Coating film, electronic device, mobile body, and coating liquid

Abstract

[Problem] To provide a coating film which is formed on the surface of a base material and thereby make it possible to minimize the adhesion of an oily component to the surface of the base material and to easily remove the oily component adhered to the surface of the base material. [Solution] A coating film which contains an organic substance and an inorganic substance, and does not contain fluorine (does not substantially contain fluorine), wherein: the inorganic substance contains SiO2; the organic substance contains a long-chain alkyl group, a polydimethylsiloxane (PDMS), and R1(R2)2R3Si; the content of the organic substance with respect to the coating film is higher on the surface side (in the upper layer including the surface) of the coating film than inside the coating film (in the lower layer and the intermediate layer); the contact angle of the coating film with water is 90° or more; and the contact angle of the coating film with oleic acid is 50° or more.

Description

Coating films, electronic devices, mobile devices, coating liquids

[0001] The present invention relates to a coating film formed on the surface of a substrate, and more particularly to an electronic device and a mobile body on which the coating film is formed, as well as to a coating liquid that is applied to the surface of a substrate in order to form the coating film.

[0002] With the development of ICT, information and communication devices such as smartphones, PCs, and car navigation systems have become widespread, and fingerprint smudges have become a problem for devices that are operated by touch. When sebum, which is transferred as fingerprints, adheres to glass surfaces, it is noticeable and difficult to wipe off, resulting in a poor appearance. Therefore, there is a need for a fingerprint-resistant coating agent that can be used on displays such as smartphones and touch panels. In addition, building exteriors and the bodies of mobile vehicles are contaminated by substances contained in the atmosphere, such as sand, dust, yellow sand, PM2.5, pollen, and insects, so there is a need for the development of a coating agent that makes it difficult for these stains to adhere and easy to remove. The following patent discloses an example of a polysilazane composition (see Patent Document 1).

[0003] Patent No. 7565253

[0004] The coating film disclosed in Patent Document 1 is a coating agent composed of polysilazane and fluoropolymer as independent components. After application, the polysilazane layer and the fluoropolymer layer undergo phase separation, achieving both antifouling and gas barrier properties. It contains polysilazane and fluoropolymer as independent components, has excellent compatibility, and is a coating film that can be cured at room temperature of about 25°C, achieving excellent antifouling properties. It is a polysilazane-based film with high water-repellent and oil-repellent properties and antifouling properties, but it is a film that contains an organic compound with fluorine atoms.

[0005] In recent years, problems have arisen regarding perfluoroalkyl and polyfluoroalkyl compounds (PFAS), including their eventual accumulation in the human body, toxicity, and environmental pollution. Therefore, there is a strong demand for the development of fluorine-free coating films that offer fingerprint resistance and stain resistance.

[0006] Therefore, an object of the present invention is to provide a coating film that is fluorine-free, can be formed on the surface of a substrate, can minimize the adhesion of water components and oil components to the surface of the substrate, and can easily remove the water components and oil components adhering to the surface of the substrate. Another object of the present invention is to provide a coating film that can form an oil-repellent coating film that is difficult for water components and oil components to adhere to on the surface of a substrate at low cost without much effort.

[0007] A first premise of the present invention for solving the above problems is a coating film containing an organic substance and an inorganic substance.

[0008] The characteristics of the coating film of the present invention in the first premise are that the coating film is non-containing fluorine (substantially does not contain fluorine), the inorganic substance contains SiO ２ and the organic substance contains a long-chain alkyl group, the content of the organic substance in the coating film is higher on the surface side (upper layer including the surface) of the coating film than in the interior (lower layer and intermediate layer) of the coating film, the contact angle of oleic acid in the coating film is 50° or more, and it has oil-repellency. Note that substantially not containing fluorine means that a fluorine compound is not intentionally added to the coating film for the purpose of imparting water and oil repellency performance to the coating film.

[0009] As an example of the coating film of the present invention, the water contact angle in the coating film is 90° or more.

[0010] As another example of the coating film of the present invention, the organic substance is polydimethylsiloxane (hereinafter abbreviated as PDMS) and R １ (R ２ ) ２ R ３ Si, (R １ = an alkyl group having 6 to 50 carbon atoms, R ２ = CH ３ , C ２ H ５ , OH, OCH ３ , OC ２ H ５ , R ３ = OH, OCH ３ , OC ２ H ５*Note that * represents the inorganic main chain or the binding species that binds to PDMS.

[0011] Another example of a coating film of the present invention is one in which PDMS is SiO ２ It is 0.2 to 1.1 times, and R １ (R ２ ) ２ R ３ Si is SiO ２ It is 0.2 to 1.1 times that.

[0012] Another example of the coating film of the present invention is the terminal hydroxyl group of PDMS and SiO ２ They are covalently bonded.

[0013] Another example of the coating film of the present invention is R １ (R ２ ) ２ R ３ Si contains at least one of either an octadecyl group or an octyl group.

[0014] Another example of the coating film of the present invention is a substrate on which the coating film is formed, which may be glass, ceramics, metal, or resin.

[0015] In the electronic device according to the present invention, a substrate on which the coating film of the present invention is formed is used in the display section.

[0016] Examples of electronic devices of the present invention include smartphones, personal computers, tablets, car navigation systems, digital signage, photocopiers, facsimile machines, scanners, printers, multifunction devices, televisions, and home appliances equipped with displays or touch panels.

[0017] The mobile body according to the present invention comprises a glass window or a vehicle body, ship hull, or aircraft body on which the coating film of the present invention is formed.

[0018] An example of a mobile body of the present invention is a train, automobile, ship, or airplane, and the glass window on which the coating film is formed is at least the windshield of the train, automobile, ship, or airplane.

[0019] A second premise of the present invention for solving the aforementioned problems is the coating liquid used when forming the coating film.

[0020] The characteristics of the coating solution of the present invention in the second premise described above are that the coating solution is fluorine-free (substantially fluorine-free), and contains polysilazane, polydimethylsiloxane (PDMS), and R １ (R ２ ) ２ R ３ Includes Si and R １ = Alkyl alkyl groups with 6 to 50 carbon atoms, R ２ =CH ３ , C ２ H ５ OH, OCH ３ , OC ２ H ５ , R ３ = OH, OCH ３ , OC ２ H ５ The key feature is that it is * (where * represents the inorganic main chain or a bonding species that binds to PDMS). Furthermore, "substantially fluorine-free" means that fluorine compounds are not intentionally added to the coating solution for the purpose of imparting water-repellent and oil-repellent properties to the coating film.

[0021] An example of the coating solution of the present invention is an inorganic polysilazane (hereinafter abbreviated as PHPS) in which the polysilazane is used.

[0022] Another example of the coating solution of the present invention is one in which PDMS has hydroxyl groups at its terminals, and the hydroxyl groups at the terminals of PDMS react with polysilazane, so that the polysilazane is covalently bonded to PDMS.

[0023] Another example of the coating solution of the present invention is one in which PDMS is 0.2 to 1.1 times the mass of polysilazane, R １ (R ２ ) ２ R ３ The amount of Si is 0.2 to 1.1 times the mass of polysilazane.

[0024] Another example of the coating solution of the present invention is R １ (R ２ ) ２ R３ Si contains at least one of n-octadecyldimethylmethoxysilane and n-octyldimethylmethoxysilane.

[0025] Another example of the coating solution of the present invention is a coating solution in which the organic solvent contained is dibutyl ether. Another example of the coating solution of the present invention is a coating solution in which the organic solvent contains at least one of low-boiling silicon and limonene, an aliphatic hydrocarbon.

[0026] According to the coating film of the present invention, the content of organic substances containing long-chain alkyl groups is higher on the surface side of the coating film (upper layer including the surface) than in the interior (lower and intermediate layers), contributing to the smoothness of the surface. Furthermore, the added PDMS gives the coating film excellent oil repellency on its surface side, and the contact angle of oleic acid in the coating film is 50° or more, so the adhesion of oily substances to the surface of the substrate can be minimized, and even if oily substances adhere to the surface of the substrate on which the coating film is formed, the oily substances adhering to the surface of the substrate can be easily removed. Because the coating film minimizes the adhesion of oily substances to the surface of the substrate, the soiling of the substrate surface by oily substances can be minimized. The coating film allows for the inexpensive and effortless formation of an oil-repellent coating film on the surface of the substrate that is resistant to the adhesion of oily substances. Because the surface of the substrate is covered with a coating film that has excellent strength and excellent scratch resistance, the surface of the substrate can be protected by the coating film, and scratches on the surface of the substrate can be prevented. Since the coating film does not contain fluoride (or is substantially fluoride-free), there is no risk of chronic poisoning such as fluoride-induced tooth mottling (dental fluoride disease) or osteosclerosis, or acute poisoning such as severe abdominal pain, vomiting, nausea, or death from poisoning.

[0027] The coating film has a water contact angle of 90° or more, and possesses excellent water repellency, minimizing the adhesion of moisture to the substrate surface and preventing soiling of the substrate surface due to moisture adhesion. The coating film allows for the inexpensive and easy formation of a water-repellent coating film on the substrate surface that resists moisture adhesion.

[0028] The coating film is made of organic materials including polydimethylsiloxane (hereinafter abbreviated as PDMS) and R １ (R ２ ) ２ R ３ Si, (R １ = Alkyl alkyl groups with 6 to 50 carbon atoms, R ２ =CH ３ , C ２ H ５ OH, OCH ３ , OC ２ H ５ , R ３ = OH, OCH ３ , OC ２ H ５ ,*,Note,* = represents the inorganic main chain or the bonding species that binds to PDMS.) As such, the coating film can be given excellent oil repellency without uneven coating, minimizing the adhesion of oily substances to the substrate surface, and even if oily substances adhere to the substrate surface on which the coating film is formed, the oily substances can be easily removed from the substrate surface. Because the coating film has excellent oil repellency, the adhesion of oily substances to the substrate surface is minimized, thus minimizing dirt on the substrate surface caused by oily substances. The coating film has excellent water repellency, which minimizes the adhesion of moisture to the substrate surface, and prevents dirt on the substrate surface caused by moisture adhesion. The coating film can be formed on the substrate surface inexpensively and without much effort, creating a coating film that is resistant to oily substances and resistant to water.

[0029] The coating film is PDMS with SiO ２ It is 0.2 to 1.1 times, and R １ (R ２ ) ２ R ３ Si is SiO ２Since the ratio is 0.2 to 1.1 times, the coating film can be given excellent oil repellency, minimizing the adhesion of oily substances to the substrate surface, and even if oily substances adhere to the substrate surface on which the coating film is formed, the oily substances can be easily removed from the substrate surface. Because the coating film has excellent oil repellency, the adhesion of oily substances to the substrate surface is minimized, thus minimizing oily staining of the substrate surface. The coating film has excellent water repellency, which minimizes the adhesion of moisture to the substrate surface, and prevents staining of the substrate surface due to moisture adhesion. The coating film can be formed on the substrate surface inexpensively and without much effort, providing a coating film with excellent oil repellency that makes it difficult for oily substances to adhere and excellent water repellency that makes it difficult for moisture to adhere.

[0030] The coating film consists of hydroxyl groups at the ends of PDMS and SiO ２The covalent bonding between these elements allows for the formation of an ultrathin film with high strength and long-lasting durability. The coating film contains a large amount of organic matter, including long-chain alkyl groups, on its surface (upper layer including the surface), contributing to its smooth surface. Furthermore, the added PDMS gives the coating film excellent oil repellency on its surface, minimizing the adhesion of oily substances to the substrate surface. Even if oily substances adhere to the substrate surface on which the coating film is formed, these substances can be easily removed. The coating film's excellent oil repellency minimizes the adhesion of oily substances to the substrate surface, thus minimizing oil-related staining of the substrate surface. The coating film also possesses excellent water repellency, minimizing the adhesion of moisture to the substrate surface and preventing staining of the substrate surface due to moisture adhesion. The coating film allows for the inexpensive and effortless formation of a coating film on the substrate surface with excellent oil repellency (making it difficult for oily substances to adhere) and excellent water repellency (making it difficult for moisture to adhere). The molecular weight of PDMS is not particularly limited, but using PDMS with a higher molecular weight can increase the contact angle between water and oleic acid. Preferred molecular weights are 100 to 100,000 g / mol, more preferably 400 to 50,000 g / mol, and even more preferably 500 to 30,000 g / mol.

[0031] The coating film not only has excellent oil repellency, but at least one of the octadecyl group and the octyl group is R １ (R ２ ) ２ R ３The inclusion of Si improves the smoothness of the coating film, creating a smooth surface on the substrate. The coating film has excellent water repellency, minimizing the adhesion of moisture to the substrate surface and preventing soiling caused by moisture. The coating film provides excellent oil repellency, making it difficult for oily substances to adhere, and excellent water repellency, making it difficult for moisture to adhere, and can be formed on the substrate surface inexpensively and without much effort. Because the substrate surface is covered with a coating film that has excellent strength, excellent scratch resistance, and excellent smoothness, the substrate surface can be made smooth, and the coating film protects the substrate surface, preventing scratches.

