JP2002187740A - Repair treatment method for water-repellent film and water repellent treatment method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treatment method which can make the bonding of a glass surface and a water-repellent film securer in the repair treatment method of the water-repellent film applied to automotive applications, etc. SOLUTION: The repair treatment method for the water-repellent film having a ground surface layer includes (1) a process step of making a water-repellent function vanished by applying a plasma jet to the water-repellent film and (2) a process step of applying a water-repellent treating liquid to a region where the water-repellent function is made vanished by the process step described above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for repairing a water-repellent film provided on an automobile glass or the like.
The present invention also relates to a method for treating a glass surface for water repellency.

[0002]

2. Description of the Related Art When a water repellent function is imparted to glass for automobiles, it is necessary to strengthen the bond between the glass surface and the water repellent film in order to improve the durability of the water repellent performance.

[0003] For this reason, conventional methods include (1) cleaning the glass surface immediately before imparting the water repellent function, and (2) providing an underlayer.

[0004] Specific cleaning methods of (1) include cleaning with alcohol, cleaning with an abrasive, and cleaning with ultraviolet light.

[0005] Further, the formation of the underlayer of (2) can increase the bonding force between the glass surface and the water repellent film, and further, can obtain an effect of preventing alkali diffusion from the inside of the glass. Can be prevented.

However, a water-repellent film having an improved durability by increasing the bonding force between the glass surface (underlayer) and the water-repellent film as described above, especially in a severe use environment for automobiles, takes several years. Since the water-repellent function is deteriorated, a repair process is required to maintain the water-repellent effect.

[0007]

In such a repair process, the existence of a water-repellent film which has already been applied and has deteriorated with time is considered as follows.
It is preferable to remove the glass (underlying layer) when newly providing a water-repellent film because it hinders the increase in the activity of the surface.

On the other hand, the above-described underlayer is preferably formed in order to further strengthen the bond between the glass surface and the water-repellent film and improve the durability.

However, the repair process is premised on a process in the aftermarket, and the above-described cleaning method cannot remove only the water-repellent film that has already been applied while leaving the base layer.

[0010] In addition to the repair treatment, when a new water-repellent film is formed on the glass surface, a clean glass surface is necessary to increase the bonding force between the glass surface and the water-repellent film. Further, as in the case of the repair process, even when a new water-repellent film is formed, since the cleaning process is based on the aftermarket process, the following problems occur when the above-described cleaning method is applied. I do.

[0011] Alcohol cleaning is the simplest cleaning method and does not affect the underlayer, and therefore can be sufficiently applied in the aftermarket. In addition, a sufficient cleaning effect can be obtained with respect to dirt of an organic component having a weak adhesive force, such as an adhered oil film. However, a sufficient cleaning effect cannot be obtained to remove the water-repellent film in a deteriorated state.

The cleaning with the abrasive can provide a sufficient cleaning effect even on stains of organic components such as oil film and stains of inorganic components such as water marks. However, since the cleaning depends on the polishing power of the abrasive, the cleaning power is too strong, and a thin underlayer is polished. Therefore, if the repair treatment is directly performed after the polishing and cleaning, the effect of the underlayer cannot be obtained, and the durability of the water-repellent film may not be sufficient.

Further, since the work must be performed using water, a waste liquid containing an abrasive is generated after washing, and the waste liquid must be treated. In addition, there is a concern that the abrasive may adhere to the coating of the body, and there is a fear that the molding around the glass may be damaged. Therefore, it is necessary to mask the periphery of the glass at the time of work, and the processing requires a long time. Further, if the polishing and washing are performed more than necessary, it may cause appearance defects such as distortion defects in the glass.

A method for removing a water-repellent film by UV / ozone treatment for cleaning with ultraviolet light is disclosed in Japanese Patent Application Laid-Open No. Hei 9-142886. This cleaning method does not affect the underlying layer, but requires ozone for processing. For this reason, it is preferable to prepare equipment for removing ozone.

In addition, the processing time is 10
It takes longer than a minute. Further, the equipment becomes large, so that it is difficult to treat glass attached to an automobile, and there is a problem in application in an aftermarket.

Accordingly, the present invention has been made in view of the above-described circumstances, and in a repair process of a water-repellent film applied to an automobile or the like, the bonding between the glass surface and the water-repellent film can be further strengthened. The purpose is to provide a simple processing method.

