JPS60231442A - Water-repellent glass - Google Patents

Abstract

PURPOSE:To obtain the titled water-repellent glass having water-repellency and excellent adhesiveness of the surface of glass by incorporating a polymer having excellent adhesiveness to glass essentially into the glass-sied part of a water- repellent film of an organo-silicon compd. to be formed on the surface of glass, and incorporating a polymer having excellent water repellency essentially into the external side of the film. CONSTITUTION:Said water-repellent glass is obtained by coating a polymer of a water-repellent component on the surface 1 of glass through a polymer as an adhesive component. Namely, a layer 3 of the adhesive component is formed on the glass side of a water-repellent film 2a, and a layer 4 of the water-repellent component is formed on the external side. A polymer of an organo-silicon compd. (e.g., tetramethylsilane) having a siloxane bond is used as said adhesive component, and a polymer of an organo-silicon compd. (e.g., tetraethoxysilane) having more carbon than said organo-silicon compd. is applied as the water- repellent component. The water-repellent glass having exceptionally excellent durability as well as surfficient water repellency can be obtained in this way.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to window glass for buildings, automobiles, and vehicles.

Windshield glass for aircraft or ships, optical glass used in eyeglasses and cameras, household glassware (e.g. glass cups, tableware, aquariums, vases, baby bottles, etc.), and other items that require water repellency. This article relates to water-repellent glass useful for glass products.

(Prior Art) Conventionally, organosilicon compounds having siloxane bonds have been widely used as water-repellent treatment agents for glass, and methods for forming a siloxane polymer film on the surface of glass to make it water-repellent include, for example. ■ A method in which monomer gas of alkylhalosilanes is applied to the glass surface and then hydrolyzed; ■ A solution of polydimethylsiloxane is applied to the glass surface and then heated and dried to form a silicone film on the glass surface. Methods to do this have been developed and used. However, water-repellent glass obtained by such conventional manufacturing methods generally has weak adhesive strength between the water-repellent film and the glass surface.
For example, in a peeling test in which an adhesive tape was applied to the surface of water-repellent glass and then peeled off, the water-repellent film easily peeled off, indicating that the durability of the water-repellent treatment (peel resistance, etc.) was poor. Furthermore, in the manufacturing process according to method (1) above, harmful hydrogen halide gas is generated, and in method (2) above, heat drying causes a decrease in the strength of the glass, and the glass manufactured according to this method is water repellent. This method has problems such as the need for a long period of time to remove the solvent from the treated membrane.

(Objective of the Invention) An object of the present invention is to provide water-repellent treated glass that not only has sufficient water repellency but also is extremely durable and does not cause the above-mentioned adverse effects due to the manufacturing method.

(Structure of the Invention) The water-repellent glass of the present invention uses an organosilicon compound as a base for the water-repellent treatment film formed on the surface of the glass, and the glass side portion of the treatment film is made of polymer that has good adhesion to the glass. By mainly distributing a substance (adhesive component) and mainly distributing a highly water-repellent polymer (water-repellent component) on the outer side of the treated membrane, good water repellency is ensured. This product aims to improve the adhesive force with the glass surface, and its composition consists of a polymer of an organosilicon compound having a siloxane bond as an adhesive component, and a carbon composition from the organosilicon compound as a water repellent component. In the glass side part of the membrane where the proportion of oxygen is high or the composition ratio of oxygen is small, all or a relatively large amount of the adhesive component polymer is contained, and in the outer part, the water repellent component polymer is contained completely or relatively. It is characterized by its high content in. Further, to explain the present invention in detail, the water-repellent glass of the present invention is prepared by adhering a polymer as an adhesive component to the surface l of the glass, and then applying a water-repellent component thereon as shown in FIG. One example is one in which a layer 3 of an adhesive component is formed on the glass side portion of the water-repellent treated film 2a by coating with a polymer, and a layer 4 of a water-repellent component is formed on the outside portion thereof. A polymer of an organosilicon compound having a siloxane bond (for example, tetramethoxysilane (Si(OCH3)4),)rimethoxymethylsilane (OHSi(0CH3)3) is used as a binding component, while the organic An organosilicon compound having a higher proportion of carbon than a silicon compound (for example, when the adhesive component compound is tetramethoxysilane, tetraethoxysilane (5i(QC,,H5),).

