JPH0764564B2 - Zirconium oxide-based precursor gel and its production method - Google Patents
Zirconium oxide-based precursor gel and its production methodInfo
- Publication number
- JPH0764564B2 JPH0764564B2 JP2631591A JP2631591A JPH0764564B2 JP H0764564 B2 JPH0764564 B2 JP H0764564B2 JP 2631591 A JP2631591 A JP 2631591A JP 2631591 A JP2631591 A JP 2631591A JP H0764564 B2 JPH0764564 B2 JP H0764564B2
- Authority
- JP
- Japan
- Prior art keywords
- zirconium oxide
- gel
- solution
- zirconium
- precursor gel
- 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.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、長期保存可能な酸化ジ
ルコニウム系薄膜作製用前駆体ゲル状物及びその製造方
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 precursor gel-like material for producing a zirconium oxide thin film which can be stored for a long period of time, and a method for producing the same.
【０００２】[0002]
【従来の技術】酸化ジルコニウム及ひ安定化剤として酸
化イットリウム、酸化カルシウム、酸化マグネシウム等
をドープした安定化酸化ジルコニウム薄膜は、耐アルカ
リ性、耐摩耗性膜として種々の用途に利用されている。
また、透明な薄膜は高屈折率薄膜として選択光反射性被
膜または選択光透過性被膜の成分として利用されてい
る。これらの酸化ジルコニウム系薄膜を製造する方法と
して、生産性が高い、装置のコストが安い等の利点か
ら、金属アルコキシドを含む溶液を成形物に塗布して、
酸化物薄膜を形成させる方法か提案されている。2. Description of the Related Art Stabilized zirconium oxide thin films doped with yttrium oxide, calcium oxide, magnesium oxide, etc. as zirconium oxide and stabilizers are used in various applications as alkali resistant and abrasion resistant films.
Further, the transparent thin film is used as a high refractive index thin film as a component of a selective light reflecting coating or a selective light transmitting coating. As a method for producing these zirconium oxide-based thin films, a solution containing a metal alkoxide is applied to a molded article because of its advantages such as high productivity and low apparatus cost.
A method for forming an oxide thin film has been proposed.
【０００３】しかし、ジルコニウムアルコキシドは加水
分解−縮合が非常に速いため、水や湿分に対する溶液の
安定性が悪く、以下の式のように、容易に加水分解され
て、酸化ジルコニウム水和物を形成し、沈殿する。However, since zirconium alkoxide undergoes very rapid hydrolysis-condensation, the stability of the solution against water and moisture is poor, and zirconium oxide hydrate is easily hydrolyzed as shown in the following formula. Form and precipitate.
【０００４】[0004]
【式１】 Ｚｒ（ＯＲ′）４＋Ｈ２Ｏ→ＺｒＯ（ＯＲ′）２＋Ｒ′ＯＨ・・・（１） ２ＺｒＯ（ＯＲ′）２→ＺｒＯ２＋Ｚｒ（ＯＲ′）４ ・・・（２）[Formula 1] Zr (OR ′) 4 + H 2 O → ZrO (OR ′) 2 + R′OH (1) 2ZrO (OR ′) 2 → ZrO 2 + Zr (OR ′) 4 (2)
【０００５】従って、溶液を塗布する場合に、均一で透
明な塗布層を得ることが困難であっった。そのために、
塗布の際の湿気をきびしく制御したり、アルコキシドの
アルコキシ基の一部または全部をキレート形成可能な
基、例えば、アセチルアセトン等で置換することによ
り、加水分解を著しく抑制して、溶液を安定化する方法
が提案された。Therefore, when applying the solution, it was difficult to obtain a uniform and transparent coating layer. for that reason,
Strictly control the moisture at the time of application, and by substituting a part or all of the alkoxy groups of the alkoxide with a group capable of forming a chelate, for example, acetylacetone, etc., hydrolysis is significantly suppressed and the solution is stabilized. A method was proposed.
