TWI286537B - Barium calcium titanate, production process thereof and capacitor - Google Patents

Abstract

A barium calcium titanate of the present invention has a remarkable effect that a fine barium calcium titanate powder having excellent dispersibility, reduced impurities and high crystallinity and being solid-dissolved at an arbitrary ratio, and a production process thereof are provided. The barium calcium titanate represented by the compositional formula: (Ba(1-X)CaX)YTiO3 (wherein 0 < X < 0.2 and 0.98 <= Y <= 1.02), which contains 3 mol% or less (including 0 mol%) of an orthorhombic perovskite compound and in which the specific surface area D is from 1 to 100 m<2>/g.

Description

1286537 九、發明說明： 【發明所屬之技術領域】 材料本於;; 電子材料。 祕型陶是電谷盗、薄膜材料等之 詳言之’關於-種鈦酸舞鋇粒子及其製造方 ^ D ^ l~100^/g^，m Rietvdd 【先前技術】 = B: ’鈦稱微偏離中心 電性另rr，電：可=二用壓 另外，鈦酸㉙槪用於將鋇之 :H子材枓使用。 ·· ，天線、電介質共振H、電介質濾、波器、電介 壓電性之層壓壓電致動哭箄ά2态、电谷态、移相器、利用 法’可列舉:將鈦酸鋇;ί二、$酸細於電子材料之方 ▲另外，最近㈣mm觸、磁器等。 結晶性的、高純度ϋ酸=分布為狹窄的、分散性優異的、高 例如’為了使型陶究電容器得以小型化、輕量化、高容 1286537 量化，必須縮小鈦酸鈣鋇之粒徑、縮短層壓之間隔、增加層壓之 數目。 然而，一般而言，一旦鈦酸鈣鋇之粒徑變小，雖然c/a比變低 而接近於立方晶，但是，一旦c/a比變低，由於強介電性降低，作 為電介質材，使用時之靜電容量將變小。因此，即使粒徑為小的， 也期望顯示高的e/a比之鈦酸_鋇。另外，為7顯示高的c/a比， 必須為南結晶的。 另外，將鈦酸鈣鋇粉末與溶劑混合後予以漿化或糊化之際， 一旦粉末凝聚時，燒結密度將降低，具有耐電壓、遷移等電特性 ΪΪΪΪ題。再者’鈦酸觸中所含之不純物也將造成電特性不 因而，為了因應於電子元件之小型化、輕量化、高性 便必須開發粒料小的、練分布為狹窄的 純度的鈦自_鋇。 ^ ^ ，知鈦酸，鋇之製造方法可以使用如下之技術手段。 (Flu:)純^且咼結晶之鈦酸鋇粒子之製造方法，可列舉··熔化 ㈣t ^此法’不僅製造成本高，作成粒子也不只是進行 ^碎而已，形成粒徑分布為廣的、分散性佳的粒子。因而， δ於將粒子作為材料之電子材料。 k 製造電子材料用之鈦酸鋇的製造方法，一般 · 化物或碳酸鹽作為原:料’利用球磨機等將此等ί末 草二i丨止於⑥800c以上之高溫使其進行反應而加以製造. ’調製草酸錯鹽’將其熱分解後得到含有鈦i复 行反應而得耻驅物；烧氧基法“二使其進 此等水解而得耿驅物等。 μ基金屬作為原料’進行 另外，鈦酸鋇之製造方法，一般之習知 液中，使鈦化合物進行生成物之水解與水溶性鋇造行反應 1286537 (專利文獻1);於強鹼中，推弁 法（專利文獻2、專利文獻3) ‘敎/二膠與鋇化合物反應的方 良。 ）4仍熱衷於研發此等合成法之改 雖然該固相法之製造成本為低的， 鋇粒子之粒徑變大的問題。若 /、有所生成的鈦酸 擔憂粒徑分布變廣而無法提高細。、=雖然粒徑變小，卻 結晶構造產生歪斜，無法得到適合ϋ 2有因粉碎而於 粉末之類的缺點。 、1化'Ν性能化的鈦酸鋇 另外，雖然該草酸鹽法可以得到齡 於草酸之碳酸基將以不純物殘存車子’歸因 的蝴留為多的，電特性將降低另於=部所捕獲水 法得到電特性優異的鈦酸鋇粉末之贿。ϋ㈣法具有無 於該水熱合成法中，雖然可以得到微粒之欽 ==内部所捕獲水_基將殘留而缺陷為多的，=得： 的鈦酸鋇粒子。另外，為了於高溫 下 具有專用設備成為必要的、成本變高之__ 件下進仃 酸鋼於可以得到較水熱合成法更為微粒之鈦 ^鋇但疋，起因於被内部所捕獲水的經基將殘留而使缺 的，難以得到電特性優異的含有鈦之複合型氧化物。、…、 【專利文獻1】日本專利特公平弘39014號公報 【專利文獻2】國際專利公開第〇〇/35811號手冊 【專利文獻3】國際專利公開第〇3/〇〇4416號手冊 【專利文獻4】日本專利特開2002-60219號公報 【專利文獻5】日本專利特開200348774號公報 【發明内容】 解決之技術問題 不於專利文獻1或專利文獻2之方法中，雖然將氫氧化鉀 或氫氧化鈉作為鹼使用，但是為了得到高純度之鈦酸鋇粒子，於 7 1286537 性兩的鈦酸鋇之情形。 、捕彳又，將有難以得到結晶 另方面，為了製造鈦酸_鋇，者卢a 將舞加入原料中進行製造的方法。铁^慮各種技術手段中， 大不相同，製造使鋇與軒以均^之原子半徑 原料化合物之殘存或是、、鈦馱鋇為困難的。因此， 合物，對應於電子元件之小i化、弓?斜方晶麵欽礦化 之製造將變得困難。另外，為了使二化的欽酸_ 溫下進行_理成為必要的，且柄、勻固溶，由於高 粒之製造變得困難之類的問題交得容易，鈦酸#5鋇微 鈣鋇之^造it利文獻3、專利文獻4與專利文獻5中，揭示鈦酸 酸之方种，雖财以得到效 應之：副產物;化合物’於競爭反 須具有文獻4之方法係-種非常複雜的步驟，必 鈦與ΐί鋇於經歷碳酸鈣、氧化 鈣鋇微粒。 、…处王，热法得到0.2μιη以下之鈦酸 t發明之課題在於提供一種鈦酸_及其製造方法 粒控分布狹窄的、分散性優異的、結日日日性高的、Ϊ特i άλμμ^μά±μ ，了達成該目的，本發明提供下列之技術手段。， jn:種鈦酸_，其特徵為：以（Bai—xCax) γΤί〇3 (盆中， /98_·02)之組成式表示，斜方晶系_ 之含有率為以下（包含〇m。粉，比表面積勿 1286537 以上、100 m2/g以下之範圍。 曰tj]如揭示於[1]之鈦酸趟鋇，其中利用取㈣ =子之C軸長與a轴長之比（⑹設為y時，該盘斤;3結 - 積£)之關係滿足下式（1)或下式（2)。 y/、忒比表面 . y&amp;_5-8.8xl(r6xD3 (其中，1必沒7 之㈤ 泠1·003 (其中，9.7&lt;Dsl〇〇之時） ⑴ 上之於[1剛之_鋇，其中鈦酸_含=%以 7如揭示於⑴至[3]中任一項之鈦酸鈣鋇， 存在lnm以上空孔之粒子含有8〇%以上。-中於粒子内不 [5]如揭示於[1]至[4]中任一項之鈦酸鈣鋇，a .%析法所求得的體積基準之平均粒徑設為切:立:1用影像 而成為5%的粒徑設為D2時，D2/m為〇 5〜ϋ，。、者起累計 间如揭示於[1]至[***均粒徑設為如：從&amp; '丄用影像 $為95%的粒徑設為D3，最大之粒徑設為以時^=者$累計1286537 IX. Description of the invention: [Technical field to which the invention pertains] Materials are based on; Electronic materials. The secret type pottery is the detailed description of the electric grain thief, film material, etc. -About the kind of titanic mahogany particles and its manufacturing method ^ D ^ l~100^/g^, m Rietvdd [prior art] = B: 'titanium It is called micro-offset center electrical rr, electricity: can be used for two pressures. In addition, titanic acid 29 槪 is used for the 子:H sub-material. ··, Antenna, dielectric resonance H, dielectric filter, wave, dielectric piezoelectric laminate piezoelectric actuation crying state 2, electric valley state, phase shifter, utilization method can be cited: barium titanate ; ί 二, $ acid is thinner than the electronic material ▲ In addition, recently (four) mm touch, magnets and so on. Crystalline, high-purity decanoic acid = narrow distribution, excellent dispersibility, and high, for example, in order to reduce the size, weight, and high-capacity 1286537 of the ceramic capacitor, the particle size of calcium titanate must be reduced. Shorten the interval between laminations and increase the number of laminations. However, in general, once the particle size of calcium barium titanate becomes small, although the c/a ratio becomes low and is close to cubic crystal, once the c/a ratio becomes low, the dielectric property is lowered as a dielectric material. The electrostatic capacity will become smaller when used. Therefore, even if the particle diameter is small, it is desirable to exhibit a high e/a ratio of titanate. In addition, a high c/a ratio of 7 is required to be crystallized in the south. Further, when the calcium titanate tantalum powder is mixed with a solvent and then slurried or gelatinized, once the powder is agglomerated, the sintered density is lowered, and electrical characteristics such as withstand voltage and migration are caused. In addition, the impurities contained in the titanic acid touch will not cause electrical properties. In order to reduce the size, weight, and high performance of electronic components, it is necessary to develop titanium with a small particle size and a narrow distribution. _barium. ^ ^ , Knowing the method of manufacturing titanic acid, niobium can use the following technical means. (Flu:) A method for producing barium titanate particles of pure and bismuth crystals, for example, melting (four) t ^ This method is not only high in manufacturing cost, but also is not only formed into particles, but also has a wide particle size distribution. , particles with good dispersion. Thus, δ is an electronic material that uses particles as materials. k A method for producing barium titanate for the production of electronic materials, in which a compound or a carbonate is used as a raw material to be produced by a ball mill or the like at a high temperature of 6800 c or higher. 'Preparation of oxalic acid stearic salt', which is thermally decomposed to obtain a reciprocal reaction containing titanium i. The alkoxy method is used to carry out the hydrolysis to obtain a ruthenium drive, etc. The μ-based metal is used as a raw material. In addition, in the conventional method of producing barium titanate, the titanium compound is subjected to hydrolysis of a product and a water-soluble oxime reaction 1286337 (Patent Document 1); in a strong base, a method of pushing a sputum (Patent Document 2) Patent Document 3) 'Fangliang of the reaction between bismuth/di-glue and ruthenium compound.) 4 Still keen to develop such a synthesis method. Although the manufacturing cost of the solid phase method is low, the particle size of ruthenium particles becomes large. The problem is that if the formed titanic acid is concerned about the widening of the particle size distribution, the fineness cannot be improved. If the particle size is small, the crystal structure is skewed, and it is impossible to obtain a suitable ϋ 2 due to pulverization and powder. Disadvantages, 1 Ν 'Ν performance of barium titanate In addition, although the oxalate method can obtain a carboxylic acid-based carbonate group, which is attributed to the damage of the vehicle remaining in the impurity, the electrical property is lowered, and the titanic acid having excellent electrical properties is obtained by the water captured by the portion.钡 之 之 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 In order to have special equipment at high temperatures, it is necessary to increase the cost of the bismuth sulphate steel to obtain more titanium particles than the hydrothermal synthesis method, but it is caused by the water trapped inside. In addition, it is difficult to obtain a composite oxide containing titanium having excellent electrical properties. [Patent Document 1] Japanese Patent Laid-Open No. 39014 (Patent Document 2) International Patent Publication No. [Patent Document 3] [Patent Document 3] International Patent Publication No. 3/4416 [Patent Document 4] Japanese Patent Laid-Open Publication No. JP-A-2002-60219 (Patent Document 5) Japanese Patent Laid-Open No. 200348774The technical problem is not in the method of Patent Document 1 or Patent Document 2, although potassium hydroxide or sodium hydroxide is used as a base, but in order to obtain high-purity barium titanate particles, barium titanate having a ratio of 7 1286537 In the case of the shovel, it is difficult to obtain crystallization. In order to manufacture titanic acid, a a 将 将 将 将 将 将 将 a a a a a a a a a a a a a a a a a a a a a a a a a a a a钡 轩 轩 以 之 之 之 之 之 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子In addition, it is difficult to carry out the problem that the production of the high-grain is difficult, and the titanic acid #5钡微钡钡^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ Department - a very complicated step, must be titanium and ΐί钡Subjected to calcium carbonate, calcium oxide, barium particles. The first problem of the invention is to provide a titanic acid of 0.2 μm or less. The object of the invention is to provide a titanic acid _ and a method for producing the same, which has a narrow particle-control distribution and excellent dispersibility, and has a high degree of daily life. Άλμμμμά±μ, in order to achieve the object, the present invention provides the following technical means. , jn: a kind of titanic acid _, which is characterized by a composition formula of (Bai-xCax) γΤί〇3 (in the pot, /98_·02), and the content of the orthorhombic system _ is the following (including 〇m. Powder, the specific surface area is not more than 1286537 or more, and the range of 100 m2/g or less. 曰tj] as disclosed in [1], the ratio of the C-axis length to the a-axis length is (4). For y, the relationship of the disk; 3 knot - product £) satisfies the following formula (1) or the following formula (2). y /, 忒 ratio surface. y &amp; _5-8.8xl (r6xD3 (where 1 must not 7 (5) 泠1·003 (where 9.7 &lt;Dsl〇〇) (1) on [1 _ _ 钡, where titanate _ contains =% to 7 as disclosed in any of (1) to [3] Calcium titanate strontium, particles having pores of 1 nm or more or more are contained in an amount of 8 % by mass or more. - The medium is not present in the particles. [5] The calcium titanate strontium according to any one of [1] to [4], a. The average particle diameter of the volume reference obtained by the % analysis method is cut: Li: 1 When the particle size is 5% with the image, D2/m is 〇5~ϋ, and the cumulative interval is as follows. The average particle size of the volume reference obtained by the spleen analysis method disclosed in [1] to [the middle of the spleen is set as : From &amp; 'Use image $ is 95% of the particle size is set to D3, the largest particle size is set to ^^ = $ cumulative

