200927659 九、發明說明 【發明所屬之技術領域】 本發明係關於鈦之金屬元 、緦、鈣、鎂、鉛之金屬元素 方法。另外，本發明係關於煅 陶瓷組成物，及使用其之陶瓷 件。 Ο 【先前技術】 鈦酸鋇、駄酸鍊、欽酸給 物粉末係作爲煅燒體原料使用 黏劑後，使用薄片成形法或印 成粉末層，接著，使锻燒成爲 成物）。因爲該陶瓷組成物係 進而半導性，所以可作爲電容 〇 熱敏電阻等之電氣•電子工業 陶瓷組成物係作爲陶瓷電 電子機器使用。隨著近年來的 、輕量化、高性能化、多機能 性能要求更加嚴格。以電腦等 瓷電容器爲例時，因爲此電容 與內部電極交互地多數重疊， 以隨著層合陶瓷電容器之小型 要求陶瓷組成物之薄層化、高 素、與含有至少一種選自鋇 之複合氧化物粉末及其製造 燒前述之複合氧化物粉末之 電子零件及層合陶瓷電子零 、鈦酸鉻酸鉛等之複合氧化 ，混合複合氧化物粉末與膠 刷法等之方法，於基板上形 煅燒體（以下亦稱爲陶瓷組 具有優異的介電性、壓電性 器、電波薄膜、點火元件、 用材料使用。 子零件，組入各種電機器· 電機器•電子機器的小型化 化，對如此陶瓷電子零件之 之積體電路所使用之層合陶 器係前述陶瓷組成物之薄層 採取電氣上並聯之結構，所 化、高容量化等之要求，更 介電常數化。因此，陶瓷組 -5- 200927659 $牧/之原材料之複合氧化物粉末之微粒子化、高結晶性化 之性能要求’另外’均質化、高分散化等之品質要求亦逐 漸明顯。另外’層合陶瓷電容器之內部電極雖使用鉑、鈀 '銀等之貴金屬材料，但試圖轉換成銅、鎳等廉價之賤金 屬材料’隨此而來，對於複合氧化物粉末，希望可以更低 溫锻燒’另外’即使於低氧分壓之環境下進行煅燒，仍不 會半導體化’具有耐還原性者。 〇 製造含有鈦之金屬元素與至少1種選自鋇、緦、鈣、 鎂、鉛之金屬元素之複合氧化物粉末，混合各元素之氧化 物或碳酸鹽，使用電氣爐或旋轉窖:爐進行煅燒之所謂的固 相合成法、於水系合成各元素之草酸鹽後進行煅燒之所謂 的草酸鹽法、於水系合成各元素之檸檬酸鹽後進行煅燒之 所謂的檸檬酸鹽法、混合各元素之水溶液及鹼水溶液，進 行水熱處理後，過濾、洗淨、乾燥之所謂的水熱合成法等 之方法，於各個方法中，進行複合氧化物粉末之微粒子化 〇 、高結晶性化等之改良硏究。記載硏究的主要目的係抑制 伴隨複合氧化物粉末之微粒子化所產生之結晶性降低，例 如記載於固相合成法中，將由加熱分解產生氧化鋇之鋇化 合物、與由X射線繞射法所求之金紅石（rutile )化率爲 30%以上，比表面積爲30m2/g以上之二氧化鈦，進行混 合、煅燒時，可得到爲微粒，成爲正方晶性（tetragonality )指標之晶格之c軸與a軸之比（c/a軸比）高之鈦酸鋇 粉末（參考專利文獻1 )。 〔專利文獻1〕特開2006 - 306632號公報 200927659 【發明內容】 發明之揭示 發明所欲解決之課題 前述專利文獻1記載之方法係由使用比表面積爲 3 〇m2/g以上之微粒子二氧化鈦，可得到微粒子’結晶性 高之鈦酸鋇粉末，但實施例之鈦酸鋇粉末之SEM徑（掃 描式電子顯微鏡徑）雖爲24至90nm程度’但結晶性指 標之c/a軸比爲1.002至1.006程度（表2) ’很難說夠 高。 課題之解決手段 本發明者等，努力硏究製造結晶性更佳之複合氧化物 粉末，尤其鈦酸鋇粉末之方法之結果，發現若使用作爲固 相合成法之原料使用之鈦氧化物之金紅石化率高於90%， 〇 100%以下，比表面積爲150至3 00m2/g者時，因爲係金 紅石型之相同結晶結構，所以可進行均勻的反應，而且， 因爲比表面積大，所以反應性變高，可得到具有所需結晶 性、粒徑之複合氧化物粉末。 另外，前述鈦氧化物之金紅石型結晶之結晶徑若爲 1 Onm以下時，發現反應性更高，可得到所需之複合氧化 物粉末。 另外，前述之鈦氧化物係發現以1 5 0 °C以下之溫度下 進fJ乾燥中和四氯化欽所得之產物者爲適宜等，完成本發 200927659 明。 亦即，本發明係 (1 )混合由X射線繞射法所求之金紅石化率高於 90%，100%以下之比表面積爲150至300m2/g之鈦氧化物 、與含有至少1種選自鋇、鋸、鈣、鎂及鉛所成群之金屬 元素之化合物，並進行煅燒爲特徵之複合氧化物粉末之製 造方法， φ ( 2 )使用前述（1 )記載之方法所製造之粒徑範圍爲 0.06〜0.15私m之複合氧化物粉末，尤其c/a軸比範圍爲 1.0075至1.010之鈦酸鋇粉末， (3) 煅燒前述（2)之複合氧化物粉末或鈦酸鋇粉末 之陶瓷組成物， (4) 具備前述（3)記載之陶瓷組成物，與設置成對 向以夾著前述陶瓷組成物之電極之陶瓷電子零件，尤其具 備含陶瓷組成物之複數層，與前述陶瓷組成物層間所形成 ❾ 之電極之層合陶瓷電子零件等。 發明之功效 本發明係製造鈦酸鋇等之複合氧化物粉末之方法中， 藉由使用由X射線繞射法所求之金紅石化率高於90%， 100%以下’比表面積爲150至3 00m2/g之鈦氧化物作爲 原料之鈦氧化物，可得到粒徑小，而且結晶性良好之複合 氧化物粉末。 具體上’可得到粒徑範圍爲0.06至〇.15/zm，而且 -8 - 200927659 c/a軸比範圍爲1.0075至1.010之具有優異正方晶性之鈦 酸鋇粉末。 另外，因爲前述之複合氧化物粉末之結晶性良好，所 以改善低溫煅燒性或耐還原性，可提高作爲煅燒體時之塡 充率，可改善介電性或壓電性等之特性。因此，使用由本 發明之方法煅燒複合氧化物粉末之陶瓷組成物時，利用該 優異特性，可得到滿足小型化、輕量化、高性能化、多機 u 能化之陶瓷電子零件，尤其層合陶瓷電子零件。 用以實施發明之最佳形態 本發明係混合鈦氧化物、與含有至少1種選自鋇、緦 、鈣、鎂及鉛所成群之金屬元素之化合物，進行煅燒之複 合氧化物粉末之製造方法，使用由X射線繞射法所求之 金紅石化率高於90%，100%以下，比表面積爲150至 3 0 0m2/g之鈦氧化物。鈦氧化物係比表面積愈大，反應性 〇 愈好，所以適宜，但過大時，因爲變得難以製造如此之鈦 氧化物，所以比表面積係以160至2 5 0m2/g爲宜，以160 至200m2/g尤佳。比表面積係由BET法之氮吸附求出。 前述之鈦氧化物係含鈦的氧化物（二氧化鈦）、或稱 爲鈦之水合氧化物、含氫氧化物、氫氧化物者，可使用選 自此等中之至少一種。另外，鈦氧化物一般係由X射線 繞射法確認金紅石型結晶、銳鈦礦型結晶、板鈦礦型結晶 。作爲本發明之鈦氧化物係前述3種結晶結構中之金紅石 型結晶多者，使用由X射線繞射法所求之鈦氧化物之金 -9- 200927659 紅石化率高於9 0 % ’ 1 ο ο %以下者，以9 5至1 〇 〇 %尤佳， 認爲無銳鈦礦型結晶 '板鈦礦型結晶之X射線繞射波峰 程度之金紅石化率1 00%更好。所謂鈦氧化物之金紅石化 率係指鈦氧化物所含金紅石型結晶之比率，由X射線繞 射（使用CuK 射線）確認金紅石型結晶、銳鈦礦型結晶 、板鈦礦型結晶之存在、或不存在，求出金紅石型結晶對 於前述三種結晶型之含有比率。另外，由金紅石型結晶之 ❹ (110)面之X射線繞射波峰之半高寬（full-width at half maximum)，使用S cherrer公式（式1 )，可求出金 紅石型結晶之結晶徑。作爲紅石型結晶之結晶徑，就反應 性之觀點’以小者爲宜，以10nm以下爲宜，以1至 1 0 n m更好。 式 1: Dhkl=K* λ / β cos θ DHKL :結晶徑（A) λ : X射線之波長 φ /3 :繞射波峰之半高寬 0 : Bragg ’ s 角 K :定數（=0_94 ) 另一方面，依據電子顯微鏡照片時，鈦氧化物之一次 粒徑係推定爲1至1 5nm程度，亦可集合該一次粒子，形 成二次粒子。鈦氧化物之二次粒子形狀係任何形狀者皆可 ，可使用例如粒狀、球狀、略球狀、紡錘狀等者。粒狀、 球狀、略球狀時，粒徑以最大粒直徑（數平均）表示時， 以1〇至3 00nm爲宜，以20至150nm尤佳，以30至 -10- 200927659 1 20nm更好。另外，所謂紡錘狀係指類似紡紗錘之形狀， 類似兩端突出之圓柱形之形狀者。因此，紡錘狀係包含一 般稱爲針狀、棒狀、柱狀、圓柱狀、多角柱狀等者。連接 粒子兩端之長度爲長軸徑，柱部最粗部份之長度爲短軸徑 ，該長軸徑之數平均（平均長軸徑）與短軸徑之數平均（ 平均短軸徑）之比爲軸比，軸比係以大者爲宜，具體上以 1.5以上尤佳。另一方面，因爲鈦氧化物成爲微粒子時， φ 難以增大軸比，所以爲1.5至5程度爲宜，以1.5至4程 度更好。鈦氧化物之平均長軸徑係以10至3 OOnm爲宜， 以20至150nm尤佳，以30至120nm更好。鈦氧化物之 二次粒子係數個至數百個進一步凝聚，形成凝聚粒子。如 此鈦氧化物之二次粒子形狀、平均長軸徑、平均短軸徑係 可以電子顯微鏡觀察、測定。 另外，例如粒狀粒子凝聚，形成更大多孔性之凝聚粒 子，紡錘狀粒子亦形成類似金平糖之凝聚粒子。 φ 關於鈦氧化物之凝聚粒子係可由下述方法，測定於水 中之粒徑（5 0 %積算徑（中値粒徑）），本發明中就固相 合成之反應性之觀點，以〇.〇6至0.2 0// m程度爲宜。 於水中之粒度分佈之測定方法 (1 )以氫氧化鈉水溶液調整鈦氧化物之糊料成 ρΗΙΟ.8後，以塗料搖擺器分散15分鐘。 (2)加入換算成PzOs爲 〇.3mg之六偏磷酸鈉之 300ml之水中，添加氫氧化鈉水溶液調整成pHl 0.5，作爲 -11 - 200927659 測定用分散溶劑。 (3) 於1公升之聚乙烯製容器，加入上述測定用分 散溶劑及數滴以塗料搖擺器製作之分散液（鈦氧化物糊料 )，進行攪拌，調製懸濁液。 (4) 於上述懸濁液中，以超音波發生器（sharp製 ，UT— 500 ) ’照射1分鐘超音波，分散試料。 (5 )使用雷射繞射式粒度分佈測定裝置（HORIBA 0 製，la- 910)，測定所得分散液中試料之粒度分佈。 本發明使用之鈦氧化物係以Ti02純度爲99重量％以 上之高純度者爲宜，以99.5重量％以上尤佳，以99.9重 量％以上更好。T i Ο 2純度係表示自1 〇 〇 ( % )扣除水份、 強熱減量成份（Ig-Loss )、氯元素、碳元素除外之不純 物（例如矽、鐵、鋁、鈮、鈉等之元素，此等之氧化物換 算量）總量的値。矽等元素係由螢光X射線法、IPC發光 分光分析法或原子吸光法分析。 〇 本發明使用之鈦氧化物係可以液相法、氣相法製法， 適當地選擇可製造所需金紅石化率、比表面積等之鈦氧化 物之條件。液相法係將硫酸駄（titanium sulfate)、硫酸 氧鈦（titanyl sulfate )、四氯化鈦、醇鹽鈦（titanium alkoxide)等之鈦化合物之溶液，進行水解、中和之方法 ，因爲可容易得到比表面積高，金紅石型結晶之結晶徑小 者’所以適宜。作爲具體之液相法，例如將中和或水解四 氯化鈦、硫酸氧鈦等所得之含氫氧化鈦，於氫氧化鈉等之 鹼金屬氫氧化物、銨化合物、碳酸銨化合物、胺化合物等 -12- 200927659 鹼化合物水溶液中進行加熱處理後，過濾•洗淨，接著， 於鹽酸等之強酸水溶液中進行加熱處理而可得。作爲前述 鹼化合物，就金紅石化率等觀點，以氫氧化鈉最適宜，爲 充分除去鈉，以進行由酸之浸析作用（Leaching)等爲宜 。另外，若於三氯化鈦之存在下進行前述鹽酸處理時，因 爲可得到長軸徑較大，結晶徑小之微細鈦氧化物微粒子， 所以爲適合之方法。將所得產物分別、乾燥。若乾燥溫度 0 過高時，因爲比表面積降低，所以乾燥溫度係以1 5 0 °C以 下之溫度爲宜。作爲其他方法，可使用中和四氯化鈦之方 法。攪拌四氯化鈦溶液下，滴入中和劑，中和四氯化鈦。 作爲中和劑，可使用氫氧化鈉等之鹼金屬氫氧化物、銨化 合物、碳酸銨化合物、胺化合物等。於此方法中，使用鹼 金屬氫氧化物作爲中和劑時，爲充分除去鹼金屬，以進行 由酸之浸析作用等爲宜。如此所得之產物係與上述同樣地 分別、乾燥》乾燥溫度係以150°C以下之溫度爲宜。乾燥 φ 溫度若高於150 °C時，因爲中和產物之比表面積容易降低 ，並不適宜。乾燥之下限溫度係只要可乾燥之溫度，任一 種溫度皆可。 另一方面，鈦氧化物之氣相合成法係以氧氣氧化四氯 化鈦之方法，或以水蒸氣水解四氯化鈦氣之方法，容易得 到高純度鈦氧化物之方法。以水蒸氣水解之方法，因爲可 容易得到比表面積高，金紅石化率高之鈦氧化物，所以更 適宜。 作爲用以製造複合氧化物粉末之另一種原料之含有至 -13- 200927659 少1種選自鋇、緦、鈣、鎂及鉛所成群之金屬元素之 物（以下亦稱爲金屬化合物）’可無例外地使用通常 合成法所使用者，可使用此等金屬元素之氧化物、氫 物、碳酸鹽等。作爲前述之金屬化合物’適合使用碳 。作爲碳酸鹽，可使用於前述之金屬元素之氯化物、 鹽、醋酸鹽等之水可溶性鹽之水溶液，添加碳酸鹼、 銨等之碳酸化合物，或吹入二氧化碳氣中和所得者。 0 之金屬化合物比較柔軟，雖然與鈦氧化物之混合過程 因鈦氧化物而容易被粉碎，但因爲金屬化合物之粒徑 響複合氧化物粉末之特性，所以若使用微粒子之金屬 物時，因爲有效地微粒子化複合氧化物粉末，所以適 例如作爲微粒子指標，若以BET法之比表面積表示 以5m2/g程度以上爲宜，以10m2/g程度以上尤佳 2 0m2/g程度以上更好。 混合前述之鈦氧化物、及金屬化合物成原料粉末 〇 者的混合量係因應目的之複合氧化物粉末而可適當設 例如製造具有以一般式AB〇3型所示之鈣鈦礦型結構 合氧化物粉末係混合以至少一種選自鋇、鋸、鈣、鎂 所成群之金屬元素（A)相對於鈦氧化物之Ti原子（ 之原子比表示，以〇·9至2.0之範圍爲宜，以0.95至 之範圍尤佳，以1.000至1.035之範圍更好。前述原 若小於〇 · 9時，難以得到所需組成之複合氧化物粉末 餘成份若殘留於複合氧化物，因爲容易損及介電性或 性等之特性’所以不適宜。另外，製造聚鈦酸鋇，具 化合 固相 氧化 酸鹽 硝酸 碳酸 前述 中， 亦影 化合 宜。 時， ，以 。兩 定。 之複 及鉛 B ) 1.05 子比 ，剩 壓電 體上 -14- 200927659 爲 B aTi2 〇 5、B aTi 4 Ο 9、B aTi 5 〇 11、B a2Ti9 〇2 ο、B a4Ti 1 3 〇3 ο 、：Ba6Ti1704G等之具有Ti/Ba之原子比X爲2以上之組成 式之鈦酸鋇係混合各原料，使相對於其規定之原子比X， 成爲（XxO.95)至（Χχΐ.05)之範圍爲宜。 此混合時，因應陶瓷組成物所需之特性，亦可添加鉻 化合物，製造鈦酸鉻酸鹽。另外，因應需要，亦可適當加 入作爲添加劑之例如鑭、鈽、釓、铽、鏑、鈥、餌、鏡等 φ 之稀土類元素或硼、鋁、矽、錳、鐵、鎳、銅、鋅、鈮、 釔、鎢、鉍等之元素。此等添加劑係可爲氧化物、氫氧化 物，亦可爲碳酸鹽，亦可爲其他的化合物。添加量係因應 目的而可適當設定。 混合係均勻混合鈦氧化物與金屬化合物至某程度之程 度即可，混合度係可適當調整。作爲混合方法，可爲乾式 混合、濕式混合中任一種，例如可使用螺旋型混合機、螺 帶型混合機、流動化型混合機等之固定型混合機、圓筒型 e 混合機、雙子圓筒型混合機等之旋轉型混合機等。另外， 混合前，使用壓縮粉碎機、衝擊壓縮粉碎型、剪斷粉碎型 、摩擦粉碎型等之粉碎機，可於混合前分別粉碎鈦氧化物 及金屬化合物，另外，亦可於粉碎時同時混合。因爲原料 粉末愈細，所得之複合氧化物粉末愈容易成爲微粒子，所 以以粉碎原料粉末爲宜，作爲粉碎機，可適合使用例如球 磨機、珠磨機、膠體磨機等之濕式粉碎機。混合狀態係使 用濕式粉碎機等，於濕潤狀態或懸濁狀態（糊料狀態）時 ，因應需要，亦可進行分別、乾燥、粉碎。 -15- 200927659 如此所得之原料粉末係因應需要，例如使用後述之流 動層锻燒或氣體流通式之煅燒法等之固相合成反應係因爲 形成適當粒度，所以適宜，可由轉動造粒、流動層造粒、 噴流層造粒、攪拌造粒、解碎造粒、壓縮造粒、擠壓造粒 、液滴固化造粒等之通常方法進行造粒。使用濕式粉碎機 等’爲懸濁狀態（糊料狀態）時，使用塗敷乾燥器等噴霧 乾燥’進行乾燥造粒爲宜。藉由噴霧乾燥之造粒，不僅防 〇 止原料粉末飛散或氣體接觸不均勻，造粒粉體之粒度係比 較整齊’可期待均勻的固相合成，所以適宜。造粒粉體之 平均粒度係可考慮可流動大小、或飛散程度而可任意調整 ，例如可爲1至100()0/^111程度，若爲5至3000//111程度 時’因爲飛散較少，所以適宜，若爲10至ΙΟΟΟμιη程度 尤佳，若爲20至5 00 # m程度更好。造粒粉體係可爲球 狀、略球狀、板狀、立方體狀、長方體狀、棒狀或於粉末 內部具有空間之中空狀等之任何形狀皆可，但以容易流動 〇 的形狀爲宜，例如球狀、略球狀、中空狀等之形狀尤佳。 另外’粉碎、混合、造粒時，因應需要，亦可配合界面活 性劑、樹脂、分散劑等之有機化合物於原料粉末等。造粒 時’尤其噴霧乾燥時，若添加樹脂時，除了作爲黏著劑作 用’調整造粒粉體之粒度之外，因爲樹脂於煅燒時分解， 由所產生的空隙成爲多孔性，亦達成自造粒粉體內部釋出 發生的氣體（例如二氧化碳氣等），所以適宜。