200927951 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種金屬微粒子及其製造方法，該金 屬微粒子除了使用作爲例如異方向性導電薄膜用的導電粒 子所使用的金屬微粒子以外，亦適合作爲基板等的配線形 成所使用的材料。 【先前技術】 隨著地面數位廣播的普及，LCD(液晶顯示器；Liquid 〇 Crystal Display)、或 PDP(電獎顯示面板；Plasma Display Panel)等FPD(平面面板顯示器；Flat Panel Display)急速地 成長。該驅動1C或微細的配線電路的電連接多半是使用異 方向性導電薄膜。 異方向性導電薄膜係在熱固性或熱塑性的絕緣性樹脂 薄膜中，使導電粒子分散之黏著劑，藉由配置在相對的配 線之間後，進行熱壓黏著而使導電粒子介於中間來得到配 線間的導通，且在面方向鄰接的配線間保持電絕緣性之連 Q 接材料。該導電粒子係廣泛地使用在聚苯乙烯或丙烯酸酯 等樹脂球表面鍍敷Ni、Au等的金屬材料來使其具有導電性 而成之導電性樹脂球、Ni、Cu、A卜Au、Ag等的金屬粉末、 或是在其表面鍍敷金屬而成的粉末等。 通常異方向性導電薄膜的導電粒子所使用的導電性樹 脂球，因爲熱壓黏著時的壓力及溫度，樹脂球會彈性變形， 所以具有能夠增大與配線的接觸面積之優點。但是因爲樹 脂球係絕緣體’不僅是難以得到良好的導通，而且因爲必 須藉由特別的處理來對表面進行金屬鍍敷，有價格非常昂 200927951 貴的缺點。 另一方面，Ni粉末等的金屬粉末能夠使用於TCP (捲帶 式封裝；Tape Carrier Package)與FPC(軟性印刷電路； Flexible Printed Circuit)的連接、TCP 與 PWB(印刷線路 板；Printed Wiring Board)的連接等之異方向性導電薄膜。 TCP或FPC、PWB等的電路基板能夠藉由Cu、或在其上施 加Sn鍍敷等而成之比較軟且容易形成氧化膜的材質來形 成微細的配線電路。使用金屬粉末而成之異方向性導電薄 0 膜具有能夠穿破配線電路上的氧化膜而來確保導通的優 點。但是例如將藉由氣體噴霧法所得到的金屬粉末作爲異 方向性導電薄膜用導電粒子時，係非常難以得到粒度分布 尖銳的粒子。因爲粒子的大小不一致，爲了能夠符合異方 向性導電薄膜的規格之粒子尺寸的分級處理，會有價格變 爲高昂之問題點。 因此，鑒於上述的課題，關於電路基板的微細配線連 接所使用的異方向性導電薄膜，本發明者提案揭示一種分 Q 散於其之導電粒子（專利文獻1)。因爲該導電粒子具有優良 的導電特性’另一方面，亦能夠達成高硬度且均勻的形狀 及粒度分布，所以適合於異方向性導電薄膜。 又’爲了在FPC或玻璃基板形成微細的電路配線，係 採用使用Ag糊之網版印刷法等。該方法係在基板上使用導 電性高的Ag糊印刷配線後，爲了防止Ag的電子移行，以 塗覆Ag配線的形式層積印刷碳糊，並焙燒來形成電路配線 之方法，依照該方法，能夠價廉地大量製造基板等。 [專利文獻1]特開2006-131978號公報 200927951 【發明內容】 [發明所欲解決之課題] 在上述先前技術，例如注視異方向性導電薄膜用導電 粒子時，雖然專利文獻1的方法係對於上述的課題顯示一 定效果之有效的手法，但是此種鎳磷（NiP)微粒子與導電性 樹脂球比較時，粒子尺寸具有偏差，有改善的餘地。 又，評價在FPC或基板等之配線形成用材料時，例如 形成配線間隔爲0.2毫米以下之較微細的配線時，由於網 版印刷的精確度、亦即由於Ag配線與層積於其之防止電子 移行用的碳糊印刷時之位置偏移，會有難以形成高精確度 的配線電路之問題點。因此，在配線形成用材料，爲了消 除因該電子移行的課題所引起的電路配線之精確度變差， 要求以導電粒子來代替Ag糊。 本發明的目的係提供一種特別是最適合使用於異方向 性導電薄膜的導電粒子且單分散性及導電特性優良的球狀 鎳磷微粒子及其製造方法。又，除此以外，提供一種最適 合形成FPC或玻璃基板等的電路配線且耐移行、導電特性 及低溫燒結性亦優良的球狀鎳磷微粒子及其製造方法。 [解決課題之手段] 本發明者對能夠應用在高精確度的微細電路之異方向 性導電薄膜用的導電粒子進行詳細地檢討。而且，作爲能 夠在基板等微細且高精確度地形成電路配線之材料，亦硏 討適合於其之導電粒子。結果藉由在先前提案之專利文獻 1的異方向性導電薄膜用導電粒子含有Cu之組成，而且在 此亦含有Sn之組成，能夠抑制粒子尺寸的偏差，而且能夠 200927951 得到提升粒子本身的導電特性之結果。 亦即，本發明係一種還原析出型球狀鎳磷微粒子，其 係由以Ni爲主體且含有P(較佳是1〜15質量％)的成分組 成所構成之球狀鎳磷微粒子，其特徵係在該成分組成含有 Cu。又，一種還原析出型球狀鎳磷微粒子，其特徵係在該 成分組成含有0.01〜18質量％之Cu。 又，本發明係還原析出型球狀鎳磷微粒子，其特徵係 在除了含有前述的Cu之成分組成之外，亦含有Sn，例如 〇 —種還原析出型球狀鎳磷微粒子，其特徵係含有0.05〜10 質量％之S η。 而且，本發明的還原析出型球狀鎳磷微粒子，較佳是 其平均粒徑 d5〇以 0.1〜70微米且其粒度分布爲 [(d9〇-di〇)/d5〇]S〇.8 (dgio、dI()、d5〇:係表示在累積分布曲 線’ 9 0體積％、1 0體積％、5 0體積％之粒徑）。在此，藉由 含有上述的Cu，特別是平均粒徑d5Q係在1〜70微米的大 粒徑側，對於調整該粒度分布係有利的。而且，藉由進而 Q 含有Sn，特別是平均粒徑d5Q係在0.1〜10微米的小粒徑 側，對於調整該粒度分布係有利的。 而且，本發明係提供一種製造方法，其係將鎳鹽的水 溶液、pH調整劑和pH緩衝劑的混合水溶液、及含磷之還 原劑水溶液混合並使其還原析出，來製造以Ni爲主體且含 有P之球狀鎳磷微粒子之方法，其中前述鎳鹽的水溶液含 有Cu，且以混合而使其開始還原析出時的PH爲大於7的 鹼性之方式來調整。前述鎳鹽的水溶液係以莫耳比爲 Ni/Cu = 4.0〜1 0000的方式含有Cu爲佳。 200927951 而且，本發明係提供一種製造方法’其中在前述還原 析出時的鎳鹽的水溶液，除了含有上述的Cu以外，亦含有 Sn，且以混合而使其開始還原析出時的PH爲大於7的鹼性 之方式來調整。此時鎳鹽的水溶液係以莫耳比爲Ni/Sn = 2.0 〜2000的方式含有Sn爲佳。 [發明之效果] 本發明之含有Cu、或更含有Sn之還原析出型球狀鎳 磷微粒子，因爲其粒子爲球狀’調配於熱固性或熱塑性的 絕緣性樹脂薄膜中時，粒子的凝聚小且分散性良好，使用 Ο 於異方向性導電薄膜的導電粒子時能夠抑制電極間的短 路。又，與其同時，即便先前難以得到良好的連接信賴性 之材質亦即A1或Cr電極等容易形成氧化皮膜之金屬電極 間的連接，亦能夠得到低連接抵抗性及高連接信賴性。 而且，本發明上述球狀鎳磷微粒子之成分組成係Ni 基的金屬粒子，因爲耐移行性及導電特性優良，同時呈現 均勻的粒子尺寸，形成FPC或玻璃基板等的電路配線時， 在低溫的燒結性良好，且能夠減少對基板的損傷。 〇 【實施方式】 本發明的特徵係在以N i爲主體，必須含有至少半金屬 之P而構成’例如專利文獻1所示之還原析出型球狀鎳磷 微粒子之中，在其含有Cu而成者，清楚地具有抑制粒子尺 寸不均之效果。因此’其Cu含量爲〇_〇1〜18質量％的成分 組成。 又’本發明之特徵係在上述含Cu之球狀鎳磷微粒子使 其含有Sn，亦清楚地具有發揮抑制不均的效果。 而且，如此地’含有Cu及Sn兩元素而成之球狀鎳磷 -10- 200927951 微粒子，其平均粒徑d5Q爲0.1〜70微米’且其粒度分布爲 [(d^-U/dso]; 〇.8之粒子尺寸一致的球狀鎳磷微粒子。 此時，在兩含有元素，選擇Cu之球狀鎳磷微粒子，其平均 粒徑係在1〜70微米的大粒徑側’抑制上述的不均之效果 優良。而且，同時含有Cu及Sn之球狀鎳磷微粒子’特別 是其平均粒徑係在0 · 1〜1 0微米的小粒徑側，抑制上述的 不均之效果優良。 而且，在製造本發明的球狀鎳磷微粒子，係藉由例如 將含Cu、或Cu及Sn之鎳鹽的水溶液、pH調整劑和pH緩 衝劑的混合水溶液、及含磷之還原劑水溶液混合並使其還 原析出之無電解還原法來製造，且較佳是以混合而使其開 始還原析出時的pH爲大於7的鹼性之方式來調整。前述含 Cu之鎳鹽的水溶液以莫耳比爲Ni/Cu = 4.0〜10000的方式 來調整Cu量爲佳。而且，若在前述含Cu之鎳鹽的水溶液 添加Sn時，以莫耳比爲Ni/Sn = 2.0〜2000的方式來調整Sn 量爲佳。 首先，本發明的球狀鎳磷微粒子在以Ni爲主體，必須 含有P，例如以含有1〜1 5質量％P之成分組成爲基本。就 此而言，使用作爲異方向性導電薄膜的導電粒子時，作爲 賦予其必要的硬度及導電性之有效方法，本發明者在專利 文獻1提案揭示一種球狀鎳磷微粒子，係在粒子的中心部 分具有結晶結構且在表層部分係金屬間化合物分散於非結 晶而成。 而且’依照專利文獻〗的方法時，係對於確保粒度分 布的均勻性顯示一定效果之有效的手法，但是本發明者重 -11- 200927951 複專心硏討的結果，查明在專利文獻1的球狀鎳磷微粒子 之中，特別是添加Cu而成者，才是能夠更抑制粒子的不 均，且亦能夠提升導電性。 在本發明的還原析出型球狀鎳磷微粒子之Cu的含量 以0·01〜1 8質量％爲佳。Cu的含量小於0.01質量％時，難 以得到抑制粒子不均之效果。又，C u的含量大於1 8質量％ 時，粒子之間變爲容易凝聚，不僅是損害單分散性，而且 例如應用於異方向性導電薄膜時，難以得到能夠適應自其 〇 連接之電路基板的微細配線、例如得到20微米以下的尺寸 之粒子。更佳是藉由含有0.40〜17質量％的Cu之成分組 成’能夠容易地得到粒子尺寸不均少，且導電性優良的金 屬微粒子。 而且，除了上述含有Cu之還原析出型球狀鎳磷微粒子 以外’在此添加S η亦同樣地能夠具有抑制粒子尺寸不均之 效果。此時，本發明的球狀鎳磷微粒子之Sn含量以0.05 〜1 0質量％爲佳。S η的含量小於0 · 0 5質量％時，難以得到 Q 抑制粒子不均之效果，特別是難以得到與後述小徑側同樣 效果之好處。又，Sn的含量大於10質量％時，不僅粒子變 爲不定形而難以得到單分散性的粒子。更佳是藉由含有 0.25〜5質量％的Sn之成分組成，能夠容易地得到粒子尺 寸之不均少，且導電性優良的金屬微粒子。 本發明之含有Cu、或Cu與Sn的兩元素之還原析出型 球狀鎳磷微粒子，較佳是使平均粒徑d5C的數値爲〇.1〜70 微米（dso:係表示在累積分布曲線，50體積％之粒徑），該 粒徑按照用途而選定。但是該粒徑係小於0.1微米時，因 -12- 200927951 爲粒子容易凝聚，在處理上變爲非常困難。另一方面，平 均粒徑d5〇大於70微米時，使粒子成長需要許多時間，難 以效率良好地得到均勻的粒子，以5 0微米以下爲佳，以 30微米以下爲更佳。又，大於20微米時，用於異方向性 導電薄膜用的導電粒子或FPC、基板等的配線形成之材料 時，其功能上的使用變爲困難。 在此，將本發明的球狀鎳磷微粒子使用作爲例如異方 向性導電薄膜用導電粒子時，較佳是使平均粒徑d5Q的數 Q 値爲1〜20微米。該粒徑小於1微米時，因爲異方向性導 電連接時在TCP或FPC、PWB等的電路基板所形成的微細 配線之高度不均無法緩衝致使接觸不安定，或是連接信賴 性降低。另一方面，d5{)大於20微米時，在配線間隔爲數 十微米之狹間隙的微細配線之連接、會有絕緣性降低且無 法確保安定的連接信賴性之可能性。因此，特別是本發明 的球狀鎳磷微粒子爲了最適合於作爲異方向性導電薄膜用 的導電粒子，d5G的値以1〜20微米爲佳，以1〜1〇微米爲 ❹ 更佳’該粒徑以配合藉由異方向性導電薄膜連接之配線間 隔及電極形狀而任意地選定爲佳。 而且，在該d5Q爲0.1〜70微米的範圍之本發明的還原 析出型球狀鎳磷微粒子，爲了調整使d5G爲上述之1微米 以上、進而爲5微米以上的大徑側，且此時抑制粒子尺寸 不均之效果優良，會有使其單獨含有Cu或Sn的兩含有元 素之中的銅之情況。 又，即便將本發明的球狀鎳磷微粒子使用作爲形成 FPC或玻璃基板等的電路配線之材料時，其平均粒徑d50 -13- 200927951 係配合用途而任意地選定，以0.1〜10微米爲佳。d5Q大於 1 〇微米時，會有無法應用於微細的配線間隔之情況’又， 形成電路配線時之燒結溫度上升，會有對基板造成損傷之 可能性。另一方面，d5〇小於0.1微米時，不僅是粒子的處 理變爲非常困難，而且因爲粒子本身價格昂貴，而難以適 應大量生產。 而且，在上述d5C爲0.1〜70微米的範圍之本發明的還 原析出型球狀鎳磷微粒子，本次爲了調整使d5G爲上述之 0 1 〇微米以下、進而爲小於5微米的小徑側，且此時抑制粒 子尺寸不均之效果優良，會有使其含有Cu與Sn的兩含有 元素之情況。 接著，本發明的還原析出型球狀鎳磷微粒子之特徵係 呈現均勻的粒度分布。粒度分布爲[(d9()-d1())/d5()]>0.8時， (d9()、d1():係表示在累積分布曲線，90體積％、10體積％ 之粒徑），例如在異方向性導電連接時，因爲參與導通之粒 子變少，會有連接信賴性變差之可能性。因此，該式所提 Q 供的粒度分布以盡可能採取較小的値爲佳，但是該値小時 必須許多成本來進行分級處理，粒度分布的[(d9D-d1())/d5()] 以0.8以下爲佳，以0.7以下爲更佳。 說明本發明的球狀鎳磷微粒子之較佳製造方法。