JPH05230079A - Titanium compound of organic acid and its production - Google Patents
Titanium compound of organic acid and its productionInfo
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- JPH05230079A JPH05230079A JP3197292A JP3197292A JPH05230079A JP H05230079 A JPH05230079 A JP H05230079A JP 3197292 A JP3197292 A JP 3197292A JP 3197292 A JP3197292 A JP 3197292A JP H05230079 A JPH05230079 A JP H05230079A
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- Prior art keywords
- organic acid
- titanium
- titanium compound
- compound
- formula
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規な有機酸チタン化
合物及びその製造方法に関し、更に詳しくは一般式(Ｉ)
または組成式Ｔｉ4Ｏ4(ＲＣＯＯ)8で表される環状有機
酸チタン化合物及びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organic acid titanium compound and a method for producing the same, more specifically, a compound represented by the general formula (I)
Further, the present invention relates to a cyclic organic acid titanium compound represented by the composition formula Ti 4 O 4 (RCOO) 8 and a method for producing the same.
【０００２】[0002]
【従来の技術】有機酸チタン化合物及びその誘導体につ
いては、アルコキシ基を含んだ環状またはラダー状チタ
ノキサン(特開昭64−52786号公報、特開平１−129032号
公報など)、二量体有機酸チタン［Z. Anorg. Chem., 29
0、第87〜95頁(1957)；J.Indian Chem. Soc., 38、第50
9頁(1961)］などが報告されている。これらはいずれも
チタンテトラアルコキシドからの置換反応により得られ
る。しかしながら、組成式Ｔｉ4Ｏ4(ＲＣＯＯ)8で表さ
れる環状有機酸チタン化合物については報告されていな
い。BACKGROUND OF THE INVENTION Organic acid titanium compounds and their derivatives include cyclic or ladder-type titanoxane containing an alkoxy group (JP-A-64-52786, JP-A-1-129032, etc.), dimer organic acid. Titanium [Z. Anorg. Chem., 29
0, pp. 87-95 (1957); J. Indian Chem. Soc., 38, 50.
Page 9 (1961)] is reported. All of these are obtained by a substitution reaction from titanium tetraalkoxide. However, a cyclic organic acid titanium compound represented by the composition formula Ti 4 O 4 (RCOO) 8 has not been reported.
【０００３】チタン酸バリウム、チタン酸鉛、チタン酸
ジルコン酸鉛などのペロブスカイト型強誘電体は、コン
デンサーや圧電素子に広く応用されている。最近、電子
材料の高性能化、小型化、低化学化というニーズに対し
て上記セラミックスの薄膜化、微細化が重要な課題とな
っている。従来、チタン酸ジルコン酸鉛はそれぞれの成
分金属の酸化物をボールミルなどにより粉砕し、その粉
末を所定比に混合した後に８００〜１３００℃という高
温での固相反応により製造されている。しかしながら、
原料酸化物の粉砕時及び混合時における不純物の混入が
避けられないこと、及び機械的粉砕では１μｍ以下の微
粒子が得られないことなどから、高品質なチタン酸ジル
コン酸鉛を得ることができないという問題点がある。Perovskite type ferroelectrics such as barium titanate, lead titanate and lead zirconate titanate are widely applied to capacitors and piezoelectric elements. Recently, thinning and miniaturization of the above-mentioned ceramics have become important issues in response to needs for high performance, miniaturization and low chemicals of electronic materials. Conventionally, lead zirconate titanate is produced by pulverizing oxides of respective component metals with a ball mill or the like, mixing the powders at a predetermined ratio, and then performing a solid phase reaction at a high temperature of 800 to 1300 ° C. However,
It is impossible to obtain high-quality lead zirconate titanate because it is unavoidable that impurities are mixed during the pulverization and mixing of the raw material oxides and that fine particles of 1 μm or less cannot be obtained by mechanical pulverization. There is a problem.