所使用之 材料並無特別限定，因應目的適當選擇，使用必要量。例 如’可使用水系丙烯酸樹脂、水系三聚氰胺樹脂、水系胺 -16- 200927659 基甲酸乙酯等作爲樹脂，以添加相對於原料粉末之1至 20重量％程度爲宜。 接著，加入前述原料粉末或將其造粒之造粒粉體（以 下’合倂原料粉末及造粒粉體，稱爲原料粉末）於煅燒裝 置。使用之煅燒裝置，可使用通常固相合成法等所使用之 煅燒爐或此外之無機化學領域，尤其陶瓷領域所使用之加 熱爐’可適合使用未滿大氣壓之可煅燒之真空煅燒爐、減 φ 壓煅燒爐或使原料粉末等流動而可煅燒之流動層煅燒爐、 氣體流通式之煅燒爐。煅燒溫度、煨燒保持時間係可因應 複合氧化物粉末而適當設定，例如可爲5 00至1 100 °C程 度，煅燒時間係可保持例如0.5至1 0小時程度。另外， 煅燒結束後係冷卻至取出溫度，但可適當設定冷卻的速度 ，可緩緩冷卻，亦可急速冷卻。 加入前述原料粉末等於煅燒裝置，自室溫開始升溫至 達成所需之煅燒溫度時，通常自該中途之溫度範圍，隨著 Q 鈦氧化物及金屬化合物反應或有機化合物分解等，發生二 氧化碳氣、水蒸氣等。若將此二氧化碳氣等排氣於熘燒裝 置外時，可得到結晶性較高之複合氧化物粉末，所以適合 。具體上，使用真空煅燒爐、減壓煅燒爐，於未滿大氣壓 下煅燒原料粉末等爲宜，於總壓lxl03Pa以下之環境壓力 下進行爲宜，於總壓ΙχΙΟ1至lxl03Pa以下之環境壓力下 進行更好。另外，爲將二氧化碳氣等排氣於熘燒裝置外， 可使用流通氣體下進行煅燒之氣體流通式煅燒爐，例如旋 轉電爐、固定床電爐等之煅燒爐。流通的氣體係可使用與 -17- 200927659 後述流動層煅燒爐使用之氣體相同者。 作爲其他方法，以使用流動層煅燒爐，使原料粉末等 於流動下進行煅燒之方法尤佳。流動狀態係以形成均勻流 動層（完全流動層）之流動狀態爲宜，另一方面，亦可爲 流動層內發生氣泡之濃厚流動層之狀態，或亦可爲部份原 料粉末形成固定層，剩餘部份爲流動之狀態。調整流動狀 態係可以原料粉末等之粒度及通氣氣體之流速（流量）等 0 進行。氣體之通氣係經過自二氧化碳氣等之發生開始溫度 範圍至發生結束溫度範圍之至少部份期間，以全部期間爲 宜進行時，因爲使原料粉末等於流動下，可將發生的二氧 化碳氣等有效率地排氣於煅燒裝置外，所以適合。另外， 因應需要，可自升溫開始階段，進行氣體通氣，亦可發生 結束以後至煅燒結束，進行氣體通氣，進而，亦可至取出 所得複合氧化物粉末之間，進行氣體通氣。二氧化碳氣等 之發生開始溫度係依使用之金屬化合物種類、組成或添加 ❹ 劑等而異，但熱分析原料粉末等時，可把握二氧化碳氣等 之發生開始溫度、發生結束溫度。例如考慮混合鈦氧化物 及碳酸鋇之原料粉末之二氧化碳氣之發生開始溫度約爲 500 °C程度。另一方面，因爲考慮發生結束溫度係約爲 8 5 0 °C程度，所以於約5 0 0至8 5 0 °C之間進行氣體通氣爲 宜。 作爲通氣之氣體，雖可使用通常流動層煅燒爐所使用 之氣體，但若含二氧化碳氣時’因爲影響複合氧化物粉末 之結晶性等，所以不適宜，以選擇二氧化碳氣含量少之氣 -18- 200927659 體或不含二氧化碳氣之氣體爲宜。因此，以使用二氧化碳 氣含量爲0至0.5容積％之氣體爲宜，以二氧化碳氣含量 爲〇至0.1容積％尤佳，以二氧化碳氣含量爲0至0.05容 積％更好。作爲如此氣體，可使用例如氮、氬、氦、空氣 、氧、合成空氣、乾燥空氣（dry air)、壓縮空氣等，可 使用選自此等之一種氣體或二種以上之混合氣體。雖然空 氣、合成空氣、乾燥空氣（dry air)、壓縮空氣中含有約 0 400ppm程度之少量二氧化碳氣，但確認此程度的量不影 響。而且，若使用空氣、合成空氣、乾燥空氣（dry air) 、壓縮空氣時，因爲煅燒時原料粉末等不易被還原，容易 得到均質之複合氧化物粉末，所以適宜。通氣的氣體，導 入煅燒裝置前，預先加熱時，因爲可防止煅燒裝置之急速 溫度降低，所以適宜。另外，雖由通氣的氣體，可將至少 部份發生的二氧化碳氣等排氣於煅燒裝置外，但另一方面 ，亦可循環使用通氣的氣體，此時循環氣體中之二氧化碳 φ 氣含量係於前述範圍爲宜。 依據前述方法，可製造微粒子，而且結晶性高之複合 氧化物粉末，具體上爲酞酸鋇、鈦酸緦、鈦酸鉛、鈦酸鉻 酸鉛、鈣改性鈦酸鋇、稀土類元素改性鈦酸鋇等之具有鈣 鈦礦型結構之化合物、具有Ti/Ba之原子比爲2以上之組 成式之鈦酸鋇等。作爲複合氧化物粉末之粒徑係以可得到 0.01至0.3// m範圍者爲宜，以0.015至0.2/zm範圍者尤 宜，以0.01至0.15#m範圍者更好，以〇.〇6至0.15/zm 範圍者最好。複合氧化物粉末之粒徑（d)係假設複合氧 -19- 200927659 化物粉末爲球狀，使用由BET法之比表面積a ( m2/g )之 下述式2求出。 式 2…d= ( 6/ /〇 ) /a 但是，p係比重，鈦酸鋇粉末時係使用P = 5 · 90。 另外，所得之複合氧化物粉末之結晶性係進行X射 線繞射測定，由某結晶面之繞射波峰之波峰高或半高寬而 評估，但更精密地係以X射線數據爲基礎，進行Rietveld 0 法解析而判斷。尤其鈦酸鋇粉末時，由晶格之c軸與a軸 之比（c/a軸比）判斷，c/a軸比愈大，正方晶系鈦酸鋇之 結晶性變高。具體上依據本發明之方法，使c/a軸比範圍 爲1.0075至1.010，以1.0080至1.010爲宜。結晶性低之 複合氧化物粉末，尤其未滿1.006之鈦酸鋇粉末，雖然作 爲電子零件使用，但因爲強介電性不足，所以增大c/a軸 比係需要進一步熱處理，導致粒成長之結果。正方晶系鈦 酸鋇之c/a軸比之理論値係由a=3.994，c = 4.038値所算 〇 出之e/a= 1.01 1，另外，立方晶系鈦酸鋇之c/a軸比爲 1.000 〇 另外’調製陶瓷組成物時，因應需要，亦可混合添加 劑於複合氧化物粉末。作爲添加劑，因應陶瓷組成物所需 的特性’亦可適當使用鑭、铈、釓、铽、鏑、鈥、餌、鏡 等之稀土類元素或硼、鋁、矽、錳、鐵、鎳、銅、鋅、鈮 、釔、鎢、鉍等之元素。另外，煅燒時，作爲用以控制粒 子成長或陶瓷組成物之電特性之添加劑，例如除了硼、鉍 以外’可舉例如鋰、鈉、鉀等之鹼金屬、鐵、錳、鈷、鎳 -20- 200927659 、鈮等之過渡金屬，進而矽、鋁等之元素之化合物。如此 添加劑係可於粉碎複合氧化物粉末之階段添加，亦可於粉 碎後混合。或是，亦可於複合氧化物粉末之煅燒階段之任 意階段添加。添加量係可適當設定需要量。混合機係可使 用通常無機化學領域，尤其陶瓷領域所使用之混合機，或 電子材料領域所使用之混合機。另外，粉碎、混合時，亦 可添加界面活性劑、樹脂、分散劑等之有機化合物。如此 0 操作，可調製陶瓷組成物原料。 至少含有複合氧化物粉末之前述陶瓷組成物原料係使 煅燒作爲陶瓷組成物，適合使用作爲例如陶瓷電子零件之 材料。陶瓷電子零件係具備陶瓷組成物，與設置成對向以 夾著前述陶瓷組成物之電極。另外，作爲陶瓷電子零件， 層合陶瓷電子零件係具備含陶瓷組成物之複數層，與前述 陶瓷組成物層間所形成之電極。具體的層合陶瓷電子零件 係層合陶瓷電容器，具備含複數層合之陶瓷組成物層（介 Ο 電體層）’與沿著此等陶瓷組成物層間之特定界面所形成 之內部電極之層合體者。層合體之內部係交互配置作爲內 部電極之第1內部電極及第2內部電極，使各端緣露出於 層合體端面之狀態，分別形成第1內部電極係電連接於第 1外部電極，第2內部電極係同樣地電連接於第2外部電 極。作爲電極’可使用例如鉑、鈀、鎳、銀、銅等之金屬 或此等之合金。層合陶瓷電子零件之陶瓷組成物之各層厚 度係儘可能愈薄愈好，以1/zm以下爲宜。 陶瓷組成物或陶瓷電子零件係可使用傳統的方法製造 -21 - 200927659 。陶瓷組成物係混合至少含有複合氧化物粉末之陶瓷組成 物原料及膠黏劑後，進行加壓成形，形成規定形狀之生球 (green pellet)，或使用薄片成形法或印刷法等之方法， 於基板上形成規定厚度之綠帶（green sheet)，接著進行 锻燒。陶瓷電子零件係可使用例如於前述綠帶的兩面，印 刷或塗佈配合電極用金屬之漿劑等，進行煅燒之方法，或 形成前述之綠帶，接著，於其上方印刷或塗佈配合內部電 0 極用金屬之漿劑等，將其多次反覆後，進行煅燒之方法等 。煅燒條件係因應陶瓷組成物原料之煅燒度而可適當設定 ，但煅燒溫度係例如以1 000至1 500°c程度爲宜，以1 100 至1 300 °C度尤佳。煅燒時間亦因應陶瓷組成物原料之組 成而可適當設定，但以0.5至10小時程度爲宜。煅燒時 之環境雖可爲氧、空氣、合成空氣、乾燥空氣（dry air) 、壓縮空氣等之含氧氣體，但以電極用金屬不被氧化之環 境爲宜，可適合使用非氧化性的氣體，例如氮、氬、氦等 φ ，另外，亦可適合使用氫、一氧化碳、氨等之還原性氣體 【實施方式】 實施例 以下係舉實施例、比較例，更詳細地說明本發明，但 本發明並非侷限於此等實施例者。 實施例1 -22- 200927659 秤量以1 3 0 °C之溫度乾燥中和四氯化鈦所得產物之鈦 氧化物（以前述方法測定之比表面積爲190m2/g，平均長 軸徑爲80nm，軸比爲3之紡錘狀二氧化鈦，Ti〇2純度爲 99.98重量％，金紅石化率爲100%，金紅石型結晶之結晶 徑爲9nm，於水中之50 %積算徑爲0.077 ym)及碳酸鋇 (比表面積爲30m2/g )，使鋇/鈦之原子比成爲1,000，使 用球磨機濕式粉碎混合，接著，蒸發乾燥混合糊料，以硏 缽粉碎成原料粉末。 接著，放入所得之原料粉末於50 cc之坩堝，使成爲 2 0 mm之厚度，放置此坩堝於可控制環境之固定床電爐， 於減壓下（ 200至500Pa)之環境氣壓下，自室溫升溫成 8 5 0 °C，保持5小時，進行煅燒，得到鈦酸鋇粉末（試料 A )。 實施例2 於上述實施例1中，除了使煅燒溫度成900°C以外’ 與實施例1同樣地操作，得到本發明之鈦酸鋇粉末（試料 B )。 實施例3 於上述實施例1中，除了使熘燒溫度成950°C以外’ 與實施例1同樣地操作，得到本發明之鈦酸鋇粉末（試料 C )。 -23- 200927659 實施例4 將前述實施例1所得之鈦氧化物及碳酸鋇之混合糊料 ’由塗敷乾燥器進行乾燥，進行造粒。造粒粉體之平均粒 徑爲50 m。 接著’加入造粒粉體於縱型小型流動層煅燒爐，將作 爲流動用氣體之乾燥空氣（含有4 0 0ppm程度之二氧化碳 氣）’以氣體直線速度1.73cm/秒進行通氣，使前述之造 〇 粒粉體流動下，自室溫升溫成9 5 0 r，保持〇 · 5小時，進 行^锻燒’得到本發明之鈦酸鋇粉末（試料D )。另外，乾 g g 2通氣係自升溫開始至試料取出之全部煅燒步驟間 進行’由乾燥空氣的通氣，使造粒粉體流動，將發生之二 氧化碳氣排出於系統外。 實施例5 於上述實施例4中，除了使保持時間爲1小時以外， G 與®施例4同樣地操作，得到本發明之鈦酸鋇粉末（試料 E )。 實施例6 於上述實施例4中，除了使保持時間爲1 .5小時以外 ’與實施例4同樣地操作，得到本發明之鈦酸鋇粉末（試 料F) 〇 比較例1 -24- 200927659 取代前述之實施例1使用之鈦氧化物，使用比表面積 爲1 1 5m2/g (金紅石化率爲i 00%，金紅石型結晶之結晶 徑爲13nm ’以175°C加熱實施例1使用之鈦氧化物者） ’於減壓下（200至500Pa )之環境下，自室溫升溫至 8 〇〇 °C ’保持5小時’進行煅燒以外，與實施例1同樣地 操作，得到鈦酸鋇粉末（試料G)。 如此所得之試料A至G之鈦酸鋇粉末，由BET法測 〇 定比表面積a ( m2/g )，求出平均粒徑d(ym)。 另外，使用X射線繞射法所得之數據，進行Rietveld 法解析，求出正方晶鈦酸鋇之晶格常數a及c，算出結晶 性評估（正方晶性）c/a軸比。 由此結果之表1可知，本發明之鈦酸鋇粉末係粒徑較 小，而且具有高 c/a軸比，具有優異的正方晶性（ tetragonality )。 煅燒條件 所得鈦酸鋇之特性 粒徑〔# m〕 c/a軸比 實施例1 固定床（減壓下） 0.089 1.0079 實施例2 固定床（減壓下） 0.096 1.0086 實施例3 固定床（減壓下） 0.116 1.0094 實施例4 流動層（乾燥空氣通氣） 0.101 1.0089 __黨施例5 流動層（乾燥空氣通氣） 0.120 1.0095 實施例6 流動層（乾燥空氣通氣） 0.079 1.0079 比較例1 固定床（減壓下） 0.077 1.0074 ❹〔表1〕 進行數次實施例1至3記載之實驗的結果’確認所得 -25- 200927659 之鈦酸鋇粉末之品質整齊。另外，確認本發明中除了欽酸 鋇之外，亦可同樣地製造鈦酸緦'鈦酸鉛、锆酸錯、欽酸 锆酸鉛、鈣改性鈦酸鋇、稀土類元素改性鈦酸鋇等之具有 鈣鈦礦型結構之化合物、具有Ti/B a之原子比爲2以上之 組成式之鈦酸鋇等。另外，煅燒所得之複合氧化物粉末， 得到陶瓷組成物，使用其作爲陶瓷電子零件時，確認本發 明之優越性。 〇 產業上利用性 因爲本發明之複合氧化物粉末係微粒子，具有高結晶 性，藉由將其煅燒，可簡便地且容易地製造具有介電性或 壓電性等優異特性之陶瓷組成物。使用該陶瓷組成物於陶 瓷電子零件，尤其層合陶瓷電子零件時，期待可滿足小型 化、輕量化、高性能化、多機能化等。 Φ 【圖式簡單說明】 〔圖1〕表示實施例1中使用之鈦氧化物之粒子結構 之電子顯微鏡照片。 〔圖2〕實施例1中使用之鈦氧化物之X射線繞射圖 型。 -26-BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal element method for a metal element, tantalum, calcium, magnesium, and lead of titanium. Further, the present invention relates to a calcined ceramic composition, and a ceramic member using the same.先前 [Prior Art] A barium titanate, a decanoic acid chain, or a phthalic acid powder is used as a raw material for a calcined body, and then a sheet forming method or a powder layer is printed, and then calcination is carried out. Since the ceramic composition is further semi-conductive, it can be used as a ceramic electronic device as an electrical/electronic industrial ceramic component such as a capacitor 热敏 thermistor. With the recent years, lightweight, high performance, and multi-function performance requirements are more stringent. When a ceramic capacitor such as a computer is taken as an example, since the capacitor and the internal electrode are mostly overlapped with each other, the thinness of the ceramic composition, the high quality, and the compound containing at least one selected from the group consisting of the small size of the laminated ceramic capacitor are required. The oxide powder and the electronic component thereof for firing the composite oxide powder described above, and the composite oxidation of the laminated ceramic electron zero, lead titanate chromate, etc., the mixed composite oxide powder and the gel brush method, etc., are