首 先，本發明者在專利文獻1提案揭示藉由將鎳鹽水溶液與 含磷之還原劑水溶液混合並使其還原析出，來製造以Ni 爲主體且含有P之球狀鎳磷微粒子，亦即無電解還原法。 該還原析出的基本原理夠利用於製造本發明的球狀鎳憐微 粒子’但是此時’在本發明重要的是在該鎳鹽水溶液中添 -14- 200927951 加Cu離子。亦即，藉由還原劑的氧化反應所放出的自由電 子’與Ni離子被還原之同時Cu還原析出，能夠得到有粒 子尺寸的偏差較小的Cu之鎳磷微粒子。 而且’本發明的重要特徵係按照必要亦有在已添加上 述的Cu離子而成之鎳鹽水溶液中添加Sn離子之情形。藉 此，在還原析出反應時，Sn亦共析而能夠得到含有粒子尺 寸偏差小Sn而成之鎳磷微粒子。 詳細地說明上述的反應機構。本發明所採用之無電解 〇 還原法係混合鎳鹽水溶液與含磷之還原劑水溶液後，緊接 著在反應的初期過程，首先含磷之還原劑、亦即次膦酸產 生氧化反應。隨著該氧化反應的進行，在溶液內存所生成 的膦酸根離子被積存，達到其界限濃度時，膦酸根離子與 游離Ni離子結合而生成作爲球狀鎳磷微粒子的核之膦酸 鎳。而且，在上述的核之表面、亦即在Ni表面，次膦酸根 離子顯示觸媒活性，且經由反應過程之氫的脫離反應而產 生氧化反應。藉由該氧化反應時所放出的自由電子，Ni、 0 Cu及/或Sn的金屬離子係連續地還原析出，來形成目標球 狀鎳磷微粒子。 但是在通常的無電解Ni-P鍍敷，爲了防止在被鍍敷物 以外有鍍敷皮膜析出，或防止鍍敷液的自然分解，能夠使 用硫脲等的硫化合物、或Pb、Bi、Tl、Sb等的重金屬離子 等作爲安定劑。上述的安定劑係比Ni優先地吸附於成爲鍍 敷液自然分解的原因之沈澱物，而具有作爲催化毒物之作 用。而且，已知Sn及Cu係僅次於上述的重金屬之使觸媒 活性降低之元素。在製造本發明的球狀鎳磷微粒子，判斷 -15- 200927951 藉由在鎳鹽的水溶液添加Cu、或Cu及Sn，在無電解還原 法的反應中途過程，藉由其催化毒物之作用，能夠抑制後 發的膦酸鎳之生成。而且，結果藉由本發明的製造方法所 得到的球狀鎳磷微粒子，分析其剖面之成分分布時，確認 其中心部係濃密地分布Cu、或Cu及Sn的兩離子（如後述 第3〜6圖及第9〜13圖的FE-SEM(電場放出型掃描電子顯 微鏡）之影像）。 而且，在上述的作用，特別是抑制粒子尺寸的偏差之 φ 適當條件，係在前述鎳鹽的水溶液調整添加Cu時，以莫耳 比爲Ni/Cu = 4.0〜10000的方式來設定。Ni/Cu低時，認爲 能夠將各自的粒子尺寸本身調整爲較大，另一方面，粒度 分布的偏差亦有變小的傾向。又，該比變高時，認爲能夠 將各自的粒子尺寸本身調整爲較小，另一方面，粒度分布 的偏差仍然有變小的傾向。在上述的莫耳比，使用調整爲 Ni/Cu =約4.56而成的鎳鹽水溶液時之還原析出反應爲 10 0%達成時，在所得到球狀鎳磷微粒子所含有的理論Cu q 量，係該P含量爲約7質量％時，爲1 8質量％。又，使用 調整爲Ni/Cu =約9999而成的鎳鹽水溶液時之還原析出反 應爲1 00 %達成時，在所得到球狀鎳磷微粒子所含有的理論 Cu量，係該P含量爲約7質量％時，爲〇.〇1質量％。 又，在含Cu之鎳鹽的水溶液更添加Sn時，與單獨添 加Cu時比較，在較小徑側之粒子尺寸偏差的抑制效果優 良，該作用係在調整添加Sn時，以莫耳比爲Ni/Sn = 2.0〜 2〇〇〇的方式來設定。Ni/Sn低時，認爲能夠將各自的粒子 尺寸本身調整爲較小，另一方面，粒度分布的偏差亦有變 -16- 200927951 小的傾向。又，該比變高時，認爲能夠將各自的粒子尺寸 本身調整爲較大，另一方面，粒度分布的偏差仍然有變小 的傾向。 而且，在該等方法，另外一項重點係在開始使其還原 析出時調整pH。這是因爲藉由以大於7的鹼性之方式來調 整時，能夠使析出反應迅速地進行，能夠效率良好地得到 含有Cu、或Cu及Sn之鎳磷微粒子。又，配合該作用效果’ 亦能夠降低在本微粒子的反應初期時之中心部的P濃度 0 (同第3〜6圖及第9〜13圖）。就此而言，用以提升本微粒 子的導電性及硬度之有利的手法，在專利文獻1亦有說明。 又，依照上述的手法所提供本發明之含有Cu、或Cu 及Sn之還原析出型球狀鎳磷微粒子，亦與專利文獻1同樣 地，爲了賦予更高硬度亦可施加加熱處理，及/或爲了降低 連接電阻，亦可施加Au等的表面被覆處理。 [實施例] (實施例1) Q 將六水合硫酸鎳與五水合硫酸銅以Ni與Cu的莫耳比 爲Ni/Cu = 23 9的方式調整，並溶解於純水來製造15(dm3) 金屬鹽水溶液。接著，乙酸鈉溶於純水並使濃度爲 1.0(kmol/m3)，並添加氫氧化鈉，來製造15(dm3)pH調整水 溶液。然後，將上述的金屬鹽水溶液與pH調整水溶液攪拌 混合，而成爲3 0 ( d m3)的混合水溶液，測定p Η時顯示8.1 的値。然後，使用Ν2氣體邊使上述的混合水溶液冒泡，邊 藉由外部加熱器加熱保持於343 (Κ)且繼續攪拌。 接著，製造將次膦酸鈉1.8(kmol/m3)的濃度溶解於純 -17- 200927951 水而成之還原劑水溶液。亦將該等以使用外部加熱器加熱 至343 (Κ)。然後，將上述3〇(dm3)的混合水溶液及15(dm3) 的還原劑水溶液以使溫度爲3 43 ±1(K)的方式調整後進行混 合，並藉由無電解還原法來得到微粒子。 使如此進行而得到的微粒子乾燥後，藉由使用雷射繞 射散射法之粒度分布計來測定粒子尺寸。平均粒徑d50的 値爲3.7微米’且d9〇及di〇各自爲5.3微米及2.8微米， 依照[(d 9 〇 - d ! 〇) / d 5 〇 ]所得到的粒度分布爲0 · 6 8。使用S E Μ (掃 0 描型電子顯微鏡觀察粒子形狀之結果，係如第1圖所示， 確認係單分散的球形狀。而且，分析微粒子的成分組成之 結果，係如下述表1所示，係含有0.4 0質量％ c U之鎳磷微 粒子。 (實施例2) 除了將六水合硫酸鎳與五水合硫酸銅的比例以Ni與 Cu的莫耳比爲Ni/Cu = 5的方式調整，並使金屬鹽水溶液、 pH調整水溶液的液量各自爲0.25(dm3)以外，與實施例1 Q 同樣地進行，並藉由無電解還原法來得到微粒子。又，混 合水溶液的pH爲9.0。 而且，藉由使用雷射繞射散射法來確認粒度分布時， 平均粒徑d5Q的値爲 8.9微米，依照[(d9G-d1())/d5()]値爲 0.58，得到如第2圖的SEM照片所示之球狀鎳磷微粒子。 又，製造粒子的剖面觀察試料，並藉由FE-SEM(電場放出 型掃描型電子顯微鏡）觀察各元素的分布時’如第3〜6圖’ 確認在從粒子中心往外側約2/3的內側，Cu係濃密地分 布。又，分析成分組成之結果，係如下述表1所不’確認 -18- 200927951[Technical Field] The present invention relates to a metal fine particle and a method for producing the same, which is used in addition to metal fine particles used as conductive particles for an anisotropic conductive film, for example. It is suitable as a material used for wiring formation of a substrate or the like. [Prior Art] With the spread of terrestrial digital broadcasting, FPD (Flat Panel Display) such as LCD (Liquid 〇 Crystal Display) or PDP (Plasma Display Panel) has rapidly grown. Most of the electrical connection of the drive 1C or the fine wiring circuit uses an isotropic conductive film. The anisotropic conductive film is a thermosetting or thermoplastic insulating resin film, and an adhesive that disperses the conductive particles is placed between the opposing wirings, and then thermally bonded to the conductive particles to obtain wiring. The electrical connection between the wirings adjacent to each other in the surface direction is electrically connected. The conductive particles are widely used by plating a metal material such as Ni or Au on a surface of a resin ball such as polystyrene or acrylate to make conductive resin balls, Ni, Cu, A, Au, and Ag. A metal powder such as a powder or a powder obtained by plating a metal on the surface thereof. In general, since the conductive resin ball used for the conductive particles of the anisotropic conductive film is elastically deformed by the pressure and temperature at the time of thermocompression bonding, there is an advantage that the contact area with the wiring can be increased. However, because the resin ball insulators are not only difficult to obtain good conduction, but also because of the special treatment to metallize the surface, there is a very expensive price of 200927951. On the other hand, metal powder such as Ni powder can be used for connection between TCP (Tape Carrier Package) and FPC (Flexible Printed Circuit), TCP and PWB (Printed Wiring Board) A conductive film of a different orientation such as a connection. A circuit board such as TCP, FPC, or PWB can form a fine wiring circuit by using Cu or a material which is relatively soft and which is easy to form an oxide film by applying Sn plating thereon. The directional conductive thinness using metal powder 0 The film has the advantage of being able to penetrate the oxide film on the wiring circuit to ensure conduction. However, for example, when the metal powder obtained by the gas atomization method is used as the conductive particles for the isotropic conductive film, it is extremely difficult to obtain particles having sharp particle size distribution. Since the particle sizes are not uniform, there is a problem that the price becomes high in order to conform to the particle size classification of the specification of the isotropic conductive film. Therefore, in view of the above-mentioned problems, the inventors of the present invention