JPH07138046A - Sol gel film and method for forming the same - Google Patents
Sol gel film and method for forming the sameInfo
- Publication number
- JPH07138046A JPH07138046A JP28119493A JP28119493A JPH07138046A JP H07138046 A JPH07138046 A JP H07138046A JP 28119493 A JP28119493 A JP 28119493A JP 28119493 A JP28119493 A JP 28119493A JP H07138046 A JPH07138046 A JP H07138046A
- Authority
- JP
- Japan
- Prior art keywords
- sol
- film
- solution
- fluororesin particles
- gel 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.)
- Granted
Links
Classifications
-
- 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
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- 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
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、多孔質形状、例えばマ
イクロピット形状を有し、しかもその形状および大きさ
等を適宜種々にコントロールすることができ、機械的強
度および耐薬品性の高いゾルゲル膜とその形成法に関
し、特にガラス基板上に被膜積層する多層膜において下
地膜や下層膜として用い格段にその性能を発揮すること
となる等、光学特性を損なうことなく強固な密着力で耐
摩耗性あるいは耐久性が優れるものとなり、建築もしく
は自動車等の窓材、各種膜付きガラス物品において有用
なゾルゲル膜およびその形成法を提供するものである。BACKGROUND OF THE INVENTION The present invention is a sol-gel having a porous shape, for example, a micropit shape, and the shape and size of which can be appropriately controlled in various ways, and which has high mechanical strength and chemical resistance. Regarding the film and its formation method, especially when it is used as a base film or a lower layer film in a multi-layer film laminated on a glass substrate, its performance is remarkably exhibited, and abrasion resistance is achieved with strong adhesion without impairing optical characteristics. The present invention provides a sol-gel film having excellent properties or durability, which is useful in window materials for construction, automobiles, etc., and glass films with various films, and a method for forming the sol-gel film.
【０００２】[0002]
【従来技術】一般に金属酸化物被膜の表面上に多孔質形
状を形成する方法としては、例えば金属酸化物被膜をフ
ッ酸やフッ硝酸等でエッチングする方法が知られてい
る。2. Description of the Related Art Generally, as a method of forming a porous shape on the surface of a metal oxide film, for example, a method of etching the metal oxide film with hydrofluoric acid or hydrofluoric nitric acid is known.
【０００３】ところが、前記多孔質形状を形成すること
ができるものの、金属酸化物被膜をフッ酸やフッ硝酸等
でエッチングする方法ではエッチング溶液であるフッ酸
やフッ硝酸等はその取扱いが厄介で作業性に極めて劣る
とともに、エッチング工程が付加することでの生産性の
低下等をも招くこととなる。However, although the above-mentioned porous shape can be formed, in the method of etching the metal oxide film with hydrofluoric acid, hydrofluoric nitric acid or the like, the hydrofluoric acid, hydrofluoric nitric acid or the like which is an etching solution is difficult to handle. In addition to being extremely inferior in productivity, the addition of an etching step causes a decrease in productivity and the like.
【０００４】[0004]
【発明が解決しようとする問題点】本発明は上記従来の
問題点を解決するものであり、その目的は、前記した従
来のエッチングを不要とし、該エッチング工程を省略し
得たなかで、特異なマイクロピット状等の多孔質形状を
形成し、密着性、耐候性に優れしかも硬いゾルゲル膜を
提供することにある。SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned conventional problems, and an object of the present invention is to eliminate the conventional etching described above and to omit the etching step. Another object of the present invention is to provide a hard sol-gel film which has a porous shape such as micropits and is excellent in adhesion and weather resistance.
【０００５】[0005]
【問題点を解決するための手段】従来のかかる問題点に
鑑みてなされたものであって、本発明は、特異なマイク
ロピット状等の多孔質形状を有する表面表層形状を制御
したもので、かつガラス基板に対して高密着性で耐久性
や耐摩耗性とを併せ持ち、単体ではもちろん下地膜ある
いは下層膜等に有用な酸化物薄膜を、厄介な工程がなく
高安全で作業効率よく安価に提供するものである。[Means for Solving the Problems] The present invention has been made in view of the above problems, and the present invention is directed to controlling the surface layer shape having a porous shape such as a unique micropit shape. In addition, the oxide thin film, which has high adhesion to glass substrates and durability and abrasion resistance, and is useful not only as a base film but also as a base film or underlayer film, is safe, work efficiency is low, and there is no troublesome process. It is provided.