formed on the substrate The calcined body (hereinafter also referred to as a ceramic group has excellent dielectric properties, a piezoelectric device, a radio wave film, an ignition element, and a material used. Sub-components, various types of electric machines, electric machines, and electronic devices are miniaturized, The laminated ceramic used in the integrated circuit of the ceramic electronic component is a structure in which the ceramic composition is electrically connected in parallel, and is required to have a higher dielectric constant. Therefore, the ceramic group is formed. -5- 200927659 The performance of the micro-particles and high crystallinity of the composite oxide powder of the raw material of the animal husbandry is required to be 'other' homogenized, highly dispersed, etc. The quality requirements are also becoming more and more obvious. In addition, the internal electrodes of the laminated ceramic capacitors use noble metal materials such as platinum and palladium 'silver, but try to convert them into cheap bismuth metal materials such as copper and nickel. It is desirable that the powder can be calcined at a lower temperature. 'Also', even if it is calcined in a low oxygen partial pressure environment, it will not be semiconductorized. 'There is no resistance to reduction. 〇The metal element containing titanium and at least one kind selected from 钡a composite oxide powder of a metal element of cerium, calcium, magnesium or lead, an oxide or a carbonate of each element, a so-called solid phase synthesis method in which an electric furnace or a rotary kiln is used for calcination, and various elements are synthesized in an aqueous system. The so-called oxalate method in which the oxalate is calcined, the so-called citrate method in which the citrate of each element is synthesized in water, the aqueous solution of each element and the aqueous alkali solution are mixed, hydrothermally treated, and then filtered. A method such as a hydrothermal synthesis method which is washed and dried, and in each method, fine particles of a composite oxide powder, high crystallinity, and the like are performed. The main purpose of the study is to suppress the decrease in crystallinity caused by the microparticulation of the composite oxide powder. For example, it is described in the solid phase synthesis method, and the ruthenium compound which generates yttrium oxide by heat decomposition and X-rays. The rutile having a rutile ratio of 30% or more and a specific surface area of 30 m 2 /g or more is obtained by a diffraction method, and when mixed and calcined, a crystal lattice is obtained, and a lattice having a tetragonality index is obtained. A barium titanate powder having a high ratio of the c-axis to the a-axis (c/a-axis ratio) (refer to Patent Document 1). [Patent Document 1] JP-A-2006-306632, No. 200927659 In the method described in the above Patent Document 1, a fine particle titanium dioxide having a specific surface area of 3 〇m 2 /g or more is used, and a barium titanate powder having a high crystallinity of fine particles can be obtained. However, the SEM of the barium titanate powder of the example is obtained. The diameter (scanning electron microscope diameter) is about 24 to 90 nm', but the c/a ratio of the crystallinity index is 1. 002 to 1. The level of 006 (Table 2) is hard to say is high enough. In order to solve the problem of the method of producing a composite oxide powder having a better crystallinity, in particular, a barium titanate powder, the present inventors have found that the use of a red oxide of titanium oxide as a raw material for solid phase synthesis is found. When the petrochemical rate is higher than 90%, 〇100% or less, and the specific surface area is 150 to 300 m2/g, since the rutile type has the same crystal structure, a uniform reaction can be performed, and since the specific surface area is large, the reaction is performed. The property becomes high, and a composite oxide powder having a desired crystallinity and particle diameter can be obtained. When the crystal diameter of the rutile crystal of the titanium oxide is 1 Onm or less, it is found that the reactivity is higher, and the desired composite oxide powder can be obtained. Further, in the above-mentioned titanium oxide, it is found that the product obtained by drying and neutralizing tetrachlorination at a temperature of 150 ° C or lower is suitable, and the like is completed. That is, the present invention (1) is a mixture of titanium oxide having a specific surface area of 150 to 300 m 2 /g and a minimum specific surface area of 100% or less, which is obtained by an X-ray diffraction method, and containing at least one kind. a method for producing a composite oxide powder characterized by being a compound of a metal element in which a group of strontium, saw, calcium, magnesium, and lead are grouped, and φ ( 2 ) using the method described in the above (1) The diameter range is 0. 06~0. 15 private m composite oxide powder, especially the c / a axial ratio range is 1. 0075 to 1. (3) The ceramic composition of the composite oxide powder or the barium titanate powder of the above (2) is calcined, and (4) the ceramic composition according to the above (3) is provided, and is disposed opposite thereto. In particular, the ceramic electronic component in which the electrode of the ceramic composition is interposed has a plurality of layers including a ceramic composition, and a laminated ceramic electronic component such as an electrode formed between the ceramic composition layer. EFFECTS OF THE INVENTION The present invention is a method for producing a composite oxide powder of barium titanate or the like, which has a specific surface area of 150 to 100% or less by using an X-ray diffraction method. A titanium oxide having a titanium oxide of 30,000 m 2 /g is used as a raw material, and a composite oxide powder having a small particle diameter and good crystallinity can be obtained. Specifically, the particle size range is 0. 06 to 〇. 15/zm, and -8 - 200927659 c/a axis ratio range is 1. 0075 to 1. 