201217272 六、發明說明： 【發明所屬之技術領域】 本發明係關 電體、半導體、 粒子、其製造方 的製造方法。 〜％ %竹、介 感應器等功能性陶瓷材料的草酸鈦氧基 法以及使用該草酸鈦氧基鋇鋇 ”卿卞之鈦酸鋇 【先前技術】 燒氧化物 以往，鈦酸鋇可藉由固相法、水熱合成法 法、草酸鹽法等而製造。 固相法中’由於係藉由混合構成原料粉末等、田 加熱該混合物之乾式方法而製造，所得到之粉末呈不規: 形狀成為凝集體’再者，為了達成所期望的特性必… ，燒。水熱合成法即使具有粉體的特性為良好的優點二 是合成步驟複雜’由於使用高壓釜而生產性差，製造於： 的價格高’於工業上非有利的。至於院氧化物法同樣二 由於起始物質的操作困冑’價格高，於卫業上非有利的。 以草酸鹽法所製得之鈦酸鋇，與水熱合成法或院氧化 勿法相比較’可價廉地製造組成為均一者’再者，與以固 相法所製造之鈦酸鋇相比較，具有組成均-的特徵。以往 之草酸鹽法’-般而言係將TiCh與純2的水溶液，於擾 拌下滴加i _4水溶液中，製得草酸欽氧基鋇，將該草 酸鈦氧基鋇锻燒的方法（例如參照非專利文獻丨及專利文 獻1)〇 201217272 【先前技術文獻】 【專利文獻】 專利文獻1:日本特開2005-500239號公報 .【非專利文獻】 非專利文獻 1: W. S. Clabaugh et al.，J. Res. Nat201217272 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing an electric body, a semiconductor, a particle, and a manufacturer thereof. ~%% of the functional ceramic materials such as bamboo, medium inductors, and the use of the titanyl oxalate method and the use of the titanyl oxalate bismuth strontium titanate [prior art] calcined oxide, in the past, barium titanate can be used It is produced by a solid phase method, a hydrothermal synthesis method, an oxalate method, etc. In the solid phase method, it is produced by mixing a dry method of heating the mixture by constituting a raw material powder or the like, and the obtained powder is irregular. : The shape becomes agglomerate. 'In addition, in order to achieve the desired characteristics, it is necessary to burn. The hydrothermal synthesis method has the advantage of having a powder property, and the synthesis step is complicated. The production is poor due to the use of an autoclave. The price of 'high' is not economically advantageous. As for the oxide method of the hospital, the same is due to the operation of the starting material. The price is high, which is not beneficial to the health industry. Titanic acid prepared by the oxalate method钡Compared with the hydrothermal synthesis method or the hospital oxidation method, the composition can be manufactured at a low cost and the composition is uniform. Compared with the barium titanate produced by the solid phase method, it has the characteristics of uniform composition. Oxalate method'- In the case of adding an aqueous solution of TiCh and pure 2 to an aqueous solution of i_4 under stirring, a method of calcining oxalic acid and preparing the calcined titanyl oxalate is carried out (for example, refer to the non-patent literature and patents). [1] 先前 201217272 [Prior Art Document] [Patent Document] Patent Document 1: JP-A-2005-500239. Non-Patent Document 1: Non-Patent Document 1: WS Clabaugh et al., J. Res. Nat
Bur. Stand., 56(5), 289-291(1956) 【發明内容】 I發明所欲解決之課題】 藉由草酸鹽法所製得之鈦酸鋇，作為介電體陶变的材 料時，除了發揮優異性能外，由於近年的要求性能變高， 期望更使性能提升。鈦酸鋇之作為介電體陶 般而言已知結晶性高者介電特性也優異（例如參照日本』 利特開2_一1 17446號公報）。再者，於草酸鹽法中，有卖 於製得粒子徑小者’即使製得也有難以得到結晶性高者白 問題。 以往，藉由草酸鹽所製得之草酸鈦氧基鋇粒子，多 的障況為平均粒徑為100至200 " m .. 糖狀。 00以m’以之粒子形狀為金 本發明者們發現於草酸鹽 的批次式進杆“ 毁孤法中，替代反應形態以習: 比習知者疋喂沄進仃，可得平均粒子4 Η者更小且其粒子形狀為 用該球狀之草者再者，發現藉由4 早酸鈦氧基鋇粒子，Bur. Stand., 56(5), 289-291 (1956) [Disclosed] The subject of the invention is to solve the problem of strontium titanate prepared by the oxalate method as a dielectric ceramic material. In addition to the excellent performance, it is expected to improve performance due to the high performance required in recent years. In the case of a barium titanate, it is known that a high crystallinity is also excellent in dielectric properties (see, for example, Japanese Patent Laid-Open No. Hei 2 No. 1-17446). Further, in the oxalate method, there is a problem that a particle diameter is small, and even if it is obtained, it is difficult to obtain a white matter with high crystallinity. In the past, the barium titanyl oxalate particles prepared by the oxalate have a plurality of barriers having an average particle diameter of 100 to 200 " m .. sugar. 00 in m's particle shape as gold, the inventors found in the oxalate batch-type "in the ruin method, instead of the reaction form to learn: than the learned 疋 feed into the 仃, can get average Particle 4 is smaller and its particle shape is the same as that of the spheroidal grass. It is found that by 4 early acid titanate particles,
異性能之草酸斂备A 袈k具有結晶性更高I 子歟鈦氧基鋇粒子。 卜本發明者們發現藉ΐ 201217272 以特定溫度範圍進行康嬙 草酿^ ^ 良好收率製得球狀的 草酸鈦氧基鋇粒子’因而完成本發明。 因此，本發明之目 狀之草酸㈣供為係且具找狀的粒子形 氧基鋇粒子。再者’提供該微細之球狀的草酸 鈦氧基鋇粒子之工金λ 之工業上有利的製造方法。此外.，本發明提 供結晶性優異之草酸鈦氧基鋇粒子。 【解決課題之手段】 本發明所提供之第1發明為以平均粒子徑0.丨至 5。"ill，粒子形狀為球狀為特徵之草酸鈦氧基鋇粒子。 再者，本發明所提供之第2發明為提供一邊將草酸及 四氣化欽混合於水中所得之水溶液U1液），以及氯化鎖水 溶液（M液）供給至反應容器，一邊由該反應容器排出反應 液’以未達50°C進行草酸鈦氧基鋇的生成反應為其特徵之 草酸鈦氧基鋇粒子的製造方法者。 再者，本發明所提供之第3發明為提供一邊將草酸水 溶液（A2液），以及四氯化鈦及氣化鋇混合於水中所得之水 :谷液（B2液），供給至反應容器，一邊由該反應容器排出反 應液，以未達50 °C進行草酸鈦氧基鋇的生成反應為其特徵 之草酸鈦氧基鋇粒子的製造方法者。 再者’本發明所提供之第4發明為提供一邊將草酸水 溶液（A3液）、氣化鋇水溶液（B3液）以及四氣化鈦混合於水 中所％之水溶液（C3液），供給至反應容器，一邊由該反應 容器排出反應液，以未達50°C進行草酸鈦氧基鋇的生成反 應為其特徵之草酸鈦氧基鋇粒子的製造方法者。 201217272 再者’本發明所提供之第5發明為提供將進行前述第 2至4發明中之任一發明所述之草酸鈦氧基鋇粒子的製造 方法所得之草酸鈦氧基鋇粒子烺燒為其特徵之鈦酸備的製 造方法。 【發明效果】 本發明之基鋇Μ為微細且纟子形狀為球狀 者’再者’ «本發明的製造方法’該草紐氧基鎖粒子 可以工業上有利的方法’有效率的製造。再者，藉由使用 該等球狀之草酸欽氧基鋇粒子，可提供結晶性高、具有優 異性能之介電體陶瓷料。 【實施方式】 以下，根據較佳的實施形態說明本發明。 本發明的草酸鈦氧基鋇輪 ㈣子’細往的草酸鈦氧基類 粒子相比較，微細且其粒子形狀有特徵。 相對於以習知的批次式 车ίΛΦ私从u 传之草酸欽氧基鋇粒子於多 丰的雷射繞射-散射法所求 上，較佳為刚至150"m，本路均粒子控為100… 雷射繞射衍射法所求得之…明的草酸鈦氧基鋇粒子以 佳為5至40, “ 子徑為0.1至5。”.，較 住馬5至40# m，更較佳為 為極微粒者》 V m，與習知者相比較 進一步地，本發明之苗 .+ 草酸銀氧基鋇粒子，其粒早來狀 為球狀亦為特徵之一。 丁具桩子形狀 該粒子形狀以500倍的件 倍率的電子顯微鏡觀察時，其 201217272 粒子形狀以觀察到為球狀的形狀為限，不必要為真正球狀。 再者，本發明之草酸鈦氧基鋇粒子以2〇〇〇倍的倍率的 掃也型電子顯微鏡觀察時的粒子表面為光滑，實質上無角 的粒子為特徵之一。 本發明之草酸鈦氧基鋇粒子的製造方法係一邊將草酸 鈦氧基鋇的生成反應的反應原料之草酸（jj2C2〇4)、氣化鋇 (BaCh)及四氣化鈦（TiCh)的水溶液，供給至反應容器，一 邊將反應溶液由反應容器排出，以未達5〇r進行草酸鈦氧 基鋇的生成反應之草酸鈦氧基鋇粒子的製造方法。因此， 本發明之草酸鈦氧基鋇粒子的製造方法，根據反應原料水 溶液的種類而有以下的形態。 又，本發明中，作為反應液為反應原料水溶液經供給 於反應容器内的液體、草酸鈦氧基鋇的生成反應所產生的 液體、含有所生成之草酸鈦氧基鋇的沉澱物的液體。 本發明之第一形態的草酸鈦氧基鋇粒子的製造方法為 一邊將草酸及四氣化鈦混合於水中所得之水溶液（液）， 以及氣化鋇水溶液（B1液）供給至反應容器，一邊由該反應 谷器排出反應液’以未達50。(：進行草酸鈦氧基鋇的生成反 應的草酸欽氧基鋇粒子的製造方法。 本發明之第二形態的草酸鈦氧基鋇粒子的製造方法為 一邊將草酸水溶液（A2液），以及四氣化鈦及氯化鋇混合於 水中所得之水溶液（B2液），供給至反應容器，一邊由該反 應容器排出反應液，以未達5〇°C進行草酸鈦氧基鋇的生成 反應的草酸欽氧基鎖粒子的製造方法。 7 201217272 本發明之第三形態的草酸鈦氧基鋇粒子的製造方法為 一邊將草酸水溶液（A3液）、氣化鋇水溶液（B3液）以及四氣 化鈦混合於水中所得之水溶液（(：3液），供給至反應容器， 一邊由該反應容器排出反應液，以未達5(rc進行草酸鈦氧 基鋇的生成反應的草酸鈦氧基鋇粒子的製造方法。 亦即，本發明之第一形態的草酸鈦氧基鋇粒子的製造 方法，係使用草酸及四氣化鈦混合於水中所得之水溶液以} 液），以及氯化鋇水溶液（B1液）作為反應原料水溶液的 態。 本發明之第一形態的草酸鈦氧基鋇粒子的製造方法中 之A1液為草酸及四氯化鈦混合於水中所得之水溶液，例 如’藉由首先將四氣化鈦混合於水中，其次將草酸混合於 所得之水溶液，或將四氯化鈦混合於草酸水溶液中而調 製。相對於以溶液中的Ti元素’草酸離子的莫耳比(草酸 離子的莫耳數/Ti元素的莫耳數）為2()至3.8,較佳為2 8 至3.. 8,更佳為3.〇至3. 藉由相對於M液中的n元素， 草酸離子的莫耳比為上述範圍，容易得到莫耳比為 "8至1.002之接近1的鈦酸鋇。再者μ液中的h元 素漠度雖無特別限制，而較佳為。〇4至3. 二： *·、、 ·至〇. 6m〇l/L。A1液中的草酸離子濃度，雖盔 別限制’較佳Λ 〇.….Omol/L，特別較佳為"至 1.4m〇l/L 〇 本發明之第一形態的草酸鈦氧基鋇粒子的製造方法中 之B1液為氣化鋇水溶液，液中的Ba元素的濃度，雖無 201217272 特別限制，而較佳為〇.〗至6. 5mol/L，将別較佳為〇 5至 1.3mol/L 。 本發明之第一形態的草酸鈦氧基鋇粒子的製造方法 中，藉由將A1液與B1液供給至反應容器，於反應容器内， 以未達50°C進行草酸鈦氧基鋇的生成反應。 此時，對反應容器之相對於Ti元素供給速度的Ba元 素供給速度比（Ba元素供給速度/Ti元素供給速度）為〇 5 至3. 0 較佳為1. 〇至1. 5。對反應容器之相對於τ丨元素 供給速度的Ba元素供給速度比，藉由為上述範圍，可得到 Ba/Ti莫耳比0.998至1.002之接近1的鈦酸鋇粒子。 本發明之第一形態的草酸鈦氧基鋇粒子的製造方法 中’藉由適宜選擇A1液中的Ti元素濃度、B1液中的Ba 元素濃度、A1液的供給速度（L/小時）及μ液的供給速度 (L/小時）’可調節對反應容器之相對於Ti元素供給速度的 Ba元素供給速度比。 