Article with film and method for producing same, and coating liquid

Abstract

Provided is an article with a film that can achieve high levels of both water repellency and oil repellency and is unlikely to harm the properties of a functional film when a functional film is formed under an antifouling film.　The article with a film 1 is equipped with a base material 2, a functional film 3 provided on the base material 2, and an antifouling film 4 provided on the functional film 3. A surface part 3A of the functional film 3 in contact with the antifouling film 4 contains silicon oxide. The antifouling film 4 is configured by coating the surface part 3A of the functional film 3 with silicone having a dimethylsiloxane unit. The sliding angle of 15 μL of water on the surface 4a of the antifouling film 4 is less than 45°, and the sliding angle of 1 μL of n-hexadecane on the surface 4a of the antifouling film 4 is less than 17°.

Description

Film-attached article, its manufacturing method, and coating liquid

[0001] The present invention relates to a film-attached article, a method for producing the film-attached article, and a coating liquid.

[0002] Conventionally, film-attached articles have been widely used, in which a film having excellent water repellency, oil repellency, etc. is provided on the surface of an article such as a glass plate. As such a film having excellent water repellency and oil repellency, a film made of an organic fluorine compound is generally known, but due to increasing interest in environmental issues, a film not containing an organic fluorine compound is desired. As a film not containing an organic fluorine compound, for example, a film containing a silicone-based polymer has been considered.

[0003] For example, Patent Document 1 below discloses a method for producing water-repellent glass in which the surface of inorganic glass is subjected to a water-repellent treatment using polydimethylsiloxane. In Patent Document 1, the water-repellent glass is produced by immersing inorganic glass in a solution consisting of a hydrocarbon that is liquid at room temperature and polydimethylsiloxane at a concentration of 5 to 10%, and then removing the glass from the solution and subjecting it to a heat treatment at a temperature in the range of 250 to 350°C for 10 to 30 minutes.

[0004] Patent Document 2 listed below discloses a composite high water-sliding coating in which the surface of a substrate is coated with a composite high water-sliding coating in which silanol-terminated silicone as a water-sliding component is dispersed in a silica matrix.

[0005] Japanese Patent Publication No. 7-76116 Japanese Patent Application Laid-Open No. 2002-263571

[0006] Incidentally, a film having water-repellent or oil-repellent properties may be formed on a functional film such as an anti-reflection film, a reflective film, or a transparent conductive film. However, for example, in a method of forming a water-repellent film by performing a heat treatment at a high temperature of 250°C or higher, as in Patent Document 1, there is a problem that the properties of the functional film formed below the water-repellent film are easily deteriorated by the high temperature heating. Furthermore, in a method of forming a water-repellent film on a functional film by dispersing a silicone-based polymer in a silica matrix, as in Patent Document 2, the thickness of the water-repellent film is easily increased, and even in this case, there is a problem that the properties of the functional film formed below the water-repellent film are easily deteriorated. Furthermore, there is a problem that it is difficult for the films formed by the methods of Patent Document 1 and Patent Document 2 to achieve both water repellency and oil repellency at a high level.

[0007] An object of the present invention is to provide a film-attached article, a method for producing the film-attached article, and a coating liquid which can achieve both water repellency and oil repellency at a high level and which, when a functional film is formed under an antifouling film, is less likely to deteriorate in properties.

[0008] The film-attached article of aspect 1 of the present invention comprises a substrate, a functional film provided on the substrate, and an anti-fouling film provided on the functional film, wherein the surface portion of the functional film that comes into contact with the anti-fouling film contains silicon oxide, and the anti-fouling film is formed by coating the surface portion of the functional film with silicone having dimethylsiloxane units, and wherein the sliding angle of 15 μL of water on the surface of the anti-fouling film is less than 45°, and the sliding angle of 1 μL of n-hexadecane on the surface of the anti-fouling film is less than 17°.

[0009] In the film-attached article of Aspect 2, in Aspect 1, it is preferable that the antifouling film has a thickness of 0.1 nm or more and 10 nm or less.

[0010] The film-attached article of Aspect 3 is preferably the same as Aspect 1 or Aspect 2, wherein the sliding angle of 1 μL of n-hexadecane with respect to the surface of the antifouling film is less than 13°.

[0011] The film-attached article of Aspect 4 is any one of Aspects 1 to 3, wherein the contact angle hysteresis of water on the surface of the antifouling film is preferably less than 25°.

[0012] The film-attached article of Aspect 5 is any one of Aspects 1 to 4, wherein the contact angle hysteresis of oleic acid with respect to the surface of the antifouling film is preferably less than 15°.

[0013] The film-attached article of Aspect 6 is any one of Aspects 1 to 5, wherein the silicone may be terminal-modified.

[0014] The film-attached article of Aspect 7 is the same as Aspect 6, wherein the terminal group of the silicone is preferably a hydroxyl group.

[0015] The film-attached article of Aspect 8 is any one of Aspects 1 to 5, in which the silicone may not be terminal-modified.

[0016] A film-attached article of Aspect 9 is any one of Aspects 1 to 8, wherein the antifouling film preferably contains substantially no fluorine.

[0017] The film-attached article of Aspect 10 is any one of Aspects 1 to 9, wherein the arithmetic mean roughness Ra of the surface of the film-attached article on the antifouling film side is preferably 0.1 nm or more and 20 nm or less.

[0018] The film-attached article of aspect 11 is any one of aspects 1 to 10, wherein the functional film is a dielectric multilayer film including a high-refractive index film having a relatively high refractive index and a low-refractive index film having a relatively low refractive index, and the outermost layer of the dielectric multilayer film is preferably the low-refractive index film containing silicon oxide.

[0019] The film-attached article of Aspect 12 is any one of Aspects 1 to 10, wherein the functional film is preferably a film containing silicon oxide as a main component.

[0020] A method for producing a film-attached article according to aspect 13 of the present invention is characterized by comprising the steps of: preparing a film-attached substrate comprising a substrate and a functional film provided on the substrate, the surface portion of the functional film containing silicon oxide; and an immersion step of immersing the film-attached substrate in a solution containing silicone having a dimethylsiloxane unit to coat the surface portion of the functional film with the silicone.

[0021] In the method for producing a film-attached article of Aspect 14, it is preferable that in the immersion step of Aspect 13, the temperature of the silicone-containing solution is 20°C or higher and 200°C or lower.

[0022] In the method for producing a film-attached article of Aspect 15, in the immersion step of Aspect 13 or Aspect 14, it is preferable that the silicone-containing solution does not contain a solvent.

[0023] The method for producing a film-attached article of aspect 16, in any one of aspects 13 to 15, preferably further comprises a cleaning step of cleaning the film-forming surface of the film-attached substrate after the immersion step to remove silicone components other than the silicone covering the surface portion of the functional film.

[0024] The method for producing a film-attached article of Aspect 17, in Aspect 16, preferably further comprises a drying step of drying the film-attached substrate at a temperature of 20° C. or higher and 200° C. or lower after the washing step.

[0025] A method for producing a film-attached article according to aspect 18 of the present invention is characterized by comprising the steps of: preparing a film-attached substrate comprising a substrate and a functional film provided on the substrate, the surface portion of the functional film comprising silicon oxide; and applying a coating liquid containing one or more selected from bifunctional silicon alkoxides and oligomers of the bifunctional silicon alkoxides, a non-volatile acid, and a solvent to at least the surface portion of the functional film in the film-attached substrate; and drying the coating liquid to coat the surface portion of the functional film with silicone having dimethylsiloxane units.

[0026] In the method for producing a film-attached article of Aspect 19, in Aspect 18, the bifunctional silicon alkoxide is preferably dimethyldimethoxysilane or dimethyldiethoxysilane.

[0027] In the method for producing a film-attached article of Aspect 20, in Aspect 18 or Aspect 19, the non-volatile acid is preferably sulfonic acid or sulfuric acid.

[0028] Aspect 21 is the method for producing a film-attached article according to any one of Aspects 18 to 20, wherein the coating liquid is preferably applied by dip coating.

[0029] Aspect 22 of the method for producing a film-attached article is any one of Aspects 18 to 21, wherein the drying temperature of the coating liquid is preferably 10° C. or higher and 40° C. or lower.

[0030] The method for producing a film-attached article of Aspect 23, in any one of Aspects 18 to 22, preferably further comprises a step of cleaning the film-forming surface of the film-attached substrate after drying the coating liquid.

[0031] The method for producing a film-attached article of Aspect 24 is any one of Aspects 18 to 23, wherein the coating step is preferably carried out at a temperature of 100° C. or less.

[0032] A coating liquid according to Aspect 25 of the present invention is characterized by containing one or more selected from dimethyldimethoxysilane, dimethyldiethoxysilane, an oligomer of dimethyldimethoxysilane, and an oligomer of dimethyldiethoxysilane, sulfonic acid or sulfuric acid, and a solvent.

[0033] In the coating liquid of Aspect 26, in Aspect 25, the sulfonic acid is preferably paratoluenesulfonic acid or benzenesulfonic acid.

[0034] According to the present invention, it is possible to provide a film-attached article, a method for manufacturing the film-attached article, and a coating liquid which can achieve high levels of both water repellency and oil repellency, and which, when a functional film is formed under an antifouling film, is less likely to deteriorate in properties.

[0035] Fig. 1 is a schematic cross-sectional view showing a film-attached article according to one embodiment of the present invention, and Fig. 2 is a schematic view for explaining the structure of the surface portion of the functional film and the antifouling film in the film-attached article according to one embodiment of the present invention.

[0036] Preferred embodiments will be described below. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments. In addition, in each drawing, components having substantially the same functions may be referred to by the same reference numerals.

[0037] [Film-attached Article] Fig. 1 is a schematic cross-sectional view showing a film-attached article according to one embodiment of the present invention. As shown in Fig. 1, the film-attached article 1 includes a substrate 2, a functional film 3, and an antifouling film 4.

