JP5326782B2 - Method for producing water-repellent article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a water-repellent article excellent in water repellency, droplet slidable (droplet slipping down nature), and also excellent in alkali resistance and wet heat resistance. <P>SOLUTION: In the method of manufacturing water-repellent article having a water-repellent layer formed on a base material by applying a water-repellent layer forming coating liquid on the base material and drying, the water-repellent layer forming coating liquid has a first coating liquid containing a low molecular weight water-repellent compound and a second coating liquid containing a high molecular weight water-repellent compound, and the water-repellent article on which the water-repellent layer is formed is manufactured by applying the first coating liquid on the base material to form a first coating film and after cleaning the first coating film, applying the second coating liquid on the first coating film to form a second coating film. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a water-repellent article having a water-repellent layer on a substrate.

  In general, it is desirable that architectural window glass and automotive window glass do not adhere to the surface thereof anything that obstructs the field of view, such as water droplets and dirt. For example, if raindrops, dust, dirt, etc. adhere to the surface of an automotive window glass, or if moisture condenses due to atmospheric humidity or temperature, the transparency and transparency will deteriorate, and the driving of the vehicle will It will interfere with driving. For this reason, water droplets adhering to the surface of the window glass for automobiles are removed by physical means such as using a wiper or wiping by hand. However, when water droplets are removed by physical means, fine scratches may be made on the surface of the window glass due to wear of foreign particles accompanying the water droplets. Furthermore, alkali components are eluted in the water droplets on the glass surface, and the surface is eroded, so-called burning occurs. Glass that has been severely burnt or glass that has fine irregularities on its surface has reduced its original function and light scattering occurs on its surface. Therefore, the glass used for window glass for buildings and automobiles has excellent water repellency and water slidability (water drop slidability) as well as alkali resistance and wet heat resistance (high temperature).・ Resistance to high humidity environment is required.

  So far, these issues have been studied. For example, a technique of adding silicone (sliding property) to a fluororesin (weather resistance / water repellency) is known (for example, see Patent Document 1).

  However, in the technique described in Patent Document 1, only the silicone to be added bleeds out on the surface, and the initial performance is good, but the wet heat resistance is not sufficient.

  In order to improve this, a technique using a copolymer obtained by previously polymerizing silicone to be added and copolymerizing with a fluororesin is known (see, for example, Patent Document 2).

  However, it has been found that the technique described in Patent Document 2 has poor sliding properties due to the use of siloxane, and does not reach the required levels of wet heat resistance and alkali resistance.

  On the other hand, in order to improve wear resistance, a technique is known in which a fine concavo-convex structure is produced using a sol-gel method and a water-repellent film (FAS) is provided thereon (see, for example, Patent Document 3). .)

  However, although the technique described in Patent Document 3 has good wear resistance, the surface is fluoroalkylsilane-based, so the water and oil repellency is very good, but the sliding property is poor. It was also found that the alkali resistance is weak because it does not contain a fluororesin.

  Furthermore, a method of applying a composite material is known (see, for example, Patent Documents 4, 5, and 6).

  However, in the techniques described in Patent Documents 4, 5, and 6, it is difficult to control the structure (low molecule on the lower side and polymer on the surface side), and both cannot be formed with high density. In addition, it has been found that there is a problem that, for example, compatibility between materials must be considered in order to combine materials, and the composite material is limited.

  Under such circumstances, it is desired to develop a method for producing a water-repellent article excellent in a water-repellent article excellent in water repellency and water slidability (water drop sliding property), and excellent in alkali resistance and wet heat resistance.

JP 2001-139745 A JP 2001-151831 A JP-A-2005-281132 Japanese Patent No. 3117498 Japanese Patent Laid-Open No. 5-1197 Japanese Patent No. 3512200

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a water-repellent article that is excellent in water repellency and water slidability (water drop slidability) and excellent in alkali resistance and wet heat resistance. It is in.

  The above object of the present invention can be achieved by the following configuration.

1. In the method for producing a water-repellent article in which a water-repellent layer is formed on the base material by applying a water-repellent layer-forming coating solution on the base material and drying the coating solution,
The coating liquid for forming the water repellent layer comprises a first coating liquid containing a low molecular weight water repellent compound selected from a fluorine-containing silane coupling agent, an alkylsilane coupling agent, and a polydimethylsiloxane skeleton compound, and a high molecular weight repellent. A second coating solution containing an aqueous compound,
Applying the first coating liquid on the substrate to form a first coating film;
After washing the first coating film,
Applying the second coating liquid on the first coating film to form a second coating film;
A method for producing a water-repellent article, comprising producing a water-repellent article on which the water-repellent layer is formed.

2 . 2. The method for producing a water-repellent article as described in 1 above, wherein the water-repellent compound has a reactive silyl group.

3 . 3. The method for producing a water-repellent article according to 1 or 2 , wherein the first coating liquid contains a surfactant.

4 . The washing is dried first coating, the production method of the water-repellent article according to any one of the items 1 to 3, characterized in that takes place after irradiation with energy ray.

5 . 5. The method for producing a water-repellent article according to any one of 1 to 4 , wherein the cleaning is performed with a good solvent for the first coating film.

6 . 6. The method for producing a water-repellent article according to any one of 1 to 5 , wherein an underlayer is formed between the water-repellent layer and the substrate.

7 . 7. The method for producing a water-repellent article as described in 6 above, wherein the underlayer is formed by atmospheric pressure plasma CVD.

8 . 8. The method for producing a water-repellent article according to any one of 1 to 7 , wherein the substrate is glass containing an alkali component.

  It was possible to provide a method for producing a water-repellent article excellent in water repellency and water slidability (water drop slidability) and excellent in alkali resistance and wet heat resistance.

It is a schematic sectional drawing of the water-repellent article which has a water-repellent layer on the base material manufactured by the manufacturing method of this invention. The schematic manufacturing process flow figure at the time of manufacturing a water-repellent article is shown. It is the schematic which showed an example of the jet type atmospheric pressure plasma film-forming apparatus. It is the schematic which shows an example of the atmospheric pressure plasma film-forming apparatus of the system which processes a base material between counter electrodes.

  The inventor has a low molecular weight water-repellent compound having a reactive silyl group having a weight average molecular weight of less than 1000, which is known as a water repellent compound, and a high molecular weight having a reactive silyl group having a weight average molecular weight of 1000 or more. As a result of diligent research on the manufacturing method of a water-repellent article using a water-repellent compound, excellent in water repellency, water slidability (waterdrop slidability), and excellent in alkali resistance and wet heat resistance, the following was found. .

  When a water-repellent layer is formed by using a low-molecular-weight water-repellent compound having a reactive silyl group having a weight average molecular weight of less than 1000, the steric hindrance is small, and the coverage on the substrate is high. The initial water repellency is excellent, but due to the low molecular weight, moisture easily penetrates into the film, and the alkali resistance and wet heat resistance are not sufficient.

  On the other hand, when a water-repellent layer is formed by using a high-molecular-weight water-repellent compound having a reactive silyl group having a weight average molecular weight of 1000 or more, the initial water repellency and water slidability (water drop slidability) are excellent. However, since the steric hindrance between the molecules is large and the coverage of the substrate is reduced, the alkali resistance and wet heat resistance are still not sufficient.

  The inventor pays attention to the coverage on the base material and the penetration of moisture into the membrane, and considers that by utilizing the respective characteristics of the water-repellent compounds having different molecular weights, the alkali resistance and wet heat resistance can be improved. A method for forming a water-repellent layer using different water-repellent compounds was investigated.

  As a result of intensive studies by the present inventors, a coating film of a low molecular weight water-repellent compound was formed on the substrate, and the substrate was coated with a water-repellent compound at a high coverage, and then the water-repellent film was washed. Then, it was found that the alkali resistance and wet heat resistance can be improved by forming a coating film of a high molecular weight water-repellent compound on the water-repellent film.

  The present inventors consider the following factors as factors that have improved alkali resistance and wet heat resistance.

  By applying a low molecular water repellent, a water repellent film can be formed on the substrate with a high coverage. However, with low-molecular water repellents alone, moisture and active species that degrade the film are likely to enter the inside of the film, so alkali resistance and wet heat resistance cannot be improved. The substrate surface to which the polymer water repellent can be bonded is partially exposed. Then, the water-repellent layer of the polymer water-repellent agent is applied so that the polymer water-repellent agent is bonded to the substrate surface exposed by applying the polymer water-repellent agent and covers the low-molecular water-repellent agent. And a multi-layer structure of a low-molecular water-repellent layer on the apparent base material and a polymer-based water-repellent layer on it is formed, which suppresses the penetration of moisture and film-degrading active species into the film. It is presumed that the water repellent layer that can be formed has improved alkali resistance and wet heat resistance.

  The water-repellent article produced by the method for producing a water-repellent article of the present invention is not only excellent in initial water repellency and water slidability (waterdrop slidability), but also has excellent performance in alkali resistance and wet heat resistance. It can be applied to water-repellent articles that require durability such as glass and window glass for vehicles.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to FIGS. 1 to 4, but the present invention is not limited thereto.

  FIG. 1 is a schematic cross-sectional view of a water-repellent article having a water-repellent layer on a substrate produced by the production method of the present invention.

  In the figure, 1 indicates a water-repellent article. The water repellent article 1 has a configuration having a base layer 102 and a water repellent layer 103 on a base 101. The entire surface of the foundation layer 102 is covered with a water repellent layer 103. The water repellent layer 103 has a low molecular weight water repellent compound and a high molecular weight water repellent compound.

  In the present invention, the low molecular weight water repellent compound is defined as a water repellent compound having a weight average molecular weight of less than 1000, and the high molecular weight water repellent compound is defined as a water repellent compound having a weight average molecular weight of 1000 or more.

  The weight average molecular weight of the low molecular weight water-repellent compound is less than 1000, preferably 100 to 900, more preferably 200 to 900.

  The weight average molecular weight of the high molecular weight water-repellent compound is 1000 or more, preferably 1000 to 200000, more preferably 2000 to 20000.

  The weight average molecular weight Mw can be measured using gel permeation chromatography using, for example, a calibration curve with 13 samples of standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) Mw = 500 to 1000000.

  The configuration of the underlayer 102 is not particularly limited, and may be one layer or may be composed of at least two layers. In this figure, the case where it consists of one layer is shown. Note that the base layer 102 can be provided as necessary.

  The hardness of the underlayer 102 is preferably 1.0 GPa to 8.0 GPa in consideration of wear resistance, scratch resistance, adhesion, and the like.

  The hardness of the underlayer 102 indicates a value measured by a nanoindentation method that measures the hardness of the water repellent film 103.

  The carbon content (carbon atom number concentration) of the underlayer 102 is 1.0 carbon atom concentration% to 20.0 carbon atom concentration% in consideration of wettability, reactivity with the water repellent and the like. Is preferred.

  The carbon atom number concentration indicating the carbon content in the present invention is calculated by the following XPS method and is defined below.

Carbon atom number concentration% (atomic concentration) = number of carbon atoms / number of all atoms × 100
In the present invention, the XPS surface analyzer used ESCALAB-200R manufactured by VG Scientific. Specifically, Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA). The energy resolution was set to be 1.5 eV to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak.