【０００６】しかし、この溶液を用いて形成した薄膜
は、加水分解−重縮合が十分に進んでいないため、未反
応アルコキシ基及ひアルコキシ基と置換した基を多量に
含んでおり、加熱して酸化物薄膜を得る場合、それらの
基の分解のために発生するピンホールやクラックによ
り、緻密な膜を形成できないという問題点がある。However, the thin film formed by using this solution contains a large amount of unreacted alkoxy groups and groups substituted with alkoxy groups because hydrolysis-polycondensation has not progressed sufficiently, When obtaining an oxide thin film, there is a problem that a dense film cannot be formed due to pinholes and cracks generated due to decomposition of these groups.
【０００７】さらに、上記のような方法を用いて加水分
解を抑制しても、未反応アルコキシ基を有するジルコニ
ウムアルコキシドが存在している溶液は、長期間大気中
に放置すると、加水分解−重縮合のため、溶液の粘度変
化や沈澱生成と言う結果を生じる、故に、長期にわた
り、この溶液を保存するには、雰囲気を制御した溶液保
存装置が必要であるという問題点があった。Further, even if hydrolysis is suppressed by using the above-mentioned method, a solution containing zirconium alkoxide having an unreacted alkoxy group is hydrolyzed and polycondensed when left in the atmosphere for a long time. Therefore, there is a problem in that a solution storage device with a controlled atmosphere is required to store the solution for a long period of time, which results in a change in the viscosity of the solution and the formation of a precipitate.
【０００８】[0008]
【発明が解決しようとする問題点】本発明が解決しよう
とする問題点は、ジルコニウムアルコキシドから調製し
た酸化ジルコニウム系前駆休が湿分に対する安定性が悪
く、しかも、酸化物薄膜形成の際に、ピンホールやクラ
ックの原因となる残留有機物が前駆休中に多量に存在し
ているという点である。さらに、もう一つの解決しよう
とする問題点は、酸化ジルコニウム系前駆休が未反応ア
ルコキシ基を多量に有するために、安定性に欠け、長期
保存が不可能であるという点である。The problem to be solved by the present invention is that the zirconium oxide precursor prepared from zirconium alkoxide has poor stability to moisture, and further, when forming an oxide thin film, This is because a large amount of residual organic substances that cause pinholes and cracks are present during the pre-deposition period. Further, another problem to be solved is that the zirconium oxide precursor has a large amount of unreacted alkoxy groups, and thus lacks stability and cannot be stored for a long period of time.
【０００９】[0009]
【問題を解決するための手段】上記の問題点を解決する
ための手段として、ジルコニウムアルコキシドとカルボ
ン酸を反応させ、アルコキシドのアルコキシ基を一部、
ＯＣＯＲ基に置換することにより、加水分解速度を制御
し、以下の式で表されるような、その化合物のゆっくり
とした加水分解−重縮合によって、制御されない場合の
速い加水分解−縮合による、上述の（１）式及び（２）
式からの沈澱生成物とはまったく異なる、未反応アルコ
キシ基のない、Ｚｒ−Ｏ−Ｚｒ結合を有する、透明な酸
化ジルコニウム系前駆体ポリマーゲル状物とすることを
主要な特徴とする。この前駆体ゲル状物が側鎖にＯＣＯ
Ｒ基を有することは乾燥させたゲルの赤外吸収スペクト
ルにおける１５６０ｃｍ−１付近と１４５０ｃｍ−１付
近の配位結合した−ＯＣＯＲに起因する２つの代表的ピ
ークから明らかである。[Means for Solving the Problems] As a means for solving the above problems, zirconium alkoxide and carboxylic acid are reacted to partially remove the alkoxy group of the alkoxide.
