JP2010285574A - Water repellent film-coated article, window glass for building, and window glass for vehicle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water repellent film-coated article with high durability (abrasion resistance and scratch resistance) which has excellent water repellency, slipperiness (falling of water drops), stain resistance, and weatherability and which maintains the performance over a long period of time. <P>SOLUTION: The water repellent film-coated article is coated with a laminate having at least a base layer and a water repellent film coating a surface of the base layer on a substrate, wherein the base layer is formed from an inorganic compound, and the water repellent film is formed from a fluorine-containing compound. The hardness of the laminate measured by a nanoindentation method is 2.0-7.0 GPa, the fluorine density of the water repellent film is 1.3-3.0 g/cm<SP>3</SP>, and the internal stress of the laminate is 10-100 MPa. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention provides a water-repellent article excellent in water repellency, water slidability (waterdrop slidability), and excellent in durability (scratch resistance and abrasion resistance) and weather resistance, and an architectural window glass and a vehicle using the same. It relates to window glass.

  In general, windshield glass for buildings, window glass for automobiles, windshield glass for vehicles, aircraft, ships, etc., road panels for construction windows, water tanks, bottom windows and soundproof walls, glass tableware, glass ornaments, etc. It is desirable that things that obstruct the field of view such as water droplets and dirt do not adhere.

  So far, water-repellent film-coated articles having a water-repellent film on the glass surface are known. For example, Japanese Patent Application Laid-Open No. 2001-139745 discloses a technique of adding silicone (sliding property) to a fluororesin (weather resistance / water repellency). Japanese Patent Application Laid-Open No. 2002-256258 discloses a technique in which a water-repellent film with good water droplet rolling property is provided on the surface of a glass plate or other base material.

  By imparting water repellency to the surface of the glass article, water droplets containing contaminants are less likely to adhere to and remain on the glass surface, so that the effect of preventing glass contamination and burning can be obtained.

  For example, by using such water-repellent glass on the windshield and side glass of automobiles, rainwater adhering to the surface during driving in rainy weather is blown away by wind pressure, ensuring the driver's field of view and improving safety, raindrops It is effective in preventing adhesion of dust, dirt, etc., and preventing transparency and transparency from being reduced due to moisture condensation under the influence of atmospheric humidity and temperature, but has the following problems.

  Water droplets adhering to the windshield surface of an automobile are removed using a wiper, and water droplets adhering to the side glass are removed by physical means such as 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, the glass component is dissolved 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 these architectural window glass and automotive window glass has excellent water repellency, water slidability (water droplet sliding property), abrasion resistance, scratch resistance (resistance to sliding of wipers, etc.) and There is a demand for durability in which these properties are maintained over a long period of time together with weather resistance. Improved water repellency, water slidability (water drop slidability), abrasion resistance, scratch resistance (resistance to sliding of wipers, etc.) and weather resistance, and durability that lasts for a long time Has been studied so far.

  For example, the environment in which a coating solution in which silicon alkoxide (or a hydrolyzate thereof) and a fluoroalkyl group-containing silane compound are dissolved in a solvent (particularly alcohol) is applied to a substrate and dried is performed in an acid or alkali atmosphere. There is known a method of obtaining a water-repellent coating composition having excellent rolling property, high scratch resistance, high weather resistance and long life (see, for example, Patent Document 1).

  A chlorosilyl group-containing compound and a fluoroalkyl group-containing silane compound were dissolved in a solvent containing alcohol and / or water, and a solution in which the chloro group of the chlorosilyl group-containing compound was substituted with an alkoxyl group or a hydroxyl group was applied to the substrate surface. It is known that post-drying to form a water-repellent coating results in a water-repellent article having a large contact angle of water droplets, excellent water-rolling properties, and high scratch resistance and weather resistance. (For example, refer to Patent Document 2).

  However, the water-repellent film obtained according to the description of Patent Documents 1 and 2 cannot sufficiently withstand the abrasion caused by the wiper as required for an automobile windshield, and has insufficient wear resistance, durability and weather resistance. It turns out that there is.

  In addition, a coating solution obtained mainly from a mixture of a sol solution obtained by hydrolyzing a tetraalkoxysilane added with a metal alkoxide and a sol solution obtained by hydrolyzing an alkyltrialkoxysilane is applied to the substrate surface. By heating and firing to form a sol-gel film having a fine uneven surface layer, and coating the sol-gel film with a water-repellent film layer, the light resistance, adhesion, and wear resistance are high, and long-term It is said that a water-repellent film capable of maintaining performance can be obtained (see, for example, Patent Document 3).

  However, the water-repellent film obtained in accordance with the description in Patent Document 3 also has a tendency to increase friction due to unevenness, so that it has enough wear resistance and scratch resistance to withstand long-term durability required for automobile windshields. It was found that the property and weather resistance were not sufficient.

  Under these circumstances, it is desired to develop a highly durable water-repellent film article that has excellent water repellency, sliding property (water droplet fallability) and weather resistance, and can maintain its performance over a long period of time. Yes.

JP 2001-172417 A JP 2003-13048 A JP-A-2005-281132

  The present invention has been made in view of the above circumstances, and has an object of having excellent water repellency, sliding property (water droplet falling property), weather resistance, and high durability capable of maintaining the performance over a long period of time. It is to provide a water-repellent film article having good properties (abrasion resistance, scratch resistance).

  The above object of the present invention has been achieved by the following constitution.

1. A water-repellent film-coated article coated with a laminate having at least a base layer and a water-repellent film covering the surface of the base layer on a substrate, wherein the base layer is formed of an inorganic compound, The water repellent film is formed of a fluorine-containing compound, the hardness of the laminate measured by the nanoindentation method is 2.0 GPa to 7.0 GPa, and the film density of the water repellent film is 1.3 g / A water-repellent film-coated article having a cm ³ to 3.0 g / cm ³ and an internal stress of the laminate of 0.1 to 10 MPa.

  2. 2. The water-repellent film-coated article according to 1 above, wherein the fluorine-containing compound is a perfluoroalkyl ether compound.

  3. 3. The water-repellent film-coated article according to 1 or 2 above, wherein the underlayer is formed by an atmospheric pressure plasma CVD method.

  4). 4. The water-repellent film-coated article according to any one of 1 to 3, wherein the inorganic compound is at least one selected from metal oxide, metal nitride, and metal oxynitride.

  5. 4. The inorganic compound according to any one of 1 to 3, wherein the inorganic compound is formed of at least one metal oxide, metal nitride, or metal oxynitride selected from Al, Si, and Ti. Water-repellent film-coated article.

  6). 4. The water repellent film-coated article according to any one of 1 to 3, wherein the inorganic compound is silicon oxide.

  7). The water-repellent film-coated article according to any one of 1 to 6, wherein the substrate is glass.

  8). An architectural window glass comprising the water-repellent film-coated article according to any one of 1 to 7 above.

  9. 8. A vehicle window glass comprising the water-repellent film-coated article according to any one of 1 to 7 above.

  The present inventor, when using a water-repellent film article having a laminate of a base layer and a water-repellent layer on the surface of a glass substrate, for a windshield of an automobile, why water repellency, sliding property (water droplet fallability) and As a result of examining whether the high durability (abrasion resistance and scratch resistance) capable of maintaining the performance of the weather resistance over a long period of time has been investigated, the following has been found.

  In a water-repellent film article having a laminate of a base layer and a water-repellent layer on the surface of a glass substrate, it was estimated that stabilization of the base layer was dominant in maintaining the performance of the water-repellent layer. In other words, by stabilizing the underlayer, the upper water-repellent layer is also stabilized, and the water-repellent layer is imparted with characteristics that maintain the original water repellency, sliding property (water droplet tumbling property), antifouling property, and weather resistance. The durability (abrasion resistance, scratch resistance) that can maintain the performance over a long period of time can be improved.

  A water-repellent film article having a laminate of a base layer and a water-repellent layer on the surface of a glass substrate is used for an automobile windshield. It was estimated that the decrease in weather resistance was due to peeling of the water-repellent layer accompanying the distortion of the underlayer.

  As a result of further examination why the distortion of the underlayer occurs, it has been found that it is caused by the stress applied by the press accompanying the reciprocating movement of the wiper or the like. As a result of further investigation, the underlayer is formed in a balanced state in the presence of the internal stress when the underlayer is formed. However, the underlayer is subjected to stress caused by the reciprocating movement of the wiper. It was found that the balance of internal stress was lost and distortion occurred partially, and the water-repellent layer could not follow the distortion and peeling occurred. That is, it was found that the water repellency and sliding property (water droplet falling property) are lowered.

  As a result of further examination of measures for improving the stress followability accompanying the reciprocating motion of the wiper applied to the underlayer, it has been found that it is effective to uniformly distribute the stress in the direction of the reciprocating motion of the wiper.

