Film and film-forming composition

Abstract

To provide a film which is excellent in water repellency and oil repellency, is excellent in stability of the film, and is easily formed because of high solubility of a silane coupling agent as a raw material, and to provide a film-forming composition capable of forming the film.SOLUTION: In the general formula (1), * represents a bond, and R1, R2, and R3 are identical to or different from each other and represent substituents each having a terminal alkyl group; Here, at least one of R1, R2, or R3 is an alkyl group having 1 to 5 carbon atoms. The film according to claim 1, wherein the silyl group is a silyl group represented by the following formula (1): SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a film and a film-forming composition. [Background technology]

[0002] In recent years, surface treatment agents have been used to impart water and oil repellency (including oil resistance and stain resistance) to a variety of products, including smartphones, devices such as solar cells, clothing, shoes, car bodies, and windshields.

[0003] As mentioned above, surface treatment agents that combine water and oil repellency mainly use compounds with a molecular structure containing a fluoroalkyl group, in which the hydrogen atoms in the hydrocarbon chain are replaced with fluorine atoms. Fluoroalkyl groups exhibit low surface free energy, inhibiting the wetting and spreading phenomenon not only of water but also of oil, and also exhibit high heat resistance.

[0004] However, PFAS (fluoroalkyl group-containing organic compounds) are highly stable, persistent in the environment, and prone to bioaccumulation, posing environmental risks and health hazards. For this reason, some PFAS with specific structures are already regulated, and there is a possibility that they will be regulated in other countries, including Japan, in the future.

[0005] From the above perspectives, there is a need for the development of water- and oil-repellent (fouling-resistant) materials that do not contain fluorine atoms. Organic compounds that exhibit low surface free energy, like PFAS, are effective as materials that repel water and oil, i.e., exhibit a high contact angle. In this regard, organosilicon (Si) compounds such as silicone not only exhibit relatively low surface free energy but also have low effects on the human body, making them promising alternatives to PFAS that exhibit water- and oil-repellent properties.

[0006] However, depending on the structure, these organosilicon compounds can be difficult to handle due to their low stability and low solubility in organic solvents. In addition, even if they repel water, they tend to be oil-soluble, meaning they are unable to exhibit sufficient oil repellency and stain resistance.

[0007] As a film formed from a water- and oil-repellent agent using such an organosilicon compound, a water- and oil-repellent film using polyhedral oligomeric silsesquioxane (POSS) has been proposed (see Patent Document 1). [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2018-123208 Summary of the Invention [Problem to be solved by the invention]

[0009] However, for example, OM-POSS has a silicone partial structure, -Si-O-, and a Si-Me group, and although a film formed using OM-POSS exhibits good water-repellency and oil-repellency, there is a problem in that the solubility of the raw material OM-POSS in solvents, etc., is extremely low when forming the film, making it difficult to use.

[0010] Furthermore, a coating that exhibits water-repellent and oil-repellent properties may come into contact with water or acid depending on the application, and is therefore required to be stable to water, etc. Patent Document 1 has the problem that stability to water, etc. is not sufficiently considered.

[0011] In view of the above circumstances, an object of the present invention is to provide a film that has excellent water and oil repellency and film stability, and that is easy to form due to the high solubility of the raw material compounds, and a film-forming composition that can form such a film. [Means for solving the problem]

[0012] As a result of extensive research, the present inventors have discovered that the above object can be achieved by using a coating having a trialkylsilyl group, and have thus completed the present invention.

