JPH08325036A - Sol-gel film and its formation - Google Patents
Sol-gel film and its formationInfo
- Publication number
- JPH08325036A JPH08325036A JP13226895A JP13226895A JPH08325036A JP H08325036 A JPH08325036 A JP H08325036A JP 13226895 A JP13226895 A JP 13226895A JP 13226895 A JP13226895 A JP 13226895A JP H08325036 A JPH08325036 A JP H08325036A
- Authority
- JP
- Japan
- Prior art keywords
- sol
- gel film
- film
- surface layer
- coating
- 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
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- Glass Melting And Manufacturing (AREA)
- Surface Treatment Of Glass (AREA)
- Chemically Coating (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、凹凸状表層の形状およ
び大きさ等を適宜種々にコントロールすることができ、
かつより簡便に得ることができる優れたコ─ティング溶
液で表面形状とその発現をより安定せしめて比表面積を
増大でき、高硬度で機械的強度および耐久性が高い酸化
物被膜となる微細な凹凸状表層を有するゾルゲル膜及び
その形成法に関する。INDUSTRIAL APPLICABILITY The present invention is capable of variously controlling the shape and size of an uneven surface layer,
In addition, it is an excellent coating solution that can be obtained more easily, and the surface shape and its manifestation can be made more stable to increase the specific surface area, resulting in an oxide film with high hardness and high mechanical strength and durability. To a sol-gel film having a surface layer and a method for forming the same.
【０００２】特にガラス基板上に被膜積層する多層膜に
おいて下地層膜として用いた際に、当該特異なゾルゲル
膜上に被覆する各種機能性膜の付着効率と密着性を高
め、しかも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、長期的に頑固な密着力で耐摩
耗性あるいは耐久性等が優れたものとすることができ、
建築用もしくは自動車用等の窓材、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。Particularly when used as an underlayer film in a multi-layer film laminated on a glass substrate, the adhesion efficiency and adhesion of various functional films coated on the peculiar sol-gel film are enhanced, and the performance is remarkably improved. It is possible to obtain excellent wear resistance or durability with long-term stubborn adhesion without impairing the optical characteristics such as exhibiting
The present invention provides a sol-gel film useful in window materials for construction or automobiles, glass products with various films, and a method for forming the same.
【０００３】[0003]
【従来の技術とその問題点】一般に金属酸化物被膜の表
面に凹凸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、ある
いは加熱処理により燃焼分解する有機高分子を金属アル
コキシド溶液中に添加する方法等が知られている。また
簡単な工程で凹凸状等を形成する方法としては、本出願
人は出発原料の異なる金属アルコキシドを加水分解なら
びに脱水縮合させたゾル溶液を混合することによる方法
を見い出している。2. Description of the Related Art Generally, as a method for forming irregularities on the surface of a metal oxide film, for example, a method of etching the metal oxide film with hydrofluoric acid, hydrofluoric nitric acid, or the like or combustion decomposition by heat treatment is carried out. A method of adding an organic polymer to a metal alkoxide solution is known. Further, as a method for forming irregularities and the like in a simple process, the present applicant has found a method by mixing a sol solution obtained by hydrolyzing and dehydrating and condensing metal alkoxides having different starting materials.
【０００４】ところが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、エッチング用溶液であ
るフッ酸やフッ硝酸等が人体に対し極端に危険な物質で
あってその取り扱いが厄介で作業性が劣るとともに、エ
ッチング工程を付加することでの生産性の低下等があ
り、また加熱処理により燃焼分解する有機高分子を金属
アルコキシド溶液中に添加する方法では、例えば一度形
成されたマイクロピット状表面が400 ℃以上の加熱焼成
により、被膜の緻密化が起こるため、その加熱処理条件
を種々制御する必要があるという制約があり、この制約
により頑固な被膜を得ることが困難であって、必ずしも
容易にとは言い難いものである。However, in the method of etching a metal oxide film with hydrofluoric acid, nitric acid, etc., the etching solution, hydrofluoric acid, hydrofluoric acid, etc., is an extremely dangerous substance to the human body, and its handling is troublesome. In addition to being poor in productivity, there is a decrease in productivity due to the addition of an etching step, and in the method of adding an organic polymer that is decomposed by combustion by heat treatment to a metal alkoxide solution, for example, micropits formed once There is a constraint that it is necessary to control the heat treatment conditions variously because the coating becomes dense by heating and baking the surface at 400 ° C or higher. Due to this constraint, it is difficult to obtain a stubborn coating, It is hard to say easily.
【０００５】そこで、本出願人は既に出願している例え
ば特開平5-298545号公報に記載のマイクロピット状表層
を有する酸化物薄膜および該薄膜を用いた多層膜、なら
びにその形成法、また例えば特開平6-298545号公報に記
載のゾルゲル膜およびその形成法、さらに特願平5-2811
93号に記載の撥水性酸化物被膜およびその形成法等が上
記の点を解決するに際し有用であることを提案してい
る。Therefore, the present applicant has already filed an application, for example, an oxide thin film having a micropit-like surface layer described in Japanese Patent Laid-Open No. 5-298545, a multilayer film using the thin film, and a method for forming the same. A sol-gel film described in JP-A-6-298545 and a method for forming the same, and Japanese Patent Application No. 5-28111
It has been proposed that the water-repellent oxide film described in No. 93 and the method for forming the same are useful in solving the above-mentioned problems.
【０００６】自動車用窓ガラス等において各種機能性膜
が実用されるようになってきている最近では、調合方法
が複雑でなくより簡便で長時間を要せず、またポットラ
イフも優れたコ−ティング溶液で、表面形状の発現がよ
り安定かつより優れしかも長期間の過酷な条件下でも機
械的膜強度あるいは耐薬品性等耐久性に優れるゾルゲル
膜がさらにますます望まれつつある。Recently, various functional films have been put into practical use in window glass for automobiles, etc. In recent years, the method of preparation is simple, does not require a long time, and has a good pot life. There is an increasing demand for a sol-gel film which is more stable and more excellent in surface shape in a coating solution and has excellent durability such as mechanical film strength or chemical resistance even under severe conditions for a long period of time.
【０００７】[0007]
【問題点を解決するための手段】本発明は、従来のかか
る問題点に鑑みてなしたものであって、特定の金属アル
コキシドを添加したテトラアルコキシシランと、特定の
アルキルトリアルコキシシランとをそれぞれ加水分解な
らびに脱水縮合させたそれぞれのゾルゲル溶液を混合す
るとともに、特定の溶剤と混合して調製することでコー
ティング溶液とし、ガラス基板に被膜し薄膜を成膜する
ことで、その性能が優れるコーティング溶液を簡便に得
ることができるとともに、得られたゾルゲル膜が高硬度
かつ高密着性であって耐久性や耐摩耗性とを併せ持ち、
例えば独立してしっかりした特異な微細な凹凸状表面表
層をより安定して発現し、比表面積の増大による被覆膜
の付着効率と密着性の向上をもたらし、格段に優れた下
地層となり、しかも高安全で厄介な工程なく、安価に効
率よく機械的膜強度および耐久性ならびに各種機能を発
揮する酸化物薄膜を得ることができる有用なゾルゲル膜
およびその形成法を提供するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and comprises a tetraalkoxysilane to which a specific metal alkoxide is added and a specific alkyltrialkoxysilane, respectively. A coating solution that has excellent performance by mixing each sol-gel solution that has been hydrolyzed and dehydrated and condensed to prepare a coating solution by mixing with a specific solvent to form a coating film on a glass substrate to form a thin film. Can be easily obtained, the obtained sol-gel film has high hardness and high adhesion, and has durability and abrasion resistance,
For example, it independently and firmly develops a unique fine uneven surface surface layer, which improves the adhesion efficiency and adhesion of the coating film by increasing the specific surface area, resulting in a significantly superior underlayer, and It is intended to provide a useful sol-gel film and a method for forming the same, which makes it possible to obtain an oxide thin film exhibiting mechanical film strength and durability and various functions efficiently at low cost without a highly safe and troublesome process.
