JPH07207255A - Composition for water-repellent coating film - Google Patents
Composition for water-repellent coating filmInfo
- Publication number
- JPH07207255A JPH07207255A JP134894A JP134894A JPH07207255A JP H07207255 A JPH07207255 A JP H07207255A JP 134894 A JP134894 A JP 134894A JP 134894 A JP134894 A JP 134894A JP H07207255 A JPH07207255 A JP H07207255A
- Authority
- JP
- Japan
- Prior art keywords
- water
- repellent coating
- composition
- surfactant
- repellent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 36
- 239000005871 repellent Substances 0.000 title claims abstract description 36
- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 9
- 239000000919 ceramic Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008199 coating composition Substances 0.000 claims description 14
- 229910052755 nonmetal Inorganic materials 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 230000002940 repellent Effects 0.000 claims description 7
- 239000011521 glass Substances 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 8
- 229920001296 polysiloxane Polymers 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- -1 polydimethylsiloxane Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- 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】本発明は自動車ガラスなどの表面
に形成される撥水被膜用の組成物に関する。FIELD OF THE INVENTION The present invention relates to a composition for a water-repellent coating formed on the surface of automobile glass or the like.
【０００２】[0002]
【従来の技術】ポリジメチルシロキサンやフルオロアル
キル基を含有した溶液をガラス板の表面に塗布し、これ
を乾燥した後に焼成することで付着した水滴の接触角を
大きくする撥水被膜とすることが従来から行われてお
り、斯かる撥水被膜に関する先行技術として、特開平４
−３３８１３７号公報、特開平４−３５９０８６号公
報、特開平５−２４８８５号公報或いは特開平５−２４
８８６号公報に開示されるものが知られている。2. Description of the Related Art A solution containing polydimethylsiloxane or a fluoroalkyl group is applied to the surface of a glass plate, dried and then baked to form a water-repellent coating for increasing the contact angle of water droplets attached thereto. As a prior art relating to such a water-repellent coating that has been conventionally performed, Japanese Patent Laid-Open No.
-338137, JP-A-4-359086, JP-A-5-24885, or JP-A-5-24.
The one disclosed in Japanese Patent No. 886 is known.
【０００３】特開平４−３３８１３７号公報にはシリコ
ーン系撥水被膜に代るものとして、ＳiＯ2を主成分とす
るセラミックスの非金属原子の一部をフルオロアルキル
基で置換したものが開示され、、特開平４−３５９０８
６号公報には金属アルコキシドを含むビヒクルに所定量
のフルオロアルキルシラン或いはアルキルシランを混合
したものが開示され、特開平５−２４８８５号公報には
ガラス表面と撥水被膜との間に透明金属皮膜を介在させ
たものが開示され、特開平５−２４８８６号公報にはガ
ラス表面にＳiＯ2膜を形成し、このＳiＯ2膜の表面に凹
凸を形成し、その上に撥水被膜を形成することが開示さ
れている。Japanese Patent Laid-Open No. 4-338137 discloses, as an alternative to a silicone-based water-repellent coating, a ceramic containing SiO 2 as a main component in which a part of non-metal atoms is substituted with a fluoroalkyl group. JP-A-4-35908
Japanese Unexamined Patent Publication No. 6-24885 discloses a vehicle containing a metal alkoxide mixed with a predetermined amount of fluoroalkylsilane or alkylsilane, and Japanese Unexamined Patent Publication No. 5-24885 discloses a transparent metallic film between a glass surface and a water repellent film. JP-A-5-24886 discloses that a SiO 2 film is formed on the surface of the glass, irregularities are formed on the surface of the SiO 2 film, and a water-repellent coating is formed thereon. Is disclosed.