又’本發明中’對反應容器之Ti元素供給速度，意指 每單為時間之π元素供給莫耳數（莫耳/小時），再者，Ba 元素供給速度’意指每單為時間之Ba元素供給莫耳數（莫 耳Λ】、時），草酸離子供給速度，意指每單位時間之草酸離 子供給莫耳數（莫耳/小時）。 因此’本發明之第一形態的草酸鈦氧基鋇粒子的製造 方法中’ 一邊將A1液及B1液供給至反應容器，一邊將反 應容器内所生成之含有草酸鈦氧基鋇的沉澱物的反應液， 由反應容器排出。此時，供給至反應容器之A1液及B1液 201217272 之合計量’與由反應容器排出之反應液的量為同量，於安 定地進行反應方面為較佳。例如，較佳為一邊將A1液以 al(L/小時）、B1液以bl(L/小時）的供給速度供給至反應容 器，且一邊由反應容器將反應液以al+bl(L/小時）的排出 速度排出。 本發明之第二形態的草酸鈦氧基鋇粒子的製造方法為 使用草酸水溶液（Α2液）與四氣化鈦及氣化鋇混合於水中所 得之水溶液（Β2液）作為反應原料水溶液之形態。 本發明之第二形態的草酸鈦氧基鋇粒子的製造方法中 之Α.2液為草酸水溶液。仏液中的草酸離子濃度， 別限制，較佳為 〇 Ί $ 7 η 1 /Τ 、 救佳馬0,1至7.0mol/L，特別較佳為〇,6至 1.4mol/L 〇 ——职桠于的製造方法中 Sr先為：氣:欽及氣化鋇混合於水中所得之水溶液，例 ^ 氯钱混合於水中.，其切氯化鋇混合於所 ^之^溶液中.，或將四氯域混合於氯化鋇水 :。相對…液中的Ti元素，^元素 ： 素的莫耳數/π元素的莫耳數） 、(Ba ^ s , )為〇.5至3.0，較佳為彳n 至u。藉由相對於B2液中的Ti , =範圍’容易得S"a/Ti莫耳比為。 、 接近1的鈦酸鋇。再者，β2液 .002之 限制，而較佳為0 Q4 1 70素濃度雖無特別 权住為 0· 04 至 4. Om〇1/L， O.Smol/L。B2液中的^元素^ 彳為0. 2至 為〇. 08至6 5mol/L Μ …又 無特別限制，較佳 〇1/L’特別較佳為 201217272 本發明之第二形態的草酸欽氧基鋇粒子的製造方法 中，藉由將A2液與B2液供給至反應容器，於反應容器内， 以未達50°C進行草酸鈦氧基鋇的生成反應。 此時’對反應容器之相對於Ti元素供給速度的草酸離 子供給速度比（草酸離子供給速度/Ti元素供給速度）為 2.0至3.8’較佳為2.8至3.· 8，特別較佳為3.0至3.3。 對反應容器之相對於Ti元素供給速度的草酸離子供給速 度比，藉由為上述範圍，可得到Ba/Ti莫耳比〇. 998至〇〇2 之接近1的鈦酸鋇粒子。 本發明之第二形態的草酸鈦氧基鋇粒子的製造方法 中’藉由適宜選擇A2液中的草酸離子濃度、B2液中的n 元素濃度A2液的供給速度（L/小時）及B2液的供給速度 (L/小時）’可調節對反應容器之相對於Ti元素供給速度的 草酸離子供給速度比。 、因此本發明之第二形態的草酸鈦氧基鋇粒子的製造 方法' 邊將A2液及B2液供給至反應容器，一邊將反 應谷器内所生成之含有草酸欽氧基鎖的沉殿物的反應液， 由：應谷器排出。此時.，供給至反應容器之Μ液及Μ液 ^計量’與由反應容器排出之反應液的量為同量’於安 、行反應方面為較佳。例如，較佳為一邊將Α2液以 3- 2 C L / y Jχ Βτί· ^ ^ R Ο ά 1 。 液以b2(L/小時）的供給速度供給至反應容 °° .邊由反應容器將反應液以a2+b2(L/小時）的排出 速度排出。 $ 本發明之第三形態的草酸銥氧基鋇粒子的製造方法為 201217272 使用草酸水溶液（A3液）與、氣化鋇水溶液液）及四氣化 見σ於水中所得之水溶液（C3液）作為反應原料水溶液之 形態》 本發明之第三形態的草酸鈦氧基鋇粒子的製造方法中 之A3液為草酸水溶液βΑ3液中的草酸離子濃度，雖無特 別限制，較佳4 i 7 〇m〇1/L ’特別較佳為〇 6至 1.4mol/L 。 本發明之第三形態的草酸鈦氧基鋇粒子的製造方法中 之B3液為氯化鋇水溶液。B3液中的&元素漠度，雖㈣ 别限制’較佳為〇」至6 5m〇1/L，特別較佳為至 1.3mol/L 。 本發明之第三形態的草酸欽氧基鋇粒子的製造方法中 之C3液為四氯化鈦混合於水中所得之水溶液。c3液中的 Π元素濃度，雖無特別限制’較佳為〇 〇4至6 〇jn〇i/L， 特別較佳為0..2至3. 〇m〇i/L。 本發明之第三形態的草酸鈦氧基鋇粒子的製造方法 :，藉由將A3液、B3液及C3液供給至反應容器，於反應 容器内’以未達5Gt進行草酸鈦氧基鋇的生成反應。 此時’對反應容器之相對於Ti元素供給速度的h元 素供給速度比（Ba元素供給速度/Ti元素供給速度）為U 至3.0 ’較佳為1.〇至15。對反應容器之相對於η元 供給速度的Ba元素供給速度比，藉由為上述範圍，可得到 Mi莫耳比ο.998 ^·002之接近ι的鈦酸鋇粒子。再 者’對反應容器之相對於以素供給速度的草酸離子供給 12 201217272 速度比（草酸離子供給速度/Ti元素供給速度）為2.0至 3.8’較佳為2.8至3_8。對反應容器之相對於Ti元素供 給速度的草酸離子供給速度比’藉由為上述範圍，可得到 Ba/Ti莫耳比0.998至1.002之接近i的鈦酸鋇粒子。 本發明之第三形態的草酸鈦氧基鋇粒子的製造方法 中，藉由適宜選擇A3液中的草酸離子濃度、B3液中的Ba 元素濃度、C3液中的Ti元素濃度、A3液的供給速度（L/ 小時）、B3液的供給速度（L/小時）及C3液的供給速度（L/ 小時），可調節對反應容器之相對於Ti元素供給速度的Ba 元素供給速度比及對反應容器之相對於Ti元素供給速度 的草酸離子供給速度比。 因此，本發明之第二形態的草酸鈦氧基鋇粒子的製造 方法中’ 一邊將A3液、B3液及C3液供給至反應容器，一 邊將反應容器内所生成之含有草酸鈦氧基鋇的沉澱物的反 應液，由反應容器排出。此時，供給至反應容器之A3液、 B3液及C3液之合計量，與由反應容器排出之反應液的量 為同量，於安定地進行反應方面為較佳。例如，較佳為一 邊將A3液以a3(L/小時）、B3液以b3(L/小時）、C3液以 c3(L/小時）的供給速度供給至反應容器，且一邊由反應容 器將反應液以a3+b3 + c3(L/小時）的排出速度排出。 本發明之草酸欽氧基鋇粒子的製造方法，例如可使用 圖1所示之溢流（over flow)方式的反應容器進行。圖 溢流方式之反應容器的模式刮面圖。圖1中，溢流方式的 反應容器1具有可裝設於反應容器側壁上部的溢流管2。 13 201217272 因此’於溢流方式的反應容器1中，由於溢流管2成為反 應液的排出口 .，反應液3的液面4的高度，通常成為益节 管2的裝設位置高度’只將供給反應原料水溶液的部八， 反應液3由溢流管2溢流’由溢流方式的反應容器排出。 亦即’於溢流方式的反應容器1中，對反應容器的反應原 料水溶液供給量，與由反應容器的反應液排出量，通常可 為同量。因此，使用溢流方式的反應容器，可—邊將反應 原料水溶液供給至反應容器，一邊將反應液由反應容器排 出。又’圖1中，溢流方式的反應容器1實際上具有其他 例如授拌裝置、加熱裝置、反應原料供給管等， *一句說明 的便利上，僅記載反應容器的輪廓，省略其他的記載。 用於進行本發明之草酸鈦氧基鋇粒子的製造方法的反 應容器’並不限定為溢流方式的反應容器，其他例如可列 舉於内部設置攪拌裝置、裝設有附有可調節反應原料水溶 液供給量的泵等之供給管以及附有可調節反應液排出量的 閥等排出管之密閉式反應容器，或於内部設置攪拌裝置、 裝叹有附有可調節反應原料水溶液供給量的泵等之供給管 以及利用泵等使反應液以一定速度排出的排出管之密閉式 反應容器等。 "" 本發明之草酸鈦氧基鋇粒子的製造方法中，反應液的 溫度，亦即反應溫度，雖可於2〇至9〇t的範圍進行，反 應’皿度為50。。以上時’由於目的之草酸鈦氧基鋇的收率有 變差的傾向，本製造方法中，反應溫度為未達5〇t，較佳 為25至4〇。(：。本發明之草酸鈦氧基鋇粒子的製造方法中， 201217272 藉由使反應溫度為前述範圍，可到收率量好之目的之草酸 鈦氧基鋇粒子。 本製造方法中.，所製得之草酸鈦氧基鋇粒子的大小， 與所生成之草酸碳氧基鋇的滯留時間有關係。亦即，藉由 使滞留時間變短，有容易製得微細者的傾向。 因此，本製造方法中，以調整所生成之草酸鈦氧基鋇 滯留時間’可適宜調整生成平均粒子徑為〇1至5〇"者。 例如，製得平均粒子握為01至5Mm時，較佳為5至4〇" 的草酸鈦氧基鋇粒子時.，所生成之草酸欽氧基鎖滞留時間 可為1至60分鐘，較佳為！至3〇分鐘。再者，製得本發 明之特別較佳的平均粒子徑範圍之1()至3Mm者時，所生 成之草酸鈦氧基鋇滞留時間以調整為ljL 15分鐘的方式即 可。 又，滞留時間未達i分鐘時，所製得之草酸欽氧基鎖 的Ba/Ti的莫耳比的調控變困難而有難以得到Ba/Ti的莫 耳比為0.998至1.002之接近i者的傾向，另一方面滯 留時間超過6G分鐘時，有生成較前述範圍的粒子徑為更大 之草酸鈦氧基鋇粒子的傾向而不佳。 本發明中，所生成之草酸鈦氧基鋇的滯留時間， 反應容器内的反應液體積（L)以由反應容器之反應液排出 速度（L/小時）相除之值（反應液體積/反應液排出速度卜 本發明之草酸鈦氧基鋇粒子的製造方法中，將由反應 容器排出之反應液固液分離，製得沉澱物，其次，必要時， 予以洗淨及乾燥，可製得草酸鈦氧基鋇。再者，所製得之 15 201217272 草酸鈦氧基鋇必要時亦可粉碎。 以該方式進行本發明之 所製得之草酸欽氧基鋇粒子欽氧基鋇粒子的製造方法 ^ a φ 飞子形狀為球狀，藉由雷射 現射散射法求出之平均粒子 5 4n a ^ 馮0. 1至50仁m，較佳為5 至4〇以m ’更較佳為10至30^ m。 再者’藉由將該球狀之箪酴 早酸鈦氧基鋇粒子煅燒，由於 可製付不僅是粒子徑小且社 a j且…日日性南的鈦酸鋇.，可得具有 異性能之介電體陶瓷材料。 本發明之鈦酸鋇得製造方法係藉由將進行本發明之草 酸鈦氧基鋇粒子的製造方法所製得之草酸鈦氧基鋇粒子煅 燒’而製得鈦酸鋇之鈦酸鋇的製造方法…進行本發明 之草酸鈦氧基鋇粒子的製造方法，關於製得草酸鈦氧基鋇 粒子的方法為前文所述者。 亦即，本發明之鈦酸鋇的製造方法，係將一邊將草酸 及四氣化鈦混合於水中所得之水溶液（A1液），以及氣化鋇 水命液（B1液）供給至反應容器，一邊由該反應容器排出反 應液，於未達50°C進行草酸鈦氧基鋇的生成反應所製得之 草酸鈦氧基鋇粒子，藉由緞燒而製得鈦酸鋇之鈦酸鋇的製 造方法。 再者，本發明之鈦酸鋇的製造方法，係將一邊將草酸 水溶液（A2液），以及四氣化鈦及氯化鋇混合於水中所得之 水溶液（B2液），供給至反應容器，一邊由該反應容器排出 反應液’以未達50 °C進行草酸鈦氧基鋇的生成反應所製得 之草酸鈦氧基鋇粒子，藉由煅燒而製得鈦酸鋇之鈦酸鋇的 201217272 製造方法。 再者’本發明之鈦酸鋇的製造方法，係將一邊將草酸 水溶液（A3液）、氣化鋇水溶液（B3液）以及四氯化鈥混合於 水中所得之水溶液（C3液），供給至反應容器，一邊由該反 應容器排出反應液，以未達5〇°C進行草酸鈦氧基鋇的生成 反應所製得之草酸鈦氧基鋇粒子，藉由煅燒而製得鈦酸鋇 之鈦酸鋇的製造方法。 最終製品中所含有之源自草酸的有機物，除了損及材 料的介電特性’同時由於為陶究化用之熱步驟中成為表現 不安定的重要原因而不佳。因此，本發明中藉由锻燒而熱 分解草酸鈦氧基鋇粒子而製得目的之碳酸鋇之同時，必須 充分地去除源自草酸的有機物。 本發明之鈦酸鋇的製造方法中，草酸鈦氧基鋇粒子煅 燒時的緞燒溫度為600至13〇(rc，較佳為7〇〇至i2〇(rc。 藉由草酸鈦氧基鋇粒子煅燒時的煅燒溫度為上述範圍，成 為粒子徑的分布小，具有高結晶性之X射線繞射分析中為 單-相之鈦酸鋇。另-方面，炮燒溫度未達上述範圍時， 難以製得X射線繞射分析中為單一相之欽酸鎖，再者，超 過上述範圍時.，所製得之鈦酸鋇粒子徑的分佈有變大的傾 向而不佳。 再者’緞燒時間較佳為2至3〇小時，特別較佳為5至 27小時。再者’锻燒環境並無特別限制，可於惰性氣體環 境下、真空環境下、氧化性氣體環境下、大氣中之任—者， 或亦可導入水蒸氣同時於前述環境中緞燒。 17 201217272 再者，本發明之鈦酸鋇的製造方法中，草酸鈦氧基鋇 粒子的煅燒，亦可以變換煅燒溫度的多階段煅燒進行。再 者.，於使粉體均-為目的時.，亦可將經一次炮燒者粉碎， 其次進行再緞燒或再粉碎。 進行本發明之鈦酸鋇的製造方法所得之鈦酸鋇，必要 時可粉碎或分級。 依此方式，進行本發明之欽酸鎖的製造方法所得之欽 酸鋇的物性’Ba/Ti的莫耳比為.〇 998至i 〇〇2之接近卜 且如上述者之為粒子徑小者且結晶性高者。 因此’進行本發明之鈦酸鋇的製造方法所得之鈦酸 鋇，作為介電體陶瓷，具有優異性能。 再者，進行本發明之鈦酸鋇的製造方法所得之欽酸銷 中’根據需要而調製介電特性及溫度特性的目的，於進行 本發月之鈦酸鋇的製造方法所得之欽酸鋇添加含有副成分 元素的化合物’可為含有副成分元素。可使用之含有副成 分70素的化合物’例如可列舉含t Sc、Y、La、Ce、Pr、The oxalic acid with different properties has a higher crystallinity, and has higher crystallinity. The present inventors have found that the present invention has been completed by the use of ΐ201217272 for a specific temperature range to obtain spherical strontium titanate oxalate particles in a good yield. Therefore, the oxalic acid (IV) of the object of the present invention is provided as a system-like and particle-shaped oxyquinone particle having a shape. Further, it is an industrially advantageous production method for providing the fine gold-like strontium titanyl oxalate particles. Further, the present invention provides barium titanyl oxalate particles excellent in crystallinity. [Means for Solving the Problem] According to the first invention of the present invention, the average particle diameter is from 0.1 to 5. "ill, the particle shape is a spherical shape of titanyl oxalate particles. Further, according to a second aspect of the present invention, an aqueous solution U1 liquid obtained by mixing oxalic acid and four gas in water, and a chlorinated lock aqueous solution (M liquid) are supplied to a reaction container, and the reaction container is provided. The method of