[0038] In this embodiment, the substrate 2 has a substantially rectangular plate shape. However, the shape of the substrate 2 is not particularly limited, and it may have a substantially circular plate shape, a lens shape, a sphere shape, a box shape, or a three-dimensional shape.

[0039] In the present embodiment, the substrate 2 is preferably a substrate that is transparent in the wavelength range used by the film-attached article 1. For example, when the film-attached article 1 is used as a cover glass for a display, the substrate 2 can have a thickness of 1.3 mm and a light transmittance of 70% or more and 99.9% or less in the wavelength range of 400 nm to 700 nm.

[0040] The substrate 2 has a first main surface 2a and a second main surface 2b that face each other. A functional film 3 is provided on the first main surface 2a of the substrate 2.

[0041] In this embodiment, the functional film 3 is a dielectric multilayer film configured by alternately stacking high-refractive-index films 5, which have a relatively high refractive index, and low-refractive-index films 6, which have a relatively low refractive index, in this order. The outermost layer of the dielectric multilayer film is the low-refractive-index film 6, which contains silicon oxide. The functional film 3 may include layers other than the high-refractive-index films 5 and the low-refractive-index film 6, as long as the outermost layer is the low-refractive-index film 6 and contains silicon oxide.

[0042] An anti-fouling film 4 is provided on the functional film 3. The anti-fouling film 4 is provided on the main surface 3a of the functional film 3 opposite to the substrate 2. The anti-fouling film 4 is made of silicone having dimethylsiloxane units. The anti-fouling film 4 is formed by coating the surface portion 3A of the functional film 3 with silicone having dimethylsiloxane units. More specifically, the anti-fouling film 4 is preferably formed by grafting silicone having dimethylsiloxane units onto the surface portion 3A of the functional film 3.

[0043] The anti-fouling film 4 may have any bonding state as long as the silicone having dimethylsiloxane units coats the surface portion 3A of the functional film 3, but a stronger bond is preferable. For example, a covalent bond is preferably formed between the silicone having dimethylsiloxane units and the surface portion 3A of the functional film 3. Whether or not a covalent bond exists between the silicone having dimethylsiloxane units and the surface portion 3A of the functional film 3 can be determined by analysis using, for example, NMR (nuclear magnetic resonance). Alternatively, if the anti-fouling film 4 remains after rinsing the film-attached article 1 with a good solvent for the silicone having dimethylsiloxane units, it can be determined that a covalent bond exists between the silicone having dimethylsiloxane units and the surface portion 3A of the functional film 3. Examples of good solvents for silicone having dimethylsiloxane units include hydrocarbon solvents such as benzene, toluene, xylene, and hexane. In the film-attached article 1, if there is a strong bond between the silicone having dimethylsiloxane units and the surface portion 3A of the functional film 3, high water repellency and oil repellency are maintained even after rinsing with a good solvent for the silicone having dimethylsiloxane units. For example, after the film-attached article 1 is immersed in hexane heated to 45°C for 2 hours, the contact angle of 3 μL of water with the surface 4a of the antifouling film 4 is preferably 90° or more, more preferably 95° or more, even more preferably 100° or more, and preferably 120° or less.

[0044] Furthermore, it is preferable that the antifouling film 4 is substantially free of antioxidants, from the viewpoint of further enhancing the adhesion between the antifouling film 4 and the surface portion 3A of the functional film 3. Note that "substantially free of antioxidants" means that the content of antioxidants in the antifouling film 4 is 0.01% by mass or less, and it is naturally preferable that the antifouling film 4 is completely free of antioxidants.

[0045] Furthermore, from the viewpoint of further enhancing water repellency and oil repellency, it is preferable that the antifouling film 4 be substantially free of silica particles. Note that "substantially free of silica particles" means that the content of silica particles in the antifouling film 4 is 0.01% by mass or less, and it is naturally preferable that the antifouling film 4 be completely free of silica particles.

[0046] In the film-attached article 1 of this embodiment, the sliding angle of 15 μL of water onto the surface 4a of the antifouling film 4 is less than 45°, and the sliding angle of 1 μL of n-hexadecane onto the surface 4a of the antifouling film 4 is less than 17°.

[0047] The sliding angle with respect to the surface 4a of the antifouling film 4 is the angle at which a droplet slides when a predetermined amount of droplet is placed on the surface 4a of the antifouling film 4 and tilted relative to the horizontal. The sliding angle can be measured, for example, by the following method. Specifically, a predetermined amount of droplet is placed on the surface 4a of the antifouling film 4, and the film-coated article 1 is tilted at a tilt speed of 1° per second or less, and the tilt angle of the surface 4a of the antifouling film 4 is measured with a goniometer at the point when it is visually confirmed that the droplet has started to move.

[0048] The film-attached article 1 of this embodiment has the above-mentioned configuration, and therefore can achieve both water repellency and oil repellency at a high level, and further, when a functional film 3 is formed under the anti-fouling film 4, the properties of the functional film 3 are less likely to deteriorate.

[0049] More specifically, in the film-attached article 1 of this embodiment, the silicone constituting the antifouling film 4 is configured by coating the surface portion 3A of the functional film 3, and therefore the thickness of the antifouling film 4 can be designed to be thin. Therefore, in the film-attached article 1, the effects of the present invention can be efficiently exhibited without deteriorating the properties of the functional film 3 provided below the antifouling film 4. Note that in the manufacturing method of the film-attached article 1 described below, the film-attached article 1 can be obtained by simply immersing the article in a solution containing silicone having a dimethylsiloxane unit without performing a high-temperature heat treatment, and therefore the obtained film-attached article 1 can efficiently exhibit the effects of the present invention without deteriorating the properties of the functional film 3 provided below the antifouling film 4.

[0050] Furthermore, in the film-attached article 1 of this embodiment, the sliding angle of 15 μL of water onto the surface 4a of the anti-fouling film 4 is less than 45°, and the sliding angle of 1 μL of n-hexadecane onto the surface 4a of the anti-fouling film 4 is less than 17°, so that the film-attached article 1 can achieve both high levels of water repellency and oil repellency.

[0051] In this embodiment, the sliding angle of 15 μL of water on the surface 4 a of the antifouling film 4 is less than 45°, preferably 40° or less, more preferably 38° or less, even more preferably 35° or less, even more preferably 30° or less, still more preferably 25° or less, and particularly preferably 20° or less. When the sliding angle of 15 μL of water on the surface 4 a of the antifouling film 4 is within the above range, the water repellency of the film-attached article 1 can be further improved. The lower limit of the sliding angle of 15 μL of water on the surface 4 a of the antifouling film 4 is not particularly limited, but can be, for example, 0.1° or more, or 1° or more.

[0052] In this embodiment, the sliding angle of 1 μL of n-hexadecane relative to the surface 4 a of the antifouling film 4 is less than 17°, preferably 15° or less, more preferably 13° or less, even more preferably less than 13°, even more preferably 10° or less, still more preferably 9° or less, and particularly preferably less than 8°. When the sliding angle of 1 μL of n-hexadecane relative to the surface 4 a of the antifouling film 4 is within the above range, the oil repellency of the film-attached article 1 can be further improved. The lower limit of the sliding angle of 1 μL of n-hexadecane relative to the surface 4 a of the antifouling film 4 is not particularly limited, but can be, for example, 0.1° or more, or 1° or more.

[0053] In this embodiment, the contact angle of 2 to 3 μL of water with the surface 4 a of the antifouling film 4 is preferably 90° or more, more preferably 95° or more, even more preferably 100° or more, and preferably 150° or less. When the contact angle of 2 to 3 μL of water is within the above range, the water repellency of the film-attached article 1 can be further improved.

[0054] The contact angle of 2 μL of n-hexadecane with the surface 4 a of the antifouling film 4 is preferably 15° or more, more preferably 20° or more, even more preferably 25° or more, and is preferably 100° or less. When the contact angle of 2 μL of n-hexadecane is within the above range, the oil repellency of the film-attached article 1 can be further improved.

[0055] The contact angle of 2 μL of oleic acid with the surface 4 a of the antifouling film 4 is preferably 30° or more, more preferably 40° or more, even more preferably 45° or more, and preferably 90° or less. When the contact angle of 2 μL of oleic acid is within the above range, the oil repellency of the film-attached article 1 can be further improved.

[0056] The contact angle (θ) of each liquid with respect to the surface 4 a of the antifouling film 4 can be measured based on the sessile drop method (θ / 2 approximation method) of JIS R 3257: 1999. For example, in this embodiment, the antifouling film 4 is placed horizontally with the surface 4 a facing upward, a predetermined amount of liquid is dropped on it, and then the contact angle can be measured using a contact angle meter (DropMaster DMe-200, manufactured by Kyowa Interface Science Co., Ltd.).

[0057] In this embodiment, the contact angle hysteresis of water on the surface 4a of the antifouling film 4 is preferably less than 25°, more preferably 20° or less, even more preferably 15° or less, even more preferably 12° or less, and even more preferably 10° or less. When the water contact angle hysteresis is less than or equal to the above upper limit value, the water repellency of the film-attached article 1 can be further improved. The lower the contact angle hysteresis of water on the surface 4a of the antifouling film 4, the better, and it may be 0°.

[0058] In this embodiment, the contact angle hysteresis of oleic acid with respect to the surface 4a of the antifouling film 4 is preferably less than 15°, more preferably 12° or less, and even more preferably 10° or less. When the contact angle hysteresis of oleic acid is less than or equal to the above upper limit value, the oil repellency of the film-attached article 1 can be further improved. The lower the contact angle hysteresis of oleic acid with respect to the surface 4a of the antifouling film 4, the better, and it may be 0°.

[0059] The contact angle hysteresis of each liquid on the surface 4a of the antifouling film 4 can be determined from the absolute value of the difference between the advancing contact angle and the receding contact angle. Specifically, the contact angle hysteresis of each liquid on the surface 4a of the antifouling film 4 can be measured by the expansion-contraction method using a contact angle meter ("DMs-401" manufactured by Kyowa Interface Science Co., Ltd.), for example.