By substituting an OCOR group, the rate of hydrolysis is controlled, by slow hydrolysis-polycondensation of the compound, as represented by the formula below, by fast hydrolysis-condensation when not controlled, as described above. Equation (1) and (2)
The main feature is to obtain a transparent zirconium oxide-based precursor polymer gel having Zr-O-Zr bonds free from unreacted alkoxy groups, which is completely different from the precipitated product from the formula. This precursor gel-like product has OCO on the side chain.
It has an R group is evident from the two representative peak due to coordinated bound -OCOR near 1560 cm -1 and near 1450 cm -1 in an infrared absorption spectrum of the dried gel.
【００１０】[0010]
【式２】 Ｚｒ（ＯＲ′）４−ｘ（ＯＣＯＲ）ｘ＋Ｈ２Ｏ →Ｚｒ（ＯＲ′）３−ｘ（ＯＣＯＲ）ｘ（ＯＨ）＋Ｒ′（ＯＨ）・・・ （３） ２Ｚｒ（ＯＲ′）３−ｘ（ＯＣＯＲ）ｘ（ＯＨ）→ （ＯＲ′）３−ｘ（ＯＣＯＲ）ｘＺｒ−Ｏ−Ｚｒ（ＯＲ′）３−ｘ（ＯＣＯＲ ）ｘ＋Ｈ２Ｏ・・・（４） （Ｘ＝１，２）[Formula 2] Zr (OR ') 4-x (OCOR) x + H 2 O → Zr (OR') 3-x (OCOR) x (OH) + R '(OH) ... (3) 2Zr (OR' ) 3-x (OCOR) x (OH) → (OR ') 3-x (OCOR) x Zr-O-Zr (OR') 3-x (OCOR) x + H 2 O (4) (X = 1, 2)
【００１１】固体ポリマーゲル状物とすることで、大気
中で、長期にわたり、湿分に対してきわめて安定な酸化
ジルコニウム系前駆体を得るという目的を実現できた。
また、このゲル状物を溶解した溶液も非常に安定で、こ
の溶液を塗布することにより、残留有機物のほとんどな
い、酸化ジルコニウム系薄膜を得るという目的も実現で
きた。By using the solid polymer gel material, it was possible to achieve the purpose of obtaining a zirconium oxide-based precursor that is extremely stable against moisture in the air for a long period of time.
Further, a solution in which this gel-like material is dissolved is also very stable, and by applying this solution, the purpose of obtaining a zirconium oxide-based thin film with almost no residual organic matter was realized.
【００１２】[0012]
【実施例】本発明を以下の実施例及び参考例についてさ
らに具体的に説明をする。The present invention will be described more specifically with reference to the following examples and reference examples.
【００１３】[0013]
【実施例１】ジルコニウムｎ−プロポキシドを０．５ｍ
ｏｌ／リットルとなるようにｎ−ブチルアルコールで希
釈及び還流した。この溶液をビーカー中で攪拌しなが
ら、酢酸（酢酸／ジルコニウムアルコキシド＝１〔ｍｏ
ｌ比〕）と水（水／ジルコニウムアルコキシド＝１．３
３〔ｍｏｌ比〕）の混合溶液を滴下し、その後１時間、
攪拌を続けた。ピーカーをフィルムで密閉し、静置し
た。酢酸とアルコキシドのアルコキシ基との反応及び加
水分解−重縮合により、側鎖にＯＣＯＣＨ３基を有し、
Ｚｒ−Ｏ−Ｚｒ結合を主鎖とする重合体を形成し、溶液
の粘度は、時間とともに上昇し、混合後、数日で、透明
のままゲル化し、酸化ジルコニウム前駆体ゲル状物を得
た。この前駆体ゲル状物が側鎖にＯＣＯＣＨ３基を有す
ることは乾燥させたゲルの赤外吸収スペクトルから確認
された。このスペクトルには添加した酢酸とは異なる２
つのピークが１５６０ｃｍ−１付近と１４５０ｃｍ−１
付近に現れており、これらのピークはＺｒに配位結合し
たＯＣＯＣＨ３基に起因するものである。このことか
ら、この酸化物ジルコニウム前駆体ゲル状物はＯＣＯＣ
Ｈ３基を有することが明らかとなった。このゲル状物の
入ったピーカーをそのまま放置したところ、３カ月後
も、ゲル状物は、全く変化しなかった。Example 1 Zirconium n-propoxide 0.5 m
It was diluted with n-butyl alcohol and refluxed so as to be ol / l. While stirring this solution in a beaker, acetic acid (acetic acid / zirconium alkoxide = 1 [mo
1 ratio]) and water (water / zirconium alkoxide = 1.3