[0013] That is, the present invention relates to the following coating and coating-forming composition. 1. On the surface, the following general formula (1) [ka] (In the general formula (1), * represents a bond, and R 1 , R 2 , and R 3 are the same or different and represent a substituent having a terminal alkyl group, provided that R 1 , R 2 , and R 3 At least one of the groups is an alkyl group having 1 to 5 carbon atoms.) A coating characterized by having a silyl group represented by the formula: 2. The above R 1 , R 2 , and R 3 Item 2. The coating according to item 1, wherein at least one of the groups is a methyl group. 3. The coating according to item 1 or 2, wherein the silyl group is a trimethylsilyl group. 4. The coating according to any one of items 1 to 3, wherein the silyl group is a tris(trimethylsilyl)methylsilyl group. 5. A film-forming composition for forming a film according to any one of items 1 to 4, comprising a compound represented by the following general formula (1): [ka] (In the general formula (1), * represents a bond, and R 1 , R 2 , and R 3 are the same or different and represent a substituent having a terminal alkyl group, provided that R 1 , R 2 , and R 3 At least one of the groups is an alkyl group having 1 to 5 carbon atoms.) A film-forming composition containing a compound having a silyl group represented by the formula: 6. The above R1 , R 2 , and R 3 Item 6. The film-forming composition according to Item 5, wherein at least one of the groups is a methyl group. 7. The film-forming composition according to item 5 or 6, wherein the silyl group is a trimethylsilyl group. 8. The film-forming composition according to any one of items 5 to 7, wherein the silyl group is a tris(trimethylsilyl)methylsilyl group. 9. The film-forming composition according to any one of items 5 to 8, wherein the compound is at least one compound selected from the group consisting of a silane coupling agent, an alcohol, and methyl methacrylate. 10. The silane coupling agent is represented by the following formula (7): [ka] (In formula (7), R 10 and R 11 are the same or different and represent a linear or branched alkylene group having 0 to 10 carbon atoms, and n represents an integer. is a silane coupling agent represented by The alcohol is represented by the following formula (10): [ka] (In formula (10), R 10 and R 11 are the same or different and represent a linear or branched alkylene group having 0 to 10 carbon atoms, and n represents an integer. is an alcohol represented by Item 10. The film-forming composition according to item 9. [Effects of the Invention]

[0014] The coating of the present invention has excellent water and oil repellency and excellent coating stability, and is easy to form due to the high solubility of the raw material compounds. Furthermore, since the coating composition of the present invention has high solubility of the raw material compounds, it can be uniformly applied to the surface of the article on which the coating is to be formed, and the coating of the present invention can be easily formed. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 is a graph showing the change in contact angle of the coating of the present invention after immersion in water in Test 1. DETAILED DESCRIPTION OF THE INVENTION

[0016] The present invention will be described in detail below.

[0017] 1. Coating The coating of the present invention has, on the surface thereof, a compound represented by the following general formula (1): [ka] (In the general formula (1), * represents a bond, and R 1 , R 2 , and R 3 are the same or different and represent a substituent having a terminal alkyl group, provided that R 1 , R 2 , and R 3 At least one of the groups is an alkyl group having 1 to 5 carbon atoms.) The coating of the present invention has a silyl group represented by the formula (1) on its surface. The coating of the present invention has the above characteristics, and as a result, it can exhibit excellent water repellency and oil repellency, and also has excellent coating stability. Furthermore, the coating of the present invention is easy to form because the silane coupling agent and / or alcohol, which are the raw materials, have high solubility.

[0018] The coating of the present invention has silyl groups represented by the following general formula (1) on the surface.

[0019] [ka]

[0020] In formula (1), * indicates a bond.

[0021] In formula (1), R 1 , R 2 , and R3 are the same or different and represent substituents having a terminal alkyl group. 1 , R 2 , and R 3 At least one of the groups is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and even more preferably a methyl group.

[0022] Substituents having a terminal alkyl group include R 1 , R 2 , and R 3 There are no particular limitations on the group, as long as at least one of them is an alkyl group having 1 to 5 carbon atoms, and examples include alkyl groups, alkoxy groups, p-tolyl groups, phenyl groups, allyl groups, aryl groups, N-alkylamino groups, and N,N-dialkylamino groups. Of these, alkyl groups are preferred, and the coating of the present invention is preferably a coating having trialkylsilyl groups on the surface.

[0023] The alkyl group preferably has 20 or less carbon atoms, more preferably 16 or less, even more preferably 12 or less, and particularly preferably 6 or less. Specific examples include methyl, ethyl, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, various nonadecyl groups, and various icosyl groups. Among these, methyl, ethyl, and various propyl groups are preferred, with methyl and ethyl groups being more preferred, and methyl being even more preferred. In formula (1), in particular, R 1 , R 2 , and R 3 is preferably a methyl group, that is, the coating of the present invention is preferably a coating having trimethylsilyl groups on the surface.