【０００４】[0004]
【発明が解決しようとする課題】上述した撥水被膜を形
成するには、撥水被膜形成用の液状組成物をディッピン
グ法、スプレー法、フローコーティング法等によってガ
ラス板（透明基板）の表面に塗布した後に焼成するので
あるが、ガラス板の周縁部、特に図２に示すように、ガ
ラス板を立てた状態で塗布する場合にはガラス板１の下
端部に表面張力によって撥水被膜形成用組成物２の廻り
込み部（液溜り部）２ａが生じ、この廻り込み部２ａと
非塗布部との境界部が目立ったり、この部分に白ぐもり
や水滴跡が発生する不利がある。In order to form the above-mentioned water-repellent coating, a liquid composition for forming the water-repellent coating is applied to the surface of a glass plate (transparent substrate) by a dipping method, a spray method, a flow coating method or the like. It is baked after being applied, but for forming a water-repellent film on the peripheral edge of the glass plate, particularly when applying the glass plate in an upright state as shown in FIG. There is a disadvantage that a wraparound portion (liquid pool portion) 2a of the composition 2 is generated, a boundary portion between the wraparound portion 2a and the non-coated portion is conspicuous, and a white cloud and a water drop mark are generated in this portion.
【０００５】[0005]
【課題を解決するための手段】上記課題を解決するため
本発明は、ＳiＯ2を主成分とするセラミックスの非金属
原子の一部がフルオロアルキル基で置換された撥水被膜
用組成物に０．００６ｗｔ％以上０．０９ｗｔ％以下の
割合で界面活性剤を添加するようにした。In order to solve the above-mentioned problems, the present invention provides a composition for a water-repellent coating in which a part of non-metal atoms of a ceramic containing SiO 2 as a main component is substituted with a fluoroalkyl group. The surfactant was added at a rate of 0.006 wt% or more and 0.09 wt% or less.
【０００６】ここで、界面活性剤の添加割合を０．００
６ｗｔ％以上０．０９ｗｔ％以下としたのは、０．００
６ｗｔ％未満だと白ぐもり、水滴跡が発生しやすく、
０．０９ｗｔ％を越えると耐久試験後の接触角が悪化す
ることによる。Here, the addition ratio of the surfactant is 0.00
The amount of 6 wt% or more and 0.09 wt% or less is 0.00
If it is less than 6 wt%, white cloudiness and water droplets tend to occur,
This is because if it exceeds 0.09 wt%, the contact angle after the durability test deteriorates.
【０００７】また、前記フルオロアルキル基で置換され
る非金属原子の全非金属原子に対する割合は１０％以下
とするのが好ましい。これは１０％を越えると撥水被膜
の硬度が不足することによる。The ratio of non-metal atoms substituted with the fluoroalkyl group to all non-metal atoms is preferably 10% or less. This is because when the content exceeds 10%, the hardness of the water-repellent coating becomes insufficient.
【０００８】更に、セラミックの主成分としてのＳiＯ2
はモル比で５０％以上含むことが好ましい。このように
することでガラス板との接着性が向上し且つ干渉色の発
生を防止することができる。Further, SiO 2 as a main component of ceramics
Is preferably 50% or more in terms of molar ratio. By doing so, the adhesiveness with the glass plate can be improved and the occurrence of interference color can be prevented.
【０００９】[0009]
【作用】撥水被膜用組成物に所定割合で界面活性剤を添
加することで、表面張力が小さくなり、廻り込み部の発
生を抑制できる。By adding a surfactant to the water-repellent coating composition in a predetermined ratio, the surface tension is reduced, and the formation of a wraparound portion can be suppressed.
【００１０】[0010]
【実施例】本発明に係る撥水被膜の形成方法は塗布溶液
の調製工程、塗布工程及び焼成工程に大別される。以下
に各工程毎に説明する。EXAMPLES The method for forming a water repellent coating film according to the present invention is roughly classified into a coating solution preparing step, a coating step and a baking step. Each step will be described below.