3 [mol ratio]), and then 1 hour
Stirring was continued. The peaker was sealed with a film and allowed to stand. Having an OCOCH 3 group in the side chain by the reaction of acetic acid and the alkoxy group of the alkoxide and hydrolysis-polycondensation,
A polymer having a Zr-O-Zr bond as a main chain was formed, the viscosity of the solution increased with time, and after mixing, gelation remained transparent within a few days to obtain a zirconium oxide precursor gel. . It was confirmed from the infrared absorption spectrum of the dried gel that this precursor gel had an OCOCH 3 group in the side chain. 2 different from acetic acid added to this spectrum
Two peaks around 1560 cm -1 and 1450 cm -1
These peaks appear in the vicinity, and these peaks are due to the OCOCH 3 group coordinate-bonded to Zr. From this fact, the oxide zirconium precursor gel-like material is OCOC.
It was revealed to have an H 3 group. When the peaker containing this gel-like substance was left as it was, the gel-like substance did not change at all even after 3 months.
【００１４】[0014]
【実施例２】ジルコニウムｎ−プロポキシドを０．５ｍ
ｏｌ／リットルとなるようにｎ−ブチルアルコールで希
釈及び還流した。この溶液をビーカー中で攪拌しなが
ら、酢酸（酢酸／ジルコニウムアルコキシド＝１．５
〔ｍｏｌ比〕）と硝酸カルシウム（カルシウム／ジルコ
ニウム＝０．１１〔原子比〕）と水（（水／ジルコニウ
ムアルコキシド＝１．５〔ｍｏｌ比〕）の混合溶液を滴
下し、その後１時間、攪拌を続けた。ビーカーをフィル
ムで密閉し、静置した。酢酸とアルコキシドのアルコキ
シ基との反応、さらに、加水分解−重縮合により、側鎖
にＯＣＯＣＨ３基を有し、Ｚｒ−Ｏ−Ｚｒ結合を主鎖と
する重合体を形成し、溶液の粘度は、時間とともに上昇
し、混合後、数日でゲル化した。溶液中では、硝酸カル
シウムは溶解し、均一に分散しており、ゲル化後もカル
シウムイオンの均一に分散した酸化カルシウムドープ酸
化ジルコニウム前駆体ゲル化状物を得た。このゲル状物
がＯＣＯＣＨ３基を有することは実施例１と同様、赤外
吸収スペクトルから確認された。Example 2 Zirconium n-propoxide 0.5 m
It was diluted with n-butyl alcohol and refluxed so as to be ol / l. While stirring the solution in a beaker, acetic acid (acetic acid / zirconium alkoxide = 1.5
[Mol ratio]), calcium nitrate (calcium / zirconium = 0.11 [atomic ratio]) and water ((water / zirconium alkoxide = 1.5 [mol ratio])) were added dropwise and then stirred for 1 hour. The beaker was sealed with a film and allowed to stand still.The reaction between acetic acid and the alkoxy group of the alkoxide, and further hydrolysis-polycondensation has an OCOCH 3 group in the side chain, and a Zr-O-Zr bond. The main chain of the polymer was formed, and the viscosity of the solution increased with time, and gelled within a few days after mixing.In the solution, calcium nitrate was dissolved and uniformly dispersed, and gelled. after obtain calcium oxide doped zirconium oxide precursor gel-like material was uniformly dispersed calcium ions. Similarly to the gel-like material has a 3 group OCOCH to example 1, the infrared absorption spectrum Et al has been confirmed.
