JPH073438A - Production of water repellent hard coating film - Google Patents

Abstract

PURPOSE:To obtain the film which is excellent in resistance to scuffing and adhesion with a base material by forming the mixed film by irradiating the object consisting of metal oxide and fluororesin while controlling respective electron beam. CONSTITUTION:The metal oxide 8 (e.g. MgO, Al2O3, SiO2, TiO2) and the fluororesin 9 (tetrafluoro ethylene-hexafluoro propylene copolymer, polychloro trilfuoro ethylene) are used as the traget. Then, ratio (If)/(Im) of the emission current (Im) of the electron beam to irradiate the object of the metal oxide and the emission current (If) of the electron beam to irradiate the object of the fluororesin is kept constant under the constant condition of the accelerating voltage of an electron gun 4. Then the object 8 and 9 are evaporated separately, the mixed film of the metal oxide 8 and the resin 9 is formed on a base stock (e.g. glass and ceramic) by a vacuum deposition method.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a water-repellent hard coat having water repellency and excellent scratch resistance, which is used as a protective film for lenses, mirrors, automobiles, window glass for construction and other transparent substrates. The present invention relates to a method for producing a coating.

[0002]

2. Description of the Related Art A highly water-repellent film is formed on a base material such as plastic or glass by vacuum deposition or sputtering with a fluororesin such as polytetrafluoroethylene (hereinafter referred to as PTFE) resin as a target material. A forming method is disclosed (Japanese Patent Laid-Open No. 1-3049).
36, JP-A-4-48068). However, although a fluororesin such as polytetrafluoroethylene resin is excellent in water repellency, it is difficult to use it as a hard coat film because it has problems with adhesion to a substrate and scratch resistance.

In order to solve this problem, a method of providing a mixed coating film of a fluorine-based resin and a metal oxide on a plastic substrate has been disclosed (JP-A-3-153859). In this method, a composite target in which a SiO ₂ target is partially coated with PTFE resin at a certain ratio is used, and high-frequency sputtering is performed at a high-frequency output of 50 W for 10 minutes to form a mixed coating having a film thickness of 500 Å on a plastic substrate. To form.

However, although a film excellent in scratch resistance can be obtained by the above method, since the fluorine-based resin and the metal oxide are sputtered with the same input power, the film formation rate is generally higher than that of the metal oxide. Fluorine resin sputtering is performed selectively, so composition control of mixed film (content of metal oxide and fluorine resin in the film)
In order to obtain a certain level of water repellency and scratch resistance, it is necessary to control the coverage of the fluororesin by trial and error. In addition, since the coverage of the fluorine-based resin changes during sputtering, it is difficult to form a coating having a certain performance with good reproducibility.

Further, if the proportion of the metal oxide is increased to improve the scratch resistance, the water repellency is lowered, and if the proportion of the fluororesin is increased to improve the water repellency, the scratch resistance is improved. However, there is a problem in that the adhesiveness with the substrate is also lowered.

[0006]

The present invention has been made in view of the above-mentioned drawbacks, and its purpose is to have water repellency, excellent scratch resistance, and excellent adhesion to a substrate. It is to provide a method for producing a water-repellent hard coat film.

[0007]

A method for producing a water-repellent hard coat film of the present invention is directed to a metal oxide and a fluororesin as targets, and each target is irradiated with a different electron beam to evaporate the target, and a vacuum is obtained. A mixed coating of a metal oxide and a fluororesin is formed on the base material by a vapor deposition method.

Metal oxide used for the above target material
Are, for example, MgO, Al₂O₃, SiO, Si
O₂, CaO, TiO₂, NiO, ZnO Ga
₂O₃, GeO₂, Y₂O₃, ZrO₂, CdO, In
₂O₃, SnO₂, BaO, HfO ₂, WO₃, Pb
O, Bi₂O₃Etc., these are used alone
Alternatively, two or more kinds may be used in combination.

Examples of the fluorine-based resin used as the target material include PTFE, tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter referred to as FEP), polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer. , Polyvinyl fluoride, polyvinylidene fluoride and the like,
Particularly, PTFE and FEP are preferable.

Examples of the base material used in the present invention include glass, plastic, metal, ceramics and the like.

In the present invention, each target is separately irradiated with an electron beam to evaporate the target, and a film is formed on the substrate by a vacuum deposition method. The electron beam irradiation is carried out under the condition that the acceleration voltage of the electron gun is constant, and the emission current (I
The ratio (If / Im) between m) and the emission current (If) of the electron beam with which the target of the fluororesin is irradiated is kept constant.

