1275569 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係關於，氧化銅超微粒子，及其製造方法者。 又本發明係關於氧化銅超微粒子在分散液中分散成膠體狀 之膠體分散液，及其之製造方法者。本發明所得氧化銅超 微粒子，例如可作爲電子機器之實裝領域中導電性膏•導 電性墨水等之塡料使用，又本發明所得之氧化銅微粒子之 膠體分散液爲低黏度之液體故可藉噴墨法塗布於基板上， 可作爲噴墨墨水使用。 【先前技術】 1次粒徑不足100 nm之氧化銅超微粒子之製造，通 常，爲抑制反應所生成之粒子粒徑之過度増大，以界面活 性劑或者以立體的大體積特定之有機化合物來保護超微粒 子表面之方法目前正被採用。一般而言，在該等製造方法 中，氧化銅超微粒子在反應液中以膠體狀態浮遊之狀態所 得者，爲了除去不純物等，在由反應液使粒子作爲固形成 份來分離時，需要高速離心分離步驟。 以下，特別關於氧化亞銅超微粒子加以説明。但是， 本發明並非只限定於氧化亞銅（cuprous oxide)超微粒子 ，就其他之氧化銅（copper oxide)而言，亦同樣適用。 例如’在中举科學論壇3 9號 1卷 p p . 1 4 · 1 8 1 9 9 4 年（Chinese Science Bulletin.1994,39，14-18)揭示，將 乙酸銅水溶液與爲界面活性劑之十二基苯磺酸一起分散於 -5- 1275569 (2) 甲苯後，將乙酸銅還原，可得到1次粒徑爲5〜1 0 nm， 表面被十二基苯磺酸所覆蓋之氧化亞銅超微粒子（方法i )。此方法稱爲微乳化法，係在爲油層之甲苯中產生直徑 數奈米〜數十奈米之極微小水滴，將該極微小水滴中所存 在之乙酸銅予以還原，而可得到氧化亞銅之方法。所得氧 化亞銅粒子之大小，被微粒化成微小液滴程度，且微粒子 之表面被界面活性劑所覆蓋而呈穩定化。 此種方法所得之氧化亞銅超微粒子，係在水或者在油 層中以浮遊成膠體狀之狀態所得，將液中之不純物除去， 使超微粒子自溶液以固形成份方式分離，則離心分離步驟 爲必要。但是，要使粒徑不足100 nm之超微粒子藉由離 心分離來分離並非容易，使轉子之旋轉氛圍減壓，使得空 氣阻力減小等之操作爲必要之超離心分離裝置一般爲必要 。因此，會有生産性降低，在大量生産爲必要之工業用途 方面實際上無法使用之問題。 一方面，在美國化學業界雜誌121卷pp.l 1 5 95 - 1 1 5 96 1 9 9 9 年（Journal of American Chemical Society，1 999, 1 2 1, 1 1 5 9 5 - 1 1 5 96 )揭示，將含有特定有機銅化合物之辛 胺溶液注入於加熱至25 0 °C之十六烷胺，在溫度成爲230 t時，使加熱停止並冷却之，來獲得平均1次粒徑爲約7 nm，表面被羊胺或者十六院胺之任一種或者兩種之界面 活性劑所覆蓋之氧化亞銅超微粒子之沈澱物（方法2)。 此方法中，可推測具有強大配位能力之氨基在氧化亞銅粒 子生成初期，被配位於粒子表面，而可抑制氧化亞銅之粒 -6 - 1275569 ’ (3) 徑増大者。 在此方法中，氧化亞銅超微粒子並非反應液中之膠體 狀態，而係以沈澱物所得之特徴，因不需離心分離故有粒 子回收容易之優點。又，沈澱物本身因粒子表面被含氨基 之有機物所覆蓋之氧化亞銅超微粒子互相爲弱凝集之軟凝 集體，此係於甲苯等適切的分散介質予以再分散而可獲得 氧化亞銅超微粒子膠體溶液。但是，該等氧化亞銅超微粒 子在粒子表面因具有分子量大的絶縁性有機化合物，在以 此作爲導電性塡料使用之場合會有導電性惡化之問題。 一方面，在粒子表面不具有特別界面活性劑或者大體積 的有機化合物之氧化亞銅超微粒子之製造方法亦爲周知。 在 Angewandte Chemie 國際版，40 卷，2 號，ρ·359 ，2 0 0 1 年(Angewandte Chemie international edition, 200 1, No· 40，vol2，p3 5 9 )揭示，將乙醯丙酮配位基（ acetylacetonato)銅錯合物溶解於多元醇，添加微量之水 ，加熱至190°C，可獲得粒徑具有30〜200 nm分布之氧 化亞銅超微粒子（方法3 )。此方法所得之氧化亞銅超微 粒子，與具有界面活性劑或者大體積的有機化合物之情形 比較，粒徑有變大之傾向。再者，所得粒子單分散性高’ 因係以膠體分散液方式獲得，故將副產物除去，以使氧化 亞銅超微粒子以固形成份方式被取出則離心分離爲必要。 因此，如上述般，在該等離心分離操作工夫與時間耗費’ 使得大量生産爲必要之工業用途上，有難以適用之問題。 在膠體及界面科學雜誌243卷，pp.85-89 2001年（ 1275569 (4) journal of Colloid and Interface Science 243, 85 -8 9 ( 2 00 1 )揭示，在以少量多元醇作爲添加劑所添加之硫酸銅 鹼性水溶液添加肼，來產生氧化亞銅超微粒子之方法被記 載（方法4)。此方法所得之氧化亞銅微粒子，1次粒徑 爲小至9〜30 nm故較佳，又，爲使2次粒徑產生200〜 1 μιη之沈澱物，則有可容易自反應液中分離之優點。但是 ，在此所得之沈澱物1次粒子間強大的凝集，而形成2次 粒子之硬凝集體，此沈澱物還是難以再分散於分散介質。 因此，使用所得粒子，要調製成氧化亞銅超微粒子在分散 介質呈浮遊狀態之膠體溶液爲不可能。 一方面，在 Zeitschrift fur anorganische und allgemeine Chemie Bd224 卷，pp. 1 07- 1 1 2 1 93 5 年揭示， 在濃厚乙酸銅水溶液添加2 0 %肼水溶液，以獲得氧化亞 銅粒子之沈澱物被記載（方法5 )。但是在本文獻，並未 明示爲原料之乙酸銅及肼之添加量，而僅記載若添加過剩 之肼，則還原至金屬銅爲止，且，亦無所得氧化亞銅之粒 徑之記載。 關於氧化亞銅超微粒子之製造將以上加以歸納時，有 製造所得之氧化亞銅微粒子，①在反應液以膠體狀態分散 之狀態所得之情形（方法1，方法3 )，②以凝集之沈澱 物方式得到之情形（方法2，方法4 )，但就粒子處理性 之觀點而言以②之方法較優。但是，方法4之方法所得之 氧化亞銅超微粒子沈澱物爲再分散不可能之硬凝集體，對 分散介質之再分散爲困難，等等之缺點。一方面，方法2 1275569 (5) 之方法所得之氧化亞銅沈澱物，可容易地再分散於分散介 質，而可容易做成爲所望之組成之膠體分散液，等等長處 ，而在粒子表面具有絶縁性之界面活性劑，所得粒子之實 態爲氧化亞銅與界面活性劑之組合物（composite )，而 在例如煅燒（burning )來獲得銅被膜用之導電性之塡料 等之用途有難以使用之問題。 本發明之課題，係提供一種平均1次粒徑爲10 0 nm 以下之氧化銅超微粒子所構成，相對於分散介質爲可再分 散之氧化銅超微粒子軟凝集體，及其製造方法。又，本發 明之另一課題，係提供氧化銅超微粒子分散於分散液中之 膠體分散液之製造方法。 【發明內容】 本發明者等人，就於上述狀況之氧化銅超微粒子進行 各種檢討試驗結果，而完成本發明。本發明具有以下之構 成。 (1 )平均1次粒徑及平均2次粒徑，分別爲1 00 nm 以下，0.2 μΠΊ以上之氧化銅超微粒子軟凝集體。 (2 )如申請專利範圍第1項之氧化銅超微粒子軟凝 集體，其中，平均1次粒徑爲25 nm以下者。 (3 )如申請專利範圍第1項之氧化銅超微粒子軟凝 集體，其中，平均1次粒徑爲10 nm以下者。 (4 )如申請專利範圍第1至3項之任一項之氧化銅 超微粒子軟凝集體’其中’在粒子表面不具界面活性劑或 -9 - 1275569 (6) 大體積的有機化合物者。 (5 ) —種製造如申請專利範圍第1至4項之任一項 之氧化銅超微粒子軟凝集體之方法，其含有在弱分散介質 中，產生氧化銅超微粒子，藉以在產生氧化銅超微粒子之 同時，形成該等軟凝集體者。 (6 ) —種製造如申請專利範圍第1至4項之任一項 之氧化銅超微粒子軟凝集體之方法，其含有：在良分散介 質中，產生氧化銅超微粒子，及其後在氧化銅超微粒子間 添加凝集力，以形成氧化銅超微粒子之軟凝集體者。 (7 ) —種製造如申請專利範圍第1至4項之任一項 之氧化銅超微粒子軟凝集體之方法，其含有在良分散介質 中產生氧化銅超微粒子之同時，在氧化銅超微粒子間添加 凝集力，以形成氧化銅超微粒子之軟凝集體者。 (8) —種氧化銅超微粒子分散體之製造方法，其特 徵爲含有，在第1溶媒中，使平均1次粒徑1 〇〇 nm以下 之氧化銅超微粒子合成之同時，得到平均2次粒徑爲 〇·2μιη以上之氧化銅超微粒子軟凝集體之第丨步驟，將該 第1步驟所得軟凝集體自第1溶媒分離之第2步驟，將第 2步驟所分離之軟凝集體再分散於第2溶媒，以得到氧化 銅超微粒子分散體之第3步驟。 (9 )如申請專利範圍第8項之氧化銅超微粒子分散 體之製造方法，其中，第3步驟所得之氧化銅超微粒子分 散體’係氧化銅超微粒子在分散體中爲浮遊之膠體狀態。 (1 〇 )如申請專利範圍第9項之氧化銅超微粒子分散 -10- 1275569 (7) 體之製造方法，其中，爲膠體狀態之氧化銅超微粒子分散 體中，氧化銅超微粒子之平均2次粒徑爲，不足200 nm 者。 (1 1 )如申請專利範圍第8〜1 0項中任一項之氧化銅 超微粒子分散體之製造方法，其中，第2溶媒含有氧化銅 超微粒子之分散補助劑者。 (1 2 )如申請專利範圍第1 1項之氧化銅超微粒子分 散體之製造方法，其中，分散補助劑爲多元醇者。 · (1 3 )如申請專利範圍第1 2項之氧化銅超微粒子分 散體之製造方法，其中，多元醇之碳數爲10以下者。 (1 4 ) 一種氧化銅超微粒子分散體，其係由如申請專 利範圍第8〜1 3項中任一項之製造方法所得者。 (1 5 )如申請專利範圍第1 4項之氧化亞銅超微粒子 分散體，其中，使可還原氧化銅超微粒子之還原劑在分散 體中含有〇·〇1〜50重量％者。 (1 6 )平均1次粒徑及平均2次粒徑，分別爲1 00 ® nm以下，不足〇.2μιη之氧化銅超微粒子。 (1 7 )如申請專利範圍第1 5項之氧化銅超微粒子， 其特徵爲，平均1次粒徑爲，2 5 n m以下者。 (1 8 )如申請專利範圍第1 5項之氧化銅超微粒子， 其中平均1次粒徑爲1 0 nm以下者。 (1 9 )如申請專利範圍第1 6至1 8項中任一項之氧化 銅超微粒子，其中，在粒子表面並無界面活性劑或者大體 積的有機化合物者。 -11 - 1275569 (8) (20)如申請專利範圍第16至19項中任一項之氧化 銅超微粒子之製造方法，其含有將申請專利範圍第1至4 項之任一項之氧化銅超微粒子軟凝集體予以分散而獲得氧 化銅超微粒子者。 (2 1 ) —種氧化銅超微粒子膠體分散液，其特徵爲， 含有在分散介質中爲浮遊狀態之申請專利範圍第1 6項至 1 9項中任一項之氧化銅超微粒子。 (22 )如申請專利範圍第2 1項之氧化銅超微粒子膠 體分散液，其中，氧化銅超微粒子之總重量相對於全分散 .液重量爲1 0重量％以上者。 (23 )如申請專利範圍第1至4項中任一項之氧化銅 超微粒子軟凝集體，其中氧化銅爲氧化亞銅。 (2 4 )如申I靑專利範圍第5至7項中任一·項之氧化銅 超微粒子軟凝集體之製造方法，其中氧化銅爲氧化亞銅。 (2 5 )如申請專利範圍第8項至第1 3項中任一項之 氧化銅超微粒子分散體之製造方法，其中氧化銅爲氧化亞 銅。 (2 6 )如申請專利範圍第1 4或1 5項之氧化銅超微粒 子分散體，其中氧化銅爲氧化亞銅。 (2 7 )如申請專利範圍第1 6項至第1 9項中任一項之 氧化銅超微粒子，其中，氧化銅爲氧化亞銅。 (2 8 )如申請專利範圍第2 0項之氧化銅超微粒子之 製造方法，其中，氧化銅爲氧化亞銅。 (2 9 )如申請專利範圍第2 1項或第2 2項之氧化銅超 -12· (9) 1275569 微粒子膠體分散液，其中氧化銅爲氧化亞銅。 (3 0 )如申請專利範圍第23項之氧化亞銅超微粒子 軟凝集體之製造方法，其含有，在含有水10重量％以上 之水溶液中’將銅羧基化合物，相對於銅羧基化合物〗莫 耳使用〇·4〜5.0莫耳之肼及/或肼衍生物加以還原以製 造氧化亞銅超微粒子。 (3 1 )如申請專利範圍第3 〇項之氧化亞銅超微粒子 軟凝集體之製造方法，其中在前述溶液中，含有選自醇化 合物，醚化合物，酯化合物及醯胺化合物所成群之至少一 種有機化合物者。 (3.2 )如申請專利範圍第3 0或3 1項之氧化亞銅超微 粒子軟凝集體之製造方法，其進而含有，在使用肼及/或 肼衍生物來還原銅羧基化合物之際，添加鹼性化合物者 (3 3 )如申請專利範圍第3 0至3 2項中任一項之氧化 亞銅超微松子軟减集體之製造方法，其中，銅竣基化合物 爲乙酸銅者。 (3 4 )如申請專利範圍第3 0至3 3項中任一項之氧化 亞銅超微粒子軟凝集體之製造方法，其中，將肼及/或肼 衍生物溶解於比20重量％更高濃度之溶液，並添加於反 應液者。 (3 5 )如申請專利範圍第2 3項之氧化亞銅超微粒子 軟凝集體之製造方法，其含有，將選自銅羧基化合物，銅 烷氧基化合物及銅二酮根化合物所成群之至少一種銅化合 物，在二乙二醇中，在160 °C以上之溫度加熱•還原，以 (10) 1275569 «得氧化亞銅超微粒子之膠體分散液，及將同膠體分散液 進一步加熱使氧化亞銅超微粒子軟凝集者。 (36) 如申請專利範圍第23項之氧化亞銅超微粒子 軟凝集體之製造方法，其含有，將選自銅羧基化合物，銅 烷氧基化合物及銅二酮根化合物所成群之至少一種銅化合 物，在二乙二醇中，於160°C以上之溫度加熱•還原，以 獲得氧化亞銅超微粒子之膠體分散液，及在此分散液添加 氧化亞銅超微粒子之凝集劑者。 (37) 如申請專利範圍第23項之氧化亞銅超微粒子 軟凝集體之製造方法，其含有，將選自銅羧基化合物，銅 烷氧基化合物及銅二酮根化合物所成群之至少一種銅化合 物，在二乙二醇中於160°C以上之溫度加熱•還原，及同 時在二乙二醇中，於反應溫度下，在二乙二醇添加可溶性 氧化亞銅超微粒子之凝集劑者。 (3 8 )如申請專利範圍第3 6或3 7項之氧化亞銅超微 粒子軟凝集體之製造方法，其中凝集劑係選自單醇化合 物，醚化合物，酯化合物，腈化合物，醯胺化合物及醯亞 胺化合物所成群之至少一種者。 (3 9 )如申請專利範圍第3 5項至3 7項中任一項之氧 化亞銅超微粒子軟凝集體之製造方法，其中在二乙二醇中 ，含有相對於銅化合物1莫耳，爲3 0莫耳以下之水者。 本發明之氧化銅超微粒子軟凝集體，平均1次粒徑及 平均2次粒徑，分別爲1〇〇 nm以下，〇·2μ1τι以上爲其特 徴者。本發明之氧化銅超微粒子軟凝集體，因2次粒徑大 1275569 β (11) 故作爲固形物之處理性優異，另一方面，可容易地分散於 分散介質中，而具有可製造超微粒子爲均勻分散之分散體 之特徴。 一般超微粒子之凝集形態，分爲微粒子彼此之間以可 再分散之弱引力互相牽引之軟凝集體，與微粒子彼此之間 爲以不可能再分散之程度以強鍵結相鍵結之硬凝集體二種 類。軟凝集體係指以物理•化學手法將構成凝集體之微粒 子予以裂開•分散爲可能之凝集體者。在此物理手法係指 ，藉由超音波，粒狀磨，高速噴射磨，螺旋攪拌，行星混 合機（planetary mixer)，三輥機等，在凝集體外加物理 能量之手法。化學手法係指，在液中添加酸•鹼來調整分 散液之pH等，以在凝集體外加化學能量之手法。而要使 軟凝集體分散，則在所構成之各個微粒子間供與超過作用 引力之能量來予以裂開•分散較佳。一方面，硬凝集體要 以物理•化學手法所構成之微粒子予以開製•分散有其困 難。 其次，所謂2次粒徑係指在凝集狀態之超微粒子粒徑 ，可以雷射散亂法估計其平均粒徑，又，替代之方案係使 粒子置於載玻片可以通常顯微鏡做實物觀察來估計其平均 値。而具有可容易形成軟凝集體傾向之超微粒子，在所得 軟凝集體間形成更爲弱之鍵結，而在形成高級次（higher order)構造體之情形，可使高級次構造體全體大小成爲2 次粒徑。如此之高級次構造體有粒徑變大之傾向，故以顯 微鏡做實物觀察較佳。 -15- 1275569 (12) 1次粒徑係指，構成爲凝集體之2次粒子之各個氧化 銅超微粒子之粒徑，亦即各個微粒子之直徑。本發明之氧 化銅超微粒子，其1次粒徑爲極端的小’故在以電子顯微 鏡觀察其形態可對其大小做估計。 凝集體之分散性，在分散處理前後中’依2次粒徑之 變化可估計其程度。本發明中，氧化銅超微粒子軟凝集體 ，分散處理後之平均二次粒徑（R2 )，相對於分散處理前 之軟凝集體之平均2次粒徑（R1 )，以具有可滿足R1/ R2〉5関係之分散性者較佳。 本發明中氧化銅超微粒子之平均1次粒徑以小粒徑者 對分散介質之再分散性有良好之傾向’較佳爲25 nm以下 ，更佳爲10 nm以下。平均1次粒徑超過1〇〇 nm時，因 會降低對分散介質之再分散性之傾向故不佳。 本發明之氧化銅超微粒子軟凝集體之平均2次粒徑爲 0.2μιη以上，較佳爲Ιμπι以上，更佳爲1〇μιη以上。平均 2次粒徑不足〇· 2 μ m之情形，作爲粒子之粉體之處理性傾 向於低故不佳。 本發明之氧化銅超微粒子在粒子表面以不具有界面活 性劑或者大體積的有機化合物者較佳。表面之界面活性劑 或者大體積的有機化合物，在使粒子作爲導電性塡料使用 之情形，因成爲絶縁性成分故不佳。 在此界面活性劑係指，在分子中具有親水基與親油基 之兩性親媒性物質，其種類方面，有陽離子系界面活性劑 ，陰離子系界面活性劑，非極性界面活性劑等。在此，係 -16- 1275569 (13) 爲低分子之醇化合物等非兩性親媒性物質，在粒子表面配 位•吸着，而顯示界面活性之化合物被除外。對界面活性 劑之分子量等並無特別限制，例如爲顯現親油性，可在具 有充分鏈長之烷基末端，可例示具有硫酸鹽，銨鹽，聚乙 二醇等具有親水基之化合物。 大體積的有機化合物係指非兩性親媒性物質，爲碳數 大之有機化合物，例如十二基苯，十三烷，十六烷等之化 合物。 籲 該等，界面活性劑或者大體積的有機化合物之碳數， 通常指8以上之有機化合物。 本發明之氧化銅超微粒子軟凝集體，在1 )軟凝集體 粒子之穩定性，2 )對軟凝集體之分散介質之再分散性，3 )再分散之氧化銅超微粒子分散體之穩定性，4)在作爲 導電性墨水或塡料使用之情形，煅燒所得銅被膜之導電性 或穩定性等，在儘量不使該等特性惡化之條件下，可使金 屬銅等之副產物含於5重量％以下之範圍。 ® 其次，就上述氧化銅超微粒子軟凝集體之製造方法加 以說明。本發明之氧化銅超微粒子軟凝集體之製造方法包 含下列之（I)〜（III)。 (I)在弱分散介質中使氧化銅超微粒子產生，在氧 化銅超微粒子產生之同時，使該等形成軟凝集體爲其特徴 之氧化銅超微粒子軟凝集體之製造方法。 (II )在良分散介質中，使氧化銅超微粒子產生後， 在氧化銅超微粒子間添加凝集力，來形成氧化銅超微粒子 -17- 1275569 (14) 之軟凝集體爲其特徴之氧化銅超微粒子軟凝集體之製造方 法。 (III)在良分散介質中使氧化銅超微粒子產生之同 時，在氧化銅超微粒間添加凝集力，以形成氧化銅超微粒 子之軟凝集體爲其特徴之氧化銅超微粒子軟凝集體之製造 方法。 在上述中，所謂氧化銅超微粒子之弱分散介質，良分 散介質，分別意指，氧化銅超微粒子之分散性差之分散介 質，及優良之分散介質。在良分散介質方面，有分子中具 有2個以上羥基之多元醇。在多元醇之中特佳之良分散介 質爲二乙二醇。又在弱分散介質方面，則有水等。 接著，在氧化銅超微粒子間所添加之凝集力係，添加 產生凝集之化學或者物理能量者，例如，有藉由加熱使超 微粒子間之衝撞頻率提高，使凝集易於產生方法，或添加 離子性化合物，使氧化銅超微粒子間之静電斥力變弱以使 凝集易於產生之方法，或添加弱分散介質之方法等。 以下，特別就氧化亞銅超微粒子軟凝集體之具體的製 造方法加以説明。 本發明之氧化亞銅超微粒子軟凝集體之具體製造方法 ，可例示以下之（1 )〜（iv)。 (i )含有：含水1 0重量％以上之水溶液中，使銅羧 基化合物，相對於銅羧基化合物1莫耳，使用0.4〜5.0 莫耳之肼及/或肼衍生物予以還原，來製造氧化亞銅超微 粒子者，之氧化亞銅超微粒子軟凝集體之製造方法。 -18- 1275569 (15) (ii )含有：將選自銅羧基化合物，銅烷氧基化合物 及銅二酮根化合物所成群之至少一種之銅化合物，在二乙 二醇中以1 60°C以上之溫度加熱•還原，以獲得氧化亞銅 超微粒子之膠體分散液者，及將同膠體分散液更予加熱使 氧化亞銅超微粒子軟凝集者，之氧化亞銅超微粒子軟凝集 體之製造方法。 (iii )含有：將選自銅羧基化合物，銅烷氧基化合物 及銅二酮根化合物所成群之至少一種之銅化合物，在二乙 二醇中以160 °C以上之溫度加熱•還原，來獲得氧化亞銅 超微粒子之膠體分散液者，及其後在此膠體分散液添加氧 化亞銅超微粒子之凝集劑者，之氧化亞銅超微粒子軟凝集 體之製造方法。 (iv )含有：選自銅殘基化合物，銅院氧基化合物及 銅二酮根化合物所成群之至少一種之銅化合物，在二乙二 醇中以160°C以上之溫度加熱•還原，及同時在二乙二醇 中，在反應溫度，於多元醇添加可溶的氧化亞銅超微粒子 之凝集劑者之，氧化亞銅超微粒子軟凝集體之製造方法。 (1)之製造方法，含有：在含有水10重量％以上之 水溶液中，使銅羧基化合物，相對於銅羧基化合物1莫耳 ，使用〇·4〜5.0莫耳之肼及/或肼衍生物予以還原，以 製造氧化亞銅超微粒子者。此製造方法中所使用之銅原料 ，爲銅羧基化合物。銅羧基化合物，係限於溶於含有水 1 0重量％以上之水溶液中，而其化學組成並無限制。例 如可使用使乙酸銅等市售之銅羧基化合物，銅鹽與含殘基 -19- (16) 1275569 化合物反應所得之銅羧基化合物等。在銅羧基化合物之中 ，最佳之化合物爲乙酸銅。 使用於銅鹽與含有羧基化合物之反應之銅鹽方面，可 例示氫氧化銅，硝酸銅，碳酸銅等。在含有羧基化合物方 面，爲在化合物分子中含有羧酸或其鹽之化合物，例如飽 和羧酸，不飽和羧酸，及該等鹽等。其之一例有甲酸，乙 酸，丙酸，仲丁基乙酸等。 銅鹽與羧基化合物之反應，可添加肼及/或肼衍生物 在變換成氧化亞銅變換之前可以相同反應容器進行，或預 先在其他反應容器中進行亦可。該等銅羧基化合物可僅使 用1種，或混合2種以上使用。 依本方法，銅羧基化合物被溶解，在含有水1 0重量 %之溶液，相對於銅羧基化合物1莫耳，投入0.4〜5.0 莫耳之肼及/或肼衍生物，使銅羧基化合物還原，而可得 到平均1次粒徑1 〇〇 nm以下之氧化亞銅超微粒子。 肼衍生物方面，有例如單甲基肼，二甲基肼，P羥乙 基肼等之烷肼，硫酸肼，中性硫酸肼，碳酸肼等之肼鹽類 等。該等係肼以外之，構造上，具有氮一氮鍵結，且具有 還原性之化合物。在肼及肼衍生物之中，以肼較佳。肼可 使用肼酐及水合肼之任一種。 就安全之觀點而言，以水合肼較佳。 在肼及/或肼衍生物爲液體之情形，可就這樣投入反 應容器，亦可稀釋之而投入反應容器。肼及/或腓衍生物 爲固體之情形，使溶於反應溶媒中，而投入反應容器較佳 -20- 1275569 (17) 。在將胼及/或肼衍生物稀釋或溶解之情形，在溶液中肼 及/或肼衍生物之濃度低時，所得之氧化亞銅超微粒子軟 凝集體之1次粒徑有變大之傾向，較佳爲比20重量％更 高之濃度，更佳爲60重量％以上之濃度。 爲調整肼之還原力，在不影響反應生成物之範圍中， 可在反應液或肼水溶液添加鹼性物質。藉由鹼性物質之添 加，有所得氧化亞銅粒子之粒徑爲小之情形，以得到小粒 徑氧化亞銅之情形爲佳。在鹼性化合物方面，以氫氧化鈉 ，氫氧化鉀等之無機鹼性化合物特佳。 本發明中，所添加之肼及/或肼衍生物之量，相對於 銅羧基化合物1莫耳爲0.4〜5.0莫耳，較佳爲0.9〜2.0。 肼及/或肼衍生物對銅羧基化合物之莫耳比不足0.4之情 形，還原反應變慢，使得氧化亞銅之平均1次粒徑超過 1 00 nm。肼及/或肼衍生物對銅羧基化合物之莫耳比超過 5.0時，生成物並非只是氧化亞銅，銅粒子亦生成50重量 %以上。 本方法（i )所用反應媒體係，單獨以水，或含有水 以外之有機化合物9 0重量％以下之混合水溶液。混合水 溶液中較佳水之量之範圍爲20重量％以上不足80%重量 。在反應媒體使用含有水以外之有機化合物之混合水溶液 時，所得氧化亞銅超微粒子之平均1次粒徑以更小爲佳。 本方法（i )之反應媒體中所用之有機化合物，可均 勻混合於水，只要不與爲還原劑之肼及/或肼衍生物反應 ，則無任何限制。可使用醇系化合物，醚系化合物，酯系 •21 - 1275569 (18) 化合物，醯胺系化合物等。就處理之觀點而言，在室溫中 爲液狀之有機化合物較佳，其中以醇系化合物較佳，具體 而言，有例如甲醇，乙醇，丙醇，丁醇，乙二醇，二乙二 醇，三乙二醇，聚乙二醇，甘油，1，2—丙二醇，1，3 — 丙二醇，1，2-丁 二醇，1，3-丁 二醇，1，4 — 丁 二醇， 2，3 — 丁二醇，戊二醇，己二醇，辛二醇等。 反應液中銅羧基化合物之較佳濃度，係相對於總和反 應液與銅羧基化合物之重量，較佳爲0.0 1重量％以上， 50重量％以下，更佳爲3重量％以上，20重量％以下。 銅羧基化合物，在.反應液中有實質上溶解之必要，其 一部分即使在反應溶媒爲未溶解，在獲得氧化亞銅超微粒 子方面實質上並無問題。銅殘基化合物之濃度不足0.01 重量％時，1次反應所得之氧化亞銅微粒子之收率變少， 超過50重量％時，會有使銅羧基化合物與，肼及/或肼 衍生物之反應不均勻之情形。 本方法（i )中，最適的反應溫度，爲銅羧基化合物 與肼及/或肼衍生物之組合，及因反應液之選擇而會變動 ，以5 °C以上不足8 5 t較佳。不足5 °C之溫度時，銅羧基 化合物之溶解度降低而有析出之情形，在8 5 °C以上，有 所得氧化亞銅之粒徑變大之傾向。例如，作爲銅羧基化合 物係使用乙酸銅，在使用水合肼爲還原劑之情形，最好之 溫度範圍爲1 5〜3 5 °C。 本發明所得之氧化亞銅超微粒子軟凝集體，係使氧化 亞銅超微粒子互相弱的接触而形成軟凝集體，在還原反應 -22- 1275569 (19) 完成後，以成爲反應器底部沈降物方式得之。 接著，（Π)之氧化亞銅超微粒子軟凝集體之製造方 法，係將選自銅羧基化合物，銅烷氧基化合物及銅二酮根 化合物所成群之至少一種銅化合物，在二乙二醇中以1 60 °C以上之溫度加熱•還原而製造氧化亞銅超微粒子之際， 將中途所得氧化亞銅超微粒子之膠體分散液進而加熱，以 使氧化亞銅超微粒子軟凝集爲其特微之氧化亞銅超微粒子 軟凝集體之製造方法。 本製造方法所用之銅原料，係選自銅羧基化合物，銅 院氧基化合物及銅二酮根化合物所成群之至少一種之銅化 合物。 銅羧基化合物，如上述，係將銅鹽與含羧基之化合物 反應所得。使用於銅鹽與含羧基化合物之反應之銅鹽方面 ，可例示氫氧化銅，硝酸銅，碳酸銅等。含羧基之化合物 方面’係在化合物分子中爲含有羧酸或其鹽之化合物，例 如有飽和羧酸，不飽和羧酸，及該等鹽等。試舉其一例， 則有甲酸，乙酸，丙酸，丁酸等。在銅羧基化合物中，最 佳之化合物爲乙酸銅。 銅垸氧基化合物爲含有烷氧基之銅化合物。所謂烷氧 基，係指烷基與氧鍵結型式之1價之原子團，例如可例示 甲氧基’乙氧基，丙氧基，丁氧基，戊氧基，己氧基等。 在銅烷氧基化合物方面有例如銅甲氧化物，銅乙氧化物等 〇 銅一酮根化合物，係具有二酮螫合化合物之銅化合物 -23- 1275569 (20) 。在二酮螫合化合物中，沒二酮螫合化合物可形成穩定的 銅化合物，故在本發明中爲特別好用。；δ二酮螫合化合物 例示之，則有乙醯丙酮，苯醯丙酮，苯醯三氟丙酮，二苯 醯甲烷，呋喃甲醯基丙酮，三氟乙醯丙酮等。銅二酮根化 合物方面有例如，銅乙醯丙酮配位基，銅一雙（2，2，6 ，6 -四甲基 3，5 -庚二醇酯（heptandiolnate))等。 本製造方法（i i )中，將銅化合物於二乙二醇中以 1 6 0 °C以上之溫度加熱，一旦得到氧化亞銅超微粒子之膠 體分散液之後，進而將此膠體分散液加熱，而獲得氧化亞 銅超微粒子軟凝集體。 氧化亞銅超微粒子之膠體分散液，因呈現黄色，故其 產生可容易判別。本方法，因可得到黄色之膠體分散液， 故接著可加熱同膠體分散液爲其特徵者。爲獲得黄色之膠 體分散液用之加熱溫度，較佳爲160 °C以上不足200 °C。 而在不足1 6 0 °C之溫度，在反應時會耗費過多時間並不佳 ，又’在2 0 0 °C以上’反應會急激進行，會有得到硬凝集 體之情形，故不佳。 在此’於得到黄色之膠體分散液後，進而加熱以獲得 軟凝集體，其加熱溫度較佳爲3(TC以上，更加爲loot以 上。自銅化合物至得到黄色之膠體分散液爲止溫度不予改 變，而以該溫度持續加熱即可。氧化亞銅超微粒子之膠體 化，及軟凝集化之加熱反應溫度超過2 0 0 °C時會有再分散 爲不可能之硬凝集體生成，故反應加熱溫度較佳上限爲 2 00。(： 0 1275569 (21) 藉由反應途中所得之氧化亞銅超微粒子之膠體分散液 之加熱，使得分散於反應液之氧化亞銅超微粒子間之衝撞 確率添加，因微粒子間之衝撞使得氧化亞銅超微粒子開始 凝集，隨著時間之增加，軟凝集體之尺寸變大，最終形成 紅褐色之沈澱物。反應液中氧化亞銅超微粒子軟凝集體之 2次粒徑，係將少量反應液適宜取出，來測定平均粒徑， 而可在反應途中監視。在平均2次粒徑爲所定大小之時間 點亦可使反應停止，也可以反應液上澄液已經沒有氧化亞 銅膠體之黄色被確認之時間點爲反應終點。 使反應液自加熱一開始，至得到黄色氧化亞銅膠體分 散液爲止之時間，及自得到黄色氧化亞銅膠體分散液至得 到軟凝集體之沈澱物爲止之時間，則依反應液中所裝入銅 化合物之量及種類，或者反應溫度而不同。例如，膠體化 與軟凝集化均以1 8 0 °C進行之情形，典型係自反應液加熱 一開始，至得到黄色氧化亞銅膠體分散液爲止之時間爲1 〜5小時，自得到黄色氧化亞銅膠體分散液至得到軟凝集 體之之沈澱物爲止之時間爲1 〇分〜1小時。 接著，（iii )之氧化亞銅超微粒子軟凝集體之製造方 法，係將選自銅羧基化合物，銅烷氧基化合物及銅二酮根 化合物所成群之至少一種銅化合物，在二乙二醇中以1 60 °C以上之溫度加熱•還原，在得到氧化亞銅超微粒子之膠 體分散液後，在此分散液，添加氧化亞銅超微粒子之凝集 劑爲其特徴。本製造法所使用之銅化合物，係與（ii )製 造方法相同。又，在獲得氧化亞銅超微粒子之膠體分散液 -25- 1275569 (22) 之際之反應溫度，較佳爲16(TC以上，不足200°C。在不 足160 °C之溫度，反應時間會耗費過長並不佳，又，在 20 0 °C以上，反應變的過激烈，而有獲得硬凝集體之情形 ，並不佳。 氧化亞銅超微粒子之凝集劑方面，若可將氧化亞銅超 微粒子予以軟凝集則其使用並無特別限制，可爲無機化合 物亦可爲有機化合物。無機化合物方面，可例示水，無機 鹽化合物等，無機鹽化合物方面，有氯化鈉，氯化鉀等。 凝集劑，可溶解於爲反應溶媒之二乙二醇較佳，凝集劑之 中特佳爲選自單醇化合物，醚化合物，酯化合物，腈化合 物’酮化合物，醯胺化合物，醯亞胺化合物，硫黄化合物 所成群之至少一種。在室溫下以液狀之化合物更佳，具體 而言，有甲醇，乙醇，丙醇，二甲基醚，二乙二醇二乙基 醚，乙酸乙酯，甲酸乙酯，乙腈，丙腈，丙酮，甲基乙基 酮，乙醯胺，N，N—二甲基甲醯胺，2—吡咯酮，N —甲 基吡咯酮，二甲基亞硕，環丁硕（sulfolane )等。 依本方法，爲獲得氧化亞銅超微粒子軟凝集體之必要 的該等凝集劑之添加量，依凝集劑之種類而異，故所得軟 凝集體之2次粒徑可一邊監視一邊添加凝集劑，在成爲所 定之粒徑時，可停止添加劑之添加。例如將N -甲基吡咯 酮作爲凝集劑使用之情形，在獲得氧化亞銅超微粒子之際 所用之二乙二醇溶媒與同體積〜數倍體積量予以添加，可 得到目的物之氧化亞銅超微粒子軟凝集體。 接著，（iv )之製造方法，係將選自銅羧基化合物， -26- 1275569 (23) 銅院氧基化合物及銅二酮根化合物所成群之至少一種之銅 化合物，在二乙二醇中，以160°C以上之溫度加熱•還原 之際，在二乙二醇中，於反應溫度可在二乙二醇添加可溶 性之氧化亞銅超微粒子之凝集劑爲其特徴之氧化亞銅超微 粒子軟凝集體之製造方法。本製造方法可使用之銅化合物 與（Π )製造方法相同。 本製造方法中所用之凝集劑，可爲無機化合物亦可爲 有機化合物，在使用有機化合物之情形，在將二乙二醇加 熱之溫度中，以均不使其全部揮發較佳，較佳之沸點爲 1 6 0 °C以上。無機化合物方面，可例示氯化鈉，氯化鉀等 之無機鹽化合物。在凝集劑當中特佳爲選自單醇化合物， 醚化合物，酯化合物，腈化合物，酮化合物，醯胺化合物 ，醯亞胺化合物，硫黄化合物所成群之至少一種。具體而 言，有辛醇，十二醇，二乙二醇二甲醚，二乙二醇二甲醚 ，二異丁酮，丙酮基丙酮，2 —乙基丁基乙酸酯，2-乙基 己基乙酸酯，r 一丁內酯，二甲基亞硕，環丁硕等。 本方法中爲得到氧化亞銅超微粒子軟凝集體’則必要 之該等凝集劑之添加量，因凝集劑之種類而異’故有必要 對最終所得之軟凝集體之2次粒徑予以檢查’同時決定最 適之凝集劑。通常，相對於反應液全體爲’〇· 1重量％以 上ίο重量％以下，更佳爲〇·ι重量％以上5重量％以下 〇 在本製造方法中，反應液之加熱溫度’較佳爲160 °C 以上不足200°C。在不足16〇°C之溫度’在反應時間會過 1275569 (24) 長故不佳，又，在2 Ο 0 °C以上，反應會過於激烈，會有得 到硬凝集體之情形，故不佳。 在（ii )〜（iv )之製造方法中，可在任一反應媒體 之二乙二醇，添加水。