JP4432433B2 - Manufacturing method of front plate for display - Google Patents

Description

The present invention relates to a method for manufacturing a front plate disposed on the front surface of a display device, and more particularly to a method for manufacturing a front plate for a display on which an antireflection film is formed.

  In recent years, various display devices such as a liquid crystal display, a projection display, and a plasma display have been developed and put into practical use, and are used as image display devices for personal computers, televisions, car navigation systems, and the like in accordance with their applications.

  Antireflection members are arranged on the surfaces of these display devices. For example, in a liquid crystal display, a protective film is usually attached to the surface to prevent external light from being reflected on the surface of the display. Since the protective film has a thin film shape, it is excellent in light transmittance. In the liquid crystal display, even if the protective film is attached, an image can be displayed in a state in which the light loss of the backlight is suppressed.

On the other hand, in projection displays that project video light from the back of a transmissive screen and display images, the “front plate” is used to enhance the image quality and protect the transmissive screen. A transparent panel is arranged, and an antireflection film is formed on the surface (see, for example, Patent Document 1).
JP-A-8-265675

  In the technique of Patent Document 1, the antireflection film can reduce the decrease in contrast due to external light reflection and the reflection of the lighting fixture / viewer itself, but the base plate of the front plate is made of a resin thicker than the protective film. Therefore, the front plate with the antireflection film is inferior in light transmittance to the protective film, and the antireflection film is required to have a higher antireflection function and film thickness uniformity than the protective film.

As a technique for forming an antireflection film on the front plate, there are known coating techniques and vapor deposition techniques. However, when an antireflection film is formed by the coating technique, uneven coating is formed on the antireflection film and the film thickness is made uniform. I can't. On the other hand, when the antireflection film is formed by the vapor deposition technique, the adhesion between the base material and the antireflection film is not good, and the antireflection film may peel from the base material.
An object of the present invention is to provide a method for producing a display front plate having a uniform antireflection film thickness and excellent adhesion between a substrate and the antireflection film.

In order to solve the above problem, the invention according to claim 1
A gas containing the first thin film forming gas is supplied to the discharge space under atmospheric pressure or a pressure in the vicinity thereof, and the gas is excited by applying a high-frequency electric field to the discharge space, and the substrate is applied to the excited gas. A method for producing a front plate for a display, wherein an antireflection film is formed on at least one surface of the base material by exposing the substrate to the substrate.
The high-frequency electric field is a superposition of the first high-frequency electric field and the second high-frequency electric field, and the frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, and the first high-frequency electric field is And the second high frequency electric field strength V2 and the discharge start electric field strength IV satisfy V1 ≧ IV> V2 or V1> IV ≧ V2, and the output density of the second high frequency electric field is Is 1 W / cm ² or more.

Invention of Claim 2 is a manufacturing method of the front plate for a display of Claim 1,
The discharge space includes a first electrode and a second electrode facing each other.

Invention of Claim 3 is a manufacturing method of the front plate for a display of Claim 1 or 2,
The output density of the second high frequency electric field is 50 W / cm ² or less.

The invention according to claim 4 is the method for manufacturing the front plate for display according to claim 3,
The output density of the second high-frequency electric field is 20 W / cm ² or less.

Invention of Claim 5 is a manufacturing method of the front board for a display as described in any one of Claims 1-4,
The output density of the first high frequency electric field is 1 W / cm ² or more.

The invention according to claim 6 is the method for producing the display front plate according to claim 5,
The output density of the first high-frequency electric field is 50 W / cm ² or less.

Invention of Claim 7 is a manufacturing method of the front plate for a display as described in any one of Claims 1-6,
The first high-frequency electric field and the second high-frequency electric field are sine waves.

Invention of Claim 8 is a manufacturing method of the front plate for a display as described in any one of Claims 2-7,
The first high-frequency electric field is applied to the first electrode, and the second high-frequency electric field is applied to the second electrode.

Invention of Claim 9 is a manufacturing method of the front plate for a display as described in any one of Claims 1-8,
90 to 99.9% by volume of the total amount of gas supplied to the discharge space is the first discharge gas.

The invention according to claim 10 is the method for manufacturing the front plate for display according to claim 9,
The first discharge gas contains 50 to 100% by volume of nitrogen gas.

Invention of Claim 11 is a manufacturing method of the front plate for a display of Claim 9 or 10,
The first discharge gas contains less than 50% by volume of a rare gas.

Invention of Claim 12 in the manufacturing method of the front plate for a display as described in any one of Claims 1-11,
The first thin film-forming gas contains at least one selected from an organometallic compound, a metal halide, and a metal hydride.

Invention of Claim 13 in the manufacturing method of the front plate for a display of Claim 12,
The organometallic compound contains at least one compound selected from an organosilicon compound, an organotitanium compound, an organotin compound, an organozinc compound, an organoindium compound, and an organoaluminum compound.

Invention of Claim 14 in the manufacturing method of the front plate for a display as described in any one of Claims 1-13,
The thickness of the base material is 1 mm or more.

Invention of Claim 15 is a manufacturing method of the front board for a display as described in any one of Claims 1-14,
On the antireflection film, it is characterized by forming a antifouling containing organometallic compound having an organic group having a fluorine atom.

The invention according to claim 16 is the method for manufacturing the front plate for display according to claim 15,
A second thin film containing the excited second discharge gas and an organometallic compound having an organic group having a fluorine atom is introduced into the discharge space and excited under atmospheric pressure or a pressure in the vicinity thereof. and formation gas are contacted outside the discharge space and indirect excitation gas, by exposing the substrate to the indirect excitation gas, characterized by forming the antifouling film on the antireflection film of the base material It is said.

Hereinafter, the present invention will be described in detail.
In the first aspect of the present invention, the plasma discharge treatment is performed under atmospheric pressure or a pressure in the vicinity thereof, and “atmospheric pressure or a pressure in the vicinity thereof” is about 20 kPa to 110 kPa, In order to obtain the good effects described in the invention, 93 kPa to 104 kPa is preferable.

  In the present invention, the gas supplied between the counter electrodes (discharge space) includes at least a first discharge gas excited by an electric field and a first thin film forming gas that receives the energy and forms a thin film in a plasma state or an excited state. Is included.

  However, in the present invention, in the first discharge gas of a rare gas such as helium or argon, the production cost when forming a thin film often depends on the cost of the first discharge gas, and is also an alternative from an environmental standpoint. The inventors have studied the use of the first discharge gas. As a result of studying air, oxygen, nitrogen, carbon dioxide, hydrogen, etc. as an alternative first discharge gas, a condition for generating high-density plasma is obtained even with these gases, and excellent thin film formability is obtained. As a result of studying conditions and methods for forming a thin film dense and uniform, the present invention has been achieved.

The discharge condition in the present invention is such that the first high-frequency electric field and the second high-frequency electric field are superimposed on the discharge space, and the frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, In addition, the relationship between the first high-frequency electric field strength V1, the second high-frequency electric field strength V2, and the discharge start electric field strength IV satisfies V1 ≧ IV> V2 or V1> IV ≧ V2. The power density of the second high frequency electric field is 1 W / cm ² or more.

High frequency refers to one having a frequency of at least 0.5 kHz.
When the superposed high-frequency electric field is both a sine wave, the frequency ω1 of the first high-frequency electric field and the frequency ω2 of the second high-frequency electric field higher than the frequency ω1 are superimposed, and the waveform is a sine of the frequency ω1. A sawtooth waveform in which a sine wave having a higher frequency ω2 is superimposed on the wave is obtained.

  In the present invention, the strength of the electric field at which discharge starts is the lowest electric field intensity that can cause discharge in the discharge space (electrode configuration, etc.) and reaction conditions (gas conditions, etc.) used in the actual thin film formation method. Point to. The discharge start electric field strength varies somewhat depending on the gas type supplied to the discharge space, the dielectric type of the electrode, or the distance between the electrodes, but in the same discharge space, it is governed by the discharge start electric field strength of the first discharge gas. .

  By applying a high-frequency electric field as described above to the discharge space, it is presumed that a discharge capable of forming a thin film is generated and high-density plasma necessary for forming a high-quality thin film can be generated.

  What is important here is that such a high-frequency electric field is applied to the opposing electrodes, that is, applied to the same discharge space. As described in Japanese Patent Application Laid-Open No. 11-16696, thin film formation according to the present invention cannot be achieved by a method in which two application electrodes are juxtaposed and different high frequency electric fields are applied to different discharge spaces.

  Although the superposition of continuous waves such as sine waves has been described above, the present invention is not limited to this, and both pulse waves may be used, one of them may be a continuous wave and the other may be a pulse wave. Further, it may have a third electric field.

  As a specific method of applying the high-frequency electric field of the present invention to the same discharge space, the first high-frequency electric field having the frequency ω1 and the electric field strength V1 is applied to the first electrode constituting the counter electrode. It is to use an atmospheric pressure plasma discharge treatment apparatus in which a power source is connected and a second power source for applying a second high frequency electric field having a frequency ω2 and an electric field strength V2 is connected to the second electrode.

  The above atmospheric pressure plasma discharge treatment apparatus includes a gas supply means for supplying a first discharge gas and a first thin film forming gas between the counter electrodes. Furthermore, it is preferable to have an electrode temperature control means for controlling the temperature of the electrode.

  Further, it is preferable to connect the first filter to the first electrode, the first power source or any of them, and connect the second filter to the second electrode, the second power source or any of them, The first filter facilitates the passage of the first high-frequency electric field current from the first power source to the first electrode, grounds the second high-frequency electric field current, and the second filter from the second power source to the first power source. It makes it difficult to pass the current of the high frequency electric field. On the other hand, the second filter makes it easy to pass the current of the second high-frequency electric field from the second power source to the second electrode, grounds the current of the first high-frequency electric field, and the second power from the first power source. A power supply having a function of making it difficult to pass the current of the first high frequency electric field to the power supply is used. Here, being difficult to pass means that it preferably passes only 20% or less of the current, more preferably 10% or less. On the contrary, being easy to pass means preferably passing 80% or more of the current, more preferably 90% or more.

  Furthermore, it is preferable that the first power source of the atmospheric pressure plasma discharge processing apparatus of the present invention has a capability of applying a higher frequency electric field strength than the second power source.

  Here, the high frequency electric field strength (applied electric field strength) and the discharge starting electric field strength referred to in the present invention are those measured by the following method.

Measuring method of high-frequency electric field strengths V1 and V2 (unit: kV / mm):
A high-frequency voltage probe (P6015A) is installed in each electrode section, and the output signal of the high-frequency voltage probe is connected to an oscilloscope (Tektronix, TDS3012B), and the electric field strength is measured.

Measuring method of electric discharge starting electric field intensity IV (unit: kV / mm):
The first discharge gas is supplied between the electrodes, the electric field strength between the electrodes is increased, and the electric field strength at which discharge starts is defined as the discharge starting electric field strength IV. The measuring instrument is the same as the high frequency electric field strength measurement.

  The positional relationship between the high-frequency voltage probe used for the measurement and the oscilloscope is shown in FIG.

  By adopting the discharge conditions defined in the present invention, even a first discharge gas having a high discharge starting electric field strength such as nitrogen gas can start discharge and maintain a high density and stable plasma state, and a high performance thin film It can be formed.

When the first discharge gas is nitrogen gas according to the above measurement, the discharge start electric field intensity IV (1/2 V _pp ) is about 3.7 kV / mm. Therefore, in the above relationship, the first high frequency electric field intensity is Is applied as V1 ≧ 3.7 kV / mm, whereby the nitrogen gas can be excited to be in a plasma state.