為5 m2/g :上、ΐί〇Ϊ4]ί;之2 J鈦酸鈣鋇’其中比表面積D5 m2/g: upper, ΐί〇Ϊ4] ί; 2 J calcium titanate 钡' where the specific surface area D

[9] 一種鈦酸鈣鋇之製造方法，其特徵為且傷. 合物之pH值10以上之驗性溶液中 ^：、，.於含有驗性化 藉由使此等進行反應而合成鈦酸鋇之步驟匕鋇 匕鈦後’ 化· ’使其進行反應而合成鈦酸賴之置入氫氧 性化合物氣化而予以去除之步驟。 、、，及接者，使該鹼 化鎖與氣氧倾之合計莫耳量·，將氧化鈦 9 1286537 鹼性溶液中，使此等氫氧化鋇、氫氧化鈣與氧化鈦予以反應而製 造鈦酸飼鋇。 允[11]如揭示於[9]或[10]之鈦酸鈣鋇之製造方法，其中於該鈦 酸鋇之合成步驟中，使該鹼性溶液中之鋇離子殘留 量的百分之-以下使其進行反應，同時，於該鈦酸^^步 驟中’使鈣離子殘留量直到置入量的百分之一以下使其進行反應。 [12] 如揭示於[9]至[丨1]中任一項之鈦酸鈣鋇之製造方法，I 中於該驗性化合物之去除步驟後’於35(rc以上、120(rc以下之'範 圍進行熱處理。 [13] 如揭示於[9]至[12]中任一項之鈦酸鈣鋇之製造方法，其 中從鈦酸鋇合成至鈦酸鈣鋇合成為止之步驟中管/ =反應溶液中碳酸基之濃度控制於。ppm以上、50；pcp=^範 中任—項之鈦酸觸之製造方法，其 τ该虱化鈦係一種含有板鈦礦型結晶者。 [^]如揭示於[9]至[14]中任-項之鈦酸舞鋇之製造方法，豆 化鈦係—種於酸性水溶液中進行鈦化合物之水解而成的氧 中:至!，任—項之鈦_鋇之製造方法，其 肀《亥鹼性化合物係於一大氣壓下或減壓 曰# a 分解rt中的至少—種以上技術手段進行氣化的=發、幵華、熱 [η如揭不於[9]至[16]中任一項之鈦酸舞 止 中該驗性化合物係-種有機驗性化合物。、之找方法’其 [18]如揭示於[9]至[17]中任一項之鈦酸鈣鋇 中該驗性化合物係—種四甲基銨氫氧化物。、I 法’ ” 之鈦^^介電材料’其特徵為：含有揭示於⑴至附任-項 鈦酸麵狀物，其特徵為：含有揭示於[1]至附任-項之 1286537 [21] 種漿狀物’其特徵為：含有揭示於⑴ 鈦酸鈣鋇。 任一項之 [22] -種薄膜狀形成物，其特徵為··含有揭 一項之鈦酸鈣鋇。 L J主〖8]中任 [23] 種電介貝磁為，其特徵為··使用揭示於⑴至⑻由 項之鈦酸鈣鋇所製造的。 [1J至[8]中任一 間-種熱電磁器，其特徵為：使用揭示於 之鈦酸鈣鋇所製造的。 』王节任一項 [25]種麼電磁益，其特徵為··使用含有揭示於中 •-項之鈦酸觸所製造的。 3 ⑴至[8]中任 S二ϊίίΐ，其特徵為··含有揭示於[23]之電介質磁器。 馆夕屬^電子设備，其特徵為··含有由揭示於[22]至[26]中任 =之_狀形成物、磁器與電容㈣成的族群中所^的6]至中少任 ⑽種感職，其特徵為：含有—種或二種以上揭示於[22] 至[25]中任一項之薄膜狀形成物或磁器。 、〖] 項之電介f細’其特徵為：含有揭祕[1]珊中任一 製得ί —種電容器，其特徵為：使_示於[29]之電介質薄膜所 發明之斂果 一種佳之鈦_鋇具有下列特別之效果：提供 以二散性優異的、不純物為少的、結晶性為高的、 任忍比例所固溶的鈦酸鈣鋇粉末及其製造方法。 料ϋΐϊ，鋇粉末及含有該粉末讀狀物、糊狀物係一種 性者，可以得到性能優異的磁器、薄膜、電介 由設備，電子設備之小型化、輕量化成為可能的。 丨貝’專膜之介電特性為優異的，因為即使薄膜化也能夠 1286537 發揮優異的特性，可應用於基板内電容器等 位相機等電子設備巾採職電容器的話，對 話或數 量化、高性能化極為有效。 義°。之小型化、輕 【實施方式】 以下’洋細說明本發明。 本發明較佳實施形態之鈦酸齊鋇係 Υ™3 (〇&lt;χ&lt;α2，__.02)所示之ί 化合物。此處之「固溶」意指並非單純的鈦石廣 鲁造能線繞射啦晶構 比例能夠由X線繞射圖之鱗位置求彳^。、4鋇巾之鋇朗的 0 0 1粉之鎖鱗的比例（固溶比）x較宜為0〜0.2，更佳為 1於il如之到所要求之電特性而進行ίί例 三===== 調整至所要求值的鈦酸舞鋇。 至狐卜之;,電书數 • 〇 98〜1 5十莫耳數與欽莫耳數的比例⑺較宜為 電ir〜lgi，最好為娜〜⑽，達到所要求之 ίΐϊ周整。比例γ較宜越接近於1，越無缺陷，結晶 Λ 善本發明較佳實施形態之鈦酸_的電特性，即使添 加其，化合物後使用，也無任何阻礙。 —般而言，為了電子設備之小型化，若比表面積較i m2/g為 了變得;二=*，严非有效的；若比表面積超過w〇 m2/g ’除 私之外，該粉末之操作職得_。本發明較佳實 形怨之鈦酸鋇，其比表面積於1〜100m2/g，較宜於5〜70m2/g， 12 1286537 法所求得的比圍。退有’於本發明巾，較宜採用以bet 置Ϊ量，&quot;&quot;軸長與a轴長之長度關係已揭示於^L ^^，38 142 (1955)等。Ca置換量越大，c軸長與 將茭仟越小。本發明較佳實施形態之鈦[9] A method for producing calcium strontium titanate, which is characterized in that an analyte solution having a pH value of 10 or more is used to synthesize titanium by reacting with the test solution. The step of strontium strontium is followed by a step of oxidizing and then removing the titanium hydride to form a oxyhydroxide compound to be vaporized and removed. And, in order to make the alkalized lock and the gas oxygen are combined, the titanium oxide 9 1286537 alkaline solution is used to react the barium hydroxide, calcium hydroxide and titanium oxide. Titanic acid feeding. [11] The method for producing calcium titanate strontium according to [9] or [10], wherein in the synthetic step of the barium titanate, the residual amount of strontium ions in the alkaline solution is made - Thereafter, the reaction is carried out, and at the same time, in the titanate step, the residual amount of calcium ions is allowed to react until it is less than one percent of the amount of the implant. [12] The method for producing calcium titanate strontium according to any one of [9] to [丨1], wherein after the step of removing the test compound, I is at 35 (rc or more, 120 (rc or less) [13] The method for producing calcium titanate strontium according to any one of [9] to [12], wherein the step from the synthesis of barium titanate to the synthesis of calcium titanate strontium / The concentration of the carbonic acid group in the reaction solution is controlled by a method for producing a titanate touch of .ppm or more, 50; pcp=^fan, wherein the titanium oxide is a brookite-type crystal. [^] For example, the method for producing a titanic acid mahogany disclosed in any one of [9] to [14], wherein the titanium bean is grown in an acidic aqueous solution to hydrolyze a titanium compound: to! The manufacturing method of titanium 钡 , 肀 亥 亥 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性 碱性The test compound is an organic compound which is not detected in the titanate dance of any one of [9] to [16]. The method of finding [18] is disclosed in [9] to [17]. Any one of them In the calcium titanate strontium, the test compound is a tetramethylammonium hydroxide. The titanium method of the I method is characterized by containing the (1) to the attached-item titanate. And characterized by comprising: 1286537 [21] of the slurry disclosed in [1] to the attached-item, characterized in that the content is contained in (1) calcium titanate. Any one of [22] A film-like formed product characterized by containing calcium titanate strontium according to the disclosure. Among the LJ main 〖8], [23] is a kind of electric magnetic material, which is characterized by the use of the items disclosed in (1) to (8). Manufactured by calcium titanate strontium. [1] to [8], the thermal electromagnetic device is characterized by: using the calcium titanate disclosed therein. Electromagnetic benefit, which is characterized by the use of a titanium acid contact disclosed in the middle item. 3 (1) to [8], S 2 ϊ ίίΐ, which is characterized by containing the dielectric disclosed in [23] The electronic device is characterized by containing the 6] to the middle of the group formed by the _ shape formation, the magnetic device and the capacitance (4) disclosed in [22] to [26]. Less than (10) kind of duty, The film is characterized in that it contains one or more of the film-like formations or magnets disclosed in any one of [22] to [25]. The dielectric of the item [] is characterized by: containing the secret [1] Any of the capacitors produced by Shan is characterized by the fact that the dielectric thin film shown in [29] has a special effect on the titanium alloy having the following special effects: providing impurities with excellent dispersibility The calcium titanate tantalum powder which is solid and soluble in a high crystallinity ratio and a method for producing the same. The material, the tantalum powder, and the powder containing the powder and the paste are one-piece. Capacitors, thin films, and dielectrics with excellent performance are possible, and miniaturization and weight reduction of electronic equipment are possible.丨 ' ' 专 专 专 专 专 专 专 ' ' ' ' ' ' ' ' ' ' ' 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 It is extremely effective. Meaning °. Miniaturization and lightness [Embodiment] Hereinafter, the present invention will be described in detail. A preferred compound of the preferred embodiment of the present invention is a compound of the strontium titanate 3 TM3 (〇 &lt;χ&lt;α2, __.02). Here, "solid solution" means that the ratio of the crystal structure of the X-ray diffraction pattern can be obtained from the scale of the X-ray diffraction pattern. The ratio of the lock scale of the 0 0 1 powder (solid solution ratio) is preferably 0 to 0.2, more preferably 1 to il as required to the required electrical characteristics. ==== Adjust the titanate to the required value. To the fox; the number of electric books • 〇 98~1 5 The ratio of the number of moles to the number of chins (7) is more suitable for electric ir~lgi, preferably Na~(10), to achieve the required ΐϊ week. The ratio γ is preferably closer to 1, and the more the defect is, the more the crystallization is. The electrical properties of the titanic acid of the preferred embodiment of the present invention are not hindered even after the addition of the compound. In general, for the miniaturization of electronic equipment, if the specific surface area is i m2 / g in order to become; two = *, strictly non-effective; if the specific surface area exceeds w 〇 m2 / g 'except for private, the powder The operation of the job _. The preferred embodiment of the present invention is barium titanate having a specific surface area of from 1 to 100 m 2 /g, more preferably from 5 to 70 m 2 /g, and a ratio of 12 1286537. It is preferable to use the size of the bet, and the relationship between the length of the axis and the length of the a-axis is disclosed in ^L ^^, 38 142 (1955) and the like. The larger the Ca substitution amount, the smaller the c-axis length and the 茭仟. Titanium according to a preferred embodiment of the present invention