  In the method of applying and drying an organosilicon compound solution as a conventionally disclosed technique, and then baking, the internal stress of the film generated at the time of baking is too high, and the film itself is formed by vacuum evaporation or sputtering. Since the internal stress is high, the stress cannot be evenly distributed.

  On the other hand, with regard to weather resistance, the main cause is considered to be deterioration of the water-repellent layer material, but as a result of intensive studies, we have selected the underlayer hardness within an appropriate range to suppress deterioration of the water-repellent layer. And found that the density of the water-repellent layer on the surface can be increased. As estimated, it is considered that by setting the hardness of the underlayer to an appropriate range, the number of reaction sites between the underlayer and the water repellent material increases, the bond becomes stronger, and the water repellent material does not easily deteriorate.

  In order to disperse stress uniformly in the direction of the reciprocating motion of the wiper, it is effective to reduce the internal stress of the underlayer, and to maintain the film hardness and water repellency that can withstand the reciprocating motion of the wiper in the water repellent layer. It has been found that the object effect of the present invention can be achieved by imparting the density of the water repellent layer, and the present invention has been achieved.

  It was possible to provide a highly durable water-repellent coated article having excellent water repellency, sliding property (water droplet falling property) and weather resistance and capable of maintaining its performance over a long period of time.

It is a schematic sectional drawing of the water-repellent film coated article of the present invention. It is a graph which shows the relationship between the pressure of a process chamber, and the internal stress of a silicon oxide film. It is the schematic which shows an example of the atmospheric pressure plasma discharge processing apparatus which forms a base layer by the atmospheric pressure plasma CVD method on the surface of the base material (glass plate) which comprises the water-repellent film coated article.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to FIGS. 1 to 3, but the present invention is not limited to these.

  FIG. 1 is a schematic sectional view of a water-repellent film-coated article of the present invention.

  In the figure, 1 indicates a water-repellent film-coated article. The water repellent film-coated article 1 has a laminate 104 having a base layer 102 and a water repellent film 103 on a base material 101. The entire surface of the base layer 102 is covered with a water repellent film 103.

  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.

  M indicates the thickness of the underlying layer 102. The thickness M is preferably 10 nm to 500 nm in consideration of durability of the water repellent film, weather resistance, generation of cracks, and the like. Furthermore, 10 nm to 200 nm is more preferable.

  N indicates the thickness of the water repellent film 103. The thickness N is preferably 1 nm to 10 nm in consideration of water repellency, sliding property (water droplet falling property), durability, and the like.

  The thickness of the underlayer 102 and the thickness of the water repellent film 103 are values 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. From each parameter, the thickness of the base layer 102, the film thickness of the water repellent film 103, and the film thickness of the laminate 104 can be obtained.

  As shown in this figure, the thickness of the water-repellent film 103 is as thin as 1 to 10 nm with respect to the thickness of the base layer 102 of the water-repellent film-coated article. As for the hardness, the internal stress and hardness of the underlayer 102 are dominant.

  The internal stress of the laminate 104 is measured by the following method. That is, a film having the same composition as the measurement film is formed on a quartz substrate having a width of 10 mm, a length of 50 mm, and a thickness of 0.1 mm by the same method so as to have a thickness of 1 μm. Upward, it can be obtained by measurement with a thin film property evaluation apparatus MH4000 manufactured by NEC Saneisha. In general, a positive curl is formed when the film side contracts with respect to the substrate due to a compressive stress, and conversely, a negative stress is expressed when a negative curl is generated due to a tensile stress.

  The internal stress can be adjusted by adjusting the degree of vacuum when a silicon oxide film is produced by, for example, a vacuum deposition method. In the case of plasma CVD, it can be adjusted by appropriately setting the power density to be applied, the amount of raw material gas supplied, the temperature during film formation, and the like.

  Hereinafter, the relationship between the pressure in the processing chamber and the internal stress of the silicon oxide film when the silicon oxide film is formed will be described.

  FIG. 2 is a graph showing the relationship between the pressure in the processing chamber and the internal stress of the silicon oxide film.

  The vertical axis represents internal stress, and the horizontal axis represents the pressure in the processing chamber. This figure shows the degree of vacuum in the processing chamber when a silicon oxide film is formed by 1 μm by vacuum deposition on a quartz substrate having a width of 10 mm, a length of 50 mm, and a thickness of 0.1 mm, and the above-described silicon oxide film formed. It is a graph which shows the relationship with the internal stress measured by the method. As shown in this figure, it can be seen that the internal stress decreases as the pressure in the processing chamber increases. That is, the internal stress can be adjusted by adjusting the degree of vacuum in the processing chamber.

  The internal stress of the laminate (underlying layer + water repellent layer) 104 (see FIG. 1) relating to the water-repellent film-coated article of the present invention is 0.1 MPa to 10 MPa. More preferably, it is 0.5 MPa to 5 MPa.

  When the internal stress is less than 0.1 MPa, there may be a partial tensile stress, which is not preferable because the film is easily cracked or cracked and has no durability.

  When the internal stress exceeds 10 MPa, it is not preferable because the stress cannot be sufficiently distributed and the durability of the laminate is lowered.

  The laminate 104 (see FIG. 1) has a hardness of 2.0 GPa to 7.0 GPa. A hardness of less than 2.0 GPa is not preferable because it is brittle in terms of mechanical strength and wear resistance is reduced. A hardness exceeding 7.0 GPa is not preferable because the water repellent material is detached and the weather resistance is lowered due to insufficient bonding with the underlying layer after the water repellent film is provided.

  Note that the hardness of the underlying layer is substantially determined from the ratio between the thickness of the underlying layer 102 (see FIG. 1) constituting the laminate 104 (see FIG. 1) and the thickness of the water repellent film 103 (see FIG. 1). ing.

  The hardness of the laminate 104 (see FIG. 1) indicates a value measured by the nanoindentation method.

  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 (H) 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 laminate 104 (see FIG. 1) was measured by a nanoindentation method with a Triscope made by Hystron attached to a Nanoscope III made by 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).

  The underlayer relating to the water-repellent film-coated article of the present invention is preferably composed of at least one inorganic compound selected from metal oxides, metal nitrides or metal oxynitrides. Furthermore, the inorganic compound is at least one metal oxide, metal nitride, or metal oxynitride selected from In, Sn, Cd, Zn, Al, Sb, Ge, W, Mo, Si, Zr, Ce, Mg, and Ti. It is preferably formed from a product. Al, Si, and Ti are particularly preferable. Specifically, silicon oxide, silicon nitride, silicon oxynitride, titanium oxide, titanium oxynitride, titanium nitride, aluminum oxide, and the like can be given. The metal oxide and metal nitride in the present invention can contain carbon within a range not exceeding 10% in terms of atomic number concentration.

  The underlayer relating to the water-repellent film-coated article of the present invention can be formed by a sputtering method with adjusted vacuum, an ion assist method, a plasma CVD method which will be described later, etc., but under an atmospheric pressure or a pressure near atmospheric pressure which will be described later. It is preferable that the film is formed by applying a plasma CVD method or the like. In particular, a method using atmospheric pressure plasma CVD is a film forming method that does not require a decompression chamber or the like and enables high-speed film formation and high productivity. By forming the underlayer by plasma CVD, it is possible to relatively easily form a film having uniform and surface smoothness and extremely low internal stress (from 0.1 MPa to 10 MPa). Because it becomes.

  As described in, for example, Japanese Patent Application Laid-Open No. 2000-246091 and Japanese Patent Application Laid-Open No. 2003-238713, the atmospheric pressure plasma CVD method is a thin film between two opposing electrodes under atmospheric pressure or a pressure in the vicinity thereof. In this method, a gas containing a forming gas and a discharge gas is supplied, a high-frequency electric field is applied between the electrodes, the gas is excited, and the thin film is formed by exposure to the excited gas.

  The atmospheric pressure or the pressure in the vicinity thereof is about 20 to 110 kPa, and 93 to 104 kPa is preferable in order to obtain a good effect described in the present invention.

  Next, an apparatus for forming an underlayer according to the water-repellent film-coated article of the present invention by atmospheric pressure plasma CVD will be described with reference to FIG.

  FIG. 3 is a schematic view showing an example of an atmospheric pressure plasma discharge processing apparatus for forming a base layer on the surface of a substrate (glass plate) constituting a water repellent film-coated article by an atmospheric pressure plasma CVD method.

  In the figure, 2 indicates an atmospheric pressure plasma discharge treatment apparatus. The atmospheric pressure plasma discharge treatment apparatus 2 includes a plasma discharge treatment chamber 3, an electric field applying means 4 having a first electrode 401 a and a second electrode 401 b housed in the plasma discharge treatment chamber 3, a gas supply means 5, , And electrode temperature adjusting means 6. Reference numeral 402 denotes a space between the first electrode 401a and the second electrode 401b (hereinafter also referred to as a discharge space). The atmospheric pressure plasma discharge treatment apparatus 2 performs plasma discharge treatment on the surface of the substrate (glass plate) S in the discharge space 402.