  Here, the frequency of the first power source is preferably 200 kHz or less. The electric field waveform may be a continuous wave or a pulse wave. The lower limit is preferably about 1 kHz.

  On the other hand, the frequency of the second power source is preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

  The application of a high frequency electric field from such two power sources is necessary to start the discharge of the first discharge gas having a high discharge starting electric field strength by the first high frequency electric field, It is an important point of the present invention to form a dense and high-quality thin film by increasing the plasma density by high frequency and high power density.

  Also, by increasing the output density of the first high-frequency electric field, the output density of the second high-frequency electric field can be improved while maintaining the uniformity of discharge. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film formation speed and an improvement in film quality can be achieved.

  In the atmospheric pressure plasma discharge processing apparatus used in the present invention, the first filter facilitates passage of the current of the first high-frequency electric field from the first power source to the first electrode, and grounds the current of the second high-frequency electric field. Thus, it is difficult to pass the current of the second high-frequency electric field from the second power source to the first power source. On the other hand, the second filter makes it easy to pass the current of the second high-frequency electric field from the second power source to the second electrode, grounds the current of the first high-frequency electric field, and the second power from the first power source. The current of the first high-frequency electric field to the power supply is made difficult to pass. In the present invention, any filter having such properties can be used without limitation.

  For example, as the first filter, a capacitor of several tens of pF to several tens of thousands of pF or a coil of about several μH can be used depending on the frequency of the second power source. As the second filter, a coil of 10 μH or more is used according to the frequency of the first power supply, and it can be used as a filter by grounding through these coils or capacitors.

  As described above, the atmospheric pressure plasma discharge treatment apparatus used in the present invention discharges between the counter electrodes, puts the gas introduced between the counter electrodes into a plasma state, and places the gas between the counter electrodes or between the electrodes. By exposing the substrate to be transferred to the plasma state gas, a thin film is formed on the substrate. As another method, the atmospheric pressure plasma discharge treatment apparatus discharges between the counter electrodes similar to the above, excites the gas introduced between the counter electrodes or puts it in a plasma state, and excites or jets the gas outside the counter electrode. There is a jet type apparatus that blows out a plasma gas and exposes a substrate (which may be stationary or transferred) in the vicinity of the counter electrode to form a thin film on the substrate. .

  According to the invention described in claims 1 to 14, since the antireflection film is formed on the base material by exposing the base material to the excited gas under special discharge conditions, it is reflected by the coating technique or the vapor deposition technique. Unlike the case where the anti-reflection film is formed on the base material, there is no problem such as uneven coating and non-uniform thickness of the anti-reflection film or poor adhesion between the base material and the anti-reflection film. It can be set as a display front plate having a uniform film thickness of the preventive film and excellent adhesion between the substrate and the antireflective film.

  According to the invention described in claims 15 and 16, since the antifouling film for preventing dirt is formed on the antireflection film of the base material, the antifouling function (dirt prevention function) such as water repellency is provided. It can be set as a display front plate.

  The best mode for carrying out the present invention will be described below with reference to the drawings. However, the scope of the invention is not limited to the illustrated examples.

FIG. 1 is a cross-sectional view schematically showing a screen structure of a display device.
The screen of the display device has a structure composed of a front plate 1, a lenticular lens 2 and a Fresnel lens 3. The front plate 1 is arranged on the front side of the display device (the viewer side of the display device), the lenticular lens 2 is arranged on the rear side of the front plate 1, and the Fresnel is arranged on the rear side of the lenticular lens 2. A lens 3 is arranged.

  As shown in the enlarged view in FIG. 1, the front plate 1 includes a base material 4 having a thickness of 1 mm or more, and a hard coat film 5, an antireflection film 6, and an antifouling film 7 are formed on the front surface of the base material 4. Are formed in this order. The front plate 1 as a display front plate according to the present invention is applicable as a front plate of all known display devices. For example, a projection display, a liquid crystal display, a plasma display, an EL (Electro Luminescent) display, a CRT (Cathode Ray) Tube) Applicable as a front plate for displays and the like.

  As the base material 4, a thin film (hard coat film 5, antireflection film 6, antifouling) is formed on the surface of a flat shape such as a plate, sheet or film, or a three-dimensional shape such as a lens or other molded product. There is no particular limitation as long as the film 7) can be formed. There are no restrictions on the form or material of the base material 4 as long as the base material 4 is exposed to a mixed gas in a plasma state regardless of whether it is in a stationary state or a transported state, and a uniform antireflection film 6 and antifouling film 7 are formed. Absent. The shape may be a planar shape or a three-dimensional shape, and examples of the planar shape include a glass plate and a resin plate. Various materials such as glass, resin, earthenware, metal, and non-metal can be used. Specifically, examples of the glass include a glass plate and a lens, and examples of the resin include a resin lens, a resin film, a resin sheet, and a resin plate.

  When the substrate 4 is made of a resin, the material is a polyolefin (polyethylene) from the viewpoint of optical properties such as transparency, refractive index and dispersion, and various physical properties such as impact resistance, heat resistance and durability. , Polypropylene, etc.), cyclopolyolefin, polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-6, 6 etc.), polystyrene, polyvinyl chloride, polyimide, polycarbonate, polyvinyl alcohol, ethylene Examples include vinyl alcohol, acrylic, cellulose-based (triacetyl cellulose, diacetyl cellulose, cellophane, etc.), and the like, or copolymers of these organic polymers.

  The hard coat film 5 is a known hard coat film for preventing the substrate 4 from being damaged, and is composed of an inorganic hard coat agent, an organic hard coat agent, an organic / inorganic hybrid coat agent, or the like.

  The antireflection film 6 is a film having a function of preventing the incident light directed from the front side of the front plate 1 to the base material 4 from being reflected, and is formed of a single layer or has a different refractive index. A plurality of layers are laminated. The “antireflection film 6” means that a gas G (see FIG. 2) containing the first thin film forming gas is supplied to the discharge space and a high-frequency electric field is applied to the discharge space under atmospheric pressure or a pressure in the vicinity thereof. Thus, the gas G is excited, and the substrate 4 is exposed to the excited gas G, whereby the film is formed on the hard coat film 5.

  The antifouling film 7 is a film having an antifouling function such as water repellency, and contains an organometallic compound having an organic group having a fluorine atom. The “antifouling film 7” means that the second discharge gas G2 (see FIG. 6) is introduced into the discharge space and excited under atmospheric pressure or a pressure in the vicinity thereof, and the excited second discharge gas G2; A second thin film forming gas M2 (see FIG. 6) containing an organometallic compound having an organic group having a fluorine atom is contacted outside the discharge space to become an indirect excitation gas, and the substrate 4 is exposed to the indirect excitation gas. As a result, the film is formed on the antireflection film 6 of the substrate 4.

  In the front plate 1, the hard coat film 5, the antireflection film 6 and the antifouling film 7 are formed only on one surface (front surface) of the substrate 4, but the other surface (rear surface) of the substrate 4 is formed. The hard coat film 5, the antireflection film 6 and the antifouling film 7 may also be formed on the above. Further, the hard coat film 5 may be formed on the base material 4 of the front plate 1 or may not be formed.

Next, an atmospheric pressure plasma discharge processing apparatus 10 that forms the antireflection film 6 on the base material 4 of the front plate 1 will be described with reference to FIGS.
As shown in FIG. 2, the atmospheric pressure plasma discharge processing apparatus 10 has a flat and long stage electrode 11. Above the stage electrode 11 as the first electrode, a plasma discharge vessel 12 having an open bottom is disposed. A plurality of rectangular tube electrodes 13 are arranged inside the plasma discharge vessel 12 and above the stage electrode 11.

  As shown in FIG. 2 and FIG. 3, each square tube electrode 13 as the second electrode and the stage electrode 11 are arranged to face each other at a predetermined interval. In the atmospheric pressure plasma discharge processing apparatus 10, the stage electrode 11 and each cylindrical electrode 13 constitute a counter electrode. A drive mechanism (not shown) is connected to the stage electrode 11, and the stage electrode 11 can be reciprocated by the action of the drive mechanism (see arrows in FIGS. 2 and 3).

  As shown in FIG. 4, the stage electrode 11 has a structure in which a flat and long metallic base material 11a is covered with a dielectric 11b. As shown in FIG. 5, the rectangular tube electrode 13 has a structure in which a rectangular tube-shaped metallic base material 13a is covered with a dielectric 13b. Details of the stage electrode 11 and each rectangular tube electrode 13 will be described later.

  The stage electrode 11 and each square tube electrode 13 are both hollow, and in the atmospheric pressure plasma discharge processing apparatus 10, the temperature adjustment is provided in the hollow portion of the stage electrode 11 and each square tube electrode 13. The medium (water, silicon, etc.) is circulated to control the temperature of the stage electrode 11 and each rectangular tube electrode 13.

  As shown in FIG. 1, three gas supply ports 14, 14, 14 for supplying a gas G into the plasma discharge container 12 are provided above the plasma discharge container 12. Above each square tube electrode 13, a mesh 15 is provided for equalizing the flow rate of G supplied into the plasma discharge vessel 12. In the atmospheric pressure plasma discharge processing apparatus 10, a gas G is supplied from each gas supply port 14 into the plasma discharge vessel 12, and further, a discharge space 16 between the stage electrode 11 and each rectangular tube electrode 13 through the mesh 15. A gas G is supplied to the gas.

  A first power source 17 is connected to the stage electrode 11, and the first power source 17 has a first frequency ω 1, electric field strength V 1, and current I 1 in the discharge space 16 between the stage electrode 11 and each rectangular tube electrode 13. The high frequency electric field is applied. On the other hand, a second power source 18 is connected to each square tube electrode 13, and the second power source 18 has a frequency ω 2, an electric field strength V 2, and a discharge space 16 between the stage electrode 11 and each square tube electrode 13. A second high frequency electric field of current I2 is applied.

  A first filter 19 is installed between the stage electrode 11 and the first power source 17. The first filter 19 facilitates the passage of current from the first power source 17 to the stage electrode 11, and the second power source 18 Is designed so that the current from the second power source 18 to the first power source 17 is hardly passed. Further, a second filter 20 is installed between each square tube electrode 13 and the second power source 18, and the second filter 20 passes a current from the second power source 18 to each square tube electrode 13. The current from the first power source 17 is grounded so that the current from the first power source 17 to the second power source 18 is difficult to pass.

  The first power supply 17 preferably applies a higher frequency electric field strength (V1> V2) than the second power supply 18. Further, the first power source 17 and the second power source 18 have the capability of having a frequency ω1 <ω2.

Further, the current between the first power supply 17 and the second power supply 18 is preferably I1 <I2. Current I1 of the first high-frequency electric field is preferably ^{0.3mA / cm 2 ~20mA / cm 2} , more preferably at ^{1.0mA / cm 2 ~20mA / cm 2} . Furthermore, current I2 of the second high-frequency electric field is preferably ^{10mA / cm 2 ~100mA / cm 2} , more preferably ^{20mA / cm 2 ~100mA / cm 2} .

  In the atmospheric pressure plasma discharge processing apparatus 10, each square tube electrode 13 is connected to the stage electrode 11 via the first filter 19, and the second power source 18 is connected to the stage electrode 11 via the second filter 20. May be.

  The stage electrode 11 and each rectangular tube type electrode 13 are subjected to sealing treatment using a sealing material made of an inorganic compound after thermal spraying ceramics as dielectrics 11b and 13b on conductive metallic base materials 11a and 13a, respectively. It is a thing. The ceramic dielectric may be covered by about 1 mm with a single wall. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed. The layers of the dielectrics 11b and 13b may be lining treated dielectrics provided with an inorganic material by lining.