[0060] In the film-attached article 1 of this embodiment, the functional film 3 and the antifouling film 4 are provided on the entire surface of the first main surface 2a of the substrate 2. However, in the present invention, the functional film 3 and the antifouling film 4 may be provided partially on the first main surface 2a of the substrate 2. Furthermore, another film may be provided between the first main surface 2a of the substrate 2 and the functional film 3.

[0061] In the film-attached article 1, the functional film 3 and the antifouling film 4 are provided only on the first main surface 2a of the substrate 2. However, in the present invention, the functional film 3 and the antifouling film 4 may also be provided on the second main surface 2b of the substrate 2.

[0062] The film-attached article 1 of the present embodiment can be suitably used for, for example, displays such as mobile phones, tablet terminals, televisions, or digital signage, exteriors of furniture, toys, play equipment, miscellaneous goods, electronic devices, eyeglass lenses, camera lenses, etc., and can be more suitably used as cover glass for touch panel displays, etc. Furthermore, the film-attached article 1 of the present embodiment is not particularly limited as long as it is used in an application requiring water repellency and oil repellency, and can be suitably used, for example, as a cover for an in-vehicle camera, etc.

[0063] Each layer constituting the film-attached article 1 will be described in more detail below.

[0064] (Substrate) Examples of materials for the substrate 2 include glass, ceramics, resins, and metals. Examples of glass include soda-lime glass, borosilicate glass, alkali-free glass, crystallized glass, quartz glass, and fluoride glass. Furthermore, aluminosilicate glass, which is used as tempered glass, may also be used. Examples of ceramics include alumina and sapphire. Examples of resins include polycarbonate, polyethylene terephthalate, polyvinyl chloride, polystyrene, and acrylic resins. Examples of metals include stainless steel (SUS), iron, aluminum, copper, zinc, nickel, titanium, and various alloys. Furthermore, the material for the substrate 2 may be a semimetal such as silicon (Si) or germanium (Ge). In this case, the wavelength range used for the film-attached article 1 may be the infrared range.

[0065] When a material that may be discolored, softened, oxidized, thermally decomposed, or otherwise deteriorated in a high-temperature environment is used for the substrate 2, it is preferable to form the functional film 3 and the antifouling film 4 at a low temperature of, for example, 200° C. or lower. For example, the surface of stainless steel may be discolored in a high-temperature environment of, for example, 200° C. or higher. Therefore, when stainless steel is used as the material for the substrate 2, it is preferable to form the functional film 3 and the antifouling film 4 at a low temperature of, for example, 150° C. or lower.

[0066] There is no particular limitation on the thickness of the substrate 2. The thickness of the substrate 2 can be appropriately set depending on the light transmittance, strength, application, etc. The thickness of the substrate 2 can be, for example, about 0.03 mm to 80 mm.

[0067] Furthermore, the surface roughness of the substrate 2 is preferably 0.1 nm to 100 nm, more preferably 0.1 nm to 20 nm, in arithmetic mean roughness. This makes it easier for the functional film 3 to exhibit the desired characteristics. The surface roughness of the film-attached article 1 is also preferably 0.1 nm to 100 nm, more preferably 0.1 nm to 20 nm, in arithmetic mean roughness. The surface roughness of the film-attached article 1 is preferably 20 nm or less, more preferably 10 nm or less, even more preferably 5 nm or less, even more preferably 1 nm or less, even more preferably 0.5 nm or less, and particularly preferably 0.3 nm or less, in arithmetic mean roughness. This allows the film-attached article 1 to achieve both water repellency and oil repellency at a higher level. The surface roughness of the film-attached article 1 is the arithmetic mean roughness Ra of the surface on the antifouling film 4 side (surface 4a of the antifouling film 4), measured with an atomic force microscope (AFM). The surface roughness can also be measured using a white light interference microscope or the like.

[0068] The surface roughness of the functional film 3 is preferably 20 nm or less, more preferably 10 nm or less, even more preferably 5 nm or less, even more preferably 1 nm or less, even more preferably 0.5 nm or less, even more preferably 0.3 nm or less, and particularly preferably 0.2 nm or less, in terms of arithmetic mean roughness. The lower limit of the surface roughness of the functional film 3 is not particularly limited, but can be, for example, 0.1 nm or more in terms of arithmetic mean roughness. This allows the film-attached article 1 to achieve a higher level of both water repellency and oil repellency. In particular, even if the surface of the substrate 2 is rough, coating the functional film 3 to smooth the surface can reduce the surface roughness (surface roughness of the surface 4a of the antifouling film 4) after coating. The surface roughness of the functional film 3 can be measured using an atomic force microscope, white light interference microscope, or the like after peeling off the antifouling film 4 from the film-attached article 1.

[0069] (Functional Film) The functional film 3 of this embodiment is a dielectric multilayer film having a high-refractive index film 5 and a low-refractive index film 6. In addition to the high-refractive index film 5 and the low-refractive index film 6, the functional film 3 may also include a metal film such as aluminum or a transparent conductive film such as ITO (tin-doped indium oxide). The functional film 3 can be used as an anti-reflection film, a reflective film, an index-matched transparent conductive film, a protective film, or the like. However, the functional film 3 is not limited to a dielectric multilayer film and may be, for example, a protective film primarily composed of silicon oxide. In this case, the surface smoothness of the substrate 2 (functional film 3) can be improved, thereby further enhancing water repellency and oil repellency when an antifouling film 4 is provided on the functional film 3. The protective film may be a gas barrier film, a chemical-resistant film, or an insulating film, and may be provided to improve mechanical strength or abrasion resistance.

[0070] The high-refractive-index film 5 may be, for example, a film containing at least one material selected from the group consisting of niobium oxide, titanium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silicon nitride, and aluminum nitride as its main component. The low-refractive-index film 6 is preferably a film containing silicon oxide as its main component. However, the low-refractive-index film 6, excluding the outermost layer, may be a film containing aluminum oxide or magnesium fluoride as its main component.

[0071] In this specification, a film containing a material as a main component refers to a film containing 50 mass % or more of that material, and is preferably a film constituted only by that material excluding impurities.

[0072] The number of layers of the high refractive index film 5 constituting the dielectric multilayer film is not particularly limited, but is preferably one or more layers, more preferably two or more layers, and is preferably 100 or less layers, more preferably 50 or less layers, and even more preferably 10 or less layers.

[0073] The number of layers of the low refractive index film 6 constituting the dielectric multilayer film is not particularly limited, but is preferably one or more layers, more preferably two or more layers, and is preferably 100 or less layers, more preferably 50 or less layers, and even more preferably 10 or less layers.

[0074] The number of layers in the entire dielectric multilayer film is not particularly limited, but is preferably 2 or more, more preferably 4 or more, and even more preferably 6 or more, and is preferably 100 or less, more preferably 40 or less, and even more preferably 20 or less.

[0075] The thickness of each layer of the high refractive index film 5 constituting the dielectric multilayer film is not particularly limited, but is preferably 1 nm or more, more preferably 5 nm or more, and is preferably 1000 nm or less, more preferably 800 nm or less.

[0076] The thickness of each layer of the low refractive index film 6 constituting the dielectric multilayer film is not particularly limited, but is preferably 1 nm or more, more preferably 10 nm or more, and is preferably 3000 nm or less, more preferably 1000 nm or less.

[0077] The thickness of the entire dielectric multilayer film is not particularly limited, but is preferably 10 nm or more, more preferably 30 nm or more, and is preferably 2000 nm or less, more preferably 1000 nm or less.

[0078] (Anti-fouling film) The anti-fouling film 4 is composed of silicone having dimethylsiloxane units. Silicone having dimethylsiloxane units is represented by the following formula (1). In the following formula (1), n ​​is, for example, an integer of 10 to 100. The side chains and terminals of the silicone having dimethylsiloxane units may all be composed of methyl groups. The silicone may also have modified terminals. Examples of the terminal groups of the silicone include methyl groups and hydroxyl groups. The silicone may also have partially modified side chains, in which case examples of the side chain include alkyl groups, phenyl groups, and hydrogen. The terminal groups and side chains of the silicone can be analyzed, for example, by MALDI-TOF MS (matrix-assisted laser desorption ionization-time of flight mass spectrometry).

[0079]

[0080] The antifouling film 4 is produced by immersing the functional film 3 in a solution containing a silicone having a dimethylsiloxane unit (hereinafter, sometimes simply referred to as "silicone") and coating the surface portion 3A of the functional film 3 with the silicone. The silicone contained in the solution may or may not be terminally modified. If the silicone is terminally modified, one or both terminals of the silicone may be modified. Furthermore, if the silicone is terminally modified, examples of the terminal group of the silicone include a hydroxyl group, a hydride group, and a chloro group. Among these, from the viewpoint of ensuring reliable coating of the surface portion 3A of the functional film 3 with the silicone, it is preferable that the terminal group of the silicone is a silanol group. Furthermore, the silicone may have a partially modified side chain, and in this case, examples of the side chain include an alkyl group, a phenyl group, and a hydride group.

[0081] From an environmental perspective, it is preferable that the antifouling film 4 be substantially free of fluorine, and in particular, it is preferable that it be substantially free of organic fluorine compounds. "Substantially free of fluorine" means that the fluorine content in the antifouling film 4 is 1 at % or less, and it goes without saying that the antifouling film 4 may contain no fluorine at all. "Substantially free of organic fluorine compounds" means that the content of organic fluorine compounds in the antifouling film 4 is 1 mass % or less, and it goes without saying that the antifouling film 4 may contain no organic fluorine compounds at all.