Polymers of tetrapropoxysilane (5i(OC3H7)4), etc.), or organosilicon compounds with a lower oxygen composition ratio than the above organosilicon compounds (for example, when the adhesive component compound is tetramethoxysilano, trimethylmethoxysilane ( (OH3)3SiOC1(3),
Dimethyldimethoxysila (((H3)2Si(OCH3
) 2) etc.) or fluorine compounds (e.g. hexafluoropropylene (CF2 = 0F-CF3)
, tetrafluoroethylene (CF2=CF2), etc.) is applied. Further, as shown in FIG. 2, the water-repellent treated glass of the present invention has a water-repellent treated film 2b in which the composition ratio of the adhesive component polymer continuously decreases from the glass side to the outside side, and It may be formed so that the composition ratio of the polymer of the component increases continuously. Furthermore, as shown in FIG. Layers 3 of water-repellent components are formed in the side portions, and in the layer 5 in the center, polymers of adhesive components and water-repellent components exist with different chemical compositions as in the case of FIG. It may be something like that. In addition, in producing the water-repellent glass of the present invention, for example, by plasma polymerization, raw materials for the adhesive component and the water-repellent component are sequentially or their mixing ratios are varied in a reduced pressure atmosphere, By coating the glass surface with adhesive and causing a polymerization reaction,
A water-repellent treated film may be formed by forming a polymer of an adhesive component and a water-repellent component in a layered manner or by continuously changing the composition ratio of both components. According to the plasma polymerization method, no harmful gases are generated during the manufacturing process, there are no problems related to solvent removal, and there is no problem such as a decrease in the strength of glass.

(Example) The present invention will be explained in detail below.

Example 1 A glass slide was placed in a Pelger type reactor, and plasma polymerization (pressure 0, l Tor
r, input i o ow , frequency 13.58 MHz)
The water-repellent glass of Example 1 (the first one) was prepared by adhering a polymer of tetramethoxysilane (adhesive component) to the glass surface and coating it with a polymer of tetraethoxysilane (water-repellent component). Figure) was manufactured. In order to know the water-repellent properties of the glass, for example, the wettability of the glass surface, the contact angle with distilled water, which is a guideline, was investigated using a surface contact angle measuring device. In the case of untreated glass slides, the contact angle was l
It was Oo. Furthermore, the water-repellent glass was transparent, and when it was immersed in water and then lifted out of the water for visual inspection, the view on the other side of the glass immediately became clear. In the case of untreated glass, the vision was blurred for a while.

Furthermore, in the case of the glass of Example 1, water on the surface of the glass could be easily wiped off with paper.

In addition, in order to find out the durability of the water repellent treatment, we conducted a peeling test (applying adhesive tape to the glass surface and then peeling off the tape) as a guide, and found that Example 1
In this case, the water-repellent film on the glass surface did not peel off.

Example 2 Plasma polymerization was carried out under the same conditions as in Example 1, while supplying tetramethoxysilane and trimethylmethoxysilane while changing their compositions continuously with the polymerization time as shown in FIG. 4. Example of forming a water-repellent film so that the composition ratio of tetramethoxysilane polymer continuously decreases and the composition ratio of trimethylmethoxysilane polymer continuously increases from the glass side to the outside side. Water-repellent treated glass No. 2 (Figure 2) was manufactured. When the water repellency of the glass was examined in the same manner as in Example 1, the contact angle on the surface was over 90@. Further, when a peeling test was conducted in the same manner as in Example 1, the surface film did not peel off.