【００１１】（調製工程）以下の（ａ）〜（ｃ）を２０
分間攪拌する。 （ａ）テトラエトキシシアン(Si(OC2H5)4) 200.00g （ｂ）フルオロアルキルシラン(CF3(CF2)7CH2CH2Si(OCH3)3) 5.46g （ｃ）エタノール 1706.40g 上記の（ａ）〜（ｃ）に対し以下の（ｄ）、（ｅ）を加
え、２時間攪拌する。 （ｄ）水 85.00g （ｅ）０．１Ｎ塩酸水溶液 105.40g 上記の混合溶液を密封容器に入れ、２５℃で９６時間放
置する。この後、この溶液をエタノールによって５倍に
希釈し、更に所定割合の界面活性剤を添加して塗布溶液
とする。(Preparation Step) The following (a) to (c) are used as
Stir for minutes. (A) tetraethoxy cyan (Si (OC 2 H 5) 4) 200.00g (b) fluoroalkyl silane (CF 3 (CF 2) 7 CH 2 CH 2 Si (OCH 3) 3) 5.46g (c) Ethanol 1706.40 g The following (d) and (e) are added to the above (a) to (c), and the mixture is stirred for 2 hours. (D) Water 85.00 g (e) 0.1 N hydrochloric acid aqueous solution 105.40 g The above mixed solution is put in a sealed container and left at 25 ° C. for 96 hours. Then, this solution is diluted 5 times with ethanol, and a surfactant in a predetermined ratio is further added to prepare a coating solution.
【００１２】界面活性剤としては非イオン系とイオン系
（アニオン系、カチオン系、両性イオン系）があり、更
にそれぞれは、フッ素系、炭化水素系及びシリコーン系
に分けられる。Surfactants include nonionic type and ionic type (anionic type, cationic type, zwitterionic type), and each of them is classified into fluorine type, hydrocarbon type and silicone type.
【００１３】（塗布工程）上記で得られた塗布溶液をフ
ロー法にてガラス板の片面に塗布する。フロー法はガラ
ス板１を上下方向に保持した状態で、ガラス板１の上縁
部にノズル３を用いて塗布溶液２を１００〜４００ｃｃ
／ｍｉｎの供給量で流し出すことで行う。塗布液を塗布
したら、乾燥室の条件を温度２１℃、湿度１８％、風速
分布０．３ｍ／ｍｉｎ〜０．５ｍ／ｍｉｎとして乾燥せ
しめた。これによりガラス板表面にウェット膜が形成さ
れる。(Coating Step) The coating solution obtained above is coated on one side of a glass plate by a flow method. In the flow method, with the glass plate 1 held in the vertical direction, 100 to 400 cc of the coating solution 2 is applied to the upper edge of the glass plate 1 using the nozzle 3.
It is performed by pouring out at a supply amount of / min. After applying the coating liquid, the drying chamber was dried under conditions of a temperature of 21 ° C., a humidity of 18%, and a wind speed distribution of 0.3 m / min to 0.5 m / min. As a result, a wet film is formed on the surface of the glass plate.
【００１４】（焼成工程）上記のウェット膜を形成した
ガラス板を大気中で１２０℃、２０分間保持して水及び
エタノールを蒸発させ、更に２５０℃に昇温し、１時間
保持することで撥水被膜を形成した。(Baking Step) The glass plate on which the wet film is formed is kept at 120 ° C. for 20 minutes in the air to evaporate water and ethanol, further heated to 250 ° C. and kept for 1 hour to repel A water film was formed.
【００１５】以下の（表１）は上記によって形成した撥
水被膜の外観性と耐久性を評価したものである。尚、外
観性としてはエッジ部の液溜り、白ぐもり、水滴跡の観
察を行い、耐久性については、往復摩擦（ネル布３００
ｇ／ｃｍ2−３０００回）及びボイル（１００℃−２時
間）後の接触角を測定した。また、添加する界面活性剤
としては、非イオン系（シリコーン系）のものを用い
た。（表１）からは界面活性剤の添加量を０．００６ｗ
ｔ％以上０．０９ｗｔ％以下とすべきであることが分
る。The following (Table 1) is an evaluation of the appearance and durability of the water-repellent coating formed as described above. As for the appearance, liquid pool, white cloudy, and water drop traces at the edge were observed.
