200844071 九、發明說明 【發明所屬之技術領域】 本發明係關於含有選自鈦、锆之至少一種的金屬元素 、與選自由鋇、緦、鈣、鎂及鉛中之至少一種的金屬元素 之複合氧化物粉末及其製造方法。再者，本發明亦關於用 前述複合氧化物粉末燒結之陶瓷組成物、使用其之陶瓷電 子零件、積層陶瓷電子零件。 【先前技術】 鈦酸鋇、鈦酸緦、鈦酸鉛、銷酸鉛、鈦酸鉻酸鉛等之 複合氧化物粉末可使用作爲燒結物之原料，將複合氧化物 粉末與黏結劑混合後，用薄片（sheet)成形法或印刷法等方 法在基板上形成粉末層，然後進行燒結作成燒結物（以下 亦稱爲陶瓷組成物）。由於該陶瓷組成物有優異的介電性 、壓電性乃至半導性，故可用作爲電容器、電波濾波器、 點火元件、熱敏電阻等電機電子工業用材料。 陶瓷組成物以作成爲陶瓷電子零件之形態而組裝使用 於各種電機電子器材中。隨著近年來之電機電子器材之小 型化、輕量化、高性能化、多功能化，對此等陶瓷電子零 件之性能要求亦日益嚴苛。以電腦等之積體電路中所用之 積層陶瓷電容器爲例，此電容器係爲前述陶瓷組成物之薄 層與內部電極交替多層積層，於電性上並聯之構造，故隨 著積層陶瓷電容器之小型化、高容量化等之要求，對陶瓷 組成物之薄層化、高介電率化有更高的期待。因此，陶瓷 -5- 200844071 組成物的原材料之複合氧化物粉末之微粒子化 之性能要求，乃至於均質化、高分散化等之品 益明顯化。又，積層陶瓷電容器之內部電極向 、鈀、銀等之貴金屬材料，人們一直設法轉換 之廉價的卑金屬材料，因此，對可在更低溫燒 使於低氧分壓周遭氣下燒結也不會半導體化， 性之複合氧化物粉末備受期盼。 含有選自鈦、鉻之至少一種金屬元素與選 耗、鎂、給中之至少一種的金屬元素的複合氧 製造，方法有：將各元素之氧化物及/或碳酸 用電氣爐或旋轉窯進行燒成之所謂的固相合成 中合成各元素之草酸鹽後進行燒成之所謂的草 水系中合成各元素之檸檬酸鹽後進行燒成之所 鹽法；將各元素之水溶液與鹼水溶液混合，進 後過濾、洗淨、乾燥之所謂的水熱合成法等。 ，都對複合氧化物粉末之微粒子化、高結晶性 進行改良硏究。硏究之著眼點爲複合氧化物粉 化所伴隨產生的結晶性降低之抑制。例如’於 中，將藉由加熱分解生成氧化鋇之鋇化合物、 繞射法求出之紅金石化率爲30%以下且用BET 表面積爲5 m2/g以上之純度99.8重量％以上之 合，在全壓力爲lxl 03 Pa以下之壓力下進行燒 微粒且正方晶性高的鈦酸鋇粉末（參照專利文膚 )。又，將比表面積爲10 m2/g以上之金屬氧化 '高結晶化 質要求也曰 來係使用鈾 爲銅、鎳等 結，並且即 且有耐還原 自鎖、總、 化物粉末之 鹽混合，使 法；於水系 酸鹽法；於 謂的檸檬酸 行水熱處理 於各方法中 化等之方法 末之微粒子 固相合成法 與以X光 法求出之比 二氧化鈦混 成，可得到 欠1中之記載 物粉末與金 -6- 200844071 屬碳酸鹽粉末混合，使得到之混合粉末於2x1 03 pa以下之 氧分壓下進行燒成，可得到粒徑小至〇·〇3〜0.2 μπι、作爲 正方晶性（tetragonality)的指標之結晶格子的c軸與a軸 之比（c/a軸比）爲高達1.0033以上、顯不充分強介電性、具 有鈣太礦（perovskite)型構造之複合氧化物（參照專利文獻2 中之記載）。 [專利文獻1]日本專利特開2002-25 5 5 52 [專利文獻2]日本專利特開200 1 -3 1 6 1 1 4 【發明內容】 (發明所欲解決之課題） 用前述專利文獻1、2中所記載的方法可得到結晶性高 的複合氧化物粉末。然而，由於係使原料粉末在減壓下或 真空下進行燒成，故於燒成過程中或各製造批次間要保持 一定的減壓壓力會有困難，因爲壓力之變動會在複合氧化 物粉末之性能、品質上造成參差，是其問題。例如，吾人 可推想其會有複合氧化物粉末之粒徑與結晶性參差不一， 乃至發生晶格缺陷之缺點。又，使用之金屬氧化物的金紅 石化率、比表面積、純度等有其限制，可使用者受到限定 ’須要可耐減壓或真空下的壓力之昂貴的裝置，由該裝置 欲大型化有困難而須爲小規模製造之方式等，故也有操作 成本高之問題。 (用以解決問題之手段） 200844071 本發明者等針對粒徑小且結晶性良好的鈦酸鋇粉末之 製造方法刻意地進行硏究。其結果發現就二氧化鈦與碳酸 鋇之化合物在大氣壓下進行燒成所得者和在減壓下或真空 下進行燒成所得者加以比較，以相同程度的粒徑爲基準， 則在大氣壓下燒成者之結晶性較低，其原因認係因燒成時 所產生的二氧化碳導致某些不良影響所致。 二氧化鈦與碳酸鋇之反應據認爲係產生下述（1)〜（3)的 反應，若將二氧化鈦與碳酸鋇之混合物進行熱解析（TG)， 可繪出圖1所示般的曲線，自50(TC左右開始二氧化鈦與碳 酸鋇發生反應而產生二氧化碳使得重量減少。據推測，於 大氣壓下進行燒成時，由於於（1)、（2)之反應中產生之二 氧化碳之大部份係留在電氣爐或旋轉窯等燒成裝置中，故 殘留之二氧化碳對鈦酸鋇粉末造成不良影響。具體而言’ 於（2)之反應所生成的反應生成物（Ba2Ti04)由於爲強鹼性 ，故容易吸附弱酸性氣體之二氧化碳，而且，若發生（2) 之逆反應會使（3)之反應難以促進而使用以生長結晶的 BaTi03的供給不足，或亦可能生成Ba2Ti05。此想法吾人 認爲可由二氧化碳流入燒成裝置中會使鈦酸鋇粉末的結晶 性降低而確認。200844071 IX. OBJECT OF THE INVENTION [Technical Field] The present invention relates to a compound containing a metal element selected from at least one of titanium and zirconium and a metal element selected from at least one of cerium, lanthanum, calcium, magnesium and lead. Oxide powder and a method of producing the same. Further, the present invention relates to a ceramic composition sintered by the above composite oxide powder, a ceramic electronic component using the same, and a laminated ceramic electronic component. [Prior Art] A composite oxide powder such as barium titanate, barium titanate, lead titanate, lead pinchate or lead titanate chromate can be used as a raw material of a sintered body, and after the composite oxide powder and the binder are mixed, A powder layer is formed on the substrate by a sheet forming method or a printing method, and then sintered to form a sintered body (hereinafter also referred to as a ceramic composition). Since the ceramic composition has excellent dielectric properties, piezoelectricity, and even semiconductivity, it can be used as a material for electrical and electronic industries such as capacitors, electric wave filters, ignition elements, and thermistors. The ceramic composition is assembled and used in various types of electrical and electronic equipment in the form of ceramic electronic parts. With the miniaturization, weight reduction, high performance, and multi-functionality of electric and electronic equipment in recent years, the performance requirements of these ceramic electronic parts are becoming increasingly stringent. In the case of a multilayer ceramic capacitor used in an integrated circuit such as a computer, the capacitor is formed by alternately laminating a thin layer and an internal electrode of the ceramic composition, and is electrically connected in parallel, so that the multilayer ceramic capacitor is small. The requirements for chemical conversion and high capacity have higher expectations for thinning and high dielectric constant of ceramic compositions. Therefore, the performance requirements of the fine particle formation of the composite oxide powder of the raw material of the composition of the ceramic -5-200844071, and the benefits of homogenization and high dispersion are conspicuous. Moreover, the internal electrode of the multilayer ceramic capacitor, the precious metal material such as palladium or silver, has been tried to convert the cheap base metal material, and therefore, it is not possible to burn at a lower temperature and burn under a low oxygen partial pressure. Semiconductorized, complex composite oxide powders are highly anticipated. The composite oxygen containing a metal element selected from the group consisting of at least one metal element of titanium and chromium and at least one of a selective consumption, a magnesium, and a donor is carried out by using an electric furnace or a rotary kiln for oxides and/or carbonic acid of each element. In the so-called solid phase synthesis in which the oxalate of each element is synthesized in the so-called solid phase synthesis, the salt method of synthesizing the citrate of each element in the so-called grass water system which is fired, and then calcining the mixture; and the aqueous solution of each element and the aqueous alkali solution The so-called hydrothermal synthesis method, such as mixing, filtration, washing, and drying. Both of them improve the fine particles and high crystallinity of the composite oxide powder. The focus of research is on the inhibition of the decrease in crystallinity associated with the oxidation of composite oxides. For example, in the middle, a ruthenium compound which generates ruthenium oxide by heat decomposition, a red gold petrochemical ratio obtained by a diffraction method of 30% or less, and a purity of 99.8 wt% or more with a BET surface area of 5 m 2 /g or more, The barium titanate powder which is sintered and has a high tetragonality is subjected to a pressure of a total pressure of 1×10 Pa or less (see Patent Skin). Further, the metal having a specific surface area of 10 m 2 /g or more is oxidized. The high crystallization quality is also required to use uranium as a knot such as copper or nickel, and it is also resistant to reduction self-locking and salt mixing of the total powder. The method of the aqueous acid salt method; the microparticle solid phase synthesis method in which the citric acid is hydrothermally treated at the end of each method, and the titanium dioxide solidified by the X-ray method, The powder of the sample is mixed with the carbonate powder of the gold-6-200844071, so that the mixed powder is fired under an oxygen partial pressure of 2x1 03 Pa or less, and the particle size is as small as 〇·〇3 to 0.2 μπι, as a square The ratio of the c-axis to the a-axis (c/a-axis ratio) of the crystal lattice of the index of tetragonality is as high as 1.0033 or more, insufficiently ferroelectric, and composite oxidation having a perovskite structure. (refer to the description in Patent Document 2). [Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-25 5 5 52 [Patent Document 2] Japanese Patent Laid-Open No. 2001-1-3 1 6 1 1 4 [Problems to be Solved by the Invention] In the method described in (2), a composite oxide powder having high crystallinity can be obtained. However, since the raw material powder is fired under reduced pressure or under vacuum, it is difficult to maintain a certain pressure reduction pressure during the firing process or between the various production batches because the pressure fluctuation occurs in the composite oxide. The performance and quality of the powder cause a difference, which is a problem. For example, we can assume that the particle size and crystallinity of the composite oxide powder are different, and even the disadvantage of lattice defects occurs. Moreover, the metal red oxide ratio, specific surface area, purity, and the like of the metal oxide used are limited, and the user is limited to an expensive device that is required to withstand pressure under reduced pressure or under vacuum, and the device is intended to be large. Difficult to be a small-scale manufacturing method, etc., there are also problems with high operating costs. (Means for Solving the Problem) 200844071 The inventors of the present invention deliberately conducted a study on a method for producing a barium titanate powder having a small particle size and good crystallinity. As a result, it has been found that those obtained by firing titanium dioxide and cesium carbonate at atmospheric pressure are compared with those obtained by firing under reduced pressure or under vacuum, and are fired at atmospheric pressure based on the same particle diameter. The crystallinity is low, and the reason is due to some adverse effects caused by carbon dioxide generated during firing. The reaction between titanium dioxide and cesium carbonate is believed to produce the following reactions (1) to (3). If the mixture of titanium dioxide and cesium carbonate is subjected to thermal analysis (TG), the curve shown in Fig. 1 can be drawn. 50 (about TC starts to react with titanium dioxide and cesium carbonate to produce carbon dioxide to reduce the weight. It is presumed that when firing at atmospheric pressure, most of the carbon dioxide generated in the reaction of (1), (2) is retained. In the firing device such as an electric furnace or a rotary kiln, the residual carbon dioxide adversely affects the barium titanate powder. Specifically, the reaction product (Ba2Ti04) produced by the reaction of (2) is strongly alkaline, so It is easy to adsorb carbon dioxide of a weak acid gas, and if the reverse reaction of (2) occurs, the reaction of (3) is difficult to promote, and the supply of BaTi03 for crystal growth is insufficient, or Ba2Ti05 may be formed. The inflow of the calcination apparatus causes the crystallinity of the barium titanate powder to be lowered and confirmed.