  As a measurement, first, the range of the binding energy of 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what elements were detected.

  Next, with respect to all the detected elements except for the etching ion species, the data capture interval was set to 0.2 eV, and the photoelectron peak giving the maximum intensity was subjected to narrow scan, and the spectrum of each element was measured.

  The obtained spectrum is COMMON DATA PROCESSING SYSTEM manufactured by VAMAS-SCA-JAPAN (preferably Ver. 2.3 or later) so as not to cause a difference in the content rate calculation result due to a difference in measuring apparatus or computer. After being transferred to the top, the processing was performed with the same software, and the content value of each analysis target element (carbon, oxygen, silicon, titanium, etc.) was determined as the atomic concentration (at%).

  Before performing the quantification process, calibration of the count scale was performed for each element, and a 5-point smoothing process was performed. In the quantitative process, the peak area intensity (cps * eV) from which the background was removed was used. For the background treatment, the method by Shirley was used. For the Shirley method, see D.C. A. Shirley, Phys. Rev. , B5, 4709 (1972).

  M indicates the thickness of the underlying layer 102. The thickness M is preferably 1 nm to 500 nm in consideration of scratch conspicuousness, wear resistance, productivity, and the like. More preferably, it is 5 nm to 200 nm.

  The thickness M indicates a value measured using “MXP21” (manufactured by Mac Science).

  The hardness of the water repellent film 103 measured by the nanoindentation method is preferably 1.0 GPa to 8.0 GPa in consideration of wear resistance, scratch resistance, adhesion, and the like.

  In the nanoindentation method, a sample is continuously loaded and unloaded with a very small load, and the hardness (Hardness, hereinafter abbreviated as H) is measured from the obtained load-displacement curve. Is the method.

  The hardness (H) of nanoindentation represents the value of the direct surface hardness of the sample. Therefore, the hardness (H) of nanoindentation is suitable as an index of surface hardness.

<Measurement of hardness (H) by nanoindentation method>
The hardness (H) of the water-repellent film 103 according to the present invention was measured by a nanoindentation method by attaching a sample of a Triscope from Hystron to a Nanoscope III from Digital Instruments. For the measurement, a triangular pyramid diamond indenter called a Belkovic indenter (tip ridge angle 142.3 °) is used as an indenter.

  A triangular pyramid-shaped diamond indenter was applied to the sample surface at a right angle, a load was gradually applied, and the load was gradually returned to 0 after reaching the maximum load. The value P / A obtained by dividing the maximum load P at this time by the projected area A of the indenter contact portion was calculated as the hardness (H). The maximum load condition at this time is 100 μN. Details regarding the principle of surface hardness measurement by the nanoindentation method are described in, for example, Handbook of Micro / Nano Tribology (CRC edited by Bharat Bhushan).

  N indicates the thickness of the water repellent film 103. The thickness N is preferably from 2 nm to 100 nm in consideration of water repellency, water slidability (water drop slidability), abrasion resistance, scratch resistance, scratch conspicuousness, alkali resistance, wet heat resistance, weather resistance, and the like.

  The thickness of the water repellent film 103 is a value obtained by measurement using “MXP21” (manufactured by Mac Science). The specific measurement of the film thickness can be performed by the following method. Copper is used as the target of the X-ray source and it is operated at 42 kV and 500 mA. A multilayer parabolic mirror is used for the incident monochromator. The incident slit is 0.05 mm × 5 mm, and the light receiving slit is 0.03 mm × 20 mm. Measurement is performed by the FT method with a step width of 0.005 ° and a step of 10 seconds from 0 to 5 ° in the 2θ / θ scan method. With respect to the obtained reflectance curve, Reflectivity Analysis Program Ver. 1 is used to perform curve fitting, and each parameter is obtained so that the residual sum of squares of the actual measurement value and the fitting curve is minimized. The film thickness of the laminated film is obtained from each parameter.

  FIG. 2 shows a schematic manufacturing process flow chart when manufacturing a water-repellent article. Fig.2 (a) shows the general | schematic manufacturing process flowchart which has a washing | cleaning process after a 1st application | coating process, when manufacturing a water-repellent article. FIG. 2B shows a schematic manufacturing process flow diagram having an active energy irradiation process between the first drying process and the cleaning process when manufacturing a water-repellent article.

  This will be described with reference to a schematic manufacturing process flowchart shown in FIG.

  In the figure, 2 shows a manufacturing process flow for manufacturing a water-repellent article. The manufacturing process 2 includes a base material supply process 201, a pretreatment process 202, a base layer formation process 203, a water repellent layer formation process 204, and a recovery process 205. The water repellent layer forming step 204 includes a first coating step 204a, a first drying step 204b, a cleaning step 204c, a second coating step 204d, and a second drying step 204e.

  Hereinafter, the manufacturing method of the water-repellent material of the present invention will be described with reference to the schematic manufacturing process flowchart shown in FIG. 2 (a). However, the present invention is limited to the manufacturing process flow exemplified here. is not.

Substrate supply process 201
Examples of the base material supplied from the base material supply step 201 include a strip-like flexible base material and a single-wafer base material, and can be selected depending on the application. However, when the belt-like flexible substrate is used, the subsequent pretreatment step 202, the underlayer forming step 203, the water-repellent layer forming step 204, and the recovery step 205 are steps corresponding to the belt-like flexible substrate. (For example, a continuous process in which a roll-shaped strip-like flexible base material is supplied, processed in each process, and then wound and collected in a roll in the recovery process). When a single-wafer substrate is used, the subsequent pretreatment process 202, the underlayer forming process 203, the water-repellent layer forming process 204, and the recovery process 205 are processes corresponding to the single-wafer substrate (for example, a batch process).

Pretreatment process 202
The pretreatment process 202 includes a removal process for removing a substrate, dust, and the like attached to the surface of the substrate supplied from the substrate supply process 201, and a base layer forming process 203 or a water repellent layer forming process 204. And a hydrophilization treatment for improving the formation stability of the base layer or the water-repellent layer. The removal process and the hydrophilization process may be performed together.

Examples of the removal treatment include dry treatment and wet treatment, and can be appropriately selected depending on the type of substrate. As the dry treatment, it is preferable to use a low-pressure mercury lamp, an excimer lamp, a plasma cleaning device, a gas spraying device, or the like. The conditions for the cleaning treatment with the low-pressure mercury lamp include, for example, the conditions for performing substrate cleaning by irradiating a low-pressure mercury lamp with a wavelength of 184.2 nm at an irradiation intensity of 5 mW / cm ² to 20 mW / cm ² and a distance of 5 mm to 15 mm. It is done. For example, atmospheric pressure plasma is preferably used as a condition for the substrate cleaning process by the plasma cleaning apparatus. As cleaning conditions, argon gas containing 1% to 5% by volume of oxygen is used, and substrate cleaning is performed at a frequency of 100 kHz to 150 MHz, a voltage of 10 V to 10 kV, and an irradiation distance of 5 mm to 20 mm. Examples of the cleaning method using the gas spraying device include gas spraying, ultrasonic gas spraying, combined use of gas spraying and suction, combined use of ultrasonic gas spraying and suction, and adhesive roll method.

  As the hydrophilic treatment, surface treatment such as corona discharge, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, plasma treatment, laser treatment, ozone oxidation treatment, and application of a silane coupling agent or the like are performed.

Underlayer forming step 203
The underlayer forming step 203 is a step for forming the underlayer before providing the water repellent layer in order to stably form the water repellent layer on the substrate. The method for forming the underlayer is not particularly limited, and the raw materials described later are sprayed, spin-coated, sputtering, ion-assisted, plasma CVD, plasma atmospheric pressure described below, or plasma CVD under atmospheric pressure. Etc. can be applied. Among these methods, it is preferable to apply the atmospheric pressure plasma method from the viewpoint that a reduced-pressure chamber or the like is unnecessary, a high-speed film formation is possible, and the productivity is high. Details of the layer forming conditions of the atmospheric pressure plasma method will be described later. Note that the underlayer forming step 203 can be provided as necessary.

Water repellent layer forming step 204
In the first coating step 204a, a first coating solution containing a low molecular weight water-repellent compound is coated on the base layer formed in the base layer forming step 203 (on the base material when not treated in the base layer forming step 203). The first coating film is formed. This low molecular weight water-repellent compound is presumed to have less steric hindrance due to its low molecular weight, improve the coverage of the water-repellent compound on the substrate surface, and improve water repellency.

  The concentration of the low molecular weight water-repellent compound in the first coating liquid is usually preferably from 0.1% by mass to 30% by mass, but is not limited thereto and can be appropriately adjusted depending on the type of the low molecular weight water-repellent compound. is there. Moreover, it is preferable to contain a fluorine-containing surfactant.

  As a coating apparatus for coating the first coating liquid, a known coating method of a pre-metering type coating method or a post-metering type coating method can be applied.

  The pre-metering type coating method is a method in which the coating liquid is ejected by an amount that forms a necessary coating liquid film, and the coating liquid is coated on the support. Examples of the pre-weighing type coating method include an extrusion coating method using a slit type die coater, a slide coating method using a slide coater, a curtain coating method, and a coating method using an inkjet head.

  The post-measuring type coating method is a method in which a coating liquid surplus than a necessary coating liquid film formation amount is discharged onto a substrate in advance, and then the surplus is removed by some scraping means. Post-weighing coating methods include dipping coating, spray coating, spin coating, blade coating, air knife coating, wire bar coating, gravure coating, reverse coating, and reverse roll coating. It is done.

  Among these coating apparatuses, preferred coating methods for the single-wafer substrate include, for example, a dipping coating method, a spray coating coating method, a spin coating coating method, and an inkjet coating method.

  Examples of a preferable coating method for the belt-like flexible substrate include a spray coating method and an ink jet coating method.

  In the first drying step 204b, the solvent in the coating film on the underlayer formed in the first coating step 204a or the first coating film on the substrate is removed. The method for removing the solvent is not particularly limited, and examples thereof include wind blowing, heat removal, or reduced pressure removal, and a combination of these.

  The first drying step 204b may not be used depending on the type of low molecular weight water repellent compound used.

  In the cleaning step 204c, after the low molecular weight water-repellent compound is immobilized on the underlayer or substrate, the low molecular weight water-repellent compound that is not immobilized on the underlayer or substrate is washed and removed. By removing the low-molecular-weight water-repellent compound that is not immobilized on the underlayer or substrate, the high-molecular-weight water-repellent compound applied in the second application step 204d can be easily fixed to the underlayer or substrate.

  For cleaning, it is preferable to use a good solvent of a low molecular weight water-repellent compound. The cleaning method is not particularly limited, and examples thereof include a spray method and a rinse method, and can be appropriately selected as necessary.

  Since the cleaning conditions vary depending on the type of low molecular weight water-repellent compound used, it is difficult to determine the temperature, time, etc. uniquely. Control the cleaning by determining the end point of the cleaning using the following method. Is possible. The determination of the end point of cleaning is not limited to this.