have proposed to disclose conductive particles in which the Q-direction conductive film is used for the connection of the fine-wiring of the circuit board (Patent Document 1). Since the conductive particles have excellent conductive properties, on the other hand, a high hardness and a uniform shape and particle size distribution can be achieved, which is suitable for an anisotropic conductive film. Further, in order to form fine circuit wiring on an FPC or a glass substrate, a screen printing method using an Ag paste or the like is used. This method is a method in which a carbon paste is printed on a substrate by using a highly conductive Ag paste, and a carbon paste is laminated in the form of an Ag wiring, and baked to form a circuit wiring, according to the method. A large number of substrates and the like can be manufactured inexpensively. [Problem to be Solved by the Invention] In the above prior art, for example, when the conductive particles for an anisotropic conductive film are observed, the method of Patent Document 1 is The above-described problems show an effective method for achieving a certain effect. However, when such nickel-phosphorus (NiP) fine particles are compared with a conductive resin ball, the particle size varies, and there is room for improvement. When the wiring for forming a wiring such as an FPC or a substrate is evaluated, for example, when a fine wiring having a wiring interval of 0.2 mm or less is formed, the accuracy of the screen printing, that is, the prevention of the Ag wiring and the lamination is prevented. The positional shift in the carbon paste printing for electron transfer has a problem that it is difficult to form a wiring circuit of high precision. Therefore, in the wiring forming material, in order to eliminate the deterioration of the accuracy of the circuit wiring due to the problem of the electron migration, it is required to replace the Ag paste with conductive particles. SUMMARY OF THE INVENTION An object of the present invention is to provide a spherical nickel-phosphorus fine particle which is particularly suitable for use in an electrically conductive particle of an anisotropic conductive film and which is excellent in monodispersity and conductivity, and a method for producing the same. Further, in addition to the above, a spherical nickel-phosphorus fine particle which is excellent in transition resistance, electrical conductivity, and low-temperature sinterability, and a method for producing the same, which are excellent in circuit wiring for forming an FPC or a glass substrate, and the like are provided. [Means for Solving the Problem] The inventors of the present invention conducted detailed review of conductive particles for an anisotropic conductive film which can be applied to a high-precision fine circuit. Further, as a material capable of forming circuit wiring finely and accurately in a substrate or the like, conductive particles suitable for the same are also known. As a result, the conductive particles for the anisotropic conductive film of Patent Document 1 proposed in the prior art contain a composition of Cu, and also contain a composition of Sn, whereby variation in particle size can be suppressed, and conductivity characteristics of the lifted particles themselves can be obtained in 200927951. The result. In other words, the present invention is a spherical nickel-phosphorus fine particle which is composed of a component mainly composed of Ni and containing P (preferably 1 to 15% by mass), which is characterized by a precipitated spherical nickel-phosphorus fine particle. It is composed of Cu in this composition. Further, a reduced-precipitated spherical nickel-phosphorus fine particle characterized in that it contains 0.01 to 18% by mass of Cu in the composition of the component. Further, the present invention is a method for reducing precipitation-precipitated spherical nickel-phosphorus fine particles, which is characterized in that it contains Sn, for example, a cerium-reducing precipitated spherical nickel-phosphorus fine particle, in addition to the composition of the above-mentioned Cu. 0.05 to 10% by mass of S η. Further, the reduced-precipitated spherical nickel-phosphorus particles of the present invention preferably have an average particle diameter d5 〇 of 0.1 to 70 μm and a particle size distribution of [(d9〇-di〇)/d5〇]S〇.8 ( Dgio, dI(), and d5〇: indicate the particle size of the cumulative distribution curve '90% by volume, 10% by volume, and 50% by volume. Here, it is advantageous to adjust the particle size distribution by including the above Cu, in particular, the average particle diameter d5Q is on the large particle diameter side of 1 to 70 μm. Further, it is advantageous to adjust the particle size distribution by further including Sn in the Q, in particular, the average particle diameter d5Q is on the side of the small particle diameter of 0.1 to 10 μm. Furthermore, the present invention provides a production method in which an aqueous solution of a nickel salt, a mixed aqueous solution of a pH adjuster and a pH buffer, and an aqueous solution of a phosphorus-containing reducing agent are mixed and reduced and precipitated to produce Ni as a main component. A method of containing spherical nickel-phosphorus particles of P, wherein the aqueous solution of the nickel salt contains Cu, and is adjusted so as to have a pH at which the pH at the time of starting reduction and precipitation is greater than 7. The aqueous solution of the above nickel salt preferably contains Cu such that the molar ratio is Ni/Cu = 4.0 to 1 0000. Further, the present invention provides a production method in which an aqueous solution of a nickel