【００１５】[0015]
【実施例３】ジルコニウムｎ−プロポキシドを０，５ｍ
ｏｌ／リットルとなるようにｎ−ブチルアルコールで希
釈及び還流した。この溶液に、１１０℃で乾燥した酢酸
イットリウム（イットリウム／ジルコニウム＝０．１８
５〔原子比〕）を混合、還流した。この溶液をビーカー
中で攪拌しながら、酢酸（酢酸／ジルコニウムアルコキ
シド＝１．５〔ｍｏｌ比〕）と硝酸（硝酸／酢酸イット
リウム＝４〔ｍｏｌ比〕）と水（（水／ジルコニウムア
ルコキシド＝２〔ｍｏｌ比〕）の混合溶液を滴下し、そ
の後１時間、攪拌を続けた。ビーカーをフィルムで密閉
し、静置した。酢酸イットリウムのＯＣＯＣＨ３基及び
添加した酢酸とアルコキシドのアルコキシ基との反応、
さらには、加水分解−重縮合により、側鎖にＯＣＯＣＨ
３基を有し、Ｚｒ−Ｏ−Ｚｒ結合を主鎖とする重合休を
形成し、溶液の粘度は、時間とともに上昇し、混合後、
数日でゲル化し、酸化イットリウムドープ酸化ジルコニ
ウム前駆体ゲル状物を得た。Example 3 Zirconium n-propoxide was added to 0.5 m.
It was diluted with n-butyl alcohol and refluxed so as to be ol / l. This solution was dried at 110 ° C. with yttrium acetate (yttrium / zirconium = 0.18).
5 (atomic ratio)) was mixed and refluxed. While stirring the solution in a beaker, acetic acid (acetic acid / zirconium alkoxide = 1.5 [mol ratio]), nitric acid (nitric acid / yttrium acetate = 4 [mol ratio]), and water ((water / zirconium alkoxide = 2 [mol ratio]). mol ratio]) was added dropwise, and stirring was continued for 1 hour thereafter.The beaker was sealed with a film and allowed to stand still.OCOCH 3 groups of yttrium acetate and the reaction between the added acetic acid and alkoxy groups of alkoxide,
Furthermore, by hydrolysis-polycondensation, OCOCH is formed on the side chain.
It has 3 groups and forms a polymerization break having a Zr-O-Zr bond as a main chain, and the viscosity of the solution increases with time, and after mixing,
Gelation took place within a few days to obtain a yttrium oxide-doped zirconium oxide precursor gel.
【００１６】酢酸イットリウムの一部またはほとんどの
ＯＣＯＣＨ３基は、還流により、ジルコニウムアルコキ
シドに配位し、イットリウムイオンは溶液中に均一に分
散している。また、酢酸イットリウムはアルコール溶媒
への溶解度はそれほど高くなく、溶液を長時間放置する
と、再結晶するため、硝酸の添加により、酢酸イットリ
ウムのＯＣＯＣＨ３基の一部またはほとんどをＮＯ３基
に置換することで再結晶を防いでいる。この操作によ
り、均一にイットリウムの分散した酸化ジルコニウム前
駆体ゲル状物が得られた。このゲル状物の入ったビーカ
ーをそのまま放置したところ、３カ月後も、ゲル状物
は、まったく変化なかった。A part or most of the OCOCH 3 groups of yttrium acetate are coordinated with the zirconium alkoxide by refluxing, and the yttrium ions are uniformly dispersed in the solution. Further, yttrium acetate has a not so high solubility in an alcohol solvent and recrystallizes when the solution is left for a long time. Therefore, by adding nitric acid, a part or most of the OCOCH 3 groups of yttrium acetate are replaced with NO 3 groups. This prevents recrystallization. By this operation, a zirconium oxide precursor gel material in which yttrium was uniformly dispersed was obtained. When the beaker containing the gel-like substance was left as it was, the gel-like substance did not change at all even after 3 months.