[0032] The coating film is applied to a substrate made of glass, ceramics, metal, or resin. Because the coating film has excellent oil-repellent properties, it minimizes the adhesion of oily substances to the glass, ceramics, metal, or resin surface. Furthermore, even if oily substances adhere to the coated surface, they can be easily removed. The coating film's excellent oil-repellent properties minimize the adhesion of oily substances to the glass, ceramics, metal, or resin surface, thus minimizing oil-related staining. The coating film also possesses excellent water-repellent properties, minimizing the adhesion of moisture to the glass, ceramics, metal, or resin surface, and preventing staining caused by moisture. The coating film provides excellent oil repellency, making it difficult for oily substances to adhere, and excellent water repellency, making it difficult for water to adhere. This coating film can be formed inexpensively and easily on glass, ceramics, metal, and resin surfaces. Because the glass, ceramics, metal, and resin surfaces are covered with a coating film that has excellent strength, excellent scratch resistance, and excellent smoothness, the surfaces of glass, ceramics, metal, and resin can be made smooth, and the coating film protects the surfaces of glass, ceramics, metal, and resin, preventing scratches.

[0033] According to the electronic device of the present invention, a coating film containing a large amount of organic matter including long-chain alkyl groups on the surface side (upper layer including the surface) is formed on the display portion of the electronic device, contributing to the smoothness of the surface. Furthermore, the excellent oil repellency of the coating film due to the added PDMS minimizes the adhesion of oily substances to the display portion of the electronic device, and even if oily substances adhere to the display portion of the electronic device on which the coating film is formed, the oily substances can be easily removed from the display portion. Because the coating film has excellent oil repellency, the adhesion of oily substances to the display portion of the electronic device is minimized, thus minimizing oily contamination of the display portion of the electronic device. The coating film has excellent water repellency, which minimizes the adhesion of moisture to the display portion of the electronic device, thus preventing contamination of the display portion of the electronic device due to moisture adhesion. Because the display portion of the electronic device is covered with a coating film having excellent strength, excellent scratch resistance, and excellent smoothness, the display portion of the electronic device can be made smooth, and the coating film can protect the display portion of the electronic device, preventing scratches on the display portion of the electronic device.

[0034] Electronic devices include smartphones, personal computers, tablets, car navigation systems, digital signage, copiers, fax machines, scanners, printers, multifunction devices, televisions, and home appliances equipped with displays or touch panels. A coating film with excellent oil-repellent properties is formed on the display units of smartphones, personal computers, tablets, car navigation systems, digital signage, copiers, fax machines, scanners, printers, multifunction devices, and televisions, as well as on the displays and touch panels of home appliances. This minimizes the adhesion of oily substances to these displays and home appliance displays and touch panels, and even if oily substances do adhere to them, they can be easily removed. The coating film, with its excellent oil-repellent properties, minimizes the adhesion of oily substances to smartphones, personal computers, tablets, car navigation systems, digital signage, copiers, fax machines, scanners, printers, multifunction devices, television displays, and the displays and touch panels of home appliances, thereby minimizing oil-related staining on these displays and touch panels. Furthermore, the coating film's excellent water-repellent properties minimize the adhesion of moisture to smartphones, personal computers, tablets, car navigation systems, digital signage, copiers, fax machines, scanners, printers, multifunction devices, television displays, and the displays and touch panels of home appliances, preventing staining caused by moisture.Electronic devices such as smartphones, personal computers, tablets, car navigation systems, digital signage, copiers, fax machines, scanners, printers, multifunction devices, television displays, and the displays and touch panels of home appliances are coated with a coating film that has excellent strength, excellent scratch resistance, and excellent smoothness. As a result, the displays and touch panels of smartphones, personal computers, tablets, car navigation systems, digital signage, copiers, fax machines, scanners, printers, multifunction devices, television displays, and home appliances can be made smooth, and the coating film can protect the displays and touch panels of smartphones, personal computers, tablets, car navigation systems, digital signage, copiers, fax machines, scanners, printers, multifunction devices, television displays, and home appliances, preventing scratches on these displays and touch panels.

[0035] According to the mobile body of the present invention, a coating film containing a large amount of organic matter including long-chain alkyl groups on the surface side (upper layer including the surface) is formed on the glass window or body of the mobile body, such as a vehicle, ship, or machine. Therefore, the excellent oil-repellent properties of the coating film minimize the adhesion of oily substances to the glass window or body of the mobile body, such as a vehicle, ship, or machine. Furthermore, even if oily substances adhere to the glass window or body of the mobile body, such as a vehicle, ship, or machine, the oily substances can be easily removed. Because the coating film with excellent oil repellency minimizes the adhesion of oily substances to the glass window or body of the mobile body, such as a vehicle, ship, or machine, the oily substances can be minimized from the glass window or body of the mobile body, such as a vehicle, ship, or machine. Because the coating film with excellent oil repellency minimizes the adhesion of water to the glass window or body of the mobile body, such as a vehicle, ship, or machine, the oily substances can be minimized from the glass window or body of the mobile body, such as a vehicle, ship, or machine. Since the glass windows or body, hull, or aircraft of the mobile body are covered with a coating film that has excellent strength, excellent scratch resistance, and excellent smoothness, the glass windows or body, hull, or aircraft of the mobile body can be made smooth, and the glass windows or body, hull, or aircraft can be protected by the coating film, preventing scratches on the glass windows or body, hull, or aircraft of the mobile body.

[0036] The moving body is one of a train, an automobile, a ship, and an airplane. Since the glass window with the coating film is at least the front glass of a train, an automobile, a ship, or an airplane, a coating film having excellent oil repellency is formed on at least the front glass of a train, an automobile, a ship, or an airplane, so that the adhesion of oil components to the front glass can be minimized. Even if oil components adhere to the front glass, the adhered oil components can be easily removed. Since the adhesion of oil components to at least the front glass of a train, an automobile, a ship, or an airplane is minimized by the coating film having excellent oil repellency, the dirt on the front glass due to oil components can be minimized. The moving body can minimize the adhesion of moisture to at least the front glass of a train, an automobile, a ship, or an airplane due to the excellent water repellency of the coating film, and can prevent the dirt on the front glass associated with the adhesion of moisture. Since at least the front glass of a train, an automobile, a ship, or an airplane is coated with a coating film having excellent strength, excellent scratch resistance function, and excellent smoothness, the front glass can be smoothed, and the front glass can be protected by the coating film, and the front glass of a train, an automobile, a ship, or an airplane can be prevented from being scratched.

[0037] According to the coating liquid of the present invention, it is fluorine-free (substantially free of fluorine), and contains polysilazane, polydimethylsiloxane (PDMS), and R １ (R ２ ) ２ R ３ Si, and R １ = an alkyl group having 6 to 50 carbon atoms, R ２ = CH ３ 、C ２ H ５ 、OH、OCH ３ 、OC ２ H ５ 、R ３ = OH、OCH ３ 、OC ２ H ５,* (Note: * = represents the inorganic main chain or the bonding species that binds to PDMS.) Therefore, the coating film made from the coating liquid has excellent oil repellency, and by coating the surface of the substrate with the coating liquid, the adhesion of oily substances to the surface of the substrate can be minimized, and even if oily substances do adhere to the surface of the substrate, a coating film can be formed that allows for easy removal of the oily substances. The coating liquid can form a coating film that minimizes the adhesion of oily substances to the surface of the substrate due to the excellent oil repellency of the coating film made from it, thus minimizing oily contamination of the surface of the substrate. The coating liquid can form a coating film that minimizes the adhesion of moisture to the surface of the substrate, thus preventing contamination of the surface of the substrate due to moisture adhesion. The coating liquid can form a coating film on the surface of the substrate that has excellent oil repellency, making it difficult for oily substances to adhere, and excellent water repellency, making it difficult for moisture to adhere, at low cost and without requiring much effort. The coating liquid forms a coating film that covers the surface of the substrate with excellent strength and scratch resistance, thus protecting the surface of the substrate and preventing scratches. Since the coating liquid does not contain fluoride (it is substantially fluoride-free), it can form a coating film that does not pose a risk of causing chronic poisoning such as fluoride mottling (dental fluoride disease) or osteosclerosis, or acute poisoning such as severe abdominal pain, vomiting, nausea, or death from poisoning.

[0038] Since the coating liquid contains polysilazane in the form of PHPS, the coating film made from the coating liquid has excellent oil repellency, excellent strength, and excellent scratch resistance. By coating the substrate surface with the coating liquid, the adhesion of oily substances to the substrate surface can be minimized. Even if oily substances adhere to the substrate surface, they can be easily removed, and the coating film made from the coating liquid can protect the substrate surface, forming a coating film that prevents scratches on the substrate surface. The coating liquid, due to the excellent oil repellency of the coating film made from it, minimizes the adhesion of oily substances to the substrate surface, thus forming a coating film that minimizes oily staining on the substrate surface. The coating liquid, due to the excellent water repellency of the coating film made from it, minimizes the adhesion of moisture to the substrate surface, forming a coating film that prevents staining of the substrate surface due to moisture adhesion.

[0039] The coating liquid is such that PDMS has a hydroxy group at its end, the hydroxy group at the end of PDMS reacts with polysilazane, and polysilazane is covalently bonded to PDMS. Therefore, a coating film of an ultrathin film with high strength can be formed from the coating liquid, and a coating film of an oleophobic ultrathin film can be made. In the coating liquid, there are many organic substances containing long-chain alkyl groups on the surface side (the upper layer including the surface) of the coating film made therefrom. The coating film made from the coating liquid has excellent oleophobicity on its surface side, can minimize the adhesion of oil components to the surface of the substrate, and even if an oil component adheres to the surface of the substrate on which the coating film is formed, a coating film that can easily remove the oil component adhering to the surface of the substrate can be formed. Since the adhesion of oil components to the surface of the substrate is minimized due to the excellent oleophobicity of the coating film made from the coating liquid, a coating film that can minimize the stain caused by the oil component on the surface of the substrate can be formed. The coating liquid is such that the coating film made therefrom has excellent water repellency, can minimize the adhesion of moisture to the surface of the substrate, and can form a coating film that can prevent the stain of the surface of the substrate associated with the adhesion of moisture.

[0040] The coating liquid is such that PDMS is 0.2 to 1.1 times in mass with respect to polysilazane, and R １ (R ２ ) ２ R ３Since the amount of Si is 0.2 to 1.1 times the mass of polysilazane, the coating film made from the coating liquid can be given excellent oil repellency, minimizing the adhesion of oily substances to the substrate surface. Furthermore, even if oily substances adhere to the substrate surface on which the coating film is formed, the coating film can be formed in a way that allows for easy removal of the oily substances. The coating liquid can form a coating film that minimizes the adhesion of oily substances to the substrate surface due to the excellent oil repellency of the coating film made from it. The coating liquid can form a coating film that minimizes the adhesion of moisture to the substrate surface, thereby preventing soiling of the substrate surface due to moisture adhesion.

[0041] The coating solution not only produces a coating film with excellent oil repellency, but also contains at least one of n-octadecyldimethylmethoxysilane and n-octyldimethylmethoxysilane, R １ (R ２ ) ２ R ３ The inclusion of Si improves the smoothness of the coating film made from the coating liquid, creating a smooth surface on the substrate. The coating liquid forms a coating film that has excellent water repellency, minimizing the adhesion of moisture to the substrate surface and preventing soiling of the substrate surface due to moisture adhesion. The coating liquid forms a coating film that has excellent strength, excellent scratch resistance, and excellent smoothness, covering the substrate surface smoothly, thus protecting the substrate surface and preventing scratches on the substrate surface.

[0042] Since the coating liquid contains dibutyl ether as its organic solvent, it can be applied evenly and smoothly to the substrate surface, forming a coating film of uniform thickness. The coating liquid forms a coating film that has excellent strength, excellent scratch resistance, and excellent smoothness, covering the substrate surface smoothly, thus protecting the substrate surface and preventing scratches. If the coating liquid contains low-boiling-point silicon as its organic solvent, it can significantly improve uneven application of the coating liquid to the substrate surface, allowing for even application and forming a coating film of uniform thickness. If the coating liquid contains limonene, an aliphatic hydrocarbon, as its organic solvent, it can mitigate the unpleasant odor of dibutyl ether, suppressing the diffusion of unpleasant odors into the surroundings when applying the coating liquid to the substrate surface.

[0043] A cross-sectional image showing an enlarged view of an example of a coating liquid coated on the surface of a substrate. A cross-sectional diagram illustrating the time-series mechanism by which an oil-repellent glass-based inorganic coating film or an oil-repellent glass-based organic / inorganic hybrid coating film is formed from the coating liquid on the surface of a substrate coated with the coating liquid. A cross-sectional image showing an enlarged view of an oil-repellent glass-based inorganic coating film or an oil-repellent glass-based organic / inorganic hybrid coating film formed on the surface of a substrate. An image showing an example of the chain length of n-octadecyldimethylmethoxysilane. An image showing an example of the chain length of n-octylmethylmethoxysilane. An image showing an example of the structure of an oil-repellent glass-based inorganic coating film. An image showing an example of the structure of an oil-repellent glass-based organic / inorganic hybrid coating film. A table illustrating the composition and measurement results of Examples 1 to 7 of the oil-repellent glass-based inorganic coating film or the oil-repellent glass-based organic / inorganic hybrid coating film.

[0044] Referring to the attached drawings, the details of the coating film 10 according to the present invention will be described as follows. Figure 1 is an enlarged cross-sectional image showing an example of a coating liquid 13 coated on the surface 12 of a substrate 11, and Figure 2 is a cross-sectional image illustrating in chronological order the mechanism by which an oil-repellent glass-based coating film 10 is formed from the coating liquid 13 on the surface 12 of the substrate 11 coated with the coating liquid 13. Figure 3 is an enlarged cross-sectional image showing the oil-repellent glass-based coating film 10 formed on the surface 12 of the substrate 11, and Figure 4 is an image showing an example of the chain length of n-octadecyldimethylmethoxysilane. Figure 5 is an image showing an example of the chain length of n-octyldimethylmethylmethoxysilane, and Figure 6 is an image showing an example of the structure of the oil-repellent glass-based coating film 10. Figure 7 is an image showing another example of the structure of the oil-repellent glass-based coating film 10.

