JPH1060665A - Hydrophilic coating film and its production - Google Patents

Hydrophilic coating film and its production

Info

Publication number
JPH1060665A
JPH1060665A JP22364996A JP22364996A JPH1060665A JP H1060665 A JPH1060665 A JP H1060665A JP 22364996 A JP22364996 A JP 22364996A JP 22364996 A JP22364996 A JP 22364996A JP H1060665 A JPH1060665 A JP H1060665A
Authority
JP
Japan
Prior art keywords
sol
titania
silica
substrate
film
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.)
Pending
Application number
JP22364996A
Other languages
Japanese (ja)
Inventor
Seiji Yamazaki
誠司 山崎
Kensuke Makita
研介 牧田
Satoko Sugawara
聡子 菅原
Yasuaki Kai
康朗 甲斐
Takashi Kiyono
俊 清野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central Glass Co Ltd
Nissan Motor Co Ltd
Original Assignee
Central Glass Co Ltd
Nissan Motor Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Central Glass Co Ltd, Nissan Motor Co Ltd filed Critical Central Glass Co Ltd
Priority to JP22364996A priority Critical patent/JPH1060665A/en
Priority to DE19736925A priority patent/DE19736925A1/en
Priority to US08/917,617 priority patent/US6071606A/en
Priority to GB9718030A priority patent/GB2316687B/en
Publication of JPH1060665A publication Critical patent/JPH1060665A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C03C17/256—Coating containing TiO2
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1225—Deposition of multilayers of inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/212—TiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/213—SiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes

Abstract

PROBLEM TO BE SOLVED: To obtain a hydrophilic film durable in hydrophilicity and excellent in weatherability by applying a composite soln. contg. the sol of metal oxides including titania and a colloidal silica with the sol chained and forming a metal oxide film contg. calcined titania and silica. SOLUTION: A composite soln. contg. the sol of metal oxides including titania and a colloidal silica with the sol chained is applied on a substrate. The coating soln. is then calcined at 300-850 deg.C to provide a metal oxide film contg. titania and silica on the substrate. Consequently, the contaminant depositing on the surface is decomposed off by the photocatalysis of the titania in addition to the hydrophilicity of silica, and an extremely durable hydrophilic surface is obtained. Further, the scuffing resistance of especially the film surface is remarkably improved by adding the chained colloidal silica.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は、親水性被膜およびその
製造方法に関し、特にガラス、ミラー、金属、プラスチ
ック等の表面に親水性被膜を形成することにより、その
親水性を長く持続させることのできる親水性被膜および
その製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic film and a method for producing the same, and more particularly, to a method of forming a hydrophilic film on a surface of glass, mirror, metal, plastic or the like to maintain the hydrophilic property for a long time. The present invention relates to a hydrophilic coating that can be formed and a method for producing the same.

【０００２】[0002]

【従来の技術】従来から、無機ガラス等は透明基材とし
ての性質を活かして、例えば窓ガラス、鏡面、眼鏡レン
ズなどの物品に広く利用されている。2. Description of the Related Art Conventionally, inorganic glass and the like have been widely used in articles such as window glasses, mirror surfaces, and spectacle lenses by utilizing the properties of a transparent substrate.

【０００３】しかしながら、これら透明基材を用いた物
品は、高温多湿の場所または温度や湿度差の大きい境界
面などに使用すると物品の表面に結露を生じ、これに起
因して物品の表面が曇りを帯びるという欠点を有する。
特に透明基材のうちでも、窓ガラス、眼鏡レンズ、鏡な
どは、製品の表面が曇ったり、あるいは傷がつきやすい
という重大な問題がある。従って各方面からこれらの改
良に関する要望がなされており、これまでに透明基材を
はじめとする各種物品に対して親水性や耐久性を付与し
ようとする試みが種々提案されている。However, when an article using such a transparent substrate is used in a high-temperature and high-humidity area or on an interface having a large difference in temperature or humidity, dew condensation occurs on the article surface, and as a result, the article surface becomes cloudy. It has the disadvantage of taking on.
Particularly, among the transparent base materials, window glasses, spectacle lenses, mirrors, and the like have a serious problem that the surface of the product is easily clouded or damaged. Accordingly, there are demands for these improvements from various fields, and various attempts have been made to impart hydrophilicity and durability to various articles such as transparent substrates.

【０００４】基材表面の曇りを防止する方法としては、
ガラス等の表面に親水性の被膜を形成することが行われ
ている。最も簡単な手段としては、界面活性剤を表面に
塗布することで曇りを防ぐことができることが古くから
知られており、界面活性剤にポリアクリル酸やポリビニ
ルアルコールなどの水溶性ポリマーを配合することでそ
の効果の持続性を上げる試みがなされている（例えば、
特開昭５２−１０１６８０号公報等）。しかしながら、
この様な方法においては一時的に親水性を付与するのみ
であり連続的な効果を期待することはできない。[0004] As a method of preventing fogging of the substrate surface,
2. Description of the Related Art A hydrophilic film is formed on a surface of glass or the like. It has long been known that fogging can be prevented by applying a surfactant to the surface as the simplest means, and a water-soluble polymer such as polyacrylic acid or polyvinyl alcohol is added to the surfactant. Attempts have been made to increase the sustainability of the effect (for example,
JP-A-52-101680, etc.). However,
In such a method, the hydrophilicity is only temporarily imparted, and a continuous effect cannot be expected.

