JPH0558636A - Production of lead titanate zirconate - Google Patents
Production of lead titanate zirconateInfo
- Publication number
- JPH0558636A JPH0558636A JP21719591A JP21719591A JPH0558636A JP H0558636 A JPH0558636 A JP H0558636A JP 21719591 A JP21719591 A JP 21719591A JP 21719591 A JP21719591 A JP 21719591A JP H0558636 A JPH0558636 A JP H0558636A
- Authority
- JP
- Japan
- Prior art keywords
- organic acid
- lead
- titanium
- salt
- lead titanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はチタン酸ジルコン酸鉛の
製造方法に関するものであり、更に詳しくは圧電素子、
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
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing lead zirconate titanate, more specifically a piezoelectric element,
The present invention relates to a method for producing lead zirconate titanate used for ferroelectric materials such as pyroelectric elements and electro-optical elements by low-temperature firing.
【０００２】[0002]
【従来の技術】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、低価格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。2. Description of the Related Art 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 higher performance, smaller size and lower price of electronic materials.
【０００３】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
入が避けれらないこと、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。更に、上記セラミックスを得るに要する１２００℃
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。Conventionally, lead zirconate titanate is produced by pulverizing oxides of respective component metals with a ball mill or the like, mixing the powders in a predetermined ratio, and then performing a solid phase reaction at a high temperature of 800 to 1300 ° C. .. However, high quality lead zirconate titanate can be obtained because it is inevitable 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 that you cannot do it. Furthermore, 1200 ° C required to obtain the above ceramics
At the above-mentioned high firing temperature, lead oxide is vaporized, and thus 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.
【０００４】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、７５４(１９９０)、特開昭62−108729号公報な
ど］、酢酸鉛と金属アルコキシド［Ｊ．Ａｐｐｌ．Ｐｈ
ｙｓ．，６４，２７１７(１９８８)］、酢酸鉛、硝酸ジ
ルコニウム、チタンブトキシド［日本セラミックス協会
誌、９９、６３０(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
が記載されている。Regarding low temperature synthesis of the above ceramics,
Metal alkoxide [eg, the Ceramic Society of Japan,
98, 754 (1990), JP-A-62-108729, etc.], lead acetate and metal alkoxide [J. Appl. Ph
ys. , 64, 2717 (1988)], lead acetate, zirconium nitrate, titanium butoxide [Journal of the Ceramic Society of Japan, 99, 630 (1991)], and low temperature sintering of lead zirconate titanate by sol-gel method. A method for synthesizing a conductive powder or a method for producing a lead zirconate titanate thin film is described.
【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−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に違いがあるた
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 easily decomposed, it is difficult to prepare a sample with a predetermined mixing ratio, and further, the storage stability of the mixed sample solution is poor. In addition, since the hydrolysis rates of metal alkoxides of lead, titanium, and zirconium are different, the composition, morphology, etc. are uniform in the sol-gel method for preparing the precursor sol of lead zirconate titanate and gel by hydrolysis. Another problem is 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, There are also problems in the process such as requiring a great deal of time for gelation.
【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が低温焼成により製造で
きる方法を提供することにある。Accordingly, it is an object of the present invention to provide a method capable of producing uniform lead zirconate titanate by low temperature firing without complicated steps.
【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、鉛、チタン、
ジルコニウムそれぞれの有機酸塩の混合溶液を低温で加
熱し、熱分解することにより均一なチタン酸ジルコン酸
鉛が得られることを見出した。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that lead, titanium,
It was found that a uniform lead zirconate titanate can be obtained by heating a mixed solution of organic acid salts of zirconium at a low temperature and thermally decomposing it.
【０００８】上記のように、従来のチタン酸ジルコン酸
鉛の低温合成のためには金属アルコキシドなどを用いた
ゾル−ゲル法が有効であるとの報告がなされているが、
本発明の製造方法によれば、縮合反応によるゾル状、及
びゲル状のチタン酸ジルコン酸鉛前駆体生成物を調製す
ることなしに、使用した有機酸塩の熱分解あるいは酸化
分解反応のみで直接チタン酸ジルコン酸鉛が製造でき
る。As described above, it has been reported that the sol-gel method using a metal alkoxide is effective for the conventional low temperature synthesis of lead zirconate titanate.
According to the production method of the present invention, without preparing a sol-like and gel-like lead zirconate titanate precursor product by a condensation reaction, the organic acid salt used is directly decomposed only by thermal decomposition or oxidative decomposition reaction. Lead zirconate titanate can be produced.