[0024] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, and a 2-ethylhexyloxy group.

[0025] The coating of the present invention may have silyl groups represented by the above general formula (1) on the surface, and may have, for example, (trissilyl)silyl groups represented by the following formula (2).

[0026] [ka]

[0027] In formula (2), * indicates a bond.

[0028] In formula (2), R 1 ~R 3 , R 4 ~R 6 , and R 7 ~R 9 are the R explained in the above formula (1), 1 ~R 3 is the same as

[0029] In formula (2), R 10 and R 11 are preferably the same or different and are linear or branched alkylene groups having 0 to 10 carbon atoms. The alkylene group preferably has 1 to 8 carbon atoms, more preferably 1 to 3 carbon atoms.

[0030] In formula (2), X 1 ~X 3 are preferably the same or different and each represents an oxygen atom or a linear or branched alkylene group having 0 to 10 carbon atoms. 1 ~X 3 are preferably the same or different and are linear or branched alkylene groups, and the alkylene group preferably has 1 to 8 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1. 1 ~X 3 By adopting the above-mentioned configuration, the stability of the coating is further improved.

[0031] In formula (2), n preferably represents an integer. Specifically, n may be an integer of 0 to 100, 0 to 50, 0 to 20, 0 to 10, 0 to 5, 0 to 3, 0 to 2, etc., or may be 0 or 1.

[0032] The coating of the present invention preferably has tris(trimethylsilyl)methylsilyl groups represented by the following formula (3) on the surface.

[0033] [ka]

[0034] In formula (3), * indicates a bond.

[0035] The (trissilyl)silyl group represented by formula (2) is preferably a tris(trialkylsilyl)alkylsilyl group represented by the following formula (4).

[0036] [ka]

[0037] In formula (4), *, R 10 , R 11 and n are the same as in formula (2).

[0038] The thickness of the coating of the present invention is not particularly limited and may be adjusted as appropriate depending on the application. For example, in the case of a water repellent coating for textile products, the thickness of the coating is preferably 5.0 μm or less, more preferably 3.0 μm or less, and even more preferably 1.0 μm or less. Furthermore, the lower limit of the coating thickness is not particularly limited, and it is sufficient if it is about 1 nm.

[0039] The coating of the present invention is formed on a substrate. The substrate is not particularly limited, and various substrates that require water repellency and oil repellency can be used. Examples of such substrates include silicon substrates, glass substrates, fabrics such as nylon cloth, polyester cloth, and cotton cloth, paper, nanofibers that may be modified with chitosan, and cellulose nanofibers.

[0040] 2. Film-forming composition The film-forming composition of the present invention is a film-forming composition for forming the film of the present invention, which is represented by the following general formula (1): [ka] In the general formula (1), * and R 1 , R 2 , and R 3 is the same as that explained above for the coating of the present invention.

[0041] The compound having a silyl group represented by the general formula (1) is not particularly limited as long as it has the general formula (1), and various compounds such as monomers and polymers can be used. Among these, silane coupling agents, alcohols, methyl methacrylate, etc. can be preferably used.

[0042] The silane coupling agent having a silyl group represented by the general formula (1) is not particularly limited as long as it acts as a silane coupling agent and has a silyl group represented by the general formula (1). Examples of the silane coupling agent include silane coupling agents represented by the following formula (5).

[0043] [ka]

[0044] In formula (5), R 1 ~R 11 , X 1 ~X 3and n are the same as in formula (2).

[0045] The silane coupling agent more preferably has a tris(trimethylsilyl)methylsilyl group represented by the above formula (3). That is, the silane coupling agent more preferably is a silane coupling agent represented by the following formula (6):

[0046] [ka]

[0047] In formula (6), R 10 , R 11 , X 1 ~X 3 and n are the same as in formula (2).

[0048] The silane coupling agent is more preferably a silane coupling agent represented by the following formula (7): By using the silane coupling agent represented by the following formula (7) as the silane coupling agent, the stability of the formed film is further improved, and the solubility of the silane coupling agent as a raw material is high, making it easier to form the film.

[0049] [ka]

[0050] In formula (7), R 10 , R 11 and n are the same as in formula (2).