【０００５】一方、特開昭５５−１５４３５１号公報に
は、ガラス基材表面に、モリブデン酸化物とタングステ
ン酸化物とのうちいずれか一種以上とリン酸化物とを含
む薄膜を物理蒸着や化学蒸着等で形成することにより親
水性に優れた親水性薄膜を得る方法が提案されている。
また、特開昭５４−１０５１２０号公報には、Ｐ2 Ｏを
含むガラスに、Ｐ2 Ｏ5 の液体または蒸気を接触させる
ことにより親水性を付与する方法が提案されている。さ
らに、特開昭５３−５８４９２号公報には、スルホン酸
型両性界面活性剤および無機塩あるいは酢酸塩を含む組
成物を低級アルコール溶液を用いて基材に塗布すること
により密着性に優れた親水膜を形成する方法が提案され
ている。しかしながら、これらの方法においても親水性
能の長期持続性に劣るという欠点があった。On the other hand, Japanese Patent Application Laid-Open No. 55-154351 discloses that a thin film containing at least one of molybdenum oxide and tungsten oxide and a phosphorus oxide is formed on a glass substrate surface by physical vapor deposition or chemical vapor deposition. There has been proposed a method for obtaining a hydrophilic thin film having excellent hydrophilicity by forming the thin film by the above method.
Further, in JP-A-54-105120, a glass containing P 2 O, a method of imparting hydrophilicity has been proposed by contacting the liquid or vapor of P 2 O 5. Further, JP-A-53-58492 discloses that a composition containing a sulfonic acid type amphoteric surfactant and an inorganic salt or an acetate is applied to a substrate by using a lower alcohol solution to obtain a hydrophilic material having excellent adhesion. A method for forming a film has been proposed. However, these methods also have a drawback that the long-term sustainability of hydrophilic performance is poor.

【０００６】[0006]

【発明が解決しようとする課題】以上説明したように、
従来の技術においては、持続性を有する親水性や耐候性
を満足する親水性被膜を得ることはできなかった。従っ
て本発明は、このような従来技術の欠点を解消するため
になされたものであり、親水性や耐候性に優れた親水性
被膜およびその製造方法を提供することを目的とする。As described above,
In the prior art, it has not been possible to obtain a hydrophilic film that satisfies the sustained hydrophilicity and weather resistance. Accordingly, the present invention has been made in order to solve such disadvantages of the related art, and an object of the present invention is to provide a hydrophilic coating excellent in hydrophilicity and weather resistance and a method for producing the same.

【０００７】[0007]

【課題を解決するための手段】本発明の上記の目的は、
チタニアを含む金属酸化物ゾルおよびゾルの形状が鎖状
であるコロイダルシリカを含む複合溶液を基板に塗布
し、焼成したチタニアおよびシリカを含む金属酸化物膜
を有することを特徴とする親水性被膜およびその製造方
法により達成された。以下、本発明について更に詳細に
説明する。SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
A hydrophilic coating characterized by having a metal oxide sol containing titania and a composite solution containing colloidal silica in which the shape of the sol is linear is applied to a substrate, and having a metal oxide film containing titania and silica baked, and This was achieved by its manufacturing method. Hereinafter, the present invention will be described in more detail.

【０００８】本発明においては、上述の構成とすること
により、シリカを含む金属酸化物膜が有する親水性に加
えて、チタニアが有する光触媒活性によって、表面に付
着する汚れの分解除去能を付与することにより、極めて
長寿命の親水表面を得ることができる。また、コロイダ
ルシリカは、通常球形のものが用いられるが、本発明で
はコロイダルシリカとして鎖状のものを添加することに
よって、特に膜表面の耐傷付き性を著しく向上するとい
う効果も得られた。[0008] In the present invention, by employing the above-described structure, in addition to the hydrophilic property of the metal oxide film containing silica, the photocatalytic activity of titania provides the ability to decompose and remove dirt attached to the surface. Thereby, an extremely long-lived hydrophilic surface can be obtained. In addition, colloidal silica is usually spherical, but in the present invention, by adding a chain-like colloidal silica, an effect of remarkably improving the scratch resistance particularly on the film surface was obtained.

【０００９】本発明において使用する基板としては、公
知の基板の中から適宜選択して使用することができ、例
えば金属、ガラス、無機、有機樹脂等の材料が挙げられ
る。チタニアはアモルファスであってもアナターゼ型や
ルチル型の結晶であっても良いが、アナターゼ型が最も
好ましい。The substrate used in the present invention can be appropriately selected from known substrates and used, for example, materials such as metal, glass, inorganic and organic resins. Titania may be amorphous or an anatase type or rutile type crystal, but an anatase type is most preferable.