在添加水之情形，水之量相對於銅 化合物1莫耳爲30莫耳以下，較佳爲0.1〜25莫耳。相 對於銅化合物1莫耳，可添加3 0莫耳以下之水，而可 使自銅化合物至氧化亞銅超微粒子之膠體化，及軟凝集化 在比較短之時間進行。所添加之水之量過多時，因所得生 成物中之氧化亞銅之比例増加故不佳。爲有效發揮水之效 .果，則水之量，相對於銅化合物1莫耳，以0.1莫耳以上 較佳，在添加水之情形，於加熱開始前添加二乙二醇較佳 〇 在（i i )〜（i v )之製造方法中，反應液中銅化合物 之濃度爲0.1重量％以上，不足50重量％較佳。銅化合 物之濃度不足0 · 1重量％，一次反應所得之氧化亞銅微粒 子之收率會過少故不佳，又在5 0重量％以上，對銅化合 物之二乙二醇之溶解性並非充分故不佳。 (i i )〜（i v )之方法所得氧化亞銅超微粒子軟凝集 體之沈澱物，通常，各個之軟凝集體間進而以弱鍵結以形 成高級次之構造體而沈澱。 接著，就氧化銅超微粒子分散體之製造方法予以記述 。本發明之氧化銅超微粒子軟凝集體，可容易地再分散於 分散介質，而可使2次粒徑減低來製造均勻之分散體或者 分散液。 -28 - 1275569 (25) 本發明之氧化銅超微粒子分散體之製造方法， 一溶媒中，獲得平均1次粒徑100 nm以下，平均 徑0·2μπι以上之氧化銅超微粒子之軟凝集體之第 ，與將該第1步驟所得軟凝集體自第1溶媒分離之 驟，將第2步驟所分離之軟凝集體再分散於第2溶 得到氧化銅分散體之第3步驟。 第1步驟係在第1溶媒中，將1次粒徑1 〇 〇 η 之氧化銅超微粒子合成，以獲得該等爲互相呈弱凝 次粒子之沈澱物之步驟。此係例如，依上述之氧化 微粒子軟凝集體之製造方法，以在反應液之底部獲 亞銅超微粒子軟凝集體沈澱物之步驟。 接著之第2步驟係在前述第1步驟所得軟凝集 澱物自第1溶媒分離之步驟。在本方法，第1步驟 銅超微粒子予以軟凝集，其軟凝集體具有沈澱程度 次粒徑，故自反應液之第1溶媒之分離爲容易。具 ，分離之方法方面，有例如以傾析（decantation ) 液除去之方法，吸引過濾方法等。分離之沈澱物， 面有反應副產物等不純物附著之情形，故以清淨溶 較佳。 接著之第3步驟’係將第2步驟所分離之軟凝 第2溶媒再分散，以得到氧化銅超微粒子之分散體 。在本步驟，係在適當的容器添加第2溶媒，與所 凝集體，並因應需要添加其他之添加劑後，可施予 處理。再分散處理之手法，有例如，超音波處理， 係在第 2次粒 1步驟 第2步 媒，以 m以下 集之2 亞銅超 得氧化 體之沈 中氧化 大之2 體而言 將上澄 在其表 媒洗淨 集體在 之步驟 得之軟 再分散 高速噴 -29- (26) 1275569 射硏磨，等之以外加物理能量之物理方法來進行，亦可在 液中添加酸•鹼，將分散液之pH予以調整等之化學方法 來進行。在該等分散手段中可組合多種加以分散。在此所 謂將氧化銅超微粒子再分散之狀態係指，使2次粒徑減低 之氧化銅超微粒子，在分散介質中呈均質分布者爲佳之狀 態，以呈膠體狀浮遊之狀態下存在亦可，與分散介質等之 氧化銅超微粒子因相互作用而呈凝膠化之狀態存在亦可。 爲得到氧化銅分散體之必要的分散時間，亦依分散方 法而定，例如，在使用超音波法之情形爲5分左右。氧化 銅超微粒子，有因氧而氧化之情形，而該等分散處理，在 氮氛圍等不活性氛圍中進行較佳。 第2步驟所得之氧化銅超微粒子軟凝集體之1次粒徑 極小，且因再分散處理可使其2次粒徑變小，藉由適當的 選擇分散介質等，而可製造氧化銅超微粒子在分散液中以 膠體狀態浮遊之膠體分散液。爲了得到氧化銅超微粒子無 沈降之穩定膠體分散液，膠體分散液中之氧化銅超微粒子 之平均2次粒徑以不足200 nm較佳。更佳爲不足100 nm ，最佳爲不足50 nm。 第3步驟所用之第2溶媒可與第1溶媒相同或相異。 相對於分散液全體之氧化銅超微粒子之固形成份之量可因 應其用途而任意調整，通常係調整成0.1〜80重量％之方 式來使用。將所得得膠體分散液用於銅配線形成等用途之 情形，以塗布膜中之固形成份高者較佳，氧化銅超微粒子 之重量相對於分散液全體，較佳爲1 0重量％以上，最佳 -30- 1275569 (27) 爲3 0重量％以上。 在第3步驟中，氧化銅超微粒子之弱凝集之2次粒子 之再分散處理中’以降低粒徑使得所有之沈澱物可分散· 浮遊於分散介質中程度爲止較佳。但是，即使再分散處理 後’在一部份爲沈澱之情形，此沈澱物，可藉由傾析或者 離心分離等之手法來分離•除去。又，爲了減少分散介質 中之氧化銅超微粒子之膠體分散液之平均粒徑，則可藉由 離心分離等之手法，來將大粒子沈降除去。 在第3步驟中，於第2溶媒中，可添加使氧化銅超微 粒子穩定的分散於第2溶媒中之分散補助劑。此等補助劑 方面，可例示具有羥基，氨基，羧基等極性基之低分子化 合物，寡聚物，聚合物。具有極性基之低分子化合物方面 有，醇系化合物，胺化合物，醯胺化合物，銨化合物，磷 系化合物等。又，可使用市售之界面活性劑。界面活性劑 方面，有陽離子系界面活性劑，陰離子系界面活性劑，非 極性界面活性劑等。具有極性基之聚合物方面，有聚乙烯 毗咯酮，聚乙烯醇，聚甲基乙烯醚等。又，補助劑方面， 可使用在表面具有極性基之無機或者有機粒子，例如使用 二氧化矽粒子，乳膠粒子，在該等粒子表面可担持•分散 金屬單體微粒子或金屬化合物微粒子。將液狀之分散助劑 作爲第2溶媒使用當然爲可行。 上述分散補助劑中以多元醇特佳。所謂多元醇係分子 中具有2個以上羥基之有機化合物，其中以碳數1 〇以下 之多元醇較佳。此等化合物有，例如乙二醇，二乙二醇， -31 - (28) 1275569 1’ 2 —丙二醇，1，3—丙二醇，1，2 — 丁 二醇，1，3-丁 二醇，1，4一丁二醇，2，3—丁二醇，戊二醇，己二醇， 辛二醇，甘油等。該等多元醇可單獨使用，亦可混合複數 之多元醇使用。 爲了將第3步驟所得氧化銅超微粒子之分散液中之不 純物進而予以減低，可將分散液中之氧化銅超微粒子再度 ’如上述已知方法予以凝集•沈澱，將沈澱物自第3溶媒 分離後，將該沈澱物以可使清淨的第3溶媒或膠體分散液 可獲得之方式再次分散於再分散爲可能之其他清淨分散溶 媒之洗淨步驟予以重複多次較佳。 在第3步驟中，可在分散液添加黏度調整劑，還原劑 ，煅燒助劑等之添加劑，又爲了調整黏度，可將第2溶媒 之一部份以濃縮等除去亦可。在分散液添加還原劑時，有 抑制氧化銅超微粒子氧化之效果。再者，將所得分散液加 熱使氧化銅變換成金屬銅，而使用於導電性墨水等用途之 情形，有還原所需之加熱溫度被減低之效果爲特佳。 在所用之還原劑方面，有例如醛類，糖醇類，糖類， 肼及其衍生物，二醯亞胺類，乙二酸等。醛類方面，有甲 醛，乙醛，丙醛，丁醛，異丁醛，正戊醛，異戊醛，三甲 基乙醛（pivalic aldehyde )，己醛，庚醛，辛醛，壬醛（ pelargonaldehy de ) -f--院酸，十二醒，十三醛，十四 醛，十五醛，十六醛，十七醛，十八醛等之脂肪族飽和醛 ，乙二醛（glyoxal ) ，丁二醛等之脂肪族二醛，丙烯醛 ，丁烯醛，丙炔醛等之脂肪族不飽和醛，苯甲醛，鄰甲苯 -32- (29) 1275569 醛，間甲苯醛，對甲苯醛，水楊醛，肉桂醛，α —萘甲醛 ，/3 -萘甲醛等之芳香族醛，糠醛等之雜環式醛等。 二醯亞胺類有例如偶氮二羧酸鹽，羥基胺- 0-磺酸 磺酸，Ν-丙二烯（all ene )磺醯基醯肼或Ν-醯基磺醯 基醯肼予以熱分解所得者。在N-丙二烯磺醯基醯肼或N -醯基磺醯基醯肼方面，對甲苯磺醯基醯勝，苯基磺醯基 醯肼，2，4，6—三異丙基苯基磺醯基醯肼，氯乙醯基醯 肼，鄰硝基苯磺醯基醯肼，間硝基苯磺醯基醯肼，對硝基 苯磺醯基醯肼等。 糖醇類方面，可例示甘油，.赤藻糖醇（erythritol) ，新戊四醇，戊五醇（pentitol)，戊醣（pentose)，己 糖醇，己糖，庚糖等。又，糖類方面，山梨糖醇，甘露糖 醇，木糖醇，蘇胺糖醇（sleitol )，氫化麥芽糖，*** 糖醇，乳糖醇，核糖醇（adonitol )核糖醇，纖維糖醇（ cellobitol)，葡萄糖，果糖，蔗糖，乳糖，甘露糖，半 乳糖，赤蘚糖（erythrose )，木酮糖，阿洛糖（al 1 〇 s e ) ，核糖，山梨糖，木糖，***糖，異麥芽糖，葡萄糖’ 葡庚糖等。 肼及其衍生物方面，除了肼及其水合物以外，有單甲 基肼，二甲基肼，Θ羥基乙基肼等之烷肼，硫酸肼’中性 硫酸肼，碳酸肼等之肼鹽類等。 還原劑之含有量，相對於分散液總重量，較佳爲0·〇 1 〜50質量％，更佳爲〇·〇1〜30質量％。 可在第3步驟使用之煅燒助劑，係將第3步驟所得之 -33- (30) 1275569 氧化銅超微粒子分散體加以煅燒以形成銅薄膜之際，用以 形成更緻密之良質銅薄膜用之添加劑，此等煅燒助劑方面 可例示聚醚化合物。聚醚化合物係在骨架中具有醚鍵結之 化合物，以可均勻分散於分散介質者爲佳。自對分散介質 之分散性之觀點而言，以非結晶性之聚醚化合物爲佳，其 中以重覆單位爲碳數1〜8之直鏈狀及環狀之氧烯烴基之 脂肪族聚醚爲佳。重覆單位爲碳數2〜8之直鏈狀及環狀 之烯烴基之脂肪族聚醚之分子構造，可爲環狀，直鏈狀， 分支狀，亦可爲2元以上之聚醚共聚物或者直鏈狀或分支 狀之2元以上之聚醚嵌段聚合物，具體而言，除了聚乙二 醇’聚丙二醇，聚丁二醇等之聚醚同元聚合物之外，有例 如乙二醇/丙二醇，乙二醇/ 丁二醇之2元共聚物，乙二 醇/丙二醇/乙二醇，丙二醇/乙二醇/丙二醇，乙二醇 /丙二醇/乙二醇等之直鏈狀3元共聚物，但並無限定於 該等。在嵌段共聚物方面，有聚乙二醇聚丙二醇，聚乙二 醇聚丁二醇等之2元嵌段共聚物，進而聚乙二醇聚丙二醇 聚乙二醇，聚丙二醇聚乙二醇聚丙二醇，聚乙二醇聚丁二 醇聚乙二醇等之直鏈狀3元嵌段共聚物等之聚醚嵌段共聚 物。該等化合物，其末端被烷基等之取代基所修飾者亦無 妨。 上述製造法所得氧化銅微粒子或者氧化銅超微粒子分 s夂體’氧化銅之粒徑極小’可比較地容易被金屬銅所還原 ’故可恰當的使用於銅配線形成材料，銅接合材料，銅電 鑛代替材料等之用途。具體而言，可恰當的使用於實裝電 -34- (31) 1275569 路基板之配線及柱（pier )內建材料，實裝電路基板之零 件接合材料，平面板（flat panel )顯示器之電極材料， 樹脂製品等之電磁屏蔽材料等之用途。因氧化銅之粒徑極 小’故可形成微細的配線爲其特徴。該等氧化銅超微粒子 分散體，可藉由網版印刷法，分配法，噴墨法，噴灑法等 塗布手法，而可塗布於目的之基材上，其中，黏度低之氧 化銅膠體分散液可以噴墨法塗布，而以噴墨墨水特別好用 ’進而’氧化銅膠體分散液，係使用施加微細加工之衝壓 (stamp)來形成微細配線之手法之微觸點（microcontact )或者微造型手法等之所謂以軟石板印刷之墨水使用。 依上述製造法所得氧化銅微粒子或者氧化銅超微粒子 分散體之其他用途方面，有木材防腐劑，船底塗料等之抗 菌用途，或者，光電能量變換材料等。 依本發明之實施例可具體説明，但本發明對該等例並 非有任何限定。以下，特別就氧化亞銅之情形加以説明， 但本發明並非限定於氧化亞銅超微粒子。 氧化亞銅超微粒子軟凝集體之平均二次粒徑，係將所 得沈澱物在載玻片上採集，以光學顯微鏡進行表面觀察， 由視野中任意選擇5個粒子，使其粒徑之平均値爲平均2 次粒徑。 氧化亞銅超粒子之平均一次粒徑係以日本分光公司製 透過型電子顯微鏡（JEM-4 000 FX )觀察表面予以測定。 依照電子顯微鏡之表面觀察中，由視野中，選擇一次粒子 徑比較集中之處所三處，對被測定物之粒徑測定以最適之 •35- (32) 1275569 倍率攝影。自各個照片選擇被認爲最爲多數存在之一次粒 子之三點，將其直徑以直尺測定，以算出一次粒子徑。以 該等値之平均値爲平均一次粒徑。 所得之粒子爲氧化亞銅，係使用Rigaku公司製X線 繞射裝置（Rigaku-RINT 2500 )，在 36.5°，及 42.4°C 觀 測來自分別爲（1 1 1 )，（ 200 )面之強繞射峰値，而以氧 化亞銅之XRD圖案一致者來確認。 對氧化亞銅超微粒子軟凝集體之分散介質之再分散性 ，係使用 Sonics and Materials公司製之超音波分散機 Biburacel .130 watt model，在輸出30瓦，進行2分鐘分 散處理予以評價。超音波處理所得之膠體分散液中氧化亞 銅之平均二次粒徑，係使用大塚電子公司製濃厚粒度分布 計（FPAR 1 000 )來測定。 【實施方式】 <實施例1 >銅羧基化合物/肼化合物莫耳比依存性- 1 將無水乙酸銅（和光純藥工業公司製）8 g添加精製 水70 ml。在25°C —邊攪拌一邊添加64重量％之肼水合 物2· 6 ml，使得胼對乙酸銅之莫耳比成爲1.2，使之反應 以得到氧化亞銅之沈澱物。沈澱物之平均一次粒徑爲2 0 nm，平均2次粒徑爲8 0 0 μ m。將本沈激物1 g放入二乙 二醇9 g，施予超音波分散時，得到氧化亞銅之膠體分散 液，其分散液中之平均2次粒徑爲8 0 nm。 (33) 1275569 <實施例2 >銅羧基化合物^/肼化合物莫耳比依存性一 2 將無水乙酸銅（和光純藥工業公司製）8 g添加精製 水70 ml。在25 °C —邊攪拌一邊添加64重量％之肼水合 物1·3 2 ml ’使得肼對乙酸銅之莫耳比成爲〇·6，使之反應 以得到氧化亞銅之沈激物。平均一次粒徑爲3 0 n m，平均 2次粒徑爲3 0 0 μ m。與實施例1同樣之方法所得膠體分散 液中之平均二次粒徑爲8 0 nm。 <實施例3 >銅羧基化合物/肼化合物莫耳比依存性一 3 .將無水乙酸銅（和光純藥工業公司製）8 g添加精製 水70 ml。在25 °C —邊攪拌一邊添加64重量％之肼水合 物6.5 m 1，使得肼對乙酸銅之莫耳比成爲3.0，使之反應 以得到氧化亞銅之沈澱物。平均一次粒徑，平均2次粒徑 分別爲60 nm，200μιη。與實施例1同樣之方法所得膠體 分散液中之平均二次粒徑爲1 2 〇 nm。 <實施例4 >銅羧基化合物/肼化合物莫耳比依存性- 4 將無水乙酸銅（和光純藥工業公司製）8 g添加精製 水70 ml。在60 °C —邊攪拌一邊添加64重量％之肼水合 物2 m 1，使得肼對乙酸銅之莫耳比成爲0 ·9，使之反應以 得到氧化亞銅之沈澱物。平均一次粒徑’平均2次粒徑分 別爲，50 nm，1 80μιη。與實施例1同樣方法所得膠體分 散液中之平均二次粒徑爲95 nm。 -37- 1275569 (34) <實施例5 >反應溶液中含有醇化合物之例- 1 將無水乙酸銅（和光純藥工業公司製）8 g添加精製 水50 ml及乙二醇20 ml。在室溫25 °C —邊攪拌一邊添加 64重量％之肼水合物2· 0 ml，使得肼對乙酸銅之莫耳比 成爲0.9，使之反應以得到氧化亞銅之沈澱物。平均一次 粒徑，平均2次粒徑分別爲1 0 nm，3 5 0 μ m。與實施例1 同樣方法所得膠體分散液中之平均二次粒徑爲45 nm。 <實施例6〉反應溶液中醇化合物含有例- 2 將精製水40ml及乙醇30 ml添加於無水乙酸銅（和 光純藥工業公司製）8 g。 在室溫2 5 °C —邊攪拌一邊添加6 4重量％之肼水合物 2.4 ml，使得肼對乙酸銅之莫耳比成爲1.1，使之反應以 得到氧化亞銅之沈澱物。平均一次粒徑，平均2次粒徑分 別爲，1 0 n m，1 9 0 μ m。與實施例1同樣之方法所得膠體 分散液中之平均二次粒徑爲4 0 nm。 <實施例7 >由氫氧化銅與乙酸酐所得銅羧基化合物之例 將氫氧化銅1.95 g (和光純藥工業公司製）及乙酸酐 3 ml添加於精製水6〇 mi。進而添加64重量％之肼水合物 1 . 6 m 1，在2 5 °C攪拌時，得到氧化亞銅之沈澱物。平均一 次粒徑，平均2次粒徑分別爲，6 0 n m，3 0 0 μ m。與實施 例1同樣方法所得膠體分散液中之平均二次粒徑爲1 0 0 -38- 1275569 (35) <實施例8 >反應時添加鹼性化合物之例一 1 將無水硫酸銅（和光純藥工業公司製）3 2 g ( 0 · 2 mo 1 )溶解於精製水600 ml，在30°C —邊攪拌一邊添加乙酸 酐（和光純藥工業公司製）20 ml。數分鐘後，一邊攪拌 一邊添加1 Μ氫氧化鈉水溶液（和光純藥工業公司製） 3 00 ml與肼水合物（和光純藥工業公司製）15 ml使之反 應，得到氧化亞銅之沈澱物。平均一次粒徑，平均2次粒 徑分別爲，1 5 nm，2 2 0 μ m。與實施例1同樣之方法所得 膠體分散液中之平均二次粒徑爲5 0 nm。 <實施例9 >反應時添加鹼性化合物之例一 2 將氫氧化銅（和光純藥工業公司製）19.5g ( 〇·2 mol )溶解於精製水600 ml，在30°C —邊攪拌一邊添加乙酸 酐（和光純藥工業公司製）20 ml。數分鐘後，一邊攪拌 一邊添加1 Μ氫氧化鈉水溶液（和光純藥工業公司製）3 0 ml與肼水合物（和光純藥工業公司製）12 ml使之反應’ 得到氧化亞銅之沈澱物。平均一次粒徑，平均2次粒徑分 別爲20 nm，130μχη。與實施例1同樣之方法所得膠體分 散液中之平均二次粒徑爲5 5 nm。 <實施例1 〇 >反應時添加鹼性化合物之例- 3 將硝酸銅（和光純藥工業公司製）47.3 g ( 0.2 mol ) 溶解於精製水600 ml，在3(TC —邊攪拌一邊添加乙酸酐 (36) 1275569 (和光純藥工業公司製）20 ml。數分後，一邊攪拌一邊 添加1M氫氧化鈉水溶液（和光純藥工業公司製）3 00 ml 與肼水合物（和光純藥工業公司製）1 5 ml使之反應，得 到氧化亞銅之沈澱物。平均一次粒徑，平均2次粒徑分別 爲15 nm，180μπΐ。與實施例1同樣之方法所得膠體分散 液中之平均二次粒徑爲4 5 nm。 <實施例1 1 >在反應時添加鹼性化合物之例- 4 將硝酸銅（和光純藥工業公司製）47.3 g ( 0.2 mol) 溶解於精製水6 0 0 ml，在3 0 °C —邊攪拌一邊添加丙酸（ 和光純藥工業公司製）20 ml。數分後，一邊攪拌一邊添 加1 Μ氫氧化鈉水溶液（和光純藥工業公司製）1 〇 ml與 肼水合物（和光純藥工業公司製）7 · 5 ml使之反應’得到 氧化亞銅之沈澱物。平均一次粒徑，平均2次粒徑分別爲 2 0 nm，2 5 0 μ m。與實施例1同樣之方法所得膠體分散液 中之平均二次粒徑爲5 0 nm。 <實施例1 2〉反應時添加鹼性化合物之例- 5 將硝酸銅（和光純藥工業公司製）47·3 g ( 〇.2mo1 ) 溶解於精製水600 ml，在30°C —邊攪拌一邊添加乙酸鈉 (和光純藥工業公司製）8 · 2 g。數分後，一邊攪拌一邊 添加1 Μ氫氧化鈉水溶液（和光純藥工業公司製）4 0 m 1 與肼水合物（和光純藥工業公司製）7· 5 使之反應，得 到氧化亞銅之沈澱物。平均一次粒徑，平均2次粒徑分別 1275569 (37) 爲20 nm，24 0 μπί。與實施例1同樣方法所得膠體分散液 中之平均二次粒徑爲60 nm。 <實施例1 3 >肼衍生物使用於還原劑之例 添加無水乙酸銅3.6 g與精製水30 ml於3 00 ml燒杯 ，攪拌20分鐘。將反應液溫度設定於3(TC —邊攪拌一邊 添加/3 -羥基乙基肼（日本肼工業公司製）2 ml，使反應 20分鐘得到氧化亞銅沈澱物。平均一次粒徑，平均2次 粒徑分別爲30 nm，200μιη。與實施例1同樣方法所得膠 體分散液中之平均二次粒徑爲8 5 nm。 <實施例1 4 >將稀釋之肼使用於還原劑之例- 1 在乙酸酐（和光純藥工業公司製）8 g添加精製水70 ml。在2 5 °C —邊攪拌一邊添加4 0重量％之肼水溶液（將 水合肼稀釋而作成）3 · 9 ml，使得肼對乙酸銅之莫耳比成 爲1 · 1，使之反應以得到氧化亞銅之沈澱物。平均一次粒 徑，平均2次粒徑分別爲22 nm，150μιη。與實施例1同 樣之方法所得膠體分散液中之平均二次粒徑爲8 0 nm。 <實施例1 5 >將稀釋之肼使用於還原劑之例- 2 在乙酸銅酐（和光純藥工業公司製）8 g添加精製水 70 ml。在25 °C —邊攪拌一邊添加20重量％之肼水溶液（ 將水合肼稀釋而作成）7·8 ml，使得肼對乙酸銅之莫耳比 成爲1 · 1，使之反應以得到氧化亞銅之沈澱物。平均〜次 -41 - (38) 1275569 粒徑，平均2次粒徑分別爲’ 3 0 nm，2 5 Ο μ m。與實施例 1同樣之方法所得膠體分散液中之平均二次粒徑爲90 nm <實施例1 6 >將稀釋之肼使用於還原劑之例- 3 在乙酸銅酐（和光純藥工業公司製）8 g添加精製水 70 ml。在25 °C —邊攪拌一邊添加5重量％之肼水溶液（ 將水合肼稀釋而作成）3 1 ·2 ml，使得肼對乙酸銅之莫耳 比成爲1 .1，使之反應以得到氧化亞銅之沈澱物。平均一 次粒徑，平均2次粒徑分別爲4 0 nm，2 0 0 μ m。與實施例 1同様之方法所得膠體分散液中之平均二次粒徑爲1 〇〇 nm <實施例1 7 >藉加熱形成軟凝集體之例- 1 將乙酸銅（和光純藥工業公司製）2.7 g懸濁於二乙 二醇（和光純藥工業公司製）90 ml，添加水0.9 g，在 1 90 °C加熱3小時使之反應，在一旦得到黄色氧化亞銅膠 體分散液後，在使溫度維持之同時進而加熱反應3 0分鐘 ，得到氧化亞銅之沈澱物。平均一次粒徑，平均2次粒徑 分別爲90 nm，290μιη。與實施例1同樣之方法所得膠體 分散液中之平均二次粒徑爲1 5 0 nm。 <實施例1 8 >藉由加熱形成軟凝集體之例- 2 銅甲氧化物（和光純藥工業公司製）1 . 9 g懸濁於二 -42- (39) 1275569 乙二醇（和光純藥工業公司製）90 ml，添加水0·9 g，在 1 9〇 °C加熱反應1小時，一旦得到黄色氧化亞銅膠體分散 液後，在使溫度維持之同時進而加熱反應20分鐘，得到 氧化亞銅之沈澱物。平均一次粒徑，平均2次粒徑分別爲 8 0 nm，90 μιη。與實施例1同樣之方法所得膠體分散液中 之平均二次粒徑爲150 nm。 <實施例1 9 >藉由加熱形成軟凝集體之例- 3 將銅乙醯丙酮配位基（和光純藥工業公司製）4.0 g 懸濁於二乙二醇（和光純藥工業公司製）9 0 ml，添加水 〇.9g，在190 °C加熱反應3小時，一旦得到黄色氧化亞銅 膠體分散液後，在使溫度維持之同時進而加熱反應3 0分 鐘，得到氧化亞銅之沈澱物。平均一次粒徑，平均2次粒 徑分別爲8 0 nm，1 0 0 μ m。與實施例1同樣之方法所得膠 體分散液中之平均二次粒徑爲1 70 nm。 <實施例20 >添加醇化合物得到軟凝集體之例 將乙酸銅（和光純藥工業公司製）2.7 g懸濁於二乙 二醇（和光純藥工業公司製）90 ml，添加水0.9 g，在 1 90 °C加熱反應3小時，一旦得到黄色氧化亞銅膠體分散 液後，在此分散液添加乙醇3 00 ml，得到氧化亞銅之沈澱 物。平均一次粒徑，平均2次粒徑分別爲90 nm，150 μιη 。與實施例1同樣之方法所得膠體分散液中之平均二次粒 徑爲1 8 0 n m。 -43- (40) 1275569 <實施例2 1 >在反應溶媒添加醇化合物以得到軟凝集體 之例 將乙酸銅（和光純藥工業公司製）2 · 7 g懸濁於二乙 二醇（和光純藥工業公司製）90 ml，添加水〇.9g與辛醇 0.5 g，在190 °C加熱反應3小時，得到氧化亞銅之沈澱物 。平均一次粒徑，平均2次粒徑分別爲95 nm，ΙΟΟμιη。 與實施例1同樣之方法所得膠體分散液中之平均二次粒徑 爲 1 8 0 nm。 <實施例22 >使用氧化亞銅超微粒子分散體以形成銅薄 膜之例一 1 與實施例1同樣之方法所得氧化亞銅微粒子軟凝集體 3.lg，添加二乙二醇6.0 g與作爲添加劑之聚乙二醇（平 均分子量2 0 0，和光純藥工業公司製）3 · 0 g。施加超音波 分散，來調製氧化亞銅超微粒子膠體分散液。將此分散液 在一邊長度120 mm之正方形玻璃板上，在塗布厚度50 μηΐ之棒塗機，在50 mmxlOO mm之面積進行塗布。將已 塗布之玻璃板，在氮氣流下之熱板上以3 5 0 °C煅燒1小時 ，在玻璃板上得到銅薄膜。所得銅薄膜爲厚度2.5 μ m， 體積電阻値7xl0_6 Qcm。 <實施例23 >使用氧化亞銅超微粒子膠體分散體形成銅 配線之例一 2 -44- (41) 1275569 與實施例1同樣方法所得氧化亞銅微粒子軟凝集體 1.0 g，添加二乙二醇6.0 g與作爲添加劑之聚乙二醇（平 均分子量200，和光純藥工業公司製）1.0 g。施加超音波 分散，來調製氧化亞銅超微粒子膠體分散液。此膠體分散 液中氧化亞銅超微粒子之2次粒徑爲1 0 0 nm。將此分散 液充塡於噴墨方式之印表頭（print head)之墨水匣，安 裝於專用之印表機。在本實施例之此噴墨方式，係使用壓 電（piezo )方式之印表頭。在載玻片玻璃上，以平均液 量4 pi (pi: —兆分之一升）噴射墨水，印刷出膜厚5μιη ’ 1 0 0 μ m線寬之直線圖案。在印刷後，將玻璃基板在氮氣 氛圍’施予3 5 0 °C / 1小時之熱處理，進行氧化亞銅之還 原。所得金屬配線之圖案之電阻爲，5x1 0_6Ω · cm之良好 値。 <實施例24 >含有還原劑之氧化亞銅超微粒子分散體之 例 與實施例1同樣之方法所得氧化亞銅微粒子軟凝集體 3 ·〇 g ’添加乙二醇6.0 g與作爲還原劑之碳酸肼0.4 g， 施予超音波分散，來調製氧化亞銅超微粒子分散體。與實 方也例22间樣在玻璃基板上塗布棒塗覆（bar coat)後，在 氮氣氛圍中昇溫時，可確認在所謂2 0 0 °C之低溫下生成銅 <比較例1 >添加之肼量比規定量多之情形 -45- 1275569 · (42) 在無水乙酸銅（和光純藥工業公司製）8 g添加精製 水70 ml。在室溫25C —邊攪拌一邊添加64重量％之肼 水合物1 2 · 0 ml，使得肼對乙酸銅之莫耳比成爲5 · 5，使之 反應，生成物約含有金屬銅20重量％。 <比較例2 >添加之肼比規定量更少之情形 在無水乙酸銅（和光純藥工業公司製）8 g添加精製 水70 ml 。在室溫25 °C —邊攪拌一邊添加64重量％之肼 水合物〇 · 6 6 m 1，使得胼對乙酸銅之莫耳比成爲〇 . 3，使之 反應，得到氧化亞銅之沈澱物，但所得氧化亞銅之平均1 次粒徑大至200 nm。 <比較例3 >將銅羧基化合物以外之銅鹽使用於原料之情 形一 1 在氯化銅（和光純藥工業公司製）〇.22 g添加精製水 10 ml。在室溫25 °C —邊攪拌一邊添加64重量％之肼水 合物50μ1’使得胼對氯化銅之莫耳比成爲〇.6，使之反應 ’但沒有得到氧化亞銅微粒子，而生成銅。 <比較例4 >將銅羧基化合物以外之銅鹽使用於原料之情 形—2 在硫酸銅（和光純藥工業公司製）〇. 2 6 g添加精製水 10 ml。在室溫25 °C —邊攪拌一邊添加64重量％之肼水合 物5 0 μ 1 ’使得肼對硫酸銅之莫耳比成爲〇 . 6，使之反應， -46 - 1275569 (43) 沒有得到氧化亞銅微粒子’而生成銅。 <比較例5 >將銅羧基化合物以外之銅鹽使用於原料之情 形一 3 在氫氧化銅（和光純藥工業公司製）〇·16 g添加精製 水10 ml。在室溫25 °C —邊攪拌一邊添加64重量％之肼 水合物7 5 μΐ，使得肼對硫酸銅之莫耳比成爲0 · 9，使之反 應，雖得到氧化亞銅之沈澱，但平均1次粒徑則大至300 <比較例6 >反應液不含水之情形 在無水乙酸銅（和光純藥工業公司製）8 g，添加二 乙二醇70 ml。在室溫25 °C —邊攪拌一邊添加64重量％ 之肼水合物2.6ml，使得肼對乙酸銅之莫耳比成爲1.2， 使之反應，所得沈澱物並非氧化亞銅而爲銅。 <比較例7 >不進行軟凝集化步驟之例 與實施例20同樣，將乙酸銅（和光純藥工業公司製 )2 · 7 g懸濁於二乙二醇（和光純藥工業公司製）9 0 ml， 添加水0·9 g，在19(TC加熱反應3小時，得到黄色之氧 化亞銅膠體分散液。氧化亞銅微粒子浮遊於反應液中，要 將其回收，則離心分離步驟爲必要。在此離心分離步驟， 首先’將所得膠體分散液在遠沈管收集重量並予分開之作 業爲必要，其後，將遠沈管設定於轉子，將此轉子以離心 -47- (44)1275569 分離機遠心作業，則非常耗費時間。1275569 (1) Description of the Invention [Technical Field] The present invention relates to copper oxide ultrafine particles and a method for producing the same. Further, the present invention relates to a colloidal dispersion in which copper oxide ultrafine particles are dispersed in a dispersion in a colloidal form, and a method for producing the same. The copper oxide ultrafine particles obtained by the present invention can be used, for example, as a conductive paste or a conductive ink in the field of mounting of an electronic device, and the colloidal dispersion of the copper oxide fine particles obtained by the present invention is a low-viscosity liquid. It is applied to a substrate by an inkjet method and can be used as an inkjet ink. [Prior Art] The production of copper oxide ultrafine particles having a primary particle diameter of less than 100 nm is generally protected by an excessively large particle size of the particles formed by the suppression of the reaction, and is protected by a surfactant or a specific organic compound in a large volume. The method of ultrafine particle surface is currently being used. In general, in such a production method, when the copper oxide ultrafine particles are floated in a colloidal state in the reaction liquid, high-speed centrifugation is required when the particles are separated as solid components by the reaction liquid in order to remove impurities or the like. step. Hereinafter, the cuprous oxide ultrafine particles will be specifically described. However, the present invention is not limited to cuprous oxide ultrafine particles, and is also applicable to other copper oxides. For example, in the China Science Forum, No. 3, No.1, p p. 1 4 · 1 8 1 9 9 4 years (Chinese Science Bulletin. 