JP2013155399A - Antifouling coated substrate, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifouling coated substrate which has a fluorine-containing organic silicon compound coating, the coating having, in addition to excellent antifouling property such as water repellency, excellent abrasion resistance such that deterioration of the antifouling property due to repeated wiping operation or the like is suppressed, and a method for producing the same.SOLUTION: The antifouling coated substrate 1 includes: a transparent substrate 2, a silicon oxide film 3 formed on a main surface of the transparent substrate 2 in an atmosphere with introduction of steam by means of sputtering, and a fluorine-containing organic silicon compound coating 4 formed on the surface of the silicon oxide film 3. The steam partial pressure of the atmosphere is preferably 0.007 Pa or more.

Description

  The present invention relates to a substrate with an antifouling film and a method for producing the same.

  Touch panels used in smartphones, tablet PCs, and the like are easily touched by human fingers during use, and thus are easily contaminated with fingerprints, sebum, sweat, and the like. These stains are difficult to remove when attached, and they are conspicuous depending on the amount of light, etc., and there is a problem that visibility and aesthetics are impaired. Furthermore, similar problems have been pointed out in display glasses, optical elements, sanitary equipment, and the like.

  In order to solve such a problem, there is known a method of using a substrate in which an antifouling film made of a fluorine-containing organosilicon compound is formed on a part touched by a human finger of these parts and devices. The antifouling film formed on the substrate is required to have high water repellency and oil repellency in order to suppress the adhesion of dirt, and also to be resistant to wiping off the adhered dirt.

  In order to improve the abrasion resistance of the antifouling film having water and oil repellency, for example, Patent Document 1 discloses that a silicon-containing target is sputtered on the surface of a glass substrate in a oxygen-containing atmosphere. There has been proposed an article with an antifouling film in which a base layer is formed and an antifouling film made of a fluorine-containing organosilicon compound is formed thereon.

  Here, Patent Document 1 shows that the durability of the antifouling film is increased by forming a silica underlayer having a thickness of about 210 mm (20 nm) by magnetic sputtering deposition using a silicon alloy cathode. ing. However, it cannot be said that the article of Patent Document 1 sufficiently satisfies the wear resistance required in actual use, and a product having an antifouling film with improved wear resistance is required.

Japanese Patent Laid-Open No. 5-237871

  The present invention has an antifouling film having a fluorine-containing organosilicon compound coating that is excellent in antifouling properties such as water repellency and excellent in abrasion resistance in which deterioration of the antifouling property is suppressed against repeated wiping operations, etc. An object of the present invention is to provide a substrate and a method for manufacturing the same.

  The substrate with an antifouling film of the present invention has a transparent substrate, a silicon oxide film formed on the main surface of the transparent substrate, and a fluorine-containing organosilicon compound film formed on the surface of the silicon oxide film, The silicon oxide film is a film formed by sputtering in an atmosphere into which water vapor is introduced.

The method for producing a substrate with an antifouling film according to the present invention is a method for producing a substrate with an antifouling film in which a fluorine-containing organosilicon compound film is formed on the main surface of a transparent substrate via a silicon oxide film, 1. A method for producing a substrate with an antifouling film, comprising the steps 1) and (2).
(1) A step of forming the silicon oxide film on the main surface of the transparent substrate by a sputtering method in an atmosphere in which water vapor is introduced.
(2) A step of forming the fluorine-containing organosilicon compound film on the surface of the silicon oxide film formed in the step (1).

  According to the present invention, an antifouling film having a fluorine-containing organosilicon compound coating excellent in antifouling properties such as water repellency and excellent in abrasion resistance in which a decrease in antifouling properties is suppressed with respect to repeated wiping operations, etc. An attached substrate and a method for manufacturing the same can be provided.

It is sectional drawing which shows one Embodiment of a base | substrate with an antifouling film of this invention. It is a typical sectional view showing an example of a water vapor introduction device used for formation of a silicon oxide film by sputtering. It is a figure which shows an example of the formation method of the silicon oxide film by sputtering. It is typical sectional drawing which shows an example of a continuous film-forming apparatus. It is a graph which shows the result of a rubbing durability (wear resistance) test.

  Hereinafter, modes for carrying out the present invention will be described. The present invention is not limited to the following embodiment. Various modifications and substitutions can be made to the following embodiments without departing from the scope of the present invention.

[Substrate with antifouling film]
The substrate with an antifouling film according to the embodiment of the present invention includes a transparent substrate, a silicon oxide film formed on the main surface of the transparent substrate by a sputtering method in an atmosphere in which water vapor is introduced, and a surface of the silicon oxide film. And a formed fluorine-containing organosilicon compound film.

  The fluorine-containing organic silicon compound film is formed, for example, by a hydrolytic condensation reaction of a fluorine-containing hydrolyzable silicon compound described later on the surface of the silicon oxide film as follows. It functions as an antifouling film by having oiliness. In the present specification, the fluorine-containing hydrolyzable silicon compound has a hydrolyzable group or a hydrolyzable silyl group having an atom bonded to the silicon atom, and further has a fluorine-containing organic group bonded to the silicon atom. Refers to a compound. The hydrolyzable group or atom constituting the hydrolyzable silyl group bonded to the silicon atom is collectively referred to as “hydrolyzable group”.

  That is, the hydrolyzable silyl group of the fluorine-containing hydrolyzable silicon compound is converted into a silanol group by hydrolysis, and these are dehydrated and condensed between molecules to form a siloxane bond represented by -Si-O-Si-. By doing so, a fluorine-containing organosilicon compound film is formed. In the resulting coating, most of the fluorine-containing organic groups bonded to the silicon atom of the siloxane bond are present near the surface of the coating on the side opposite to the transparent substrate. Due to the action of the fluorine-containing organic groups, water repellency and oil repellency are obtained. Expression is possible. Moreover, the silanol group produced | generated above chemically bonds with the hydroxyl group of the silicon oxide film surface which is a film-forming surface in which this film is formed by dehydration condensation reaction, and forms the point adhere | attached through the siloxane bond.

  In a substrate with an antifouling film having a fluorine-containing organic silicon compound film formed on the surface of the silicon oxide film through such a process, the silicon oxide film and the fluorine-containing organic silicon are increased by increasing the hydroxyl group density on the surface of the silicon oxide film. It is considered that a substrate with an antifouling film having high abrasion resistance that can withstand repeated wiping operations and the like is obtained with improved adhesion to the compound film.

  In the present invention, the antifouling obtained by providing a silicon oxide film formed by sputtering in an atmosphere into which water vapor is introduced as a base film on the main surface of the transparent substrate on which the fluorine-containing organic silicon compound film is formed. The abrasion resistance of the film-coated substrate is raised to a high level. Although the detailed mechanism is not clear, in the present invention, the hydroxyl group density on the surface of the formed silicon oxide film is increased by sputtering in an atmosphere into which water vapor is introduced, and the silicon oxide film and the fluorine-containing organosilicon compound film are formed. It is considered that the wear resistance of the fluorine-containing organosilicon compound coating is improved by increasing the adhesiveness of. The increase in the density of hydroxyl groups on the surface of the silicon oxide film is considered to be caused by the generation of new hydroxyl groups due to the presence of water molecules.