[0045] Figure 3 shows the terminal hydroxyl group of PDMS (polydimethylsiloxane) and SiO ２ Although the covalent bond between the two is illustrated as a visually observable image, in reality, the covalent bond cannot be visually observed. In Figures 4 and 5, the chain lengths of n-octyldimethylmethoxysilane and n-octadecyldimethylmethoxysilane are illustrated as a visually observable image, but in reality, the chain lengths cannot be visually observed. Figure 2(a) shows the state immediately after coating the surface 12 of the substrate 11 with the coating liquid 13, and Figure 2(b) shows the state in which an oil-repellent glass-based coating film 10 is being formed from the coating liquid 13. Figure 2(c) shows the state after the coating liquid 13 has completely hardened and an oil-repellent glass-based coating film 10 has been formed on the surface 12 of the substrate 11.

[0046] The oil-repellent glass-based coating film 10 is made by coating (applying) the coating liquid 13 to the surface 12 (front and back) of the substrate 11 to be coated. The cured coating liquid 13 forms an oil-repellent glass-based coating film 10 of a predetermined thickness that covers the surface 12 of the substrate 11.

[0047] The coating liquid 13 that forms the oil-repellent glass-based coating film 10 contains polysilazane, PDMS, and R １ (R ２ ) ２ R ３ It contains Si and an organic solvent. The coating solution 13 is substantially fluorine-free and fluorine-free. The polysilazane used to form the coating solution 13 is an inorganic polysilazane, specifically a Si-N type perhydropolysilazane. Furthermore, Si-C-N type organopolysilazanes and Si-C type polycarbosilanes can be used as polysilazanes, and SiC-O, Si-B-C-N, and Si-Ti-N type polysilazanes can also be used. Organopolysiloxanes can also be used.

[0048] As the polysilazane forming the coating solution 13, modified polysilazanes such as methylpolysilazane, dimethylpolysilazane, phenylpolysilazane, and vinylpolysilazane, which are organic polysilazanes, can also be used. Alternatively, crosslinked polysilazanes can be used that are chemically crosslinked with compounds such as hydrocarbon compounds having reactive groups such as hydroxyl groups, vinyl groups, amino groups, and silyl groups, cyclic saturated hydrocarbon compounds, cyclic unsaturated hydrocarbon compounds, saturated heterocyclic compounds, unsaturated heterocyclic compounds, and silicon compounds, which chemically react with polysilazane to form a crosslinked structure.

[0049] In addition, polysilazane compositions can also be used, such as polyborosilazane, inorganic silazane high polymers or modified polysilazanes, copolymerized silazanes, low-temperature ceramicized polysilazanes obtained by adding or adding catalytic compounds to polysilazanes to promote ceramicization, silicon alkoxide-added polysilazanes, glycidol-added polysilazanes, acetylacetonate complex-added polysilazanes, metal carboxylate-added polysilazanes, and polysilazane compositions obtained by adding amines and / or acids to the above various polysilazanes or modified products.

[0050] The polysilazane can be a single polysilazane, a mixture of two or more polysilazanes selected from various polysilazanes, or a polysilazane copolymer consisting of two or more polysilazane structures, and each molecule contains at least one hydrogen atom directly bonded to a silicon atom. The polysilazane forming the coating liquid 13 has a weight-average molecular weight in the range of 100 to 100,000,000 g / mol, preferably 1,000 to 1,000,000 g / mol, and more preferably 2,000 to 500,000 g / mol, from the viewpoint of solubility in the solvent and workability during application. If the weight-average molecular weight is 100 or more, it is highly volatile, and the film quality of the coating may deteriorate due to the evaporation of the solvent and the evaporation of the polysilazane itself during the curing process.

[0051] Since the coating liquid 13 has a number-average molecular weight of polysilazanes (such as perhydropolysilazanes, organopolysilazanes, and organopolysiloxanes) within the aforementioned range, the coating liquid 13 containing polysilazanes can maintain a predetermined viscosity, and an oil-repellent glass-based inorganic coating film 10 or an oil-repellent glass-based organic / inorganic hybrid coating film 10 can be formed from the coating liquid 13. Since the coating liquid 13 is coated onto the surface 12 of the substrate 11 to be coated while maintaining a predetermined viscosity, even if the coating liquid 13 is applied to the surface 12 of the substrate 11 where minute pores or meshes are formed, the coating liquid 13 will not penetrate into the interior of the substrate 11, and an oil-repellent glass-based coating film 10 with a substantially uniform film thickness can be formed on the surface 12 of the substrate 11.

[0052] Inorganic polysilazanes are represented by the general formula (Chemical Formula 1).

[0053] Inorganic polysilazanes contain linear structures with structural units, have a molecular weight of 690 to 2,000, and contain 3 to 10 SiH molecules per molecule. ３ Examples of perhydropolysilazanes include those having a group and having elemental ratios determined by chemical analysis of Si: 59-61, N: 31-34, and H: 6.5-7.5% by weight, and perhydropolysilazanes having an average molecular weight in polystyrene terms in the range of 3,000-20,000.

[0054] Perhydropolysilazanes contain both a chain-like and a cyclic portion within their molecule and are represented by the following chemical formula (Chemical Formula 2).

[0055] An example of the structure of a perhydropolysilazane is represented by the following chemical formula (Chemical Formula 3).

[0056] Another example of the perhydropolysilazane group is represented by the following general formula (Chemical Formula 4), which consists of a Si-N bond and a functional group (R １ ~R ３ ) has -(SiR １ R ２ -NR ３ ) - A polymer formed from units, with a functional group R that directly bonds to Si. １ , R ２ It is an organic polymer in which at least one of the elements is formed from an organic functional group such as an alkyl group having carbon (C).

[0057] Furthermore, perhydropolysilazanes are functional groups (R) of organic compounds that have a structure in which a carbon atom is replaced by three hydrogen atoms. １ ~R ３ ) is one of the methyl groups (CH ３ The content of ) is 50% or more. Also, perhydropolysilazane is one type of -(SiR １ R ２ -NR ３ ) - Not only polymers formed from units, but also functional groups (R １ ~R ３ Multiple types of (SiR) with different compositions １ R ２ -NR ３ ) - It may be a polymer formed from units. Furthermore, the perhydropolysilazane may be a polymer having a chain-like, cyclic, or cross-linked structure, or a polymer having a combination of these structures. １ , R ２ , R ３R represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a group other than those listed above in which the group directly bonded to silicon is carbon, an alkylsilyl group, an alkylamino group, or an alkoxy group. However, R １ , R ２ , R ３ At least one of them is a hydrogen atom.

[0058] As an example, perhydropolysilazane (A) is represented by the following general formula (Chemical Formula 5) - (SiH(CH ３ )-NH)-unit,-(Si(CH ３ )2-NH)-unit,-(SiR １ (CH ３ ) - NR ３ ) - A polymer containing units. - (SiR １ (CH ３ ) - NR ３ ) - In the unit, the functional group R1 is H or CH ３ The functional group R3, which directly bonds with N, is an organic functional group that promotes the reaction. The inclusion of perhydropolysilazane (A) in the coating solution 13 promotes the reaction after the coating solution 13 is coated onto the surface 12 of the substrate 11, allowing for the early formation of an oil-repellent glass-based coating film 10 on the surface 12 of the substrate 11.

[0059] Another example is perhydropolysilazane (B), which is represented by the following general formula (Chemical Formula 6) - (SiH(CH ３ )-NH)-unit,-(SiR １ (CH ３ A polymer containing a )-NH- unit, and -(SiR １ (CH ３ )-NH-unit functional group R １ This is an organic functional group that enables high heat resistance. The inclusion of perhydropolysilazane (B) in the coating liquid 13 enhances the heat resistance of the oil-repellent glass-based coating film 10 that covers the surface 12 of the substrate 11.

[0060] The perhydropolysilazane contained in the coating liquid 13 may be a mixture of several types of perhydropolysilazanes with different polymer structures. For example, it may be a perhydropolysilazane mixture of perhydropolysilazane (A) and perhydropolysilazane (B). Experiments on mixing these perhydropolysilazanes (A) and perhydropolysilazane (B) showed that a blending ratio of 50% by mass of perhydropolysilazane (A) and 50% by mass of perhydropolysilazane (B) exhibited rust prevention properties equivalent to or better than perhydropolysilazane (A) alone, and a reduction in curing time (formation time of the oil-repellent glass-based coating film 10) was confirmed compared to perhydropolysilazane (B) alone.

[0061] Organopolysilazane is R in the above general formula (Chemical Formula 4). １ and R ２ A hydrogen atom, R ３ It has an organic group. - (R ２ A polysilazane having a cyclic structure with a degree of polymerization of 3 to 5, with SiHNH)- as a repeating unit, (R ３ (otherHNH) ｘ [(R ２ SiH) １．５ N] １－Ｘ A polysilazane having both a chain structure and a cyclic structure within the molecule represented by the chemical formula (0.4 < X < 1), in the above general formula (Chemical Formula 4), R １ A hydrogen atom, R ２ , R ３ Polysilazane having an organic group, R １ and R ２ Organic group, R ３ It has a hydrogen atom - (R １ R ２ SiNR ３ There are polysilazanes that have a cyclic structure with a degree of polymerization of mainly 3 to 5, using ) as a repeating unit.

[0062] For example, organopolysilazanes having a cross-linking structure other than the one shown in the general formula (Chemical Formula 4) above can be represented by the following general formula (Chemical Formula 7).

[0063] Also, for example, R １ Six ３Polysilazane R having a cross-linked structure obtained by the ammonia decomposition of (X: halogen) １ Si (NH) ｘ , R １ Six ３ and R ２ ２ Six ２ The polysilazane structure obtained by the co-ammonia decomposition of the following general formula (Chemical Formula 8) is represented by the following general formula.

[0064] Examples of organopolysiloxanes include the average unit formula (A): (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d There is a polymer that has R in the average unit formula (A). １ Each of these is an independent monovalent organic group, preferably a monovalent ethylenically unsaturated group, a monovalent hydrocarbon group (excluding ethylenically unsaturated groups), or a monovalent substituted hydrocarbon group (excluding ethylenically unsaturated groups). 1 The number of carbon atoms is preferably 1 to 8, more preferably 1 to 6. The monovalent substituted hydrocarbon group has a hydrocarbon group as its basic skeleton and includes at least one functional group selected from the group consisting of, for example, a hydroxyl group, a mercapto group, an amino group, an isothiocyanate group, a nitro group, and a carbonyl group. 1 Preferably, is a monovalent ethylenically unsaturated group or a monovalent hydrocarbon group, and more preferably is a monovalent ethylenically unsaturated group.

[0065] Examples of monovalent ethylenically unsaturated groups include alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl groups. The number of carbon atoms in the alkenyl group is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 3. Examples of monovalent ethylenically unsaturated groups include (meth)acryloyloxyalkyl groups, i.e., formula (B):-R 12 -OC(=O)-CR11 There are also groups represented by =CH2. Specifically, these include the acryloyloxypropyl group and the methacryloyloxypropyl group. R in formula (B) 11 R is a hydrogen atom or a methyl group, 12 This is an alkanediyl group, preferably an alkanediyl group having 1 to 5 carbon atoms. Note that (meth)acrylic is used as a general term for acrylic and methacrylic, and (meth)acryloyl is used as a general term for acryloyl and methacryloyl.

[0066] Among monovalent ethylenically unsaturated groups, alkenyl groups are preferred, vinyl groups and allyl groups are preferred, and vinyl groups are more preferred. Examples of monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups; aryl groups such as phenyl, tolyl, and xylyl groups; and aralkyl groups such as benzyl and phenethyl groups. The number of carbon atoms in the monovalent hydrocarbon group is preferably 1 to 8, more preferably 1 to 5, and even more preferably 1 to 3.

[0067] Examples of monovalent substituted hydrocarbon groups include the 3-mercaptopropyl group (-(CH2)3-SH) and the 3-aminopropyl group (-(CH2)3-NH2). 1 From the viewpoint of miniaturization, these are preferably an alkyl group or an alkenyl group, more preferably an alkyl group having 1 to 3 carbon atoms, a vinyl group or an allyl group, and even more preferably a methyl group or a vinyl group.

[0068] In one molecule of organopolysiloxane having the average unit formula (A), at least a portion of R 1 The group is a functional group (L) containing a monovalent ethylenically unsaturated group, an aryl group, or an aralkyl group, preferably a monovalent ethylenically unsaturated group, and more preferably an alkenyl group. The total proportion of the monovalent ethylenically unsaturated group, aryl group, or aralkyl group is the total R in one molecule of organopolysiloxane. 1Based on this, the amount is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more. The monovalent ethylenically unsaturated group, aryl group, or aralkyl group is a hydrophobic group containing a nonionic functional group that can coordinate to a metal ion.

[0069] In the average unit formula (A), a, b, c, and d are each of the constituent units (R 1 3SiO 1 / 2 ), (R 1 2SiO 2 / 2 ), (R 1 SiO 3 / 2 ) and (SiO 4 / 2 This represents the average value of the mole fractions of the constituent units. The sum of the mole fractions of each constituent unit, a, b, c, and d, is 1. a is R 1 3SiO 1 / 2 This is the mole fraction of siloxane units expressed in (M units). a is 0 or more and 0.5 or less, preferably 0.4 or less, more preferably 0.3 or less, even more preferably 0.2 or less, and particularly preferably 0.1 or less.