010 of barium titanate powder having excellent tetragonality. In addition, since the crystallinity of the composite oxide powder described above is good, the low-temperature calcination property and the reduction resistance are improved, and the charge ratio in the case of the calcined body can be improved, and the properties such as dielectric properties and piezoelectric properties can be improved. Therefore, when the ceramic composition of the composite oxide powder is fired by the method of the present invention, ceramic electronic parts satisfying miniaturization, weight reduction, high performance, and multi-machine energy can be obtained by using the excellent characteristics, especially laminated ceramics. Electronic parts. BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a method for producing a composite oxide powder obtained by mixing a titanium oxide and a compound containing at least one metal element selected from the group consisting of ruthenium, osmium, calcium, magnesium and lead. The method uses a titanium oxide having a gold-red petrochemical rate higher than 90%, 100% or less, and a specific surface area of 150 to 300 m 2 /g as determined by an X-ray diffraction method. The titanium oxide has a larger specific surface area and a higher reactivity, so it is suitable, but when it is too large, since it becomes difficult to produce such a titanium oxide, the specific surface area is preferably 160 to 250 m 2 /g, and 160. It is especially good to 200m2/g. The specific surface area is determined by nitrogen adsorption by the BET method. The above titanium oxide-based titanium oxide (titanium dioxide), or titanium hydrated oxide, hydroxide-containing or hydroxide may be used, at least one selected from the group consisting of. Further, titanium oxide is generally confirmed by an X-ray diffraction method as a rutile crystal, an anatase crystal, or a brookite crystal. As the titanium oxide of the present invention, the rutile type crystal in the above three kinds of crystal structures is used, and the gold oxide of the titanium oxide obtained by the X-ray diffraction method is more than 90%. 1 ο ο % or less, especially from 9 5 to 1 〇〇%, and it is considered that the X-ray diffraction peak of the anatase-type crystal slabite crystal is more preferably 100%. The gold-red petrochemical ratio of titanium oxide refers to the ratio of rutile-type crystals contained in titanium oxide, and rutile crystals, anatase crystals, and brookite crystals are confirmed by X-ray diffraction (using CuK rays). The presence or absence of the rutile crystal is determined as a ratio of the above three crystal forms. In addition, from the full-width at half maximum of the X-ray diffraction peak of the ruthenium (110) plane of the rutile crystal, the crystal of the rutile crystal can be obtained by using the Scherrer formula (Formula 1). path. The crystal diameter of the red stone type crystal is preferably small in view of reactivity, and is preferably 10 nm or less, more preferably 1 to 10 nm. Formula 1: Dhkl=K* λ / β cos θ DHKL : crystal diameter (A) λ : wavelength of X-ray φ /3 : half-height width of diffraction peak 0 : Bragg ' s angle K : constant (=0_94 ) On the other hand, according to the electron micrograph, the primary particle diameter of the titanium oxide is estimated to be about 1 to 15 nm, and the primary particles may be collected to form secondary particles. The shape of the secondary particles of the titanium oxide may be any shape, and for example, a granular shape, a spherical shape, a slightly spherical shape, a spindle shape or the like may be used. In the case of granules, spheres, and spheroids, when the particle diameter is expressed by the maximum particle diameter (number average), it is preferably from 1 〇 to 300 nm, particularly preferably from 20 to 150 nm, and from 30 to -10-200927659 1 20 nm. it is good. In addition, the so-called spindle shape refers to a shape similar to a spinning hammer, similar to the shape of a cylindrical shape in which both ends protrude. Therefore, the spindle type includes generally referred to as a needle shape, a rod shape, a column shape, a column shape, a polygonal column shape, and the like. The length of the two ends of the connecting particles is the long axis diameter, and the length of the thickest part of the column portion is the short axis diameter, and the number average of the long axis diameters (average long axis diameter) and the number of short axis diameters (average short axis diameter) The ratio is the axial ratio, and the axial ratio is preferably the larger one, specifically 1. More than 5 is especially good. On the other hand, when titanium oxide is a fine particle, it is difficult to increase the axial ratio by φ, so it is 1. 5 to 5 is appropriate, to 1. 5 to 4 degrees is better. The average major axis diameter of the titanium oxide is preferably from 10 to 300 nm, more preferably from 20 to 150 nm, even more preferably from 30 to 120 nm. The secondary particle coefficient of the titanium oxide is further agglomerated to several hundreds to form aggregated particles. The secondary particle shape, the average major axis diameter, and the average minor axis diameter of the titanium oxide can be observed and measured by an electron microscope. Further, for example, the granulated particles are agglomerated to form agglomerated particles having a larger porosity, and the spindle-like particles also form aggregated particles similar to the ginseng sugar. φ The agglomerated particle of titanium oxide can be measured by the following method, and the particle diameter in water (50% of the calculated diameter (the median diameter)), and the viewpoint of the reactivity of the solid phase synthesis in the present invention is 〇. 〇6 to 0. 2 0 / / m is appropriate. Method for determining the particle size distribution in water (1) Adjusting the paste of titanium oxide with sodium hydroxide aqueous solution to form ρΗΙΟ. After 8 , it was dispersed by a paint shaker for 15 minutes. (2) Adding to PzOs is 〇. 3mg of sodium hexametaphosphate in 300ml of water, add sodium hydroxide aqueous solution to adjust to pHl 0. 5, as -11 - 200927659 dispersion solvent for measurement. (3) In a 1 liter polyethylene container, the above-mentioned dispersion solvent for measurement and a plurality of dispersions (titanium oxide paste) prepared by a paint shaker were added and stirred to prepare a suspension. (4) Ultrasonic waves were irradiated for 1 minute in an ultrasonic generator (sharp system, UT-500) in the above suspension to disperse the sample. (5) The particle size distribution of the sample in the obtained dispersion was measured using a laser diffraction type particle size distribution measuring apparatus (manufactured by HORIBA 0, la-910). The titanium oxide used in the present invention is preferably a purity of 99% by weight or more of TiO2, and is preferably 99. More than 5 wt% is particularly good, with 99. More than 9% by weight is better. The purity of T i Ο 2 means that the water, the heat-reducing component (Ig-Loss), the chlorine element, and the impurity other than carbon (such as strontium, iron, aluminum, strontium, sodium, etc.) are deducted from 1 〇〇 (%). , the amount of such oxide conversion amount). Elements such as ruthenium are analyzed by fluorescent X-ray method, IPC luminescence spectrometry or atomic absorption method.