  FIG. 1 is a cross-sectional view showing an embodiment of a substrate with an antifouling film of the present invention. The substrate 1 with an antifouling film of the embodiment includes a transparent substrate 2, a silicon oxide film 3 formed on the main surface of the transparent substrate 1, and a fluorine-containing organosilicon compound film formed on the surface of the silicon oxide film 3. 4. Here, the silicon oxide film 3 is formed by sputtering in an atmosphere into which water vapor is introduced. Sputtering in an atmosphere in which water vapor is introduced may be referred to as water vapor introducing sputtering treatment. Hereinafter, each element which comprises the base | substrate 1 with an antifouling film of embodiment is demonstrated.

<Transparent substrate>
The transparent substrate 2 is not particularly limited as long as it is made of a transparent material that is generally required to impart antifouling property by an antifouling film, and is composed of glass, resin, or a combination thereof (composite material, laminated layer). Those made of materials, etc.) are preferably used. Examples of the glass include ordinary soda lime silicate glass, aluminosilicate glass, borosilicate glass, alkali-free glass, and quartz glass. Examples of the resin include acrylic resins such as polymethyl methacrylate, aromatic polycarbonate resins such as bisphenol A carbonate, and aromatic polyester resins such as polyethylene terephthalate.

  As the transparent substrate 2, it is preferable to use a soda lime silicate glass plate from the viewpoint of adhesion to the silicon oxide film 3 provided on the main surface thereof. From the viewpoint of strength, it is preferable to use a tempered glass plate (for example, manufactured by Asahi Glass Co., Ltd., trade name: Dragon Trail) reinforced with an aluminosilicate glass plate. Further, when a film made of the resin is used as the transparent substrate 2, it is preferable to use a polyethylene terephthalate film.

  The shape of the transparent substrate 2 may be a flat plate shape, or the entire surface or a part thereof may have a curvature. The thickness of the transparent substrate 2 can be appropriately selected according to the use of the substrate 1 with the antifouling film, but is generally preferably 0.5 to 10 mm.

  As the transparent substrate 2 used in the present invention, depending on the purpose, acid treatment (treatment using diluted hydrofluoric acid, sulfuric acid, hydrochloric acid, etc.), alkali treatment (treatment using aqueous sodium hydroxide, etc.), Alternatively, those subjected to ultrasonic cleaning or the like with ultrapure water or an organic solvent may be used.

  When the transparent substrate 2 is a soda lime silicate glass plate, it is preferable in terms of durability to provide a film that prevents Na ions from eluting. Further, in the case where the transparent substrate 1 is a glass plate manufactured by a float process, it is possible to provide a fluorine-containing organosilicon compound coating 4 on a top surface with a small amount of surface tin via a silicon oxide film 3 described later. This is preferable.

<Silicon oxide film>
In the substrate 1 with an antifouling film of the present invention, the silicon oxide film 3 provided on the main surface of the transparent substrate 2 is a film formed by sputtering in an atmosphere into which water vapor is introduced. The atmosphere when forming the silicon oxide film 3 of the present invention by sputtering is an atmosphere in which water vapor is positively introduced from the outside (hereinafter also referred to as a water vapor introduction atmosphere), and is not simply an atmosphere containing moisture. . In general, a sufficiently evacuated vacuum vessel contains moisture that cannot be removed even by evacuation. The moisture pressure in such an atmosphere is the water vapor partial pressure (0. 007 Pa or higher). Even if the silicon oxide film 3 is formed by performing sputtering in such an atmosphere, a sufficiently high wear resistance cannot be obtained.

(Water vapor introduction atmosphere)
The atmosphere for introducing water vapor when forming the silicon oxide film 3 in the present invention is an atmosphere having a partial pressure of water vapor of 0.007 Pa or more. As described above, when sputtering is performed in an atmosphere where the partial pressure of water vapor is less than 0.007 Pa, the substrate 1 with the antifouling film having sufficiently high wear resistance cannot be obtained. The partial pressure of water vapor is preferably 0.1 Pa or less from the viewpoint of film formation stability of a composition having a fluorine-containing hydrolyzable silicon compound described later.

  Such a water vapor introducing atmosphere is created using a water vapor introducing device. FIG. 2 is a schematic cross-sectional view showing an example of a water vapor introducing apparatus used for the water vapor introducing sputtering process. The water vapor introduction atmosphere can be obtained by supplying and introducing water vapor into the vacuum vessel (film formation tank) in which the sputtering process is performed by the water vapor introduction device 10.

  The water vapor introducing device 10 is provided in the middle of the heating vessel 11 into which water, preferably pure water is placed, the piping 12 connecting the heating vessel 11 and a vacuum vessel (film formation tank) (not shown), and the piping 12. A variable valve 13 for controlling the amount of steam supplied to the vacuum vessel that is not to be provided, and a supply portion 14 that is provided at the tip of the pipe 12 and provided in the vacuum vessel. The heating container 11 is provided with a heater 15 for heating and evaporating water, preferably pure water, contained therein.

  With such a water vapor introducing device 10, water in the heating container 11, preferably pure water, is evaporated, and water vapor is supplied into the vacuum container through the pipe 12. Thereby, the atmosphere in a vacuum vessel can be made into the atmosphere containing a water | moisture content (water vapor | steam). Sputtering, which will be described later, is carried out in the vacuum vessel in which the atmosphere contains water vapor in this way, and the silicon oxide film 3 is formed.

  The water vapor introducing device 10 is preferably one in which the partial pressure of water vapor in the vacuum vessel is 0.007 Pa or more. The adjustment of the partial pressure of water vapor in the vacuum vessel is, for example, adjusting the amount of water vapor supplied into the vacuum vessel by a variable valve 13 provided in the middle of the pipe 12 connecting the heating vessel 11 and the vacuum vessel. Or by adjusting the amount of water vapor by adjusting the temperature of the water in the heating container 11, preferably pure water, with the heater 15.

  When adjusting the partial pressure of water vapor by adjusting the temperature of water in the heating vessel 11, preferably pure water, the partial pressure of water vapor in the vacuum vessel is 0.007 Pa or more by adjusting the temperature of the water to 45 ° C. or higher. Can be. Moreover, the partial pressure of water vapor | steam can be 0.01 Pa or more by making temperature of water etc. into 60 degreeC or more. Usually, a temperature of about 45 ° C is sufficient for water, etc.

(Sputtering)
The silicon oxide film 3 in the present invention is a film formed by performing sputtering in a vacuum vessel into which water vapor has been introduced by the water vapor introducing device 10 described above.