Jr=ET法所求得㈣^ lyTtTTm&quot;^ (c/a 為〜滿足下式⑴或⑵，顯示為微粒的，高的.」又 yM.0095-8.8xl0 6xD3 (其中，1红)级7 之時） ya.003 (其中 ’9.7&lt;IK100 之時） 、) 礦化施形態之欽酸鎖中，副產物之斜方晶系触 物，f有3mol%以下之範圍。斜方晶系賴礦化合 出/另外，H為大之情形’作為x線繞射之波峰被檢測 U匕ϋίίΐ為G1%以下之情形，能夠求出鈦娜貝之 測定均Ca狀量之差。欽酸1弓鋇之固溶比係藉由 正ίϋΐίί 或三個逐次相轉移點之中的斜方晶系鱼 用:itn點，得的。所有粉末之平均Ca混人量能夠利 光X線法i二；)，=將/= 用婦描式電伽㈣狀不同，利 分之驗佳魏職之⑽_也可时找低於千 刀之莫耳原枓之虱氧化妈、氫氧化納、氧化欽。 為單？丄卜樹trdrs鈦酸_係—種具有8。％以上 早晶能夠藉由TEM (穿透式電子顯彳评ϋ 為早曰曰。 粒子予以薄膜化後進行觀察鏡）硯察（較宜細_貝 以上=之形態之鈦酸觸，其粒子内不存在1邮 上工孔之粒子為所有粒子的80%以上， 為100%。粒子内是否存在經基或起因於經基脫離之缺陷，或是即 13 1286537 使存在’其大小較宜低於。 近之ΐί於鋇讀基储由紅⑽分析法檢卿(KW附 乂波峰’除了粒子内之經基外，同時也檢測存在於之。 t ’因為於較70(rc為低的溫度下，存在於表面 ^，Jr=ET method (4)^ lyTtTTm&quot;^ (c/a is ~ satisfying the following formula (1) or (2), which is shown as a particle, high." yM.0095-8.8xl0 6xD3 (of which 1 red) level 7 At the time) ya.003 (where '9.7&lt;IK100),) The orthorhombic contact of the by-product in the mineralized lock of the mineralization mode, f has a range of 3 mol% or less. The orthorhombic system is combined with mineralization and/or H is a large case. As the peak of the x-ray diffraction is detected as U匕ϋίίΐ is less than G1%, the difference between the measured Ca-like amounts of Tiñabei can be obtained. . The solid solution ratio of the acid is 1 by positive or 三个 ϋΐ ί 斜 斜 正 正 正 正 正 正 正 正 it 正 it it 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正 正The average Ca-mixed amount of all powders can be used to benefit the X-ray method i2;), ================================================================================== The Mo's original 虱 虱 虱 oxidation, mother, sodium hydroxide, oxidation. Is it a single?丄 树 tree trdrs titanic acid _ system - species has 8. % or more of the early crystals can be observed by TEM (transmission electron spectroscopy is early 曰曰. After the particles are thinned and observed, the observation mirror is observed) (it is better to be thinner than the above-mentioned form of titanate touch, its particles There is no particle in the postal hole of more than 80% of all particles, which is 100%. Whether there is a radical in the particle or a defect caused by the detachment of the meridine, or 13 1286537, the presence of 'the size is lower In the near ΐ 钡 钡 钡 基 基 基 基 基 基 基 基 基 基 基 基 基 KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW KW Next, exists on the surface ^,

^預聽7G(TC進行熱處理後，進行紅外線分析而檢測粒H 本發赚佳實施形態之鈦酸觸，粒子内不存在inm 之粉末占所有粉末之80%以上，由於粒子内幾乎 = 起因於縣脫離之缺陷，介電常數將變高。奸不存在經基或 的髀iir交ί實施，之鈦酸鈣鋇係將利用影像解析法所求得 粒Αίί D2之ΙΪΪϋΙ〒、從粒徑小者起累計而成為5%的 ίϋ$ 粒徑設為D3、最大之粒徑設為D4時， 較且為0·5〜1之靶圍。D3/D1較宜滿足1〜1.8之笳in，m/ni =滿足1〜/2。由於本發雜佳實施形態中之鈦酸躺，^粒徑 的斜方晶系鈣鈦礦化合物為少的，粒徑分布變窄。、八&quot;二’、、、 越好娜1、D3/D1之各值織薇1，—:綠仇練分布越窄 Μ以本上實施形態之D2/D1為G.5以上、1以下，較宜為 另外，本發明較佳實施形態之D3/D1為j以 宜為1以上、1.7以下。 ι.δ以卜 ，者，本發明較佳實施形態之D_為丨以上、2 且為1以上、1·9以下。 平 如此之鈦酸鈣鋇係粒徑為小的，並且，介 ，藉由細此所得_電介_二=; =賴_魏容器料型電子元件，進―賴 子兀件丄電子設備之小型化、輕量化將成為可能的。 、 接著，說明本發明鈦酸鈣鋇之製造方法。 本發明鈦酸_之製造方法較錄缝化鋇與氫氧倾的莫 14 1286537 之任意範圍’相對於氫氧化鋇與氫氧化約 溶液中，使此等反應物得以進行反應。此時， • Ξ。中3氫氧化鋇與氧化鈦進行反應而合成鈦酸 』。”、、後接者，置人魏化触-步使其進行反應而製造鈦酸舞 先使氫氧化鋇與氧化鈦進行反應而生成鈦 若同時Ϊ人所触此鈦_進行反應而剌鈦酸舞鋇。 m二 有的蛊氧化鋇、氫氧化鈣與氧化鈦而使其進行反 ί爭化鈦酸鋇之反應將導致 ▲禮m 斜方日日糸倾礦化合物之傾向，另外，最多 預先二二若根據本發明較佳之方法，因為於 太酸鎖之後’使触行反應，能夠製造斜方 ΐ ^，3 mGl%以下之鈦酸觸，較宜為2m〇1%以 L旁ίί4 下’尤以Om〇i%以下更為理想。另外，若 的話’㈣製造將至多約_顧置換成 〇更具體而言，本發明較佳實施形態的話，以任 人 ΐ二匕氫ί化鋇、氫氧化鈣與氧化鈦溶膠成為既定比 以任心比例X、γ之鈦酸鈣鋇。例如，藉由置入^Pre-listening 7G (after TC heat treatment, the infrared ray analysis is carried out to detect the granule H. The titanate touch is good, and the powder which does not exist in the particle accounts for 80% or more of all the powder, because the particle is almost = The defect of the county detachment, the dielectric constant will become higher. The glutinous calcium titanate system will be obtained by image analysis method, and the particle size will be small. When the cumulative value is 5%, the particle size is D3, and the maximum particle size is D4, which is more than 0. 5~1. D3/D1 should preferably satisfy 1~1.8. m/ni = satisfies 1 to /2. Since the titanic acid in the present embodiment is small, the orthorhombic perovskite compound having a small particle size is small, and the particle size distribution is narrowed. ',,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, In the preferred embodiment of the present invention, D3/D1 is preferably 1 or more and 1.7 or less. ι.δ, in the preferred embodiment of the present invention, D_ is 丨 or more, 2 and 1 or more, 1 · 9 or less. Flat calcium titanate has a small particle size, and it is obtained by fine-grained _ _ _ 2 =; 赖 _ Wei container material type electronic components, into the 兀 兀 丄 electronic The miniaturization and weight reduction of the device will be possible. Next, the method for producing the calcium titanate strontium of the present invention will be described. The method for producing the titanic acid of the present invention is more than any range of the recording of enthalpy and hydrogen oxyhydration. 'Reacting these reactants with respect to about cesium hydroxide and hydrazine hydroxide. At this time, Ξ. 3 cesium hydroxide reacts with titanium oxide to synthesize titanic acid.", followed by The Weihua touch-step is used to react to produce a titanic acid dance, which first reacts cerium hydroxide with titanium oxide to form titanium, and at the same time, the titanium cerium is reacted to react with strontium titanate. Some bismuth oxides, calcium hydroxide and titanium oxide cause the reaction of barium titanate to cause the tendency of ▲ m m 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜A preferred method of the invention, because after a too acid lock, 'to make a touch reaction, It is possible to manufacture a titanic ΐ ^, 3 mGl% or less of titanic acid contact, preferably 2m 〇 1% with L ί ίί4 under 'except for Om〇i%. More if, '(4) manufacturing will be at most More specifically, in the preferred embodiment of the present invention, the calcium titanate having a predetermined ratio of X and γ is used as a predetermined ratio of hydrazine, calcium hydroxide and titanium oxide sol.钡. For example, by placing