【０００４】更に、上記セラミックスを得るに要する１
２００℃以上という高い焼成温度では酸化鉛が気化する
ことから、組成の均一性に欠けるという問題点がある。
そこで、最近では組成が均一で、かつ低温焼成できるチ
タン酸ジルコン酸鉛の製造方法が要望されている。上記
セラミックスの低温合成に関しては、金属アルコキシド
［例えば日本セラミックス協会誌、98、第754頁(199
0)、特開昭62−108729号公報など］、酢酸鉛と金属アル
コキシド［J. Appl. Phys., 64、第2717頁(1991)］の加
水分解を利用したゾル−ゲル法によるチタン酸ジルコン
酸鉛の低温焼結性粉末の合成法あるいはチタン酸ジルコ
ン酸鉛薄膜の作製法が知られている。Further, it is necessary to obtain the above ceramics 1
Since lead oxide is vaporized at a high firing temperature of 200 ° C. or higher, there is a problem that the composition is not uniform.
Therefore, recently, a method for producing lead zirconate titanate, which has a uniform composition and can be fired at a low temperature, has been demanded. Regarding the low temperature synthesis of the above-mentioned ceramics, metal alkoxides [eg, Ceramic Society of Japan, 98, p. 754 (199
0), JP-A-62-108729, etc.], zircon titanate by sol-gel method utilizing hydrolysis of lead acetate and metal alkoxide [J. Appl. Phys., 64, p. 2717 (1991)]. A method for synthesizing low-temperature sinterable powder of lead oxide or a method for producing a lead zirconate titanate thin film is known.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記の
金属アルコキシドを原料として用いるゾルーゲル法によ
るチタン酸ジルコン酸鉛の製造方法では、使用する金属
アルコキシドが本質的にわずかの水分の存在下でも加水
分解され易いため、所定の混合比に試料を調製すること
が難しく、更に混合試料溶液の保存安定性が悪いという
問題点がある。また、鉛、チタン、ジルコニウムそれぞ
れの金属アルコキシドの加水分解速度の違いがあるた
め、加水分解によりチタン酸ジルコン酸鉛の前駆体ゾル
及びゲルを調製するゾル−ゲル法では組成、形態などが
均一なチタン酸ジルコン酸鉛を得ることが難しいという
問題点もある。これらのことに加えて、ゾル−ゲル法に
よるチタン酸ジルコン酸鉛前駆体を調製する際には上記
問題点を解決するために多種の添加剤の使用を含めた複
雑な処理を必要とし、更に、ゲル化に多大な時間を要す
るなどのプロセス上の問題点もある。However, in the method for producing lead zirconate titanate by the sol-gel method using the above metal alkoxide as a raw material, the metal alkoxide used is essentially hydrolyzed even in the presence of a slight amount of water. Since it is easy, it is difficult to prepare a sample with a predetermined mixing ratio, and there is a problem that the storage stability of the mixed sample solution is poor. In addition, since there is a difference in the hydrolysis rate of metal alkoxides of lead, titanium, and zirconium, the sol-gel method for preparing the precursor sol and gel of lead zirconate titanate by hydrolysis causes uniform composition, morphology, etc. There is also a problem that it is difficult to obtain lead zirconate titanate. In addition to these, when preparing a lead zirconate titanate precursor by the sol-gel method, a complicated treatment including the use of various additives is required to solve the above problems, and further, However, there are also problems in the process such that it takes a long time to gel.
【０００６】従って、本発明の目的は、複雑な工程なし
に均一なチタン酸ジルコン酸鉛、その他酸化チタンを含
む複合酸化物あるいは酸化チタンを低温焼成により製造
する際のチタン成分の原料として、空気中で安定な化合
物並びにその製造方法を提供することにある。Therefore, an object of the present invention is to use air as a raw material of a titanium component when producing uniform lead zirconate titanate, other complex oxides containing titanium oxide or titanium oxide by low temperature firing without complicated steps. In particular, it is to provide a stable compound and a method for producing the same.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記目的
を達成するために鋭意研究を重ねた結果、チタンテトラ
アルコキシドと１価の有機酸から有機酸チタン化合物を
容易に合成する方法及び該方法により得られる有機酸チ
タン化合物群が、アルコキシ基を含まない空気中で安定
な新規な化合物群であること、並びにこれらの有機酸チ
タン化合物がＰ(Ｌ)ＺＴ強誘電体等の複合酸化物セラミ
ックス、あるいは酸化チタンの膜を低温焼成により得る
塗布熱分解法の材料として極めて有効であることを見出
し、本発明を完成した。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found a method for easily synthesizing an organic acid titanium compound from titanium tetraalkoxide and a monovalent organic acid, and The organic acid titanium compound group obtained by the method is a novel compound group which does not contain an alkoxy group and is stable in air, and these organic acid titanium compound groups are complex oxides of P (L) ZT ferroelectrics and the like. The present invention has been completed by discovering that it is extremely effective as a material for a coating pyrolysis method in which a ceramics film or a titanium oxide film is obtained by low temperature firing.