Ratio of the above emission current (If / Im)
By keeping constant, it is possible to form a mixed coating film having a constant ratio of the metal oxide and the fluororesin in the film thickness direction on the substrate.

Since the metal oxide has a high melting point and is hard to evaporate when the emission current of the electron beam becomes small, it is preferable to irradiate the electron beam having an emission current larger than that of the fluororesin.

As the heating method used in the above vacuum vapor deposition method, for example, a resistance heating method, an electron beam heating method, a high frequency induction heating method and the like can be preferably used. The heating method may be appropriately selected depending on the material to be evaporated, but in general,
The electron beam heating method is preferable because the metal oxide has a high melting point and is difficult to evaporate, and the resistance heating method is preferable because the fluorine-based resin has a low melting point.

A method for forming a mixed coating of a metal oxide and a fluororesin on a substrate using the vacuum vapor deposition apparatus shown in FIG. 1 will be described below. In the figure, 1 indicates a vacuum tank, and the vacuum tank 1 is kept at a predetermined pressure by an exhaust device (not shown) in which an oil rotary pump and an oil diffusion pump are combined.

A water-cooled copper hearth 2 provided in the lower part of the vacuum chamber 1 is provided with three crucibles 3a, 3b and 3c. Further, the water-cooled copper hearth 2 is provided with an electron gun 4, and the electrons generated by the electron gun 4 are accelerated under a high voltage and are finely focused into an electron beam having a high energy density. Each target filled inside is branched and irradiated.

The electron gun 4 can irradiate three crucibles with different electron beams having different emission currents, and can adjust the emission currents of the electron beams with which the individual targets are irradiated under a constant acceleration voltage. Thus, the evaporation amount of each target can be adjusted.

A mounting jig 6 for mounting the base material 5 on which the water-repellent hard coat film is formed is provided at a position facing the copper hearth 2 in the upper portion of the vacuum vapor deposition apparatus. A shutter 7 is interposed between 6 and the copper hearth 2.

First, the crucible 3b is filled with the metal oxide 8 and the crucible 3c is filled with the fluorine resin 9, and the base 5 is placed on the mounting jig 6. At this point, the shutter 7 is still closed. Then, the inside of the vacuum chamber 1 was evacuated to 1.3 × 10 ⁻³ Pa or less with an exhaust device, and the metal oxide 8 and the fluororesin 9 were irradiated with electron beams with different emission currents, respectively, and then the state was stabilized. At that time, the shutter 7 is opened to form a film on the surface of the base material 5, thereby forming a water-repellent hard coat film on the base material 5 in which the ratio of the metal oxide and the fluororesin is constant in the film thickness direction. To be done.

When the emission current (Im) to the metal oxide 8 becomes small, the evaporation of the metal oxide does not occur, and when it becomes large, the evaporation rate increases the internal stress of the film and the substrate 5 warps or the film cracks. Because it occurs
When SiO ₂ is used as the metal oxide at an accelerating voltage of 10 KV, it is preferably 20 to 120 mA, more preferably 30 to 90 mA.

The emission current (If) to the fluorine-based resin 9 is determined by the mixing ratio of the metal oxide in the coating film and the fluorine-based resin 9, and when the emission current is large, the evaporation rate of the fluorine-based resin is too high as compared with the metal oxide. Therefore, the scratch resistance of the coating is impaired, so that when PTFE is used as the fluororesin at an accelerating voltage of 10 KV, 0.3 to 12 mA is preferable, and 1 to 6 mA is more preferable.

In the above vacuum vapor deposition apparatus, the metal oxides arranged in different crucibles were simultaneously vaporized by one electron gun. However, the vapor deposition method is not limited to this and, for example,
A method in which two electron guns are placed in a vacuum chamber and metal oxides and fluororesins placed in different crucibles are vaporized by different electron beams; an electron gun and a resistance heater are combined in the vacuum chamber. Using a device to evaporate a metal oxide with a high melting point by an electron beam and evaporate a fluororesin with a low melting point by resistance heating; using a device with two resistance heaters in a vacuum chamber A method of evaporating the metal oxide and the fluorine-based resin arranged in the resistance heater from different resistance heaters may be adopted.

