JPH05345641A - Method for forming water-repelling film - Google Patents
Method for forming water-repelling filmInfo
- Publication number
- JPH05345641A JPH05345641A JP15664592A JP15664592A JPH05345641A JP H05345641 A JPH05345641 A JP H05345641A JP 15664592 A JP15664592 A JP 15664592A JP 15664592 A JP15664592 A JP 15664592A JP H05345641 A JPH05345641 A JP H05345641A
- Authority
- JP
- Japan
- Prior art keywords
- water
- film
- repellent
- repellent film
- glass
- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
-
- 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
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は撥水膜の形成方法に関す
る。本発明で形成される撥水膜は、自動車のウインドガ
ラス、ミラーなどに利用できる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a water repellent film. The water-repellent film formed by the present invention can be used for windshields and mirrors of automobiles.
【０００２】[0002]
【従来の技術】雨天時などにウインドガラスやサイドミ
ラーに付着した水滴をはじき、視界を良好とすることを
目的として、撥水ガラスが検討されている。例えばガラ
ス自体を撥水化することが考えられるが、現時点では技
術的に解決すべき課題が多々あり、実用化には至ってい
ない。そこでガラス基板表面に撥水性の透明皮膜を形成
することが想起され、種々の提案がなされている。2. Description of the Related Art Water-repellent glass has been studied for the purpose of repelling water droplets adhering to windshields and side mirrors and improving the visibility in rainy weather. For example, it is conceivable to make the glass itself water-repellent, but at the present time there are many technical problems to be solved and it has not been put to practical use. Therefore, it has been suggested to form a water-repellent transparent film on the surface of the glass substrate, and various proposals have been made.
【０００３】例えば、ガラス基板表面にポリジメチルシ
ロキサンなどのシリコーン系の樹脂皮膜をもつ撥水ガラ
スが提案されている。シリコーン系樹脂は極めて良好な
撥水性を有するので、この撥水ガラスは優れた撥水性を
備えている。また、Journal of Non-Crystalline Solid
s 121(1990)344-347には、少量のトリメトキシフルオロ
アルキルシランとＺＴＯ（Zirconium Tetra-Octylate)
との反応物から、フッ素含有ＺｒＯ2 よりなる撥水性皮
膜を鋼板に形成する方法が記載されている。For example, a water-repellent glass having a silicone-based resin film such as polydimethylsiloxane on the surface of a glass substrate has been proposed. Since the silicone resin has extremely good water repellency, this water repellent glass has excellent water repellency. Also, Journal of Non-Crystalline Solid
s 121 (1990) 344-347 contains a small amount of trimethoxyfluoroalkylsilane and ZTO (Zirconium Tetra-Octylate).
A method for forming a water-repellent coating made of fluorine-containing ZrO 2 on a steel sheet from the reaction product of
【０００４】[0004]
【発明が解決しようとする課題】ところがシリコーン系
樹脂皮膜をもつ撥水ガラスでは、撥水膜の耐候性が不十
分であり、実用に際して撥水性の寿命が短いという不具
合がある。そしてこの原因としては、以下の機構による
ことも明らかとなっている。すなわち、シリコーン系樹
脂皮膜は水の透過が可能である。そのため水が撥水膜を
透過してガラス基板に達し、ガラス基板中に含まれるア
ルカリ成分を溶出させる。一方シリコーン系樹脂は耐ア
ルカリ性が良好とはいい難く、そのアルカリ成分により
加水分解を受け撥水性が低下してしまう。However, the water-repellent glass having a silicone resin film has a drawback that the water-repellent film has insufficient weather resistance and has a short life of water repellency in practical use. It is also clear that this is due to the following mechanism. That is, the silicone resin film is permeable to water. Therefore, water permeates the water-repellent film and reaches the glass substrate to elute the alkaline component contained in the glass substrate. On the other hand, it is difficult to say that the silicone-based resin has good alkali resistance, and the alkali component causes hydrolysis to reduce the water repellency.
【０００５】またフッ素含有ＺｒＯ2 皮膜は撥水性は有
しているが、ガラスとのなじみが悪いためガラス基板に
形成した場合には剥離が生じ易い。さらにフッ素含有Ｚ
ｒＯ 2 は屈折率が１．９程度と極めて高い。そのためガ
ラス基板にフッ素含有ＺｒＯ 2 の薄膜を形成した場合に
は光干渉により反射色が着色するため、自動車用として
は適さない。Fluorine-containing ZrO2The film has water repellency
However, it is not compatible with glass, so
When formed, peeling easily occurs. Fluorine-containing Z
rO 2Has a very high refractive index of about 1.9. Therefore,
Fluorine-containing ZrO on lath substrate 2When a thin film of
Is used for automobiles because the reflected color is colored by light interference.