  Examples of the conductive metallic base materials 11a and 13a include titanium metal or titanium alloy, silver, platinum, stainless steel, aluminum, iron, and other metals, a composite material of iron and ceramics, or a composite material of aluminum and ceramics. Although titanium metal or a titanium alloy is particularly preferable for the reasons described later.

  The distance between the electrodes of the stage electrode 11 and the rectangular tube electrode 13 facing each other is the shortest between the surface of the dielectric and the surface of the conductive metallic base material of the other electrode when a dielectric is provided on one of the electrodes. Say distance. When a dielectric is provided on both electrodes, it means the shortest distance between the dielectric surfaces. The distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metallic base material, the magnitude of the applied electric field strength, the purpose of using the plasma, etc. From the viewpoint of performing 0.15 mm, 0.1 to 20 mm is preferable, and 0.5 to 2 mm is particularly preferable.

  Details of the conductive metallic base materials 11a and 13a and the dielectrics 11b and 13b will be described later.

  The plasma discharge vessel 12 is preferably a processing vessel made of Pyrex (R) glass or the like, but may be made of metal as long as it can be insulated from the stage electrode 11 or the rectangular tube electrode 13. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be thermally sprayed to obtain insulation.

As the first power source 17 (high frequency power source) installed in the atmospheric pressure plasma discharge processing apparatus 10,
Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500
A2 Shinko Electric 5kHz SPG5-4500
A3 Kasuga Electric 15kHz AGI-023
A4 Shinko Electric 50kHz SPG50-4500
A5 HEIDEN Research Laboratories 100kHz * PHF-6k
A6 Pearl Industry 200kHz CF-2000-200k
A7 Pearl Industry 400kHz CF-2000-400k
And the like, and any of them can be used.

As the second power source 18 (high frequency power source),
Applied power supply symbol Manufacturer Frequency Product name B1 Pearl Industry 800kHz CF-2000-800k
B2 Pearl Industry 2MHz CF-2000-2M
B3 Pearl Industry 13.56MHz CF-5000-13M
B4 Pearl Industry 27MHz CF-2000-27M
B5 Pearl Industry 150MHz CF-2000-150M
And the like, and any of them can be preferably used.

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

  In the present invention, it is preferable that the atmospheric pressure plasma discharge treatment apparatus 10 employs the stage electrode 11 and the rectangular tube electrode 13 that can maintain a uniform and stable discharge state by applying such an electric field.

In the present invention, the electric power applied between the stage electrode 11 and the rectangular tube type electrode 13 supplies electric power (power density) of 1 W / cm ² or more to each rectangular tube type electrode 13 (second high frequency electric field). One discharge gas is excited to generate plasma, energy is applied to the first thin film forming gas, and a thin film is formed. The upper limit value of the power supplied to the second electrode 18 is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to the sum of the areas in the range where discharge occurs in each square tube electrode 13.

Further, by supplying power (output density) of 1 W / cm ² or more to the first electrode 17 (first high-frequency electric field), the output density is improved while maintaining the uniformity of the second high-frequency electric field. It can be made. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. Preferably it is 5 W / cm ² or more. The upper limit value of the power supplied to the first electrode 17 is preferably 50 W / cm ² .

  Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode and an intermittent oscillation mode called ON / OFF intermittently called a pulse mode. Either of them may be adopted, but at least the rectangular tube electrode 13 side ( The second high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.

  The stage electrode 11 and each rectangular tube electrode 13 used in such a method of forming a thin film by atmospheric pressure plasma must be able to withstand severe conditions in terms of structure and performance. As such a stage electrode 11 and each rectangular tube type electrode 13, it is preferable that the metal base materials 11a and 13a are covered with dielectrics 11b and 13b.

In the stage electrode 11 and each square tube type electrode 13 used in the present invention, it is preferable that the characteristics match between the various metallic base materials 11a, 13a and the dielectrics 11b, 13b. This is a combination in which the difference in coefficient of linear thermal expansion between the metallic base materials 11a and 13a and the dielectrics 11b and 13b is 10 × 10 ⁻⁶ / ° C. or less. It is preferably 8 × 10 ⁻⁶ / ° C. or less, more preferably 5 × 10 ⁻⁶ / ° C. or less, and further preferably 2 × 10 ⁻⁶ / ° C. or less. The linear thermal expansion coefficient is a well-known physical property value of a material.

As a combination of the conductive metallic base materials 11a and 13a and the dielectrics 11b and 13b within which the difference in linear thermal expansion coefficient is in this range,
1: Metal base materials 11a and 13a are pure titanium or titanium alloy, and dielectrics 11b and 13b are ceramic sprayed coatings 2: Metal base materials 11a and 13a are pure titanium or titanium alloy, and dielectrics 11b and 13b are glass. Lining 3: Metal base materials 11a and 13a are stainless steel, dielectrics 11b and 13b are ceramic sprayed coatings 4: Metal base materials 11a and 13a are stainless steel, and dielectrics 11b and 13b are glass linings 5: Metal Base materials 11a, 13a are composite materials of ceramics and iron, dielectrics 11b, 13b are ceramic sprayed coatings 6: Metal base materials 11a, 13a are composite materials of ceramics and iron, and dielectrics 11b, 13b are glass linings 7. : Metal base materials 11a and 13a are composite materials of ceramics and aluminum. Body 11b, 13b ceramics sprayed coating 8: metal base material 11a, 13a is a composite material of ceramics and aluminum, a dielectric 11b, 13b there is a glass-lined, and the like. From the viewpoint of the difference in linear thermal expansion coefficient, the above 1 or 2 and 5 to 8 are preferable, and 1 is particularly preferable.

  In the present invention, the metal base materials 11a and 13a are particularly useful from the above characteristics. By using the metal base materials 11a and 13a as titanium or a titanium alloy, and by setting the dielectrics 11b and 13b as described above, deterioration of the stage electrode 11 and each rectangular tube electrode 13 in use, particularly cracking and peeling, There is no dropout and can withstand long-term use under harsh conditions.

  The metal base materials 11a and 13a of the stage electrode 11 and each rectangular tube electrode 13 useful for the present invention are titanium alloys or titanium metals containing 70 mass% or more of titanium. In the present invention, if the titanium content in the titanium alloy or titanium metal is 70% by mass or more, it can be used without any problem, but preferably contains 80% by mass or more of titanium. As the titanium alloy or titanium metal useful in the present invention, those generally used as industrial pure titanium, corrosion resistant titanium, high strength titanium and the like can be used. Examples of pure titanium for industrial use include TIA, TIB, TIC, TID, etc., all of which contain very little iron atom, carbon atom, nitrogen atom, oxygen atom, hydrogen atom, etc. As content, it has 99 mass% or more. As the corrosion-resistant titanium alloy, T15PB can be preferably used, and it contains lead in addition to the above-mentioned atoms, and the titanium content is 98% by mass or more. Further, as the titanium alloy, T64, T325, T525, TA3, etc. containing aluminum and vanadium or tin in addition to the above atoms except lead can be preferably used. As a quantity, it contains 85 mass% or more. These titanium alloys or titanium metals have a thermal expansion coefficient smaller than that of stainless steel, for example, AISI 316, and are described below as dielectric materials applied on the titanium alloys or titanium metals as the metallic base materials 11a and 13a. The combination with 11b and 13b is good and it can endure use at high temperature for a long time.

  On the other hand, as the required characteristics of the dielectrics 11b and 13b, specifically, an inorganic compound having a relative dielectric constant of 6 to 45 is preferable, and as the dielectrics 11b and 13b, alumina, There are ceramics such as silicon nitride, or glass lining materials such as silicate glass and borate glass. In this, what sprayed the ceramics mentioned later and the thing provided by glass lining are preferable. In particular, dielectrics 11b and 13b provided by spraying alumina are preferable.

  Alternatively, as one of the specifications that can withstand high power as described above, the porosity of the dielectrics 11b and 13b is 10% by volume or less, preferably 8% by volume or less, and preferably exceeds 0% by volume to 5%. % By volume or less. The porosity of the dielectrics 11b and 13b can be measured by a BET adsorption method or a mercury porosimeter. In the examples described later, the porosity is measured by using pieces of dielectrics 11b and 13b covered with metallic base materials 11a and 13a by a mercury porosimeter manufactured by Shimadzu Corporation. High durability is achieved by the dielectrics 11b and 13b having a low porosity. Examples of the dielectrics 11b and 13b having such voids and low porosity include high-density, high-adhesion ceramic sprayed coatings by the atmospheric plasma spraying method described later. In order to further reduce the porosity, it is preferable to perform sealing treatment.

  The above-mentioned atmospheric plasma spraying method is a technique in which fine powder such as ceramics, wire or the like is put into a plasma heat source and sprayed onto the metal base materials 11a and 13a to be coated as fine particles in a molten or semi-molten state to form a film. It is. A plasma heat source is a high-temperature plasma gas in which a molecular gas is heated to a high temperature, dissociated into atoms, and further given energy to release electrons. This plasma gas injection speed is high, and compared with conventional arc spraying and flame spraying, the sprayed material collides with the metallic base materials 11a and 13a at a high speed, so that the adhesion strength is high and a high-density coating can be obtained. I can do it. Specifically, reference can be made to a thermal spraying method for forming a heat shielding film on a high-temperature exposed member described in JP-A No. 2000-301655. By this method, the porosity of the dielectrics 11b and 13b (ceramic sprayed film) to be coated can be obtained.

  Another preferred specification that can withstand high power is that the dielectrics 11b and 13b have a thickness of 0.5 to 2 mm. The film thickness variation is desirably 5% or less, preferably 3% or less, and more preferably 1% or less.

In order to further reduce the porosity of the dielectrics 11b and 13b, it is preferable to further perform a sealing treatment with an inorganic compound on the thermal spray film such as ceramics as described above. As the inorganic compound, a metal oxide is preferable, and among these, a compound containing silicon oxide (SiO _x ) as a main component is particularly preferable.

  The inorganic compound for sealing treatment is preferably formed by curing by a sol-gel reaction. In the case where the inorganic compound for sealing treatment contains a metal oxide as a main component, a metal alkoxide or the like is applied as a sealing liquid on the ceramic sprayed film and cured by a sol-gel reaction. When the inorganic compound is mainly composed of silica, it is preferable to use alkoxysilane as the sealing liquid.

  Here, it is preferable to use energy treatment for promoting the sol-gel reaction. Examples of the energy treatment include thermal curing (preferably 200 ° C. or less) and ultraviolet irradiation. Furthermore, as a method of sealing treatment, when the sealing liquid is diluted and coating and curing are repeated several times in succession, the mineralization is further improved, and the dense stage electrode 11 and the rectangular tube electrode 13 without deterioration can be formed. .

When sealing the ceramic sprayed film using the metal alkoxide or the like of the stage electrode 11 and the rectangular tube type electrode 13 coated with the dielectrics 11b and 13b according to the present invention as a sealing liquid, and performing a sealing process that cures by a sol-gel reaction The content of the metal oxide after curing is preferably 60 mol% or more. When alkoxysilane is used as the metal alkoxide of the sealing liquid, the content of SiO _x (x is 2 or less) after curing is preferably 60 mol% or more. The cured SiO _x content is measured by analyzing the tomographic layers of the dielectrics 11b and 13b by XPS (X-ray photoelectron spectroscopy).