  As sputtering, a DC (direct current) sputtering method, an AC (alternating current) sputtering method, an RF (high frequency) sputtering method, or the like can be used. Among these, the DC magnetron sputtering method or the AC sputtering method has a stable process, is easy to operate because it uses a DC power source or an AC power source with a simple device structure, and is advantageous in terms of film thickness control. It is a membrane method. Moreover, since it is easy to form a film over a large area, it is preferably used. The DC magnetron sputtering method includes a method of applying a voltage in the form of a pulse wave. Such a pulsed DC magnetron sputtering method is effective in preventing abnormal discharge. Further, when an insulating material such as quartz (silicon dioxide) is used as a target, an RF sputtering method is used. A suitable combination of the target material and the sputtering method will be described later.

  As a target in sputtering, a target mainly containing silicon (Si) or silicon oxide is used. It is desirable that the target containing silicon (Si) as a main component has a certain degree of conductivity so that DC sputtering can be performed. Therefore, as a target having silicon (Si) as a main component, a target made of polycrystalline silicon, or a known dopant such as phosphorus (P), boron (B) or the like in single crystal silicon is within a range that does not impair the characteristics of the present invention. It is preferable to use a material doped with. Such a target made of polycrystalline silicon and a target obtained by doping single crystal silicon with phosphorus (P), boron (B) or the like can be used in any of DC sputtering, AC sputtering, and RF sputtering. it can.

  Examples of the target mainly composed of silicon oxide include those made of quartz (silicon dioxide). Such a target mainly composed of silicon oxide is used for the RF sputtering method.

When using a target mainly composed of silicon (Si) such as polycrystalline silicon, it is necessary to use a reactive gas containing oxygen as a gas other than the water vapor introduced in sputtering (hereinafter referred to as a sputtering gas). For example, only oxygen, a mixed gas of oxygen and an inert gas, or the like can be used. Examples of the inert gas include noble gases such as helium (He), neon (Ne), and argon (Ar). Further, an oxidizing gas other than oxygen may be added as a component of the mixed gas. The oxidizing gas means an oxygen atom-containing gas. For example, nitrous oxide (N ₂ O) or nitric oxide (NO) can be added to the mixed gas. As the reactive sputtering gas containing oxygen, it is preferable to use a mixed gas of oxygen and Ar in terms of easy control of the gas composition, economy, and ease of discharge.

  When a silicon oxide film 3 is formed by RF sputtering using a target made of quartz (silicon dioxide), only an inert gas (for example, Ar) can be used as a sputtering gas. In such a case as well, a reactive gas such as the above-mentioned mixed gas of oxygen and Ar can be used as the sputtering gas.

  In the mixed gas of oxygen and Ar used as the sputtering gas, the oxygen concentration is not particularly limited, but is preferably 20 to 100% by volume. The partial pressure of the sputtering gas is not particularly limited as long as it is a pressure at which glow discharge is stably performed. The total pressure of the deposition gas, which is the sum of the partial pressure of the sputtering gas and the partial pressure of the water vapor, is preferably 0.7 Pa or less. When the total pressure of the film forming gas is 0.7 Pa or less, high wear resistance can be obtained as the substrate 10 with the antifouling film in a wider range of the film thickness of the silicon oxide film 3.

Target power density (applied power divided by the area of the target value) is preferably from 0.1 to 10 / cm ^2, and more preferably 0.5~7W / cm ^2. When the power density is less than 0.1 W / cm ² , the discharge is not stable. If the power density exceeds 10 W / cm ² , the target may be broken by the generated heat. Furthermore, the temperature of the transparent substrate 1 during sputtering is preferably room temperature (25 ° C.) to 400 ° C. The film formation time may be determined according to the film formation rate and the desired film thickness.

  A desired silicon oxide film 3 can be formed by performing sputtering in an atmosphere into which water vapor is introduced. The thickness of the silicon oxide film 3 is preferably 4 nm or more and 100 nm or less, and more preferably 5 nm or more and 20 nm or less. By making the thickness of the silicon oxide film 3 in the range of 4 nm or more and 100 nm or less, the adhesion between the silicon oxide film 3 and the fluorine-containing organosilicon compound coating 4 formed on the surface thereof is further improved, and high resistance to resistance is achieved. Abrasion can be obtained. The thickness of the silicon oxide film 3 is a thickness obtained by measurement with a stylus type surface roughness measuring machine (hereinafter also referred to as a stylus type step gauge).

  An example of a method for forming the silicon oxide film 3 by the above-described water vapor introduction sputtering treatment is shown in FIG. As shown in this figure, the water vapor introducing device 10 and the sputtering device 30 are arranged close to each other in a film forming tank 20 which is a vacuum vessel. Further, a sputtering gas supply mechanism 21 that supplies the sputtering gas into the film forming tank 20 is disposed in the vicinity of the sputtering apparatus 30. Then, the sputtering gas is supplied into the film forming tank 20 by the sputtering gas supply mechanism 21, the water vapor is introduced by the water vapor introducing device 10, and the sputtering is performed in an atmosphere containing the water vapor.

  The sputtering apparatus 30 includes a target 31, a sputter electrode 32 that holds the target 31, a power source (for example, an AC power source) 33 that supplies power to the sputter electrode 32, and a transformer that adjusts the amount of power from the power source 33. Power control means (not shown). The target 31 is a flat plate made of a material such as silicon dioxide or polycrystalline silicon, and is held by the sputtering electrode 32 so as to face the main surface of the transparent substrate 2 on which the silicon oxide film is to be formed. . The sputter electrode 32 is connected to a power source 33 through power control means.

  The sputter gas supply mechanism 21 has a sputter gas supply pipe 22 as a supply path for the sputter gas S, and the front end opening of the sputter gas supply pipe 22 is disposed so as to be close to the target 31. The sputtering gas supply mechanism 21 has a mass flow controller (not shown) provided in the middle of the sputtering gas supply pipe 22 outside the film formation tank 20. The mass flow controller is a device that adjusts the flow rate of the sputtering gas, for example, an inlet for the sputtering gas to flow in, an outlet for flowing the sputtering gas to the piping, and a sensor for detecting the mass flow rate of the gas flowing from the inlet. And a control valve for adjusting the flow rate of the gas, and an electronic circuit for controlling the control valve based on the flow rate detected by the sensor. In the electronic circuit, a desired flow rate can be set from the outside.