Next, the present invention 2 will be described. In the second aspect of the present invention, the ratio (If) of the emission current (Im) to the metal oxide and the emission current (If) to the fluorine-based resin is maintained under the condition that the acceleration voltage of the electron gun is constant.
/ Im) is irradiated with an electron beam so that it gradually increases with time, and a film is formed on the substrate by a vacuum evaporation method.

The same metal oxide and fluorine resin as those used in the present invention are used.

As the above-mentioned substrate, the same one as used in the present invention is used.

Ratio of the above emission current (If / Im)
By irradiating the substrate with an electron beam so as to gradually increase with time, the ratio of the metal oxide increases on the surface of the base material, so that the adhesion to the base material is good, and as the surface of the base material progresses to the coating surface, A water-repellent hard coat film having excellent water repellency and scratch resistance, in which the content of the fluorine-based resin with respect to the oxide is gradually increased, is formed.

Ratio of the above emission current (If / Im)
May be appropriately determined depending on the purpose. For example, it may be reduced if the scratch resistance is emphasized, and may be increased if the water repellency is emphasized.

Next, the present invention 3 will be described. In the present invention 3, the ratio (Wf / Wm) of the high-frequency power (Wm) applied to the metal oxide target and the high-frequency power (Wf) applied to the fluorine-based resin target is kept constant, and high-frequency sputtering is performed. A mixed coating of a metal oxide and a fluororesin is formed on the material.

Examples of the metal oxide and the fluorine-based resin used for the target include the same metal oxide portion and the fluorine-based resin as those used in Example 1.

The same base material as that used in Example 1 is used as the base material.

The ratio of the input high frequency power (Wf / W
By keeping m) constant, it is possible to form a mixed coating film having a constant ratio of the metal oxide and the fluororesin in the film thickness direction on the substrate.

A method for forming a mixed coating of a metal oxide and a fluororesin on a base material by using the high frequency sputtering apparatus shown in FIG. 2 will be described below. Reference numeral 21 in the drawing denotes a vacuum tank, and the vacuum tank 21 is exhausted to a predetermined pressure (1 × 10 ⁻⁵ Torr or less) by an exhaust device (not shown) that is a combination of an oil rotary pump and a cryopump.

Two targets A and B are arranged in the lower part of the vacuum chamber 21, and each target is connected to a matching box 22 and a high frequency power source 23, respectively, and the targets A and B are connected to each other. Alternatively, they can be sputtered with different high frequency power. Also, by switching the target B to the DC power supply 24,
DC sputtering is possible. When a conductive material is used as the metal oxide, the metal oxide may be B and direct current sputtering may be performed. In this high-frequency sputtering device, the mixing ratio of the obtained coating film can be changed by individually controlling the electric power supplied to the targets A and B.

At the upper part of the vacuum chamber 21, a base material C is attached to a sputter table 25 provided at a position facing the targets A and B. The base material C is formed while rotating by a motor 26 connected to the sputter table 25. The sputter table 25
A shutter 27 is provided between the target and the targets A and B.

First, as the target A, a fluororesin,
After disposing metal oxides as targets B respectively,
The substrate C is rotated at 10 to 100 rpm. At this time, the shutter 27 is kept closed.

Then, the evacuation device is used to evacuate the vacuum chamber 21.
1 x 10^-FiveAfter exhausting below Torr,
Open the valve 28 and use an inert gas such as argon gas in a vacuum chamber.
21. The pressure in the vacuum chamber 21 is controlled by introducing an inert gas.
The input amount is controlled by the mass flow controller 29,
The pressure in the vacuum chamber 21 during film formation is 1 × 10^-3~ 1 x 10 ^-1
It is preferably in the range of Torr.

Subsequently, high-frequency power (high-frequency power and direct-current power when a conductive material is used as B) is applied to the targets A and B from independent power sources to cause discharge, and each target is sputtered. After setting the high frequency power (Wf) applied to the target A and the high frequency power (Wm) applied to the target B to predetermined values,
The shutter 27 is opened to start film formation on the base material C.

By keeping the ratio (Wf / Wm) of the high frequency power applied to the targets A and B after the film formation is started, the ratio of the metal oxide and the fluororesin on the base material 5 is changed in the film thickness direction. A uniform water-repellent hard coat film is formed.

Next, the present invention 4 will be described. In the present invention 4, the ratio (Wf / Wm) of the high frequency power (Wm) applied to the metal oxide target to the high frequency power (Wf) applied to the fluorine resin target is gradually increased with time. A high frequency power is applied and high frequency sputtering is performed to form a mixed coating of a metal oxide and a fluororesin on the substrate.

