JPH07335122A - Water repellent, oil repellent treatment film forming method, device thereof, and picture display - Google Patents

Abstract

PURPOSE:To provide a water repellent, oil repellent treatment film forming method, its device, and a picture display, in which reflecting characteristics of an unreflecting treatment film is not damaged, appearance defects caused by uneven coating are not generated, and quality is enhanced. CONSTITUTION:In a method for forming a chemical adsorption monomolecular film containing a water repellent, oil repellent group, a water repellent, oil repellent treatment solution is vacuumed, and the surface on which a film is to be formed is exposed in a vapor produced. The water repellent, oil repellent chemical adsorption monomolecular film is formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a water-repellent or oil-repellent film on an image display surface of a cathode ray tube or a liquid crystal display device, an optical lens, an eyeglass lens, etc. The present invention relates to a device and an image display device.

[0002]

2. Description of the Related Art Image display surfaces of cathode ray tubes and liquid crystal display devices,
When stains such as fingerprints adhere to the optical lens, the spectacle lens, etc., the stains impair the image quality and the visual quality.
In general, these surfaces are often subjected to antireflection treatment consisting of a multilayer vapor deposition film or a heterogeneous film in order to prevent reflection of extraneous light, and when dirt is attached to such surfaces, There is a problem that this stain is particularly noticeable and difficult to remove.

As a method of reducing the adherence of such dirt or improving the removability thereof, a water-repellent or oil-repellent film is formed on the image display surface of a cathode ray tube or a liquid crystal display device, the optical lens, or the antireflection surface of an eyeglass lens. There is known a method for forming anti-fouling property and improving antifouling property. Examples of the water-repellent and oil-repellent treatments include a method of applying a fluorocarbon resin by spraying or a dipping method, a method of dipping in a solvent mixed with alkoxysilane, chlorosilane, fluoroalkylsilane and fluoroalkylchlorosilane. Are known.

As a disclosure of this type of prior art, there is, for example, Japanese Patent Laid-Open No. 4-124047.

[0005]

Among the above methods for reducing the adhesion of dirt or improving the removability, the former method does not uniformly form a water-repellent or oil-repellent film only on a monomolecular layer. It is difficult and the processed film is formed as a thick film, so that there is a problem that the antireflection effect originally possessed by the anti-reflection processed film is impaired.

Further, the latter method has a problem that the coating agent is likely to remain as coating unevenness on the surface to be formed unless the processing agent runs out of liquid when the water and oil repellent film is applied. The coating unevenness of the water and oil repellent treatment agent can be wiped off with a solvent at the time when the treatment agent is not dried, but it is difficult to wipe it off cleanly. There was a problem that the effect was lost.

In order to solve the above-mentioned problems of the prior art, an object of the present invention is to make it easy to remove stains on fingerprints and the like on the image display surface of a cathode ray tube, liquid crystal display device, optical lens, spectacle lens, etc. The water-repellent and oil-repellent treated film that enhances the so-called antifouling effect does not impair the reflection characteristics of the non-reflective treated film that is the surface on which the film is formed, does not cause defects in appearance due to uneven coating, and has excellent water repellency. The object of the present invention is to provide a method for forming a monomolecular layer of a film having an oil repellent effect, its apparatus and an image display apparatus.

[0008]

In order to achieve the above object, the first invention according to claim 1 is a method for forming a chemisorption monomolecular film containing a water-repellent or oil-repellent group, wherein It is characterized in that the oil repellent treatment liquid is decompressed and the surface to be formed is exposed to the generated vapor to form a water repellent and oil repellent chemisorption monomolecular film.

The second aspect of the present invention is characterized in that the chemisorption monomolecular film containing water-repellent and oil-repellent groups is siloxane-bonded to the surface to be formed. And claim 3
According to a third aspect of the present invention, in the apparatus for forming the water-repellent / oil-repellent treatment film of the first and second aspects, a decompression mechanism for generating vapor of the water-repellent / oil-repellent treatment liquid is provided. , A shutter mechanism for blocking the water-repellent and oil-repellent treatment liquid from the air, and a mechanism for replacing with an inert gas.