  In the stage electrode 11 according to the thin film forming method of the present invention, the maximum height (Rmax) of the surface roughness defined by JIS B 0601 on the side in contact with the base material 4 of the stage electrode 11 is 10 μm or less. The adjustment is preferable from the viewpoint of obtaining the effects described in the present invention, but more preferably, the maximum value of the surface roughness is 8 μm or less, and particularly preferably 7 μm or less. As described above, by polishing the surface of the dielectric 11b of the stage electrode 11, the thickness of the dielectric 11b and the gap between the stage electrode 11 and the rectangular tube electrode 13 can be kept constant, and the discharge state is stabilized. In addition, distortion and cracking due to thermal shrinkage difference and residual stress can be eliminated, and durability can be greatly improved with high accuracy. The polishing finish on the surface of the dielectric 11b is preferably performed at least on the dielectric 11b on the side in contact with the substrate 4. Furthermore, the centerline average surface roughness (Ra) defined by JIS B 0601 is preferably 0.5 μm or less, more preferably 0.1 μm or less.

  In the stage electrode 11 and each rectangular tube electrode 13 covered with the dielectrics 11b and 13b used in the present invention, another preferred specification that can withstand high power is that the heat-resistant temperature is 100 ° C. or higher. More preferably, it is 120 degreeC or more, Most preferably, it is 150 degreeC or more. The upper limit is 500 ° C. The heat-resistant temperature refers to the highest temperature that can withstand normal discharge without causing dielectric breakdown at the voltage used in the atmospheric pressure plasma treatment. Such a heat-resistant temperature can be obtained by applying the dielectric materials 11b and 13b provided by the above-described ceramic spraying or layered glass linings with different amounts of bubbles mixed, or by using the metallic base materials 11a and 13a and the dielectric materials 11b and 13b. This can be achieved by appropriately combining means for appropriately selecting materials within the range of differences in linear thermal expansion coefficients.

Next, “gas G” supplied to the discharge space 16 will be described.
The gas G supplied to the discharge space 16 contains at least a first discharge gas and a first thin film forming gas. The first discharge gas and the first thin film forming gas may be mixed and supplied, or may be supplied separately.

  The “first discharge gas” is a gas capable of causing glow discharge capable of forming a thin film. Examples of the first discharge gas include nitrogen, rare gas, air, hydrogen gas, oxygen, and the like. These may be used alone as the first discharge gas or mixed. In the present invention, nitrogen is preferable as the first discharge gas. It is preferable that 50-100 volume% of 1st discharge gas is nitrogen gas. At this time, as the first discharge gas, the first discharge gas other than nitrogen preferably contains a rare gas of less than 50% by volume. Moreover, it is preferable to contain 90-99.9 volume% of the quantity of 1st discharge gas with respect to the total gas quantity supplied to discharge space.

  The “first thin film forming gas” is a raw material that is excited to become active and is chemically deposited on the substrate 4 to form a thin film.

  Next, the gas G supplied to the discharge space 16 in order to form the thin film used for this invention is demonstrated. Basically, the first discharge gas and the first thin film forming gas, but an additive gas may be further added. The total amount of gas supplied to the discharge space 16 preferably contains 90 to 99.9% by volume of the first discharge gas.

  Examples of the first thin film forming gas used in the present invention include organometallic compounds, halogen metal compounds, and metal hydrogen compounds.

The organometallic compounds useful in the present invention are preferably those represented by the following general formula (I).
R ¹ _x MR ² _y R ³ _z (I)

In formula (I), M is a metal, R ¹ is an alkyl group, R ² is an alkoxy group, R ³ is a β-diketone complex group, a β-ketocarboxylic acid ester complex group, a β-ketocarboxylic acid complex group, and a ketooxy group (ketooxy group). Complex group), and when the valence of the metal M is m, x + y + z = m, x = 0 to m, or x = 0 to m−1, y = 0 to m, z = 0 to m, each of which is 0 or a positive integer. Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxy group for R ² include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a 3,3,3-trifluoropropoxy group. Further, a hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the group selected from the β-diketone complex group, β-ketocarboxylic acid ester complex group, β-ketocarboxylic acid complex group and ketooxy group (ketooxy complex group) of R ³ include, for example, 2,4 -Pentanedione (also called acetylacetone or acetoacetone), 1,1,1,5,5,5-hexamethyl-2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedione 1,1,1-trifluoro-2,4-pentanedione, etc., and β-ketocarboxylic acid ester complex groups include, for example, acetoacetic acid methyl ester, acetoacetic acid ethyl ester, acetoacetic acid propyl ester, trimethyl Examples thereof include ethyl acetoacetate and methyl trifluoroacetoacetate. As β-ketocarboxylic acid, Eg to acetoacetate, can be mentioned trimethyl acetoacetate, and as Ketookishi, for example, acetoxy group (or an acetoxy group), a propionyloxy group, Buchirirokishi group, acryloyloxy group, methacryloyloxy group and the like. The number of carbon atoms of these groups is preferably 18 or less, including the above-mentioned organometallic compounds. Further, as illustrated, it may be linear or branched, or a hydrogen atom substituted with a fluorine atom.

In the present invention, an organometallic compound having a low risk of explosion is preferred from the viewpoint of handling, and an organometallic compound having at least one oxygen in the molecule is preferred. As such, an organometallic compound containing at least one alkoxy group of R ² , a β-diketone complex group, a β-ketocarboxylic acid ester complex group, a β-ketocarboxylic acid complex group and a ketooxy group (ketooxy group) of R ³ A metal compound having at least one group selected from (complex group) is preferred.

A specific organometallic compound will be described later.
In the present invention, the gas G supplied to the discharge space 16 may be mixed with an additive gas for promoting a reaction for forming a thin film, in addition to the first discharge gas and the first thin film forming gas. Examples of the additive gas include oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen, ammonia and the like, but oxygen, carbon monoxide and hydrogen are preferable, and components selected from these are mixed. It is preferable to do so. The content is preferably 0.01 to 5% by volume based on the total amount of gas, whereby the reaction is promoted and a dense and high-quality thin film can be formed.

  The thickness of the formed oxide or composite compound thin film is preferably in the range of 0.1 to 1000 nm.

  In the present invention, Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V are used as the metal of the organometallic compound, metal halide, and metal hydride compound used for the first thin film forming gas. , Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta , W, Tl, Pb, Bi, Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and the like.

  In the thin film forming method of the present invention, various high-functional thin films can be obtained by using a metal compound such as an organic metal compound, a halogen metal compound, or a metal hydrogen compound together with the first discharge gas. Although the example of the thin film of this invention is shown below, this invention is not limited to this.

Electrode film: Au, Al, Ag, Ti, Ti, Pt, Mo, Mo-Si
Dielectric protective film: SiO ₂ , SiO, Si ₃ N ₄ , Al ₂ O ₃ , Al ₂ O ₃ , Y ₂ O ₃
Transparent conductive film: In ₂ O ₃ , SnO ₂
Electrochromic film: WO ₃ , IrO ₂ , MoO ₃ , V ₂ O ₅
Fluorescent film: ZnS, ZnS + ZnSe, ZnS + CdS
Magnetic recording film: Fe—Ni, Fe—Si—Al, γ-Fe ₂ O ₃ , Co, Fe ₃ O ₄ , Cr, SiO ₂ , AlO ₃
Super conductive film: Nb, Nb-Ge, NbN
Solar cell film: a-Si, Si
Reflective film: Ag, Al, Au, Cu
Selective absorption membrane: ZrC-Zr
Selective permeable membrane: In ₂ O ₃ , SnO ₂
Antireflection film: SiO ₂ , TiO ₂ , SnO ₂
Shadow mask: Cr
Abrasion resistant film: Cr, Ta, Pt, TiC, TiN
Corrosion resistant film: Al, Zn, Cd, Ta, Ti, Cr
Heat-resistant film: W, Ta, Ti
Lubricating film: MoS ₂
Decorative film: Cr, Al, Ag, Au, TiC, Cu

  The nitridation degree of the nitride, the oxidation degree of the oxide, the sulfide degree of the sulfide, and the carbonization degree of the carbide are merely examples, and the composition ratio with the metal may be changed as appropriate. In addition to the metal compound, the thin film may contain impurities such as a carbon compound, a nitrogen compound, and a hydrogen compound.

  In the present invention, particularly preferred metals of the metal compound are Si (silicon), Ti (titanium), Sn (tin), Zn (zinc), In (indium), and Al (aluminum) among these metals. Of the metal compounds that bind to, the organometallic compounds represented by the general formula (I) are preferred. Examples of the organometallic compound will be described later.

Next, an antifouling film forming atmospheric pressure plasma discharge treatment apparatus 40 for forming the antifouling film 7 on the substrate 4 of the front plate 1 will be described with reference to FIG.
As shown in FIG. 6, the atmospheric pressure plasma discharge treatment apparatus 40 for forming an antifouling film has four plate electrodes 41, 42, 43, and 44, and the side portions of the plate electrodes 41 to 44 are square plate-like. The lids 47 and 47 are closed. The plate electrodes 42 and 43 are connected to the high frequency power supply 5, and the plate electrodes 41 and 44 are installed by a ground 46. In the atmospheric pressure plasma discharge treatment apparatus 40 for forming an antifouling film, the plate electrode 41 and the plate electrode 42 constitute a counter electrode, and the plate electrode 43 and the plate electrode 44 constitute a counter electrode.

  Each flat plate electrode 41 to 44 is composed of a metal base material and a dielectric, and a combination of coating the dielectric of inorganic properties by lining the metal base material, and after spraying ceramics to the metal base material, You may be comprised by the combination which coat | covers the dielectric material which carried out the sealing process by the substance of an inorganic property. As the metal base material, metals such as silver, platinum, stainless steel, aluminum, iron, titanium, copper, and gold can be used. Dielectric lining materials include silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass, etc. Of these, borate glass is preferable because it is easy to process. As the ceramic used for the thermal spraying of the dielectric, alumina is preferable, and it is preferable to perform a sealing treatment with silicon oxide or the like. As the sealing treatment, the alkoxysilane sealing material can be made inorganic by a sol-gel reaction.

  In the plate electrodes 41 and 42 constituting the counter electrode, it is sufficient that the metal base material of at least one plate electrode is covered with a dielectric. Similarly, in the flat electrodes 43 and 44 constituting the counter electrode, the metal base material of at least one flat electrode may be covered with a dielectric.

  In the atmospheric pressure plasma discharge processing apparatus 40 for forming an antifouling film, the high frequency power supply 45 applies a voltage between the flat plate electrodes 41 and 42 and between the flat plate electrodes 43 and 44. The high frequency power supply 45 is not particularly limited. As the high frequency power supply 45, a high frequency power supply (3 kHz) manufactured by Shinko Electric, a high frequency power supply (5 kHz) manufactured by Shinko Electric, a high frequency power supply manufactured by Shinko Electric (15 kHz), a high frequency power supply manufactured by Shinko Electric (50 kHz), a high frequency power supply manufactured by HEIDEN Laboratory (continuous) Mode use, 100 kHz), high frequency power supply from Pearl Industries (200 kHz), high frequency power supply from Pearl Industries (800 kHz), high frequency power supply from Pearl Industries (2 MHz), high frequency power supply from JEOL (13.56 MHz), high frequency power supply from Pearl Industries ( 27 MHz), a high frequency power source (150 MHz) manufactured by Pearl Industry, etc. can be used. Alternatively, a power source that oscillates at 433 MHz, 800 MHz, 1.3 GHz, 1.5 GHz, 1.9 GHz, 2.45 GHz, 5.2 GHz, or 10 GHz may be used.

When the antifouling film 7 is formed on the substrate 4, the frequency of the high frequency electric field applied between the flat plate electrodes 41 and 42 and between the flat plate electrodes 43 and 44 is not particularly limited, but is 0.5 kHz or more and 2.45 GHz. The following is preferred. The power supplied between the flat plate electrodes 41 and 42 and between the flat plate electrodes 43 and 44 is preferably 0.1 W / cm ² or more and 50 W / cm ² or less. The voltage application area (cm ² ) in the flat plate electrodes 41 and 42 and the flat plate electrodes 43 and 44 refers to the area where discharge occurs. The high-frequency voltage applied between the plate electrodes 41 and 42 and between the plate electrodes 43 and 44 may be an intermittent pulse wave or a continuous sine wave.