[0082] The thickness of the antifouling film 4 is preferably 0.1 nm or more, more preferably 1.1 nm or more, even more preferably 1.5 nm or more, particularly preferably 2 nm or more, and preferably 20 nm or less, more preferably 15 nm or less, even more preferably 12 nm or less, even more preferably 10 nm or less, even more preferably 7 nm or less, and particularly preferably 5 nm or less. When the thickness of the antifouling film 4 is equal to or greater than the above-mentioned lower limit, the water repellency and oil repellency of the film-attached article 1 can be further improved. When the thickness of the antifouling film 4 is equal to or less than the above-mentioned upper limit, deterioration of the properties of the functional film 3 can be further prevented. The thickness of the antifouling film 4 can be calculated, for example, from the change in spectral reflectance in the spectral reflectance spectrum before and after the formation of the antifouling film 4. The thickness of the antifouling film 4 may also be measured by X-ray reflectivity or spectroscopic ellipsometry. Alternatively, the thickness of the antifouling film 4 may be measured by observing a cross-section of the antifouling film 4 with a microscope such as a transmission electron microscope (TEM).

[0083] The thickness of the antifouling film 4 may also be measured by the following method. First, the spectral reflectance after the antifouling film 4 is applied to the film-attached article 1 is measured using, for example, a microspectrometer. Next, the antifouling film 4 is peeled off from the film-attached article 1, and the spectral reflectance of the functional film 3 after the antifouling film 4 is peeled off is measured. From the spectral reflectance of the functional film 3, the thickness of the functional film 3 is optimized as a parameter, and the detailed thickness is calculated. The calculated thickness of each layer of the functional film 3 is fixed, and the antifouling film 4 is added as the outermost layer, and the thickness is optimized as a parameter for the spectral reflectance after the antifouling film 4 is applied, thereby calculating the thickness of the antifouling film 4.

[0084] Hereinafter, a first method and a second method will be described as specific examples of the method for producing the film-attached article 1.

[0085] [Method for manufacturing film-attached article 1] (First method) In the first method, first, a substrate 2 is prepared. Next, a functional film 3 composed of, for example, a dielectric multilayer film is formed on the prepared substrate 2. At this time, the outermost layer of the dielectric multilayer film constituting the functional film 3 is formed as a low refractive index film 6 containing silicon oxide. In this way, a film-attached substrate is prepared in which the surface portion 3A of the functional film 3 contains silicon oxide.

[0086] Each layer in the dielectric multilayer film constituting the functional film 3 can be formed by, for example, sputtering, vapor deposition, pulsed laser deposition (PLD), spray coating, spin coating, dip coating, etc. Furthermore, the functional film 3 is not limited to a dielectric multilayer film, and may be, for example, one or more protective films containing silicon oxide as a main component.

[0087] Next, the prepared film-attached substrate is immersed in a solution containing silicone having a dimethylsiloxane unit, and the surface portion 3A of the functional film 3 is coated with the silicone having a dimethylsiloxane unit.

[0088] The coating of the silicone on the surface 3A of the functional film 3 can be explained as occurring when the silicone having dimethylsiloxane units is hydrolyzed by the small amount of moisture present on the surface of the functional film 3, and then bonds to the silicon oxide contained in the surface 3A of the functional film 3, as shown in Figure 2.

[0089] From the viewpoint of further promoting the hydrolysis of the silicone, it is desirable to wash or immerse the film-attached substrate in water before immersing it in the solution containing the silicone. In particular, it is preferable to immerse the film-attached substrate in water in warm water. After immersion in warm water, the film-attached substrate may be pulled out and dried. The temperature of the warm water is not particularly limited, but can be, for example, 30°C or higher and 90°C or lower.

[0090] In the step of immersing the film-coated substrate in the silicone-containing solution, the temperature of the silicone-containing solution is preferably 20° C. or higher, more preferably 40° C. or higher, and even more preferably 60° C. or higher, and is preferably 200° C. or lower, more preferably 160° C. or lower, and even more preferably 120° C. or lower. When the temperature of the silicone-containing solution is equal to or higher than the above-mentioned lower limit, the silicone having dimethylsiloxane units can be more reliably covered by the surface portion 3A of the functional film 3. Furthermore, when the temperature of the silicone-containing solution is equal to or lower than the above-mentioned upper limit, deterioration of the properties of the functional film 3 can be made even less likely to occur.

[0091] Furthermore, the immersion time of the film-attached substrate in the silicone-containing solution is preferably 1 hour or more, more preferably 2 hours or more, even more preferably 6 hours or more, even more preferably 7 hours or more, and preferably 48 hours or less, more preferably 42 hours or less, even more preferably 36 hours or less, even more preferably 30 hours or less, and even more preferably 24 hours or less. When the immersion time in the silicone-containing solution is equal to or greater than the above-mentioned lower limit, the silicone having dimethylsiloxane units can be more reliably covered by the surface portion 3A of the functional film 3. When the immersion time in the silicone-containing solution is equal to or less than the above-mentioned upper limit, deterioration of the properties of the functional film 3 can be more unlikely to occur. Furthermore, the productivity of the obtained film-attached article 1 can be further improved.

[0092] The kinematic viscosity of the silicone-containing solution is preferably 2 mm at 25°C. ２ / s or more, more preferably 5 mm ２ / s or more, more preferably 10 mm ２ / s or more, and even more preferably 50 mm ２ / s or more, and even more preferably 70 mm ２ / s or more, and particularly preferably 100 mm ２ / s or more, preferably 10,000 mm ２ / s or less, more preferably 8000 mm ２ / s or less, more preferably 6000 mm ２ / s or less, and even more preferably 5000 mm ２ / s or less, and even more preferably 3000 mm ２ / s or less, and even more preferably 1000 mm ２ / s or less, and even more preferably 500 mm ２ / s or less, particularly preferably 200 mm ２ When the kinetic viscosity of the silicone-containing solution is within the above range, the water repellency and oil repellency of the resulting film-attached article 1 can be further improved.

[0093] The kinematic viscosity of the silicone-containing solution can be measured, for example, by an Ubbelohde viscometer.

[0094] In the step of immersing the film-attached substrate in the solution containing silicone, the concentration of silicone in the solution containing silicone is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 98% by mass or more. In this case, the water repellency and oil repellency of the obtained film-attached article 1 can be further improved. In particular, when silicone oil without a solvent is used as the solution containing silicone, the water repellency and oil repellency of the obtained film-attached article 1 can be more significantly improved.

[0095] As the solvent, an organic solvent can be used, and examples of the organic solvent include hydrocarbon solvents such as benzene, toluene, xylene, and hexane, and chlorinated hydrocarbon solvents.

[0096] After the immersion step, it is desirable to wash the film-forming surface of the film-coated substrate to remove silicone components other than the silicone coating the surface portion 3A of the functional film 3. In this case, the water repellency and oil repellency of the obtained film-coated article 1 can be further improved, while the deterioration of the properties of the functional film 3 can be further prevented.

[0097] The film-forming surface of the film-coated substrate can be washed, for example, with hexane and then with ethanol.

[0098] After the washing step, it is desirable to dry the film-coated substrate. The film-coated substrate can be dried at a temperature of, for example, 20°C or higher and 200°C or lower.

[0099] In the first method, the surface portion 3A of the functional film 3 can be coated with silicone by immersing the film-attached substrate in a solution containing silicone as described above. Since high-temperature heat treatment is not required in this process, deterioration of the properties of the functional film 3 is unlikely to occur. Furthermore, since the anti-fouling film 4 is formed by coating the surface portion 3A of the functional film 3 with silicone, the thickness of the anti-fouling film 4 can be designed to be thin, and therefore deterioration of the properties of the functional film 3 is unlikely to occur. In addition, the present inventors have found that the method of coating the surface portion 3A of the functional film 3 with silicone in a solution containing silicone can significantly improve the water repellency and oil repellency of the resulting film-attached article 1.

[0100] Therefore, according to the first method, it is possible to obtain a film-attached article 1 that can achieve both water repellency and oil repellency at a high level, and when a functional film 3 is formed under the anti-fouling film 4, the properties of the functional film 3 are less likely to deteriorate.

[0101] (Second Method) In the second method, a substrate 2 is also first prepared. Next, a functional film 3 composed of, for example, a dielectric multilayer film is formed on the prepared substrate 2. At this time, the outermost layer of the dielectric multilayer film constituting the functional film 3 is formed as a low refractive index film 6 containing silicon oxide. In this way, a film-coated substrate is prepared in which the surface portion 3A of the functional film 3 contains silicon oxide.

[0102] Each layer in the dielectric multilayer film constituting the functional film 3 can be formed by, for example, sputtering, vapor deposition, pulsed laser deposition (PLD), spray coating, spin coating, dip coating, etc. Furthermore, the functional film 3 is not limited to a dielectric multilayer film, and may be, for example, one or more protective films containing silicon oxide as a main component.

[0103] Meanwhile, a coating liquid is prepared, which contains one or more selected from the group consisting of bifunctional silicon alkoxides and oligomers of the bifunctional silicon alkoxides, a non-volatile acid, and a solvent.

[0104] As the bifunctional silicon alkoxide, for example, dimethyldimethoxysilane or dimethyldiethoxysilane can be used. Alternatively, the bifunctional silicon alkoxide may be produced by reacting, for example, chlorosilane or hydridosilane with an alcohol contained in a solvent (Si-Cl + ROH → Si-OR + HCl or Si-H + ROH → Si-OR + H ２ ). Examples of oligomers of bifunctional silicon alkoxides include oligomers of dimethyldimethoxysilane and oligomers of dimethyldiethoxysilane. Specifically, examples of oligomers of bifunctional silicon alkoxides include tetramethyldisiloxane. In this case, for example, a catalyst such as tetrabutylphosphonium hydroxide is mixed with tetramethyldisiloxane to hydrolyze the Si—H of tetramethyldisiloxane (Si—H+H ２ O → Si-OH + H ２ ) or alcoholysis (Si-H+R-OH→Si-OR), and then mixing with other raw materials to prepare a coating liquid. The total content of the bifunctional silicon alkoxide and the oligomer of the bifunctional silicon alkoxide contained in the coating liquid is, in weight percentage, preferably 0.5% or more, more preferably 2% or more, and preferably 20% or less, more preferably 10% or less.