The contact angle was measured after g / cm 2 -3000 times) and boiling (100 ° C.-2 hours). As the surfactant to be added, a nonionic (silicone) type was used. From (Table 1), the amount of surfactant added was 0.006w.
It is found that the content should be t% or more and 0.09 wt% or less.
【００１６】[0016]
【表１】 [Table 1]
【００１７】以下の（表２）は界面活性剤の種類を異な
らせて外観性と耐久性について実験した結果を示すもの
であり、界面活性剤の種類にかかわらず外観性について
は全ての界面活性剤において効果があったが、耐久性に
ついては非イオン系の界面活性剤が好ましいことが分
る。非イオン系の界面活性剤の具体的な化学式の一例を
以下の（数１）に示す。The following (Table 2) shows the results of experiments on appearance and durability with different kinds of surfactants. All appearances of surface active agents are irrespective of the kinds of surfactants. Although the agent was effective, it is understood that a nonionic surfactant is preferable for durability. An example of a specific chemical formula of the nonionic surfactant is shown in (Formula 1) below.
【００１８】[0018]
【表２】 [Table 2]
【００１９】[0019]
【数１】 [Equation 1]
【００２０】尚、実施例にあっては本発明に係る撥水被
膜用組成物をフローコーティング法に適用した例を示し
たが、この他の塗布方法、例えばディッピング法、スプ
レー法、或いはスピンコート法にも本発明に係る撥水被
膜用組成物を適用することができる。但し、ディッピン
グ法による場合は必要でない面までコーティングされ、
これを防止すべくテープ等によるマスキングを施しても
シワなどの間から液が滲み込み、作業も面倒である。ま
たスプレー法による場合は膜厚の分布を均一にしにく
く、更にスピンコート法による場合は自動車ガラスのよ
うな大寸法のガラス板を高速で回転することになるの
で、構造的に無理が生じる。従って、使用する塗布液の
量も比較的少なくて済み、且つ膜厚も均一にできるフロ
ーコーティング法が自動車ガラスのような大寸法のガラ
ス板に対しては最も好ましいと言えるが、特にこの方法
に限定されるわけではない。In the examples, the water-repellent coating composition according to the present invention was applied to the flow coating method. However, other coating methods such as dipping method, spraying method, and spin coating are used. The water-repellent coating composition according to the present invention can also be applied to the method. However, in the case of the dipping method, it is coated on the unnecessary surface,
Even if masking is done with tape to prevent this, the liquid will seep into the space between the wrinkles and the work is troublesome. Further, in the case of the spray method, it is difficult to make the film thickness distribution uniform, and in the case of the spin coat method, a large-sized glass plate such as automobile glass is rotated at a high speed, so that structurally unreasonable occurs. Therefore, it can be said that the flow coating method, which requires a relatively small amount of the coating liquid to be used and has a uniform film thickness, is the most preferable for a large-sized glass plate such as an automobile glass. It is not limited.
【００２１】[0021]
【発明の効果】以上に説明したように本発明によれば、
撥水被膜用組成物として、０．００６ｗｔ％以上０．０
９ｗｔ％以下の割合で界面活性剤を含むようにしたの
で、例えばフローコーティング法等によって透明基板に
撥水被膜用組成物を塗布する場合に、撥水被膜用組成物
溶液は透明基板の下端部に留まる液量が少なくなるため
に、膜厚むらが小さく目立ちにくくなり、水滴跡も少な
くなる。また、撥水被膜としては、外観上の欠点がな
く、耐久性（接触角）に優れたものが得られる。また、
界面活性剤を添加すると摩擦抵抗が低くなり、撥水性ガ
ラスの帯電性を抑えることもできる。As described above, according to the present invention,
As a water-repellent coating composition, 0.006 wt% or more 0.0
Since the surfactant is contained in an amount of 9 wt% or less, when the water repellent coating composition is applied to a transparent substrate by, for example, a flow coating method, the water repellent coating composition solution is applied to the lower end portion of the transparent substrate. Since the amount of liquid staying in the film is reduced, the unevenness of the film thickness is small and it becomes inconspicuous, and the traces of water drops are reduced. Further, as the water-repellent coating, it is possible to obtain a coating excellent in durability (contact angle) without any defects in appearance. Also,
When a surfactant is added, the frictional resistance becomes low and the chargeability of the water-repellent glass can be suppressed.