【０００８】すなわち、本発明は、ガラス基板の表面上
に、アセチルアセトンで安定化した金属アルコキシドを
添加したテトラアルコキシシランを加水分解ならびに脱
水縮合させたゾル溶液Ａと、１つの官能基をアルキル基
化したアルキルトリアルコキシシランを加水分解ならび
に脱水縮合したゾル溶液Ｂとを混合した混合物と、イソ
プロピルアルコ−ルを主成分とする溶媒とからなるコ−
ティング溶液を被膜し、加熱焼成することで得る微細な
凹凸状表層を有する酸化物薄膜で成ることを特徴とする
ゾルゲル膜。That is, according to the present invention, a sol solution A obtained by hydrolyzing and dehydrating and condensing a tetraalkoxysilane to which a metal alkoxide stabilized with acetylacetone is added, and one functional group is converted into an alkyl group on the surface of a glass substrate. A mixture of a sol solution B obtained by hydrolyzing and dehydrating and condensing the above-mentioned alkyltrialkoxysilane and a solvent containing isopropyl alcohol as a main component.
A sol-gel film comprising an oxide thin film having a fine uneven surface layer obtained by coating with a coating solution and heating and baking.
【０００９】ならびに、前記金属アルコキシドの金属
が、Ti、Al、Zrまたはこれらの複合金属であることを特
徴とする上述したゾルゲル膜。また、前記アセチルアセ
トンで安定化した金属アルコキシドを添加したテトラア
ルコキシシランに対するアルキルトリアルコキシシラン
の混合割合が、酸化物換算で２〜６倍であることを特徴
とする上述したゾルゲル膜。In addition, the sol-gel film described above, wherein the metal of the metal alkoxide is Ti, Al, Zr or a composite metal thereof. Further, the above-mentioned sol-gel film, wherein the mixing ratio of the alkyltrialkoxysilane to the tetraalkoxysilane to which the metal alkoxide stabilized with acetylacetone is added is 2 to 6 times in terms of oxide.
【００１０】さらに、前記イソプロピルアルコ−ルを主
成分とする溶媒が、イソプロピルアルコ−ルにブタノ−
ルを添加した溶媒であることを特徴とする上述したゾル
ゲル膜。Further, the solvent containing isopropyl alcohol as a main component is mixed with isopropyl alcohol butanol.
The sol-gel film as described above, wherein the sol-gel film is a solvent to which a solvent is added.
【００１１】さらにまた、前記コ−ティング溶液におけ
る固形分濃度が、酸化物換算で0.2〜5.0w％であること
を特徴とする上述したゾルゲル膜。さらにまた、前記被
膜時における湿度が、25℃の温度雰囲気下で45〜60％RH
であることを特徴とする上述したゾルゲル膜。Furthermore, the solid content concentration in the coating solution is 0.2 to 5.0 w% in terms of oxide, and the sol-gel film described above. Furthermore, the humidity at the time of the film coating is 45 to 60% RH in a temperature atmosphere of 25 ° C.
The sol-gel film described above.
【００１２】また、ガラス基板の表面上に、アセチルア
セトンで安定化した金属アルコキシドを添加したテトラ
アルコキシシランを加水分解ならびに脱水縮合させたゾ
ル溶液Ａと、１つの官能基をアルキル基化したアルキル
トリアルコキシシランを加水分解ならびに脱水縮合した
ゾル溶液Ｂとを混合し、30℃の保持温度で３〜24時間乃
至50℃の保持温度で１〜12時間攪拌した混合物を作製
し、該混合物をイソプロピルアルコ−ルを主成分とする
溶媒で希釈調製してなるコ−ティング溶液を25℃の温度
雰囲気下で45〜60％RHである湿度環境において被膜し、
乾燥加熱焼成し微細な凹凸状表層を有する酸化物薄膜で
成るようにすることを特徴とするゾルゲル膜の形成法。Further, on the surface of the glass substrate, a sol solution A obtained by hydrolyzing and dehydrating and condensing a tetraalkoxysilane to which a metal alkoxide stabilized with acetylacetone is added, and an alkyltrialkoxy having one functional group alkylated A sol solution B obtained by hydrolyzing and dehydrating and condensing silane was mixed and stirred at a holding temperature of 30 ° C. for 3 to 24 hours to 50 ° C. for 1 to 12 hours to prepare a mixture, and the mixture was mixed with isopropyl alcohol. Coating solution prepared by diluting with a solvent whose main component is a solvent in a humidity environment of 45 to 60% RH under a temperature atmosphere of 25 ° C.,
A method of forming a sol-gel film, characterized by comprising heating and drying to form an oxide thin film having a fine uneven surface layer.
【００１３】さらに、前記前記金属アルコキシドの金属
が、Ti、Al、Zrまたはこれらの複合金属であることを特
徴とする上述したゾルゲル膜の形成法。さらにまた、前
記アセチルアセトンで安定化した金属アルコキシドを添
加したテトラアルコキシシランに対するアルキルトリア
ルコキシシランの混合割合が、酸化物換算で２〜６倍に
なるようにしたことを特徴とする上述したゾルゲル膜の
形成法。The method for forming a sol-gel film as described above, wherein the metal of the metal alkoxide is Ti, Al, Zr or a composite metal thereof. Furthermore, the mixing ratio of the alkyltrialkoxysilane to the tetraalkoxysilane to which the metal alkoxide stabilized with acetylacetone is added is 2 to 6 times in terms of oxide. Forming method.
【００１４】さらにまた、前記イソプロピルアルコ−ル
を主成分とする溶媒が、イソプロピルアルコ−ルにブタ
ノ−ルを添加した溶媒であることを特徴とする上述した
ゾルゲル膜の形成法。Furthermore, the above-mentioned method for forming a sol-gel film, wherein the solvent containing isopropyl alcohol as a main component is a solvent obtained by adding butanol to isopropyl alcohol.
【００１５】さらにまた、前記コ−ティング溶液におけ
る固形分濃度が、酸化物換算で0.2〜5.0w％になるよう
希釈調製することを特徴とする上述したゾルゲル膜の形
成法。Furthermore, the above-mentioned method for forming a sol-gel film is characterized in that the coating solution is diluted to a solid content concentration of 0.2 to 5.0 w% in terms of oxide.
【００１６】またさらに、前記コーティング溶液を、１
〜10cPに粘度調製することでなるコーテイング溶液とす
ることを特徴とする上述したゾルゲル膜の形成法をそれ
ぞれ提供するものである。Further, the coating solution is added to 1
The above-mentioned methods for forming a sol-gel film are provided, each of which is a coating solution prepared by adjusting the viscosity to -10 cP.
【００１７】ここで、前記したように、アセチルアセト
ンで安定化した金属アルコキシドを添加したテトラアル
コキシシランを加水分解ならびに脱水縮合させたゾル溶
液Ａと、１つの官能基がアルキル基化したアルキルトリ
アルコキシシランを加水分解ならびに脱水縮合したゾル
溶液Ｂとを混合した混合物を用いることとしたのは、容
易に溶液調製することができかつポットライフを長くで
き、成膜した前記微細な凹凸状表層の表面形状を有する
ものとなり、かつ機械的膜強度、耐薬品性に優れ、酸化
物薄膜の透明性や硬度が高く、耐久性にも優れたものと
なり、比較的安価で入手し易いものであるので該二つの
ゾル溶液を用いることとした。Here, as described above, a sol solution A obtained by hydrolyzing and dehydrating and condensing a tetraalkoxysilane to which a metal alkoxide stabilized with acetylacetone is added, and an alkyltrialkoxysilane in which one functional group is an alkyl group. The use of a mixture obtained by mixing the sol solution B obtained by hydrolysis and dehydration condensation with is that the solution can be easily prepared and the pot life can be lengthened, and the surface shape of the film-shaped fine uneven surface layer can be formed. And has excellent mechanical film strength and chemical resistance, the transparency and hardness of the oxide thin film are high, and the durability is also excellent. Therefore, it is relatively inexpensive and easily available. It was decided to use one sol solution.