【０００９】本発明により製造し得るチタン酸ジルコン
酸鉛は、一般式：ＰｂＺｒxＴｉ1-xＯ3(ただし、０≦ｘ
≦１.０)で表される組成を有するＰｂＺｒＯ3とＰｂＴ
ｉＯ3の固溶体である。また、この固溶体に他の成分元
素を添加する場合(例えばＮｂ、Ｔａ、Ｆｅ、Ｍｇ、
Ｙ、Ｌａなど)、添加元素の有機酸塩をチタン酸ジルコ
ン酸鉛原料有機酸塩溶液に混合することにより容易に均
一組成のものが得られる。Lead zirconate titanate which can be produced according to the present invention has the general formula: PbZr x Ti 1-x O 3 (where 0 ≦ x
PbZrO 3 and PbT having a composition represented by ≦ 1.0)
It is a solid solution of iO 3 . When other component elements are added to this solid solution (for example, Nb, Ta, Fe, Mg,
Y, La, etc.), and an organic acid salt of an additional element are mixed with a lead zirconate titanate raw material organic acid salt solution to easily obtain a uniform composition.
【００１０】本発明において、チタン酸ジルコン酸鉛は
有機酸鉛、有機酸ジルコニウム、及び有機酸チタンを有
機溶媒にそれぞれ所定量溶解した溶液を混合することに
より得られる溶液、あるいは有機酸鉛、有機酸ジルコニ
ウム、及び有機酸チタンの各所定量を有機溶媒に混合す
ることにより得られる溶液を２０〜１５０℃の温度で乾
燥した後、５００〜１０００℃に加熱焼成することによ
り、製造することができる。In the present invention, the lead zirconate titanate is a solution obtained by mixing a lead organic acid, a zirconium organic acid, and a solution of titanium organic acid in an organic solvent in a predetermined amount, or a lead organic acid, an organic acid It can be produced by drying a solution obtained by mixing each of predetermined amounts of zirconium acid and organic acid titanium in an organic solvent at a temperature of 20 to 150 ° C. and then baking the solution at 500 to 1000 ° C.
【００１１】本発明方法に用いることができる鉛化合物
は、一般式：Ｐｂ(ＯＣＯＲ)2で表され、具体的には例
えばステアリン酸鉛、ラウリン酸鉛、カプリル酸鉛、２
−エチルヘキサン酸鉛、ネオデカン酸鉛、ナフテン酸鉛
などを挙げることができ、これらは１種単独でも、２種
以上でも用いることができる。The lead compound which can be used in the method of the present invention is represented by the general formula: Pb (OCOR) 2 , and specifically, for example, lead stearate, lead laurate, lead caprylate, 2
Examples thereof include lead ethylhexanoate, lead neodecanoate, and lead naphthenate. These may be used alone or in combination of two or more.
【００１２】また、本発明方法に用いられるチタン化合
物は、一般式：Ｔｉ(ＯＣＯＲ)4で表され、具体的には
例えばステアリン酸チタン、ラウリン酸チタン、カプリ
ル酸チタン、２−エチルヘキサン酸チタン、ネオデカン
酸チタン、ナフテン酸チタンなどを挙げることができ、
これらは１種単独でも、２種以上でも用いることができ
る。The titanium compound used in the method of the present invention is represented by the general formula: Ti (OCOR) 4 , specifically, for example, titanium stearate, titanium laurate, titanium caprylate, titanium 2-ethylhexanoate. , Titanium neodecanoate, titanium naphthenate and the like,
These may be used alone or in combination of two or more.
【００１３】更に、本発明方法に用いられるジルコニウ
ム化合物は、一般式：Ｚｒ(ＯＣＯＲ)4あるいはＺｒＯ
(ＯＣＯＲ)2で表され、具体的には例えばステアリン酸
ジルコニウム、ラウリン酸ジルコニウム、カプリル酸ジ
ルコニウム、２−エチルヘキサン酸ジルコニウム、ネオ
デカン酸ジルコニウム、ナフテン酸ジルコニウムあるい
はステアリン酸ジルコニル、カプリル酸ジルコニル、２
−エチルヘキサン酸ジルコニル、ネオデカン酸ジルコニ
ル、ナフテン酸ジルコニルなどを挙げることができ、こ
れらは１種単独でも、２種以上でも用いることができる
が、加水分解の起こらない有機酸ジルコニルを用いるこ
とが望ましい。Further, the zirconium compound used in the method of the present invention has a general formula: Zr (OCOR) 4 or ZrO.
