JP2671722B2 - Transparent water-repellent film - Google Patents
Transparent water-repellent filmInfo
- Publication number
- JP2671722B2 JP2671722B2 JP4207932A JP20793292A JP2671722B2 JP 2671722 B2 JP2671722 B2 JP 2671722B2 JP 4207932 A JP4207932 A JP 4207932A JP 20793292 A JP20793292 A JP 20793292A JP 2671722 B2 JP2671722 B2 JP 2671722B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- repellent
- film
- porous film
- transparent
- 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.)
- Expired - Fee Related
Links
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Laminated Bodies (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、自動車のウインドガラ
スなどの表面に形成されて撥水性を付与する透明撥水皮
膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent water repellent film which is formed on the surface of windshields of automobiles to impart water repellency.
【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を有する透明皮膜
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 drops adhering to a window glass or a side mirror in rainy weather or the like and improving visibility. For example, it is conceivable to make the glass itself water-repellent, but at present there are many technical problems to be solved and the glass has not been put to practical use. Therefore, it was conceived to form a transparent coating having water repellency on the surface of the glass substrate, and various proposals have been made.
【０００３】例えば特開平３−２３２７４７号公報に
は、ガラス基板表面にポリジメチルシロキサンなどのシ
リコーン系の撥水皮膜を形成することが提案されてい
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、この撥水皮膜は優れた撥水性を備えている。For example, Japanese Patent Application Laid-Open No. 3-232747 proposes to form a silicone-based water-repellent film such as polydimethylsiloxane on the surface of a glass substrate. Since the silicone resin has extremely good water repellency, this water repellent film has excellent water repellency.
【０００４】[0004]
【発明が解決しようとする課題】ところでシリコーン系
の撥水皮膜では、含まれる撥水基が皮膜の表面側に配向
し、ＳｉＯ基がガラス基板側に配向した状態となってい
る。そのためガラスクリーナなどで磨かれたりした場合
に最表面が磨耗すると、配向性が乱れ撥水基の脱落も生
じて撥水性が低下し、ついには撥水性が早期に消失する
という不具合があった。By the way, in a silicone-based water-repellent coating, the contained water-repellent groups are oriented on the surface side of the coating, and the SiO groups are oriented on the glass substrate side. Therefore, when the outermost surface is worn when it is polished with a glass cleaner or the like, the orientation is disturbed, the water-repellent group is also dropped off, the water repellency is lowered, and finally the water repellency disappears at an early stage.
【０００５】本発明はこのような事情に鑑みてなされた
ものであり、優れた撥水性を長期間維持できる透明撥水
皮膜と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 provide a transparent water-repellent film capable of maintaining excellent water repellency for a long period of time.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決する本発
明の透明撥水皮膜は、フッ素含有ポリマーからなる多孔
質膜の空孔中に透明セラミックスが含有保持され、表面
には該多孔質膜と該透明セラミックスの両方が表出して
いることを特徴とする。フッ素含有ポリマーとしては撥
水性を示すものが用いられ、ポリテトラフルオロエチレ
ン（ＰＴＦＥ）、ポリクロロトリフルオロエチレン（Ｐ
ＣＴＦＥ）、４フッ化エチレン−６フッ化プロピレン共
重合体、ポリフッ化ビニル（ＰＶＦ）、ポリフッ化ビニ
リデン（ＰＦＶＤ）などが挙げられる。The transparent water-repellent coating of the present invention which solves the above-mentioned problems has a structure in which transparent ceramics are contained and retained in the pores of a porous film made of a fluorine-containing polymer ,
Both the porous film and the transparent ceramics are exposed in the
And said that you are. As the fluorine-containing polymer, those exhibiting water repellency are used, such as polytetrafluoroethylene (PTFE) and polychlorotrifluoroethylene (P
CTFE), tetrafluoroethylene-6 fluoropropylene copolymer, polyvinyl fluoride (PVF), polyvinylidene fluoride (PFVD) and the like.