producing the titanyl oxalate particles characterized by the formation reaction of titanyl oxalate at a temperature of less than 50 ° C is discharged. Further, according to a third aspect of the present invention, there is provided a water: a gluten solution (B2 liquid) obtained by mixing an aqueous oxalic acid solution (A2 liquid), titanium tetrachloride and vaporized hydrazine in water, and supplying the mixture to a reaction container. A method for producing a titanyl oxalate particle characterized by a reaction of generating a titanyl oxalate at a temperature of less than 50 ° C while discharging the reaction liquid from the reaction vessel. In addition, the fourth invention provided by the present invention provides an aqueous solution (C3 liquid) in which an aqueous oxalic acid solution (A3 liquid), an aqueous vaporized hydrazine solution (B3 liquid), and a titanium tetrahydrate are mixed in water, and is supplied to the reaction. In the container, the reaction liquid is discharged from the reaction container, and the method for producing titanyl oxalate particles characterized by the formation reaction of titanyl oxalate at 50 ° C is used. In addition, the fifth invention of the present invention provides the titanyl oxalate particles obtained by the method for producing titanyl oxalate particles according to any one of the second to fourth inventions described above. A method for producing a titanate prepared by the method. [Effect of the Invention] The base of the present invention is fine and the shape of the scorpion is spherical. Further, the production method of the present invention can be efficiently produced by an industrially advantageous method. Further, by using the spherical oxalic acid cerium oxide particles, a dielectric ceramic material having high crystallinity and excellent properties can be provided. [Embodiment] Hereinafter, the present invention will be described based on preferred embodiments. The titanyl oxalate wheel of the present invention has a finer particle shape and a finer particle shape. Compared with the laser diffraction-scattering method of the oxalic acid oxime granules of the conventional batch type car Λ Λ 私 私 于 于 于 于 于 于 于 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 雷 雷 雷 雷 雷 雷 雷 雷 散射 散射 散射 散射 散射The control is 100... The laser diffraction method is obtained by the laser diffraction method. The titanyl oxalate particles are preferably 5 to 40, "the sub-path is 0.1 to 5.", which is 5 to 40 # m. More preferably, it is a very fine particle "V m". Further, in comparison with a conventional one, the seedling of the present invention + the silver oxalate oxychloride particle is one of the characteristics in which the grain is spherical as it is. Drill pile shape When the particle shape is observed by an electron microscope at a magnification of 500 times, the shape of the 201217272 particle is limited to a spherical shape, and it is not necessary to be truly spherical. Further, the barium titanyl oxalate particles of the present invention are characterized in that the surface of the particles is smooth and substantially non-angular particles are observed by a scanning electron microscope at a magnification of 2 times. The method for producing titanyl oxalate particles of the present invention is an aqueous solution of oxalic acid (jj2C2〇4), vaporized cerium (BaCh), and titanium tetratitanate (TiCh) as a reaction raw material for the formation reaction of titanyl oxalate. A method for producing titanyl oxalate particles which is supplied to a reaction vessel while discharging the reaction solution from the reaction vessel to carry out a reaction for forming a titanyl oxalate of less than 5 Torr. Therefore, the method for producing titanyl oxalate particles of the present invention has the following forms depending on the type of the aqueous solution of the reaction raw material. In the present invention, the reaction liquid is a liquid obtained by a reaction of a liquid to be supplied to a reaction vessel in a reaction vessel, a titanyl oxalate formation reaction, and a precipitate containing the produced titanyl oxalate. The method for producing titanyl oxalate particles according to the first aspect of the present invention is an aqueous solution (liquid) obtained by mixing oxalic acid and titanium tetrachloride in water, and a vaporized hydrazine aqueous solution (B1 liquid) is supplied to the reaction container. The reaction liquid was discharged from the reaction vessel to less than 50. (Method for producing oxalic acid cerium oxide particles by the formation reaction of titanyl oxalate. The method for producing titanyl oxalate particles according to the second aspect of the present invention is a method of producing an aqueous oxalic acid solution (A2 liquid) and four An aqueous solution (B2 liquid) obtained by mixing vaporized titanium and cerium chloride in water, and supplied to a reaction container, and discharging the reaction liquid from the reaction container, and oxalic acid which is formed by the titanyl oxalate formation reaction at less than 5 ° C Method for producing octyloxy steric acid particles. 7 201217272 A method for producing titanyl oxalate particles according to a third aspect of the present invention is to use an aqueous oxalic acid solution (A3 liquid), an aqueous hydrazine hydrate solution (B3 liquid), and titanium tetra-titanate. The aqueous solution ((3 liquid) obtained by mixing in water is supplied to the reaction container, and the reaction liquid is discharged from the reaction container, and the titanyl oxalate particles of oxalic acid are not subjected to the formation reaction of titanyl oxalate In the method for producing titanyl oxalate particles according to the first aspect of the present invention, an aqueous solution obtained by mixing oxalic acid and titanium tetra-titanate in water is used, and barium chloride is used. The aqueous solution (B1 liquid) is in the form of a reaction raw material aqueous solution. The A1 liquid in the method for producing titanyl oxalate particles according to the first aspect of the present invention is an aqueous solution obtained by mixing oxalic acid and titanium tetrachloride in water, for example, First, four titanium carbides are mixed in water, and then oxalic acid is mixed in the obtained aqueous solution, or titanium tetrachloride is mixed in an aqueous oxalic acid solution to prepare a molar ratio (oxalic acid) relative to the Ti element in the solution. The molar number of ions / the molar number of the Ti element is from 2 () to 3.8, preferably from 2 8 to 3.. 