How to determine the end point of cleaning Compare the water contact angle before cleaning with the water contact angle after cleaning, and the water repellency deteriorates within the range of 3 ° to 5 ° from the water contact angle before cleaning (water contact angle The end point of washing was defined as the point where the

  In practice, a calibration curve was created in advance regarding the relationship between the water contact angle and the cleaning conditions (concentration of cleaning solution and cleaning time), and the end point of cleaning was controlled by determining the cleaning conditions from the calibration curve.

  In the second coating step 204d, a second coating solution containing a high molecular weight water-repellent compound is applied on the first coating film treated in the cleaning step 204c to form a second coating film.

  The concentration of the high molecular weight water-repellent compound in the second coating solution is usually preferably from 0.1% by mass to 30% by mass, but is not limited thereto, and can be appropriately adjusted depending on the type of the high molecular weight water-repellent compound. is there. Moreover, it is preferable to contain a fluorine-containing surfactant.

  Part of the applied second coating solution enters the position of the low molecular weight water-repellent compound that has been treated and removed in the cleaning step 204c and is fixed to the underlayer or the substrate. Thereby, durability of a water-repellent layer improves by forming the 2nd coating film in which one part was fixed to the base layer or the base material on the 1st coating film.

  As the coating apparatus for coating the second coating liquid, it is possible to use the same coating apparatus as the coating apparatus used for coating the first coating liquid depending on the substrate to be used.

  In the second drying step 204e, the solvent in the second coating film formed in the second coating step 204d is removed. By removing the solvent, a water-repellent article having a water-repellent layer formed from the base layer / first coating film and the second coating film on the substrate is produced.

  There is no limitation in particular as a method of removing a solvent, The same method as the 1st drying process 204b is mentioned.

  The drying conditions in the second drying step 204e are not particularly limited, but it is usually preferable to perform drying for about 1 minute to 14 days in the range of room temperature to 200 ° C.

  This will be described with reference to a schematic manufacturing process flowchart shown in FIG.

  In the figure, 2 'represents a manufacturing process flow for manufacturing a water-repellent article. The only difference from the schematic manufacturing process flow chart shown in FIG. 2A is that an energy beam irradiation process 204f is provided between the first drying process 204b and the cleaning process 204c. Since this is the same as the schematic manufacturing process flow shown in FIG.

  Next, the manufacturing method of the water-repellent material of the present invention will be described with reference to the schematic manufacturing process flow chart shown in FIG. 2B. However, the present invention is limited to the manufacturing process flow exemplified here. It is not a thing.

  In the energy ray irradiation step 204f, the first coating film that has been treated in the first drying step 204b is irradiated with energy rays to break the bond between the low molecular weight water-repellent compound immobilized on the substrate and the substrate. By removing the low molecular weight water-repellent compound cut in the subsequent washing step, the high-molecular weight water-repellent compound applied in the second application step 204d can be easily fixed to the underlayer or the substrate.

  Examples of energy rays include ultraviolet rays, electron rays, γ rays, etc., and any energy source that can break the bond between the low molecular weight water-repellent compound and the substrate surface can be used without limitation, but ultraviolet rays and electron rays are preferred. . In particular, ultraviolet rays are preferable because they are easy to handle and high energy can be easily obtained. As the ultraviolet light source, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used.

The irradiation conditions vary depending on the type of water-repellent compounds of the respective light sources and low molecular weight, but the amount of light irradiated is preferably from 1 mJ / cm ² or more, more preferably from 10000 mJ / cm ² from 20 mJ / cm ^2, particularly preferably, 50 mJ / cm ² to 2000 mJ / cm ² .

  Moreover, an electron beam can be used similarly. The electron beam is from 50 keV to 1000 keV, preferably from 100 keV emitted from various electron beam accelerators such as cockroft Walton type, bandegraph type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type. An electron beam having an energy of 300 keV can be given.

  Since the energy ray irradiation conditions vary depending on the type of low molecular weight water-repellent compound used, it is difficult to determine the amount of energy, time, etc. uniquely, so the end point of energy ray irradiation should be determined by the following method. It is possible to control the irradiation of energy rays. The determination of the end point of energy beam irradiation is not limited to this.

Determination method of end point of energy beam irradiation After measuring the water contact angle of the sample before irradiating the energy beam to A, measuring the water contact angle after irradiating the energy beam to B, and irradiating the active energy beam Compared with the water contact angle of the water, the water repellency deteriorates (the water contact angle becomes larger) within the range of 3 ° to 5 ° than the water contact angle before the energy ray irradiation. Was the end point.

  In addition, the water contact angle B is a water contact angle after washing | cleaning with the good solvent of the coating liquid of the coating film to wash | clean after irradiating an energy ray.

  In practice, a calibration curve was created in advance regarding the relationship of the water contact angle to the irradiation condition (energy amount, time) of the energy beam, and the cleaning end point was controlled from the calibration curve to control the end point of the cleaning.

  Next, in the method for producing a water-repellent article of the present invention, an example of a plasma film forming apparatus used for forming a base layer will be described with reference to FIGS.

  As described in, for example, Japanese Patent Laid-Open No. 2000-246091 and Japanese Patent Laid-Open No. 2003-238713, the atmospheric pressure plasma CVD method is used to form a thin film forming gas and a discharge in the discharge space under atmospheric pressure or in the vicinity thereof. In this method, a thin film is formed by supplying a gas containing a gas, exciting the gas by applying a high-frequency electric field to the discharge space, and exposing the gas to the excited gas.

  The atmospheric pressure plasma CVD method used for forming the underlayer related to the water-repellent film-coated article of the present invention is a plasma CVD method performed under atmospheric pressure or a pressure in the vicinity thereof. What is atmospheric pressure or a pressure in the vicinity thereof? The pressure is about 20 kPa to 110 kPa, and 93 kPa to 104 kPa is preferable in order to obtain the good effects described in the present invention.

  Hereinafter, an apparatus for forming an underlayer using an atmospheric pressure plasma CVD method near atmospheric pressure will be described.

  FIG. 3 is a schematic view showing an example of a jet type atmospheric pressure plasma film forming apparatus.

  A jet type atmospheric pressure plasma film forming apparatus includes a plasma discharge processing apparatus, an electric field applying means having two power supplies, and a gas supply means (not shown) and an electrode temperature adjusting means (not shown). It is.

The atmospheric pressure plasma film forming apparatus 3 has a counter electrode composed of a first electrode 301 and a second electrode 302, and the frequency from the first power supply 303 is from the first electrode 301 between the counter electrodes. A _first high-frequency electric field of ω ₁ , electric field intensity V ₁ , and current I ₁ is applied, and a second frequency of ω ₂ , electric field intensity V ₂ , and current I ₂ from the second power source 304 is applied from the second electrode 302. A high frequency electric field is applied. The first power source 303 can apply a higher frequency electric field strength (V ₁ > V ₂ ) than the second power source 304, and the first frequency ω ₁ of the first power source 303 is higher than the second frequency ω ₂ of the second power source 304. A low frequency can be applied.

  A first filter 305 is installed between the first electrode 301 and the first power supply 303 to facilitate passage of current from the first power supply 3031 to the first electrode 301, and current from the second power supply 304. Is designed so that the current from the second power supply 304 to the first power supply 303 is difficult to pass.

  In addition, a second filter 306 is installed between the second electrode 302 and the second power source 304 to facilitate the passage of current from the second power source 304 to the second electrode, and from the first power source 303. The current is grounded so that it is difficult to pass the current from the first power supply 303 to the second power supply.

  A gas G is introduced from the gas supply means as shown in FIG. 4 into the space between the opposing electrodes (discharge space) 307 between the first electrode 301 and the second electrode 302, and from the first electrode 301 and the second electrode 302. A discharge is generated by applying a high-frequency electric field, and while the gas G is in a plasma state, the gas G is blown out in the form of a jet to the lower side of the counter electrode (the lower side of the paper), and the processing space created by the lower surface of the counter electrode and the substrate E is plasma. A thin film is formed on the substrate E in the vicinity of the processing position 308 and filled with the state gas G °.

  As the substrate E, it is possible to use a flexible belt-shaped substrate or a single-wafer substrate.

  Reference numerals 309 and 310 denote high-frequency voltage probes, and reference numerals 311 and 312 denote oscilloscopes. The high frequency voltage probes 309 and 310 and the oscilloscopes 311 and 312 can measure the high frequency electric field strength (applied electric field strength) and the discharge start electric field strength.

  During the formation of the thin film, the medium heats or cools the electrode through the pipe from the electrode temperature adjusting means as shown in FIG. Depending on the temperature of the base material during the plasma discharge treatment, the properties, composition, etc. of the thin film obtained may change, and it is desirable to appropriately control this. As the temperature control medium, an insulating material such as distilled water or oil is preferably used. During the plasma discharge treatment, it is desirable to uniformly adjust the temperature inside the electrode so that the temperature unevenness of the substrate in the width direction or the longitudinal direction does not occur.

  A plurality of jet-type atmospheric pressure plasma discharge treatment apparatuses are arranged in series and arranged in series and can discharge the gas in the same plasma state at the same time, so that they can be processed many times and processed at high speed. Different layers can also be formed if each device jets different plasma gases.

  FIG. 4 is a schematic view showing an example of an atmospheric pressure plasma film forming apparatus in which a substrate is processed between opposing electrodes.

  In the figure, 4 indicates an atmospheric pressure plasma film forming apparatus. The atmospheric pressure plasma film forming apparatus 4 is an apparatus including at least a plasma discharge processing apparatus 5, an electric field applying means 6 having two power supplies, a gas supplying means 7, and an electrode temperature adjusting means 8.

  The atmospheric pressure plasma film forming apparatus 4 includes a plasma discharge processing apparatus 5, a counter electrode (discharge space) 503 between a roll rotating electrode (first electrode) 501 and a square tube-type fixed electrode group (second electrode) 502. F is subjected to plasma discharge treatment to form a thin film.

  The plasma discharge treatment apparatus 5 forms one electric field with a pair of square tube type fixed electrode group (second electrode) 502 group and a roll rotating electrode (first electrode) 501, and with this one unit, for example, A low carbon atom number concentration layer is formed. In the plasma discharge processing apparatus 5 shown in this figure, a configuration example is shown in which a total of five units having such a configuration are provided. In each unit, the type of raw material to be supplied, the output voltage, etc. can be arbitrarily set. By controlling it independently, it is possible to continuously form a laminated base layer.

The roll rotating electrode (first electrode) 501 receives a first high-frequency electric field having a frequency ω ₁ , an electric field strength V ₁ , and a current I ₁ from the first power source 601, and a rectangular tube-shaped fixed electrode (second electrode) 502 group. Are applied with a second high-frequency electric field of frequency ω ₂ , electric field strength V ₂ , and current I ₂ from the corresponding second power source 602.