【０００６】すなわち、本発明は、ガラス基板の表面上
に、金属アルコキシド系化合物を加水分解ならびに脱水
縮合させたゾル溶液と、フッ素樹脂粒子あるいはフッ素
樹脂粒子の懸濁液を溶剤とともに混合した溶液をコーテ
イング液とし、該コーテイング液を塗布し、加熱焼結
し、薄膜表層が微細な多孔質形状で成ることを特徴とす
るゾルゲル膜。That is, the present invention provides a sol solution obtained by hydrolyzing and dehydrating and condensing a metal alkoxide compound on the surface of a glass substrate and a solution in which fluororesin particles or a suspension of fluororesin particles is mixed with a solvent. A sol-gel film comprising a coating liquid, applying the coating liquid, and heating and sintering the thin film surface layer having a fine porous shape.
【０００７】ならびに、前記した薄膜の多孔質形状表層
における形状ならびにその径の制御を、前記ゾル溶液の
分子量、前記フッ素樹脂粒子の平均粒子径、前記コーテ
イング液における固形分率、ならびに前記コーテイング
液を調製する際の溶剤の種類の選択により行うことを特
徴とする上述したゾルゲル膜。In addition, the shape and diameter of the thin film in the porous surface layer are controlled by controlling the molecular weight of the sol solution, the average particle diameter of the fluororesin particles, the solid content of the coating solution, and the coating solution. The sol-gel film as described above, which is characterized by being selected by selecting the type of solvent at the time of preparation.
【０００８】さらに、前記コーテイング液において、該
コーテイング液中の固形分のうち、ゾル溶液の固形分に
対してフッ素樹脂が５〜４５０ｗｔ％であることを特徴
とする上述したゾルゲル膜。Further, in the coating liquid, the sol-gel film is characterized in that the fluororesin is 5 to 450 wt% with respect to the solid content of the sol solution in the solid content in the coating liquid.
【０００９】また、ガラス基板の表面上に、金属アルコ
キシド系化合物を加水分解ならびに脱水縮合させたゾル
溶液と、フッ素樹脂粒子あるいはフッ素樹脂粒子の懸濁
液を溶剤とともに混合した溶液をコーテイング液とし、
該コーテイング液を塗布し、フッ素樹脂の分解温度以上
の温度で加熱焼結することを特徴とするゾルゲル膜の形
成法。On the surface of the glass substrate, a sol solution obtained by hydrolyzing and dehydrating and condensing a metal alkoxide compound, and a solution in which fluororesin particles or a suspension of fluororesin particles are mixed with a solvent are used as a coating liquid,
A method for forming a sol-gel film, which comprises applying the coating solution and heating and sintering at a temperature equal to or higher than the decomposition temperature of the fluororesin.
【００１０】ここで、ガラス基板としては、車両用、船
舶用、航空機用あるいは建築用等に用いられる市販のソ
ーダライムガラスを採用することができる。また、強化
ガラス、合わせガラス、ミラー用ガラスであってもよ
い。Here, as the glass substrate, commercially available soda lime glass used for vehicles, ships, aircraft, construction, etc. can be adopted. Further, it may be tempered glass, laminated glass, or mirror glass.
【００１１】また、前記表面表層にマイクロピット状等
の多孔質形状を有する酸化物薄膜は、少なくともシリカ
ゾル溶液とフッ素樹脂粒子あるいはフッ素樹脂粒子の懸
濁液を混合してなる溶液をガラスに塗布して加熱、焼結
することにより形成する。Further, the oxide thin film having a porous shape such as micropits on the surface layer is obtained by coating a glass with a solution prepared by mixing at least a silica sol solution with fluororesin particles or a suspension of fluororesin particles. It is formed by heating and sintering.
【００１２】またさらに、シリカゾル溶液としては、シ
リコンのアルコキシドまたはモノメチルアルコキシドを
出発原料とし、加水分解、縮重合した溶液が用いられ、
該溶液には他種金属、例えばAl、Zr、Tiなどのアルコキ
シド、モノメチルアルコキシドまたはアセチルアセトネ
ート塩およびそれらの縮重合物が含有していてもよい。Furthermore, as the silica sol solution, a solution obtained by hydrolyzing and polycondensing a silicon alkoxide or a monomethyl alkoxide as a starting material is used.