8, more preferably from 3. to 3. by relative to the n element in the M liquid When the molar ratio of the oxalic acid ion is in the above range, it is easy to obtain barium titanate having a molar ratio of <8 to 1.002 which is close to 1. Further, the elemental moisture in the μ liquid is not particularly limited, but is preferably. 〇4 to 3. 2: *·, ··至至〇. 6m〇l/L. The concentration of oxalic acid ion in the A1 liquid, although the helmet is not limited to 'better Λ ......Omol/L, particularly preferably " In the method for producing titanyl oxalate particles according to the first aspect of the present invention, the B1 liquid is an aqueous solution of vaporized hydrazine, and the liquid is at least 1.4 m〇l/L. The concentration of the Ba element, although not particularly limited by 201217272, is preferably from 〇. to 6.5 mol/L, and more preferably 〇5 to 1.3 mol/L. The titanyl oxalate of the first form of the present invention In the method for producing ruthenium particles, the A1 liquid and the B1 liquid are supplied to the reaction container, and the formation reaction of titanyl oxalate is carried out in the reaction container at less than 50 ° C. At this time, the reaction container is opposed to the reaction container. The ratio of the Ba element supply rate of the Ti element supply rate (the Ba element supply rate / the Ti element supply rate) is 〇5 to 3.0, preferably 1. 〇 to 1.5. The supply rate of the reaction vessel relative to the τ丨 element. By the ratio of the Ba element supply rate, by the above range, barium titanate particles having a Ba/Ti molar ratio of approximately 0.998 to 1.002 can be obtained. In the method for producing titanyl oxalate particles according to the first aspect of the present invention, 'the concentration of Ti element in the A1 liquid, the Ba element concentration in the B1 liquid, the supply rate of the A1 liquid (L/hour), and μ are appropriately selected. The supply rate (L/hour) of the liquid can adjust the Ba element supply speed ratio to the supply rate of the Ti element to the reaction vessel. Further, in the present invention, the supply rate of the Ti element to the reaction container means that the number of moles per unit of time is supplied to the number of moles (mole/hour), and further, the supply rate of the Ba element means that each time is time. The Ba element is supplied with a molar number (mole), and the oxalic acid ion supply rate means that the oxalic acid ion per unit time is supplied with a molar number (mol/hr). Therefore, in the method for producing titanyl oxalate particles according to the first aspect of the present invention, the precipitate containing the titanyl oxalate formed in the reaction container is supplied while the A1 liquid and the B1 liquid are supplied to the reaction container. The reaction solution is discharged from the reaction vessel. In this case, the total amount of the A1 liquid and the B1 liquid 201217272 supplied to the reaction container is the same as the amount of the reaction liquid discharged from the reaction container, and it is preferable to carry out the reaction stably. For example, it is preferred to supply the A1 liquid to the reaction vessel at a supply rate of dl (L/hour) in a ratio of a (L/hour) and B1 liquid, and to agitate the reaction liquid with a + bl (L/hour) from the reaction vessel. The discharge speed is discharged. The method for producing titanyl oxalate particles according to the second aspect of the present invention is a method in which an aqueous solution (Β2 liquid) obtained by mixing an aqueous solution of oxalic acid and a vaporized titanium and a vaporized cerium in water is used as a reaction raw material aqueous solution. In the method for producing titanyl oxalate particles according to the second aspect of the present invention, the second liquid is an aqueous oxalic acid solution. The concentration of oxalic acid ions in the mash is not limited, and is preferably 〇Ί $ 7 η 1 /Τ, 救佳马 0,1 to 7.0 mol/L, particularly preferably 〇, 6 to 1.4 mol/L 〇 In the manufacturing method of the occupation, Sr is first: gas: an aqueous solution obtained by mixing hydrazine and gasification hydrazine in water, for example, chlorohydrin is mixed in water, and the cerium chloride is mixed in the solution of the hydrazine, or Mix the tetrachlorodomain with cesium chloride water: Relative to the Ti element in the liquid, ^ element: the number of moles of the element / the number of moles of the π element), (Ba ^ s , ) is 〇.5 to 3.0, preferably 彳n to u. The S"a/Ti molar ratio is easily obtained by the range of Ti with respect to Ti in the B2 solution. , barium titanate close to 1. Further, the β2 liquid .002 is limited, and preferably 0 Q4 1 70 concentration is not particularly limited to 0. 04 to 4. Om〇1/L, O.Smol/L. The element ^ 彳 in the B2 liquid is 0.2 to 〇. 08 to 6 5 mol / L Μ ... without any particular limitation, preferably 〇 1 / L ' particularly preferably 201217272 The second form of the invention is oxalic acid In the method for producing oxyanthracene particles, the A2 liquid and the B2 liquid are supplied to the reaction container, and the formation reaction of titanyl oxalate is carried out in the reaction container at less than 50 °C. At this time, the ratio of the oxalic acid ion supply rate (the oxalic acid ion supply rate / the Ti element supply rate) to the supply rate of the Ti element in the reaction container is 2.0 to 3.8', preferably 2.8 to 3. 8 , particularly preferably 3.0. To 3.3. The ratio of the oxalic acid ion supply rate to the supply rate of the Ti element in the reaction vessel is such that, in the above range, barium titanate particles having a Ba/Ti molar ratio of 998 to 〇〇2 close to one can be obtained. In the method for producing titanyl oxalate particles according to the second aspect of the present invention, 'the oxalic acid ion concentration in the A2 liquid, the n element concentration in the B2 liquid, the supply rate of the liquid A2 (L/hour), and the B2 liquid are appropriately selected. The feed rate (L/hour)' adjusts the oxalic acid ion supply speed ratio to the supply rate of the Ti element to the reaction vessel. Therefore, in the method for producing titanyl oxalate particles according to the second aspect of the present invention, the A2 liquid and the B2 liquid are supplied to the reaction container, and the oxalic acid-containing oxygen-containing lock formed in the reaction cell is formed. The reaction solution, by: should be discharged from the bar. In this case, the amount of the sputum and the sputum supplied to the reaction vessel is the same as the amount of the reaction liquid discharged from the reaction vessel, which is preferable in terms of the reaction. For example, it is preferred to use 22 liquid as 3- 2 C L / y J χ ίτί· ^ ^ R Ο ά 1 . The liquid was supplied to the reaction volume at a supply rate of b2 (L/hour), and the reaction liquid was discharged