salt at the time of the above-mentioned reduction precipitation contains Sn in addition to the above-mentioned Cu, and the pH at which the precipitation is started to reduce and precipitate is greater than 7. Alkaline way to adjust. In this case, it is preferred that the aqueous solution of the nickel salt contains Sn in such a manner that the molar ratio is Ni/Sn = 2.0 to 2,000. [Effect of the Invention] The Cu-containing or Sr-containing reductive-precipitated spherical nickel-phosphorus microparticles of the present invention have a small aggregation of particles when the particles are spherically formulated in a thermosetting or thermoplastic insulating resin film. The dispersibility is good, and when a conductive particle of an anisotropic conductive film is used, a short circuit between electrodes can be suppressed. At the same time, it is possible to obtain low connection resistance and high connection reliability even in a material which is difficult to obtain a good connection reliability, that is, a metal electrode which is likely to form an oxide film such as an A1 or a Cr electrode. Further, the metal particles of the Ni-based component of the spherical nickel-phosphorus fine particles of the present invention have excellent transition resistance and electrical conductivity, and exhibit uniform particle size, and form a circuit wiring such as an FPC or a glass substrate at a low temperature. Sinterability is good, and damage to the substrate can be reduced.实施 EMBODIMENT OF THE INVENTION The present invention is characterized in that N i is mainly contained, and it is necessary to contain at least a semi-metal P to form, for example, a reductive precipitation type spherical nickel-phosphorus fine particle represented by Patent Document 1, which contains Cu. As a result, it clearly has the effect of suppressing particle size unevenness. Therefore, the composition of the composition is such that the Cu content is 〇_〇1 to 18% by mass. Further, the present invention is characterized in that the Cu-containing spherical nickel-phosphorus particles are made to contain Sn, and the effect of suppressing unevenness is clearly exhibited. Further, the spherical nickel-phosphorus-10-200927951 microparticles containing the two elements of Cu and Sn have an average particle diameter d5Q of 0.1 to 70 μm and a particle size distribution of [(d^-U/dso);球.8 spherical nickel-phosphorus fine particles having the same particle size. At this time, in the two elements, the spherical nickel-phosphorus particles of Cu are selected, and the average particle diameter is on the large particle diameter side of 1 to 70 μm. Further, the effect of unevenness is excellent, and the spherical nickel-phosphorus fine particles containing both Cu and Sn are excellent in the effect of suppressing the above unevenness, particularly in the case where the average particle diameter is on the small particle diameter side of 0·1 to 10 μm. Further, in the production of the spherical nickel-phosphorus fine particles of the present invention, for example, an aqueous solution containing Cu, or a nickel salt of Cu and Sn, a mixed aqueous solution of a pH adjuster and a pH buffer, and an aqueous solution containing a reducing agent containing phosphorus are mixed. It is produced by an electroless reduction method in which it is reduced and precipitated, and is preferably adjusted so as to have a pH at which the pH at the time of starting reduction and precipitation is greater than 7. The aqueous solution of the Cu-containing nickel salt is in the form of a molar. It is preferable to adjust the amount of Cu in a manner of Ni/Cu = 4.0 to 10000. Moreover, When Sn is added to the aqueous solution of the Cu-containing nickel salt, the amount of Sn is preferably adjusted so that the molar ratio is Ni/Sn = 2.0 to 2000. First, the spherical nickel-phosphorus particles of the present invention are mainly composed of Ni. It is necessary to contain P, for example, a composition containing 1 to 15% by mass of P. Basically, when using conductive particles as an anisotropic conductive film, it is an effective method for imparting necessary hardness and conductivity. The inventors of the present invention have proposed a spherical nickel-phosphorus microparticle having a crystal structure in a central portion of a particle and an intermetallic compound dispersed in a non-crystalline portion in the surface layer portion, and in accordance with the method of the patent document. In order to ensure a uniform effect of the uniformity of the particle size distribution, it is effective to increase the uniformity of the particle size distribution. However, the inventors of the present invention have focused on the results of the concentrating begging of -11-200927951, and found that among the spherical nickel-phosphorus particles of Patent Document 1, especially Cu is added. In addition, it is possible to suppress the unevenness of the particles and to improve the conductivity. The content of Cu in the reduced-precipitated spherical nickel-phosphorus particles of the present invention is from 0. 