The solution may contain other metals such as alkoxides of Al, Zr and Ti, monomethylalkoxides or acetylacetonate salts and polycondensates thereof.
【００１３】なかでも、アルコキシドまたはモノメチル
アルコキシドとして好ましいものをあげれば、（モノメ
チル）メトキシド、（モノメチル）エトキシド、（モノ
メチル）イソプロポキシド、（モノメチル）ｎーブトキ
シドなどであり、またアセチルアセトネート塩として好
ましいものをあげれば、アセチルジルコニウム、アセチ
ルアセトネートチタンなどである。Among them, preferred examples of the alkoxide or monomethyl alkoxide include (monomethyl) methoxide, (monomethyl) ethoxide, (monomethyl) isopropoxide, (monomethyl) n-butoxide and the like, and preferred as acetylacetonate salt. Examples thereof include acetyl zirconium and titanium acetylacetonate.
【００１４】さらにまた、フッ素樹脂としては、主に炭
素とフッ素からなる重合体であり、ポリテトラフルオロ
エチレン、ポリクロロフルオロエチレン、ポリビニリデ
ンフルオライド、ポリビニルフルオライド、テトラフル
オロエチレンとヘキサフルオロプロピレンの共重合体、
テトラフルオロエチレンとエチレンの共重合体、テトラ
フルオロエチレンとパーフルオロアルキルビニルエーテ
ルの共重合体、クロロトリフルオロエチレンとエチレン
の共重合体などがあげられ、該フッ素樹脂は粉末として
シリカゾル溶液中に混合してもよく、また分散した懸濁
液として混合してもよい。Further, the fluororesin is a polymer mainly composed of carbon and fluorine, and includes polytetrafluoroethylene, polychlorofluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene and hexafluoropropylene. Copolymer,
Examples thereof include copolymers of tetrafluoroethylene and ethylene, copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ether, and copolymers of chlorotrifluoroethylene and ethylene.The fluororesin is mixed as a powder in a silica sol solution. Alternatively, they may be mixed as a dispersed suspension.
【００１５】なかでも、ポリテトラフルオロエチレンの
粉末としては例えば商品名ポリフロン（Ｍー１２、１
４、１５）、ルブロン（Ｌー２、５）〔ダイキン工業
（株）〕、テトラフルオロエチレンとエチレンの共重合
体としては例えば商品名ネオフロン（ＥＴＦＥ）〔ダイ
キン工業（株）〕、ポリテトラフルオロエチレン粉末の
懸濁液としては例えば商品名ポリフロン（Ｄー１、Ｄー
２、Ｄー２Ｃ）、ルブロン（ＬＤＷ）〔ダイキン工業
（株）〕、テトラフルオロエチレンとヘキサフルオロプ
ロピレンの共重合体の懸濁液としては例えば商品名ネオ
フロン（ＮＤー１、２、４）〔ダイキン工業（株）〕、
テトラフルオロエチレンとパーフルオロアルキルビニル
エーテルの共重合体粉末の懸濁液としては例えば商品名
ネオフロン（ＡＤー１、ＡＤー２）〔ダイキン工業
（株）〕などがあげられる。Among them, the polytetrafluoroethylene powder is, for example, polyflon (M-12, 1)
4, 15), Lubron (L-2, 5) [Daikin Industry Co., Ltd.], and as a copolymer of tetrafluoroethylene and ethylene, for example, trade name NEOFLON (ETFE) [Daikin Industry Co., Ltd.], polytetrafluoro Examples of the suspension of ethylene powder include polyflon (D-1, D-2, D-2C), Lubron (LDW) [Daikin Industry Co., Ltd.], a copolymer of tetrafluoroethylene and hexafluoropropylene. As the suspension, for example, the trade name NEOFLON (ND-1, 2, 4) [Daikin Industries, Ltd.],
Examples of the suspension of the tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer powder include Neoflon (AD-1, AD-2) under the trade name of Daikin Industries, Ltd.
【００１６】また、フッ素樹脂粉末の平均粒子径として
は、約０．６μｍ以下、好ましくは０．１〜０．６μｍ
程度である。さらに、シリカに対するフッ素樹脂の混合
割合としては、５重量％未満であると目的とする膜表面
表層の多孔質形状が得られず、また４５０重量％を超え
ると膜強度が充分でないうえ、被膜の透明度が損なわれ
るため、５〜４５０重量％の範囲にすることが好まし
い。The average particle size of the fluororesin powder is about 0.6 μm or less, preferably 0.1 to 0.6 μm.