(OCOR) 2 , specifically, for example, zirconium stearate, zirconium laurate, zirconium caprylate, zirconium 2-ethylhexanoate, zirconium neodecanoate, zirconium naphthenate or zirconyl stearate, zirconyl caprylate, 2
Examples thereof include zirconyl ethylhexanoate, zirconyl neodecanoate, and zirconyl naphthenate. These may be used alone or in combination of two or more, but it is preferable to use zirconyl organic acid that does not cause hydrolysis. ..
【００１４】本発明方法に用いる有機溶媒としては、ｎ
−プロパノール、ｉ−プロパノール、ｎ−ブタノールな
どのアルコール類、ヘキサン、ヘプタン、シクロヘキサ
ンなどの炭化水素類、ベンゼン、トルエン、キシレンな
どの芳香族類など上記有機酸金属塩を溶解する有機溶媒
であればどんな溶媒でも使用することができ、これらは
１種単独でも、２種以上でも用いることができる。ま
た、混合する溶媒量については特に限定されるものでは
ないが、通常有機酸塩１重量部に対して有機溶媒３〜２
０重量部程度を用いるのが好ましい。The organic solvent used in the method of the present invention is n
An organic solvent capable of dissolving the above organic acid metal salt such as alcohols such as propanol, i-propanol and n-butanol, hydrocarbons such as hexane, heptane and cyclohexane, aromatics such as benzene, toluene and xylene. Any solvent can be used, and these can be used alone or in combination of two or more. Further, the amount of the solvent to be mixed is not particularly limited, but usually 3 to 2 organic solvents per 1 part by weight of the organic acid salt.
It is preferable to use about 0 parts by weight.
【００１５】混合溶液は始めに乾燥し、次いで焼成す
る。乾燥は２０〜１５０℃で、０.２〜２時間、焼成は
５００〜１０００℃、好ましくは５００〜８００℃で
０.５〜２時間行うのが好ましい。The mixed solution is first dried and then calcined. Drying is preferably performed at 20 to 150 ° C. for 0.2 to 2 hours, and firing is preferably performed at 500 to 1000 ° C., preferably 500 to 800 ° C. for 0.5 to 2 hours.
【００１６】[0016]
【実施例】次に、実施例により本発明を詳細に説明す
る。 実施例１ オクチル酸鉛５０.０ｇ、オクチル酸ジルコニル２０.６
ｇ、オクチル酸チタン２７.６ｇをｎ−ブタノール９０
０ｇに希釈溶解した。その際の各金属分の原子比はＰ
ｂ：Ｚｒ：Ｔｉ＝１：０.５３：０.４７である。まず、
この溶液の水分安定性について調べた。常温で空気中で
放置することによる安定性試験を試みたところ、１月以
上放置しても安定であった。比較としてチタン化合物と
してオクチル酸チタンの代わりにチタンテトライソプロ
ポキシド、ｎ−ブトキシドを用いた場合は、１時間放置
しただけで、酸化チタン水和物の沈澱が析出しはじめ、
２日間放置すると完全に加水分解して白色沈澱が析出し
た。次に、上記オクチル酸鉛、オクチル酸ジルコニル、
オクチル酸チタンのｎ−ブタノール溶液を１００℃で１
時間乾燥した後に４００℃、５００℃、６００℃の各所
定温度で１時間加熱焼成し、得られた生成物を粉末Ｘ線
回折分析により調べた。その結果は図１ないし図３に示
す通りであり、４００℃(図１)では結晶性が悪く、Ｘ線
回折パターンからは生成物を特定できなかったが、５０
０℃(図２)、６００℃(図３)での生成物のＸ線回折パタ
ーンは、チタン酸シルコン酸鉛(Pb2Zr0.52Ti0.48O3：Ｊ
ＣＰＤＳ、Powder Diffraction File、３３−７８３)の
Ｘ線回折パターンとよく一致していた。この結果から、
オクチル酸鉛、オクチル酸ジルコニル、オクチル酸チタ
ンのｎ−ブタノール溶液を空気中で加熱すると、５００
℃以上でチタン酸ジルコン酸鉛が生成することがわかっ
た。残留炭素分は４００℃では４％、５００℃では１％
であったが、６００℃では検出されなかった(＜０.１
％)。EXAMPLES Next, the present invention will be described in detail with reference to examples. Example 1 Lead octylate 50.0 g, zirconyl octylate 20.6
g, titanium octylate 27.6 g and n-butanol 90
It was diluted and dissolved in 0 g. At that time, the atomic ratio of each metal component is P
b: Zr: Ti = 1: 0.53: 0.47. First,
The water stability of this solution was investigated. When a stability test was performed by leaving it in the air at room temperature, it was stable even if left for one month or more. For comparison, when titanium tetraisopropoxide or n-butoxide was used in place of titanium octylate as the titanium compound, the titanium oxide hydrate precipitates only after standing for 1 hour.