[0051] The alcohol having a trialkylsilyl group is not particularly limited as long as it has a hydroxyl group and a trialkylsilyl group, and is preferably an alcohol having a trialkylsilyl group represented by the above general formula (1).

[0052] The alcohol includes alcohols represented by the following formula (8).

[0053] [ka]

[0054] In formula (8), R 1 ~R 11 , X 1 ~X 3 and n are the same as in formula (2).

[0055] The alcohol more preferably has a tris(trimethylsilyl)methylsilyl group represented by the above formula (3). That is, the alcohol more preferably is an alcohol represented by the following formula (9).

[0056] [ka]

[0057] In formula (9), R 10 , R 11 , X 1 ~X 3 and n are the same as in formula (2).

[0058] Furthermore, the alcohol is more preferably an alcohol represented by the following formula (10): By using an alcohol represented by the following formula (10) as the alcohol, the stability of the film to be formed is further improved, and the solubility of the alcohol as a raw material is high, making it easier to form the film.

[0059] [ka]

[0060] In formula (10), R 10 , R 11 and n are the same as in formula (2).

[0061] In the film-forming composition of the present invention, the silane coupling agent and the alcohol may be used alone or in combination.

[0062] Examples of the methyl methacrylate having a silyl group represented by the general formula (1) include a monomer of methyl methacrylate having a silyl group represented by the general formula (1) and a polymer obtained by polymerizing a monomer of methyl methacrylate having a silyl group represented by the general formula (1).

[0063] Examples of the methyl methacrylate monomer having a silyl group represented by the above general formula (1) include monomers represented by the following formula.

[0064] [ka]

[0065] Examples of the polymer obtained by polymerizing a methyl methacrylate monomer having a silyl group represented by the above general formula (1) include polymers represented by the following formula.

[0066] [ka]

[0067] In the above formula, I represents an integer. Specifically, I may be an integer of 0 to 100, 0 to 50, 0 to 20, 0 to 10, 0 to 5, 0 to 3, or 0 to 2, or may be 0 or 1.

[0068] The content of the compound in the film-forming composition is preferably 0.5 to 20% by mass, more preferably 0.5 to 5% by mass, and even more preferably 1 to 2% by mass, based on 100% by mass of the film-forming composition. By ensuring that the lower limit of the compound content falls within the above range, the water repellency and oil repellency of the film formed are further improved. Furthermore, by ensuring that the upper limit of the compound content falls within the above range, the film can be uniformly applied to the surface of the article on which the film is to be formed, making it easier to form the film of the present invention.

[0069] The film-forming composition may contain other components in addition to the compound having a silyl group represented by the general formula (1), such as additives and solvents.

[0070] The additives include ordinary additives used in film-forming compositions, such as antioxidants, ultraviolet absorbers, antistatic agents, antifoaming agents, and crosslinking agents (polyisocyanates, melamine resins, etc.).

[0071] The content of the additives in the film-forming composition is not particularly limited as long as it is within a range that does not inhibit film formation.

[0072] The solvent is not particularly limited as long as it can dissolve or disperse the compound having a silyl group represented by the general formula (1) above and additives added as needed, and examples thereof include water, alcohol solvents, acetone, toluene, chloroform, and petroleum-based solvents.

[0073] The amount of solvent in the film-forming composition is not particularly limited, and may be the balance between the content of the compound having a silyl group represented by the general formula (1) above and the content of additives added as needed.

[0074] The method for producing the film-forming composition is not particularly limited, and the film-forming composition can be produced by adding the compound having a silyl group represented by the general formula (1) above and additives added as needed to a solvent, stirring, and dissolving or dispersing the compound.

[0075] 3. Film formation method The method for forming the film of the present invention is not particularly limited. For example, the film can be formed on a substrate by applying the film-forming composition of the present invention onto the substrate and curing it.

[0076] The coating method for applying the film-forming composition to the substrate is not particularly limited, and can be any conventionally known method. Examples of such coating methods include dip coating and spray coating. Alternatively, the substrate may be immersed in the film-forming composition to apply the composition.

[0077] The film-forming composition may be cured by leaving it at room temperature as described above, or may be heated. The heating temperature is not particularly limited as long as it can cure the film-forming composition, and is preferably 100 to 200°C, and more preferably 120 to 180°C.