  Sputtering gas S is supplied from the sputtering gas supply mechanism 21 to the sputtering region in the film forming tank 20, and water vapor is introduced by the water vapor introducing device 10 so that the periphery of the target 31 contains water vapor at a predetermined partial pressure. When an alternating voltage is applied to the sputtering electrode 32 from a power source 33 such as an AC power source in a gas atmosphere, a part of the sputtering gas around the target 31 emits electrons and is ionized. For example, since a leakage magnetic field is formed on the surface of the target 31 by the magnet disposed on the sputter electrode 32, the emitted electrons circulate in the magnetic field generated near the surface of the target 31. A strong plasma is generated along the trajectory of the electrons, and ions of the sputtering gas are accelerated toward the plasma and collide with the target 31, whereby atoms and particles on the surface of the target 31 (for example, the target 31 is polycrystalline). In the case of silicon, Si atoms and Si particles) are knocked out. The struck Si atoms and Si particles react with an oxidizing gas component (for example, oxygen) in the sputtering gas and adhere to the surface of the transparent substrate 2 to form a thin silicon oxide film 3. The transparent substrate 2 is preferably grounded as shown in FIG.

<Fluorine-containing organosilicon compound coating>
In the substrate 1 with the antifouling film according to the embodiment of the present invention, a method for forming the fluorine-containing organosilicon compound coating 4 includes a fluoroalkyl such as a perfluoroalkyl group; a fluoroalkyl group containing a perfluoro (polyoxyalkylene) chain. A method of applying a heat treatment after applying a composition of a silane coupling agent having a group to the surface of the silicon oxide film 3 by a spin coating method, a dip coating method, a casting method, a slit coating method, a spray coating method, or the like; Examples thereof include a vacuum vapor deposition method in which a fluorine organic silicon compound is vapor-deposited on the silicon oxide film 3 and then heat-treated. In order to obtain a fluorine-containing organosilicon compound film having high adhesion, it is preferably formed by a vacuum deposition method. The formation of the fluorine-containing organosilicon compound film 4 by a vacuum deposition method is preferably performed using a film-forming composition containing a fluorine-containing hydrolyzable silicon compound.

  The film forming composition is not particularly limited as long as it is a composition containing a fluorine-containing hydrolyzable silicon compound and can form a film by a vacuum deposition method. The film-forming composition may contain an optional component other than the fluorine-containing hydrolyzable silicon compound, or may be composed of only the fluorine-containing hydrolyzable silicon compound. Examples of the optional component include a hydrolyzable silicon compound having no fluorine atom (hereinafter referred to as “non-fluorine water-decomposable silicon compound”), a catalyst, and the like, which are used within a range not impairing the effects of the present invention.

  In addition, when blending the fluorine-containing hydrolyzable silicon compound and optionally the non-fluorine hydrolyzable silicon compound into the film forming composition, each compound may be blended as it is, and its partial hydrolysis condensation It may be blended as a product. Moreover, you may mix | blend with the composition for film formation as a mixture of this compound and its partial hydrolysis-condensation product.

  When two or more hydrolyzable silicon compounds are used in combination, each compound may be blended as it is in the film-forming composition, or each may be blended as a partially hydrolyzed condensate. Moreover, it may be further blended as a partially hydrolyzed cocondensate of two or more compounds. Moreover, the mixture of these compounds, a partial hydrolysis condensate, and a partial hydrolysis cocondensate may be sufficient. However, the partially hydrolyzed condensate and partially hydrolyzed cocondensate used should have a degree of polymerization that allows vacuum deposition. Hereinafter, the term of a hydrolyzable silicon compound is used in the meaning including such a partial hydrolysis condensate and a partial hydrolysis cocondensate in addition to the compound itself.

(Fluorine-containing hydrolyzable silicon compound)
The fluorine-containing hydrolyzable silicon compound used for forming the fluorine-containing organic silicon compound film 4 of the present invention is such that the resulting fluorine-containing organic silicon compound film 4 has antifouling properties such as water repellency and oil repellency. There is no particular limitation.

  Specific examples include fluorine-containing hydrolyzable silicon compounds having one or more groups selected from the group consisting of perfluoropolyether groups, perfluoroalkylene groups, and perfluoroalkyl groups. These groups exist as a fluorine-containing organic group bonded directly to the silicon atom of the hydrolyzable silyl group via a linking group. The perfluoropolyether group refers to a divalent group having a structure in which perfluoroalkylene groups and etheric oxygen atoms are alternately bonded. In addition, it is preferable that the number average molecular weights (Mn) of the fluorine-containing hydrolyzable silicon compound in this invention are 2000-10000, and it is more preferable that it is 3000-5000. When the number average molecular weight (Mn) is within the above range, the antifouling performance is sufficiently exhibited and a film having excellent wear resistance can be obtained. In addition, the number average molecular weight (Mn) in this specification means what was measured by the gel permeation chromatograph.

  As described above, the fluorine-containing organic silicon compound coating obtained by reacting the fluorine-containing hydrolyzable silicon compound on the surface of the silicon oxide film 3 formed on the transparent substrate 1 contains the fluorine-containing organic group. By being present in the vicinity of the surface of the fluorine organic silicon compound film on the silicon oxide film 3 side, it becomes a film having antifouling properties such as water repellency and oil repellency. Specific examples of the fluorine-containing hydrolyzable silicon compound having these groups include compounds represented by the following general formulas (I) to (V). In the present specification, the compound represented by the general formula (I) is sometimes referred to as the compound (I). The same applies to compounds represented by other general formulas.

In formula (I), R ^f1 is a linear perfluoroalkyl group having 1 to 16 carbon atoms (eg, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group). , R ¹ is a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.), and X ¹ is a hydrolyzable group (for example, Amino group, alkoxy group, acyloxy group, alkenyloxy group, isocyanate group, etc.) or halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), m is 1-50, preferably 1-30. An integer, n is 0 to 2, preferably 1 or 2, and p is 1 to 10, preferably 1 to 8.

In the compound (I), R ^f1 preferably has 1 to 4 carbon atoms. R ¹ is preferably a methyl group. The hydrolyzable group represented by X ^1, preferably an alkoxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group are more preferable.

_{C q F 2q + 1 CH 2} CH 2 Si (NH 2) 3 ... (II)
In formula (II), q is 1 or more, preferably an integer of 2 to 20.
Examples of the compound represented by the general formula (II) include n-trifluoro (1,1,2,2-tetrahydro) propylsilazane (n-CF ₃ CH ₂ CH ₂ Si (NH ₂ ) ₃ ), n-heptafluoro. (1,1,2,2-tetrahydro) Penchirushirazan _{(n-C 3 F 7 CH} 2 CH 2 Si (NH 2) 3) or the like can be exemplified.

C _r F _{2r + 1} CH ₂ CH ₂ Si (OCH ₃ ) ₃ (III)
In formula (III), r is 1 or more, preferably an integer of 1-20.
Examples of the compound represented by the general formula (III), 2- (perfluorooctyl) ethyltrimethoxysilane _{(n-C 8 F 17 CH} 2 CH 2 Si (OCH 3) 3) or the like can be exemplified.