[0070] b is R 1 2SiO 2 / 2 This is the mole fraction of siloxane units expressed in (D units). b is 0 or more and 0.5 or less, preferably 0.4 or less, more preferably 0.3 or less, even more preferably 0.2 or less, and particularly preferably 0.1 or less. c is R 1 SiO 3 / 2 This is the mole fraction of siloxane units expressed in (T units). c is 0.3 or more and 1 or less, preferably 0.4 or more, 0.5 or more or 0.6 or more, more preferably 0.7 or more, even more preferably 0.8 or more, and particularly preferably 0.9 or more.

[0071] d is SiO 4 / 2This is the mole fraction of siloxane units expressed in (Q units). d is 0 or more and 0.7 or less, preferably 0.6 or less, 0.5 or less, or 0.4 or less, more preferably 0.3 or less, even more preferably 0.2 or less, and particularly preferably 0.1 or less. The sum of c and d, which represent the total sum of the branched constituent units, is preferably 0.6 or more, more preferably 0.7 or more, even more preferably 0.8 or more, and particularly preferably 0.9 or more.

[0072] Organopolysiloxanes are constituent units (R) in the average unit formula (A). 1 3SiO 1 / 2 If it has a constituent unit (R 1 2SiO 2 / 2 ) and (R 1 SiO 3 / 2 The same applies to the organopolysiloxane. 1 At least a portion of R 2 It may have constituent units that have been replaced by O. R in the average unit formula (A) 2 R is a hydrogen atom or an alkyl group. 2 O represents a hydroxyl group or alkoxy group bonded to a silicon atom in the organopolysiloxane skeleton. Examples of alkyl groups include methyl, ethyl, and propyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 3.

[0073] R in each of the above-mentioned constituent units 1 At least a portion of R 2 The amount of the constituent unit replaced by O is preferably 0 to 0.10, more preferably 0 to 0.05, and even more preferably 0 to 0.03, relative to 1, which is the sum of the mole fractions of the constituent units a, b, c, and d. The alkoxy group in the constituent unit is, for example, an alkoxy group that is hydrolyzable and contained in the alkoxysilane described later, and which remains in the molecule without hydrolysis or polycondensation. The hydroxyl group in this constituent unit is, for example, a hydroxyl group that remains in the molecule without polycondensation after hydrolysis of the alkoxy group.

[0074] The organopolysiloxane is preferably a silsesquioxane. A silsesquioxane is a compound whose main chain skeleton consists of Si-O bonds and whose main constituent unit is (R 1 SiO 3 / 2 The organopolysiloxane contains units and has c of 0.7 or more. Examples of silsesquioxane structures include random structures, complete cage structures, incomplete cage structures, and ladder structures, but among these, silsesquioxane having a random structure is preferred from the viewpoint of ease of manufacture.

[0075] The aforementioned constituent unit (R 1 3SiO 1 / 2 As for the alkoxysilanes that form ) R 1 3Si(OR 2 Examples of compounds represented by ) include methoxydimethylvinylsilane, ethoxydimethylvinylsilane, methoxydimethylphenylsilane, and ethoxydimethylphenylsilane; as well as methoxytrimethylsilane and ethoxytrimethylsilane.

[0076] The aforementioned constituent unit (R 1 2SiO 2 / 2 As for the alkoxysilanes that form ) R 1 2Si( OR 2 Examples of compounds represented by )2 include dimethoxymethylvinylsilane, diethoxymethylvinylsilane, and dimethoxybenzylmethylsilane; as well as dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethylsilane, dipropoxydimethylsilane, and dipropoxydiethylsilane.

[0077] The aforementioned constituent unit (R 1 SiO 3 / 2 As for the alkoxysilanes that form ) R 1 Si ( OR 2Compounds represented by )3 are examples. Specific examples include, for example, trimethoxyvinylsilane, triethoxyvinylsilane, trimethoxyallylsilane, triethoxyallylsilane, (3-(meth)acryloyloxypropyl)trimethoxysilane and (3-(meth)acryloyloxypropyl)triethoxysilane; as well as methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane and butyltrimethoxysilane. The constituent unit (SiO 4 / 2 As for the alkoxysilanes that form ), Si (OR 2 Examples of compounds represented by 4 include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.

[0078] PDMS (polydimethylsiloxane) is a compound that has heat resistance, low surface tension, and water repellency, and is represented by the following general formula (Chemical Formula 9).

[0079] In the coating solution 13, the PDMS has hydroxyl groups at its ends, and these hydroxyl groups react with the polysilazane, causing the polysilazane to covalently bond with the PDMS (see Figure 1). In the coating solution 13, the mass of PDMS is between 0.2 and 1.1 times the mass of the polysilazane forming it. If the mass of PDMS is less than 0.2 times the mass of polysilazane, the oil-repellent glass-based coating film 10 made from the coating solution 13 cannot be imparted with excellent oil repellency. In the coating solution 13, since the mass of PDMS is within the above range relative to the mass of polysilazane, the oil-repellent glass-based coating film 10 made from the coating solution has excellent oil repellency and water repellency.

[0080] R １ (R ２ ) ２ R ３ Of the Si, R １ R is an alkyl group having 6 to 50 carbon atoms. ２ CH ３ , C ２ H５ OH, OCH ３ , OC ２ H ５ That is. R ３ OH, OCH ３ , OC ２ H ５ , * (* represents the bond species that binds to the inorganic main chain or PDMS). In the coating solution, R is used relative to the mass of the polysilazane that forms it. １ (R ２ ) ２ R ３ The mass of Si is between 0.2 and 1.1 times. R is the mass of polysilazane. １ (R ２ ) ２ R ３ If the mass of Si is less than 0.2 times, it is not possible to impart excellent oil repellency to the oil-repellent glass-based coating film 10 made from the coating liquid. In the coating liquid, R is the mass of polysilazane. １ (R ２ ) ２ R ３ Since the mass of Si is within the aforementioned range, the oil-repellent glass-based coating film 10 made from the coating liquid 13 has excellent oil repellency.

[0081] R １ (R ２ ) ２ R ３ Si includes n-octadecyldimethylmethoxysilane or n-octyldimethylmethoxysilane. Alternatively, R １ (R ２ ) ２ R ３ Si includes n-octadecyldimethylmethoxysilane and n-octyldimethylmethoxysilane.

[0082] n-octadecyldimethylmethoxysilane, as shown in the illustrative diagram in Figure 4, is represented by the following general formula (Chemical Formula 10).

[0083] n-octyldimethylmethoxysilane, as shown in the illustrative diagram in Figure 5, is represented by the following general formula (Chemical Formula 10).

[0084] R comprising at least one of n-octadecyldimethylmethoxysilane and n-octyldimethylmethoxysilane １ (R ２ ) ２ R ３ A coating solution containing Si can improve the smoothness of the oil-repellent glass-based coating film 10 shown in Figure 3, which is made from the coating solution, and can create a smooth surface on the surface 12 of the substrate 11 with the oil-repellent glass-based coating film 10.

[0085] R １ (R ２ ) ２ R ３Si includes methoxy(dimethyl)octadecylsilane n-octadecyldimethylmethoxysilane and methoxy(dimethyl)-n-octylsilane, as well as 1-chloromethyldimethylmethoxysilane, 1-chloromethylmethyldiethoxysilane, 1-chloromethyldimethylethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyldimethoxymethylsilane, 3-chloropropylmethyldiethoxysilane, and 3-chloropropyldimethylethoxysilane. 1-Bromomethyltrimethoxysilane, 1-Bromomethyltriethoxysilane, 1-Bromomethylmethyldimethoxysilane, 1-Bromomethylmethyldiethoxysilane, 1-Bromomethyldimethylmethoxysilane, 1-Bromomethyldimethylethoxysilane, 3-Bromopropyltrimethoxysilane, 3-Bromopropyltriethoxysilane, 3-Bromopropylmethyldimethoxysilane, 3-Bromopropylmethyldiethoxysilane, 3-Bromopropyldimethylethoxysilane, 3-Chloropropyltri Octoxysilane, 3-chloropropylmethyldioctoxysilane, 3-chloropropyltrihexaoxysilane, 3-chloropropylmethyldihexaoxysilane, 3-chloropropyltridecaoxysilane, 3-chloropropylmethyldecaoxysilane, 3-chloropropyltrioctadecaoxysilane, 3-chloropropylmethyldioctadecaoxysilane, 3-chloropropylethoxydiethyleneglycoxysilane, 3-chloropropylmethyldiethyleneglycoxysilane, reaction product of 3-chloropropyltrimethoxysilane and polyethylene glycol (repeating units 1-8) monobutyl ether, reaction product of 3-chloropropyltrimethoxysilane and polyethylene glycol (repeating units 1-8) monoethyl ether, reaction product of 3-chloropropyltrimethoxysilane and polyethylene glycol (repeating units 1-8) monomethyl ether, reaction product of 3-chloropropyltrimethoxysilane and 2-methyl-1,3-propanediol, reaction product of 3-chloropropyltrimethoxysilane and 2,2-dimethyl-1,The reaction product of 3-propanediol, the reaction product of 3-chloropropyltrimethoxysilane and N-methyldiethanolamine, the reaction product of 3-chloropropyldimethoxymethylsilane and N-methyldiethanolamine, the reaction product of 3-chloropropyltrimethoxysilane and N-butyldiethanolamine, the reaction product of 3-chloropropyldimethoxymethylsilane and N-butyldiethanolamine, 3-chloropropylsilatolan, and 3-chloromethylsilatolan may be included, or two or more of these may be included.

[0086] Dibutyl ether is used as an organic solvent. Dibutyl ether has the molecular formula C ８ H １８ It is a compound belonging to the ether class represented by O. Since the organic solvent contained in the coating liquid is dibutyl ether, the coating liquid 13 can be applied evenly and smoothly to the surface 12 of the base 11, and an oil-repellent glass-based coating film 10 of uniform thickness can be formed on the surface 12 of the substrate 11.

[0087] Organic solvents may include one or more of the following: ketones such as methyl ethyl ketone (2-butanone), methyl isobutyl ketone (4-methyl-2-pentanone), and cyclohexanone; glycol derivatives (ether compounds, ester compounds, ether ester compounds, etc.) such as PGMEA (2-acetoxy-1-methoxypropane), ethylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether, and ethylene glycol ethyl ether acetate; amides such as N,N-dimethylacetamide; esters such as ethyl acetate, propyl acetate, and butyl acetate; pyrrolidones such as N-methyl-pyrrolidone (specifically, 1-methyl-2-pyrrolidone, etc.); aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as cyclohexane, heptane, and limonene; ethers such as tetrahydrofuran, dioxane, diethyl ether, and dibutyl ether; and silicons such as low-boiling point dimethyl silicon. When the organic solvent contains low-boiling point dimethyl silicon, the unevenness of the coating liquid 13 when applying it to the surface 12 of the substrate 11 can be greatly improved, allowing the coating liquid 13 to be applied evenly to the surface 12 of the substrate 11, and forming a coating film 10 of uniform thickness on the surface 12 of the substrate 11. When the organic solvent contains limonene, an aliphatic hydrocarbon, the unpleasant odor of dibutyl ether can be mitigated, suppressing the diffusion of unpleasant odors into the surroundings when applying the coating liquid 13 to the surface 12 of the substrate 11.

[0088] In the coating liquid 13, the content of polysilazanes (such as perhydropolysilazane, organopolysilazane, or organopolysiloxane) is in the range of 1% by mass or more and 15% by mass or less relative to 100% by mass of the coating liquid 13. If the polysilazane content is less than 1% by mass, the polysilazane content in the coating liquid 13 is low, and it is not possible to form an oil-repellent glass-based coating film 10 with excellent flexibility, impact resistance, and corrosion resistance on the surface 12 of the substrate 11. If the polysilazane content exceeds 15% by mass, the viscosity of the coating liquid 13 increases more than necessary, and the film thickness of the oil-repellent glass-based coating film 10 becomes more than necessary, making it impossible to form a glass-based coating film 10 with the planned film thickness on the surface 12 of the substrate 11. Since the polysilazane content of the coating liquid 13 is within the aforementioned range, it is possible to use the coating liquid 13 to form an oil-repellent glass-based coating film 10 with a planned thickness and excellent flexibility, impact resistance, and corrosion resistance on the surface 12 of the substrate 11.

[0089] In the coating liquid 13, the content of the organic solvent it contains is in the range of 70% by mass or more and 98% by mass or less relative to 100% by mass of the coating liquid 13. If the blending ratio of the organic solvent is less than 70% by mass, the viscosity of the coating liquid 13 becomes high, and the thickness of the oil-repellent glass-based coating film 10 made from the coating liquid 13 becomes unnecessarily large, making it impossible to form an oil-repellent glass-based coating film 10 of the planned thickness on the surface 12 of the substrate 13. Since the content of the organic solvent it contains in the coating liquid 13 is within the above range, it is possible to use the coating liquid 13 to form an oil-repellent glass-based coating film 10 on the surface 12 of the substrate 11 with excellent flexibility, impact resistance, corrosion resistance, appropriate viscosity, and the planned thickness.

[0090] The coating liquid 13 is coated or sprayed onto the surface 12 of the substrate 11 to be coated, and reacts chemically with moisture to form a single-layer or multi-layer ultrathin oil-repellent glass-based coating film 10 (film formation). The average film thickness of the oil-repellent glass-based coating film 10 is in the range of 5 nm to 1 μm, preferably in the range of 50 nm to 500 nm.