Specifically, in a water-repellent film having an underlayer, the water-repellent function of the water-repellent film is lost without impairing the function of the underlayer, thereby repairing the water-repellent film while leaving the underlayer. Provides a processing method.

Needless to say, the treatment method of the present invention can be applied to a repair treatment of a water-repellent film having no underlayer. Furthermore, it can be applied as a cleaning method when a new water-repellent film is formed.

In the present specification, “washing” may mean not only cleaning the surface of the base material but also a treatment for developing the original surface activity of the base material.

[0020]

In order to solve the above-mentioned problems, the point of the present invention is to first remove the water-repellent film and activate and clean the surface of the substrate by using a plasma jet. Water treatment.

That is, the present invention provides,
(1) a step of irradiating the water-repellent film formed on the glass substrate with plasma to lose the water-repellent function;
(2) a process of applying a water-repellent treatment liquid to a region in which the water-repellent function has been lost by the above-mentioned process.

According to a second aspect of the present invention, in the method for repairing a water-repellent film according to the first aspect, the plasma irradiation is performed to clean and activate the surface of the glass substrate. Processing method.

According to a third aspect of the present invention, in the method for repairing a water-repellent film according to the first aspect, the water-repellent film is a water-repellent film having a water-repellent layer provided on a silica base layer. Processing method.

According to a fourth aspect of the present invention, in the method for repairing a water-repellent film according to the first aspect, the water-repellent film has a water-repellent layer formed integrally with a silica-based glass skeleton layer. Is a repair processing method.

According to a fifth aspect of the present invention, there is provided the method for repairing a water-repellent film according to the first aspect, wherein the plasma irradiation conditions are as follows. Distance from irradiation nozzle to substrate: 5 to 15
mm Irradiation nozzle moving speed parallel to glass substrate surface: 1 to 1
60mm / sec. Times

According to a sixth aspect of the present invention, there is provided (1) a step of irradiating a plasma to the surface of the glass substrate to clean and activate the surface of the glass substrate, and (2) a step of irradiating the surface of the glass substrate irradiated with the plasma. A step of applying a water treatment liquid.

According to the method of the present invention, when the water-repellent film is removed, the underlayer is not removed and the underlayer remains. For this reason, in the subsequent water repellent treatment, the presence of the underlayer strengthens the bond between the glass surface and the water repellent film, and the effect of preventing alkali diffusion from inside the glass increases the durability of the water repellent film. It has the effect of improving.

Since there is no effect on the painted surface of an automobile, there is also an advantage that it is not necessary to perform masking on portions other than the treated surface during the treatment.

Further, in the apparatus used in the method of the present invention, it is possible to take into consideration that aftermarket correspondence is possible. In other words, the processing device for removing the water-repellent film can be made compact, and can be made movable by attaching a caster to the power supply unit.

The head of the apparatus for generating a plasma jet is also compact and can be handled with one hand. Since only a cable for supplying a high voltage between the electrode rod and the electrode plate from the power supply unit and a power supply cable to the air flow generation unit need only be connected to the head unit, handling is easy.

Therefore, it is possible to easily process glass attached to an automobile,
This is a treatment method that is sufficiently applicable in the aftermarket.

As described above, the present invention is a method capable of coping with both equipment and aftermarket.

[0033]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a plasma jet generator will be described. FIG. 1 is a schematic view of a plasma jet generator 1. This apparatus includes a plasma jet irradiation nozzle 10, a power supply unit 50 mounted on a carrier 51, and a cable 60 connecting these. Although not shown, a high voltage supply cable for supplying a high voltage from the power supply unit 50 is connected to the electrode rod and the electrode plate of the irradiation nozzle 10, and a power supply cable is connected to the motor of the air flow generation unit. Have been.

Power supply unit 50 of plasma jet generator
Is mounted on a carrier 51 having casters 52, legs 53 and grips 54. The illustrated plasma jet generator 1 has two irradiation nozzles 1.
This is an example with 0. The size of the power supply unit 50 is 50
It is 8 × 229 × 610 mm and weighs 58 kg. Since such a small size and a caster are provided, the operator can easily move the power supply unit 50 by holding the grip 54.

On the front face of the power supply unit 50, a main power switch 55 and operation lamps 56 for each of the two irradiation nozzles are provided.
, An ON switch 57 and an OFF switch 58.

FIG. 2 is an enlarged front view of the plasma jet irradiation nozzle 10 used in the present invention, and shows a state in which the object (water-repellent glass plate 40) is irradiated with the plasma jet.