Is not suitable.
【０００６】本発明はこのような事情に鑑みてなされた
ものであり、高い撥水性を有し耐候性に優れた撥水膜を
形成することを目的とする。The present invention has been made in view of such circumstances, and an object thereof is to form a water repellent film having high water repellency and excellent weather resistance.
【０００７】[0007]
【課題を解決するための手段】上記課題を解決する本発
明の撥水膜の形成方法は、Ｍ（ＯＲ）4 で表される金属
アルコキシドと、アルコキシル基の一部がフルオロアル
キル基にて置換された置換金属アルコキシドと、アルコ
ールと、水と、酸または塩基とを配合した溶液を調整す
る溶液調整工程と、前記溶液を被塗布物表面に塗布して
塗膜を形成する塗布工程と、前記塗膜をフルオロアルキ
ルシラン蒸気を含む雰囲気中で焼成して撥水皮膜を形成
する焼成工程と、を順次行うことを特徴とする。A method for forming a water-repellent film of the present invention which solves the above-mentioned problems is a metal alkoxide represented by M (OR) 4 and a part of an alkoxyl group substituted with a fluoroalkyl group. A substituted metal alkoxide, an alcohol, water, a solution adjusting step of adjusting a solution containing an acid or a base, a coating step of forming a coating film by coating the solution on the surface of an object to be coated, The invention is characterized in that the coating film is fired in an atmosphere containing fluoroalkylsilane vapor to form a water-repellent film in sequence.
【０００８】置換金属アルコキシドとしては、置換シリ
コンアルコキシドが代表的に用いられる。この場合、置
換シリコンアルコキシドの量は、全アルコキシドの量の
３％（ｍｏｌ％）未満とすることが好ましい。これによ
り撥水膜の撥水性と硬度とを両立させることができる。
置換シリコンアルコキシドの量が３％を超えると、撥水
膜の硬度が低下して実用に供し得ない。１．５％以下の
量とすれば、特に硬度に優れた撥水膜が得られる。A substituted silicon alkoxide is typically used as the substituted metal alkoxide. In this case, the amount of substituted silicon alkoxide is preferably less than 3% (mol%) of the total amount of alkoxides. This makes it possible to achieve both water repellency and hardness of the water repellent film.
When the amount of the substituted silicon alkoxide exceeds 3%, the hardness of the water-repellent film decreases and it cannot be put to practical use. When the amount is 1.5% or less, a water-repellent film having excellent hardness can be obtained.
【０００９】また金属アルコキシドとしては、シリコン
アルコキシドが代表的に用いられるが、シリコンアルコ
キシドの量の５０％（ｍｏｌ％）以下のチタンアルコキ
シド、ジルコニウムアルコキシド、アルミニウムアルコ
キシドなどの金属アルコキシドを含有させることもでき
る。これにより撥水膜の屈折率を調整することができ、
耐水腐食性が向上する効果もある。なおシリコンアルコ
キシドの量が５０ｍｏｌ％より少なくなると、撥水膜の
ガラス基板との付着性が低下したり、干渉色が生じるた
め好ましくない。Silicon alkoxide is typically used as the metal alkoxide, but metal alkoxide such as titanium alkoxide, zirconium alkoxide and aluminum alkoxide may be contained in an amount of 50% (mol%) or less of the amount of silicon alkoxide. .. This makes it possible to adjust the refractive index of the water-repellent film,
It also has the effect of improving water corrosion resistance. If the amount of silicon alkoxide is less than 50 mol%, the adhesion of the water-repellent film to the glass substrate is deteriorated or interference color is generated, which is not preferable.