[0105] The coating liquid may also contain a monofunctional silane. The monofunctional silane serves as the terminal of the silicone having a dimethylsiloxane unit, and can more reliably suppress excessive polymerization of the bifunctional silicon alkoxide or the oligomer of the bifunctional silicon alkoxide. Examples of the monofunctional silane include trimethylchlorosilane, trimethylhydridosilane, trimethylsilanol, trimethylmethoxysilane, trimethylethoxysilane, hexamethyldisiloxane, and hexamethyldisilazane. For example, the monofunctional silane may be trimethylchlorosilane ((CH ３ ) ３ In the case of (CH 2 -Si-Cl), trimethylchlorosilane is mixed with denatured ethanol and reacted ((CH ３ )３ -Si-Cl+R-OH→(CH ３ ) ３ Alternatively, a monofunctional alkoxide (—Si—OR+HCl) may be produced, and then other raw materials may be mixed therewith to prepare a coating liquid.

[0106] Furthermore, it is preferable that the coating liquid is substantially free of tri- or higher functional silanes. If tri- or higher functional silanes are contained, the anti-fouling film may have poor slippage. The content of tri- or higher functional silanes contained in the coating liquid is preferably 1% or less, more preferably 0.5% or less, and even more preferably 0.1% or less by weight, and it is particularly preferable that the coating liquid is completely free of tri- or higher functional silanes.

[0107] Examples of non-volatile acids that can be used include sulfuric acid, sulfonic acid, phosphonic acid, and phosphoric acid. Hydroxy acids that are solid at room temperature and normal pressure can also be used as non-volatile acids. Among these, sulfonic acid or sulfuric acid is preferably used as the non-volatile acid. When the non-volatile acid is sulfonic acid or sulfuric acid, sulfonic acid or sulfuric acid has a strong catalytic effect because it is a strong acid, and is also easily soluble in water and organic solvents, making it easy to remove by washing.

[0108] Examples of sulfonic acids include paratoluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, biphenyldisulfonic acid, metaxylenesulfonic acid, and paraxylenesulfonic acid.

[0109] The content of the non-volatile acid contained in the coating liquid is preferably 0.05% or more, more preferably 0.1% or more, and is preferably 10% or less, more preferably 5% or less, in weight percentage.

[0110] Examples of the solvent include alcohols, ketones, ethers, cellosolves, esters, glycol ethers, etc. Among these, isopropyl alcohol, normal propyl alcohol, ethanol, tetrahydrofuran, etc. are preferred as the solvent. These solvents may be used alone or in combination.

[0111] The content of the solvent in the coating liquid is preferably 50% or more, more preferably 70% or more, and preferably 99% or less, more preferably 96% or less, by weight. The content of water in the coating liquid is preferably 10% or less, more preferably 5% or less, even more preferably 2% or less, even more preferably 1% or less, even more preferably 0.5% or less, and particularly preferably 0.1% or less, by weight. The coating liquid may not contain water. In this case, the stability of the coating liquid can be further improved.

[0112] Next, the coating liquid is applied to the surface 3A of the functional film 3 of the prepared film-attached substrate and dried, thereby coating the surface 3A of the functional film 3 with silicone having dimethylsiloxane units.

[0113] In coating the surface 3A of the functional film 3 with the silicone, when the coating liquid is applied to the surface 3A of the functional film 3 and dried, the solvent evaporates, while the non-volatile acid remains as a catalyst on the surface 3A of the functional film 3. Therefore, it is believed that the small amount of moisture present on the surface 3A of the functional film 3 causes a polycondensation reaction of bifunctional silicon alkoxide to proceed, starting from the silicon oxide contained in the surface 3A of the functional film 3. It is believed that this allows the surface 3A of the functional film 3 to be coated with silicone having dimethylsiloxane units.

[0114] In order to further promote the polycondensation reaction of the bifunctional silicon alkoxide, it is desirable to wash or immerse the film-attached substrate in water before applying the coating liquid. In particular, it is preferable to immerse the film-attached substrate in water in warm water. After immersion in warm water, the film-attached substrate may be pulled out and dried. The temperature of the warm water is not particularly limited, but can be, for example, 30°C or higher and 90°C or lower.

[0115] The method for applying the coating liquid is not particularly limited, and examples thereof include spray coating, dip coating, spin coating, roll coating, slit coating, and bar coating. Among these, dip coating is preferred for applying the coating liquid. In this case, loss of the liquid, i.e., the amount of the liquid adhering to the wall of the apparatus or being discharged outside the system, can be reduced.

[0116] The drying temperature of the coating liquid is not particularly limited, but is preferably 10° C. or higher, more preferably 15° C. or higher, and preferably 40° C. or lower, more preferably 35° C. or lower. In this case, it is preferable to use a solvent having a boiling point of 100° C. or lower. Specifically, the solvent is preferably isopropyl alcohol, normal propyl alcohol, ethanol, or tetrahydrofuran.

[0117] After the drying step, it is preferable to wash the film-forming surface of the film-coated substrate. This makes it possible to remove bifunctional silicon alkoxides, their polycondensates, and non-volatile acids that do not adhere strongly enough to the surface 3A of the functional film 3. In this case, it is possible to further reduce the likelihood of deterioration of the properties of the functional film 3.

[0118] The film-forming surface of the film-coated substrate may be cleaned by immersing the film-coated substrate in a cleaning solution, or by wiping with a cloth soaked in the cleaning solution. Examples of the cleaning solution that can be used include isopropyl alcohol, normal propyl alcohol, ethanol, and tetrahydrofuran.

[0119] In the second method, the specific coating liquid is applied to a film-coated substrate and then dried, thereby coating the surface portion 3A of the functional film 3 with silicone having dimethylsiloxane units. Since high-temperature heat treatment is not required, deterioration of the properties of the functional film 3 is unlikely to occur. Furthermore, since the anti-fouling film 4 is formed by coating the surface portion 3A of the functional film 3 with silicone, the thickness of the anti-fouling film 4 can be designed to be thin, and therefore deterioration of the properties of the functional film 3 is unlikely to occur. In addition, the present inventors have found that the method of applying the specific coating liquid to a film-coated substrate and then drying can significantly improve the water repellency and oil repellency of the resulting film-coated article 1.

[0120] Therefore, according to the second method, it is possible to obtain a film-attached article 1 that can achieve both water repellency and oil repellency at a high level, and when a functional film 3 is formed under the anti-fouling film 4, the properties of the functional film 3 are less likely to deteriorate.

[0121] In the second method, the coating step in the method for producing the film-attached article 1 is preferably performed at a temperature of 100°C or less, more preferably 80°C or less, even more preferably 60°C or less, even more preferably 50°C or less, and particularly preferably 40°C or less. The coating step may be performed at a temperature of 10°C or more, or at a temperature of 20°C or more. The coating step refers to a step of applying a coating liquid to at least the surface portion of the functional film in the film-attached substrate and drying it to coat the surface portion of the functional film with silicone. In the second method, all steps in the method for producing the film-attached article 1 are preferably performed at a temperature of 100°C or less, more preferably 80°C or less, even more preferably 60°C or less, even more preferably 50°C or less, and particularly preferably 40°C or less. All steps may be performed at a temperature of 10°C or more, or at a temperature of 20°C or more. In these cases, the productivity of the film-attached article 1 can be further improved. Furthermore, since the second method does not require heating or baking, it is possible to obtain a film-attached article 1 in which the properties of the functional film 3 are less likely to deteriorate when the functional film 3 is formed under the antifouling film 4. Furthermore, since no equipment for heating or baking is required, the manufacturing cost can be reduced and the method can be applied to substrates of various shapes and large sizes.

[0122] In the second method, the difference in luminous reflectance between the film-coated article 1 after the antifouling film 4 is formed and the film-coated substrate before the antifouling film 4 is preferably 0.30% or less, more preferably 0.20% or less, and even more preferably 0.10% or less. In this case, the properties of the functional film 3 provided below the antifouling film 4 can be made even less susceptible to deterioration. The luminous reflectance can be measured, for example, in accordance with JIS Z8781-3-2016.

[0123] The present invention will be described in more detail below with reference to specific examples. The present invention is not limited to the following examples, and can be practiced with appropriate modifications within the scope of the present invention.

[0124] (Example 1) First, a chemically strengthened glass plate (manufactured by Nippon Electric Glass Co., Ltd., product number "T2X-1") was prepared as a substrate. Next, a functional film (anti-reflection film) composed of a dielectric multilayer film was formed on one main surface of the prepared substrate by sputtering. Specifically, from the substrate side, SiO ２ film (thickness: 50 nm), Nb ２ O ５ film (thickness: 11 nm), SiO ２ film (thickness: 36 nm), Nb ２ O ５ film (thickness: 106 nm), SiO ２ The films (thickness: 87 nm) were deposited in this order to form a five-layer dielectric multilayer film. This resulted in a substrate with a film, the surface of which contained silicon oxide. The thickness of the anti-reflection film described above was optimized using the film thickness of each layer as a parameter based on the spectral reflectance measured using a microspectrophotometer (described below).

[0125] Next, the prepared film-coated substrate was subjected to alkaline ultrasonic cleaning, then rinsed with pure water, and then pulled out of hot pure water and dried. Next, the film-coated substrate was immersed in polydimethylsiloxane silicone oil (kinematic viscosity (25°C): 100 mm) heated to a temperature of 100°C. ２ The substrate was then immersed for 24 hours in a solution containing a silicone (e.g., dimethylsiloxane / s, no terminal modification). The substrate with the film was then washed with hexane and then ethanol to remove silicone components other than the silicone coating the surface of the functional film, and then dried. In this way, a film-attached article was obtained, which had an antifouling film in which the surface of the functional film was coated with a silicone having dimethylsiloxane units.