1994, 39, 14-18) discloses that after the aqueous copper acetate solution is dispersed in the -5 - 1275569 (2) toluene together with the dodecylbenzenesulfonic acid which is the surfactant, the copper acetate is reduced to obtain the primary particle diameter. It is a 5 to 10 nm surface of cuprous oxide ultrafine particles covered with dodecylbenzenesulfonic acid (method i). This method is called micro-emulsification, which produces tiny water droplets with a diameter of several nanometers to several tens of nanometers in the toluene of the oil layer, and reduces the copper acetate present in the tiny water droplets to obtain cuprous oxide. The method. The size of the obtained cuprous oxide particles is microparticulated to a fine droplet size, and the surface of the fine particles is stabilized by being covered with a surfactant. The cuprous oxide ultrafine particles obtained by the method are obtained by floating in a colloidal state in water or in an oil layer, and the impurities in the liquid are removed, so that the ultrafine particles are separated from the solution in a solid form, and the centrifugation step is necessary. However, it is generally necessary to separate the ultrafine particles having a particle diameter of less than 100 nm by separation by centrifugation, and it is necessary to decompress the rotating atmosphere of the rotor to reduce the air resistance and the like. Therefore, there is a problem that productivity is lowered and it is practically unusable in mass production for necessary industrial use. On the one hand, in the American Chemical Industry Journal, Volume 121 pp. l 1 5 95 - 1 1 5 96 1 9 9 9 (Journal of American Chemical Society, 1 999, 1 2 1, 1 1 5 9 5 - 1 1 5 96 ) reveals that octylamine containing a specific organic copper compound The solution is injected into hexadecylamine heated to 25 ° C. When the temperature is 230 t, the heating is stopped and cooled to obtain an average primary particle diameter of about 7 nm, and the surface is made of mutosamine or hexamethyleneamine. A precipitate of cuprous oxide ultrafine particles covered by either or both of the surfactants (Method 2). In this method, it is presumed that the amino group having a strong coordination ability is coordinated to the surface of the particle at the initial stage of the formation of cuprous oxide particles, and the particle size of the cuprous oxide -6 - 1275569 ' (3) can be suppressed. In this method, the cuprous oxide ultrafine particles are not in the colloidal state in the reaction liquid, but are obtained by the precipitate, and the particles are easily recovered because they are not required to be centrifuged. Further, the precipitate itself is a soft agglomerate in which the cuprous oxide ultrafine particles covered by the amino group-containing organic substance are weakly agglomerated with each other, and are re-dispersed in a suitable dispersion medium such as toluene to obtain a cuprous oxide ultrafine particle. Colloidal solution. However, these super cuprous oxide fine particles have a problem that conductivity is deteriorated when they are used as a conductive material on the surface of the particles because of an organic compound having a large molecular weight. On the one hand, a method for producing cuprous oxide ultrafine particles which does not have a special surfactant or a large volume of an organic compound on the surface of the particles is also known. In Angewandte Chemie International Edition, Volume 40, No. 2, ρ·359, 2001 (Angewandte Chemie international edition, 200 1, No. 40, vol2, p3 5 9 ) reveals that the acetone acetone ligand ( The acetylacetonato) copper complex is dissolved in a polyol, and a trace amount of water is added thereto, and heated to 190 ° C to obtain a cuprous oxide ultrafine particle having a particle diameter of 30 to 200 nm (method 3). The cuprous oxide ultrafine particles obtained by this method tend to have a larger particle size than a surfactant having a large amount of an organic compound. Further, since the obtained particles have high monodispersity, since they are obtained as a colloidal dispersion, it is necessary to remove by-products so that the cuprous oxide ultrafine particles are taken out as a solid component. Therefore, as described above, there is a problem that it is difficult to apply in the industrial use where the centrifugal separation operation time and time are required to make mass production necessary. In the Journal of Colloid and Interface Science, Volume 243, pp. 85-89 2001 (1275569 (4) journal of Colloid and Interface Science 243, 85 -8 9 (2001) reveals the addition of cerium to an alkaline aqueous solution of copper sulphate added with a small amount of polyol as an additive to produce oxidation. The method of cuprous ultrafine particles is described (method 4). The cuprous oxide fine particles obtained by the method have a primary particle diameter as small as 9 to 30 nm, and are preferably used to produce a secondary particle diameter of 200 to 1 μm. The precipitate has the advantage that it can be easily separated from the reaction liquid. However, the precipitate obtained here has strong agglutination between the primary particles, and forms a hard aggregate of the secondary particles, and the precipitate is difficult to redisperse in the precipitate. Dispersing medium. Therefore, it is impossible to prepare a colloidal solution in which the cuprous oxide ultrafine particles are in a floating state in the dispersion medium using the obtained particles. On the one hand, in the Zeitschrift fur anorganische und allgemeine Chemie Bd224, pp. 1 07- 1 1 2 1 93 5 Revealed that a 20% hydrazine aqueous solution was added to a thick copper acetate aqueous solution to obtain a precipitate of oxidized cuprous particles (method 5). However, in this document, the amount of copper acetate and cerium added as a raw material is not shown, but only the excess strontium is added, and it is reduced to metallic copper, and the particle diameter of the obtained cuprous oxide is not described. When the above production of the cuprous oxide ultrafine particles is summarized, there are cases in which the obtained cuprous oxide fine particles, 1 are obtained in a state in which the reaction liquid is dispersed in a colloidal state (method 1, method 3), and 2 are agglomerated precipitates. The method obtained (method 2, method 4), but in terms of particle handling, the method of 2 is superior. However, the cuprous oxide ultrafine particle precipitate obtained by the method of the method 4 is a hard aggregate which is impossible to redisperse, is difficult to redisperse the dispersion medium, and the like. On the one hand, the cuprous oxide precipitate obtained by the method of the method 2 1275569 (5) can be easily redispersed in the dispersion medium, and can easily be used as a colloidal dispersion of the desired composition, etc., and has a long surface on the particle surface. An intrinsic surfactant, the actual state of the obtained particles is a composite of cuprous oxide and a surfactant, and it is difficult to use for, for example, baking to obtain a conductive material for a copper film. The problem of use. An object of the present invention is to provide a copper oxide ultrafine particle which is composed of an average primary particle diameter of 100 nm or less, which is a redispersible copper oxide ultrafine particle, and a method for producing the same. Further, another object of the present invention is to provide a method for producing a colloidal dispersion in which copper oxide ultrafine particles are dispersed in a dispersion. SUMMARY OF THE INVENTION The present inventors completed the present invention by conducting various review test results on the copper oxide ultrafine particles in the above-described state. The present invention has the following constitution. (1) The average primary particle size and the average secondary particle diameter are respectively below 100 nm, 0. More than 2 μΠΊ of copper oxide ultrafine particles soft aggregate. (2) The copper oxide ultrafine particles soft gelling group according to item 1 of the patent application, wherein the average primary particle diameter is 25 nm or less. (3) The copper oxide ultrafine particles soft gelling group according to item 1 of the patent application, wherein the average primary particle diameter is 10 nm or less. (4) The copper oxide ultrafine particles soft aggregates of any one of claims 1 to 3, wherein the particles have no surfactant or -9 - 1275569 (6) large volume of organic compounds on the surface of the particles. (5) A method for producing a copper oxide ultrafine particle soft aggregate according to any one of claims 1 to 4, which comprises producing a copper oxide ultrafine particle in a weakly dispersed medium, thereby producing a copper oxide super At the same time as the microparticles, the soft aggregates are formed. (6) A method for producing a copper oxide ultrafine particle soft aggregate according to any one of claims 1 to 4, which comprises: producing a copper oxide ultrafine particle in a good dispersion medium, and thereafter oxidizing A cohesive force is added between the copper ultrafine particles to form a soft aggregate of the copper oxide ultrafine particles. (7) A method for producing a copper oxide ultrafine particle soft aggregate according to any one of claims 1 to 4, which comprises a copper oxide ultrafine particle while generating a copper oxide ultrafine particle in a good dispersion medium A cohesive force is added to form a soft aggregate of copper oxide ultrafine particles. (8) A method for producing a copper oxide ultrafine particle dispersion, characterized in that, in the first solvent, an average primary particle diameter of 1 〇〇 nm or less of copper oxide ultrafine particles is synthesized, and an average of 2 times is obtained. The second step of the copper oxide ultrafine particles soft aggregate having a particle diameter of 〇·2 μmη or more, the second step of separating the soft aggregate obtained in the first step from the first solvent, and the soft agglomerate separated in the second step The third step of dispersing the second solvent to obtain a copper oxide ultrafine particle dispersion. (9) The method for producing a copper oxide ultrafine particle dispersion according to the eighth aspect of the invention, wherein the copper oxide ultrafine particle dispersion obtained in the third step is a colloidal colloidal state in the dispersion. (1) The method for producing a copper oxide ultrafine particle dispersion -10- 1275569 (7) according to the scope of claim 9 wherein the average of the copper oxide ultrafine particles in the colloidal copper ultrafine particle dispersion is 2 The secondary particle size is less than 200 nm. (1) The method for producing a copper oxide ultrafine particle dispersion according to any one of claims 8 to 10, wherein the second solvent contains a dispersion aid of copper oxide ultrafine particles. (1) A method for producing a copper oxide ultrafine particle dispersion according to the first aspect of the patent application, wherein the dispersion auxiliary agent is a polyol. (1) A method for producing a copper oxide ultrafine particle dispersion according to claim 12, wherein the carbon number of the polyol is 10 or less. (1) A copper oxide ultrafine particle dispersion obtained by the production method according to any one of claims 8 to 13. (1) The cuprous oxide ultrafine particle dispersion of claim 14, wherein the reducing agent of the reducible copper oxide ultrafine particles contains 1 to 50% by weight of ruthenium in the dispersion. (1 6 ) The average primary particle size and the average secondary particle size are less than 1 00 ® nm, respectively. 2μιη of copper oxide ultrafine particles. (1) The copper oxide ultrafine particles of the fifteenth aspect of the patent application are characterized in that the average primary particle diameter is 2 5 n m or less. (1) The copper oxide ultrafine particles of the fifteenth aspect of the patent application, wherein the average primary particle diameter is 10 nm or less. (1) The copper oxide ultrafine particles according to any one of the first to sixth aspects of the invention, wherein there is no surfactant or a large amount of organic compound on the surface of the particles. The method for producing a copper oxide ultrafine particle according to any one of claims 16 to 19, which comprises the copper oxide according to any one of claims 1 to 4. Ultrafine particles are softly aggregated to obtain copper oxide ultrafine particles. (2 1 ) A copper oxide ultrafine particle colloidal dispersion characterized by containing the copper oxide ultrafine particles of any one of claims 16 to 19 in a floating state in a dispersion medium. (22) The copper oxide ultrafine particle colloidal dispersion of claim 2, wherein the total weight of the copper oxide ultrafine particles is relative to the total dispersion. The weight of the liquid is 10% by weight or more. (23) The copper oxide ultrafine particle soft aggregate according to any one of claims 1 to 4, wherein the copper oxide is cuprous oxide. (2) A method for producing a copper oxide ultrafine particle soft aggregate according to any one of items 5 to 7 of the invention, wherein the copper oxide is cuprous oxide. (2) A method for producing a copper oxide ultrafine particle dispersion according to any one of claims 8 to 13, wherein the copper oxide is cuprous oxide. (2) A copper oxide ultrafine particle dispersion as claimed in claim 14 or claim 15, wherein the copper oxide is cuprous oxide. (2) The copper oxide ultrafine particles according to any one of the above-mentioned claims, wherein the copper oxide is cuprous oxide. (2) A method for producing copper oxide ultrafine particles according to claim 20, wherein the copper oxide is cuprous oxide. (2 9 ) A copper oxide super -12·(9) 1275569 microparticle colloidal dispersion according to claim 2 or 2, wherein the copper oxide is cuprous oxide. (3) A method for producing a cuprous oxide ultrafine particle soft aggregate according to claim 23, which contains a copper carboxyl compound in relation to a copper carboxyl compound in an aqueous solution containing 10% by weight or more of water. Ear use 〇·4~5. The molybdenum and/or hydrazine derivative is reduced to produce cuprous oxide ultrafine particles. (3) The method for producing a cuprous oxide ultrafine particle soft aggregate according to the third aspect of the invention, wherein the solution contains a group selected from the group consisting of an alcohol compound, an ether compound, an ester compound and a guanamine compound. At least one organic compound. (3. 