【００１８】また、二つのゾル溶液の一つが、アセチル
アセトンで安定化した金属アルコキシドを添加したテト
ラアルコキシシランである金属アルコキシド系化合物を
用い、加水分解ならびに脱水縮合したゾル溶液Ａと、ゾ
ル溶液のもう一つが１つの官能基をアルキル基化したア
ルキルトリアルコキシシランを用い、加水分解ならびに
脱水縮合したゾル溶液Ｂとしたのは、ゾル溶液Ａでは例
えばーSiーO ーSiー（但し、Siの上下方向の線は省略す
る）三次元構造が発達しやすいものと該骨格が生成しに
くいものを共存させる。一方、ゾル溶液Ｂでは、加水分
解および脱水縮合反応が起こらないアルキル基が存在す
るため、三次元構造のSiーO ーSi結合等の骨格が生成し
にくい。よってゾル溶液Ａとゾル溶液Ｂとを混合するこ
とにより被膜した際に種々の表層が発現するようにな
り、数％程度の異種金属元素が加わることにより、同一
金属元素からなる薄膜を緻密化させる働きが生じ、機械
的膜強度および耐薬品性等耐久性に優れる、しかも制御
されかつ再現性よく安定した形状と性能の微細な凹凸状
表層薄膜となる。Further, one of the two sol solutions uses a metal alkoxide compound which is a tetraalkoxysilane to which a metal alkoxide stabilized with acetylacetone is added, and a sol solution A hydrolyzed and dehydrated and condensed, and another sol solution In the sol solution A, for example, in the sol solution A, -Si-O-Si- (provided that Si-O-Si- (The direction line is omitted.) Coexist with those in which the three-dimensional structure easily develops and those in which the skeleton does not easily form. On the other hand, in the sol solution B, since an alkyl group that does not cause hydrolysis and dehydration condensation reaction is present, a skeleton such as a Si—O—Si bond having a three-dimensional structure is less likely to be generated. Therefore, when the sol solution A and the sol solution B are mixed, various surface layers are developed and a thin film made of the same metal element is densified by adding several% of different metal elements. A fine concavo-convex surface layer thin film having a function and excellent durability such as mechanical film strength and chemical resistance, and having a stable shape and performance which is controlled and reproducible.
【００１９】さらに前記金属としては、格別特定するも
のではないが、Ti、AlまたはZrを選択するのが好まし
く、具体的なものとしては、例えばチタンテトラノルマ
ルブトキシド〔Ti(O-n-Bu)4 Bu:C4H9 〕、アルミニウム
トリノルマルブトキシド〔Al(0-n-Bu)3 〕、ジルコニウ
ムテトラノルマルブトキシド〔Zr(O-n-Bu)4 〕、または
Ti、Al、Zrのアセチルアセトネ−ト塩等が好適である。Further, although the metal is not particularly specified, it is preferable to select Ti, Al or Zr. Specific examples thereof include titanium tetranormal butoxide [Ti (On-Bu) 4 Bu. : C 4 H 9 ], aluminum trinormal butoxide [Al (0-n-Bu) 3 ], zirconium tetranormal butoxide [Zr (On-Bu) 4 ], or
Acetylacetonate salts of Ti, Al and Zr are suitable.
【００２０】またさらに、前記１つの官能基をアルキル
基化したアルキルトリアルコキシシランとしては、具体
的には例えば、メチルトリエトキシシラン〔MeSi(OE
t)3〕、メチルトリメトキシシラン〔MeSi(OMe)3〕等が
好適である。Further, as the alkyltrialkoxysilane in which the one functional group is alkylated, specifically, for example, methyltriethoxysilane [MeSi (OE
t) 3 ], methyltrimethoxysilane [MeSi (OMe) 3 ] and the like are preferable.
【００２１】また、微細な凹凸状表層における形状なら
びにその制御については、先ず前記ゾル溶液Ａおよびゾ
ル溶液Ｂの官能基ならびに分子量であり、特に前記した
ような現象を発現する異種官能基、ことに４と３の官能
基のものが主であり、また例えば分子量としてはその範
囲が100 〜100,000 であり、100 未満では原料の加水分
解が不充分なため被膜時に膜ハジキが生じやすく、成膜
性が悪く、また100,000 を超えるとゾル溶液がゲル化を
生じ、ゾル溶液の安定性が悪くなる。好ましくは1,000
〜50,000程度のものがよい。Regarding the shape of the fine uneven surface layer and its control, firstly, the functional groups and molecular weights of the sol solutions A and B, especially the different functional groups that exhibit the above-mentioned phenomenon, The functional groups of 4 and 3 are mainly used, and the molecular weight is, for example, in the range of 100 to 100,000. If it is less than 100, hydrolysis of the raw material is insufficient and film cissing is likely to occur during film formation. When it exceeds 100,000, the sol solution gels and the stability of the sol solution deteriorates. Preferably 1,000
~ 50,000 is recommended.
【００２２】もしくはならびに前記ゾル溶液の混合物か
らコ−ティング溶液を調製する際の溶剤の種類であり、
イソプロピルアルコ−ル、ブタノ−ル、エタノ−ルのア
ルコ−ル溶媒であり、ことにイソプロピルアルコールを
主成分としてなるアルコールであって、なかでもコ−テ
ィング溶液の調製における希釈溶媒としては、イソプロ
ピルアルコールにブタノ−ルを約10wt％添加した希釈溶
媒がよく、得られる薄膜の微細な凹凸状表層の表面形状
の発現の安定性に役立つこととなる。And / or the kind of the solvent used for preparing the coating solution from the mixture of the sol solutions,
Isopropyl alcohol, butanol, ethanol alcohol solvent, especially an alcohol containing isopropyl alcohol as a main component, among which isopropyl alcohol is used as a diluting solvent in the preparation of the coating solution. It is preferable to use a diluting solvent containing butanol in an amount of about 10% by weight, and this will help stabilize the development of the surface profile of the fine uneven surface layer of the resulting thin film.
【００２３】もしくはならびにゾル溶液における酸化物
換算での固形分の混合比であり、例えばゾル溶液Ａの固
形分１ｇに対してゾル溶液Ｂの固形分は２〜６ｇ程度で
あり、２ｇ未満では得られた薄膜の表層が平坦状にな
り、また６ｇを超えると得られる薄膜の表層は粗大化す
ることとなり、所期のめざすものとはならない。好まし
くはゾル溶液Ａの固形分１ｇに対してゾル溶液Ｂの固形
分は2.5 〜5.5ｇ程度である。Alternatively, it is the mixing ratio of the solid content of the sol solution in terms of oxide. For example, the solid content of the sol solution B is about 2 to 6 g with respect to 1 g of the solid content of the sol solution A. The surface layer of the obtained thin film becomes flat, and when it exceeds 6 g, the surface layer of the obtained thin film becomes coarse, which is not what is expected. Preferably, the solid content of the sol solution B is about 2.5 to 5.5 g per 1 g of the solid content of the sol solution A.
【００２４】さらに、被膜する際の環境、とくに温度と
相対湿度、例えばことに約25℃の温度雰囲気下で45〜60
％程度にコントロールすることによっても、種々の表層
形状ならびにその径を再現性よく安定制御し得ることも
ある。Furthermore, in the environment for coating, in particular in temperature and relative humidity, for example in the temperature atmosphere of about 25 ° C., 45-60%.
By controlling to about 10%, various surface layer shapes and their diameters may be reproducibly and stably controlled.
【００２５】さらに、前記コーテイング溶液の粘度を１
〜10cPに調製するのは、１cP未満では粘性が低すぎて膜
となり難く、また10cPを超えると被膜した際に過剰に塗
膜され加熱乾燥過程で膜中にクラツク等が生じてしまう
ためである。Further, the viscosity of the coating solution is 1
The reason for adjusting to 10 cP is that if it is less than 1 cP, the viscosity is too low to form a film, and if it exceeds 10 cP, the film is excessively coated when coated and cracks and the like occur in the film during the heating and drying process. .
【００２６】またさらに、前記コーテイング溶液の酸化
物換算固形分濃度を0.2 〜5.0 wt％としたのは、0.2 wt
％未満では希薄すぎるため膜の形態となり難く、また5.
0 wt％を超えると濃度が高すぎるため膜厚が厚くなり、
膜中にクラツクの発生を生じたりあるいは成膜時に白濁
を生じたりして良質な薄膜が得られないこととなるもの
である。Furthermore, the solid concentration of the coating solution in terms of oxide is 0.2 to 5.0 wt%, which is 0.2 wt.
If it is less than%, it is too thin and it is difficult to form a film.