【００１７】[0017]
【実施例４】実施例１において、カルボン酸として、酢
酸の代わりに、ｎ−酪酸を使用し、その他は実施例１と
同様の条件で、ゲル状物の調製を行った。ｎ−酪酸と水
の混合溶液をアルコキシド溶液に滴下した後でも、溶液
は透明であった。数週間後、溶液はゲル化し、酸化ジル
コニウム前駆体ゲル状物を得た。カルボン酸の炭素数か
多くなると、加水分解がさらに抑制されるため、ゲル化
に時間がかかる結果となった。Example 4 A gel-like product was prepared under the same conditions as in Example 1 except that n-butyric acid was used as the carboxylic acid instead of acetic acid. Even after the mixed solution of n-butyric acid and water was added dropwise to the alkoxide solution, the solution was transparent. After a few weeks, the solution gelled and a zirconium oxide precursor gel was obtained. When the carbon number of the carboxylic acid is increased, the hydrolysis is further suppressed, resulting in the gelation taking a long time.
【００１８】[0018]
【参考例】実施例１及び実施例３で得た酸化ジルコニウ
ム系前駆体ゲル状物を使用して、酢酸：ｎ−ブチルアル
コール：ゲル状物＝２．４：２３．８：２３．８〔重量
比〕となるように秤量し、酢酸とｎ−ブチルアルコール
の混合溶液にゲル状物を混合した。そして、８０℃以下
の加熱により、完全にゲル状物を溶解した。これらの溶
液を、ガラス基板に塗布し、５００℃で加熱処理するこ
とにより、透明で緻密な酸化ジルコニウム系薄膜を得
た。また、このようにして調製した溶液は、６カ月間、
大気中に放置しても、粘度変化及ひ沈澱生成等の変化は
まったく見られなかった。Reference Example Using the zirconium oxide-based precursor gels obtained in Examples 1 and 3, acetic acid: n-butyl alcohol: gel = 2.4: 23.8: 23.8 [ Weight ratio], and the gel-like material was mixed with a mixed solution of acetic acid and n-butyl alcohol. Then, the gel-like substance was completely dissolved by heating at 80 ° C. or lower. These solutions were applied on a glass substrate and heat-treated at 500 ° C. to obtain a transparent and dense zirconium oxide thin film. In addition, the solution thus prepared,
Even when left in the air, no change in viscosity or precipitation was observed.
【００１９】[0019]
【発明の効果】以上、実施例に述べたように、本発明で
は、カルボン酸の添加により、加水分解を抑止して、ゆ
っくりと十分な加水分解−重縮合を行わせることで、ジ
ルコニウムアルコキシドの速い加水分解一重縮合によ
る、ＺｒＯ２水和物の沈澱生成を抑制し、Ｚｒ−Ｏ−Ｚ
ｒ網目を有し、未反応アルコキシ基をほとんど含まない
酸化ジルコニウム系前駆体ゲル状物を形成することで、
従来まで不可能であった、大気中の湿分の影響を受けな
い前駆体を、安定に長期間、保存するということが可能
になった。また、参考例に述べたように、本発明のゲル
状物を有機溶媒に溶解することにより、従来までの方法
では難しかった、安定性の非常に高い薄膜作製用溶液を
容易に得ることが可能となった。さらに、この溶液を成
形物に塗布、焼成することにより、従来の薄膜作製用溶
液からでは、残留有機物の影響で困難であった、緻密で
透明な酸化ジルコニウム系薄膜が得られるため、酸化ジ
ルコニウム系薄膜の光学材料としての用途を大いにひろ
げるものである。INDUSTRIAL APPLICABILITY As described above in the Examples, in the present invention, the addition of carboxylic acid suppresses the hydrolysis, and a sufficient hydrolysis-polycondensation is slowly carried out to obtain a zirconium alkoxide. Suppresses the formation of ZrO 2 hydrate precipitate due to rapid hydrolysis polycondensation, and Zr-O-Z
By forming a zirconium oxide-based precursor gel having an r-network and containing almost no unreacted alkoxy group,
It has become possible to stably store a precursor that is not affected by atmospheric moisture, which has been impossible until now, for a long period of time. Further, as described in Reference Example, by dissolving the gel-like material of the present invention in an organic solvent, it is possible to easily obtain a highly stable solution for forming a thin film, which was difficult by the conventional method. Became. Furthermore, by applying this solution to a molded product and firing it, a dense and transparent zirconium oxide-based thin film, which was difficult due to the effect of residual organic substances, can be obtained from the conventional thin film-forming solution. This greatly expands the use of thin films as optical materials.