[0126] (Example 2) As a solution containing silicone, a polydimethylsiloxane silicone oil (kinematic viscosity (25°C): 61.4 mmHg) whose terminals are modified with hydroxyl groups (silanol-modified) was used. ２ A film-attached article was obtained in the same manner as in Example 1 except that the film-attached article was used.

[0127] Example 3 A film-attached article was obtained in the same manner as in Example 2, except that the silicone-containing solution was used at 20° C. without heating.

[0128] (Example 4) After being pulled out of the hot pure water and dried, the film-attached substrate was immersed in polydimethylsiloxane silicone oil (kinematic viscosity (25°C): 100 mm) heated to a temperature of 120°C. ２ A film-attached article was obtained in the same manner as in Example 1, except that the film was immersed in a solution containing a silicone (a copolymer of hydroxypropyltrimonials (HPO4) and hydroxypropyltrimonials (HPO4), unmodified at the terminals) for 7 hours.

[0129] (Example 5) Kinematic viscosity at 25°C: 200 mm ２ A film-attached article was obtained in the same manner as in Example 4, except that a polydimethylsiloxane silicone oil (without terminal modification) having a molecular weight of 1 / s was used.

[0130] (Example 6) Kinematic viscosity at 25°C: 1000 mm ２ A film-attached article was obtained in the same manner as in Example 4, except that a polydimethylsiloxane silicone oil (without terminal modification) having a molecular weight of 1 / s was used.

[0131] (Example 7) After being pulled out of the hot pure water and dried, the film-attached substrate was immersed in polydimethylsiloxane silicone oil (kinematic viscosity (25°C): 5000 mm) heated to a temperature of 120°C. ２ A film-attached article was obtained in the same manner as in Example 1, except that the film was immersed in a solution containing a silicone consisting of PEG-140 / s, not end-modified) for 17 hours.

[0132] Comparative Example 1 A film-attached substrate obtained in the same manner as in Example 1 was used as a film-attached article without being immersed in a solution containing silicone.

[0133] (Comparative Example 2) Polydimethylsiloxane silicone oil (kinematic viscosity (25°C): 100 mm ２ / s, no terminal modification) was mixed with a solvent (n-hexane) to prepare a solution with a silicone concentration of 2.5 mass %. Using this solution, the film-coated substrate obtained in the same manner as in Example 1 was pulled up at a pulling speed of 2 mm / s, thereby dip-coating the film-coated substrate. The dip-coated film-coated substrate was subjected to a heat treatment at 350°C for 30 minutes to obtain a film-coated article.

[0134] (Comparative Example 3) Polydimethylsiloxane silicone oil whose terminals are modified with hydroxyl groups (silanol-modified) (kinematic viscosity (25°C): 61.4 mm ２ / s) was mixed with a solvent (n-hexane) to prepare a solution with a silicone concentration of 2.5 mass %. Using this solution, the film-coated substrate obtained in the same manner as in Example 1 was pulled up at a pulling speed of 2 mm / s, thereby dip-coating the film-coated substrate. After dip-coating, the film-coated substrate was dried at room temperature (20°C) for 24 hours and then washed with hexane and ethanol in that order to obtain a film-coated article.

[0135] [Evaluation] (Contact Angle Measurement) For the film-attached articles obtained in Examples 1 to 7 and Comparative Examples 1 to 3, the contact angle was measured based on the sessile drop method (θ / 2 approximation method) of JIS R 3257:1999. Specifically, a contact angle meter ("DropMaster DMe-200" manufactured by Kyowa Interface Science Co., Ltd.) was used to drop a predetermined amount of liquid onto each film-attached article placed horizontally, and measurement was performed. The predetermined amount of liquid used was 3 μL of water and 2 μL of n-hexadecane, respectively.

[0136] (Measurement of sliding angle) The sliding angle was evaluated for the film-attached articles obtained in Examples 1 to 7 and Comparative Examples 1 to 3. A predetermined amount of liquid droplet was placed on a surface held horizontally (0°), and the surface was slowly tilted (at a tilt rate of 1° per second or less) in 2.5° increments, and the tilt angle at which the droplet began to move was taken as the sliding angle. 15 μL of water and 1 μL of n-hexadecane were used as the predetermined amount of liquid. In Comparative Example 1, the droplet lost its shape when tilted, and flowed with a trail, making it impossible to measure the sliding angle.

[0137] (Measurement of Antifouling Film Thickness) The spectral reflectance of the film-coated articles obtained in Examples 1 to 7 and Comparative Examples 2 and 3 was measured using a microspectrophotometer (manufactured by Olympus Corporation, product number "USPM-RU"), and the thickness of the antifouling film was calculated from the change in spectral reflectance before and after application of the antifouling film. That is, first, the thickness of each layer of the antireflection film (dielectric multilayer film) was optimized using the spectral reflectance before application of the antifouling film as a parameter, and the specific film thickness was calculated. Then, the calculated thickness of each layer of the antireflection film was fixed, and an antifouling film was added to the outermost layer. The thickness of the antifouling film was then optimized using the thickness as a parameter for the spectral reflectance after application of the antifouling film, thereby calculating the thickness of the antifouling film. Here, it was assumed that the refractive index and thickness of each layer of the antireflection film remained unchanged before and after application, and the refractive index of the antifouling film was set to 1.4. In Examples 1 to 7 and Comparative Example 3, the spectral reflectance calculated from the calculated thicknesses of the antireflection and antifouling films closely matched the measured spectral reflectance values ​​after application of the antifouling film. However, in Comparative Example 2, the results did not closely match, and therefore the thickness of the antifouling film could not be measured. It is believed that the high-temperature heat treatment in Comparative Example 2 caused changes in the thickness and refractive index of each layer of the antireflection film. Furthermore, it was confirmed that the thickness of the antifouling film was similar not only measured by changes in spectral reflectance, but also by X-ray reflectometry and observation of the cross-section of the antifouling film using a transmission electron microscope (TEM). For X-ray reflectometry measurements, an X-ray diffractometer (trade name "SmartLab," manufactured by Rigaku Corporation) was used. The thickness of the antifouling film was determined by fitting the measured X-ray reflectivity curve to a theoretical profile using analysis software (software name "GlobalFit," manufactured by Rigaku Corporation). The transmission electron microscope (TEM) used was a JEOL Ltd. product number "JEM-F200."

[0138] (Measurement of Arithmetic Average Roughness) For the film-attached articles obtained in Examples 1 to 7 and Comparative Examples 2 and 3, the arithmetic average roughness of the functional film surface and the arithmetic average roughness of the antifouling film surface were measured. The arithmetic average roughness of each surface was measured using an atomic force microscope ("Nanonavi S-Image" manufactured by SII Nanotechnology Inc.) in dynamic force mode. Specifically, measurements were performed under the following conditions: scanner 20 μm, cantilever SI-DF20 (with aluminum backside), scanning area 2000 nm, X data count 128, Y data count 128, and scanning speed 1 Hz. The obtained profile images were subjected to third-order tilt correction to determine the arithmetic average roughness. In Examples 1 to 7 and Comparative Examples 2 and 3, the arithmetic average roughness of the functional film surface was 0.9 nm. The arithmetic average roughness of the antifouling film surface was also 0.9 nm.

[0139] (Measurement of Color Difference ΔE) The color difference ΔE between the film-coated articles obtained in Examples 1 to 7 and Comparative Examples 2 and 3 and the film-coated substrate before the formation of the antifouling film was measured. The color difference ΔE was calculated from the change in spectral reflectance before and after the application of the antifouling film, measured using a microspectrophotometer (manufactured by Olympus Corporation, product number "USPM-RU"). The calculation was performed using a D65 light source, a 2-degree visual field, and L ＊ a ＊ b ＊ L in color system ＊ Value, a ＊ value, and b ＊ Calculate the value, ΔE = [(ΔL ＊ ) ２ + (Δa ＊ ) ２ + (Δb ＊ ) ２ 〕 １／２ The color difference ΔE was calculated from the above.

[0140] The film-coated articles obtained in Examples 1 to 7 were immersed in hexane heated to 45°C for 2 hours, rinsed with ethanol, and dried, and then the contact angle and sliding angle of water and n-hexadecane, as well as the film thickness, were evaluated, but no significant changes were observed. From this, it was determined that a strong bond existed between the antifouling film having dimethylsiloxane units and the antireflection film surface.

[0141] The results are shown in Table 1 below.

[0142]

[0143] (Example 8) First, a chemically strengthened glass plate (manufactured by Nippon Electric Glass Co., Ltd., product number "T2X-1") was prepared as a substrate. Next, a functional film (anti-reflection film) composed of a dielectric multilayer film was formed on one main surface of the prepared substrate by sputtering. Specifically, from the substrate side, SiO ２ film (thickness: 50 nm), Nb ２ O ５ film (thickness: 11 nm), SiO ２ film (thickness: 36 nm), Nb ２ O ５ film (thickness: 106 nm), SiO ２ The films (thickness: 87 nm) were deposited in this order to form a five-layer dielectric multilayer film. This resulted in a film-coated substrate in which the surface of the functional film contained silicon oxide. The thickness of the antireflection film was optimized based on the spectral reflectance measured by the microspectrophotometer, using the film thickness of each layer as a parameter. The arithmetic mean roughness of the antireflection film surface was 0.9 nm. The prepared film-coated substrate was then subjected to alkaline ultrasonic cleaning, rinsed with pure water, and then pulled out of warm pure water and dried.

[0144] On the other hand, a coating liquid containing dimethyldimethoxysilane, isopropyl alcohol, and paratoluenesulfonic acid hydrate in a weight ratio of 13.3:100:0.84 was prepared. The amount of water derived from paratoluenesulfonic acid hydrate was calculated to be 0.07% by weight based on the total weight of the coating liquid. Using this coating liquid, the film-coated substrate after being pulled up from the hot pure water and dried was dip-coated at a lifting speed of 1 mm / s. Next, the dip-coated film-coated substrate was dried at 22 ° C for 3 minutes, and then rinsed with isopropyl alcohol, water, and ethanol in that order. In this way, a film-coated article was obtained, which has an anti-fouling film formed by coating the surface of the functional film with a silicone having a dimethylsiloxane unit.