The same metal oxide and fluorine resin as those used in the present invention are used.

As the above-mentioned substrate, the same one as used in the present invention is used.

When the ratio of the high frequency power (Wf / Wm) is gradually increased with time, the ratio of the metal oxide on the surface of the base material increases, so that the adhesion to the base material is good and From the material surface to the coating surface,
A water-repellent hard coat film excellent in water repellency and scratch resistance, in which the content of the fluorine-based resin with respect to the metal oxide is gradually increased, is formed.

The ratio of the high-frequency power to be input (Wf / W
m) may be appropriately determined depending on the purpose, and for example, it may be reduced if the scratch resistance is emphasized, and may be increased if the water repellency is emphasized.

[0044]

EXAMPLES Examples of the present invention will be described below.

(Examples 1 to 3) A slide glass ("S1111" manufactured by Matsunami Co., Ltd.) was attached as the substrate 5 to the substrate attachment jig 6 of the vacuum vapor deposition apparatus shown in FIG. 1, and SiO was attached to the crucible 3b as a target. ₂ (metal oxide, manufactured by Yamanaka Semiconductor Co., Ltd.) was used as a rod-shaped PTFE on the crucible 3c.
(Fluorine-based resin, manufactured by Nippon Bulker Kogyo Co., Ltd.) was cut and filled.

Then, the inside of the vacuum chamber 1 was evacuated to the pressure shown in Table 1, and then an electron beam was irradiated at an accelerating voltage of 10 KV and a predetermined emission current shown in Table 1 to evaporate SiO ₂ in the crucible 3b. At the same time, the PTFE in the crucible 3c is gradually evaporated as shown in Table 1 by irradiating it with an electron beam to evaporate it, and the proportion of PTFE gradually increases as it goes to the coating surface on the slide glass. A mixed coating of SiO ₂ and PTFE was formed.

Example 4 The same procedure as in Example 1 was repeated except that FEP (made by Yodogawa Kasei Co., Ltd.) was used instead of PTFE, and the vacuum chamber 1 was evacuated to the pressure shown in Table 1. A mixed coating of SiO ₂ and FEP was obtained on the material.

Example 5 TiO ₂ was formed on the substrate in the same manner as in Example 2 except that TiO ₂ was used instead of SiO ₂ and the vacuum chamber 1 was evacuated to the pressure shown in Table 1. ₂ and P
A mixed film of TFE was obtained.

Example 6 A polycarbonate plate (“Lexan” manufactured by Asahi Glass Co., Ltd.) was used as a substrate, and the inside of the vacuum chamber 1 was evacuated to the pressure shown in Table 1 in the same manner as in Example 1. A mixed coating of SiO ₂ and PTFE was obtained on the substrate.

(Embodiment 7) After the inside of the vacuum chamber 1 was evacuated to the pressure shown in Table 1, an electron beam was radiated with the predetermined emission current shown in Table 1 to make SiO ₂ in the crucible 3b and the crucible 3c. In the same manner as in Example 1 except that the PTFE inside was evaporated at the same time, SiO ₂ and P were formed on the slide glass.
A mixed film having a constant mixing ratio of TFE was formed.

Example 8 A mixed film having a constant mixing ratio of SiO ₂ and FEP was formed on a slide glass in the same manner as in Example 7 except that PTFE was changed to FEP.

(Comparative Example 1) Vacuum evaporation was performed in the same manner as in Example 1 except that only SiO ₂ was used as the target and the inside of the vacuum chamber 1 was evacuated to the pressure shown in Table 1. A SiO ₂ film was formed on the substrate.

(Comparative Example 2) In the crucible 3b, SiO ₂ as a metal oxide and 1 mm thick PTFE as a fluororesin were used.
Sheets (manufactured by Nippon Bulker Kogyo Co., Ltd.) cut into a size of 2 mm × 2 mm were mixed and filled at a weight ratio of 50:50, and the vacuum chamber 1 was evacuated to the pressure shown in Table 1. After that, vacuum evaporation was performed in the same manner as in Comparative Example 1 to form a mixed film of SiO ₂ and PTFE on the slide glass.