【００１０】本発明の親水性被膜に含まれる、チタニア
以外の金属酸化物としては、具体的には、例えばチタン
酸鉄、酸化鉄、酸化ビスマス、酸化モリブデン、酸化ニ
ッケル、酸化タングステン、シリカ、アルミナ、酸化イ
ットリウム、酸化錫、酸化マンガン、酸化亜鉛、酸化コ
バルト、酸化銅、酸化銀、酸化バナジウム、酸化クロム
および酸化ジルコニウム等から成る群から選ばれる少な
くとも１種が挙げられる。The metal oxides other than titania contained in the hydrophilic coating of the present invention include, for example, iron titanate, iron oxide, bismuth oxide, molybdenum oxide, nickel oxide, tungsten oxide, silica, alumina And at least one selected from the group consisting of yttrium oxide, tin oxide, manganese oxide, zinc oxide, cobalt oxide, copper oxide, silver oxide, vanadium oxide, chromium oxide, and zirconium oxide.

【００１１】この親水性被膜は、チタニアを含む金属酸
化物ゾルとゾルの形状が鎖状であるコロイダルシリカを
含むゾル溶液を基板上に塗布し、次いでその塗布液を３
００〜８５０℃で焼成することにより得られるチタニア
およびシリカを含む金属酸化物膜を基板上に設けること
により製造することができる。The hydrophilic film is formed by applying a metal oxide sol containing titania and a sol solution containing colloidal silica whose sol has a chain shape to a substrate, and then applying the coating solution to the substrate.
It can be manufactured by providing a metal oxide film containing titania and silica obtained by baking at 00 to 850 ° C. on a substrate.

【００１２】金属酸化物ゾルは、金属アルコキシドから
作製することができる。チタニアゾルは、例えばチタン
テトライソプロポキシドやテトラエトキシチタンなどの
ようなチタンアルコキシドを加水分解や脱水縮合して得
ることもできる。この反応に際しては、反応性を制御す
るために配位子を用いてもよい。The metal oxide sol can be prepared from a metal alkoxide. The titania sol can be obtained, for example, by hydrolyzing or dehydrating a titanium alkoxide such as titanium tetraisopropoxide or tetraethoxytitanium. In this reaction, a ligand may be used to control the reactivity.

【００１３】また、金属アルコキシドから作製したゾル
溶液に、金属の硫酸塩、硝酸塩、炭酸塩、酢酸塩、ステ
アリン酸塩、また塩化物や臭化物などのハロゲン化物や
その縮合物などを添加してもよい。金属酸化物として
は、市販されているものを用いることもできる。具体的
には、例えばシリカゾルとしてはスーパーセラ（大八化
学工業所製の商品名）、セラミカ（日板研究所製の商品
名）、ＨＡＳ（コルコート株式会社製の商品名）、アト
ロンＳｉＮ−５００（日本曹達株式会社製の商品名）、
ＣＧＳ−ＤＩ−０６００（チッソ株式会社製の商品名）
などを利用することができる。また、ＴＡ−１０，ＴＡ
−１５（日産化学工業株式会社製の商品名）、アトロン
ＴｉＮ−５００（日本曹達株式会社製の商品名）などの
チタニアゾル、ＮＺＳ−３０Ａ，ＮＺＳ−３０Ｂ（日産
化学工業株式会社製の商品名）やＡＺＳ−Ａ，ＡＺＳ−
ＮＢ，ＡＺＳ−Ｂ（日本触媒化学工業株式会社製の商品
名）などのジルコニアゾル、アルミナゾル−１００、ア
ルミナゾル−２００、アルミナゾル−５２０（日産化学
工業株式会社製の商品名）、カタロイドＡＳ−３（触媒
化成工業株式会社製の商品名）などのアルミナゾルなど
も用いることができる。Further, to a sol solution prepared from a metal alkoxide, a metal sulfate, a nitrate, a carbonate, an acetate, a stearate, or a halide such as chloride or bromide or a condensate thereof may be added. Good. Commercially available metal oxides can also be used. Specifically, for example, silica sols such as Super Cera (trade name, manufactured by Daihachi Chemical Industry Co., Ltd.), Ceramica (trade name, manufactured by Nippon Laboratories), HAS (trade name, manufactured by Colcoat Co., Ltd.), Atron SiN-500 (Product name manufactured by Nippon Soda Co., Ltd.),
CGS-DI-0600 (trade name of Chisso Corporation)
And so on. Also, TA-10, TA
Titania sols such as -15 (trade name of Nissan Chemical Industries, Ltd.) and Atron TiN-500 (trade name of Nippon Soda Co., Ltd.), NZS-30A, NZS-30B (trade names of Nissan Chemical Industries, Ltd.) And AZS-A, AZS-
Zirconia sol such as NB, AZS-B (trade name of Nippon Shokubai Chemical Co., Ltd.), alumina sol-100, alumina sol-200, alumina sol-520 (trade name of Nissan Chemical Industry Co., Ltd.), cataloid AS-3 ( Alumina sol such as a catalyst manufactured by Catalyst Chemicals Co., Ltd.) can also be used.

【００１４】鎖状のコロイダルシリカとしては、鎖の径
が５０ｎｍ以下、鎖の長さが４０〜５００ｎｍの範囲に
あるものが好ましい。鎖の長さが４０ｎｍ未満になる
と、シリカが球状に近くなるため膜質向上効果が小さく
なり、逆に鎖の径が５０ｎｍおよび鎖の長さが５００ｎ
ｍを超えると、形成された膜に濁りが生じ透明膜が得ら
れにくい。The chain colloidal silica preferably has a chain diameter of 50 nm or less and a chain length of 40 to 500 nm. If the chain length is less than 40 nm, the effect of improving the film quality is reduced because the silica becomes nearly spherical, and conversely, the chain diameter is 50 nm and the chain length is 500 n.
If it exceeds m, the formed film becomes cloudy and it is difficult to obtain a transparent film.