【０００８】即ち、本発明に係る有機酸チタン化合物
は、次の一般式(Ｉ)で示されることを特徴とする：That is, the organic acid titanium compound according to the present invention is characterized by being represented by the following general formula (I):
【化２】 (式中、Ｒは炭素原子数１〜１７の１価の有機基を表す)[Chemical 2] (In the formula, R represents a monovalent organic group having 1 to 17 carbon atoms)
【０００９】また、上記一般式(Ｉ)で表される有機酸チ
タン化合物は、テトラアルコキシチタンと炭素原子数２
〜１８の１価の有機酸を、還流処理することを特徴とし
て製造することができる。The organic acid titanium compound represented by the general formula (I) is tetraalkoxytitanium and has 2 carbon atoms.
A monovalent organic acid of -18 can be produced by a reflux treatment.
【００１０】本発明の有機酸チタン化合物は、上記一般
式(Ｉ)あるいは組成式Ｔｉ4Ｏ4(ＲＣＯＯ)8で表される
環状有機酸チタン化合物である。式中のＲは同一でも異
なっていてもよい炭素原子数１〜１７の１価の有機基、
例えば炭素原子数１〜１７のアルキル基である。ただ
し、Ｒは不飽和結合、枝分かれ、ハロゲン原子、エステ
ル基、アミノ基、水酸基等の置換基、鎖中の酸素、窒
素、硫黄等の異節原子などを含んでしてもよい。The organic acid titanium compound of the present invention is a cyclic organic acid titanium compound represented by the above general formula (I) or compositional formula Ti 4 O 4 (RCOO) 8 . R in the formula may be the same or different, and is a monovalent organic group having 1 to 17 carbon atoms,
For example, it is an alkyl group having 1 to 17 carbon atoms. However, R may contain an unsaturated bond, branching, a halogen atom, a substituent such as an ester group, an amino group, a hydroxyl group, a hetero atom such as oxygen, nitrogen, and sulfur in the chain.
【００１１】本発明の有機酸チタン化合物は、チタンテ
トラアルコキシドと炭素原子数２〜１８の１価の有機酸
を、還流処理することにより容易に得られる。The organic acid titanium compound of the present invention can be easily obtained by refluxing titanium tetraalkoxide and a monovalent organic acid having 2 to 18 carbon atoms.
【００１２】本発明に使用されるテトラアルコキシチタ
ンとしては、一般式(II)：Ｔｉ(ＯＲ1)(ここに、Ｒ1は
炭素原子数１〜６の低級アルキル基である)で示される
チタン化合物が挙げられる。The tetraalkoxytitanium used in the present invention is titanium represented by the general formula (II): Ti (OR 1 ), wherein R 1 is a lower alkyl group having 1 to 6 carbon atoms. Compounds.
【００１３】次に、本発明の有機酸チタン化合物の製造
方法の概略を述べる。テトラアルコキシチタンを、必要
な場合は、式Ｒ1ＯＨ［ここに、Ｒ1は一般式(II)と同意
義である］で表されるアルコール、またはトルエンなど
の有機溶媒に溶解し、テトラアルコキシチタンに対し、
４当量の一般式(III)：ＲＣＯＯＨ［ここに、Ｒは一般
式(Ｉ)と同意義である］で表される有機酸を添加し、還
流した後、生成したアルコール、エステル、溶媒のアル
コール等の低沸成分を留去し、更に、系内に残った有機
酸を留去または濾過により除く。Next, the outline of the method for producing the organic acid titanium compound of the present invention will be described. If necessary, tetraalkoxytitanium is dissolved in an alcohol represented by the formula R 1 OH [wherein R 1 has the same meaning as in the general formula (II)] or an organic solvent such as toluene to give tetraalkoxytitanium. For titanium,
4 equivalents of an organic acid represented by the general formula (III): RCOOH [wherein R has the same meaning as in the general formula (I)] is added, and the mixture is refluxed. The low-boiling components such as are distilled off, and the organic acid remaining in the system is removed by distillation or filtration.
