Coating films, electronic devices, mobile devices, coating liquids

Abstract

The present invention provides a coating film that, when formed on the surface of a substrate, minimizes the adhesion of oily substances to the substrate surface and allows for easy removal of any oily substances that do adhere to the substrate surface. [Solution] The coating film contains organic and inorganic substances, is fluorine-free (substantially fluorine-free), the inorganic substance contains SiO2, and the organic substance contains long-chain alkyl groups, PDMS (polydimethylsiloxane), and R1(R2)2R3Si. The content of organic substances in the coating film is greater on the surface side of the coating film (including the surface and upper layer) than in the interior (lower and intermediate layers), the water contact angle of the coating film is 90° or more, and the oleic acid contact angle of the coating film is 50° or more.

Description

[Technical Field]

[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. [Background technology]

[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). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Patent No. 7565253 [Overview of the Initiative] [Problems that the invention aims to solve]

[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, and when formed on the surface of a substrate, minimizes the adhesion of water and oil components to the surface of the substrate, and allows for easy removal of water and oil components that have adhered 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 resistant to the adhesion of water and oil components on the surface of a substrate inexpensively and without requiring much effort. [Means for solving the problem]

[0007] The first premise of the present invention for solving the aforementioned problems is a coating film containing organic and inorganic materials.

[0008] The characteristics of the coating film of the present invention under the first premise described above are that the coating film is fluorine-free (substantially fluorine-free), contains SiO2 as an inorganic substance, contains long-chain alkyl groups as an organic substance, the content of organic substances in the coating film is greater on the surface side of the coating film (including the surface and upper layer) than in the interior (lower and intermediate layers), the contact angle of oleic acid in the coating film is 50° or more, and it possesses oil-repellent properties. It should be noted that "substantially fluorine-free" means that fluorine compounds are not intentionally added to the coating film for the purpose of imparting water-repellent and oil-repellent properties to the coating film.

[0009] An example of a coating film according to the present invention is one in which the water contact angle of the coating film is 90° or more.

[0010] Another example of the coating film of the present invention is an organic material consisting of polydimethylsiloxane (hereinafter abbreviated as PDMS) and R1(R2)2R3Si, (R1 = alkyl group having 6 to 50 carbon atoms, R2 = CH3, C2H5, OH, OCH3, OC2H5, R3 = OH, OCH3, OC2H5, *, where * represents the inorganic main chain or the bond species that binds to PDMS).

[0011] Another example of the coating film of the present invention is one in which PDMS is 0.2 to 1.1 times the amount of SiO2, and R1(R2)2R3Si is 0.2 to 1.1 times the amount of SiO2.

[0012] Another example of the coating film of the present invention is one in which the terminal hydroxyl groups of PDMS are covalently bonded to SiO2.

[0013] As another example of the coating film of the present invention, R1(R2)2R3Si contains at least one of an octadecyl group and 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 under the second premise described above are that the coating solution is fluorine-free (substantially fluorine-free), contains polysilazane, polydimethylsiloxane (PDMS), and R1(R2)2R3Si, where R1 = an alkyl group having 6 to 50 carbon atoms, R2 = CH3, C2H5, OH, OCH3, OC2H5, R3 = OH, OCH3, OC2H5, * (where * represents the inorganic main chain or a bonding species that bonds with PDMS). 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) as the polysilazane.

[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, and R1(R2)2R3Si is 0.2 to 1.1 times the mass of polysilazane.

[0024] As another example of the coating solution of the present invention, R1(R2)2R3Si contains at least one of n-octadecyldimethylmethoxysilane and n-octyldimethylmethoxysilane.

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

[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 it 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 composed of polydimethylsiloxane (hereinafter abbreviated as PDMS) and R1(R2)2R3Si (R1 = alkyl group with 6 to 50 carbon atoms, R2 = CH3, C2H5, OH, OCH3, OC2H5, R3 = OH, OCH3, OC2H5, *, where * represents the inorganic main chain or the bond species that bonds with PDMS). Therefore, the coating film can be given excellent oil repellency without uneven coating, 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 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 soiling of the substrate surface by oil. The coating film also 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 film can be formed on the substrate surface inexpensively and without requiring much effort, providing oil-repellent properties that make it difficult for oily substances to adhere and water-repellent properties that make it difficult for water to adhere.

