JPH0248418A - Zirconia composite sol - Google Patents
Zirconia composite solInfo
- Publication number
- JPH0248418A JPH0248418A JP19629488A JP19629488A JPH0248418A JP H0248418 A JPH0248418 A JP H0248418A JP 19629488 A JP19629488 A JP 19629488A JP 19629488 A JP19629488 A JP 19629488A JP H0248418 A JPH0248418 A JP H0248418A
- Authority
- JP
- Japan
- Prior art keywords
- sol
- zirconia
- oxide
- composite sol
- based composite
- 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 150000003754 zirconium Chemical class 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 15
- 239000007864 aqueous solution Substances 0.000 abstract description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000084 colloidal system Substances 0.000 abstract description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003957 anion exchange resin Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical class [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はジルコニア系複合ゾルに関するものであって、
さらに詳しくは、ジルコニア以外の金属酸化物を核とし
、その核がジルコニアで被覆された形態のコロイド粒子
を分散質とするジルコニア系複合ゾルに係る。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a zirconia-based composite sol,
More specifically, the present invention relates to a zirconia-based composite sol in which the dispersoid is colloidal particles in which the core is a metal oxide other than zirconia and the core is coated with zirconia.
［従来の技術］
ジルコニアと他の金属酸化物とが混合状態にあるゾルや
そうしたゾルの製造方法は公知であって、例えば特開昭
５５−４７１３７号公報には、チタン（ＩＶ）塩及びス
ズ（ＩＶ）塩からなる群より選ばれた少なくとも１種と
、ジルコニウム（ＩＶ）塩水溶液を混合し、この水溶液
のｐＨを１〜３に調整してジルコニウムとスズ又はチタ
ンとの酸化金属水和物の混合ゾルを得る方法が記載され
ている。[Prior Art] Sols containing zirconia and other metal oxides in a mixed state and methods for producing such sol are known. (IV) At least one selected from the group consisting of salts and a zirconium (IV) salt aqueous solution are mixed, and the pH of this aqueous solution is adjusted to 1 to 3 to form a metal oxide hydrate of zirconium and tin or titanium. A method for obtaining a mixed sol is described.
また特開昭６０−１７６９２０号公報には、ジルコニウ
ムとカルシウムなどの２価金属の水酸化物を共沈させ、
この共沈物を２価金属水酸化物が溶出しない程度に濃厚
な２価金属水酸化物水溶液で洗浄後、共沈水酸化物と２
価金属水酸化物水溶液との混合懸濁液又は糊状物を、９
０〜２００℃の温度で加熱熟成して２価金属イオンを含
むジルコニア系単結晶超微粒子が分散したゾルの製造方
法が教示されている。Furthermore, in Japanese Patent Application Laid-open No. 176920/1983, hydroxides of divalent metals such as zirconium and calcium are co-precipitated,
After washing this coprecipitate with a divalent metal hydroxide aqueous solution concentrated to the extent that the divalent metal hydroxide does not elute, the coprecipitate and the two
A mixed suspension or paste-like substance with an aqueous solution of a valent metal hydroxide, 9
A method for producing a sol in which zirconia single crystal ultrafine particles containing divalent metal ions are dispersed by heating and aging at a temperature of 0 to 200° C. is taught.
特開昭６２−２２６８１５号公報には、ジルコニウム塩
水溶液又はジルコニウム塩とイツトリウム、カルシウム
及びマグネシラ１１よりなる群から選ばれた少なくとも
一種の金属元素の塩とを含む水溶液を、加水分解するこ
とによってコロイド溶液を生成させ、次いで濾過膜を使
用してこのコロイド溶液を洗浄し、高純度のジルコニア
系コロイド溶液を製造する方法が記載されている。JP-A-62-226815 discloses that a colloid is produced by hydrolyzing an aqueous solution of a zirconium salt or an aqueous solution containing a zirconium salt and a salt of at least one metal element selected from the group consisting of yttrium, calcium, and magnesilla-11. A method is described for producing a highly pure zirconia-based colloidal solution by forming a solution and then using a filter membrane to wash the colloidal solution.
