201211283 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種導電性糊用銅粉以及使 導 性糊用鋼粉之導電性糊。詳細地說，關於—種可以適= 用於電電路之形成或陶瓷電容器之外部電極之形成等之 ί! 及適合作為該導電性糊之導電填充物之銅粉。 【先前技術】 [背景技術] 中使導電性糊係在由樹脂系黏合劑和溶媒所成之載色劑 電填充物分散之流動性組成物，廣泛地使用於電 之形成或H電容ϋ之外部電極之形成等。 此種導電性糊，有藉由樹脂之硬化而壓合導電性填 2物來確保導通之樹脂硬化型以及藉由煅燒而揮發有機成 / 刀來繞結導電性填充物而確保導通之煅燒型。 剐者之樹脂硬化型導電性糊一般係包含由金屬粉末 所成之導電填充物和由環氧樹脂等熱硬化性樹脂所成之有 機黏合劑的糊狀組成物，藉由加入熱量而一起硬化收縮熱 硬化型樹脂和導電填充物，透過樹脂而壓合導電填充物彼 此成為接觸狀態，確保導通性。該樹脂硬化型導電性糊係 可以在loot：至最多200〇C為止之比較低溫區域，進行處 理’熱損傷少’因此，使用於印刷電路基板或者是對於熱 呈微弱之樹脂基板等。 另一方面，後者之煅燒型導電性糊係一般使導電填充 物（金屬粉末）和玻璃燒結料分散於有機載色劑中而成之 322882 3 201211283 糊狀組成物，藉由在400至80(TC，進行煅燒，來揮發有 機載色劑’進一步藉由燒結導電填充物，而確保參通性。 此時’玻璃燒結料係具有使該導電膜接合於基板之作用， 有機載色劑係發揮作為用以能夠印刷金屬粉末和玻璃燒結 料之有機液體媒體之作用。 煅燒型導電性糊係煅燒溫度高，因此，無法使用於印 刷電路基板或樹脂材料，但是，進行燒結而使得金屬呈一 體化，因此，可以實現低電阻化，例如使用在積層陶瓷電 容器之外部電極等。 即使是在樹脂硬化型導電性糊和高溫煅燒型導電性 糊之任何一種，向來雖大多使用銀粉作為導電填充物，但 是’使用銅粉比較便宜，並且不容㈣生遷移，也具有良 好之财銲錫性，目此，❹鋪之導紐蚊在進行通用 化。但是’銅粉係具有所謂於空氣中容易氧化而使得銅粉 表面之氧化膜造成連接電阻之增大之課題。 於是，關於使用在導電性糊之銅粉而言，向來係提議 各種之防止銅粉表面氧化之方法。 例如在專利文獻！，㈣義在導電性糊内，細己具有還 原作用之物質，抑制銅表面之氧化。 此外’在專利文獻2 ’提議以具有耐氧化性之銀塗佈 粒子表面，在專利文獻3，提議以無機氧化物進行塗佈。 在專利文獻4，揭示一種導電材料糊用鋼合金，係在 主成分之Cu中添加Zii和Sn之至少任何一種而進行合金 化之銅合金粉，該銅合金粉中之Zn及/或％之含有量為 322882 4 201211283 • 0.02至1.2質量％ ，並且該銅合金粉含有0.005至0.05質 量％之P。 此外，在專利文獻5，揭示藉由在銅粉粒子内部含有 0.1 atm%至lOatm%之Si，可得到粒度微細同時而才氧化性 良好以及導電性之平衡。 [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]日本特開平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2010— 13726號公報 【發明内容】 [發明之概要] [發明所欲解決之課題] 近年來，在電性電路等，隨著微細間距化之進行而使 得導電性糊用銅粉末也微細粉末化，隨著銅粉末之比表面 積變大，導電性糊用銅粉成為更加容易氧化之狀態。 使用於煅燒型導電性糊之銅粉係藉由加熱來形成燒 結膜，而確保導電性。這個之燒結溫度在理想上，可以藉 由基板、用途、糊之調配組成等，而可自由地調整於500 至900°C之範圍。 習知之銅粉係在锻燒步驟氧化銅粉而妨礙锻燒，因 此，具有所謂不容易藉由基板、用途、糊之調配組成等而 5 322882 201211283 進行調控來滿足各種要求之燒結溫度特性之課題。 於是，本發明係提供-種可以維持耐氧化性並且也在 ,至之範圍呈自由地調控燒結溫度特性之新的導 電性糊用銅粉及導電性糊。 [用以解決課題之手段] 本發明係提議一種導電性糊用銅粉，係含有si (矽） 。和P(磷）之導電性糊用銅粉，其特徵為：si濃度係〇 〇1&恤 %以上且未達1.2atm% ，並且，藉由該Si濃度（atm% ) 和以雷射繞射散亂式粒度分布測定法測定所得到之體積基 準粒度分布之D50 ( ym)之乘積所算出之Si換算量（Si 濃度XD50)係3.50以下。 本發明之導電性糊用銅粉係可以維持耐氧化性並且 也調控燒結溫度特性。也就是說，可以藉由在Si濃度為 O.Olatm%以上且未達12atm%之範圍内，規定Si濃度（atm % )和D50 ( //m)之乘積（Si濃度❿卯）之值為3 50以 下’而在500至900¾之範圍，調整燒結起始溫度。於是， 可根據基板、用途、糊之調配組成等而調控燒結溫度特性， 因此’非常適合作為導電性糊用銅粉。例如可以極為良好 地適用於藉由網版印刷加成（additive)法之導體電路形成 用或者是積層陶瓷電容器之外部電極用等之各種電接點構 件用之導電性糊之導電材料等。 【實施方式】 [用以實施發明之形態] 接著’根據實施形態例而說明本發明，但是，本發明 6 322882 201211283 . 係並非限定於以下說明之實施形態。 <導電性糊用銅粉> 本實施形態之導電性糊用銅粉（在以下，稱為「本銅 粉」。）係含有Si (矽）和p (磷）之導電性糊用銅粉。可 以是含有Si (矽）和p (磷）之組成的銅粉，也可以含有201211283 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to a conductive paste copper powder and a conductive paste for a conductive paste steel powder. Specifically, it is suitable for the formation of an electric circuit, the formation of an external electrode of a ceramic capacitor, etc., and a copper powder suitable as a conductive filler of the conductive paste. [Prior Art] [Background Art] A fluid composition in which a conductive paste is dispersed in a vehicle-based electrical filler made of a resin-based binder and a solvent is widely used for forming electricity or H-capacitor Formation of external electrodes, etc. Such a conductive paste has a resin-hardened type in which a conductive filler is bonded by curing of a resin to ensure conduction, and a calcination type in which a conductive filler is volatilized by firing to form a conductive filler to ensure conduction. . The resin-hardened conductive paste of the latter is generally a paste-like composition comprising an electrically conductive filler made of a metal powder and an organic binder made of a thermosetting resin such as an epoxy resin, which is hardened together by adding heat. The thermosetting resin and the conductive filler are shrunk, and the conductive filler is brought into contact with each other through the resin to ensure electrical conductivity. The resin-curable conductive paste can be treated in a relatively low temperature region from a loot: up to 200 〇C, and has a small "thermal damage". Therefore, it can be used for a printed circuit board or a resin substrate which is weak in heat. On the other hand, the latter calcined conductive paste is generally obtained by dispersing a conductive filler (metal powder) and a glass frit in an organic vehicle to form a paste composition of 322882 3 201211283, by 400 to 80 ( TC is calcined to volatilize the organic vehicle' to further improve the conductivity by sintering the conductive filler. At this time, the glass frit has the function of bonding the conductive film to the substrate, and the organic vehicle is used. It functions as an organic liquid medium capable of printing metal powder and glass frit. The calcined conductive paste has a high calcination temperature and therefore cannot be used for a printed circuit board or a resin material, but is sintered to make the metal integrated. Therefore, it is possible to achieve a low resistance, for example, an external electrode used in a laminated ceramic capacitor, etc. Even in any of a resin-curable conductive paste and a high-temperature calcined conductive paste, silver powder is often used as a conductive