If it exceeds 0 wt%, the concentration will be too high and the film thickness will increase.
A crack is generated in the film, or white turbidity is generated during the film formation, so that a high quality thin film cannot be obtained.
【００２７】さらにまた、ガラス基板への膜付け法とし
ては、ノズルフロ−コ−ト法、ディッピング法、スプレ
ー法、フローコート法あるいはスピンコート法、ならび
にそれらの併用等既知の塗布手段を適宜採用し得るもの
である。Further, as a method for applying a film on a glass substrate, a known coating means such as a nozzle flow coating method, a dipping method, a spraying method, a flow coating method or a spin coating method, and a combination thereof are appropriately adopted. I will get it.
【００２８】また前記下地層であるゾルゲル膜の成膜す
る際における風乾等の乾燥後の加熱温度については、10
0 ℃以上700 ℃以下程度、好ましくは約500 ℃程度以上
670℃以下程度、さらに薄膜をより強固にするため、例
えば600 ℃程度あるいはそれ以上の温度による焼成であ
って、具体的にはガラス板の曲げあるいは／および強化
工程における温度であり、該温度でも消失することもな
く、種々の前記表面形状表層とすることができるもので
ある。Regarding the heating temperature after drying such as air drying when forming the sol-gel film as the underlayer,
0 ℃ or more and 700 ℃ or less, preferably about 500 ℃ or more
In order to further strengthen the thin film at about 670 ° C or lower, for example, firing at a temperature of about 600 ° C or higher, specifically, the temperature in the bending and / or strengthening step of the glass plate, Various surface shape surface layers can be formed without disappearing.
【００２９】さらにまた、前記ガラス基板としては、フ
ロ−トガラス等各種無機質の透明板ガラスであって、無
色または着色、ならびにその種類あるいは色調、形状等
に特に限定されるものではなく、さらに曲げ板ガラスと
してはもちろん、各種強化ガラスや強度アップガラス、
平板や単板で使用できるとともに、複層ガラスあるいは
合せガラスとしても使用できることは言うまでもない。Further, the glass substrate is a transparent glass plate made of various inorganic materials such as float glass, and is not particularly limited to colorless or colored, and its kind, color tone, shape, etc. Of course, various tempered glass and strength up glass,
It goes without saying that it can be used as a flat plate or a single plate, and can also be used as a multilayer glass or a laminated glass.
【００３０】[0030]
【作用】前述したとおり、本発明の微細な凹凸状表層を
有するゾルゲル膜ならびにその形成法により、上述した
アセチルアセトンで安定化した金属アルコキシドを添加
したテトラアルコキシシランである４官能を有するもの
と、１つの官能基をアルキル基化したアルキルトリアル
コキシシランである３官能を有するものとの二つの特定
系化合物を加水分解ならびに脱水縮合した２種類のゾル
溶液を、特定の希釈溶媒で希釈して特定選択し組み合わ
せて調製し用いることによってコーテイング溶液を得、
さらによりよくは特定環境のなかで成膜することによ
り、コーテイング溶液として簡便に調合調製ができしか
も優れた安定性とその性能を有するものとでき、被膜で
特異な挙動を発現せしめて特異な形状構造をもたらし、
加熱乾燥または焼成および高温焼成等を行うことによ
り、緻密化して平坦化することなく、従来より独立性等
があって深見のある、明確でしっかりし安定した微細な
凹凸状表層となり、かつ膜強度の高い酸化物薄膜とな
り、しかも表面表層を制御でき、付着性も向上し強固な
薄膜とすることができ、ガラス基板との界面はもちろ
ん、多層膜での被覆膜との膜と膜の界面においても密着
性を格段に向上せしめ、被覆含浸または化学的結合をさ
せた撥水性薄膜等機能性薄膜を含め優れた機械的強度、
耐候性、耐久性を有するものとなり、従来より格段に長
期的に及ぶ優れた耐久性を有するものとなり、透明で硬
度が高い、しかも光学特性等も充分に満足できるものと
でき、屋外でも使用できることはもちろんであり、高安
全で厄介な工程なく、安価に効率よく得られることとな
るものであり、ことに建築用はもちろん、自動車用等の
車輌用の窓材として格段に有用である。As described above, according to the sol-gel film having the fine uneven surface layer of the present invention and the method for forming the sol-gel film, the tetraalkoxysilane, which is a tetraalkoxysilane to which the metal alkoxide stabilized with acetylacetone is added, and 1 Specific selection by diluting two kinds of sol solutions obtained by hydrolyzing and dehydrating and condensing two specific compounds, one having an alkyltrialkoxysilane having three functional groups with one functional group being an alkyl group, with a specific diluting solvent A coating solution is obtained by preparing and using a combination of
Even better, by forming a film in a specific environment, it can be easily prepared as a coating solution and has excellent stability and its performance. Bring structure,
By performing heat-drying or baking and high-temperature baking, it becomes a fine, concavo-convex surface layer that is clearer, more stable and stable, with more independence and deeper than before, without densification and flattening. The oxide thin film has a high heat resistance, the surface layer can be controlled, the adhesion can be improved, and a strong thin film can be formed. Not only the interface with the glass substrate but also the interface between the film and the coating film in the multilayer film In addition, the adhesiveness is remarkably improved, and excellent mechanical strength including functional thin films such as coating-impregnated or chemically bonded water-repellent thin films,
It has weather resistance and durability, and has excellent durability for a significantly longer period than before, and it is transparent and has high hardness, and its optical characteristics can be sufficiently satisfied, and it can be used outdoors. Of course, it is highly safe and can be obtained efficiently at low cost without troublesome processes, and is particularly useful as a window material for vehicles such as automobiles as well as construction.
【００３１】[0031]
【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。The present invention will be described below in detail with reference to examples. However, the present invention is not limited to the embodiment.
【００３２】実施例１ 大きさ約100mm ｘ100mm 、厚さ約２mmのクリア・フロ−
トガラス基板を中性洗剤、水すすぎ、アルコ−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 flow having a size of about 100 mm x 100 mm and a thickness of about 2 mm.
The glass substrate was sequentially washed with a neutral detergent, rinsed with water and alcohol, dried and then wiped with acetone to obtain a glass substrate for coating.
【００３３】テトラエトキシシラン（Si（OC2H5)4 ：TE
0S）の重合ゾル（平均分子量 Mv=約2000〜3000）とアセ
チルアセトンで安定化したテトラブトキシチタン（Ti(O
-Bu) 4 ）との混合ゾル（アセチルアセトンで安定化した
テトラブトキシチタンの含有量は酸化物換算でSiO2に対
して約0.25wt％、モル比で約 20mol％である）を、イソ
プロピルアルコ−ル（iPA ）、ブタノ−ル、エタノ−ル
のアルコ−ル溶媒を加え、固形分濃度として酸化物換算
で約５wt％になるまで希釈したものをゾル溶液Ａとし
た。〔例えば、大八化学工業（株）製、CG19-Ti-1 〕 メチルトリメトキシシラン（CH3Si(OCH3)3：MTMS）の重
合ゾル（平均分子量 Mv=約1,000 ）にイソプロピルアル
コ−ル（iPA ）を加え、固形分濃度として酸化物換算で
約20wt％になるまで希釈したものをゾル溶液Ｂとした。
〔例えば、大八化学工業（株）製、MTS-2 〕 上記ゾル溶液Ａ20ｇとゾル溶液Ｂ20ｇと、加水分解およ
び脱水縮合反応の反応速度を調整するため調合用ブタノ
−ル（BuOH、水分量2000ppm 、例えば150 〜3500ppm の
範囲であればよい）約50ｇを約50℃で約3 時間密栓状態
で混合攪拌し、さらに90wt％iPA ／10wt％BuOHの混合系
溶媒で希釈してコ−テイング溶液を得た。この際の固形
分濃度は酸化物換算で約0.5 〜0.6w％程度であった。Tetraethoxysilane (Si (OC2HFive)Four: TE
0S) polymerized sol (average molecular weight Mv = approximately 2000-3000)
Tetrabutoxytitanium (Ti (O
-Bu) Four ) Mixed sol (stabilized with acetylacetone)
The content of tetrabutoxy titanium is SiO in terms of oxide.2Against
Is about 0.25 wt% and the molar ratio is about 20 mol%).