(Comparative Example 3) In the crucible 3b, SiO ₂ as a metal oxide and 1 mm thick PTFE as a fluororesin were used.
Vacuum deposition was carried out in the same manner as Comparative Example 2 except that a sheet (manufactured by Nippon Bulker Kogyo Co., Ltd.) cut into a size of 2 mm × 2 mm was mixed and filled so that the weight ratio was 25:75. done, SiO ₂ and PT on a glass slide
A mixed film of FE was formed.

(Comparative Example 4) A rod-shaped PT was used instead of SiO _2.
Vacuum deposition was performed in the same manner as in Comparative Example 1 except that the one obtained by cutting FE was used, and PTFE was placed on the slide glass.
Was formed.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[Evaluation of Performance of Coating Film] The coating films obtained in the above Examples and Comparative Examples were evaluated for the following performance, and the results are shown in Table 1. (1) Film thickness measurement A film is formed by masking a part of the base material, and the step between the masking part and the film forming part is measured by a surface shape measuring instrument (“Dektak3030” manufactured by Sloan Co., Ltd.) to obtain the film thickness. I asked. (2) Scratch resistance test: After the coating film was reciprocated 20 times while pressing # 0000 steel wool against the coating surface with a certain pressure, the surface state of the coating film was visually observed, and when the coating surface was not scratched. The maximum pressure was used as an index of scratch resistance. (3) Water repellency test Evaluation was made by the contact angle with water. (4) Adhesion test A cross-cut adhesive tape peeling test was performed according to JIS K5400, and the adhesion was evaluated according to the following evaluation criteria. <Evaluation Criteria> 10 points: Each cut is thin and smooth on both sides, and there is no peeling at each intersection of cuts and each square. 8 points: There was peeling at the intersection of the cuts, and there was no peeling at every square, and the area of the defective portion was within 5% of the total square area. 6 points: There is peeling on both sides of the cut and at the intersection, and the area of the defective portion is 5 to 15% of the total square area. 4 points: The width of peeling due to a cut is wide, and the area of the defective portion is 15 to 35% of the total square area. 2 points: The width of peeling due to a cut is wider than 4 points (evaluation standard), and the area of the defective portion is 35 to 65% of the total square area. 0 points: The area of peeling is 65% or more of the total square area.

[0060]

[Table 4]

(Examples 9 to 12) The base material C was placed on the sputtering table 25 of the multi-source simultaneous sputtering apparatus shown in FIG.
Attach a slide glass as the
After arranging SiO ₂ on the TFE and the target B respectively, the vacuum chamber 21 is evacuated to 1 × 10 ⁻⁵ Torr or less,
Ar gas as a sputtering gas was introduced into the vacuum chamber 21 at 45 sccm using the mass flow controller 29,
The pressure in the vacuum chamber 21 was set to 5 × 10 ⁻³ Torr. Next, while rotating the sputter table 25 at a rotation speed of 20 rpm, high frequency power was applied to the targets A and B, and then the shutter 27 was opened to start film formation. As shown in Table 5, the high frequency power applied to each target during film formation is constant power for the target B, and sputtering is performed for the target A while gradually increasing the power, and the PTFE is increased toward the surface of the film. A mixed coating of SiO ₂ and PTFE having an increased ratio of SiO ₂ was formed.

(Embodiment 13) An SiO 2 film was prepared in the same manner as in Embodiment 11 except that FEP was used instead of PTFE.
A mixed coating of ₂ and FEP was formed.

[0063] Instead of (Example 14) SiO ₂ ZrO ₂
In the same manner as in Example 12 except that Zr was used.
A mixed coating of O ₂ and FEP was formed.

(Embodiments 15 and 16) As shown in Table 6, Si was prepared in the same manner as in Embodiment 9 except that the targets A and B were charged so as to have a constant power.
A mixed film having a constant mixing ratio of O ₂ and FEP was formed.

(Comparative Example 5) Using only the target B,
In the same manner as in Example 9 except that the constant high frequency power shown in Table 7 was applied to the SiO ₂ of the target B, S
It was formed of iO ₂ coating.

(Comparative Example 6) As shown in FIGS. 3 and 4,
A composite target 30 (surface coverage of 10) in which SiO ₂ 30a is partially coated with a PTFE sheet 30b having a thickness of 2 mm
%) Was used, and a mixed coating of SiO ₂ and PTFE was formed in the same manner as in Example 9 except that the constant power shown in Table 7 was applied.

(Comparative Example 7) SiO by PTFE sheet
SiO ₂ and PTF were prepared in the same manner as in Example 9 except that a composite target having a coverage of ₂ of 70% was used.
A mixed coating of E was formed.