BaC03 + Ti〇2">BaTi03 + Co2 个 ……（1) BaC03 + BaTi〇3^Ba2Ti〇4 + C〇2 I ……(2) Ba2Ti〇4 + Ti〇2 + 2BaTi〇3 ............( 3 ) 200844071 本發明者等基於上述之見解，更進一步進行硏究之結 果’發現：即使於大氣壓程度的壓力下，爲使在燒成步驟 中所產生之二氧化碳的不良影響減低，可藉由邊以氣體流 通而使原料流動之下進行燒成，可提高鈦酸鋇粉末的結晶 性，與在前述專利文獻1、2中所記載的在減壓下或真空下 進行燒成者相比，可得到相同程度的結晶性，於減壓下或 真空下進行並非必要，由於可於大氣壓程度或因氣體通氣 而較大氣壓稍高的壓力下進行，故裝置等的限制少，且可 用均一條件進行燒成，得到之複合氧化物粉末的品質參差 亦小，而且，由於可如此般使用通常的燒成裝置，故可廉 價地製造等，本發明於焉得以完成。 再者，此方法並非限定於鈦酸鋇之製造，亦可適用於 含有鈦或鍩之金屬氧化物與選自由鋇、緦、鈣、鎂及鉛所 構成的群中之至少一種之金屬碳酸鹽的原料粉末之燒成方 法中於燒成時會產生二氧化碳之反應中，可得到良好的結 果。本發明於焉得以完成。 亦即，本發明爲： (1) 一種複合氧化物粉末之製造方法，係將至少有鈦 及/或锆之金屬氧化物與選自由鋇、緦、鈣、鎂及鉛所構 成的群中之至少一種的金屬碳酸鹽混合所成之原料粉末燒 成以製造複合氧化物粉末的方法；其特徵爲於因原料粉末 之燒成而產生二氧化碳氣體之間的至少一部份期間，邊使 氣體流動以使原料粉末流動而進行燒成。 (2) 如（1)項之複合氧化物粉末之製造方法，其係使用 200844071 以原料粉末造粒之造粒粉體。 (3) 如（2)項之複合氧化物粉末之製造方法，其係將原 料粉末之漿液噴霧乾燥而造粒。 (4) 如（1)項之複合氧化物粉末之製造方法，其係使用 將原料粉末粉碎後進行造粒之造粒粉體。 (5) 如（2)項之複合氧化物粉末之製造方法，其係用大 小爲10〜1000 μιη之造粒粉體。 (6) 如（1)項之複合氧化物粉末之製造方法，其係使用 至少有鈦的氧化物與鋇的碳酸鹽所混合成之原料粉末。 (7) 如（6)項之複合氧化物粉末之製造方法，其係使用 比表面積爲20 m2/g以上之鈦的氧化物。 (8 )如（1)項之複合氧化物粉末之製造方法，其係於因 原料粉末之燒成而產生二氧化碳氣體之間’邊使氣體流動 以使原料粉末流動而進行燒成。 (9) 如（1)項之複合氧化物粉末之製造方法’其使用藉 由X光繞射法求出的金紅石化比例高於90°/。且爲100%以下 ，而且比表面積爲30 m2/g以上之鈦的氧化物。 (10) —種複合氧化物粉末，其特徵爲’係以如（1)至 (9)項中任一項之方法所製造，粒徑爲〇. 01〜0· 3 μιη的範圍 〇 (11) 一種鈦酸鋇粉末’其特徵爲’係以如（1)至（9)項 中任一項之方法所製造’粒徑爲0 ·01〜0 ·3 μ m的範圍。 (1 2)如（1 1)項之駄酸鋇粉末，該欽酸鋇之c /a軸比爲 1.007〜1.010 ° -10- 200844071 (13) —種陶瓷組成物，其特徵爲係由至少以（10)項之 複合氧化物粉末或（1 1 )項之鈦酸鋇粉末燒結而成。 (14) 一種陶瓷電子零件，其特徵爲具備（13)項之陶瓷 組成物、與包夾著該陶瓷組成物並相向地配置的電極。 (15) —種積層陶瓷電子零件，其特徵爲具備含有（13) 項之陶瓷組成物的複數層、與形成於該陶瓷組成物之層間 的電極。 (發明之效果） 本發明爲製造鈦酸鋇等之複合氧化物粉末的方法，係 爲了使於燒成步驟中產生之二氧化碳不被原料粉末吸附， 於產生二氧化碳之間，邊使氣體流動以使原料粉末流動而 進行燒成的方法。藉由本發明之方法得到的複合氧化物粉 末即使爲微粒子，亦有高結晶性，可抑制因微粒子化所伴 隨產生之結晶性降低。而且，裝置、材料等之限制少，並 可於相同條件燒成，故同一製造批次得到之複合氧化物粉 末的品質參差甚小，且於各批次間亦小，可得到均質之成 品。 具體而言，可容易地得到粒徑爲〇.〇1〜0.3 μιη的範圍 ，且有優異的結晶性的複合氧化物粉末，例如鈦酸鋇粉末 ，尤其可得到粒徑爲〇·〇1〜〇·3 μιη的範圍，且c/a軸比爲 1.0 0 7〜1.0 10的範圍之有優異的正方晶性之鈦酸鋇粉末。 又，由於前述之複合氧化物粉末爲微粒子，故可改善 低溫燒結性，可提高作成燒結物時之塡充率，並可改善介 -11 - 200844071 電性與壓電性等特性。又，由於有高結晶性、均質性，故 可改善耐還原性。因此，使用藉由本發明之方法燒結複合 氧化物粉末所成之陶瓷組成物，利用其優異的特性，可得 到滿足小型化、輕量化、高性能化、多功能化之陶瓷電子 零件，尤其是積層陶瓷電子零件。 【實施方式】 本發明爲複合氧化物粉末的製造方法，係將至少有鈦 及/或锆之金屬氧化物與選自由鋇、緦、鈣、鎂及鉛所構 成的群中之至少一種的金屬碳酸鹽混合所成之原料粉末或 者其所造粒之造粒粉體（以下，亦有將原料粉末與造粒粉 末通稱爲原料粉末之情形），於燒成裝置中進行燒成者； 於使原料粉末自室溫昇溫至既定溫度並保持既定時間之燒 成步驟時，於產生二氧化碳氣體之間的至少一部份期間（ 以全部時間爲佳），邊使氣體流動以使原料粉末流動而進 行燒成。藉由如此般進行燒成，使氣體通過原料粉末的附 近，可使二氧化碳的至少一部份有效地排出至燒成裝置外 。又，藉由使用以原料粉末造粒得到的造粒粉末，可改善 流動性’使其與通氣的氣體有良好的接觸，可有效地使產 生之二氧化碳排出。 本發明中所用的原料粉末爲將至少有鈦及/或鉻之金 屬氧化物與選自由鋇、緦、鈣、鎂及鉛所構成的群中之至 少一種的金屬碳酸鹽混合所成之混合粉末。金屬氧化物， 可無例外地使用通常之固相合成法中所使用者，具體而言 -12- 200844071 ，可使用鈦、鉻之氧化物、或包含選自鈦、鉻之各自的水 和氧化物、含水氧化物、氫氧化物中之至少一種。尤以二 氧化鈦、二氧化锆爲佳。使用微粒子之金屬氧化物，於複 合氧化物粉末之微粒子化有效，故爲較佳’例如’作爲微 粒子之指標以比表面積計，以20 m2/g的程度以上爲佳， 以30 m2/g的程度以上爲較佳，以50m2/g的程度以上爲更 佳，而以1 00-300 m2/g的程度又更佳，以1 50-3 00 m2/g的 程度爲特更佳。鈦氧化物之比表面積愈大，反應性愈好， 而若過大，則由於此種鈦氧化物不易製造，就此觀點考量 ，比表面積以1 60-25 0 m2/g爲更佳，以1 60-200 m2/g爲特 佳。比表面積可藉由BET法之氮吸附求出。又，於以鈦 氧化物作爲主劑（指佔50重量％以上之成分）的情況，以锆 作爲添加劑（指未滿5 0重量％之成分）時，可用鉻氧化物， 亦可用其以外之鉻化合物；相反地，於以鉻氧化物作爲主 劑的情況’可用鈦氧化物或其以外之鈦化合物作爲添加劑 。氧化物以外之化合物的形態並無特別限定，可使用氯化 物、硫酸鹽、硝酸鹽、碳酸鹽、醋酸鹽等。 本發明中所用之欽氧化物包含鈦的氧化物（二氧化鈦） 、或鈦的水和物、含水氧化物、氫氧化物，可使用選自其 等中之至少一種。又，鈦化合物通常可藉由X光繞射波 峰確認其爲金紅石型結晶、銳鈦礦型結晶、板鈦礦 (Brookite)型結晶，可用任何結晶形，亦可用二種以上的 結晶粒子之混合物或二種以上的結晶形之混晶物。本發明 中’較佳者爲前述3種結晶構造中之金紅石型結晶較多之 -13- 200844071 鈦氧化物’以藉由X光繞射法求出之鈦氧化物之金紅石 化率高於90%爲100%以下爲較佳，以95〜100%爲更佳，尤 以無法察知銳鈦礦型結晶、板欽礦型結晶之X光繞射波 峰的程度之金紅石化率1 0 0 %者爲更佳。所謂鈦氧化物之 金紅石化率’係指鈦氧化物中所含有之金紅石型結晶之比 例，藉由X光繞射（使用CuK α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，求出對前述 3種結晶形之金紅石型結晶的含有比例。基於上述者，本 發明中以藉由X光繞射法求出之金紅石化率高於90%爲 100%以下，且比表面積爲30 m2/g以上之鈦氧化物爲更佳 ，並以50 m2/g以上爲更佳，以1 00-3 00 m2/g又更佳，以 1 5 0-3 00 m2/g 爲特佳。 又，由金紅石型結晶之（11〇)面的X光繞射波峰之半 値寬度用協勒算式（式1)可求出金紅石型結晶之結晶格徑 。作爲金紅石型結晶之結晶格徑，就反應性的觀點考量以 較小爲佳，以1 0 nm以下爲更佳，以1〜1 〇 nm又更佳。 式 1: Dhkl = K* λ / β cos θ D Η K L :結晶格徑（A ) λ : X光之波長 /3 :繞射波峰之半値寬度 0 :卜拉格角（Bragg’s angle) K :常數（ = 〇·94) 另一方面，依據電子顯微鏡照相之鈦氧化物的一次粒 徑以1〜1 5 n m的程度之微結晶爲佳’該一次粒子集合而形 -14- 200844071 成二次粒子亦可。鈦氧化物之二次粒子的形狀可爲任何形 狀，可用例如粒狀、球狀、近似球狀、紡錘狀等者。於粒 狀、球狀、近似球狀的情況，若以粒徑之最大直徑（數平 均）表示，以1〇〜3 00 nm爲佳，以20〜150 nm爲更佳，以 3 0〜12 0爲特佳。又，所謂紡錘狀者係指與紡錘相似之形狀 ，爲近似於兩端縮小之圓柱形之形狀。因此，紡錘狀中包 含通常稱爲針狀、棒狀、柱狀、多角柱狀等者。以連結粒 子的兩端之長度作爲長軸徑，以柱部之最粗部份的長度作 爲短軸徑，以該長軸徑的數平均（平均長軸徑）與短軸徑的 數平均（平均短軸徑）之比作爲軸比，則軸比以愈大者爲佳 ，具體而言，以1 . 5以上爲佳。另一方面，鈦氧化物若成 爲微粒子，由於軸比會難以較大，故以1.5〜5的程度爲較 佳，以1.5〜4的程度爲更佳。鈦氧化物之平均長軸徑以 10〜300 nm爲佳，以20〜150 nm爲更佳，以30〜120 nm爲 特佳。鈦氧化物之二次粒子，有由數個至數百個凝集而形 成凝集粒子之情況。此種鈦氧化物之二次粒子的形狀、平 均長軸徑、平均短軸徑可用電子顯微鏡觀察、測定。 再者，例如，粒狀粒子再凝集而形成更大的多孔質凝 集粒子，紡錘狀粒子亦有形成近似於球形糖（（葡）c〇nfeito) 之凝集粒子。 有關鈦氧化物之凝集粒子，可藉由下述方法測定在水 中之粒徑（50%累積徑（中値徑）），於本發明中就固相合成 的反應性之觀點考量，以〇.〇6〜0·20 μπι的程度爲佳。 -15- 200844071 於水中之粒徑分布之測定方法 (1) 對鈦氧化物之漿液用氫氧化鈉水溶液調整pH爲 10.8後’以塗料搖混器（paint shaker)使其分散15分鐘。 (2) 於加入有換算爲p2〇5爲〇.3 mg之六偏磷酸鈉的水 3 0 0ml中，添加氫氧化鈉水溶液調整pH爲10.5，作成爲 測定用分散媒。 (3) 於1L之聚乙烯製容器中加入數滴的前述測定用分 散媒與以塗料搖混器製作的分散液（鈦氧化物漿液），進行 攪拌調製成懸浮液。 (4) 對前述懸浮液以超音波產生器（夏普製，UT-5 00) 進行1分鐘超音波照射，使試料分散。 (5 )用雷射繞射散亂式粒徑分布測定裝置（η 〇 RIB A製 ，L A - 9 1 0)測定得到的分散液中之試料的粒徑分布。 本發明中所用之鈦氧化物以Ti02純度爲99重量％以上 的局純度者爲佳’以99.5重量％以上爲較佳，以99.9重量％ 以上爲更佳。TiO2純度爲自1〇 〇(%)減除水分、強熱減量成 分（Ig-Loss)、氯元素、碳元素除外的雜質（例如，矽、鐵 、鋁、鈮、鈉等元素，其等之氧化物換算量）的合計量之 値。矽等之元素係藉由螢光X光法、ICP發光分光分析法 或原子吸光進行分析。 本發明中所用之鈦氧化物可用液相法、氣相法製造， 可選擇適當的條件製造所要的比表面積、金紅石化率等之 欽氧化物。液相法爲使硫酸欽、氧化硫酸欽、四氯化欽、 院氧基鈦（t i t a n a 1 k ο X i d e)等之欽化合物進行水解、中和的 -16- 200844071 方法，由於可容易得到比表面積高、金紅石型結晶之結晶 格徑小者，故爲較佳。作爲具體的液相法爲，使例如四氯 化鈦、氧化硫酸鈦等經中和或水解得到的含水氫氧化鈦， 在氫氧化鈉等之鹼金屬氫氧化物、銨化合物、碳酸銨化合 物、胺化合物等之鹼化合物水溶液中進行加熱處理之後， 過濾、洗淨、然後於鹽酸等之強酸水溶液中進行加熱處理 而製得。作爲前述鹼化合物，基於金紅石化率等之考量以 氫氧化鈉爲更佳，爲充分除去鈉以進行酸洗（acid leaching)等爲佳。再者，前述鹽酸處理若在三氯化鈦存在 下進行，可得到長軸徑比較大、結晶格徑小的微細的鈦氧 化物微粒子，故爲較佳的方法。將得到之生成物分級並乾 燥。乾燥溫度若過高，比表面積會降低，故乾燥溫度以 1 50 °C以下的溫度爲佳。作爲其他的方法，可用將四氯化 鈦中和的方法。於邊攪拌四氯化鈦下滴入中和劑，將四氯 化鈦中和。作爲中和劑可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。此方法中，於 用鹼金屬氫氧化物作爲中和劑的情況，爲充分除去鹼金屬 ，以進行酸洗爲佳。如此做法得到之生成物，與前述同樣 地進行分級並乾燥。乾燥溫度以1 5 (TC以下的溫度爲佳。 乾燥溫度若高於1 5 0 °C，由於中和生成物之比表面積易降 低故不佳。乾燥之下限溫度，只要爲可乾燥之溫度皆可。 另一方面，鈦氧化物之氣相合成法爲將四氯化鈦氣體 氧化的方法、或將四氯化鈦氣體以水蒸汽水解之方法，是 可容易製得高純度鈦氧化物的方法。以水蒸汽水解的方法 -17- 200844071 ，由於可容易製得比表面積高、金紅石化率高之鈦氧化物 ，故爲較佳。 本發明所用之原料粉末中所含有之金屬碳酸鹽，通常 的固相合成法中所用者可無例外地使用，可依複合氧化物 粉末的組成自由鋇、緦、鈣、鎂及鉛所構成的群中之至少 一種的金屬碳酸鹽適當地選擇。又，亦可使用於鋇、鋸、 鈣、鎂及鉛之金屬元素的氯化物、硝酸鹽、醋酸鹽等之水 溶液中添加碳酸銨等之碳酸化合物，或灌入二氧化碳進行 中和而得到者。金屬碳酸鹽比較軟，於與氧化鈦或氧化鉻 之混合過程中，因此等粒子而較容易粉碎，但金屬碳酸鹽 之粒徑會影響及複合氧化物粉末的特性，故若使用微粒子 之金屬碳酸鹽，於複合氧化物粉末之微粒子化有效用，故 爲較佳。例如，以作爲微粒子的指標之比表面積表示時， 以5 m2/g之程度以上爲佳，以10 m2/g之程度以上爲較佳 ，以20 m2/g之程度以上爲更佳。又，於以碳酸鋇作爲主 劑（指佔5 0重量％以上之成分）的情況，以緦、鈣、鎂及鉛 之金屬元素作爲添加劑（指未滿50重量％之成分）使用時， 此等金屬元素可爲碳酸鹽之形態，亦可爲其他化合物之形 態。於以碳酸鋸、碳酸鈣、碳酸鎂及碳酸鉛之任一者作爲 主劑的情況，添加劑同樣地可爲碳酸鹽，亦可爲碳酸鹽以 外的化合物之形態。碳酸鹽以外的化合物之形態並無特別 限定，可使用氯化物、硫酸鹽、硝酸鹽、氧化物等。 將前述金屬氧化物與金屬碳酸鹽混合作爲原料粉末。 兩者之混合量可依所需目的之複合氧化物粉末而適當地設 -18- 200844071 定。例如，欲製造以通式abo3表示之鈣鈦礦型構造之複 合氧化物粉末時，以於金屬碳酸鹽之金屬原子（A)對金屬 氧化物之金屬原子（B)之原子比表示爲〇·9〜2.0的範圍混合 爲佳，以0.95〜1.05的範圍爲較佳，以1.000〜1.03 5的範圍 爲更佳。前述原子比若小於〇 · 9，則難以得到所要的組成 之複合氧化物粉末，過剩的成分會殘存於複合氧化物中易 損及介電性與壓電性等特性，故不佳。又，欲製造多鈦酸 鋇（具體而言，爲 BaTi205、BaTi4〇9、BaTi5On、Ba2Ti9O20、 Ba4Ti1303()、Ba6Ti1704〇)等之Ti/Ba之原子比X爲2以上的 組成式之鈦酸鋇時，較佳者爲，相對於既定的原子比X， 混合（Xx〇.95)〜（Χχΐ.05)的範圍之金屬氧化物與金屬碳酸鹽 〇 混合時，依陶瓷組成物所須的特性，可適當地添加例 如鑭、铈、釓、铽、鏑、鈥、餌、鏡等稀土元素或硼、鋁 、砂、錶、鐵、錬、銅、鲜、fg、iZi、鶴、祕等兀素作爲 添加劑。此等添加劑可爲氧化物，亦可爲碳酸鹽，亦可爲 其他之化合物。添加量可依目的而適當地設定。 混合只要金屬氧化物與金屬碳酸鹽可一定程度均一地 混合即可，混合度可適當地調整。作爲混合方法，乾式混 合、濕式混合皆可，可用例如，螺旋型混合機、螺帶 (ribbon)型混合機、流動化型混合機等之固定型混合機、 圓筒型混合機、雙子圓筒型混合機等之旋轉型混合機等。 又’可於混合之前用壓縮粉碎型、衝擊壓縮粉碎型、剪斷 粉碎型、摩擦粉碎型等粉碎機，分別將金屬氧化物與金屬 -19- 200844071 碳酸鹽於混合前粉碎，又，亦可於粉碎時同時混合。原料 粉末愈微細’得到的複合氧化物粉末愈容易成爲微粒子， 故以將原料粉末粉碎爲佳，作爲粉碎機，較佳者可使用例 如球磨機、珠磨機、膠體硏磨機等濕式粉碎機。於使用濕 式粉碎機等時之混合狀態爲濕潤狀態或懸浮狀態（漿液狀 態）之情況’視需要可進行過濾、乾燥、粉碎。 .如此得到之原料粉末，視需要宜進行造粒以得到適當 的粒徑，可藉由轉動造粒、流動層造粒、噴流層造粒、攪 拌造粒、碎裂造粒、壓縮造粒、擠壓造粒、液滴固化造粒 等通常的方法進行造粒。於用濕式粉碎機等爲懸浮狀態（ 漿液狀態）之情況，以用噴霧乾燥機等進行噴霧乾燥再進 行乾燥造粒爲佳。藉由噴霧乾燥之造粒，不僅可防止原料 粉末之飛散與氣體接觸不均一，造粒粉體的粒徑亦可較整 齊’可期待均一的流動狀態，故爲較佳。造粒粉體之平均 粒徑可考慮可流動之大小或飛散的程度而任意地調整，例 如，可爲1〜1 0000 μιη，而若爲5〜3 000 μιη的程度，飛散程 度可更小爲較佳，以10〜1 000 μπι程度爲更佳，以20〜500 μιη程度爲特佳。造粒粉體可爲球狀、近似球狀、板狀、 立方體狀、長方體狀、棒狀、或於粉末內部有空間之中空 狀等任何形狀，以容易流動的形狀爲佳，例如，以球狀、 近似球狀、中空狀等形狀爲佳。又，於混合、粉碎、造粒 時，視需要可於原料粉末中調配以界面活性劑、樹脂、分 散劑等之有機化合物。於造粒時，尤其於噴霧乾燥時若添 加樹脂，除了發揮作爲結合劑之作用以調整造粒粉體的粒 -20- 200844071 徑之外，因樹脂於燒成時會分解生成空隙而成爲多孔質， 可期造粒粉體內部之二氧化碳的釋出，故爲較佳。可使用 之材料並無特別限定，可依目的而適當地選擇使用必要的 量。例如，作爲樹脂可用水系丙烯酸樹脂、水系三具氰胺 樹脂、水系氨基甲酸酯樹脂等，添加量以對原料粉末等爲 1〜2 0重量％的程度爲佳。 然後，將前述原料粉末等放入燒成裝置中，開始自室 溫昇溫至既定的燒成溫度，通常於途中的溫度區域起會產 生金屬氧化物與金屬碳酸鹽反應或有機化合物的分解所生 成之二氧化碳。用以使原料粉末流動以防止二氧化碳之吸 附並且使二氧化碳排出之氣體的通氣，須於自二氧化碳產 生之開始溫度區域至產生終了溫度區域的至少一部份期間 (以在全部期間爲佳）進行。又，視需要，亦可自昇溫開始 的階段進行氣體之通氣，亦可於二氧化碳產生終了之後至 燒成完成之間進行氣體之通氣，再者，亦可於冷卻至取出 得到之複合氧化物粉末的溫度之前的期間進行氣體之通氣 。亦可在此等二氧化碳產生前、產生終了後的階段，藉由 氣體之通氣使原料粉末等流動，亦可使原料粉末等作爲固 定層、半固定層之狀態。二氧化碳產生開始溫度依使用的 金屬氧化物、金屬碳酸鹽的種類、組成與添加劑等而異， 惟可藉由對原料粉末等進行熱分析而掌握二氧化碳之產生 開始溫度與產生終了溫度。例如，混合二氧化鈦與碳酸鋇 之原料粉末的二氧化碳之產生開始溫度依據圖1爲約5 00 的程度’故自室溫至5 00 °C程度間不進行氣體之通氣亦可 -21 · 200844071 ，較佳者爲，自昇溫達到較二氧化碳開始產生之溫度低約 5 0。(：的溫度之階段（亦即達到約45 0 °C程度之階段）起進行 氣體之通氣。另一方面，吾人認爲二氧化碳產生終了溫度 爲約8 5 0 °C的程度，故以於約5 0 0〜8 5 0 °C之間進行氣體之通 氣爲佳。其後之達到既定的燒成溫度之間、燒成之間、其 後的冷卻之間之任一者可不進行氣體之通氣’亦可繼續進 行氣體之通氣。由室溫至達到燒成溫度爲止之昇溫速度可 適當地設定，亦可於產生二氧化碳之溫度區域一度保持 0.5〜5小時之程度，其後再昇溫至燒成溫度。燒成溫度、 燒成保持時間可依複合氧化物粉末而設當地設定，例如， 可爲5 00〜U00°C之程度，燒成時間可爲例如保持0.5〜10小 時。又，於燒成終了後須冷卻至取出溫度，冷卻速度可適 當地設定，可緩緩冷卻，亦可急速冷卻。 使用之燒成裝置，可用通常固相合成法等所用的燒成 爐，或其他無機化學產業（尤其是陶瓷產業）所用的加熱爐 ，只要是可邊使原料粉末等流動邊進行燒成之任何裝置皆 可使用。通常以使用流動層燒成爐爲佳。二氧化碳產生時 之流動狀態的調整，可藉由原料粉末等之粒徑與通氣之氣 體的流速（流重）_進fjgJI整。流動層燒成爐內之原料粉末 等以可形成爲均一流動層（完全流動層）的流動狀態爲佳， 另一方面’於流動層內產生氣泡濃密之流動層狀態亦可達 成本發明之效果’故亦可。或者，原料粉末等之一部份形 成固定層’其餘爲流動狀態者，只要可達成本發明之效果 皆可。於粉末狀悲下難以流動，會產生氣體的通氣孔致只 «22- 200844071 有原料粉末之一部份可與氣體接觸之情形，或相反地，因 氣體的浮力會使原料飛散致無法燒成，因此，原料粉末以 造粒成適當粒徑而使用爲佳。由於氣體之通氣量係依燒成 裝置的形狀、原料粉末等之置入量等而異，故無法一槪地 規定，惟若以過多量的氣體通氣，原料粉末等會飛散，故 須兼顧結晶性之提高與飛散量做考量，以可達成本發明之 效果的適當通氣量進行。例如，於使用造粒成50〜1〇〇 μηι 的造粒粉體之情況（造粒粉體之表觀比重爲1 g / c m3的情況） ，室溫下於流動層燒成爐內之分散板位置的氣體線速度爲 0.9 c m /秒起開始流動，於1 . 7 c m /秒達到均一流動狀態， 並於超過1 〇 c m /秒成爲濃厚流動狀態，故氣體線速度以 1 .7〜10 cm/秒的程度爲特佳。 作爲通氣之氣體，可用通常之流動層燒成爐等燒成裝 置所使用之氣體，惟若含有二氧化碳則會影響及複合氧化 物粉末之結晶性，故不佳，必須選擇二氧化碳含有量少之 氣體或不含二氧化碳之氣體。因此，以使用二氧化碳含有 墓爲0〜0.5谷積％之氣體爲佳’較佳者爲二氧化碳含有量爲 〇〜〇·1容積％，更佳者爲二氧化碳含有量爲〇〜〇.