  The gas supply means 5 has a gas generator 501, and the thin film forming gas G generated by the gas generator 501 is controlled in flow rate by a gas flow rate adjusting means (not shown) and plasma discharge treatment is performed from the air supply port 502. It is introduced into the chamber 3.

  Subsequently, a high frequency electric field is applied between the first electrode 401 a and the second electrode 401 b to generate discharge plasma in the discharge space 402. The surface of the substrate (glass plate) F is treated with a plasma state gas. Discharged treated exhaust gas G ′ is discharged from the exhaust port 301.

  During the plasma treatment, in order to heat or cool the first electrode 401a and the second electrode 401b, the medium whose temperature is adjusted by the electrode temperature adjusting means 6 is transferred to the first electrode 401a and the first electrode 401a via the pipe 601 by the liquid feed pump P. The temperature is adjusted from the inside of the electrode by feeding it to the two electrodes 401b. In this figure, the case where the temperature of only the second electrode 401b is adjusted is shown. Similarly to the second electrode 401b, the temperature of the first electrode 401a can be adjusted from the inside of the electrode.

  Here, the frequency of the high frequency power source is 1 kHz to 2500 MHz, and 100 kHz to 60 MHz can be preferably used. The electric field waveform may be a continuous wave or a pulse wave.

In order to change the nanoindentation hardness of the laminate relating to the water-repellent film-coated article of the present invention from 2.0 GPa to 7.0 GPa, the output power is 0.1 W / cm ² between the opposing electrodes. The above power is supplied to excite the discharge gas to generate plasma. The upper limit is preferably 50 W / cm ² and more preferably 20 W / cm. The lower limit is preferably 0.5 W / cm ² . The discharge area (cm ² ) refers to an area in a range where discharge occurs between the electrodes.

  As the power supply (high frequency power supply) installed in the atmospheric pressure plasma discharge treatment apparatus 2, SPG5-4500 (5 kHz) manufactured by Shinko Electric Co., Ltd., PHF-6k (100 kHz *) manufactured by HEIDEN LABORATORY, CF-2000-200k manufactured by PEARL INDUSTRY CO., LTD. 200 kHz) and the same CF-5000-13M (13.56 MHz) and the like, and any of them can be 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.

  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.

  The first electrode 401a and the second electrode 401b are obtained by disposing a conductive metal base material and a ceramic dielectric on the surface of at least one of the electrodes with respect to the discharge space. The electrode structure (not shown) preferably has a jacket structure that can control the electrode surface temperature during plasma discharge treatment. In this drawing, a plate-like electrode is used as the shape of the electrode, but it can be appropriately selected depending on the base material such as cylindrical or columnar.

  The ceramic dielectric may be a single-walled coating with a thickness of about 1 mm to 5 mm. The method of coating the ceramic is not particularly limited, but a method of performing ceramic spraying on the metal base material is preferable. As the ceramic material, alumina, silicon nitride or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed. The dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.

  Examples of the conductive metallic base material include titanium metal or titanium alloy, metal such as silver, platinum, stainless steel, aluminum, and iron, a composite material of iron and ceramics, or a composite material of aluminum and ceramics. I can do it.

  When the dielectric is provided on one of the electrodes, the distance between the opposing first electrode 401a and second electrode 401b is the shortest distance between the dielectric surface and the conductive metallic base material surface of the other electrode. Say that. The distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metallic base material, the magnitude of the applied electric field strength, and the degree of processing. In any case, from the viewpoint of uniform discharge The thickness is preferably 0.1 mm to 20 mm, particularly preferably 0.5 mm to 5 mm.

  The plasma discharge processing chamber 3 is preferably a processing vessel made of Pyrex (registered trademark) glass or the like, but may be made of metal as long as it can be insulated from the electrodes. For example, polyimide resin or the like may be adhered to the inner surface of an aluminum or stainless steel frame, and ceramic spraying may be performed on these frames to achieve insulation.

  As described above, the atmospheric pressure plasma discharge treatment apparatus 2 shown in this figure is a base material that is discharged in the discharge space, puts the gas introduced into the discharge space into a plasma state, and is left in the discharge space or transported through the discharge space. The surface of the substrate (glass plate) F is treated by exposing the (glass plate) F to a plasma state gas. As another method, the gas introduced into the discharge space after being discharged in the discharge space is excited or turned into a plasma state, and the excited or plasma state gas is blown out of the discharge space to discharge the first electrode 401a and the second electrode. It may be a so-called jet type apparatus (not shown) that performs processing by exposing a substrate (glass plate) in the vicinity of 401b (which may be left still or transferred).

  When the atmospheric pressure plasma treatment is performed by the atmospheric pressure plasma discharge treatment apparatus 2, the gas used is basically a mixed gas of an inert gas and a reactive gas. The reaction gas is a component selected from oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen, and nitrogen. The reaction gas is preferably contained in an amount of 0.001% to 10% by volume with respect to the mixed gas.

  Examples of the inert gas include Group 18 elements of the periodic table, specifically, rare gases such as helium, neon, argon, krypton, xenon, and radon, or nitrogen. Among these, helium, argon Nitrogen is preferably used. The inert gas is preferably contained in an amount of 90% by volume or more with respect to 100% by volume of the mixed gas. More preferably, it is 95 volume% or more.

  A desired process can be performed by selecting the reaction gas and appropriately selecting the composition ratio of the discharge gas, the gas supply rate, or the output conditions during the plasma discharge process.

  In the atmospheric pressure plasma treatment, the substrate (glass plate) temperature is preferably 250 ° C. or less, more preferably at a temperature of 100 ° C. to 200 ° C., and it can be carried out at a relatively low temperature. .

  As the source gas for forming the underlayer, an organic metal compound that is a gas or liquid at room temperature, particularly an alkyl metal compound, a metal alkoxide compound, or an organic metal complex compound is used. The phase state in these raw materials does not necessarily need to be a gas phase at normal temperature and normal pressure, and any liquid phase or solid phase can be used as long as it can be vaporized through heating, decompression, etc. through melting, evaporation, sublimation, etc. But it can be used.

  The source gas contains a component that is in a plasma state in the discharge space and forms a thin film, and is an organometallic compound, an organic compound, an inorganic compound, or the like.

  For example, as a silicon compound, silane, tetramethoxysilane, tetraethoxysilane (TEOS), tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane , Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethyl Silane, bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide Diethylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane, 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, octamethylcyclotetrasiloxane, tetramethylcyclo Examples include, but are not limited to, tetrasiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  Titanium compounds include organometallic compounds such as tetradimethylaminotitanium, metal hydrogen compounds such as monotitanium and dititanium, metal halogen compounds such as titanium dichloride, titanium trichloride and titanium tetrachloride, tetraethoxy titanium, tetraisopropoxy titanium Examples thereof include, but are not limited to, metal alkoxides such as tetrabutoxy titanium.

  As aluminum compounds, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum diisopropoxide ethyl acetoacetate, aluminum ethoxide, aluminum hexafluoropentanedionate, aluminum isopropoxide, 4-pentanedionate Dimethylaluminum chloride and the like, but are not limited thereto.

  These raw materials may be used alone or in combination of two or more components.

《Water repellent material》
There is no restriction | limiting in particular as a fluorine-containing compound used for the water-repellent film of this invention, For example, an organic type fluorine compound, a fluorine-containing organic silicon compound, a fluorine-containing organometallic compound etc. can be mentioned. Each of these compounds may be applied directly in a solution state, dispersed in an appropriate solvent in the form of fine particles, or may be applied in the form of a polymer.

  The organometallic compound and perfluoroether compound having an organic group containing a fluorine atom preferably used in the present invention will be described in detail.

  In the organometallic compound having an organic group containing a fluorine atom, examples of the organic group containing a fluorine atom include an organic group having an alkyl group, an alkenyl group, an aryl group, etc. having a fluorine atom. As the organometallic compound having an organic group containing a fluorine atom, the organic group containing a fluorine atom is a metal atom, for example, silicon, titanium, germanium, zirconium, tin, aluminum, indium, antimony, yttrium. An organometallic compound directly bonded to a metal such as lanthanum, iron, neodymium, copper, gallium, or hafnium. Of these metals, silicon, titanium, germanium, zirconium, tin and the like are more preferable, and silicon and titanium are particularly preferable. These organic groups containing fluorine atoms may be bonded to the metal compound in any form. For example, when a compound having a plurality of metal atoms such as siloxane has these organic groups, at least one metal atom May have an organic group containing a fluorine atom, and the position thereof is not limited.

  According to the thin film formation method using the organometallic compound having an organic group containing a fluorine atom, the organometallic compound having an organic group containing a fluorine atom easily forms a bond with a substrate such as silica or glass, It is estimated that the excellent effect of the present invention can be achieved.