01 to 18. When the content of Cu is less than 0.01% by mass, it is difficult to obtain an effect of suppressing particle unevenness. Further, when the content of Cu is more than 18% by mass, the particles become easily aggregated, which is not only impairing monodispersity. Further, for example, when applied to an anisotropic conductive film, it is difficult to obtain fine wiring capable of being adapted to a circuit board connected thereto, for example, a particle having a size of 20 μm or less, more preferably containing 0.40 to 17% by mass of Cu. In addition to the above-described Cu-containing reduction-precipitated spherical nickel-phosphorus particles, the addition of S η can also be suppressed in the same manner as in the composition of the component. The effect of uneven particle size. In this case, the spherical nickel-phosphorus fine particles of the present invention preferably have a Sn content of 0.05 to 10% by mass. When the content of S η is less than 0.05 mass%, it is difficult to obtain an effect of suppressing particle unevenness by Q, and in particular, it is difficult to obtain the same effect as that of the small-diameter side described later. Further, when the content of Sn is more than 10% by mass, not only the particles become indefinite, but it is difficult to obtain monodisperse particles. More preferably, it is composed of a component containing 0.25 to 5% by mass of Sn, and metal fine particles having less unevenness in particle size and excellent conductivity can be easily obtained. The reduced-precipitated spherical nickel-phosphorus fine particles containing Cu or Cu and Sn in the present invention are preferably such that the average particle diameter d5C is 〇1 to 70 μm (dso: expressed in a cumulative distribution curve) , 50% by volume of the particle size), the particle size is selected according to the use. However, when the particle diameter is less than 0.1 μm, the particles tend to aggregate due to -12 to 200927951, which makes it extremely difficult to handle. On the other hand, when the average particle diameter d5 〇 is larger than 70 μm, it takes a lot of time to grow the particles, and it is difficult to obtain uniform particles efficiently, preferably 50 μm or less, more preferably 30 μm or less. Further, when it is larger than 20 μm, it is difficult to use the conductive particles for the anisotropic conductive film or the wiring formed of the FPC or the substrate. When the spherical nickel-phosphorus particles of the present invention are used as, for example, conductive particles for an anisotropic conductive film, the number Q 値 of the average particle diameter d5Q is preferably 1 to 20 μm. When the particle diameter is less than 1 μm, the unevenness of the fine wiring formed on the circuit board such as TCP, FPC or PWB at the time of the anisotropic conductive connection cannot be buffered, resulting in unstable contact or reduced connection reliability. On the other hand, when d5{) is larger than 20 μm, the connection of the fine wiring having a narrow gap of a wiring interval of several tens of micrometers may lower the insulation property and the possibility of ensuring stable connection reliability. Therefore, in particular, the spherical nickel-phosphorus particles of the present invention are preferably used as the conductive particles for the anisotropic conductive film, and the d5G is preferably 1 to 20 μm, more preferably 1 to 1 μm. The particle diameter is arbitrarily selected in accordance with the wiring interval and the electrode shape to be connected by the anisotropic conductive film. In addition, in the reduced-precipitated spherical nickel-phosphorus fine particles of the present invention in which the d5Q is in the range of 0.1 to 70 μm, d5G is adjusted to have a large diameter side of 1 μm or more and further 5 μm or more, and is suppressed at this time. The effect of uneven particle size is excellent, and there is a case where copper is contained between two contained elements of Cu or Sn alone. In addition, when the spherical nickel-phosphorus particles of the present invention are used as a material for forming a circuit wiring such as an FPC or a glass substrate, the average particle diameter d50 -13 - 200927951 is arbitrarily selected in accordance with the use, and is 0.1 to 10 μm. good. When d5Q is larger than 1 〇 micrometer, there is a case where it is not possible to apply to a fine wiring interval. Further, when the circuit wiring is formed, the sintering temperature rises, which may cause damage to the substrate. On the other hand, when d5 〇 is less than 0.1 μm, not only the treatment of the particles becomes very difficult, but also because the particles themselves are expensive, it is difficult to adapt to mass production. In addition, in the case of the above-described d5C, the reduced-precipitated spherical nickel-phosphorus fine particles of the present invention in the range of 0.1 to 70 μm are adjusted so that d5G is less than or equal to the above-mentioned 0 1 〇 micrometer and further smaller than 5 μm. In this case, the effect of suppressing particle size unevenness is excellent, and there are cases where two elements including Cu and Sn are contained. Next, the reduced-precipitated spherical nickel-phosphorus particles of the present invention are characterized by a uniform particle size distribution. When the particle size distribution is [(d9()-d1())/d5()]> 0.8, (d9(), d1(): is expressed in the cumulative distribution curve, 90% by volume, 10% by volume of the particle size) For example, in the case of an electrically conductive connection in an opposite direction, since the number of particles participating in conduction is reduced, there is a possibility that connection reliability is deteriorated. Therefore, the particle size distribution provided by the Q is preferably as small as possible, but the hour must be stratified by many costs, [(d9D-d1())/d5()] It is preferably 0.8 or less, and more preferably 0.7 or less. A preferred method of producing the spherical nickel phosphorus fine particles of the present invention will be described. First, the inventors of the present invention proposed in Patent Document 1 that a nickel salt aqueous solution and a phosphorus-containing reducing agent aqueous solution