  The distance between the flat plate electrodes 41 and 42 and the distance between the flat plate electrodes 43 and 44 take into consideration the thickness of the dielectric on the metal base material of each flat plate electrode 41 to 44, the magnitude of the applied voltage, the purpose of using plasma, and the like. Determined. In the flat plate electrodes 41 and 42 and the flat plate electrodes 43 and 44, the shortest distance between the dielectric when the dielectric is installed on one of the flat electrodes and the dielectric between the dielectrics when the dielectric is installed on both of the flat electrodes The distance between the electrodes is preferably 0.1 mm to 20 mm, more preferably 0.2 to 10 mm from the viewpoint of performing uniform discharge in any case.

  As shown in FIG. 6, a conveyor belt 48 is provided below the flat plate electrodes 41 to 44. The conveyor belt 48 constitutes a part of the belt conveyor and conveys the substrate 4 so as to reciprocate in only one direction or both directions from the right side to the left side (or from the left side to the right side) in FIG. is there. In FIG. 6, the conveyor belt 48 is disposed so as to face each of the flat plate electrodes 41 to 44 with a predetermined distance from the lower end of each of the flat plate electrodes 41 to 44.

  In the atmospheric pressure plasma discharge treatment apparatus 40 for forming an antifouling film having such a configuration, when a voltage is applied from the high frequency power supply 45 between the plate electrodes 41 and 42 and between the plate electrodes 43 and 44, A discharge space is formed between the plate electrodes 43 and 44, and the second discharge gas G2 enters the discharge space from above between the plate electrodes 41 and 42 and between the plate electrodes 43 and 44. Is introduced, and the second discharge gas G2 is excited in the discharge space. Further, no discharge occurs between the flat plate electrodes 42 and 43, and a second thin film forming gas M2 containing an organometallic compound having an organic group having a fluorine atom is introduced here. In the atmospheric pressure plasma discharge treatment apparatus 40 for forming the antifouling film, the excited second discharge gas G2 and the second thin film forming gas M2 are brought into contact with each other at the outside of the discharge space 49 below the respective plate electrodes 41 to 44. The substrate 4 is exposed to the indirectly excited gas, and the antifouling film 7 is formed on the surface of the substrate 4.

Next, the “second discharge gas G2” supplied to the discharge space between the plate electrodes 41 and 42 and between the plate electrodes 43 and 44 will be described.
The second discharge gas G2 is a gas that can cause discharge. Examples of the second discharge gas G2 include nitrogen, rare gas, air, hydrogen, and oxygen, and these may be used alone or in combination. The amount of the second discharge gas G2 is preferably 70 to 100% by volume with respect to the total amount of gas supplied to the discharge space.

Next, the “second thin film forming gas M2” supplied between the flat plate electrodes 42 and 43 will be described.
The second thin film forming gas M <b> 2 is a gas that contains an organometallic compound having an organic group having a fluorine atom and is chemically deposited on the substrate 4 to form the antifouling film 7. As content of the organometallic compound which has the organic group which has the above-mentioned fluorine atom with respect to 2nd thin film formation gas M2, it is preferable that it is the range of 0.001-30.0 volume%.

  The second thin film forming gas M2 can contain nitrogen, a rare gas, or the like described as the second discharge gas G2. Note that the second thin film forming gas M2 may be used by mixing 0.001% to 30% by volume of auxiliary gas such as hydrogen gas, oxygen gas, nitrogen gas, and air.

  Here, the details of the organometallic compound having an organic group having a fluorine atom, contained in the second thin film forming gas M2, will be described.

  In the organometallic compound having an organic group having a fluorine atom, examples of the organic group having a fluorine atom include an organic group containing an alkyl group, an alkenyl group, an aryl group, etc. having a fluorine atom. The organometallic compound having an organic group having a fluorine atom is a compound in which the organic group having a fluorine atom is a metal atom, for example, silicon, titanium, germanium, zirconium, tin, aluminum, indium, antimony, yttrium, lanthanium, iron , An organometallic compound directly bonded to a metal such as neodymium, copper, gallium, and half-new. Of these metals, silicon, titanium, germanium, zirconium, tin and the like are preferable, and silicon and titanium are more preferable. These fluorine-containing organic groups 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 is fluorine. The position may be any as long as it has an organic group having.

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

In the general formula (1), 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 having a fluorine atom, for example, having a fluorine atom. An organic group containing an alkyl group, an alkenyl group or an aryl group is preferable. Examples of the alkyl group having a fluorine atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and 4,4. , 3, 3, 2, 2, 1, 1-octafluorobutyl group and the like, as the alkenyl group having a fluorine atom, for example, a group such as 3, 3, 3-trifluoro-1-propenyl group In addition, examples of the aryl group having 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 preferably at least one is bonded. . 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.

Of 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, and 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 alkyl groups, alkenyl groups, aryl groups, alkoxy groups, alkenyloxy groups, and aryloxy groups that are the monovalent groups, preferred are 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, the organic group having a fluorine atom or other groups represented by these R ₁ to R _6, and ^{is, R 1 R 2 R 3 M-} (M represents the metal atom, R ^1, R ² R ³ represents a monovalent group, and the monovalent group represents an organic group having the fluorine atom or a group other than the organic group having the fluorine atom exemplified as R _{1 to} R ₆ . A structure having a plurality of metal atoms further substituted by the group represented may be used. Examples of these metal atoms include Si and Ti, and examples thereof include a silyl group, an alkylsilyl group, and an alkoxysilyl group.

Wherein R ₁ alkyl group is a group having the recited fluorine atom in to R _6, an alkenyl group, or an alkoxy group formed from these, the alkyl group in the alkenyloxy group, the alkenyl group, hereinafter the general formula (F) The group represented by these is preferable.

Formula (F)
_{Rf-X- (CH 2) k} -
In the general formula (F), Rf represents an alkyl group or an alkenyl group in which at least one of hydrogen is substituted with a fluorine atom, and examples thereof include a trifluoromethyl group, a pentafluoroethyl group, a perfluorooctyl group, and a heptafluoropropyl group. Groups such as perfluoroalkyl groups, groups such as 3,3,3-trifluoropropyl groups, 4,4,3,3,2,2,1,1-octafluorobutyl groups, and 1 An alkenyl group substituted by a fluorine atom such as 1,1-trifluoro-2-chloropropenyl group is preferable, among which a trifluoromethyl group, a pentafluoroethyl group, a perfluorooctyl group, a heptafluoropropyl group, and the like And 3,3,3-trifluoropropyl group, 4,4,3,3,2,2,1,1-octafluorobutyl group Alkyl group having at least two or more fluorine atoms, such as Le group.

X is a simple bond or a divalent group. The divalent group is a group such as —O—, —S—, —NR— (R represents a hydrogen atom or an alkyl group), —CO—, and the like. , -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 substituents 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 (F Or a group represented by 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 linked to form a ring.

  Of the general formula (2), more preferred are compounds represented by the following general formula (3).

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

  In this embodiment, the other preferable example of the organometallic compound having a fluorine atom includes a compound represented by the following general formula (4).

In the general formula (4), R ₁ to R ₆ have the same meanings as R ₁ to R ₆ in the general formula (1). Also in this case, at least one of R _{1 to} R ₆ is an organic group having the fluorine atom, and a 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 150, 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 embodiment, there is an organometallic compound having 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 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 listed as the substituent for R _{1 to} R _{6 in} the general formula (1). May be substituted. Moreover, in General formula (5), it is m + n + p = 3, m is at least 1, n represents 0-2, p represents the integer of 0-2. It is preferable that m + p = 3, that is, n = 0.

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

General formula (6)
^{_{R f1 (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), R ^f1 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 An integer of ˜50, n1 is an integer of 0 to 3, p1 is an integer of 0 to 3, q1 is an integer of 1 to 6, and 6 ≧ n1 + p1> 0.

As for carbon number of the linear or branched perfluoroalkyl group which can be introduce ^| transduced into Rf1, 1-16 are more preferable, and 1-3 are the most preferable. Therefore, the _{^{R f1, -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 carbon such as a hydrogen atom or an alkyl group. 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.

  As for m1 in the said General formula (6), it is more preferable that it is 1-30, and it is still more preferable that it is 5-20. 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 embodiment, there is an organometallic compound having a fluorine atom represented by the following 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, Z is a fluorine atom or a trimethyl group. A fluoromethyl group, R ²¹ represents a hydrolyzable group, R ²² represents a hydrogen atom or an inert monovalent organic group, a, b, c and d are each an integer of 0 to 200, e is 0 or 1 , M and n are integers of 0 to 2, and p is 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, R ²⁵ is usually a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms such as an alkylidene group. More preferred are a chlorine atom, a CH ₃ O group, a C ₂ H ₅ O group, and a C ₃ H ₇ O group.

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 C ₃ F ₇ group, a is an integer of 1 to 50, b, c and d is 0 , E is 1, Z is a fluorine atom, and n is 0.

  In this embodiment, typical compounds of the organic metal compound having an organic group having fluorine and the compounds represented by the general formulas (1) to (7), which are preferably used as the silane compound having a fluorine atom, are listed below. However, the present embodiment is not limited to these compounds.

1: (CF ₃ CH ₂ CH ₂ ) ₄ Si
2: (CF ₃ CH ₂ CH ₂ ) ₂ (CH ₃ ) ₂ Si
_{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—O—CH 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 = 11~30),
_{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 _{Three
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 organometallic 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

  Each compound mentioned in these specific examples is Toray Dow Corning Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd., Daikin Industries Co., Ltd. (for example, OPTOOL DSX), and Gelest Inc. In addition to being easily marketed, for example, J.A. Fluorine Chem. 79 (1). 87 (1996), material technology, 16 (5), 209 (1998), Collect. Czech. Chem. Commun. 44, 750-755, J. MoI. Amer. Chem. Soc. 1990, 112, 2341-2348, Inorg. Chem. 10: 889-892, 1971, U.S. Pat. No. 3,668,233, etc., JP-A 58-122979, JP-A 7-242675, JP-A 9-61605, etc. 11-29585, JP-A No. 2000-64348, JP-A No. 2000-144097 and the like, or a synthesis method according to the synthesis method.

Next, a method for manufacturing the front plate 1 will be described.
First, a hard coat film 5 made of an inorganic hard coat agent, an organic hard coat agent, an organic / inorganic hybrid coat agent, or the like is formed on the substrate 4 using a known coating technique.

  When the hard coat film 5 is formed on the substrate 4, the antireflection film 6 is formed on the hard coat film 5 using the atmospheric pressure plasma discharge processing apparatus 10. The method of forming the antireflection film 6 on the substrate 4 together with the action of the atmospheric pressure plasma discharge treatment apparatus 10 will be described in detail. First, the substrate 4 with the hard coat film 5 is arranged and fixed on the stage electrode 11. The stage electrode 11 is reciprocated in the left-right direction in FIG. In synchronism with this, gas G is supplied from each gas supply port 14 to the discharge space 16 between the stage electrode 11 and each rectangular tube electrode 13 under atmospheric pressure or a pressure in the vicinity thereof, and the first power supply 17 A first high frequency electric field having a frequency ω1, an electric field strength V1, and a current I1 is applied to the discharge space 16 from a second power source 18 and a second high frequency electric field having a frequency ω2, an electric field strength V2, and a current I2 is applied from the second power source 18 to the discharge space 16.