[0091] There are no particular limitations on the coating method in the coating process of the coating liquid 13 onto the surface 12 of the substrate 11, and the coating is performed using a coating method suitable for the shape of the substrate 11 to be coated (covered). For example, coating can be performed by spraying, dipping, brushing, roll coating, gravure coating, flexographic coating, inkjet coating, wiping, etc. Immediately after coating the surface 12 of the substrate 11 with the coating liquid 13, as shown in Figure 1, an organic substance containing a long-chain alkyl group (PDMS (polydimethylsiloxane), containing at least one of n-octadecyldimethylmethoxysilane and n-octyldimethylmethoxysilane) １ (R ２ ) ２ R ３ Si is evenly dispersed throughout the entire coating liquid 13, and organic matter is not present in large quantities on the surface 14 side of the coating liquid 13 (upper layer including the surface 14).

[0092] There are no particular limitations on the amount of coating liquid 13 applied; the amount is determined according to the required surface performance of the substrate 11 to be coated. Generally, it is 0.1 to 20 g / m² in terms of solid content. 2 The coating amount is 0.1 g / m². 2 If the amount is less than 20 g / m², the oil-repellent glass-based coating film 10 with the desired properties will not be formed, and the coating amount will not exceed 20 g / m². 2 If the thickness exceeds a certain limit, the thickness of the oil-repellent glass-based coating film 10 increases excessively, and the flexibility of the coating film 10 is lost.

[0093] As a pretreatment step preceding the coating process of the coating liquid 13, water (H) such as purified water is applied to the surface 12 of the substrate 11. ２ The solution O) may be sprayed to allow water to adhere to the surface 12 of the substrate 11. By doing so, the chemical reaction between the water adhered to the surface 12 of the substrate 11 and the components contained in the coating liquid 13 is promoted, allowing for the rapid formation of an oil-repellent glass-based coating film 10 on the surface 12 of the substrate 11, and enabling the formation of a strong coating film 10 on the surface 12 of the substrate 11.

[0094] As a pretreatment step preceding the coating process of the coating liquid 13, the surface 12 of the substrate 11 can also be coated with a coating liquid 13 mainly composed of inorganic polysilazane as a primer. For example, if the coating liquid 13 is coated after coating with an inorganic polysilazane solution (1 wt% solution), the rust prevention (durability) of the oil-repellent glass-based coating film 10 is improved compared to simply coating with the coating liquid 13 alone.

[0095] Based on Figure 2, the mechanism by which an oil-repellent glass-based coating film 10 is formed on the surface 12 of the substrate 11 is as follows: In the formation (film formation) of the oil-repellent glass-based coating film 10, a coating liquid 13 is coated onto the surface 12 of the substrate 11 by a coating process, and then the surface 12 of the substrate 11 is heated to 400°C or higher by irradiating it with ultraviolet light and infrared light.

[0096] Alternatively, in the formation (film formation) of the oil-repellent glass-based coating film 10, after coating the surface 12 of the substrate 11 with the coating liquid 13 in the coating process, the surface 12 of the substrate 11 is left at room temperature without heating. Alternatively, after coating the surface 12 of the substrate 11 with the coating liquid 13, the surface 12 of the substrate 11 is irradiated with ultraviolet light while being left at room temperature. Alternatively, after coating the surface 12 of the substrate 11 with the coating liquid 13, the surface 12 of the substrate 11 is irradiated with ultraviolet light while also being irradiated with infrared light to heat the temperature of the surface 12 of the substrate 11 to less than 400°C.

[0097] A small amount of moisture (water droplets) adheres to the surface 12 of the substrate 11 due to condensation or humidity in the air (water (H ２ (Including the case where O) is sprayed.) When the coating liquid 13 is coated in a thin film on the surface 12 of the substrate 11 by the coating process, the unit components that make up the polysilazane (perhydropolysilazane, organopolysilazane, organopolysiloxane, etc.) contained in the coating liquid 13 are absorbed by moisture in the air (H ２0) reacts chemically with the substrate 11 to form an organic composite structure on the surface 12 of the substrate 11 in which organic functional groups are attached as side chains to a part of the main chain by siloxane bonds (Si-O-Si) (an example of the structural image of the oil-repellent glass-based coating film 10 shown in Figure 6 - (Si(CH ３ ) ２ -O-Si(CH ３ ) ２ An oil-repellent glass-based coating film 10 (glass coating layer 18 (amorphous glass coating)) having a unit is formed (generated). The oil-repellent glass-based coating film 10 is almost 100% vitrified (mineralized).

[0098] Furthermore, the unit components that make up the polysilazane (perhydropolysilazane, organopolysilazane, organopolysiloxane, etc.) contained in the coating liquid 13 are moisture (H) in the air. ２ 0) reacts chemically with the substrate 11 to form an organic composite structure on the surface 12 of the substrate 11 in which organic functional groups are attached as side chains to a part of the main chain by siloxane bonds (Si-O-Si) (an example of the structural image of the oil-repellent glass-based coating film 10 shown in Figure 7 - (Si(CH ３ ) ２ -O-Si(CH ３ ) ２ An oil-repellent glass-based coating film 10 having a )-unit is formed (generated). A small amount of gas (NH) is produced in the above chemical reaction. ３ , H ２ Although some gases are generated as a by-product, these gases do not remain on the surface 12 of the substrate 11 and volatilize (are released) into the atmosphere.

[0099] As shown in Figure 2(b), polysilazanes (perhydropolysilazane, organopolysilazane, organopolysiloxane, etc.), PDMS (polydimethylsiloxane), and R containing n-octyldimethylmethoxysilane and n-octadecyldimethylmethoxysilane are available. １ (R ２ ) ２ R ３The coating liquid 13, formed from Si and an organic solvent, undergoes a chemical reaction (deammonia crosslinking) with moisture in the air at the surface 14 layer that comes into contact with the air. This causes gases such as hydrogen and ammonia, which are by-products of the oil-repellent glass-based coating film 10, to volatilize from the surface 12 of the substrate 11 into the outside air, and simultaneously forms (generates) a glass coating layer 18 of the oil-repellent glass-based coating film 10 on the surface 14 side of the coating liquid 13.

[0100] The coating liquid 13 coated on the surface 12 of the substrate 11 undergoes a chemical reaction (deammonia crosslinking) with moisture (water droplets) adhering to the surface 12 of the substrate 11 or with hydroxyl groups -OH present as termini on the surface 12 of the substrate 11 in the back layer 15 that is in contact with the surface 12 of the substrate 11. As a result, gases such as hydrogen and ammonia rise within the coating layer 18 and volatilize from the surface 12 of the substrate 11 into the outside air, and an oil-repellent glass coating layer 18 of the glass coating film 10 is formed on the back layer 15 side of the coating liquid 13.

[0101] First, a coating layer 18 (a vitrified (inorganized) portion, or a vitrified (inorganized) portion and an organic portion) is formed on the surface layer 14 and the back layer 15 of the coating liquid 13. Next, the coating layer 18 is formed and expands from the surface layer 14 towards the back layer 15, and also expands from the back layer 15 towards the surface layer 14, so that the coating layer 18 is formed sequentially on the intermediate layer 16, and finally an oil-repellent glass-based coating film 10 is formed (generated) on the surface layer 14 that is in contact with the outside air, the back layer 15 that is in contact with the surface 12 of the substrate 11, and the intermediate layer 16 between the surface layer 14 and the back layer 15.

[0102] Furthermore, in the process of forming an oil-repellent glass-based inorganic coating film 10 or an oil-repellent glass-based organic / inorganic hybrid coating film 10 from the coating liquid 13, an organic substance (containing at least one of polydimethylsiloxane (PDMS), n-octadecyldimethylmethoxysilane, and n-octyldimethylmethoxysilane) with relatively low surface free energy that easily migrates to the air-film interface is used. １ (R ２ ) ２ R ３Si gradually concentrates on the surface 14 side of the coating liquid 13 (the upper layer including the surface 14), and as shown in Figure 3, organic matter becomes more abundant on the surface 14 side of the coating film 10 (the upper layer including the surface 14) than inside the oil-repellent glass-based coating film 10 (the lower and intermediate layers).

[0103] The coating solution 13 is fluorine-free and contains polysilazane, PDMS (polydimethylsiloxane), and R １ (R ２ ) ２ R ３ Includes Si and R １ = Alkyl alkyl groups with 6 to 50 carbon atoms, R ２ =CH ３ or C ２ H ５ , R ３ = OH, OCH ３ , OC ２ H ５ Since * (* = represents a bonding species that binds to the main chain of an inorganic substance or PDMS), the oil-repellent glass-based coating film 10 made from the coating liquid 13 has excellent oil repellency, and by coating the surface 12 of the substrate 11 with the coating liquid 13, the adhesion of oily substances to the surface 12 of the substrate 11 can be minimized, and even if oily substances adhere to the surface 12 of the substrate 11, an oil-repellent glass-based coating film 10 can be formed that allows for easy removal of the oily substances adhering to the surface 12 of the substrate 11.

[0104] The coating liquid 13 can form an oil-repellent glass-based coating film 10 that minimizes the adhesion of oily substances to the surface 12 of the substrate 11 due to the excellent oil-repellent properties of the oil-repellent glass-based coating film 10 formed from it, thereby minimizing oily contamination of the surface 12 of the substrate 11. The coating liquid 13 can form an oil-repellent glass-based coating film 10 that minimizes the adhesion of moisture to the surface 12 of the substrate 11 due to moisture adhesion, as the oil-repellent glass-based coating film 10 formed from it has excellent water repellency, thereby minimizing the adhesion of moisture to the surface 12 of the substrate 11, and thus preventing contamination of the surface 12 of the substrate 11 due to moisture adhesion. The coating liquid 13 can form an oil-repellent glass-based coating film 10 that has excellent oil-repellency, excellent water repellency, and excellent oil-repellent properties on the surface 12 of the substrate 11, without requiring much effort and at low cost.

[0105] The coating liquid 13 forms an oil-repellent glass-based coating film 10 that covers the surface 12 of the substrate 11 with excellent strength and excellent scratch resistance. Therefore, the coating film 10 can protect the surface 12 of the substrate 11 and prevent scratches on the surface 12 of the substrate 11. Since the coating liquid 13 does not contain fluoride (it is substantially fluoride-free), it can form an oil-repellent glass-based coating film 10 that does not pose a risk of causing chronic poisoning such as fluoride mottling (dental fluoride disease) or osteosclerosis, or acute poisoning such as severe abdominal pain, vomiting, nausea, or death from poisoning.

[0106] The oil-repellent glass-based coating film 10 is a glass coating layer 18 that is almost 100% vitrified (inorganized). The oil-repellent glass-based coating film 10 is formed from a glass coating layer 18 (amorphous glass coating layer 18) and an organic coating layer 18. The oil-repellent glass-based coating film 10 is mainly composed of SiO2 produced by reacting polysilazanes (perhydropolysilazane, organopolysilazane, organopolysiloxane), which allows the formation of a glass coating layer that spreads easily in a planar manner, has high density and high hardness (pencil hardness of about 3H), and becomes an ultrathin film structure at the nano level.

[0107] The oil-repellent glass-based coating film 10 is formed as an ultrathin film at the nanoscale by the coating liquid 13 containing polysilazane (perhydropolysilazane, organopolysilazane, organopolysiloxane). Its film thickness is in the range of 5 nm to 1 μm, preferably in the range of 50 nm to 500 nm. Despite being a coating film mainly composed of SiO2, the oil-repellent glass-based coating film 10 has excellent flexibility, and combined with the anchoring effect of the anchor portion 17, it will not peel off even if the surface 12 of the substrate 11 is deformed, such as by a cloth or nonwoven fabric, and can maintain the coating state of the coating film 10 by following the deformation of the surface 12 of the substrate 11.

[0108] As shown in the structural image of the oil-repellent glass-based coating film 10 in Figure 6 or as an example of the structural image of the oil-repellent glass-based coating film 10 in Figure 7, -(Si(OH) ２ -O-Si(OH) ２ )-unit hydrolysis products cause crosslinking reactions between the siloxane bonds (Si-O-Si) and a portion of the main chain in each coating layer 18 (surface layer 14, intermediate layer 16, back layer 15), forming a crosslinked structure, which gives the oil-repellent glass-based coating film 10 a dense and flexible structure. As a result of the formation of the crosslinked structure, hydrophobic methyl groups (CH₂) derived from polysilazanes (perhydropolysilazane, organopolysilazane, organopolysiloxane) are present on the surface 14 of the coating film 10. ３ ) and hydrophilic hydroxyl groups (OH) derived from hydrolysis products can be coordinated.

[0109] As shown in Figure 2(c), the surface 12 of the substrate 11 before being covered with the oil-repellent glass-based coating film 10 has numerous microscopic irregularities formed on it due to small scratches and other imperfections that occur during the manufacturing process, unless special surface treatments such as mirror finishing are performed. When the coating liquid 13 is coated onto the surface 12 of the substrate 11 and hardens while penetrating into the irregularities, the anchor portion 17 of the coating film 10 that has hardened inside these irregularities exerts an anchoring effect, causing the oil-repellent glass-based coating film 10 to adhere even more firmly to the surface 12 of the substrate 11.