钛 The titanium oxide used in the present invention can be suitably selected from a liquid phase method or a gas phase method, and a condition for producing a desired titanium oxide such as a ruthenium salt ratio and a specific surface area can be appropriately selected. The liquid phase method is a method of hydrolyzing and neutralizing a solution of a titanium compound such as titanium sulfate, titanyl sulfate, titanium tetrachloride or titanium alkoxide, because it is easy to use. It is suitable to obtain a high specific surface area and a small crystal diameter of the rutile crystal. Specific liquid phase methods include, for example, neutralization or hydrolysis of titanium tetrachloride, titanium oxysulfate, etc., titanium hydroxide, alkali metal hydroxide, ammonium compound, ammonium carbonate compound, and amine compound. Iso-12-200927659 After heating in an aqueous solution of an alkali compound, it is filtered, washed, and then heat-treated in a strong acid aqueous solution such as hydrochloric acid. As the alkali compound, from the viewpoint of the ruthenium-like rate, etc., sodium hydroxide is most preferable, and sodium is sufficiently removed to carry out acid leaching (Leaching) or the like. Further, when the hydrochloric acid treatment is carried out in the presence of titanium trichloride, a fine titanium oxide fine particle having a large major axis diameter and a small crystal diameter can be obtained, which is a suitable method. The resulting product was separately and dried. If the drying temperature is too high, since the specific surface area is lowered, the drying temperature is preferably a temperature of 150 ° C or less. As another method, a method of neutralizing titanium tetrachloride can be used. While stirring the titanium tetrachloride solution, a neutralizing agent was dropped to neutralize titanium tetrachloride. As the neutralizing agent, an alkali metal hydroxide such as sodium hydroxide, an ammonium compound, an ammonium carbonate compound, an amine compound or the like can be used. In the method, when an alkali metal hydroxide is used as the neutralizing agent, the alkali metal is sufficiently removed to carry out acid leaching or the like. The product thus obtained is preferably dried in the same manner as described above, and the drying temperature is preferably 150 ° C or lower. Drying φ If the temperature is higher than 150 °C, it is not suitable because the specific surface area of the neutralized product is easily lowered. The lower limit of the drying temperature is any temperature as long as it can be dried. On the other hand, the gas phase synthesis method of titanium oxide is a method of oxidizing titanium tetrachloride by oxygen or a method of hydrolyzing titanium tetrachloride by steam to easily obtain a high-purity titanium oxide. In the method of hydrolyzing water vapor, it is more preferable because titanium oxide having a high specific surface area and a high gold-sulfur ratio can be easily obtained. As another raw material for producing a composite oxide powder, a metal element (hereinafter also referred to as a metal compound) selected from the group consisting of lanthanum, cerium, calcium, magnesium, and lead is contained in the range of -13 to 2009. The user of the usual synthesis method can be used without exception, and an oxide, a hydrogen substance, a carbonate or the like of these metal elements can be used. As the metal compound described above, carbon is suitably used. As the carbonate, an aqueous solution of a water-soluble salt such as a chloride, a salt or an acetate of the above-mentioned metal element may be added to a carbonated compound such as a carbonate or ammonium, or a carbon dioxide gas may be neutralized. The metal compound of 0 is relatively soft, and although the mixing process with titanium oxide is easily pulverized by titanium oxide, since the particle size of the metal compound is characteristic of the composite oxide powder, when the metal material of the fine particles is used, it is effective In the case of the granules, the specific surface area of the BET method is preferably 5 m 2 /g or more, and more preferably about 10 m 2 /g or more, more preferably 20 m 2 /g or more. The compounding amount of the above-mentioned titanium oxide and the metal compound-forming raw material powder may be appropriately set, for example, to produce a perovskite-type structural oxidation represented by the general formula AB〇3. The powder is mixed with at least one metal element (A) selected from the group consisting of ruthenium, saw, calcium, and magnesium, and is represented by an atomic ratio of Ti atoms of the titanium oxide to 9·9 to 2. The range of 0 is appropriate, with 0. 95 to the range is particularly good, to 1. 000 to 1. The range of 035 is better. When the amount of the composite oxide powder which is difficult to obtain the desired composition is less than 〇·9, it is not preferable because the residual component of the composite oxide powder remains in the composite oxide because it easily deteriorates the properties such as dielectric properties. Further, the production of polybarium titanate and the combination of a solid phase oxyacid carbonate and carbonic acid are also suitable for the above. When, to . Both. Complex and lead B) 05 subratio, the remaining piezoelectric body -14- 200927659 is B aTi2 〇5, B aTi 4 Ο 9, B aTi 5 〇11, B a2Ti9 〇2 ο, B a4Ti 1 3 〇3 ο , : Ba6Ti1704G, etc. The barium titanate having a composition ratio of Ti/Ba having an atomic ratio of 2 or more is mixed with each other so that the atomic ratio X is (XxO. 95) to (Χχΐ. 05) The range is appropriate. In this mixing, a chromium compound can be added to produce a titanate chromate in response to the desired properties of the ceramic composition. In addition, as necessary, a rare earth element such as yttrium, lanthanum, cerium, lanthanum, cerium, lanthanum, bait, mirror, or the like, or boron, aluminum, lanthanum, manganese, iron, nickel, copper, or zinc may be appropriately added as an additive. , 铌, 钇, tungsten, 铋 and other elements. These additives may be oxides, hydroxides, carbonates or other compounds. The amount of addition can be appropriately set depending on the purpose. The mixed system uniformly mixes the titanium oxide and the metal compound to a certain extent, and the degree of mixing can be appropriately adjusted. As the mixing method, any of dry mixing and wet mixing may be used. For example, a fixed type mixer such as a spiral type mixer, a ribbon type mixer, or a fluidized type mixer, a cylindrical type e mixer, or a double type may be used. A rotary mixer such as a sub-cylinder mixer. In addition, before the mixing, a pulverizer such as a compression pulverizer, an impact compression pulverization type, a shear pulverization type, or a friction pulverization type may be used, and the titanium oxide and the metal compound may be separately pulverized before mixing, or may be simultaneously mixed at the time of pulverization. . The finer the raw material powder, the more easily the obtained composite oxide powder becomes fine particles, so that the raw material powder is preferably pulverized, and as the pulverizer, a wet pulverizer such as a ball mill, a bead mill or a colloid mill can be suitably used. In the mixed state, a wet pulverizer or the like is used, and in a wet state or a suspended state (paste state), it may be separately dried, pulverized, if necessary. -15- 200927659 The raw material powder thus obtained is required to be, for example, a solid phase synthesis reaction using a fluidized layer calcination or a gas flow type calcination method, which will be described later, because it forms an appropriate particle size, and is suitably rotatably granulated and