  A first filter 603 is installed between the roll rotation electrode (first electrode) 501 and the first power source 601, and the first filter 603 is transferred from the first power source 601 to the roll rotation electrode (first electrode) 501. Is designed so that the current from the second power source 602 is grounded and the current from the second power source 602 to the first power source 601 is difficult to pass. Further, a second filter 604 is provided between the square tube type fixed electrode (second electrode) 502 group and the second power source 602, and the second filter 604 is connected to the square tube type from the second power source 602. Designed to facilitate the passage of current to the fixed electrode (second electrode) 502 group, ground the current from the first power source 601 and make it difficult to pass the current from the first power source 601 to the second power source 602. Has been.

The roll rotation electrode 501 may be the second electrode, and the square tube fixed electrode 502 group may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. The first power supply preferably applies a higher high-frequency electric field strength (V ₁ > V ₂ ) than the second power supply. Further, the frequency has the ability to satisfy ω ₁ <ω ₂ .

The current is preferably I ₁ <I ₂ . The current I ₁ of the first high-frequency electric field is preferably 0.3 mA / cm ² to 20 mA / cm ² , more preferably 1.0 A / cm ² to 20 mA / cm ² . The current I ₂ of the second high-frequency electric field is preferably 10 A / cm ² to 100 mA / cm ² , more preferably 20 A / cm ² to 100 mA / cm ² .

  The gas G generated by the gas generator 701 of the gas supply means 7 is introduced into the plasma discharge processing container 504 from the air supply port while controlling the flow rate.

  The substrate F is unwound from the original winding (not shown) and conveyed, or is conveyed from the previous process, and the air etc. that is accompanied by the substrate F by the nip roll 802 through the guide roll 801. The roll rotation electrode (first electrode) 501 and the square tube type fixed electrode (second electrode) 502 group are cut off and transferred between the square tube type fixed electrode 502 group while winding while being in contact with the roll rotation electrode 501. An electric field is applied from both of them to generate discharge plasma between the counter electrodes (discharge space) 503.

  The base material F forms a thin film with a gas in a plasma state while being wound while being in contact with the roll rotating electrode 501. The substrate F passes through the nip roll 803 and the guide roll 804 and is wound up by a winder (not shown) or transferred to the next step. The treated exhaust gas G ′ that has been subjected to the discharge treatment is discharged from the exhaust port 505.

  During the thin film formation, in order to heat or cool the roll rotating electrode (first electrode) 501 and the square tube type fixed electrode (second electrode) 502 group, a medium whose temperature is adjusted by the electrode temperature adjusting means 8 is fed. Pump P is sent to both electrodes via pipe 801, and the temperature is adjusted from the inside of the electrode. Reference numerals 506 and 507 denote partition plates that partition the plasma discharge processing vessel 504 from the outside.

  The distance between the opposing first electrode and second electrode is the shortest distance between the surface of the dielectric and the surface of the conductive metallic base material of the other electrode when a dielectric is provided on one of the electrodes. Say that.

  When a dielectric is provided on both electrodes, it means the shortest distance between the dielectric surfaces. The distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metal base material, the magnitude of the applied electric field strength, the purpose of using the plasma, etc. From the viewpoint of performing, it is preferably 0.1 mm to 20 mm, particularly preferably 0.5 mm to 2 mm.

  Details of the conductive metallic base material and dielectric useful in the present invention will be described later.

  The plasma discharge treatment vessel 504 is preferably a treatment vessel made of Pyrex (registered trademark) glass or the like, but may be made of metal as long as insulation from the electrode can be obtained. For example, polyimide resin or the like may be applied to the inner surface of an aluminum or stainless steel frame, and ceramic spraying may be applied to the metal frame to provide insulation. In FIG. 4, it is preferable to cover both side surfaces of the parallel electrodes (up to the vicinity of the base material surface) with the material as described above.

As the first power source (high frequency power source) installed in the atmospheric pressure plasma discharge processing apparatus according to the method for producing the water-repellent article of the present invention,
Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500
A2 Shinko Electric 5kHz SPG5-4500
A3 Kasuga Electric 15kHz AGI-023
A4 Shinko Electric 50kHz SPG50-4500
A5 HEIDEN Research Laboratories 100kHz * PHF-6k
A6 Pearl Industry 200kHz CF-2000-200k
A7 Pearl Industry 400kHz CF-2000-400k
And the like, and any of them can be used.

As the second power source (high frequency power source),
Applied power supply symbol Manufacturer Frequency Product name B1 Pearl Industry 800kHz CF-2000-800k
B2 Pearl Industry 2MHz CF-2000-2M
B3 Pearl Industry 13.56MHz CF-5000-13M
B4 Pearl Industry 27MHz CF-2000-27M
B5 Pearl Industry 150MHz CF-2000-150M
And the like, and any of them can be preferably used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave.

  In the present invention, it is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma discharge treatment apparatus.

In the present invention, the power applied between the electrodes facing each other is such that power (power density) of 1 W / cm ² or more is supplied to the second electrode (second high-frequency electric field) to excite the discharge gas to generate plasma. The energy is applied to the thin film forming gas to form a thin film. The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to an area in a range where discharge occurs in the electrode.

Further, by supplying power (output density) of 1 W / cm ² or more to the first electrode (first high frequency electric field), the output density is improved while maintaining the uniformity of the second high frequency electric field. I can do it. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. Preferably it is 5 W / cm ² or more. The upper limit value of the power supplied to the first electrode is preferably 50 W / cm ² .

  Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode, an intermittent oscillation mode called ON / OFF intermittently called a pulse mode, and either of them may be adopted, but at least the second electrode side (second The high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.

  Further, when the film quality of the underlayer is controlled in the present invention, it can also be achieved by controlling the electric power on the second power source side.

  An electrode used in such a method for forming a thin film by atmospheric pressure plasma must be able to withstand severe conditions in terms of structure and performance. Such an electrode is preferably a metal base material coated with a dielectric.

In the dielectric-coated electrode used in the present invention, it is preferable that the characteristics match between various metallic base materials and dielectrics. One of the characteristics is linear thermal expansion between the metallic base material and the dielectric. The combination is such that the difference in coefficient is 10 × 10 ⁻⁶ / ° C. or less. It is preferably 8 × 10 ⁻⁶ / ° C. or less, more preferably 5 × 10 ⁻⁶ / ° C. or less, and particularly preferably 2 × 10 ⁻⁶ / ° C. or less. The linear thermal expansion coefficient is a well-known physical property value of a material.

As a combination of a conductive metallic base material and a dielectric whose difference in linear thermal expansion coefficient is within this range,
1: Metal base material is pure titanium or titanium alloy, dielectric is ceramic sprayed coating 2: Metal base material is pure titanium or titanium alloy, dielectric is glass lining 3: Metal base material is stainless steel, Dielectric is ceramic spray coating 4: Metal base material is stainless steel, Dielectric is glass lining 5: Metal base material is a composite material of ceramics and iron, Dielectric is ceramic spray coating 6: Metal base material Ceramic and iron composite material, dielectric is glass lining 7: Metal base material is ceramic and aluminum composite material, dielectric is ceramic spray coating 8: Metal base material is ceramic and aluminum composite material, dielectric The body has glass lining. From the viewpoint of the difference in linear thermal expansion coefficient, the above-mentioned item 1 or item 2 and items 5 to 8 are preferable, and item 1 is particularly preferable.

  In the present invention, titanium or a titanium alloy is particularly useful as the metallic base material from the above characteristics. By using titanium or titanium alloy as the metal base material, the dielectric is used as described above, so that there is no deterioration of the electrode in use, especially cracking, peeling, dropping off, etc., and it can be used for a long time under harsh conditions. Can withstand.

  The atmospheric pressure plasma discharge treatment apparatus applicable to the present invention is described in, for example, JP-A-2004-68143, 2003-49272, WO 02/48428, etc., in addition to the above description. And an atmospheric pressure plasma discharge treatment apparatus.

A first coating solution containing a low molecular weight water-repellent compound is applied onto the substrate, and after washing or irradiation with active energy rays, a second coating solution containing a high molecular weight water-repellent compound is applied and dried. The following effects can be given by the method for producing a water-repellent article obtained by doing so.
1. Because of its high water repellency, it has good water droplet repelling and water slipperiness, so it can quickly remove water droplets from the surface of the substrate, ensuring good visibility, and maintaining “burn” and basicity. Deterioration due to alkali components eluted from the material can be suppressed, and the durability of high water repellency and high water slidability (water drop slidability) can be greatly improved.
2. In particular, it has become possible to expand the range of application to water-repellent articles that require durability and water repellency (for example, architectural window glass, vehicle window glass, etc.).

  Next, materials related to the method for producing a water-repellent article of the present invention will be described.

(Base material)
The strip-like flexible substrate and the single-wafer substrate as the base material are preferably substrates having excellent transparency, the transparent resin substrate is used as the strip-like flexible substrate, and the transparent glass substrate is used as the single-wafer substrate. Etc.

  Examples of transparent resin base materials include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate phthalate, and cellulose nitrate. Cellulose esters or their derivatives, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide, polyether sulfone, polysulfones, polyether ketone imide , Polyamide, fluororesin, nylon, polymethyl methacrylate Acrylic or polyarylates, or organic-inorganic hybrid resins such as these resin and silica.

  Examples of the glass substrate applicable to the present invention include inorganic glass having a functional group (hydroxyl group, amino group, thiol group, etc.) on the surface, organic glass, alkali-containing glass substrate such as soda lime silicate glass substrate, borosilicate Examples include alkali-free glass substrates such as acid glass substrates. The glass substrate may be laminated glass, tempered glass, or the like.

  In the present invention, from the viewpoint of imparting excellent properties such as water repellency, water slidability and durability of the present invention, the substrate is a transparent glass substrate, and as a final water-repellent article, in the visible light region. An average transmittance of 85% or more is preferable from the viewpoint of obtaining excellent transparency when applied to architectural window glass or vehicle window glass.

  The average transmittance in the visible light region referred to in the present invention is obtained by integrating the transmittances in the visible light region obtained by measuring the transmittance in the visible light region from 400 nm to 700 nm at least every 5 nm, and calculating an average value thereof. Defined as For the transmittance at each measurement wavelength, a conventionally known measuring device can be used. For example, a spectrophotometer UVIDFC-610 manufactured by Shimadzu Corporation, a 330-type self-recording spectrophotometer manufactured by Hitachi, Ltd., a U-3210-type self-recording It can be determined by measuring using a spectrophotometer, a U-3410 type self-recording spectrophotometer, a U-4000 type self-recording spectrophotometer, or the like.

(Underlayer)
In the present invention, the underlayer preferably contains silicon oxide. In the atmospheric pressure plasma film forming apparatus shown in FIGS. 3 and 4, for example, silicon oxide can be obtained by using a silicon compound as a raw material compound and oxygen as a decomposition gas, and carbon dioxide can be used as the decomposition gas. By using this, silicon carbonate is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

  As such an inorganic material, as long as it contains a typical or transition metal element, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use by a solvent and organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents can be used for a solvent. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

  Examples of the silicon compound forming the base layer which is such a silicon oxide film include silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, and tetra-t- Butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, Hexamethyldisiloxane, bis (dimethylamino) dimethylsilane, bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (to Methylsilyl) carbodiimide, diethylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetra Methyldisilazane, tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t -Butylsilane, 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane , Phenyltrimethylsilane, propargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclo Examples thereof include tetrasiloxane, tetramethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  The decomposition gas for decomposing the source gas containing these silicon atoms to obtain a silicon oxide film is, for example, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas. Nitrous oxide gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, chlorine gas, etc. .