Example 3 Trimethoxymethylsilane and hexafluoropropylene in 1 part
Plasma polymerization was performed (other conditions were the same as in Example 1) while the compositions of both were continuously changed as shown in Figure 5, and the water-repellent film was applied from the glass side to the outside side. The water-repellent glass of Example 3 was produced in which the composition ratio of the polymer of trimethoxymethylsilane was continuously decreased and the composition ratio of the polymer of hexafluoride propylene was continuously increased. When measured in the same manner as in Example 1, the contact angle on the surface of this treated glass was 95°, confirming that it was non-wettable glass. Furthermore, in the same peeling test as in Example 1, the water-repellent treated film on the glass surface did not peel off.

Example 4 Using trimethoxymethylsilane and tetrafluoroethylene as raw materials, plasma polymerization was performed with the compositions of both changed as shown in Figure 6 (other conditions were the same as in Example 1) to produce a water-repellent treated film. A layer of a polymer of trimethoxymethylsilane is formed on the glass side of the glass, a layer of a polymer of tetrafluoroethylene is formed on the outer side of the glass, and a layer of a polymer of trimethoxysilane and a polymer of tetrafluoroethylene is formed on the central part of the glass. A water-repellent treated glass (FIG. 3) of Example 4 was produced in which the composition ratio of . The contact angle on the surface of this glass was 100'.

In the peeling test, the water-repellent treated film did not peel off. Note that the measurement conditions are the same as in Example 1.

(Effects of the Invention) As explained above, in the water-repellent glass of the present invention, a polymer of an organosilicon compound having a siloxane bond is mainly arranged in the glass-side portion of the water-repellent-treated film, and the outer portion It has sufficient water repellency by mainly arranging an organosilicon compound with a higher carbon composition ratio or a lower oxygen composition ratio than that compound, or a polymer of a fluorine compound,
The surface is hard to stain, easy to dry even after washing, and remains clean even after drying. Also, even if you sprinkle water on it, the view on the other side of the glass will immediately appear clearly. In addition, the glass water-repellent treatment film of the present invention has strong adhesion to the glass surface, and the durability of the water-repellent treatment is significantly improved. Moreover, the water-repellent glass of the present invention can be produced by plasma polymerization, and in this case, the production process does not cause various adverse effects (such as the generation of harmful gases) that occur in the prior art.

[Brief explanation of drawings]

Figures 1 to 3 are sectional views showing the main parts of various typical examples of water-repellent treated glass of the present invention, and Figures 4 to 6 are water-repellent treated glasses of Examples 2 to 4 of the present invention. 1 is a graph showing plasma polymerization conditions for producing glass. In the figure, 1...Glass surface 2a, 2b, 2c...Water repellent treated film 3...Adhesive component layer 4...Water repellent component layer C Angin Kai 4th figure 5th figure, sec Fang 6th figure double number time gate, trade C

Claims (4)

[Claims] (1) A polymer of an organosilicon compound having a siloxane bond as an adhesive component, and a polymer of a blue component with a higher carbon content than the organosilicon compound or oxygen as a water repellent component on the surface of the glass. 1. A water-repellent treated glass characterized by containing all or a relatively large amount of polymerized water-repellent components, and containing all or a relatively large amount of polymerized water-repellent components in the outer portion thereof. (2) A layer of an adhesive component is formed on the glass side portion of the water-repellent treated film, and a layer of a water-repellent component is formed on the outside portion thereof. Water-repellent glass. (3) The water-repellent treated film was formed so that the composition ratio of the adhesive component polymer continuously decreased and the composition ratio of the water-repellent component polymer continuously increased from the glass side to the outside side. A water-repellent treated glass according to claim 1, characterized in that: (4) A water-repellent treated film is formed by coating a glass surface with a compound of an adhesive component and a water-repellent component and polymerizing the same using a plasma polymerization method. Water-repellent glass as described in any one of Item 3.