特開昭６２−２３０６１０号公報には、ホウ素以外の異
種金属種Ｍを含むホウ塩化ジルコニウムゾルが記載され
、異種金属種Ｍとして２価、３価、４価又は５価の金属
の化合物が例示されている。JP-A-62-230610 describes a borochlorinated zirconium sol containing a different metal species M other than boron, and examples of the different metal species M include compounds of divalent, trivalent, tetravalent, or pentavalent metals. has been done.
また、米国特許節３，８６４，１４２号には、ＳｉＯ□
として５〜４０重景％のシリカゾルに金属塩化物を加え
て反応させ、得られた反応生成物を陰イオン交換樹脂で
処理することにより、金属酸化物で被覆されたシリカの
ゾルを製造する方法が教示されている。Also, in U.S. Patent Section 3,864,142, SiO□
A method for producing a silica sol coated with a metal oxide by adding a metal chloride to a silica sol containing 5 to 40% by weight and reacting it, and treating the resulting reaction product with an anion exchange resin. is taught.
［発明が解決しようとする課題］ ジルコニアを含有するゾルは、これをガラス。[Problem to be solved by the invention] Sol containing zirconia is made of glass.
プラスチックなどの透明な基体表面に塗布し、膜厚１０
０〜２００００ｎｍ程度の被膜を形成させることで、そ
の基体に反射防止能、紫外線吸収能、耐候性などを付与
することができ、これがジルコニア含有ゾルの重要な用
途の一つである。しかし、従来のジルコニア含有ゾルは
、特に被膜の耐候性の点で必ずしも充分な結果が得られ
ない不満がある。Coated on the surface of a transparent substrate such as plastic, with a film thickness of 10
By forming a film with a thickness of about 0 to 20,000 nm, antireflection ability, ultraviolet absorption ability, weather resistance, etc. can be imparted to the substrate, and this is one of the important uses of zirconia-containing sols. However, conventional zirconia-containing sols have the drawback that satisfactory results cannot always be obtained, particularly in terms of the weather resistance of the coating.
従って、本発明は従来のジルコニア含有ゾルに比較して
耐候性に優れた被膜を得ることができ、しかも透明度、
反射防止能、紫外線吸収能などの点では、従来のジルコ
ニア含有ゾルに優るとも劣らない被膜を得ることができ
るジルコニア系複合ゾルとその製造法を提供する。Therefore, the present invention makes it possible to obtain a film with excellent weather resistance compared to conventional zirconia-containing sols, as well as transparency and
Provided is a zirconia-based composite sol and a method for producing the same, which can provide a coating film that is superior to, but not inferior to, conventional zirconia-containing sols in terms of antireflection ability, ultraviolet absorption ability, and the like.
［課題を解決するための手段」
本発明のジルコニア系複合ゾルは、その分散質であるコ
ロイド粒子が、ジルコニア以外の金属酸化物を核とし、
その核の表面にジルコニアが付着し、典型的には核がジ
ルコニアにて被覆された形態にある点で、コロイド粒子
がジルコニアと他の金属酸化物との単なる混合物で構成
される従来のジルコニア含有ゾルと区別される。[Means for Solving the Problems] The zirconia-based composite sol of the present invention has colloidal particles as its dispersoid having a core of a metal oxide other than zirconia,
Zirconia is attached to the surface of the core, and the core is typically coated with zirconia, unlike conventional zirconia-containing colloid particles in which the colloidal particles are simply a mixture of zirconia and other metal oxides. Distinguished from sol.