2) A method for producing a cuprous oxide ultrafine particle soft aggregate according to the patent application No. 30 or 31, which further contains an alkalinity when a copper carboxyl compound is reduced by using a ruthenium and/or an anthracene derivative The compound (3 3) is a method for producing a cuprous oxide ultrafine pine nut soft reduction collective according to any one of claims 30 to 32, wherein the copper sulfonium compound is copper acetate. (3) The method for producing a cuprous oxide ultrafine particle soft aggregate according to any one of claims 30 to 3, wherein the cerium and/or cerium derivative is dissolved at a higher than 20% by weight The concentration of the solution is added to the reaction solution. (3) A method for producing a cuprous oxide ultrafine particle soft aggregate according to the second aspect of the patent application, which comprises a group selected from the group consisting of a copper carboxyl compound, a copper alkoxide compound and a copper diketone compound. At least one copper compound, heated and reduced in diethylene glycol at a temperature above 160 ° C, to (10) 1275569 « a colloidal dispersion of oxidized cuprous ultrafine particles, and further heating the same colloidal dispersion to oxidize Cuprous ultrafine particles soft agglutinator. (36) A method for producing a cuprous oxide ultrafine particle soft aggregate according to claim 23, which comprises at least one selected from the group consisting of a copper carboxyl compound, a copper alkoxide compound and a copper diketone compound The copper compound is heated and reduced in diethylene glycol at a temperature of 160 ° C or higher to obtain a colloidal dispersion of cuprous oxide ultrafine particles, and a coagulant of addition of cuprous oxide ultrafine particles to the dispersion. (37) A method for producing a cuprous oxide ultrafine particle soft aggregate according to claim 23, which comprises at least one selected from the group consisting of a copper carboxyl compound, a copper alkoxide compound and a copper diketone compound Copper compound, heated and reduced in diethylene glycol at a temperature above 160 ° C, and at the same time in diethylene glycol, at the reaction temperature, in the addition of soluble cuprous oxide ultrafine particles in diethylene glycol . (3) A method for producing a cuprous oxide ultrafine particle soft aggregate according to the patent application No. 36 or 37, wherein the aggregating agent is selected from the group consisting of a monool compound, an ether compound, an ester compound, a nitrile compound, and a guanamine compound. And at least one of the group of quinone imine compounds. (3) The method for producing a cuprous oxide ultrafine particle soft aggregate according to any one of claims 35 to 37, wherein in the diethylene glycol, the molar is relative to the copper compound, It is a water below 30 m. The ultra-fine particle size of the copper oxide ultrafine particles of the present invention has an average primary particle diameter and an average secondary particle diameter of 1 〇〇 nm or less, respectively, and 〇·2μ1 τι or more is a special one. The copper oxide ultrafine particles soft aggregate of the present invention is excellent in the solid matter because the secondary particle diameter is 1275569 β (11). On the other hand, it can be easily dispersed in the dispersion medium, and the ultrafine particles can be produced. It is a feature of a dispersion that is uniformly dispersed. Generally, the agglomerated form of the ultrafine particles is divided into soft agglomerates in which the microparticles are mutually pulled by a redistributable weak gravitational force, and the microparticles are hardly agglomerated with a strong bond phase to the extent that they are impossible to redisperse. Two types of body. A soft agglomerate system refers to a physical and chemical method that splits and disperses the particles that make up the aggregate into possible aggregates. Here, the physical technique refers to a method of applying physical energy to an aggregate by means of ultrasonic waves, granular grinding, high-speed jet milling, spiral agitation, a planetary mixer, a three-roller machine, and the like. The chemical method refers to the method of adding acid and alkali to the liquid to adjust the pH of the dispersion to add chemical energy to the aggregate. In order to disperse the soft aggregates, it is preferable to disperse and disperse the energy of the applied gravitational force between the constituent microparticles. On the one hand, it is difficult for the hard aggregates to be made up of microparticles composed of physical and chemical techniques. Secondly, the so-called secondary particle size refers to the ultrafine particle size in the agglutinated state, and the average particle diameter can be estimated by the laser scattering method. Alternatively, the alternative method is to place the particles on the glass slide, and the microscope can be observed by a microscope. Estimate its average 値. On the other hand, ultrafine particles having a tendency to easily form a soft aggregate form a weaker bond between the obtained soft aggregates, and in the case of forming a higher order structure, the overall size of the high-order substructure can be made large. 2nd particle size. Such a high-order substructure has a tendency to become larger in particle size, and therefore it is preferable to use a micromirror for physical observation. -15- 1275569 (12) The primary particle diameter refers to the particle diameter of each of the copper oxide ultrafine particles which constitute the secondary particles of the aggregate, that is, the diameter of each of the fine particles. The ultra-fine copper oxide particles of the present invention have an extremely small primary particle size, so the size can be estimated by observing the morphology by an electron microscope. The dispersibility of the aggregate can be estimated by the change of the secondary particle size before and after the dispersion treatment. In the present invention, the copper oxide ultrafine particles are soft aggregated, and the average secondary particle diameter (R2) after the dispersion treatment is equal to the average secondary particle diameter (R1) of the soft aggregate before the dispersion treatment, so as to satisfy the R1/ The dispersion of the R2>5 relationship is preferred. In the present invention, the average primary particle diameter of the copper oxide ultrafine particles has a good tendency to be redispersible to the dispersion medium, and is preferably 25 nm or less, more preferably 10 nm or less. When the average primary particle diameter exceeds 1 〇〇 nm, the tendency to redispersibility of the dispersion medium is lowered, which is not preferable. The average secondary particle size of the copper oxide ultrafine particles soft aggregate of the present invention is 0. 2 μιη or more, preferably Ιμπι or more, more preferably 1 〇μιη or more. In the case where the average secondary particle diameter is less than 〇· 2 μ m, the rationality of the powder as a particle tends to be low. The copper oxide ultrafine particles of the present invention are preferably those having no interfacial activator or a large volume of organic compound on the surface of the particles. A surfactant on the surface or a large-volume organic compound is not preferable because it is used as a conductive material because it is an indispensable component. Here, the surfactant refers to an amphiphilic substance having a hydrophilic group and an oleophilic group in the molecule, and examples thereof include a cationic surfactant, an anionic surfactant, and a nonpolar surfactant. Here, the -16- 1275569 (13) is a non-amphiphilic substance such as a low molecular alcohol compound, which is coordinated and adsorbed on the surface of the particle, and the compound exhibiting the interface activity is excluded. The molecular weight of the surfactant is not particularly limited. For example, in order to exhibit lipophilicity, a compound having a hydrophilic group such as a sulfate, an ammonium salt or a polyethylene glycol can be exemplified as an alkyl terminal having a sufficient chain length. A large volume of an organic compound means a non-amphiphilic substance, and is a compound having a large carbon number such as a compound such as dodecylbenzene, tridecane or hexadecane. The carbon number of the surfactant or a large volume of the organic compound is generally referred to as an organic compound of 8 or more. The copper oxide ultrafine particles soft aggregate of the present invention, 1) the stability of the soft aggregated particles, 2) the redispersibility of the dispersion medium of the soft aggregate, and 3) the stability of the redispersed copper oxide ultrafine particle dispersion (4) In the case of being used as a conductive ink or a crucible, the conductivity or stability of the obtained copper film obtained by calcination may be such that a by-product such as metallic copper is contained in a condition that the properties are not deteriorated as much as possible. The range of weight % or less. ® Next, explain the manufacturing method of the above-mentioned copper oxide ultrafine particles soft aggregate. The method for producing a copper oxide ultrafine particle soft aggregate of the present invention comprises the following (I) to (III). (I) A method for producing a copper oxide ultrafine particle soft aggregate in which a copper oxide ultrafine particle is produced in a weak dispersion medium and a copper oxide ultrafine particle is produced. (II) In a good dispersion medium, after the copper oxide ultrafine particles are generated, a cohesive force is added between the copper oxide ultrafine particles to form a soft agglomerate of the copper oxide ultrafine particles-17- 1275569 (14) A method of manufacturing ultrafine particles soft aggregates. (III) In the production of ultra-fine particles of copper oxide in a good dispersion medium, a coagulation force is added between the copper oxide ultrafine particles to form a soft aggregate of copper oxide ultrafine particles, which is specially made of a copper oxide ultrafine particle soft aggregate. method. In the above, the weak dispersion medium of the ultra-fine copper oxide particles and the good dispersion medium mean a dispersion medium having poor dispersibility of the copper oxide ultrafine particles, and an excellent dispersion medium. In terms of a good dispersion medium, there are polyols having two or more hydroxyl groups in the molecule. A particularly good dispersion medium among the polyols is diethylene glycol. In the case of weakly dispersed media, there are water and the like. Next, the cohesive force added between the ultra-fine copper oxide particles is added to the chemical or physical energy which causes agglomeration. For example, there is a method in which the collision frequency between the ultrafine particles is increased by heating, so that aggregation is easy to occur, or ionicity is added. The compound is a method in which the electrostatic repulsion between the ultrafine copper oxide particles is weakened to facilitate aggregation, or a method of adding a weakly dispersed medium. Hereinafter, a specific manufacturing method of the cuprous oxide ultrafine particle soft aggregate will be specifically described. The specific production method of the cuprous oxide ultrafine particles soft aggregate of the present invention can be exemplified by the following (1) to (iv). (i) containing: in an aqueous solution containing more than 10% by weight of water, the copper carboxylate compound is used in an amount of 0. 4~5. 0 A method for producing a cuprous oxide ultrafine particle soft aggregate which is obtained by reduction of molybdenum and/or anthracene derivatives to produce cuprous oxide ultrafine particles. -18- 1275569 (15) (ii) A copper compound containing at least one selected from the group consisting of a copper carboxyl compound, a copper alkoxide compound and a copper diketone compound, in a diethylene glycol at 1 60° Heating and reducing at a temperature above C to obtain a colloidal dispersion of cuprous oxide ultrafine particles, and heating the same colloidal dispersion to make the cuprous oxide ultrafine particles soft agglomerate, and the cuprous oxide ultrafine particles are softly aggregated. Production method. (iii) containing: a copper compound selected from the group consisting of a copper carboxyl compound, a copper alkoxide compound, and a copper diketone compound, which is heated and reduced in diethylene glycol at a temperature of 160 ° C or higher. A method for producing a colloidal dispersion of cuprous oxide ultrafine particles, and then adding a cuprous oxide ultrafine particles agglomerating agent to the colloidal dispersion, and a cuprous oxide ultrafine particle soft aggregate. (iv) containing: a copper compound selected from the group consisting of a copper residue compound, a copper compound compound, and a copper diketone compound, which is heated and reduced in diethylene glycol at a temperature of 160 ° C or higher. And a method for producing a cuprous oxide ultrafine particles soft agglomerate in a diethylene glycol at the reaction temperature and adding a soluble cuprous oxide ultrafine particle agglomerating agent to the polyol. (1) A method for producing a method comprising: using a copper carboxyl compound in an aqueous solution containing 10% by weight or more of water; and using 〇·4~5 with respect to the copper carboxyl compound 1 molar. A molybdenum and/or an anthracene derivative is reduced to produce a cuprous oxide ultrafine particle. The copper raw material used in this production method is a copper carboxyl compound. The copper carboxyl compound is limited to being dissolved in an aqueous solution containing 10% by weight or more of water, and its chemical composition is not limited. For example, a commercially available copper carboxyl compound such as copper acetate, a copper salt compound obtained by reacting a copper salt with a compound containing a residue -19-(16) 1275569, or the like can be used. Among the copper carboxyl compounds, the most preferred compound is copper acetate. The copper salt used in the reaction of the copper salt with the carboxyl group-containing compound may, for example, be copper hydroxide, copper nitrate or copper carbonate. The compound containing a carboxylic acid or a salt thereof in the molecule of the compound, for example, a saturated carboxylic acid, an unsaturated carboxylic acid, and the like. One of them is formic acid, acetic acid, propionic acid, sec-butylacetic acid or the like. The reaction of the copper salt with the carboxy compound may be carried out by adding the hydrazine and/or hydrazine derivative to the same reaction vessel before conversion to cuprous oxide, or may be carried out in other reaction vessels in advance. These copper carboxyl compounds may be used alone or in combination of two or more. According to the method, the copper carboxyl compound is dissolved, and a solution containing 10% by weight of water is used, and 0 is charged with respect to the copper carboxyl compound. 