【００１４】一般式(III)の有機酸としては、カプロン
酸、カプリン酸、カプリル酸、２−エチルヘキサン酸、
ネオデカン酸、ラウリン酸、パルミチン酸、ステアリン
酸、オレイン酸、リノール酸、リノレイン酸などが挙げ
られる。As the organic acid of the general formula (III), caproic acid, capric acid, caprylic acid, 2-ethylhexanoic acid,
Examples thereof include neodecanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid and linoleic acid.
【００１５】本発明において還流を行う際の条件として
は、還流温度は９０〜１００℃(バス温度)、還流圧力は
常圧、還流時間は１〜５時間、好ましくは２時間程度と
するのが好ましい。In the present invention, the conditions for refluxing are as follows: the reflux temperature is 90 to 100 ° C. (bath temperature), the reflux pressure is normal pressure, and the reflux time is 1 to 5 hours, preferably about 2 hours. preferable.
【００１６】本発明において還流を行う際、使用する有
機酸が固体のときはそれを溶かす有機溶媒を使用する
が、上記有機溶媒としては、メタノール、エタノール、
ｎ−プロピルアルコール、イソプロピルアルコール、ブ
チルアルコール、ペンチルアルコール、ヘキシルアルコ
ールなどのアルコール類(原料のアルコキシ基と同一の
Ｒ1をもつもの)、またはトルエンなどが挙げられる。使
用する場合の使用量は、有機酸に対して１０倍量(重量
基準)までが好ましい。In the present invention, when the reflux is carried out, when the organic acid used is a solid, an organic solvent which dissolves it is used. Examples of the organic solvent include methanol, ethanol,
Alcohols such as n-propyl alcohol, isopropyl alcohol, butyl alcohol, pentyl alcohol, and hexyl alcohol (having the same R 1 as the alkoxy group as the raw material), toluene, etc. may be mentioned. When used, the amount used is preferably up to 10 times (weight basis) the amount of the organic acid.
【００１７】本発明の有機酸チタン化合物は、圧電素
子、焦電素子、電気光学素子などの強誘電体材料に使用
されるチタン酸ジルコン酸鉛を低温焼成により製造する
方法のチタン成分材料、その他複合酸化物セラミック
ス、その膜のチタン成分材料、紫外線カットガラスの酸
化チタン膜のコーティング材料、ガラスのアルカリバリ
ア剤として有用である。The organic acid titanium compound of the present invention is used as a titanium component material in a method for producing lead zirconate titanate used for a ferroelectric material such as a piezoelectric element, a pyroelectric element and an electro-optical element by low temperature firing, and the like. It is useful as a composite oxide ceramic, a titanium component material of the film, a coating material of a titanium oxide film of ultraviolet cut glass, and an alkali barrier agent of glass.
【００１８】[0018]
実施例 本発明を実施例により更に詳細に説明する。ただし、本
発明の範囲は以下の実施例により何等限定されるもので
はない。 ２−エチルヘキサン酸チタンの合成 撹拌装置、温度計、還流冷却器、窒素導入用コックを備
えた反応フラスコを窒素置換した後、テトライソプロポ
キシチタン５０７ｇ(１.７８モル)を仕込み、２−エチ
ルヘキサン酸１０２９ｇ(１.７８×４モル)を加え、９
０〜１００℃で加熱撹拌した。生成したイソプロピルア
ルコールが還流を始めてから２時間加熱撹拌し、その後
イソプロピルアルコールを系外に留去した。反応液をあ
る程度冷却した後、トルエンを５００ｍｌ加えて撹拌混
合し、５Ｃの濾紙で微量不純物を濾別した。得られた濾
液を蒸留装置に仕込み、常圧下でトルエンを留去した
後、減圧留去(１３０℃、３トール)により低沸物を除
き、黄褐色粘性液体６２０ｇを得た(収率９９％)。得ら
れた物質の分子量は凝固点降下法により測定した結果、
１４４０(理論値１４０１)であった。また、この液体の
元素分析結果は下記の通りであった(％は重量比)。 得られた物質のＩＲチャートを図１に、ＮＭＲチャート
を図２に示す。ＮＭＲチャートよりこの化合物はイソプ
ロポキシ基を含まないことが確認された。EXAMPLES The present invention will be described in more detail by way of examples. However, the scope of the present invention is not limited to the following examples. Synthesis of titanium 2-ethylhexanoate After replacing a reaction flask equipped with a stirrer, a thermometer, a reflux condenser, and a cock for introducing nitrogen with nitrogen, 507 g (1.78 mol) of tetraisopropoxytitanium was charged, and 2-ethyl Hexanoic acid 1029 g (1.78 × 4 mol) was added to