fluidized. Granulation is carried out by a usual method such as granulation, spray granulation, agitation granulation, pulverization granulation, compression granulation, extrusion granulation, droplet solidification granulation, and the like. When a wet pulverizer or the like is used in a suspended state (paste state), it is preferable to carry out dry granulation by spray drying using a coating drier or the like. By granulation by spray drying, not only the raw material powder is scattered or the gas contact is uneven, but the particle size of the granulated powder is relatively uniform, and a uniform solid phase synthesis can be expected. The average particle size of the granulated powder can be arbitrarily adjusted in consideration of the flowable size or the degree of scattering, and can be, for example, 1 to 100 () 0 / ^ 111 degree, if it is 5 to 3000 / / 111 degree 'because of scattering Less, so suitable, if it is 10 to ΙΟΟΟμιη, especially if it is 20 to 500 00 # m. The granulated powder system may be any shape such as a spherical shape, a slightly spherical shape, a plate shape, a cubic shape, a rectangular parallelepiped shape, a rod shape, or a hollow shape having a space inside the powder, but it is preferably a shape that is easy to flow. For example, a spherical shape, a slightly spherical shape, a hollow shape, or the like is particularly preferable. Further, when pulverizing, mixing, or granulating, an organic compound such as an interface active agent, a resin, or a dispersing agent may be added to the raw material powder or the like as needed. In the case of granulation, when the resin is added, when the resin is added, in addition to the particle size of the granulated powder, the resin is decomposed during calcination, and the resulting void becomes porous and self-made. It is suitable to release a gas (for example, carbon dioxide gas) generated inside the granular powder. The materials to be used are not particularly limited, and the necessary amounts are used in accordance with the purpose. For example, a water-based acrylic resin, an aqueous melamine resin, an aqueous amine-16-200927659 ethyl urethane or the like can be used as the resin, and it is preferably added in an amount of from 1 to 20% by weight based on the raw material powder. Next, the raw material powder or the granulated powder (hereinafter referred to as the raw material powder and the granulated powder, referred to as raw material powder) obtained by granulating the raw material powder is placed in a calcining apparatus. The calcining apparatus to be used may be a calcining furnace used in a usual solid phase synthesis method or the like, or in addition to the field of inorganic chemistry, in particular, a heating furnace used in the field of ceramics may be suitable for use in a calcined vacuum calcining furnace which is less than atmospheric pressure, and reduces φ A calcining furnace or a fluidized bed calcining furnace in which a raw material powder or the like is flowed to be calcined, or a gas-flowing calcining furnace. The calcination temperature and the calcination holding time can be appropriately set in accordance with the composite oxide powder, and for example, it can be in the range of 500 to 1 100 ° C, and the calcination time can be maintained, for example, at 0. 5 to 10 hours. Further, after the completion of the calcination, it is cooled to the take-out temperature, but the cooling rate can be appropriately set, and the cooling can be gradually performed, and the cooling can be rapidly performed. The addition of the raw material powder is equal to the calcining apparatus, and when the temperature is raised from room temperature until the desired calcination temperature is reached, carbon dioxide gas and water are generated from the temperature range in the middle, as the Q titanium oxide and the metal compound react or the organic compound decomposes. Vapor, etc. When the carbon dioxide gas or the like is exhausted outside the calcining device, a composite oxide powder having high crystallinity can be obtained, which is suitable. Specifically, it is preferred to use a vacuum calcining furnace or a vacuum calcining furnace to calcine the raw material powder at a pressure of less than atmospheric pressure, preferably at an ambient pressure of less than lx10 PaPa, and at an ambient pressure of from 1 to 1×10 3 Pa. better. Further, in order to exhaust carbon dioxide gas or the like to the calcining apparatus, a gas flow type calcining furnace which is calcined under a flowing gas, for example, a calcining furnace such as a rotary electric furnace or a fixed bed electric furnace, may be used. The gas system to be circulated may be the same as the gas used in the fluidized bed calciner described later in -17-200927659. As another method, it is particularly preferable to use a fluidized bed calciner to calcine the raw material powder under a flow. The flow state is preferably a flow state in which a uniform flow layer (complete flow layer) is formed, and on the other hand, a state in which a thick flow layer of bubbles occurs in the fluid layer, or a fixed layer may be formed as a part of the raw material powder. The rest is in a flowing state. The flow state can be adjusted by the particle size of the raw material powder or the flow rate (flow rate) of the ventilation gas. When the gas is ventilated from at least a part of the temperature range from the occurrence of the carbon dioxide gas or the like to the end temperature range, it is preferable to carry out the entire period, because the raw material powder is equal to the flow, and the generated carbon dioxide gas or the like can be efficiently used. It is suitable for exhausting outside the calcining unit. Further, if necessary, the gas may be aerated from the start of the temperature rise, or the gas may be aerated after the completion of the calcination, or the gas may be vented between the obtained composite oxide powders. The start temperature of the carbon dioxide gas or the like varies depending on the type, composition, or addition of the metal compound to be used. However, when the raw material powder or the like is thermally analyzed, the onset temperature and the end temperature of the carbon dioxide gas or the like can be grasped. For example, it is considered that the starting temperature of the carbon dioxide gas of the raw material powder of the mixed titanium oxide and cerium carbonate is about 500 °C. On the other hand, since it is considered that the end temperature is about 850 °C, it is preferable to perform gas aeration between about 50,000 and 850 °C. As the gas for aeration, a gas used in a normal fluidized bed calciner can be used. However, when carbon dioxide gas is contained, it is not suitable because it affects the crystallinity of the composite oxide powder. - 200927659 Body or gas containing no carbon dioxide gas is suitable. Therefore, the use of carbon dioxide gas content is 0 to 0. 5 vol% of gas is suitable, with a carbon dioxide gas content of 〇 to 0. 1% by volume is particularly good, with a carbon dioxide gas content of 0 to 0. 