Tl ^^t^Bao^Cao.o.Tii 耳比，能夠製造=9c%lTi^^ ·乳化欽=90: 10 : 100之莫 100 佳Λ藉由置/&quot;氨氧化鋇：氫氧化舞：氧化鈦= 99.0 : 1.0 ·· 氧化鋇：笱^卜製造Β^.990%0107103·000粉末；藉由置入氫 : ιαο: 1〇°·0^^^^ ^ 本發明較佳實施形態之鈦酸转鎖之製造方法 存在鹼性化合物之驗性溶液。軸理由尚未較，但是 15 1286537 之Γη信A I’n貝離子、鈣離子越容易與氧化鈦進行反應。溶液 物t入旦的卜ρΓ/上、較宜為13以上、更佳為14以上。鹼性化合 』令ΐ限係成為相對於其驗性化合物中水的飽和溶解度。 10以較佳實施形態中，於存在驗性化合物之ΡΗ值 下，較千^貝離子殘存量直到為置入量的百分之一以 二目ii i i之一以下，使其與氧化鈦進行反應而合成鈦 一 置之ί氧化舞之後，舞離子殘存量直到為置入量的 刀 1下，較宜直到為千分之一以下，使其進行反鹿而势造 低ίΐ丄能，造原料之氫氧化鋇、i氧化“鈦 鋇！：二夕莫耳，較宜為低於千分之-莫耳的鈦酸鈣 宜4tii丄：ί，χ、γ之值控制至百分之-數量級，較 且才工fjj至千分之一數量級的鈦酸鈣鋇。 分予u離子量、_子量係將反應溶液之固體成 液中之各“ί予發光法或原子吸光法等’將反應 入旦係如上所述，反應後溶液中各離子的合計濃度直到置 為止，較宜直到千分之一以下為止使其反 ί庫iHtr為止使其反應。藉此，提高對鈦酸_之 減低未反應之虱氧化物、氧化鈦等原料，予以高純度化， 晶性。反應後合計濃度之減少率能_用下式⑶而求出。 ([A1’] + [A2’]) xL2/ ([A1] + [A2]) (3) [A1 ]、[A2’]:將各別反應後之溶液中A1離 離子重量濃舒以換算後所求出的莫耳濃度（mGl/ml)。^ A2 [Al]、[A2]:置人各別反應之氫氧化物的莫耳數。 L2 ··反應液量（ml)。 另該合成反應最為工業化的方式是經加熱、擾摔而 、。尤，、’一旦進行機械式攪拌時，適合原料相互間混合。另外， 16 1286537 由於反應液為鹼性的，容易吸收空氣中之c〇2。因此，欲使反應 液不與空氣接觸’較宜—面？以密封或是喷人不活性氣體等，並 二面進行反應。一旦c〇2被反應液所吸收時，於反應液中便含有 石屄酸基。此碳酸基（碳酸種類包含C〇2、pj2C〇3、—與⑺32—、 係與氫氧化鋇或氫氧化鈣進行反應而生成安定之碳酸鋇盥碳酸 鈣。碳酸鋇或碳酸鈣並不與氧化鈦進行反應，而是於鈦酸鈣鋇中， 以不純物方式殘存之傾向。因而，較宜控制反應液中之碳酸 费浪度（c〇2換算值。以下，只要無特別之申明，則為相同的。）。 藉由控制碳酸基濃度，能夠穩定地製造純度高的鈦酸每鋇。 所旦反應液中之C〇2換异濃度為0〜500質量ppm，較宜為0〜200 二= ppm，更佳為0〜100質量ppm。為了減少反應液中之碳酸基 浪度，較宜於即將製造之前，對於溶解鹼性化合物前的水， 加熱處理而脫除碳酸。 声了提高鈦酸觸之結晶性，期望盡可能提高反應溫 ^針對k*反應溫度，雖然KKTC〜溶液臨界溫度為止之水熱反 應為可能的，因此，必須具有考量熱壓器等安全上之設備。 因而，較宜煮沸至95。(：以上，維持溫度後進行。 氫氧化鋇與氧化鈦之反應時間，通常為2小時以上， f佳ί4小時社。另外，氫氧化1$置人後之反^ 間，通吊為2小日卞以上，較宜為4小時以上，更佳為6小時以上。 鈦酸·之電特性造成不良影響的不純物，可列舉： ^里ίίίΐ子或陰離子等成分。為了去除此等之不純物，可列 二击j用電减、離子交換、水洗、酸洗、渗透膜等，進行反應 二i之漿狀物的處理等各種方法。然而，於此等方法之中，^ 離同時與不純物離子’也同時與鈦_鋇中所含之鋇 部分溶於漿狀物中之情形，補依所要求之比例而ί 予簡溶將變得困難，因為結晶巾也將有產生缺陷、姓曰 之^形而必須加以注意。另外’由於反應液為驗性的^ 孔中之-减碳將容易狀此等之處理中。因此，鈇g_鋇中所 17 1286537 含之碳酸鹽將有變多之情形。 藉此，選定不純物少的原料之同時，較宜進行防止於合成反 ，，煅燒之不純物混入。再加上，較宜於合成反應結束後之一大 氣壓下或減壓下、室溫〜可煅燒溫度之溫度範圍，藉由蒸發、昇華 巧/或熱分解而將不純物形成氣體後予以去除。此時，較宜同時分 解於鹼溶液中所含之鹼性化合物，形成氣體後予以去除。 刀 一般而言，煅燒係為了使含有鈦之複合型氧化物之結晶性予 =提高所進行的，另一方面，藉由進行煅燒，可以進行蒎發、 f與/或熱分解而將不純物形成氣體後予以去除。利用此^ ，去除的不純物可列舉：碳數低的有機胺、紐之氫氧化物匕 ^鹼以及補巾所含之不純物賴量有機物、碳義等當， iff於35G〜12GG°C之可職的溫度τ進行。職之環境氣體並 …、任何限制，通常可於空氣中或減壓中進行。 、、 於人麟之難4減低或結晶性提高峨點，較宜 吏’進行漿狀物之固液分離後進 g ίΓϊίΓη農縮、過濾'與/或乾燥、碎解之步驟。藉刀由 韻、而能夠去除溶於溶液中之不純物。為了改變ί it’也可以朗凝聚臟分散劑。該凝聚劑或分 純物ϊϊί ^一^行水份蒸發的步驟，根據驗性化合ώ不 華f谢解㈣-部分或所有 繼等方法。通常，乾燥係於室溫^冷 煉之環境氣體並無特別之限制，一纟 恰。乾 減壓=。1,也可以利用適=力 =性氣體中或 的話:不論或化物為氫氧化物 也可=用：_類而製===限定。另外’ 5…、用於本备明之氧化鈦溶膠並無特別之限制，期望 18 1286537 ^有板鈦礦型結晶之氧化鈦溶膠。或是，期望於酸性溶液中， 行鈦鹽之水解而得到的氧化鈦溶膠。 若為含有板鈦礦型結晶者的話，可以單獨含有板鈦礦型纟士曰曰 、鈦’也可以含有金紅石型結晶或銳鈦礦型結晶之氧化=。曰 3有金紅石型結晶或銳鈦礦型結晶之氧化鈦的情形，氧化鈦 ^鈦礦型結晶氧化鈦的比例並無特別之限制，通常為1〜刚 0 ^宜為10〜100質量％，更佳為5〇〜膽f量％。於溶劑中， ΐΐίΐ將氧化鈦粉末作成分散性極佳者，由於料單粒化，座 散為結晶性的，由於板欽礦型結晶氧化鈦之^ i曰r/m 由尚未明確’認為與pH值2之板鈦礙型 、口曰日人ξ電位較五紅石型結晶或銳鈦礦型結晶為高有關。&quot; t有板鈦礦型結晶之氧化鈦粉末的製造方法，可 ΐ化ϊίΐίϋϊΐ粉末，ί理而得到含有板鈦礦型結晶之 烧氧美5 楚或疋’藉由進行四氯化鈦、三氯化鈦、 鈦♦刀末之氧化鈦溶黟所得到的液相中等製造方法。力政乳化Tl ^^t^Bao^Cao.o.Tii Ear ratio, can produce =9c%lTi^^ ·Emulsified Qin =90: 10:100% 100 Good by setting /&quot;Ammonia Oxide: Hydrogenation Dance : Titanium oxide = 99.0 : 1.0 ·· 钡 钡 笱 笱 卜 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 990 The manufacturing method of the titanate shifting has an assay solution of a basic compound. The reason for the axis is not yet the same, but the more easily the I In n, the calcium ion of the 15 1286537 is more likely to react with the titanium oxide. The solution t is preferably at least 13 or more, more preferably 14 or more. Alkaline compounding limits the saturation of water relative to the water in its test compound. In a preferred embodiment, in the presence of the enthalpy of the test compound, the amount of residual ions is less than one percent of the amount of the implant, and one or less of one of the two After the reaction and the synthesis of titanium, the oxidative dance, the amount of dance ions until the amount of the knife 1 is placed, preferably less than one thousandth, so that it is anti-deer and low. The raw material of barium hydroxide, i oxidation "titanium bismuth!: Erxi Moore, preferably less than a thousandth - Molar calcium titanate should be 4tii 丄: ί, χ, γ value controlled to percent - It is of the order of magnitude, and it is more than one-thousandth of an order of calcium titanate. The amount of u ions and the amount of _ sub-components are the liquids of the reaction solution, such as luminescence or atomic absorption. The reaction is carried out as described above, and the total concentration of each ion in the solution after the reaction is allowed to stand until it is less than one thousandth, and is allowed to react until it is inverted. As a result, raw materials such as cerium oxide and titanium oxide which are unreacted by the increase in titanic acid are increased, and the crystallinity is improved. The reduction rate of the total concentration after the reaction can be obtained by the following formula (3). ([A1'] + [A2']) xL2/ ([A1] + [A2]) (3) [A1 ], [A2']: Convert the A1 ion weight in the solution after each reaction The molar concentration (mGl/ml) obtained afterwards. ^ A2 [Al], [A2]: The number of moles of hydroxides that are reacted separately. L2 ··Reaction liquid amount (ml). The most industrial way of synthesizing this reaction is by heating and disturbing. In particular, when mechanical agitation is performed, suitable materials are mixed with each other. In addition, 16 1286537, because the reaction solution is alkaline, it is easy to absorb c〇2 in the air. Therefore, it is better to make the reaction liquid not in contact with air. Seal or spray an inert gas, etc., and carry out the reaction on both sides. Once c〇2 is absorbed by the reaction solution, it contains a sulphate group in the reaction solution. The carbonic acid group (carbonic acid type includes C〇2, pj2C〇3, and (7)32-, reacts with barium hydroxide or calcium hydroxide to form stable barium carbonate calcium carbonate. Barium carbonate or calcium carbonate does not oxidize Titanium reacts, but it tends to remain as an impurity in calcium titanate. Therefore, it is preferable to control the carbonation rate in the reaction liquid (c〇2 conversion value. Hereinafter, unless otherwise specified, The same.) By controlling the concentration of the carbonic acid group, it is possible to stably produce high-purity titanic acid per ruthenium. The concentration of C〇2 in the reaction liquid is 0 to 500 ppm by mass, preferably 0 to 200. = ppm, more preferably 0 to 100 ppm by mass. In order to reduce the degree of carbonation in the reaction liquid, it is preferred to remove the carbonic acid by heat treatment before dissolving the water before the alkaline compound is dissolved. The acidity of the acid touch is expected to increase the reaction temperature as much as possible. For the k* reaction temperature, although the hydrothermal reaction of the KKTC to the critical temperature of the solution is possible, it is necessary to have a safety device such as an autoclave. It is better to boil to 95. (: Above, after maintaining the temperature. The reaction time of barium hydroxide and titanium oxide is usually 2 hours or more, f is good for 4 hours. In addition, after the oxidation of 1$ is placed, the pass is 2 small. Above the sundial, it is more preferably 4 hours or more, more preferably 6 hours or more. The impurities which are adversely affected by the electrical properties of the titanate include: ^ ίίίί ΐ or an anion, etc. In order to remove such impurities, The second step is to use various methods such as electric reduction, ion exchange, water washing, pickling, permeable membrane, etc., to carry out the treatment of the slurry of the reaction ii. However, among these methods, the simultaneous and impurity ions are At the same time, in the case where the yttrium contained in the titanium yttrium is partially dissolved in the syrup, it will become difficult to supplement the required ratio, because the crystallization towel will also have defects, and the surname The shape must be taken care of. In addition, because the reaction liquid is an inspective hole, carbon reduction will be easily treated in this way. Therefore, the carbonate contained in 12g_钡中17 1286537 will be more In this case, when raw materials with less impurities are selected, The anti-purification of the calcination is prevented, and it is more suitable for the temperature range of one atmosphere or under reduced pressure and the room temperature to the calcination temperature after the end of the synthesis reaction, by evaporation, sublimation and/or After the thermal decomposition, the impurities are formed into a gas and then removed. At this time, it is preferable to simultaneously decompose the basic compound contained in the alkali solution to form a gas and then remove it. Generally, the calcination system is for oxidizing the composite containing titanium. On the other hand, by performing calcination, it is possible to carry out the formation of a gas by bursting, f and/or thermal decomposition, and then removing the impurities, and removing the impurities by this means: The organic amine having a low carbon number, the hydroxide of the neon, and the impurities contained in the towel are organic matter, carbon, etc., and iff is carried out at a temperature τ of 35 G to 12 GG °C. Environmental gases and ..., any restrictions, usually in the air or under reduced pressure. ,, in the case of Renlin's Difficulty 4 reduction or increase in crystallinity, it is better to carry out the solid-liquid separation of the slurry and then enter the steps of g ίΓϊίΓη, shrinking, filtering and/or drying and disintegrating. By means of the rhyme, it is possible to remove impurities dissolved in the solution. In order to change ί it', it is also possible to condense the dirty dispersant. The coagulant or the fraction of the pure substance 蒸发 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Usually, the ambient gas which is dried at room temperature and cooled is not particularly limited. Dry decompression =. 1, can also use the appropriate = force = sex gas in the words: whether the compound is a hydroxide or = use: _ class and === limited. Further, '5..., the titanium oxide sol used in the present invention is not particularly limited, and it is desired that 18 1286537^ has a brookite-type crystal titanium oxide sol. Alternatively, it is desirable to obtain a titanium oxide sol obtained by hydrolysis of a titanium salt in an acidic solution. In the case of a brookite-type crystal, it may contain brookite-type gentils, titanium, or rutile-type crystals or anatase-type crystals.曰3 In the case of rutile-type crystal or anatase-type crystallized titanium oxide, the ratio of the titanium oxide-titanium-type crystalline titanium oxide is not particularly limited, and is usually from 1 to just 0%, preferably from 10 to 100% by mass. More preferably, it is 5〇~biliary f%%. In the solvent, 氧化钛ίΐ is excellent in dispersibility of titanium oxide powder. Due to the granulation of the material, the dispersion is crystalline, and the ^ i曰r/m of the zirconia-type crystalline titanium oxide has not been clearly defined as The titanium plate of pH 2 has a higher zeta potential than that of pentsite crystal or anatase crystal. &quot; t There is a method for producing titanium oxide powder of brookite type crystal, which can be obtained by purifying ϊ ΐ ΐ ϋϊΐ , , , , , 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉A liquid phase intermediate manufacturing method obtained by dissolving titanium oxide of titanium trichloride and titanium ♦ at the end of the knife. Force emulsification