【００１５】この鎖状のコロイダルシリカの具体例とし
ては、例えばＳＴ−ＵＰやＳＴ−ＯＵＰ（日産化学工業
株式会社製の商品名）などを挙げることができる。鎖状
コロイダルシリカの含有量は２０〜７０重量％の範囲で
あることが好ましい。鎖状コロイダルシリカの含有量が
２０重量％未満になると、親水化および膜硬度を向上さ
せる効果が不足し、７０重量％を超えるとチタニアの含
有率が減少し過ぎて光触媒性能が不足する。Specific examples of the chain colloidal silica include, for example, ST-UP and ST-OUP (trade names of Nissan Chemical Industries, Ltd.). The content of the chain colloidal silica is preferably in the range of 20 to 70% by weight. When the content of the chain colloidal silica is less than 20% by weight, the effect of improving the hydrophilicity and the film hardness is insufficient. When the content is more than 70% by weight, the content of titania is excessively reduced and the photocatalytic performance is insufficient.

【００１６】上記ゾル溶液は、必要に応じて水や有機溶
媒などで希釈して用いることができる。使用する有機溶
媒としては、金属酸化物とアルカリ金属化合物とを溶解
するものであれば何でもよく、例えば、メタノール、エ
タノールおよびプロピルアルコール等の１級アルコー
ル、イソプロピルアルコール等の２級アルコール、ター
シャルブタノール等の３級アルコール、アセトンやメチ
ルエチルケトン等のケトン類、エーテル類、ベンゼン、
トルエン、キシレン、クロロホルム、ペンタン、ヘキサ
ン、シクロヘキサン等の脂肪族、芳香族、脂環式の炭化
水素等の一般的な溶媒が挙げられ、これらを単独でまた
は混合して用いることができる。The above sol solution can be used by diluting it with water or an organic solvent, if necessary. Any organic solvent may be used as long as it dissolves the metal oxide and the alkali metal compound. Examples thereof include primary alcohols such as methanol, ethanol and propyl alcohol, secondary alcohols such as isopropyl alcohol, and tert-butanol. Tertiary alcohols, ketones such as acetone and methyl ethyl ketone, ethers, benzene,
General solvents such as aliphatic, aromatic, and alicyclic hydrocarbons such as toluene, xylene, chloroform, pentane, hexane, and cyclohexane are used, and these can be used alone or in combination.

【００１７】基板上に上記のゾル溶液を塗布する方法と
しては、公知の塗布手段の中から適宜選択して使用する
ことができ、例えば浸漬引き上げ法（ディッピング
法）、スプレー法、フローコート法、スピンコート法な
どを挙げることができる。塗布風乾した後に３００〜８
５０℃で焼成することによって親水性被膜が得られる。
焼成温度が３００℃より低いと、膜硬度が不足し、逆に
８５０℃より高いとチタニアがルチル型に相転移しやす
く充分な防汚性が得られなくなる。As a method for applying the sol solution on the substrate, any of known coating means can be appropriately selected and used, for example, a dipping and pulling method (dipping method), a spray method, a flow coating method, and the like. A spin coating method can be used. 300-8 after air-drying
By baking at 50 ° C., a hydrophilic coating is obtained.
If the firing temperature is lower than 300 ° C., the film hardness is insufficient, and if it is higher than 850 ° C., titania tends to undergo a phase transition to a rutile type, and sufficient antifouling properties cannot be obtained.

【００１８】この親水性被膜の膜厚は２０〜５００ｎｍ
の範囲であることが好ましい。膜厚が２０ｎｍ未満にな
ると親水性能が不足し、逆に５００ｎｍを超えると焼成
時クラックなどが発生しやすく、透明な膜が得られにく
くなる。The thickness of the hydrophilic coating is 20 to 500 nm.
Is preferably within the range. When the film thickness is less than 20 nm, the hydrophilic property is insufficient, and when it exceeds 500 nm, cracks and the like are liable to be generated at the time of firing, and it is difficult to obtain a transparent film.

【００１９】本発明においては、基板上に第１層として
金属酸化物膜を形成し、その第１層上に第２層として該
親水性被膜を形成した２層構成とすることもできる。第
１層の金属酸化物としては、例えばシリカなどを用いる
ことができる。In the present invention, a two-layer structure in which a metal oxide film is formed as a first layer on a substrate, and the hydrophilic coating is formed as a second layer on the first layer, may be employed. As the metal oxide of the first layer, for example, silica or the like can be used.