Furthermore, a fourth aspect of the present invention is a cathode ray tube having a water-repellent and oil-repellent treatment film formed by the forming method of the first and second inventions and the manufacturing apparatus of the third invention. ,
The image display device includes a liquid crystal display device and other optical devices. That is, according to the present invention, the treatment agent having a water-repellent or oil-repellent group is decompressed, and the generated vapor is formed on a surface to be formed (a cathode ray tube or an image display surface of a liquid crystal display device, an optical lens,
It is characterized by forming a chemisorption monomolecular film having excellent water and oil repellency by exposing it to an eyeglass lens.

Further, this water-repellent and oil-repellent treated film is characterized in that it is siloxane-bonded to the surface to be formed. Examples of the treatment agent for obtaining the water and oil repellency effect of the present invention include alkylsilane, chlorosilane, fluoroalkylsilane and fluoroalkylchlorosilane, but trifluoropropyltrichlorosilane, tridecafluorooctyltrichlorosilane, heptadeca It is preferable to use fluoroalkylchlorosilanes such as fluorodecyltrichlorosilane and heptadecafluorodecylmethyldichlorosilane because they are excellent in water and oil repellency and generate steam at low pressure.

This fluoroalkylchlorosilane treatment agent does not generate steam at atmospheric pressure, so it is necessary to reduce the pressure. Further, when water in the air reacts with the treating agent under reduced pressure, it becomes cloudy (hydrolyzed gel). Therefore, the apparatus for forming a water-repellent and oil-repellent treatment film of the present invention includes a decompression mechanism for generating vapor of the treatment agent, a shutter mechanism for shutting off the treatment agent and air (moisture in the air), and air. It is characterized by having a mechanism for replacing with an inert gas.

[0013]

A non-reflective film formed on a cathode ray tube, an image display surface of a liquid crystal display device, an optical lens, an eyeglass lens or the like is generally made of a substance having a different refractive index in order to obtain an antireflection effect in a wide range of visible light. Are each formed of a multi-layer film laminated so as to have a constant film thickness, or a heterogeneous film having fine unevenness such that the refractive index continuously changes.

Therefore, if the film thickness distribution of these non-reflective films and the depth of fine irregularities change, the reflection characteristics also change and the original antireflection effect cannot be obtained. Therefore, the water and oil repellent film formed on the film must have a film thickness that does not affect the antireflection property. The water-repellent and oil-repellent treated film formed by the present invention is an extremely thin monomolecular film having a nanometer level, and therefore does not impair the original antireflection property of the antireflection film.

Image quality, visual quality and practical strength are naturally important for the cathode ray tube, the image display surface of a liquid crystal display device, optical lenses, spectacle lenses and the like. For this reason, the water-repellent and oil-repellent film thus formed is required to have sufficient film strength without any defect in appearance. Since the water-repellent and oil-repellent treatment film of the present invention is a method of exposing the surface where the water-repellent and oil-repellent treatment liquid is generated to the surface to be formed, the water-repellent and oil-repellent treatment liquid is mixed in the coating liquid. Unlike the dipping method, the treatment agent does not remain and uneven coating is not generated, so that the treatment agent is uniformly formed.

Further, this water-repellent and oil-repellent treated film has sufficient adhesion strength because it is chemically bonded to the surface to be formed. That is, since the hydrophilic groups on the surface to be formed and the silanol groups on the water-repellent and oil-repellent film are siloxane-bonded at a nanometer level film thickness, sufficient adhesion strength is obtained. The water / oil repellent film forming apparatus according to the present invention depressurizes the fluoroalkylchlorosilane treating agent with a vacuum pump to generate steam. Also,
The white turbidity caused by the reaction of fluoroalkylchlorosilane with the water in the air is formed by a device that has a mechanism that blocks the air and a mechanism that replaces the air with the inert gas when the water and oil repellent film is formed. White turbidity can be prevented and deterioration of the treatment agent can be prevented.