At this time, the first high-frequency electric field and the second high-frequency electric field overlap each other. However, regarding these high-frequency electric fields, the frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field. The relationship between the electric field strength V1, the second high-frequency electric field strength V2, and the discharge start electric field strength IV satisfies V1 ≧ IV> V2 or V1> IV ≧ V2, and the second high-frequency electric field A high frequency electric field is applied to the discharge space 16 from the first power source 17 and the second power source 18 so that the output density is 1 W / cm ² or more.

  In this state, the gas G supplied to the discharge space 16 is excited, the substrate 4 on the stage electrode 11 is exposed to the excited gas G, and a thin film is formed on the hard coat film 5 of the substrate 4. It is formed.

  Here, the atmospheric pressure plasma discharge treatment apparatus 10 is configured to form a thin film on the substrate 4 by performing the above-described operation, and to form a single-layer antireflection film 6 having a desired refractive index, Alternatively, the antireflection film 6 in which a plurality of layers having different refractive indexes are laminated is formed by appropriately changing the material of the first thin film forming gas.

  The first thin film forming gas for forming the thin film is not limited as long as it is a compound capable of obtaining an appropriate refractive index, but a titanium compound is preferably used as the first thin film forming gas for forming the high refractive index layer. As the second thin film forming gas for forming the low refractive index layer, a silicon compound, a fluorine compound, or a mixture of a silicon compound and a fluorine compound can be preferably used. In order to adjust the refractive index of these compounds, a mixture of two or more kinds may be used as the first thin film forming gas for forming any layer.

  Examples of the titanium compound used in the first thin film forming gas for forming the high refractive index layer include an organic titanium compound, a titanium hydrogen compound, a titanium halide, etc. Examples of the organic titanium compound include triethoxy titanium and trimethoxy titanium. , Triisopropoxy titanium, tributoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, methyl dimethoxy titanium, ethyl triethoxy titanium, methyl triisopropoxy titanium, triethyl titanium, triisopropyl titanium, tributyl titanium, tetraethyl titanium, tetraisopropyl titanium , Tetrabutyltitanium, tetradimethylaminotitanium, dimethyltitanium di (2,4-pentanedionate), ethyltitanium tri (2,4-pentanedionate), titanium tris (2,4-pentanedioate) ), Titanium tris (acetmethyl acetate), triacetoxy titanium, dipropoxypropionyloxy titanium, etc., dibutylyloxy titanium, titanium hydrogen compound as monotitanium hydrogen compound, dititanium hydrogen compound, etc., as titanium halide, Examples thereof include trichlorotitanium and tetrachlorotitanium. Two or more of these first thin film forming gases can be mixed and used at the same time.

  Examples of the silicon compound used for the first thin film forming gas for forming the low refractive index layer include an organic silicon compound, a silicon hydrogen compound, a halogenated silicon compound, etc. Examples of the organic silicon compound include tetraethylsilane, Tetramethylsilane, tetraisopropylsilane, tetrabutylsilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethylsilanedi (2,4-pentanedionate), methyltrimethoxy Silane, methyltriethoxysilane, ethyltriethoxysilane, etc., silicon hydrogen compounds such as tetrahydrogenated silane, hexahydrogenated disilane, etc., and halogenated silicon compounds such as tetrachlorosilane, methyltrichlorosilane, diethyldichloromethane It can be mentioned silane. Moreover, the said fluorine compound can be used. Two or more of these first thin film forming gases can be mixed and used at the same time. In addition, two or more of these tin compounds, titanium compounds, and silicon compounds may be appropriately mixed and used for fine adjustment of the refractive index.

  The organotitanium compound or organosilicon compound is preferably a metal hydride compound or an alkoxy metal from the viewpoint of handling, and is preferably an alkoxy metal because it is not corrosive, does not generate harmful gases, and has little contamination in the process. It is done. Further, in order to introduce the above-mentioned organotin compound, organotitanium compound or organosilicon compound into the discharge space 16 (between the stage electrode 11 and each square tube electrode 13), both are at normal temperature and normal pressure, gas, liquid Any solid state may be used. In the case of gas, it can be introduced into the discharge space 16 as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, decompression or ultrasonic irradiation. When an organotin compound, an organotitanium compound or an organosilicon compound is vaporized by heating, a metal alkoxide such as tetraethoxy metal or tetraisopropoxy metal that is liquid at room temperature and has a boiling point of 200 ° C. or less is suitable for forming a thin film. Used for. The alkoxy metal may be used after being diluted with a solvent. In this case, the alkoxy metal may be vaporized into a rare gas by a vaporizer or the like and used as a mixed gas. As the solvent, organic solvents such as methanol, ethanol, isopropanol, butanol, n-hexane, and mixed solvents thereof can be used.

  From the viewpoint of forming a uniform thin film on the substrate 4 by discharge plasma treatment, the content of the first thin film forming gas in the total gas G is preferably 0.01 to 10% by volume, more preferably. Is 0.01 to 1% by volume.

  When the antireflection film 6 is formed on the substrate 4, the antifouling film 7 is formed on the antireflection film 6 using the atmospheric pressure plasma discharge treatment apparatus 40 for forming the antifouling film. The method of forming the antifouling film 7 on the substrate 4 together with the action of the antifouling film forming atmospheric pressure plasma discharge treatment apparatus 40 will be described in detail. First, the flat plate electrode 41 under atmospheric pressure or near atmospheric pressure. , 42 and the two discharge spaces between the flat plate electrodes 43 and 44, respectively, and a high frequency voltage is applied between the flat plate electrodes 41 and 42 and between the flat plate electrodes 43 and 44 by the high frequency power supply 45. Applied to excite the second discharge gas G2 present in the discharge space. At this time, no discharge occurs between the plate electrodes 42 and 43. The second discharge gas G2 excited in the discharge space is pressed by the second discharge gas G2 newly introduced into the discharge space, and discharged from the discharge space to the outside of the discharge space 49.

  In synchronization with this, the second thin film forming gas M2 is introduced between the flat plate electrodes 42 and 43. The introduced second thin film forming gas M2 is pressed by the newly introduced second thin film forming gas M2 as in the case of the second discharge gas G2, passes between the flat plate electrodes 42 and 43, and is discharged into the discharge space. Released to the outside 49.

  In the outside of the discharge space 49, the excited second discharge gas G2 and the second thin film forming gas M2 come into contact with each other to generate indirect excitation gas.

  In this state, the conveyance belt 48 is operated so that the base material 4 passes through the discharge space outside 49, and the base material 4 is exposed to the discharge space outside 49 where the indirectly excited gas exists. Thereby, the antifouling film 7 is formed on the surface of the substrate 4, and the front plate 1 is manufactured.

  In the present embodiment described above, the atmospheric pressure plasma discharge processing apparatus 10 exposes the base material 4 to the excited gas G under special discharge conditions to form the antireflection film 6 on the base material 4. Therefore, unlike the case where the antireflection film 6 is formed on the base material 4 by the coating technique or the vapor deposition technique, the front plate 1 has uneven coating and the film thickness of the antireflection film 6 is not uniform. There is no problem such as poor adhesion to the antireflection film 6, the film thickness of the antireflection film 6 is uniform, and the adhesion between the substrate 4 and the antireflection film 6 is excellent. Further, since the antifouling film 7 for preventing dirt is formed on the antireflection film 6 of the base material 4 by the atmospheric pressure plasma discharge treatment apparatus 40 for forming the antifouling film, the front plate 1 is antifouling such as water repellency. Excellent function (stain prevention function).

  In addition, in manufacture of the front plate 1 of the said embodiment, although the hard-coat film | membrane 5, the antireflection film 6, and the antifouling film | membrane 7 were formed only on one surface of the base material 4, it was manufactured by the manufacturing method similar to the above. The hard coat film 5, the antireflection film 6 and the antifouling film 7 may also be formed on the other surface of the substrate 4. Further, although the hard coat film 5 is formed on the base material 4 of the front plate 1 by a coating technique, the antireflection film 6 may be directly formed on the base material 4 without forming the hard coat film 5. Good.

  Further, in the above embodiment, the anti-reflection film 6 is formed on the substrate 4 by the atmospheric pressure plasma discharge treatment apparatus 10 shown in FIG. 2, but instead of the atmospheric pressure plasma discharge treatment apparatus 10 shown in FIG. The antireflection film 6 may be formed on the substrate 4 by the jet-type atmospheric pressure plasma discharge treatment apparatus 30 shown in FIG.

  Here, the jet type atmospheric pressure plasma discharge treatment apparatus 30 will be described with reference to FIG. However, in the following description of the atmospheric pressure plasma discharge processing apparatus 30, the components already described in the description of the atmospheric pressure plasma discharge processing apparatus 10 are denoted by the same reference numerals as those of the atmospheric pressure plasma discharge processing apparatus 10 and their configurations. Detailed descriptions of elements are omitted.

  As shown in FIG. 7, in the atmospheric pressure plasma discharge processing apparatus 30, the two rectangular tube electrodes 13 are arranged to face each other with a predetermined interval. A first power source 17 is connected to one square tube electrode 13 (first electrode), and a second power source 18 is connected to the other square tube electrode 13 (second electrode).

  A first filter 19 is installed between the one square tube electrode 13 and the first power supply 17. The first filter 19 facilitates the passage of current from the first power source 17 to the one of the rectangular tube-shaped electrodes 13, grounds the current from the second power source 18, and transfers from the second power source 18 to the first power source 17. It is designed to make it difficult for current to pass through.

  A second filter 20 is installed between the other rectangular tube electrode 13 and the second power source 18. The second filter 20 facilitates the passage of a current from the second power source 18 to the other rectangular tube electrode 13, grounds the current from the first power source 17, and the first power source 17 to the second power source 18 It is designed to make it difficult to pass current.

  In the atmospheric pressure plasma discharge processing apparatus 30, if the high-frequency voltage probes 31, 32 and the oscilloscopes 33, 34 are installed as shown in FIG. 6, the high-frequency electric field strengths V1, V2 (applied electric field strength) and the discharge start electric field strength Can be measured.

  In the case of forming a thin film on the substrate 4 by the atmospheric pressure plasma discharge treatment apparatus 30 having such a configuration, the gas G is supplied from the gas supply means (not shown) into the discharge space 35 between the square tube electrodes 13. Introducing, generating a discharge by applying a high-frequency electric field from each square tube electrode 13, while blowing the gas G to the lower side (the lower side of the paper surface) of each square tube electrode 13 in a plasma state, A processing space formed by the lower surface of each square tube electrode 13 and the base material 4 is filled with a plasma state gas G °, and the base material 4 is exposed to the plasma state gas G ° in the vicinity of the processing position 36 to form a thin film on the base material 4. To form. Also in this case, similarly to the above, a plurality of layers having different refractive indexes can be formed by forming a single-layer antireflection film 6 having a desired refractive index or by appropriately changing the material of the first thin film forming gas. An antireflection film 6 is formed by laminating layers.

  During the formation of the thin film, a medium passes from the electrode temperature adjusting means (not shown) through the pipe to heat or cool each square tube electrode 13. Depending on the temperature of the substrate 4 during the plasma discharge treatment, the properties, composition, etc. of the thin film to be obtained may change, and it is desirable to appropriately control this. As the temperature control medium, an insulating material such as distilled water or oil is preferably used. During the plasma discharge treatment, it is desired to uniformly adjust the temperature inside each square tube electrode 13 so that temperature unevenness of the base material 4 in the width direction or the longitudinal direction does not occur as much as possible.

  A plurality of jet type atmospheric pressure plasma discharge treatment devices 30 are arranged in series, and different thin film forming gases are jet-jetted from the respective atmospheric pressure plasma discharge treatment devices 30 to form the antireflection film 6. Also good.