【００２０】[0020]

【発明の実施の形態】一般的にアナターゼ構造を含むチ
タニア膜は、表面に付着した汚れを光触媒反応により分
解するので、あるレベル以上の紫外線の照射下では親水
性表面が保たれる。しかし、紫外線量があるレベル以下
の場合や紫外線が照射されていない場合には、付着した
汚れが分解されないため親水性が徐々に失われる。シリ
カのような親水性化合物を添加すると汚れが付着しても
親水性が保たれやすく、紫外線がない状態が長時間続い
た場合であっても親水維持性を向上させることができ
る。また、このとき添加するシリカとしては鎖状のコロ
イドを用いることによって、膜硬度や耐摩耗性を向上さ
せることができると共に、チタニアの結晶性の低下を防
止することができる。DETAILED DESCRIPTION OF THE INVENTION Generally, a titania film having an anatase structure decomposes dirt attached to the surface by a photocatalytic reaction, so that a hydrophilic surface is maintained under irradiation of a certain level or more of ultraviolet light. However, when the amount of ultraviolet light is lower than a certain level or when no ultraviolet light is irradiated, the adhered dirt is not decomposed and the hydrophilicity is gradually lost. When a hydrophilic compound such as silica is added, the hydrophilicity is easily maintained even if dirt adheres, and the hydrophilicity can be improved even when there is no ultraviolet light for a long time. Further, by using a chain colloid as the silica to be added at this time, the film hardness and abrasion resistance can be improved, and a decrease in the crystallinity of titania can be prevented.

【００２１】チタニアの光触媒特性によって汚れを分解
するための光源としては、４００ｎｍ以下の紫外線を含
むものが良く、例えば太陽光、水銀等、蛍光灯、ハロゲ
ンランプ、ショートアークセキノン光、レーザー光等が
挙げられる。本発明では、親水性被膜を形成した部分に
直接光が照射されるように光源を設けてもよいが、通常
は特別に光源を要せず、例えば室内の蛍光灯や太陽など
の自然光によって充分に性能を得ることができる。The light source for decomposing dirt by the photocatalytic properties of titania preferably contains ultraviolet light of 400 nm or less, such as sunlight, mercury, fluorescent lamp, halogen lamp, short arc sequinone light, laser light, etc. Is mentioned. In the present invention, a light source may be provided so that light is directly applied to the portion where the hydrophilic film is formed. However, in general, no special light source is required, and for example, natural light such as indoor fluorescent lamps or the sun is sufficient. Performance can be obtained.

【００２２】以上説明したように本発明によれば、チタ
ニアを含む金属酸化物と鎖状のシリカコロイドとを含有
する複合溶液を基板に塗布し、焼成したチタニアおよび
シリカを含む金属酸化物膜を基板上に形成することによ
って、極めて長寿命の親水性被膜を得ることができる。As described above, according to the present invention, a composite solution containing a metal oxide containing titania and chain colloidal silica is applied to a substrate, and a baked metal oxide film containing titania and silica is formed. By forming it on a substrate, a hydrophilic film having a very long life can be obtained.

【００２３】[0023]

【実施例】以下、本発明を実施例によって更に詳細に説
明するが、本発明はこれによって限定されるものではな
い。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

【００２４】性能の評価は膜表面の水滴接触角によって
行った。接触角と親水性との関係を確認したところ、水
滴接触角が１５゜以下であれば、息を吹きかけても曇ら
ずに防曇性があった。The performance was evaluated based on the contact angle of water drops on the film surface. When the relationship between the contact angle and the hydrophilicity was confirmed, if the water droplet contact angle was 15 ° or less, it was not fogged even when breath was blown, and had antifogging properties.

【００２５】実施例１〜３および比較的１〜２ 大きさ１００ｍｍ×１００ｍｍ、厚さ１．９ｍｍのクリ
アフロートガラス基板を中性洗剤、水、エタノールで順
次洗浄し、乾燥して被膜用基板とした。チタンのアルコ
キシドとしてチタンテトライソプロポキシドをエタノー
ルに０．５ｍｏｌ／Ｌとなるように溶解し、この溶液に
２−メチル−２，４ペンタンジオールをアルコキシド１
ｍｏｌに対して１ｍｏｌ加えて１時間還流した。室温ま
で冷却し、この中に硝酸を添加し酸性になるよう調整し
た後、水をアルコキシドと等モル量滴下し、１時間の還
流を行ない、チタニアゾルを得た。Examples 1 to 3 and Comparative Examples 1 to 2 A clear float glass substrate having a size of 100 mm.times.100 mm and a thickness of 1.9 mm was sequentially washed with a neutral detergent, water and ethanol, dried, and dried to form a coating substrate. did. Titanium tetraisopropoxide as an alkoxide of titanium is dissolved in ethanol at a concentration of 0.5 mol / L, and 2-methyl-2,4 pentanediol is added to the alkoxide 1 in this solution.
1 mol per mol was added and the mixture was refluxed for 1 hour. After cooling to room temperature, nitric acid was added to the mixture to make it acidic, water was added dropwise in an equimolar amount to the alkoxide, and the mixture was refluxed for 1 hour to obtain a titania sol.

【００２６】上述のようにして得られたチタニアゾル溶
液と鎖状コロイダルシリカとしてＳＴ−ＯＵＰ（日産化
学工業株式会社製の商品名）とを混合し、固形分濃度が
３％となるように水とエタノールの１：１（重量比）溶
液で希釈し塗布溶液を得た。コロイダルシリカの添加量
を１０重量％、２０重量％、５０重量％、７０重量％、
８０重量％としたものをそれぞれ作成し、それぞれ比較
例１、実施例１、実施例２、実施例３、比較例２とし
た。The titania sol solution obtained as described above is mixed with ST-OUP (trade name of Nissan Chemical Industries, Ltd.) as chain colloidal silica, and mixed with water so as to have a solid content of 3%. It was diluted with a 1: 1 (weight ratio) solution of ethanol to obtain a coating solution. The amount of colloidal silica added was 10% by weight, 20% by weight, 50% by weight, 70% by weight,
Those having 80% by weight were prepared, respectively, and designated as Comparative Example 1, Example 1, Example 2, Example 3, and Comparative Example 2, respectively.

