pulverization method has an impurity in the obtained copper powder as compared with the wet reduction method in which H is used. Residual/agricultural reduction, and at the same time, from the surface of the particles of the obtained steel powder Department of Fine 323054 9 201202447 The advantages of less pores. κ ^ The conductive material of the paste is used to make the copper powder used for less conductivity, and the gas is pulverized by the process; 3: gouache method (-heart)蚪2 he). So that the oxygen dissolved in the water will make the Hungarian micronization. By carrying out the watering method, the particle diameter can be changed to the gas pulverization method and both are preferably high pressure. The pulverization method can be produced by the method, and the squeezing method refers to a method of pulverizing in the pulverization method by using a water pressure of about 5% to about 10. The copper powder obtained by the method can also be subjected to reduction treatment. By reducing, °, one step reduces the oxygen concentration on the surface of the copper powder which is easy to be oxidized. Such a reduction treatment is preferably a reduction in the workability from the viewpoint of workability. The above-mentioned reduction treatment is preferably carried out at a temperature of 15 Torr to 3 Torr (c, preferably at a temperature of 1 M to 2 Torr. The reason is as follows: If the household is not up to 15GC, the reduction rate is slow, and the result of the treatment cannot be fully expressed. If the above temperature exceeds 3 GGt has a tendency to cause agglomeration or sintering of copper powder. If the temperature is 170 to 21 (TC can reduce the efficiency of oxygen concentration, and can also inhibit the aggregation or sintering of copper powder. The copper powder is preferably classified. 201202447 This classification can be easily carried out by using a suitable classification device to separate the coarse powder from the fine powder in a manner that makes the particle size of the target central. The steel powder can be used for shape processing and then used. For example, the spherical particle powder (: _ or more is a powder composed of spherical particles) can be mechanically processed and processed. A non-spherical particle powder such as a flake, a scaly or a flat plate (80% or more is a powder composed of non-spherical particles). More specifically, it can be mechanically flattened (pressed or stretched) by using a beads mill, a ball mill, an attritor, a vibrating mill, etc., and A particle powder processed into a flake shape (80% or more is a powder composed of flaky particles). In this case, in order to prevent the particles from aggregating or bonding and simultaneously processing the particles in an independent state, it is preferred to add an auxiliary agent such as a fatty acid such as stearic acid or an surfactant. Further, the copper powder processed by such a shape may be used, or it may be mixed with the original powder which has not been subjected to shape processing. <Use> Since the steel powder can control the sintering temperature characteristics depending on the composition of the substrate, the use, and the paste, it is used as a conductive paste copper powder, particularly as a conductive paste fired at a high temperature of 500 to 900 C. The copper powder system is quite excellent. It can be used very well as a conductive paste for various electrical contact members, such as those used for forming a conductor circuit by an additive printing process, or for laminating a ceramic capacitor. 11 323054 201202447 Materials, etc. The copper powder is suitable as a conductive filler for use in, for example, a fired conductive paste. Therefore, for example, the steel powder can be blended in an organic vehicle to prepare a fired conductive paste. The copper powder for conductive paste obtained by using the present copper powder as a conductive filler can be suitably used for various electrical connections such as those used for forming a conductor circuit by a screen printing addition method or for external electrodes of a laminated ceramic capacitor. Conductive paste for point components. Further, the copper powder for conductive paste of the present invention can also be used for a wafer component such as an internal electric motor, an inductor or a register of a laminated ceramic capacitor, a single-layer capacitor electrode, a tantalum capacitor electrode, and a resin. Multi-layer substrate, ceramic (LTCC) multilayer substrate, flexible printed circuit board (FPC), antenna switch module, PA module and active filter, PDP front panel and back Electromagnetic shielding film for panel or PDP color filter, crystal solar cell surface electrode and extraction electrode, conductive adhesive, EMI shielding, radio frequency identification (RF-ID), PC keyboard, etc. Diaphragm switches, anisotropic conductive films (ACF/ACP), etc. <Description of Statements> In the present invention, when "X to Y" (X, Y is an arbitrary number), when it is not particularly limited, it means "X or more γ or less", and also includes "It is better to be greater than X" or "preferably less than Y". In addition, when "X or above" (X is an arbitrary number) or "Y below" (Y is a number of words), it also means "better than X" or "better 12 323054 201202447" γ" means. [Examples] Hereinafter, the present invention will be described in further detail based on the following examples and comparative examples. With respect to the copper powders obtained in the examples and the comparative examples, the respective characteristics were evaluated by the methods shown below. (1) Element concentration The sample was dissolved in acid and analyzed by ICP. (2) Oxygen concentration (〇2 concentration) The oxygen concentration (also referred to as the initial oxygen concentration) of the copper powder (sample) was analyzed using an oxygen/nitrogen analyzer ("EMGA-520C model" manufactured by Horiba, Ltd.). (3) Particle size distribution 0.2 g of copper powder (sample) was placed in pure water of 10 0 in 1 and dispersed by ultrasonic irradiation (3 minutes), and then the particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd.) (Microtrac (trade name) FRA (model))) The volume cumulative particle diameter D50 was measured. (4) BET specific surface area (SSA) using Monosorb (trade name) manufactured by Yuasa Ionics Co., Ltd., and measuring method of specific surface area according to gas adsorption BET method of JISR1626-1996C precision ceramic powder) (3. 