It is a degree. Further, if the mixing ratio of the fluororesin to silica is less than 5% by weight, the desired porous shape of the surface layer of the film surface cannot be obtained, and if it exceeds 450% by weight, the film strength is insufficient and the coating film Since the transparency is impaired, it is preferably in the range of 5 to 450% by weight.
【００１７】また、コーテイング液を調製する際に、ゾ
ル溶液、フッ素樹脂とともに混合する溶媒としては、メ
チルアルコール、エチルアルコール、イソプロピルアル
コール等の低級アルコールのほか、エチレングリコール
モノエチルエーテルといったセロソルブ類が採用できる
ものである。When a coating solution is prepared, lower solvents such as methyl alcohol, ethyl alcohol and isopropyl alcohol, and cellosolves such as ethylene glycol monoethyl ether are used as the solvent mixed with the sol solution and the fluororesin. It is possible.
【００１８】さらに、本発明における酸化物被膜の膜厚
としては、０．０１μｍ程度以下であれば目的とする膜
表面表層の多孔質形状が得られず、また１μｍ程度を超
えると膜にクラックが生じるため、好ましくは０．０２
〜１μｍ程度、より好ましくは０．０３〜０．９μｍ程
度とするものである。Further, if the thickness of the oxide film in the present invention is about 0.01 μm or less, the desired porous shape of the surface layer of the film cannot be obtained, and if it exceeds about 1 μm, the film is cracked. Therefore, it is preferably 0.02.
˜1 μm, more preferably about 0.03 to 0.9 μm.
【００１９】また、ガラス基板への膜付け法としては、
ディッピング法、スプレー法、フローコート法、スピン
コート法ならびに各種印刷法等、既知の塗布手段が適宜
採用し得るものである。Further, as a method for attaching a film to a glass substrate,
Known coating means such as a dipping method, a spray method, a flow coating method, a spin coating method and various printing methods can be appropriately adopted.
【００２０】さらにまた、塗布膜の加熱、焼結温度とし
ては、フッ素樹脂の分解温度以下であると、膜表面表層
に出現する多孔質形状が充分に明確で深みのあるものと
ならないため、コーテイング液中に混合したフッ素樹脂
の分解温度以上であることが好ましい。また、膜表面表
層に形成される多孔質形状は、膜強度を向上させるため
の焼成（例えば約６００℃程度以上）によっても消失す
ることなく、膜強度が優れた多孔質金属酸化物被膜が得
られる。Furthermore, when the coating film is heated and sintered at a temperature not higher than the decomposition temperature of the fluororesin, the porous shape appearing on the surface layer of the film will not be sufficiently clear and deep, so that the coating will not occur. It is preferably at least the decomposition temperature of the fluororesin mixed in the liquid. In addition, the porous shape formed on the surface layer of the film does not disappear even by firing to improve the film strength (for example, about 600 ° C. or higher), and a porous metal oxide film having excellent film strength is obtained. To be
【００２１】ここで、各種フッ素樹脂の分解温度を表１
に例示する。The decomposition temperatures of various fluororesins are shown in Table 1.
For example.
【００２２】[0022]
【表１】 [Table 1]
【００２３】[0023]
【実施例】以下、実施例により本発明を具体的に説明す
る。ただし本発明は係る実施例に限定されるものではな
い。EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the embodiment.
【００２４】実施例１ 大きさ約１００mm×１００mm、厚さ約２mmのクリア・フ
ロートガラス基板を中性洗剤、水すすぎ、アルコールで
順次洗浄し、乾燥した後、アセトンで払拭し被膜用ガラ
ス基板とした。 Example 1 A clear float glass substrate having a size of about 100 mm × 100 mm and a thickness of about 2 mm was sequentially washed with a neutral detergent, water rinse, alcohol, dried and then wiped with acetone to form a glass substrate for coating. did.
【００２５】先ず、テトラエトキシシラン〔Ｓｉ（ＯＣ
2 Ｈ 5）4 ：ＴＥＯＳ〕を１６ｇ、エタノール（ＥｔＯ
Ｈ）を６８．５ｇ、水（予めＨＣｌでｐＨ４に調整）を
５．５ｇそれぞれ秤り取り、約８０℃で約４時間加熱還
流を行いシリカゾル溶液を得ておく。First, tetraethoxysilane [Si (OC
2 H 5 ) 4 : TEOS], 16 g of ethanol (EtO
68.5 g of H) and 5.5 g of water (preliminarily adjusted to pH 4 with HCl) are weighed and heated under reflux at about 80 ° C. for about 4 hours to obtain a silica sol solution.