〇5容積％。 作爲此種氣體’可使用例如氮、氨、氮、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 中之一種或二種以上之氣體。於空氣、合成空氣、乾燥空 氣（dry air)、壓縮空氣中含有約400 ppm的程度之少量二 氧化碳，此程度的量經確認不會有影響。而且，若用空氣 、合成空氣、乾燥空氣（dry air)、壓縮空氣，由於於燒成 -23· 200844071 時原料粉末不易還原，故容易得到均質的複合氧化物粉末 ，爲較佳。通氣之氣體，若於導入燒成裝置前預先加熱， 可防止燒成裝置之溫度急速降低，故爲較佳。又，藉由通 氣之氣體可將產生之二氧化碳之至少一部份排出至燒成裝 置之外，另一方面，通氣之氣體亦可循環使用，此時之循 環氣體中之二氧化碳含有量以定爲前述範圍爲佳。 藉由前述方法可得到微粒子且結晶性高的複合氧化物 粉末，尤其是欽酸鎖粉末。具體而§可舉出欽酸鎖、欽酸 緦、鈦酸鉛、鍩酸鉛、鈦酸锆酸鉛、鈣改質鈦酸鋇、稀土 元素改質鈦酸鋇等之鈣鈦礦型構造之化合物、Ti/Ba之原 子比爲2以上之組成式的多鈦酸鋇等。得到之複合氧化物 粉末之粒徑以〇.〇1〜0.3 μιη的範圍爲佳，以〇·〇15〜0.3 μπι 的範圍爲較佳，以0.02〜0.3 μιη的範圍爲更佳，以 0.03〜0.3 μιη的範圍又更佳，以0.05〜0.3 μιη的範圍爲特佳 ，以0.0 6〜0.1 5 μιη的範圍爲特佳。複合氧化物粉末之粒徑 (d)係假定複合氧化物粉末爲球狀，用依據BET法求出之 比表面積a(m2/g)藉由下述式2求出。 式 2 ......d = (6/ p )/a 其中，P爲比重，於鈦酸鋇時，用p =5.90。 又，得到之複合氧化物粉末之結晶性係藉由X光繞 射測定，由特定結晶面之繞射波峰之波峰高度或半寬度値 進行評價，須更精密時可依據X光繞射數據進行立特貝 -24- 200844071 爾特解析作判斷。尤其，於鈦酸鋇粉末的情況，係由結晶 格的c軸與a軸之比（c / a軸比）作判斷，c / a軸比愈大，正 方晶系鈦酸鋇之結晶性較高。具體而言，依據本發明之方 法，可使c/a軸比作成爲1.0033以上，較佳者爲1.0033〜1.011 的範圍，更佳者爲，又更佳者爲1·〇〇6〜1.011的範圍，特 佳者爲1.006〜1.010的範圍，最佳者爲1.007〜1.010的範圍 。尤其，若使用以X光繞射法求出之金紅石化率高於90 重量％而爲100%以下，比表面積爲150〜3 00 m2/g之鈦氧化 物，鈦酸鋇粉末之c/a軸比可達到更佳之1.0075〜1.010的 更佳範圍，乃至1 . 〇 〇 8 0〜1 · 0 1 〇之更佳的範圍。若用結晶性 降低之複合氧化物粉末，尤其是未滿1 · 〇 〇 3 3之鈦酸鋇粉末 ，作爲電子零件用之時，半導體之強介電性會不足，故爲 使c/a軸比增大必須進一步熱處理而導致粒子成長之結果 。正方晶鈦酸鋇之c/a軸比之理論値爲由a = 3.994、 c = 4.038算出c/a=1.011，另一方面’立方晶欽酸鋇之c/a 軸比爲1.0 0 0。 複合氧化物粉末可視需要而進行粉碎。作爲粉碎機可 用壓縮粉碎型、衝擊壓縮粉碎型、剪斷粉碎型、摩擦粉碎 型等之粉碎機，其中以用壓縮粉碎機爲佳。所謂壓縮粉碎 機係兼具有壓縮作用與磨碎作用之粉碎機，將複合氧化物 粉末放入壓縮粉碎機粉碎時’於藉由壓縮作用而壓緊爲薄 片狀之同時，亦藉由摩擦作用可微細地粉碎。作爲壓緊粉 碎機可用例如擂碎機、輪碾機（edge runner mill)、輥硏磨 機、邊碾機（fret mill)。 -25- 200844071 又，於複合氧化物粉末中視需要亦可混合以添加劑。 作爲添加劑，可依陶瓷組成物所須特性適當地使用例如： 鑭、鈽、釓、铽、鏑、鈥、餌、鏡等稀土元素、鋁、矽、 錳、鐵、鎳、銅、鋅、鈮、釔、鎢、鉍等元素。又，作爲 於燒結時用以控制粒子成長與陶瓷組成物之電氣特性的添 加劑可舉出例如··硼、鉍、以及鋰、鈉、鉀等鹼金屬、鐵 、錳、鈷、鎳、鈮等轉移金屬，乃至矽、鋁等元素之化合 物。此等添加劑可於複合氧化物粉末之粉碎階段添加，亦 可於粉碎後混合。或者，於複合氧化物粉末之燒結步驟的 任意階段添加。添加量可適當地設定必要量。混合機可用 通常無機化學產業（尤其是陶瓷產業）所用的混合機，或電 子材料產業中所用的混合機。又，於粉碎、混合時，亦可 添加界面活性劑、樹脂、分散劑等有機化合物。如此做法 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，經 燒結作成爲陶瓷組成物可較佳地用於例如陶瓷電子零件之 材料。陶瓷電子零件具備此陶瓷組成物、與包夾著該陶瓷 組成物並相向地配置的電極。又，作爲陶瓷電子零件，爲 具備含有陶瓷組成物的複數層、與形成於該陶瓷組成物之 層間的電極。具體的積層陶瓷電子零件爲積層陶瓷電容器 ，其具備有複數的積層之陶瓷組成物層（介電體層）、與沿 著此等陶瓷組成物層間的界面形成之內部電極的積層物。 於積層物內部交替配置有作爲電極之第1內部電極與第2內 部電極，爲使第1內部電極係與第1外部電極連接、使第2 -26- 200844071 內部電極同樣地與第2內部電極連接，係分別形成爲使各 端緣露出於積層物的端面之狀態。作爲電極，可用例如鉑 、鈀、鎳、同等金屬或其等之合金。積層陶瓷電子零件之 陶瓷組成物的各層之厚度宜儘可能地較薄，以1 μιη以下 爲佳。 陶瓷組成物與陶瓷電子零件可用習知的方法製造方法 。陶瓷組成物之製造，例如，可使至少含有複合氧化物粉 末之陶瓷組成物原料與黏結劑混合後，進行加壓成形形成 既定性狀的生胚粒狀物（green pallet)，或用薄片成形法或 印刷法等方法在基板上形成既定厚度的生胚薄片，然後進 行燒結。陶瓷電子零件之製造，可用例如，可在前述生胚 粒狀物之兩面印刷或塗佈調配有電極用金屬之糊等，再進 行燒結的方法；或形成前述生胚薄片，然後在其上印刷或 塗佈調配有電極用金屬之糊等，於反復數次之後進行燒結 的方法等。燒結條件可依陶瓷組成物之燒結度而適當地設 定，燒結溫度例如以1 〇 〇 〇〜1 5 0 0 °C之程度爲佳，以 1 100〜1 3 0 0 °C之程度爲更佳。燒結時間亦可依陶瓷組成物 原料之組成而設當地設定。以〇·5〜10小時之程度爲佳。燒 結時之周遭氣可爲氧、空氣、合成空氣、乾燥空氣（dry air)、壓縮空氣等之含有氧的氣體，以不會使電極用金屬 氧化之周遭氣爲佳，較佳者可使用非氧化性氣體，例如， 氮、Μ、氦等，又氫、一氧化碳、錢等之還原性氣體亦可 較佳地適用。 -27- 200844071 [實施例] 以下舉出實施例、比較例就本發明更詳細地作說明， 惟本發明並非限定於此等實施例。 (實施例1) 秤量市售之二氧化鈦（比表面積190 m2/g)與碳酸鋇（比 表面積30 m2/g)，使鋇/鈦之原子比成爲1.000，用球磨機 進行濕式粉碎混合。於得到之二氧化鈦與碳酸鋇的混合漿 液中添加水系丙烯酸系樹脂（8重量％)，藉由噴霧乾燥機進 行乾燥與造粒。造粒粉體之平均粒徑爲5 0 μηι。 然後，將造粒粉體放入縱式之小型流動層燒成爐，作 爲流動用氣體係以乾燥空氣（含有二氧化碳400 ppm之程 度）以氣體線速度1.73 cm/秒進行通氣，邊使前述造粒粉體 流動之下自室溫昇溫至900 °C，保持1小時進行燒成，得到 本發明之鈦酸鋇粉末（試料A)。又，乾燥空氣之通氣係於 開始昇溫至試料取出爲止之燒成全程之間進行，藉由乾燥 空氣之通氣使造粒粉體流動，使產生的二氧化碳排出至系 統外。 (實施例2) 於前述實施例1中，除了將燒成溫度定爲95(TC之外， 係以與實施例1同樣的做法，得到本發明之鈦酸鋇粉末（試 料B) 〇 -28- 200844071 (實施例3 ) 於前述實施例1中，除了將燒成溫度定爲1000°C之外 ，係以與實施例1同樣的做法，得到本發明之鈦酸鋇粉末（ 試料C)。 (實施例4) 秤量由四氯化鈦中和得到之生成物於1 3 0 °c之溫度下 乾燥所得鈦氧化物（以前述方法測定之比表面積爲1 90 m2/g、平均長軸徑80 nm、軸比3之紡錘狀二氧化鈦，Ti〇2 純度99.9 8重量％，金紅石化率100°/。，金紅石型結晶之結 晶格徑9 nm，於水中之50%累積徑0.077 μηι)與鈦酸鋇（比 表面積30 m2/g)，使原子比成爲1.000，用球磨機進行濕式 粉碎混合，將得到之混合漿液以噴霧乾燥機乾燥並造粒。 造粒粉體之平均粒徑爲50 μπι。 然後，將造粒粉體放入縱式之小型流動層燒成爐，作 爲流動用氣體係以乾燥空氣（含有二氧化碳400 ppm之程 度）以氣體線速度1.73 cm/秒進行通氣，邊使前述造粒粉體 流動之下自室溫昇溫至95 0 °C，保持0.5小時進行燒成/得 到本發明之鈦酸鋇粉末（試料D)。又，乾燥空氣之通氣係 於開始昇溫至試料取出爲止之燒成全程之間進行，藉由乾 燥空氣之通氣使造粒粉體流動，使產生的二氧化碳排出至 系統外。 (實施例5) 29- 200844071 於前述實施例4中，除了將保持時間定爲1小時之外， 係以與實施例4同樣的做法，得到本發明之鈦酸鋇粉末（試 料E)。 (實施例6) 於前述實施例4中，除了將保持時間定爲〗.5小時之外 ，係以與實施例4同樣的做法，得到本發明之鈦酸鋇粉末（ 試料F)。 (比較例1) 以與實施例1同樣的做法藉由噴霧構造機得到造粒粉 體（平均粒徑爲50 μιη)，然後，將得到之造粒粉體放入50 cc之坩鍋中使其成爲20 mm之厚度，將此坩鍋放置於固 定床電氣爐中，於大氣中（不吹入空氣下）自室溫昇溫至 8 5 0°C，保持5小時進行燒成，得到鈦酸鋇粉末（試料G)。 (比較例2) 以與實施例1同樣的做法藉由噴霧構造機得到造粒粉 體（平均粒徑爲50 μπα)，然後，將得到之造粒粉體放入50 cc之坩鍋中使其成爲20 mm之厚度，將此坩鍋放置於可 控制周遭氣之固定床電氣爐中，於減壓下（1〇 Pa〜100 Pa) 自室溫昇溫至900 °C，保持5小時進行燒成，得到鈦酸鋇粉 末（試料H)。 -30- 200844071 (比較例3) 手平量市售之二氧化鈦（比表面積19〇 m2/g)與碳酸鋇（比 表面積30 m2/g)，使鋇/鈦之原子比成爲1〇〇〇，用球磨機 進行濕式粉碎混合，然後，將混合漿液蒸發乾燥，以樁搗 器粉碎作成爲原料粉末。 然後’將得到之原料粉末放入5 〇 cc之坩鍋中使其成 爲20 mm之厚度，將此坩鍋放置於固定床電氣爐中，於大 氣中（不吹入空氣下）自室溫昇溫至8 〇 〇 °c，保持5小時進行 燒成，得到鈦酸鋇粉末（試料I)。 (比較例4) 於前述比較例3中，除了將燒成溫度定爲85 0 t之外， 係以與比較例3同樣的做法，得到鈦酸鋇粉末（試料】）。 (比較例5) 以與比較例3同樣的做法得到原料粉末，然後，將得 到之原料粉末放入50 cc之坩鍋中使其成爲2〇 mm之厚度 ’將此坩鍋放置於可控制周遭氣之固定床電氣爐中，於減 壓下（10 Pa〜100 Pa)自室溫昇溫至90(rc，保持$小時進行 燒成，得到鈦酸鋇粉末（試料K)。 (比較例6) 以與比較例3同樣的做法得到原料粉末，然後，將得 到之原料粉末放入50 cc之坩鍋中使其成爲2〇 mm之厚度 31 - 200844071 ，一邊將氮氣（氮氣純度99.999容積％)以流量4L/分鐘吹入 下自室溫至8 75 °C，保持5小時進行燒成，得到鈦酸鋇粉末 (試料L)。又，氮氣之通氣係於開始昇溫至試料取出爲止 之燒成全程之間進行，藉由氮氣之通氣使造粒粉體流動， 使產生的二氧化碳排出至系統外。 (比較例7) 以與比較例3同樣的做法得到原料粉末，然後，將得 到之原料粉末放入50 cc之坩鍋中使其成爲20 mm之厚度 ，一邊將二氧化碳（二氧化碳純度99.5容積％)以流量4L/分 鐘吹入下自室溫至800 °C，保持5小時進行燒成，得到鈦酸 鋇粉末（試料M)。又，二氧化碳之通氣係於開始昇溫至試 料取出爲止之燒成全程之間進行。 對上述般藉由不同的燒成處理得到之試料A〜Μ之鈦 酸鋇粉末以簡易BET法測定比表面積a(m2/g)，將粉末假 定爲球體，以前述式2求出其平均粒徑（1(μιη)。 再用X光繞射法得到之數據，進行立特貝爾特解析 求出正方晶鈦酸鋇之晶格常數a與c，算出結晶性評價（正 方晶性）c/a軸比。 由得到之結果可知：本發明之鈦酸鋇粉末具有與在真 空中（減壓下）燒成之同等程度的粒徑、c/a軸比，並有優 異的正方晶性（tetragonality)，另一方面，與用固定床燒 成裝置之在大氣中氮氣通氣下、二氧化碳通氣下之燒成相 比，以相同程度之粒徑爲基準下有優異的c/a軸比。 •32- 200844071 [表i] 試料 編號 燒成條件 Ti〇2+BaC〇3 原料粉末 得到之鈦酸鋇之特性 粒徑(μιη) c/a軸比 實施例1 A 流動層(乾燥空氣通氣） 造粒粉末 0.131 1.0081 實施例2 B 流動層(乾燥空氣通氣） 造粒粉末 0.134 1.0080 實施例3 C 流動層(乾燥空氣通氣） 造粒粉末 0.200 1.0083 實施例4 D 流動層(乾燥空氣通氣） 造粒粉末 0.101 1.0089 實施例5 E 流動層(乾燥空氣通氣） 造粒粉末 0.120 1.0095 實施例6 F 流動層(乾燥空氣通氣） 造粒粉末 0.079 1.0079 比較例1 G 固定床(無氣體通氣） 造粒粉末 0.138 1.0063 比較例2 Η 固定床(減壓下） 造粒粉末 0.129 1.0083 比較例3 I 固定床(無氣體通氣） 粉末 0.117 1.0056 比較例4 J 固定床(無氣體通氣） 粉末 0.148 1.0067 比較例5 K 固定床(減壓下） 粉末 0.129 1.0087 比較例6 L 固定床(氮氣通氣） 粉末 0.120 1.0069 比較例7 Μ 固定床(二氧化碳通氣） 粉末 0.132 1.0053 數次進行實施例1〜6所記載的實驗之結果，確認得知 得到之鈦酸鋇粉末的品質上參差少。又，經確認得知於本 發明之鈦酸鋇之外，鈦酸緦、鈦酸鉛、鉻酸鉛、鈦酸鍩酸 鉛、鈣改質鈦酸鋇、稀土元素改質鈦酸鋇等之鈣鈦礦型構 造之化合物、Ti/Ba之原子比爲2以上之組成式的多鈦酸鋇 等亦可同樣地製造。再者，對得到之複合氧化物粉末進行 燒結得到陶瓷組成物，用其作成爲陶瓷電子零件的情況， 確認得知本發明之優越性。 (產業上之可利用性） -33- 200844071 由於本發明之複合氧化物粉末爲微粒子且有高結晶性 ，故藉由將其燒結，可簡便而容易地製造具有優異的介電 性與壓電性等特性之陶瓷組成物。使用該陶瓷組成物於陶 瓷電子零件，尤其是積層陶瓷電子零件，可期待可滿足小 型化、輕量化、高性能化、多機能化等要求。 【圖式簡單說明】 圖1爲表不二氧化駄與碳酸鋇粉末之原料粉末於熱分 析之重量減少之圖。 圖2爲表示實施例4中所用之鈦氧化物的粒子構造之電 子顯微鏡照相。 圖3爲實施例4中所用之鈦氧化物之X光繞射圖案。 -34-BaC03 + Ti〇2">BaTi03 + Co2 ......(1) BaC03 + BaTi〇3^Ba2Ti〇4 + C〇2 I ......(2) Ba2Ti〇4 + Ti〇2 + 2BaTi〇3 . . . . . . . . . . . . (3) 200844071 The inventors of the present invention have further studied the results based on the above findings and found that even under the pressure of atmospheric pressure, in order to reduce the adverse effects of carbon dioxide generated in the firing step, When the raw material is circulated by the gas, the raw material is fired, and the crystallinity of the barium titanate powder is improved, and compared with those of the above-described Patent Documents 1 and 2, which are fired under reduced pressure or under vacuum. The same degree of crystallinity can be obtained, and it is not necessary to carry out under reduced pressure or under vacuum. Since it can be carried out under atmospheric pressure or under a relatively high pressure due to gas aeration, the restriction of the apparatus and the like is small, and uniform conditions can be used. The quality of the composite oxide powder obtained by firing is also small, and since a usual firing apparatus can be used as such, it can be produced at low cost, and the present invention can be completed. Furthermore, the method is not limited to the production of barium titanate, and may be applied to a metal carbonate containing at least one metal oxide of titanium or cerium and at least one selected from the group consisting of cerium, lanthanum, calcium, magnesium and lead. In the method of firing the raw material powder, a good result can be obtained in the reaction of generating carbon dioxide during firing. The present invention has been completed. That is, the present invention is: (1) A method for producing a composite oxide powder, which comprises at least a metal oxide of titanium and/or zirconium and a group selected from the group consisting of ruthenium, osmium, calcium, magnesium and lead. a method of producing a composite oxide powder by firing a raw material powder of at least one metal carbonate; characterized by flowing a gas during at least a portion of a carbon dioxide gas generated by firing of the raw material powder The raw material powder is flowed to be fired. (2) The method for producing a composite oxide powder according to (1), which uses 200844071 granulated powder granulated with a raw material powder. (3) The method for producing a composite oxide powder according to (2), wherein the slurry of the raw material powder is spray-dried and granulated. (4) The method for producing a composite oxide powder according to (1), which is a granulated powder obtained by pulverizing a raw material powder and then granulating the raw material powder. (5) A method for producing a composite oxide powder according to (2), which is a granulated powder having a size of 10 to 1000 μm. (6) A method for producing a composite oxide powder according to (1), which is a raw material powder obtained by mixing at least an oxide of titanium and a carbonate of cerium. (7) A method for producing a composite oxide powder according to (6), which is an oxide of titanium having a specific surface area of 20 m 2 /g or more. (8) The method for producing a composite oxide powder according to the item (1), wherein the gas is caused to flow while the raw material powder is generated by the firing of the raw material powder to cause the gas to flow. (9) The method for producing a composite oxide powder according to (1), wherein the ratio of the golden-red petrochemical obtained by the X-ray diffraction method is higher than 90°/. And it is an oxide of titanium which is 100% or less and has a specific surface area of 30 m 2 /g or more. (10) A composite oxide powder characterized by being produced by the method according to any one of (1) to (9), wherein the particle size is 〇. The range of 01 to 0·3 μηη 11(11) A barium titanate powder characterized by 'manufactured by the method of any one of (1) to (9)' having a particle size of 0·01~0 • A range of 3 μm. (1 2) The bismuth citrate powder of (1 1), the c / a ratio of the bismuth citrate is 1. 