Comparative Example 8 PTF was prepared in the same manner as in Example 9 except that only the target A was used and the constant power shown in Table 7 was applied to the PTFE of the target A.
A coating of E was formed.

[0069]

[Table 5]

[0070]

[Table 6]

[0071]

[Table 7]

The coatings obtained in the above Examples and Comparative Examples were subjected to the same performance evaluations as in (1) to (4) above, and the results are shown in Table 8.

[0073]

[Table 8]

[0074]

The method for producing a water-repellent hard coat film of the present invention is as described above, and it is possible to form a film having both water repellency and scratch resistance on a substrate by a vacuum vapor deposition method, Water repellency and scratch resistance can be controlled according to the purpose. In the method for producing the water-repellent hard coat film of the present invention 2, since the mixing ratio of the metal oxide and the fluororesin in the film can be changed by the vacuum vapor deposition method, the ratio of the fluororesin at the substrate interface can be increased. Then, by increasing the proportion of fluororesin toward the coating surface,
A film having excellent adhesion to the substrate can be obtained.

The method for producing the water-repellent hard coat film of the present invention 3 is as described above, and it is possible to form a film having both water repellency and scratch resistance on the substrate by high frequency sputtering, and to achieve the purpose. Water repellency and scratch resistance can be controlled accordingly. In the method for producing the water-repellent hard coat film of the present invention 4, since the mixing ratio of the metal oxide and the fluororesin in the film can be changed by high frequency sputtering, the ratio of the fluororesin at the substrate interface can be increased. By increasing the proportion of the fluororesin toward the coating surface, a coating having excellent adhesion to the substrate can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a vacuum vapor deposition apparatus used in the present invention and the present invention 2.

FIG. 2 is a schematic view showing an example of a sputtering apparatus used in the present invention 3 and the present invention 4.

FIG. 3 is a side view showing a composite target used in Comparative Example 6.

FIG. 4 is a plan view showing a composite target used in Comparative Example 6.

[Explanation of symbols]

 1 Vacuum Tank 2 Water-Cooled Copper Hearth 3a, 3b, 3c Crucible 4 Electron Gun 5 Base Material 6 Mounting Jig 7 Shutter 8 Metal Oxide 9 Fluorine Resin 10 Vacuum Valve 11 Peep Window 21 Vacuum Tank 22 Matching Box 23 High Frequency Power Supply 24 DC Power supply 25 Sputter table 26 Motor 27 Shutter 28 Gas introduction valve 29 Mass flow controller 30 Composite target A, B Target C Base material

Claims (4)

[Claims] 1. An emission current (Im) of an electron beam for irradiating a metal oxide target with a metal oxide and a fluororesin under the conditions of a constant acceleration voltage of an electron gun and a fluororesin target. Ratio (If / I) of the emission current (If) of the electron beam irradiated to the
While keeping m) constant, each target is irradiated with a different electron beam to evaporate the target, and a mixed coating film of a metal oxide and a fluororesin is formed on the base material by a vacuum deposition method. A method for producing a water-repellent hard coat film. 2. The method for producing a water-repellent hard coat film according to claim 1, wherein the accelerating voltage of the electron gun is constant.
The ratio (If / Im) of the emission current (Im) of the electron beam irradiating the target of the metal oxide to the emission current (If) of the electron beam irradiating the target of the fluororesin is gradually increased with time. A method for producing a water-repellent hard coat film, which comprises irradiating the substrate with an electron beam and forming a mixed film of a metal oxide and a fluororesin on the substrate by a vacuum deposition method. 3. A ratio (Wf /) of a high frequency power (Wm) applied to a metal oxide target and a high frequency power (Wf) applied to a target of a fluorine resin, targeting a metal oxide and a fluororesin. High-frequency power is applied to each target while Wm) is kept constant, and a mixed coating of a metal oxide and a fluorine-based resin is formed on the base material by high-frequency sputtering to produce a water-repellent hard coat coating. . 4. The method for producing a water-repellent hard coat film according to claim 3, wherein high-frequency power (Wm) applied to the metal oxide target and high-frequency power (Wf) applied to the fluorine-based resin target. A water-repellent hard coat characterized in that a high-frequency power is applied so that the ratio (Wf / Wm) gradually increases with time, and a mixed film of a metal oxide and a fluorine-based resin is formed on a base material by high-frequency sputtering. Method of manufacturing coating film.