【００２６】第１液として液中のフッ素樹脂が、該シリ
カゾル溶液（平均分子量約３０００）の固形分に対して
約８０重量％となるように、シリカゾル溶液中にフッ素
樹脂粒子の懸濁液〔商品名ネオフロンＮＤー１（ダイキ
ン工業（株））〕を添加混合した溶液を調製する。次に
第１液を、全体の固形分が約３重量％となるように溶媒
としてエチレングリコールモノエチルエーテルで希釈
し、第２液とする。A suspension of fluororesin particles in a silica sol solution [as a first liquid] is prepared so that the content of the fluororesin in the liquid is about 80% by weight based on the solid content of the silica sol solution (average molecular weight: about 3000). A brand name NEOFLON ND-1 (Daikin Industries, Ltd.) is added and mixed to prepare a solution. Next, the first liquid is diluted with ethylene glycol monoethyl ether as a solvent so that the total solid content becomes about 3% by weight to obtain a second liquid.
【００２７】次いで該第２液をコーテイング液としてガ
ラス基板の表面に塗布した後、約６２０℃で約１０分間
加熱処理を行い、膜厚約０．１μｍのＳｉＯ2 薄膜を形
成した。Next, the second liquid was applied as a coating liquid to the surface of the glass substrate and then heat-treated at about 620 ° C. for about 10 minutes to form a SiO 2 thin film having a thickness of about 0.1 μm.
【００２８】得られた該薄膜を走査形電子顕微鏡により
約２万倍の倍率で表面形状を観察したところ、図１に示
すようにマイクロピット状を有する多孔質形状の表層と
なっており、その孔径は約７０ｎｍ程度であった。また
各種膜評価でも密着性、耐摩耗性、耐久性等を充分有し
優れるものとなっていた。The surface shape of the obtained thin film was observed under a scanning electron microscope at a magnification of about 20,000. As a result, a porous surface layer having micropits was formed as shown in FIG. The pore size was about 70 nm. In addition, the evaluation of various films revealed that the film had excellent adhesion, abrasion resistance, durability, etc. and was excellent.
【００２９】実施例２ ガラス基板および第１液の調製までは実施例１と同様に
し、次に第１液を、全体の固形分が約２重量％となるよ
うにエチレングリコールモノエチルエーテルで希釈し、
第２液とした。その他は実施例１と同様にした。 Example 2 The same procedure as in Example 1 was carried out until the preparation of the glass substrate and the first liquid, and then the first liquid was diluted with ethylene glycol monoethyl ether so that the total solid content was about 2% by weight. Then
The second liquid was used. Others were the same as in Example 1.
【００３０】得られたＳｉＯ2 薄膜の表面形状を実施例
１と同様に観察したところ、図２に示すように、実施例
１と同様なマイクロピット状を有する多孔質形状の表層
となっており、その孔径は約１００ｎｍ程度であった。
また各種膜評価でも密着性、耐摩耗性、耐久性等を充分
有し優れるものとなっていた。The surface shape of the obtained SiO 2 thin film was observed in the same manner as in Example 1. As a result, as shown in FIG. 2, it was a porous surface layer having micropit shapes similar to those in Example 1. The pore size was about 100 nm.
In addition, the evaluation of various films revealed that the film had excellent adhesion, abrasion resistance, durability, etc. and was excellent.
【００３１】実施例３ 第１液を希釈する際の溶媒をメチルアルコールとした他
は実施例１と同様にした。 Example 3 The same as Example 1 except that the solvent for diluting the first liquid was methyl alcohol.
【００３２】得られたＳｉＯ2 薄膜の表面形状を実施例
１と同様に観察したところ、図３に示すように、マイク
ロピット状を有する多孔質形状の表層となっているもの
の、単位面積あたりの孔の数が実施例１と比較して少な
いものであった。また各種膜評価でも密着性、耐摩耗
性、耐久性等を充分有し優れるものとなっていた。When the surface shape of the obtained SiO 2 thin film was observed in the same manner as in Example 1, as shown in FIG. 3, although it was a porous surface layer having micropits, The number of holes was smaller than that in Example 1. In addition, the evaluation of various films revealed that the film had excellent adhesion, abrasion resistance, durability, etc. and was excellent.