[0145] (Example 9) A film-attached article was obtained in the same manner as in Example 8, except that a coating liquid containing benzenesulfonic acid hydrate in the same proportion as paratoluenesulfonic acid hydrate was prepared. The amount of water derived from the benzenesulfonic acid hydrate was calculated to be 0.08% by weight based on the total weight of the coating liquid.

[0146] (Example 10) In the same manner as in Example 8, a film-coated substrate was prepared after being pulled up in hot pure water and dried. Meanwhile, a coating liquid containing dimethyldiethoxysilane, tetrahydrofuran, and paratoluenesulfonic acid hydrate in a weight ratio of 13.3:100:0.84 was prepared. The amount of water derived from paratoluenesulfonic acid hydrate was calculated to be 0.07% by weight based on the total weight of the coating liquid. Using this coating liquid, the film-coated substrate after being pulled up in hot pure water and dried was dip-coated at a pulling speed of 1 mm / s. Next, the dip-coated film-coated substrate was dried at 22 ° C. for 5 minutes, and then rinsed with isopropyl alcohol, water, and ethanol in this order. In this way, a film-coated article was obtained having an anti-fouling film formed by coating the surface of the functional film with a silicone having a dimethylsiloxane unit.

[0147] (Example 11) A coating liquid containing dimethyldimethoxysilane, trimethylchlorosilane, denatured ethanol, and benzenesulfonic acid hydrate in a weight ratio of 14:1.4:100:1.0 was prepared. The amount of water derived from the benzenesulfonic acid hydrate was calculated to be 0.09% by weight percentage relative to the total weight of the coating liquid. In preparing the coating liquid, first, trimethylchlorosilane ((CH ３ ) ３ —Si—Cl) was mixed with denatured ethanol and reacted ((CH ３ ) ３ -Si-Cl+R-OH→(CH ３ ) ３ A monofunctional alkoxide was produced by adding the alkoxide (-Si-OR + HCl). Then, other raw materials were mixed to prepare a coating liquid. A film-coated article was obtained in the same manner as in Example 10, except that this coating liquid was used.

[0148] Example 12 A coating liquid containing tetramethyldisiloxane, tetrabutylphosphonium hydroxide (40% aqueous solution), denatured ethanol, and benzenesulfonic acid hydrate in a weight ratio of 13:0.2:100:0.9 was prepared. The total amount of water derived from the tetrabutylphosphonium hydroxide (40% aqueous solution) and benzenesulfonic acid hydrate was calculated to be 0.08% by weight based on the total weight of the coating liquid. In preparing the coating liquid, first, tetramethyldisiloxane, denatured ethanol, and tetrabutylphosphonium hydroxide were mixed, and the Si—H of the tetramethyldisiloxane was hydrolyzed (Si—H+H ２ O → Si-OH + H ２ ) or alcoholysis (Si-H+R-OH → Si-OR+H ２ ) Then, other raw materials were mixed to prepare a coating liquid. A film-coated article was obtained in the same manner as in Example 8, except that this coating liquid was used.

[0149] (Example 13) First, a chemically strengthened glass plate (manufactured by Nippon Electric Glass Co., Ltd., product number "T2X-1") was prepared as a substrate. Next, a functional film (anti-reflection film) composed of a dielectric multilayer film was formed on one main surface of the prepared substrate by a sputtering method. Specifically, from the substrate side, SiO ２ film (thickness: 50 nm), Nb ２ O ５ film (thickness: 11 nm), SiO ２ film (thickness: 36 nm), Nb ２ O ５ Four layers of SiO2 films (thickness: 106 nm) were laminated in this order. ２A film (thickness: 87 nm) was formed to form a five-layer dielectric multilayer film. For dip coating, a coating solution containing tetraethoxysilane, isopropyl alcohol, acetic acid, and water in a weight ratio of 12.8:100:1.1:4.3 was prepared. The dip coating was performed at a lifting speed of 2 mm / s. The dip-coated dielectric multilayer film was dried at 120°C for 3 minutes. This resulted in a film-coated substrate in which the surface of the functional film contained silicon oxide. The thickness of the antireflection film was optimized from the spectral reflectance measured by the microspectrophotometer, using the film thickness of each layer as a parameter. The arithmetic mean roughness of the antireflection film surface was 0.2 nm. Next, the SiO of the prepared film-coated substrate was measured. ２ The surface of the membrane was subjected to plasma cleaning (Yamato Scientific Co., Ltd., "Plasma Cleaner PR200", dry air 50 mL / min, plasma output 50 W, 3 minutes).

[0150] A film-coated article having an antifouling film was obtained in the same manner as in Example 8, except that this plasma-cleaned film-coated substrate was used.

[0151] (Comparative Example 4) A film-coated article was obtained in the same manner as in Example 4, except that a coating liquid containing dimethyldimethoxysilane, isopropyl alcohol, acetic acid, and water in a weight ratio of 13.3:100:0.7:0.14 was prepared.

[0152] [Evaluation] (Contact Angle Measurement) For the film-attached articles obtained in Examples 8 to 13 and Comparative Example 4, static contact angles were measured based on the sessile drop method (θ / 2 approximation method) of JIS R 3257:1999. Specifically, a contact angle meter ("DMs-401" manufactured by Kyowa Interface Science Co., Ltd.) was used to drop a predetermined amount of liquid onto each film-attached article placed horizontally, and measurements were taken. 2 μL of water and 2 μL of oleic acid were used as the predetermined amount of liquid. Furthermore, for the film-attached articles obtained in Examples 8 to 13 and Comparative Example 4, the advancing contact angle and receding contact angle were measured using a contact angle meter ("DMs-401" manufactured by Kyowa Interface Science Co., Ltd.) by the expansion / contraction method, and the contact angle hysteresis was calculated from the difference between the measured values. For the measurement of advancing and receding contact angles, images for contact angle measurement were continuously acquired under the following conditions (software FAMAS, autodispenser AD-301, field of view wide 1, waiting time before measurement 0 ms, measurement time interval 17 ms, number of continuous measurements 120, liquid volume control 7 μL, discharge level 1000). A 22G stainless steel syringe needle was used for water, and an 18G Teflon (registered trademark) coated needle was used for oleic acid. A baseline was manually drawn from the acquired images, and the contact angle at each instant was measured using a perfect circle fitting (fit interval 30 dots). For the measurement of advancing and receding contact angles, the average of the left and right contact angles at the time when the contact radius began to increase and decrease, respectively, was taken. Three measurements were performed, and the average was used as the measured value for the advancing and receding contact angles.

[0153] (Evaluation of Sliding Property) The sliding property of the film-attached articles obtained in Examples 8 to 13 and Comparative Example 4 was evaluated. Specifically, a predetermined amount of liquid droplet was placed on a surface held horizontally (0°), and then tilted by 20° to evaluate whether the droplet slid off. 20 μL of water and 5 μL of oleic acid were used as the predetermined amount of liquid. Note that the case where the droplet slid off was evaluated as ◯, and the case where the droplet did not slide off was evaluated as ×.

[0154] (Measurement of Antifouling Film Thickness) The spectral reflectance of the film-coated articles obtained in Examples 8 to 13 and Comparative Example 4 was measured using a microspectrophotometer (manufactured by Olympus Corporation, product number "USPM-RU"), and the thickness of the antifouling film was calculated from the change in spectral reflectance before and after application of the antifouling film. Specifically, the thickness of each layer of the antireflection film (dielectric multilayer film) was first optimized using the spectral reflectance before application of the antifouling film as a parameter, and the specific film thickness was calculated. Then, the calculated thickness of each layer of the antireflection film was fixed, and an antifouling film was added to the outermost layer. The thickness of the antifouling film was then optimized using the thickness as a parameter for the spectral reflectance after application of the antifouling film, thereby calculating the thickness of the antifouling film. Here, it was assumed that the refractive index and thickness of each layer of the antireflection film remained unchanged before and after application, and the refractive index of the antifouling film was set to 1.4 for the calculation. In Examples 8 to 13 and Comparative Example 4, the spectral reflectances calculated from the calculated film thicknesses of the antireflection film and the antifouling film closely matched the measured spectral reflectances after the antifouling film was applied.

[0155] (Measurement of luminous reflectance) The difference in luminous reflectance between the film-coated articles obtained in Examples 8 to 13 and Comparative Example 4 and the film-coated substrate before the formation of the antifouling film was measured. When measuring the luminous reflectance, spectral reflectance was measured using a microspectrometer (manufactured by Olympus Corporation, product number "USPM-RU") in accordance with JIS Z8781-3:2016, and the tristimulus value Y was calculated using a 2-degree visual field and a D65 light source, and this was used as the luminous reflectance.

[0156] The results are shown in the following Table 2. The arithmetic mean roughness was measured in the same manner as in Examples 1 to 7.

[0157]

[0158] As shown in Table 2, the film-attached articles of Examples 8 to 13 obtained using a coating liquid containing a bifunctional silicon alkoxide and a non-volatile acid were able to achieve high levels of both water repellency and oil repellency, and the difference in luminous reflectance before and after the formation of the anti-soiling film was small, confirming that the properties of the functional film provided below the anti-soiling film were not easily deteriorated. On the other hand, the film-attached article of Comparative Example 4 obtained using a coating liquid not containing a non-volatile acid did not have sufficient water repellency and oil repellency.

[0159] The contact angles and sliding angles of the film-attached articles obtained in Examples 8 to 13 were measured in the same manner as in Examples 1 to 7 and Comparative Examples 1 to 3. The results are shown in Table 3 below.

[0160]

[0161] As is clear from Table 3, the film-coated articles of Examples 8 to 13 obtained using a coating liquid containing a bifunctional silicon alkoxide and a non-volatile acid had even better water repellency and oil repellency than Example 3, and it was confirmed that both water repellency and oil repellency could be achieved at an extremely high level.