[Production of electrodes]
A stage electrode and a rectangular tube electrode were prepared as follows. A hollow jacketed titanium alloy T64 stage electrode and square tube electrode were prepared as follows. High-density, high-adhesion alumina sprayed coatings were coated on the mutually facing surfaces of the stage electrode and the rectangular tube type electrode by the atmospheric plasma method. Thereafter, a solution obtained by diluting tetramethoxysilane with ethyl acetate was applied and dried, and then cured by ultraviolet irradiation to perform sealing treatment. The surface of the dielectric thus coated was polished and smoothed so that the Rmax was 5 μm. The final dielectric porosity was 5% by volume. At this time, the SiO _x content of the dielectric layer was 75 mol%. The final dielectric film thickness was 1 mm (thickness variation within ± 1%), and the relative dielectric constant of the dielectric was 10. Further, the difference in coefficient of linear thermal expansion between the conductive metallic base material and the dielectric was 1.6 × 10 ⁻⁶ / ° C., and the heat resistant temperature was 250 ° C.

[Atmospheric pressure plasma discharge treatment equipment]
Using the atmospheric pressure plasma discharge treatment apparatus shown in FIG. 2, the stage electrode and the rectangular tube electrode produced above are spaced apart so that the distance between the rectangular tube electrode and the surface of the substrate is 1 mm. The first electric field and the second electric field shown in Table 1 were installed to face each other in parallel. The power source A5 was used at a continuous mode of 100 kHz (the same applies to the following examples). Sample No. No. 16 used a DC pulse power source for the first electric field, and the ON / OFF repetition frequency was 10 kHz. Both electrodes were adjusted and kept at 65 ° C. In either case, a filter was installed so that the current from the stage electrode and the rectangular tube electrode did not flow backward.

[Preparation of titanium oxide thin film]
A mixed gas having the following composition was applied on a commercially available PMMA (polymethyl methacrylate) plate (substrate) having a thickness of 2 mm with a hard coat film, and the electric field shown in Table 1 was applied between the stage electrode and each square tube electrode. Then, discharge was performed to form a thin film, and Samples 1 to 16 were produced. In addition, the electric discharge start electric field strength in this system was 4.5 kV / mm.

<Mixed gas composition>
First discharge gas: nitrogen 97.9% by volume
First thin film forming gas: tetraisopropoxy titanium 0.1% by volume
Additive gas: 2.0% by volume of hydrogen

[Evaluation]
<Discharge state>
The discharge status was divided into the following ranks between the counter electrodes (between the stage electrode and the rectangular tube type electrode).
○: Stable discharge is occurring Δ: Discharge is occurring but somewhat unstable ×: No discharge occurs

<Refractive index>
The reflection spectra were measured for each sample 1 to 16 using a spectrophotometer U-4000 type (manufactured by Hitachi, Ltd.) under the condition of regular reflection at 5 degrees. In the measurement, the surface of the base material on which the thin film is not formed by the atmospheric pressure plasma discharge treatment is roughened, and then light absorption treatment is performed using a black spray to prevent reflection of light on the back surface of the base material. A reflection spectrum having a wavelength of ˜700 nm was measured, an optical film thickness was calculated from a λ / 4 value of the spectrum, and a refractive index was calculated based on the optical film thickness. The low refractive index means that the layer structure lacks the density and there are a large number of holes, and the phenomenon that air enters into the holes during measurement and the particles generated in the discharge space may be taken into the film. There is a bad film.

  Sample No. above. For 1 to 16, the discharge state was observed and the refractive index was measured, and the results are shown in Table 1.

(result)
Relationship between the frequency (ω1, ω2) of the first and second high-frequency electric fields applied from the first and second electrodes, the strength (V1, V2) of the first and second high-frequency electric fields, and the discharge of the first discharge gas The relationship between the strength of the starting electric field (IV) and the output density of the second high-frequency electric field is the sample No. About 1-10, the discharge condition was also favorable and the precise | minute thin film (it can judge by the magnitude | size of a refractive index) was formed. On the other hand, in the samples 11 to 16 of the high-frequency electric field other than the relationship of the present invention, the ability to form a thin film is insufficient even if the discharge is good, and a dense thin film with many holes cannot be obtained (refractive index). Is small), or discharge did not occur and a thin film could not be formed.

  Samples 17 to 23 were produced in the same manner as in Example 1 except that the first electric field and the second electric field shown in Table 2 were changed and the first filter and the second filter shown in Table 2 were installed.

  Sample No. The above evaluation was performed for 17 to 23, and the results are shown in Table 2.

(result)
Samples 17 to 20 in which a filter was installed as shown in Table 2 and a thin film was formed using an atmospheric pressure plasma discharge treatment apparatus were normally discharged, and the thin film was also formed normally. On the other hand, in sample 21, since the combination of the filters was not appropriate for the frequencies of the first electric field and the second electric field, no discharge occurred and a thin film could not be formed. Samples 22 and 23 are normal atmospheric discharge plasma thin film forming apparatuses, in which the counter electrode is an application electrode and a ground electrode (no filter is used). In sample 22, a higher frequency is applied to the application electrode than is normally used. Although it was applied from the power source, it was not discharged and a thin film could not be formed. In Sample 23, the applied power source was applied using a lower frequency one, but although it was discharged, a good thin film could not be formed. It was.

  A commercially available PMMA plate with a hard coat film having a thickness of 2 mm was used as the substrate, and an atmospheric pressure plasma discharge treatment apparatus similar to that shown in FIG. 2 was used as the apparatus. A base material was placed on the stage electrode to form an antireflection film. Specifically, the stage electrode is reciprocated to form a high refractive index layer on the hard coat film, and then a low refractive index layer is laminated on the high refractive index layer. A high refractive index layer is laminated on the refractive index layer, and then a low refractive index layer is laminated on the high refractive index layer to form a substrate / hard coat layer / high refractive index layer / A front plate (sample Nos. 24-27) with an antireflection film of low refractive index layer / high refractive index layer / low refractive index layer was produced.

[Preparation of front plate with antireflection film]
During plasma discharge, the stage electrode and each square tube electrode were adjusted and kept at 65 ° C., and a thin film was formed as follows. The first electric field and the second electric field in the film formation of each layer were the same as those shown in Table 3. The pressure is 103 kPa, the following mixed gas is introduced into each discharge space and the plasma discharge vessel, and a high refractive index layer, a low refractive index layer, a high refractive index layer on the hard coat film of the PMMA base material, A plasma discharge thin film was formed in the order of the low refractive index layer, and a four-layered front plate with an antireflection film was prepared.

<< High refractive index layer mixed gas composition >>
First discharge gas: nitrogen 99.4% by volume
First thin film forming gas: tetraisopropoxy titanium 0.1% by volume
(Vaporized by mixing with argon gas using a vaporizer manufactured by Lintec)
Additive gas: 0.5% by volume of oxygen gas
<< High refractive index layer conditions >>
Output density: Stage electrode side 1 W / cm ²
: Square tube type electrode side 5W / cm ²

<< Low refractive index layer mixed gas composition >>
First discharge gas: 98.9% by volume of nitrogen
First thin film forming gas: tetraethoxysilane 0.1% by volume
(Vaporized by mixing with argon gas using a vaporizer manufactured by Lintec)
Additive gas: 1% by volume of oxygen gas
<< Low refractive index layer conditions >>
Output density: Stage electrode side 1 W / cm ²
: Square tube electrode side 3W / cm ²

(Preparation of antireflection film by vacuum deposition)
As the vacuum deposition apparatus, a continuous vacuum deposition apparatus provided with a preheating chamber, a first deposition chamber, and a second deposition chamber independently was used. The PMMA base material is mounted on a support, put into a preheating chamber, heated in a vacuum atmosphere for a predetermined time, and then brought into a first vapor deposition chamber that is already in a vacuum state without being exposed to the outside air by a transfer device provided inside. Then, an antireflection film was formed in the first vapor deposition chamber as follows.

First, a PMMA substrate heated to a temperature suitable for this deposition is vacuum-deposited by a vacuum deposition method (vacuum degree 2 × 10 ⁻⁵ Torr), and an ion beam assist method of irradiating the PMMA substrate with an oxygen ion beam. 4 layers of anti-reflective coating with a layer made of titanium, a layer made of silicon dioxide by the vacuum evaporation method, a layer made of titanium dioxide by the ion beam assist method, and a layer made of silicon dioxide by the vacuum evaporation method A face plate was prepared and used as Sample 28.

(Preparation of antireflection film by coating)
As described below, a high refractive index layer, a low refractive index layer, a high refractive index layer, and a low refractive index layer were applied in this order to prepare a front plate with an antireflection film. A method for manufacturing each layer is described below.

<< Preparation of high refractive index layer >>
On the PMMA substrate, the following high refractive index layer composition H-1 was applied with an extrusion coater, dried at 70 ° C. for 7 minutes, and then irradiated with ultraviolet light at 175 mJ / cm using a high-pressure mercury lamp (80 W). ² Irradiated and cured to provide a high refractive index layer.

<High refractive index layer composition H-1>
Isopropyl alcohol 445 parts by weight Water 1.5 parts by weight Propylene glycol monomethyl ether 223 parts by weight Methyl ethyl ketone 73 parts by weight Tetra (n) butoxytitanium 545 parts by weight γ-methacryloxypropyltrimethoxysilane (KBM503, Shin-Etsu Chemical Co., Ltd.) 0.8 parts by weight Part 10% silicone oil (KF-96-1,000C manufactured by Shin-Etsu Chemical Co., Ltd.)
S, solvent: methyl ethyl ketone) 1.4 parts by mass

<< Production of low refractive index layer >>
On the high refractive index layer, the following low refractive index layer composition L-1 was applied by an extrusion coater, dried at 60 ° C. for 7 minutes, further thermally cured at 70 ° C. for 15 minutes, and further irradiated with ultraviolet rays. A low refractive index layer was provided by curing by irradiation with 175 mJ / cm ² .

<Preparation of tetraethoxysilane hydrolyzate A>
580 g of tetraethoxysilane and 1144 g of ethanol are mixed, and after adding an aqueous citric acid solution (5.4 g of citric acid monohydrate dissolved in 272 g of water), the mixture is stirred at room temperature (25 ° C.) for 1 hour. Thus, a tetraethoxysilane hydrolyzate was prepared.

(Low refractive index layer composition L-1)
Propylene glycol monomethyl ether 303 parts by mass Isopropyl alcohol 305 parts by mass Tetraethoxysilane hydrolyzate A 139 parts by mass γ-methacryloxypropyltrimethoxysilane (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.) 1.6 parts by mass 10% FZ-2207, propylene glycol Monomethyl ether solution (Nippon Unicar) 1.3 parts by mass

<< Preparation of high refractive index layer >>
The high refractive index layer composition H-1 is applied onto the low refractive index layer by an extrusion coater, dried at 70 ° C. for 7 minutes, and then irradiated with ultraviolet rays at 175 mJ / high using a high pressure mercury lamp (80 W). A high refractive index layer was provided by curing by irradiating cm ² .

<< Production of low refractive index layer >>
On the high refractive index layer, the low refractive index layer composition L-1 is applied by an extrusion coater, dried at 60 ° C. for 7 minutes, further thermally cured at 70 ° C. for 15 minutes, and further irradiated with ultraviolet rays. A low refractive index layer was provided by curing by irradiation with 175 mJ / cm ² .

  As a result, a four-layer antireflection front plate was prepared and used as Sample 29.

For samples 24-29, the discharge state was evaluated in the same manner as in Example 1,
And the following evaluation was performed and the result was shown in Table 3.