filler. But 'the use of copper powder is cheaper, and it is not allowed to (4) transfer, but also has good wealth soldering properties. The genus Mosquito is generalized. However, the 'copper powder has a problem that it is easily oxidized in the air to cause an increase in the connection resistance of the oxide film on the surface of the copper powder. Therefore, the copper powder used in the conductive paste is used. In other words, various methods for preventing the surface oxidation of copper powder have been proposed. For example, in the patent literature!, (4) In the conductive paste, a substance having a reducing action is finely inhibited from oxidation of the copper surface. Further, 'Patent Document 2' It is proposed to coat the surface of the particles with silver having oxidation resistance, and it is proposed to coat with an inorganic oxide in Patent Document 3. In Patent Document 4, a steel alloy for a conductive material paste is disclosed, which is added to Cu of a main component. a copper alloy powder alloyed with at least one of Sn, the content of Zn and/or % in the copper alloy powder is 322882 4 201211283 • 0.02 to 1.2% by mass, and the copper alloy powder contains 0.005 to 0.05 mass Further, in Patent Document 5, it is disclosed that by containing 0.1 atm% to 10 atm% of Si in the inside of the copper powder particles, it is possible to obtain a fine particle size while having good oxidizability and [PATENT DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. [Patent Document 4] JP-A-2009-99443 [Patent Document 5] JP-A-2010- 13726 SUMMARY OF INVENTION [Summary of the Invention] [Problems to be Solved by the Invention] In recent years, In the electric circuit or the like, the copper powder for the conductive paste is finely powdered as the fine pitch is progressed, and the copper powder for the conductive paste is more easily oxidized as the specific surface area of the copper powder increases. The copper powder used in the calcined conductive paste is formed by heating to form a sintered film to ensure electrical conductivity. The sintering temperature of this is ideally adjustable by the substrate, the use, the composition of the paste, and the like, and can be freely adjusted in the range of 500 to 900 °C. The conventional copper powder is oxidized by the copper powder in the calcination step to hinder the calcination. Therefore, it is difficult to adjust the sintering temperature characteristics to be satisfied by the substrate, the use, the composition of the paste, etc., 5 322882 201211283. . Accordingly, the present invention provides a novel copper powder for conductive paste and a conductive paste which can maintain oxidation resistance and which are also capable of freely controlling the sintering temperature characteristics in the range. [Means for Solving the Problem] The present invention proposes a copper powder for conductive paste containing Si (矽). And P (phosphorus) conductive paste copper powder, characterized in that the si concentration is 〇〇1 &%% or less and less than 1.2 atm%, and by the Si concentration (atm%) and by laser The Si conversion amount (Si concentration XD50) calculated by multiplying the D50 (ym) of the volume-based particle size distribution obtained by the scattering-type particle size distribution measurement method is 3.50 or less. The copper powder for conductive paste of the present invention can maintain oxidation resistance and also control sintering temperature characteristics. That is, the value of the product (Si concentration ❿卯) of the Si concentration (atm % ) and D50 ( //m) can be specified by the Si concentration being more than O.Olatm% and less than 12 atm%. The sintering initiation temperature is adjusted below 3 50' and in the range of 500 to 9003⁄4. Therefore, the sintering temperature characteristics can be controlled depending on the substrate, the use, the composition of the paste, and the like. Therefore, it is very suitable as a copper powder for conductive paste. For example, it can be applied to a conductor material for forming a conductor circuit by a screen printing additive method or a conductive material for a conductive paste for various electrical contact members such as an external electrode of a multilayer ceramic capacitor. [Embodiment] [Embodiment for Carrying Out the Invention] Next, the present invention will be described based on an embodiment. However, the present invention is not limited to the embodiment described below. <Copper powder for conductive paste> Copper powder for conductive paste of the present embodiment (hereinafter referred to as "the present copper powder") is a copper for conductive paste containing Si (yttrium) and p (phosphorus) powder. It may be a copper powder containing a composition of Si (矽) and p (phosphorus), or may contain