[0029] The coating film has a PDMS content of 0.2 to 1.1 times that of SiO2, and a R1(R2)2R3Si content of 0.2 to 1.1 times that of SiO2. Therefore, the coating film 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 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 contamination of the substrate surface. The coating film also has excellent water repellency, minimizing the adhesion of moisture to the substrate surface and preventing contamination of the substrate surface due to moisture adhesion. The coating film can be formed on the substrate surface inexpensively and without much effort, providing 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 can form an ultrathin film with high strength and long-lasting durability due to the covalent bonding of the terminal hydroxyl groups of PDMS with SiO2. The coating film has a high concentration of organic matter containing long-chain alkyl groups on its surface (including the upper layer), contributing to its surface smoothness. 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, 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 contamination of the substrate surface. The coating film also has excellent water repellency, minimizing the adhesion of moisture to the substrate surface and preventing contamination of the substrate surface due to moisture adhesion. The coating film can be formed on the substrate surface inexpensively and without much effort, providing excellent oil repellency (making it difficult for oily substances to adhere) and excellent water repellency (making it difficult for water 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 possesses excellent oil repellency, but also, because at least one of the octadecyl group and octyl group is contained in R1(R2)2R3Si, the smoothness of the coating film can be improved, 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 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 that has excellent oil repellency (making it difficult for oily substances to adhere) and excellent water repellency (making it difficult for moisture to adhere). 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 substrate surface can be protected by the coating film, preventing scratches on the substrate surface.

[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 dirt on the display portion of the electronic device caused by oily substances. The coating film has excellent water repellency, which minimizes the adhesion of moisture to the display portion of the electronic device, thus preventing dirt on the display portion of the electronic device caused by 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 display portion of the electronic device can be protected by the coating film, 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] Since the moving object 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, a coating film with excellent oil repellency is formed on at least the windshield of the train, automobile, ship, or airplane, minimizing the adhesion of oily substances to the windshield, and even if oily substances do adhere to the windshield, the adhered oily substances can be easily removed. Because the coating film with excellent oil repellency minimizes the adhesion of oily substances to at least the windshield of the train, automobile, ship, or airplane, dirt on the windshield caused by oily substances can be minimized. Due to the excellent water repellency of the coating film, the moving object can minimize the adhesion of moisture to at least the windshield of the train, automobile, ship, or airplane, and can prevent dirt on the windshield caused by moisture adhesion. Since the moving object is covered with a coating film that has excellent strength, excellent scratch resistance, and excellent smoothness, the windshield can be made smooth, and the coating film can protect the windshield, preventing scratches on at least the windshield of the train, automobile, ship, or airplane.

[0037] The coating liquid according to the present invention is fluorine-free (substantially fluorine-free), contains polysilazane, polydimethylsiloxane (PDMS), and R1(R2)2R3Si, where R1 = alkyl group having 6 to 50 carbon atoms, R2 = CH3, C2H5, OH, OCH3, OC2H5, R3 = OH, OCH3, OC2H5, * (where * represents the inorganic main chain or a bonding species that bonds with PDMS). Therefore, the coating film made from the coating liquid has excellent oil repellency, and by coating the surface of a substrate with the coating liquid, the adhesion of oily substances to the surface of the substrate can be minimized. Furthermore, even if oily substances adhere to the surface of the substrate, a coating film can be formed that allows for easy removal of the oily substances adhering to the surface of the substrate. Because the coating liquid 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, a coating film can be formed that minimizes oily contamination of the surface of 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 can form a coating film on the substrate surface 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 with little effort. The coating liquid forms a coating film that covers the substrate surface with excellent strength and excellent scratch resistance, thus protecting the surface of the substrate and preventing scratches on the substrate surface. 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 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 (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 solution has PDMS with hydroxyl groups at its ends, and these hydroxyl groups react with polysilazane, causing the polysilazane to covalently bond with the PDMS. Therefore, the coating solution can form an ultrathin coating film with high strength, and an oil-repellent ultrathin coating film can be created. The coating solution has a large amount of organic matter containing long-chain alkyl groups on the surface side (upper layer including the surface) of the coating film made from it. The coating film made from the coating solution has excellent oil repellency on its surface, 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 oily substances can be easily removed. Because the coating solution's excellent oil repellency minimizes the adhesion of oily substances to the substrate surface, it can form a coating film that minimizes oily contamination of the substrate surface. The coating liquid can form 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.