【００２７】被膜用基板に上記塗布溶液をスピンコーテ
ィング法により、１０００ｒｐｍの条件でコーティング
し、風乾後５００℃で３０分間焼成した。得られた被膜
は膜厚１０ｎｍの透明なものであった。得られた被膜表
面の接触角、２４時間暗箱中に放置した後の接触角、さ
らに可塑剤のＤＯＰ（ジオクチルスタレート）を付着さ
せた時の接触角、および０．５ｍＷ／ｃｍ2 の紫外線を
１時間照射した後の接触角を表１に示す。表１に示すよ
うに、コロイダルシリカの添加量が１０重量％では暗箱
放置後の接触角増加量が大きく、維持性が悪い。また８
０重量％では一旦汚染された後の接触角が低下せず、汚
れの分解性能が悪いことがわかる。The coating solution was coated on the substrate for coating by spin coating at 1,000 rpm, air-dried, and baked at 500 ° C. for 30 minutes. The obtained film was a transparent film having a thickness of 10 nm. The contact angle of the obtained coating surface, the contact angle after leaving it in a dark box for 24 hours, the contact angle when a plasticizer DOP (dioctyl sterate) is adhered, and the ultraviolet ray of 0.5 mW / cm 2 Table 1 shows the contact angles after irradiation for one hour. As shown in Table 1, when the amount of colloidal silica added was 10% by weight, the increase in the contact angle after standing in a dark box was large, and the maintainability was poor. Also 8
At 0% by weight, the contact angle after being once contaminated does not decrease, indicating that the decomposition performance of the contaminants is poor.

【００２８】[0028]

【表１】 [Table 1]

【００２９】実施例４〜７および比較的３〜４ 基板として石英ガラスを用い、実施例２と全く同様にコ
ロイダルシリカの添加量を５０重量％とした塗布液を同
様にスピンコートした。焼成温度を２００℃、３５０
℃、５００℃、７００℃、８００℃、９００℃としてそ
れぞれ３０分間焼成して得られたものをそれぞれ比較例
３、実施例４、実施例５、実施例６、実施例７、比較例
４とした。Examples 4 to 7 and comparatively 3 to 4 A coating liquid containing 50% by weight of colloidal silica was spin-coated in the same manner as in Example 2 except that quartz glass was used as the substrate. Firing temperature 200 ° C, 350
C., 500.degree. C., 700.degree. C., 800.degree. C., and 900.degree. C., each of which was baked for 30 minutes to obtain Comparative Example 3, Example 4, Example 5, Example 6, Example 7, Comparative Example 4, respectively. did.

【００３０】得られた被膜表面の接触角、２４時間暗箱
中に放置した後の接触角、さらにＤＯＰを付着させた時
の接触角、および０．５ｍＷ／ｃｍ2 の紫外線を１時間
照射した後の接触角を表２に示す。表２に示すように、
２００℃で焼成したものは親水性が低く触媒性能も不足
し、９００℃で焼成したものは触媒性能が悪いことがわ
かる。The contact angle of the surface of the obtained coating film, the contact angle after leaving it in a dark box for 24 hours, the contact angle when DOP was adhered, and the irradiation angle of 0.5 mW / cm 2 for 1 hour. Are shown in Table 2. As shown in Table 2,
It can be seen that those fired at 200 ° C. have low hydrophilicity and insufficient catalytic performance, and those fired at 900 ° C. have poor catalytic performance.

【００３１】[0031]

【表２】 [Table 2]

【００３２】実施例８〜１０および比較的５ 基板上にシリカゾルとしてアトロンＮ−Ｓｉ５００（日
本曹達株式会社製の商品名）をスピンコーティングし、
６００℃で３０分間焼成し、膜厚が５０ｎｍ、１００ｎ
ｍ、２００ｎｍ、４００ｎｍの第１層を形成した。この
第１層上に実施例２と全く同様にコロイダルシリカを５
０重量％としたものを用いて実施例１と全く同様にして
被膜を形成した。Examples 8 to 10 and relatively 5 Atron N-Si500 (trade name, manufactured by Nippon Soda Co., Ltd.) was spin-coated on a substrate as silica sol,
Baking at 600 ° C for 30 minutes, film thickness 50nm, 100n
First layers of m, 200 nm, and 400 nm were formed. On the first layer, colloidal silica was added in the same manner as in Example 2.
A coating was formed in exactly the same manner as in Example 1 except that the amount was 0% by weight.

【００３３】得られた被膜表面の接触角、２４時間暗箱
中に放置した後の接触角、さらにＤＯＰを付着させた時
の接触角、および０．５ｍＷ／ｃｍ2 の紫外線を１時間
照射した後の接触角を表３に示す。The contact angle of the obtained film surface, the contact angle after leaving it in a dark box for 24 hours, the contact angle when DOP was adhered, and the irradiation angle of 0.5 mW / cm 2 UV for 1 hour Are shown in Table 3.