Si (矽）和p (磷）以外之金屬元素，但是，典型係— P — Si型銅粉。 本銅粉之特徵係Si濃度為0.01 atm%以上且未達 1.2atm% ，並且，藉由該si濃度（atm% )和以雷射繞射 散亂式粒度分布測定法測定所得到之體積基準粒度分布之 D50 (以m)之乘積所算出之Si換算量（Si濃度xD5〇)為 3.50以下。 可以發現在含有P (磷）之銅粉中添加Si (矽）時， 如果Si (矽）濃度為0 01atm%以上且未達丨2扣瓜％之範 圍内的話’則有可以藉由提高Si濃度而提高燒結起始溫度 之傾白此外也可以破認如果粒控變小的話，則有降低 燒結起始溫度之傾向。但是，也確認在僅規定Si (矽）濃 度和粒徑之任何一種，無法確實地調控燒結性，具體地說， 無法確實地調控燒結起始溫度。於是，在檢討兩者之乘積、 也就是si濃度xD50之乘積（Si濃度xD5〇)作為基準值之 時，可以發現在至少Si濃度為一定範圍内，能夠呈階段性 地調控燒結起始溫度。 由此種觀點來看的話，則本銅粉之Si濃度XD5G為3 5 以下係重要的，最好是0.001至3.4〇、特別是讀5至3.〇〇, 322882 7 201211283 其中特別可以是0.01至2.80。 此種銅粉係正如在後面之製造方法之項目所說明 的，可以根據實施例，藉由調整喷霧條件而進行製造。但 是，並非限定於該方法。 分析本銅粉、也就是Si濃度XD50成為3.50以下之銅 粉，結果得知在銅粉粒子之表面，Si呈濃化。作為更加具 體之標準係確認比起由銅粉粒子表面開始之深度l〇nm之 Si濃度，由表面開始之深度2nm之Si濃度變高。Metal elements other than Si (矽) and p (phosphorus), but typically - P - Si type copper powder. The copper powder is characterized by a Si concentration of 0.01 atm% or more and less than 1.2 atm%, and the volume basis obtained by the Si concentration (atm%) and the laser diffraction scattering particle size distribution measurement method. The amount of Si (Si concentration xD5〇) calculated by the product of D50 (in m) of the particle size distribution is 3.50 or less. It can be found that when Si (germanium) is added to the copper powder containing P (phosphorus), if the concentration of Si (矽) is 0 01 atm% or more and it is less than the range of 丨2, it can be improved by Si. It is also possible to reduce the whitening of the sintering initiation temperature by the concentration. If the grain size is small, the sintering initiation temperature tends to be lowered. However, it has been confirmed that only one of the Si (矽) concentration and the particle diameter is specified, and the sinterability cannot be reliably controlled. Specifically, the sintering initiation temperature cannot be surely controlled. Then, when the product of the sum of the Si concentration xD50 (Si concentration xD5〇) is used as the reference value, it can be found that the sintering initiation temperature can be adjusted stepwise in at least the Si concentration. From such a viewpoint, it is important that the Si concentration of the copper powder XD5G is 35 or less, preferably 0.001 to 3.4 Å, especially 5 to 3. 〇〇, 322882 7 201211283, which may be 0.01 in particular. To 2.80. Such a copper powder can be produced by adjusting the spray conditions according to the embodiment as explained in the item of the subsequent manufacturing method. However, it is not limited to this method. The copper powder, that is, the copper powder having a Si concentration XD50 of 3.50 or less was analyzed, and as a result, it was found that Si was concentrated on the surface of the copper powder particles. As a more specific standard, it was confirmed that the Si concentration at a depth of 2 nm from the surface became higher than the Si concentration at a depth of 10 nm from the surface of the copper powder particles.
Si濃度極為低，因此，不容易定量地進行分析，但是， 由於在銅粉粒子整體之表面可形成氧化矽之薄膜，因此， 氧不容易進入至内部，其結果能夠推測可以提高燒結性， 以及是否也無法提高耐氧化性。 此外，可以認為在本銅粉，如果在表面Si呈濃化之銅粉 粒子（稱為「本銅粉粒子」）為主材料的話，則即使是1〇〇 °/〇全部之銅粉粒子並非在表面Si呈濃化之銅粉粒子，也得 到相同之效果。於是，在本銅粉，在表面Si呈濃化之銅粉 粒子係最好是佔有整體之50wt%以上、最好是80 wt%以 上、特別是90 wt%以上（包含1 OOwt% )。 為了像這樣，在銅粉粒子之表面濃化Si，因此，正如 在後面之製造方法之項目來說明，可以列舉根據實施例而 調整喷霧條件之方法。但是，並非限定於該方法。 本銅粉粒子之Si濃度重要的是在O.Olatm%以上且未 達1.2atm%之範圍。可以藉由在此種範圍調整Si濃度量， 而維持耐氧化性，並且在500至900°C之範圍，更加理想 8 322882 201211283 地調整燒結起始溫度。 像這樣’由财氧化性之维姓 觀點來看的話，本銅粉粒子之^^起始溫度之調控之 1，辰度係最好是0.01 atm% 、之範圍，更加理想特別是0‘03atm% Γ =!、0.05atm%以上更佳，或者特別是未達〇·— % ’其中未達0.1 atm%更佳。 粒子之P(们濃度係並無特別限定，但是，p (磷）之含有量係最好是〇 〇1 %以上、或者* 0蝴以下，：%、：別是〇.〇2atm 或〇.〇6atm%以下之比例含有為較佳。 上 如果在此種範圍來含有Ρ (碟 細粒度和耐氧化性，不損宝 具有微 小，降低氧濃度。形狀或粒度之偏差變 =_點㈣的話，則本_粒子較 拉子内部，以G施竭以上、⑽4 ^疋在 Ρ (磷）。 卜之比例含有 本鋼粉粒子係最好是呈現粒狀 :r:=:r均長直徑除料以 、至 左右之形狀，特別是長寬度比— 左右之形狀，稱為球狀。此外，形 致於 稱為不定形狀。形成此種粒狀之鋼粉係致之 u ’在使餘導電_之導電㈣等情況縷繞 之分散性，，因此非常理想。 阿在糊中 在本鋼粉，以雷射繞射散亂式粒度分布剛 〜在剩定所 322882 9 201211283 得到之體積基準粒度分布之D50,與Si濃度，由&濃度χ D50之值，來規定其範圍，其中，最好是〇1以111至⑺从瓜。 藉由在此種範圍調整D50，可維持耐氧化性，並且在 500至900°C之範圍，更加理想地調整燒結起始溫度。 由耐氧化性維持和燒結起始溫度調控之觀點來看的 話，則本銅粉粒子之D50係最好是〇.1/Zm至1〇“m，更 加理想特別是0.3 μ m以上或5 μ m以下，其中，再較佳為 0.5 /zm以上或3/zm以下。 本銅粉之（初期）氧濃度係最好是8〇〇ppm至 5000ppm。如果氧濃度為此種範圍的話，則可以使得作為 導電性糊之導電材料的導電性及耐氧化性，成為良好之範 圍。 本銅粉粒子係正如前面之敘述，可以認為在銅粉粒子 之表面，濃化Si，在銅粉粒子整體之表面，形成氧化矽之 薄膜’氧不容易進人至粒子㈣，因此，即使是初期氧濃 度比較高，也可以藉由表面之氧化梦被覆膜而良好地維持 耐氧化性。 由此種觀點來看的話，則本銅粉之（初期）氣濃 最好是800ppm至50〇〇ppm，更加理想特別是1〇〇〇卯二以 上或4000ppm以下，其中特別較佳是12〇〇ppm以上或 3000ppm 以下。 本銅粉之燒結起始溫度係最好是5〇〇至9〇〇<t。如果 可以在此種溫度範圍内調整燒結起始溫度的話，則可以根 據基板、用途、糊之調配組成等而調控燒結溫度特性，變 322882 10 201211283 • 得極為便利。 此外’本銅粉係除了 Si (發）和p (鱗）以外，也可 以含有例如 Ni、Ti、Fe、Co、Cr、Mg、Mn、Mo、W、Ta、 In'Zr'Nb'B'Ge、$11、211、則等之中之至少一種以上 之元素成分。 可以藉由添加這些’而調整例如降低熔點來提高燒結 性等之導電性糊之所要求之各種特性。 <製法> 接著’就本銅粉之理想具體之製造方法而進行說明。 本銅粉係能夠藉由在熔融之銅中將Si成分和其他之 添加元素成分以母合金或化合物等之形態來添加規定量之 後，以規定之噴霧法，進行粉體化而製造。 此種銅粉係能夠由包含銅鹽之溶液等藉由還原劑來 析出之廣式還原法、對於銅鹽進行加熱氣化而於氣相中還 原之氣相還原法、或者是以惰性氣體或水等之冷煤來急冷 已炼融之銅塊錠而進行粉末化之喷霧法等，來進行製造。 在這些當中’喷霧法比起一般廣泛地利用之濕式還原法， 具有所謂能夠使得到之銅粉中之不純物殘留濃度降低同時 可使由得到之銅粉粒子之表面開始到達至内部之細孔減小 的優點。因此’藉由噴霧法所製造之銅粉在使用於導電性 糊之導電材料之情況，具有所謂能夠減少在糊硬化時之氣 體產生量同時能夠大幅度地抑制氧化進行的優點。 作為喷霧法係最好是可以採用水喷霧法。不僅是可以 藉由進行水喷霧而在粒子之表面呈更加有效地濃化Si，或 11 322882 201211283 者是也可以達到粒子之微細化。此外，在進行水喷霧之時， 水中之溶存氧係進入奚粒子内，因此，認為有提高氧濃度 之傾向。 即使是在水喷霧法中，如果藉由高壓嘴霧法的話，則 可以微細且均勻地製造粒子而理想。 