【０００７】透明セラミックとしては透明であれば特に
制限されないが、ＳｉＯ2 、ＴｉＯ 2 、ＺｒＯ2 、Ａｌ
2 Ｏ3 などから種々選択される。上記フッ素含有ポリマ
ーからなる多孔質膜の空孔中に透明セラミックスを保持
させるには、実施例でも説明するように、フッ素基含有
ポリマーから形成された多孔質膜に有機シラン化合物な
どのゾルを含浸させ、加水分解によるゲル化により空孔
中に含有保持させることができる。If the transparent ceramic is transparent,
SiO is not limitedTwo, TiO Two, ZrOTwo, Al
TwoOThreeVariously selected from the above. Fluorine-containing polymer
Holding transparent ceramics in the pores of a porous membrane
In order to do so, as described in the examples, fluorine group-containing
A porous film made of a polymer does not contain organic silane compounds.
Voids due to which sol is impregnated and gelled by hydrolysis
It can be contained and retained.
【０００８】なお、透明性を向上させるためには、透明
セラミックスと多孔質膜の屈折率は近いほど好ましい。In order to improve transparency, it is preferable that the transparent ceramics and the porous film have similar refractive indices.
【０００９】[0009]
【作用】本発明の透明撥水皮膜では、撥水性を示すフッ
素含有ポリマーからなる多孔質膜が基体をなしている。
したがって表面の撥水材料（多孔質膜）が磨耗により除
去されたとしても、新たな撥水材料（多孔質膜）が次か
ら次へと表出するため、撥水性を長期間維持することが
できる。In the transparent water-repellent coating of the present invention, a porous membrane made of a fluorine-containing polymer showing water repellency serves as a substrate.
Therefore, even if the water-repellent material (porous film) on the surface is removed due to abrasion, a new water-repellent material (porous film) appears one after another, so that water repellency can be maintained for a long time. it can.
【００１０】また撥水材料はポリマーであるので、それ
自体では耐磨耗性など機械的特性に劣るが、空孔中に保
持された透明セラミックで保護されているため撥水皮膜
としては充分な機械的特性を備えている。さらに、フッ
素含有ポリマーからなる多孔質膜自体は、含まれる多く
の空孔における光散乱により白濁し透明性に劣る。しか
し本発明の透明撥水皮膜では、透明セラミックスが空孔
を充填していることにより光散乱が防止され、高い透明
性が確保される。Further, since the water repellent material is a polymer, it is inferior in mechanical properties such as abrasion resistance by itself, but it is sufficient as a water repellent film because it is protected by the transparent ceramics held in the pores. It has mechanical properties. Furthermore, the porous film itself made of the fluorine-containing polymer is opaque due to light scattering in many pores contained therein and is inferior in transparency. However, in the transparent water-repellent coating of the present invention, since the transparent ceramics fills the pores, light scattering is prevented and high transparency is secured.
【００１１】[0011]
【実施例】以下、実施例により具体的に説明する。 （実施例１）図１に、本発明の一実施例の撥水皮膜の模
式的断面図を示す。この撥水皮膜２はガラス基板１上に
厚さ約１０μｍに形成されたものであり、ＰＴＦＥから
なる多孔質膜２０と、多孔質膜２０の空孔２１内に充填
されＳｉＯ2 からなる透明セラミックス２２と、から構
成されている。The present invention will be specifically described below with reference to examples. (Embodiment 1) FIG. 1 shows a schematic cross-sectional view of a water-repellent coating according to an embodiment of the present invention. The water-repellent film 2 is formed on the glass substrate 1 to have a thickness of about 10 μm, and has a porous film 20 made of PTFE and transparent ceramics made of SiO 2 filled in the pores 21 of the porous film 20. 22 and 22.
【００１２】以下、この撥水皮膜２の製造方法を説明し
て、構成の詳細な説明に代える。先ず、延伸により作製
されたＰＴＦＥ製多孔質膜２０を用意する。この多孔質
膜２０は、膜厚１０μｍ、空孔２１の平均孔径は０．１
μｍ、空孔率５０％である。一方では、ＳｉＯ2 ゾルを
用意する。このＳｉＯ2 ゾルは、テトラエトキシシラン
２０８ｇとエタノール４２７ｇを１リットルのビーカ中
で２０分間攪拌する。そしてさらに、水８３ｇと０．１
Ｎ塩酸水溶液１０４ｇを加えて２時間攪拌混合し、密封
容器中で２５℃にて２４時間熟成することにより形成し
たものである。Hereinafter, a method for producing the water-repellent coating 2 will be described to replace the detailed description of the structure. First, the PTFE porous membrane 20 produced by stretching is prepared. The porous membrane 20 has a thickness of 10 μm and the pores 21 have an average pore diameter of 0.1.