Wherein ^{(IV), R} f2 _{is, - (OC 3 F 6)} s - (OC 2 F 4) t - is a (s, t, u are each independently 0 to 200 integer - _(OCF 2) u R ² and R ³ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, n -Propyl group, isopropyl group, n-butyl group and the like. X ² and X ³ are independently hydrolyzable groups (for example, amino group, alkoxy group, acyloxy group, alkenyloxy group, isocyanate group, etc.) or halogen atoms (for example, fluorine atom, chlorine atom, bromine atom, iodine atom) D and e are independently an integer of 1 to 2, c and f are independently an integer of 1 to 5 (preferably 1 to 2), and a and b are independently 2 or 3 is there.

In R ^f2 of the compound (IV), s + t + u is preferably 20 to 300, and more preferably 25 to 100. R ² and R ³ are preferably a methyl group, an ethyl group, or a butyl group. As a hydrolysable group shown by X < ² >, X < ³ >, a C1-C6 alkoxy group is preferable and a methoxy group and an ethoxy group are more preferable. Further, a and b are each preferably 3.

_{F- (CF 2) v - (} OC 3 F 6) w - (OC 2 F 4) y - (OCF 2) z (CH 2) h O (CH 2) i Si (X 4) 3-k (R ⁴ ) _k ......... (V)
In the formula (V), v is an integer of 1 to 3, w, y and z are each independently an integer of 0 to 200, h is 1 or 2, and i is an integer of 2 to 20. , X ⁴ is a hydrolyzable group, R ⁴ is a linear or branched hydrocarbon group having 1 to 22 carbon atoms, and k is an integer of 0 to 2. w + y + z is preferably 20 to 300, and more preferably 25 to 100. Further, i is preferably 2 to 10. X ⁴ is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably a methoxy group or an ethoxy group. R ⁴ is preferably an alkyl group having 1 to 10 carbon atoms.

  In addition, as a fluorine-containing organic silicon compound (fluorine-containing hydrolyzable silicon compound) having one or more groups selected from the group consisting of a commercially available perfluoropolyether group, perfluoroalkylene group and perfluoroalkyl group, KP-801 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), X-71 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY-130 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY178 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) Co., Ltd.), Optur (registered trademark) DSX (trade name, manufactured by Daikin Industries, Ltd.) and the like can be preferably used.

  In addition, about the fluorine-containing hydrolyzable silicon compound of a commercial item, when this is supplied with a solvent, a solvent is removed and used. The film-forming composition used in the present invention is prepared by mixing the above-mentioned fluorine-containing hydrolyzable silicon compound and optional components added as necessary, and is subjected to vacuum deposition.

  A film-forming composition containing such a fluorine-containing hydrolyzable silicon compound is deposited on the surface of the silicon oxide film 3 formed on the transparent substrate 1 and reacted to form a film, whereby a fluorine-containing organic silicon compound is formed. A coating 4 is obtained. As specific vacuum deposition methods and reaction conditions, conventionally known methods and conditions can be applied. For example, the substrate 1 with an antifouling film can be produced by forming such a fluorine-containing organosilicon compound film 4 by the production method described below.

  The film thickness of the fluorine-containing organic silicon compound film 4 is preferably 50 nm or less from the viewpoint of appearance and cost, and the lower limit is the thickness of the monomolecular layer. The film thickness of the fluorine-containing organosilicon compound film 4 is more preferably 2 to 30 nm, and particularly preferably 5 to 20 nm.

<Method for producing substrate with antifouling film>
In the manufacturing method of the substrate 1 with an antifouling film according to the embodiment of the present invention, the substrate 1 with an antifouling film in which the fluorine-containing organosilicon compound coating 4 is formed on the main surface of the transparent substrate 2 via the silicon oxide film 3. And (1) a step of forming the silicon oxide film 3 and (2) a step of forming the fluorine-containing organosilicon compound coating 4 in this order. (1) The process of forming the silicon oxide film 3 is a process of forming the silicon oxide film 3 on the main surface of the transparent substrate 2 by a sputtering method in an atmosphere in which water vapor is introduced. In addition, (2) the step of forming the fluorine-containing organic silicon compound film is performed by vapor-depositing a composition containing a fluorine-containing hydrolyzable silicon compound on the surface of the silicon oxide film 3 formed in the step (1). In this step, the fluorine-containing organosilicon compound coating 4 is formed.

  According to such a manufacturing method, the fluorine-containing organosilicon compound coating 4 is formed on the transparent substrate 1 with high adhesion via the silicon oxide film 3. It is possible to achieve both antifouling properties such as water repellency and oil repellency and a high level of wear resistance.

  FIG. 4 is a cross-sectional view schematically showing a continuous film forming apparatus that can be used in an embodiment of the method for manufacturing the substrate 1 with the antifouling film. Hereinafter, each step will be described with reference to FIG. When the continuous film forming apparatus 40 shown in FIG. 4 is used, the transparent substrate 2 is transferred from the left side to the right side of the drawing by the transfer means 41, and includes a front chamber 42, a vacuum chamber 43 that is a continuous film forming tank, and a substrate take-out chamber. 44 and passing through the vacuum chamber 43 through the formation process of the silicon oxide film 3 by sputtering in a steam-introducing atmosphere and the formation process of the fluorine-containing organosilicon compound film 4 by vapor deposition in order. 1

  In the continuous film forming apparatus 40, a silicon oxide film forming unit including a water vapor introducing apparatus 10 and a sputtering apparatus 30 and a vacuum vapor deposition apparatus 50 are sequentially provided in the vacuum chamber 43 from the front chamber 42 side. ing.

  Before being introduced into the vacuum chamber 43, the transparent substrate 2 is transported to a front chamber 42 that is connected to the vacuum chamber 43 and configured to be independently capable of supplying and exhausting air. After the transparent substrate 2 is transported, the front chamber 42 is sealed and evacuated, and then the door (not shown) between the front chamber 42 and the vacuum chamber 43 is opened to transport the transparent substrate 2 to the vacuum chamber 43. . In the vacuum chamber 43, a silicon oxide film forming unit including a water vapor introducing device 10 and a sputtering device 30 is provided on the front chamber 42 side, and subsequently a vapor deposition device for forming a fluorine-containing organosilicon compound film 50 is provided.

  Further, in order to take out the transparent substrate 2 (substrate 1 with antifouling film) after deposition from the vacuum chamber 43 while maintaining the vacuum state, the side opposite to the side connected to the front chamber 42 of the vacuum chamber 43 is supplied independently. It is connected to a substrate take-out chamber 44 configured to be evacuated. When the substrate 1 with the antifouling film after vapor deposition is transported from the vacuum chamber 43 to the substrate take-out chamber 44, the substrate take-out chamber 44 is brought into a vacuum state. Thereafter, when taking out the substrate 1 with the antifouling film after deposition from the substrate take-out chamber 44, the door (not shown) between the substrate take-out chamber 44 and the vacuum chamber 43 is closed, and the vacuum in the vacuum chamber 43 is thereby closed. State is preserved.