[0040] The coating liquid has a mass ratio of PDMS to polysilazane of 0.2 to 1.1 times, and R1(R2)2R3Si to polysilazane of 0.2 to 1.1 times, so it can impart excellent oil repellency to the coating film made from the coating liquid, minimizing the adhesion of oily substances to the substrate surface, and forming a coating film that allows for easy removal of oily substances even if they adhere to the substrate surface on which the coating film is formed. 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, thus minimizing oily contamination of the substrate surface. The coating liquid can form a coating film that has excellent water repellency, minimizing the adhesion of moisture to the substrate surface, and preventing contamination of the substrate surface due to moisture adhesion.

[0041] The coating liquid not only produces a coating film with excellent oil repellency, but also improves the smoothness of the coating film produced by the coating liquid because at least one of n-octadecyldimethylmethoxysilane and n-octyldimethylmethoxysilane is included in R1(R2)2R3Si, allowing for the creation of a smooth surface on the substrate. The coating liquid produces a coating film with excellent water repellency, minimizing the adhesion of moisture to the substrate surface and forming a coating film that prevents soiling of the substrate surface due to moisture adhesion. The coating liquid forms a coating film with excellent strength, excellent scratch resistance, and excellent smoothness that smoothly covers the substrate surface, thus protecting the substrate surface and preventing scratches on the substrate surface.

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

[0043] [Figure 1] A magnified cross-sectional image showing an example of a coating liquid applied to the surface of a substrate. [Figure 2] 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 on the surface of a substrate coated with a coating liquid. [Figure 3] A magnified cross-sectional image showing 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. [Figure 4] An illustrative diagram showing an example of the chain length of n-octadecyldimethylmethoxysilane. [Figure 5] An illustrative diagram showing an example of the chain length of n-octylmethylmethoxysilane. [Figure 6] An illustrative diagram showing an example of the structure of an oil-repellent glass-based inorganic coating film. [Figure 7] An illustrative diagram showing an example of the structure of an oil-repellent glass-based organic / inorganic hybrid coating film. [Figure 8] 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. [Modes for carrying out the invention]

[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 view 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 illustrates the covalent bond between the terminal hydroxyl group of PDMS (polydimethylsiloxane) and SiO2 as a visually observable image, but in reality, the covalent bond cannot be visually observed. Figures 4 and 5 illustrate the chain lengths of n-octyldimethylmethoxysilane and n-octadecyldimethylmethoxysilane as visually observable images, but in reality, the chain length 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 solution 13 that forms the oil-repellent glass-based coating film 10 contains polysilazane, PDMS, R1(R2)2R3Si, and an organic solvent. The coating solution 13 is substantially fluorine-free. The polysilazane used to form the coating solution 13 is an inorganic polysilazane, specifically a Si-N type perhydropolysilazane. In addition, Si-CN type organopolysilazanes and Si-C type polycarbosilanes can be used as polysilazanes, and furthermore, SiC-O, Si-BCN, 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, cross-linked polysilazanes can be used that are chemically cross-linked 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 cross-linked 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 solution 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] [ka] Inorganic polysilazanes include perhydropolysilazanes that contain linear structures with structural units, have a molecular weight of 690 to 2,000, have 3 to 10 SiH3 groups in one molecule, and whose elemental ratios determined by chemical analysis are Si: 59 to 61, N: 31 to 34, and H: 6.5 to 7.5% by weight, and perhydropolysilazanes with an average polystyrene-equivalent molecular weight in the range of 3,000 to 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] [ka] An example of the structure of a perhydropolysilazane is represented by the following chemical formula (Chemical Formula 3).

[0056] [ka] Another example of the perhydropolysilazane compound group is represented by the following general formula (Formula 4), having a Si-N bond and a functional group (R 1 ~R 3 ), and is a polymer formed from -(SiR1R2-NR3)- units, wherein at least one of the functional groups R1, R2 directly bonded to Si is an organic functional group such as an alkyl group having carbon (C), etc., and is an organic polymer.

