JPH04285036A - Water-repellent film for glass - Google Patents
Water-repellent film for glassInfo
- Publication number
- JPH04285036A JPH04285036A JP3074706A JP7470691A JPH04285036A JP H04285036 A JPH04285036 A JP H04285036A JP 3074706 A JP3074706 A JP 3074706A JP 7470691 A JP7470691 A JP 7470691A JP H04285036 A JPH04285036 A JP H04285036A
- Authority
- JP
- Japan
- Prior art keywords
- water
- coating layer
- glass
- repellent
- repellent film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005871 repellent Substances 0.000 title claims abstract description 35
- 239000011521 glass Substances 0.000 title claims abstract description 29
- 239000011247 coating layer Substances 0.000 claims abstract description 31
- 239000010410 layer Substances 0.000 claims abstract description 10
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000007740 vapor deposition Methods 0.000 description 7
- 230000002940 repellent Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Laminated Bodies (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、例えば自動車のウィン
ドウやドアミラー等のガラス基板の表面に撥水性を与え
るための撥水膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-repellent film for imparting water repellency to the surfaces of glass substrates such as automobile windows and door mirrors.
【０００２】0002
【従来の技術】従来より、このような撥水膜を形成する
ために例えばシリコーンまたはフロロシリコーン撥水剤
が用いられている。この撥水剤は水酸基との反応基を成
分として含んでおり、被覆すべきソーダガラス等のガラ
ス基板側に付く水酸基との反応により撥水膜が形成され
る。また、この撥水膜は、ガラス基板上に直接形成する
よりも、ガラス基板上に二酸化ケイ素のコーティング層
を設けた上で形成したほうが耐久性に優れることが知ら
れている。これは、ガラス基板の表面よりもコーティン
グ層の方が水酸基を多く有していて、撥水膜との結合力
が強くなるためである。2. Description of the Related Art Conventionally, silicone or fluorosilicone water repellents, for example, have been used to form such water repellent films. This water repellent agent contains as a component a group that reacts with a hydroxyl group, and a water-repellent film is formed by reaction with the hydroxyl group attached to the side of the glass substrate such as soda glass to be coated. Furthermore, it is known that this water-repellent film is more durable if it is formed after providing a silicon dioxide coating layer on the glass substrate than if it is formed directly on the glass substrate. This is because the coating layer has more hydroxyl groups than the surface of the glass substrate and has a stronger bond with the water-repellent film.
【０００３】0003
【発明が解決しようとする課題】このコーティング層は
、二酸化ケイ素を原料として蒸着やスパッタリングを行
なうことによりガラス基板上に形成することが可能であ
るが、このような方法では、コーティング時の基板の温
度を約２５０℃程度以上の高温に設定しなければ基板に
対してコーティング層が十分に付着せず、低い基板温度
ではガラス基板に対するコーティング層の十分な付着力
が得られないという問題があった。[Problems to be Solved by the Invention] This coating layer can be formed on a glass substrate by vapor deposition or sputtering using silicon dioxide as a raw material. There was a problem that unless the temperature was set to a high temperature of about 250°C or higher, the coating layer would not adhere sufficiently to the substrate, and if the substrate temperature was low, sufficient adhesion of the coating layer to the glass substrate could not be obtained. .
【０００４】したがって、本発明の解決すべき技術的課
題は、蒸着等の方法によるコーテイング層の形成を低い
基板温度で行なってもガラス基板に対する十分な付着力
を得られるようにして、撥水膜としての耐久性の低下を
防止することである。Therefore, the technical problem to be solved by the present invention is to provide a water-repellent film that can obtain sufficient adhesion to a glass substrate even when a coating layer is formed by a method such as vapor deposition at a low substrate temperature. This is to prevent a decline in durability as a material.