007~1. 010 ° -10- 200844071 (13) A ceramic composition characterized by being sintered by at least the composite oxide powder of the item (10) or the barium titanate powder of the item (1). (14) A ceramic electronic component characterized by comprising the ceramic composition of (13), and an electrode disposed to face the ceramic composition. (15) A laminated ceramic electronic component characterized by comprising a plurality of layers containing the ceramic composition of (13) and an electrode formed between the layers of the ceramic composition. (Effect of the Invention) The present invention is a method for producing a composite oxide powder such as barium titanate, in order to prevent the carbon dioxide generated in the calcination step from being adsorbed by the raw material powder, and to cause the gas to flow between the generation of carbon dioxide. A method in which a raw material powder flows and is fired. The composite oxide powder obtained by the method of the present invention has high crystallinity even in the form of fine particles, and can suppress a decrease in crystallinity which is accompanied by the formation of fine particles. Further, since the limitations of the apparatus, materials, and the like are small and can be fired under the same conditions, the quality of the composite oxide powder obtained in the same production batch is extremely small, and is small among batches, and a homogeneous product can be obtained. Specifically, the particle size can be easily obtained. 〇1~0. A composite oxide powder having an excellent crystallinity, such as a barium titanate powder, having a range of 3 μm, particularly having a particle diameter of 〇·〇1 to 〇·3 μιη, and having a c/a ratio of 1. 0 0 7~1. An excellent tetragonal barium titanate powder in the range of 0 10 . Further, since the composite oxide powder is fine particles, the low-temperature sinterability can be improved, the charge rate at the time of forming a sintered body can be improved, and the electrical and piezoelectric properties of the dielectric layer can be improved. Further, since it has high crystallinity and homogeneity, the reduction resistance can be improved. Therefore, by using the ceramic composition obtained by sintering the composite oxide powder by the method of the present invention, ceramic electronic parts satisfying miniaturization, weight reduction, high performance, and multi-functionality can be obtained by using the excellent characteristics, especially laminated layers. Ceramic electronic parts. [Embodiment] The present invention relates to a method for producing a composite oxide powder, which is a metal having at least one of a metal oxide of titanium and/or zirconium and at least one selected from the group consisting of ruthenium, osmium, calcium, magnesium, and lead. a raw material powder obtained by mixing carbonate or a granulated powder obtained by granulation (hereinafter, a raw material powder and a granulated powder are collectively referred to as a raw material powder), and are fired in a firing apparatus; When the raw material powder is heated from room temperature to a predetermined temperature and maintained for a predetermined period of time, during at least a part of the generation of the carbon dioxide gas (preferably all time), the gas is caused to flow to cause the raw material powder to flow and burn. to make. By performing the firing as described above, the gas is allowed to pass through the vicinity of the raw material powder, so that at least a part of the carbon dioxide can be efficiently discharged to the outside of the firing device. Further, by using the granulated powder obtained by granulating the raw material powder, the fluidity can be improved to make good contact with the ventilating gas, and the generated carbon dioxide can be efficiently discharged. The raw material powder used in the present invention is a mixed powder obtained by mixing at least a metal oxide of titanium and/or chromium with a metal carbonate selected from at least one of the group consisting of ruthenium, osmium, calcium, magnesium and lead. . The metal oxide can be used without exception, in the usual solid phase synthesis method, specifically -12-200844071, titanium, chromium oxide, or water and oxidation containing titanium, chromium, and the like can be used. At least one of a substance, an aqueous oxide, and a hydroxide. In particular, titanium dioxide or zirconium dioxide is preferred. The use of the metal oxide of the fine particles is effective in the granulation of the composite oxide powder. Therefore, it is preferable to use, for example, as an index of the fine particles, in terms of specific surface area, preferably 20 m 2 /g or more, and 30 m 2 /g. The degree is preferably more than 50 m2/g, more preferably from 100 to 300 m2/g, and even more preferably from 1 50 to 300 m2/g. The larger the specific surface area of the titanium oxide, the better the reactivity, and if it is too large, since the titanium oxide is not easy to manufacture, it is preferable from the viewpoint that the specific surface area is 1 60-25 0 m 2 /g, and 1 60 -200 m2/g is especially good. The specific surface area can be determined by nitrogen adsorption by the BET method. In the case where titanium oxide is used as a main component (referred to as a component of 50% by weight or more), when zirconium is used as an additive (refer to a component of less than 50% by weight), a chromium oxide may be used, or other than A chromium compound; conversely, in the case of using chromium oxide as a main component, titanium oxide or a titanium compound other than it may be used as an additive. The form of the compound other than the oxide is not particularly limited, and a chloride, a sulfate, a nitrate, a carbonate, an acetate or the like can be used. The cerium oxide used in the present invention contains an oxide of titanium (titanium dioxide), or a water and a substance of titanium, an aqueous oxide, or a hydroxide, and at least one selected from the group consisting of them. Further, the titanium compound is usually confirmed to be a rutile crystal, an anatase crystal, or a brookite crystal by an X-ray diffraction peak, and any crystal form may be used, or two or more crystal particles may be used. A mixture or a mixture of two or more crystal forms. In the present invention, 'the preferred one is -13-200844071 titanium oxide having a larger rutile type crystal in the above three crystal structures'. The gold oxide ratio of the titanium oxide obtained by the X-ray diffraction method is high. 90% is preferably 100% or less, and more preferably 95% to 100%, especially the degree of gold-red petrochemical rate of the degree of X-ray diffraction peak of anatase crystal and plate-type crystal. 0% is better. The ratio of the gold-red petrochemical rate of the titanium oxide refers to the ratio of the rutile-type crystal contained in the titanium oxide, and the rutile crystal and the anatase crystal are confirmed by X-ray diffraction (using the CuK α line). The presence or absence of brookite-type crystals is determined as a ratio of the above-mentioned three crystal forms of rutile crystals. Based on the above, in the present invention, it is more preferable to use a titanium oxide having a specific gravity of 30 m 2 /g or more and a specific surface area of 30 m 2 /g or more, which is obtained by an X-ray diffraction method. More preferably 50 m2/g or more, more preferably 1 00-3 00 m2/g, and particularly preferably 1 500-00 m2/g. Further, the crystal lattice diameter of the rutile crystal can be obtained by using the Coriolis formula (Formula 1) from the width of the X-ray diffraction peak of the (11 Å) plane of the rutile crystal. The crystal lattice diameter of the rutile crystal is preferably small in view of reactivity, more preferably 10 nm or less, and still more preferably 1 to 1 〇 nm. Equation 1: Dhkl = K* λ / β cos θ D Η KL : crystal lattice diameter (A ) λ : wavelength of X light / 3 : half width of the diffraction peak 0: Bragg's angle K : constant ( = 〇·94) On the other hand, the primary particle diameter of the titanium oxide photographed by electron microscopy is preferably about 1 to 15 nm, and the primary particle is shaped as -14-200844071 into secondary particles. Also. The shape of the secondary particles of titanium oxide may be any shape, and may be, for example, a granular shape, a spherical shape, an approximately spherical shape, a spindle shape or the like. In the case of granular, spherical or nearly spherical, if it is expressed by the largest diameter (number average) of the particle diameter, it is preferably 1 〇 to 300 nm, more preferably 20 to 150 nm, and 3 0 to 12 0 is especially good. Further, the so-called spindle-shaped means a shape similar to a spindle, and is a cylindrical shape which is reduced to the both ends. Therefore, the spindle shape is generally referred to as a needle shape, a rod shape, a column shape, a polygonal column shape or the like. The length of both ends of the connecting particles is taken as the major axis diameter, and the length of the thickest portion of the column portion is taken as the minor axis diameter, and the number average (average major axis diameter) and the minor axis diameter of the major axis diameter are averaged ( The ratio of the average minor axis diameter is taken as the axial ratio, and the larger the axial ratio is, in particular, 1 . 