from the reaction vessel at a discharge rate of a2+b2 (L/hour). A method for producing cerium oxalate cerium particles according to a third aspect of the present invention is as follows: 201217272 using an aqueous solution of oxalic acid (A3 liquid) and an aqueous solution of hydrazine hydrate, and an aqueous solution (C3 liquid) obtained by seeing σ in water as four gasifications. The form of the oxalic acid ion concentration in the oxalic acid aqueous solution βΑ3 liquid in the method for producing the titanyl oxalate particles according to the third aspect of the present invention is not particularly limited, and is preferably 4 i 7 〇m〇. 1/L ' is particularly preferably 〇6 to 1.4 mol/L. In the method for producing titanyl oxalate particles according to the third aspect of the present invention, the B3 liquid is an aqueous solution of ruthenium chloride. The & elemental indifference in the B3 liquid, although (4) is not limited to 'preferably 〇' to 6 5 m 〇 1 / L, particularly preferably to 1.3 mol / liter. In the method for producing oxalic acid cerium oxide particles according to the third aspect of the present invention, the C3 liquid is an aqueous solution obtained by mixing titanium tetrachloride in water. The concentration of the cerium element in the c3 liquid is not particularly limited, and is preferably 〇4 to 6 〇jn〇i/L, particularly preferably 0..2 to 3. 〇m〇i/L. A method for producing titanyl oxalate particles according to a third aspect of the present invention, wherein the A3 liquid, the B3 liquid, and the C3 liquid are supplied to a reaction container, and the titanyl oxalate is carried out in a reaction container at a temperature of less than 5 Gt. Generate a reaction. At this time, the h element supply speed ratio (Ba element supply speed / Ti element supply speed) to the supply rate of the Ti element in the reaction container is U to 3.0 Å, preferably 1. 〇 to 15. With respect to the Ba element supply speed ratio of the reaction container with respect to the η element supply rate, by the above range, barium titanate particles having a Mi molar ratio of ο. 998 ^·002 close to ι can be obtained. Further, the ratio of the oxalic acid ion supply to the reaction container at the supply rate of 12 201217272 (the oxalic acid ion supply rate / the Ti element supply rate) is preferably 2.0 to 3.8', preferably 2.8 to 3-8. The oxalic acid ion supply rate ratio with respect to the supply rate of the Ti element in the reaction vessel is 'by the above range, and barium titanate particles having a Ba/Ti molar ratio of 0.998 to 1.002 close to i can be obtained. In the method for producing titanyl oxalate particles according to the third aspect of the present invention, the oxalic acid ion concentration in the A3 liquid, the Ba element concentration in the B3 liquid, the Ti element concentration in the C3 liquid, and the supply of the A3 liquid are appropriately selected. The speed (L/hour), the supply rate of the B3 liquid (L/hour), and the supply rate of the C3 liquid (L/hour) can adjust the Ba element supply speed ratio and the reaction rate to the supply rate of the Ti element to the reaction vessel. The oxalic acid ion supply speed ratio of the container relative to the Ti element supply rate. Therefore, in the method for producing titanyl oxalate particles according to the second aspect of the present invention, the A3 liquid, the B3 liquid, and the C3 liquid are supplied to the reaction container, and the titanyl oxalate-containing product formed in the reaction container is used. The reaction liquid of the precipitate is discharged from the reaction vessel. In this case, the total amount of the A3 liquid, the B3 liquid, and the C3 liquid supplied to the reaction container is the same as the amount of the reaction liquid discharged from the reaction container, and it is preferable to carry out the reaction in a stable manner. For example, it is preferable to supply the A3 liquid to the reaction container at a supply rate of a3 (L/hour), B3 liquid at b3 (L/hour), and C3 liquid at c3 (L/hour), and the reaction container will be The reaction solution was discharged at a discharge rate of a3 + b3 + c3 (L / hour). The method for producing oxaloxyl oxalate particles of the present invention can be carried out, for example, by using a reaction container of an overflow type as shown in Fig. 1 . Figure Schematic diagram of the reaction vessel in the overflow mode. In Fig. 1, an overflow type reaction vessel 1 has an overflow pipe 2 which can be installed in an upper portion of a side wall of a reaction vessel. 13 201217272 Therefore, in the reaction vessel 1 of the overflow type, since the overflow pipe 2 serves as the discharge port of the reaction liquid, the height of the liquid surface 4 of the reaction liquid 3 is usually the height of the installation position of the beneficial pipe 2 The portion 8 to which the aqueous solution of the reaction raw material is supplied and the reaction liquid 3 are overflowed from the overflow pipe 2 are discharged from the reaction vessel of the overflow system. That is, in the reaction vessel 1 of the overflow type, the amount of the aqueous solution of the reaction raw material to the reaction vessel and the amount of the reaction liquid discharged from the reaction vessel are usually the same amount. Therefore, by using the reaction vessel of the overflow type, the reaction solution can be discharged from the reaction vessel while supplying the aqueous solution of the reaction raw material to the reaction vessel. Further, in Fig. 1, the reaction container 1 of the overflow type actually has other means such as a mixing device, a heating device, a reaction material supply pipe, and the like. * For the convenience of description, only the outline of the reaction container will be described, and other descriptions will be omitted. The reaction vessel for carrying out the method for producing the titanyl oxalate particles of the present invention is not limited to the reaction vessel of the overflow type, and other examples thereof include a stirring device provided therein and an aqueous solution containing an adjustable reaction raw material. a supply pipe of a supply amount of a pump or the like, and a closed reaction vessel having a discharge pipe such as a valve for regulating the discharge amount of the reaction liquid, or a stirring device provided therein, and a pump having a supply amount of the adjustable reaction raw material aqueous solution The supply tube and the sealed reaction container of the discharge tube which discharges the reaction liquid at a constant speed by a pump or the like. "" In the method for producing titanyl oxalate particles of the present invention, the temperature of the reaction