Claims (6)
ＯＣＯＲ基（ここで、Ｒは炭素数１〜４までの直鎖また
は分岐のあるアルキル基を示す）を有する重合体から成
る、酸化ジルコニウム前駆体ゲル状物。1. From a polymer having a Zr—O—Zr bond as a main chain and an OCOR group (wherein R represents a linear or branched alkyl group having 1 to 4 carbon atoms) in a side chain. A zirconium oxide precursor gel.
ＯＣＯＲ基を有する重合体及びＹ、Ｌａ、Ｍｇ、Ｃａ、
Ｓｒ、Ｂａのうち、一種または二種以上の金属イオンを
含む酸化ジルコニウム系複合酸化物前駆体ゲル状物。2. A polymer having a Zr—O—Zr bond as a main chain and an OCOR group in a side chain, and Y, La, Mg, Ca,
A zirconium oxide-based complex oxide precursor gel containing one or more metal ions of Sr and Ba.
を有機溶媒中で混合、反応させることを特徴とする特許
請求の範囲第１項記載の酸化ジルコニウム前駆体ゲル状
物の製造方法。3. The method for producing a zirconium oxide precursor gel-like product according to claim 1, wherein Zr (OR ') 4 , RCOOH and water are mixed and reacted in an organic solvent.
及びＭ（ＯＣＯＣＨ３）ｎ及び硝酸を有機溶媒中で混
合、反応させることを特徴とする特許請求の範囲第２項
記載の酸化ジルコニウム系前駆休ゲル状物の製造方法。
（Ｍは、Ｙ、Ｌａ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａのいずれか
を示す。ｎはＭの価数を示す。）4. The zirconium oxide system according to claim 2, wherein Zr (OR ') 4 , RCOOH, water, M (OCOCH 3 ) n and nitric acid are mixed and reacted in an organic solvent. A method for producing a precursor gel material.
(M represents any one of Y, La, Mg, Ca, Sr, and Ba. N represents the valence of M.)
及びＭ（ＮＯ３）ｎを有機溶媒中で混合、反応させるこ
とを特徴とする特許請求の範囲第２項記載の酸化ジルコ
ニウム系前駆体ゲル状物の製造方法。5. The zirconium oxide precursor according to claim 2, wherein Zr (OR ′) 4 and RCOOH, water and M (NO 3 ) n are mixed and reacted in an organic solvent. Method for producing gel-like material.