[Evaluation]
(Total light transmittance)
The total transmitted light amount with respect to the incident light amount of visible light was measured according to ASTM D-1003.

<Spectral reflectance>
Using a spectrophotometer U-4000 type (manufactured by Hitachi, Ltd.), the reflectance was measured under the condition of regular reflection at 5 degrees. For measurement, after roughening the surface of the front plate with antireflection film without the antireflection film, light absorption treatment is performed using black spray to prevent reflection of light on the back side of the front plate with antireflection. , A reflection spectrum having a wavelength of 400 to 700 nm was measured, and a spectral reflectance was obtained for a wavelength within the range.
◎: Less than 2% over 400 to 700 nm ○: Over 2% to less than 5% over 400 to 700 nm Δ: 5% or more X: Measurement is impossible due to insufficient film formation

(Adhesion of antireflection film)
According to JIS K-5400, the number of peels per 100 grids provided on the antireflection film was measured by a grid tape method.
○: No peeling Δ: 1-90th peeling ×: 91-100th peeling

(Appearance of front plate with antireflection film)
Light absorption treatment is performed using black spray to prevent reflection of light on the back surface of the front plate with the antireflection film, and the illuminance of external light is set to 300 lux (lx). The presence or absence was evaluated visually.

(result)
As the front plate with the antireflection film (samples 24 and 25) formed by alternately laminating four layers of the high refractive index layer and the low refractive index layer, those having the spectral reflectance as the target were obtained. In addition, the discharge state in all apparatuses was normal. On the other hand, the sample 26 to which an electric field was applied by a method other than the present invention was in a discharged state, but the spectral reflectance was inferior to that of the present invention. Sample 27 was not discharged and a thin film was not obtained. Sample 28 produced by vapor deposition had some color unevenness, and the adhesion of the antireflection film to the substrate was poor. Color unevenness was confirmed in the sample 29 produced by coating.

[Preparation of Sample 30]
(Atmospheric pressure plasma discharge treatment equipment for antifouling film formation)
An antifouling film was formed on the antireflection film of the sample 25 produced in Example 3 using the atmospheric pressure plasma discharge treatment apparatus for forming an antifouling film shown in FIG. The following gas type A was introduced as the second discharge gas between the flat plate electrodes forming the discharge space, and the following gas type B was introduced as the second thin film forming gas between the flat plate electrodes not forming the discharge space.

<Gas type A: second discharge gas>
Argon gas 98.5% by volume
Hydrogen gas 1.5% by volume
<Gas type B: second thin film forming gas>
Argon gas 99.8% by volume
Organometallic compound (CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ) 0.2% by volume
(Vaporization of organometallic compounds in argon gas by a vaporizer manufactured by Estec)

<electrode>
Stainless steel SUS316 is used as the plate electrode, and further, the surface of the plate electrode constituting the discharge space is spray-coated with alumina ceramic until the thickness becomes 1 mm, and then a coating solution in which the alkoxysilane monomer is dissolved in an organic solvent is used. It was applied to the coating and dried, and then heated at 150 ° C. for sealing treatment to form a dielectric. A portion of the plate electrode not covered with the dielectric was connected to a high-frequency power source or grounded with an earth. The gap between the second discharge gas (excited second discharge gas) and the second thin film forming gas discharge port (below each plate electrode) and the substrate was 10 mm.

<High frequency power supply>
As a high-frequency power source, a high-frequency power source (frequency: 13.56 MHz) manufactured by Pearl Industry was used, and a discharge power of 5 W / cm ² was applied between the plate electrodes.

<Formation of antifouling film>
The second discharge gas (gas species A) is excited in the discharge space, and the excited second discharge gas and the second thin film forming gas (gas species B) are brought into contact with each other in a region outside the discharge space to form an indirect excitation gas. The material was exposed to an indirect excitation gas, and an antifouling film was formed on the antireflection film of the substrate to obtain a sample 30. At this time, the substrate was moved in a direction perpendicular to the emission angle of the second thin film forming gas. This movement was performed by scanning in the horizontal direction in FIG. The ratio of the amount of use of gas type B and gas type A was 1: 1 by volume ratio.

[Preparation of Sample 31]
CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ was diluted with isopropyl alcohol on the antireflection film of Sample 25 prepared in Example 3 so that the average dry film thickness was 10 nm. The coating solution was applied by bar coating so that the wet film thickness was 15 μm, and after drying, heat treatment was performed at 70 ° C. for 8 hours to prepare a comparative sample 31.

[Preparation of Sample 32]
In preparation of the sample 30, 6-fluorinated propylene was used in place of CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ used as the raw material for the gas type B. A comparative sample 32 was prepared in the same manner as the sample 30 except for the above.

[Preparation of Sample 33]
In preparation of the sample 30, methyltriethoxysilane was used in place of CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ used as the raw material for the gas type B. A comparative sample 33 was prepared in the same manner as the sample 30 except for the above.

[Preparation of Sample 34]
In the preparation of the sample 30, a high-frequency power source manufactured by Shinko Electric Co., Ltd. (50 kHz) is used as a high-frequency power source using the atmospheric pressure plasma discharge processing apparatus of FIG. A voltage of 5 W / cm ² was applied to the first electric field, and the gas type A and gas type B were mixed before being exposed to the discharge space, and then gas was supplied. A comparative sample 34 was prepared in the same manner as the sample 30 except for the above.

[Measurement and Evaluation of Characteristic Values of Samples 30 to 34]
(Measurement of contact angle)
About each sample 30-34, the contact angle with respect to the water of the antifouling film | membrane surface was measured in 23 degreeC and 55% environment using Kyowa Interface Science company contact angle meter CA-W. In addition, the measurement was performed at 10 locations at random and the average value was obtained.

(Evaluation of wiping resistance)
The chamois was immersed in water at 25 ° C. for 5 minutes and taken out into the air, and the surface of each sample 30 to 34 (surface on which the antifouling film was formed) was rubbed 500 times with the chamois. A 500 g load was applied to the chamois skin. Then, the contact angle with respect to the water of the surface of each sample 30-34 was measured by the method similar to the measurement of the said contact angle.

(Evaluation of fingerprint adhesion)
As an evaluation of the surface contamination of each sample 30-34, after each sample 30-34 was conditioned for 2 hours at 25 ° C. and a relative humidity of 60%, a fingerprint was attached to the surface of each sample 30-34, The state when it was wiped off with a cleaning cloth was observed. Moreover, the state when the adhesion and the wiping off of the fingerprint were repeated 20 times was observed. Evaluation of fingerprint adhesion in each sample 30 to 34 was performed according to the following criteria.
◎: Fingerprints can be completely wiped by lightly wiping ○: Fingerprints can be completely wiped △: Fingerprints remain a little ×: Fingerprints can hardly be wiped off

(Appearance evaluation)
Each sample 30 to 34 was visually observed to see if there was any interference color variation or interference color change (observed whether each sample 30 to 34 had an appearance that could be used as a front plate).

  Table 4 shows the results obtained as described above.

  As is clear from Table 4, sample 30 in which an antifouling film was formed using an organometallic compound having an organic group having a fluorine atom as a raw material for the second thin film forming gas was compared with comparative samples 31-34. It can be seen that it is excellent in water repellency and fingerprint wiping property. In particular, it can also be seen that the sample 30 continues to maintain the antifouling function and is excellent in durability even though the attachment of the fingerprint and the wiping off of the sample 30 were repeated 20 times.

It is sectional drawing which shows schematically the screen structure of a display apparatus. It is sectional drawing which shows schematic structure of an atmospheric pressure plasma discharge processing apparatus. It is a perspective view which shows the arrangement | positioning relationship between a stage electrode and each square tube type electrode. It is a perspective view which shows a stage electrode. It is a perspective view which shows a rectangular tube type electrode. It is a perspective view which shows schematic structure of the atmospheric pressure plasma discharge processing apparatus for antifouling film formation. It is sectional drawing which shows the modification of the atmospheric pressure plasma discharge processing apparatus of FIG.

Explanation of symbols

1 Front plate (front plate for display)
2 Lenticular lens 3 Fresnel lens 4 Base material 5 Hard coat film 6 Antireflection film 7 Antifouling film 10, 30 Atmospheric pressure plasma discharge treatment device 11 Stage electrode (first electrode)
12 Plasma discharge vessel 13 Square tube electrode (second electrode)
14 Gas supply port 15 Mesh 16 Discharge space 17 1st power supply 18 2nd power supply 19 1st filter 20 2nd filter 40 Atmospheric pressure plasma discharge processing apparatus for antifouling film formation

Claims (16)

A gas containing the first thin film forming gas is supplied to the discharge space under atmospheric pressure or a pressure in the vicinity thereof, and the gas is excited by applying a high-frequency electric field to the discharge space, and the substrate is applied to the excited gas. A method for producing a front plate for a display, wherein an antireflection film is formed on at least one surface of the base material by exposing the substrate to the substrate.
The high-frequency electric field is a superposition of the first high-frequency electric field and the second high-frequency electric field, and the frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, and the first high-frequency electric field is And the second high frequency electric field strength V2 and the discharge start electric field strength IV satisfy V1 ≧ IV> V2 or V1> IV ≧ V2, and the output density of the second high frequency electric field is Is 1 W / cm ² or more, A method for producing a display front plate. The method for manufacturing a display front plate according to claim 1, wherein the discharge space includes a first electrode and a second electrode facing each other. The method for producing a display front plate according to claim 1 or 2, wherein an output density of the second high-frequency electric field is 50 W / cm ² or less. The method for producing a display front plate according to claim 3, wherein the output density of the second high-frequency electric field is 20 W / cm ² or less. 5. The method for manufacturing a display front plate according to claim 1, wherein an output density of the first high-frequency electric field is 1 W / cm ² or more. 6. The method for manufacturing a display front plate according to claim 5, wherein an output density of the first high-frequency electric field is 50 W / cm < ² > or less. The method for manufacturing a display front plate according to any one of claims 1 to 6, wherein the first high-frequency electric field and the second high-frequency electric field are sine waves. 8. The display device according to claim 2, wherein the first high-frequency electric field is applied to the first electrode, and the second high-frequency electric field is applied to the second electrode. Manufacturing method of face plate. The method for manufacturing a front plate for a display according to any one of claims 1 to 8, wherein 90 to 99.9% by volume of the total gas supplied to the discharge space is the first discharge gas. . The method for manufacturing a display front plate according to claim 9, wherein the first discharge gas contains 50 to 100% by volume of nitrogen gas. The method for manufacturing a display front plate according to claim 9 or 10, wherein the first discharge gas contains a rare gas of less than 50% by volume. The display front plate according to claim 1, wherein the first thin film forming gas contains at least one selected from an organometallic compound, a metal halide, and a metal hydride. Manufacturing method . The organic metal compound contains at least one compound selected from an organosilicon compound, an organotitanium compound, an organotin compound, an organozinc compound, an organoindium compound, and an organoaluminum compound. Manufacturing method of front plate for display. The method of manufacturing a front plate for a display according to any one of claims 1 to 13, wherein the base material has a thickness of 1 mm or more. On the antireflection film, the display front plate according to any one of claims 1 to 14, characterized in that to form the antifouling film containing an organometallic compound having an organic group having a fluorine atom Manufacturing method . A second thin film containing the excited second discharge gas and an organometallic compound having an organic group having a fluorine atom is introduced into the discharge space and excited under atmospheric pressure or a pressure in the vicinity thereof. and formation gas are contacted outside the discharge space and indirect excitation gas, by exposing the substrate to the indirect excitation gas, characterized by forming the antifouling film on the antireflection film of the base material The method for producing a display front plate according to claim 15.

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