所謂高壓喷霧法係在水喷霧法中，藉由50MPa至 150Mpa左右之水壓力而進行喷霧之方法。 藉由喷霧所得到之銅粉可以進行還原處理。可以藉由 還原處理而更加地減低谷易進行氧化之銅粉表面之氧濃 度。 作為此種還原處理係由作業性之觀點來看的話，則最 好是藉由氣體之還原。該還原處理用氣體並無特別限定， 但是，可以列舉例如氫氣、氨氣、丁烷氣體等。 前述之還原處理係最好是於150至300°C之溫度進 行’特別更加理想是於170至210°C之溫度進行。為何如 此，因為在前述之溫度未達150°C時，還原速度變得緩慢， 無法充分地表現處理效果，在前述溫度超過時，恐 怕引起銅粉之凝集或燒結，在前述溫度為17代至210(>c 時，可以達到氧濃度效率良好之減低化，同時也確實地抑 制銅粉之凝集或燒結之緣故。 進行粉體化後之銅粉係最好是進行分級。 該分級係可以藉由使用適當之分級裝置，以目的粒度 為主的方式’分離粗粉或微粉而容易地實施。 (形狀加工） 322882 12 201211283 « • 本銅粉係可以以其原樣直接地利用，也可以在對於本 銅粉進行形狀加工處理之後利用。 例如可以對於球狀粒子粉末（80%以上是由球狀粒子 所成之粉末）機械地進行形狀加工而加工成為薄片狀、鱗 片狀、平板狀等非球狀粒子粉末（80%以上是由非球狀粒 子所成之粉末）。 更加具體地說，可以藉由使用顆粒軋磨機、球磨機、 喷霧器、振動軋磨機等，機械地進行偏平化加工（軋壓延 伸或伸展），而形狀加工成為薄片狀粒子粉末（80%以上是 由薄片狀粒子所成之粉末）。在此時，為了防止粒子彼此間 之凝集或結合而同時以獨立之狀態來加工各粒子，因此， 最好是添加例如硬脂酸等脂肪酸或界面活性劑等助劑。 接著，可以利用經此方式之形狀加工處理之銅粉，並 且，也可以混合無形狀加工之原粉末和該銅料而利用。 <用途> 本銅粉係適合作為例如使用於樹脂硬化型導電性糊 和煅燒型導電性糊之任何一種之導電填充物。 於是，例如可以在由環氧樹脂等熱硬化性樹脂所成之 有機黏合劑中，調配本銅粉而調製樹脂硬化型導電性糊， 或者，也可以在有機載色劑中，調配本銅粉而調製煅燒型 導電性糊。 使用本銅粉作為導電填充物之導電性糊用銅粉可以 適合使用作為例如藉由網版印刷加成（additive )法而成之 導體電路形成用或者是積層陶瓷電容器之外部電極用等之 13 322882 201211283 各種電接點構件用之導電性糊。 此外，本發明之導電性糊用銅粉也可以使用在積層陶 瓷電容器之内部電極、電感器（inductor)或電阻器等晶片構 件、單板電容器電極、鈕電容器電極、樹脂多層基板、陶 瓷（LTCC)多層基板、可撓性印刷電路基板（FPC)、天 線開關模組、PA模組或高頻主動濾波器等模組、PDP前面 板及背面板或PDP彩色濾波器用電磁遮蔽膜、結晶型太陽 能電池表面電極及背面拉出電極、導電性接著劑、EMI屏 蔽件、RF— ID和PC鍵盤等薄膜開關、異方性導電膜（ACF /ACP)等。 <用語之說明> 在本說明書，在表現為「X至Y」（X、Y係任意之數 字）之情況，並非特別限制於此，也包含「X以上、Υ以 下」之意義以及「最好是大於X」或「最好是小於Υ」之 意義。 此外，在表現為「X以上」（X係任意之數字）或「Υ 以下」（Υ係任意之數字）之情況，也包含「最好是大於X」 或「最好是未達Υ」之意思之意圖。 [實施例] 在以下，根據下列之實施例及比較例而更加詳細地敘 述本發明。 關於在實施例及比較例來得到之銅粉，藉由以下顯示 之方法而評價各種特性。 (1)元素含有量 14 322882 201211283 • 以酸溶解試料，藉由ICP進行分析。 (2) 氧濃度 使用氧•氮分析裝置（堀場製作所股份有限公司製、 「EMGA—520(型號）」）而分析鋼粉（樣本）之氧濃度（也 稱為初期氧濃度）。 (3) 粒度分析 在銅粉（樣本）0.2g加入至純水i〇〇mi中而照射（3分 鐘）超音波來進行分散之後，藉由粒度分布測定裝置（日機 裝股份有限公司製、「Microtrack(商品名稱）、fra(型號）」） 而測定體積累積粒徑D50。 (4) BET比表面積（SSA) 使用Yuasa-ionics (股）公司製之Monosorb (商品名 稱）’根據JIS R 1626-1996 (藉由微細陶瓷粉體之氣體吸 附BET法而成之比表面積之測定方法）之「6 2流動法之 (3. 5) —點法」，進行BET比表面積（SSA)之測定。在 此時’使用成為載體氣體之氦和成為吸附質氣體之氮之混 合氣體。 (5) 燒結起始溫度及燒結性之評價 使用成為精工儀器公司製之熱機械分析敦置（丁訄八裝 置）之TMA/SS6000而研究燒結起始溫度。 關於燒結性，在本發明之銅粉，最好是比起含有p(磷） 之銅而還適度地比較延遲燒結，也就是比起含有p (磷） 之銅之燒結起始溫度（49(TC前後）而使得燒結起始溫度適 度地變得比較高。因此，在本實施例之「燒結性之評 322882 15 201211283 係以500至900°C之範圍内者，作為「〇」，其中之低溫區 域之500至550°C之範圍者，作為「◎」，500至900。(：之 範圍外者，作為「x」而進行評價。 <樣本之调製：實施例•比較例> 在熔解電解銅（銅純度Cu : 99.95% )之熔融金屬液 (1350C)中，添加作為純金屬之si以及銅—磷之母合金 (P: 15wt% )，充分地進行攪拌混合而製作i〇〇kg之熔融 金屬液。 接著’藉由在水喷霧裝置之中間流槽之中，注入前述 之溶融金屬液100kg(保持溫度丨3〇〇。匚），由中間流槽底部 之喷嘴（口彳k 5mm )，落下炫融金屬液（流量5kg/ min )， 同時，由全圓錐型喷嘴（口徑26mm)之喷射孔，使得水 成為逆圓錐狀之水流形狀’而在前述之熔融金屬液，進行 喷灑喷射（水壓lOOMPa、水量350L/min)，進行水喷霧， 來製造銅粉。 接著’藉由分級裝置（日清工程股份有限公司製、 「Turbo Classifier (商品名稱）、TC—25 (型號）」，而分級 得到之銅粉，來得到銅粉（樣本）。 此外，就實施例6至7而言，將水喷霧所得到之銅粉 藉由分級裝置（日清工程股份有限公司製、「Turb〇 Classifier (商品名稱）、TC—25 (型號）」分級所得到的銅 粉（樣本）’使用顆粒軋磨機而機械式地偏平化加工。 16 322882 201211283 /—s 1A 表 ◎ ◎ 〇 〇 〇 〇 〇 X X X X X 垅 〇。 寸 CM in CO CO m 00 in m τ— CO CO 卜 00 s CO 00 Τ— 卜 § 寸 ο σ> ο α> ο σ> ο σ> CJ 〇 E α α O) CO 〇> S § GO QO s σ> CO C>4 00 00 CO ΙΟ in σ> Ο 〇5 (Ν ο ίο CO 卜· 卜 C0 CNi f— LU ffl be \ E d d s o CSJ 〇 〇 00 CO 卜 5 〇 〇 ΙΛ ο C0 Ο § ο 寸 〇 〇 in ο d Ο ΙΟ Q X ω 劣 E la • E a CO (O o d σ> T~ d O) CO CO O CN1 CM σ> csi CM d 00 C0 eg d ο ο ο CO CO ΙΟ C0 CO ΙΟ CO ιο CD CO CO LO csi CO cd CSI ο ΙΟ Q E CO CNJ 卜 •r— csi LO l〇 csi LO csi 00 ID cJ CD CO CSJ to ο csi 05 ΙΟ csi 5 艺 in CO m 卜· ·|-( GO 求 E 1e σ> s d 00 00 O o CO CO d CO CO 00 d csi CO T™ T— 00 CO o o 00 s d ο ο ο S CO τ™ 05 JO τ— g 5 ο ο in CL, 求 E 1〇 寸 s o s o d s o ? o d O) g o 穿 o d e> Lf) 〇 d CO ιη ο ο 浮 ο ο S ο ο in o o ο S ο CO 〇> S o £L s o 0 1 3 〇 CO 00 00 o o a s o o 3 o (/) CO CO T~ o a. o 0 1 3 o c〇 CO CO 00 0 1 Q. σ> S 〇 o i/> CN4 C9 T- T a σ> 〇 o 3 o (/) 00 CO 0 o 1 a σ> 寸 ο ο 3 Ο C/) 00 s d 1 a CO in 〇 o D o CL C0 ιη ο ο 3 Ο C/) S C0 -Τ Ι 告 lf> ο ο 3 ο 00 ο 写 Τ Ι CL 穿 ο ο 1 3 ο CO 寸 o o a. JO o o D o 00 § τ^· \ CL ιη 艺 ο 3 Ο r- ΐΚ <M ΐΚ CO ίΚ 寸 U3 ίΚ ❿ ί (Μ 00 寸 £ 10 17 322882 201211283 藉由電子顯微鏡等而觀察及分析在實施例1至5得到 之銅粉，結果得知幾乎是球狀粒子，比起由銅粉粒子表面 開始之深度l〇nm之Si濃度’由表面開始之深度2nm之 si濃度變得比較高，Si於表面層濃化。 此外’藉由電子顯微鏡等而觀察及分析在實施例6至 7得到之銅粉，結果得知幾乎是薄片狀粒子，比起由銅粉 教子表面開始之深度l〇nm之Si濃度，由表面開始之深度 之Si濃度變得比較高，si於表面層濃化。 在比較檢討實施例、比較例時，認為在含有p (構） 之鋼粉添加Si (矽）時，如果Si (矽）濃度為O.olatm〇/〇 以上、未達1.2atm%之範圍的話，則確認有可以藉由提高 S *、 1濃度而可提高燒結起始溫度之傾向。但是，由燒結性之 觀點來看的話，則實施例1及實施例2係特別良好，因此， ^此種觀點，可以認為最好是si (矽）濃度未達〇1〇atm 此外’藉由其他之試驗而確認如果粒徑小的話，則有 幾結起始溫度降低之傾向。但是，確認在僅規定Si (石） 度和粒控之任何一種，無法調控燒結起始溫度。另一方 在檢討Si濃度xD50之乘積（Si漢度xD50)作為基準 後時’發現可以在500至900°C之範圍調控燒結起始溫度。 由此種觀點來看的話，則可以認為本銅粉之Si濃度xD5〇 、\5〇以下為重要的，最好是〇 〇〇ι至3 4〇、特別是〇 〇〇5 1 3·〇〇，其中，再特別可以是〇 〇1至2 8〇。 正如本實施例之銅粉，關於可以調控燒結溫度特性之 18 . 322882 201211283 理由而言，並非可以呈試驗性地確認之理由’但是’可以 認為存在於銅粉粒子表面之微量之si (矽）係在煅燒時， 優先地成為氧化物，結果，可以偏析氧化物成分、也就是 陶瓷成分，可以藉由該偏析之程度而改變燒結溫度特性。 並且，在此時，氧化物成分係在燒結後’偏析於粒界’因 此，在不妨礙導電性之方面’也變得良好。 在實施例，藉由固定D50 ’改變Si濃度，而改變Si 濃度xD50之值，但是，即使是在至1〇em左右之 範圍來改變D50而改變Si濃度XD50之值’也可以得到相 同之效果 此外’此種效果係確定不被p(鱗）濃度所衫響。p (磷）濃度係影響到微粒化或耐氧化性，因此’可以認為 P (磷）之含有量係最好是以0.01至之比例來含 有。 【圖式簡單說明】 無。 【主要元件符號說明】 無。 