【００３３】実施例４ 使用するシリカゾル液の平均分子量を約３００００とし
た他は、実施例１と同様にした。 Example 4 Example 4 was repeated except that the silica sol liquid used had an average molecular weight of about 30,000.
【００３４】得られたＳｉＯ2 薄膜の表面形状を実施例
１と同様に観察したところ、図４に示すように、マイク
ロピット状を有する多孔質形状の表層となっているもの
の、実施例１と比較して表層の孔の分散状態が比較的不
均一であった。また各種膜評価でも密着性、耐摩耗性、
耐久性等を充分有し優れるものとなっていた。The surface shape of the obtained SiO 2 thin film was observed in the same manner as in Example 1. As a result, as shown in FIG. 4, although the surface layer was a porous surface having micropits, In comparison, the distribution of pores in the surface layer was relatively non-uniform. Also in various film evaluations, adhesion, wear resistance,
It had excellent durability and the like and was excellent.
【００３５】比較例１ 実施例１と同様のガラス基板に、実施例１で用いた固形
分が約５重量％のシリカゾル溶液（平均分子量約３００
０）をコーテイング液とし、塗布後、約６２０℃で約１
０分間加熱処理を行った。 Comparative Example 1 A silica sol solution having a solid content of about 5% by weight (average molecular weight of about 300) was used on a glass substrate similar to that of Example 1.
0) as the coating liquid, and after coating, at about 620 ° C for about 1
Heat treatment was performed for 0 minutes.
【００３６】得られたＳｉＯ2 薄膜の表面形状を実施例
１と同様に観察したところ、図５に示すように、平坦な
表面であり、めざす所期の多孔質形状と言えるものでは
到底なかった。When the surface shape of the obtained SiO 2 thin film was observed in the same manner as in Example 1, it was a flat surface as shown in FIG. 5, and it could not be said that the desired porous shape was obtained. .
【００３７】比較例２ 比較例１と同様にして得られた薄膜上を、約０．２重量
％のフッ酸水溶液で約５分間のエッチング処理を施し
た。 Comparative Example 2 The thin film obtained in the same manner as in Comparative Example 1 was subjected to etching treatment for about 5 minutes with an aqueous solution of hydrofluoric acid of about 0.2% by weight.
【００３８】得られたフッ酸エッチング処理後の薄膜表
面層を実施例１と同様に観察したところ、図６に示すよ
うに、めざすマイクロピット状とは多少異なる凹凸状の
表面表層となっていた。When the obtained thin film surface layer after the hydrofluoric acid etching treatment was observed in the same manner as in Example 1, as shown in FIG. 6, the surface layer had an uneven surface slightly different from the desired micropit shape. .
【００３９】[0039]
【発明の効果】以上前述したように、本発明によれば、
手軽に容易な形成手段でもって薄膜を安価に効率よく得
られ、該薄膜において特異な形状を有する強固な多孔質
状表層が得られ、しかもその孔径を制御することができ
るようになり、単層膜としてはもちろん、ことに多層膜
の下地膜や下層膜において格段にその性能を発揮して、
光学特性を損なうことなく、密着性、耐久性等に優れる
ものとなる等、建築用もしくは自動車用窓材をはじめ、
各種ガラス物品等、種々の被覆膜に広く採用できる利用
価値の高い、有用な多孔質形状表面表層を有するゾルゲ
ル膜、ならびにその形成法を提供するものである。As described above, according to the present invention,
A thin film can be obtained inexpensively and efficiently by a simple and easy forming means, a strong porous surface layer having a peculiar shape can be obtained in the thin film, and the pore size can be controlled. Not only as a film, but especially in the underlying film and lower layer film of a multilayer film, it demonstrates its performance remarkably.
Being excellent in adhesion, durability, etc. without impairing optical properties, such as architectural or automobile window materials,
It is intended to provide a sol-gel film having a useful porous surface layer, which can be widely applied to various coating films such as various glass articles, and a method for forming the sol-gel film.
【図１】実施例１における、本発明の多孔質形状表面表
層を有するゾルゲル膜の表層面状態を、走査型電子顕微
鏡により約２万倍の倍率で観察した写真で示す説明図で
ある。FIG. 1 is an explanatory view showing a surface state of a sol-gel film having a porous surface layer of the present invention in Example 1 as a photograph observed with a scanning electron microscope at a magnification of about 20,000.