When left for 2 days, hydrolysis was completed and a white precipitate was deposited. Next, the lead octylate, zirconyl octylate,
A solution of titanium octylate in n-butanol was added at 100 ° C for 1 hour.
After drying for an hour, the product was heated and calcined at each predetermined temperature of 400 ° C, 500 ° C and 600 ° C for 1 hour, and the obtained product was examined by powder X-ray diffraction analysis. The results are shown in FIGS. 1 to 3, and the crystallinity was poor at 400 ° C. (FIG. 1), and the product could not be identified from the X-ray diffraction pattern.
The X-ray diffraction pattern of the product at 0 ° C. (FIG. 2) and 600 ° C. (FIG. 3) shows lead titanate silconate (Pb 2 Zr 0.52 Ti 0.48 O 3 : J
It was in good agreement with the X-ray diffraction pattern of CPDS, Powder Diffraction File, 33-783). from this result,
When a solution of lead octylate, zirconyl octylate, and titanium octylate in n-butanol is heated in air, 500
It was found that lead zirconate titanate was formed above ℃. Residual carbon content is 4% at 400 ° C and 1% at 500 ° C
However, it was not detected at 600 ° C (<0.1
%).
【００１７】実施例２ ネオデカン酸鉛、ネオデカン酸ジルコニル、ネオデカン
酸チタンを上記実施例１と同様にＰｂ：Ｚｒ：Ｔｉ＝
１：０.５３：０.４７の原子比になるように混合し、ブ
タノールに溶解した。この溶液もまた上記と同様に空気
中で１月以上放置しても安定なままであった。この溶液
を１００℃で１時間乾燥した後に、４００℃、５００
℃、６００℃の各所定温度で１時間加熱焼成して得られ
た生成物を粉末Ｘ線回折分析により調べた結果は実施例
１の結果と同様であり、５００℃以上でチタン酸ジルコ
ン酸鉛が生成することがわかった。残留炭素分も実施例
１の結果と同様であった。EXAMPLE 2 Lead neodecanoate, zirconyl neodecanoate, and titanium neodecanoate were mixed with Pb: Zr: Ti = as in Example 1 above.
The mixture was mixed at an atomic ratio of 1: 0.53: 0.47 and dissolved in butanol. This solution also remained stable upon standing in air for over a month, as above. This solution was dried at 100 ° C for 1 hour and then dried at 400 ° C, 500
The results of examining the product obtained by heating and calcining at each predetermined temperature of 600 ° C. and 600 ° C. for 1 hour by powder X-ray diffraction analysis are the same as the results of Example 1, and lead zirconate titanate at 500 ° C. or higher. Was found to be generated. The residual carbon content was similar to the result of Example 1.
【００１８】[0018]
【発明の効果】本発明において用いる鉛、チタン、ジル
コニウムそれぞれの有機酸塩の混合溶液は、従来報告さ
れているチタン酸ジルコン酸鉛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行う必要がない。
本発明方法を採用することで、成分金属の酸化物を原料
とする従来法に比して、はるかに低温でチタン酸ジルコ
ン酸鉛を製造でき、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、これに比して本発明方法で用いる原料
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。INDUSTRIAL APPLICABILITY The mixed solution of the organic acid salts of lead, titanium and zirconium used in the present invention is much more stable in water than the conventionally reported metal alkoxide solution which is a raw material for the low temperature synthesis of lead zirconate titanate. Therefore, it is not necessary to perform a complicated operation such as adding a chelate compound or an alkanolamine when preparing a solution.