  From the viewpoint of production stability, the pressure in the vacuum chamber 43 is preferably maintained at 1 Pa or less, and more preferably 0.1 Pa or less.

  The configuration of the silicon oxide film forming portion including the water vapor introducing apparatus 10 and the sputtering apparatus 30 and the method for forming the silicon oxide film in the water vapor introducing atmosphere are as described above. The transport speed of the transparent substrate 2 is not particularly limited. The higher the transport speed of the transparent substrate 2 is, the better from the viewpoint of productivity, but it is limited from the time required for making the front chamber 42 vacuum.

  In the step of forming the fluorine-containing organic silicon compound film 4 by vapor deposition, a composition containing a fluorine-containing hydrolyzable silicon compound on the surface of the silicon oxide film 3 formed on the transparent substrate 2 in the silicon oxide film forming portion. Vapor deposits and reacts. In addition, the composition containing a fluorine-containing hydrolyzable silicon compound is called a film forming composition as described above.

  The method for attaching the film-forming composition to the surface of the silicon oxide film is not particularly limited as long as it is a method usually used for forming a layer of a fluorine-containing hydrolyzable silicon compound. Examples thereof include a CVD method and a sputtering method. The vacuum deposition method is preferable from the viewpoint of suppressing the decomposition of the fluorine-containing hydrolyzable silicon compound to be used and the simplicity of the apparatus.

  In particular, when a film-forming composition is deposited immediately after the silicon oxide film forming step in the same vacuum chamber 43 using the continuous film forming apparatus 40 as shown in FIG. Is preferred.

  The vacuum deposition method can be subdivided into resistance heating method, electron beam heating method, high frequency induction heating method, reactive deposition, molecular beam epitaxy method, hot wall deposition method, ion plating method, cluster ion beam method, etc. However, either method can be applied. The resistance heating method can be suitably used from the viewpoint of suppressing the decomposition of the fluorine-containing hydrolyzable silicon compound to be used and the simplicity of the apparatus. The vacuum deposition apparatus is not particularly limited, and a known apparatus can be used. Hereinafter, a method for depositing the film-forming composition on the surface of the silicon oxide film using the vacuum deposition method, particularly the resistance heating method, in the vacuum chamber 43 shown in FIG. 4 will be described.

  As described above, the pressure in the vacuum chamber 43 is preferably maintained at 0.7 Pa or less, and more preferably 0.2 Pa or less. If it is this pressure, the vacuum evaporation by a resistance heating method can be performed without a problem.

  The vacuum deposition apparatus 50 is provided on the substrate take-out chamber 44 side in the vacuum chamber 43. It should be noted that the position of the transparent substrate 2 on which the steam-introducing sputtering process is performed and the position of the transparent substrate 2 on which the fluorine-containing hydrolyzable silicon compound is deposited by the vacuum deposition apparatus 50 are not affected by each other. Specifically, it is preferable that the distance is 20 mm or more, and it is more preferable to perform the treatment in a separate vacuum chamber.

  The vacuum deposition apparatus 50 supplies a raw material heating container 51 that heats the film-forming composition outside the vacuum chamber 43 and a raw material vapor such as a fluorine-containing hydrolyzable silicon compound from the raw material heating container 51 into the vacuum chamber 43. A raw material vapor pipe 52 and a manifold 53 having an injection port for injecting the raw material vapor connected to the raw material vapor pipe 52 and supplied from the raw material heating vessel 51 onto the surface of the silicon oxide film 3 of the transparent substrate 2 are provided. In the vacuum chamber 43, the transparent substrate 2 is held so that the injection port of the manifold 53 and the surface of the silicon oxide film 3 that is the film formation surface of the transparent substrate 2 face each other.

  The raw material heating container 51 has a heating means that can heat the film forming composition as a vapor deposition source to a temperature at which it has a sufficient vapor pressure. Although it depends on the type of the film-forming composition, the heating temperature is specifically preferably from 30 ° C to 400 ° C, particularly preferably from 50 ° C to 300 ° C. When the heating temperature is equal to or higher than the lower limit of the above range, the film formation rate is good. When the amount is not more than the upper limit of the above range, a film having antifouling properties can be formed on the surface of the silicon oxide film 3 without causing decomposition of the fluorine-containing hydrolyzable silicon compound.

  Here, at the time of vacuum deposition, after the temperature of the film-forming composition containing the fluorine-containing hydrolyzable silicon compound in the raw material heating vessel 51 is raised to the deposition start temperature, the vapor is heated for a predetermined time. It is preferable to perform a pretreatment for discharging outside. By this pretreatment, it is possible to remove low molecular weight components that normally affect the durability of the resulting coating, which are normally contained in fluorine-containing hydrolyzable silicon compounds, and to stabilize the composition of the raw material vapor supplied from the evaporation source Is possible. This makes it possible to stably form the highly durable fluorine-containing organosilicon compound coating 4.

  Specifically, on the upper part of the raw material heating vessel 51, a pipe (not shown) connected to an openable / closable exhaust port for discharging the initial steam out of the system separately from the raw material steam pipe 52 connected to the manifold 53. It is sufficient to use a method such as trapping outside the system.

  Moreover, it is preferable that the temperature of the transparent base | substrate 2 at the time of vacuum deposition is the range from room temperature (20-25 degreeC) to 200 degreeC. When the temperature of the transparent substrate 2 is 200 ° C. or lower, the film formation rate is good. The upper limit of the temperature of the transparent substrate 2 is more preferably 150 ° C, and particularly preferably 100 ° C.

  The manifold 53 is preferably provided with a heater so that the raw material vapor supplied from the raw material heating vessel 51 can be condensed in order to prevent condensation. About the raw material vapor | steam piping 52, in order to prevent the raw material vapor | steam from the raw material heating vessel 51 condensing in the middle, it is preferable to design so that it may be heated with the raw material heating vessel 51.

  Further, in order to control the film forming speed, a variable valve 54 is provided on the raw material vapor pipe 52, and the opening degree of the variable valve 54 is based on a value detected by a film thickness meter 55 provided in the vacuum chamber 43. Is preferably controlled. By providing such a configuration, it becomes possible to control the amount of vapor of the composition containing the fluorine-containing hydrolyzable silicon compound supplied to the surface of the silicon oxide film 3 of the transparent substrate 2. Thereby, the fluorine-containing organosilicon compound coating 4 having a target thickness can be accurately formed on the surface of the silicon oxide film 3 of the transparent substrate 2. As the film thickness meter 55, a crystal resonator monitor or the like can be used. Furthermore, the measurement of the film thickness is, for example, when an X-ray diffractometer ATX-G for thin film analysis (manufactured by RIGAKU) is used as the film thickness meter 55, the interference pattern of reflected X-rays by the X-ray reflectivity method. And can be calculated from the vibration period of the interference pattern.