In the present invention, the method of preventing clouding of the treating agent has been described, but a method of supplying a fixed amount required for the forming apparatus may be used. The water-repellent and oil-repellent treated film thus formed has an excellent antifouling effect because the surface layer contains a fluorine group having excellent water repellency and oil repellency.

[0018]

Embodiments of the present invention will now be described in detail with reference to the drawings. FIG. 1 is an explanatory view of a processing procedure for explaining an embodiment in which the water-repellent and oil-repellent treatment film forming method according to the present invention is applied to an image display surface of a cathode ray tube. In the figure, first, the image display surface of a cathode ray tube on which an antireflection film made of a non-reflective telepanel or an inhomogeneous film is formed is cleaned with a neutral detergent, an alkaline detergent, pure water or the like (Process 1, hereinafter P- 1).

This cathode ray tube is set in the processing tank of the water and oil repellent film forming apparatus (P-2). In the steam treatment tank, a fluoroalkylchlorosilane accommodating container that is shielded from the atmosphere in the tank by a shutter is usually stored. After setting the cathode ray tube in the treatment tank, the inside of the treatment tank is sufficiently replaced with dry nitrogen (P-3).

The shutter of the fluoroalkylchlorosilane container is opened, and the pressure is reduced to about 760 mmHg by a vacuum pump (P-4). As a result, a vapor of fluoroalkylchlorosilane (heptadecafluorodecyltrichlorosilane) is generated in the treatment tank, and the fluoroalkylchlorosilane vapor generated on the image display surface of the cathode ray tube is exposed (P-5).

Then, the vacuum pump is stopped and held for 5 minutes to form a water and oil repellent film (P-6). After that, the shutter is closed and the inside of the processing tank is purged by introducing dry nitrogen (P-7), and the cathode ray tube is removed from the processing tank (P-8). Furthermore, if necessary, this cathode ray tube is heated and baked at a temperature of about 100 to 150 ° C.

The water-repellent and oil-repellent film thus formed has a very thin film thickness (about 10 to 20 angstroms), so that the multi-layer film or the heterogeneous film formed on the image display surface. It does not impair the antireflection property of the antireflection film made of, and has no defect in appearance. Add stains such as fingerprints to the water- and oil-repellent film thus formed,
As a result of comparison with a similar cathode ray tube not subjected to water and oil repellent treatment, the adhesion of dirt to the image display surface of the cathode ray tube provided with the water repellent and oil repellent film of the present invention is significantly reduced. The dirt that adhered was easily removed by simply wiping it with a dry cloth, whereas the dirt was clearly visible on the image display surface of the untreated cathode ray tube and could not be removed by just rubbing it strongly with a dry cloth.

Although the above-described embodiment is applied to the case where the present invention is applied to the image display surface of the cathode ray tube, the same applies to the surface (covered surface) of the liquid crystal display device and other optical devices. The contact angle of the water-repellent and oil-repellent film with water is 90 to 100 degrees when the antireflection film formed on the surface to be formed is a multilayer film, and 120 to 130 when it is a heterogeneous film.
It was degree.

Further, this film is manufactured by Lion Corporation "50-3
When the contact angle after rubbing 50 times with a 0 "eraser was measured, there was almost no change from that before rubbing, and it had a sufficiently strong adhesive strength. FIG. 2 is a cross section of a cathode ray tube having a water repellent and oil repellent treatment film formed on the image display surface by the water and oil repellent treatment film forming method of the present invention, where 1 is a cathode ray tube and 2 is an image display surface (panel). ) 3 is a funnel, 4 is a neck, 5 is a fluorescent screen, 6 is a shadow mask, 7 is a mask frame, 8 is a shadow mask suspension mechanism, 9 is a magnetic shield, 10 is an electron gun, 11 is a deflection yoke, and 12 is external. Correction magnetic device, 13
Is a frit glass for joining the image display surface and the funnel, and 14 is a reinforcing band.

In FIG. 1, this cathode ray tube is a so-called shadow mask type color cathode ray tube, and the image display surface 2, the funnel 3 and the neck 4 constitute a vacuum envelope, and the inside surface of the image display surface 2 is fluorescent. Surface 5 is applied. A shadow mask 6 is arranged close to the fluorescent screen 5. The shadow mask 6 is held by the mask frame 7 and is suspended and supported by the shadow mask suspension mechanism 8 on the inner wall of the image display surface 2. A magnetic shield 9 for shielding the electron beam from external magnetism is fixed to the mask frame 7.

An electron gun 1 housed in the neck 4 is equipped with a deflection yoke 11 at the transition between the funnel 3 and the neck 4.
The three electron beams Bs × 2, Bc emitted from 0 are deflected in two directions, horizontal and vertical, to form an image on the image display surface 2. The external correction magnetic device 12 finely adjusts the path of the electron beam to perform centering or purity correction.

The image display surface 2 and the funnel 3 are joined by a frit glass 13 and are tightened by a reinforcing band 14.
FIG. 3 is a cross-sectional view of a main part for explaining a first example of the image display surface in FIG. 2. A so-called telepanel having a multilayer vapor deposition film formed as a method for preventing reflection of external light of a cathode ray tube is a resin image display surface. The image display surface attached to the surface of FIG.

In the figure, 2a is a panel glass, 2b
Is a non-reflective telepanel having a multilayer vapor deposition film formed thereon, 2c is a resin for adhering the panel glass to the telepanel, and 2d.
Indicate water-repellent and oil-repellent treated films formed by the method of the present invention, respectively. On the surface of the panel image 2a of the cathode ray tube, a non-reflective telepanel 2b having a multi-layer vapor deposition film formed by a resin 2c is adhered.

On the outer surface of the telepanel 2b, a water-repellent and oil-repellent treated film 2d formed by the above-described forming method of the present invention is formed. According to the first example, the reflection characteristics of the non-reflection-treated film are not impaired, appearance defects such as coating unevenness do not occur, and excellent water and oil repellent treatment effects are achieved. FIG. 4 is a cross-sectional view of an essential part for explaining a second example of the image display surface in FIG. 2, and shows an image display surface in which a heterogeneous film is directly formed on the cathode ray tube as a method for preventing reflection of external light of the cathode ray tube.

In the figure, 2e is a high refractive index conductive film and 2e is a conductive film.
Reference symbol f represents a heterogeneous film having fine irregularities, and reference symbol 2d represents a water-repellent or oil-repellent treated film formed by the method of the present invention. The high-refractive-index conductive film 2e is directly formed on the surface of the panel image 2a of the cathode ray tube, and the water-repellent and oil-repellent treated film 2d formed by the above-described forming method of the present invention is formed on the outer surface thereof.

According to the second example, similarly to the above, the reflection characteristics of the antireflection film are not impaired, no external defects such as coating unevenness are generated, and an excellent water and oil repellent effect is obtained. Play. FIG. 5 is a schematic diagram for explaining an example of the water / oil repellent film forming apparatus of the present invention for forming a water / oil repellent film on the image display surface of the cathode ray tube as the surface to be formed. A treatment tank constituting a water and oil repellent treatment film forming device, 16 is a vacuum pump for generating vapor from the fluoroalkyl chloro treating agent, 17 is a vacuum gauge, and 18 is for blocking the fluoroalkyl chloro treating agent from air. Shutter, 19
Is dry nitrogen for replacing the atmosphere in the processing tank, 20
Are containers for containing a fluoroalkylchlorosilane (here, heptadecafluorodecyltrichlorosilane) treating agent.

In the figure, a neutral detergent, an alkaline detergent,
The non-reflective telepanel described with reference to FIG. 3 cleaned with pure water or the like, or the image display surface of the cathode ray tube 1 on which the antireflection film including the heterogeneous film described with reference to FIG. Set. In the processing bath 15, a fluoroalkylchlorosilane storage container 20 which is normally shielded from the atmosphere in the bath by a shutter 18 is stored.

After setting the cathode ray tube in the treatment tank 15, the inside of the treatment tank is sufficiently replaced with dry nitrogen 19, the shutter 18 of the fluoroalkylchlorosilane container 20 is opened, and the vacuum pump 16 is operated to reduce the pressure to about 760 mmHg. . As a result, a vapor of fluoroalkylchlorosilane is generated in the processing tank 15, the fluoroalkylchlorosilane vapor generated on the image display surface of the cathode ray tube is evaporated, and the image display surface is exposed.