  As the organometallic compound having an organic group containing a fluorine atom used in the present invention, a compound represented by the following general formula (1) is preferable.

In the formula, M represents Si, Ti, Ge, Zr or Sn. R ₁ to R ₆ each represent a hydrogen atom or a monovalent group, and at least one of the groups represented by R ₁ to R ₆ is an organic group containing a fluorine atom. An organic group having an alkyl group, an alkenyl group or an aryl group is preferred, and examples of the alkyl group containing a fluorine atom include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, 1 , 1,2,2,3,3,4,4-octafluorobutyl group and the like, as the alkenyl group containing a fluorine atom, for example, 3,3,3-trifluoro-1-propenyl group, etc. Examples of the aryl group containing a fluorine atom include groups such as a pentafluorophenyl group. In addition, an alkyl group, an alkenyl group, an alkoxy group formed from an aryl group, an alkenyloxy group, an aryloxy group, or the like can also be used.

  Further, in the alkyl group, alkenyl group, aryl group, etc., any number of fluorine atoms may be bonded to any position of the carbon atom in the skeleton, but at least one fluorine atom may be bonded. preferable. The carbon atom in the skeleton of the alkyl group or alkenyl group includes, for example, other atoms such as oxygen, nitrogen and sulfur, and divalent groups containing oxygen, nitrogen and sulfur, such as a carbonyl group and a thiocarbonyl group. It may be substituted with a group.

Among the groups represented by R ₁ to R ₆ , other than the organic group having a fluorine atom, represents a hydrogen atom or a monovalent group. Examples of the monovalent group include a hydroxy group, an amino group, and an isocyanate group. , Halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, alkoxy groups, alkenyloxy groups, aryloxy groups, and the like, but are not limited thereto. j represents an integer of 0 to 150, preferably 0 to 50, and more preferably j is in the range of 0 to 20.

  Of the monovalent groups, the halogen atom is preferably a chlorine atom, a bromine atom or an iodine atom. Among the monovalent groups, the alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, and aryloxy group are preferably an alkoxy group, an alkenyloxy group, and an aryloxy group.

  Of the metal atoms represented by M, Si and Ti are preferable.

  The monovalent group may be further substituted with other groups, and is not particularly limited. Preferred substituents include amino groups, hydroxyl groups, isocyanate groups, fluorine atoms, chlorine atoms, bromine atoms and the like. Atom, alkyl group, cycloalkyl group, aryl group such as alkenyl group, phenyl group, alkoxy group, alkenyloxy group, aryloxy group, acyl group, acyloxy group, alkoxycarbonyl group, alkaneamide group, arylamide group, alkylcarbamoyl And groups such as an arylcarbamoyl group, a silyl group, an alkylsilyl group, and an alkoxysilyl group.

Further, an organic group having a fluorine atom, or addition to the group represented by _{R 6} from these _{R 1} ^{of, R 1 R 2 R 3 M-} (M represents the metal ^atom, R 1, ^{R 2} , R ³ each represents a monovalent group, and the monovalent group represents a group other than the organic group having a fluorine atom or the organic group having a fluorine atom listed as R ₁ to R ₆ . It may be a structure having a plurality of metal atoms further substituted by the group represented. Examples of these metal atoms include Si and Ti, and examples thereof include a silyl group, an alkylsilyl group, and an alkoxysilyl group.

Examples of the alkyl group and alkenyl group, which are groups containing fluorine atoms listed in R ₁ to R ₆ , and the alkoxy group and alkenyl group in the alkenyloxy group, include the following general formula (F ) Is preferred.

Formula (F)
_{Rf-X- (CH 2) k} -
Here, Rf represents an alkyl group or an alkenyl group in which at least one of hydrogen is substituted by a fluorine atom. For example, Rf represents a perfluoro group such as a trifluoromethyl group, a pentafluoroethyl group, a perfluorooctyl group, or a heptafluoropropyl group. Groups such as alkyl groups, groups such as 3,3,3-trifluoropropyl groups, 1,1,2,2,3,3,4,4-octafluorobutyl groups, and 1,1,1 -An alkenyl group substituted by a fluorine atom such as a trifluoro-2-chloropropenyl group is preferred, among which a group such as a trifluoromethyl group, a pentafluoroethyl group, a perfluorooctyl group, a heptafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, etc. With alkyl groups containing two or more fluorine atoms are preferred.

X is a simple bond or a divalent group. Examples of the divalent group include a group such as —O—, —S—, —NR— (where R represents a hydrogen atom or an alkyl group), —CO—. _{, -CO-O -, - CONH} -, - SO 2 NH -, - SO 2 -O -, - OCONH-,

Represents a group such as

  k represents an integer of 0 to 50, preferably 0 to 30.

In addition to the fluorine atom, other substituents may be substituted in Rf, and examples of the substitutable group include the same groups as those exemplified as the substituent in R ₁ to R ₆ . The skeletal carbon atom in Rf is another atom, for example, —O—, —S—, —NR ₀ — (R ₀ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and the general formula ( A group represented by F) may be partially substituted with a group such as a carbonyl group, —NHCO—, —CO—O—, —SO ₂ NH— or the like.

  Of the compounds represented by the general formula (1), preferred are compounds represented by the following general formula (2).

General formula (2)
_{[Rf-X- (CH 2)} k] q -M (R 10) r (OR 11) t
In general formula (2), M represents the same metal atom as in general formula (1), Rf and X represent the same groups as Rf and X in general formula (F), and k represents the same integer. To express. R ₁₀ represents an alkyl group or an alkenyl group, and R ₁₁ represents an alkyl group, an alkenyl group or an aryl group, each of which is the same as the group exemplified as the substituent for R ₁ to R _{6 in} the general formula (1). May be substituted, but preferably represents an unsubstituted alkyl group or alkenyl group. Further, q + r + t = 4, q ≧ 1, and t ≧ 1. Further, when r ≧ 2, two R ₁₀ may be connected to form a ring.

  Of the general formula (2), more preferred is a compound represented by the following general formula (3).

General formula (3)
_{Rf-X- (CH 2) k} -M (OR 12) 3
Here, Rf, X or k has the same meaning as in the general formula (2). R _{12 is} also synonymous with R ₁₁ in the general formula (2). M is the same as M in the general formula (2), but Si and Ti are particularly preferable, and Si is most preferable.

  In the present invention, another preferred example of the organometallic compound having an organic group containing a fluorine atom includes a compound represented by the following general formula (4).

In the general formula (4), _{R 6} from _{R 1} has the same meaning of _{R 1} and _{R 6} in the general formula (1). Also in this case, at least one of R ₁ to R ₆ is the organic group having a fluorine atom, and the group represented by the general formula (F) is preferable. R ₇ represents a hydrogen atom or a substituted or unsubstituted alkyl group. J represents an integer of 0 to 100, preferably 0 to 50, and most preferably j is in the range of 0 to 20.

  As another preferable compound having a fluorine atom used in the present invention, there is an organometallic compound having an organic group containing a fluorine atom represented by the following general formula (5).

General formula (5)
_{[Rf-X- (CH 2)} k -Y] m -M (R 8) n (OR 9) p
In the general formula (5), M represents In, Al, Sb, Y, or La. Rf and X represent the same groups as Rf and X in the general formula (F), and Y represents a simple bond or oxygen. k also represents an integer of 0 to 50, and is preferably an integer of 30 or less. R ₉ represents an alkyl group or an alkenyl group, and R ₈ represents an alkyl group, an alkenyl group or an aryl group, each of which is the same as the group exemplified as the substituent for R ₁ to R _{6 in} the general formula (1). May be substituted. In the general formula (5), m + n + p = 3, m is at least 1, n represents 0 to 2, and p represents an integer of 0 to 2. It is preferable that m + p = 3, that is, n = 0.

  As another preferable compound containing a fluorine atom used in the present invention, there is an organometallic compound having an organic group having a fluorine atom represented by the following general formula (6).

General formula (6)
^{_{Rf 1 (OC 3 F 6)}} m1 -O- (CF 2) n1 - (CH 2) p1 -Z- (CH 2) q1 -Si- (R 2) 3
In the general formula (6), Rf ¹ represents a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, R ² represents a hydrolyzable group, Z represents —OCONH— or —O—, and m1 represents 1 N1 is an integer from 0 to 3, p1 is an integer from 0 to 3, q1 is an integer from 1 to 6, and 6 ≧ n1 + p1> 0.

The number of carbon atoms of the linear or branched perfluoroalkyl group that can be introduced into Rf ¹ is more preferably 1 to 16, and most preferably 1 to 3. Therefore, the _{^{Rf 1, -CF 3, -C 2}} F 5, -C 3 F 7 and the like are preferable.