本発明のジルコニア系複合ゾルは、ジルコニア以外の金
属酸化物ゾルと、ジルコニウム塩水溶液との混合液を加
熱処理した後、洗浄することにより製造することができ
る。この場合、ジルコニア以外の酸化物ゾルとしては、
酸化セリウム、酸化チタン、酸化スズ、酸化アンチモン
、酸化イツトリウム、アルミナ、酸化鉄、シリカ、酸化
バナジウム、酸化クロム、酸化タングステンなどのゾル
の１種もしくは２種以上が使用できる。なかでも、酸化
セリウム、酸化チタン及び酸化鉄のゾルは、その分散粒
子をジルコニアで被覆して得られるジルコニア系複合ゾ
ルの被膜が、紫外線吸収能及び耐候性に優れているので
好ましい。The zirconia-based composite sol of the present invention can be produced by heating a mixed solution of a metal oxide sol other than zirconia and an aqueous zirconium salt solution, and then washing the mixture. In this case, the oxide sol other than zirconia is
One or more types of sols such as cerium oxide, titanium oxide, tin oxide, antimony oxide, yttrium oxide, alumina, iron oxide, silica, vanadium oxide, chromium oxide, and tungsten oxide can be used. Among these, cerium oxide, titanium oxide, and iron oxide sols are preferred because a zirconia-based composite sol coating obtained by coating their dispersed particles with zirconia has excellent ultraviolet absorption ability and weather resistance.
上記したような酸化物ゾルには市販品を使用することが
できるほか、これを公知の方法で調製することもできる
。しかし、いずれの場合でも、そのコロイド粒子の粒径
は５０〜５００人の範囲にあることが好ましい。粒子径
が５０人より小さい場合はゾルが不安定になり、５００
人より大きい場合は最終的に得られるジルコニア系複合
ゾルの透明性が低下する。As the above-mentioned oxide sol, a commercially available product can be used, or it can also be prepared by a known method. However, in any case, the particle size of the colloidal particles is preferably in the range of 50 to 500 particles. If the particle size is smaller than 50, the sol becomes unstable and
If it is larger than a person, the transparency of the final zirconia composite sol will decrease.
本発明のジルコニウム塩水溶液としては、塩化ジルコニ
ル、硝酸ジルコニル、硫酸ジルコニル、酢酸ジルコニル
などで例示される可溶性ジルコニウム塩の水溶液が使用
可能である。その濃度はＺｒＯ□換算で０．１〜５ｗｔ
％、好ましくは０．１〜０．３ｗｔ％程度とすることが
、酸化物ゾルとの混合に際してそのゲル化を確実に防止
する上で有効である。同様な意味で、酸化物ゾルは酸化
物換算で０．１〜２ｔｚｔ％程度に希釈してジルコニウ
ム塩水溶液と混合することが好ましい。尚、混合液中の
ジルコニウム塩濃度は、最終的に得られるジルコニア系
複合ゾルの透明性に影響を及ぼし、濃度が高くなると、
ジルコニア系複合ゾルの透明性が低下する傾向にある。As the zirconium salt aqueous solution of the present invention, aqueous solutions of soluble zirconium salts such as zirconyl chloride, zirconyl nitrate, zirconyl sulfate, and zirconyl acetate can be used. Its concentration is 0.1 to 5wt in terms of ZrO□
%, preferably about 0.1 to 0.3 wt%, is effective in reliably preventing gelation when mixed with the oxide sol. In the same sense, it is preferable that the oxide sol is diluted to about 0.1 to 2 tzt% in terms of oxide and mixed with the zirconium salt aqueous solution. The zirconium salt concentration in the mixed solution affects the transparency of the zirconia-based composite sol that is finally obtained, and as the concentration increases,
The transparency of the zirconia composite sol tends to decrease.
酸化物ゾルとジルコニウム塩水溶液の混合割合は、最終
的に得られるジルコニア系複合ゾルの分散粒子が、ジル
コニア以外の金属酸化物を１〜９５νｔ％含有し、ジル
コニアを９９〜５ｗｔ％含有することになるように、好
ましくはジルコニア以外の金属酸化物を１〜５０ｗｔ％
含有し、ジルコニアを９９〜５０ｗｔ％含有することに
なるように選択される。混合液は次いで５０〜２００℃
、好ましくは９０〜１５０℃の温度で１〜７２時間加熱
処理され、これにより混合液中のジルコニウム塩は加水
分解し、共存する酸化物のコロイド粒子の表面にジルコ
ニアとして析出する。この場合、ジルコニアの析出量が
多ければ、酸化物のコロイド粒子はジルコニアで被覆さ
れることになる。The mixing ratio of the oxide sol and the zirconium salt aqueous solution is such that the finally obtained dispersed particles of the zirconia-based composite sol contain 1 to 95 νt% of metal oxides other than zirconia and 99 to 5 wt% of zirconia. Preferably, the metal oxide other than zirconia is contained in an amount of 1 to 50 wt%.
