JPH04265225A - Zirconium oxide-based gelatinous precursor and its production - Google Patents
Zirconium oxide-based gelatinous precursor and its productionInfo
- Publication number
- JPH04265225A JPH04265225A JP2631591A JP2631591A JPH04265225A JP H04265225 A JPH04265225 A JP H04265225A JP 2631591 A JP2631591 A JP 2631591A JP 2631591 A JP2631591 A JP 2631591A JP H04265225 A JPH04265225 A JP H04265225A
- Authority
- JP
- Japan
- Prior art keywords
- zirconium oxide
- solution
- gel
- oxide precursor
- zirconium
- 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.)
- Granted
Links
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 25
- 239000002243 precursor Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 229910021645 metal ion Inorganic materials 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910013720 M(NO3)n Inorganic materials 0.000 claims 1
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims 1
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 229910052788 barium Inorganic materials 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 27
- 229910052726 zirconium Inorganic materials 0.000 description 14
- 239000010409 thin film Substances 0.000 description 13
- -1 zirconium alkoxide Chemical class 0.000 description 13
- 125000003545 alkoxy group Chemical group 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 150000004703 alkoxides Chemical class 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- GGROONUBGIWGGS-UHFFFAOYSA-N oxygen(2-);zirconium(4+);hydrate Chemical compound O.[O-2].[O-2].[Zr+4] GGROONUBGIWGGS-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Abstract
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 for producing a zirconium oxide thin film that 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び安定化剤として酸
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
物薄膜を形成指せる方法が提案されている。BACKGROUND OF THE INVENTION Stabilized zirconium oxide thin films doped with zirconium oxide and stabilizers such as yttrium oxide, calcium oxide, magnesium oxide, etc. are used in various applications as alkali-resistant and wear-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 manufacturing these zirconium oxide thin films, there are advantages such as high productivity and low equipment cost.
A method has been proposed in which a solution containing a metal alkoxide is applied to a molded article to form a thin oxide film.
【０００３】しかし、ジルコニウムアルコキシドは加水
分解−縮合が非常に強いため、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 has very strong hydrolysis and condensation, the stability of the solution against water and moisture is poor, and it is easily hydrolyzed to form zirconium oxide hydrate 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+H2O→ZrO(OR')2+
R'OH...(1) 2ZrO(OR')2→
ZrO2+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。[0005] Therefore, when applying a solution, it has been difficult to obtain a uniform and transparent coating layer. To this end, hydrolysis can be significantly suppressed by strictly controlling the humidity during application and by substituting some or all of the alkoxy groups of the alkoxide with groups capable of forming chelates, such as acetylacetone. A stabilizing 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
アルコキシ基及び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 using this solution contains a large amount of unreacted alkoxy groups and groups substituted for alkoxy groups because the hydrolysis and polycondensation have not progressed sufficiently, and they are oxidized by heating. When obtaining a thin film, pinholes and cracks occur due to the decomposition of these groups,
There is a problem that a dense film cannot be formed.
【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、溶液の粘膜変
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。Furthermore, even if hydrolysis is suppressed using the above method, if a solution containing zirconium alkoxide with unreacted alkoxy groups is left in the atmosphere for a long period of time, it will undergo hydrolysis-polycondensation. This results in changes in the mucous membranes of the solution and the formation of precipitates.Therefore, in order to preserve this solution for a long period of time, a solution storage device with a controlled atmosphere is required.
【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体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体中に多量に存在し
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体が未反応ア
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。Problems to be Solved by the Invention The problems to be solved by the present invention are that the zirconium oxide precursor prepared from zirconium alkoxide has poor stability against moisture, and moreover, when forming an oxide thin film, The problem is that the precursor contains a large amount of residual organic matter that causes pinholes and cracks. Furthermore, another problem to be solved is that since the zirconium oxide precursor has a large amount of unreacted alkoxy groups, it lacks stability and cannot be stored for a long 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。[Means for solving the problem] As a means for solving the above problems, the hydrolysis rate can be increased by reacting zirconium alkoxide with carboxylic acid and replacing some of the alkoxy groups of the alkoxide with OCOR groups. (1) and (2) by slow hydrolysis-polycondensation of the compound as expressed by
The main feature is that it is a transparent zirconium oxide-based precursor polymer gel having Zr--O--Zr bonds, without unreacted alkoxy groups, which is completely different from the precipitated product from formula (2).
【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+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)
【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。[0011] By forming a solid polymer gel, the object of obtaining a zirconium oxide precursor that is extremely stable against moisture in the atmosphere for a long period of time has been achieved. Furthermore, the solution containing this gel-like material is also very stable, and by applying this solution, we were able to achieve the objective of obtaining a zirconium oxide thin film with almost no residual organic matter.