4~5. 0 Moth's ruthenium and/or ruthenium derivative, which reduces the copper carboxy compound, and obtains a cuprous oxide ultrafine particle having an average primary particle size of 1 〇〇 nm or less. Examples of the hydrazine derivative include alkane oxime such as monomethyl hydrazine, dimethyl hydrazine, P hydroxyethyl hydrazine, barium sulfate, neutral barium sulfate, barium carbonate and the like. In addition to these systems, a compound having a nitrogen-nitrogen bond and having a reducing property is structurally. Among the hydrazine and hydrazine derivatives, hydrazine is preferred. Any of phthalic anhydride and hydrazine hydrate can be used. From the standpoint of safety, it is preferred to use hydrazine. In the case where the hydrazine and/or the hydrazine derivative is a liquid, it may be put into the reaction vessel as it is, or may be diluted and put into the reaction vessel. When the ruthenium and/or ruthenium derivative is a solid, it is dissolved in the reaction solvent, and is preferably introduced into the reaction vessel -20- 1275569 (17). In the case where the ruthenium and/or ruthenium derivative is diluted or dissolved, when the concentration of ruthenium and/or ruthenium derivative in the solution is low, the primary particle size of the obtained cuprous oxide ultrafine particles soft aggregate tends to become large. Preferably, it is a concentration higher than 20% by weight, more preferably 60% by weight or more. In order to adjust the reducing power of the crucible, an alkaline substance may be added to the reaction liquid or the aqueous solution of hydrazine in the range which does not affect the reaction product. In the case where the particle size of the obtained cuprous oxide particles is small by the addition of the alkaline substance, it is preferable to obtain a small-diameter cuprous oxide. In terms of the basic compound, an inorganic basic compound such as sodium hydroxide or potassium hydroxide is particularly preferred. In the present invention, the amount of the ruthenium and/or ruthenium derivative added is 0 with respect to the copper carboxyl compound 1 molar. 4~5. 0 mole, preferably 0. 9~2. 0. The molar ratio of the ruthenium and/or osmium derivative to the copper carboxyl compound is less than 0. In the case of 4, the reduction reaction is slow, so that the average primary particle size of cuprous oxide exceeds 100 nm. The molar ratio of bismuth and/or hydrazine derivatives to copper carboxyl compounds exceeds 5. At 0, the product is not only cuprous oxide, but also copper particles are 50% by weight or more. The reaction medium used in the method (i) is water alone or a mixed aqueous solution containing 90% by weight or less of an organic compound other than water. The amount of water preferably in the mixed aqueous solution is in the range of 20% by weight or more and less than 80% by weight. When a mixed aqueous solution containing an organic compound other than water is used in the reaction medium, the average primary particle diameter of the obtained cuprous oxide ultrafine particles is preferably smaller. The organic compound used in the reaction medium of the method (i) can be uniformly mixed with water without any limitation as long as it does not react with the hydrazine and/or hydrazine derivative as a reducing agent. An alcohol-based compound, an ether-based compound, an ester-based compound, a 21- 1275569 (18) compound, a guanamine-based compound, or the like can be used. From the viewpoint of the treatment, an organic compound which is liquid at room temperature is preferred, and among them, an alcohol-based compound is preferable, specifically, for example, methanol, ethanol, propanol, butanol, ethylene glycol, and diethyl ether. Glycol, triethylene glycol, polyethylene glycol, glycerin, 1,2-propylene glycol, 1,3 - propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol , 2,3 - butanediol, pentanediol, hexanediol, octanediol, and the like. The preferred concentration of the copper carboxyl compound in the reaction liquid is preferably 0. by weight based on the weight of the total reaction liquid and the copper carboxyl compound. 0% by weight or more and 50% by weight or less, more preferably 3% by weight or more and 20% by weight or less. Copper carboxyl compound, in. There is a need for substantial dissolution in the reaction liquid, and a part of the reaction liquid has substantially no problem in obtaining the cuprous oxide ultrafine particles even if the reaction solvent is not dissolved. The concentration of the copper residue compound is less than 0. When the amount is 0.01% by weight, the yield of the cuprous oxide fine particles obtained by the primary reaction is small, and when it exceeds 50% by weight, the reaction between the copper carboxyl compound and the ruthenium and/or the ruthenium derivative may be uneven. In the method (i), the optimum reaction temperature is a combination of a copper carboxyl compound and an anthracene and/or an anthracene derivative, and varies depending on the selection of the reaction liquid, and is preferably 5 ° C or more and less than 8 5 t. When the temperature is less than 5 °C, the solubility of the copper carboxyl group compound is lowered and precipitated. At 85 ° C or higher, the particle size of the obtained cuprous oxide tends to increase. For example, copper acetate is used as the copper carboxyl compound, and in the case where hydrazine hydrate is used as the reducing agent, the temperature is preferably in the range of 15 to 35 °C. The cuprous oxide ultrafine particles soft aggregate obtained by the invention is such that the cuprous oxide ultrafine particles are weakly contacted with each other to form a soft aggregate, and after the reduction reaction-22-1275569 (19) is completed, the reactor bottom sediment is formed. Ways to get it. Next, the method for producing a cuprous oxide ultrafine particle soft aggregate of (Π) is at least one copper compound selected from the group consisting of a copper carboxyl compound, a copper alkoxide compound and a copper diketone compound. When the carbon dioxide is heated and reduced at a temperature of 1 60 ° C or higher to produce the cuprous oxide ultrafine particles, the colloidal dispersion of the cuprous oxide ultrafine particles obtained in the middle is further heated to make the cuprous oxide ultrafine particles softly aggregate. A method for producing micro-copper oxide ultrafine particles soft aggregates. The copper raw material used in the production method is a copper compound selected from the group consisting of a copper carboxyl compound, a copper oxide compound, and a copper diketone compound. The copper carboxyl compound, as described above, is obtained by reacting a copper salt with a compound having a carboxyl group. The copper salt used for the reaction of the copper salt with the carboxyl group-containing compound may, for example, be copper hydroxide, copper nitrate or copper carbonate. The compound containing a carboxyl group is a compound containing a carboxylic acid or a salt thereof in the molecule of the compound, and examples thereof include a saturated carboxylic acid, an unsaturated carboxylic acid, and the like. As an example, there are formic acid, acetic acid, propionic acid, butyric acid and the like. Among the copper carboxyl compounds, the most preferred compound is copper acetate. The copper ruthenium compound is a copper compound containing an alkoxy group. The alkoxy group means a monovalent atomic group of an alkyl group and an oxygen-bonded type, and examples thereof include a methoxy 'ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group and the like. As the copper alkoxide compound, there are, for example, copper methoxide, copper ethoxylate or the like bismuth copper ketone compound, which is a copper compound having a diketone chelating compound -23- 1275569 (20). Among the diketone chelating compounds, the diketone chelating compound can form a stable copper compound, and is therefore particularly useful in the present invention. The δ diketone chelating compound is exemplified by acetamidineacetone, benzoquinone acetone, benzoquinone trifluoroacetone, diphenylmethane, furanylacetone, trifluoroacetone, and the like. The copper diketone compound is, for example, a copper acetamone ligand, copper bis (2,2,6,6-tetramethyl 3,5-heptandiolnate) or the like. In the production method (ii), the copper compound is heated in diethylene glycol at a temperature of 1 60 ° C or higher, and once the colloidal dispersion of the cuprous oxide ultrafine particles is obtained, the colloidal dispersion is further heated. Obtained a soft aggregate of cuprous oxide ultrafine particles. Since the colloidal dispersion of cuprous oxide ultrafine particles is yellow, its production can be easily discriminated. In this method, since a yellow colloidal dispersion can be obtained, the same colloidal dispersion can be heated. The heating temperature for obtaining the yellow colloidal dispersion is preferably less than 200 °C above 160 °C. At a temperature of less than 160 ° C, it takes a lot of time to react during the reaction, and the reaction proceeds rapidly at temperatures above 200 ° C. The hard aggregates are obtained, which is not preferable. Here, after obtaining a yellow colloidal dispersion, it is further heated to obtain a soft aggregate, and the heating temperature thereof is preferably 3 (TC or more, more preferably loot or more. The temperature is not allowed from the copper compound until the yellow colloidal dispersion is obtained. Change, and continue to heat at this temperature. The colloidalization of cuprous oxide ultrafine particles and the softening reaction temperature of the soft agglomeration exceed 200 ° C, there will be redispersion into an impossible hard aggregate formation, so the reaction The upper limit of the heating temperature is preferably 200. (: 0 1275569 (21) By the heating of the colloidal dispersion of the cuprous oxide ultrafine particles obtained during the reaction, the collision accuracy between the cuprous oxide ultrafine particles dispersed in the reaction liquid is added. Due to the collision between the particles, the cuprous oxide ultrafine particles begin to aggregate. As time increases, the size of the soft aggregate becomes larger, and finally a reddish brown precipitate is formed. In the reaction liquid, the cuprous oxide ultrafine particles are softly aggregated. For the secondary particle size, a small amount of the reaction solution is appropriately taken out to measure the average particle diameter, and can be monitored during the reaction. The average secondary particle diameter can be measured at a predetermined time. The reaction is stopped, and the time point at which the yellow liquid of the cuprous colloid has been confirmed in the reaction liquid is the end point of the reaction. The time from the start of the reaction liquid to the time when the yellow cuprous oxide colloidal dispersion is obtained, and The time until the yellow cuprous oxide colloidal dispersion is obtained until the precipitate of the soft aggregate is obtained varies depending on the amount and type of the copper compound charged in the reaction liquid or the reaction temperature. For example, both colloidization and soft agglutination When it is carried out at 180 ° C, the time from the start of heating of the reaction liquid to the time of obtaining the yellow cuprous oxide colloidal dispersion is 1 to 5 hours, and the yellow cuprous oxide colloid dispersion is obtained until soft agglomeration is obtained. The time until the precipitate of the body is 1 minute to 1 hour. Next, the method for producing the cuprous oxide ultrafine particles soft aggregate of (iii) is selected from the group consisting of a copper carboxyl compound, a copper alkoxide compound and a copper dioxide. At least one copper compound grouped in a ketone compound, heated and reduced in diethylene glycol at a temperature of 1 60 ° C or higher, to obtain a rubber of ultrafine particles of cuprous oxide After the dispersion, a flocculating agent of the cuprous oxide ultrafine particles is added to the dispersion. The copper compound used in the production method is the same as (ii) the production method. Further, in obtaining the ultrafine particles of cuprous oxide The reaction temperature of the colloidal dispersion -25- 1275569 (22) is preferably 16 (TC or more, less than 200 ° C. At a temperature of less than 160 ° C, the reaction time is too long and not good, and Above 20 °C, the reaction becomes too intense, and it is not good to obtain a hard aggregate. In the case of the agglomerating agent of the cuprous