  Various silicon carbides, silicon nitrides, silicon oxides, silicon halides, and silicon sulfides can be obtained by appropriately selecting a source gas containing silicon element and a decomposition gas.

  A discharge gas that tends to be in a plasma state is mixed with these reactive gases, and the gas is sent to the plasma discharge generator. As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used.

  The discharge gas and the reactive gas are mixed, and a film is formed by supplying the mixed gas as a mixed gas to a plasma discharge generator (plasma generator). Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

(Low molecular weight water repellent compound)
Examples of the low molecular weight water repellent compound include a fluorine-containing silane coupling agent, a silane compound having a reactive silyl group, and a polydimethylsiloxane skeleton compound. The number of reactive silyl groups is preferably 1 to 10 in the molecule.

  As the fluorine-containing silane coupling agent, a compound having a polyfluoroalkyl group and a reactive silyl group is suitably employed. The polyfluoroalkyl group is preferably a perfluoroalkylethyl group, and the reactive silyl group is preferably a reactive silyl group selected from an alkoxy group, a chloro group, an isocyanate group, a carboxyl group, a hydroxyl group and an epoxy group. Of these, an alkoxy group is preferred.

Specific examples of the fluorine-containing silane coupling agent include, for example, 3,3,3-trifluoropropyltrichlorosilane, methyl-3,3,3-trifluoropropyldichlorosilane, dimethoxymethyl-3,3,3-trimethyl. fluoropropyl silane, 3,3,3-trifluoropropyl triethoxy silane, 3,3,4,4,5,5,6,6,6-nonafluorohexyl _{trichlorosilane, CF 3 CH 2 CH 2 Si} (OCH _{3) 3, CF 3 (CF} 2) 5 CH 2 CH 2 Si (OCH 3) 3, CF 3 (CF 2) 7 CH 2 CH 2 Si (OCH 3) 3 and the like.

  Examples of the fluorine-containing silane coupling agent include Toray Dow Corning Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd., Daikin Industries Co., Ltd. (for example, OPTOOL DSX), Gelest Inc. It is marketed by Solvay Solexis Co., Ltd. and can be obtained easily. Also, for example, J.A. Fluorine Chem. 79 (1). 87 (1996), material technology, 16 (5), 209 (1998), Collect. Czech. Chem. Commun. 44, 750-755, J.M. Amer. Chem. Soc. 1990, 112, 2341-2348, Inorg. Chem. 10: 889-892, 1971, U.S. Pat. No. 3,668,233, etc., JP-A-58-122979, JP-A-7-242675, JP-A-9-61605, etc. 11-29585, JP-A No. 2000-64348, JP-A No. 2000-144097 and the like, or a synthesis method based on the synthesis method.

  These fluorine-containing silane coupling agents may be used in combination of two or more.

  The molecular weight of the fluorine-containing silane coupling agent is less than 1000, preferably 100 to 700, and more preferably 200 to 600.

  As the fluorine-based organic solvent used in the fluorine-containing silane coupling agent, Novec HFE (hydrofluoroether) manufactured by Sumitomo 3M Limited can be preferably used.

  Examples of the polydimethylsiloxane skeleton compound include compounds having the following structural formula.

In the formula, R ₁ represents a hydrogen atom or a methyl group, and X ₁ represents a reactive organic group. Examples of the reactive organic group include an epoxy group, a hydroxyl group, a diol group, a carboxyl group, a methacryl group, an alkoxy group, a chloro group, and an isocyanate group. n represents an integer of 1 to 22.

[4-functional silane coupling agent]
The coating liquid (first coating liquid) containing a low molecular weight water-repellent compound preferably contains a tetrafunctional silane coupling agent in addition to the low molecular weight water-repellent compound. Addition of a tetrafunctional silane coupling agent improves wear resistance.

  The tetrafunctional silane coupling agent is a silane coupling agent having four reactive groups. Examples of the reactive group include an alkoxy group, an alkoxyalkoxy group, an acyloxy group, an aryloxy group, an aminoxy group, and an amide group. And ketoxime groups, isocyanate groups, halogen atoms and the like. A group obtained by removing a hydrogen atom from a hydroxyl group of a monohydric alcohol such as an alkoxy group or an alkoxyalkoxy group is preferred. In particular, an alkoxy group is preferred, and the number of carbon atoms is preferably 4 or less, particularly preferably 1 to 2.

  Specific examples of the tetrafunctional silane coupling agent include tetramethoxysilane, tetraethoxysilane, isocyanatepropyltrimethoxysilane, isocyanatepropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyl. Trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-meta Acryloxypropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercap Examples include topropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, vinylsilyltriisocyanate, tetraisocyanatesilane, ethoxysilanetriisocyanate, and the like.

  These tetrafunctional silane coupling agents may be used alone or in combination of two or more. These silane coupling agents are monomers, but when one or more silane coupling agents are added by partial condensation reaction, the adhesion to the substrate is improved by the anchor effect. In order to strengthen the adhesion to glass, a silane coupling agent containing an isocyanate group is preferred. A partial condensation reaction product of aminosilane is also preferable because of its high anchoring effect.

  The blending amount of the tetrafunctional silane coupling agent is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the low-molecular water-repellent compound having the reactive silyl group. Parts by weight, more preferably 20 to 50 parts by weight.

(High molecular weight water repellent compound)
Examples of the high molecular weight water-repellent compound include a fluorine-containing polymer having a reactive silyl group, a cyclic fluorine-containing polymer, and a silane compound having a perfluoropolyether skeleton.

The reactive silyl group is preferably a reactive silyl group selected from an alkoxy group, a chloro group, an isocyanate group, a silazane group, a carboxyl group, a hydroxyl group and an epoxy group. Of these, an alkoxy group is preferred. The reactive silyl group preferably has 2 to 50 reactive silyl groups in the molecule.

  In the present invention, a fluorine-containing polymer having a reactive silyl group selected from an alkoxy group, a chloro group, an isocyanate group, a silazane group, a carboxyl group, a hydroxyl group and an epoxy group is preferable.

(Fluorine-containing polymer having a reactive silyl group)
The fluorine-containing polymer having a reactive silyl group can be obtained, for example, by introducing a reactive silyl group by reacting a fluorine-containing polymer having a hydroxy group with a silane modifier. The fluorine-containing polymer having a hydroxy group is obtained by copolymerizing a fluoroolefin and a hydroxy group-containing monomer such as hydroxyalkyl vinyl ether or allyl alcohol as a main monomer component. In this case, in addition to these components, an alkyl vinyl ether is used. , Vinyl ester, allyl ether, isopropenyl ether and other monomer components may be obtained by copolymerization.

  The fluoroolefin is not particularly limited, and those commonly used as monomers for fluororesins are used, and perfluoroolefin is preferred, and among them, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, perfluoroolefin, Fluoropropyl vinyl ether and mixtures thereof are particularly preferred.

  The hydroxy group-containing monomer is not particularly limited, but is preferably a hydroxyalkyl vinyl ether having a linear or branched alkyl group having 2 to 5 carbon atoms, particularly hydroxybutyl vinyl ether.

  Furthermore, the polymer can be made flexible by other monomer components. In this case, as the other monomer component, an alkyl vinyl ether having one or two or more alkyl groups selected from a cyclohexyl group and linear and branched alkyl groups having 1 to 8 carbon atoms is preferable. In such a copolymer using an alkyl vinyl ether, the fluoroolefin content is preferably 40 to 70 mol% in order to sufficiently exhibit heat resistance, weather resistance and chemical resistance. .

  Specific examples of the fluorine-containing polymer having a hydroxy group in the side chain obtained by copolymerizing the monomer components described above include Lumiflon LF-100, 200, 300, 400, 600 (all manufactured by Asahi Glass Co., Ltd.) Any of them is preferably used, but Lumiflon LF-100, 200 or 600 is preferably used.

  As the silane modifier for obtaining a fluorine-containing polymer having an alkoxy group as a reactive silyl group, an alkoxysilane having an isocyanate group represented by the following formula (1) is suitable, and one or more of these are used.

OCN (CH ₂ ) ₃ SiX _n R _(3-n) (1)
(In the formula, R is hydrogen or a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and X is an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group or An ethoxy group.)
Of these, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and γ-isocyanatopropyltrimethoxysilane are preferably used.

  The fluorine-containing polymer having a reactive silyl group used in the present invention is obtained by the reaction of the above-mentioned fluorine-containing polymer having a hydroxy group in the side chain and a silane modifier. In this reaction, a metal such as tin or titanium is used. Catalysts and organometallic catalysts such as dibutyltin laurate can be used. Among these, tin, titanium, and these organometallic catalysts promote the above reaction efficiently, as well as hydrolysis of reactive silyl groups obtained by the reaction and condensation crosslinking with silanol obtained by hydrolysis. It can be suitably used because it can promote adhesion by chemical bonding to the substrate.

  The reaction can be performed in a solvent. As the solvent, those having no active hydrogen that reacts with an isocyanate group and those that dissolve a fluorine-containing polymer having a hydroxy group and an alkoxysilane having an isocyanate group are used. For example, toluene, xylene, fluorine-based organic solvents, etc. May be used solvents such as silane fluorinate, Novec HFE (manufactured by 3M), Galden (manufactured by Montefluos), trifluoromethylbenzene, hydrofluorocarbon and the like. The reaction is usually carried out at 10 ° C. to 70 ° C. for 1 hour to 3 hours. In this case, the reaction is preferably carried out in an inert atmosphere such as nitrogen. The reaction with the silane modifier is preferably performed in the presence of a fluorine-containing surfactant described later. In this case, the fluorine-containing surfactant may have a hydroxy group, and at least a part thereof may be modified with a reactive silyl group.

  The fluorine-containing polymer having a reactive silyl group can also be obtained by copolymerizing a fluoroolefin with an ethylenically unsaturated monomer having a reactive silyl group and, if necessary, other monomers. Here, the same thing as the above-mentioned thing is employ | adopted for a fluoro olefin and another monomer. As the ethylenically unsaturated monomer having a reactive silyl group, vinylalkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane are preferable.

  The fluorine-containing polymer preferably has a reactive silyl group, but when it does not have a reactive silyl group, the fluorine-containing polymer contains a silane coupling agent such as a tetrafunctional silane coupling agent described later in the fluorine-containing polymer. The same effect can be obtained by mixing with the containing coating solution or by forming a base layer having a silane coupling agent between the substrate and the layer having the coating material.

(Cyclic fluorinated polymer)
Examples of the cyclic fluorine-containing polymer include fluorine-containing polymers such as Cytop (Asahi Glass Co., Ltd.). Cytop's M grade has a reactive silyl group, while A grade does not have a reactive silyl group and is used in combination with a separate silane coupling agent or between the substrate and the layer having the coating material. It is preferable to form an underlayer having a coupling agent.