19 322882Since the concentration of Si is extremely low, it is not easy to perform quantitative analysis. However, since a film of cerium oxide can be formed on the entire surface of the copper powder particles, oxygen does not easily enter the inside, and as a result, it is estimated that the sinterability can be improved, and It is also impossible to improve oxidation resistance. In addition, it is considered that if the copper powder is concentrated on the surface Si, the copper powder particles (referred to as "the copper powder particles") are the main materials, even if the copper powder particles of 1 〇〇 ° / 〇 are not The same effect was obtained also on the copper powder particles which were concentrated on the surface Si. Therefore, in the present copper powder, the copper powder particles concentrated on the surface Si preferably occupy 50% by weight or more, preferably 80% by weight or more, particularly 90% by weight or more (including 100% by weight). In order to concentrate Si on the surface of the copper powder particles as described above, a method of adjusting the spray conditions according to the examples can be exemplified as described in the following. However, it is not limited to this method. The Si concentration of the copper powder particles is important in the range of O.Olatm% or more and less than 1.2 atm%. The oxidation resistance can be maintained by adjusting the Si concentration amount in such a range, and the sintering initiation temperature is adjusted in the range of 500 to 900 ° C, more preferably 8 322882 201211283. In this way, from the point of view of the oxidative property of the oxidizing property, the control of the initial temperature of the copper powder particles is preferably in the range of 0.01 atm%, more ideally, especially 0'03 atm. % Γ =!, 0.05 atm% or more is better, or especially less than 〇·-% 'where less than 0.1 atm% is better. The particle concentration (the concentration of the particles is not particularly limited, but the content of p (phosphorus) is preferably 〇〇1% or more, or *0 butterfly or less, and %:: 〇.〇2atm or 〇.比例6atm% or less is preferable. If it contains Ρ in this range (disc fine particle size and oxidation resistance, it does not damage the carbon, and reduces the oxygen concentration. The deviation of shape or grain size becomes _ point (four)) , the _ particle is more than the inside of the pull, G is exhausted above, (10) 4 ^ 疋 in the 磷 (phosphorus). The ratio of the content of the steel containing the steel powder is preferably granular: r: =: r average diameter The shape of the material to the left and right, especially the long-width ratio - the shape of the left and right, is called a spherical shape. In addition, the shape is called an indefinite shape. The formation of such a granular steel powder causes u' to make the remaining conductive _ The conductive (four) and other conditions are scattered, so it is very ideal. A paste in the steel powder, with laser diffraction scattered particle size distribution just ~ in the remaining 322882 9 201211283 obtained volume reference particle size The distribution of D50, and Si concentration, by the value of & concentration χ D50, to specify its range, of which, the best 〇1 is from 111 to (7) from the melon. By adjusting D50 in this range, oxidation resistance can be maintained, and the sintering initiation temperature is more ideally adjusted in the range of 500 to 900 ° C. Maintenance and sintering by oxidation resistance From the standpoint of the initial temperature control, the D50 of the copper powder particles is preferably 〇.1/Zm to 1〇"m, more preferably 0.3 μm or more or 5 μm or less, wherein Preferably, it is 0.5 / zm or more or 3 / zm or less. The (initial) oxygen concentration of the copper powder is preferably 8 〇〇 ppm to 5000 ppm. If the oxygen concentration is in this range, the conductive paste can be made conductive. The conductivity and oxidation resistance of the material are in a good range. The copper powder particle system is as described above, and it can be considered that Si is concentrated on the surface of the copper powder particle, and a film of yttrium oxide is formed on the surface of the copper powder particle as a whole. 'Oxygen does not easily enter the particles (4). Therefore, even if the initial oxygen concentration is relatively high, the oxidation resistance can be favorably maintained by the surface oxidized dream coating. From this point of view, the copper is The powder (initial) gas concentration is preferably 800ppm It is more preferably 50 〇〇 ppm, more preferably 1 〇〇〇卯 2 or more or 4,000 ppm or less, and particularly preferably 12 〇〇 ppm or more or 3,000 ppm or less. The sintering initiation temperature of the copper powder is preferably 5 〇〇. To 9〇〇<t. If the sintering initiation temperature can be adjusted within such a temperature range, the sintering temperature characteristics can be adjusted according to the substrate, the use, the composition of the paste, etc., 322882 10 201211283 • It is extremely convenient. In addition, the present copper powder may contain, for example, Ni, Ti, Fe, Co, Cr, Mg, Mn, Mo, W, Ta, In'Zr'Nb'B' in addition