05% of the volume is better. As such a gas, for example, nitrogen, argon, helium, air, oxygen, synthetic air, dry air, compressed air or the like can be used, and a gas selected from the above or a mixed gas of two or more kinds can be used. Although air, synthetic air, dry air, and compressed air contain a small amount of carbon dioxide gas of about 0 400 ppm, it is confirmed that the amount is not affected. Further, when air, synthetic air, dry air, or compressed air is used, since the raw material powder or the like is hardly reduced during firing, a homogeneous composite oxide powder is easily obtained, which is preferable. The ventilated gas is preferably heated before it is introduced into the calcining apparatus because it can prevent the rapid temperature of the calcining apparatus from decreasing. Further, although at least a part of the generated carbon dioxide gas or the like may be exhausted from the calcining apparatus by the ventilating gas, on the other hand, the ventilated gas may be recycled, and the carbon dioxide φ gas content in the circulating gas is at this time. The foregoing range is suitable. According to the foregoing method, a composite oxide powder having fine particles and high crystallinity can be produced, specifically, bismuth ruthenate, barium titanate, lead titanate, lead titanate chromate, calcium-modified barium titanate, and rare earth elements. A compound having a perovskite structure such as barium titanate or the like, barium titanate having a composition ratio of Ti/Ba having an atomic ratio of 2 or more. The particle size of the composite oxide powder is 0. 01 to 0. 3 / / m range is appropriate, with 0. 015 to 0. 2/zm range is particularly suitable, with 0. 01 to 0. 15#m range is better, to 〇. 〇6 to 0. The 15/zm range is best. The particle diameter (d) of the composite oxide powder is assumed to be a composite oxygen -19-200927659 compound powder, and is obtained by the following formula 2 using a specific surface area a (m2/g) of the BET method. Formula 2...d= ( 6/ /〇 ) /a However, the p-specific gravity and the barium titanate powder are P = 5 · 90. Further, the crystallinity of the obtained composite oxide powder is measured by X-ray diffraction, and is evaluated by the peak height or the full width at half maximum of the diffraction peak of a certain crystal face, but more precisely based on X-ray data. Judging by Rietveld 0 method. In particular, when the barium titanate powder is used, the ratio of the c-axis to the a-axis (c/a-axis ratio) of the crystal lattice is determined, and the larger the c/a-axis ratio is, the higher the crystallinity of the tetragonal barium titanate is. Specifically, according to the method of the present invention, the c/a axis ratio range is 1. 0075 to 1. 010, to 1. 0080 to 1. 010 is appropriate. A composite oxide powder having low crystallinity, especially less than 1. Although the barium titanate powder of 006 is used as an electronic component, since the dielectric constant is insufficient, the c/a ratio is increased to require further heat treatment, resulting in grain growth. The theoretical c/a ratio of the tetragonal barium titanate is from a=3. 994,c = 4. 038値 calculated e/a= 1. 01 1, in addition, the c/a ratio of cubic titanate is 1. 000 〇 In addition, when the ceramic composition is prepared, an additive may be mixed with the composite oxide powder as needed. As an additive, depending on the characteristics required for the ceramic composition, rare earth elements such as lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, bait, and mirror, or boron, aluminum, lanthanum, manganese, iron, nickel, and copper may be suitably used. , elements such as zinc, antimony, bismuth, tungsten, and antimony. Further, as the additive for controlling the growth of the particles or the electrical properties of the ceramic composition, for example, in addition to boron or cerium, an alkali metal such as lithium, sodium, potassium or the like, iron, manganese, cobalt, nickel-20 may be mentioned. - 200927659, a transition metal such as ruthenium, and a compound of an element such as ruthenium or aluminum. Such an additive may be added at the stage of pulverizing the composite oxide powder or may be mixed after pulverization. Alternatively, it may be added at any stage of the calcination stage of the composite oxide powder. The amount of addition can be appropriately set. The mixer system can be used in the field of general inorganic chemistry, especially in the field of ceramics, or in the field of electronic materials. Further, an organic compound such as a surfactant, a resin or a dispersant may be added during pulverization or mixing. With this 0 operation, the ceramic composition material can be prepared. The ceramic composition raw material containing at least the composite oxide powder is calcined as a ceramic composition, and is suitably used as a material such as a ceramic electronic component. The ceramic electronic component is provided with a ceramic composition and an electrode which is disposed to face the ceramic composition. Further, as a ceramic electronic component, a laminated ceramic electronic component includes an electrode formed of a plurality of layers including a ceramic composition and a layer of the ceramic composition. A specific laminated ceramic electronic component is a laminated ceramic capacitor having a laminate of a plurality of laminated ceramic composition layers (intermediate dielectric layers) and internal electrodes formed along a specific interface between the ceramic composition layers By. The inside of the laminate is alternately disposed as the first internal electrode and the second internal electrode of the internal electrode, and the respective end edges are exposed to the end faces of the laminate, and the first internal electrodes are electrically connected to the first external electrodes, respectively. The internal electrode is similarly electrically connected to the second external electrode. As the electrode ', a metal such as platinum, palladium, nickel, silver, copper or the like or an alloy thereof can be used. The thickness of each layer of the ceramic composition of the laminated ceramic electronic component is as thin as possible, preferably 1/zm or less. Ceramic compositions or ceramic electronic parts can be manufactured using conventional methods -21 - 200927659. The ceramic composition is mixed with a ceramic composition raw material and an adhesive containing at least a composite oxide powder, and then subjected to press molding to form a green pellet having a predetermined shape, or a method such as a sheet molding method or a printing method. A green sheet having a predetermined thickness is formed on the substrate, followed by calcination. For the ceramic electronic component, for example, a method of performing calcination on the both sides of the green belt, printing or coating a metal paste for an electrode, or the like, or forming the green belt described above, and then printing or coating the inside thereof The electric 0-pole is a metal paste or the like, and the method of firing is repeated after repeated times. The calcination conditions can be appropriately set in accordance with the degree of calcination of the raw material of the ceramic composition, but the calcination temperature is preferably, for example, about 1 000 to 1,500 ° C, and particularly preferably 1 100 to 1 300 ° C. The calcination time can also be appropriately set in accordance with the composition of the ceramic composition raw material, but is 0. 