[0057] [Chemical Formula] In addition, perhydropolysilazane has a structure in which carbon atoms are substituted by three hydrogen atoms, and the content of the methyl group (CH3), which is one of the functional groups (R 1 ~R 3 ), is 50% or more. Further, perhydropolysilazane may be not only a polymer formed from one type of -(SiR1R2-NR3)- unit, but also a polymer formed from a plurality of types of -(SiR1R2-NR3)- units having different compositions of functional groups (R1 to R3). Furthermore, perhydropolysilazane may be a polymer having a linear, cyclic or crosslinked structure, or a polymer having a composite of these structures. R 1 , R 2 , R 3 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a group other than these groups in which the group directly bonded to silicon has carbon, an alkylsilyl group, an alkylamino group, or an alkoxy group. However, at least one of R 1 , R 2 , R 3 is a hydrogen atom.

[0058] As an example, perhydropolysilazane (A) is a polymer containing -(SiH(CH3)-NH)- units, -(Si(CH3)2-NH)- units, and -(SiR 1 (CH3)-NR3)- units represented by the following general formula (Formula 5). -(SiR 1 (CH3)-NR 3In the )-unit, the functional group R1 is either H or CH3, and the functional group R3 that 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] [ka] Another example is perhydropolysilazane (B), which is represented by the following general formula (Chemical Formula 6) and consists of the -(SiH(CH3)-NH)- unit and -(SiR 1 It is a polymer containing (CH3)-NH)- units, and -(SiR 1 (CH3)-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 covering the surface 12 of the substrate 11.

[0060] [ka] 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 has a hydrogen atom, R 3 has an organic group. -(R 2 SiHNH)- as a repeating unit, a polysilazane having a cyclic structure with a degree of polymerization of 3 to 5, (R 3 SiHNH) x [(R 2 SiH) 1.5 N] 1-X (0.4 < X < 1), a polysilazane having both a chain structure and a cyclic structure in the molecule represented by the chemical formula, in the above general formula (Chemical Formula 4) R 1 has a hydrogen atom, R 2 , R 3 has an organic group, a polysilazane, R 1 and R 2 has an organic group, R 3 has a hydrogen atom -(R 1 R 2 SiNR 3 )- as a repeating unit, there is a polysilazane mainly having a cyclic structure with a degree of polymerization of 3 to 5.

[0062] For example, an organopolysilazane having a cross-linked structure other than the above general formula (Chemical Formula 4) in the molecule is represented by the following general formula (Chemical Formula 7).

[0063]

Chemical Formula

[0064]

Chemical Formula

[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)-CR 11 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 some 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. 1 Based 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 SiO3 / 2 ) and (SiO 4 / 2 This represents the average value of the mole fractions of ). 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 between 0.3 and 1, preferably 0.4 or higher, 0.5 or higher, or 0.6 or higher, more preferably 0.7 or higher, even more preferably 0.8 or higher, and particularly preferably 0.9 or higher.

[0071] d is SiO 4 / 2 This 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) is the same. The organopolysiloxane may have a structural unit in which at least a part of R in each of the above structural units is replaced by R 1 O. R in the average unit formula (A) is a hydrogen atom or an alkyl group. R 2 O means a hydroxy group or an alkoxy group bonded to a silicon atom contained in the organopolysiloxane skeleton. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. The number of carbon atoms of the alkyl group is preferably 1 or more and 3 or less. 2 is a hydrogen atom or an alkyl group. R 2 O means a hydroxy group or an alkoxy group bonded to a silicon atom contained in the organopolysiloxane skeleton. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. The number of carbon atoms of the alkyl group is preferably 1 or more and 3 or less.

[0073] The amount of the structural unit in which at least a part of the above R in each of the above structural units is replaced by R 1 O is preferably 0 or more and 0.10 or less, more preferably 0 or more and 0.05 or less, and still more preferably 0 or more and 0.03 or less, based on the total of a, b, c, and d, which is the sum of the mole fractions of the above structural units. The alkoxy group in the above structural unit is, for example, an alkoxy group which is a hydrolyzable group contained in an alkoxysilane described later and remains in the molecule without hydrolysis and polycondensation. The hydroxy group in this structural unit is, for example, a hydroxy group which remains in the molecule without polycondensation after the alkoxy group is hydrolyzed. 2 O is preferably 0 or more and 0.10 or less, more preferably 0 or more and 0.05 or less, and still more preferably 0 or more and 0.03 or less, based on the total of a, b, c, and d, which is the sum of the mole fractions of the above structural units. The alkoxy group in the above structural unit is, for example, an alkoxy group which is a hydrolyzable group contained in an alkoxysilane described later and remains in the molecule without hydrolysis and polycondensation. The hydroxy group in this structural unit is, for example, a hydroxy group which remains in the molecule without polycondensation after the alkoxy group is hydrolyzed.