  In this way, the film-forming composition containing the fluorine-containing hydrolyzable silicon compound is attached to the surface of the silicon oxide film 3. Further, at the same time or after the adhesion, the fluorine-containing hydrolyzable silicon compound undergoes a hydrolytic condensation reaction to chemically bond to the surface of the silicon oxide film 3 in which the density of hydroxyl groups is increased by sputtering in the water vapor introduction atmosphere, By forming a siloxane bond between the molecules, the fluorine-containing organosilicon compound coating 4 is obtained.

  The hydrolytic condensation reaction of the fluorine-containing hydrolyzable silicon compound proceeds on the surface of the silicon oxide film 3 at the same time as the adhesion. Further, in order to further accelerate the reaction, the fluorine-containing organic silicon compound film is formed as necessary. After the transparent substrate 2 having 4 formed thereon is taken out from the vacuum chamber 43, a heat treatment using a hot plate or a constant temperature and humidity chamber may be performed. Examples of the heat treatment conditions include a heat treatment at a temperature of 80 to 200 ° C. for 10 to 60 minutes.

  The substrate 1 with an antifouling film obtained by such a production method is excellent in antifouling properties such as water repellency and oil repellency, and has high wear resistance that can withstand repeated wiping operations. This is because the hydrolyzable silyl group of the fluorine-containing hydrolyzable silicon compound reacts with the hydroxyl group on the silicon oxide film 3 formed by performing sputtering in a water vapor introduction atmosphere and having an increased hydroxyl group density on the surface. Thus, it is considered that the adhesion between the silicon oxide film 3 and the fluorine-containing organosilicon compound coating 4 is improved.

  Specific examples will be described below, but the present invention is not limited to these examples. Examples 1-2 are examples, and examples 3-4 are comparative examples.

  Using a continuous film forming apparatus 40 as shown in FIG. 4, that is, an apparatus capable of continuously forming a silicon oxide film by sputtering and a fluorine-containing organosilicon compound film by vacuum deposition in a vacuum chamber 43, The silicon oxide film 3 and the fluorine-containing organosilicon compound coating 4 were formed in this order on the transparent substrate 2 by the following procedure, and the substrate 1 with the antifouling film of Examples 1 to 4 was obtained. Next, the antifouling film-coated substrate 1 was evaluated by performing a water-repellent abrasion resistance test.

(Equipment, constituent materials and raw materials for antifouling-coated substrates)
As a continuous film forming apparatus 40, a vertical in-line film forming apparatus (device name: SDP-850VT (manufactured by ULVAC)) having a front chamber 42, a vacuum chamber 43, a substrate take-out chamber 44, and a transfer means 41 for transferring the transparent substrate 2 is used. Was used. In the vacuum chamber 43 of the continuous film forming apparatus 40, the water vapor introducing device 10, the sputtering device 30, and the vacuum vapor deposition device 50 are provided in this order from the front chamber 42 side.

  As shown in FIG. 2, the water vapor introducing device 10 is provided in a stainless steel heating container 11, a pipe 12 connecting the heating container 11 and the vacuum chamber 43, and disposed in the vacuum chamber 43 at the tip of the pipe 12. It is assumed that the supply unit 14 and the heater 15 disposed in the heating container 11 are provided. The size of the heating container 11 is 70 mm in diameter × 120 mm in height, and the opening of the supply unit 14 is a shape in which holes of 1 mm in diameter are drilled at a pitch of 30 mm in a pipe of length 800 mm, and the supply unit 14 and the transparent substrate 1 are closest The distance was 70 mm, and pure water was put into the heating container 11.

  The sputtering apparatus 30 has a target 31 (manufactured by ULVAC, length 600 mm × width 126 mm × thickness) made of polycrystalline silicon, connected to a cathode (sputter electrode 32) connected with an AC power source (manufactured by Huchinga: TruPlasma 3020) as a power source 33. (12 mm in length). A vertical deposition source (manufactured by Hitachi Zosen Corporation) was used for the vacuum deposition apparatus 50.

  As the transparent substrate 2, a square soda lime glass substrate having a thickness of 1.1 mm and a side length of 100 mm, Dragonrail (trade name: manufactured by Asahi Glass Co., Ltd.) was used. Before applying to the continuous film forming apparatus 40, the transparent substrate 2 is washed with an alkaline detergent, Sunwash TL 2% solution (trade name, manufactured by Lion Corporation), followed by ultrasonic cleaning with ultrapure water. Carried out.

  The composition for forming the fluorine-containing organic silicon compound film 4 includes OPTOOL (registered trademark) DSX (trade name, manufactured by Daikin Industries, Ltd.) agent (20% by mass of hydrolyzable silicon compound having a fluorine-containing organic group). The solution was used after removing the solvent.

(Manufacture of substrate with antifouling film)
Examples 1-4
After setting the transparent substrate 2 in the front chamber 42 of the continuous film forming apparatus 40, the transparent substrate 2 is passed through the vacuum chamber 43 at a transfer speed of 900 mm / min (= 15 mm / sec) to form the silicon oxide film 3 by sputtering. Then, in the same vacuum chamber 43, the surface of the formed silicon oxide film 3 is vacuum-deposited with a film forming composition (fluorine-containing hydrolyzable silicon compound) using a vacuum vapor deposition apparatus 50. A silicon compound coating 4 was formed.

  Here, in the formation of the silicon oxide film 3, a mixed gas of 50% oxygen and 50% argon as a sputtering gas is supplied into the vacuum chamber 43 by the sputtering gas supply mechanism 21, and the sputtering gas is supplied. The film forming gas pressure (total pressure), which is the sum of the pressure of water vapor and the pressure of water vapor described later, was set to a predetermined value shown in Table 1. In Examples 1 and 2, the pure water in the heating container 11 is heated to 45 ° C., water vapor is introduced into the vacuum chamber 43 through the supply unit 14, and the partial pressure of water vapor in the vacuum chamber 43 is shown in Table 1. It was set as the value shown. In Examples 3 and 4, such water vapor was not introduced, but due to moisture that was not excluded even by vacuum evacuation, the water vapor partial pressure shown in Table 1 was shown in the vacuum chamber 43. The water vapor partial pressure in the vacuum chamber 43 is a value measured using a residual gas analyzer (trade name: QuuleCGM-052 manufactured by ULVAC).

  As described above, the film forming gas pressure (total pressure) shown in Table 1 is the total pressure of the atmosphere in which the silicon oxide film 3 is formed by sputtering, and the pressure of the sputtering gas and the partial pressure of water vapor are Indicates the total value. In addition, the pressure of the mixed gas of oxygen and argon which is sputtering gas was measured with the diaphragm vacuum gauge.