are mixed and precipitated to produce spherical nickel-phosphorus fine particles containing P as a main component, that is, no Electrolytic reduction method. The basic principle of the reduction precipitation is sufficient for the production of the spherical nickel particles of the present invention. However, in this case, it is important to add Cu ions to the aqueous solution of the nickel salt by adding -14 to 200927951. In other words, the free electrons e released by the oxidation reaction of the reducing agent and the Ni ions are reduced while Cu is reduced and precipitated, whereby nickel nickel phosphorus particles having a small variation in particle size can be obtained. Further, the important feature of the present invention is that a Sn ion is added to an aqueous nickel salt solution obtained by adding the above Cu ions as necessary. Therefore, when the precipitation reaction is reduced, Sn is also eutectoidized, and nickel-phosphorus fine particles having a small Sn size variation can be obtained. The above reaction mechanism will be described in detail. The electroless ruthenium reduction method used in the present invention is followed by mixing an aqueous solution of a nickel salt with an aqueous solution of a phosphorus-containing reducing agent, and immediately after the initial stage of the reaction, first, a phosphorus-containing reducing agent, i.e., a phosphinic acid, generates an oxidation reaction. As the oxidation reaction proceeds, the phosphonate ions generated in the solution are accumulated, and when the concentration is reached, the phosphonate ions combine with the free Ni ions to form a nickel phosphonate as a nucleus of spherical nickel-phosphorus particles. Further, on the surface of the above-mentioned core, i.e., on the surface of Ni, the phosphinate ion exhibits catalytic activity, and an oxidation reaction occurs by the desorption reaction of hydrogen in the reaction process. The metal ions of Ni, 0 Cu and/or Sn are continuously reduced and precipitated by the free electrons emitted during the oxidation reaction to form target spherical nickel-phosphorus particles. However, in general electroless Ni-P plating, in order to prevent deposition of a plating film other than the object to be plated or to prevent natural decomposition of the plating solution, a sulfur compound such as thiourea or Pb, Bi, Tl, or the like may be used. A heavy metal ion such as Sb or the like acts as a stabilizer. The stabilizer described above is preferentially adsorbed to the precipitate which is a cause of natural decomposition of the plating solution, and has a function as a catalytic poison. Further, it is known that Sn and Cu are second only to the elements of the above-mentioned heavy metals which reduce the catalytic activity. In the production of the spherical nickel-phosphorus particles of the present invention, it is judged that -15-200927951 can be added to the aqueous solution of the nickel salt by adding Cu, or Cu and Sn, and in the middle of the reaction of the electroless reduction method, by the action of the catalytic poison, The formation of nickel phosphonate is inhibited. In addition, when the spherical nickel-phosphorus particles obtained by the production method of the present invention are analyzed for the composition distribution of the cross-section, it is confirmed that the central portion is densely distributed with Cu or Cu and Sn ions (for example, 3 to 6 to be described later). Fig. 9 and Fig. 9 to Fig. 13 are images of FE-SEM (Electrical Field Release Scanning Electron Microscope). Further, in the above-described action, particularly, the φ which suppresses the variation in the particle size is appropriately set in the case where Cu is added to the aqueous solution of the nickel salt, and the molar ratio is set to be Ni/Cu = 4.0 to 10,000. When Ni/Cu is low, it is considered that the respective particle sizes themselves can be adjusted to be large, and on the other hand, the variation in particle size distribution tends to be small. Further, when the ratio is high, it is considered that the respective particle sizes themselves can be adjusted to be small, and on the other hand, the variation in the particle size distribution tends to be small. In the above molar ratio, when the reduction precipitation reaction in the case of using a nickel salt aqueous solution adjusted to have Ni/Cu = about 4.56 is 10%, the theoretical Cu q amount contained in the obtained spherical nickel phosphorus fine particles is When the P content is about 7% by mass, it is 18% by mass. Further, when the reduction precipitation reaction in the case of using a nickel salt aqueous solution adjusted to have Ni/Cu = about 9999 is 100%, the theoretical Cu amount contained in the obtained spherical nickel phosphorus fine particles is about P content. When it is 7 mass%, it is 〇.