5 or more is better. On the other hand, if the titanium oxide is formed into fine particles, since the axial ratio is difficult to be large, it is 1. The degree of 5 to 5 is better, to 1. The degree of 5 to 4 is better. The average major axis diameter of the titanium oxide is preferably 10 to 300 nm, more preferably 20 to 150 nm, and particularly preferably 30 to 120 nm. The secondary particles of titanium oxide may be formed by agglomerating particles from several to several hundreds of agglomerates. The shape of the secondary particles of the titanium oxide, the average major axis diameter, and the average minor axis diameter can be observed and measured by an electron microscope. Further, for example, the granulated particles reaggregate to form larger porous aggregated particles, and the spindle-shaped particles also form aggregated particles similar to spherical sugars ((gluco)). Regarding the agglomerated particles of titanium oxide, the particle diameter in water (50% cumulative diameter (medium diameter)) can be measured by the following method, and the viewpoint of the reactivity of solid phase synthesis in the present invention is considered. The degree of 〇6~0·20 μπι is better. -15- 200844071 Determination of particle size distribution in water (1) The pH of the slurry of titanium oxide is adjusted to 10. After 8', it was dispersed by a paint shaker for 15 minutes. (2) For the addition, the conversion is p2〇5. 3 mg of sodium hexametaphosphate in water 300 ml, add sodium hydroxide aqueous solution to adjust the pH to 10. 5, as a dispersion medium for measurement. (3) A few drops of the above-mentioned measurement dispersing medium and a dispersion liquid (titanium oxide slurry) prepared by a paint shaker were placed in a 1 L polyethylene container, and stirred to prepare a suspension. (4) The suspension was subjected to ultrasonic irradiation for 1 minute with an ultrasonic generator (Sharp, UT-5 00) to disperse the sample. (5) The particle size distribution of the sample in the obtained dispersion was measured by a laser diffraction type particle size distribution measuring apparatus (manufactured by η RIB A, L A - 9 10 ). The titanium oxide used in the present invention is preferably a purity of 99% by weight or more of TiO2. More preferably, 5 wt% or more is 99. More than 9% by weight is more preferred. TiO2 purity is an impurity (such as bismuth, iron, aluminum, bismuth, sodium, etc.) which is dehydrated from 1 〇〇 (%) by water, strong heat loss component (Ig-Loss), chlorine element, or carbon element. The total amount of the oxide conversion amount). The elements such as ruthenium are analyzed by fluorescence X-ray, ICP emission spectrometry or atomic absorption. The titanium oxide used in the present invention can be produced by a liquid phase method or a gas phase method, and an appropriate conditions can be selected to produce a desired specific surface area, a ruthenium oxide ratio, and the like. The liquid phase method is a method for hydrolyzing and neutralizing a compound such as sulphate, oxidized sulphate, tetrachlorin, or titan 1 k X Xide, since the ratio can be easily obtained. It is preferred because the surface area is high and the crystal lattice diameter of the rutile crystal is small. The specific liquid phase method is an aqueous titanium hydroxide obtained by neutralizing or hydrolyzing, for example, titanium tetrachloride or titanium oxysulfate, an alkali metal hydroxide such as sodium hydroxide, an ammonium compound, or an ammonium carbonate compound. After the heat treatment is carried out in an aqueous solution of an alkali compound such as an amine compound, it is filtered, washed, and then heat-treated in a strong acid aqueous solution such as hydrochloric acid to obtain a solution. As the alkali compound, sodium hydroxide is more preferable based on the ratio of the rhodogen ratio, etc., and it is preferable to sufficiently remove sodium for acid leaching or the like. Further, when the hydrochloric acid treatment is carried out in the presence of titanium trichloride, fine titanium oxide fine particles having a large major axis diameter and a small crystal lattice diameter can be obtained, which is a preferred method. The resulting product was fractionated and dried. If the drying temperature is too high, the specific surface area will decrease, so the drying temperature is preferably 1 50 ° C or lower. As another method, a method of neutralizing titanium tetrachloride can be used. The neutralizer was added dropwise while stirring titanium tetrachloride, and the titanium tetrachloride was neutralized. 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 this method, in the case where an alkali metal hydroxide is used as the neutralizing agent, it is preferred to sufficiently remove the alkali metal for pickling. The product thus obtained was classified and dried in the same manner as described above. The drying temperature is preferably 1 5 (temperature below TC). If the drying temperature is higher than 150 ° C, the specific surface area of the neutralized product is liable to be lowered, so the lower limit temperature of drying is as long as the temperature can be dried. On the other hand, the gas phase synthesis method of titanium oxide is a method of oxidizing titanium tetrachloride gas or a method of hydrolyzing titanium tetrachloride gas by steam, so that high-purity titanium oxide can be easily obtained. The method of hydrolyzing water vapor is -17-200844071, since it is easy to produce a titanium oxide having a high specific surface area and a high ruthenium ratio, and is preferably a metal carbonate contained in the raw material powder used in the present invention. The one used in the usual solid phase synthesis method can be used without exception, and can be appropriately selected depending on the metal oxide of at least one of the group consisting of ruthenium, osmium, calcium, magnesium and lead depending on the composition of the composite oxide powder. Further, a carbonate compound such as ammonium carbonate or the like may be added to an aqueous solution of a metal element such as barium, saw, calcium, magnesium or lead, or an aqueous solution of ammonium carbonate or the like, or may be obtained by neutralizing carbon dioxide. The metal carbonate is relatively soft, and is mixed with titanium oxide or chromium oxide, so it is easier to pulverize with other particles, but the particle size of the metal carbonate affects the characteristics of the composite oxide powder, so if the metal carbonate of the fine particles is used, The salt is preferably used in the form of a fine particle of the composite oxide powder. For example, when the specific surface area is an index of the fine particles, it is preferably 5 m 2 /g or more, and more preferably 10 m 2 /g or more. Preferably, it is more preferably 20 m 2 /g or more, and in the case of strontium carbonate as a main component (referred to as a component of 50% by weight or more), a metal element of barium, calcium, magnesium and lead is used. When used as an additive (indicating less than 50% by weight of the component), the metal elements may be in the form of a carbonate or in the form of other compounds. In the case of a carbonic acid saw, calcium carbonate, magnesium carbonate and lead carbonate In the case of the main component, the additive may be a carbonate or a compound other than the carbonate. The form of the compound other than the carbonate is not particularly limited, and a chloride or a sulfate may be used. a nitrate, an oxide, etc. The metal oxide and the metal carbonate are mixed as a raw material powder. The compounding amount of the two may be appropriately set according to the desired composite oxide powder, -18-200844071. For example, When a composite oxide powder having a perovskite structure represented by the formula abo3 is produced, the atomic ratio of the metal atom (A) of the metal carbonate to the metal atom (B) of the metal oxide is expressed as 〇·9~2 . The range of 0 is mixed as well, with 0. 95~1. The range of 05 is better, to 1. 000~1. The range of 03 5 is better. When the atomic ratio is less than 〇·9, it is difficult to obtain a composite oxide powder having a desired composition, and the excess component remains in the composite oxide, which is susceptible to damage, dielectric properties, and piezoelectric properties, which is not preferable. Further, in order to produce barium titanate (specifically, BaTi205, BaTi4〇9, BaTi5On, Ba2Ti9O20, Ba4Ti1303(), Ba6Ti1704〇), the atomic ratio of Ti/Ba having an atomic ratio of X or more is 2 or more. Preferably, it is mixed with respect to a given atomic ratio X (Xx〇. 95) ~ (Χχΐ. When the metal oxide of the range of 05) is mixed with the metal carbonate ruthenium, a rare earth element such as lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, bait or mirror or boron may be appropriately added depending on the characteristics required for the ceramic composition. , aluminum, sand, table, iron, bismuth, copper, fresh, fg, iZi, crane, secret and other halogen as an additive. These additives may be oxides, carbonates or other compounds. The amount of addition can be appropriately set depending on the purpose. Mixing may be carried out as long as the metal oxide and the metal carbonate are uniformly mixed to some extent, and the degree of mixing can be appropriately adjusted. As the mixing method, dry mixing or wet mixing is possible, and for example, a fixed type mixer such as a spiral type mixer, a ribbon type mixer, a fluidized type mixer, a cylindrical type mixer, and a twin type can be used. A rotary mixer such as a cylindrical mixer. In addition, it is