【００１０】さらに、燐アルコキシドを全アルコキシド
の量の２０％（ｍｏｌ％）以下の量で混合することも好
ましい。これにより燐元素がガラス基板中のアルカリイ
オンをトラップして、アルカリイオンが撥水膜中を膜表
面に向かって拡散するのが抑制され、一層長寿命とする
ことができる。塗布工程は、ディッピング、スピンコー
ト、スプレーなどの公知の塗布手段で行うことができ
る。塗膜厚は特に制限されないが、乾燥時で通常１００
０〜２００ｎｍとされる。Furthermore, it is also preferable to mix the phosphorus alkoxide in an amount of 20% (mol%) or less of the total amount of alkoxide. Thereby, the phosphorus element traps the alkali ions in the glass substrate, and the diffusion of the alkali ions in the water-repellent film toward the film surface is suppressed, and the life can be further extended. The coating step can be performed by a known coating means such as dipping, spin coating or spraying. The thickness of the coating film is not particularly limited, but it is usually 100 when dried.
It is set to 0 to 200 nm.
【００１１】焼成工程は、上記塗膜を焼成して撥水膜を
形成する工程であり、本発明ではフルオロアルキルシラ
ン蒸気を含む雰囲気中で焼成するところに大きな特色を
有する。自動車用の撥水ガラスとしての撥水膜には、高
い耐候性が要求される。しかし本発明者らの研究によれ
ば、フルオロアルキル基にて置換された置換金属アルコ
キシドを用いて形成された撥水膜でも、自動車用として
十分な耐候性を有しているとは言えなかった。これは紫
外線などによるフルオロアルキル基の切断に起因してい
ると考えられた。そこでさらに多くのフルオロアルキル
基を導入することが想起された。The firing step is a step of firing the coating film to form a water repellent film, and the present invention has a great feature in firing in an atmosphere containing fluoroalkylsilane vapor. A water-repellent film as a water-repellent glass for automobiles is required to have high weather resistance. However, according to the research conducted by the present inventors, it cannot be said that even a water-repellent film formed using a substituted metal alkoxide substituted with a fluoroalkyl group has sufficient weather resistance for automobiles. .. It was considered that this was due to the cleavage of the fluoroalkyl group by ultraviolet rays or the like. Therefore, it was recalled to introduce more fluoroalkyl groups.
【００１２】膜中にフルオロアルキル基を多量に存在さ
せるには、上記溶液中のフルオロアルキル基で置換され
た置換金属アルコキシドの比率を高めることが考えられ
る。ところが本発明者らの研究によれば、置換金属アル
コキシドの含有量がある範囲を超えると、得られる撥水
膜の撥水性が飽和してしまい、それ以上の撥水性を得る
ことが困難となることが判明した。そこで他の手段を鋭
意研究した結果、フルオロアルキルシラン蒸気を含む雰
囲気中で上記塗膜を焼成することにより、得られる撥水
膜の撥水性と耐候性が著しく向上することを発見し本発
明を完成したものである。In order to make a large amount of fluoroalkyl groups exist in the film, it is conceivable to increase the ratio of the substituted metal alkoxide substituted with the fluoroalkyl groups in the solution. However, according to the study by the present inventors, when the content of the substituted metal alkoxide exceeds a certain range, the water repellency of the obtained water repellent film is saturated, and it becomes difficult to obtain more water repellency. It has been found. Then, as a result of earnest research on other means, it was discovered that the water repellency and weather resistance of the obtained water repellent film are remarkably improved by baking the above coating film in an atmosphere containing fluoroalkylsilane vapor. It has been completed.
【００１３】この焼成工程は、雰囲気中に少量の水蒸気
を導入して行うことも好ましい。このようにすればフル
オロアルキルシラン蒸気の加水分解が生じ、撥水膜表面
のシラノール基などとの反応が促進されるため、さらに
多くのフルオロアルキル基を導入することができる。な
お、フルオロアルキルシランとしては、一般式ＲfxＳｉ
Ｘ4-x （Ｒfxはフルオロアルキル基、Ｘはアルコキシル
基，ハロゲン基などを示す）で表され、水酸基と反応し
てＳｉ−Ｏ−Ｓｉ結合などを形成するものを利用でき
る。This firing step is also preferably carried out by introducing a small amount of water vapor into the atmosphere. In this way, the fluoroalkylsilane vapor is hydrolyzed and the reaction with the silanol groups on the surface of the water repellent film is promoted, so that more fluoroalkyl groups can be introduced. The fluoroalkylsilane is represented by the general formula R fx Si
A compound represented by X 4-x (R fx is a fluoroalkyl group, X is an alkoxyl group, a halogen group, etc.) and reacts with a hydroxyl group to form a Si—O—Si bond or the like can be used.