【００２２】更に、フルオロアルキル基で置換される非
金属原子の撥水被膜用組成物中の全非金属原子に対する
割合を１０％以下とすることで、撥水被膜の硬度を高め
ることができ、また、撥水被膜用組成物中のＳiＯ2の割
合をモル比で５０％とすることで、ガラス板との接着性
が向上し且つ干渉色が生じることもない。Furthermore, the hardness of the water-repellent coating can be increased by setting the ratio of the non-metal atoms substituted by the fluoroalkyl group to all the non-metal atoms in the composition for water-repellent coating to be 10% or less. Further, by setting the molar ratio of SiO 2 in the water repellent coating composition to 50%, the adhesiveness to the glass plate is improved and no interference color is generated.
【図１】本発明に係る撥水被膜用組成物を塗布している
状態を示す図FIG. 1 is a diagram showing a state in which a water-repellent coating composition according to the present invention is applied.
【図２】従来の撥水被膜用組成物を用いて塗布した場合
を説明した図FIG. 2 is a diagram illustrating a case where a conventional water-repellent coating composition is used for coating.
１…ガラス板、２…撥水被膜用組成物、３…ノズル。 1 ... Glass plate, 2 ... Water repellent coating composition, 3 ... Nozzle.
Claims (3)
用組成物において、この撥水被膜用組成物はＳiＯ2を主
成分とするセラミックスの非金属原子の一部がフルオロ
アルキル基で置換され、更に０．００６ｗｔ％以上０．
０９ｗｔ％以下の割合で界面活性剤を含んでいることを
特徴とする撥水被膜用組成物。1. A composition for a water-repellent coating, which becomes a water-repellent coating when fired, wherein the composition for a water-repellent coating has a fluoroalkyl group as a part of non-metal atoms of a ceramic containing SiO 2 as a main component. Substituting, and 0.006 wt% or more of 0.
A water-repellent coating composition comprising a surfactant in an amount of 09 wt% or less.
いて、前記フルオロアルキル基で置換される非金属原子
の全非金属原子に対する割合は１０％以下であることを
特徴とする撥水被膜用組成物。2. The water-repellent coating composition according to claim 1, wherein the ratio of non-metal atoms substituted with the fluoroalkyl group to all non-metal atoms is 10% or less. Coating composition.
いて、前記ＳiＯ2はモル比で５０％以上含まれることを
特徴とする撥水被膜用組成物。3. The water repellent coating composition according to claim 1, wherein the SiO 2 is contained in a molar ratio of 50% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP134894A JPH07207255A (en) | 1994-01-11 | 1994-01-11 | Composition for water-repellent coating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP134894A JPH07207255A (en) | 1994-01-11 | 1994-01-11 | Composition for water-repellent coating film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07207255A true JPH07207255A (en) | 1995-08-08 |
Family
ID=11498993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP134894A Pending JPH07207255A (en) | 1994-01-11 | 1994-01-11 | Composition for water-repellent coating film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07207255A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11293232A (en) * | 1998-04-14 | 1999-10-26 | Toyota Motor Corp | Liquid repellent film and liquid repellent |
| JP2009114243A (en) * | 2007-11-02 | 2009-05-28 | Kazufumi Ogawa | Method for manufacturing solar energy utilization device |
-
1994
- 1994-01-11 JP JP134894A patent/JPH07207255A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11293232A (en) * | 1998-04-14 | 1999-10-26 | Toyota Motor Corp | Liquid repellent film and liquid repellent |
| JP2009114243A (en) * | 2007-11-02 | 2009-05-28 | Kazufumi Ogawa | Method for manufacturing solar energy utilization device |
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