[0074] The organopolysiloxane is preferably a silsesquioxane. A silsesquioxane is an organopolysiloxane in which the main chain skeleton is composed of Si-O bonds, contains (R 1 SiO 3 / 2 ) units as the main structural units, and c is 0.7 or more. Examples of the structure of the silsesquioxane include a random structure, a complete cage structure, an incomplete cage structure, and a ladder structure. Among these, from the viewpoint of ease of production, a silsesquioxane having a random structure is preferable.

[0075] Examples of the alkoxysilane forming the above structural unit (R 1 3SiO 1 / 2 ) include R 1 3Si(OR2 ) Compounds represented by are exemplified. Specific examples thereof include, for example, methoxydimethylvinylsilane, ethoxydimethylvinylsilane, methoxydimethylphenylsilane and ethoxydimethylphenylsilane; and methoxytrimethylsilane and ethoxytrimethylsilane.

[0076] The alkoxysilane forming the above structural unit (R 1 2SiO 2 / 2 ) includes compounds represented by R 1 2Si(OR 2 )2. Specific examples thereof include, for example, dimethoxymethylvinylsilane, diethoxymethylvinylsilane and dimethoxybenzylmethylsilane; and dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethylsilane, dipropoxydimethylsilane and dipropoxydiethylsilane.

[0077] The alkoxysilane forming the above structural unit (R 1 SiO 3 / 2 ) includes compounds represented by R 1 Si(OR 2 )3. Specific examples thereof include, for example, trimethoxyvinylsilane, triethoxyvinylsilane, trimethoxyallylsilane, triethoxyallylsilane, (3-(meth)acryloyloxypropyl)trimethoxysilane and (3-(meth)acryloyloxypropyl)triethoxysilane; and methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane and butyltrimethoxysilane. The alkoxysilane forming the above structural unit (SiO 4 / 2 ) includes compounds represented by Si(OR 2 )4. Specific examples thereof include, for example, 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] [ka] 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] In R1(R2)2R3Si, R1 is an alkyl group having 6 to 50 carbon atoms, and R2 is CH3, C2H5, OH, OCH3, or OC2H5. R3 is OH, OCH3, OC2H5, or * (* represents a bonding species that bonds to the main chain of an inorganic substance or PDMS). In the coating solution, the mass of R1(R2)2R3Si is between 0.2 and 1.1 times the mass of the polysilazane forming it. If the mass of R1(R2)2R3Si is less than 0.2 times the mass of the polysilazane, it is not possible to impart excellent oil repellency to the oil-repellent glass-based coating film 10 made from the coating solution. In the coating solution, since the mass of R1(R2)2R3Si is within the above range relative to the mass of the polysilazane, the oil-repellent glass-based coating film 10 made from the coating solution 13 has excellent oil repellency.

[0081] R1(R2)2R3Si contains n-octadecyldimethylmethoxysilane or n-octyldimethylmethoxysilane. Alternatively, R1(R2)2R3Si contains both 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] [ka] n-octyldimethylmethoxysilane, as shown in the illustrative diagram in Figure 5, is represented by the following general formula (Chemical Formula 10).