【００１４】[0014]
【作用】本発明の撥水膜の形成方法では、溶液調製工程
あるいは焼成工程において、金属アルコキシドが加水分
解して水酸化物が生成する。そして焼成工程において水
酸化物が互いに、あるいはガラス基板などと反応してシ
ロキサン結合などが形成され、緻密で硬度の高い皮膜が
形成される。この皮膜中にはフルオロアルキル基が含ま
れているため、撥水膜として機能する。In the method for forming a water-repellent film of the present invention, the metal alkoxide is hydrolyzed to form a hydroxide in the solution preparation step or the firing step. Then, in the firing step, the hydroxides react with each other or with a glass substrate or the like to form a siloxane bond or the like, and a dense and highly hard film is formed. Since this film contains a fluoroalkyl group, it functions as a water-repellent film.
【００１５】ここで塗膜の焼成工程は、フルオロアルキ
ルシラン蒸気の存在下で行われる。このとき塗膜表面に
てフルオロアルキルシランの反応が生じ、塗膜にフルオ
ロアルキル基が固定されると考えられる。したがって得
られる撥水膜のフルオロアルキル基の含有量がその分増
大し、撥水性が向上するとともに耐候性も向上する。Here, the baking process of the coating film is performed in the presence of fluoroalkylsilane vapor. At this time, it is considered that a fluoroalkylsilane reaction occurs on the surface of the coating film, and the fluoroalkyl group is fixed to the coating film. Therefore, the content of the fluoroalkyl group in the obtained water repellent film is increased by that amount, and the water repellency is improved and the weather resistance is also improved.
【００１６】[0016]
【実施例】以下、実施例及び比較例により具体的に説明
する。 （比較例） （１）溶液調整工程 テトラエトキシシラン ２００ ｇ フルオロアルキルシラン（CF3(CF2)7CH2CH2Si(OCH3)3) ５．４６ ｇ エタノール ４２６．５ ｇ を、１リットルのビーカ中で２０分間攪拌混合する。そしてさらに 水 ８３ ｇ ０．１Ｎ塩酸水溶液 １０４ ｇ を加えて混合し、２時間攪拌する。次いでこの溶液を密
封容器に入れ、２５℃で２４時間放置する。 （２）塗布工程 上記で得られた溶液中にソーダライムガラス基板を浸漬
し、引き上げ速度３０mm/minで引き上げてウェット塗膜
を形成した。EXAMPLES Hereinafter, examples and comparative examples will be specifically described. Comparative Example (1) Solution Preparation Step Tetraethoxysilane 200 g Fluoroalkylsilane (CF 3 (CF 2 ) 7 CH 2 CH 2 Si (OCH 3 ) 3 ) 5.46 g Ethanol 426.5 g 1 liter Stir in a beaker for 20 minutes. Then, 83 g of water and 104 g of 0.1N hydrochloric acid aqueous solution are further added and mixed, and the mixture is stirred for 2 hours. The solution is then placed in a sealed container and left at 25 ° C for 24 hours. (2) Coating Step A soda lime glass substrate was dipped in the solution obtained above and pulled up at a pulling rate of 30 mm / min to form a wet coating film.
【００１７】なお、ガラス基板として用いられるガラス
としては特に制限されず、他にも珪酸ガラス、珪酸アル
カリガラス、鉛アルカリガラス、カリ石灰ガラス、バリ
ウムガラスなどの珪酸塩ガラス、Ｂ2 Ｏ3 及びＳｉＯ2
を有する硼珪酸ガラス、Ｐ2Ｏ5 を含有する燐酸塩ガラ
スなどから選択して用いることができる。 （３）焼成工程 上記のウェット塗膜をもつガラス基板を大気下、２５０
℃にて１時間焼成して膜厚８０ｎｍの撥水膜を形成し
た。 （４）試験 得られた撥水ガラスについて、撥水膜の水との接触角を
測定したところ１１０度と高い撥水性を示した。そして
ＪＩＳによるテーバー磨耗試験後のヘイズ値の増加は３
％程度であった。さらに撥水膜の屈折率は約１．４５で
あり、ガラス基板の屈折率より僅かに小さいために反射
色に若干の着色がみられた。また屋外暴露試験を行った
ところ、１年経過後の水との接触角は８０度に低下して
いた。The glass used as the glass substrate is not particularly limited, and in addition, silicate glass such as silicate glass, alkali silicate glass, lead alkali glass, potassium lime glass, barium glass, B 2 O 3 and SiO. 2
It is possible to select and use borosilicate glass having Pd, phosphate glass containing P 2 O 5, and the like. (3) Firing step The glass substrate having the above wet coating film was exposed to air at 250
A water-repellent film having a film thickness of 80 nm was formed by baking at 0 ° C for 1 hour. (4) Test When the contact angle of the water-repellent film with water of the obtained water-repellent glass was measured, it showed high water repellency of 110 degrees. And the increase of haze value after Taber abrasion test by JIS is 3
It was about%. Further, the refractive index of the water-repellent film was about 1.45, which was slightly smaller than the refractive index of the glass substrate, so that the reflection color was slightly colored. Further, when an outdoor exposure test was conducted, the contact angle with water after one year had decreased to 80 degrees.