The plasma jet irradiation nozzle 10 has a structure in which a blower mount 13 is attached to a main body 12 in which a flow path 11 for narrowing an air flow generated by a motor fan or the like is formed.

FIG. 3 is a sectional view taken along line 2-2 of FIG. In the figure,
A motor 21 and a fan 23 attached to a motor shaft are attached to the blower mount 13. Further, a vortex chamber 24 surrounding the fan 23 and an air intake port 25 provided with a net 26 are formed in the blower mount section 13.
Function as

Further, an electrode rod 30 is inserted from above the main body 12. Further, an electrode plate 31 is provided below the main body 12 so as to face the flow path 11.

When a high voltage is applied between the electrode rod 30 and the electrode plate 31, an arc discharge 32 occurs in the space between the electrode rod 30 and the electrode plate 31, and plasma is generated. At this time, a high-speed airflow is supplied from the airflow generation unit 20 to the space. Then, the high-speed plasma jet 33 is irradiated from the nozzle 14 and the target (for example,
It reaches the water-repellent glass plate 40).

Here, features of the plasma jet processing used in the present invention will be described.・ Because the plasma generated in the atmosphere is used,
There is no need to provide a booth or the like for special processing. -It is possible to treat the substrate to be treated without thermally affecting it. After the treatment, a washing step and a drying step are unnecessary, and another treatment can be immediately performed.・ Dry process. -Control and operation are simpler than other surface treatment methods.

For this reason, it is effective as a pretreatment for bonding, joining, painting, printing, coating surface, and the like. Further applicable substrates include plastic, metal, rubber, glass, ceramic and the like.

The mechanism of the plasma jet treatment is that the molecular bonds on the substrate surface are decomposed by the plasma particles. For example, when plasma jet treatment is performed on a perfluoroalkylsilane or the like that exhibits a water-repellent function, the bond between the alkyl group and Si is decomposed, so that the water-repellent function can be eliminated.

Further, even when there is a dirt (organic substance) on the surface of the substrate, the plasma particles decompose the dirt, so that there is also an effect of cleaning the surface of the substrate.

Further, since a hydrophilic group such as an OH group serving as a reaction active site with the water-repellent film is formed on the treated surface, the surface activity is improved. Therefore, if a water-repellent treatment is performed after the plasma jet treatment, the bonding of the water-repellent agent becomes strong, and a water-repellent film with good durability can be formed.

Further, depending on the base material, it is expected that irregularities at the molecular level are formed on the surface of the base material by the plasma particles. In this case, an anchor (anchoring) effect can be expected in the subsequent processing.

When the output is constant, the processing capacity of the plasma jet is determined by the distance between the head and the work, the head feed speed, and the number of times of processing.

As the processing conditions in the present invention, when the output of plasma jet irradiation is 0.5 kW per nozzle, the distance between the head and the work is preferably 5 to 15 mm. If this distance is less than 5 mm, there is a possibility that a thermal effect may be exerted on the treated surface, which is not preferable. On the other hand, 15m
If it exceeds m, the processing efficiency is deteriorated because it is out of the effective processing range of the plasma jet.

The head feed speed converted per processing is preferably 100 mm / (sec · times) or less.
mm / (sec. times) or less, more preferably 20 mm / (sec. times).
(sec times) or less is preferable.

Here, when the same processing surface is subjected to the plasma jet process a plurality of times, the actual head feed speed is divided by the number of times of processing to obtain a head feed speed converted per process.

The head feed speed is 100 mm / (sec)
If the number of times exceeds, the processing capacity is insufficient, and the water repellent function cannot be sufficiently eliminated. On the other hand, if the head feed speed is too low, the processing area cannot be gained, and it is not economical. Therefore, it is preferable to process at a feed speed that does not cause a shortage of processing capacity.

Further, the irradiation output of the plasma jet can be controlled by controlling the frequency, applied voltage and the like in the power supply unit. The range is 0.1 to 1.0 kW per nozzle. The irradiation output of the plasma jet may be selected stepwise according to the material of the substrate to be treated or the formed water-repellent film.

EXAMPLES The present invention will be described in more detail with reference to the following Examples.

(Preparation of Water Repellent Film with Underlayer) To 98.6 g of ethanol (manufactured by Nacalai Tex), 0.4 g of tetraethoxysilane (manufactured by Shin-Etsu Silicone), concentrated hydrochloric acid (35%)
(% By weight, manufactured by Kanto Chemical Co., Ltd.) 1 g was processed with stirring to obtain a silica base layer treatment liquid.