於製造原料中使用含有板鈦礦型結晶之氧化， 較宜使用於酸性溶液中進行氧化鈦粉 解：K 化鈦溶膠之製造方法，例如，較宜為可』= 熱水中添加四氯化鈦，於抑以 猎由於75〜100 c之 控制氯離子濃度，並-面進行四氣占以下的溫度，一面 1副糊開' 鈦’再於硝酸根離子、磷酸根離子之任水::二：， 於75。(：以上之溶液彿點以下的溫声，ϋ疋-種的存在下’ 子與磷酸根離子之合計濃产，计二二、面拴制氯離子、硝酸根離 有板鈦礦型結晶之氧化“末作化鈦之水解’將含 公開第99/58451號手冊）。卞成，合膠而侍到的方法（國際專利 19 1286537 如此方式所得刺板鈦礦型結晶之氧化鈦粉末大小，1 ϋϊίοί控通常為1〜1GGnm，較宜為3〜5Gnm，更佳為5〜20邮。 的；將作t原料所製造之含有鈦複合型氧化物粉末 &amp;形 於製造氧化鈦粉末之步驟上，财操作困難 幵；，射進行雖之水觸制的氧化鈦溶膠之情 乳鈦之結晶型並無限制，也非局限於板欽礦型結晶相 ，較於中性或鹼性之溶液中進行，若 因為氣離子、硫酸根離。另外， 子於製造含有 速度苡方二=行水解時，大多反應 將如此核躲賴狀之情形。 之情形，即使所得到:=徑=有物粉末 步驟，將有絲4ί=ί二末之㈣，於其後之 ，要:酸==解=氧化欽溶膠之方法， =鈦作為原料，於裝設回流冷^。較宜以四 開平術液維持酸性的方法（日本專= -曰紐溶液中的濃度較宜為_〜^l。^ 起過5m‘時，將有水解之反應速度變大而得^: 20 1286537 大的、分散性差的氧化鈦溶膠之情形，低 為將5所得到的氧化鈦濃度變少、生產^變差之的話，因 氧化鈦溶膠之置入方法，雖然並無 ^ 乂 、制氧化鈦溶膠之凝聚、分散性優異的^，到抑 次少量地置入進行加熱、攪拌中上，鈣鋇鹽，每 ►此鹼性化合物並無任何限制，較宜為於一丁土。雖= 驗。h病f生為一*數低之有機胺、銨鹽的氫氧化物等有機 作為ίί之的物—旦溶人水中，解離度為高的，發揮 低彿點之故，將有難以使用之情形。 作抓為弱的、 (ΤΙ^ΪΓί化知工業上之膽鹼、四f基録氫氧化物 1 ;電i?購得。尤其’四甲基銨氫氧化物已使用 於135〜140'。(：工^，_得金屬離子等少的不純物，也適合 進仃熱分解而㈣崎財式予以去除。 化鐘合型氧化物粉末也能夠使用廉價之氫氧 、-=化納、氫氧化鉀等無機化合物而加以製造。 -種^也可H匕勿並無特別之限制，此等化合物可以單獨使用 如并方4 思之比例混合二種以上化合物後使用均無問題。 狹窄的ίίίί造的欽酸1弓鎖粉末，其粒徑為小的、粒徑分布 ::Ϊ:、Γ優異的、結晶性為高的、電特性優異的，尤其； 、‘、、、少、’使鋇與朗溶成任意比例的粉末，成形成電介質磁 21 1286537 器、=器、壓電磁器、薄獏狀形成物。 成===有 £ίί^ 用之=化=脂較無特別之限制，可以使用泛 ^ : fΑ#ίΐ1 ^ ^ 劑中=::^ 得到漿狀物;^物/f _合物中而 :?=:f纖维素，或是齡二種以:以 …、-4分散於溶劑中或該樹脂組成物與溶劑之混合物 22 1286537 利用_合劑進行處理。麵合劑並非特別受 == 可列舉:矽烷_、鈦酸鹽系耦合劑、銘酸 夕曰^ ☆二i。由於耦合劑之親水基將與含有本發明鈦酸鈣鋇粉末 Mfcir上:，的活性氫進行反應而被覆於表面，於溶劑中之分散 °麵合劑之疏水基能觸由此選擇而提高對樹脂之 。例如，姻旨制縣旨之獅，官能基之-較宜且有 ίϊί任=ΐί、，子苯乙烯基、環氧基、11硫基、苯胺i、 =真、的石夕’合劑，或是官能基之—較宜具有碟酸鹽、 細^用、％氧基、氫硫基等任—種的鈦酸鹽系轉合劑。 = 胺樹脂之情形’官能基之一較宜具有，基、二 ί二;a ^専任―種的魏輕合劑’或是官能基之—較宜具有 一月女基、二胺基等任一種的鈦酸鹽系耦合劑。 /、 用。可以單獨使用此等耦合劑之中的一種或混合二種以上而使 摻合量並無_之限定’只要能夠被覆鈦酸軸 而、全部的話即可’多的話則有可能未反應下維持_ 視響，過少的話則有可能使搞合劑效果變低。因而 而i，較粒徑與比表面積、填充劑之種類 ⑽益t 擇此夠使填充劑予以均勻分散的摻合量，期望含右 鈦I鈣鋇粉末之填充劑約〇·〇5〜20質量％的摻合量。 有 為了使耦合劑之親水基與含有鈦酸詞鋇末 =鼠之^得以結束，較宜含有形絲狀物後進行加^2= ^加熱溫度鱗間並無任何關，較綱〜% 加熱處理。另外’溶劑之沸點為i〇(rc以下時，加熱溫二 為洛=丨之_以下，因應於此而可以增長加熱時間。 〜又 圖。第1圖係顯示電容器-例之層壓型陶竟電容器的橫剖面示意 如第1 ®所示，此層壓咖魏容器i係由電介質層 曰聖内部電極3、4而成的層壓物5、與裝設於此層壓物5之夕^部 23 5 1286537 電极6、7所構成的。内部電極34苴一 + 之側面，各-端部分別連接於外部電分別露出層壓物 而成Ϊ介等Γ欽酸觸粉末予以固化成形Oxidation containing brookite-type crystals is used in the production of raw materials, and it is preferably used in an acidic solution to carry out titanium oxide pulverization: a method for producing K-titanium sol, for example, it is preferable to add tetrachloric acid to hot water. Titanium, in the case of hunting, the concentration of chloride ions controlled by 75~100 c, and the temperature of the four gases accounted for the following, one side of the paste is opened, and the titanium is added to the water of the nitrate ion and the phosphate ion:: Two:, at 75. (: The above solution is the warm sound below the Buddha's point, in the presence of ϋ疋-species, the total amount of the sub- and phosphate ions is concentrated, and the chlorite and nitrate are separated from the brookite-type crystal. Oxidation "hydrolysis of titanium for the last time" will contain the manual No. 99/58451). The method of forming a gelatinized compound (International Patent No. 19 1286537) The size of the titanium oxide powder of the slab-type crystallization of the obtained slab-type crystal, 1 ϋϊίοί control is usually 1 to 1 GGnm, more preferably 3 to 5 Gnm, more preferably 5 to 20 Å. The titanium-containing composite oxide powder &amp; On the other hand, the operation of the financial operation is difficult; the crystal form of the titanium oxide sol that is sprayed by the water is not limited, and is not limited to the plate crystal phase, compared to the neutral or alkaline solution. In the case of gas ionization and sulphate separation, in the case of production, the rate of enthalpy is reduced, and most of the reaction will be so nucleated. Even if it is obtained: = diameter = matter The powder step will be silky 4 ί = ί 末 (4), after which, To: acid == solution = oxidized sol method, = titanium as raw material, installed in the reflux cold ^. It is better to use Sikaiping liquid to maintain acidity (Japan's special = - 曰 New solution concentration is better _~^l.^ When 5m' is obtained, the reaction rate of hydrolysis is increased to obtain a large titania sol of poor dispersion: 20 1286537, which is low in concentration of titanium oxide obtained in 5 In the case of the production of the titanium oxide sol, the method of the titanium oxide sol is not used, and the aggregation of the titanium oxide sol is excellent, and the dispersibility is excellent, and it is placed in a small amount to be heated and stirred. Calcium strontium salt, there is no limit to each alkaline compound, and it is preferably a butyl soil. Although it is tested, the disease is a low number of organic amines, ammonium hydroxides, etc. The object - in the dissolved water, the degree of dissociation is high, playing the low point of the Buddha, it will be difficult to use. To grasp the weak, (ΤΙ ^ ΪΓ 化 know the industrial choline, four f base Recorded hydroxide 1; electricity i? purchased. Especially 'tetramethylammonium hydroxide has been used in 135~140'. (:工^,_得金It is also suitable for the removal of impurities such as ions, which are suitable for thermal decomposition, and (4) removal by the Kawasaki type. The oxide-type oxide powder can also be produced by using an inorganic compound such as inexpensive hydrogen, -= sodium or potassium hydroxide. - Kind of ^ can also be H 匕 并无 并无 并无 并无 并无 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此The particle size is small, and the particle size distribution is: Ϊ: Γ is excellent, the crystallinity is high, and the electrical properties are excellent, especially; ',,, less, 'the powder is dissolved in an arbitrary ratio. , forming a dielectric magnetic 21 1286537, =, pressure electromagnetic, thin braided formation. === There are £ίί^ Use ===Lipid is not particularly limited, you can use the general ^ : fΑ#ίΐ1 ^ ^ agent =:: ^ to get the slurry; ^ material / f _ :? =: f cellulose, or two kinds of ages: disperse in a solvent, or a mixture of the resin composition and a solvent 22 1286537 with a mixture. The masking agent is not particularly affected == Listed: decane _, titanate coupling agent, lauric acid 曰 曰 ^ ☆ two i. Since the hydrophilic group of the coupling agent is reacted with the active hydrogen containing the calcium titanate powder of the present invention, it is coated on the surface, and the hydrophobic group in the solvent is dispersed to select the resin to improve the resin. It. For example, the lion of the county system, the functional group - preferably and has ίϊί任 = ΐί,, styryl, epoxy, 11 thio, aniline i, = true, Shi Xi' mixture, or It is a functional group - preferably a titanate-based coupling agent of any of a dish salt, a fine electrode, a % oxy group, a thiol group or the like. = In the case of an amine resin, one of the functional groups preferably has a base, a ruthenium; a 専 専 任 ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ Titanate-based coupling agent. /, use. One of these coupling agents may be used alone or in combination of two or more, and the blending amount is not limited to _ as long as it can cover the titanate axis, and if it is all, it may be maintained without reaction. If you look too low, it may make the effect of the combination lower. Therefore, i, the specific particle diameter and the specific surface area, the type of the filler (10) are preferable to the amount of the filler which is uniformly dispersed, and it is desirable that the filler containing the right titanium I calcium strontium powder is about 〇·〇5~20 The amount of mass % blended. In order to make the hydrophilic group of the coupling agent and the titanate containing the titanate = end of the mouse, it is better to add the shape of the filament and then add ^2 = ^ heating temperature without any correlation between the scales, less than ~% heating deal with. In addition, when the boiling point of the solvent is i 〇 (when rc or less, the heating temperature is 2 or less, the heating time can be increased by this.) Fig. 1 shows the capacitor - the laminated ceramic of the example The cross-sectional view of the capacitor is shown in the first ® , and the laminate is a laminate 5 made of a dielectric layer 内部 Saint internal electrodes 3 and 4, and is mounted on the laminate 5 ^部23 5 1286537 The electrodes 6 and 7 are formed on the side of the internal electrode 34苴+, and the respective ends are respectively connected to the external electricity to expose the laminate, respectively, and the tantalum acid contact powder is solidified and formed.