oxide ultrafine particles, if the cuprous oxide ultrafine particles can be softly aggregated, they are used. The inorganic compound may be an organic compound, and examples of the inorganic compound include water, an inorganic salt compound, and the like, and inorganic salt compounds include sodium chloride and potassium chloride. The aggregating agent is preferably dissolved in diethylene glycol as a reaction solvent, and among the aggregating agents, it is particularly preferably selected from the group consisting of a monool compound, an ether compound, an ester compound, a nitrile compound, a ketone compound, a guanamine compound, and a quinone compound. At least one of the group of sulfur compounds. More preferably, the compound is liquid at room temperature, specifically, methanol, ethanol, propanol, dimethyl ether, diethylene glycol diethyl ether, ethyl acetate, ethyl formate, acetonitrile, propionitrile. , acetone, methyl ethyl ketone, acetaminophen, N, N-dimethylformamide, 2-pyrrolidone, N-methylpyrrolidone, dimethyl arsenic, sulfolane and the like. According to the method, the amount of the aggregating agent required to obtain the softened aggregate of the cuprous oxide ultrafine particles varies depending on the type of the aggregating agent, so that the secondary particle diameter of the obtained soft aggregate can be added while collecting the aggregating agent. When the particle size is determined, the addition of the additive can be stopped. For example, when N-methylpyrrolidone is used as a coagulant, the diethylene glycol solvent used in obtaining the cuprous oxide ultrafine particles is added in the same volume to several times the volume to obtain the cuprous oxide of the target substance. Ultrafine particles soft aggregate. Next, the manufacturing method of (iv) is a copper compound selected from the group consisting of a copper carboxyl compound, -26-12755692 (23) a copper oxide compound and a copper diketone compound, in diethylene glycol. In the case of heating and reduction at a temperature above 160 ° C, in the diethylene glycol, a coagulant of soluble cuprous oxide ultrafine particles added to diethylene glycol at the reaction temperature is a special cuprous oxide super A method of manufacturing a microparticle soft gel. The copper compound which can be used in the production method is the same as the (Π) production method. The aggregating agent used in the production method may be an inorganic compound or an organic compound. In the case of using an organic compound, in the temperature at which the diethylene glycol is heated, it is preferably not volatilized, preferably a boiling point. It is above 1 60 °C. The inorganic compound may, for example, be an inorganic salt compound such as sodium chloride or potassium chloride. Among the aggregating agents, at least one selected from the group consisting of a monool compound, an ether compound, an ester compound, a nitrile compound, a ketone compound, a guanamine compound, a quinone imine compound, and a sulfur compound is preferred. Specifically, there are octanol, dodecanol, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diisobutyl ketone, acetone acetone, 2-ethyl butyl acetate, 2-B Hexyl acetate, r-butyrolactone, dimethyl aristotle, cyclobutene and the like. In the present method, in order to obtain the cuprous oxide ultrafine particles soft aggregate, the amount of the aggregating agents required is different depending on the type of the aggregating agent. Therefore, it is necessary to inspect the secondary particle diameter of the finally obtained soft aggregate. 'At the same time determine the optimum agglutinating agent. In general, the total amount of the reaction liquid is '〇·1% by weight or more, 重量% by weight or less, more preferably 5% by weight or more and 5% by weight or less. 本 In the present production method, the heating temperature of the reaction liquid is preferably 160. Below °C is less than 200 °C. In the temperature less than 16 °C, 'the reaction time will exceed 1275569 (24). It is not good, and at 2 Ο 0 °C, the reaction will be too intense, and there will be hard aggregates, so it is not good. . In the production methods of (ii) to (iv), water may be added to diethylene glycol in any of the reaction media. In the case of adding water, the amount of water is 30 mol or less, preferably 0, with respect to the copper compound 1 molar. 1 to 25 moles. With respect to the copper compound 1 mole, water of 30 m or less can be added, and the colloidalization of the copper compound to the cuprous oxide ultrafine particles can be carried out, and the soft agglomeration can be carried out in a relatively short period of time. When the amount of water added is too large, the proportion of cuprous oxide in the resulting product is not preferable. To effectively exert the effect of water. Fruit, the amount of water, relative to the copper compound 1 mole, to 0. Preferably, in the case of adding water, it is preferred to add diethylene glycol before the start of heating. In the manufacturing method of (i i ) to (i v ), the concentration of the copper compound in the reaction liquid is 0. 1% by weight or more and less than 50% by weight are preferred. The concentration of the copper compound is less than 0.1% by weight, and the yield of the cuprous oxide fine particles obtained by the primary reaction is too small, which is not preferable, and is more than 50% by weight, and the solubility in the diethylene glycol of the copper compound is not sufficient. Not good. The precipitate of the cuprous oxide ultrafine particles soft agglomerate obtained by the method of (i i ) to (i v ) is usually precipitated by weakly bonding the respective soft aggregates to form a higher order structure. Next, a method for producing a copper oxide ultrafine particle dispersion will be described. The copper oxide ultrafine particles soft aggregate of the present invention can be easily redispersed in a dispersion medium, and the secondary particle diameter can be reduced to produce a uniform dispersion or dispersion. -28 - 1275569 (25) The method for producing a copper oxide ultrafine particle dispersion of the present invention, wherein a soft aggregate of copper oxide ultrafine particles having an average primary particle diameter of 100 nm or less and an average diameter of 0·2 μm or more is obtained in a solvent First, in the third step of redispersing the soft aggregate separated in the second step from the second solvent to obtain the copper oxide dispersion, the step of separating the soft aggregate obtained in the first step from the first solvent. In the first step, in the first solvent, the primary particles of the copper oxide having a particle diameter of 1 〇 〇 η are synthesized to obtain the precipitates which are mutually weakly condensed particles. This is, for example, a step of obtaining a cuprous ultrafine particle soft aggregate deposit at the bottom of the reaction liquid according to the above-described method for producing an oxidized microparticle soft aggregate. Next, the second step is a step of separating the soft aggregate obtained in the first step from the first solvent. In the present method, in the first step, the ultrafine copper particles are softly aggregated, and the soft aggregates have a secondary particle size, so separation from the first solvent of the reaction liquid is easy. For the method of separation and separation, there are, for example, a method of removing with a decantation liquid, a suction filtration method, and the like. The precipitate is separated, and impurities such as reaction by-products are adhered to the surface, so that it is preferably dissolved in a clean solution. Next, in the third step, the soft coagulation second solvent separated in the second step is redispersed to obtain a dispersion of the copper oxide ultrafine particles. In this step, the second solvent is added to an appropriate container, and the aggregate is added to the aggregate, and other additives are added as needed, and then the treatment can be carried out. The method of redispersion treatment, for example, ultrasonic treatment, is carried out in the second step of the second granule 1 step, and the second oxidized body of the oxidized body of the second cup of copper is obtained. Cheng is in the process of washing the collective in the soft re-dispersion high-speed spray -29- (26) 1275569 shot honing, etc. plus the physical method of physical energy, can also add acid and alkali in the liquid It is carried out by a chemical method such as adjusting the pH of the dispersion. A plurality of them may be combined and dispersed in the dispersion means. Here, the state in which the copper oxide ultrafine particles are redispersed means that the copper oxide ultrafine particles having a reduced secondary particle diameter are preferably in a state of being homogeneously distributed in the dispersion medium, and may be present in a colloidal state. It may be in a state of being gelled by interaction of copper oxide ultrafine particles such as a dispersion medium. The dispersion time necessary for obtaining the copper oxide dispersion is also determined by the dispersion method, for example, about 5 minutes in the case of using the ultrasonic method. The copper oxide ultrafine particles are oxidized by oxygen, and the dispersion treatment is preferably carried out in an inert atmosphere such as a nitrogen atmosphere. The primary particle diameter of the copper oxide ultrafine particles soft aggregate obtained in the second step is extremely small, and the secondary particle diameter can be reduced by the redispersion treatment, and the copper oxide ultrafine particles can be produced by appropriately selecting a dispersion medium or the like. A colloidal dispersion that floats in a colloidal state in the dispersion. In order to obtain a stable colloidal dispersion of copper oxide ultrafine particles without sedimentation, the average secondary particle diameter of the copper oxide ultrafine particles in the colloidal dispersion is preferably less than 200 nm. More preferably less than 100 nm, and most preferably less than 50 nm. The second solvent used in the third step may be the same as or different from the first solvent. The amount of the solid content of the copper oxide ultrafine particles relative to the entire dispersion can be arbitrarily adjusted depending on the use thereof, and is usually adjusted to 0. It is used in an amount of 1 to 80% by weight. When the obtained colloidal dispersion liquid is used for applications such as copper wiring formation, it is preferable that the solid content of the coating film is high, and the weight of the copper oxide ultrafine particles is preferably 10% by weight or more based on the entire dispersion liquid. Good -30- 1275569 (27) is more than 30% by weight. In the third step, in the redispersion treatment of the weakly agglomerated secondary particles of the copper oxide ultrafine particles, it is preferable to reduce the particle diameter so that all the precipitates can be dispersed and floated in the dispersion medium. However, even if the portion is precipitated after the redispersion treatment, the precipitate can be separated and removed by decantation or centrifugation. Further, in order to reduce the average particle diameter of the colloidal dispersion of the copper oxide ultrafine particles in the dispersion medium, the large particles can be sedimented and removed by centrifugation or the like. In the third step, a dispersion auxiliary agent which is dispersed in the second solvent to stabilize the copper oxide ultrafine particles can be added to the second solvent. Examples of such a supplementary agent include low molecular weight compounds, oligomers, and polymers having a polar group such as a hydroxyl group, an amino group, or a carboxyl group. Examples of the low molecular compound having a polar group include an alcohol compound, an amine compound, a guanamine compound, an ammonium compound, a phosphorus compound and the like. Further, a commercially available surfactant can be used. Examples of the surfactant include a cationic surfactant, an anionic surfactant, and a nonpolar surfactant. Examples of the polymer having a polar group include polyvinylpyrrolidone, polyvinyl alcohol, polymethyl vinyl ether, and the like. Further, as the auxiliary agent, inorganic or organic particles having a polar group on the surface, for example, cerium oxide particles or latex particles can be used, and metal monomer fine particles or metal compound fine particles can be supported on the surface of the particles. It is of course possible to use a liquid dispersing aid as the second solvent. Among the above dispersing agents, polyhydric alcohols are particularly preferred. The organic compound having two or more hydroxyl groups in the polyol-based molecule is preferably a polyol having a carbon number of 1 Å or less. Such compounds are, for example, ethylene glycol, diethylene glycol, -31 - (28) 1275569 1' 2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, pentanediol, hexanediol, octanediol, glycerin, and the like. These polyols may be used singly or as a mixture of plural polyols. In order to further reduce the impurities in the dispersion of the copper oxide ultrafine particles obtained in the third step, the copper oxide ultrafine particles in the dispersion may be agglomerated and precipitated as described above by the known method, and the precipitate is separated from the third solvent. Thereafter, the precipitate is preferably repeated a plurality of times in a washing step in which the third solvent or the colloidal dispersion which can be obtained is re-dispersed in a redispersible solvent. In the third step, an additive such as a viscosity adjusting agent, a reducing agent or a calcining aid may be added to the dispersion, and in order to adjust the viscosity, one part of the second solvent may be removed by concentration or the like. When the reducing agent is added to the dispersion, there