【図２】実施例２における、本発明の多孔質形状表面表
層を有するゾルゲル膜の表層面状態を、走査型電子顕微
鏡により約２万倍の倍率で観察した写真で示す説明図で
ある。FIG. 2 is an explanatory diagram showing a surface state of a sol-gel film having a porous surface layer of the present invention in Example 2 observed with a scanning electron microscope at a magnification of about 20,000 times.
【図３】実施例３における、本発明の多孔質形状表面表
層を有するゾルゲル膜の表層面状態を、走査型電子顕微
鏡により約２万倍の倍率で観察した写真で示す説明図で
ある。FIG. 3 is an explanatory view showing a surface state of a sol-gel film having a porous surface layer of the present invention in Example 3, observed by a scanning electron microscope at a magnification of about 20,000 times.
【図４】実施例４における、本発明の多孔質形状表面表
層を有するゾルゲル膜の表層面状態を、走査型電子顕微
鏡により約２万倍の倍率で観察した写真で示す説明図で
ある。FIG. 4 is an explanatory view showing a surface state of a sol-gel film having a porous surface layer according to the present invention in Example 4, observed by a scanning electron microscope at a magnification of about 20,000 times.
【図５】比較例１における、平坦な表面を有するゾルゲ
ル膜の表面状態を、走査型電子顕微鏡により約２万倍の
倍率で観察した写真で示す説明図である。5 is an explanatory view showing a surface state of a sol-gel film having a flat surface in Comparative Example 1 as a photograph observed with a scanning electron microscope at a magnification of about 20,000 times. FIG.
【図６】比較例２における、比較例１で得た平坦な表面
のゾルゲル膜をフッ酸エッチング処理した表面状態を、
走査型電子顕微鏡により約２万倍の倍率で観察した写真
であり、凹凸状表面層を示す説明図である。FIG. 6 shows a surface state obtained by subjecting the sol-gel film having a flat surface obtained in Comparative Example 1 to Comparative Example 2 to hydrofluoric acid etching.
It is a photograph observed with a scanning electron microscope at a magnification of about 20,000 times, and is an explanatory view showing an uneven surface layer.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大谷 充孝 三重県松阪市大口町1510 セントラル硝子 株式会社硝子研究所内 (72)発明者 西田 佳弘 三重県松阪市大口町1510 セントラル硝子 株式会社硝子研究所内 (72)発明者 中村 一郎 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 上村 隆三 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 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 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsutaka Otani 1510 Oguchi-cho, Matsusaka-shi, Mie Central Glass Co., Ltd. Glass Research Institute (72) Inventor Yoshihiro Nishida 1510 Oguchi-cho, Matsusaka-shi, Mie Central Glass Co., Ltd. 72) Inventor Ichiro Nakamura, 2 Takaracho, Kanagawa-ku, Yokohama, Kanagawa Nissan Motor Co., Ltd. (72) Ryuzo Uemura, 2 Takaracho, Kanagawa-ku, Yokohama, Kanagawa Nissan Motor Co., Ltd. (72) Satoshi Sugawara, Kanagawa 2 Takaracho, Kanagawa-ku, Yokohama-shi Nissan Motor Co., Ltd.
Claims (4)
ド系化合物を加水分解ならびに脱水縮合させたゾル溶液
と、フッ素樹脂粒子あるいはフッ素樹脂粒子の懸濁液を
溶剤とともに混合した溶液をコーテイング液とし、該コ
ーテイング液を塗布し、加熱焼結し、薄膜表層が微細な
多孔質形状で成ることを特徴とするゾルゲル膜。1. A coating solution comprising a sol solution obtained by hydrolyzing and dehydrating and condensing a metal alkoxide compound on the surface of a glass substrate and a solution prepared by mixing fluororesin particles or a suspension of fluororesin particles together with a solvent, A sol-gel film characterized in that the thin film surface layer is formed into a fine porous shape by applying the coating liquid and heating and sintering.
形状ならびにその径の制御を、前記ゾル溶液の分子量、
前記フッ素樹脂粒子の平均粒子径、前記コーテイング液
における固形分率、ならびに前記コーテイング液を調製
する際の溶剤の種類の選択により行うことを特徴とする
請求項１記載のゾルゲル膜。2. The control of the shape and the diameter of the thin film in the porous surface layer is performed by controlling the molecular weight of the sol solution,
2. The sol-gel film according to claim 1, wherein the sol-gel film is selected by selecting the average particle size of the fluororesin particles, the solid content in the coating liquid, and the type of solvent used in preparing the coating liquid.