[0110] If the surface 12 of the substrate 11 is a smooth surface without any irregularities, the surface 12 of the substrate 11 may be roughened as a pretreatment before coating with the coating liquid 13 to create irregularities on the surface 12 of the substrate 11 with an average roughness of about 1 to 500 μm. By roughening the surface in this way, an anchoring effect can be obtained from the anchor portion 17 of the oil-repellent glass-based coating film 10. After the roughening treatment, a cleaning treatment is performed using an air spraying means such as an air gun to blow away metal powder, plastic powder, etc. generated on the surface 12 of the substrate 11. After the cleaning treatment, a predetermined time is allowed to occur to cause condensation on the surface 12 of the substrate 11, and naturally occurring moisture is allowed to adhere to it.

[0111] In this case, after roughening and cleaning the surface 12 of the substrate 11, moisture is actively applied to the surface 12 of the substrate 11, which has uneven surfaces formed by roughening, using a moisture-applying means such as a spray bottle, and then the coating liquid 13 is applied. This promotes the chemical reaction between the moisture applied to the surface 12 of the substrate 11 and the coating liquid 13 in contact with the surface 12 of the substrate 11. Alternatively, moisture may be applied using a moisture-applying means without roughening the surface 12 of the substrate 11. Since the uneven surfaces initially formed on the surface 12 of the substrate 11 before being covered with the oil-repellent glass-based coating film 10 are covered by the coating film 10, the surface 12 of the substrate 11 becomes smoother after coating with the coating film 10 than before coating.

[0112] The oil-repellent glass-based coating film 10 contains an organic substance containing a long-chain alkyl group (polydimethylsiloxane (PDMS), at least one of n-octadecyldimethylmethoxysilane and n-octyldimethylmethoxysilane R １ (R ２ ) ２ R ３ Si and SiO ２ It contains inorganic substances including the organic substances. The organic substances are more abundant on the surface side (upper layer including the surface 14) than in the interior (lower and intermediate layers) of the oil-repellent glass coating film 10. In the oil-repellent glass coating film 10, the terminal hydroxyl groups of polydimethylsiloxane (PDMS) and the SiO２ They are covalently bonded.

[0113] In the oil-repellent glass-based coating film 10, the mass of PDMS is between 0.2 and 1.1 times the mass of the polysilazane (inorganic polysilazane, organic polysilazane) forming the film. If the mass of PDMS is less than 0.2 times the mass of polysilazane, the oil-repellent glass-based coating film 10 will not exhibit excellent oil repellency, and it will not be possible to impart excellent oil repellency to the coating film 10. In the oil-repellent glass-based coating film 10, the mass of PDMS is within the above range relative to the mass of polysilazane, so the coating film 10 has excellent oil repellency.

[0114] In the oil-repellent glass-based coating film 10, R is a factor relative to the mass of the polysilazane (inorganic polysilazane, organic polysilazane) forming it. １ (R ２ ) ２ R ３ The mass of Si is between 0.2 and 1.1 times. R is the mass of polysilazane. １ (R ２ ) ２ R ３ If the mass of Si is less than 0.2 times, the oil-repellent glass-based coating film 10 will not exhibit excellent oil repellency, and it will not be possible to impart excellent oil repellency to the coating film 10. In the oil-repellent glass-based coating film 10, R is the mass of polysilazane. １ (R ２ ) ２ R ３ Since the mass of Si is within the aforementioned range, the coating film 10 has excellent oil repellency. Furthermore, the oil-repellent glass-based coating film 10 has excellent water repellency in addition to excellent oil repellency.

[0115] The oil-repellent glass-based coating film 10 has excellent oil repellency, and its surface 14 has extremely low affinity for oil, causing oil to bead up and bead up. Furthermore, the oil-repellent glass-based coating film 10 has excellent water repellency, and its surface 14 has extremely low affinity for water, causing water to bead up and bead up.

[0116] The oil-repellent glass-based coating film 10 (coating film) has a water contact angle of 90° or more and an oleic acid contact angle of 50° or more. The water contact angle (°) was measured in reference to JIS R 3257. The tip of a needle (needle size 18G) was brought into contact with the soda-lime glass substrate, and an appropriate amount of water, 1.0 μL, was dropped onto the upper surface of the soda-lime glass substrate from above the needle. After the water was dropped onto the upper surface of the soda-lime glass substrate and settled on the surface of the plate, a wait of 5 seconds was held until the water stabilized on the upper surface of the plate. Next, the water settled on the upper surface of the soda-lime glass substrate was photographed with a camera, and the water contact angle (°) on the plate was calculated using the θ / 2 method (θ = 2arctan h / r).

[0117] The oleic acid contact angle (°) was measured according to JIS R 3257. The tip of a needle (needle size 22G) was brought into contact with a soda-lime glass substrate and a single-crystal silicon substrate, and 1.0 μL of oleic acid was dropped onto the upper surfaces of the soda-lime glass substrate and the single-crystal silicon substrate from above the needle. After the oleic acid was dropped onto the upper surfaces of the soda-lime glass substrate and the single-crystal silicon substrate and settled on the surfaces, a wait of 60 seconds was held for the oleic acid to stabilize on the surfaces of the plates. Next, the oleic acid settled on the upper surfaces of the soda-lime glass substrate and the single-crystal silicon substrate was photographed with a camera, and the contact angle (°) of the oleic acid on those plates was calculated using the θ / 2 method (θ = 2arctan h / r).

[0118] The oil-repellent glass-based coating film 10 contains an organic substance containing a long-chain alkyl group (PDMS (polydimethylsiloxane), at least one of n-octadecyldimethylmethoxysilane and n-octyldimethylmethoxysilane R １ (R ２ ) ２ R ３Since the Si content is higher on the surface 14 side of the coating film 10 (upper layer including the surface 14) than in the interior (lower and intermediate layers) of the coating film 10, and the contact angle of oleic acid is 50° or more, the coating film 10 has excellent oil repellency on its surface 14 side, the adhesion of oily substances to the surface 12 of the substrate 11 can be minimized, and even if oily substances adhere to the surface 12 of the substrate 11 on which the coating film 10 is formed, the oily substances adhering to the surface 12 of the substrate 11 can be easily removed.

[0119] The oil-repellent glass-based coating film 10 minimizes the adhesion of oily substances to the surface 12 of the substrate 11, thereby minimizing oily contamination of the surface 12 of the substrate 11. Furthermore, the oil-repellent glass-based coating film 10 has a water contact angle of 90° or more, which provides excellent water repellency, minimizing the adhesion of moisture to the surface 12 of the substrate 11, and preventing contamination of the surface 12 of the substrate 11 due to moisture adhesion.

[0120] The oil-repellent glass-based coating film 10 allows for the inexpensive and effortless formation of an oil-repellent coating film 10 on the surface 12 of the substrate 11, which is resistant to both oil and water adhesion. The oil-repellent glass-based coating film 10 covers the surface 12 of the substrate 11 with a coating film 10 that has excellent strength, excellent scratch resistance, and excellent smoothness, thus making the surface 12 of the substrate 11 smooth and protecting the surface 12 of the substrate 11 with the coating film 10, preventing scratches on the surface 12 of the substrate 11. Since the oil-repellent glass-based coating film 10 does not contain fluoride (it is substantially fluoride-free), there is no risk of chronic poisoning such as fluorosis (dental fluoride disease) or osteosclerosis caused by fluoride, or acute poisoning such as severe abdominal pain, vomiting, nausea, or death from poisoning.

[0121] Figure 8 is a table illustrating the composition and measurement results of Examples 1 to 7 of the oil-repellent glass-based coating film 10. In Figure 8, oil-repellent glass-based coating films 10 of Examples 1 to 7 were prepared, and their contact angles (water contact angle, oleic acid contact angle) and 3H hardness (after 3 hours) were measured, and uneven coating was checked (microscopic examination). Furthermore, data indicating density segregation within the film was measured using a high-resolution X-ray thin film evaluation device SuperLab (manufactured by Rigaku Corporation), and the reflectance profile was analyzed and obtained by fitting. As a result, it was found that the organic matter content was higher closer to the air-film interface than inside the substrate.

[0122] The manufacturing process for coating solution 13 of Example 1 is as follows: 6.67 g of perhydropolysilazane (Merck Electronics K.K., product name: DURAZANE 2400-15) and 91.33 g of dibutiether (TCI, product code: B0721) were added to a glass reaction vessel. This was placed in a stirrer and stirred for about 1 minute. 1 g of polydimethylsiloxane hydroxyl group-terminated (M.W. 4200, thermo scientific, Cat. No: 043769.Ak) was gradually added to the stirring solution, and after all of it had been added, the mixture was stirred for about 5 minutes. Then, 1 g of n-dimethyloctadecylmethoxysilane was added and the mixture was stirred for about 1 minute.

[0123] The coating solution 13 of Example 1 had a composition of 1 wt% inorganic polysilazane (PHPS), 1 wt% PDMS (polydimethylsiloxane), and 1 wt% n-octadecyldimethylmethoxysilane based on the total mass (wt) of the coating solution 13. The coating solution 13 was applied to the surface 12 of the substrate 11 by spraying, and a coating film 10 was formed from the coating solution 13. The water contact angle of the coating film 10 of Example 1, measured according to JIS R 3257, was 104.3°, and the oleic acid contact angle, measured according to JIS R 3257, was 54.6°. The contact angle was judged as ○. The result of the 3H hardness test (after 3 hours) for the coating film 10 of Example 1 was ×, but the result of the uneven coating check (microscopic check) was ○. The coating film 10 of Example 1 had a problem with film strength, as the 3H hardness test result was ×.

[0124] The manufacturing process for coating solution 13 of Example 2 is as follows: 13.32 g of perhydropolysilazane (Merck Electronics K.K., product name: DURAZANE 2400-15) and 84.67 g of dibutiether (TCI, product code: B0721) were added to a glass reaction vessel. This was placed in a stirrer and stirred for about 1 minute. 1 g of polydimethylsiloxane hydroxyl group-terminated (M.W. 4200, thermo scientific, Cat. No: 043769.Ak) was gradually added to the stirring solution, and after all of it had been added, the mixture was stirred for about 5 minutes. Then, 1 g of n-dimethyloctadecylmethoxysilane was added and the mixture was stirred for about 1 minute.

[0125] The coating solution 13 of Example 2 had a composition of inorganic polysilazane 2 (PHPS) (wt%), PDMS (polydimethylsiloxane) 1 (wt%), and n-octadecyldimethylmethoxysilane 1 (wt%) relative to the total mass (wt) of the coating solution 13. The coating solution 13 was coated (applied) to the surface 12 of the substrate 11 by the dipping method, and a coating film 10 was formed (film-formed) from the coating solution 13. The water contact angle of the coating film 10 of Example 2, measured according to JIS R 3257, was 104.8°, and the oleic acid contact angle, measured according to JIS R 3257, was 55.4°, and the contact angle was judged as ○. The result of the 3H hardness test (after 3 hours) for the coating film 10 of Example 2 was ×, but the result of the uneven coating check (microscopic check) was ○. The coating film 10 of Example 2 had a problem with film strength, as the 3H hardness test result was ×.

[0126] The manufacturing process for coating solution 13 of Example 3 is as follows: 13.32 g of perhydropolysilazane (Merck Electronics K.K., product name: DURAZANE 2400-15) and 84.67 g of dibuty ether (TCI, product code: B0721) were added to a glass reaction vessel. This was placed in a stirrer and stirred for about 1 minute. 0.1 g of polydimethylsiloxane hydroxyl group-terminated (M.W. 4200, thermo scientific, Cat. No: 043769.Ak) was gradually added to the stirring solution, and after all of it had been added, the mixture was stirred for about 5 minutes.

[0127] The coating solution 13 of Example 3 had a composition of 2 wt% inorganic polysilazane (PHPS), 1 wt% PDMS (polydimethylsiloxane), and 0 wt% n-octadecyldimethylmethoxysilane based on the total mass (wt) of the coating solution 13. The coating solution 13 was applied to the surface 12 of the substrate 11 by spraying, and a coating film 10 was formed from the coating solution 13. The water contact angle of the coating film 10 of Example 3, measured according to JIS R 3257, was 104.9°, and the oleic acid contact angle, measured according to JIS R 3257, was 55.1°. The contact angle was judged as ○. The result of the 3H hardness test (after 3 hours) of the coating film 10 of Example 3 was ○, but the result of the uneven coating check (microscopic check) was ×. The coating film 10 of Example 3 had a problem in that it could not be coated flat, as the result of the uneven coating check was ×.

[0128] The manufacturing process for coating solution 13 in Example 4 is as follows: 6.67 g of perhydropolysilazane (Merck Electronics K.K., product name: DURAZANE 2400-15) and 92.33 g of dibuty ether (TCI, product code: B0721) were added to a glass reaction vessel. This was placed in a stirrer and stirred for about 1 minute. 0.5 g of polydimethylsiloxane hydroxyl group-terminated (M.W. 4200, thermo scientific, Cat. No: 043769.Ak) was gradually added to the stirring solution, and after all of it had been added, the mixture was stirred for about 5 minutes. Then, 0.5 g of n-dimethyloctadecylmethoxysilane was added and the mixture was stirred for about 1 minute.

[0129] The coating solution 13 of Example 4 had a composition of 1 wt% inorganic polysilazane (PHPS), 0.5 wt% PDMS (polydimethylsiloxane), and 0.5 wt% n-octadecyldimethylmethoxysilane relative to the total mass (wt) of the coating solution 13. The coating solution 13 was applied to the surface 12 of the substrate 11 by a brush application method, and a coating film 10 was formed from the coating solution 13. The coating film 10 of Example 4 had a water contact angle of 104.6° measured according to JIS R 3257, and an oleic acid contact angle of 53.6° measured according to JIS R 3257, with a contact angle rating of ○. The coating film 10 of Example 4 also had a 3H hardness test result (after 3 hours) and a coating unevenness check (microscopic examination) result of ○. The coating film 10 produced under the conditions of Example 4 passed the water contact angle and oleic acid contact angle tests, passed the 3H hardness test (after 3 hours), and passed the coating unevenness check (microscopic examination). All results were satisfactory.