99 to 50 wt% of zirconia. The mixture is then heated to 50-200℃
, preferably at a temperature of 90 to 150° C. for 1 to 72 hours, whereby the zirconium salt in the mixed solution is hydrolyzed and precipitated as zirconia on the surface of coexisting oxide colloidal particles. In this case, if the amount of zirconia precipitated is large, the oxide colloid particles will be covered with zirconia.
いずれにしても、上記の加水分解により、ジルコニア以
外の金属酸化物粒子を核として、その表面にジルコニア
が付着した形態のコロイド粒子を分散質とするジルコニ
ア系複合ゾルを得ることができる。In any case, by the above-mentioned hydrolysis, it is possible to obtain a zirconia-based composite sol in which particles of a metal oxide other than zirconia are used as cores, and colloidal particles with zirconia attached to the surface thereof are used as dispersoids.
このゾルは加水分解によって生じた酸及び未加水分解の
ジルコニウム塩を含有しているので、必要に応じて濃縮
後、例えば限外濾過膜等で好ましくはＰＩ（３〜５の条
件下に洗浄することにより、これら夾雑物を除去するこ
とができる。また、本発明のジルコニア系複合ゾルはこ
れを陰イオン交換樹脂に通すことにより、コロイド粒子
に吸着されている陰イオンを除去することもできる。本
発明のジルコニア系複合ゾルは濃縮の程度にもよるが、
通常５〜３０ｗｔ％程度の固形分濃度に調製される。Since this sol contains an acid generated by hydrolysis and an unhydrolyzed zirconium salt, after concentrating it if necessary, it is washed with an ultrafiltration membrane, etc., preferably under the conditions of PI (3 to 5). In addition, by passing the zirconia-based composite sol of the present invention through an anion exchange resin, anions adsorbed on colloidal particles can be removed. The zirconia-based composite sol of the present invention depends on the degree of concentration, but
The solid content concentration is usually adjusted to about 5 to 30 wt%.
［実 施 例］
実施例１
テトライソプロピルチタネートの加水分解で調製した平
均粒子径８０人のチタニアゾルをイオン交換水で希釈し
てＴｉ０ｚとして０．２ｗｔ％のゾル５２を調製した。[Examples] Example 1 A titania sol with an average particle diameter of 80 prepared by hydrolysis of tetraisopropyl titanate was diluted with ion-exchanged water to prepare a 0.2 wt % sol 52 as Ti0z.
オキシ塩化ジルコニウム（ＺｒＯＣ２゜・８Ｈ２０）２
６２ｇを４５Ｑのイオン交換水に溶解した溶液に、前記
の希釈チタニアゾルを混合し、この混合液を還流器付き
加熱装置に入れ、９８℃で２４時間加熱処理を行った。Zirconium oxychloride (ZrOC2゜・8H20)2
The above-mentioned diluted titania sol was mixed with a solution in which 62 g of titania sol was dissolved in 45Q ion-exchanged water, and the mixed solution was placed in a heating device equipped with a reflux device and heat-treated at 98° C. for 24 hours.
こうして得られた処理液を限外濾過膜（旭化成５ＩＰ−
１０１３）でＩＱまで脱水濃縮し１次いでＩＱの液量を
保持しなから５Ｑのイオン交換水で洗浄してＰＨ３，５
の乳白色半透明のジルコニア系複合ゾルを得た。The treated solution thus obtained was filtered through an ultrafiltration membrane (Asahi Kasei 5IP-
1013) to IQ, then wash with 5Q ion-exchanged water to pH 3.5 while maintaining the liquid volume of IQ.
A milky white translucent zirconia composite sol was obtained.
このジルコニア系複合ゾルに陰イオン交換樹脂を加えて
イオン交換処理を行い、ＰＨ４，４のジルコニア系複合
ゾルとした。このゾルの特性を表−１に示す。An anion exchange resin was added to this zirconia-based composite sol to perform ion exchange treatment to obtain a zirconia-based composite sol with a pH of 4.4. The properties of this sol are shown in Table 1.