possible to crush the metal oxide and the metal -19-200844071 carbonate before mixing by using a crusher such as a compression pulverization type, an impact compression pulverization type, a shear pulverization type or a friction pulverization type before mixing. Mix while pulverizing. The finer the raw material powder is, the more easily the obtained composite oxide powder becomes fine particles, so that the raw material powder is preferably pulverized. As the pulverizer, a wet pulverizer such as a ball mill, a bead mill or a colloid honing machine can be preferably used. . When the mixed state at the time of using a wet pulverizer or the like is in a wet state or a suspended state (slurry state), filtration, drying, and pulverization may be carried out as needed. . The raw material powder thus obtained is preferably granulated as needed to obtain a suitable particle size, which can be granulated by rotary granulation, granulation of a flowing layer, granulation of a spray layer, agitation granulation, granulation by crushing, granulation by compression, extrusion Granulation is carried out by a usual method such as pressure granulation or droplet solidification granulation. In the case of using a wet pulverizer or the like in a suspended state (slurry state), it is preferred to carry out spray granulation by a spray dryer or the like followed by drying granulation. By granulation by spray drying, not only the scattering of the raw material powder and the gas contact are prevented, but also the particle size of the granulated powder can be relatively uniform, and a uniform flow state can be expected, which is preferable. The average particle diameter of the granulated powder can be arbitrarily adjusted in consideration of the size of the flowable or the degree of scattering, and for example, it can be 1 to 1 0000 μm, and if it is 5 to 3 000 μm, the degree of scattering can be made smaller. Preferably, it is preferably from 10 to 1 000 μm, and particularly preferably from 20 to 500 μm. The granulated powder may have any shape such as a spherical shape, a substantially 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, and is preferably a shape that is easy to flow, for example, a ball. Shapes such as a spherical shape, a hollow shape, and the like are preferred. Further, when mixing, pulverizing, or granulating, an organic compound such as a surfactant, a resin, or a dispersing agent may be blended in the raw material powder as needed. In the case of granulation, in particular, when a resin is added during spray drying, in addition to the function of a binder, the granules of the granulated powder are adjusted to have a diameter of -20-200844071, and the resin is decomposed to form voids during firing to become porous. It is preferred to release the carbon dioxide inside the granulated powder. The material that can be used is not particularly limited, and the necessary amount can be appropriately selected depending on the purpose. For example, a water-based acrylic resin, an aqueous tri-cyanamide resin, or an aqueous urethane resin may be used as the resin, and the amount thereof is preferably from 1 to 20% by weight based on the raw material powder or the like. Then, the raw material powder or the like is placed in a firing device, and the temperature is raised from room temperature to a predetermined firing temperature, and a metal oxide is reacted with a metal carbonate or a decomposition of an organic compound is usually generated in a temperature region in the middle. carbon dioxide. The aeration of the gas used to flow the raw material powder to prevent the adsorption of carbon dioxide and to vent the carbon dioxide is carried out during the period from the start of the temperature range in which the carbon dioxide is generated to at least a portion of the end temperature region (preferably in all periods). Further, if necessary, the gas may be ventilated from the beginning of the temperature rise, or the gas may be ventilated between the end of the carbon dioxide generation and the completion of the firing, or may be cooled to the composite oxide powder obtained by the removal. The gas is ventilated during the period before the temperature. In the stage before and after the generation of the carbon dioxide, the raw material powder or the like may be caused to flow by the aeration of the gas, or the raw material powder or the like may be in a state of a fixed layer or a semi-fixed layer. The starting temperature of carbon dioxide generation varies depending on the type of metal oxide or metal carbonate used, the composition and the additive, etc., but the generation temperature and the end temperature of carbon dioxide can be grasped by thermal analysis of the raw material powder or the like. For example, the starting temperature of carbon dioxide in the raw material powder of the mixed titanium oxide and the cerium carbonate is about 500 degrees according to FIG. 1 'The gas is not ventilated from room temperature to 500 ° C. - 21 200844, preferably. The self-heating temperature is about 50 lower than the temperature at which carbon dioxide begins to be produced. (At the stage of temperature (that is, the stage of reaching about 45 ° C), the gas is ventilated. On the other hand, we believe that the end temperature of carbon dioxide is about 850 °C, so Gas venting is preferably performed between 5 0 0 and 8 5 ° C. Thereafter, any of the predetermined firing temperatures, between firing, and subsequent cooling may be performed without gas aeration. 'The gas can also be ventilated. The temperature rise rate from room temperature to the firing temperature can be set appropriately, or it can be maintained at 0. After 5 to 5 hours, the temperature was raised to the firing temperature. The baking temperature and the baking holding time can be set locally according to the composite oxide powder, and for example, it can be 500 to U00 ° C, and the firing time can be, for example, 0. 5 to 10 hours. In addition, after the completion of the firing, it must be cooled to the take-out temperature, and the cooling rate can be appropriately set, and the cooling can be gradually cooled or rapidly cooled. The firing device to be used may be a firing furnace used in a usual solid phase synthesis method or the like, or a heating furnace used in other inorganic chemical industries (especially in the ceramics industry), as long as it can be fired while flowing raw material powder or the like. The device can be used. It is generally preferred to use a fluidized bed firing furnace. The flow state during the generation of carbon dioxide can be adjusted by the particle size of the raw material powder and the flow rate (flow weight) of the ventilated gas. It is preferable that the raw material powder or the like in the fluidized bed firing furnace is formed in a flow state in which a uniform fluidized bed (complete fluidized layer) can be formed, and on the other hand, the effect of the present invention can be achieved by generating a fluidized layer in which the bubble is dense in the fluidized bed. 'It is also possible. Alternatively, a part of the raw material powder or the like may be formed into a fixed layer, and the rest may be in a flowing state as long as the effect of the invention can be achieved. It is difficult to flow under powdery sorrow, and gas vents are generated. Only [22-200844071 has a part of the raw material powder that can be in contact with the gas, or conversely, the buoyancy of the gas causes the raw material to fly and cannot be fired. Therefore, it is preferred that the raw material powder be granulated into an appropriate particle diameter. Since the amount of gas to be ventilated varies depending on the shape of the firing device, the amount of raw material powder, and the like, it cannot be specified at once. However, if a large amount of gas is ventilated, the raw material powder or the like may scatter, so it is necessary to consider crystallization. Improvements in the amount of sex and the amount of scattering are considered in order to achieve an appropriate ventilation of the effect of the invention. For example, in the case of using a granulated powder granulated into 50 to 1 〇〇μηι (in the case where the apparent specific gravity of the granulated powder is 1 g / c m 3 ), it is allowed to be at room temperature in a fluidized bed firing furnace. The gas line velocity at the position of the dispersing plate is 0. Starting at 9 c m / sec, at 1 . 7 c m / sec reaches a uniform flow state, and becomes a thick flow state after more than 1 〇 c m / sec, so the gas linear velocity is 1 . The degree of 7 to 10 cm/sec is particularly good. As the gas for aeration, a gas used in a firing device such as a normal fluidized bed firing furnace can be used. However, if carbon dioxide is contained, the crystallinity of the composite oxide powder is affected, so that it is not preferable, and it is necessary to select a gas having a small carbon dioxide content. Or a gas that does not contain carbon dioxide. Therefore, to use carbon dioxide containing tombs for 0~0. 5% of the gas is good. 'Better than the carbon dioxide content is 〇~〇·1% by volume, and even more preferably the carbon dioxide content is 〇~〇. 