Propyl alcohol (iPA), butanol, ethanol
Alcohol solvent is added to convert the solid content to oxide.
Sol solution A diluted to approximately 5 wt%
Was. [For example, Daihachi Chemical Industry Co., Ltd., CG19-Ti-1] Methyltrimethoxysilane (CH3Si (OCH3)3: MTMS)
Combined sol (average molecular weight Mv = about 1,000) with isopropyl alcohol
Call (iPA) was added, and the solid content concentration was converted to oxide.
The sol solution B was diluted to about 20 wt%.
[For example, MTS-2 manufactured by Daihachi Chemical Industry Co., Ltd.] 20 g of the sol solution A and 20 g of the sol solution B described above are used for hydrolysis and hydrolysis.
Butano for compounding to control the reaction rate of the condensation reaction
-BuOH, water content 2000ppm, for example 150 to 3500ppm
It should be in the range) About 50g sealed at about 50 ℃ for about 3 hours
Mix with and stir, then mix system of 90wt% iPA / 10wt% BuOH
Diluted with a solvent to obtain a coating solution. Solid at this time
The concentration was about 0.5 to 0.6 w% in terms of oxide.
【００３４】なお上述したなかで、ゾル溶液Ａとゾル溶
液Ｂとの比は固形分の重量比で約１：４程度、より好ま
しい当該比は約１：3.5 〜5.5 程度である。またなお混
合後の攪拌時間は、例えば好ましい当該攪拌時間は約50
℃の温度であれば１〜６時間（蜜栓）程度乃至約30℃の
温度であれば３〜６時間（蜜栓）程度である。In the above description, the ratio of the sol solution A to the sol solution B is about 1: 4 by weight of the solid content, and the more preferable ratio is about 1: 3.5 to 5.5. The stirring time after mixing is, for example, preferably about 50.
If the temperature is ℃, it is about 1 to 6 hours (honey plug) to about 30 ° C., it is about 3 to 6 hours (honey plug).
【００３５】ついで、該コーテイング溶液をノズルフロ
−コ−ト法により、前記ガラス基板表面に、約25℃、相
対湿度約45％RH、約50％RH、約55％RH、約60％RHの環境
で塗布被膜し、約５分間放置し風乾し、微細な凹凸状表
層を発現形成しているゲル膜を成膜性よく成膜した。続
いて約250 ℃で約30分間加熱仮焼成した後、さらに約60
0 ℃で約３分間加熱本焼成し、膜厚約60nmの SiO2-TiO2
薄膜を有する薄膜を得た。なお当該仮焼成段階で溶媒や
有機物が蒸発または分解し膜の硬さが増大し、さらに本
焼成で有機物、アルキル基、アルコキシル基等の分解が
進み、膜硬度は飛躍的に増大する。Then, the coating solution is applied to the surface of the glass substrate by a nozzle flow coating method at about 25 ° C., relative humidity of about 45% RH, about 50% RH, about 55% RH, about 60% RH. Then, the gel film was applied and coated, and allowed to stand for about 5 minutes and air-dried to form a gel film expressing a fine uneven surface layer with good film-forming property. Then, heat calcination at about 250 ° C for about 30 minutes, and then about 60
Main firing is performed by heating at 0 ℃ for about 3 minutes, and the film thickness of SiO 2 -TiO 2 is about 60 nm.
A thin film having a thin film was obtained. The solvent and organic substances are evaporated or decomposed in the calcination stage to increase the hardness of the film, and the main calcination further decomposes the organic substances, alkyl groups, alkoxyl groups and the like, resulting in a dramatic increase in the film hardness.
【００３６】得られたゾルゲル膜（下地層）の評価を下
記のように行った。 〔表層表面形状の観察〕成膜時の湿度を温度25℃で約45
％RH、約50％RH、約55％RH、約60％RHのそれぞれについ
て、該薄膜表層の表面形状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図１乃至４に示す。また原子
力間電子顕微鏡による表面形状状態を観察し図５乃至８
に示す。これらから明らかに所期の微細な凹凸状表層と
なっていた。 〔初期ヘイズ（曇価）値Ｈ％〕ヘイズメ−タ−による測
定で約0.1 ％程度であり、ガラス基板並で良好であっ
た。 〔耐摩耗性〕テ−バ−摩耗試験において、摩耗輪CS-10F
で20回転後のヘイズ値の増加分△Ｈ＝約0.2 ％程度であ
り、ガラス基板並の膜硬度を示しきわめて良好であっ
た。The sol-gel film (underlayer) thus obtained was evaluated as follows. [Observation of surface morphology] Humidity during film formation is about 45 at 25 ℃
The surface morphology of the surface layer of the thin film for each of% RH, about 50% RH, about 55% RH, and about 60% RH was observed by a scanning electron microscope at a magnification of about 20,000 and is shown in FIGS. Also, the state of the surface shape was observed by an atomic force electron microscope and the results shown in FIGS.
Shown in From these, it was clearly the desired fine uneven surface layer. [Initial haze (cloudiness value) H%] It was about 0.1% as measured by a haze meter, which was as good as that of a glass substrate. [Abrasion resistance] Wear wheel CS-10F in a table abrasion test
The increase in haze value after 20 rotations was about ΔH = about 0.2%, and the film hardness was as good as that of a glass substrate, which was extremely good.
【００３７】さらに次いで該 SiO2-TiO2薄膜を下地層と
した際についてその効果を確認するため、当該薄膜上
に、例えば予めヘプタデカトリデシルフルオロアルキル
シラン〔CF3(CF2)7CH2CH2Si(OCH3)3〕１ｇとiPA 約５
ｇ、60％硝酸１ｇをビーカーに入れ、常温で充分に混合
攪拌し、フルオロアルキルトリメトキシシランの部分加
水分解溶液を調製したものを塗布し、約140 ℃ならびに
約250 ℃に設定された電気炉に約30分間入れ焼成し、撥
水処理を行い、撥水性酸化物被膜を得た。Next, in order to confirm the effect when the SiO 2 —TiO 2 thin film is used as an underlayer, for example, heptadecatridecyl fluoroalkylsilane [CF 3 (CF 2 ) 7 CH 2 is previously formed on the thin film. CH 2 Si (OCH 3 ) 3 ] 1g and iPA about 5
g, 1g of 60% nitric acid in a beaker, mix and stir at room temperature thoroughly, apply a partially hydrolyzed fluoroalkyltrimethoxysilane solution, and apply it to an electric furnace set at about 140 ° C and about 250 ° C. Then, it was put in a sol. For about 30 minutes and baked to carry out water repellent treatment to obtain a water repellent oxide film.
【００３８】得られた撥水処理ガラスの評価を下記のよ
うに行った。 〔撥水性試験〕該被膜の大気中（約25℃）での水に対す
る接触角を、協和界面科学製CA-A型を用いて測定した。
その結果、初期接触角は約112 °と良好であった。The water-repellent treated glass thus obtained was evaluated as follows. [Water repellency test] The contact angle of the coating film with respect to water in the atmosphere (about 25 ° C) was measured using CA-A type manufactured by Kyowa Interface Science.
As a result, the initial contact angle was good at about 112 °.
【００３９】さらに初期転落角は45μl の水滴で約30°
と良好であった。 〔上水を用いた耐摺動試験〕該被膜を自動車用ワイパー
ブレードによる摺動耐久性により評価した。Further, the initial falling angle is about 30 ° with a water droplet of 45 μl.
And was good. [Sliding resistance test using tap water] The coating was evaluated by sliding durability with an automobile wiper blade.
【００４０】条件：上水を流しながら約15ｇ／cmの荷重
をかけて約18万回（往復を１回とする）摺動を行い、接
触角の低下量と、摺動後のサンプルのキズの発生の有無
を目視により評価した。Conditions: Performing sliding about 180,000 times (one reciprocation once) by applying a load of about 15 g / cm while running clean water, decreasing the contact angle and scratching the sample after sliding. The presence or absence of occurrence was visually evaluated.