[0130] The manufacturing process for coating solution 13 in Example 5 is as follows: 6.67 g of perhydropolysilazane (Merck Electronics K.K., product name: DURAZANE 2400-15) and 91.33 g of dibutiether (TCI, product code: B0721) were added to a glass reaction vessel. This was placed in a stirrer and stirred for about 1 minute. 0.8 g of polydimethylsiloxane hydroxyl group-terminated (M.W. 4200, thermo scientific, Cat. No: 043769.Ak) was gradually added to the stirring solution, and after all of it had been added, the mixture was stirred for about 5 minutes. Then, 0.2 g of n-dimethyloctadecylmethoxysilane was added and the mixture was stirred for about 1 minute.

[0131] The coating solution 13 of Example 5 had a composition of 1 wt% inorganic polysilazane (PHPS), 0.8 wt% PDMS (polydimethylsiloxane), and 0.2 wt% n-octadecyldimethylmethoxysilane relative to the total mass (wt) of the coating solution 13. The coating solution 13 was coated (applied) to the surface 12 of the substrate 11 by the roll coating method, and a coating film 10 was formed (film-formed) from the coating solution 13. The water contact angle of the coating film 10 of Example 5, measured according to JIS R 3257, was 104.7°, and the oleic acid contact angle, measured according to JIS R 3257, was 54.6°. The contact angle was judged as ○. The coating film 10 of Example 5 was judged as ○ in the 3H hardness test (after 3 hours) and as ○ in the coating unevenness check (microscopic examination). The coating film 10 produced under the conditions of Example 5 passed the water contact angle and oleic acid contact angle tests, passed the 3H hardness test (after 3 hours), and passed the coating unevenness check (microscopic examination). In short, all results were satisfactory.

[0132] The manufacturing process for coating solution 13 of Example 6 is as follows: 1.00 g of organopolysilazane (Merck Electronics K.K., product name: DURAZANE 1500SC) and 98 g of dibutiether (TCI, product code: B0721) were added to a glass reaction vessel. This was placed in a stirrer and stirred for about 1 minute. 0.5 g of polydimethylsiloxane hydroxyl group-terminated (M.W. 4200, thermo scientific, Cat. No: 043769.Ak) was gradually added to the stirring solution, and after all of it had been added, the mixture was stirred for about 5 minutes. Then, 0.5 g of n-dimethyloctadecylmethoxysilane was added and the mixture was stirred for about 1 minute.

[0133] The coating solution 13 of Example 6 had a composition of 1 wt% inorganic polysilazane (PHPS), 0 wt% PDMS (polydimethylsiloxane), and 1 wt% n-octadecyldimethylmethoxysilane based on the total mass (wt) of the coating solution 13. The coating solution 13 was applied to the surface 12 of the substrate 11 by a brush application method, and a coating film 10 was formed from the coating solution. The coating film of Example 6 had a water contact angle of 90° measured according to JIS R 3257, and an oleic acid contact angle of 10° or less measured according to JIS R 3257, resulting in a "fail" judgment for the contact angle. The coating film 10 of Example 6 had a "pass" result in the 3H hardness test (after 3 hours) and a "pass" result in the uneven coating check (microscopic examination). The coating film 10 of Example 6 had poor water contact angle and oleic acid contact angle, indicating problems with oil repellency and water repellency.

[0134] The manufacturing process for coating solution 13 in Example 7 is as follows: 6.67 g of organopolysilazane (Merck Electronics K.K., product name: DURAZANE 1500SC) and 92.33 g of dibutiether (TCI, product code: B0721) were added to a glass reaction vessel. This was placed in a stirrer and stirred for about 1 minute. 0.5 g of polydimethylsiloxane hydroxyl group-terminated (M.W. 4200, thermo scientific, Cat. No: 043769.Ak) was gradually added to the stirring solution, and after all of it had been added, the mixture was stirred for about 5 minutes. Then, 0.5 g of n-dimethyloctadecylmethoxysilane was added and the mixture was stirred for about 1 minute.

[0135] The coating solution 13 of Example 7 had a composition of 1 wt% organic polysilazane (OPSZ), 0.5 wt% PDMS (polydimethylsiloxane), and 0.5 wt% n-octadecyldimethylmethoxysilane relative to the total mass (wt) of the coating solution 13. The coating solution 13 was coated (applied) to the surface 12 of the substrate 11 by the dipping method, and a coating film 10 was formed (film-formed) from the coating solution 13. The water contact angle of the coating film 10 of Example 7, measured according to JIS R 3257, was 103.1°, and the oleic acid contact angle, measured according to JIS R 3257, was 53.8°. The contact angle was judged as ○. The result of the 3H hardness test (after 3 hours) of the coating film 10 of Example 7 was ×, but the result of the uneven coating check (microscopic check) was ○. The coating film 10 of Example 7 failed the 3H hardness test, indicating a problem with film strength. The manufacturing process of the coating solution 13 of Example 8 is as follows: 72.33 g of perhydropolysilazane (Merck Electronics K.K., TCI, product code: B0721), 10 g of (+) limonene (TCI, product code L0047), and 10 g of KF-96L-0.65cSt (Shin-Etsu Chemical Co., Ltd.) were added to a glass reaction vessel. This was placed in a stirrer and stirred for about 1 minute. 0.5 g of polydimethylsiloxane hydroxyl group-terminated (viscosity 750cst, Sigma-Aldrich, product No: 481963) was gradually added to the stirring solution, and after all of it had been added, the mixture was stirred for about 5 minutes. Then, 0.5 g of n-dimethyloctadecylmethoxysilane was added and the mixture was stirred for about 1 minute. The coating solution 13 of Example 8 had a composition of 1 wt% inorganic polysilazane (PHPS), 0.5 wt% PDMS (polydimethylsiloxane), and 0.5 wt% n-octadecyldimethylmethoxysilane based on the total mass (wt) of the coating solution 13. The coating solution 13 was applied to the surface 12 of the substrate 11 by a wiping method, and a coating film 10 was formed from the coating solution 13. The wettability to the substrate at this time made it easier to apply, and it became possible to easily form a film without uneven coating. In addition, by adding (+)-limonene, it was possible to suppress the unpleasant odor during application.The coating film 10 of Example 8 had a water contact angle of 105.6° measured according to JIS R 3257, and an oleic acid contact angle of 56.5° measured according to JIS R 3257, with the contact angle judged as ○. The coating film 10 of Example 8 also passed the 3H hardness test (after 3 hours) and the uneven coating check (microscopic examination) with a ○. The coating film 10 produced under the conditions of Example 8 had a water contact angle and an oleic acid contact angle judged as ○, a 3H hardness test (after 3 hours) with a ○, and an uneven coating check (microscopic examination) with a ○, resulting in all results being ○.

[0136] Furthermore, the substrate 11 on which the oil-repellent glass-based inorganic coating film 10 or the oil-repellent glass-based organic / inorganic hybrid coating film 10 is formed can be glass, ceramics, metal, or resin. An oil-repellent glass-based coating film 10 made from the coating liquid 13 is formed (film-formed) on the glass surface 12. The glass on which the oil-repellent glass-based coating film 10 is formed includes all currently manufactured glass such as float glass, tempered glass, heat-insulating glass, heat-shielding glass, low-reflection glass, laminated glass, high-transparency glass, design glass, film glass, and heat-resistant glass, as well as all glass that will be developed in the future. The glass is processed into glass molded products in the form of plates, rods, columns, and various other three-dimensional shapes, and the oil-repellent glass-based coating film 10 is formed on the surface 12 of the various glass molded products.

[0137] Various glass molded products on which an oil-repellent glass-based coating film 10 is formed can minimize the adhesion of oily substances to their surface 12, and even if oily substances do adhere to the surface 12 of the various glass molded products, the oily substances can be easily removed. Because the excellent oil-repellent properties of the oil-repellent glass-based coating film 10 minimize the adhesion of oily substances to the surface 12 of the various glass molded products, oily contamination of the surface 12 of the various glass molded products can be minimized.

[0138] Various glass molded products have an oil-repellent glass-based coating film 10 formed on their surface 12, which has excellent water repellency, minimizing the adhesion of moisture to the surface 12 of the various glass molded products and preventing soiling of the surface 12 due to moisture adhesion. Since the surface 12 of the various glass molded products is covered with an oil-repellent glass-based coating film 10 that has excellent strength, excellent scratch resistance, and excellent smoothness, the surface 12 of the various glass molded products can be made smooth, and the surface 12 of the various glass molded products can be protected by the coating film 10, preventing scratches on the surface 12 of the various glass molded products.

[0139] Ceramics that form an oil-repellent glass-based coating film 10 include engineering ceramics and machinable ceramics. Engineering ceramics include alumina (Al ２ O ３ ), silicon nitride (Si ３ N ４ ), Zirconia (ZrO ２ ), silicon carbide (SiC), aluminum nitride (AlN engineering type), mullite (3Al ２ O ３ ・2SiO ２ ), cordierite (2MgO・2Al ２ O ３ ・5SiO ２ ), ferrite (M 2＋ Examples of porous ceramics include steatite (MgO・SiO2), barium titanate (BaTiO3), lead zirconate titanate (Pb(Zr,Ti)O3), forsterite (2MgO・SiO2), mullite (3Al2O3・2SiO2), and porous ceramics. Machinable ceramics include Hotober, Macerite S, Macerite SP, Macerite HSP, Macerite NT, Macerite CSP, Almatite, Machinax, Macol, Shapeal HiM Soft (machineable aluminum nitride type), boron nitride (BN, boron nitride), Mycarex MM400 (Mycarex M-31), and Mycarex MM600 (Mycarex M-25).

[0140] An oil-repellent glass-based coating film 10 is formed on the surface 12 of these ceramics. The ceramics on which the oil-repellent glass-based coating film 10 is formed can minimize the adhesion of oily substances to their surface 12, and even if oily substances do adhere to the surface 12 of the ceramics, the oily substances can be easily removed from the surface 12 of the ceramics. Because the excellent oil-repellent properties of the oil-repellent glass-based coating film 10 minimize the adhesion of oily substances to the surface 12 of the ceramics, oily staining of the surface 12 can be minimized.

[0141] These ceramics have an oil-repellent glass-based coating film 10 formed on their surface 12, which has excellent water repellency, minimizing the adhesion of moisture to the ceramic surface 12 and preventing soiling of the ceramic surface 12 due to moisture adhesion. Since the ceramic surface 12 is covered with an oil-repellent glass-based coating film 10 that has excellent strength, excellent scratch resistance, and excellent smoothness, the ceramic surface 12 can be made smooth, and the ceramic surface 12 can be protected by the coating film 10, preventing scratches on the ceramic surface 12.

[0142] The metals used to form the oil-repellent glass-based coating film 10 include all currently manufactured metals such as iron, aluminum, duralumin, stainless steel, copper, gold, silver, titanium, nickel, various steel materials, various alloys, various non-ferrous metals, and various non-ferrous alloys, as well as all metals that will be developed in the future. The metals are processed into metal molded products in the form of plates, rods, columns, and various other three-dimensional shapes, and the oil-repellent glass-based coating film 10 is formed on the surface of these metal molded products.

[0143] Various metal molded products on which an oil-repellent glass-based coating film 10 is formed can minimize the adhesion of oily substances to their surface 12, and even if oily substances do adhere to the surface 12 of the various metal molded products, the oily substances can be easily removed. Because the excellent oil-repellent properties of the oil-repellent glass-based coating film 10 minimize the adhesion of oily substances to the surface 12 of the various metal molded products, oily contamination of the surface 12 of the various metal molded products can be minimized.

[0144] Various metal molded products have an oil-repellent glass-based coating film 10 formed on their surface 12, which has excellent water repellency, minimizing the adhesion of moisture to the surface 12 of the various metal molded products and preventing soiling of the surface 12 due to moisture adhesion. Since the surface 12 of the various metal molded products is covered with an oil-repellent glass-based coating film 10 that has excellent strength, excellent scratch resistance, and excellent smoothness, the surface 12 of the various metal molded products can be made smooth, and the surface 12 of the various metal molded products can be protected by the coating film 10, preventing scratches on the various metal molded products.

[0145] The resin used to form the oil-repellent glass-based coating film 10 includes known thermoplastic resins such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyamide (nylon), vinyl chloride resin, acrylic resin, silicone resin, fluororesin, polyimide resin, and polysulfone resin, as well as thermosetting resins such as epoxy resin, melamine resin, phenolic resin, and unsaturated polyester resin. The resin (plastic) is processed into plastic molded products of various three-dimensional shapes, such as films, sheets, plates, columns, and others, and the oil-repellent glass-based coating film 10 is formed on the surface 12 of the various plastic molded products.

[0146] The resins used to form the oil-repellent glass-based coating film 10 include natural rubber (NR), nitrile rubber (NBR), silicone rubber (SI), fluororubber (FKM), urethane rubber (U), acrylic rubber (ACM), isoprene rubber (IR), styrene rubber (SBR), butadiene rubber (BR), butyl rubber (IIR), ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), ethylene-vinyl acetate rubber (EVA), chloroprene rubber (CR), Hypalon (CSM), chlorinated polyethylene rubber (CM), epichlorohydrin rubber (CO / ECO), polysulfide rubber (T), and the like. The aforementioned resins (rubbers) are processed into rubber molded products of various three-dimensional shapes, such as sheets, plates, columns, spheres, rings, and others, and the oil-repellent glass-based coating film 10 is formed on the surface 12 of the various rubber molded products.