The mixture was heated and stirred at 0 to 100 ° C. The generated isopropyl alcohol was heated and stirred for 2 hours after starting to reflux, and then isopropyl alcohol was distilled out of the system. After cooling the reaction solution to some extent, 500 ml of toluene was added, and the mixture was stirred and mixed, and a trace amount of impurities was filtered off with a 5C filter paper. The obtained filtrate was charged into a distillation apparatus, toluene was distilled off under normal pressure, and low-boiling substances were removed by distillation under reduced pressure (130 ° C., 3 Torr) to obtain 620 g of a yellowish brown viscous liquid (yield 99%. ). The molecular weight of the obtained substance was measured by the freezing point depression method,
It was 1440 (theoretical value 1401). The results of elemental analysis of this liquid were as follows (% is weight ratio). An IR chart and an NMR chart of the obtained substance are shown in FIG. 1 and FIG. 2, respectively. From the NMR chart, it was confirmed that this compound did not contain an isopropoxy group.
【００１９】[0019]
【発明の効果】本発明の有機酸チタン化合物を用いて酸
化チタンの成膜を行う場合、膜剤溶液は、従来報告され
ている酸化チタンの低温合成の原料である金属アルコキ
シド溶液よりもはるかに水分安定性があり、キレート化
合物、アルカノールアミン類などを添加するなどの溶液
調製時の複雑な操作をする必要がない。このことは、チ
タン成分を含む複合酸化物セラミックスの原料として用
いる場合も同様である。When a titanium oxide film is formed using the organic acid titanium compound of the present invention, the film agent solution is far more than the metal alkoxide solution which is a raw material for the low temperature synthesis of titanium oxide which has been conventionally reported. It is water-stable and does not require complex operations such as adding chelate compounds and alkanolamines when preparing a solution. This also applies to the case where it is used as a raw material for a composite oxide ceramic containing a titanium component.
【００２０】本発明の有機酸チタン化合物を例えばチタ
ン酸ジルコン酸鉛(ＰＺＴ)の製造に採用することによ
り、成分金属の酸化物を原料とする従来法に比して、は
るかに低温でのチタン酸ジルコン酸鉛が製造でき、大幅
なエネルギーの節減につながり、経済的に有利である。
また、固相反応とは異なり、有機酸塩の均一溶液の熱分
解によりチタン酸ジルコン酸鉛が生成するため、微細な
レベルで均一組成のものができる。更に、金属アルコキ
シドなどを用いるゾル−ゲル法では加水分解の制御を行
うために複雑な操作及び工程が必要となるが、本発明の
有機酸チタン化合物は加水分解性が全くないか、非常に
小さいので、取り扱いが容易となり、混合、乾燥などの
操作が簡便になると共に保存安定性も大幅に改善され
る。この場合、好ましくは他の金属成分材料として、２
−エチルヘキサン酸ジルコニル、２−エチルヘキサン酸
鉛を用い、更に、本発明の有機酸成分として２−エチル
ヘキサンを用いるのがよい。また、本発明の有機酸チタ
ン化合物は下記に示す種々のプロセスによるチタン酸ジ
ルコニル酸鉛の製造方法に応用することができる。約４
００〜６００℃という低温焼成により均一組成のチタン
酸ジルコン酸鉛が製造できることから、スプレードライ
法などによる均一粒子の微粉末の合成に応用できる。更
に、スクリーン印刷、オフセット印刷などの印刷法、ス
プレー法、ディッピング法、スピンコーティング法など
により均一組成の薄膜の合成にも応用でき、チタン酸ジ
ルコン酸鉛の薄膜化、微細化に十分対応できる。同様に
その他のチタンを含む複合酸化物、酸化チタンについて
も応用できる。By employing the organic acid titanium compound of the present invention in the production of, for example, lead zirconate titanate (PZT), titanium at a much lower temperature than the conventional method using the oxide of the component metal as a raw material. Lead acid zirconate can be produced, resulting in significant energy saving and economically advantageous.