【００３４】[0034]

【表３】 [Table 3]

【００３５】表３に示すように、第１層を４００ｎｍの
膜厚としたものは焼成後基板に反りが生じたことがわか
る。As shown in Table 3, when the first layer had a thickness of 400 nm, the substrate was warped after firing.

【００３６】比較的６〜８ 実施例１と全く同様にして準備したチタニアゾルをエタ
ノールで固形分濃度が２重量％となるように希釈したも
のを塗布溶液とした。この塗布溶液を実施例１のように
洗浄を行なったガラス基板上にスピンコーティング法に
より１０００ｒｐｍの条件で塗布し、５００℃で焼成す
ることを２回繰り返したものを比較例６とした。得られ
た被膜は膜厚１００ｎｍの透明なものであった。Comparatively 6 to 8 A titania sol prepared in exactly the same manner as in Example 1 was diluted with ethanol to a solid concentration of 2% by weight to obtain a coating solution. Comparative Example 6 was obtained by applying this coating solution onto a glass substrate which had been washed as in Example 1 by spin coating at 1000 rpm and baking it at 500 ° C. twice. The obtained film was a transparent film having a thickness of 100 nm.

【００３７】一方、ゾルの形状が球形であるコロイダル
シリカとしてＳＴ−Ｏ（日産化学工業株式会社製の商品
名）を用いた他は、実施例１と全く同様に形成した。シ
リカの添加量を２０重量％、５０重量％とし、それぞれ
比較例７、比較例８とした。On the other hand, except that ST-O (trade name, manufactured by Nissan Chemical Industries, Ltd.) was used as the colloidal silica having a spherical sol shape, it was formed in exactly the same manner as in Example 1. The amount of silica added was set to 20% by weight and 50% by weight, and Comparative Examples 7 and 8 were used.

【００３８】比較的６〜８で得られた被膜表面の接触
角、２４時間暗箱中に放置した後の接触角、さらにＤＯ
Ｐを付着させた時の接触角、および０．５ｍＷ／ｃｍ2
の紫外線を１時間照射した後の接触角を表４に示す。The contact angle of the surface of the coating film relatively obtained at 6 to 8, the contact angle after being left in a dark box for 24 hours, and the DO angle
Contact angle when P is deposited, and 0.5 mW / cm 2
Table 4 shows the contact angles after irradiation with the ultraviolet ray for 1 hour.

【００３９】[0039]

【表４】 [Table 4]

【００４０】実施例１〜３で得られた被膜と比較的６〜
８で得られた被膜とについて綿布にクレンザーを付けて
１０回こすり、水洗いした後の被膜表面の状態を表５に
示す。The coatings obtained in Examples 1 to 3 and 6 to 6
Table 5 shows the condition of the surface of the film obtained after rubbing the film obtained in 8 with a cleanser on a cotton cloth 10 times and washing with water.

【００４１】[0041]

【表５】 [Table 5]

【００４２】表５に示すように、比較的６で得られたチ
タニア膜は、親水維持性が悪く、耐摩耗性も十分でな
く、また、比較的７〜８で得られた球状のコロイダルシ
リカを用いたものは実施例１で得られた被膜と比較して
耐摩耗性が劣っていることがわかる。As shown in Table 5, the titania film obtained in Comparative Example 6 had poor hydrophilicity retention and insufficient abrasion resistance, and the spherical colloidal silica obtained in Comparative Example 7-8. It can be seen that those using No. were inferior in wear resistance as compared with the coating obtained in Example 1.

【００４３】[0043]

【発明の効果】本発明の親水性被膜は、親水性に優れ、
かつ親水効果が長く持続される上に、耐摩耗性に優れる
と共に、光触媒機能により防汚染性の効果もある。ま
た、本発明では、コロイダルシリカとして鎖状のものを
添加することによって、膜表面の耐傷つき性を著しく向
上させることができる。The hydrophilic film of the present invention has excellent hydrophilicity,
In addition to having a long-lasting hydrophilic effect, it has excellent abrasion resistance, and also has an effect of preventing contamination by a photocatalytic function. Further, in the present invention, the damage resistance of the film surface can be remarkably improved by adding a chain-like colloidal silica.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 菅原 聡子 神奈川県横浜市神奈川区宝町２番地 日産 自動車株式会社内 (72)発明者 甲斐 康朗 神奈川県横浜市神奈川区宝町２番地 日産 自動車株式会社内 (72)発明者 清野 俊 神奈川県横浜市神奈川区宝町２番地 日産 自動車株式会社内 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Satoko Sugawara, Nissan Motor Co., Ltd., 2nd Takaracho, Kanagawa-ku, Yokohama, Kanagawa Prefecture (72) Inventor Yasuo Kai 2nd Takaracho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture 72) Inventor Shun Kiyono Nissan Motor Co., Ltd., 2 Takara-cho, Kanagawa-ku, Yokohama-shi, Kanagawa