【００１８】次に溶液中のフルオロアルキルシランの添
加量と撥水性との関係を調べるために、フルオロアルキ
ルシランの添加量を変化させてそれぞれの溶液を調製
し、それぞれ同様にして撥水膜を形成した。そしてそれ
ぞれの撥水膜の水との接触角を測定し、結果を図２に示
す。図２より、溶液中のフルオロアルキルシランの添加
量が５ｇを超えると接触角はほぼ１１０度で一定とな
り、撥水性が飽和状態となっていることが分かる。これ
は、溶液中のフルオロアルキルシランの濃度を増しても
得られる撥水膜の撥水性には限度があり、この方法では
撥水性及び耐候性のさらなる向上は望めないことを示し
ている。 （実施例１）塗布工程までは比較例と同様に行った。 （３）焼成工程 上記のウェット塗膜をもつガラス基板を室温にて１０分
間放置し、塗膜を乾燥させた。次に、雰囲気調整が可能
な炉（炉内容積１ｍ3 ）中に入れ、窒素ガスにて炉内を
置換した後、窒素ガス中にフルオロアルキルシラン（CF
3(CF2)7CH2CH2Si(OCH3)3) の蒸気を５％含んだ混合ガス
を流しながら焼成を行った。混合ガスの流量は、炉内温
度が１６８℃までは１０００cc/min、それ以後は１００
００cc/minである。また焼成の温度条件を図１に示す。
図１において約１２０℃で１０分間保持しているのは、
揮発成分を概ね除去するために設定している。そして昇
温速度を３段階で徐々に緩やかにしているのは、過昇温
を防止するためである。Next, in order to investigate the relationship between the amount of fluoroalkylsilane added to the solution and the water repellency, each solution was prepared by changing the amount of fluoroalkylsilane added, and the water repellent film was formed in the same manner. Formed. Then, the contact angle of each water repellent film with water was measured, and the results are shown in FIG. From FIG. 2, it can be seen that when the amount of the fluoroalkylsilane added to the solution exceeds 5 g, the contact angle becomes almost constant at 110 degrees and the water repellency is saturated. This indicates that even if the concentration of fluoroalkylsilane in the solution is increased, the water repellency of the water-repellent film obtained is limited, and further improvement in water repellency and weather resistance cannot be expected by this method. (Example 1) Up to the coating step, the same procedure as in Comparative Example was performed. (3) Firing step The glass substrate having the above wet coating film was left at room temperature for 10 minutes to dry the coating film. Next, after putting in a furnace (internal volume of 1 m 3 ) capable of adjusting the atmosphere and replacing the inside of the furnace with nitrogen gas, fluoroalkylsilane (CF
Firing was performed while flowing a mixed gas containing 5% of 3 (CF 2 ) 7 CH 2 CH 2 Si (OCH 3 ) 3 ) vapor. The flow rate of the mixed gas is 1000 cc / min up to a furnace temperature of 168 ° C, and 100 after that.
It is 00cc / min. The temperature conditions for firing are shown in FIG.
In FIG. 1, holding at about 120 ° C. for 10 minutes is
It is set to remove most volatile components. The reason why the temperature rising rate is gradually decreased in three steps is to prevent excessive temperature rising.