Further, unlike the solid phase reaction, lead zirconate titanate is produced by thermal decomposition of a uniform solution of an organic acid salt, so that a fine composition with a uniform level can be obtained. Further, in the sol-gel method using a metal alkoxide or the like, complicated operations and steps are required to control hydrolysis, but the organic acid titanium compound of the present invention has no or very little hydrolyzability. Therefore, handling is easy, operations such as mixing and drying are simple, and storage stability is greatly improved. In this case, preferably 2 as the other metal component material.
It is preferable to use zirconyl ethylhexanoate and lead 2-ethylhexanoate, and further use 2-ethylhexane as the organic acid component of the present invention. Further, the organic acid titanium compound of the present invention can be applied to a method for producing lead zirconate titanate by various processes shown below. About 4
Since lead zirconate titanate having a uniform composition can be produced by firing at a low temperature of 00 to 600 ° C., it can be applied to the synthesis of fine powder of uniform particles by a spray drying method or the like. Further, it can be applied to the synthesis of a thin film having a uniform composition by a printing method such as screen printing or offset printing, a spraying method, a dipping method, a spin coating method, etc., and can sufficiently cope with thinning and miniaturization of lead zirconate titanate. Similarly, it can be applied to other complex oxides containing titanium and titanium oxide.
【図１】実施例で得られた物質のＩＲチャートである。FIG. 1 is an IR chart of the substances obtained in Examples.
【図２】実施例で得られた物質のＮＭＲチャートであ
る。FIG. 2 is an NMR chart of substances obtained in Examples.
Claims (2)
化合物： 【化１】 (式中、Ｒは炭素原子数１〜１７の１価の有機基を表す)1. An organic acid titanium compound represented by the following general formula (I): (In the formula, R represents a monovalent organic group having 1 to 17 carbon atoms)
〜１８の１価の有機酸を、還流処理することからなる請
求項１記載の有機酸チタン化合物の製造方法。2. Tetraalkoxy titanium and 2 carbon atoms
The method for producing an organic acid titanium compound according to claim 1, which comprises subjecting the monovalent organic acid of -18 to reflux treatment.
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| JP03197292A JP3228776B2 (en) | 1992-02-19 | 1992-02-19 | Organic acid titanium compound and method for producing the same |
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| JP03197292A JP3228776B2 (en) | 1992-02-19 | 1992-02-19 | Organic acid titanium compound and method for producing the same |
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| JP3228776B2 JP3228776B2 (en) | 2001-11-12 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007008856A (en) * | 2005-06-30 | 2007-01-18 | Kawaken Fine Chem Co Ltd | Compound metal alkoxide |
| US7819965B2 (en) | 2006-10-12 | 2010-10-26 | Adeka Corporation | Coating formulation and process for the production of titanate-based ceramic film with the coating formulation |
| US20140349834A1 (en) * | 2008-05-28 | 2014-11-27 | Mitsubishi Materials Corporation | Composition for ferroelectric thin film formation, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method thereof |
| CN105541600A (en) * | 2014-10-28 | 2016-05-04 | 日油株式会社 | A method of producing fatty acid titanium |
-
1992
- 1992-02-19 JP JP03197292A patent/JP3228776B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007008856A (en) * | 2005-06-30 | 2007-01-18 | Kawaken Fine Chem Co Ltd | Compound metal alkoxide |
| US7819965B2 (en) | 2006-10-12 | 2010-10-26 | Adeka Corporation | Coating formulation and process for the production of titanate-based ceramic film with the coating formulation |
| US20140349834A1 (en) * | 2008-05-28 | 2014-11-27 | Mitsubishi Materials Corporation | Composition for ferroelectric thin film formation, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method thereof |
| US9502636B2 (en) * | 2008-05-28 | 2016-11-22 | Mitsubishi Materials Corporation | Composition for ferroelectric thin film formation, method for forming ferroelectric thin film, and ferroelectric thin film formed by the method thereof |
| CN105541600A (en) * | 2014-10-28 | 2016-05-04 | 日油株式会社 | A method of producing fatty acid titanium |
| KR20160049991A (en) | 2014-10-28 | 2016-05-10 | 니치유 가부시키가이샤 | A method of producing fatty acid titanium |
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| JP3228776B2 (en) | 2001-11-12 |
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