to Si (fat) and p (scale). An elemental component of at least one of Ge, $11, 211, and the like. By adding these, it is possible to adjust various characteristics required for the conductive paste such as sinterability by, for example, lowering the melting point. <Production Method> Next, a description will be given of an ideal specific production method of the present copper powder. The copper powder can be produced by adding a predetermined amount to the Si component and other additive element components in the form of a master alloy or a compound in molten copper, and then powdering it by a predetermined spraying method. Such a copper powder can be a generalized reduction method in which a solution containing a copper salt or the like is precipitated by a reducing agent, a vapor phase reduction method in which a copper salt is heated and vaporized and reduced in a gas phase, or an inert gas or The cold coal such as water is produced by rapidly cooling the pulverized copper ingot and performing a powdering method. Among these, the 'spray method' has a so-called wet reduction method which is widely used, and has a so-called reduction in the concentration of impurities in the copper powder to be obtained, and the surface of the obtained copper powder particles can be reached to the inside. The advantage of reduced holes. Therefore, when the copper powder produced by the spray method is used for the conductive material of the conductive paste, there is an advantage that the amount of gas generated at the time of paste hardening can be reduced and the oxidation progress can be greatly suppressed. As the spray method, a water spray method is preferably used. Not only can Si be more effectively concentrated on the surface of the particles by water spray, or 11 322882 201211283 can also achieve particle miniaturization. Further, when the water spray is performed, the dissolved oxygen in the water enters the ruthenium particles, and therefore it is considered that the oxygen concentration tends to increase. Even in the water spray method, it is preferable to produce the particles finely and uniformly by the high pressure nozzle mist method. The high-pressure spray method is a method in which a water spray method is used to spray a water pressure of about 50 MPa to 150 MPa. The copper powder obtained by spraying can be subjected to reduction treatment. The oxygen concentration on the surface of the copper powder which is easily oxidized by the reduction can be further reduced by the reduction treatment. As such a reduction treatment, from the viewpoint of workability, it is preferable to carry out reduction by gas. The gas for the reduction treatment is not particularly limited, and examples thereof include hydrogen gas, ammonia gas, and butane gas. The above reduction treatment is preferably carried out at a temperature of from 150 to 300 ° C, particularly preferably at a temperature of from 170 to 210 ° C. Why is this because when the temperature is less than 150 ° C, the reduction rate becomes slow, and the treatment effect cannot be sufficiently expressed. When the temperature exceeds, the copper powder may be aggregated or sintered, and the temperature is 17 generations. In the case of 210 (>c, it is possible to achieve a reduction in the efficiency of the oxygen concentration, and also to suppress the aggregation or sintering of the copper powder. The copper powder after the powdering is preferably classified. It is easy to carry out by separating the coarse powder or fine powder in a manner based on the target size by using a suitable classifying device. (Shape processing) 322882 12 201211283 « • This copper powder system can be used directly as it is, or The copper powder is used after the shape processing. For example, the spherical particle powder (80% or more is a powder made of spherical particles) can be mechanically processed into a sheet shape, a scaly shape, or a flat shape. Spherical particle powder (80% or more is a powder made of non-spherical particles). More specifically, it can be used by using a particle mill, a ball mill, The mister, the vibrating mill, and the like are mechanically subjected to a flattening process (rolling and stretching or stretching), and the shape is processed into a flaky particle powder (80% or more is a powder made of flaky particles). In order to prevent the particles from aggregating or bonding with each other and simultaneously processing the particles in an independent state, it is preferable to add an auxiliary agent such as a fatty acid such as stearic acid or a surfactant, etc. Next, the shape processing by this method can be utilized. The treated copper powder may be used by mixing the original powder of the shapeless processing and the copper material. <Use> The copper powder is suitably used, for example, as a resin-curable conductive paste and a calcined conductive paste. Any of the conductive fillers. For example, the copper powder