【００４１】その結果、初期接触角が約112 °で、約18
万回摺動後の接触角は上記約250 ℃焼成の際約83°程
度、上記約140 ℃焼成の際約80°程度であり、耐久性の
高いものであった。また摺動後のサンプルにはキズの発
生はなかった。 〔汚水を用いた耐摺動試験〕該被膜を自動車用ワイパー
ブレードによる摺動耐久性により評価した。As a result, the initial contact angle is about 112 °, and the initial contact angle is about 18 °.
The contact angle after sliding 10,000 times was about 83 ° when firing at about 250 ° C. and about 80 ° when firing at about 140 ° C., indicating high durability. No scratches were found on the sample after sliding. [Sliding resistance test using dirty water] The coating was evaluated by sliding durability with an automobile wiper blade.
【００４２】条件：汚水を流しながら約15ｇ／cmの荷重
をかけて約７千回（往復を１回とする）摺動を行い、接
触角の低下量と、摺動後のサンプルのキズの発生の有無
を目視により評価した。（汚水は、JIS Z 8901に規定す
る１種、２種及び８種の３種類のダストを配合比１：7
0：29の割合に配合して混合し、水に対し 0.5wt％混合
ダスト濃度としたもの） その結果、初期接触角が約112 °で、約７千回摺動後の
接触角は上記約250 ℃ならびに約140 ℃焼成の際約100
°程度であり、耐久性の高いものであった。また摺動後
のサンプルへのキズの発生は実用上全く問題になるほど
ではなく良好であった。 〔耐候性試験〕該被膜をスーパーUV耐候促進試験により
評価した。Conditions: Approximately 7,000 times (one reciprocation) was slid by applying a load of about 15 g / cm while flowing sewage, and the decrease in contact angle and scratches on the sample after sliding The presence or absence of occurrence was visually evaluated. (As for sewage, the mixing ratio of 1 type, 2 types and 8 types of dust specified in JIS Z 8901 is 1: 7.
As a result, the initial contact angle was about 112 °, and the contact angle after sliding about 7,000 times was about the above value. About 100 at 250 ℃ and about 140 ℃
The degree was about ° and the durability was high. In addition, the scratches on the sample after sliding were so good as not to pose any problem in practical use. [Weather resistance test] The coating was evaluated by a super UV weather resistance accelerated test.
【００４３】条件：約75mW／cm2 、ランプとサンプル間
距離約25mm、温度約35℃、湿度約50％RHで約 900時間の
耐久性試験を行った。 その結果、初期接触角が約112 °程度が、約900 時間経
過後でも約90°程度に留まり、例えば75°±5 °程度を
合格基準とすれば、これは約３年間程度高い撥水性を保
持することに相当する等耐候性の高いものであり、自動
車用フロント、ドアならびにバック等の窓ガラスに対し
て充分な薄膜であった。Conditions: A durability test was conducted for about 900 hours at about 75 mW / cm 2 , a distance between a lamp and a sample of about 25 mm, a temperature of about 35 ° C. and a humidity of about 50% RH. As a result, the initial contact angle was about 112 °, but it remained at about 90 ° even after about 900 hours. For example, if about 75 ° ± 5 ° was used as the acceptance criterion, it would have high water repellency for about 3 years. The film had high weather resistance equivalent to holding, and was a sufficiently thin film for window glasses of automobile fronts, doors and backs.
【００４４】なお本発明のゾルゲル膜でなる下地層を施
すことなく、直接ガラス面に上記撥水処理を行ったとこ
ろ、初期接触角が約105 °程度が、約230 時間経過後約
60°程度に低下した。When the above-mentioned water repellent treatment was performed directly on the glass surface without applying the underlayer made of the sol-gel film of the present invention, the initial contact angle was about 105 °, but after about 230 hours,
It decreased to about 60 °.
【００４５】実施例２ 実施例１と同様なガラス基板に、実施例１のテトラブト
キシチタン〔Ti(O-Bu) 4 〕に替えてトリブトキシアルミ
ニウム〔Al(O-Bu)3 〕を用い、他は実施例１と同様に溶
液ＡとＢを得た。次いで攪拌条件のみ約30℃で約６時間
（蜜封）と替え他は実施例１と同様に調製しコーテイン
グ溶液とした。[0045]Example 2 On the same glass substrate as in Example 1, the tetrabutane of Example 1 was added.
Xytitanium (Ti (O-Bu) Four] In place of tributoxy aluminum
Nium (Al (O-Bu)3], And the same as in Example 1 except that
Liquids A and B were obtained. Next, only stirring conditions at about 30 ℃ for about 6 hours
Preparation with the same procedure as in Example 1 except for (honey sealed)
Solution.
【００４６】次いで、環境湿度のみ約53％RHと替えたの
みで、実施例１と同様の成膜法で成膜した。得られた膜
厚約74nm程度の Al2O3・SiO2薄膜は、該ゾルゲル膜の表
面形状状態を走査型電子顕微鏡により約２万倍の倍率で
観察したところ、図９に示すように、実施例１と同様の
微細な凹凸状表層を示し、初期ヘイズ値Ｈは約0.1 ％程
度であり、テ−バ−摩耗試験後の△Ｈは約0.6 程度と膜
硬度がやや劣るものの自動車用ドアならびにバック窓ガ
ラスに対しては充分耐えうるものである。Then, only the environmental humidity was changed to about 53% RH, and a film was formed by the same film forming method as in Example 1. The obtained Al 2 O 3 .SiO 2 thin film with a thickness of about 74 nm was observed with a scanning electron microscope at a magnification of about 20,000 to observe the surface shape of the sol-gel film. It shows a fine uneven surface layer similar to that of Example 1, the initial haze value H is about 0.1%, and the ΔH after the Taber abrasion test is about 0.6, which is a little inferior in film hardness, but it is an automobile door. In addition, it can sufficiently withstand the back window glass.
【００４７】該薄膜を下地層として実施例１と同様に用
いた際、実施例１とほぼ同様の結果を得た。比較例１ 実施例１でのゾル溶液Ａとゾル溶液Ｂの固形分の比を
１：２に替え、攪拌時間を約30℃で約６時間（蜜封）に
替えたのみでそれ以外は実施例１と同様にしてゾルゲル
膜を得た。When the thin film was used as an underlayer in the same manner as in Example 1, almost the same results as in Example 1 were obtained. Comparative Example 1 The ratio of the solid content of the sol solution A and the sol solution B in Example 1 was changed to 1: 2, and the stirring time was changed to about 6 hours (honey comb) at about 30 ° C. A sol-gel film was obtained in the same manner as in Example 1.
【００４８】該ゾルゲル膜の表面形状状態を走査型電子
顕微鏡により約２万倍の倍率で観察したところ、図10に
示すように、フラットな表層面である他は、実施例１と
同様であるも、所期のめざすゾルゲル膜ではなかった。When the surface shape of the sol-gel film was observed with a scanning electron microscope at a magnification of about 20,000, it was the same as that of Example 1 except that it was a flat surface layer, as shown in FIG. However, it was not the desired sol-gel film.
【００４９】比較例２ 実施例１において、成膜時の湿度を約25℃で約40％RHと
したのみで成膜した。その結果、該ゾルゲル膜の表面形
状状態を走査型電子顕微鏡により約２万倍の倍率で観察
したところ、図11に示すように、フラットな表層面であ
る他は、実施例１と同様であるも、所期のめざすゾルゲ
ル膜ではなかった。 Comparative Example 2 In Example 1, the film was formed only by setting the humidity during film formation to about 40% RH at about 25 ° C. As a result, when the surface shape of the sol-gel film was observed with a scanning electron microscope at a magnification of about 20,000, it was the same as that of Example 1 except that it was a flat surface layer as shown in FIG. However, it was not the desired sol-gel film.
【００５０】比較例３ 実施例１において、ゾル溶液Ａとゾル溶液Ｂの固形分の
比を１：６に替え、攪拌時間を約30℃で約24時間（蜜
封）に替えたのみでそれ以外は実施例１と同様にしてゾ
ルゲル膜を得た。 Comparative Example 3 In Example 1, the solid content ratio of the sol solution A and the sol solution B was changed to 1: 6, and the stirring time was changed to about 24 hours at about 30 ° C. (honey sealed). A sol-gel film was obtained in the same manner as in Example 1 except for the above.