【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。EXAMPLES The present invention will be explained in more detail 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〔ｍｏｌ
比〕）と水（水／ジルコニウムアルコキシド＝１．３３
〔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、全く変化しなかった。[Example 1] 0.5 m of zirconium n-propoxide
The mixture was diluted with n-butyl alcohol and refluxed to give a concentration of 1 ol/liter. While stirring this solution in a beaker, acetic acid (acetic acid/zirconium alkoxide = 1 [mol
ratio]) and water (water/zirconium alkoxide = 1.33
A mixed solution of [molar ratio]) was added dropwise, and stirring was continued for 1 hour. The beaker was sealed with film and left to stand. Through the reaction of acetic acid with the alkoxy group of alkoxide and hydrolysis-polycondensation, Zr
A polymer having an -O-Zr bond as a main chain was formed, and the viscosity of the solution increased with time, and within several days after mixing, it gelled while remaining transparent to obtain a zirconium oxide precursor gel. When the beaker containing this gel-like material was left as it was, the gel-like material did not change at all even after three 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〔ｍ
ｏｌ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Ｏ
ＣＯＣＨ３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。[Example 2] 0.5 m of zirconium n-propoxide
The mixture was diluted with n-butyl alcohol and refluxed to give a concentration of 1 ol/liter. While stirring this solution in a beaker, acetic acid (acetic acid/zirconium alkoxide = 1.5 [m
A mixed solution of calcium nitrate (calcium/zirconium = 0.11 [atomic ratio]) and water ((water/zirconium alkoxide = 1.5 [mol ratio]) was added dropwise, and then stirred for 1 hour. The beaker was sealed with a film and left to stand. O
Forms a polymer with COCH3 groups and Zr-O-Zr bonds as the main chain, and the viscosity of the solution increases with time.
After mixing, it gelled within a few days. In the solution, calcium nitrate was dissolved and uniformly dispersed, and even after gelation, a gelled product of calcium oxide-doped zirconium oxide precursor in which calcium ions were dispersed was obtained.
【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、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] 0.5 m of zirconium n-propoxide
The mixture was diluted with n-butyl alcohol and refluxed to give a concentration of 1 ol/liter. Add yttrium acetate (yttrium/zirconium = 0.18
5 [atomic ratio]) were mixed and refluxed. While stirring this 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]) A mixed solution of [molar ratio]) was added dropwise, and stirring was continued for 1 hour.The beaker was sealed with a film and left to stand.The reaction between the OCOCH3 group of yttrium acetate and the added acetic acid and the alkoxy group of the alkoxide,
Furthermore, by hydrolysis-polycondensation, OCOCH was added to the side chain.
3 groups, forming a polymer with Zr-O-Zr bonds as the main chain, the viscosity of the solution increases with time, and after mixing,
It gelated in 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。[0016] Some or most of the OCOCH3 groups in yttrium acetate are coordinated to the zirconium alkoxide by reflux, and the yttrium ions are uniformly dispersed in the solution. In addition, yttrium acetate does not have very high solubility in alcohol solvents, and recrystallizes if the solution is left for a long time. Therefore, by adding nitric acid, some or most of the OCOCH3 groups in yttrium acetate can be replaced with NO3 groups. Prevents recrystallization. Through this operation, a zirconium oxide precursor gel in which yttrium was uniformly dispersed was obtained. When the beaker containing this gel-like substance was left as it was, the gel-like substance remained after 3 months.
There was no change at all.