実施例２
実施例１に於いて、チタニアゾルの代わりに硝酸第二セ
リウムアンモニウム水溶液の加水分解により調製（Ｂｊ
、Ｉｔｚ法）した平均粒径１２０人のセリアゾルを使用
した以外は実施例１と全く同様にしてジルコニア系複合
ゾルを調製した。このゾルの調製条件及び特性を表−１
に示す。Example 2 In Example 1, instead of titania sol, Bj
A zirconia-based composite sol was prepared in exactly the same manner as in Example 1, except that a ceria sol with an average particle diameter of 120 was used. Table 1 shows the preparation conditions and characteristics of this sol.
Shown below.
実施例３
硝酸第二鉄水溶液を陰イオン交換樹脂で処理して得られ
たゾルをデキストランで安定化したところの、幅が約２
０人、長さが８０〜１００人の針状粒子の鉄ゾルを、実
施例１のチタニアゾルの代わりに使用した以外は実施例
］−と全く同様にしてジルコニア系複合ゾルを調製した
。このゾルの調製条件及び特性を表−１に示す。Example 3 When a sol obtained by treating an aqueous ferric nitrate solution with an anion exchange resin was stabilized with dextran, the width was approximately 2
A zirconia-based composite sol was prepared in exactly the same manner as in Example]-, except that an iron sol with needle-like particles of 0 and 80 to 100 particles in length was used instead of the titania sol in Example 1. Table 1 shows the preparation conditions and properties of this sol.
比較例１
実施例】で使用したチタニアゾルと市販のジルコニアゾ
ルを実施例１で得られたジルコニア系複合ゾルと同一組
成になるよう混合して混合ゾルを得た。このゾルの特性
を表−１に示す。Comparative Example 1 The titania sol used in Example and the commercially available zirconia sol were mixed to have the same composition as the zirconia composite sol obtained in Example 1 to obtain a mixed sol. The properties of this sol are shown in Table 1.
比較例２
水酸化チタンを過酸化水素に溶解して調製した過チタン
酸液と、オキシ塩化ジルコニル水溶液を所定の割合で混
合し、得られた混合液を９８°Ｃで２４時間加熱処理し
た。この処理で得られたゾルを実施例１と同様に処理し
てジルコニア系複合ゾルを得た。このゾルの調製条件と
特性を表−１に示す。Comparative Example 2 A pertitanic acid solution prepared by dissolving titanium hydroxide in hydrogen peroxide and an aqueous zirconyl oxychloride solution were mixed at a predetermined ratio, and the resulting mixed solution was heat-treated at 98° C. for 24 hours. The sol obtained by this treatment was treated in the same manner as in Example 1 to obtain a zirconia-based composite sol. Table 1 shows the preparation conditions and characteristics of this sol.
実施例４
実施例１〜３及び比較例１〜２で得られたゾルをそれぞ
れ濃度１０％のポリビニルアルコールに全酸化物濃度と
して１．０％となるように混合し、ガラス板に均一に塗
布し、次いで温風乾燥して約１０μｍ厚の被膜を形成さ
せた。Example 4 The sols obtained in Examples 1 to 3 and Comparative Examples 1 to 2 were mixed in polyvinyl alcohol with a concentration of 10% so that the total oxide concentration was 1.0%, and the mixture was uniformly applied to a glass plate. Then, it was dried with hot air to form a film with a thickness of about 10 μm.
得られた被膜の特性を表−１に示す。The properties of the obtained film are shown in Table 1.
表−１
［発明の効果］
本発明のジルコニア系複合ゾルは、ジルコニアゾルとし
ての特性に、ジルコニア以外の金属酸化物ゾルとしての
特性が加味された性質を備えているので、これを例えば
熱可塑性樹脂と混合して透明な基体に塗布して得られる
被膜は、屈折率が高く、透明性に優れ、高い紫外線吸収
能を示し、しかもこれら特性に関して優れた耐候性を発
揮する。Table 1 [Effects of the Invention] The zirconia-based composite sol of the present invention has properties that include the properties of a zirconia sol and the properties of a metal oxide sol other than zirconia. The coating obtained by mixing it with a resin and applying it to a transparent substrate has a high refractive index, excellent transparency, high ultraviolet absorption ability, and exhibits excellent weather resistance in relation to these properties.