may be blended in an organic binder made of a thermosetting resin such as an epoxy resin to prepare a resin-curable conductive paste, or may be in an organic carrier. In the agent, the copper powder is blended to prepare a calcined conductive paste. The copper powder for conductive paste using the copper powder as a conductive filler can be suitably used, for example, by The conductive paste for forming a conductor circuit or the external electrode for a laminated ceramic capacitor, etc. 13 322882 201211283 Conductive paste for various electrical contact members. Further, the conductive paste copper of the present invention The powder may also be used as an internal electrode of a multilayer ceramic capacitor, a wafer member such as an inductor or a resistor, a single-plate capacitor electrode, a button capacitor electrode, a resin multilayer substrate, a ceramic (LTCC) multilayer substrate, or a flexible printed circuit board. (FPC), antenna switch module, PA module or high frequency active filter module, PDP front panel and back panel or PDP color filter electromagnetic shielding film, crystalline solar cell surface electrode and back pull-out electrode, conductive Adhesives, EMI shields, membrane switches such as RF-ID and PC keyboards, and anisotropic conductive films (ACF / ACP). <Description of Terms> In the present specification, the case of "X to Y" (a number of X and Y numbers) is not particularly limited thereto, and includes the meaning of "X or more and below" and " It is better to be greater than X" or "preferably less than Υ". In addition, in the case of "X or above" (X number is arbitrary) or "Υ" ("any number"), it also includes "preferably greater than X" or "preferably not reached" Intentional meaning. [Examples] Hereinafter, the present invention will be described in more detail based on the following examples and comparative examples. With respect to the copper powder obtained in the examples and the comparative examples, various characteristics were evaluated by the method shown below. (1) Element content 14 322882 201211283 • The sample was dissolved in acid and analyzed by ICP. (2) Oxygen concentration The oxygen concentration (also referred to as the initial oxygen concentration) of the steel powder (sample) was analyzed using an oxygen/nitrogen analyzer ("MEGA-520 (model)" manufactured by Horiba, Ltd.). (3) Particle size analysis After 0.2 g of copper powder (sample) was added to pure water i〇〇mi and irradiated (3 minutes) with ultrasonic waves for dispersion, the particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., The volume cumulative particle diameter D50 was measured by "Microtrack (product name), fra (model)"). (4) BET specific surface area (SSA) using Monosorb (trade name) manufactured by Yuasa-ionics Co., Ltd. according to JIS R 1626-1996 (Determination of specific surface area by gas adsorption BET method of fine ceramic powder) Method] The "6 2 flow method (3. 5) - point method" was carried out to measure the BET specific surface area (SSA). At this time, a mixed gas which is a carrier gas and a nitrogen which becomes an adsorbate gas is used. (5) Evaluation of sintering initiation temperature and sinterability The sintering initiation temperature was investigated using a TMA/SS6000 which was a thermomechanical analysis manufactured by Seiko Instruments Co., Ltd. Regarding the sinterability, in the copper powder of the present invention, it is preferable to moderately compare the delayed sintering compared to the copper containing p (phosphorus), that is, the sintering initiation temperature (49 (compared to copper containing p (phosphorus)). Before and after TC, the sintering initiation temperature is moderately high. Therefore, in the case of the sinterability evaluation 322882 15 201211283 in the range of 500 to 900 ° C, it is referred to as "〇", among which In the range of 500 to 550 ° C in the low temperature region, it is "◎", and it is 500 to 900. (The outside of the range is evaluated as "x". <Modulation of sample: Example: Comparative Example> In the molten metal liquid (1350C) in which electrolytic copper (copper purity Cu: 99.95%) was melted, si as a pure metal and a mother alloy of copper-phosphorus (P: 15% by weight) were added, and the mixture was sufficiently stirred and mixed to prepare i〇. 〇kg of molten metal liquid. Next, by injecting 100 kg of the molten metal solution (maintaining temperature 丨3〇〇.