【０００５】[0005]
【課題を解決するための手段】上述の技術的課題を解決
するため、本発明に係るガラス用撥水膜は以下のように
構成されている。すなわち、ガラスの表面にケイ素と酸
素を成分として形成されたコーティング層と、このコー
ティング層の表面に形成されたシリコーンまたはフロロ
シリコーン撥水層とからなるガラス用撥水膜であって、
コーティング層の組成をＳｉＯｘと表したときに、ｘが
、０．８≦ｘ＜２の範囲内に設定されたことを特徴とし
ている。[Means for Solving the Problems] In order to solve the above-mentioned technical problems, the water-repellent film for glass according to the present invention is constructed as follows. That is, it is a water-repellent film for glass comprising a coating layer formed on the surface of glass with silicon and oxygen as components, and a silicone or fluorosilicone water-repellent layer formed on the surface of this coating layer,
When the composition of the coating layer is expressed as SiOx, x is characterized in that it is set within the range of 0.8≦x<2.
【０００６】[0006]
【作用・効果】酸素とケイ素で組成されたコーティング
層は、成分中の酸素の比率が減少するにつれて、成膜時
の基板温度が低くてもガラス面への付着力が向上する。
この構成ではｘの値を０．８以上で２よりも小さな値に
規制しているので、従来の二酸化ケイ素（ｘ＝２）に比
較して、同一の付着力を得るのであれば基板温度の低温
化が可能となる。このような条件でコーティング層を形
成してもコーティング層中には水酸基が多く含まれるの
で、フロロシリコーン等の撥水層を強い付着力で形成し
て撥水性を長期にわたって維持することができる。[Function/Effect] As the proportion of oxygen in the components decreases, the coating layer composed of oxygen and silicon improves its adhesion to the glass surface even if the substrate temperature during film formation is low. In this configuration, the value of x is restricted to 0.8 or more and less than 2, so compared to conventional silicon dioxide (x = 2), if the same adhesion force is to be obtained, the substrate temperature will be lower. It becomes possible to lower the temperature. Even if the coating layer is formed under such conditions, the coating layer contains many hydroxyl groups, so a water-repellent layer made of fluorosilicone or the like can be formed with strong adhesion and maintain water repellency over a long period of time.
【０００７】[0007]
【実施例】以下に、図１から図３に示した本発明の１実
施例に係るガラス用撥水膜について詳細に説明する。図
１はこの撥水膜を表面に形成したソーダガラス等のガラ
ス基板の断面を示しており、１はガラス基板、２は酸素
とケイ素から組成されたコーティング層、３はフロロシ
リコーン撥水剤からなる撥水層である。[Embodiment] Below, a water-repellent film for glass according to an embodiment of the present invention shown in FIGS. 1 to 3 will be explained in detail. Figure 1 shows a cross section of a glass substrate such as soda glass on which this water-repellent film is formed. 1 is the glass substrate, 2 is a coating layer composed of oxygen and silicon, and 3 is a fluorosilicone water repellent. It is a water repellent layer.
【０００８】コ−ティング層２は、酸化ケイ素を原料と
して蒸着法により形成し、撥水層３はその表面にフロロ
シリコーン撥水剤を塗布し、加熱硬化させて形成した。
コーティング層２の成膜時の蒸着条件は以下の通りであ
る。
蒸発源材料 ： ＳｉＯ
ガラス基板温度 ： ９０℃〜２００℃酸素ガス圧
： １．３×１０−２Ｐａ膜厚
： １００ｎｍ屈折率（測定値）
： １．５５The coating layer 2 was formed by a vapor deposition method using silicon oxide as a raw material, and the water-repellent layer 3 was formed by applying a fluorosilicone water-repellent to the surface thereof and curing it by heating. The vapor deposition conditions for forming the coating layer 2 are as follows. Evaporation source material: SiO Glass substrate temperature: 90°C to 200°C Oxygen gas pressure: 1.3×10-2Pa Film thickness
: 100nm refractive index (measured value)
: 1.55
【０００９】コーティング層２は、この実施例のように
蒸着により形成する場合には、成分としてのケイ素と酸
素の比率を連続的に変化させることが可能である。すな
わち、コーティング層２の組成を仮にＳｉＯｘと表した
ときに、ｘの値（ケイ素に対する酸素の割合）を、Ｓｉ
ＯやＳｉＯ２のような１や２だけでなく、その間の任意
の値に設定することが可能である。一方、このようにし
てｘの値を変化させた場合は、屈折率も連続的に変化す
る。この対応関係を、図２において、ｘの値を縦軸に、
屈折率を横軸に取ったグラフで示している。上述した蒸
着条件で形成した本実施例のコーティング層２の屈折率
の測定値は１．５５であるので、ｘの値はこのグラフか
ら１．５であることが読取れる。When the coating layer 2 is formed by vapor deposition as in this embodiment, it is possible to continuously change the ratio of silicon and oxygen as components. That is, when the composition of the coating layer 2 is temporarily expressed as SiOx, the value of x (ratio of oxygen to silicon) is expressed as SiOx.