【００５１】その結果、該ゾルゲル膜の表面形状状態を
走査型電子顕微鏡により約２万倍の倍率で観察したとこ
ろ、図12に示すように、粗な凸状表層面である他は、実
施例１と同様であったものの、表層表面の粗大化の割り
に表面積の増大は小さく、到底微細な凹凸状表層とは言
い難いく所期のめざすゾルゲル膜ではなかった。As a result, the state of the surface shape of the sol-gel film was observed with a scanning electron microscope at a magnification of about 20,000. As a result, as shown in FIG. Although it was the same as that of No. 1, the surface area did not increase in spite of the coarsening of the surface layer, and it was not the intended sol-gel film that could not be said to be an extremely fine uneven surface layer.
【００５２】比較例４ 実施例１において、希釈溶媒を90wt％iPA ／10wt％BuOH
の混合系溶媒ではなくiPA 単一系とし替えた場合であっ
て、それ以外は実施例１と同様にしてゾルゲル膜を得
た。 Comparative Example 4 In Example 1, the diluting solvent was 90 wt% iPA / 10 wt% BuOH.
A sol-gel film was obtained in the same manner as in Example 1 except that the iPA single system was used instead of the mixed solvent of 1.
【００５３】その結果、膜ハジキがなく成膜性がよく所
望の微細な凹凸状をもたらす湿度の範囲が極端に狭いだ
けでなく、成膜性と表面形状の両方を所期のめざすもの
に両立させる範囲が存在しないと言えるものであった。As a result, not only the film repellency is excellent but the film-forming property is good, and the range of humidity for producing the desired fine irregularities is not only extremely narrow, but also both the film-forming property and the surface shape are compatible for the intended purpose. It could be said that there is no range to make it.
【００５４】なお、希釈溶媒のBuOHに替えて、例えば酢
酸n-ブチル、エチルセロソルブ、エタノ−ル（EtOH）の
系では成膜性と表面形状の両方を所期のめざすものに両
立させる範囲が存在しない系であり、また例えば1-プロ
パノ−ル、2-メチル-1- プロパノ−ルの系では成膜性と
表面形状の両方を所期のめざすものに両立させる範囲は
非常に狭い系である。In place of BuOH as a diluting solvent, for example, in a system of n-butyl acetate, ethyl cellosolve, and ethanol (EtOH), there is a range in which both the film forming property and the surface shape are compatible with the intended one. It is a system that does not exist, and for example, in the system of 1-propanol and 2-methyl-1-propanol, the range in which both the film-forming property and the surface shape are compatible with the intended one is very narrow. is there.
【００５５】[0055]
【発明の効果】以上前述したように、本発明によれば、
コ−ティング溶液としてより簡単に調合調製できかつ飛
躍的な安定性および性能を発揮し、より簡便に容易な膜
形成手段でもって特異な薄膜を安価に効率よく得られ、
特定の二つを選択したゾル溶液ならびに希釈溶液を巧み
な組み合わせることによって、特異な形状を有する強固
な微細な凹凸状表層が得られるようになって多層膜の下
地層薄膜として格段にその性能を発揮し、その表面に優
れた撥水性能薄膜等各種機能性薄膜を被膜して、光学特
性を損なうことなく、撥水性能等各種性能が優れること
はもとより、密着性、ことに機械的強度、耐候性等の耐
久性に優れるものとなり、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、有用な微細な凹凸状表層を有す
るゾルゲル膜およびその形成法を提供するものである。As described above, according to the present invention,
It can be easily prepared and prepared as a coating solution and exhibits dramatic stability and performance, and a peculiar thin film can be obtained efficiently at low cost by a simple and easy film forming means,
By skillfully combining sol solutions and dilute solutions selected from two specific ones, it is possible to obtain a strong fine uneven surface layer with a unique shape, and its performance is dramatically improved as a base layer thin film of a multilayer film. It exhibits excellent water repellency performance thin film on its surface, and various functional thin films such as water repellency performance are not impaired, and various performances such as water repellency performance are excellent, as well as adhesion, mechanical strength, It has excellent durability such as weather resistance, and can be widely used for various coating films such as window materials for construction or automobiles, various glass articles, etc. It has high utility value and has a useful fine rugged surface layer. A film and a method for forming the film are provided.
【図１】実施例１における、湿度45％RHで成膜した本発
明のゾルゲル膜の表層面を、走査型電子顕微鏡により約
２万倍の倍率で観察処理した写真であって、微細な凹凸
状表層の状態を示す図である。FIG. 1 is a photograph of a surface layer surface of a sol-gel film of the present invention formed at a humidity of 45% RH in Example 1, which is observed with a scanning electron microscope at a magnification of about 20,000 times, showing fine irregularities. It is a figure which shows the state of the surface layer.
【図２】実施例１における、湿度50％RHで成膜した本発
明のゾルゲル膜の表層面を、走査型電子顕微鏡により約
２万倍の倍率で観察処理した写真であって、微細な凹凸
状表層の状態を示す図である。FIG. 2 is a photograph of the surface layer surface of the sol-gel film of the present invention formed at a humidity of 50% RH in Example 1, which is observed with a scanning electron microscope at a magnification of about 20,000 times, showing fine irregularities. It is a figure which shows the state of the surface layer.
【図３】実施例１における、湿度55％RHで成膜した本発
明のゾルゲル膜の表層面を、走査型電子顕微鏡により約
２万倍の倍率で観察処理した写真であって、微細な凹凸
状表層の状態を示す図である。FIG. 3 is a photograph of the surface layer surface of the sol-gel film of the present invention formed at a humidity of 55% RH in Example 1, observed with a scanning electron microscope at a magnification of about 20,000 times, showing fine irregularities. It is a figure which shows the state of the surface layer.
【図４】実施例１における、湿度60％RHで成膜した本発
明のゾルゲル膜の表層面を、走査型電子顕微鏡により約
２万倍の倍率で観察処理した写真であって、微細な凹凸
状表層の状態を示す図である。FIG. 4 is a photograph obtained by observing the surface layer surface of the sol-gel film of the present invention formed at a humidity of 60% RH in Example 1 with a scanning electron microscope at a magnification of about 20,000 times. It is a figure which shows the state of the surface layer.
【図５】実施例１における、湿度45％RHで成膜した本発
明のゾルゲル膜の表層面を、原子力間電子顕微鏡により
観察した写真であって、微細な凹凸状表層の状態を示す
図である。5 is a photograph of the surface layer surface of the sol-gel film of the present invention formed at a humidity of 45% RH in Example 1, observed by an atomic force electron microscope, showing a state of a fine uneven surface layer. FIG. is there.
【図６】実施例１における、湿度50％RHで成膜した本発
明のゾルゲル膜の表層面を、原子力間電子顕微鏡により
観察した写真であって、微細な凹凸状表層の状態を示す
図である。FIG. 6 is a photograph of the surface layer surface of the sol-gel film of the present invention formed in Example 1 at a humidity of 50% RH, observed by an atomic force electron microscope, showing a state of a fine uneven surface layer. is there.
【図７】実施例１における、湿度55％RHで成膜した本発
明のゾルゲル膜の表層面を、原子力間電子顕微鏡により
観察した写真であって、微細な凹凸状表層の状態を示す
図である。7 is a photograph of the surface layer surface of the sol-gel film of the present invention formed at a humidity of 55% RH in Example 1, observed by an atomic force electron microscope, showing a state of a fine uneven surface layer. FIG. is there.
【図８】実施例１における、湿度60％RHで成膜した本発
明のゾルゲル膜の表層面を、原子力間電子顕微鏡により
観察した写真であって、微細な凹凸状表層の状態を示す
図である。8 is a photograph of the surface layer surface of the sol-gel film of the present invention formed at a humidity of 60% RH in Example 1, observed by an atomic force electron microscope, showing a state of a fine uneven surface layer. FIG. is there.
【図９】実施例２におけるゾルゲル膜の表層面を、走査
電子顕微鏡により約２万倍の倍率で観察処理した写真で
あり、微細な凹凸状表層の状態を示す図である。9 is a photograph obtained by observing the surface layer surface of the sol-gel film in Example 2 with a scanning electron microscope at a magnification of about 20,000 times, showing a state of a fine uneven surface layer. FIG.