By adopting the method of the present invention, lead zirconate titanate can be produced at a much lower temperature than in the conventional method using an oxide of a component metal as a raw material, which leads to significant energy saving and is economically advantageous. Is. Also, unlike solid-phase reactions,
Since lead zirconate titanate is produced by thermal decomposition of a uniform solution of an organic acid salt, a composition having a uniform composition can be obtained at a fine level. Further, in the sol-gel method using a metal alkoxide or the like, complicated operations and steps are required to control the hydrolysis. In contrast, the raw material used in the method of the present invention has no hydrolyzability. Since it is very small, handling is easy, operations such as mixing and drying are simple, and storage stability is greatly improved.
【００１９】また、本発明方法は下記に示す種々のプロ
セスによるチタン酸ジルコン酸鉛の製造方法に応用する
ことができる。約５００〜６００℃という低温焼成によ
り均一組成のチタ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
ものである。Further, the method of the present invention can be applied to a method for producing lead zirconate titanate by the following various processes. Since lead titanate having a uniform composition can be produced by firing at a low temperature of about 500 to 600 ° C., it can be applied to the synthesis of fine powder of uniform particles by a spray drying method or the like. Furthermore, it can be applied to the synthesis of thin films of uniform composition by printing methods such as screen printing and offset printing, spraying methods, dipping methods, spin coating methods, etc., and can sufficiently cope with the thinning and miniaturization of lead zirconate titanate. Is.
【図１】実施例１で４００℃の焼成温度で得られた生成
物の粉末Ｘ線回折パターンである。FIG. 1 is a powder X-ray diffraction pattern of the product obtained in Example 1 at a firing temperature of 400 ° C.
【図２】実施例１で５００℃の焼成温度で得られた生成
物の粉末Ｘ線回折パターンである。FIG. 2 is a powder X-ray diffraction pattern of the product obtained in Example 1 at a firing temperature of 500 ° C.
【図３】実施例１で６００℃の焼成温度で得られた生成
物の粉末Ｘ線回折パターンである。FIG. 3 is a powder X-ray diffraction pattern of the product obtained in Example 1 at a firing temperature of 600 ° C.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年１月１７日[Submission date] January 17, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１２[Correction target item name] 0012
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１２】また、本発明方法に用いられるチタン化合
物は、一般式：ＴｉＯｘ（ＯＣＯＲ）４−２ｘ（ただし
０≦ｘ≦１．０）で表され、具体的には例えばステアリ
ン酸チタン、ラウリン酸チタン、カプリル酸チタン、２
−エチルヘキサン酸チタン、ネオデカン酸チタン、ナフ
テン酸チタンなど及びそれらの重合体を挙げることがで
き、これらは１種単独でも、２種以上でも用いることが
できる。The titanium compound used in the method of the present invention has the general formula: TiO x (OCOR) 4-2x (provided that
0 ≦ x ≦ 1.0) , and specifically, for example, titanium stearate, titanium laurate, titanium caprylate, 2
-Titanium ethylhexanoate, titanium neodecanoate, titanium naphthenate , and the like and polymers thereof can be mentioned, and these can be used alone or in combination of two or more.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１６[Correction target item name] 0016
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１６】[0016]
【実施例】次に、実施例により本発明を詳細に説明す
る。 実施例１ オクチル酸鉛５０．０ｇオクチル酸ジルコニル２０．６
ｇ、オクチル酸チタン２７．６ｇをｎ−ブタノール９０
０ｇに希釈溶解した。その際の各金属分の原子比はＰ
ｂ：Ｚｒ：Ｔｉ＝１：０．５３：０．４７である。ま
ず、この溶液の水分安定性について調べた。常温で空気
中で放置することによる安定性試験を試みたところ、１
月以上放置しても安定であった。比較としてチタン化合
物としてオクチル酸チタンの代わりにチタンテトライソ
プロポキシド、ｎ−ブトキシドを用いた場合は、１時間
放置しただけで、酸化チタン水和物の沈澱が析出しはじ
め、２日間放置すると完全に加水分解して白色沈澱が析
出した。次に、上記オクチル酸鉛、オクチル酸ジルコニ
ル、オクチル酸チタンのｎ−ブタノール溶液を１００℃
で１時間乾燥した後に４００℃、５００℃、６００℃の
各所定温度で１時間加熱焼成し、得られた生成物を粉末
Ｘ線回折分析により調べた。その結果は図１ないし図３
に示す通りであり、４００℃（図１）では結晶性が悪
く、Ｘ線回折パターンからは生成物を特定できなかった
が、５００℃（図２）、６００℃（図３）での生成物の
Ｘ線回折パターンは、チタン酸ジルコン酸鉛（Ｐｂ２Ｚ
ｒ０．５２Ｔｉ０．４８Ｏ３：ＪＣＰＤＳ、Ｐｏｗｄｅ
ｒ Ｄｉｆｆｒａｃｔｉｏｎ Ｆｉｌｅ、 ３３−７８
３）のＸ線回折パターンとよく一致していた。この結果
から、オクチル酸鉛、オクチル酸ジルコニル、オクチル
酸チタンのｎ−ブタノール溶液を空気中で加熱すると、
５００℃以上でチタン酸ジルコン酸鉛が生成することが
わかった。残留炭素分は４００℃では４％、５００℃で
は１％であったが、６００℃では検出されなかった（＜
０．１％）。EXAMPLES Next, the present invention will be described in detail with reference to examples. Example 1 Lead octylate 50.0 g Zirconyl octylate 20.6
g, titanium octylate 27.6 g and n-butanol 90
It was diluted and dissolved in 0 g. At that time, the atomic ratio of each metal component is P
b: Zr: Ti = 1: 0.53: 0.47. First, the water stability of this solution was investigated. A stability test was conducted by leaving it in the air at room temperature.