is an effect of suppressing oxidation of the ultrafine particles of copper oxide. Further, when the obtained dispersion liquid is heated to convert copper oxide into metallic copper, and it is used for applications such as conductive ink, the effect of reducing the heating temperature required for reduction is particularly preferable. As the reducing agent to be used, there are, for example, aldehydes, sugar alcohols, sugars, hydrazine and derivatives thereof, diimine, oxalic acid and the like. In terms of aldehydes, there are formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, n-pentanal, isovaleraldehyde, pivalic aldehyde, hexanal, heptaldehyde, octanal, furfural ( Pelargonaldehy de ) -f--house acid, twelve awakening, tridecanal, tetradecanal, pentadecal, hexadecanal, heptadecal, octadecyl, etc. aliphatic saturated aldehyde, glyoxal , aliphatic dialdehydes such as succinaldehyde, aliphatic unsaturated aldehydes such as acrolein, crotonaldehyde, propargaldehyde, benzaldehyde, o-toluene-32- (29) 1275569 aldehyde, m-tolualdehyde, p-tolualdehyde An aromatic aldehyde such as salicylaldehyde, cinnamaldehyde, α-naphthaldehyde, /3-naphthaldehyde or the like, a heterocyclic aldehyde such as furfural or the like. The diquinone imines are, for example, azodicarboxylate, hydroxylamine- 0-sulfonic acid sulfonic acid, fluorene-propadienyl (all ene) sulfonyl hydrazine or fluorenyl-fluorenyl sulfonyl hydrazine. Decompose the winner. In terms of N-propadiensulfonylhydrazine or N-mercaptosulfonylhydrazine, p-toluenesulfonyl sulfonate, phenylsulfonylhydrazine, 2,4,6-triisopropylbenzene Alkyl sulfonyl hydrazine, chloroethyl hydrazino, o-nitrophenylsulfonyl hydrazine, m-nitrophenylsulfonyl hydrazine, p-nitrophenylsulfonyl hydrazine, and the like. In the case of sugar alcohols, glycerin can be exemplified. Erythritol, pentaerythritol, pentitol, pentose, hexitol, hexose, heptose, and the like. Also, in terms of sugars, sorbitol, mannitol, xylitol, sleitol, hydrogenated maltose, arabitol, lactitol, adonitol ribitol, cellobitol, Glucose, fructose, sucrose, lactose, mannose, galactose, erythrose, xylulose, allose (al 1 〇se ), ribose, sorbose, xylose, arabinose, isomaltose, glucose 'Glucose and so on. In terms of hydrazine and its derivatives, in addition to hydrazine and its hydrates, there are monomethyl hydrazine, dimethyl hydrazine, hydrazine hydroxyethyl hydrazine, etc., barium sulfate 'neutral barium sulfate, barium carbonate and the like. Classes, etc. The content of the reducing agent is preferably from 0 to 〇 1 to 50% by mass, more preferably from 1 to 30% by mass based on the total weight of the dispersion. The calcining aid which can be used in the third step is obtained by calcining the -33-(30) 1275569 copper oxide ultrafine particle dispersion obtained in the third step to form a copper thin film for forming a dense and good copper film. The additive may, for example, be a polyether compound in terms of such a calcination aid. The polyether compound is a compound having an ether bond in the skeleton, and it is preferably one which can be uniformly dispersed in a dispersion medium. From the viewpoint of dispersibility of the dispersion medium, an amorphous polyether compound in which a repeating unit is a linear and cyclic oxyalkyl group-based aliphatic polyether having a carbon number of 1 to 8 is preferred. It is better. The molecular structure of the aliphatic polyether having a linear or cyclic olefin group having a carbon number of 2 to 8 may be cyclic, linear, branched, or a polyether copolymer of 2 or more. a polyether block polymer having a linear or branched shape of 2 or more, specifically, in addition to a polyether homopolymer such as polyethylene glycol 'polypropylene glycol or polytetramethylene glycol; Ethylene glycol/propylene glycol, ethylene glycol/butanediol 2-copolymer, ethylene glycol/propylene glycol/ethylene glycol, propylene glycol/ethylene glycol/propylene glycol, ethylene glycol/propylene glycol/ethylene glycol, etc. A ternary copolymer, but is not limited thereto. In terms of block copolymer, there are two-member block copolymers such as polyethylene glycol polypropylene glycol and polyethylene glycol polybutylene glycol, and further polyethylene glycol polypropylene glycol polyethylene glycol, polypropylene glycol polyethylene glycol A polyether block copolymer such as a linear ternary block copolymer such as polypropylene glycol or polyethylene glycol polybutylene glycol polyethylene glycol. It is also possible that these compounds are modified by a substituent such as an alkyl group. The copper oxide fine particles or the copper oxide ultrafine particles obtained by the above-mentioned production method are extremely small in the particle size of the copper oxide, which is relatively easy to be reduced by the metallic copper. Therefore, it can be suitably used for a copper wiring forming material, a copper bonding material, and copper. The use of electric ore instead of materials. Specifically, it can be suitably used for the wiring and pillar built-in materials of the mounted electric-34-(31) 1275569 substrate, the component bonding material for mounting the circuit substrate, and the electrode of the flat panel display. Uses of electromagnetic shielding materials such as materials and resin products. Since the particle size of the copper oxide is extremely small, it is possible to form fine wiring. The copper oxide ultrafine particle dispersion can be applied to a substrate by a screen printing method, a dispensing method, an inkjet method, a spray method or the like, wherein the copper oxide colloid dispersion having a low viscosity is used. It can be applied by inkjet method, and the inkjet ink is particularly easy to use 'further' copper oxide colloidal dispersion, which is a microcontact or micro-forming method using a micro-machining stamp to form fine wiring. The so-called ink used for soft slate printing. Other uses of the copper oxide fine particles or the copper oxide ultrafine particle dispersion obtained by the above production method include wood preservatives, antibacterial uses such as ship bottom coatings, and photoelectric energy conversion materials. The embodiment of the present invention can be specifically described, but the present invention is not limited thereto. Hereinafter, the case of cuprous oxide will be specifically described, but the present invention is not limited to the cuprous oxide ultrafine particles. The average secondary particle size of the cuprous oxide ultrafine particles soft aggregates is obtained by collecting the obtained precipitate on a glass slide, and observing the surface by an optical microscope, and arbitrarily selecting five particles from the field of view to make the average particle diameter of the particles Average 2nd particle size. The average primary particle diameter of the cuprous oxide super particles was measured by observing the surface of a transmission electron microscope (JEM-4 000 FX) manufactured by JASCO Corporation. According to the surface observation of the electron microscope, three points of the primary particle diameter are selected from the field of view, and the particle size of the object to be measured is measured at an optimum magnification of 35-(32) 1275569. Three points of the primary particle which is considered to be the most abundant are selected from each photograph, and the diameter is measured by a ruler to calculate the primary particle diameter. The average enthalpy of the enthalpy is the average primary particle size. The obtained particles were cuprous oxide, and an X-ray diffraction apparatus (Rigaku-RINT 2500) manufactured by Rigaku Co., Ltd. was used. 5°, and 42. The 4°C observations were obtained from strong diffraction peaks of (1 1 1 ) and (200) planes, respectively, and confirmed by the XRD pattern of cuprous oxide. For the redispersibility of the dispersion medium of the cuprous oxide ultrafine particles, a supersonic disperser Biburacel manufactured by Sonics and Materials was used. The 130 watt model was evaluated by outputting 30 watts and performing dispersion treatment for 2 minutes. The average secondary particle size of cuprous oxide in the colloidal dispersion obtained by the ultrasonic treatment was measured using a thick particle size distribution meter (FPAR 1 000) manufactured by Otsuka Electronics Co., Ltd. [Embodiment] <Example 1> Copper carboxy compound/ruthenium compound Mohr ratio-dependent 1 8 g of anhydrous copper acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 70 ml of purified water. While stirring at 25 ° C, 64 wt% of hydrazine hydrate was added to 2 ml, so that the molar ratio of cerium to copper acetate was 1.2, and it was reacted to obtain a precipitate of cuprous oxide. The average primary particle size of the precipitate was 20 nm, and the average secondary particle size was 800 μm. When 1 g of the present solution was placed in 9 g of diethylene glycol and subjected to ultrasonic dispersion, a colloidal dispersion of cuprous oxide was obtained, and the average secondary particle diameter in the dispersion was 80 nm. (33) 1275569 <Example 2> Copper carboxy compound / oxime compound Mohr ratio dependency 2 2 g of anhydrous copper acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 70 ml of purified water. At 25 ° C, 64 wt% of hydrazine hydrate was added while stirring, so that the molar ratio of cerium to copper acetate became 〇·6, and it was reacted to obtain a cuprous oxide. The average primary particle size is 30 n m and the average secondary particle size is 300 μm. The average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 80 nm. <Example 3 > Copper carboxy compound / oxime compound Mohr ratio- 3% 3. 8 g of anhydrous copper acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 70 ml of purified water. At 25 ° C, 64 wt% of a hydrazine hydrate of 6.5 m was added while stirring, so that the molar ratio of cerium to copper acetate was 3.0, and it was reacted to obtain a precipitate of cuprous oxide. The average primary particle diameter and the average secondary particle diameter were 60 nm and 200 μmη, respectively. The average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 12 〇 nm. <Example 4> Copper carboxy compound / oxime compound Mohr ratio- s 4 g of anhydrous copper acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 70 ml of purified water. At 60 ° C, 64 wt% of hydrazine hydrate 2 m 1 was added while stirring, so that the molar ratio of cerium to copper acetate was 0.9, which was allowed to react to obtain a precipitate of cuprous oxide. The average primary particle size 'average secondary particle size is 50 nm, 1 80 μιη, respectively. The average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 95 nm. -37- 1275569 (34) <Example 5> Example of the alcohol compound contained in the reaction solution - 1 8 g of anhydrous copper acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 50 ml of purified water and 20 ml of ethylene glycol. At room temperature of 25 ° C, 64% by weight of hydrazine hydrate was added in an amount of 2.0 ml, and the molar ratio of cerium to copper acetate was 0.9, which was allowed to react to obtain a precipitate of cuprous oxide. The average primary particle size, the average secondary particle size is 10 nm, 350 μm. The average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 45 nm. <Example 6> In the reaction solution, the alcohol compound was contained in Example - 2, and 40 ml of purified water and 30 ml of ethanol were added to 8 g of anhydrous copper acetate (manufactured by Wako Pure Chemical Industries, Ltd.). At room temperature 2 5 ° C, 2.4 ml of 肼 肼 hydrate 2.4 ml was added while stirring, so that the molar ratio of cerium to copper acetate was 1.1, and it was reacted to obtain a precipitate of cuprous oxide. The average primary particle size, the average secondary particle size is 1, 10 n m, and 1 90 μm. The average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 40 nm. <Example 7> Example of copper carboxyl compound obtained from copper hydroxide and acetic anhydride 1.95 g of copper hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 3 ml of acetic anhydride were added to 6 〇 of purified water. Further, 64% by weight of hydrazine hydrate was added to 1. 6 m 1, and when it was stirred at 25 ° C, a precipitate of cuprous oxide was obtained. The average primary particle size, the average secondary particle size is 60 n m, 300 μm. The average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 1 0 0 - 38 - 1275569 (35) <Example 8> Example 1 of adding a basic compound during the reaction 1 3 g of anhydrous copper sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 600 ml of purified water at 30 ° C - 20 ml of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) was added while stirring. After a few minutes, a solution of 3 00 ml of a sodium hydroxide aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 15 ml of hydrazine hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) were added to the mixture to obtain a precipitate of cuprous oxide. . The average primary particle size, with an average of 2 particle diameters, is 15 nm, 2 2 0 μm. The average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 50 nm. <Example 9> Example 1 of adding a basic compound during the reaction. 