Examples of the hydrolyzable group that can be introduced into R ² include —Cl, —Br, —I, —OR ¹¹ , —OCOR ¹¹ , —CO (R ¹¹ ) C═C (R ¹² ) ₂ , —ON═C (R _{^{11) 2, -ON = CR 13}} , -N (R 12) 2, are preferred, such as -R 12 NOCR ^11. R ¹¹ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as an alkyl group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, and R ¹² represents a hydrogen atom, an alkyl group or the like. R 1 represents an aliphatic hydrocarbon having 1 to 5 carbon atoms, and R ¹³ represents a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms such as an alkylidene group. Among these hydrolyzable groups, —OCH ₃ , —OC ₂ H ₅ , —OC ₃ H ₇ , —OCOCH ₃ and —NH ₂ are preferable.

  In the general formula (6), m1 is more preferably 1 to 30, and still more preferably 5 to 20. n1 is more preferably 1 or 2, and p1 is more preferably 1 or 2. Further, q1 is more preferably 1 to 3.

  As another preferable compound having a fluorine atom used in the present invention, there is an organometallic compound having an organic group containing a fluorine atom represented by the general formula (7).

In the general formula (7), Rf is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, X is an iodine atom or a hydrogen atom, Y is a hydrogen atom, or a lower alkyl group, and Z is a fluorine atom or A trifluoromethyl group, R ²¹ represents a hydrolyzable group, R ²² represents a hydrogen atom or an inactive monovalent organic group, a, b, c and d are each an integer of 0 to 200, and e is 0 Or 1, m and n each represents an integer of 0 to 2, and p represents an integer of 1 to 10.

In the general formula (7), Rf is usually a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, preferably a CF ₃ group, a C ₂ F ₅ group, or a C ₃ F ₇ group. It is. Examples of the lower alkyl group for Y usually include those having 1 to 5 carbon atoms.

Examples of the hydrolyzable group of R ²¹ include halogen atoms such as chlorine atom, bromine atom and iodine atom, R ²³ O group, R ²³ COO group, (R ²⁴ ) ₂ C═C (R ²³ ) CO group, ( R ²³ ) ₂ C═NO group, R ²⁵ C═NO group, (R ²⁴ ) ₂ N group, and R ²³ CONR ²⁴ group are preferred. Here, R ²³ is usually an aliphatic hydrocarbon group having 1 to 10 carbon atoms such as an alkyl group or an aromatic hydrocarbon group usually having 6 to 20 carbon atoms such as a phenyl group, and R ²⁴ is a hydrogen atom or an alkyl group. Usually a lower aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ²⁵ is usually a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms such as an alkylidene group. Further, a chlorine atom, a CH ₃ O group, a C ₂ H ₅ O group, and a C ₃ H ₇ O group are preferable.

R ²² is a hydrogen atom or an inert monovalent organic group, and is preferably a monovalent hydrocarbon group usually having 1 to 4 carbon atoms such as an alkyl group. a, b, c, and d are integers of 0 to 200, preferably 1 to 50. m and n are integers of 0 to 2, preferably 0. p is an integer of 1 or 2 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5. The number average molecular weight is 5 × 10 ² to 1 × 10 ⁵ , preferably 1 × 10 ³ to 1 × 10 ⁴ .

Further, as a preferred structure of the silane compound represented by the general formula (7), Rf is a C ₃ F ₇ group, a is an integer of 1 to 50, and b, c, and d are 0. , E is 1, Z is a fluorine atom, and n is 0.

  Representative compound examples of organometallic compounds having an organic group containing fluorine and compounds represented by the general formulas (1) to (7) that are preferably used as fluorine-containing compounds for the water-repellent film-coated article of the present invention Are listed below, but the present invention is not limited to these compounds.

1: (CF ₃ CH ₂ CH ₂ ) ₄ Si
2: (CF ₃ CH ₂ CH ₂ ) ₂ Si (CH ₃ ) _{2
3: (C 8 F 17 CH} 2 CH 2) Si (OC 2 H 5) 3
_{4: CH 2 = CH 2 Si} (CF 3) 3
5: (CH ₂ = CH ₂ COO) Si (CF ₃ ) ₃
6: (CF ₃ CH ₂ CH ₂ ) ₂ SiCl (CH ₃ )
7: C ₈ F ₁₇ CH ₂ CH ₂ Si (Cl) _{3
8: (C 8 F 17 CH} 2 CH 2) 2 Si (OC 2 H 5) 2
9: CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃
10: CF ₃ CH ₂ CH ₂ SiCl ₃
11: CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ SiCl _{3
12: CF 3 (CF 2)} 5 CH 2 CH 2 SiCl 3
13: CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃
14: CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCl ₃
15: CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃
16: CF ₃ (CF ₂ ) ₈ CH ₂ Si (OC ₂ H ₅ ) ₃
17: CF ₃ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
18: CF ₃ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃
19: CF ₃ (CH ₂ ) ₂ Si (OC ₄ H ₉ ) ₃
20: CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
21: CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃
22: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
23: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃
24: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) (OC ₃ H ₇ ) ₂
25: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ OC ₃ H ₇
26: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OCH ₃ ) ₂
27: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OC ₂ H ₅ ) ₂
28: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OC ₃ H ₇ ) ₂
29: (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
30: C ₇ F ₁₅ CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) _{3
31: C 8 F 17 SO 2} NH (CH 2) 3 Si (OC 2 H 5) 3
32: C ₈ F ₁₇ (CH ₂ ) ₂ OCONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃
33: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
34: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂
35: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂
36: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OCH ₃ ) ₂
37: CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OC ₃ H ₇ ) ₂
38: CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
39: CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂
40: CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) _{2
41: CF 3 (CF 2)} 5 (CH 2) 2 Si (CH 3) (OCH 3) 2
_{42: CF 3 (CF 2)} 5 (CH 2) 2 Si (CH 3) (OC 3 H 7) 2
_{43: CF 3 (CF 2)} 2 O (CF 2) 3 (CH 2) 2 Si (OC 3 H 7) 3
_{44: C 7 F 15 CH 2} O (CH 2) 3 Si (OC 2 H 5) 3
_{45: C 8 F 17 SO 2} O (CH 2) 3 Si (OC 2 H 5) 3
_{46: C 8 F 17 (CH} 2) 2 OCHO (CH 2) 3 Si (OCH 3) 3
47: CF ₃ (CF ₂ ) ₅ CH (C ₄ H ₉ ) CH ₂ Si (OCH ₃ ) ₃
48: CF ₃ (CF ₂ ) ₃ CH (C ₄ H ₉ ) CH ₂ Si (OCH ₃ ) _{3
49: (CF 3) 2 (} p-CH 3 -C 6 H 5) COCH 2 CH 2 CH 2 Si (OCH 3) 3
_{50: CF 3 CO-OCH 2} CH 2 CH 2 Si (OCH 3) 3
51: CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (CH ₃ ) Cl
52: CF ₃ CH ₂ CH ₂ (CH ₃ ) Si (OCH ₃ ) _{2
53: CF 3 CO-O-} Si (CH 3) 3
54: CF ₃ CH ₂ CH ₂ Si (CH ₃ ) Cl _{2
55: (CF 3) 2 (} p-CH 3 -C 6 H 5) COCH 2 CH 2 Si (OCH 3) 3
_{56: (CF 3) 2 (} p-CH 3 -C 6 H 5) COCH 2 CH 2 Si (OC 6 H 5) 3
_{57: (CF 3 C 2 H} 4) (CH 3) 2 Si-O-Si (CH 3) 3
_{58: (CF 3 C 2 H} 4) (CH 3) 2 Si-O-Si (CF 3 C 2 H 4) (CH 3) 2
_{59: CF 3 (OC 3 F} 6) 24 -O- (CF 2) 2 -CH 2 -O-CH 2 Si (OCH 3) 3
_{60: CF 3 O (CF (} CF 3) CF 2 O) m CF 2 CONHC 3 H 6 Si (OC 2 H 5) 3 (m = 11 to 30),
_{61: (C 2 H 5 O} ) 3 SiC 3 H 6 NHCOCF 2 O (CF 2 O) n (CF 2 CF 2 O) p CF 2 CONHC 3 H 6 Si (OC 2 H 5) 3 (n / p = About 0.5, number average molecular weight = about 3000)
_{62: C 3 F 7 - (} OCF 2 CF 2 CF 2) q-O- (CF 2) 2 - [CH 2 CH {Si- (OCH 3) 3}] 9 -H (q = about 10)
_{63: F (CF (CF 3} ) CF 2 O) 15 CF (CF 3) CONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
64: F (CF ₂ ) ₄ [CH ₂ CH (Si (OCH ₃ ) ₃ )] _2.02 OCH _{3
65: (C 2 H 5 O} ) 3 SiC 3 H 6 NHCO- [CF 2 (OC 2 F 4) 10 (OCF 2) 6 OCF 2] -CONHC 3 H 6 Si (OC 2 H 5) 3
_{66: C 3 F 7 (OC} 3 F 6) 24 O (CF 2) 2 CH 2 OCH 2 Si (OCH 3) 3
67: CF ₃ (CF ₂ ) ₃ (C ₆ H ₄ ) C ₂ H ₄ Si (OCH ₃ ) ₃
68: (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) _{2
69: CF 3 (CF 2)} 3 (C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2
_{70: CF 3 (CF 2)} 5 (C 6 H 4) C 2 H 4 Si (OC 2 H 5) 3
71: CF ₃ (CF ₂ ) ₃ C ₂ H ₄ Si (NCO) ₃
72: CF ₃ (CF ₂ ) ₅ C ₂ H ₄ Si (NCO) _{3
73: C 9 F 19 CONH (} CH 2) 3 Si (OC 2 H 5) 3
74: C ₉ F ₁₉ CONH (CH ₂ ) ₃ SiCl ₃
75: C ₉ F ₁₉ CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) _{3
76: C 3 F 7 O (} CF (CF 3) CF 2 O) 2 -CF (CF 3) -CONH (CH 2) Si (OC 2 H 5) 3
77: CF ₃ O (CF (CF ₃ ) CF ₂ O) ₆ CF ₂ CONH (CH ₂ ) ₃ SiOSi (OC ₂ H ₅ ) ₂ (CH ₂ ) ₃ NHCOCF ₂ (OCF ₂ CF (CF ₃ )) ₆ OCF _{3
78: C 3 F 7 COOCH 2} Si (CH 3) 2 OSi (CH 3) 2 CH 2 OCOC 3 F 7
_{79: CF 3 (CF 2)} 7 CH 2 CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 (CH 2) 3 OCH 2 CH 2 (CF 2) 7 CF 3
_{80: CF 3 (CF 2)} 5 CH 2 CH 2 O (CH 2) 2 Si (CH 3) 2 OSi (CH 3) 2 (OC 2 H 5)
_{81: CF 3 (CF 2)} 5 CH 2 CH 2 O (CH 2) 2 Si (CH 3) 2 OSi (CH 3) (OC 2 H 5) 2
_{82: CF 3 (CF 2)} 5 CH 2 CH 2 O (CH 2) 2 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (OC 2 H 5)
In addition to the compounds exemplified above, as fluorine-substituted alkoxysilanes,
83: (Perfluoropropyloxy) dimethylsilane 84: Tris (perfluoropropyloxy) methylsilane 85: Dimethylbis (nonafluorobutoxy) silane 86: Methyltris (nonafluorobutoxy) silane 87: Bis (perfluoropropyloxy) diphenylsilane 88: Bis (perfluoropropyloxy) methylvinylsilane 89: Bis (1,1,1,3,3,4,4,4-octafluorobutoxy) dimethylsilane 90: Bis (1,1,1,3,3) , 3-Hexafluoroisopropoxy) dimethylsilane 91: Tris (1,1,1,3,3,3-hexafluoroisopropoxy) methylsilane 92: Tetrakis (1,1,1,3,3,3-hexafluoro Isopropoxy) silane 93: dimethylbis (nonaf) (Luoro-t-butoxy) silane 94: bis (1,1,1,3,3,3-hexafluoroisopropoxy) diphenylsilane 95: tetrakis (1,1,3,3-tetrafluoroisopropoxy) silane 96: Bis [1,1-bis (trifluoromethyl) ethoxy] dimethylsilane 97: Bis (1,1,1,3,3,4,4,4-octafluoro-2-butoxy) dimethylsilane 98: Methyltris [2 , 2,3,3,3-pentafluoro-1,1-bis (trifluoromethyl) propoxy] silane 99: diphenylbis [2,2,2-trifluoro-1- (trifluoromethyl) -1-tolyl Ethoxy] silane and the following compounds,
_{100: (CF 3 CH 2)} 3 Si (CH 2 -NH 2)
_{101: (CF 3 CH 2)} 3 Si-N (CH 3) 2