【００１９】この焼成により得られた撥水膜の膜厚は８
０ｎｍであった。 （４）試験 得られた撥水ガラスについて、撥水膜の水との接触角を
測定したところ１２０度と高い撥水性を示した。そして
ＪＩＳによるテーバー磨耗試験後のヘイズ値の増加は２
％程度であり、ガラス基板との密着性に優れていた。ま
た屋外暴露試験を行ったところ、１年経過後の水との接
触角は１０５度であり、耐候性にも優れていた。 （実施例２）焼成工程において、実施例１と同様の混合
ガスとともに、炉内の温度における水の飽和蒸気圧分の
水蒸気を含んだ窒素ガスを、それぞれ実施例１と同様の
流量で流したこと以外は実施例１と同様にして撥水膜を
形成した。得られた撥水膜の膜厚は９０ｎｍである。The water-repellent film obtained by this firing has a film thickness of 8
It was 0 nm. (4) Test The water-repellent glass obtained showed a high water repellency of 120 ° when the contact angle of the water-repellent film with water was measured. And the increase of haze value after the Taber abrasion test by JIS is 2
%, And the adhesiveness with the glass substrate was excellent. Further, when an outdoor exposure test was conducted, the contact angle with water after one year was 105 degrees, and the weather resistance was also excellent. (Example 2) In the firing step, together with the same mixed gas as in Example 1, nitrogen gas containing water vapor at the saturated vapor pressure of water at the temperature in the furnace was flowed at the same flow rates as in Example 1. A water repellent film was formed in the same manner as in Example 1 except for the above. The thickness of the obtained water repellent film is 90 nm.
【００２０】得られた撥水ガラスについて、撥水膜の水
との接触角を測定したところ１２０度と高い撥水性を示
した。そしてＪＩＳによるテーバー磨耗試験後のヘイズ
値の増加は１．５％程度であり、ガラス基板との密着性
に優れていた。また屋外暴露試験を行ったところ、１年
経過後の水との接触角は１１５度であり、耐候性にも優
れていた。With respect to the water-repellent glass thus obtained, the contact angle of the water-repellent film with water was measured and it showed a high water repellency of 120 degrees. The increase in haze value after the Taber abrasion test according to JIS was about 1.5%, and the adhesiveness with the glass substrate was excellent. Further, when an outdoor exposure test was conducted, the contact angle with water after one year was 115 degrees, and the weather resistance was also excellent.
【００２１】すなわち、焼成時にフルオロアルキルシラ
ン蒸気とともに水蒸気を存在させることにより、実施例
１よりも高い撥水性と耐候性に優れた撥水膜が得られる
ことが明らかである。 （実施例３）焼成工程において、窒素ガス中にフルオロ
アルキルシラン（CF3(CF2)7CH2CH2Si(Cl)3) の蒸気を５
％含んだ混合ガスを流しながら焼成を行った。混合ガス
の流量は、炉内温度が２００℃までは１０００cc/min、
それ以後は１００００cc/minである。他の条件は実施例
１と同様にして撥水膜を形成した。得られた撥水膜の膜
厚は８０ｎｍである。That is, it is clear that the presence of water vapor along with the fluoroalkylsilane vapor during firing makes it possible to obtain a water repellent film having higher water repellency and weather resistance than those of Example 1. (Example 3) In the firing step, vapor of fluoroalkylsilane (CF 3 (CF 2 ) 7 CH 2 CH 2 Si (Cl) 3 ) was added to nitrogen gas in an amount of 5%.
Firing was performed while flowing a mixed gas containing 100%. The flow rate of the mixed gas is 1000 cc / min until the furnace temperature reaches 200 ° C.
After that, it is 10,000 cc / min. A water repellent film was formed under the other conditions in the same manner as in Example 1. The thickness of the obtained water repellent film is 80 nm.
【００２２】得られた撥水ガラスについて、撥水膜の水
との接触角を測定したところ１２０度と高い撥水性を示
した。そしてＪＩＳによるテーバー磨耗試験後のヘイズ
値の増加は３％程度であり、ガラス基板との密着性に優
れていた。また屋外暴露試験を行ったところ、１年経過
後の水との接触角は１０５度であり、耐候性にも優れて
いた。With respect to the water-repellent glass thus obtained, the contact angle of the water-repellent film with water was measured and it showed a high water repellency of 120 degrees. The increase in the haze value after the Taber abrasion test according to JIS was about 3%, and the adhesion to the glass substrate was excellent. Further, when an outdoor exposure test was conducted, the contact angle with water after one year was 105 degrees, and the weather resistance was also excellent.