【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が
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 in the same manner as in Example 1 except that n-butyric acid was used instead of acetic acid as the carboxylic acid. Even after dropping the mixed solution of n-butyric acid and water into the alkoxide solution, the solution remained clear. After several weeks, the solution gelled and a zirconium oxide precursor gel was obtained. As the number of carbon atoms in the carboxylic acid increases, hydrolysis is further suppressed, resulting in a longer gelation 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、粘度変化及び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 precursor gel 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 into a mixed solution of acetic acid and n-butyl alcohol. Then, the gel-like material was completely dissolved by heating at 80° C. or lower. These solutions were applied to a glass substrate and heat-treated at 500°C to obtain a transparent and dense zirconium oxide thin film. Further, even when the solution thus prepared was left in the air for 6 months, no changes such as viscosity change or precipitation formation were 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、加水分解を抑制して、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−重縮合による
、ＺｒＯ２水和物の沈澱生成を抑制し、Ｚｒ−Ｏ−Ｚｒ
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成用溶液を容
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、従来の薄膜作成溶液か
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。Effects of the Invention As described above in the Examples, in the present invention, hydrolysis is suppressed by adding carboxylic acid and sufficient hydrolysis-polycondensation is carried out slowly, thereby producing zirconium alkoxide. Precipitate formation of ZrO2 hydrate due to rapid hydrolysis-polycondensation is suppressed, and Zr-O-Zr
By forming a gel-like zirconium oxide precursor that has a network and contains almost no unreacted alkoxy groups, it is possible to stably produce a precursor that is unaffected by atmospheric moisture, which was previously impossible. It has become possible to store it for a long time. In addition, as described in the 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 thin films, which was difficult with conventional methods. It became. Furthermore, by applying this solution to a molded object and firing it, it is possible to obtain a dense and transparent zirconium oxide thin film, which was difficult to obtain with conventional thin film preparation solutions due to the influence of residual organic matter. This greatly expands its uses as an optical material.
Claims (6)
に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。Claim 1: From a polymer having a Zr-O-Zr bond as the main chain and an OCOR group (here, R represents a linear or branched alkyl group having 1 to 4 carbon atoms) in the side chain. A zirconium oxide precursor gel.
にＯＣＯＲ基を有する重合体及びＹ、Ｌａ、Ｍｇ、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。[Claim 2] A polymer having a Zr-O-Zr bond as the main chain and an OCOR group in the side chain, and Y, La, Mg, Sr
, a zirconium oxide-based composite oxide precursor gel containing one or more metal ions among 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 according to claim 1, which comprises mixing and reacting Zr(OR')4, RCOOH, and water 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体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 precursor according to claim 2, characterized in that Zr(OR')4, RCOOH, water, M(OCOCH3)n, and nitric acid are mixed and reacted in an organic solvent. Method for producing body gel. (M represents either Y, La, Mg, Ca, Sr, or 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. Zirconium oxide precursor gel according to claim 2, characterized in that Zr(OR')4, RCOOH, water and M(NO3)n are mixed and reacted in an organic solvent. A method for manufacturing a shaped article.
ー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 manufacturing method according to claim 3, claim 4, and 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 true JPH04265225A (en) | 1992-09-21 |
| JPH0764564B2 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 (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0697372A1 (en) * | 1994-08-19 | 1996-02-21 | Cerdec Aktiengesellschaft Keramische Farben | Water-free and hydoxyl-free gels or xerogels, process for their preparation and their use |
| DE19538333A1 (en) * | 1995-10-14 | 1997-04-17 | Basf Ag | Process for the subcritical production of aerogels |
| JP2003512287A (en) * | 1999-10-28 | 2003-04-02 | スリーエム イノベイティブ プロパティズ カンパニー | Zirconia sol and method for producing the same |
| JP2007327071A (en) * | 2007-08-23 | 2007-12-20 | Kawasaki Heavy Ind Ltd | Method for producing hydrophilic coating composition |
| JP2008523230A (en) * | 2004-12-14 | 2008-07-03 | ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング | Anhydrous metal oxide colloids and metal oxide polymers, their preparation and use |
| JP2021004269A (en) * | 2019-06-25 | 2021-01-14 | 日油株式会社 | Aliphatic acid zirconium, aliphatic acid zirconium composition and zirconium oxide formation material |
Families Citing this family (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 |
-
1991
- 1991-02-20 JP JP2631591A patent/JPH0764564B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0697372A1 (en) * | 1994-08-19 | 1996-02-21 | Cerdec Aktiengesellschaft Keramische Farben | Water-free and hydoxyl-free gels or xerogels, process for their preparation and their use |
| DE19538333A1 (en) * | 1995-10-14 | 1997-04-17 | Basf Ag | Process for the subcritical production of aerogels |
| JP2003512287A (en) * | 1999-10-28 | 2003-04-02 | スリーエム イノベイティブ プロパティズ カンパニー | Zirconia sol and method for producing the same |
| JP2008523230A (en) * | 2004-12-14 | 2008-07-03 | ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング | Anhydrous metal oxide colloids and metal oxide polymers, their preparation and use |
| JP2007327071A (en) * | 2007-08-23 | 2007-12-20 | Kawasaki Heavy Ind Ltd | Method for producing hydrophilic coating composition |
| JP2021004269A (en) * | 2019-06-25 | 2021-01-14 | 日油株式会社 | Aliphatic acid zirconium, aliphatic acid zirconium composition and zirconium oxide formation material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0764564B2 (en) | 1995-07-12 |
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