liquid, i.e., the reaction temperature, can be carried out in the range of 2 Torr to 9 Torr, and the reaction's degree is 50. . In the above case, the yield of titanyl oxalate is deteriorated due to the purpose, and in the production method, the reaction temperature is less than 5 Torr, preferably 25 to 4 Torr. (: In the method for producing titanyl oxalate particles of the present invention, 201217272, by setting the reaction temperature to the above range, it is possible to obtain titanyl oxalate particles of oxalate for the purpose of good yield. The size of the obtained titanyl oxalate particles is related to the residence time of the produced oxyalkyl oxalate. In other words, by shortening the residence time, it is easy to obtain a finer one. In the production method, it is preferable to adjust the residence time of the titanyl oxalate formed to adjust the average particle diameter to be 〇1 to 5 〇. For example, when the average particle grip is 01 to 5 Mm, it is preferably 5 to 4 〇" of the titanyl oxalate particles, the resulting oxalic acid oxime lock retention time may be from 1 to 60 minutes, preferably from ! to 3 minutes. Further, the invention is prepared When the average particle diameter range is from 1 () to 3 Mm, the residence time of the titanyl oxalate formed may be adjusted to ljL for 15 minutes. Further, when the residence time is less than i minutes, Modulation of the molar ratio of Ba/Ti in oxalic acid It is difficult to obtain a tendency that the molar ratio of Ba/Ti is close to i of 0.998 to 1.002. On the other hand, when the residence time exceeds 6 G minutes, titanyl oxalate having a larger particle diameter than the above range is formed. In the present invention, the residence time of the produced titanyl oxalate, and the volume (L) of the reaction liquid in the reaction vessel are divided by the reaction liquid discharge rate (L/hour) of the reaction vessel. Value (reaction liquid volume / reaction liquid discharge rate) In the method for producing titanyl oxalate particles of the present invention, the reaction liquid discharged from the reaction container is solid-liquid separated to obtain a precipitate, and then, if necessary, washed and Drying can produce titanyl oxalate. Further, 15 201217272 titanyl oxalate can also be pulverized if necessary. In this way, the oxalic acid oxime particles prepared by the present invention are oxidized. The method of manufacturing the base particle ^ a φ The shape of the flying object is spherical, and the average particle obtained by the laser-based scattering method is 5 4 n a ^ von 0.1 to 50 ren, preferably 5 to 4 〇. m ' is more preferably 10 to 30^m. Again, 'by The spherical strontium barium titanate particles are calcined, and a dielectric ceramic material having different properties can be obtained because it can be produced not only in the barium titanate having a small particle diameter but also in the south. The method for producing barium titanate according to the present invention is a method for producing barium titanate of barium titanate by calcining the titanyl oxalate particles obtained by the method for producing titanyl oxalate particles of the present invention. Method for carrying out the method for producing titanyl oxalate particles of the present invention, and the method for producing titanyl oxalate particles is as described above. That is, the method for producing barium titanate of the present invention is to An aqueous solution (A1 liquid) obtained by mixing oxalic acid and titanium tetrahydrate in water, and a gasified hydrazine aqueous liquid (B1 liquid) are supplied to the reaction container, and the reaction liquid is discharged from the reaction container, and oxalic acid is carried out at less than 50 ° C. A method for producing barium titanate oxalate particles obtained by the formation reaction of titanyl ruthenium, and barium titanate is prepared by satin burning. Furthermore, the method for producing barium titanate according to the present invention is an aqueous solution (B2 solution) obtained by mixing an aqueous solution of oxalic acid (A2 liquid) and titanium tetrachloride and cerium chloride in water, and supplying it to a reaction container. The reaction liquid is discharged from the reaction vessel, and the titanyl oxalate particles obtained by the formation reaction of titanyl oxalate at less than 50 ° C are produced by calcination to produce barium titanate barium titanate 201217272. method. In addition, the method for producing barium titanate according to the present invention is to supply an aqueous solution (C3 solution) obtained by mixing an aqueous solution of oxalic acid (A3 solution), an aqueous solution of hydrazine hydrate (B3 solution), and ruthenium tetrachloride in water. In the reaction vessel, the reaction liquid is discharged from the reaction vessel, and the titanyl oxalate particles obtained by the formation reaction of titanyl oxalate at less than 5 ° C are used to obtain titanium barium titanate by calcination. A method of producing acid bismuth. The oxalic acid-derived organic matter contained in the final product, in addition to damaging the dielectric properties of the material, is also poor because it is an important cause of instability in the thermal step for ceramics. Therefore, in the present invention, the strontium carbonate oxalate particles are thermally decomposed by calcination to obtain the desired cerium carbonate, and the oxalic acid-derived organic substance must be sufficiently removed. In the method for producing barium titanate according to the present invention, the satin burning temperature at the time of calcination of the titanyl oxalate particles is 600 to 13 Torr (rc, preferably 7 Å to i2 〇 (rc. by titanyl oxalate) The calcination temperature at the time of calcination of the particles is in the above range, and the distribution of the particle diameter is small, and the X-ray diffraction analysis having high crystallinity is a single-phase barium titanate. On the other hand, when the calcination temperature is less than the above range, It is difficult to obtain a single-phase acid-locking in the X-ray diffraction analysis. Further, when it exceeds the above range, the distribution of the particle diameter of the barium titanate particles obtained tends to be large. The burning time is preferably 2 to 3 hours, particularly preferably 5 to 27 hours. Further, the 'calcining environment is not particularly limited, and it can be used in an inert gas atmosphere, a vacuum environment, an oxidizing gas atmosphere, or the atmosphere. In addition, in the method for producing barium titanate of the present invention, the calcination of titanyl oxalate particles can also change the calcination temperature. Multi-stage