^ 1, ；!7^«Γλ； c Ni' Pd ' Ag C 鍍所構成的。 ’、十§、Cu、Ni等燒結物進行奶電 電容器之製造方法—例加以說明。 物。漿狀物較宜“進结劑、分散劑與水而製造聚狀 η ί著J用刮刀法等，藉由將此襞狀物塗布祕板之德，造 進-電介質層上， =而ΓΓ复進行此步驟，可^====== 電極而成的層壓物。另外，爲网此h I貿S /、内W5 内部電極予以相密著。a i物較且猎由壓縮而使電介質層與 接著’將層&gt;1物裁斷成電容器大小之後，進 6〇f 850^ ^ ^ 電鍵。 之炮燒。最後，於外部電極表面進行见 1。進行如此方式’可以得到顯示於第^圖之層壓型陶竟電容器 〜fi該縣咖技容111係將本發痛佳實施形態之高介 ί常ΐ，_乍為電介質使用，能夠提高電容心r 里。另外’因為韻壓型喊電容器丨係將本^ 1, ;! 7^«Γλ; c Ni' Pd 'Ag C plating. The method of manufacturing a milk capacitor using a sintered product such as §, §, Cu, or Ni is described as an example. Things. Preferably, the slurry is made of a binder, a dispersant, and water to form a poly-type, such as a doctor blade method, and the like, by applying the enamel to the dielectric layer, Repeat this step, ^====== the electrode is formed into a laminate. In addition, for the net I I trade S /, the inner W5 internal electrode is closely related. Ai matter is compared and hunting is made by compression After the dielectric layer and then the 'layer> object is cut into capacitor size, enter 6 〇 f 850 ^ ^ ^ key. The gun is burned. Finally, the surface of the external electrode is seen as 1. In this way 'can be displayed in the first ^The laminated ceramic capacitors of the figure ~fi The county's coffee technology 111 series will be the best of the implementation of this form of high-yield ί Chang, _ 乍 for the use of dielectric, can improve the capacitance of the core. In addition, because of the rhyme Type shout capacitor