It is possible to set not only 1 or 2 such as O or SiO2 but also any value between them. On the other hand, when the value of x is changed in this way, the refractive index also changes continuously. This correspondence relationship is shown in Figure 2 with the value of x on the vertical axis.
It is shown in a graph with the refractive index on the horizontal axis. Since the measured value of the refractive index of the coating layer 2 of this example formed under the above-described vapor deposition conditions is 1.55, it can be read from this graph that the value of x is 1.5.
【００１０】本実施例のコーティング層２は基板温度を
９０℃〜２００℃という比較的低温に設定して蒸着法に
より形成したものであるが、この膜の耐久性が十分なも
のであるか否かを判定するために、アルカリ洗剤に浸し
たネル布（＃３００）を用いて往復摩擦による耐摩耗試
験を行なった。また、比較例として、ガラス基板上にフ
ロロシリコーンの撥水層を直接形成したものを作成し、
この撥水膜に対しても同様の耐摩耗試験を行なった。The coating layer 2 of this example was formed by vapor deposition with the substrate temperature set at a relatively low temperature of 90° C. to 200° C., but it is unclear whether this film has sufficient durability. In order to determine this, an abrasion resistance test was conducted using reciprocating friction using flannel cloth (#300) soaked in an alkaline detergent. In addition, as a comparative example, we created a fluorosilicone water-repellent layer directly formed on a glass substrate.
A similar abrasion resistance test was also conducted on this water-repellent film.
【００１１】その結果を図３のグラフに示している。こ
のグラフの縦軸には各撥水層に対する水の接触角を、横
軸には往復摩擦回数を取っており、実線が本実施例の撥
水膜での試験結果を、１点鎖線が比較例の撥水膜での試
験結果を示している。このグラフに示すように、試験前
にはそれぞれ１１０゜であった接触角が、１０００回の
摩擦試験後には、比較例で約９５゜、本実施例で１０９
゜に変化していた。また２０００回の摩擦試験後には、
比較例で接触角が約５５゜程度まで低下しているのに比
べ、本実施例のものは依然として１００゜以上の接触角
を維持していた。さらに、本実施例のものについては５
０００回の摩耗試験を行なったが、この場合にも約９５
゜程度の接触角を維持していた。The results are shown in the graph of FIG. The vertical axis of this graph shows the contact angle of water with respect to each water-repellent layer, and the horizontal axis shows the number of reciprocating frictions.The solid line shows the test results for the water-repellent film of this example, and the dashed-dotted line shows the comparison. The test results for the example water-repellent film are shown. As shown in this graph, the contact angle was 110° before the test, but after 1000 friction tests, it became approximately 95° in the comparative example and 109° in the present example.
It had changed to ゜. Also, after 2000 friction tests,
While the contact angle of the comparative example decreased to about 55°, the contact angle of the present example still maintained a contact angle of 100° or more. Furthermore, in this example, 5
The wear test was conducted 000 times, and in this case also about 95
The contact angle was maintained at about .