〇1 mass%. Further, when Sn is further added to the aqueous solution of the nickel salt containing Cu, the effect of suppressing the variation in particle size on the smaller diameter side is superior to that in the case where Cu is added alone, and this effect is obtained by adjusting the addition of Sn to the molar ratio. Ni/Sn = 2.0~2〇〇〇 way to set. When Ni/Sn is low, it is considered that the respective particle sizes themselves can be adjusted to be small, and on the other hand, the variation in the particle size distribution also tends to be small -16 to 200927951. Further, when the ratio is increased, it is considered that the respective particle sizes themselves can be adjusted to be large, and the variation in the particle size distribution tends to be small. Moreover, in these methods, another important point is to adjust the pH at the beginning of its reduction and precipitation. This is because the precipitation reaction can be rapidly performed by adjusting to a basicity of more than 7, and nickel-phosphorus fine particles containing Cu, Cu, and Sn can be efficiently obtained. Further, by blending the action effect', the P concentration 0 at the center portion at the initial stage of the reaction of the fine particles can be reduced (the same as Figs. 3 to 6 and Figs. 9 to 13). In this regard, a method for improving the conductivity and hardness of the fine particles is also described in Patent Document 1. Further, in the same manner as in Patent Document 1, the reduction-precipitated spherical nickel-phosphorus fine particles containing Cu, Cu, and Sn according to the present invention can be subjected to heat treatment in accordance with the above-described method, and/or In order to reduce the connection resistance, a surface coating treatment such as Au may be applied. [Examples] (Example 1) Q Nickel sulfate hexahydrate and copper sulfate pentahydrate were adjusted so that the molar ratio of Ni and Cu was Ni/Cu = 23 9 and dissolved in pure water to produce 15 (dm3). Aqueous metal salt solution. Next, sodium acetate was dissolved in pure water to a concentration of 1.0 (kmol/m3), and sodium hydroxide was added to prepare a 15 (dm3) pH-adjusted aqueous solution. Then, the above aqueous metal salt solution and the pH-adjusted aqueous solution were stirred and mixed to obtain a mixed aqueous solution of 30 (d m3), and when p Η was measured, 値 was obtained. Then, the above mixed aqueous solution was bubbled with Ν2 gas while being maintained at 343 (Κ) by heating with an external heater and stirring was continued. Next, an aqueous solution of a reducing agent obtained by dissolving a concentration of sodium phosphinate 1.8 (kmol/m3) in pure -17-200927951 water was produced. Also heat these to 343 (Κ) using an external heater. Then, the mixed aqueous solution of 3 〇 (dm3) and the aqueous reducing agent of 15 (dm3) were adjusted so that the temperature was 3 43 ± 1 (K), and the mixture was mixed, and fine particles were obtained by an electroless reduction method. After the fine particles obtained in this manner were dried, the particle size was measured by a particle size distribution meter using a laser diffraction scattering method. The average particle diameter d50 is 3.7 μm and d9〇 and di〇 are 5.3 μm and 2.8 μm, respectively, and the particle size distribution obtained according to [(d 9 〇- d ! 〇) / d 5 〇] is 0 · 6 8 . As a result of observing the particle shape by a scanning electron microscope, the spherical shape of the monodisperse was confirmed as shown in Fig. 1. Further, the results of analyzing the composition of the fine particles were as shown in Table 1 below. a nickel-phosphorus microparticle containing 0.40% by mass of c U. (Example 2) except that the ratio of nickel sulfate hexahydrate to copper sulfate pentahydrate is adjusted so that the molar ratio of Ni to Cu is Ni/Cu = 5, and The amount of the metal salt aqueous solution and the pH-adjusted aqueous solution was 0.25 (dm3), and the same procedure as in Example 1 Q was carried out, and fine particles were obtained by an electroless reduction method. Further, the pH of the mixed aqueous solution was 9.0. When the particle size distribution was confirmed by the laser diffraction scattering method, the 値 of the average particle diameter d5Q was 8.9 μm, and [ was obtained according to [(d9G-d1())/d5()] 0.5 0.58, and the SEM as shown in Fig. 2 was obtained. The spherical nickel-phosphorus particles shown in the photographs. When the cross-section observation sample of the particles was produced, and the distribution of each element was observed by FE-SEM (electric field emission type scanning electron microscope), the image was confirmed as shown in Fig. 3 to Fig. 6 From the center of the particle to the outside of about 2/3 of the outer side, the Cu system is densely divided. In addition, the results of analyzing the composition of the components are as shown in Table 1 below. -18- 200927951
Cu爲14.36質量％。 (實施例3 ) 除了將六水合硫酸鎳與五水合硫酸銅的比例以Ni與 Cu的莫耳比爲Ni/Cu = 39的方式調整，而且將pH調整劑變 更爲乙酸鈉及順丁烯二酸二鈉且各自的濃度爲 0-65(km〇l/m3)、〇.175(kmol/m3)來調製pH調整劑水溶液以 外’與實施例1同樣地進行，並藉由無電解還原法來得到 微粒子。又，混合水溶液的pH爲8.2。 〇 而且’藉由使用雷射繞射散射法來確認粒度分布時， 平均粒徑d5G的値爲67.1微米，依照[(d9Q-d1())/d5()]値爲 〇_51。又，藉由SEM觀察上述的微粒子之結果係如第7圖 所示’確認係單分散的球形狀。而且，分析成分組成之結 果，係如下述表1所示，確認C u爲2.7 5 0質量％。 (實施例4) 依照專利文獻 1，將未添加 Cu之鎳鹽的水溶液、 0.9(kmol/m3)氫氧化鈉及 1.0(kmol/m3)乙酸鈉的混合水溶 Q 液各自製造〇.25(din3)，邊從外部加熱邊進行攪拌，混合2 液作爲混合水溶液，使N2氣體流動進行冒泡，並調整使混 合水溶液的溫度爲3 43 ±1(K)。 另一方面，製造〇.25(dm3)將次膦酸鈉以1.8(kmol/m3) 的濃度溶解於純水而成之還原劑水溶液，亦將該等以使用 外部加熱器加熱至343(K)。並藉由與實施例1同樣的方 法，得到球狀鎳磷微粒子。藉由使用雷射繞射散射法來確 認粒度分布時’平均粒徑 d5〇的値爲 2.9微米，依照 [(dgo-ditO/dso]値爲〇.76。而且，從表1的成分組成的分析 • 19- 200927951 結果，只能夠確認Cu爲不純物的程度（小於0.001質量％)。 (實施例5) 除了使用六水合硫酸鎳、五水合硫酸銅及三水合錫酸 鈉，並以^/(^的莫耳比爲24、^/311的莫耳比爲4.8的方 式調整，與實施例1同樣地進行，並藉由無電解還原法來 得到微粒子。又，混合水溶液的pH爲9.6。 而且，藉由使用雷射繞射散射法來確認粒度分布時， 平均粒徑d5Q的値爲1.2微米，依照[(d9Q-d1C))/d5Q]値爲 〇 0.67，得到如第8圖的SEM照片所示之球狀鎳磷微粒子。 又，製造粒子的剖面觀察試料，並藉由FE-SEM觀察各元 素的分布時，如第9〜13圖，確認分布有Cu及Sn»而且， 分析成分組成之結果’係如下述表1所示’確認Cu爲3 _ 96 質量％，S η爲0.6 7質量％。 [表1] 微粒子的成分組成(質量％) 備考 Cu Sn P Ni* 實施例1 0.402 <0,01 7.0 殘餘 本發明例 實施例2 14.363 <0.01 6.7 殘餘 實施例3 2.750 <0.01 6.0 殘餘 實施例4 <0.001 <0.01 7.5 殘餘 參考例(專利文獻1) 實施例5 3.960 0.67 10.3 殘餘 本發明例 ※含有不純物 -20- 200927951 [產業上之利用可能性] 具有均勻的粒子尺寸之本發明的球狀鎳磷微粒子，除 了能夠應用於異方向性導電薄膜用的導電粒子以外，亦能 夠應用於必須具有同樣特性之異方向性導電糊或熱封接合 物等作爲導電粒子。 【圖式簡單說明】 第1圖係本發明的球狀鎳磷微粒子之一個例子之電子 顯微鏡照片。 0 第2圖係本發明的球狀鎳磷微粒子之一個例子之電子 顯微鏡照片。 第3圖係本發明的球狀鎳磷微粒子的剖面結構之一個 例子之電子顯微鏡照片。 第4圖係觀察第3圖的剖面之Ni濃度分布之測繪照 片。 第5圖係觀察第3圖的剖面之Cu濃度分布之測繪照 片。 H 第6圖係觀察第3圖的剖面之P濃度分布之測繪照片。 第7圖係本發明的球狀鎳磷微粒子之一個例子之電子 顯微鏡照片。 第8圖係本發明的球狀鎳磷微粒子之一個例子之電子 顯微鏡照片。 第9圖係本發明的球狀鎳磷微粒子的剖面結構之一個 例子之電子顯微鏡照片。 