〇 5 vol%. As such a gas, for example, nitrogen, ammonia, nitrogen, air, oxygen, synthetic air, dry air, compressed air or the like can be used, and one or more gases selected from the group consisting of these can be used. A small amount of carbon dioxide of about 400 ppm is contained in air, synthetic air, dry air, and compressed air. This amount is confirmed to have no effect. Further, when air, synthetic air, dry air, or compressed air is used, since the raw material powder is not easily reduced at the time of firing -23·200844071, it is preferable to obtain a homogeneous composite oxide powder. The gas to be ventilated is preferably heated before being introduced into the firing device to prevent the temperature of the firing device from rapidly decreasing. Further, at least a part of the generated carbon dioxide can be discharged to the outside of the firing device by the aeration gas, and the ventilating gas can be recycled, and the carbon dioxide content in the circulating gas is determined as The foregoing range is preferred. By the above method, a composite oxide powder having fine particles and high crystallinity, in particular, a chitin-lock powder can be obtained. Specifically, § can be exemplified by a perovskite structure such as a succinate lock, a bismuth citrate, a lead titanate, a lead citrate, a lead zirconate titanate, a calcium modified barium titanate, a rare earth element modified barium titanate or the like. The compound or the atomic ratio of Ti/Ba is a polybasic titanate having a composition formula of 2 or more. The particle size of the obtained composite oxide powder is 〇. 〇1~0. The range of 3 μιη is better, with 〇·〇15~0. The range of 3 μπι is better, with 0. 02~0. The range of 3 μιη is better, with 0. 03~0. The range of 3 μιη is even better, with 0. 05~0. The range of 3 μιη is particularly good, with 0. 0 6~0. The range of 1 5 μηη is particularly good. The particle diameter (d) of the composite oxide powder is assumed to be spherical, and the specific surface area a (m2/g) obtained by the BET method is determined by the following formula 2. Equation 2 . . . . . . d = (6/ p )/a where P is the specific gravity and p = 5. for barium titanate. 90. Further, the crystallinity of the obtained composite oxide powder is measured by X-ray diffraction, and is evaluated by the peak height or half width 绕 of the diffraction peak of the specific crystal face, and can be performed based on the X-ray diffraction data when more precise is required. Litbe-24 - 200844071 Erte analysis for judgment. In particular, in the case of barium titanate powder, it is judged from the ratio of the c-axis to the a-axis of the crystal lattice (c/a-axis ratio), and the larger the c/a-axis ratio, the crystallinity of the tetragonal barium titanate. high. Specifically, according to the method of the present invention, the c/a axis can be made to be 1. Above 0033, preferably 1. 0033~1. The range of 011 is better, and the better is 1·〇〇6~1. The range of 011 is 1. 006~1. The range of 010, the best is 1. 007~1. The range of 010. In particular, if a gold sulphurization rate determined by X-ray diffraction is more than 90% by weight and is 100% or less, a specific surface area is 150 to 300 m2/g of titanium oxide, and barium titanate powder c/ The a-axis ratio can be better. 0075~1. A better range of 010, or even 1 . 〇 〇 8 0~1 · 0 1 更 Better range. When a composite oxide powder having reduced crystallinity, in particular, barium titanate powder which is less than 1 · 〇〇 3 3 is used as an electronic component, the dielectric property of the semiconductor is insufficient, so that the c/a axis is made. The ratio is increased as a result of further heat treatment resulting in particle growth. The theoretical 値 of the c/a ratio of tetragonal barium titanate is a = 3. 994, c = 4. 038 calculates c/a=1. 011, on the other hand, the c/a axial ratio of cubic crystal bismuth is 1. 0 0 0. The composite oxide powder can be pulverized as needed. As the pulverizer, a pulverizer such as a compression pulverization type, an impact compression pulverization type, a shear pulverization type, or a friction pulverization type can be used, and a compression pulverizer is preferably used. The so-called compression pulverizer is a pulverizer having a compression action and a grinding action, and when the composite oxide powder is placed in a compression pulverizer, it is pressed into a sheet shape by compression, and also by friction. It can be crushed finely. As the compacting pulverizer, for example, a masher, an edge runner mill, a roll honing machine, and a fret mill can be used. -25- 200844071 Further, an additive may be mixed in the composite oxide powder as needed. As the additive, it is possible to suitably use, for example, rare earth elements such as lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, bait, and mirror, aluminum, lanthanum, manganese, iron, nickel, copper, zinc, lanthanum according to the characteristics required for the ceramic composition. , bismuth, tungsten, antimony and other elements. Further, examples of the additive for controlling the growth of the particles and the electrical properties of the ceramic composition during sintering include, for example, boron, barium, and alkali metals such as lithium, sodium, and potassium, iron, manganese, cobalt, nickel, rhodium, and the like. A compound that transfers metals, even elements such as bismuth and aluminum. These additives may be added during the pulverization stage of the composite oxide powder or may be mixed after pulverization. Alternatively, it is added at any stage of the sintering step of the composite oxide powder. The amount of addition can be appropriately set as necessary. Mixers are available for use in mixers commonly used in the inorganic chemical industry (especially in the ceramics industry) or in the electronics industry. Further, an organic compound such as a surfactant, a resin or a dispersant may be added during pulverization or mixing. In this way, the ceramic composition material can be prepared. The above-mentioned ceramic composition raw material containing at least a composite oxide powder can be preferably used for a material such as a ceramic electronic component by sintering as a ceramic composition. The ceramic electronic component includes the ceramic composition and an electrode disposed to face the ceramic composition. Further, the ceramic electronic component is provided with a plurality of layers including a ceramic composition and electrodes formed between the layers of the ceramic composition. The specific laminated ceramic electronic component is a laminated ceramic capacitor comprising a plurality of laminated ceramic composition layers (dielectric layers) and a laminate of internal electrodes formed along the interface between the ceramic composition layers. The first internal electrode and the second internal electrode as electrodes are alternately arranged in the laminate, and the first internal electrode is connected to the first external electrode, and the second internal electrode is connected to the second internal electrode in the same manner. The connection is formed such that each end edge is exposed to the end surface of the laminate. As the electrode, for example, an alloy of platinum, palladium, nickel, an equivalent metal or the like can be used. The thickness of each layer of the ceramic composition of the laminated ceramic electronic component is preferably as thin as possible, preferably 1 μm or less. Ceramic compositions and ceramic electronic parts can be manufactured by conventional methods. For the production of the ceramic composition, for example, a ceramic composition material containing at least a composite oxide powder may be mixed with a binder, and then subjected to pressure molding to form a green pallet of a predetermined shape, or a sheet forming method. Or a method such as a printing method forms a green sheet of a predetermined thickness on a substrate and then performs sintering. For the production of ceramic electronic parts, for example, a method of printing or coating a paste for electrode metal on both sides of the green granules may be used, or sintering may be performed; or the green sheet may be formed and then printed thereon. Alternatively, a method in which a paste of an electrode metal or the like is applied, and sintering is performed after repeated several times. The sintering condition can be appropriately set depending on the degree of sintering of the ceramic composition, and the sintering temperature is preferably, for example, 1 Torr to 1 500 ° C, and more preferably 1 100 to 130 ° C. . The sintering time can also be set locally depending on the composition of the ceramic composition material. It is better to use 〇·5~10 hours. The ambient gas during sintering may be oxygen-containing gas such as oxygen, air, synthetic air, dry air, compressed air, etc., so that the gas for oxidizing the electrode with the metal is not preferred, and preferably, the gas may be used. An oxidizing gas such as nitrogen, helium, neon or the like, and a reducing gas such as hydrogen, carbon monoxide or money can be preferably used. -27- 200844071 [Examples] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the examples. (Example 1) A commercially available titanium oxide (specific surface area: 190 m 2 /g) and cerium carbonate (specific surface area: 30 m 2 /g) were weighed so that the atomic ratio of cerium/titanium became 1. 000, wet pulverizing mixing with a ball mill. A water-based acrylic resin (8% by weight) was added to the obtained mixed slurry of titanium dioxide and cesium carbonate, and dried and granulated by a spray dryer. The average particle size of the granulated powder is 50 μm. Then, the granulated powder was placed in a vertical small-sized fluidized bed firing furnace as a flowing gas system to dry air (having a degree of carbon dioxide of 400 ppm) at a gas line speed of 1. At a temperature of 73 cm/sec, the granulated powder was heated from room temperature to 900 °C, and the mixture was heated for 1 hour to be calcined to obtain a barium titanate powder of the present invention (sample A). Further, the ventilation of the dry air is performed between the start of the heating until the sample is taken out, and the granulated powder is caused to flow by the aeration of the dry air, and the generated carbon dioxide is discharged to the outside of the system. (Example 2) The barium titanate powder of the present invention (sample B) was obtained in the same manner as in Example 1 except that the firing temperature was set to 95 (TC). - 200844071 (Example 3) The barium titanate powder of the present invention (sample C) was obtained in the same manner as in Example 1 except that the firing temperature was set to 1000 °C. (Example 4) A titanium oxide obtained by drying a product obtained by neutralizing titanium tetrachloride at a temperature of 130 ° C was weighed (the specific surface area measured by the above method was 1 90 m 2 /g, and the average major axis diameter) Spindle-shaped titanium dioxide with 80 nm and axial ratio of 3, Ti〇2 purity 99. 