calcination. In addition, so that the powder is all - for the purpose In the case of a gunner, it may be pulverized by a single burner, followed by re-satin or re-pulverization. The barium titanate obtained by the method for producing barium titanate of the present invention may be pulverized or classified as necessary. The molar ratio of the physical property 'Ba/Ti obtained by the method for producing the acid-acid lock of the present invention is close to that of 〇998 to i 〇〇2, and the particle diameter is small as described above and the crystallinity is high. Therefore, the barium titanate obtained by the method for producing barium titanate of the present invention has excellent performance as a dielectric ceramic. Further, in the method of producing the barium titanate of the present invention, For the purpose of modulating the dielectric properties and the temperature characteristics as needed, the compound containing the accessory component obtained by the method for producing barium titanate of the present invention may be a component containing an accessory component. The compound of the composition of 70 is, for example, t c, Y, La, Ce, Pr,
Nd、Pm、Sm、Eu、、π n u rNd, Pm, Sm, Eu, π n u r
Gd Tb、Dy、Η〇ϋ、Yb、Lu 之稀 土類 το 素，Ba、T ι· d · nGd Tb, Dy, Η〇ϋ, Yb, Lu, the rare earth class το素, Ba, T ι· d · n
Bl、Zn、Mn、A1、Si、Ca、Sr、Co、Bl, Zn, Mn, A1, Si, Ca, Sr, Co,
Ni、Cr、Fe、Μσ、τ · 之至少-種-去^、^^及^所成群組選出 之至夕種疋素的化合物。 含有副成分元素的化合物，可為無機物或有機物之任 一者。例如，可列觀—Α 1 氣 别述元素之氧化物、氫氧化物、 乳化物、硝酸豳、甘A compound selected from the group consisting of Ni, Cr, Fe, Μσ, τ · at least - species, de-^, ^^, and ^. The compound containing a subcomponent element may be either an inorganic substance or an organic substance. For example, it can be listed - Α 1 gas, other oxides, hydroxides, emulsions, cerium nitrate, gan
a I酸鹽、羧酸鹽及烷氧化物等。含有副 成分7C素的化人 A 匕口物為含彳Si元素的化合物時，除的氧化物 201217272 含有副成分元素的化 。其添加量或添加化 等之外，亦可使用矽膠或矽酸鈉等。 物了 1種或.2種以上適宜組合使用 口物的組合，根據一般方法進行即可 欽酸鋇中含有副成分元素 有副成分元素的化合物均一混 可將草酸鈦氧基鋇粒子與含有 合後’進行煅燒。 時，例如，可將鈦酸鋇與含 合後，進行煅燒。或者，亦 副成分元素的化合物均一混 使用本發明之鈦酸鋇得製诰 仔“方法所得之鈦酸鋇，例如 =層陶究電容器時，首先，將欽酸鎖粉末與含有副成 …之以往習知的添加劑、有機系黏合劑、塑化劑、分 散劑等-起混合分散於適當的溶媒中予以浆體化，進行片 成型°藉此，可得使用於積層陶究電容器得製造之陶兗片。 由該陶究片製作積層陶究電容器時，首先，於該陶竟片的 =面印刷内部電極形成用導電f。乾燥後，積層複數張的 刖述陶’藉由;^厚度方向塵合而作成積層冑。其次， 加熱處理該積層體進行脫黏合劑處理，製得煅燒之煅燒 體。進一步地，於該煅燒體塗佈Ni膏、“膏、鎳合金膏、 銅膏、銅合金膏等而燒結，製得積層陶瓷電容器。 再者，進行本發明之鈦酸鋇得製造方法所得之欽酸鋇 的粉末’例如調配於環氧樹脂、聚醋樹脂、$酿亞胺樹脂 等樹脂中，作為樹脂片、樹脂膜、接著劑等時，由於為用 於抑制印刷電路板及多層印刷電路板等材料、内部電極與 介電體之收縮差異的共通材料，可使用作為電極陶瓷電路 基板，玻璃陶瓷電路基板、電路周邊材料及無機EL用的介 19 201217272 電體材料。 再者，進行本發明之欽酸鋇的製造方法所得之欽酸 鎖，適合使用於作為使用於排氣去除、化學合成等反應時 之觸媒’或賦予抗靜電、清潔效果之印刷調色劑之表 質材。 【實施例】 以下.，雖藉由實施例詳細說明本發明，但本發明不限 定該等者。 (實施例1) 於水2154g中經加入草酸2水合物25〇g的水溶液中， 混合Ti為2.56m〇l/L濃度之四氯化鈦水溶液332g，製作 草酸為uw/l、Ti m1/L之草酸及四氣化鈦混 合於水中所得之水溶液（A1幻”亦即，於A1液中相對於 T」元素之草酸離子的莫耳比為3卜再者，將氯化鋇叫 溶解於水963g中，製作以為〇 8〇m〇1/L的氣化鋇水溶液 (B1液）。其:欠，於反應容器中館入純水，保持於35°C，於 攪拌下將A1液及B1液以〇 9L/小時、〇 4L/小時的速度供 給至反應容器。亦即，相對於對反應容器的Ti元素供給速 度之Ba 70素供給速度的比為I.3,進行生成草酸鈦氧基鋇 的滯留時間為14分鐘的反應。 由反應容器所排出的反應液，進行固液分離，製得沉 澱物，洗淨後乾燥，製得草酸鈦氧基鋇粒子。 再者’求出Ba與Ti的反應率的結果，Ba為8〇%，π 為 99% 〇 20 201217272 又，反應率係於反應結東時以ICP測定所溶出之肫與 Τι ’該溶出分作為未反應份，由進料量與減去未反應份作 為反應份，以進料的百分率表示者。該反應率高表示未反 應之殘存的Ba及Ti的成分少之反應效率及高收率。 為了測定所得之草酸鈦氧基鋇的Ba/Ti莫耳比，將草 酸鈦氧基鋇煅燒後，進行螢光χ射線分析時.，塊材（buik) 的Ba/Ti莫耳比為1. 〇〇1。 再者，乾燥後的草酸鈦氧基鋇，藉由雷射繞射_散射法 (堀場製作所；雷射繞射/散射式粒度分布測定裝置 (LA-920))所求出之平均粒子徑為2〇"m。 再者’所製得之草酸鈦氧基鋇粒子的電子顯微鏡照相 圖示於圖2 ’ SEM照相圖示於圖3及圖4。 進一步地所製得之草酸鈦氧基粒子，於9〇〇。(：煅燒 24 !時，製得欽酸鋇。關於所製得之鈦酸鋇，結晶性指標 之c轴與a轴的長度比（c軸/a轴比）藉由xrd測定時為 1. 00 93，藉由BET法測定比表面積時為2. 〇m2/g。 (參考例1) 除了於55°C進行草酸鈦氧基鋇的生成反應以外，與實 施例1同樣的操作及條件進行反應’製得草酸鈦氧基鋇粒 子。再者，與實施例1同樣方式球出以與Ti的反應率結 果 ’ Ba 為 70%，Ti 為 95%。 因此，與實施例1相比較，未反應之殘存的Ba及Ti 的成分多’可之反應效率及收率降低。 (比較例1) 21 201217272 準備批次式反應容器’於55°C水1400g中溶解草酸2 水合物325g’製作草酸為1.. 73mol/L的草酸水溶液（A11 液）。於水1830g中經添加氣化鋇325g之水溶液中，混合 Ή為2. 6mol/L濃度的四氣化欽水溶液63〇g，製作氣化鎖 為〇_55m〇l/L，ΤΪ為〇.52mal/L之氯化鋇及四氯化鈦混合 於水中所得之水溶液（B11液）。亦即.，Bn液中，相對於 Ti元素之Ba元素的莫耳比為L ；!。其次，於55t的aii 液中，於攪拌下以0.7L/小時的速度滴加B11液供給至反 應容器《亦即相對於B11液滴加完成時的反應容器内的h 元素’草酸離子的比為2. 1。 〇. 5小時熟成後，將反應液固液分離，製得沉澱物， 洗淨後乾燥’製得草酸鈦氧基鋇。 將所得之草酸鈦氧基鋇煅燒後，進行螢光χ射線分析 時’塊材的Ba/Ti莫耳比為〇 999。 再者，乾燥後的草酸鈦氧基鋇藉由雷射繞射-散射法 (堀場製作所；雷射繞射/散射式粒度分布測定裝置 (LA-920))所求出之平均粒子徑為145vm。 再者’所製得之草酸鈦氧基鋇粒子電子顯微鏡照相圖 示於圖5。 +時，製 1.0090, 所製得之草酸鈦氧基鋇粒子於9〇〇<>c煅燒24 得鈦酸鋇。所得鈦酸鋇藉由XRD之c軸/a轴比為 藉由BET法之比表面積為j 5mz/g。 鋇 由圖2及圖5所示可知 粒子為粒子形狀係實質上 ’相對於本發明之草酸鈦氧基 為球狀的’比較例1所製得之 22 201217272 草酸鈦氧基鋇粒[粒子形狀為金平糖狀。 進步地，由圖4可知，本發明之草酸鈦氧基鋇粒子， 粒子表面為光滑，為實質上無角的粒子。 【圖式簡單說明】 圖1為溢流方式的反應容器的模式剖面圖。 圖2為顯示實施例1所得之草酸鈦氧基鋇粒子的粒子 形狀的電子顯微鏡圖（倍率500,倍）。 圖3為顯示實施例1所得之草酸鈦氧基鋇粒子的粒子 形狀的SEM照相圖（倍率500倍）。 圖4為顯示實施例1所得之草酸鈦氧基鋇粒子的粒子 形狀的SEM照相圖（倍率2000倍）。 圖5為顯示實施例1所得之草酸鈦氧基鋇粒子的粒子 形狀的電子顯微鏡照相圖（倍率100倍）。 【主要元件符號說明】 1溢流方式的反應容器 2溢流管 3反應液 23a I acid salt, carboxylate, alkoxide, and the like. When the chemical A-containing substance containing the sub-component 7C is a compound containing 彳Si element, the oxide 201217272 contains a sub-component element. In addition to the amount of addition or addition, it is also possible to use silicone or sodium citrate. A combination of one or two or more kinds of suitable substances may be used, and according to a general method, a compound containing a sub-component element and a sub-component element may be uniformly mixed, and the titanyl oxalate particles may be combined with the compound. After 'calcining. For example, barium titanate may be calcined after being combined. Alternatively, the compound of the subcomponent element is uniformly mixed with the barium titanate of the present invention to obtain the barium titanate obtained by the method, for example, when the layer of the ceramic capacitor is used, firstly, the acid is locked and the powder is contained. Conventional additives, organic binders, plasticizers, dispersants, and the like are mixed and dispersed in a suitable solvent to be slurried, and sheet molding is carried out. Thus, it can be used for the production of laminated ceramic capacitors. When the ceramic tile is used to make a laminated ceramic capacitor, first, the conductive electrode f for the internal electrode is printed on the surface of the ceramic tile. After drying, a plurality of layers of the ceramics are described. The laminated body is heat-treated to perform debonding treatment to obtain a calcined calcined body. Further, a Ni paste, a paste, a nickel alloy paste, a copper paste, and the like are applied to the calcined body. A copper alloy paste or the like is sintered to obtain a laminated ceramic capacitor. In addition, the powder of the bismuth phthalate obtained by the method for producing barium titanate of the present invention is blended, for example, in a resin such as an epoxy resin, a polyester resin or an ammine resin, as a resin sheet, a resin film, and an adhesive. In the case of a common material for suppressing the difference in shrinkage between the internal electrode and the dielectric, such as a printed circuit board and a multilayer printed circuit board, it can