[0162] The film-coated articles obtained in Examples 8 to 13 were immersed in hexane heated to 45°C for 2 hours, rinsed with ethanol, and dried, and then the contact angle and sliding angle of water and n-hexadecane, as well as the film thickness, were evaluated, but no significant changes were observed. From this, it was determined that a strong bond existed between the antifouling film having dimethylsiloxane units and the antireflection film surface.

[0163] Example 14 First, a polyethylene terephthalate film was prepared as a substrate. Next, SiO ２ A film (gas barrier film as a functional film, thickness: 103 nm) was formed. For dip coating, a coating liquid containing tetraethoxysilane, isopropyl alcohol, acetic acid, and water in a weight ratio of 12.8:100:1.1:4.3 was used. The dip coating was performed at a pull-up speed of 3 mm / s. The dip-coated substrate was dried at 120°C for 3 minutes. SiO ２ The thickness of the film was measured using a stylus step gauge (manufactured by Bruker, product number "DektakXT-S"). ２ The arithmetic mean roughness of the film surface was 0.2 nm. ２ The surface of the membrane was subjected to plasma cleaning (Yamato Scientific Co., Ltd., "Plasma Cleaner PR200", dry air 50 mL / min, plasma output 50 W, 3 minutes).

[0164] A film-coated article was obtained in the same manner as in Example 8, except that this plasma-cleaned film-coated substrate was used.

[0165] Example 15 First, a stainless steel plate (SUS304, surface finish 2B) was prepared as a substrate. Next, a coating liquid containing tetraethoxysilane, methyltriethoxysilane, isopropyl alcohol, 1N nitric acid, and water in a weight ratio of 30.8:6.6:100:5.7:7.3 was prepared. The prepared substrate was dip-coated with this coating liquid at a lifting speed of 7 mm / s. Next, the dip-coated substrate was baked at 150°C for 30 minutes, and a protective film (SiO ２ -CH ３ SiO １．５ Next, the prepared substrate with the film was subjected to alkaline ultrasonic cleaning, rinsed with pure water, and then pulled out of warm pure water and dried.

[0166] On the other hand, a coating liquid containing dimethyldimethoxysilane, isopropyl alcohol, and paratoluenesulfonic acid hydrate in a weight ratio of 13.3:100:0.84 was prepared. Using this coating liquid, the film-coated substrate after the hot pure water lift-up and drying was dip-coated at a lift-up speed of 1 mm / s. Next, the dip-coated film-coated substrate was dried at 22 ° C for 3 minutes, and then rinsed with isopropyl alcohol, water, and ethanol in this order. In this way, a film-coated article was obtained, which has an anti-fouling film, in which the silicone having dimethylsiloxane units coats the surface of the functional film.

[0167] (Comparative Example 5) An antifouling film was not formed on the film-coated substrate obtained in the same manner as in Example 15, and the film-coated substrate was used as it was as a film-coated article. Note that in the film-coated article of Comparative Example 5, only a protective film as a functional film was provided on the substrate.

[0168] [Evaluation] The film-attached articles obtained in Examples 14 and 15 and Comparative Example 5 were subjected to measurement of contact angle and evaluation of sliding properties in the same manner as in Examples 8 to 13. In addition, in Example 14, after the production of the film-attached article, the presence or absence of deterioration (wrinkles, waviness) of the polyethylene terephthalate film was visually confirmed. For Example 15 and Comparative Example 5, after the production of the film-attached article, the presence or absence of discoloration of the stainless steel plate was visually confirmed. The results are shown in Table 4 below.

[0169]

[0170] The contact angles and sliding angles of the film-attached articles obtained in Examples 14 and 15 and Comparative Example 5 were measured in the same manner as in Examples 1 to 7 and Comparative Examples 1 to 3. The results are shown in Table 5 below.

[0171]

[0172] As is clear from Tables 4 and 5, even when polyethylene terephthalate film or stainless steel plate is used as the substrate, the film-attached articles of Examples 14 and 15 obtained using a coating liquid containing bifunctional silicon alkoxide and non-volatile acid have better water repellency and oil repellency than Comparative Example 5, in which no antifouling film is formed on the functional film (protective film), and it was confirmed that both water repellency and oil repellency can be achieved at an extremely high level.In addition, in Example 14, it was confirmed that no deterioration (wrinkles, wavy) occurred in the polyethylene terephthalate film as the substrate after the production of the film-attached article, and in Example 15, it was confirmed that no discoloration occurred in the stainless steel plate as the substrate after the production of the film-attached article.

[0173] The film-coated articles obtained in Examples 14 and 15 were immersed in hexane heated to 45°C for 2 hours, rinsed with ethanol, and dried. The contact angles and sliding angles of water and n-hexadecane were evaluated, but no significant changes were observed. From this, it was determined that a strong bond existed between the antifouling film having dimethylsiloxane units and the antireflection film surface.

[0174] REFERENCE SIGNS LIST 1... Film-attached article 2... Substrate 2a... First main surface 2b... Second main surface 3... Functional film 3a... Main surface 3A... Surface portion 4... Antifouling film 4a... Surface 5... High refractive index film 6... Low refractive index film

Claims

1. A film-attached article comprising: a substrate; a functional film disposed on said substrate; and an anti-fouling film disposed on said functional film, wherein a surface portion of said functional film in contact with said anti-fouling film contains silicon oxide, said anti-fouling film is formed by coating said surface portion of said functional film with a silicone having a dimethylsiloxane unit, wherein the sliding angle of 15 μL of water onto the surface of said anti-fouling film is less than 45°, and the sliding angle of 1 μL of n-hexadecane onto the surface of said anti-fouling film is less than 17°.

2. The film-attached article according to claim 1, wherein the antifouling film has a thickness of 0.1 nm or more and 10 nm or less.

3. The film-attached article according to claim 1 or 2, wherein the sliding angle of 1 μL of n-hexadecane on the surface of the antifouling film is less than 13°.

4. The film-attached article according to claim 1 or 2, wherein the contact angle hysteresis of water on the surface of the antifouling film is less than 25°.

5. The film-attached article according to claim 1 or 2, wherein the contact angle hysteresis of oleic acid on the surface of the antifouling film is less than 15°.

6. The film-attached article according to claim 1 or 2, wherein the silicone is terminally modified.

7. The film-attached article according to claim 6, wherein the terminal group of said silicone is a hydroxyl group.

8. The film-attached article according to claim 1 or 2, wherein the silicone is not terminally modified.

9. The film-attached article according to claim 1 or 2, wherein the anti-fouling film is substantially free of fluorine.

10. The film-attached article according to claim 1 or 2, wherein the arithmetic mean roughness Ra of the surface of the film-attached article on the antifouling film side is 0.1 nm or more and 20 nm or less.

11. The film-attached article according to claim 1 or 2, wherein the functional film is a dielectric multilayer film including a high refractive index film having a relatively high refractive index and a low refractive index film having a relatively low refractive index, and the outermost layer of the dielectric multilayer film is the low refractive index film containing silicon oxide.

12. The film-attached article according to claim 1 or 2, wherein the functional film is a film containing silicon oxide as a main component.

13. A method for producing a film-attached article, comprising: a step of preparing a film-attached substrate comprising a substrate and a functional film provided on the substrate, the surface portion of the functional film containing silicon oxide; and an immersion step of immersing the film-attached substrate in a solution containing silicone having a dimethylsiloxane unit to coat the surface portion of the functional film with the silicone.

14. The method for producing a film-attached article according to claim 13, wherein the temperature of the silicone-containing solution in the immersion step is 20°C or higher and 200°C or lower.

15. The method for producing a film-attached article according to claim 13 or 14, wherein in the immersion step, the silicone-containing solution does not contain a solvent.

16. A method for producing a film-attached article according to claim 13 or 14, further comprising a cleaning step of cleaning the film-forming surface of the film-attached substrate after the immersion step to remove silicone components other than the silicone covering the surface portion of the functional film.

17. The method for producing a film-attached article according to claim 16, further comprising a drying step of drying the film-attached substrate at a temperature of 20°C or higher and 200°C or lower after the washing step.

18. A method for producing a film-attached article, comprising: a step of preparing a film-attached substrate comprising a substrate and a functional film provided on the substrate, the surface portion of the functional film comprising silicon oxide; and a coating step of applying a coating liquid containing one or more selected from bifunctional silicon alkoxides and oligomers of the bifunctional silicon alkoxides, a non-volatile acid, and a solvent to at least the surface portion of the functional film on the film-attached substrate, and drying the coating liquid to coat the surface portion of the functional film with silicone having a dimethylsiloxane unit.

19. The method for producing a film-attached article according to claim 18, wherein the bifunctional silicon alkoxide is dimethyldimethoxysilane or dimethyldiethoxysilane.

20. The method for producing a film-attached article according to claim 18 or 19, wherein the non-volatile acid is sulfonic acid or sulfuric acid.

21. The method for producing a film-attached article according to claim 18 or 19, wherein the coating liquid is applied by dip coating.

22. The method for producing a film-attached article according to claim 18 or 19, wherein the drying temperature of the coating liquid is 10°C or higher and 40°C or lower.

23. The method for producing a film-coated article according to claim 18 or 19, further comprising a step of cleaning the film-forming surface of the film-coated substrate after drying the coating liquid.

24. The method for producing a film-attached article according to claim 18 or 19, wherein the coating step is carried out at a temperature of 100°C or less.

25. A coating liquid comprising one or more selected from dimethyldimethoxysilane, dimethyldiethoxysilane, an oligomer of dimethyldimethoxysilane, and an oligomer of dimethyldiethoxysilane, sulfonic acid or sulfuric acid, and a solvent.

26. The coating liquid according to claim 25, wherein the sulfonic acid is paratoluenesulfonic acid or benzenesulfonic acid.

Images