ル類である特許請求の範囲第３項及び特許請求の範囲第
４項及び特許請求の範囲第５項記載の製造方法。6. The production method according to claim 3, claim 4 or claim 5, wherein the organic solvent is an alcohol having 1 to 5 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2631591A JPH0764564B2 (en) | 1991-02-20 | 1991-02-20 | Zirconium oxide-based precursor gel and its production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2631591A JPH0764564B2 (en) | 1991-02-20 | 1991-02-20 | Zirconium oxide-based precursor gel and its production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04265225A JPH04265225A (en) | 1992-09-21 |
| JPH0764564B2 true JPH0764564B2 (en) | 1995-07-12 |
Family
ID=12189950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2631591A Expired - Fee Related JPH0764564B2 (en) | 1991-02-20 | 1991-02-20 | Zirconium oxide-based precursor gel and its production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0764564B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2668226C1 (en) * | 2017-10-10 | 2018-09-27 | Акционерное общество "Государственный Ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (АО "ГНИИХТЭОС") | Method of obtaining organometal oxane yttrium oxane aluminoxanes, binding and impregnation materials based thereon |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4429533A1 (en) * | 1994-08-19 | 1996-02-22 | Cerdec Ag | Gels and xerogels free of water and hydroxyl groups, process for their preparation and their use |
| DE19538333A1 (en) * | 1995-10-14 | 1997-04-17 | Basf Ag | Process for the subcritical production of aerogels |
| US6376590B2 (en) * | 1999-10-28 | 2002-04-23 | 3M Innovative Properties Company | Zirconia sol, process of making and composite material |
| US7807723B1 (en) * | 2004-12-14 | 2010-10-05 | Chemetall Gmbh | Water-free metaloxide colloids and metal oxide polymers, method for the production thereof and use thereof |
| JP2007327071A (en) * | 2007-08-23 | 2007-12-20 | Kawasaki Heavy Ind Ltd | Method for producing hydrophilic coating composition |
| JP7232405B2 (en) * | 2019-06-25 | 2023-03-03 | 日油株式会社 | Fatty acid zirconium, fatty acid zirconium composition and material for forming zirconium oxide |
-
1991
- 1991-02-20 JP JP2631591A patent/JPH0764564B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2668226C1 (en) * | 2017-10-10 | 2018-09-27 | Акционерное общество "Государственный Ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (АО "ГНИИХТЭОС") | Method of obtaining organometal oxane yttrium oxane aluminoxanes, binding and impregnation materials based thereon |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04265225A (en) | 1992-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2768442B2 (en) | Manufacturing method of semiconductor-containing glass | |
| US4886654A (en) | Process for producing barium titanates | |
| JPH0764564B2 (en) | Zirconium oxide-based precursor gel and its production method | |
| JP3708117B2 (en) | Vanadium oxide colloidal dispersion and antistatic coating | |
| JPH11106935A (en) | Production of metal oxide thin film and metal oxide thin film | |
| JPH07121817B2 (en) | Zirconium oxide-based precursor gel and its production method | |
| Sun et al. | Design of reflective tantala optical coatings using sol-gel chemistry with ethanoic acid catalyst and chelator | |
| JPH0688780B2 (en) | Aluminum oxide precursor gel and method for producing the same | |
| JP2001233604A (en) | Application solution for forming thin oxide film, method for producing the same and method for producing thin oxide film | |
| RU2118402C1 (en) | Method of preparing metal oxide coatings (variants thereof) | |
| JP2003095651A (en) | Precursor sol for forming dielectric film, method for preparing precursor sol, dielectric film and method for forming dielectric film | |
| US6074471A (en) | Sol-gel route to transparent metal oxide films | |
| JP4023578B2 (en) | Hafnium-containing composite oxide coating and method for producing the same | |
| JPH0761871B2 (en) | Method for producing thin film from zirconium oxide-based precursor gel-like material | |
| JPS59199506A (en) | Formation of coated film of oxide | |
| JPH04139064A (en) | Production of lead titanate zirconate | |
| JP2920000B2 (en) | Method for producing lead zirconate titanate containing lanthanum | |
| Schneller | Simple alkoxide based precursor systems | |
| EP0370067B1 (en) | Preparation of thin layers of iron iii oxide for optical and/or magnetic recording | |
| JPS61190076A (en) | Formation of titanium oxide film | |
| JP7076575B2 (en) | Zirconium-containing alcohol solution | |
| JPH11278846A (en) | Pzt precursor sol, its preparation and formation of thin pzt film using same | |
| JPH11106934A (en) | Production of metal oxide thin film and metal oxide thin film | |
| JPH0633014A (en) | Coating agent composition | |
| JP2003240908A (en) | Antireflection film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19960123 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |