JP2001259515A - Substrate coated with functional film having gradation part and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To remove the gradation part of a functional film made from an organic compound or the functional film freely and easily by a dry process. SOLUTION: In the production of a substrate coated with the functional film having the gradation part in which the functions of a functional part in which the surface of the substrate is coated with the functional film made from the organic compound and the functional film are changed gradually, an area corresponding to the gradation part or a film removing part is subjected to corona discharge, exposure to plasma, or ultraviolet irradiation to form the gradation part or the film removing part.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a construction, a vehicle,
Functional film coating having an organic compound coated on the surface of an industrial or mirror surface, particularly a water-repellent coating, which has a blurred part in which the function of the functional film is gradually changed The present invention relates to a substrate and a method for manufacturing the substrate.

[0002]

2. Description of the Related Art The following patent applications relating to partially water-repellent treated glass having a portion having a water-repellent coating formed on the surface of a substrate such as glass and a portion having no water-repellent coating are known.

For example, Japanese Patent Application Laid-Open No. Hei 7-157336 discloses that a transparent substrate surface has a water-repellent film forming portion and a non-film forming portion, and a solvent is applied to the non-film forming portion at the time of coating. A method for forming a water-repellent film is described, in which the liquid and a part thereof are applied so as to gradually reduce the thickness of the boundary portion so that the boundary between the liquid-repellent film and the non-formed portion is less noticeable. Japanese Unexamined Patent Publication No. Hei 9-142888 discloses that a glass substrate is patterned with characters, patterns and / or patterns, a transparent water-repellent film is formed on the patterned portion, and the light scattering intensity when water such as waterdrops or raindrops adheres. A decorative glass in which the patterning portion is lifted by the difference between the two is described. In Japanese Patent Application Laid-Open No. 10-297939, a water-repellent film is applied only to a wiper wiping portion of an automotive window glass.
In other parts, a partially water-repellent treated glass which does not have a water-repellent film is disclosed.

Japanese Patent Application Laid-Open No. H11-194202 discloses that, in order to prevent foreign substances from adhering to the surface of an optical element during a manufacturing process, an organic molecular substance having a group that does not chemically bond to an outermost layer substance of the optical element is disclosed. An optical element is disclosed in which a temporary protective film is formed, and in a final step, the temporary protective film on the surface of the optical element and foreign substances adhering thereto are removed together by irradiation with ultraviolet rays.

[0005]

However, the above-mentioned Japanese Patent Application Laid-Open Nos. Hei 7-157336 and Hei 9-14288.
No. 8, JP-A-10-297939 discloses a method of manufacturing a partially water-repellent glass by masking a portion not subjected to the water-repellent treatment before performing the water-repellent treatment, or performing a water-repellent treatment. After that, the part where the film is not removed is masked, and the partially water-repellent glass is manufactured by removing the water-repellent film by ceria polishing or alkali treatment, etc. These methods have low productivity and are widely used practically In addition, in the method of masking a portion that is not subjected to the water-repellent treatment before the water-repellent treatment, the effect of the adhesive component of the masking material remains on the substrate surface after the masking is removed, and the contact angle with respect to the water droplet is reduced. Problems such as enlargement also occur.

Further, the method disclosed in Japanese Patent Application Laid-Open No. 7-157336 is capable of continuously controlling the water-repellent performance at the boundary area between the water-repellent film-forming portion and the non-film-forming portion, and properly controlling the width of the boundary. It is difficult to control, and there are problems such as generation of a large amount of waste liquid. Also, Japanese Patent Application Laid-Open No. 11-19420
The method of removing the film described in Japanese Patent Publication No. 2 is to finally remove all of the formed temporary protective film, which complicates the process and is inefficient. In addition, the protective film component to be decomposed is an organic polymer substance having a group that does not chemically bond to the outermost layer of the optical element, and the purpose is to prevent foreign matter from adhering, and the patterning method for removing a part of the functional film of the present invention is used. The purpose is different.

[0007]

Means for Solving the Problems The present inventors have conducted various studies in view of the above-mentioned problems, and as a result, have been able to freely remove the blurred portion of the functional film made of an organic compound or the functional film by a dry method. A functional film-coated substrate having a blurred portion that can be easily manufactured with higher productivity and a method for manufacturing the same have been found.

That is, the functional film-coated substrate having a blurred portion of the present invention forms a functional portion in which a functional film made of an organic compound is coated on the substrate surface and a blurred portion in which the function of the functional film gradually changes. In addition, the blurred portion is formed by changing the concentration of the functional material without changing the thickness of the functional film.

Further, the functional film-coated substrate having a blurred portion according to the present invention is characterized in that the functional film is a water-repellent film, and has a water-repellent functional portion having a contact angle to a water droplet of 70 ° or more. A water-repellent portion and a blurred portion having a gradually changing contact angle are provided, and a non-water-repellent portion having a contact angle to a water droplet of 20 ° or less is provided adjacent to the blurred portion. And

Furthermore, the functional film-coated substrate having a blurred portion according to the present invention is characterized in that the contact angle of the blurred portion with respect to a water drop is continuously changed. Furthermore, the functional film-coated substrate having a blurred portion of the present invention is characterized in that the film thickness of the water-repellent portion and the blurred portion is 20 nm or less, and the water-repellent portion and the blurred portion are a fluoroalkyl group-containing silane. It is characterized by forming a water-repellent coating made of a compound.

Further, the method for producing a functional film-coated substrate having a blurred portion according to the present invention comprises a functional portion in which a functional film made of an organic compound is coated on the substrate surface and a blurred portion in which the function of the functional film gradually changes. When manufacturing a functional film-coated substrate having the following, a region corresponding to the blurred portion is subjected to corona discharge, plasma exposure or ultraviolet irradiation treatment to form a blurred portion.

Further, the method for producing a functional film-coated substrate having a blurred portion according to the present invention includes forming the blurred portion by changing the treatment time and / or the intensity of corona discharge, plasma exposure or ultraviolet irradiation. In addition, the function of the blurred portion is continuously changed by continuously changing the processing time and / or processing intensity of corona discharge, plasma exposure or ultraviolet irradiation.

Still further, according to the method of the present invention for producing a functional film-coated substrate having a blurred portion, the functional film is coated on the substrate surface, and then a region corresponding to a non-functional portion provided adjacent to the blurred portion is provided. The functional film is removed by performing corona discharge, plasma exposure, or ultraviolet irradiation. Further, the method for producing a functional film-coated substrate having a blurred portion according to the present invention is characterized in that the functional film is a water-repellent film.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The functional film of the present invention is not particularly limited as long as it is a film made of an organic compound. For example, a water-repellent film, a heat ray shielding film, an ultraviolet ray shielding film, an antifogging film And a film made of an organic compound such as a colored film. In addition to organic compounds,
It can also be used for a film made of an inorganic hybrid. The function of the functional film of the present invention refers to water repellency, heat ray shielding property, ultraviolet ray shielding property, anti-fogging property, coloring and the like with respect to the functional film.

Hereinafter, a functional film-coated substrate having a blurred portion according to the present invention and a method for manufacturing the same will be described by taking a water-repellent coating as a typical example of the functional film of the present invention.
The water repellent coating of the present invention can be produced, for example, by the following steps. (1) A step of forming a water-repellent coating by applying a water-repellent liquid to the entire surface of one side of a glass substrate and then drying the liquid-repellent coating. (2) Corona discharge and plasma are applied to the water-repellent coating corresponding to the non-water-repellent portion. A step of removing the film by performing exposure or ultraviolet irradiation treatment to form a non-water repellent portion; (3) a portion corresponding to the blurred portion is subjected to corona discharge, plasma exposure, or ultraviolet irradiation treatment to form a blurred portion Forming a.

As the water-repellent liquid for forming the water-repellent film, for example, a predetermined amount of a water-repellent agent composed of a fluoroalkyl group-containing silane compound, a diluting solvent and an acidic aqueous solution as a catalyst are mixed for a predetermined time. The hydrolysis reaction is terminated by stirring, then a dehydrating agent is added to the solution, and the solution is subjected to a dehydration treatment for a predetermined time to carry out polycondensation.

The starting material mentioned above is a fluoroalkylalkoxysilane-based compound or a fluoroalkylhalogenated silane-based compound as a water-repellent, such as CF ₃ (CF ₂ ) ₁₁ CH ₂ CH ₂ Si.
(OR) ₃ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (O
R) ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OR) ₃ , C
F ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OR) ₃ , CF ₃ (C
F ₂ ) ₁₁ CH ₂ CH ₂ SiR (OR) ₂ , CF ₃ (CF ₂ ) ₉
CH ₂ CH ₂ SiR (OR) ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ C
H ₂ SiR (OR) ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si
R (OR) ₂ , CF ₃ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF
₂ ) ₇ CH ₂ CH ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂
SiRCl ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ SiCl ₃ ,
CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ SiRCl ₂ or the like can be used. Note that R in the above chemical formula is CH ₃ , C ₂ H
₅ represents an alkyl group such as C ₃ H ₇ .

As the diluting solvent, isopropyl alcohol
(Hereinafter abbreviated as “i-PA”), methanol,
A lower alcohol solvent having 5 or less carbon atoms, such as ethanol, may be used, and ethers and ketones can be used in addition to alcohols. Particularly, alcohols containing isopropyl alcohol as a main component can be used. It is preferable as a diluting solvent in preparing a coating solution.

The acidic aqueous solution used as the catalyst may be an inorganic acid such as nitric acid, hydrochloric acid or sulfuric acid or an organic acid such as acetic acid or citric acid having a concentration of 0.01 N or more, preferably about 0.1 N to 13 N. it can. The water repellent: diluting solvent: acidic aqueous solution is 1: 5 to 50: 0.09 in weight ratio.
A range of from 1.0 to 1.0 is preferable, but is not limited to these ranges.

As the dehydrating agent, silica gel, synthetic zeolite, activated alumina and the like can be used, but it is not limited thereto. In addition, there is no particular limitation on the case where polycondensation is performed after the completion of hydrolysis or the case where polycondensation starts during the hydrolysis.

The water-repellent liquid is not limited to the above-mentioned method, and a dimethylsilicone-based water-repellent, a mixed water-repellent of the dimethylsilicone-based water-repellent, and a fluororesin hybridized to silica sol. It is also possible to use a water-repellent coating or the like. In addition, the solid content concentration in terms of oxide of the coating solution for obtaining the hybrid film is 0.2 to 20 watts.
It is good to be t%. If it is less than 0.2 wt%, it is too dilute to form a film, and if it exceeds 20 wt%, the concentration is too high and the film thickness becomes large, causing cracks in the film or clouding during film formation. This leads to a failure to obtain a high-quality thin film and an increase in material costs.

As a method for applying a water-repellent liquid to a glass substrate,
Hand coating (brush coating, rubbing), nozzle flow
Various coating methods such as known coating methods such as a coating method, a dipping method, a spray method, a reverse coating method, a flexographic method, a printing method, a flow coating method or a spin coating method, and a combination thereof can be appropriately adopted. It is. The viscosity of the water-repellent liquid is preferably adjusted to 0.001 to 0.1 N · s / m ^2, and if it is less than 0.001 N · s / m ² , the viscosity is too low to form a film. If it exceeds s / m ² , it is not preferable because the film is excessively formed when the film is formed, and the film forming property is deteriorated.

The condition for applying the water-repellent liquid on the surface of the glass substrate is that the humidity of the atmosphere is usually about 75 to activate the reaction between the silanol group of the water-repellent component and the hydroxyl group on the surface of the substrate.
% RH or less is preferable, but not limited thereto. It is preferable that the surface of the glass substrate to which the water repellent liquid is applied is subjected to an acid treatment in advance so that the surface of the glass substrate is increased in strength and the like. The film thickness of the water-repellent coating is preferably about 20 nm or less, and is preferably about 10 nm on average, and is a stack of a single molecule to several molecules. Since the water-repellent film formed from the fluoroalkyl group-containing silane compound or the like is a compound having high reactivity (chemical bonding) with the glass substrate, the obtained water-repellent film is strongly bonded to the surface of the glass substrate. It is in a state of being combined with.

The substrate used in the present invention is not particularly limited to the above-mentioned glass, plastics, metals, ceramics and the like, but in the case of a water-repellent coating, a transparent substrate such as glass or plastic is used. Is particularly effective and preferable. The water-repellent liquid applied to the glass surface
Subsequently, by drying and curing at a temperature of about 150 ° C. or less, a glass coated with a water-repellent film having a water-repellent film formed on the entire surface is obtained. In some cases, it may be left at room temperature for curing.

Next, a method for forming a non-water-repellent portion from a glass coated with a water-repellent film in which a water-repellent film is formed on one entire surface of a glass substrate will be described below. First, when the portion from which the water-repellent coating is to be removed is strip-shaped, a high voltage is applied to the discharge wire at the portion where the coating is to be removed without providing a blocking member, and the portion passing directly below the wire is subjected to corona discharge. Exposure to degrade the film, and turn off the voltage of the discharge wire to the part where the film is not removed.
It is also possible to perform only by switching the ON / OFF control of the discharge.

When it is desired to remove the water-repellent coating in a more complicated pattern, a masking material or a masking material for blocking the unremoved portions so as to expose corona discharge or plasma only to the portions where the coating is desired to be removed. It is also possible to dispose a shielding body such as a shielding plate in a portion where the water-repellent coating is not desired to be removed. Note that the shield may be disposed immediately above the substrate that is the object to be exposed, or may be provided near the discharge wire. The masking material is not particularly limited as long as it can effectively block corona and ion plasma caused by discharge, and a masking material such as a plastic film can be used, and the film is not removed. The part can be directly covered with a masking material.
In particular, in the case of ultraviolet irradiation, a method of performing irradiation treatment using a masking plate that continuously changes the intensity of ultraviolet light transmitted through the light shielding plate is effective.

Exposure to corona discharge can be performed as follows. Corona discharge exposure conditions (output, output frequency,
The output waveform, exposure time, distance to the film, etc.) can be appropriately selected as appropriate depending on the type of the substrate, the quality of the water-repellent film, the film thickness, and the like. The output of the corona discharge is about 0.1 to 2.0 kW, and the output frequency is about 35 kHz ± 5 k
Hz, the output waveform is a sine wave, and the exposure time can be adjusted by changing the time required for the substrate glass to pass through the processing surface of the glass within a range of about 0.1 to 3.0 m / min. Further, the distance between the discharge electrode and the ground electrode plate needs to be about 10 mm or less, and the distance between the discharge electrode and the coating is about 2 to 5 mm, preferably 2.
It is good to be about 5 mm. On the other hand, when the plasma is exposed, the output is about 0.1 to 2.0 kW, and the exposure time is about 0.1 to 3.0 m / sec.
min. The distance between the discharge gun and the coating is about 2 to 30 mm, preferably about 8 to 10 mm. Since a plasma jet does not require an earth electrode, it is more suitable for a molded product having a two-dimensional or three-dimensional shape such as bent glass.

As described above, when corona discharge, plasma or ultraviolet rays having high energy is exposed to the fluoroalkylsilane compound (FAS) which is a water-repellent film, electrons and ions (corona,
Plasma), Si-C bonds and C-
The C bond is broken and decomposed / degraded. At this time, it is appropriate to minimize the exposure time, and unnecessary treatment for a long time not only lowers the productivity, but also raises the temperature of the substrate glass abnormally and generates harmful ozone. This is undesirable because of the increased volume. When the masking material is directly applied to the surface of the film, the masking material is removed, washed with water, and dried to obtain a partially water-repellent glass in which only the portion covered with the masking material has a water-repellent film. .

Next, a method of forming a blurred portion will be described. In the glass substrate from which the water-repellent film was removed by the corona discharge treatment as described above to form a non-water-repellent portion, immediately after the wire wire reached the region corresponding to the blurred portion, the application was performed in the non-water-repellent portion. The voltage is changed without changing the transfer speed only to the transfer speed at the time of forming the non-water-repellent portion, for example, 0.1 to 2.0 m / min in about several seconds,
Immediately after that, the power is turned off (OFF) for corona discharge, and at the same time, the wafer is transported at a normal transport speed (2.0 m / min). By this treatment, a blurred portion in which the contact angle continuously increased over a certain width was formed. The width of the blurred part, the inclination of the contact angle with water from the water-repellent part to the non-water-repellent part, etc. can be freely selected by appropriately selecting the conditions such as the conveying speed, the time to switch the conveying speed, the time to turn off the power of the corona discharge, etc. It is possible to In the plasma exposure, similarly to the corona discharge, by appropriately selecting conditions such as the transport speed, the time for switching the transport speed, and the time for turning off the power of the apparatus, the width of the blurred portion, the water-repellent portion to the non-water-repellent portion, Can be freely selected. Also, the width, contact angle and the like of the blurred portion can be freely changed by selecting the exposure intensity of the corona discharge or plasma exposure treatment. As described above, the water-repellent coating was subjected to corona discharge, plasma exposure or ultraviolet irradiation treatment to form a blurred portion, but the change in the contact angle did not correspond to the change in the film thickness, but was formed on the glass substrate. It is considered to depend on the concentration of the fluoroalkylsilane-based compound, that is, the coverage or area of the fluoroalkylsilane-based compound.

The present invention is not limited to the above embodiment. For example, only a water-repellent portion and a blurred portion may be formed without providing a non-water-repellent portion on the substrate surface.
In addition, the blurred portion may be appropriately selected according to the purpose, such as by continuously changing the contact angle indicating the water repellency, or by gradually changing the contact angle in a stepped manner or the like. Further, in the above example, after forming a water-repellent coating on the entire surface of one side of the substrate, the film corresponding to the non-water-repellent portion was removed. The masking is not limited to forming a non-water-repellent portion. Furthermore, although the above describes the processing method by corona discharge, plasma exposure or ultraviolet irradiation, the same effect can be obtained by changing the processing time and processing intensity in various dry methods such as ion etching and electron beam irradiation. Needless to say, this is obtained.

The glass coated with a water-repellent film having a blurred portion of the water-repellent film obtained by the above-mentioned method must have an appropriate contact angle in order for the water-repellent film coated on the glass surface to exhibit excellent water repellency. It is important to have both θ (°) and falling property δ (μl). For example, the contact angle θ is preferably 70 ° or more, more preferably 90 ° or more as the water-repellent portion. The contact angle of the portion is preferably set to 20 ° or less. The contact angle of the blurred portion may be between the water-repellent portion and the non-water-repellent portion.

When the substrate is glass, it is not particularly limited to colorless or colored, and its type, color tone, shape and the like. Needless to say, it can be used as a laminated sheet or as a laminated glass. Further, various coatings such as an ultraviolet shielding film, a heat ray shielding film, and a conductive film may be formed on the inner surface of the glass vehicle. In the above, an example was described in which glass was used as the substrate and a water-repellent coating was used as the functional coating.However, various functional coatings were partially applied to other substrates such as plastics and other functional films in the same manner. It is possible to obtain a substrate that has been removed.

Uses of the functional film-coated substrate having a blurred portion produced according to the present invention include:
It can be used for industrial purposes, mirrors, etc., but is not particularly limited to these uses. For example, in the case of a door glass for an automobile, a strip-shaped region near a portion of the door glass that is slid by a stabilizer is a portion where a water-repellent coating is not formed, and other portions are partially repelled with a water-repellent coating. By using water glass, the contact angle with water of the water-repellent film forming portion in rainy weather is about 70 ° or more, and the non-water-repellent portion has a contact angle of about 1 ° which is the same as that of a normal glass surface.
0 to 60 ° or less, and different contact angles with water droplets coexist in the same glass surface.However, during rainy weather, the driver usually sees through the large contact angle portion where the water-repellent coating is formed. This makes it possible to clearly see the scenery outside the vehicle or the door mirror, thereby improving safety. In the above case, if a water-repellent coating is formed on the entire surface including the portion slid by the stabilizer, the coating on the sliding portion is worn faster than other portions, and the contact angle of the portion slid by the stabilizer is reduced. In particular, when the weather is rainy, the portion rises like a streak, which is not preferable in appearance.

In the case of a relatively simple partial treatment in which only the front part of the door glass is subjected to non-water-repellent treatment, partial non-water-repellent treatment can be performed only by ON / OFF operation of corona discharge. Sticking of materials is basically unnecessary.
Of course, when complicated patterning is required, it is possible to cope with it by attaching a masking material, or to provide a shielding plate between the electrode and the glass surface instead of the masking material. Further, the processing time can be further reduced by using a plurality of discharge wires. Further, the shape of the electrode may be a needle shape or the like instead of a wire shape, but a wire shape is preferable because it is easy to operate.

[0035]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment.

(1) Preparation of Glass An automobile door glass was prepared as a substrate. The glass surface on the outside of the vehicle door glass was polished with a brush polisher using an abrasive solution (Mirek A manufactured by Mitsui Kinzoku Kogyo Co., Ltd. in water at about 1%), and then thoroughly washed with water.
Next, an “acid treatment” of immersing in a 0.1N sulfuric acid aqueous solution at 35 ° C. for 1 minute was performed.

(2) Water-repellent treatment Water-repellent treatment was applied to the entire surface of one side of the door glass for automobile. The water-repellent treatment is performed by applying a water-repellent liquid (under an environment of 23 ° C. and 45% RH), dropping a water-repellent liquid of about 4 ml / pc onto a glass substrate, and sufficiently stretching the entire surface of the glass with a cotton cloth (trade name: Bencott). ) And air-dried for 5 minutes to obtain a water-repellent coating. In addition,
The water-repellent liquid is diluted with heptadecafluorodecyltrimethoxysilane (CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ : KBM-7803 manufactured by Shin-Etsu Chemical, hereinafter referred to as FAS) as a water-repellent. Isopropyl alcohol (i-PA) as a solvent,
0.1N nitric acid (HNO ₃ ) was mixed with the acid catalyst at a weight ratio of 1: 25: 0.3, and the mixture was stirred at room temperature for 2 hours. (Equivalent to molecular sieve 4A), dehydrated for about 16 hours, and finally obtained by filtration through filter paper.

(3) Film Removal Using a corona discharge device, the water-repellent coating is formed on the entire outer surface of the vehicle by the above-mentioned (2). (Contact angle 20
° or less), and after passing through a blurred portion where the contact angle continuously increases over about 100 mm, the contact angle becomes 105
Next, a method for producing a partially water-repellent coated glass having a blurred portion having a water-repellent coating exhibiting an angle of about 110 ° will be specifically described.

First, as shown in FIG. 1, a door glass 1 which has been subjected to a water-repellent treatment on the entire surface on one side of a glass is placed on a conveyor belt 2 with the coating face up, and a corona discharge device 3 (C
T-0212 (Kasuga Electric Co., Ltd.). The corona discharge device 3 has bar-shaped terminals 4 and 5 disposed on both sides of the conveyor belt 2, and between the terminals 4 and 5 is a surface of the door glass 1 having a curved shape and one electrode. It is stretched so that the distance from the wire 6 is equal. Further, an aluminum plate was provided as the ground electrode 8 along the lower surface of the door glass 1. When the door glass 1 in which the water-repellent coating is coated on the entire exterior side (convex side) of the door glass 1 is carried into the corona discharge device 3,
At the same time, a voltage of 0.4 kW is applied between the electrodes, and the corona discharge 7 is exposed over the entire width of the door glass 1 from the entire width of the wire 6. At this time, assuming that the glass conveyance speed was constant at 0.1 m / min, the contact angle of the surface after the treatment was about 10 °, and the water-repellent coating was completely removed and the surface was hydrophilized.

Next, immediately after the wire 6 reaches the area corresponding to the blurred portion, the transport speed is set to 0.1 m / mi.
n to 2.0 m / min for about 6 seconds (0.1 min), and immediately thereafter, the corona discharge power is turned off (OF).
At the same time as F), it was transported at a normal transport speed (2.0 m / min). By this treatment, a blurred portion was formed in which the contact angle with respect to a water droplet continuously increased over a width of about 100 mm. FIG. 2 shows a change in the contact angle on the center line 9 (FIG. 1) of the water-repellent film-coated glass 1 having the blurred portion obtained in FIG. As described above, the contact angle of the blurred portion continuously changed almost linearly from about 10 ° of the non-water-repellent portion to 105 ° of the water-repellent portion.

Since the length of the glass varies depending on the type of vehicle, the pattern of the change in the contact angle of the blurred portion can be changed by changing the exposure conditions such as the discharge output and the distance between the wire 6 and the glass. Furthermore, when used for actual production, the output of corona discharge is 0.4 kW,
The distance from the discharge wire 6 to the glass surface is 2.0 to
The conveyance speed during corona discharge was simply changed from 0.1 to 2.0 m / min while keeping at 2.5 mm, and the consistency with the preceding and following processing steps was also good. Also,
In the processing of the above non-water-repellent portion, the transport speed is 0.5 m
Even if it is increased to / min, the contact angle is 20 ° or less, and the processing time can be shortened by increasing the transport speed or increasing the number of discharge wires.

Further, in the removal of the water-repellent film, various types of the corona discharge device (provided that the wire is stretched so that the distance between the wire 6 and the flat glass is equal at every portion). A test was performed on the contact angle of the glass surface obtained by processing at the transport speed with respect to water droplets. The result is shown in FIG. As a result, as shown in FIG. 3, there is a substantially positive correlation between the contact angle and the transfer speed in a certain transfer speed region, and by changing the transfer speed at a certain constant acceleration, the contact angle is continuously changed. It was found that it could be changed.