μm, porosity 50%. On the other hand, a SiO 2 sol is prepared. This SiO 2 sol is obtained by stirring 208 g of tetraethoxysilane and 427 g of ethanol in a 1 liter beaker for 20 minutes. Furthermore, 83 g of water and 0.1
It was formed by adding 104 g of N hydrochloric acid aqueous solution, stirring and mixing for 2 hours, and aging at 25 ° C. for 24 hours in a sealed container.
【００１３】そして上記多孔質膜２０を上記ＳｉＯ2 ゾ
ルに浸漬し、減圧にして多孔質膜２０の空孔２１に含浸
させる。その後、ＳｉＯ2 ゾル含浸済みの多孔質膜２０
をソーダライムガラス基板１表面に乗せ、ローラにて押
しつけた後自然乾燥させる。それを密閉系に置かれた浸
漬装置に配置し、０．５気圧の減圧下でガラス基板１上
の多孔質膜２０に再度ＳｉＯ2 ゾルを含浸させる。そし
て大気圧に戻してから、ガラス基板１を多孔質膜２０と
ともに３０ｍｍ／分の引き上げ速度で引き上げ、ＳｉＯ
2 ゾルを全体に成膜して自然乾燥させる。Then, the porous film 20 is dipped in the SiO 2 sol and reduced in pressure to impregnate the pores 21 of the porous film 20. Then, the porous film 20 impregnated with SiO 2 sol
Is placed on the surface of the soda lime glass substrate 1, pressed by a roller, and then naturally dried. It is placed in a dipping device placed in a closed system, and the porous film 20 on the glass substrate 1 is again impregnated with SiO 2 sol under a reduced pressure of 0.5 atm. Then, after returning to atmospheric pressure, the glass substrate 1 is pulled up together with the porous film 20 at a pulling rate of 30 mm / min.
2 Film the sol on the whole surface and let it dry naturally.
【００１４】その後、焼き付け炉に配置し３００℃で１
時間焼き付けて、多孔質膜２０の空孔２１に含浸したＳ
ｉＯ2 ゾル及びその表面に形成された膜状のＳｉＯ2 ゾ
ルをゲル化させる。このようにして作製された撥水ガラ
スは、多孔質膜２０の空孔２１中に含浸しゲル化したＳ
ｉＯ2 からなる透明セラミックス２２がガラス基板１と
強固に密着し、多孔質膜２０もそれによりガラス基板１
に密着している。しかしこのままでは、多孔質膜２０表
面をＳｉＯ2 ゲル皮膜が覆っているため撥水性を示さな
い。そこで、セリア研磨剤が懸濁したスラリーで表面を
研磨し、多孔質膜２０表面を表出させる。これにより本
実施例の撥水皮膜２をもつ撥水ガラスが作製される。After that, it is placed in a baking oven and heated at 300 ° C. for 1 hour.
After baking for a period of time, S impregnated into the pores 21 of the porous film 20
The iO 2 sol and the film-like SiO 2 sol formed on the surface thereof are gelled. The water-repellent glass thus produced is impregnated into the pores 21 of the porous film 20 to form gelled S.
The transparent ceramics 22 made of iO 2 firmly adheres to the glass substrate 1, and the porous film 20 is thereby also adhered to the glass substrate 1.
Closely adhered to. However, as it is, it does not show water repellency because the surface of the porous film 20 is covered with the SiO 2 gel film. Therefore, the surface is polished with a slurry in which the ceria abrasive is suspended to expose the surface of the porous film 20. As a result, a water-repellent glass having the water-repellent coating 2 of this embodiment is manufactured.