(Silane compound having a perfluoropolyether skeleton)
Examples of the silane compound having a perfluoropolyether skeleton include fluorine-containing polymers such as OPTOOL (Daikin Industries).

[Fluorine-containing surfactant]
The fluorine-containing surfactant used in the first coating solution and the second coating solution is not particularly limited. Fluorine-containing surfactants are commercially available under the trade names such as MegaFac (Dainippon Ink Chemical), Ftop (Tochem Products), Surflon (Asahi Glass), Footgent (Neos), Unidyne (Daikin Industries), etc. . Of these, oil-soluble ones are preferable, and Surflon S-381, Surflon S-382 and the like are exemplified as suitable ones.

(Other materials that can be added)
In the first coating liquid and the second coating liquid, other resins such as a fluororesin, an acrylic resin, a polyester resin, a polyether resin, and a polyurethane resin are used as necessary without departing from the object of the present invention. Epoxy resins and the like, and various additives such as surfactants, extenders, color pigments, rust preventive pigments, fluororesin powders, silicone resin powders, rust preventives, dyes, waxes and the like may be added.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

Example 1
(Preparation of water repellent layer forming coating solution)
A coating solution for forming a water-repellent layer having a low molecular weight water-repellent compound and a high molecular weight water-repellent compound as shown in Table 1 was prepared by the method shown below. 1-1 to 1-5.

Water repellent layer forming coating solution No. 1-1 Preparation As a low molecular weight water-repellent compound, a fluorine-containing silane coupling agent (CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , molecular weight 568) having a solid content concentration of 0.2 % Of the coating solution for forming a water-repellent layer by diluting with IPA to give 1-1.

Water repellent layer forming coating solution No. Preparation of 1-2 As a low molecular weight water-repellent compound, an alkylsilane coupling agent (CH ₃ (CH ₂ ) ₉ Si (OCH ₃ ) ₃ , molecular weight 262) is added so that the solid content concentration is 0.2%. Dilute with xylene and apply coating solution No. 1-2.

Water repellent layer forming coating solution No. Preparation of 1-3 100 g of Lumiflon LF-200 (manufactured by Asahi Glass Co., Ltd.) as a fluoropolymer having a hydroxy group in the side chain was diluted with 400 g of xylene, and KBE-9007 (γ-isocyanatopropyltriethoxysilane as a silane modifier) As a high molecular weight water-repellent compound having triethoxysilane (reactive silyl group) by adding 15 g of Shin-Etsu Chemical Co., Ltd.) and 0.017 g of dibutyltin dilaurate and stirring for 2 hours at room temperature / nitrogen atmosphere, A fluoropolymer (weight average molecular weight of 7000 or more, solution) was obtained. The obtained fluoropolymer was diluted with xylene so that the solid content concentration would be 1%. 1-3.

Water repellent layer forming coating solution No. Preparation of 1-4 As a high molecular weight water-repellent compound, 1 g of OPTOOL AES-6 (manufactured by Daikin Industries) (weight average molecular weight 6000 or more, solution) is diluted with 100 g of Novec HFE7100 (manufactured by Sumitomo 3M Co., Ltd.). The solid content concentration was adjusted to 0.2%, and the water-repellent layer forming coating solution No. 1-4.

Water repellent layer forming coating solution No. Preparation of 1-5 Polydimethylsiloxane skeleton compound X-24-9011 (manufactured by Shin-Etsu Chemical Co., Ltd. (weight average molecular weight 1500 or more, solution)) as a high molecular weight water-repellent compound so that the solid content concentration becomes 1% And diluted with ethyl acetate to form a water repellent layer-forming coating solution No. 1-5.

(Preparation of base material)
A commercially available 3 mm thick soda lime glass (manufactured by Opton) was sequentially washed with a neutral detergent, water and alcohol and dried, and then wiped with acetone to obtain a substrate.

(Production of water-repellent articles)
In accordance with the schematic manufacturing process flow chart shown in FIG. 1-1 to 1-5 are combined as shown in Table 2, and coated by the method shown below to produce a water-repellent article. 101 to 119. Note that the underlayer was not formed.

Sample No. Preparation of water-repellent layer forming coating liquid No. 101 prepared on the prepared base material. 1-1 (first coating solution) was applied by a dipping coating method and then dried at 23 ° C. for 5 minutes to form a first coating film having a thickness of 6 nm. Thereafter, after curing at 150 ° C. for 30 minutes, the surface of the first coating film was washed using IPA, which is a good solvent for the fluorinated silane coupling agent, and dried in a dryer at 150 ° C. for 30 minutes. The water repellent layer-forming coating solution No1-3 (second coating solution) was applied by dipping coating method and dried in a dryer at 150 ° C. for 60 minutes to form a second coating film having a thickness of 40 nm. A 45 nm water-repellent article was prepared and sample No. 101.

  The film thickness of the first coating film, the second coating film, and the total film thickness are values measured by “MXP21” (manufactured by Mac Science).

Cleaning conditions for the first coating film The substrate on which the first coating film was formed was immersed in a container containing IPA as a good solvent, and the entire container was immersed in an ultrasonic cleaner to perform cleaning for 30 minutes. The base material taken out from the xylene container was dried at room temperature, then the surface was further washed with running water, water droplets were removed with high-pressure air, and the first coating film washing step was completed.

Sample No. Preparation of Sample No. 102 When producing 101, the second coating liquid was No. 101. Sample No. 4 except that the drying conditions of the second coating film were changed to 1-4. A water-repellent article was produced under the same conditions as in No. 101. 102.

Drying condition of the second coating film The coating film was left to dry at 23 ° C. for one day (24 hours).

Sample No. Sample No. 103 When producing 101, the second coating liquid was No. 101. Sample No. 1 except that the drying conditions of the second coating film were changed to 1-5. A water-repellent article was produced under the same conditions as in No. 101. 103.

Drying conditions for the second coating film: The film was dried in a dryer at 150 ° C. for 60 minutes.

Sample No. Production of No. 104 On the prepared base material, the prepared coating liquid No. 1-2 (first coating solution) was applied by a dipping coating method and then dried at 150 ° C. for 30 minutes to form a first coating film having a thickness of 5 nm. Thereafter, the surface of the first coating film is washed with xylene, which is a good solvent for the alkylsilane coupling agent, dried at 150 ° C. for 30 minutes, and then coated with water-repellent layer forming coating solution No1-3 (second coating). Liquid) was applied by a dipping coating method and dried at 150 ° C. for 60 minutes to form a second coating film having a thickness of 40 nm to produce a water-repellent article having a total thickness of 44 nm. 104.

  The film thickness of the first coating film and the film thickness of the second coating film were measured according to Sample No. The value measured by the same method as 101 is shown.

Cleaning conditions for the first coating film As a cleaning liquid, xylene, which is a good solvent, was used. Washing was performed in the same manner as in 101.

Sample No. Sample No. 105 When producing 104, the second coating solution was designated as No. 104. Sample No. 4 except that the drying conditions of the second coating film were changed to 1-4. A water-repellent article was produced under the same conditions as in No. 104. 105.

Drying condition of the second coating film The coating film was left to dry at 23 ° C. for one day (24 hours).

Sample No. Preparation of sample No. 106 When producing 104, the second coating solution was designated as No. 104. Sample No. 1 except that the drying conditions of the second coating film were changed to 1-5. A water-repellent article was produced under the same conditions as in No. 104. 106.

Drying conditions for the second coating film The coating film was dried in a dryer at 150 ° C. for 60 minutes.

Sample No. Preparation of No. 107 All samples No. 1 except that the first coating film was not washed. A water-repellent article was prepared under the same conditions as in No. 101. 106. The first coating film had a thickness of 6 nm and a total thickness of 45 nm.

Sample No. No. 108 Sample No. 108 except that the first coating film was not washed. A water-repellent article was produced under the same conditions as in No. 102. 108. The first coating film had a thickness of 6 nm and a total thickness of 15 nm.

Sample No. No. 109 Sample No. 109 was prepared except that the first coating film was not cleaned. A water-repellent article was produced under the same conditions as in Comparative Sample No. 103. 109. The first coating film had a thickness of 6 nm and a total thickness of 13 nm.

Sample No. 110 No. Sample No. 110 except that the first coating film was not cleaned. A water-repellent article was prepared under the same conditions as in No. 104. 110. The first coating film had a thickness of 5 nm and a total thickness of 44 nm.

Sample No. Production of Sample No. 111 except that the first coating film was not washed. A water-repellent article was produced under the same conditions as in No. 105. 111. The first coating film had a thickness of 5 nm and a total thickness of 14 nm.

Sample No. Preparation of Sample No. 112 All except that the first coating film was not washed. A water-repellent article was produced under the same conditions as in Comparative Example No. 106. 112. In addition, the film thickness of the 1st coating film was 5 nm, and the total thickness was 12 nm.

Sample No. Preparation of No. 113 On the prepared base material, the prepared coating liquid No. After coating only 1-1 (first coating solution) by the dipping coating method, the coating film was dried at 23 ° C. for 5 minutes to form a first coating film having a thickness of 40 nm. Thereafter, a curing treatment was performed at 150 ° C. for 30 minutes to produce a water-repellent article. 113. The film thickness of the 1st coating film is sample No.2. The value measured by the same method as 101 is shown.

Sample No. 114 Preparation On the prepared base material, the prepared coating liquid No. After coating only 1-2 (first coating solution) by the dipping coating method, it was dried at 150 ° C. for 30 minutes to form a first coating film having a thickness of 40 nm. 114.

  The film thickness of the 1st coating film is sample No.2. The value measured by the same method as 101 is shown.

Sample No. Preparation of No. 115 On the prepared base material, the prepared coating liquid No. After coating only 1-3 (second coating solution) by the dipping coating method, it was dried at 150 ° C. for 60 minutes to form a coating film having a thickness of 40 nm. Thereafter, a curing treatment was performed at 150 ° C. for 30 minutes to produce a water-repellent article. 115.

  The film thickness of the 1st coating film is sample No.2. The value measured by the same method as 101 is shown.

Sample No. 116. On the prepared base material, the prepared coating liquid No. After coating only 1-4 (second coating solution) by the dipping coating method, it was left to dry at 23 ° C. for 1 day (24 hours) to form a coating film having a thickness of 8 nm. Thereafter, a curing treatment was performed at 150 ° C. for 30 minutes to produce a water-repellent article. 116.

  The film thickness of the 1st coating film is sample No.2. The value measured by the same method as 101 is shown.

Sample No. Preparation of 117 On the prepared base material, the prepared coating liquid No. After applying only 1-5 (second coating solution) by the dipping coating method, it was dried at 150 ° C. for 60 minutes to form a coating film having a thickness of 6 nm. Thereafter, a curing treatment was performed at 150 ° C. for 60 minutes to produce a water-repellent article. 117.

  The film thickness of the 1st coating film is sample No.2. The value measured by the same method as 101 is shown.