Then, the vacuum pump 16 is stopped and held for about 5 minutes to form a water and oil repellent film. After that, the shutter 18 is closed, the inside of the processing bath 15 is purged by introducing dry nitrogen 19, and the cathode ray tube is removed from the processing bath. If necessary, this cathode ray tube should be
It is heated and baked at a temperature of about 150 ° C.

In this way, a thin water and oil repellent film is formed on the image display surface of the cathode ray tube 1. According to this device, the water-repellent and oil-repellent treated film does not impair the antireflection property of the antireflection film formed of the multilayer film or the heterogeneous film formed on the image display surface and has no defect in appearance. Is obtained.

[0036]

As described above, according to the method for forming a water-repellent and oil-repellent film according to the present invention and the apparatus therefor, it is formed on a cathode ray tube, an image display surface of a liquid crystal display device, an optical lens, an eyeglass lens or the like. A chemically adsorbed monomolecular film with excellent water repellency and oil repellency that does not impair the antireflection property of the existing non-reflective film and has no defects in appearance can be formed without water repellency or deterioration of the oil repellent treatment liquid. .

Therefore, it is possible to provide a cathode ray tube, a liquid crystal image display device, an optical lens, a spectacle lens, etc. which are extremely durable and have an excellent antifouling effect.

[Brief description of drawings]

FIG. 1 is an explanatory view of a processing procedure for explaining an embodiment in which the water-repellent and oil-repellent treatment film forming method according to the present invention is applied to an image display surface of a cathode ray tube.

FIG. 2 is a cross section of a cathode ray tube in which a water-repellent and oil-repellent treatment film is formed on the image display surface by the water-repellent and oil-repellent treatment film forming method of the present invention.

FIG. 3 is a cross-sectional view of main parts for explaining a first example of the image display surface in FIG.

FIG. 4 is a cross-sectional view of main parts for explaining a second example of the image display surface in FIG.

FIG. 5 is a schematic diagram illustrating an example of a water / oil repellent film forming apparatus of the present invention for forming a water / oil repellent film on an image display surface of a cathode ray tube as a surface to be formed.

[Explanation of symbols]

1 cathode ray tube 2 image display surface (panel) 3 funnel 4 neck 5 fluorescent surface 6 shadow mask 7 mask frame 8 shadow mask suspension mechanism 9 magnetic shield 10 electron gun 11 deflection yoke 12 external correction magnetic device 13 frit glass 14 reinforcing band 15 repellent Water and oil repellent treatment film forming treatment tank 16 Vacuum pump 17 Vacuum gauge 18 Shutter 19 Dry nitrogen 20 Container for containing fluoroalkylchlorosilane treatment agent.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Masahiro Ieda 3300 Hayano, Mobara-shi, Chiba Hitachi, Ltd. Electronic Device Division

Claims (4)

[Claims] 1. A method for forming a chemisorption monomolecular film containing a water-repellent or oil-repellent group, wherein the water-repellent or oil-repellent treatment liquid is decompressed, and the surface to be formed is exposed to the generated vapor, A method for forming a water-repellent and oil-repellent treated film, which comprises forming an oil-repellent chemisorption monomolecular film. 2. A method for forming a water-repellent or oil-repellent treated film, wherein a chemisorption monomolecular film containing a water-repellent or oil-repellent group is siloxane-bonded to the surface to be formed. 3. A depressurizing mechanism for generating steam of the water-repellent / oil-repellent treatment liquid, a shutter mechanism for blocking the water-repellent / oil-repellent treatment liquid from air, and a mechanism for replacing with an inert gas. A water-repellent and oil-repellent film forming device. 4. A method for forming a water / oil repellent film according to any one of claims 1 and 2, and a water / oil repellent process formed by the apparatus for forming a water / oil repellent film according to claim 3. An image display device having a film on the image display surface.