[0147] Various plastic molded products and various rubber molded products on which an oil-repellent glass-based coating film 10 is formed can minimize the adhesion of oily substances to their surfaces 12, and even if oily substances do adhere to the surfaces 12 of the various plastic molded products and various rubber molded products, the oily substances adhering to the surfaces 12 of the various plastic molded products and various rubber molded products can be easily removed. Because the excellent oil-repellent properties of the oil-repellent glass-based coating film 10 minimize the adhesion of oily substances to the surfaces 12 of the various plastic molded products and various rubber molded products, oily contamination of the surfaces 12 of the various plastic molded products and various rubber molded products can be minimized.

[0148] Various plastic molded products and various rubber molded products have an oil-repellent glass-based coating film 10 formed on their surface 12, which has excellent water repellency, minimizing the adhesion of moisture to the surface 12 of the various plastic molded products and various rubber molded products, and preventing soiling of the surface 12 of the various plastic molded products and various rubber molded products due to moisture adhesion. Since the surface 12 of the various plastic molded products and various rubber molded products is covered with an oil-repellent glass-based coating film 10 that has excellent strength, excellent scratch resistance and excellent smoothness, the surface 12 of the various plastic molded products and various rubber molded products can be made smooth, and the surface 12 of the various plastic molded products and various rubber molded products can be protected by the coating film 10, preventing scratches on the various plastic molded products and various rubber molded products.

[0149] The substrate 11 on which the oil-repellent glass-based coating film 10 is formed is the display part of an electronic device. Electronic devices include smartphones, personal computers, tablets, car navigation systems, digital signage, photocopiers, facsimile machines, scanners, printers, multifunction devices, televisions, and home appliances equipped with displays or touch panels. Furthermore, electronic devices include all those that will be developed in the future. The display parts of these electronic devices include the image display parts, operation panels, glass parts, metal parts, plastic parts, and glossy black parts of these electronic devices. The glossy black parts are the parts of the electronic device that reflect light specularly and appear shiny and glossy. An oil-repellent glass-based coating film 10 made from the coating liquid 13 is formed (film-formed) on the display parts (surfaces 12) of these electronic devices.

[0150] An electronic device display unit on which an oil-repellent glass-based coating film 10 is formed can minimize the adhesion of oily substances to its surface 12, and even if oily substances do adhere to the surface 12 of the display unit of the electronic device, the oily substances can be easily removed from the surface 12 of the display unit. Because the excellent oil-repellent properties of the oil-repellent glass-based coating film 10 minimize the adhesion of oily substances to the surface 12 of the display unit of these electronic devices, oily contamination of the surface 12 of the display unit can be minimized.

[0151] The display portion of these electronic devices has an oil-repellent glass-based coating film 10 formed on its surface 12, which has excellent water repellency, minimizing the adhesion of moisture to the surface 12 of the display portion and preventing soiling of the surface 12 due to moisture adhesion. Since the surface 12 of the display portion of these electronic devices is covered with an oil-repellent glass-based coating film 10 that has excellent strength, excellent scratch resistance, and excellent smoothness, the surface 12 of the display portion can be made smooth, and the surface 12 of the display portion can be protected by the coating film 10, preventing scratches on the display portion.

[0152] The substrate 11 on which the oil-repellent glass-based coating film 10 is formed includes the body of a moving vehicle, the hull of a ship, the body of an aircraft, and glass windows. Moving vehicles include trains, automobiles, ships, and airplanes. Trains include all trains currently in use and being manufactured, such as Shinkansen trains, express trains, local trains, and freight trains, as well as all trains to be developed in the future. The oil-repellent glass-based coating film 10 is formed on the body of a train and glass windows (at least the windshield).

[0153] The train car body and glass windows on which the oil-repellent glass-based coating film 10 is formed can minimize the adhesion of oily substances to their surfaces 12, and even if oily substances do adhere to the surfaces 12 of the train car body and glass windows, the oily substances can be easily removed from the surfaces 12 of the train car body and glass windows. Because the excellent oil-repellent properties of the oil-repellent glass-based coating film 10 minimize the adhesion of oily substances to the surfaces 12 of the train car body and glass windows, oil-based staining of the surfaces 12 of the train car can be minimized.

[0154] The train's body and glass windows have an oil-repellent glass-based coating film 10 formed on their surfaces 12, which has excellent water repellency, minimizing the adhesion of moisture to the body and glass window surfaces 12 and preventing dirt from accumulating on the body and glass window surfaces 12 due to moisture adhesion. Because the train's body and glass window surfaces 12 are covered with an oil-repellent glass-based coating film 10 that has excellent strength, excellent scratch resistance, and excellent smoothness, the body and glass window surfaces 12 can be made smooth, and the coating film 10 can protect the body and glass window surfaces 12, preventing scratches on the body and glass windows.

[0155] Automobiles include all bicycles currently in use and manufactured, as well as all bicycles to be developed in the future. The oil-repellent glass-based coating film 10 is formed on the body and glass windows (at least the windshield) of the automobile. The body and glass windows of an automobile on which the oil-repellent glass-based coating film 10 is formed can minimize the adhesion of oily substances to their surfaces 12, and even if oily substances adhere to the surfaces 12 of the automobile body and glass windows, the oily substances adhering to the surfaces 12 of the automobile body and glass windows can be easily removed. Because the excellent oil-repellent properties of the oil-repellent glass-based coating film 10 minimize the adhesion of oily substances to the surfaces 12 of the automobile body and glass windows, dirt caused by oily substances on the surfaces 12 of the automobile body and glass windows can be minimized.

[0156] The body and glass windows of an automobile have an oil-repellent glass-based coating film 10 formed on their surfaces 12, which has excellent water repellency, minimizing the adhesion of moisture to the body and glass window surfaces 12 and preventing dirt from accumulating on the body and glass window surfaces 12 due to moisture adhesion. Because the body and glass window surfaces 12 of the automobile are covered with an oil-repellent glass-based coating film 10 that has excellent strength, excellent scratch resistance, and excellent smoothness, the body and glass window surfaces 12 can be made smooth, and the coating film 10 can protect the body and glass window surfaces 12, preventing scratches on the body and glass windows.

[0157] The term "ship" includes all ships currently in use and being manufactured, as well as all ships to be developed in the future, such as passenger ships, merchant ships, cargo ships, workboats, warships, and fishing vessels. The oil-repellent glass-based coating film 10 is formed on the hull and glass windows (at least the windshield) of the ship. The hull and glass windows of a ship on which the oil-repellent glass-based coating film 10 is formed can minimize the adhesion of oily substances to their surfaces 12, and even if oily substances do adhere to the surfaces 12 of the hull and glass windows, the oily substances can be easily removed from the surfaces 12 of the hull and glass windows. Because the excellent oil-repellent properties of the oil-repellent glass-based coating film 10 minimize the adhesion of oily substances to the surfaces 12 of the hull and glass windows, the ship can minimize oily staining of the surfaces 12 of the hull and glass windows.

[0158] The hull and glass windows of a ship have an oil-repellent glass-based coating film 10 formed on their surfaces 12, which has excellent water repellency, minimizing the adhesion of moisture to the hull and glass window surfaces 12 and preventing soiling of the hull and glass window surfaces 12 due to moisture adhesion. Because the hull and glass window surfaces 12 of the ship are covered with an oil-repellent glass-based coating film 10 that has excellent strength, excellent scratch resistance, and excellent smoothness, the hull and glass window surfaces 12 can be made smooth, and the coating film 10 can protect the hull and glass window surfaces 12, preventing scratches on the hull and glass windows.

[0159] Airplanes include all aircraft currently in use and being manufactured, as well as all aircraft to be developed in the future, such as passenger planes, cargo planes, military aircraft, and helicopters. The oil-repellent glass-based coating film 10 is formed on the aircraft's fuselage and glass windows (at least the windshield). The aircraft's fuselage and glass windows, on which the oil-repellent glass-based coating film 10 is formed, can minimize the adhesion of oily substances to their surfaces 12, and even if oily substances do adhere to the surfaces 12 of the aircraft's fuselage and glass windows, the oily substances can be easily removed from the surfaces 12 of the fuselage and glass windows. Because the excellent oil-repellent properties of the oil-repellent glass-based coating film 10 minimize the adhesion of oily substances to the surfaces 12 of the aircraft's fuselage and glass windows, dirt caused by oily substances on the surfaces 12 of the aircraft can be minimized.

[0160] The aircraft's fuselage and glass windows have an oil-repellent glass-based coating film 10 formed on their surfaces 12, which has excellent water repellency, minimizing the adhesion of moisture to the fuselage and glass window surfaces 12 and preventing soiling of the fuselage and glass window surfaces 12 due to moisture adhesion. Because the aircraft's fuselage and glass window surfaces are covered with an oil-repellent glass-based coating film 10 that has excellent strength, excellent scratch resistance, and excellent smoothness, the fuselage and glass window surfaces 12 can be made smooth, and the coating film 10 can protect the fuselage and glass window surfaces 12, preventing scratches on the fuselage and glass windows.

[0161] 10 Oil-repellent glass-based inorganic coating film 10 Oil-repellent glass-based organic / inorganic hybrid coating film 11 Substrate 12 Surface 13 Coating liquid 14 Surface 15 Back 16 Intermediate 17 Anchor part 18 Coating layer

Claims

1. A coating film comprising an organic substance and an inorganic substance, wherein the coating film is fluorine-free (substantially fluorine-free), and the inorganic substance is SiO ２ A coating film comprising the following: the organic substance comprises a long-chain alkyl group; the content of the organic substance relative to the coating film is greater on the surface side of the coating film (upper layer including the surface) than in the interior (lower and intermediate layers); the contact angle of oleic acid in the coating film is 50° or more; and the coating film is characterized by having oil-repellent properties.

2. The coating film according to claim 1, wherein the water contact angle of the coating film is 90° or more.

3. The organic substance is polydimethylsiloxane (hereinafter abbreviated as PDMS) and R １ (R ２ ) ２ R ３ Si(R １ = an alkyl group having 6 to 50 carbon atoms, R ２ = CH ３ , C ２ H ５ , OH, OCH ３ , OC ２ H ５ R ３ = OH, OCH ３ , OC ２ H ５ , *, and furthermore, * represents a bonding species that binds to the main chain of the inorganic substance or PDMS.) The coating film according to claim 1 or claim 2.

4. The PDMS is the SiO ２ It is 0.2 to 1.1 times, and the R １ (R ２ ) ２ R ３ Si is the aforementioned SiO ２ The coating film according to claim 3, wherein the ratio is 0.2 to 1.1 times.

5. The terminal hydroxyl group of the PDMS and the SiO ２ The coating film according to claim 3 or claim 4, wherein the two are covalently bonded.

6. The aforementioned R １ (R ２ ) ２ R ３ The coating film according to claim 3 or claim 4, wherein Si contains at least one of an octadecyl group and an octyl group.

7. The coating film according to claim 1, wherein the substrate on which the coating film is formed is any of glass, ceramics, metal, or resin.

8. An electronic device characterized in that the substrate according to claim 7, on which the coating film according to claim 1 is formed, is used in the display section.

9. The electronic device according to claim 8, wherein the electronic device is a smartphone, personal computer, tablet, car navigation system, digital signage, copier, facsimile machine, scanner, printer, multifunction device, television, or consumer electronics equipped with a display or touch panel.

10. A mobile body characterized by comprising a glass window or a vehicle body, ship hull, or machine body having the coating film described in claim 1 formed thereon.

11. The mobile body according to claim 10, wherein the mobile body is one of a train, automobile, ship, or airplane, and the glass window on which the coating film is formed is at least the windshield of the train, automobile, ship, or airplane.

12. In a coating solution used when forming a coating film, the coating solution is fluorine-free (substantially fluorine-free), and contains polysilazane, polydimethylsiloxane (PDMS), and R １ (R ２ ) ２ R ３ Includes Si and R １ = Alkyl alkyl groups with 6 to 50 carbon atoms, R ２ =CH ３ , C ２ H ５ OH, OCH ３ , OC ２ H ５ , R ３ = OH, OCH ３ , OC ２ H ５ A coating liquid characterized by being * (where * represents a bonding species that binds to the main chain of an inorganic substance or PDMS).

13. The coating solution according to claim 12, wherein the polysilazane is an inorganic polysilazane (hereinafter abbreviated as PHPS).

14. The coating solution according to claim 12 or claim 13, wherein the PDMS has a hydroxyl group at its terminal, and the hydroxyl group at the terminal of the PDMS reacts with the polysilazane, and the polysilazane is covalently bonded to the PDMS.

15. The PDMS is 0.2 to 1.1 times the polysilazane, and the R １ (R ２ ) ２ R ３ The coating solution according to claim 12 or claim 13, wherein the amount of Si is 0.2 to 1.1 times that of the polysilazane.

16. The aforementioned R １ (R ２ ) ２ R ３ The coating solution according to claim 12 or claim 13, wherein Si comprises at least one of n-octadecyldimethylmethoxysilane and n-octyldimethylmethoxysilane.

17. The coating liquid according to claim 12 or claim 13, wherein the organic solvent contained in the coating liquid is dibutyl ether.

18. The coating solution according to claim 17, wherein the organic solvent comprises at least one of low-boiling silicon and limonene, which is an aliphatic hydrocarbon.

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