【００１２】このように、ガラス基板とフロロシリコー
ン撥水層との間に設けるコーティング層２におけるケイ
素に対する酸素の割合ｘを１．５に設定することにより
、基板温度が低温であったにも拘わらずガラス基板とコ
ーティング層との十分な付着力が得られたので、その結
果として耐摩耗性の優れた撥水膜を形成することができ
た。なお、ｘの値は本実施例のように１．５に限るもの
ではなく、０．８≦ｘ＜２程度の範囲内に設定しておけ
ば、基板温度を低温に設定して蒸着を行なっても耐久性
の良好な撥水膜を得ることができる。また、図２に示し
ているように、ｘの値が小さくなるほど屈折率が大きく
なり、短波長の光が吸収されやすくなるため、ガラスが
黄もしくは赤みを帯びやすくなるが、膜厚を比較的薄く
設定しておけば着色による影響は実用上殆ど生じない。As described above, by setting the ratio x of oxygen to silicon in the coating layer 2 provided between the glass substrate and the fluorosilicone water-repellent layer to 1.5, even though the substrate temperature is low, First, sufficient adhesion between the glass substrate and the coating layer was obtained, and as a result, a water-repellent film with excellent abrasion resistance could be formed. Note that the value of x is not limited to 1.5 as in this example, but if it is set within the range of 0.8≦x<2, the substrate temperature can be set to a low temperature to conduct the deposition. However, a water-repellent film with good durability can be obtained. In addition, as shown in Figure 2, the smaller the value of x, the larger the refractive index, and the easier it is to absorb short wavelength light, making the glass more likely to take on a yellow or reddish color. If it is set thinly, there will be practically no effect due to coloring.
【図１】 本発明の１実施例に係るガラス用撥水膜の
断面図である。FIG. 1 is a sectional view of a water-repellent film for glass according to an embodiment of the present invention.
【図２】 コーティング層における酸素とケイ素の成
分比に対する屈折率の変化を示すグラフである。FIG. 2 is a graph showing changes in refractive index with respect to the component ratio of oxygen and silicon in a coating layer.
【図３】 この撥水膜に対する往復摩擦試験による接
触角の変化を示すグラフである。FIG. 3 is a graph showing the change in contact angle of this water-repellent film in a reciprocating friction test.
１ ガラス基板 ２ コーティング層 ３ 撥水層 1 Glass substrate 2 Coating layer 3. Water repellent layer
Claims (1)
成分として形成されたコーティング層（２）と、該コー
ティング層（２）の表面に形成されたシリコーンまたは
フロロシリコーン撥水層（３）とからなるガラス用撥水
膜において、上記コーティング層（２）の組成をＳｉＯ
ｘと表したときに、ｘの値が、０．８≦ｘ＜２の範囲内
に設定されたことを特徴とするガラス用撥水膜。1. A coating layer (2) formed on the surface of a glass (1) containing silicon and oxygen as components, and a silicone or fluorosilicone water-repellent layer (3) formed on the surface of the coating layer (2). In the water-repellent film for glass, the composition of the coating layer (2) is SiO
A water-repellent film for glass, characterized in that, when expressed as x, the value of x is set within the range of 0.8≦x<2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07470691A JP3266284B2 (en) | 1991-03-14 | 1991-03-14 | Water repellent film for glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07470691A JP3266284B2 (en) | 1991-03-14 | 1991-03-14 | Water repellent film for glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04285036A true JPH04285036A (en) | 1992-10-09 |
| JP3266284B2 JP3266284B2 (en) | 2002-03-18 |
Family
ID=13554944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07470691A Expired - Fee Related JP3266284B2 (en) | 1991-03-14 | 1991-03-14 | Water repellent film for glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3266284B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04285037A (en) * | 1991-03-14 | 1992-10-09 | Tokai Rika Co Ltd | Electrochromic mirror with water-repellent film |
| US6001485A (en) * | 1996-11-18 | 1999-12-14 | Nippon Sheet Glass Co., Ltd. | Water repellant glass plate and method for manufacturing the same |
-
1991
- 1991-03-14 JP JP07470691A patent/JP3266284B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04285037A (en) * | 1991-03-14 | 1992-10-09 | Tokai Rika Co Ltd | Electrochromic mirror with water-repellent film |
| US6001485A (en) * | 1996-11-18 | 1999-12-14 | Nippon Sheet Glass Co., Ltd. | Water repellant glass plate and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3266284B2 (en) | 2002-03-18 |
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