Sample No. Production of 118 water-repellent layer forming coating solution No. 1-1 (first coating solution) was applied by a dipping coating method and then dried at 23 ° C. for 5 minutes to form a first coating film having a thickness of 6 nm. Thereafter, after curing at 150 ° C. for 30 minutes, the surface of the first coating film was washed with IPA which is a good solvent for the fluorine-containing silane coupling agent, dried at 150 ° C. for 30 minutes, and then water-repellent. A layer forming coating solution No. 1-2 (second coating solution) is applied by a dipping coating method, dried at 150 ° C. for 30 minutes to form a second coating film having a thickness of 6 nm, and a water-repellent article having a total thickness of 11 nm. The prepared comparative sample No. 118.

  The film thicknesses of the first coating film, the second coating film, and the total thickness are shown in Sample No. The value measured by the same measuring method as 101 is shown.

Cleaning conditions for the first coating film Sample No. The same conditions as in 101 were used.

Sample No. Preparation of 119 On the prepared base material, the prepared coating liquid No. 1-3 (first coating solution) was applied by a dipping coating method and then dried at 150 ° C. for 60 minutes to form a first coating film having a thickness of 40 nm. The surface of the first coating film is washed with xylene which is a good solvent for Lumiflon LF-200 silyl modified product (Asahi Glass Co., Ltd.), dried at 150 ° C. for 30 minutes, and then a coating solution for forming a water repellent layer. No1-4 (second coating solution) was applied by dipping coating method and left to dry at 23 ° C. for one day (24 hr) to form a second coating film with a thickness of 9 nm to produce a water-repellent article with a total thickness of 48 nm. Comparative sample No. 119.

  The film thicknesses of the first coating film, the second coating film, and the total thickness are shown in Sample No. The value measured by the same measuring method as 101 is shown.

Cleaning conditions for the first coating film As the cleaning liquid, xylene, a good solvent, was used. Washing was performed in the same manner as in 101.

  Sample No. The cleaning conditions at the time of manufacturing 101 to 119 were compared with the water contact angle before cleaning and the water contact angle after cleaning. A calibration curve was created for the relationship of the water contact angle to the concentration of the cleaning solution and the cleaning time, and the cleaning conditions were determined from the calibration curve.

Evaluation Each sample No. Table 3 shows the results of evaluations according to the evaluation ranks shown below, with the test methods shown below attached to the initial water repellency, wet heat resistance, and alkali resistance.

Initial water repellency test method About the initial water repellency of each water-repellent article produced, the static contact angle using water as a test solution was measured by a contact angle meter (CA-DT, manufactured by Kyowa Interface Science Co., Ltd.). The static contact angle with a water droplet having a mass of 3 μl was measured, and the initial water repellency was evaluated according to the following evaluation rank. The larger the value of the static contact angle, the better the initial water repellency.

Evaluation rank of initial water repellency ◎: Static contact angle is 100 ° or more ○: Static contact angle is 90 ° or more and less than 100 ° △: Static contact angle is 85 ° or more and less than 90 ° ×: Static contact angle Is less than 85 ° Test method for water slidability (water drop slidability) About each water-repellent article produced, using a contact angle meter (CA-DT, manufactured by Kyowa Interface Science Co., Ltd.), 50 μl of water drops were dropped. Gradually tilt the stage holding the water-repellent article from 0 ° (horizontal) to 90 ° (right-angle) to obtain the angle at which water droplets begin to roll on the surface of the water-repellent article. Evaluation of (water drop sliding property) was performed. The smaller the critical sliding angle, the better the dynamic water repellency.For example, it means that raindrops attached to the windshield window of a running car are likely to scatter and the driver's visibility is not hindered. Yes.

Evaluation rank of sliding performance ◎: Critical sliding angle is less than 10 ° ○: Critical sliding angle is 10 ° or more and less than 20 ° △: Critical sliding angle is 20 ° or more and less than 30 ° ×: Critical sliding angle is 30 ° or more Resistance test method About the wet heat resistance of each manufactured water-repellent article, after storing it in an environment of a temperature of 50 ° C. and a humidity of 95% RH for 500 hours, a static contact angle using water as a test solution was measured using a contact angle meter (CA -DT, manufactured by Kyowa Interface Science Co., Ltd.), the static contact angle with a water droplet of 3 μl was measured, and wet heat resistance was evaluated according to the following evaluation rank. The larger the value of this static contact angle, the better the resistance to wet heat.

Evaluation rank of wet heat resistance ◎: Static contact angle is 90 ° or more ○: Static contact angle is 80 ° or more and less than 90 ° △: Static contact angle is 70 ° or more and less than 80 ° ×: Static contact angle is Less than 70 ° Alkali resistance test method Regarding the alkali resistance of each water-repellent article produced, after immersion in a 0.001N caustic soda solution at a temperature of 25 ° C. for 2 hours, a static contact angle using water as a test solution was measured. The static contact angle with a water droplet of 3 μl was measured with an angle meter (CA-DT, manufactured by Kyowa Interface Science Co., Ltd.), and the alkali resistance was evaluated according to the following evaluation rank. The larger the value of the static contact angle, the better the alkali resistance.

Evaluation rank of alkali resistance ◎: Static contact angle is 90 ° or more ○: Static contact angle is 80 ° or more and less than 90 ° △: Static contact angle is 70 ° or more and less than 80 ° ×: Static contact angle is Less than 70 °

  A water-repellent layer-forming coating solution (first coating solution) containing a low molecular weight water-repellent compound is applied on the substrate to form the first coating, and then the first coating is washed, The water-repellent article of the present invention for producing a water-repellent article having a water-repellent layer formed by applying a water-repellent-layer-forming coating liquid (second coating liquid) containing a water-repellent compound having a molecular weight. The water-repellent article No. produced by the production method of 101 to 106 are comparative sample Nos. Compared with 107 to 119, the initial water repellency, water slidability (water drop slidability), wet heat resistance, and alkali resistance were all excellent, confirming the effectiveness of the present invention.

Example 2
The same results as in Example 1 were obtained as a result of producing water-repellent articles under the same conditions except that the base material used in Example 1 was changed to a polyethylene terephthalate film as a belt-like flexible base material.

Example 3
(Preparation of coating solution for forming water-repellent layer with different molecular weight)
As shown in Table 4, a coating solution for forming a water repellent layer containing a water repellent compound having a different molecular weight and having a changed weight average molecular weight was prepared. 3-1 to 3-3.

Water repellent layer forming coating solution No. 3-1 Preparation As a low molecular weight water-repellent compound, a polydimethylsiloxane skeleton compound (weight average molecular weight 800) is diluted with ethyl acetate so that the solid content concentration is 0.2%, and is applied to form a water-repellent layer. Liquid No. 3-1.

First coating solution No. 3-2 Preparation As a low-molecular-weight water-repellent compound, a polydimethylsiloxane skeleton compound (weight average molecular weight 1000) is diluted with ethyl acetate so that the solid content concentration is 0.2%. Liquid No. It was set to 3-2.

First coating solution No. 3-3 Preparation As a low molecular weight water-repellent compound, a polydimethylsiloxane skeleton compound (weight average molecular weight 1200) is diluted with ethyl acetate so that the solid content concentration is 0.2%, and is applied to form a water-repellent layer. Liquid No. 3-3.

(Preparation of base material)
A commercially available 3 mm thick soda lime glass (manufactured by Opton) was sequentially washed with a neutral detergent, water and alcohol and dried, and then wiped with acetone to obtain a substrate.

(Production of water-repellent articles)
In accordance with the schematic manufacturing process flow chart shown in FIG. 3-1 to 3-3 were combined as shown in Table 5 and applied by the method shown below to produce a water-repellent article. 301 to 309. Note that the underlayer was not formed.

Sample No. Production of No. 301 On the prepared base material, the prepared coating liquid No. After applying 3-1 by a dipping coating method, it was dried at 150 ° C. for 30 minutes to form a first coating film having a thickness of 6 nm. Thereafter, the surface of the first coating film is washed with ethyl acetate which is a good solvent for the polydimethylsiloxane skeleton compound, dried at 150 ° C. for 30 minutes, and then dipped with a water repellent layer forming coating solution No3-1. And then dried at 150 ° C. for 30 minutes to form a second coating film having a thickness of 5 nm to produce a water-repellent article having a total thickness of 10 nm. 301.

  As for the film thickness of the first coating film, the film thickness and the total thickness of the second coating film indicate values measured by the same method as in Example 1.

Cleaning conditions for the first coating film The substrate formed up to the first coating film was immersed in a container containing ethyl acetate, and the container was immersed in an ultrasonic cleaner to perform ultrasonic cleaning for 30 minutes. The end point of washing was determined by the same method as in Example 1.

Sample No. Preparation of sample No. 302 When preparing 301, water-repellent layer forming coating liquid No3-1 (second coating liquid) was changed to water-repellent layer-forming coating liquid No3-2 (second coating liquid). A water-repellent article was prepared under the same conditions as in Sample No. 301. 302.

Sample No. Sample No. 303 When preparing 301, water-repellent layer forming coating solution No3-1 (second coating solution) was changed to water-repellent layer-forming coating solution No3-3 (second coating solution). A water-repellent article was prepared under the same conditions as in Sample No. 301. 303.

Sample No. Sample No. 304 When preparing 301, water-repellent layer forming coating solution No3-1 (first coating solution) was changed to water-repellent layer-forming coating solution No3-2 (first coating solution). A water-repellent article was prepared under the same conditions as in Sample No. 301. 304.

Sample No. Sample No. 305 When producing 301, the water repellent layer forming coating solution No3-1 (first coating solution) is changed to the water repellent layer forming coating solution No3-2 (first coating solution), and the water repellent layer forming coating solution No3. -4 (second coating solution) was changed to water repellent layer forming coating solution No 3-5 (second coating solution). A water-repellent article was prepared under the same conditions as in Sample No. 301. 305.

Sample No. Sample No. 306 When producing 301, the water repellent layer forming coating solution No3-1 (first coating solution) is changed to the water repellent layer forming coating solution No3-2 (first coating solution), and the water repellent layer forming coating solution No3. -4 (second coating solution) was changed to water-repellent layer forming coating solution No 3-6 (second coating solution). A water-repellent article was prepared under the same conditions as in Sample No. 301. 306.

Sample No. Sample No. 307 When preparing 301, water-repellent layer forming coating liquid No3-1 (first coating liquid) was changed to water-repellent layer-forming coating liquid No3-3 (first coating liquid). A water-repellent article was prepared under the same conditions as in Sample No. 301. 307.

Sample No. Preparation of Sample No. 308 Sample No. When producing 301, the water repellent layer forming coating solution No3-1 (first coating solution) is changed to the water repellent layer forming coating solution No3-3 (first coating solution), and the water repellent layer forming coating solution No3. -4 (second coating solution) was changed to water repellent layer forming coating solution No 3-5 (second coating solution). A water-repellent article was prepared under the same conditions as in Sample No. 301. 308.

Sample No. Sample No. 309 When producing 301, the water repellent layer forming coating solution No3-1 (first coating solution) is changed to the water repellent layer forming coating solution No3-3 (first coating solution), and the water repellent layer forming coating solution No3. -4 (second coating solution) was changed to water-repellent layer forming coating solution No 3-6 (second coating solution). A water-repellent article was prepared under the same conditions as in Sample No. 301. 309.