  Furthermore,

Silazanes such as
106: CF ₃ CH ₂ —CH ₂ TiCl ₃
107: CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ TiCl ₃
108: CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Ti (OCH ₃ ) ₃
109: CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ TiCl ₃
110: Ti (OC ₃ F ₇ ) ₄
111: (CF ₃ CH ₂ —CH ₂ O) ₃ TiCl ₃
112: (CF ₃ C ₂ H ₄ ) (CH ₃ ) ₂ Ti—O—Ti (CH ₃ ) ₃
Examples thereof include organic titanium compounds having fluorine such as fluorine-containing organic metal compounds as follows.

_{113: CF 3 (CF 2)} 3 CH 2 CH 2 O (CH 2) 3 GeCl
114: CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ OCH ₂ Ge (OCH ₃ ) ₃
115: (C ₃ F ₇ O) ₂ Ge (OCH ₃ ) ₂
116: [(CF ₃ ) ₂ CHO] ₄ Ge
117: [(CF ₃ ) ₂ CHO] ₄ Zr
_{118: (C 3 F 7 CH} 2 CH 2) 2 Sn (OC 2 H 5) 2
_{119: (C 3 F 7 CH} 2 CH 2) Sn (OC 2 H 5) 3
120: Sn (OC ₃ F ₇ ) ₄
121: CF ₃ CH ₂ CH ₂ In (OCH ₃ ) ₂
122: In (OCH ₂ CH ₂ OC ₃ F ₇ ) ₃
123: Al (OCH ₂ CH ₂ OC ₃ F ₇ ) ₃
124: Al (OC ₃ F ₇ ) ₃
125: Sb (OC ₃ F ₇ ) ₃
126: Fe (OC ₃ F ₇ ) ₃
127: Cu (OCH ₂ CH ₂ OC ₃ F ₇ ) _{2
128: C 3 F 7 (OC} 3 F 6) 24 O (CF 2) 2 CH 2 OCH 2 Si (OCH 3) 3
The method for forming the water repellent film is not particularly limited, such as spin coating, dip coating, extrusion coating, roll coating coating spray coating, gravure coating, wire bar coating, and air knife coating. Alternatively, coating may be performed using a vacuum deposition method. Among these, a dip coating method in which an organic metal compound having an organic group containing a fluorine atom is diluted with a solvent and a glass substrate is immersed therein and applied is simple and preferable.

In the present invention, the film density of the water repellent layer is 1.30 g / cm ³ or more and 3.00 g / cm ³ or less, preferably 1.40 g / cm ³ or more and 1.50 g / cm ^3. The following is a preferred embodiment. A film density of less than 1.3 g / cm ³ is not preferable because the water-repellent film on the surface becomes too sparse and the water repellency becomes insufficient. If it exceeds 3.0 g / cm ³ , the surface roughness becomes large and the sliding property is lowered, which is not preferable.

  In the present invention, the method of setting the film density of the water-repellent layer to the range specified above includes selection of the type of fluorine-containing compound, type and addition amount of the organometallic compound, and hardness of the metal oxide layer located below. Can be achieved by selecting.

  As a perfluoroether compound which is a fluorine-containing compound preferably used in the present invention, it can be produced, for example, by the method described in Japanese Patent No. 2874715, and particularly a perfluoroether silane having a reactive silyl group. Compounds are preferred.

  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 following compounds can be obtained as commercial products.

  Examples include OPTOOL AES series manufactured by Daikin Industries, Ltd., DOW CORNING 2603 COATING manufactured by Toray Dow Corning Co., Ltd., and the like.

  The film density of the water repellent film according to the present invention can be measured by the X-ray reflectivity method described above.

  Specifically, as a measuring apparatus, MXP21 manufactured by Mac Science Co., Ltd. is used, copper is used as a 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, the light receiving slit is 0.03 mm × 20 mm, and the 2θ / θ scan method is used to measure from 0 to 5 ° by the FT method with a step width of 0.005 ° and a step of 10 seconds. . With respect to the obtained reflectance curve, Reflectivity Analysis Program Ver. 1 is used to obtain the parameters so that the residual sum of squares of the measured value and the fitting curve is minimized, and the film density can be obtained from each parameter.

(Base material)
The substrate is not particularly limited. For example, glass includes silicate glass (silicate glass, alkali silicate glass, lead alkali glass, soda lime glass, potassium lime glass, barium glass), borosilicate glass, phosphate glass, and the like. And plate glass made of these glasses (for example, general plate glass (normal plate glass, mold plate glass, polished plate glass, float glass), composite glass, laminated glass, tempered glass, etc.). These may be colorless or colored.

  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 derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide, polyethersulfone, polysulfones, polyether Ketoneimide, polyamide, fluororesin, nylon, polymethylmeta Relate, and organic-inorganic hybrid resins such as acrylic or polyarylates, or these resins and silica.

  Hereinafter, although an example is given and the concrete effect of the present invention is shown, the present invention is not limited to these.

Example 1
When producing a water-repellent film-coated article, the physical properties (internal stress, hardness) of the laminate having the base layer and the water-repellent film on the substrate constituting the water-repellent film-coated article are governed by the base layer. Therefore, the internal stress and hardness of the laminate were changed by changing the internal stress and hardness of the underlayer.