[0043]

According to the present invention, a functional film such as a water-repellent film formed in advance is selectively removed in a short time, efficiently and simply by corona discharge, plasma exposure or ultraviolet irradiation. Forming the non-water-repellent part, particularly as a method for forming the blurred part, by continuously changing the treatment time or treatment intensity such as corona discharge, plasma exposure or ultraviolet irradiation on the functional film such as the water-repellent coating. It can be formed by continuously changing the contact angle of the blurred portion. In addition, the present invention partially removes the water-repellent film as a post-process on “normal water-repellent glass having the entire surface subjected to the water-repellent treatment” obtained from the same process as the existing line until the water-repellent treatment. It can be selectively performed, and has a remarkable effect such as very simple steps and high productivity because of the dry method.

[Brief description of the drawings]

FIG. 1 is a lateral view of a partial water repellent treatment method using a corona discharge device.

FIG. 2 is a view showing a change in a contact angle on a center line of the obtained glass coated with a water-repellent film having a blurred portion.

FIG. 3 is a diagram illustrating a relationship between a transport speed and a contact angle during a corona discharge process.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Door glass 2 Conveyor belt 3 Corona discharge device 4 Terminal 5 Terminal 6 Wire wire 7 Corona discharge 8 Ground electrode 9 Center line

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C03C 17/28 C03C 17/28 A 17/30 17/30 B (72) Inventor Hiroaki Arai Matsusaka-shi, Mie 1510 Oguchicho Central Glass Co., Ltd.Glass Research Laboratory Co., Ltd. FA05 FB05

Claims (13)

[Claims] 1. A functional part having a blurred part characterized by being formed on a substrate surface with a functional part covered with a functional film made of an organic compound and a blurred part in which the function of the functional film gradually changes. Film-coated substrate. 2. The blurred portion has a constant functional film thickness,
2. The functional film-coated substrate having a blurred portion according to claim 1, wherein the concentration of the functional material changes. 3. The functional film-coated substrate having a blurred portion according to claim 1, wherein the functional film is a water-repellent film. 4. A blur according to claim 3, further comprising a water-repellent portion which is a functional portion having a water-repellent property with a contact angle to a water droplet of 70 ° or more and a blur portion whose contact angle gradually changes. Functional film-coated substrate having a portion. 5. The functional film-coated substrate having a blurred portion according to claim 3, further comprising a non-water-repellent portion having a contact angle with water droplets of 20 ° or less adjacent to the blurred portion. . 6. The functional film-coated substrate having a blurred portion according to claim 3, wherein the blurred portion has a continuously changing contact angle with respect to a water drop. 7. The film thickness of the water-repellent portion and the blurred portion is 20 n
7. The functional film-coated substrate having a blurred portion according to claim 3, wherein m is not more than m. 8. The functional film-coated substrate having a blurred portion according to claim 3, wherein the water-repellent portion and the blurred portion are formed by forming a water-repellent coating made of a fluoroalkyl group-containing silane compound. . 9. A method of manufacturing a functional film-coated substrate having a functional portion in which a functional film made of an organic compound is coated on the surface of a substrate and a functional film-coated substrate in which the function of the functional film gradually changes. A method for producing a functional film-coated substrate having a blurred portion, wherein corona discharge, plasma exposure or ultraviolet irradiation treatment is performed on a corresponding region to form a blurred portion. 10. The functional film-coated substrate having a blurred portion according to claim 9, wherein the blurred portion is formed by changing a processing time and / or a processing intensity of corona discharge, plasma exposure or ultraviolet irradiation. Manufacturing method. 11. The function of the blurred portion is continuously changed by continuously changing a processing time and / or a processing intensity of corona discharge, plasma exposure or ultraviolet irradiation. A method for producing a functional film-coated substrate having a blurred portion. 12. A method according to claim 1, wherein after coating a functional film made of an organic compound on the surface of the substrate, a region corresponding to a non-functional portion provided adjacent to the blurred portion is subjected to corona discharge, plasma exposure or ultraviolet irradiation. The method for producing a functional film-coated substrate having a blurred portion according to claim 9, wherein the functional film is removed by: 13. The method according to claim 9, wherein the functional film is a water-repellent film.