【図10】比較例１における、ゾルゲル膜の表層面を、走
査電子顕微鏡により約２万倍の倍率で観察処理した写真
であり、フラット表層の状態を詳細に示す図である。FIG. 10 is a photograph of the surface layer surface of the sol-gel film in Comparative Example 1, which was observed with a scanning electron microscope at a magnification of about 20,000 times, and is a diagram showing the state of the flat surface layer in detail.
【図11】比較例２における、ゾルゲル膜の表層面を、走
査電子顕微鏡により約２万倍の倍率で観察処理した写真
であり、フラット表層の状態を詳細に示す図である。FIG. 11 is a photograph in which the surface layer surface of the sol-gel film in Comparative Example 2 is observed by a scanning electron microscope at a magnification of about 20,000 times, and is a diagram showing a state of a flat surface layer in detail.
【図12】比較例３における、ゾルゲル膜の表層面を、走
査電子顕微鏡により約２万倍の倍率で観察処理した写真
であり、粗な凸状表層の状態を詳細に示す図である。FIG. 12 is a photograph in which the surface layer surface of the sol-gel film in Comparative Example 3 is observed by a scanning electron microscope at a magnification of about 20,000 times, and is a diagram showing in detail the state of a rough convex surface layer.
Claims (12)
ンで安定化した金属アルコキシドを添加したテトラアル
コキシシランを加水分解ならびに脱水縮合させたゾル溶
液Ａと、１つの官能基をアルキル基化したアルキルトリ
アルコキシシランを加水分解ならびに脱水縮合したゾル
溶液Ｂとを混合した混合物と、イソプロピルアルコ−ル
を主成分とする溶媒とからなるコ−ティング溶液を被膜
し、加熱焼成することで得る微細な凹凸状表層を有する
酸化物薄膜で成ることを特徴とするゾルゲル膜。1. A sol solution A obtained by hydrolyzing and dehydrating and condensing a tetraalkoxysilane to which a metal alkoxide stabilized with acetylacetone is added on the surface of a glass substrate, and an alkyltrialkoxy having one functional group as an alkyl group. Fine uneven surface layer obtained by coating a coating solution containing a mixture of a sol solution B obtained by hydrolyzing and dehydrating and condensing silane and a solvent containing isopropyl alcohol as a main component and heating and baking A sol-gel film comprising an oxide thin film having:
l、Zrまたはこれらの複合金属であることを特徴とする
請求項１記載のゾルゲル膜。2. The metal of the metal alkoxide is Ti, A
The sol-gel film according to claim 1, wherein the sol-gel film is l, Zr or a composite metal thereof.
アルコキシドを添加したテトラアルコキシシランに対す
るアルキルトリアルコキシシランの混合割合が、酸化物
換算で２〜６倍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 mixture ratio of the alkyltrialkoxysilane to the tetraalkoxysilane added with the metal alkoxide stabilized with acetylacetone is 2 to 6 times in terms of oxide.
The sol-gel film described.
する溶媒が、イソプロピルアルコ−ルにブタノ−ルを添
加した溶媒であることを特徴とする請求項１乃至３記載
のゾルゲル膜。4. The sol-gel film according to claim 1, wherein the solvent containing isopropyl alcohol as a main component is a solvent obtained by adding butanol to isopropyl alcohol.
度が、酸化物換算で0.2 〜5.0w％であることを特徴とす
る請求項１乃至４記載のゾルゲル膜。5. The sol-gel film according to claim 1, wherein the solid content concentration in the coating solution is 0.2 to 5.0 w% in terms of oxide.
雰囲気下で45〜60％RHであることを特徴とする請求項１
乃至５記載のゾルゲル膜。6. The humidity during the coating is 45 to 60% RH in a temperature atmosphere of 25 ° C. 1.
6. The sol-gel film described in 5 above.
ンで安定化した金属アルコキシドを添加したテトラアル
コキシシランを加水分解ならびに脱水縮合させたゾル溶
液Ａと、１つの官能基をアルキル基化したアルキルトリ
アルコキシシランを加水分解ならびに脱水縮合したゾル
溶液Ｂとを混合し、30℃の保持温度で３〜24時間乃至50
℃の保持温度で１〜12時間攪拌した混合物を作製し、該
混合物をイソプロピルアルコ−ルを主成分とする溶媒で
希釈調製してなるコ−ティング溶液を25℃の温度雰囲気
下で45〜60％RHである湿度環境において被膜し、乾燥加
熱焼成し微細な凹凸状表層を有する酸化物薄膜で成るよ
うにすることを特徴とするゾルゲル膜の形成法。7. A sol solution A obtained by hydrolyzing and dehydrating and condensing a tetraalkoxysilane to which a metal alkoxide stabilized with acetylacetone is added, and an alkyltrialkoxy in which one functional group is an alkyl group, on the surface of a glass substrate. Mix with sol solution B obtained by hydrolyzing and dehydrating and condensing silane, and hold at a holding temperature of 30 ° C. for 3 to 24 hours to 50.
A coating solution was prepared by stirring the mixture at a holding temperature of ° C for 1 to 12 hours and diluting the mixture with a solvent containing isopropyl alcohol as a main component to prepare a coating solution at a temperature of 25 ° C for 45 to 60 ° C. A method for forming a sol-gel film, which comprises coating the film in a humidity environment of% RH and drying and heating to form an oxide thin film having a fine uneven surface layer.
i、Al、Zrまたはこれらの複合金属であることを特徴と
する請求項７記載のゾルゲル膜の形成法。8. The metal of the metal alkoxide is T
The method for forming a sol-gel film according to claim 7, which is i, Al, Zr or a composite metal thereof.
アルコキシドを添加したテトラアルコキシシランに対す
るアルキルトリアルコキシシランの混合割合が、酸化物
換算で２〜６倍になるようにしたことを特徴とする請求
項７乃至８記載のゾルゲル膜の形成法。9. The mixing ratio of the alkyltrialkoxysilane to the tetraalkoxysilane to which the metal alkoxide stabilized with acetylacetone is added is 2 to 6 times in terms of oxide. 9. A method of forming a sol-gel film according to any one of 8 to 8.
する溶媒が、イソプロピルアルコ−ルにブタノ−ルを添
加した溶媒であることを特徴とする請求項７乃至９記載
のゾルゲル膜の形成法。10. The method for forming a sol-gel film according to claim 7, wherein the solvent containing isopropyl alcohol as a main component is a solvent obtained by adding butanol to isopropyl alcohol.
度が、酸化物換算で0.2 〜5.0w％になるよう希釈調製す
ることを特徴とする請求項７乃至10記載のゾルゲル膜の
形成法。11. The method for forming a sol-gel film according to claim 7, wherein the coating solution is prepared by diluting so that the solid content concentration in the coating solution becomes 0.2 to 5.0 w% in terms of oxide.
度調製することでなるコーテイング溶液とすることを特
徴とする請求項７乃至11記載のゾルゲル膜の形成法。12. The method for forming a sol-gel film according to claim 7, wherein the coating solution is a coating solution prepared by adjusting the viscosity to 1 to 10 cP.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13226895A JP3183806B2 (en) | 1995-05-30 | 1995-05-30 | Sol-gel film and method for forming the same |
| EP96108568A EP0748775A3 (en) | 1995-05-30 | 1996-05-30 | Water-repellent glass plate having minutely roughed metal-oxide base film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13226895A JP3183806B2 (en) | 1995-05-30 | 1995-05-30 | Sol-gel film and method for forming the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08325036A true JPH08325036A (en) | 1996-12-10 |
| JP3183806B2 JP3183806B2 (en) | 2001-07-09 |
Family
ID=15077317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13226895A Expired - Fee Related JP3183806B2 (en) | 1995-05-30 | 1995-05-30 | Sol-gel film and method for forming the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3183806B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0882686A4 (en) * | 1996-12-18 | 2000-05-03 | Nippon Sheet Glass Co Ltd | Nonfogging and stainproof glass articles |
-
1995
- 1995-05-30 JP JP13226895A patent/JP3183806B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0882686A4 (en) * | 1996-12-18 | 2000-05-03 | Nippon Sheet Glass Co Ltd | Nonfogging and stainproof glass articles |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3183806B2 (en) | 2001-07-09 |
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