  In this way, reactive AC sputtering was performed in an atmosphere in which the film forming gas pressure and the water vapor partial pressure were adjusted to form a silicon oxide film 3 having a thickness of 10 nm on the transparent substrate 2. Here, the thickness of the silicon oxide film 3 was adjusted to 10 nm by applying predetermined AC power. That is, the substrate transfer speed was set constant (900 mm / min) in advance, sputtering was performed by changing the AC power input under each gas condition, and the relationship between the thickness of the formed silicon oxide film 3 and the input power was examined. . Then, the input AC power with a film thickness of 10 nm was determined, and AC sputtering was performed at that value. The film thickness of the silicon oxide film 3 was measured with a stylus type step gauge (manufactured by KAL-Tencor, apparatus name: Alphastep 500).

  In the formation of the fluorine-containing organic silicon compound film 4, a film forming composition (fluorine-containing hydrolyzable silicon compound) is applied to the surface of the silicon oxide film 3 formed on the transparent substrate 2 using a vacuum vapor deposition device 40. A fluorine-containing organosilicon compound coating 4 having a thickness of 10 nm was formed by vacuum deposition and reaction. Specifically, the film thickness was controlled by performing vacuum deposition while adjusting the film formation rate while measuring the film thickness with a crystal resonator monitor. The final film thickness was measured with a spectroscopic ellipsometer (UVISEL: manufactured by Horiba, Ltd.) after film formation.

  Specifically, the formation of the fluorine-containing organosilicon compound coating 4 was performed as follows. An OPTOOL DSX agent as a vapor deposition material was introduced into the raw material heating vessel 51. Thereafter, the inside of the raw material heating vessel 51 was deaerated with a vacuum pump for 10 hours or more to remove the solvent in the solution, thereby obtaining a composition for forming a film. Subsequently, the raw material heating container 51 containing the composition for forming a film was heated to 270 ° C. After reaching 270 ° C., that state was maintained for 10 minutes until the temperature stabilized. Thereafter, the transparent substrate 2 on which the silicon oxide film 3 was formed was moved to a predetermined position, and film formation was performed while measuring the film thickness with the crystal oscillator monitor so that the film thickness was 10 nm. When the film thickness reached 10 nm, the film formation was completed, and the film was taken out from the vacuum chamber 43 through the substrate take-out chamber 44. Further, the substrate with the deposited film taken out was placed on a hot plate with the film surface facing upward, and heat treated in the atmosphere at 150 ° C. for 60 minutes to obtain a substrate 1 with an antifouling film.

  About the base | substrate 1 with an antifouling film | membrane of Examples 1-4, rubbing durability (wear resistance) was evaluated with the following method. The results are shown in Table 1 and the graph of FIG.

(Rubbing durability (wear resistance) test)
First, the water contact angle of the antifouling film surface of the antifouling film-coated substrate 3 obtained above was measured. Next, a rubbing test was performed by the following method, and the contact angle of water on the antifouling film surface was measured after each predetermined number of rubbing. The water contact angle on the antifouling film surface was measured by dropping 1 μL of pure water using an automatic contact angle meter DM-501 (manufactured by Kyowa Interface Science). The number of measurement points of the water contact angle on the surface of the antifouling film was 10 and the average was calculated and used for evaluation.

  A specific rubbing test method was performed according to the following procedure. That is, first, a plain weave cotton cloth No. 3 was attached to the surface of a flat metal indenter having a bottom surface of 10 mm × 10 mm to make a friction element for rubbing the sample. Next, a wear test was performed using a plane wear tester triple system (manufactured by Daiei Kagaku Seisakusho Co., Ltd.) using the above friction element. Specifically, first, the indenter is attached to a wear tester so that the bottom surface of the indenter contacts the antifouling film surface of the sample, and a weight is placed so that the load on the friction element is 1000 g, the average speed is 6400 mm / min, one way Reciprocated at 40 mm. The test was conducted with one reciprocation and two rubs.

  From the evaluation results of Table 1 and the graph of FIG. 5 illustrating the results, the following can be understood. That is, in the formation of the silicon oxide film 3, the substrate 1 with the antifouling film of Examples 1 and 2 obtained by performing sputtering in an atmosphere having a water vapor partial pressure of 0.007 Pa or more introduced into the vacuum chamber includes a vacuum chamber. Compared with the substrate 1 with antifouling film of Example 3 and Example 4 obtained by performing sputtering without introducing water vapor only by evacuating the inside, the water contact angle can be increased even when rubbing more than 100,000 times. A substrate 1 with an antifouling film excellent in water repellency and wear resistance is obtained.

  DESCRIPTION OF SYMBOLS 1 ... Base | substrate with antifouling film | membrane, 2 ... Transparent base | substrate, 3 ... Silicon oxide film, 3 ... Fluorine-containing organosilicon compound coating, 10 ... Water vapor introducing apparatus, 11 ... Heating container, 12 ... Piping, 13 ... Variable valve, 14 ... Supply unit, 15 ... heater, 20 ... film formation tank, 21 ... sputter gas supply mechanism, 30 ... sputtering apparatus, 31 ... target, 32 ... sputter electrode, 33 ... power supply, 40 ... continuous film formation apparatus, 41 ... transport means, DESCRIPTION OF SYMBOLS 42 ... Front chamber, 43 ... Vacuum chamber, 44 ... Substrate take-out chamber, 50 ... Vacuum vapor deposition apparatus, 51 ... Raw material heating vessel, 52 ... Raw material steam piping, 53 ... Manifold, 54 ... Variable valve, 55 ... Film thickness meter

Claims (6)

A transparent substrate;
A silicon oxide film formed on the main surface of the transparent substrate;
A fluorine-containing organosilicon compound film formed on the surface of the silicon oxide film,
The substrate with an antifouling film, wherein the silicon oxide film is a film formed by sputtering in an atmosphere into which water vapor is introduced.   The substrate with an antifouling film according to claim 1, wherein the partial pressure of water vapor in the atmosphere is 0.007 Pa or more.   The substrate with an antifouling film according to claim 1 or 2, wherein the transparent substrate is a glass substrate. A method for producing a substrate with an antifouling film in which a fluorine-containing organosilicon compound coating is formed on a main surface of a transparent substrate via a silicon oxide film, comprising the following steps (1) and (2): A method for producing a substrate with an antifouling film.
(1) A step of forming the silicon oxide film on the main surface of the transparent substrate by sputtering in an atmosphere in which water vapor is introduced.
(2) A step of forming the fluorine-containing organosilicon compound film on the surface of the silicon oxide film formed in the step (1).   The method for producing a substrate with an antifouling film according to claim 4, wherein, in the step (1), the partial pressure of water vapor in the atmosphere is 0.007 Pa or more.   In the step (2), a composition containing a fluorine-containing hydrolyzable silicon compound is caused to adhere to the surface of the silicon oxide film formed in the step (1) and reacted to form the fluorine-containing organic silicon compound film. The manufacturing method of the base | substrate with an antifouling film | membrane of Claim 4 or 5 which forms these.

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