また、本発明のジルコニア系複合ゾルはセラミック粉の
焼成用又はロストワックス用バインダーなどの用途にも
有用である。Furthermore, the zirconia-based composite sol of the present invention is also useful for use as a binder for firing ceramic powder or lost wax.
特許出願人 触媒化成工業株式会社波長５００１μ
の光の透過率（％）を測定。Patent applicant: Catalysts & Chemicals Industry Co., Ltd. Wavelength 5001μ
Measure the light transmittance (%) of.
（２）コーティングされたガラス板の波長５００１１Ａ
Ｉの光の透過率（％）をｍ＋定。(2) Wavelength of coated glass plate: 50011A
The light transmittance (%) of I is m + constant.
過率（％）を測定した。The pass rate (%) was measured.
Claims (1)
ルコニアにて被覆された形態のコロイド粒子を分散質と
するジルコニア系複合ゾル。 ２、ジルコニア以外の金属酸化物ゾルと、ジルコニウム
塩水溶液との混合物を加熱処理することからなるジルコ
ニア系複合ゾルの製造法。 ３、請求項１記載のジルコニア系複合ゾルを基体表面に
塗布乾燥してなる被膜形成体。[Scope of Claims] 1. A zirconia-based composite sol whose dispersoid is colloidal particles having a core of a metal oxide other than zirconia and coated with zirconia. 2. A method for producing a zirconia-based composite sol, which comprises heat-treating a mixture of a metal oxide sol other than zirconia and an aqueous zirconium salt solution. 3. A film-forming body obtained by coating the zirconia-based composite sol according to claim 1 on the surface of a substrate and drying it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63196294A JP2686103B2 (en) | 1988-08-05 | 1988-08-05 | Zirconia-based composite sol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63196294A JP2686103B2 (en) | 1988-08-05 | 1988-08-05 | Zirconia-based composite sol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0248418A true JPH0248418A (en) | 1990-02-19 |
| JP2686103B2 JP2686103B2 (en) | 1997-12-08 |
Family
ID=16355413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63196294A Expired - Lifetime JP2686103B2 (en) | 1988-08-05 | 1988-08-05 | Zirconia-based composite sol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2686103B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5366545A (en) * | 1992-07-07 | 1994-11-22 | Hoya Corporation | Coating compositions |
| US5460738A (en) * | 1992-07-07 | 1995-10-24 | Nissan Chemical Industries Ltd. | Modified stannic oxide-zirconium oxide composite sol and process for preparing the same |
| FR2719502A1 (en) * | 1994-05-09 | 1995-11-10 | Rhone Poulenc Chimie | Colloidal dispersion based on cerium oxide and titanium oxide its preparation process, its application to the coating of substrates and substrates thus coated. |
| US5472797A (en) * | 1992-07-07 | 1995-12-05 | Hoya Corporation | Optical elements having cured coating film |
| EP1516855A1 (en) * | 2003-09-15 | 2005-03-23 | Toyota Jidosha Kabushiki Kaisha | Cerium-Zirconium composite metal oxide with a cerium oxide core surrounded by zirconium oxide |
| US7384888B2 (en) | 2003-09-15 | 2008-06-10 | Toyota Jidosha Kabushiki Kaisha | Cerium-zirconium composite metal oxide |
| JP2010155729A (en) * | 2008-12-26 | 2010-07-15 | Sumitomo Osaka Cement Co Ltd | Transparent ceramic formed body |
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| JPS5319320A (en) * | 1976-06-21 | 1978-02-22 | Seizou Shibuya | Method of producing such as artificial stone and wood |
| JPS5529577A (en) * | 1978-08-16 | 1980-03-01 | Bayer Ag | Production of titanium dioxide pigment |
| JPS61168527A (en) * | 1985-01-22 | 1986-07-30 | Jgc Corp | Production of raw material of titanate-type ceramic |
| JPS61227919A (en) * | 1985-04-03 | 1986-10-11 | Nissan Chem Ind Ltd | Antimony pentoxide sol electrified in positive and its production |