【００２３】[0023]
【発明の効果】したがって本発明の撥水膜の形成方法に
よれば、大気中で焼成する場合に比べて撥水性が向上
し、その結果耐候性も向上した撥水膜を容易に形成する
ことができる。Therefore, according to the method of forming a water-repellent film of the present invention, it is possible to easily form a water-repellent film having improved water repellency and weather resistance as compared with the case of baking in the air. You can
【図１】本発明の実施例における焼成条件を示すグラフ
である。FIG. 1 is a graph showing firing conditions in an example of the present invention.
【図２】本発明の比較例におけるフルオロアルキルシラ
ンの添加量と接触角の関係を示すグラフである。FIG. 2 is a graph showing the relationship between the addition amount of fluoroalkylsilane and the contact angle in the comparative example of the present invention.
Claims (1)
ドと、アルコキシル基の一部がフルオロアルキル基にて
置換された置換金属アルコキシドと、アルコールと、水
と、酸または塩基とを配合した溶液を調整する溶液調整
工程と、 前記溶液を被塗布物表面に塗布して塗膜を形成する塗布
工程と、 前記塗膜をフルオロアルキルシラン蒸気を含む雰囲気中
で焼成して撥水皮膜を形成する焼成工程と、を順次行う
ことを特徴とする撥水膜の形成方法。1. A metal alkoxide represented by M (OR) 4 , a substituted metal alkoxide in which a part of the alkoxyl group is substituted with a fluoroalkyl group, an alcohol, water, and an acid or a base are blended. A solution adjusting step of adjusting a solution, an applying step of applying the solution to the surface of an object to be coated to form a coating film, and baking the coating film in an atmosphere containing fluoroalkylsilane vapor to form a water repellent coating film. A method of forming a water-repellent film, which comprises sequentially performing a firing step of
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4156645A JP2668178B2 (en) | 1992-06-16 | 1992-06-16 | Method of forming water repellent film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4156645A JP2668178B2 (en) | 1992-06-16 | 1992-06-16 | Method of forming water repellent film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05345641A true JPH05345641A (en) | 1993-12-27 |
| JP2668178B2 JP2668178B2 (en) | 1997-10-27 |
Family
ID=15632192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4156645A Expired - Lifetime JP2668178B2 (en) | 1992-06-16 | 1992-06-16 | Method of forming water repellent film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2668178B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0658525A2 (en) * | 1993-11-10 | 1995-06-21 | Central Glass Company, Limited | Multilayered water-repellent film and method of forming same on glass substrate |
| WO2009125803A1 (en) * | 2008-04-09 | 2009-10-15 | 株式会社 アルバック | Film deposition apparatus and film deposition method |
| JP2013036733A (en) * | 2011-07-12 | 2013-02-21 | Denso Corp | Water repellent base material, heat exchanger, and method for manufacturing water repellent base material |
-
1992
- 1992-06-16 JP JP4156645A patent/JP2668178B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0658525A2 (en) * | 1993-11-10 | 1995-06-21 | Central Glass Company, Limited | Multilayered water-repellent film and method of forming same on glass substrate |
| EP0658525A3 (en) * | 1993-11-10 | 1995-09-13 | Central Glass Co Ltd | Multilayered water-repellent film and method of forming same on glass substrate. |
| US5674625A (en) * | 1993-11-10 | 1997-10-07 | Central Glass Company, Limited | Multilayered water-repellent film and method of forming same on glass substrate |
| US5856016A (en) * | 1993-11-10 | 1999-01-05 | Central Glass Company Limited | Multilayered water-repellent film and method of forming same on glass substrate |
| EP0866037A3 (en) * | 1993-11-10 | 1999-02-10 | Central Glass Company, Limited | Multilayered water-repellent film and method of forming same on glass substrate |
| WO2009125803A1 (en) * | 2008-04-09 | 2009-10-15 | 株式会社 アルバック | Film deposition apparatus and film deposition method |
| JP5101690B2 (en) * | 2008-04-09 | 2012-12-19 | 株式会社アルバック | Film forming apparatus and film forming method |
| US9310524B2 (en) | 2008-04-09 | 2016-04-12 | Ulvac, Inc. | Film deposition apparatus and film deposition method |
| JP2013036733A (en) * | 2011-07-12 | 2013-02-21 | Denso Corp | Water repellent base material, heat exchanger, and method for manufacturing water repellent base material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2668178B2 (en) | 1997-10-27 |
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