Evaluation Each sample No. 301 to 309, the initial water repellency, water slidability (water drop slidability) wet heat resistance, and alkali resistance were tested in the same test method as in Example 1, and the results evaluated according to the same evaluation rank as in Example 1 are shown in Table 6. Show.

  A water-repellent layer-forming coating solution (first coating solution) containing a low-molecular-weight water-repellent compound having a weight average molecular weight of less than 1000 is applied on the substrate to form the first coating film, and then the first coating is formed. The film is washed, and subsequently a water repellent layer forming coating solution (second coating solution) containing a high molecular weight water repellent compound having a weight average molecular weight of 1000 or more is applied to form a second coating film, The water-repellent article No. 1 produced by the method for producing a water-repellent article of the present invention for producing the formed water-repellent article. Nos. 302 and 303 showed excellent results in initial water repellency, water slidability (waterdrop slidability), wet heat resistance, and alkali resistance, confirming the effectiveness of the present invention.

Example 4
(Preparation of low molecular weight water repellent coating solution)
The water repellent layer forming coating solution No. 1 prepared in Example 1 was used. When preparing 1-1, a coating solution for forming a water repellent layer containing a low molecular weight water repellent compound was prepared in the same manner except that the amount of surfactant added was changed as shown in Table 7. 4-1 to 4-5. In addition, Sumitomo 3M Novec FC-4430 was used as the surfactant.

(Preparation of coating solution for forming a high molecular weight water-repellent layer)
The water repellent layer forming coating solution No. 1 prepared in Example 1 was used. The same water repellent layer-forming coating solution as in No. 1-5 was prepared and 4-6.

(Preparation of base material)
The same soda lime glass (manufactured by Opton) as in Example 1 was washed successively with a neutral detergent, water and alcohol, dried, and then wiped with acetone to form a substrate.

(Production of water-repellent articles)
In accordance with the schematic manufacturing process flow chart shown in FIG. 2A, a water repellent layer forming coating solution (first coating solution) No. 1 prepared on a substrate prepared as shown in Table 8 was prepared. 4-1 to 4-5, and a water-repellent layer forming coating solution (second coating solution) No. 4-6 was applied by the method shown below to prepare a water-repellent article. 401 to 406. Note that the underlayer was not formed.

Sample No. Preparation of No. 401 On the prepared base material, the prepared coating liquid No. 4-1 (first coating solution) was applied by a dipping coating method and then dried at 23 ° C. for 5 minutes to form a first coating film having a thickness of 7 nm. Thereafter, after curing at 150 ° C. for 30 minutes, the surface of the first coating film was washed using IPA which is a good solvent for the fluorinated silane coupling agent, dried at 150 ° C. for 30 minutes, and then a water repellent layer Coating liquid for formation No. 4-6 (second coating solution) was applied by a dipping coating method and dried at 150 ° C. for 60 minutes to form a second coating film having a thickness of 6 nm to produce a water-repellent article having a total thickness of 12 nm. 401.

  A 1st coating film, a 2nd coating film, and total thickness show the value measured by the same method as Example 1. FIG.

Cleaning conditions for the first coating film The substrate formed up to the first coating film was immersed in a container containing IPA, and the container was immersed in an ultrasonic cleaner to perform ultrasonic cleaning for 30 minutes. The end point of washing was determined by the same method as in Example 1.

Sample No. Preparation of Sample No. 402 When producing 401, the water-repellent layer forming coating solution (first coating solution) was changed to No. 401. Sample No. 4 was changed except that it was changed to 4-2. A water-repellent article was produced under the same conditions as in No. 401. 402.

Sample No. Sample No. 403 When producing 401, the water-repellent layer forming coating solution (first coating solution) was changed to No. 401. Sample No. 4 was changed except that it was changed to 4-3. A water-repellent article was produced under the same conditions as in No. 401. 403.

Sample No. Preparation of sample No. 404 When producing 401, the water-repellent layer forming coating solution (first coating solution) was changed to No. 401. Sample No. 4 was changed except that it was changed to 4-4. A water-repellent article was produced under the same conditions as in No. 401. 404.

Sample No. No. 405 Sample No. When producing 401, the water-repellent layer forming coating solution (first coating solution) was changed to No. 401. Sample No. 4 was changed except that it was changed to 4-5. A water-repellent article was produced under the same conditions as in No. 401. 405.

Evaluation Each sample No. No. 401 to No. 405, the initial water repellency, water slidability (water droplet slidability) wet heat resistance, and alkali resistance were tested in the same test method as in Example 1, and the results evaluated according to the same evaluation rank as in Example 1 are shown in Table 9. Show.

  By adding the surfactant to the coating liquid for forming the water repellent layer (first coating liquid), the initial water repellency, water slidability (water droplet slidability), wet heat resistance, and alkali resistance were all excellent. The effectiveness of the invention was confirmed.

Example 5
In Example 1, sample no. When producing 101 to 106, according to the schematic manufacturing process flow chart shown in FIG. 2 (b), before carrying out the cleaning treatment of the first coating film, all were irradiated under the same conditions except that the energy rays were irradiated under the following conditions. A water-repellent article was prepared by washing and application of the second coating solution. 501 to 506.

Energy Ray Irradiation Conditions UV rays having a wavelength of 340 nm and an intensity of 0.6 W / cm ² are used on the side having the water-repellent layer on the surface side having the water-repellent layer using an ultraviolet ray tester (I Super UV Tester W-13, manufactured by Iwasaki Electric Co., Ltd.). Are irradiated for 2 hours under the condition of a black panel temperature of 48 ± 2 ° C.

  The end point of irradiation with energy rays is irradiated with the water contact angle and energy rays of the sample before irradiation with energy rays, and washed with a good solvent of the first coating solution (most preferably using a diluted solvent of the coating solution). Create a calibration curve for the relationship between the water contact angle and the irradiation condition (energy amount, time) of the energy beam in advance at the point where the difference from the water contact angle after the treatment is 3 ° larger. decided.

Evaluation Each sample No. Table 10 shows the results of 501 to 506, in which initial water repellency, water slidability (water drop slidability) wet heat resistance, and alkali resistance were tested in the same test method as in Example 1, and evaluated according to the same evaluation rank as in Example 1. Show.

  Before carrying out the cleaning treatment, the water-repellent article No. 1 produced by irradiating energy rays was used. Nos. 501 to 506 showed excellent results in initial water repellency, water slidability (waterdrop slidability), wet heat resistance, and alkali resistance, confirming the effectiveness of the present invention.

Example 6
(Preparation of a glass substrate on which an underlayer is formed)
A commercially available 3 mm thick soda lime glass (manufactured by Opton) as a glass substrate was washed with a neutral detergent, water and alcohol in order, dried and then wiped with acetone, and then the atmospheric pressure plasma film forming apparatus shown in FIG. 3 was used. A glass substrate having a base layer formed by changing the gas mixing ratio as shown in Table 11 and forming a base layer having a thickness of 45 nm with a changed carbon content (carbon atom number concentration) under the following discharge conditions. No. produced. 6-1 to 6-5.

Plasma discharge conditions <Gas conditions>
Nitrogen gas was used as the discharge gas, tetraethoxysilane (mixed with nitrogen gas by a vaporizer manufactured by Lintec Corporation) and oxygen gas was used as the additive gas.

<Power supply conditions>
1st electrode side Power supply type
Frequency 80kHz
Output density 10W / cm ²
Second electrode side Power supply type High frequency power supply manufactured by Pearl Industrial Co., Ltd.
Frequency 13.56MHz
Output density 8W / cm ²
The carbon atom number concentration of the formed first layer was measured by XPS method using ESCALAB-200R manufactured by VG Scientific, and the carbon content (carbon atom concentration) was 9 atom%. .

  The carbon content (carbon atom number concentration) was changed by changing the ratio of the thin film forming gas contained in the discharge gas.

(Preparation of water-repellent layer forming coating solution (first coating solution) containing a low molecular weight water-repellent compound)
The coating liquid No. 1 for forming the water repellent layer of Example 1 was used. The same water repellent layer forming coating solution as 1-1 was prepared.

(Preparation of water-repellent layer forming coating solution (second coating solution) containing a high molecular weight water-repellent compound)
The coating liquid No. 1 for forming the water repellent layer of Example 1 was used. The same water repellent layer forming coating solution as 1-5 was prepared.

(Production of water-repellent articles)
According to the schematic manufacturing process flow chart shown in FIG. The first coating solution and the second coating solution prepared on 6-1 to 6-5 were mixed with the sample No. 1 of Example 1. A water-repellent article was prepared by applying the same method as in No. 106, and sample No. 601 to 605.

Evaluation Each sample No. Table 12 shows the results of the evaluation of the initial water repellency, water slidability (waterdrop slidability), wet heat resistance, and alkali resistance in the same test method as in Example 1 and evaluated according to the same evaluation rank as in Example 1. Shown in

  The effectiveness of the present invention was confirmed.

DESCRIPTION OF SYMBOLS 1 Water repellent article 101 Base | substrate 102 Undercoat layer 103 Water repellent layer 2 Manufacturing process flow 201 Base material supply process 202 Pretreatment process 203 Underlayer formation process 204 Water repellent layer formation process 204a 1st application process 204b 1st drying process 204c Cleaning process 204d Second coating step 204e Second drying step 204f Energy beam irradiation step 3, 4 Atmospheric pressure plasma film forming apparatus 301 First electrode 302 Second electrode 5 Plasma discharge treatment apparatus 6 Electric field applying means 7 Gas supply means

Claims (8)

In the method for producing a water-repellent article in which a water-repellent layer is formed on the base material by applying a water-repellent layer-forming coating solution on the base material and drying the coating solution,
The coating liquid for forming the water repellent layer comprises a first coating liquid containing a low molecular weight water repellent compound selected from a fluorine-containing silane coupling agent, an alkylsilane coupling agent, and a polydimethylsiloxane skeleton compound, and a high molecular weight repellent. A second coating solution containing an aqueous compound,
Applying the first coating liquid on the substrate to form a first coating film;
After washing the first coating film,
Applying the second coating liquid on the first coating film to form a second coating film;
A method for producing a water-repellent article, comprising producing a water-repellent article on which the water-repellent layer is formed. The method for producing a water-repellent article according to claim 1 , wherein the water-repellent compound has a reactive silyl group. The method for producing a water-repellent article according to claim 1 or 2 , wherein the first coating liquid contains a surfactant. The washing is dried first coating, the production method of the water-repellent article according to any one of claims 1 to 3, characterized in that it is performed after the irradiation with the energy ray. The method for producing a water-repellent article according to any one of claims 1 to 4 , wherein the cleaning is performed with a good solvent for the first coating film. The method for producing a water-repellent article according to any one of claims 1 to 5 , wherein a base layer is formed between the water-repellent layer and the substrate. The method for producing a water-repellent article according to claim 6 , wherein the underlayer is formed by atmospheric pressure plasma CVD. The method for producing a water-repellent article according to any one of claims 1 to 7 , wherein the substrate is glass containing an alkali component.

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