態的粒徑，】、的鈦_鋇作為電介質使用，能夠薄化電介質H 24 1286537 此’能夠將電容ϋ本身予則、型化。另外 變薄而更提高電容器之靜電容量。 ⑽夠猎由使電介質層 ,如此之小型層壓型陶瓷電容器能夠適用於電子机偌，，士 行動電話為主之攜帶式儀器的零件。 °又備颂尤乂 魅何 (介電常數測定方法：測定1〜4) 定。所得到的鈦酸之介電常數係進行如下方式般之進行測 使鈦酸軸MgO (日本協和化學玉業股份有限公之 ΐϊΐί 3= Y2〇3 (日本信越化學股份有限公司^之微粉 司制夕陶垄j I 1 rBa&lt;&gt;Ll203 (曰本旭Tedm〇glasS股份有限公 衣之陶瓷低溫燒結用玻璃添加劑）成為1〇〇 : 2 : 15 ·· 2莫耳比 ί之°姻i3mm權具，進行吨混合粉之單軸成型之 焊j ;氮軋％境下，以表1所示之煅燒溫度，維持2小時進行煅 (測定1) 燒結物係於煅燒溫度l〇8(TC所得到的。 (測定2) 燒結物係於煅燒溫度U2(TC所得到的。 (測定3) 燒結物係於锻燒溫度1060°C所得到的。 (測定4) 燒結物係於煅燒溫度l〇4〇°c所得到的。 命精f测定經如此方式所得到的燒結物尺寸後，塗布烘烤用銀 ，藉由於一大氣壓下、於8〇(rc進行1〇分鐘煅燒後形成電極 而作成單板電容器。 測定該電容器之面積、厚度、重量而求出燒結密度。 25 1286537 '、氫2鈣T所算出的理論收率，實際收率之比例為99.9%。 粉末=====糊脈法默财之比表面積， 光譜3射m于此粉末之評估。將此時之X線繞射 c軸長之長度所求出的y為1細，献⑴式。長之長度與 結果掃描式電子顯微鏡進行粉末形狀之放大觀察。將 立使Ϊ所得到的試料’ _穿透式電子顯微鏡（日本曰 夕1 Η-90⑽111110進行觀察。利用EDX進行元素分析 後’如弟5圖所示’得知粉末中均勻地固溶鋇與約。” 針對粉末中所含之碳酸基的量，使用紅外分光分 司製之FTS6_進行定量。若假設所 j歧鋇、碳酸舞，相t於約丨f量％的碳酸基將被檢 ΪΪ出Ϊ應於結晶格子_基的35GGem—1附近之_的吸收波峰 實施例2 制補1所制的粉末，置人電爐（股份有限公3 Denken =之KDFMG)後進行城。職齡係 ，’於，維持2小時後，進行自然冷卻之條件刀。 式，得到實闕2之鈦_粉末。 疋仍此万 2 ^ ^ 另外，將熱處理後之鈦酸鈣鋇粉末的X線繞射光譜顯示於楚 圖。如第6圖所示，斜方晶系辑鈦礦化合物之波峰並未觀，察到， 27 1286537 除了將實施例1所得到的粉末，於1000它維持2 同於實關2之方式’藉由進行域而_實施例3之欽 鎖。 實施例3的欽酸舞鋇粉末之比表面積為51 y 另 =93，滿足（1)式。進-步利用影像解析法所求 為 〇·6，D3/D1 為 1.7，D4/D1 為 U。 局 ^將介電常數之測定結果係顯示於表丨。（測定丨盘測 ^ 了設定氫氧化鋇^水和物之置入量為肌27g、氮氧化舞之 如)里為4.45§之外’藉由進行相同於實施例1之操作，製得實施 例4之鈦酸鈣鋇粉末。 Λ 所得到的實關4之鈦酸觸粉末的比表面積為49 ^ ^ ’於其X線繞射光譜中’斜方晶系賴礦化合物之波峰並未觀 不到’斜方晶系鈣鈦礦化合物之含有率為3莫耳％以下。 進-步纟X雜射賊進行Rietveld騎之後，所得到的粉 =固溶鋇鑛之Ba〇_85〇Ca〇i5〇Ti〇3粉末，另外，y為i.難 疋（2)式。 座„’、針5實施例4之粉末，藉由穿透式電子顯微鏡，以倍 :萬倍進行觀察，起因於羥基脫離之缺陷並未觀察到。 ΐΜΜΛ 、&gt;除了將實施例4所得到的粉末，於11〇〇〇c維持2小時之外， 實施例2之方式，藉由進行锻燒而制實施例5之欽 綠植到的貫施例5粉末之比表面積為5 m2/g。另外，於其χ 光譜中，斜方晶㈣鈦礦化合物之波峰並未觀察到，斜方 、=、，鈦鑛化合物之含有率為3莫耳％以下。再者，y為1〇〇92， 式。進一步再利用影像解析法所求出的d2/idi為〇.6， D3/D1 為 1.8，D4/D1 為 1.9。 29 1286537 入裝設回流冷卻器之反應器内，一面攪拌形成1?11值14之水溶 液，並一面進行煮沸。接著，進行相同於實施例丨之方式而調 氧化鈦溶膠，藉由電滲透裝置而使氯離子直到500ppm為止予^ 去除此溶膠之後’將進行沈澱濃縮所得到的213g之氧化鈦濃产 質量％的凝膠，以每分鐘7g之速度滴人反應如。—面於此^ 下直接進行攪拌，並-面維持4小時之煮沸。將反應液中之一^ 分予以過it ’糊ICP發光法測定舰中之鋇，鋇離子為 直到鋇離子為置入量的千分之一以下進行反應。 之後，除了上述之外的操作係進行相同於實 製得比較例1之鈦酸鈣鋇粉末。 所得到的粉末之比表面積為38 m2/g。另外 ，二於第10圖?第11圖。第11圖係第10圖:放大圖： 々圖中’將斜方晶系触礦化合物之波峰標示〇符號。如此方 於比較例1之鈦酸_巾，觀察到斜方晶系触礦化人物之 ^例藉2此而得知斜方晶_太礦化合物之含有率大於3莫耳. I TtT^5 ^ 1000〇c^2 ^ 例之方式，藉由進行锻燒而得到比較例2之鈦 於第13 μ，U日m圖係第12圖之放大圖。 方式，於航合物之鱗標槐。如此 二二而===物之/有率，耳 與正方晶系之相轉移點為_15。^ ^ ’測疋斜方晶系 _1為0.4，D3/m為2 0，CD4/^為1〜像解析法所求出的 越=€ f數之败結果顯祕表1。·(败丨與測定4) 1286537 除了設定氫氧化鋇八水和物 水和物之置入量為4.45g之:物之置入量為肌27g、氫氧化鈣八 比較例3之鈦酸j弓鋇粉末。 行相同於比較例1之操作，得到 化合物之含有率大於3峰。藉此而得知斜方日日日系趟鈦鑛 比較例4 除了將比較例3所得到的粉末 進行相同於實施例2之操作，葬Α、# ϋ C維持2小時之外， 酸約鋇粉末。 祕糾進推燒而得到比較例4之鈦 所得到的粉末之比表面積為5·3 m2/g。 1中丄觀察到斜方晶系触礦化合物之波峰‘知斜 式。推一牛划莫耳％ °另外’y為LGG81，並未滿足⑴ D4/D1為^ 8象解析法所求出的D2/D1為〇.3，D3/D1為2.2， 將介電常數之測定結果顯示於表丨。（測定丨與測定4) (表1)In the state of the particle size, titanium 钡 is used as a dielectric, and the dielectric H 24 1286537 can be thinned. This enables the capacitor ϋ itself to be advanced and shaped. In addition, it is thinned to increase the electrostatic capacity of the capacitor. (10) The hunting layer is made of a dielectric layer, and such a small laminated ceramic capacitor can be applied to electronic parts, and parts of a portable type of mobile phone. ° Also prepared for the 乂 乂 何 ( (Dielectric constant measurement method: Determination 1~4). The dielectric constant of the obtained titanic acid was measured in the following manner to make the titanate axis MgO (Japan Concord Chemical Jade Co., Ltd. ΐϊΐί 3= Y2〇3 (Japan Shin-Etsu Chemical Co., Ltd.夕陶陵j I 1 rBa&lt;&gt;Ll203 (Sakamoto Asahi Tedm〇glasS shares limited public clothing ceramic low-temperature sintering glass additive) becomes 1〇〇: 2 : 15 ·· 2 Mo Er Bi ί ° marriage i3mm right With the uniaxial forming welding of the mixed powder of ton; in the case of nitrogen rolling, the calcination temperature shown in Table 1 is maintained for 2 hours for calcination (measurement 1). The sinter is at the calcination temperature l 〇 8 (TC (Measure 2) The sintered product was obtained at a calcination temperature U2 (TC). (Measure 3) The sintered product was obtained at a calcination temperature of 1060 ° C. (Measure 4) The sintered product was calcined at a temperature of l〇. 4 〇 °c obtained. After measuring the size of the sinter obtained in this manner, the silver for baking was applied, and the electrode was formed by calcination at 8 Torr (rc for 1 Torr) at atmospheric pressure. Single-plate capacitor. The area, thickness, and weight of the capacitor were measured to determine the sintered density. 6537 ', the theoretical yield calculated by hydrogen 2 calcium T, the ratio of the actual yield is 99.9%. Powder ===== The specific surface area of the paste vein method, the spectrum 3 shot m of this powder evaluation. In the case of the X-ray diffraction, the length of the c-axis length is 1:1, and the formula (1) is used. The length of the length and the result of scanning electron microscopy are used to magnify the shape of the powder. A transmission electron microscope (Osaka 1 1 90-90 (10) 111110 was observed. After elemental analysis by EDX, 'as shown in the figure 5', it is known that the powder is uniformly dissolved in the powder and about." For the carbonic acid contained in the powder The amount of the base is quantified using the FTS6_ system of the infrared spectroscopy division. If it is assumed that the 钡 钡 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸 碳酸Absorption peak of _ in the vicinity of 35GGem-1 Example 2 The powder prepared by the preparation of 1 is placed in a furnace (shared by Denken = KDFMG), and then it is carried out. The service is carried out for 2 hours. The condition of the natural cooling knife. The formula, the titanium of the real _ 2 powder. 疋 still this 2 2 ^ ^ In addition, will The X-ray diffraction spectrum of the calcined calcium titanate powder after heat treatment is shown in Chutu. As shown in Fig. 6, the peak of the orthorhombic titanium compound is not observed, and it is observed that 27 1286537 except for Example 1 The obtained powder, at 1000, maintains 2 in the same manner as in the real 2, by the domain. The interlocking effect of Example 3 is as follows: The specific surface area of the dimethoate powder of Example 3 is 51 y and the other is 93. It satisfies the formula (1). The step-by-step method uses the image analysis method to find 〇·6, D3/D1 is 1.7, and D4/D1 is U. The results of the measurement of the dielectric constant are shown in Table 丨. (Measurement of the 丨 测 了 了 设定 设定 设定 设定 设定 水 水 水 水 水 水 水 水 水 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌 肌Calcium titanate tantalum powder of Example 4. Λ The obtained titanate touch powder has a specific surface area of 49 ^ ^ ' in its X-ray diffraction spectrum. The peak of the orthorhombic lysate compound is not observable 'orthogonal calcium and titanium The content of the mineral compound is 3 mol% or less. After the Rietveld ride of the -X 杂X thief, the obtained powder = Ba〇_85〇Ca〇i5〇Ti〇3 powder of solid solution bismuth ore, and y is i. difficult 疋(2). The powder of Example 4 of the needle „′, needle 5 was observed by a transmission electron microscope at a magnification of 10,000 times, and the defect due to the detachment of the hydroxyl group was not observed. ΐΜΜΛ , &gt; The powder of Example 5 was made to have a specific surface area of 5 m 2 /g of the powder of Example 5 by calcination in the manner of Example 2 except that the powder was maintained at 11 ° C for 2 hours. In addition, in the χ spectrum, the peak of the orthorhombic (tetra) titanium ore compound was not observed, and the content of the orthorhombic, =, and titanium ore compound was 3 mol% or less. Furthermore, y was 1〇〇. 92. The d2/idi obtained by the image analysis method is 〇.6, D3/D1 is 1.8, and D4/D1 is 1.9. 29 1286537 is placed in a reactor equipped with a reflux cooler and stirred while being formed. An aqueous solution of a value of 1 to 11 was boiled on one side. Then, the titanium oxide sol was adjusted in the same manner as in the example, and the chloride ion was removed by an electroosmotic device until 500 ppm. Precipitating and concentrating 213 g of titanium oxide to produce a mass% of gel, per minute The reaction rate of 7g is as follows: - the surface is directly stirred, and the surface is maintained for 4 hours. The one of the reaction liquids is subjected to it 'paste ICP luminescence method to determine the sputum in the ship, 钡The ion was subjected to a reaction until the cerium ion was one thousandth or less of the amount of the cerium ion. Thereafter, the operation was carried out in the same manner as the above, and the calcium titanate cerium powder of Comparative Example 1 was obtained. The specific surface area of the obtained powder. It is 38 m2/g. In addition, it is in Fig. 10 and Fig. 11. Fig. 11 is the tenth figure: enlarged view: In the figure, the peak of the orthorhombic ore-contacting compound is marked with the 〇 symbol. Comparing the titanate _ towel of the first example, it was observed that the orthorhombic susceptibility of the orthorhombic character was found to be greater than 3 moles. I TtT^5 ^ 1000〇 In the manner of c^2 ^, by the calcination, the titanium of the comparative example 2 is obtained in the enlarged view of the 13th, U-day m diagram, Fig. 12. The mode is the scale of the aircraft. Second, ===physical/promising rate, the phase transition point between the ear and the tetragonal system is _15. ^ ^ 'The measured orthorhombic system _1 is 0.4, D3/m is 2 0, CD4/^ is 1 ~image The result of the analysis is that the result of the failure of the number of f = f is shown in Table 1. (Defects and Measurements 4) 1286537 In addition to setting the amount of ytterbium hydroxide and water and substances, the amount is 4.45g: The amount of the solution was 27 g of muscle, calcium hydroxide, and the titanate powder of Comparative Example 3. The same procedure as in Comparative Example 1 was carried out to obtain a compound having a content of more than 3 peaks. Japanese Nob Nielite Comparative Example 4 The powder obtained in Comparative Example 3 was subjected to the same operation as in Example 2, and the fungus and #ϋC were maintained for 2 hours, and the acid was about 钡 powder. The powder obtained by the comparative study of the titanium obtained in Comparative Example 4 had a specific surface area of 5·3 m 2 /g. 1 The peak of the orthorhombic ore-contacting compound was observed in the middle 丄. Push a cow to draw a mole % ° Another 'y is LGG81, not satisfied (1) D4 / D1 is ^ 8 like the analytical method to find D2 / D1 is 〇.3, D3 / D1 is 2.2, the dielectric constant The results of the measurements are shown in Table 丨. (Measurement 丨 and determination 4) (Table 1)