29.5 g of copper hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 600 ml of purified water at 30 ° C. 20 ml of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) was added while stirring. After a few minutes, 30 ml of a 1 N aqueous solution of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 12 ml of hydrazine hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) were added to make a reaction to obtain a precipitate of cuprous oxide. . The average primary particle size, the average secondary particle size is 20 nm, 130 μχη. The average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 55 nm. <Example 1> Example of adding a basic compound during the reaction - 3 47.3 g (0.2 mol) of copper nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 600 ml of purified water, and stirred at 3 (TC - while stirring 20 ml of acetic anhydride (36) 1275569 (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After the addition, a 1 M sodium hydroxide aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added to a mixture of 300 ml and hydrazine hydrate (Wako Pure Chemical Industries, Ltd.). Industrial Co., Ltd.) 15 ml was reacted to obtain a precipitate of cuprous oxide. The average primary particle diameter and the average secondary particle diameter were 15 nm and 180 μπ, respectively. The average of the colloidal dispersions obtained in the same manner as in Example 1 was obtained. The secondary particle size is 45 nm. <Example 1 1 > Example of adding a basic compound at the time of the reaction - 4 47.3 g (0.2 mol) of copper nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in purified water 600 ml at 30 °C - 20 ml of propionic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added while stirring. After a few minutes, 1 〇ml of a 1 N aqueous solution of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 肼 hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 7 5 ml were reacted to obtain a cuprous oxide. Precipitate. The average primary particle size, the average secondary particle diameter is 20 nm, 250 μm. The average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 50 nm. <Example 1 2>Example of addition of a basic compound at the time of the reaction - 5 Copper nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) 47·3 g (〇.2mo1 ) was dissolved in 600 ml of purified water at 30 ° C Sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 8 · 2 g was added while stirring. After a few minutes, a 1 m sodium hydroxide aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) 40 m 1 and a hydrazine hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 7·5 were added to the reaction to obtain a cuprous oxide. Precipitate. The average primary particle size, the average secondary particle size of 1275569 (37) is 20 nm, 24 0 μπί. The average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 60 nm. <Example 1 3> Examples of the hydrazine derivative used in the reducing agent 3.6 g of anhydrous copper acetate and 30 ml of purified water were added to a beaker of 300 ml, and stirred for 20 minutes. 2 ml of /3 -hydroxyethyl hydrazine (manufactured by Nippon Paint Co., Ltd.) was added while stirring at a temperature of 3 (TC), and a reaction of 20 minutes was carried out to obtain a cuprous oxide precipitate. The average primary particle diameter was 2 times on average. The particle diameters were 30 nm and 200 μm, respectively, and the average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 85 nm. <Example 1 4> Example of using a diluted hydrazine for a reducing agent - 1 70 ml of purified water was added to 8 g of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.). Adding 40% by weight of hydrazine aqueous solution (diluted by hydrazine hydrate) to 3 · 9 ml while stirring at 25 ° C, so that the molar ratio of cerium to copper acetate becomes 1.7, and reacts to obtain oxidation. Precipitate of cuprous copper. The average primary particle diameter was 22 nm and 150 μιη, respectively. The average secondary particle diameter in the colloidal dispersion obtained by the same method as in Example 1 was 80 nm. <Example 1 5 > Example of using a diluted hydrazine for a reducing agent - 2 To 70 g of purified water (manufactured by Wako Pure Chemical Industries, Ltd.), 70 ml of purified water was added. Adding a 20% by weight aqueous solution of hydrazine (diluted by hydrazine hydrate) to 7·8 ml while stirring at 25 ° C, so that the molar ratio of cerium to copper acetate becomes 1.7, and reacts to obtain cuprous oxide. Precipitate. The average ~ times -41 - (38) 1275569 particle size, the average secondary particle size is ' 30 nm, 2 5 Ο μ m. The average secondary particle size in the colloidal dispersion obtained in the same manner as in Example 1 was 90 nm. <Example 1 6> Example of using a diluted hydrazine for a reducing agent - 3 To a solution of 8 g of copper acetate anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), 70 ml of purified water was added. At 25 ° C, while stirring, a 5 wt% aqueous solution of hydrazine (diluted with hydrazine hydrate) was added to make 3 1 · 2 ml, so that the molar ratio of cerium to copper acetate became 1.1, and the reaction was carried out to obtain an oxidized sub Copper precipitate. The average primary particle size, the average secondary particle size is 40 nm, 200 μm. The average secondary particle size in the colloidal dispersion obtained by the same method as in Example 1 was 1 〇〇 nm <Example 1 7> Example of forming a soft aggregate by heating - 1 2.7 g of copper acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) 90 ml, and added 0.9 g of water was heated at 1 90 ° C for 3 hours to react. After the yellow cuprous oxide colloidal dispersion was obtained, the reaction was further heated for 30 minutes while maintaining the temperature to obtain a precipitate of cuprous oxide. The average primary particle size, the average secondary particle size was 90 nm, 290 μιη, respectively. The average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 150 nm. <Example 1 8 > Example of forming a soft aggregate by heating - 2 Copper methyl oxide (manufactured by Wako Pure Chemical Industries, Ltd.) 1. 9 g suspended in di-42-(39) 1275569 ethylene glycol ( 90 ml of Wako Pure Chemical Industries Co., Ltd., adding 0. 9 g of water, and heating at 19 ° C for 1 hour. Once the yellow cuprous oxide colloidal dispersion is obtained, the reaction is heated for 20 minutes while maintaining the temperature. A precipitate of cuprous oxide is obtained. The average primary particle diameter, the average secondary particle diameter is 80 nm, 90 μιη, respectively. The average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 150 nm. <Example 1 9 > Example of forming a soft aggregate by heating - 3 Suspending a 4.0 g of copper acetoacetone ligand (manufactured by Wako Pure Chemical Industries, Ltd.) in diethylene glycol (Wako Pure Chemical Industries, Ltd.) 90 ml, adding water 〇.9g, heating at 190 °C for 3 hours, once the yellow cuprous oxide colloidal dispersion is obtained, while maintaining the temperature, the reaction is further heated for 30 minutes to obtain cuprous oxide. Precipitate. The average primary particle size, with an average of 2 particle diameters of 80 nm and 100 μm, respectively. The average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 1,70 nm. <Example 20> Example of adding an alcohol compound to obtain a soft aggregate. 2.7 g of copper acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) 90 ml, and water was added thereto. g, the reaction was heated at 1 90 ° C for 3 hours. Once the yellow cuprous oxide colloidal dispersion was obtained, 300 ml of ethanol was added to the dispersion to obtain a precipitate of cuprous oxide. The average primary particle size, the average secondary particle size is 90 nm, 150 μιη, respectively. The average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 1 800 n m. -43- (40) 1275569 <Example 2 1> Example of adding an alcohol compound to a reaction solvent to obtain a soft aggregate. 2,7 g of copper acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) 90 ml, adding 9 g of hydrazine and 0.5 g of octanol, and heating at 190 ° C for 3 hours to obtain a precipitate of cuprous oxide. The average primary particle size, the average secondary particle diameter is 95 nm, ΙΟΟμιη. The average secondary particle diameter in the colloidal dispersion obtained in the same manner as in Example 1 was 180 nm. <Example 22> Example 1 using a cuprous oxide ultrafine particle dispersion to form a copper thin film The same procedure as in Example 1 gave a cuprous oxide microparticle soft coagulant 3. lg, adding diethylene glycol 6.0 g and As an additive, polyethylene glycol (average molecular weight of 20,000, manufactured by Wako Pure Chemical Industries, Ltd.) was 3.0 g. Ultrasonic dispersion is applied to prepare a cuprous oxide ultrafine particle colloidal dispersion. This dispersion was applied to a square glass plate having a length of 120 mm on a bar coater having a thickness of 50 μη, and coated at an area of 50 mm x 100 mm. The coated glass plate was calcined at 350 ° C for 1 hour on a hot plate under a nitrogen stream to obtain a copper film on a glass plate. The obtained copper film had a thickness of 2.5 μm and a volume resistance of x7x10_6 Qcm. <Example 23> Example 2 of forming a copper wiring using a cuprous oxide ultrafine particle colloidal dispersion 2 - 44- (41) 1275569 A cuprous oxide microparticle soft coagulum 1.0 g obtained in the same manner as in Example 1 was added thereto. The diol was 6.0 g and the polyethylene glycol (average molecular weight 200, and Wako Pure Chemical Industries, Ltd.) 1.0 g as an additive. Ultrasonic dispersion is applied to prepare a cuprous oxide ultrafine particle colloidal dispersion. The secondary particle size of the cuprous oxide ultrafine particles in the colloidal dispersion is 100 nm. The dispersion was filled in an ink cartridge of an ink jet type print head and mounted on a dedicated printer. In the ink jet method of this embodiment, a piezo type printing head is used. On the slide glass, ink was ejected at an average liquid volume of 4 pi (pi: - mega-liter), and a linear pattern having a line thickness of 5 μm Å 100 μm was printed. After the printing, the glass substrate was heat-treated at 305 ° C / 1 hour in a nitrogen atmosphere to carry out reduction of cuprous oxide. The resistance of the pattern of the obtained metal wiring was good at 5x1 0_6 Ω · cm. <Example 24 > Example of a cuprous oxide ultrafine particle dispersion containing a reducing agent. The cuprous oxide fine particles of the softened coagulum obtained in the same manner as in Example 1 were added with ethylene glycol 6.0 g as a reducing agent. The cerium carbonate 0.4 g was subjected to ultrasonic dispersion to prepare a dispersion of ultrafine oxide particles of cuprous oxide. After coating with a bar coating on a glass substrate in the same manner as in Example 22, when the temperature was raised in a nitrogen atmosphere, it was confirmed that copper was formed at a low temperature of 200 ° C. <Comparative Example 1 > When the amount of the added amount is more than the predetermined amount -45 - 1275569 - (42) 70 ml of purified water is added to 8 g of anhydrous copper acetate (manufactured by Wako Pure Chemical Industries, Ltd.). While stirring at room temperature 25C, 64% by weight of hydrazine hydrate 1 2 · 0 ml was added so that the molar ratio of cerium to copper acetate was 5.9, and the reaction was carried out, and the product contained about 20% by weight of metallic copper. <Comparative Example 2 > When the amount of hydrazine added was less than the predetermined amount, 70 ml of purified water was added to 8 g of anhydrous copper acetate (manufactured by Wako Pure Chemical Industries, Ltd.). At room temperature 25 ° C - while adding 64 wt% of hydrazine hydrate · 6 6 m 1 while stirring, the molar ratio of cerium to copper acetate becomes 〇. 3, and reacted to obtain a precipitate of cuprous oxide. However, the average primary particle size of the obtained cuprous oxide is as large as 200 nm. <Comparative Example 3 > In the case of using a copper salt other than a copper carboxyl group as a raw material, 1 ml of purified water (10 ml) was added to copper chloride (manufactured by Wako Pure Chemical Industries, Ltd.). At room temperature 25 ° C - while adding 64 wt% of hydrazine hydrate 50 μl ' while stirring, the molar ratio of bismuth to copper chloride is 〇.6, so that it reacts 'but no cuprous oxide particles are obtained, and copper is formed. . <Comparative Example 4 > In the case of using a copper salt other than a copper carboxyl group as a raw material, 2 ml of purified water was added to 2 6 g of copper sulfate (manufactured by Wako Pure Chemical Industries, Ltd.). Adding 64% by weight of hydrazine hydrate 50 μ 1 ' while stirring at room temperature 25 ° C, so that the molar ratio of cerium to copper sulphate becomes 〇. 6, and reacts, -46 - 1275569 (43) The cuprous oxide particles "form" to form copper. <Comparative Example 5 > In the case of using a copper salt other than a copper carboxyl group as a raw material, 3 ml of purified water was added to 氢氧化·16 g of copper hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.). Adding 64% by weight of hydrazine hydrate 7 5 μΐ at room temperature to 25 ° C while stirring, so that the molar ratio of cerium to copper sulphate becomes 0 · 9, and reacts, although the precipitation of cuprous oxide is obtained, but the average The primary particle size is as large as 300 <Comparative Example 6 > In the case where the reaction liquid was not contained in water, 8 g of copper acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and 70 ml of diethylene glycol was added. At room temperature 25 ° C, 2.6 ml of 64 wt% hydrazine hydrate was added while stirring, so that the molar ratio of cerium to copper acetate was 1.2, and the reaction was carried out, and the obtained precipitate was not cuprous oxide but copper. <Comparative Example 7 > In the same manner as in Example 20, the copper acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 2·7 g was suspended in diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) 90 ml, adding water 0.9 g, and heating at 19 (TC for 3 hours to obtain a yellow cuprous oxide colloidal dispersion. The cuprous oxide particles float in the reaction solution, and to be recovered, the centrifugation step In this centrifugal separation step, it is necessary to first collect the weight of the obtained colloidal dispersion in the remote tube and separate it. After that, set the distal tube to the rotor and centrifuge the rotor to -47- (44) The 1275569 separator is very time consuming and is very time consuming.
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