9 8 wt%, gold red petrochemical rate of 100 ° /. , rutile crystal knot, lattice diameter 9 nm, 50% cumulative diameter in water 0. 077 μηι) and barium titanate (specific surface area 30 m2/g), making the atomic ratio 1. 000, wet pulverizing and mixing by a ball mill, and the obtained mixed slurry was dried by a spray dryer and granulated. The granulated powder has an average particle diameter of 50 μm. Then, the granulated powder was placed in a vertical small-sized fluidized bed firing furnace as a flowing gas system to dry air (having a degree of carbon dioxide of 400 ppm) at a gas line speed of 1. The air was ventilated at 73 cm/sec, and the temperature of the granulated powder was raised from room temperature to 95 0 °C under the flow of the granulated powder. The baking was carried out for 5 hours/the barium titanate powder of the present invention (sample D) was obtained. Further, the ventilation of the dry air is performed between the start of the heating until the sample is taken out, and the granulated powder is flowed by the aeration of the dry air to discharge the generated carbon dioxide to the outside of the system. (Example 5) 29-200844071 The barium titanate powder of the present invention (Sample E) was obtained in the same manner as in Example 4 except that the holding time was set to 1 hour. (Embodiment 6) In the foregoing Embodiment 4, except that the holding time is set to 〖. The barium titanate powder of the present invention (sample F) was obtained in the same manner as in Example 4 except for 5 hours. (Comparative Example 1) A granulated powder (having an average particle diameter of 50 μm) was obtained by a spray structure machine in the same manner as in Example 1, and then the obtained granulated powder was placed in a 50 cc crucible. The thickness of the crucible is 20 mm, and the crucible is placed in a fixed bed electric furnace, and is heated from room temperature to 850 ° C in the atmosphere (without blowing air), and baked for 5 hours to obtain barium titanate. Powder (sample G). (Comparative Example 2) A granulated powder (having an average particle diameter of 50 μπα) was obtained by a spray structure machine in the same manner as in Example 1, and then the obtained granulated powder was placed in a 50 cc crucible. It has a thickness of 20 mm, and the crucible is placed in a fixed bed electric furnace capable of controlling ambient gas, and is heated from room temperature to 900 ° C under reduced pressure (1 〇 Pa to 100 Pa), and kept for 5 hours for firing. , barium titanate powder (sample H) was obtained. -30- 200844071 (Comparative Example 3) A commercially available titanium dioxide (specific surface area: 19 〇 m 2 /g) and cerium carbonate (specific surface area: 30 m 2 /g) were used to make the atomic ratio of cerium/titanium to 1 Å. The mixture was wet-pulverized and mixed by a ball mill, and then the mixed slurry was evaporated to dryness, and pulverized by a pile grinder to obtain a raw material powder. Then, the raw material powder was placed in a 5 〇cc crucible to a thickness of 20 mm. The crucible was placed in a fixed bed electric furnace and heated from room temperature in the atmosphere (without blowing air). 8 〇〇 °c, and baking was carried out for 5 hours, and the barium titanate powder (sample I) was obtained. (Comparative Example 4) In the same manner as in Comparative Example 3, a barium titanate powder (sample) was obtained in the same manner as in Comparative Example 3 except that the firing temperature was changed to 85 Torr. (Comparative Example 5) Raw material powder was obtained in the same manner as in Comparative Example 3, and then the obtained raw material powder was placed in a 50 cc crucible to have a thickness of 2 mm, and the crucible was placed in a controllable area. In a gas fixed bed electric furnace, the temperature was raised from room temperature to 90 (rc, under reduced pressure (10 Pa to 100 Pa), and calcined for $hour to obtain barium titanate powder (sample K). (Comparative Example 6) The raw material powder was obtained in the same manner as in Comparative Example 3. Then, the obtained raw material powder was placed in a 50 cc crucible to have a thickness of 2 〇 mm 31 - 200844071, while nitrogen gas (purity of nitrogen was 99. 999 vol%) was blown at a flow rate of 4 L/min. From room temperature to 8 75 ° C, and baking was carried out for 5 hours to obtain barium titanate powder (sample L). Further, the nitrogen gas is ventilated between the start of the heating until the sample is taken out, and the granulated powder is caused to flow by the aeration of nitrogen gas, and the generated carbon dioxide is discharged to the outside of the system. (Comparative Example 7) Raw material powder was obtained in the same manner as in Comparative Example 3, and then the obtained raw material powder was placed in a 50 cc crucible to have a thickness of 20 mm while carbon dioxide (carbon dioxide purity of 99. 5 vol%)) was blown at room temperature to 800 °C at a flow rate of 4 L/min, and baked for 5 hours to obtain barium titanate powder (sample M). Further, the ventilation of carbon dioxide is performed between the start of the heating until the sample is taken out. The specific surface area a (m 2 /g) of the sample A to bismuth titanate powder obtained by the different baking treatments was measured by a simple BET method, and the powder was assumed to be a sphere, and the average particle was obtained by the above formula 2. The diameter (1 (μιη). The data obtained by the X-ray diffraction method was analyzed by Littbelt analysis to determine the lattice constants a and c of the tetragonal barium titanate, and the crystallinity evaluation (orthogonality) c/ was calculated. From the results obtained, it is understood that the barium titanate powder of the present invention has a particle diameter and a c/a axial ratio which are equivalent to those fired under vacuum (under reduced pressure), and has excellent tetragonality ( On the other hand, it has an excellent c/a axial ratio based on the same degree of particle diameter as compared with the firing of a fixed bed firing apparatus in a nitrogen atmosphere under a nitrogen atmosphere and a carbon dioxide atmosphere. 32- 200844071 [Table i] Sample No. Burning Condition Ti〇2+BaC〇3 The characteristic particle diameter of the barium titanate obtained from the raw material powder (μιη) c/a axis ratio Example 1 A Flow layer (dry air ventilation) Granular powder 0. 131 1. 0081 Example 2 B Flow layer (dry air aeration) Granulation powder 0. 134 1. 0080 Example 3 C Flow layer (dry air aeration) Granulation powder 0. 200 1. 0083 Example 4 D Flow layer (dry air aeration) Granulation powder 0. 101 1. 0089 Example 5 E Flow layer (dry air aeration) Granulation powder 0. 120 1. 0095 Example 6 F Flow layer (dry air aeration) Granulation powder 0. 079 1. 0079 Comparative Example 1 G Fixed bed (no gas aeration) Granulated powder 0. 138 1. 0063 Comparative Example 2 固定 Fixed bed (under reduced pressure) Granulated powder 0. 129 1. 0083 Comparative Example 3 I Fixed bed (no gas aeration) Powder 0. 117 1. 0056 Comparative Example 4 J Fixed bed (no gas venting) Powder 0. 148 1. 0067 Comparative Example 5 K Fixed bed (under reduced pressure) Powder 0. 129 1. 0087 Comparative Example 6 L Fixed bed (nitrogen aeration) Powder 0. 120 1. 0069 Comparative Example 7 固定 Fixed bed (carbon dioxide ventilation) powder 0. 132 1. The results of the experiments described in Examples 1 to 6 were carried out several times, and it was confirmed that the quality of the obtained barium titanate powder was small. Further, it has been confirmed that, in addition to the barium titanate of the present invention, barium titanate, lead titanate, lead chromate, lead titanate citrate, calcium-modified barium titanate, rare earth element modified barium titanate, etc. A compound of a perovskite structure or a polybasic barium titanate having an atomic ratio of Ti or Ba of 2 or more may be produced in the same manner. Further, the obtained composite oxide powder was sintered to obtain a ceramic composition, and when it was used as a ceramic electronic component, the superiority of the present invention was confirmed. (Industrial Applicability) -33- 200844071 Since the composite oxide powder of the present invention is fine particles and has high crystallinity, it can be easily and easily produced with excellent dielectric properties and piezoelectricity by sintering it. Ceramic composition of properties such as sex. The use of the ceramic composition in ceramic electronic parts, especially laminated ceramic electronic parts, is expected to meet the requirements of miniaturization, weight reduction, high performance, and multi-functionality. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the weight reduction of a raw material powder of cerium oxide and cerium carbonate powder in thermal analysis. Fig. 2 is a photomicrograph showing the particle structure of the titanium oxide used in Example 4. 3 is an X-ray diffraction pattern of titanium oxide used in Example 4. -34-