[0084] [ka] A coating solution containing R1(R2)2R3Si, which includes at least one of n-octadecyldimethylmethoxysilane and n-octyldimethylmethoxysilane, 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] R1(R2)2R3Si 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-chloropropyldimethyl Toxysilane, 1-bromomethyltrimethoxysilane, 1-bromomethyltriethoxysilane, 1-bromomethylmethyldimethoxysilane, 1-bromomethylmethyldiethoxysilane, 1-bromomethyldimethylmethoxysilane, 1-bromomethyldimethylethoxysilane, 3-bromopropyltrimethoxysilane, 3-bromopropyltriethoxysilane, 3-bromopropylmethyldimethoxysilane, 3-bromopropylmethyldiethoxysilane, 3-bromopropyldimethylethoxysilane, 3-chlorop Ropiltrioctoxysilane, 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 the organic solvent. Dibutyl ether has the molecular formula C8H 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 when applying the coating liquid 13 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 solution 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 solution 13. If the polysilazane content is less than 1% by mass, the polysilazane content in the coating solution 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 solution 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 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 chemically reacts 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, organic matter containing long-chain alkyl groups (PDMS (polydimethylsiloxane), R1(R2)2R3Si containing at least one of n-octadecyldimethylmethoxysilane and n-octyldimethylmethoxysilane) is evenly dispersed throughout the coating liquid 13, and there is not much organic matter 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 to be 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 Below this amount, an oil-repellent glass-based coating film 10 with the desired properties is not formed, and the coating amount is 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 (H2O) such as purified water may be sprayed onto the surface 12 of the substrate 11 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 over 400°C 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 (including when water (H2O) is sprayed). When the coating liquid 13 is coated in a thin film onto the surface 12 of the substrate 11 by the coating process, the unit components constituting the polysilazane (perhydropolysilazane, organopolysilazane, organopolysiloxane, etc.) contained in the coating liquid 13 chemically react with moisture (H2O) in the air, thereby forming (generating) an oil-repellent glass-based coating film 10 (glass coating layer 18 (amorphous glass coating)) on the surface 12 of the substrate 11. This is an organic composite structure (the -(Si(CH3)2-O-Si(CH3)2)- unit in an example of the structural image of the oil-repellent glass-based coating film 10 shown in Figure 6) in which an organic functional group is attached as a side chain to a part of the main chain of siloxane bonds (Si-O-Si). The oil-repellent glass-based coating film 10 undergoes approximately 100% vitrification (inorganization).

[0098] Furthermore, the unit components constituting the polysilazane (perhydropolysilazane, organopolysilazane, organopolysiloxane, etc.) contained in the coating liquid 13 chemically react with moisture (H2O) in the air, forming (generating) an oil-repellent glass-based coating film 10 on the surface 12 of the substrate 11. This film has an organic composite structure (the -(Si(CH3)2-O-Si(CH3)2)- unit in an example of the structural image of the oil-repellent glass-based coating film 10 shown in Figure 7), in which an organic functional group is attached as a side chain to a part of the main chain of siloxane bonds (Si-O-Si). Although trace amounts of gas (NH3, H2) are generated as a by-product in the above chemical reaction, these gases do not remain on the surface 12 of the substrate 11 but volatilize (release) into the atmosphere.

[0099] As shown in Figure 2(b), the coating liquid 13, formed from polysilazane (perhydropolysilazane, organopolysilazane, organopolysiloxane, etc.), PDMS (polydimethylsiloxane), R1(R2)2R3Si containing n-octyldimethylmethoxysilane or n-octadecyldimethylmethoxysilane, and an organic solvent, undergoes a chemical reaction (deammonia crosslinking) with moisture in the air at the surface 14 layer that is in 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 a glass coating layer 18 of the oil-repellent glass-based coating film 10 is formed (generated) on the surface 14 side of the coating liquid 13.

[0100] The coating liquid 13 applied to 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. This causes gases such as hydrogen and ammonia to rise within the coating layer 18 and volatilize from the surface 12 of the substrate 11 into the outside air, while simultaneously forming (generating) an oil-repellent glass coating layer 18 of the glass coating film 10 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 sequentially formed 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, organic substances (polydimethylsiloxane (PDMS), R1(R2)2R3Si, which includes at least one of n-octadecyldimethylmethoxysilane and n-octyldimethylmethoxysilane) that have relatively low surface free energy and are easily migrated to the air-film interface, gradually concentrate on the surface 14 side of the coating liquid 13 (the upper layer including the surface 14), and as shown in Figure 3, the organic substances become more abundant on the surface 14 side of the coating film 10 (the upper layer including the surface 14) than in the interior (lower and intermediate layers) of the oil-repellent glass-based coating film 10.