Next, the above-mentioned silica base treatment liquid is applied on a washed soda-lime silicate glass substrate (300 × 300 mm) at a relative humidity of 30% and room temperature by a flow coating method, and dried for about 1 minute. , Glass substrate surface thickness is about 40nm
Was coated with a silica underlayer.

The hardness of the silica film was measured by a pencil hardness method. As a result, even if the film was scratched with an H pencil, the film was not damaged.

Subsequently, 1 g of CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ (heptadecafluorodecyltrimethoxysilane, manufactured by Toshiba Silicone) was used as a water-repellent (repair) liquid. Dissolved in 98 g of ethanol,
1 g of 0.1 N hydrochloric acid was added, and the mixture was stirred for 1 hour to obtain a water-repellent (repair) liquid.

Then, 3 mL of the above-mentioned water-repellent treatment liquid is applied to the surface of the glass substrate coated with the silica base layer, and the excess water-repellent treatment liquid is wiped off with a fresh cotton cloth. A glass was obtained.

(Preparation of Water Repellent Film without Underlayer) Soda-lime silicate glass substrate (300 × 300 m
m), 3 mL of the above-mentioned water-repellent treatment liquid was applied to a cotton cloth, and the excessively attached water-repellent liquid was wiped off with a fresh cotton cloth to obtain a water-repellent glass.

The water-repellent glass having the underlayer and the water-repellent glass having no underlayer were left exposed to the outdoors for the same period, and a sample having a contact angle of 70 ° or less was used.
Repair processing was performed.

First, the two types of glass are subjected to three types of processes, a plasma jet process, a celico cleaning process, and an alcohol cleaning process, and then the water repellent glass is treated again in the same manner as the original water repellent process. Obtained. Here, samples with an underlayer are referred to as 1-1, 1-2, and 1-3, and samples without an underlayer are referred to as 2-1, 2-2, and 2-3, respectively.

The plasma jet treatment was performed under the following conditions. Processing equipment: Plasma jet processing equipment (PJ-1) manufactured by Corotech Co., Ltd. Processing conditions: output 0.5 kW / nozzle Head-to-work distance: 8 mm Conversion head feed speed: 20 mm / (sec. Times) Plasma jet flow rate: about 7 m / Sec When pure water was dropped on the glass surface after this treatment, it was confirmed that the glass was uniformly wet and the water repellent function had disappeared.

The cerico washing was carried out using a paste-like glass detergent containing celico (Kirobin: manufactured by Takehara Co., Ltd.) while the glass surface was well polished, and then washed off with water. When pure water was dropped on the glass surface after this treatment, it was confirmed that the glass was uniformly wet and the water repellent function had disappeared.

Further, the alcohol washing was performed by soaking ethyl alcohol in a cotton cloth and wiping the glass surface. When pure water was dropped on the glass surface after performing this treatment, a uniform wet state was not exhibited, and the removal of the water-repellent film was insufficient.

Using a contact angle meter (CA-DT, manufactured by Kyowa Interface Science Co., Ltd.), 2 mg of water droplets were dropped on the surface of the repaired water-repellent treated glass.
An initial static contact angle (hereinafter, simply referred to as a contact angle) was measured.

As a friction test, a dry cloth was attached to the repaired water-repellent treated glass to a reciprocating abrasion tester (manufactured by Shinto Kagaku), and the surface of the water-repellent film was applied under a load of 0.3 kg / cm ^2. After reciprocating sliding 3,000 times, the contact angle was measured.

As a weather resistance test, a UV tester (I-Super W-13, manufactured by Iwasaki Electric Co., Ltd.)
6 ± ² mW / cm ² , black panel temperature 48 ± 2
UV irradiation was performed at 600C for 600 hours under the continuous irradiation condition, and then the contact angle was measured.

Table 1 shows the measurement results of the contact angle in each of the test items described above. The judgment by the contact angle was that the contact angle after both the wear test and the weather resistance test was 80 °.
Those that were above were rated as ◎, those with either one of 80 ° or more were rated as ○, and those with any contact angle less than 80 ° were rated X.