32 1286537 溫度特性係滿足EIA規格之X7R者標示〇，未滿足者標示為 X 〇 、 *係使製造電谷為時之鈦酸鋇與MgO (日本協合化學工業股 份有限公司製之高純度氧化鎂500-04R)、Y2〇3 (日本信越化學股 份有限公司製之微粉末釔UU-HP)、Si02-Ba0-Li203 (曰本旭 Technoglass股份有限公司製之陶瓷低溫燒結用玻璃添加劑）成為 100 : 0·5 : 1.5 : 2莫耳比般之予以置入。 將單板電容器進行介電常數評估之結果顯示於表1。 實施例2、3、5、7之本發明鈦酸鈣鋇，其燒結密度為高的（95 φ % )，此時之溫度特性滿足ΕΙΑ規格之X7R (〇）。 比較例2、4之鈦酸鈣鋇，由於其燒結密度為低的（9〇〜92% )， 一旦提咼锻燒溫度（1080°C )時，並未滿足溫度特性（X)。另一 方面，一旦降低锻燒溫度（l〇4〇°c )時，雖然其溫度特性滿足 規格之X7R (〇），但是，介電常數變低（1〇〇〇〜11〇〇)。 【圖式簡單說明】 第1圖係本發明較佳實施形態之層壓型陶瓷電容器的橫剖面 示意圖一例。 第2圖係顯示具備第1圖之層壓型陶瓷電容器的行動電話内 w部構造之分解圖一例。 &quot; 第3圖係實施例1之Ba〇.95〇Ca_〇Ti〇3粉末的X線繞射光譜圖 一例0 第4圖係貫施例1之Ba^Ca^oTiO3粉末的掃描式電子顯微 鏡相片一例。 弟5圖係貫施例1之Ba^oCao.osoTiO3粉末的穿透式電子顯微 鏡相片與利用EDX之元素分析圖一例。 … 弟6圖係貫施例2之Ba〇.95〇Ca〇.〇5〇Ti〇3粉末的X線繞射光譜圖 一例0 33 1286537 弟7圖係實施例2之Ba〇.95〇Ca〇.〇5〇Ti〇3粉末的掃扣^電^ 弟8圖係實施例2之Ba〇.95〇Ca〇.〇5〇Ti〇3粉末的穿透卞恭 鏡相片與利用EDX之元素分析圖一例。 工包食 第9圖係以25萬倍進行觀察實施例2之Ba^oCac^oTK^粉 末的穿透式電子顯微鏡相片一例。 弟10圖係比較例1之Ba〇.95〇Ca〇,〇5〇Ti〇3粉末的X線繞射光譜 圖一例。 第11圖係放大第10圖之X線繞射光譜圖一例。32 1286537 Temperature characteristics are X7R markings that meet the EIA specifications. Unsatisfied are marked as X 〇, * is the production of electricity valleys of barium titanate and MgO (Japan Syngas Chemical Co., Ltd. high purity oxidation) Magnesium 500-04R), Y2〇3 (micro-powder 钇UU-HP manufactured by Shin-Etsu Chemical Co., Ltd.), and SiO2-Ba0-Li203 (glass additive for low-temperature sintering of ceramics manufactured by Sakamoto Asahi Technoglass Co., Ltd.) become 100 : 0·5 : 1.5 : 2 Moore is put into it. The results of dielectric constant evaluation of the single-plate capacitor are shown in Table 1. The calcium titanate tantalum crucible of the present invention of Examples 2, 3, 5 and 7 has a high sintered density (95 φ %), and the temperature characteristics at this time satisfy the X7R (〇) of the ΕΙΑ specification. In the calcium titanate of Comparative Examples 2 and 4, since the sintered density was low (9 〇 to 92%), the temperature characteristic (X) was not satisfied once the calcination temperature (1080 ° C) was raised. On the other hand, once the calcination temperature (l〇4〇°c) is lowered, although the temperature characteristic satisfies the specification X7R (〇), the dielectric constant becomes low (1〇〇〇~11〇〇). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a laminated ceramic capacitor according to a preferred embodiment of the present invention. Fig. 2 is an exploded view showing an example of the structure of the w portion of the mobile phone having the laminated ceramic capacitor of Fig. 1. &quot; Fig. 3 is an X-ray diffraction spectrum of Ba〇.95〇Ca_〇Ti〇3 powder of Example 1. An example of FIG. 4 is a scanning electron of Ba^Ca^oTiO3 powder of Example 1. An example of a microscope photo. Figure 5 is an example of a transmission electron micrograph of Ba^oCao.osoTiO3 powder of Example 1 and an elemental analysis chart using EDX. ... Figure 6 is an example of the X-ray diffraction spectrum of Ba〇.95〇Ca〇.〇5〇Ti〇3 powder of Example 2, 0 33 1286537, Figure 7 is the Ba〇.95〇Ca of Example 2. 〇.〇5〇Ti〇3 powder sweeping ^Electricity brother 8 Figure 2 Example 2 Ba〇.95〇Ca〇.〇5〇Ti〇3 powder penetration 卞 镜 mirror photo and the use of EDX elemental analysis An example. Fig. 9 is an example of a transmission electron microscope photograph of Ba^oCac^oTK^ powder of Example 2 observed at 250,000 times. The figure 10 is an example of the X-ray diffraction spectrum of the Ba〇.95〇Ca〇,〇5〇Ti〇3 powder of Comparative Example 1. Fig. 11 is an example of an X-ray diffraction spectrum of the enlarged Fig. 10.

第12圖係比較例2之Ba〇.95〇Ca〇.㈣Ti〇3粉末之X線繞射光譜 圖一例。 第13圖係放大第12圖之X線繞射光譜圖一例。 【主要元件符號說明】 1〜層壓型陶瓷電容器（電容器） 2〜電介質層 3〜内部電極 4〜内部電極 5〜層壓物 6〜外部電極 7〜外部電極 W〜行動電話 11〜電路基板 34Fig. 12 is a graph showing the X-ray diffraction spectrum of the Ba〇.95〇Ca〇. (IV) Ti〇3 powder of Comparative Example 2. Fig. 13 is an example of an enlarged X-ray diffraction spectrum of Fig. 12. [Description of main component symbols] 1~ Laminated ceramic capacitor (capacitor) 2 to dielectric layer 3 to internal electrode 4 to internal electrode 5 to laminate 6 to external electrode 7 to external electrode W to mobile phone 11 to circuit substrate 34

Claims (1)

1286537 步驟；及 接著，使該驗性化合物氣化而予以去除之步驟。 e l〇H晴專利範圍第9項之鈇酸詞鋇之製造方法，其中將氫 •氧”氧倾的莫耳比設為1 :。〜。·8 : G·2之範圍，同時，相 •對於氫氧化鋇與氫氧化狀合計莫耳量，將氧化欽量設為 0.98〜1.02倍，於驗性溶液中，使此等氫氧化鎖、氮氧化_氧化 鈦進行反應而製造鈦酸詞鋇。 11·如申請專利範圍第9或10項之鈦酸約鋇之製造方法，其 中於該鈦酸鋇之合成步驟巾，令其進行反應直至碰性溶液中之 鋇離子殘留篁成為置入量的百分之一以下，且於該鈦酸觸之合 成步驟中，令其進行反應直至約離子殘留量成為置入量的百分之 一以下。 12·如申請專利範圍第9或1〇項之鈦酸鈣鋇之製造方法，其 中於該鹼性化合物之去除步驟後，在35〇艺以上、12〇(rc以下之溫 度範圍進行熱處理。 13·如申請專利範圍第9或1〇項之鈦酸鈣鋇之製造方法，其 中從鈦酸鋇合成至鈦酸鈣鋇合成為止之步驟中，將反應溶液中之 碳酸基之濃度控制於經c〇2換算為0ppm以上、500ppm以下之範 圍。 擊 14·如申請專利範圍第9或10項之鈦酸鈣鋇之製造方法，其 中該氧化鈦係含板鈦礦型結晶者。 15·如申請專利範圍第9或1〇項之鈦酸鈣鋇之製造方法，其 • 中該氧化鈦係一種於酸性水溶液中進行鈦化合物之水解而成的氧 化鈦溶膠。 16.如申請專利範圍第9或1〇項之鈦酸鈣鋇之製造方法，其 中該鹼性化合物係於一大氣壓下或減壓下，利用蒸發、昇華、熱' 分解之中的至少一種以上方式進行氣化的物質。 17·如申請專利範圍第9或1〇項之鈦酸鈣鋇之製造方法，其 中該鹼性化合物係一種有機鹼性化合物。 八 36 1286537 18·如申請專利範圍第9或1〇項之鈦酸鈣鋇之製造方法，其 中該鹼性化合物係一種四甲基銨氫氧化物。 19· 一種介電材料，其特徵為··將包含申請專利範圍第1至8 ’項中任一項之鈦酸鈣鋇，及擇自由Y203、Dy203、Ho203及Er203 所構成群之中至少1種成分之混合物，於1〇〇(rc以上的溫度鍛燒。 20· —種糊狀物’其特徵為··包含申請專利範圍第1至8項中 任一項之鈦酸鈣鋇、黏結劑、分散劑及溶劑。 21· —種漿狀物，其特徵為··包含申請專利範圍第丨至8項中 任一項之鈦酸鈣鋇、黏結劑、分散劑及溶劑。 ,22·種薄膜狀形成物，其特徵為··包含申請專利範圍第j 至8項中任一項之鈦酸鈣鋇，及黏結劑。 23· —種電介質磁器，其特徵為：係將申請專利範圍第1至8 欽酸賴與黏結劑及溶劑混合而使裝狀化或糊狀化 灸’使〜發以形成電介質I，再進行燒结之方法所製造的。 熱二申用請專利範圍第1至8項中任-項之欽酸觸，係作為 壓電ί器n請專利範圍第1至8項中任一項之鈦酸妈銷，係作為 26·種電谷器，其特徵為：包含申請專利範圍第23項之雷 Ag、Cu，所構成;之中至=二= 二自由Ni ’、 之電ill:種行動電話’其特徵為：包含由申請專利範圍第26項 使用沈如申請專利範圍第24至25項之鈦_貝，係作為感測器 S 種電介質細，其特徵為：係將包含中請專利範圍第1 使二=====·， 37 1286537 30. —種電容器，其特徵為：含有申請專利範圍第29項之電 介質薄膜及金屬電極層。 十一、囷式：1286537 Step; and Next, the step of removing the test compound by gasification. The manufacturing method of the 鈇 钡 钡 第 〇 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 〇 〇 〇 〇 〇 〇 〇 〇 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢 氢For the total amount of strontium hydroxide and hydroxide, the oxidation amount is set to 0.98 to 1.02 times, and in the test solution, the hydroxide lock and the nitrogen oxide-titanium oxide are reacted to produce titanate. 11. The method for producing a titanic acid about the ninth or tenth aspect of the patent application, wherein the step of synthesizing the barium titanate is allowed to react until the residual amount of cerium ions in the viscous solution becomes a loading amount. One hundredth or less, and in the synthesis step of the titanate, it is allowed to react until the residual amount of ions becomes less than one percent of the amount of the implant. 12·If the scope of claim 9 or 1 The method for producing calcium strontium titanate, wherein after the step of removing the basic compound, the heat treatment is performed at a temperature of 35 以上 or more and 12 〇 (the temperature range below rc. 13) as claimed in claim 9 or 1 Method for producing calcium titanate strontium, which is synthesized from barium titanate to calcium titanate In the steps up to the above, the concentration of the carbonate group in the reaction solution is controlled to be in the range of 0 ppm or more and 500 ppm or less in terms of c 〇 2. The method for producing calcium titanate strontium according to claim 9 or 10 Wherein the titanium oxide is a brookite-type crystallizer. 15. The method for producing calcium titanate strontium according to claim 9 or claim 1, wherein the titanium oxide is a titanium compound in an acidic aqueous solution. A method for producing a calcium silicate sol according to the ninth or first aspect of the invention, wherein the basic compound is subjected to evaporation, sublimation, under atmospheric pressure or under reduced pressure. A method for producing a gasification of at least one of the above-mentioned methods of heat decomposition. The method for producing calcium titanate strontium according to claim 9 or claim 1, wherein the basic compound is an organic basic compound. The method for producing calcium titanate strontium according to claim 9 or claim 1, wherein the basic compound is a tetramethylammonium hydroxide. 19. A dielectric material characterized by Will contain Please select a mixture of at least one of the group consisting of Y203, Dy203, Ho203 and Er203 in any one of the first to eighth aspects of the patent range, at a temperature above 1 rc. The calcined product is characterized in that it contains the calcium titanate strontium titanate, the binder, the dispersing agent and the solvent of any one of the claims 1 to 8. 21· The invention is characterized in that it contains calcium titanate, a binder, a dispersing agent and a solvent of any one of the above-mentioned patents from item 丨 to item 8. 22 film-like formations, characterized by including patents Calcium barium titanate of any of items j to 8 and a binder. 23·-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- Manufactured by the method of sintering. The application of the hot acid application in the scope of items 1 to 8 of the patent scope is the piezoelectric acid n device. Please use the titanate product of any of the patent scopes 1 to 8 as the 26· An electric barn, which is characterized by: comprising Ag, Cu, which is the 23rd item of the patent application scope; medium to = two = two free Ni ', electric ill: a kind of mobile phone' characterized by: Article 26 of the scope of application for patents uses Titanium, which is the subject of patent application No. 24 to 25, which is used as the S-type dielectric of the sensor. It is characterized in that it will contain the patent scope of the first claim 2 === ==·, 37 1286537 30. A capacitor comprising a dielectric film and a metal electrode layer of claim 29 of the patent application. XI, 囷 type: 3838