5 to 10 hours is appropriate. The environment during calcination may be an oxygen-containing gas such as oxygen, air, synthetic air, dry air, compressed air, etc., but the electrode metal is not oxidized, and a non-oxidizing gas is suitable. For example, φ such as nitrogen, argon or helium may be used, and a reducing gas such as hydrogen, carbon monoxide or ammonia may be suitably used. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. The invention is not limited to such embodiments. Example 1 -22- 200927659 Weighing titanium oxide obtained by neutralizing titanium tetrachloride at a temperature of 130 ° C (the specific surface area measured by the above method is 190 m 2 /g, the average major axis diameter is 80 nm, axis The ratio of the spindle-shaped titanium dioxide of 3, the purity of Ti〇2 is 99. 98% by weight, the rutile ratio is 100%, the crystal diameter of rutile crystal is 9nm, and the 50% calculated diameter in water is 0. 077 ym) and cerium carbonate (specific surface area: 30 m2/g), the atomic ratio of cerium/titanium was 1,000, and the mixture was wet-pulverized and mixed by a ball mill, and then the mixed paste was evaporated and dried, and pulverized into a raw material powder. Next, the obtained raw material powder is placed at a temperature of 50 cc to a thickness of 20 mm, and placed in a fixed bed electric furnace of a controllable environment under ambient pressure at a reduced pressure (200 to 500 Pa) from room temperature. The temperature was raised to 850 ° C for 5 hours, and calcination was carried out to obtain barium titanate powder (sample A). (Example 2) In the same manner as in Example 1 except that the calcination temperature was changed to 900 °C, the barium titanate powder of the present invention (sample B) was obtained. (Example 3) In the same manner as in Example 1 except that the calcination temperature was changed to 950 ° C, the barium titanate powder of the present invention (sample C) was obtained. -23- 200927659 Example 4 The mixed paste of titanium oxide and cerium carbonate obtained in the above Example 1 was dried by a coating drier and granulated. The granulated powder has an average particle diameter of 50 m. Then, the granulated powder was added to the vertical small-sized fluidized bed calciner, and the dry air (containing carbon dioxide gas of about 400 ppm) as a flowing gas was taken at a linear velocity of the gas. The barium titanate powder of the present invention (sample D) was obtained by aeration at 73 cm/sec, and the above-mentioned granulated powder was flowed, and the temperature was raised to 905 rpm from room temperature to maintain 〇·5 hours. Further, the dry g g 2 aeration system is subjected to aeration by the dry air from the start of the temperature rise to the completion of the sample extraction, and the granulated powder is caused to flow, and the generated carbon dioxide gas is discharged outside the system. [Example 5] In the above-mentioned Example 4, G was applied in the same manner as in Example 4 except that the holding time was 1 hour, and the barium titanate powder of the present invention (sample E) was obtained. Embodiment 6 In the above Embodiment 4, except that the holding time is set to 1. In the same manner as in Example 4, the barium titanate powder of the present invention (sample F) was obtained in the same manner as in Example 4, Comparative Example 1 - 24 - 200927659 In place of the titanium oxide used in the above Example 1, the specific surface area was 1 1 5m2/g (gold red petrochemical rate i 00%, rutile crystal crystal diameter is 13nm 'heating the titanium oxide used in Example 1 at 175 ° C) 'under reduced pressure (200 to 500Pa) environment The barium titanate powder (sample G) was obtained in the same manner as in Example 1 except that the temperature was raised from room temperature to 8 ° C and kept for 5 hours. The barium titanate powder of the samples A to G thus obtained was measured for a specific surface area a (m2/g) by a BET method to obtain an average particle diameter d (ym). Further, the data obtained by the X-ray diffraction method was analyzed by Rietveld method to determine the lattice constants a and c of tetragonal barium titanate, and the crystallinity evaluation (orthogonality) c/a axial ratio was calculated. As is apparent from Table 1 of the results, the barium titanate powder of the present invention has a small particle diameter and a high c/a axial ratio, and has excellent tetragonality. Calcination conditions Characteristics of barium titanate obtained Particle size [# m] c/a axial ratio Example 1 Fixed bed (under reduced pressure) 0. 089 1. 0079 Example 2 Fixed bed (under reduced pressure) 0. 096 1. 0086 Example 3 Fixed bed (under reduced pressure) 0. 116 1. 0094 Example 4 Flow layer (dry air ventilation) 0. 101 1. 0089 __Party Example 5 Mobile layer (dry air ventilation) 0. 120 1. 0095 Example 6 Flow layer (dry air ventilation) 0. 079 1. 0079 Comparative Example 1 Fixed bed (under reduced pressure) 0. 077 1. 0074 ❹ [Table 1] The results of the experiments described in the first to third examples were carried out. It was confirmed that the quality of the barium titanate powder obtained in the -25-200927659 was neat. Further, it was confirmed that in the present invention, in addition to bismuth citrate, barium titanate 'titanium titanate, zirconium citrate, lead zirconate titanate, calcium-modified barium titanate, rare earth element-modified titanic acid can be similarly produced. A compound having a perovskite structure, such as barium titanate having a composition ratio of Ti/B a having an atomic ratio of 2 or more. Further, the obtained composite oxide powder was fired to obtain a ceramic composition, and when it was used as a ceramic electronic component, the superiority of the present invention was confirmed. 〇 Industrial Applicability The composite oxide powder-based fine particles of the present invention have high crystallinity, and by firing the ceramic composition, it is possible to easily and easily produce a ceramic composition having excellent properties such as dielectric properties and piezoelectric properties. When the ceramic composition is used for ceramic electronic parts, in particular, ceramic electronic parts are laminated, it is expected to be small, lightweight, high-performance, and multi-functional. Φ [Simplified description of the drawing] Fig. 1 is an electron micrograph showing the particle structure of the titanium oxide used in Example 1. [Fig. 2] An X-ray diffraction pattern of the titanium oxide used in Example 1. -26-