(Preparation of base material)
A transparent soda lime glass having a thickness of 3 mm and a size of 10 mm × 50 mm, which was previously degreased with alcohol, was prepared as a base material.

<Formation of underlayer>
(Preparation of glass plate Nos. 1-1 to 1-7 with a base layer formed)
Using a plasma CVD apparatus Model PD-270STP manufactured by Samco as a low-pressure plasma apparatus, on the prepared soda-lime glass substrate, as shown in Table 1 under the conditions shown below, a thickness of 100 nm with different internal stress and film hardness is shown. Glass plate No. _{2 with} SiO ₂ layer formed and underlying layer formed. 1-1 to 1-7.

Film formation conditions Oxygen pressure: Gas pressure changed from 70 Pa to 130 Pa Reaction gas: Tetraethoxysilane (TEOS) 5 sccm (standard cubic centimeter per minute)
Power: 100W at 13.56MHz
Substrate holding temperature: 80 ° C
(Preparation of glass plate Nos. 1-8 to 1-22 with a base layer formed)
Using the atmospheric pressure plasma discharge treatment apparatus shown in FIG. 2, on the prepared soda-lime glass substrate, a SiO ₂ layer having a thickness of 100 nm having different internal stress and film hardness as shown in Table 1 under the conditions shown below. Glass plate No. with a base layer formed 1-8 to 1-22. The processing chamber pressure was adjusted by controlling the exhaust speed from the exhaust port 301.

  The thickness indicates a value obtained by measurement using MXP21 (manufactured by Mac Science).

  The internal stress was measured with a thin film property evaluation apparatus MH4000 manufactured by NEC Sanei Co., Ltd. on a quartz glass having a thickness of 100 μm, a width of 10 mm, and a length of 50 mm under the same conditions to form a base layer with a thickness of 1 μm.

  The hardness is a Triboscope manufactured by Hysitron and a sample is mounted on a Nanoscope III manufactured by Digital Instruments. A nano-indentation described in the text is used using a triangular pyramid-type diamond indenter called a Belkovic indenter (tip ridge angle 142.3 °) as an indenter. Measured by the method.

Production of glass plate with underlying layer formed when atmospheric pressure plasma discharge treatment apparatus shown in FIG. 2 is used Film formation conditions <Power supply conditions>
Power supply type High frequency power supply made by Pearl Industrial Co., Ltd. Frequency 13.56MHz
Output density 10W / cm ²
<Electrode conditions>
Two plate-like electrodes are used, and the gap between the electrodes is set to 1 mm. A discharge is formed in the gap, and plasma is ejected from the electrodes toward the substrate surface, whereby the substrate surface is plasma treated. The base material of the plate electrode is stainless steel (SUS304), but ceramic is sprayed on the surface with a thickness of 1 mm. A cooling refrigerant (water) was passed through the electrode at a temperature of 25 ° C. for discharging.

<Gas conditions>
TEOS (tetraethoxysilane) as a source gas was vaporized by bubbling and supplied to the discharge space, and a base layer mainly composed of SiO ₂ was formed on the surface of the substrate by utilizing a decomposition reaction by plasma energy.

Discharge gas: Argon gas 2 slm / cm
Reaction gas: Oxygen gas 0.01 slm / cm
Gas for forming a thin film: 200 ml of TEOS raw material is prepared in a 500 ml glass bubbling container and kept at 25 ° C. Argon gas of 0.05 slm / cm is supplied as a carrier gas for supplying vaporized TEOS to the discharge space.

  The hardness was changed by changing the oxygen partial pressure and the output density under the above conditions. The higher the oxygen partial pressure, the lower the output density, the lower the hardness, and the higher the oxygen partial pressure, the slightly higher internal stress.

Preparation of water-repellent film-coated article (Preparation of water-repellent film-forming coating solution No. 1)
1 g of DOW CORNING 2604 COATING (manufactured by Dow Corning) as a fluorine compound is diluted with 100 g of Novec HFE7100 (manufactured by Sumitomo 3M) to prepare a coating solution for forming a water repellent layer having a solid content concentration of 0.2% of the fluorine compound. Prepared.

(Preparation of water repellent film forming coating solution No. 2)
As a fluorine compound, 1 g of DOW CORNING 2604 COATING (manufactured by Dow Corning) and 0.08 g of TEOS (tetraethoxysilane) are diluted with 100 g of Novec HFE7100 (manufactured by Sumitomo 3M), and the solid content concentration is 0.2%. A coating solution was prepared.

(Preparation of water-repellent film-forming coating solution No. 3)
Except for using 0.06 g of TMT (tetramethyltin) in place of TEOS, the coating liquid No. A coating solution was prepared in the same manner as in 2.

(Preparation of water-repellent film forming coating solution No. 4)
Except that the amount of TMT (tetramethyltin) added was changed to 0.08 g, the coating liquid No. A coating solution was prepared in the same manner as in No. 3.

(Application of water repellent film forming coating solution)
The prepared coating liquid No. 1 to No. No. 3 prepared glass sheet No. The product was coated and dried on 1-1 to 1-22, and water-repellent film-coated articles shown in Table 2 were prepared. 101 to 122.

Preparation of water-repellent film-coated articles 101 to 117, 121, and 122 A water-repellent film forming coating solution No. 1-1-1-17, 1-21, 1-22 prepared by dipping is used. 1 was applied and dried, and then stored for 1 day in a room temperature and humidity environment, and then the excess component of the water repellent layer was removed by alcohol washing to produce a water repellent coated article having a 6 nm thick water repellent film. No. 101 to 117, 121, and 122.

Preparation of water-repellent film-coated article 118 Prepared glass layer No. On top of No. 1-18, a water repellent film forming coating solution No. 1 prepared by a dipping method was used. After applying and drying 2, the water-repellent coated article having a 6 nm thick water-repellent film was prepared by removing excess components of the water-repellent layer by washing with alcohol after being stored overnight at room temperature and humidity. No. 118.

Preparation of water-repellent film-coated article 119 Prepared glass layer No. On top of No. 1-19, a water repellent film-forming coating solution No. 1 prepared by a dipping method. 3 was applied and dried, and then stored for 1 day in a room temperature and humidity environment, and then the excess component of the water repellent layer was removed by washing with alcohol to produce a water repellent coated article having a 6 nm thick water repellent film. No. 119.

Preparation of Water-repellent Film-Coated Article 120 Glass plate No. On top of 1-20, a coating solution No. 1 for forming a water repellent film prepared by a dipping method was used. 4 is applied and dried, and then stored for one day in a room temperature and humidity environment, and then the excess component of the water repellent layer is removed by alcohol washing to produce a water repellent coated article having a 6 nm thick water repellent film. No. 120.

  The film density indicates a value measured by an X-ray reflectance method using MXP21 manufactured by Mac Science.

  The internal stress of the laminate (underlayer + water repellent film) indicates a value measured by the same method as that for the underlayer. The hardness of the water-repellent film of the water-repellent film-coated article indicates a value measured by the same method as that for the underlayer.

Evaluation Each sample No. It is attached to 101 to 122, and the antifouling property, water repellency (initial water repellency, initial sliding property), durability (abrasion resistance test), and weather resistance are measured by the following methods, and evaluated according to the following evaluation ranks. The results are shown in Table 3.

<< Initial water repellency: Measurement of static contact angle of water >>
3 μL of water is dropped on the surface of the water-repellent film-coated article, and the static contact angle 15 seconds after dropping is measured using a contact angle measuring device (contact angle meter CA-DT, manufactured by Kyowa Interface Science Co., Ltd.) Evaluation based on the following criteria was used as the initial water repellency evaluation.

Initial water repellency evaluation rank ◎: Static contact angle is 110 ° or more ○: Static contact angle is 100 ° or more and less than 110 ° △: Static contact angle is 90 ° or more and less than 100 ° ×: Static contact The angle is less than 90 °.

<Initial sliding property: Measurement of water falling angle>
50 μL of water is dropped on the surface of the water-repellent film of the sample, and the angle of the stage holding the water-repellent article of the contact angle measuring device (contact angle meter CA-DT manufactured by Kyowa Interface Science Co., Ltd.) is 0 ° (horizontal ) Gradually from 90 ° (vertical) direction, the angle at which water droplets begin to move through the water-repellent article was measured, and evaluated according to the following criteria as the initial sliding evaluation.

Initial sliding property evaluation rank ◎: The sliding angle is less than 10 ° ○: The falling angle is 10 ° or more and less than 20 ° △: The falling angle is 20 ° or more and less than 30 ° ×: The falling angle is 30 ° or more.