【００１５】得られた撥水皮膜２は透明であり、水に対
して１００度という接触角を示し高い撥水性を有してい
た。また耐久性を調査するために、コンパウンド入りの
ガラスクリーナを含ませたネル布を用い、３００ｇ／ｃ
ｍ2 の荷重にて１万回往復して磨いたが、撥水性の低下
は認められず高い堅牢度を有していた。なお、多孔質膜
２０の空孔２１の孔径は０．２μｍ以下とすることが望
ましい。孔径が０．２μｍより大きくなると、空孔内に
含浸した透明セラミックス２２とその周囲の多孔質膜２
０との間で光学散乱が生じ、白濁して透明性が低下する
場合がある。The water-repellent coating 2 thus obtained was transparent, had a contact angle of 100 degrees with water, and had high water repellency. In addition, in order to investigate the durability, a flannel cloth containing a glass cleaner containing compound was used, and 300 g / c
Although it was reciprocated 10,000 times under a load of m 2 , polishing was performed, and no deterioration in water repellency was observed and it had high fastness. The pore diameter of the pores 21 of the porous film 20 is preferably 0.2 μm or less. When the pore diameter becomes larger than 0.2 μm, the transparent ceramics 22 impregnated in the pores and the porous film 2 around it are formed.
There is a case where optical scattering occurs between 0 and opaque and the transparency is lowered.
【００１６】また、多孔質膜２０の空孔率は２０〜９０
％の範囲が望ましい。空孔率がこの範囲より小さくなる
と透明セラミックス２２との一体性が低下し、堅牢度が
低下する。また空孔率がこの範囲より大きくなると、多
孔質膜２０の占める面積が少なくなり撥水性が低下した
り、撥水性のばらつきが生じる場合がある。 （実施例２）膜厚が１μｍと、実施例１の１／１０の厚
さの多孔質膜を用いたこと以外は実施例１と同様にして
撥水皮膜を形成した。その結果、実施例１と同様の撥水
性と堅牢度をもつ撥水皮膜が形成できた。The porosity of the porous film 20 is 20 to 90.
% Is desirable. When the porosity is smaller than this range, the integrity with the transparent ceramics 22 is reduced and the robustness is reduced. If the porosity is higher than this range, the area occupied by the porous film 20 may be reduced, and the water repellency may be reduced or the water repellency may be varied. (Example 2) A water-repellent film was formed in the same manner as in Example 1 except that a porous film having a film thickness of 1 µm and a thickness of 1/10 of Example 1 was used. As a result, a water repellent film having the same water repellency and fastness as in Example 1 could be formed.
【００１７】ところが、本実施例の撥水皮膜をもつガラ
ス基板では、撥水皮膜表面の反射スペクトル（５度反
射）を図２に示すように、僅かであるが光干渉による着
色が認められた。これは撥水皮膜の屈折率が平均１．４
であり、ソーダライムガラスの屈折率１．５３と異な
り、また撥水皮膜の膜厚が薄いことに起因している。 （実施例３）そこで実施例１のＳｉＯ2 ゾルの代わり
に、ＳｉＯ2 −ＴｉＯ2 混合ゾルを用いるとともに、膜
厚が１μｍと実施例１の１／１０の厚さの多孔質膜を用
いたこと以外は実施例１と同様にして撥水皮膜を形成し
た。なお、ＳｉＯ2 −ＴｉＯ2混合ゾルは、テトラノル
マルブトキシチタン６０ｇとエタノール６０ｇとを混合
し、これを実施例１で作製し２４時間熟成したＳｉＯ2
ゾル全量に混合して１時間攪拌したものを用いた。However, in the glass substrate having the water-repellent coating of this example, the reflection spectrum (5 degree reflection) on the surface of the water-repellent coating was slightly colored as shown in FIG. . The average refractive index of the water-repellent coating is 1.4.
Is different from the refractive index of soda lime glass of 1.53, and is due to the thin film of the water repellent film. (Example 3) Therefore, in place of the SiO 2 sol of Example 1, a SiO 2 —TiO 2 mixed sol was used, and a porous film having a film thickness of 1 μm and 1/10 of that of Example 1 was used. A water repellent film was formed in the same manner as in Example 1 except for the above. Incidentally, SiO 2 -TiO 2 mixed sol by mixing the tetra-n-butoxy titanium 60g ethanol 60g, SiO 2 This was prepared and aged for 24 hours in Example 1
What was mixed with the total amount of the sol and stirred for 1 hour was used.