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 チタニアを含む金属酸化物ゾルおよびゾ
ルの形状が鎖状であるコロイダルシリカを含む複合溶液
を基板に塗布し、焼成したチタニアおよびシリカを含む
金属酸化物膜を有することを特徴とする親水性被膜。1. A metal oxide film containing titania and silica, which is obtained by applying a metal oxide sol containing titania and a composite solution containing colloidal silica whose sol has a chain shape to a substrate and firing the substrate. Hydrophilic coating. 【請求項２】 シリカの含有量が２０〜７０重量％の範
囲であることを特徴とする請求項１記載の親水性被膜。2. The hydrophilic coating according to claim 1, wherein the content of silica is in the range of 20 to 70% by weight. 【請求項３】 コロイダルシリカの鎖の径が５〜５０ｎ
ｍ、および鎖の長さが４０〜５００ｎｍの範囲であるこ
とを特徴とする請求項１乃至２記載の親水性被膜。3. The colloidal silica chain has a diameter of 5 to 50 n.
3. The hydrophilic coating according to claim 1, wherein m and the chain length are in the range of 40 to 500 nm. 【請求項４】 金属酸化物の膜厚が２０〜５００ｎｍの
範囲であることを特徴とする請求項１乃至３記載の親水
性被膜。4. The hydrophilic coating according to claim 1, wherein the thickness of the metal oxide is in the range of 20 to 500 nm. 【請求項５】 基板上に第１層として金属酸化物膜を形
成し、該第１層上に第２層として請求項１乃至４記載の
金属酸化物膜を形成したことを特徴とする親水性被膜。5. A hydrophilic structure wherein a metal oxide film is formed as a first layer on a substrate, and the metal oxide film according to claim 1 is formed as a second layer on the first layer. Film. 【請求項６】 チタニアを含む金属酸化物ゾルおよびゾ
ルの形状が鎖状であるコロイダルシリカを含む複合溶液
を基板に塗布し、次いでその塗布液を３００〜８５０℃
で焼成することにより得られるチタニアおよびシリカを
含む金属酸化物膜を前記基板上に設けることを特徴とす
る親水性被膜の製造方法。6. A substrate is coated with a metal oxide sol containing titania and a composite solution containing colloidal silica in which the shape of the sol is a chain, and then the coating solution is heated at 300 to 850 ° C.
Providing a metal oxide film containing titania and silica obtained by sintering on said substrate.
JP22364996A 1996-08-26 1996-08-26 Hydrophilic coating film and its production Pending JPH1060665A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP22364996A JPH1060665A (en) 1996-08-26 1996-08-26 Hydrophilic coating film and its production
DE19736925A DE19736925A1 (en) 1996-08-26 1997-08-25 Hydrophilic film and method for producing the same on a substrate
US08/917,617 US6071606A (en) 1996-08-26 1997-08-26 Hydrophilic film and method for forming same on substrate
GB9718030A GB2316687B (en) 1996-08-26 1997-08-26 Hydrophilic film and method for forming same on substrate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP22364996A JPH1060665A (en) 1996-08-26 1996-08-26 Hydrophilic coating film and its production

Publications (1)

Publication Number Publication Date
JPH1060665A true JPH1060665A (en) 1998-03-03

Family

ID=16801499

Family Applications (1)

Application Number Title Priority Date Filing Date
JP22364996A Pending JPH1060665A (en) 1996-08-26 1996-08-26 Hydrophilic coating film and its production

Country Status (1)

Country Link
JP (1) JPH1060665A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10237353A (en) * 1997-02-24 1998-09-08 Tao:Kk Hydrophilic coating agent and surface hydrophilic substrate
JPH10237352A (en) * 1997-02-24 1998-09-08 Tao:Kk Polyfunctional coating agent
EP1182174A1 (en) 2000-08-22 2002-02-27 Central Glass Company, Limited Glass plate with oxide film and process for producing same
WO2004096935A1 (en) * 2003-04-30 2004-11-11 Ube Nitto Kasei Co., Ltd. Photocatalyst coating liquid, photocatalyst film and photocatalyst member
CN102634280A (en) * 2012-04-23 2012-08-15 苏州晶瑞化学有限公司 Solid hot-melting strong acid-resistant spray wax and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10237353A (en) * 1997-02-24 1998-09-08 Tao:Kk Hydrophilic coating agent and surface hydrophilic substrate
JPH10237352A (en) * 1997-02-24 1998-09-08 Tao:Kk Polyfunctional coating agent
EP1182174A1 (en) 2000-08-22 2002-02-27 Central Glass Company, Limited Glass plate with oxide film and process for producing same
US6866937B2 (en) 2000-08-22 2005-03-15 Central Glass Company, Limited Glass plate with oxide film and process for producing same
WO2004096935A1 (en) * 2003-04-30 2004-11-11 Ube Nitto Kasei Co., Ltd. Photocatalyst coating liquid, photocatalyst film and photocatalyst member
JPWO2004096935A1 (en) * 2003-04-30 2006-07-13 宇部日東化成株式会社 Photocatalyst coating liquid, photocatalyst film and photocatalyst member
CN100381527C (en) * 2003-04-30 2008-04-16 宇部日东化成株式会社 Photocatalyst coating liquid, photocatalyst film and photocatalyst member
CN102634280A (en) * 2012-04-23 2012-08-15 苏州晶瑞化学有限公司 Solid hot-melting strong acid-resistant spray wax and preparation method thereof

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