| JPS62182115A (en) * | 1986-02-03 | 1987-08-10 | Nissan Chem Ind Ltd | Organoantimony pentoxide sol and production thereof |
| JPS6348358A (en) * | 1986-08-15 | 1988-03-01 | Nippon Shokubai Kagaku Kogyo Co Ltd | Sol for use in coating ceramic and coating method using same |
| JPS63185820A (en) * | 1986-09-26 | 1988-08-01 | Catalysts & Chem Ind Co Ltd | Production of modified titania sol |
| JPS6469512A (en) * | 1987-09-07 | 1989-03-15 | Iwao Jiki Kogyo | Production of alumina-zirconia complex powder and sintered product therefrom |
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1988
- 1988-08-05 JP JP63196294A patent/JP2686103B2/en not_active Expired - Lifetime
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|---|---|---|---|---|
| JPS5319320A (en) * | 1976-06-21 | 1978-02-22 | Seizou Shibuya | Method of producing such as artificial stone and wood |
| JPS5529577A (en) * | 1978-08-16 | 1980-03-01 | Bayer Ag | Production of titanium dioxide pigment |
| JPS61168527A (en) * | 1985-01-22 | 1986-07-30 | Jgc Corp | Production of raw material of titanate-type ceramic |
| JPS61227919A (en) * | 1985-04-03 | 1986-10-11 | Nissan Chem Ind Ltd | Antimony pentoxide sol electrified in positive and its production |
| JPS62182115A (en) * | 1986-02-03 | 1987-08-10 | Nissan Chem Ind Ltd | Organoantimony pentoxide sol and production thereof |
| JPS6348358A (en) * | 1986-08-15 | 1988-03-01 | Nippon Shokubai Kagaku Kogyo Co Ltd | Sol for use in coating ceramic and coating method using same |
| JPS63185820A (en) * | 1986-09-26 | 1988-08-01 | Catalysts & Chem Ind Co Ltd | Production of modified titania sol |
| JPS6469512A (en) * | 1987-09-07 | 1989-03-15 | Iwao Jiki Kogyo | Production of alumina-zirconia complex powder and sintered product therefrom |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5366545A (en) * | 1992-07-07 | 1994-11-22 | Hoya Corporation | Coating compositions |
| US5460738A (en) * | 1992-07-07 | 1995-10-24 | Nissan Chemical Industries Ltd. | Modified stannic oxide-zirconium oxide composite sol and process for preparing the same |
| US5472797A (en) * | 1992-07-07 | 1995-12-05 | Hoya Corporation | Optical elements having cured coating film |
| FR2719502A1 (en) * | 1994-05-09 | 1995-11-10 | Rhone Poulenc Chimie | Colloidal dispersion based on cerium oxide and titanium oxide its preparation process, its application to the coating of substrates and substrates thus coated. |
| EP0681992A1 (en) * | 1994-05-09 | 1995-11-15 | Rhone-Poulenc Chimie | Colloidal dispersion of cerium oxide and titanium oxide, process for its preparation, its use for coating substrates and thus coated substrates |
| US5688439A (en) * | 1994-05-09 | 1997-11-18 | Rhone-Poulenc Chimie | Colloidal dispersions of cerium oxide core/titanium oxide sheath particulates and photocatalytic coatings provided thereby |
| EP1516855A1 (en) * | 2003-09-15 | 2005-03-23 | Toyota Jidosha Kabushiki Kaisha | Cerium-Zirconium composite metal oxide with a cerium oxide core surrounded by zirconium oxide |
| US7384888B2 (en) | 2003-09-15 | 2008-06-10 | Toyota Jidosha Kabushiki Kaisha | Cerium-zirconium composite metal oxide |
| USRE44802E1 (en) | 2003-09-15 | 2014-03-11 | Toyota Jidosha Kabushiki Kaisha | Cerium-zirconium composite metal oxide |
| JP2010155729A (en) * | 2008-12-26 | 2010-07-15 | Sumitomo Osaka Cement Co Ltd | Transparent ceramic formed body |
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|---|---|
| JP2686103B2 (en) | 1997-12-08 |
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