5) - Point method" The BET specific surface area (SSA) was measured. At this time, a mixed gas of helium gas as a carrier gas and nitrogen gas as an adsorbate gas is used. 13 323054 201202447 (ATG) Using a differential thermogravimetric simultaneous measuring device (TG/DTA) (made by Seiko Instruments Inc., TG/DTA6300 high temperature type) (heating rate: l〇°C/min, air flow rate: 200 mL/min) TG (%) of copper powder (sample) at 40 ° C to 800 ° C, and TG (%) at 40 ° C as a reference value, and the weight change rate (TG) of the reference value and 800 ° C was obtained. (W) difference (ATG). (Powder resistance) A copper powder (sample) is placed in a 15 g cylindrical container to form a compression-molded measurement sample at a pressure of 40 x 106 Pa (408 kgf/cm 2 ), and Volume resistivity (Ω · cm) was measured by Loresta Ap and Loresta PD-41 (all manufactured by Mitsubishi Chemical Corporation). (7) Evaluation of sinterability was performed using a thermal machine analyzer (TMA apparatus) manufactured by Seiko Instruments Inc. TMA/SS600, the sintering start temperature was measured in a nitrogen atmosphere, and evaluated according to the following criteria: ◎: The sintering start temperature was 600 ° C or more and 8501 or less. 〇: The sintering start temperature was higher than 850 ° C, and was 900. Below °C. X: Sintering start temperature exceeds 900 °C, or less than 600 Ϊ, or no Sintering. <Preparation of Samples: Examples 1 to 4 and Comparative Example 1> In the molten soup (1350 ° C) obtained by dissipating electrically refined copper (copper purity: Cu 99. 95%), only the addition was carried out. A suitable amount of pure metal A1 and a copper-phosphorus parent alloy (P15wt%) are thoroughly stirred and mixed to prepare a 丨〇〇kg melt. 323054 14 201202447 Next, 'injection into the tundish of the pulverizing device After the above-mentioned melt 100 kg (holding temperature 1350 C), the melt (flow rate: 5 kg/min) was flowed from the nozzle (caliber 5 mm) at the bottom of the tank, and the full cone nozzle was used for the melt. The injection hole (having a diameter of 26 mm) sprays water so as to have a shape of a reverse cone-shaped water flow (water pressure: 1 MPa, water amount: 350 L/min), and pulverization is carried out to produce copper powder. The copper powder was classified by a classification device ("TURBOCLASSFIER (trade name) TC-25C model) manufactured by Nissin Engineering Co., Ltd.) to obtain steel powder (sample). Further, Comparative Example 1 did not add A1. <Comparative Example 2> Copper powder was produced in the following manner based on Example 1 of JP-A-2009-235556. After the argon gas is filled in the chamber and the raw material melting chamber of the gas pulverizing device (manufactured by Nisshin Technology Co., Ltd., NEVA-GP2 type), the raw material is heated and melted by carbon enthalpy located in the dissolution chamber to be melted. (In the molten soup obtained by melting the electric refined copper, 1.74 g of metal aluminum and a mother alloy of Pb-Lin (P15 wt%) were added to prepare a melt of 800 g, and the mixture was thoroughly stirred and mixed). After that, the melt was poured from a nozzle having a diameter of 1.5 mm to 1250. (: 3. OMPa was sprayed to obtain copper powder containing aluminum inside the particles. Then, the final copper powder (sample) was obtained as a sifted product by sieving with a test sieve of m. 15 323054 201202447 [r-Η玺 sinterability ◎ ◎ 〇〇 XX volume resistivity 〇 G• G 1.3x1 O'3 2.4x1 O'3 4. 5x10-3 1_ 9. 5x1 O'3 1 2·2x10-1 1.0x1 O'3 △ TG 2.50 2.83 3.30 m ζό 24.95 CO 〇2 concentration ppm 2298 2317 1628 1885 1955 185.1 00 bO eg ε CD 〇· 0. 58 0.55 CO in <=> inch c=> 〇S m 2.82 〇〇oi 2.78 2. 73 CO inch c<i 1 25. 39 Α1 concentration atm% 49. 76 37.12 20.73 〇〇· 0. 00 69.30 Ρ concentration atm% CO ltd o 〇· 0.049 0. 050 1 1 LO 〇 ◦· CO ltd <〇<=» 〇〇<=> o Composition Cu-0.053P-49.76A1 Cu-0.049P-37.12A1 Cu-0.050P-20.73A1 Cu-0.051P-10.10A1 Cu- O. 053P Cu-0. 048P-69. 30A1 Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 16 323054 201202447 The copper powder obtained in the examples was observed by an electron microscope or the like and analyzed. All for the ball Further, the copper powder obtained in Examples 1 to 4 and the paste were mixed and fired, and the mixture was fired in the air at a temperature of about 800 ° C to 900 ° C. Review of the examples, comparative examples, and test results up to now. It can be understood that if the A1 concentration is higher than 10% at at least 65.0 atm%, the conductivity can be improved, and in particular, the volume resistivity can be remarkably lowered. Further, it is confirmed that these effects are not affected by P ( The ratio of the P (phosphorus) concentration of the P (phosphorus) is affected by the microparticles and the oxidation resistance, and the P (phosphorus) content is preferably a ratio of 0.01 to 0.3 atm%. The copper powder of 2 was not sintered in the sinterability evaluation test. The reason for this was that the particle diameter was too large. When the copper powders obtained in Examples 1 to 4 were analyzed, the alloy crystals of Cu and A1 were segregated on the surface of the particles, and A1 was not confirmed. Since the particle surface tends to be concentrated, it is considered that Cu and A1 are alloyed inside the particle. Therefore, the copper powder of the present invention is also considered to be an aluminum-copper alloy powder. [Simple description of the diagram] None. [Main component symbol description] None. 17 323054