[0103] The coating liquid 13 is fluorine-free and contains polysilazane, PDMS (polydimethylsiloxane), and R1(R2)2R3Si, where R1 = an alkyl group having 6 to 50 carbon atoms, R2 = CH3 or C2H5, and R3 = OH, OCH3, OC2H5, * (* = represents the inorganic main chain or a bonding species that bonds with PDMS). Therefore, 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. Furthermore, 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 forms 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 forms an oil-repellent glass-based coating film 10 that minimizes the adhesion of moisture to the surface 12 of the substrate 11, thereby 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-repellent properties that make it difficult for oily substances to adhere, as well as excellent water-repellent and oil-repellent properties that make it difficult for moisture to adhere, on the surface 12 of the substrate 11 at low cost and without requiring much effort.

[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, thereby protecting the surface 12 of the substrate 11 and preventing 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. By using SiO2 produced by reacting polysilazanes (perhydropolysilazane, organopolysilazane, organopolysiloxane) as the main component, the oil-repellent glass-based coating film 10 forms 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 made of a fabric or nonwoven material that undergoes deformation, and the coating film 10 can maintain its covering state by following the deformation of the surface 12 of the substrate 11.

[0108] As shown in the structural image of the oil-repellent glass coating film 10 in Figure 6 or as an example of the structural image of the oil-repellent glass coating film 10 in Figure 7, a crosslinking reaction occurs between the hydrolysis product having a -(Si(OH)2-O-Si(OH)2)- unit and a part of the main chain of siloxane bonds (Si-O-Si) in each coating layer 18 (surface layer 14, intermediate layer 16, back layer 15), and a crosslinked structure is formed, resulting in a dense and flexible structure for the oil-repellent glass coating film 10. With the formation of the crosslinked structure, hydrophobic methyl groups (CH3) derived from polysilazanes (perhydropolysilazane, organopolysilazane, organopolysiloxane) and hydrophilic hydroxyl groups (OH) derived from hydrolysis products can be coordinated to the surface 14 of the coating film 10.

[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 by blowing away metal powder, plastic powder, etc. generated on the surface 12 of the substrate 11 using an air spraying means such as an air gun. After the cleaning treatment, condensation is created on the surface 12 of the substrate 11 by allowing naturally occurring moisture to adhere to it by leaving it for a predetermined time.

[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), R1(R2)2R3Si containing at least one of n-octadecyldimethylmethoxysilane and n-octyldimethylmethoxysilane) and an inorganic substance containing SiO2. The organic substance is more abundant on the surface side 14 (upper layer including the surface 14) than in the interior (lower and intermediate layers) of the oil-repellent glass-based coating film 10. In the oil-repellent glass-based coating film 10, the terminal hydroxyl groups of polydimethylsiloxane (PDMS) are covalently bonded to the SiO2.

[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, the mass of R1(R2)2R3Si is between 0.2 and 1.1 times the mass of the polysilazane (inorganic polysilazane, organic polysilazane) forming it. If the mass of R1(R2)2R3Si 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 R1(R2)2R3Si is within the above range relative to the mass of polysilazane, so the coating film 10 has excellent oil repellency. In addition to excellent oil repellency, the oil-repellent glass-based coating film 10 also has excellent water 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. In addition, 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 surface 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 surface of the soda-lime glass substrate and the single-crystal silicon substrate and settled on the surface of the plates, a wait of 60 seconds was held for the oleic acid to stabilize on the surface of the plates. Next, the oleic acid settled on the upper surface 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 the plates was calculated using the θ / 2 method (θ = 2arctan h / r).

[0118] The oil-repellent glass-based coating film 10 has a higher content of organic substances containing long-chain alkyl groups (PDMS (polydimethylsiloxane), R1(R2)2R3Si, which includes at least one of n-octadecyldimethylmethoxysilane and n-octyldimethylmethoxysilane) 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. As a result, the coating film 10 has excellent oil repellency on its surface 14 side, so that 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 were prepared according to Examples 1 to 7, 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 system SuperLab (manufactured by Rigaku Corporation), and the reflectance profile was analyzed and fitted. 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 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. While stirring, 1 g of polydimethylsiloxane hydroxyl group-terminated (MW4200, thermo scientific, Cat. No: 043769.Ak) was gradually added to the 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 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 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. While stirring, 1 g of polydimethylsiloxane hydroxyl group-terminated (MW4200, thermo scientific, Cat. No: 043769.Ak) was gradually added to the 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 in 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 in 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 in Example 2 was ×, but the result of the uneven coating check (microscopic check) was ○. The coating film 10 in 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 (MW4200, 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 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 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 coating film 10 of Example 3 passed the 3H hardness test (after 3 hours) and failed the uneven coating check (microscopic examination). The coating film 10 of Example 3 failed the uneven coating check and had a problem in that it could not be coated flat.