匚) into the intermediate flow tank of the water spray device, the nozzle at the bottom of the intermediate flow tank彳k 5mm ), drop the molten metal (flow 5kg / min), at the same time, by the full circle The injection hole of the cone-shaped nozzle (having a diameter of 26 mm) causes the water to be in the shape of a reverse cone-shaped water flow, and the molten metal liquid is sprayed (water pressure 100 MPa, water amount 350 L/min), and water spray is performed. Copper powder was produced. Then, the copper powder obtained by classification was obtained by a classification device (Turbo Classifier (trade name), TC-25 (model) manufactured by Nissin Engineering Co., Ltd.) to obtain copper powder (sample). Further, in the examples 6 to 7, the copper powder obtained by the water spray was classified by a classification device (manufactured by Nissin Engineering Co., Ltd., "Turb〇 Classifier (trade name), TC-25 (model)"). The obtained copper powder (sample) was mechanically flattened using a particle mill. 16 322882 201211283 /—s 1A Table ◎ ◎ 〇〇〇〇〇XXXXX 垅〇. Inch CM in CO CO m 00 in m τ - CO CO 00 s CO 00 Τ - 卜 § ο σ gt ο α gt ο σ σ σ σ λ λ λ λ λ ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω ω CO ΙΟ in σ> Ο 〇5 (Ν ο ίο CO 卜 · Bu C0 CNi F— LU ffl be \ E ddso CSJ 〇〇00 CO 卜 5 〇〇ΙΛ ο C0 Ο § ο 〇〇 〇〇 in ο d Ο ΙΟ QX ω Inferior E la • E a CO (O od σ> T~ d O) CO CO O CN1 CM σ> csi CM d 00 C0 eg d ο ο ο CO CO ΙΟ C0 CO ΙΟ CO ιο CD CO CO LO csi CO cd CSI ο ΙΟ QE CO CNJ 卜•r— csi LO l〇csi LO csi 00 ID cJ CD CO CSJ to ο csi 05 ΙΟ csi 5 Art in CO m Bu··|-(GO seeking E 1e σ> sd 00 00 O o CO CO d CO CO 00 d csi CO TTM T— 00 CO oo 00 Sd ο ο ο S CO τTM 05 JO τ— g 5 ο ο in CL, seeking E 1 inch sosodso? od O) go wearing od e> Lf) 〇d CO ιη ο ο floating ο S ο ο in oo ο S ο CO 〇> S o £L so 0 1 3 〇CO 00 00 ooasoo 3 o (/) CO CO T~ o a. o 0 1 3 oc〇CO CO 00 0 1 Q. σ> S 〇oi /> CN4 C9 T- T a σ> 〇o 3 o (/) 00 CO 0 o 1 a σ> inch ο ο 3 Ο C/) 00 sd 1 a CO in 〇o D o CL C0 ιη ο ο 3 Ο C/) S C0 -Τ 告 告> ο ο 3 ο 00 ο Write Τ CL wear ο ο 1 3 ο CO 寸 oo a. JO oo D o 00 § τ^ \ CL ιη 艺ο 3 Ο r- ΐΚ <M ΐΚ CO Κ U U3 ίΚ ❿ ί (Μ 00 寸 £ 10 17 322882 201211283 The copper powder obtained in Examples 1 to 5 was observed and analyzed by an electron microscope or the like, As a result, it was found that almost spherical particles were relatively higher in Si concentration from the surface at a depth of 2 nm from the surface of the copper powder particles, and Si was concentrated in the surface layer. Further, 'the copper powder obtained in Examples 6 to 7 was observed and analyzed by an electron microscope or the like, and as a result, it was found that almost the flaky particles were compared with the Si concentration at a depth of 10 nm from the surface of the copper powder, from the surface. The Si concentration at the beginning of the depth becomes relatively high, and si is concentrated in the surface layer. When comparing the examples and the comparative examples, it is considered that when Si (矽) is added to the steel powder containing p (structure), if the Si (矽) concentration is above O.olatm〇/〇, and it is less than 1.2 atm%, Further, it was confirmed that the sintering initiation temperature can be increased by increasing the concentrations of S* and 1. However, from the viewpoint of sinterability, Example 1 and Example 2 are particularly excellent. Therefore, it is considered that the concentration of si (矽) is preferably less than 〇1〇atm. In other tests, it was confirmed that if the particle diameter is small, there is a tendency that the initial temperature of the knot is lowered. However, it was confirmed that the sintering initiation temperature could not be regulated by specifying only one of Si (stone) degree and grain control. On the other hand, after reviewing the product of the Si concentration xD50 (Si Han xD50) as a reference, it was found that the sintering initiation temperature can be adjusted in the range of 500 to 900 °C. From this point of view, it can be considered that the Si concentration of the copper powder is below xD5〇, \5〇 or less, preferably 〇〇〇ι to 3 4〇, especially 〇〇〇5 1 3·〇 〇, in which, in particular, it can be 〇〇1 to 2〇. As for the copper powder of the present embodiment, for the reason that the sintering temperature characteristic can be controlled 18 322882 201211283, it is not possible to experimentally confirm the reason 'but' can be considered to exist in the trace amount of the copper powder particle si (矽) When calcined, it is preferentially an oxide, and as a result, an oxide component, that is, a ceramic component, can be segregated, and the sintering temperature characteristics can be changed by the degree of segregation. Further, at this time, the oxide component is segregated in the grain boundary after sintering, and therefore it is also excellent in that it does not interfere with conductivity. In the embodiment, the value of the Si concentration xD50 is changed by fixing the D50' to change the Si concentration, but the same effect can be obtained even if the value of the Si concentration XD50 is changed by changing the D50 to a range of about 1 〇em. In addition, this effect is determined not to be stunned by the concentration of p (scale). Since the concentration of p (phosphorus) affects the atomization or oxidation resistance, it is considered that the content of P (phosphorus) is preferably contained in a ratio of 0.01 to. [Simple description of the diagram] None. [Main component symbol description] None. 19 322882