《Abrasion resistance test》
As a wear resistance test, felt (0.63 g / cm ³ ) was attached as a wear material to a reciprocating wear tester (HEIDON-14DR manufactured by Shinto Kagaku Co., Ltd.), and the water repellency of the sample was applied under a load of 600 g / cm ^2. The membrane surface was slid back and forth 10,000 times at a speed of 100 mm / sec. At that time, the felt wear material was replaced with a new one at the end of the 5000 reciprocations, and the reciprocating sliding was continued 5000 times for a total of 10,000 reciprocating slides. At the end of 10,000 times, the water repellency and the sliding property were evaluated according to the above evaluation criteria to determine the abrasion resistance.

《Weather resistance test》
The weather resistance test was performed using a UV resistance tester (I Super UV Tester W-13, manufactured by Iwasaki Electric Co., Ltd.). On the surface side of each antifouling 7 laminate having the antifouling layer, ultraviolet rays having a wavelength of 340 nm and an irradiation hardness of 0.6 W / cm ² are irradiated in a dark condition at a black panel temperature of 48 ± 2 ° C. for 20 hours. : UV irradiation for a total of 400 hours was performed under the condition of showering with ion-exchanged water for 30 seconds every hour in a cycle of 4 hours. The contact angle of the surface (antifouling layer surface) of each antifouling laminate after the weathering test was measured by the same method as above, and the water repellency after the weathering test was evaluated with the same rank. . It represents that it is excellent in a weather resistance, so that the fall of a contact angle is small with respect to the contact angle immediately after said preparation.

(Evaluation rank of weather 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 70 Less than °.

As is apparent from the results shown in Table 3, the underlayer formed from the inorganic compound specified in the present invention, the hardness is 2.0 GPa to 7.0 GPa, and the film density is 1.3 g / cm ³ to 3.0 g / The water-repellent film formed of a fluorine-containing compound at cm ³ and the water-repellent film article of the present invention having an internal stress of the laminate of 0.1 MPa to 10 MPa are water-repellent (initial water-repellent, It was confirmed that the initial sliding property), durability (wear resistance test), and weather resistance were excellent. The effectiveness of the present invention was confirmed.

Example 2
(Preparation of base material)
The same transparent soda lime glass as the transparent soda lime glass prepared in Example 1 was prepared.

《Preparation of glass plate with base layer formed》
Glass plate No. 1 with a base layer formed in Example 1 was prepared. An underlayer-formed glass plate on which the same underlayer as 1-15 was formed was prepared.

<Formation of water repellent film>
On the base layer of the prepared base layer-formed glass plate, as shown in Table 4, the water-repellent film is coated by changing the type of the fluorine compound that forms the water-repellent film and the mixed coating liquid of the fluorine compound and the organometallic compound. An article was prepared and sample no. 201 to 208. Thickness, hardness, and fluorine density are values measured by the same method as in Example 1.

(Production of water-repellent film-coated article (Sample No. 201))
Preparation of coating solution for forming water repellent film Compound 9 and 1 g as a fluorine compound were diluted with 100 g of Novec HFE7100 (manufactured by Sumitomo 3M) to prepare a water repellent coating solution 1 having a solid content concentration of 0.2% of the fluorine compound. Prepared.

Application of water-repellent film-forming coating solution Next, the water-repellent layer formed by dipping method while adjusting the pulling speed so that the film thickness after drying becomes 6 nm on the base material having the base layer prepared above. The coating solution was applied and dried, and stored for one day in a room temperature and humidity environment, and then the excess component of the water repellent layer was removed by washing with alcohol to prepare a water repellent film-coated article. 201.

(Water repellent film coated article (production of sample Nos. 202 to 208))
Preparation of coating solution for forming water-repellent film As shown in Table 4, sample No. A water repellent film forming coating solution was prepared in the same manner as the water repellent film forming coating solution used in 201.

Application of Water-repellent Film Forming Coating Liquid Next, the prepared water-repellent film-forming coating liquid was applied to a sample having a base layer having the above prepared underlayer. The product was coated and dried under the same conditions as in 201 to prepare a water-repellent film-coated article. 202 to 208.

Evaluation Each sample No. Nos. 201 to 208 were measured for antifouling property, water repellency (initial water repellency, initial sliding property), durability (abrasion resistance test), and weather resistance in the same manner as in Example 1. The results of evaluation according to the evaluation rank are shown in Table 5.

  As is clear from the results shown in Table 5, the water-repellent film article having a water-repellent film having a fluorine compound on the base layer formed from the inorganic compound defined in the present invention has a water-repellent property (initial water-repellent property). It was confirmed that it was particularly excellent in water resistance, initial sliding property), durability (abrasion resistance test), and weather resistance. The effectiveness of the present invention was confirmed.

Example 3
(Preparation of base material)
The same transparent soda lime glass as in Example 1 was prepared.

《Preparation of glass plate with base layer formed》
Using the atmospheric pressure plasma discharge treatment apparatus shown in FIG. 2, on the soda lime glass substrate previously degreased with alcohol, the underlayer forming material and film thickness are changed as shown in Table 6 under the conditions shown below. Other than that, the glass plate No. 1 with the base layer formed in Example 1 was used. In the same method as in 1-15, a base layer having a thickness of 60 nm was formed, and the glass layer No. 3-1 to 3-6.

  In addition, the thickness, the internal stress, and the hardness of the underlayer indicate values measured by the same method as in Example 1.

Metal oxide A: SiO ₂ (source gas: tetraethoxysilane)
B: TiO ₂ (Raw material gas: Tetraisopropoxy titanium was used instead of tetraethoxysilane)
C: Al ₂ O ₃ (Raw material gas: aluminum n-butoxide was used instead of tetraethoxysilane)
Metal oxynitride D: SiO _x N _y (source gas: tetraethoxysilane and oxygen and ammonia as reactive gases)
E: TiOxNy (Raw material gas: Tetraisopropoxy titanium and hydrogen as reactive gas)
_{F: Al 2 O x N y} ( source gas: using ammonia as aluminum n- butoxide and the reaction gas)
<< Production of water-repellent film-coated articles >>
Prepared glass layer No. 1 with a base layer formed thereon. Sample No. 2 of Example 2 was formed on the underlayer of 3-1 to 3-6. The same water-repellent film was formed by the same method as in No. 205, and a water-repellent film-coated article was prepared as shown in Table 7. 301 to 306.

Evaluation Each sample No. 301 to 306, water repellency (initial water repellency, initial sliding property), durability (wear resistance test), and weather resistance were measured by the same method as in Example 1, and evaluated according to the same evaluation rank as in Example 1. The results are shown in Table 8.

  As is clear from the results shown in Table 8, the inorganic layer has an internal stress specified in the present invention, and the underlying layer is formed of at least one metal oxide or metal oxynitride selected from Al, Si, and Ti. A water-repellent film article having a water-repellent film having a hardness of 5.8 GPa, a perfluoroalkyl ether compound and a film density within the range specified in the present invention on the underlayer formed of the compound is water-repellent (initial repellent). It was confirmed that it was excellent in water resistance, initial sliding property), durability (abrasion resistance test), and weather resistance. The effectiveness of the present invention was confirmed.

DESCRIPTION OF SYMBOLS 1 Water repellent film coated article 101 Base material 102 Underlayer 103 Water repellent film 104 Laminated body 2 Atmospheric pressure plasma discharge processing apparatus 3 Plasma discharge processing chamber 4 Electric field application means 401a 1st electrode 401b 2nd electrode 402 Discharge space 5 Gas supply means 6 Electrode temperature control means N, M Thickness

Claims (9)

A water-repellent film-coated article coated with a laminate having at least a base layer and a water-repellent film covering the surface of the base layer on a substrate, wherein the base layer is formed of an inorganic compound, The water repellent film is formed of a fluorine-containing compound, the hardness of the laminate measured by the nanoindentation method is 2.0 GPa to 7.0 GPa, and the film density of the water repellent film is 1.3 g / A water-repellent film-coated article having a cm ³ to 3.0 g / cm ³ and an internal stress of the laminate of 0.1 to 10 MPa.   The water-repellent film-coated article according to claim 1, wherein the fluorine-containing compound is a perfluoroalkyl ether compound.   The water-repellent film-coated article according to claim 1 or 2, wherein the underlayer is formed by an atmospheric pressure plasma CVD method.   The water-repellent film-coated article according to any one of claims 1 to 3, wherein the inorganic compound is at least one selected from a metal oxide, a metal nitride, and a metal oxynitride.   The inorganic compound is formed of at least one metal oxide, metal nitride, or metal oxynitride selected from Al, Si, and Ti. Water-repellent film coated article.   The water-repellent film-coated article according to any one of claims 1 to 3, wherein the inorganic compound is silicon oxide.   The water-repellent film-coated article according to any one of claims 1 to 6, wherein the substrate is glass.   An architectural window glass comprising the water-repellent film-coated article according to any one of claims 1 to 7.   A window glass for a vehicle comprising the water-repellent film-coated article according to any one of claims 1 to 7.

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