[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 (MW4200, 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 passed the 3H hardness test (after 3 hours) and the coating unevenness check (microscopic examination) was also successful. 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 uneven coating 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 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. 0.8 g of polydimethylsiloxane hydroxyl group-terminated (MW4200, 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 (deposited) 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 also passed the 3H hardness test (after 3 hours) and the unevenness check (microscopic examination) was also successful. 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 uneven coating check (microscopic examination). 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 (MW4200, 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 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. 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 passed the 3H hardness test (after 3 hours) and passed the unevenness check (microscopic examination). The coating film 10 of Example 6 had problems with oil repellency and water repellency, as indicated by the "fail" judgment for both the water contact angle and the oleic acid contact angle.

[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 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 (MW4200, 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 in Example 7 failed the 3H hardness test, indicating a problem with film strength. The manufacturing process for 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-0.65 cSt (Shin-Etsu Chemical Co., Ltd.) were added to a glass reaction vessel. This was placed in a stirrer and stirred for about 1 minute. While the solution was stirring, 0.5 g of polydimethylsiloxane hydroxyl group-terminated (viscosity 750 cst, Sigma-Aldrich, product No: 481963) was gradually added, 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 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 the 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, the unpleasant odor during application was suppressed by adding (+)-limonene. The water contact angle of the coating film 10 of Example 8, measured according to JIS R 3257, was 105.6°, and the oleic acid contact angle, measured according to JIS R 3257, was 56.5°. The contact angle was judged as "○". The coating film 10 of Example 8 passed the 3H hardness test (after 3 hours) and the uneven coating check (microscopic examination) also passed. The coating film 10 produced under the conditions of Example 8 passed the water contact angle and oleic acid contact angle tests, passed the 3H hardness test (after 3 hours), and passed the uneven coating check (microscopic examination), resulting in all results being positive.

[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 (Al2O3), silicon nitride (Si3N4), zirconia (ZrO2), silicon carbide (SiC), aluminum nitride (AlN4 engineering type), mullite (3Al2O3·2SiO2), cordierite (2MgO·2Al2O3·5SiO2), and ferrite (M 2+Examples of porous ceramics include O·Fe2O3) 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), 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 with the oil-repellent glass-based coating film 10 on them have minimal adhesion of oily substances to their surface 12, and even if oily substances do adhere to the surface 12, they 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 ceramics, oil-related staining of the ceramic 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. Because 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 that form the oil-repellent glass-based coating film 10 include all metals currently manufactured, 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 resins used to form the oil-repellent glass-based coating film 10 include 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), etc. 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, fax 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] The display portion of an electronic device 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 portion of the electronic device, the oily substances can be easily removed from the surface 12 of the display portion. 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 portion of these electronic devices, oily contamination of the surface 12 of the display portion 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] Substrates 11 on which the oil-repellent glass-based coating film 10 is formed include the bodies of mobile vehicles, ships, aircraft, and glass windows. Mobile vehicles include trains, automobiles, ships, and airplanes. Trains include all trains currently in use and being manufactured, such as Shinkansen, limited 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 the 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 can be easily removed from the surfaces 12 of the 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 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 being left 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 to 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 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 fouling 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 and staining of the aircraft's fuselage and glass windows 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. [Explanation of symbols]

[0161] 10. Oil-repellent glass-based inorganic coating film 10. Oil-repellent glass-based organic / inorganic hybrid coating film 11 Base material 12 sides 13 Coating liquid 14 Surface 15 Back 16 intermediate 17 Anchor section 18 Covering layer

Claims

1. A coating film containing organic and inorganic materials, The coating film is fluorine-free (substantially fluorine-free), and the inorganic material is SiO ２ The organic substance includes a long-chain alkyl group, A coating film characterized in that the content of the organic substance in the coating film is greater on the surface side of the coating film (upper layer including the surface) 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 the coating film is oil-repellent.

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

3. where 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 , *, where * 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 home appliance 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, an automobile, a ship, or an airplane, and the glass window on which the coating film is formed is at least the windshield of the train, the automobile, the ship, or the 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 the inorganic main chain or a binding species that binds to 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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