be used as an electrode ceramic circuit substrate, a glass ceramic circuit substrate, a circuit peripheral material, and an inorganic material. EL 19 for use in the electrical material of 201217272. Further, the acid-acid lock obtained by the method for producing the bismuth citrate of the present invention is suitably used as a catalyst for use in a reaction such as exhaust gas removal or chemical synthesis, or a printing toner which imparts an antistatic and cleaning effect. The material of the watch. [Embodiment] Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited thereto. (Example 1) 332 g of an aqueous solution of titanium tetrachloride having a concentration of 2.56 m〇l/L was added to 2154 g of water by adding an aqueous solution of 25 g of oxalic acid dihydrate to prepare oxalic acid as uw/l, Ti m1/ The aqueous solution obtained by mixing L-oxalic acid and titanium tetra-titanate in water (A1 magic), that is, the molar ratio of oxalic acid ion in the A1 liquid relative to the T" element is 3, and the ruthenium chloride is dissolved in A water vaporized hydrazine aqueous solution (B1 liquid) of 〇8〇m〇1/L was prepared in 963 g of water. It was owed, and pure water was placed in the reaction vessel, and it was kept at 35 ° C, and the A1 liquid was stirred under stirring. The B1 solution is supplied to the reaction vessel at a rate of L9 L/hour and 〇4 L/hour, that is, the ratio of the supply rate of the Ba 70 element to the supply rate of the Ti element to the reaction vessel is 1.3, and the formation of titanyl oxalate is carried out. The residence time of the basement is 14 minutes. The reaction liquid discharged from the reaction vessel is subjected to solid-liquid separation to obtain a precipitate, which is washed and dried to obtain titanyl oxalate particles. As a result of the reaction rate with Ti, Ba is 8〇%, and π is 99%. 〇20 201217272 Further, the reaction rate is measured by ICP when the reaction is terminated. The dissolved enthalpy and Τι 'the elution fraction is taken as the unreacted fraction, and the amount of the feed and the unreacted fraction are subtracted as the reaction fraction, which is expressed as a percentage of the feed. The high reaction rate indicates the unreacted residual Ba and Ti. The reaction efficiency and high yield are small. In order to measure the Ba/Ti molar ratio of the obtained titanyl oxalate, the titanyl oxalate is calcined and then subjected to fluorescence ray analysis. The Ba/Ti molar ratio is 1. 〇〇1. Further, the dried titanyl oxalate is dried by laser diffraction-scattering method (field field production; laser diffraction/scattering particle size distribution measurement) The average particle diameter determined by the device (LA-920) was 2 〇 " m. Further, the electron micrograph of the titanyl oxalate particles prepared by the 'Fig. 2' SEM photograph is shown in the figure. 3 and Fig. 4. Further prepared titanyl oxalate particles are obtained at 9 Å. (: calcination 24 Å, bismuth phthalate is obtained. Regarding the prepared barium titanate, the c-axis of the crystallinity index The ratio of the length to the a-axis (c-axis/a-axis ratio) is 1. 00 93 when measured by xrd, and is 2. 〇m2/g when the specific surface area is measured by the BET method. Reference Example 1) A reaction was carried out in the same manner and under the same conditions as in Example 1 except that the formation reaction of titanyl oxalate was carried out at 55 ° C to obtain titanyl oxalate particles. Further, in the same manner as in Example 1. As a result of the reaction rate with Ti, the Ba was 70% and the Ti was 95%. Therefore, compared with Example 1, the reaction efficiency and yield of the unreacted remaining Ba and Ti components were reduced. (Comparative Example 1) 21 201217272 A batch type reaction vessel was prepared to dissolve oxalic acid 2 hydrate 325 g in 1400 g of water at 55 ° C to prepare an oxalic acid aqueous solution (A11 liquid) having a oxalic acid content of 1.73 mol/L. In an aqueous solution of 325 g of gasification hydrazine in 1830 g of water, 63 〇g of a tetrahydrogenated aqueous solution of 2.6 g/L was mixed, and the gasification lock was made into 〇_55 m〇l/L, and ΤΪ was 〇. An aqueous solution (B11 liquid) obtained by mixing 52 mol/L of cerium chloride and titanium tetrachloride in water. That is, in the Bn solution, the molar ratio of the Ba element relative to the Ti element is L; Next, in a 55t aii liquid, the B11 liquid was supplied dropwise to the reaction vessel at a rate of 0.7 L/hr under stirring, that is, the ratio of the h element 'oxalate ion in the reaction vessel when the B11 droplet was added was completed. Is 2.1. 5. After 5 hours of aging, the reaction solution was solid-liquid separated to obtain a precipitate, which was washed and dried to obtain titanyl oxalate. After the obtained titanyl oxalate was calcined, the Ba/Ti molar ratio of the bulk material was 〇 999 when subjected to fluorescence ray analysis. Further, the dried titanyl oxalate has an average particle diameter of 145 vm obtained by a laser diffraction-scattering method (field field production facility; laser diffraction/scattering particle size distribution measuring device (LA-920)). . Further, an electron micrograph of the titanyl oxalate particles prepared by the invention is shown in Fig. 5. When it was 1.0, the obtained titanyl oxalate particles were calcined at 9 Å >> to obtain barium titanate. The obtained barium titanate has a c-axis/a-axis ratio by XRD of a specific surface area by the BET method of j 5 mz/g. As shown in Fig. 2 and Fig. 5, it is understood that the particles have a particle shape and are substantially 'spherical with respect to the titanyl oxalate of the present invention'. 22 201217272 oxalic acid titanyl silicate particles [particle shape] It is a sugary sugar. Progressively, as can be seen from Fig. 4, the titanyl oxalate particles of the present invention have smooth particle surfaces and are substantially non-angular particles. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view of a reaction vessel in an overflow mode. Fig. 2 is an electron micrograph (magnification: 500, magnification) showing the particle shape of the titanyl oxalate particles obtained in Example 1. Fig. 3 is a SEM photograph (magnification: 500 times) showing the particle shape of the titanyl oxalate particles obtained in Example 1. Fig. 4 is a SEM photograph (magnification: 2000 times) showing the particle shape of the titanyl oxalate particles obtained in Example 1. Fig. 5 is an electron micrograph (magnification: 100 times) showing the particle shape of the titanyl oxalate particles obtained in Example 1. [Explanation of main component symbols] 1 Reflow type reaction vessel 2 Overflow tube 3 Reaction liquid 23