[0069]

[Table 1] ―――――――――――――――――――――――――――――――――― Sample Water-repellent film removal method for water-repellent film After wear test After weather resistance test Judgment type Contact angle (°) Contact angle (°) ――――――――――――――――――――――― ――――――― 1-1 Underlayer Plasma J 100 85 ◎ 1-2 Underlayer Celiko Cleaning 85 75 ○ 1-3 Underlayer Alcohol 69 59 × ――――――――――― ――――――――――――――――――――――――― 2-1 No base layer Plasma J 83 72 ○ 2-2 No base layer Celico cleaning 85 75 ○ 2-3 No base layer Alcohol 61 57 × ――――――――――――――――――――――――――――――――――

From the above results, it can be seen that by performing the plasma jet treatment on the water-repellent glass having the underlayer, the water-repellent film can be removed while leaving the underlayer. further,
Subsequently, it was also clarified that when the water repellent treatment was performed, the underlayer and the water repellent film could be strongly bonded. It was also found that the durability of the water-repellent film of the glass without an underlayer was better in the plasma jet treatment than in the alcohol cleaning.

The water-repellent film of Sample 1-1 described above is
It was a water-repellent film having a two-layer structure with an underlayer. The plasma jet treatment in the present invention is not limited to a water-repellent film having a two-layer structure, but is also effective for a water-repellent film having a water-repellent layer formed integrally with a silica-based glass skeleton layer.

In such an integral water-repellent film, perfluoroalkyl groups exhibiting a water-repellent function are naturally arranged on the surface. Therefore, the water-repellent function can be eliminated by irradiation with the plasma jet.

As a method for producing an integral water-repellent film, there is a method disclosed in Japanese Patent Application Laid-Open No. H11-71682. The integral water-repellent film formed by these methods was irradiated with a plasma jet. When pure water was dropped on the surface, it was confirmed that the surface was uniformly wet and the water repellent function had disappeared.

Further, when this plasma jet treatment was used for cleaning when directly applying a water-repellent treatment to the glass substrate, water-repellent performance equivalent to or higher than that of the above-mentioned sample 2-1 was obtained. Therefore, the plasma jet treatment is effective as a cleaning method when directly performing a water-repellent treatment on a glass substrate.

[0075]

As described above, according to the method for repairing a water-repellent film of the present invention, the following effects can be obtained.

Since the plasma jet process does not affect the underlayer, the repair process can be performed while maintaining the effect of the underlayer. -Since the plasma jet treatment is effective for cleaning and activating the surface of the base material, it can be applied as a pretreatment for water repellency.・ Since the head of the plasma jet device is easy to handle and the treatment itself is a dry process,
Without affecting the paint around the glass substrate, etc.
It is possible to process the glass as it is mounted on the actual vehicle. -Since the plasma jet device can be compactly assembled and can be made movable, it can be used in the aftermarket.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a plasma jet generator.

FIG. 2 is a front view of a plasma jet irradiation nozzle used in the present invention.

FIG. 3 is a sectional view of a plasma jet irradiation nozzle.

[Explanation of symbols]

 1: Plasma jet generator 10: Plasma jet irradiation nozzle 11: Flow path 12: Main body 13: Blower mount 14: Nozzle 20: Air flow generator 21: Motor 22: Motor shaft 23: Fan 24: Vortex chamber 25: air intake 26: net 30: electrode rod 31: electrode plate 32: arc discharge 33: plasma jet 40: water repellent glass plate 50: power supply unit 51: carrier 52: caster 53: leg 54: grip 55: Main power switch 56: Operation lamp 57: ON switch 58: OFF switch 60: Cable

Claims (6)

[Claims] (1) a step of irradiating a plasma to a water-repellent film formed on a glass substrate to lose the water-repellent function; and (2) a step of eliminating the water-repellent function by the step. Applying a water-repellent treatment liquid to the region. 2. The method for repairing a water-repellent film according to claim 1, wherein the surface of the glass substrate is cleaned and activated by irradiating the plasma. 3. The method according to claim 1, wherein said water-repellent film is a water-repellent film having a water-repellent layer provided on a silica-based underlayer. 4. The method according to claim 1, wherein the water-repellent film is a water-repellent film having a water-repellent layer formed integrally with a silica-based glass skeleton layer. . 5. The method for repairing a water-repellent film according to claim 1, wherein the plasma irradiation conditions are as follows. Distance from irradiation nozzle to substrate: 5 to 15 mm Moving speed of irradiation nozzle parallel to glass substrate surface: 1 to 60
mm / sec. times 6. A step of (1) irradiating a plasma on a surface of a glass substrate to clean and activate the surface of the glass substrate.
(2) a step of applying a water-repellent treatment liquid to the surface of the glass substrate irradiated with the plasma.