It was stable even if left for more than a month. As a comparison, when titanium tetraisopropoxide or n-butoxide was used instead of titanium octylate as the titanium compound, the titanium oxide hydrate precipitates immediately after standing for 1 hour, and when it is left for 2 days, it is completely removed. To a white precipitate. Next, the n-butanol solution of the above-mentioned lead octylate, zirconyl octylate, and titanium octylate was heated to 100 ° C.
After drying for 1 hour at 400 ° C., 500 ° C. and 600 ° C., the obtained product was examined by powder X-ray diffraction analysis. The results are shown in FIGS.
, The crystallinity was poor at 400 ° C. (FIG. 1), and the product could not be identified from the X-ray diffraction pattern, but the products at 500 ° C. (FIG. 2) and 600 ° C. (FIG. 3) were obtained. the X-ray diffraction pattern of the titanate di Rukon lead (Pb 2 Z
r 0.52 Ti 0.48 O 3 : JCPDS, Powder
r Diffraction File, 33-78
It was in good agreement with the X-ray diffraction pattern of 3). From this result, when an n-butanol solution of lead octylate, zirconyl octylate, and titanium octylate was heated in air,
It was found that lead zirconate titanate was formed at 500 ° C or higher. The residual carbon content was 4% at 400 ° C and 1% at 500 ° C, but was not detected at 600 ° C (<
0.1%).
Claims (1)
ルコニウムの有機酸塩の混合溶液を乾燥、焼成すること
を特徴とするチタン酸ジルコン酸鉛の製造方法。1. A method for producing lead zirconate titanate, which comprises drying and firing a mixed solution of an organic acid salt of lead, an organic acid salt of titanium and an organic acid salt of zirconium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3217195A JP2996776B2 (en) | 1991-08-28 | 1991-08-28 | Method for producing lead zirconate titanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3217195A JP2996776B2 (en) | 1991-08-28 | 1991-08-28 | Method for producing lead zirconate titanate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0558636A true JPH0558636A (en) | 1993-03-09 |
| JP2996776B2 JP2996776B2 (en) | 2000-01-11 |
Family
ID=16700351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3217195A Expired - Fee Related JP2996776B2 (en) | 1991-08-28 | 1991-08-28 | Method for producing lead zirconate titanate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2996776B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007314366A (en) * | 2006-05-24 | 2007-12-06 | Murata Mfg Co Ltd | Thin film-forming composition and dielectric thin film |
| 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 |
| EP2520692A2 (en) | 2011-05-06 | 2012-11-07 | Seiko Epson Corporation | Precursor Solution for Piezoelectric Films, Method for Manufacturing the same, and Method for Manufacturing Piezoelectric Film |
-
1991
- 1991-08-28 JP JP3217195A patent/JP2996776B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007314366A (en) * | 2006-05-24 | 2007-12-06 | Murata Mfg Co Ltd | Thin film-forming composition and dielectric thin film |
| 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 |
| EP2520692A2 (en) | 2011-05-06 | 2012-11-07 | Seiko Epson Corporation | Precursor Solution for Piezoelectric Films, Method for Manufacturing the same, and Method for Manufacturing Piezoelectric Film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2996776B2 (en) | 2000-01-11 |
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