イング液中の固形分のうち、ゾル溶液の固形分に対して
フッ素樹脂が５〜４５０ｗｔ％であることを特徴とする
請求項１乃至２記載のゾルゲル膜。3. The sol-gel according to claim 1, wherein, in the coating liquid, the fluororesin accounts for 5 to 450 wt% of the solid content of the sol solution in the solid content of the coating liquid. film.
ド系化合物を加水分解ならびに脱水縮合させたゾル溶液
と、フッ素樹脂粒子あるいはフッ素樹脂粒子の懸濁液を
溶剤とともに混合した溶液をコーテイング液とし、該コ
ーテイング液を塗布し、フッ素樹脂粒子の分解温度以上
の温度で加熱焼結することを特徴とするゾルゲル膜の形
成法。4. A coating solution comprising a sol solution obtained by hydrolyzing and dehydrating and condensing a metal alkoxide compound on the surface of a glass substrate and a solution prepared by mixing fluororesin particles or a suspension of fluororesin particles together with a solvent, A method for forming a sol-gel film, which comprises applying the coating solution and heating and sintering at a temperature equal to or higher than the decomposition temperature of the fluororesin particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28119493A JP3461016B2 (en) | 1993-11-10 | 1993-11-10 | Sol-gel film and method for forming the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28119493A JP3461016B2 (en) | 1993-11-10 | 1993-11-10 | Sol-gel film and method for forming the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07138046A true JPH07138046A (en) | 1995-05-30 |
| JP3461016B2 JP3461016B2 (en) | 2003-10-27 |
Family
ID=17635661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28119493A Expired - Fee Related JP3461016B2 (en) | 1993-11-10 | 1993-11-10 | Sol-gel film and method for forming the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3461016B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0798272A1 (en) * | 1996-03-27 | 1997-10-01 | Asahi Glass Company Ltd. | Laminate and process for its production |
| EP0835849A1 (en) * | 1996-10-14 | 1998-04-15 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Method and coating composition for the production of an antireflective coating |
| US6403225B1 (en) | 1998-11-10 | 2002-06-11 | Nissan Motor Co., Ltd. | Article superior in slipping waterdrops down surface thereof |
| WO2008059170A2 (en) * | 2006-11-14 | 2008-05-22 | Saint-Gobain Glass France | Porous layer, its manufacturing process and its applications |
-
1993
- 1993-11-10 JP JP28119493A patent/JP3461016B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0798272A1 (en) * | 1996-03-27 | 1997-10-01 | Asahi Glass Company Ltd. | Laminate and process for its production |
| EP0835849A1 (en) * | 1996-10-14 | 1998-04-15 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Method and coating composition for the production of an antireflective coating |
| US6403225B1 (en) | 1998-11-10 | 2002-06-11 | Nissan Motor Co., Ltd. | Article superior in slipping waterdrops down surface thereof |
| WO2008059170A2 (en) * | 2006-11-14 | 2008-05-22 | Saint-Gobain Glass France | Porous layer, its manufacturing process and its applications |
| WO2008059170A3 (en) * | 2006-11-14 | 2008-10-02 | Saint Gobain | Porous layer, its manufacturing process and its applications |
| JP2010509175A (en) * | 2006-11-14 | 2010-03-25 | サン−ゴバン グラス フランス | Porous layer, production method thereof and use thereof |
| EP2423172A1 (en) * | 2006-11-14 | 2012-02-29 | Saint-Gobain Glass France | Porous layer, method for manufacturing same and uses thereof |
| EP2423171A1 (en) * | 2006-11-14 | 2012-02-29 | Saint-Gobain Glass France | Porous layer, method for manufacturing same and uses thereof |
| CN103921507A (en) * | 2006-11-14 | 2014-07-16 | 法国圣戈班玻璃厂 | Porous Layer, Its Manufacturing Process And Its Applications |
| KR101485891B1 (en) * | 2006-11-14 | 2015-01-26 | 쌩-고벵 글래스 프랑스 | Porous layer, its manufacturing process and its applications |
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| Publication number | Publication date |
|---|---|
| JP3461016B2 (en) | 2003-10-27 |
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