【００１８】得られた撥水ガラスの撥水皮膜表面の反射
スペクトルを図３に示す。図３のように、反射光には着
色は認められなかった。これは撥水皮膜中にＴｉＯ2 が
混合されたため屈折率が増大し、ガラス基板の屈折率と
近くなったためである。なお、本実施例で得られた撥水
皮膜は、実施例１と同様に優れた撥水性と堅牢度を示し
た。The reflection spectrum of the surface of the water-repellent film of the water-repellent glass obtained is shown in FIG. As shown in FIG. 3, coloring was not recognized in the reflected light. This is because TiO 2 was mixed in the water-repellent film, so that the refractive index increased and became close to that of the glass substrate. The water-repellent film obtained in this example showed excellent water repellency and fastness as in Example 1.
【００１９】[0019]
【発明の効果】すなわち本発明の撥水皮膜によれば、コ
ンパウンド入りのガラスクリーナなどで磨いても撥水性
が低下したり消失したりすることがないので、撥水性が
長期間維持され耐久性に優れている。According to the water-repellent coating of the present invention, the water-repellent property does not decrease or disappear even if it is polished with a compounded glass cleaner or the like. Is excellent.
【図１】本発明の一実施例の撥水皮膜と、その撥水皮膜
をもつガラス基板の模式的断面図である。FIG. 1 is a schematic cross-sectional view of a water-repellent film according to an embodiment of the present invention and a glass substrate having the water-repellent film.
【図２】実施例２の撥水皮膜表面の反射スペクトルであ
る。FIG. 2 is a reflection spectrum of the surface of the water-repellent coating of Example 2.
【図３】実施例３の撥水皮膜表面の反射スペクトルであ
る。FIG. 3 is a reflection spectrum of the surface of the water-repellent coating of Example 3.
１：ガラス基板 ２：撥水皮膜 ２０：多孔
質膜 ２１：空孔 ２２：透明セラミックス1: Glass substrate 2: Water repellent film 20: Porous film 21: Porosity 22: Transparent ceramics
Claims (1)
空孔中に透明セラミックスが含有保持され、表面には該
多孔質膜と該透明セラミックスの両方が表出しているこ
とを特徴とする透明撥水皮膜。1. A transparent ceramic is contained and held in the pores of a porous film made of a fluorine-containing polymer, and the transparent ceramic is contained on the surface.
A transparent water-repellent film, characterized in that both a porous film and the transparent ceramic are exposed .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4207932A JP2671722B2 (en) | 1992-08-04 | 1992-08-04 | Transparent water-repellent film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4207932A JP2671722B2 (en) | 1992-08-04 | 1992-08-04 | Transparent water-repellent film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0649265A JPH0649265A (en) | 1994-02-22 |
| JP2671722B2 true JP2671722B2 (en) | 1997-10-29 |
Family
ID=16547934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4207932A Expired - Fee Related JP2671722B2 (en) | 1992-08-04 | 1992-08-04 | Transparent water-repellent film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2671722B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2553899B2 (en) * | 1986-10-17 | 1996-11-13 | バクスター、インターナショナル、インコーポレイテッド | Method and apparatus for estimating hematocrit in a blood component processing system |
| JP2001329105A (en) * | 2000-05-25 | 2001-11-27 | Japan Gore Tex Inc | Silica gel composite membrane |
| JP5512939B2 (en) * | 2008-07-29 | 2014-06-04 | 日本ゴア株式会社 | Organic / inorganic composite film and method for producing organic / inorganic composite film |
| JP5449739B2 (en) * | 2008-10-17 | 2014-03-19 | 日本ゴア株式会社 | Method for producing breathable composite sheet |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54139972A (en) * | 1978-04-24 | 1979-10-30 | Sumitomo Electric Ind Ltd | Porous composite structure and its manufacture |
-
1992
- 1992-08-04 JP JP4207932A patent/JP2671722B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0649265A (en) | 1994-02-22 |
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