第1 0圖係觀察第9圖的剖面之Ni濃度分布之測繪照 片。 -21 - 200927951 第1 1圖係觀察第9圖的剖面之Cu濃度分布之測繪照 片。 第1 2圖係觀察第9圖的剖面之Sn濃度分布之測繪照 片。 第1 3圖係觀察第9圖的剖面之P濃度分布之測繪照 片。 【主要元件符號說明】 〇Cu was 14.36% by mass. (Example 3) The ratio of nickel sulfate hexahydrate to copper sulfate pentahydrate was adjusted so that the molar ratio of Ni to Cu was Ni/Cu = 39, and the pH adjuster was changed to sodium acetate and maleic acid. In the same manner as in Example 1, except that the concentration of the acid disodium was 0-65 (km〇l/m3) and 〇.175 (kmol/m3) to prepare an aqueous solution of the pH adjuster, and the electroless reduction method was used. To get the microparticles. Further, the pH of the mixed aqueous solution was 8.2. 〇 And when the particle size distribution is confirmed by the laser diffraction scattering method, the 値 of the average particle diameter d5G is 67.1 μm, which is 〇_51 according to [(d9Q-d1())/d5()]値. Further, the result of observing the above-mentioned fine particles by SEM was as shown in Fig. 7 to confirm the monodisperse spherical shape. Further, as a result of analyzing the composition of the components, as shown in the following Table 1, it was confirmed that Cu was 2.75% by mass. (Example 4) According to Patent Document 1, an aqueous solution in which no nickel salt of Cu is added, a mixed water solution of 0.9 (kmol/m3) sodium hydroxide and 1.0 (kmol/m3) sodium acetate is produced in each of 〇.25 (din3) The mixture was stirred while being heated from the outside, and the two liquids were mixed as a mixed aqueous solution, and the N2 gas was bubbled and adjusted so that the temperature of the mixed aqueous solution was 3 43 ±1 (K). On the other hand, a reducing agent aqueous solution obtained by dissolving sodium phosphinate in pure water at a concentration of 1.8 (kmol/m3) was produced by 〇.25 (dm3), and was also heated to 343 (K) using an external heater. ). Further, spherical nickel phosphorus fine particles were obtained in the same manner as in Example 1. The 値 of the average particle diameter d5〇 was 2.9 μm when the particle size distribution was confirmed by the laser diffraction scattering method, and [(dgo-ditO/dso]値 was 〇.76. Further, it was composed of the components of Table 1. Analysis • 19-200927951 As a result, only the extent to which Cu was an impurity (less than 0.001% by mass) was confirmed. (Example 5) Except that nickel sulfate hexahydrate, copper sulfate pentahydrate, and sodium stannate trihydrate were used, and ^/( The Mohr ratio of ^ was adjusted to be 4.8 in the range of 4.8, and the molar ratio was 4.8, and the fine particles were obtained by the electroless reduction method in the same manner as in Example 1. Further, the pH of the mixed aqueous solution was 9.6. When the particle size distribution is confirmed by the laser diffraction scattering method, the 値 of the average particle diameter d5Q is 1.2 μm, and SEM 0.67 is obtained according to [(d9Q-d1C))/d5Q] ,, and an SEM photograph as shown in Fig. 8 is obtained. The spherical nickel-phosphorus particles are shown. When the cross-section observation sample of the particles is produced and the distribution of each element is observed by FE-SEM, as shown in the figures 9 to 13, it is confirmed that Cu and Sn» are distributed and the composition of the components is analyzed. The result 'is as shown in the following Table 1' to confirm that Cu is 3 _ 96% by mass, and S η is 0.6 7 mass. [Table 1] Composition of the fine particles (% by mass) Preparation Cu Sn P Ni* Example 1 0.402 < 0,01 7.0 Residues Inventive Example Example 2 14.363 <0.01 6.7 Residual Example 3 2.750 <0.01 6.0 Residual Example 4 < 0.001 < 0.01 7.5 Residual Reference Example (Patent Document 1) Example 5 3.960 0.67 10.3 Residual Example of the Invention ※ Containing impurities-20- 200927951 [Industrial Applicability] Uniform particle size The spherical nickel-phosphorus particles of the present invention can be applied to conductive particles for an anisotropic conductive film, and can also be applied as conductive particles such as an anisotropic conductive paste or a heat-sealed joint which must have the same characteristics. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an electron micrograph of an example of spherical nickel-phosphorus microparticles of the present invention. 0 Fig. 2 is an electron micrograph of an example of spherical nickel-phosphorus microparticles of the present invention. An electron micrograph of an example of the cross-sectional structure of the spherical nickel-phosphorus microparticles of the present invention. Fig. 4 is a photograph showing a survey of the Ni concentration distribution in the cross section of Fig. 3. 5 is a picture of the Cu concentration distribution of the cross section of Fig. 3. H Fig. 6 is a photograph of the P concentration distribution of the cross section of Fig. 3. Fig. 7 is a view of the spherical nickel phosphorus particles of the present invention. An electron micrograph of an example. Fig. 8 is an electron micrograph of an example of the spherical nickel-phosphorus microparticles of the present invention. Fig. 9 is an electron micrograph of an example of the cross-sectional structure of the spherical nickel-phosphorus microparticles of the present invention. Fig. 10 is a photograph of a survey of the Ni concentration distribution of the cross section of Fig. 9. -21 - 200927951 Figure 11 is a picture of the Cu concentration distribution of the cross section of Fig. 9. Fig. 1 is a photograph of a survey of the Sn concentration distribution of the cross section of Fig. 9. Fig. 13 is a photograph of the P concentration distribution of the cross section of Fig. 9 observed. [Main component symbol description] 〇
-22--twenty two-