[0078] The curing time for curing the film-forming composition is preferably from 1 to 300 minutes, more preferably from 10 to 200 minutes, and even more preferably from 20 to 150 minutes.

[0079] The film-forming composition may be cured by leaving it at room temperature. In this case, the curing temperature is not particularly limited as long as it can cure the film-forming composition, and is preferably 0 to 50°C, more preferably 5 to 40°C, and even more preferably 10 to 30°C.

[0080] By the film forming method described above, a film can be formed on a substrate.

[0081] 4.Layered coating The coating of the present invention may be formed directly on a substrate, or a pre-coating layer and a polydimethylsiloxane coating layer (hereinafter also referred to as a "PDMS coating layer") may be laminated between the substrate and the coating of the present invention, in that order from the substrate side. That is, the present invention may be a laminate having, from below (from the substrate side), a pre-coating layer and / or a PDMS layer and the coating of the present invention, or a laminate having, from below (from the substrate side), a pre-coating layer, a PDMS coating layer, and the coating of the present invention. The pre-coating layer and the PDMS coating layer will be described below.

[0082] (Pre-coating layer) The pre-coating layer is a layer that facilitates adhesion between a substrate and the PDMS coating layer or the film of the present invention. The pre-coating layer is preferably a layer containing a hydrolyzate of an alkoxysilane and formed by hydrolyzing the alkoxysilane.

[0083] The alkoxysilane is not particularly limited as long as it can form a film by a sol-gel method through hydrolysis, and examples include tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), etc. Among these, tetraethoxysilane is preferred because of its superior adhesion to the substrate.

[0084] The pre-coating layer is a layer that does not contain trialkylsilyl groups, and is distinguished from the coating of the present invention in this respect.

[0085] The thickness of the pre-coating layer is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. When the lower limit of the thickness of the pre-coating layer is within the above range, the adhesion between the substrate and the PDMS coating layer or the film of the present invention is further improved. When the upper limit of the thickness of the pre-coating layer is within the above range, the stability of the laminate is further improved.

[0086] The method for forming the pre-coating layer is not particularly limited, and the alkoxysilane may be dissolved in a solvent such as water or an organic solvent to prepare a composition for forming the pre-coating layer, which may then be applied onto a substrate.

[0087] The curing time for curing the pre-coating layer-forming composition is preferably 10 to 120 minutes, more preferably 10 to 30 minutes.

[0088] When the pre-coating layer-forming composition is cured, it may be left to dry at room temperature (23°C), or it may be heated. When heated, the heating temperature is preferably 20 to 150°C, and more preferably 80 to 120°C.

[0089] (Polydimethylsiloxane coating layer) The PDMS coating layer is a layer that facilitates adhesion between the substrate or pre-coating layer and the film of the present invention. The PDMS coating layer is preferably a layer containing polydimethylsiloxane (PDMS). Examples of polydimethylsiloxanes used to form such layers include 1,3-dichloro-1,1,3,3-tetramethyldisiloxane (DCTMDSO). Among these, 1,3-dichloro-1,1,3,3-tetramethyldisiloxane is preferred from the viewpoint of facilitating adhesion between the substrate or pre-coating layer and the film of the present invention.

[0090] The PDMS coating layer is a layer that does not have a trialkylsilyl group, and is different from the film of the present invention in this respect.

[0091] The thickness of the PDMS coating layer is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The lower limit of the thickness of the PDMS coating layer is not particularly limited, but may be about 1 nm.

[0092] The method for forming the PDMS coating layer is not particularly limited, and may involve dissolving the polydimethylsiloxane in a solvent such as water or an organic solvent to prepare a composition for forming a PDMS coating layer, and then applying the composition to a pre-coating layer or a substrate.

[0093] The curing time for curing the composition for forming a PDMS coating layer is preferably 30 to 120 minutes, more preferably 30 to 60 minutes.

[0094] When the composition for forming a PDMS coating layer is cured, it may be left to dry at room temperature (23°C), or may be heated. When heated, the heating temperature is preferably 80 to 120°C, and more preferably 100 to 110°C.

[0095] The coating of the present invention has the above-described structure, and therefore has excellent water- and oil-repellency, excellent film stability, and is easy to form due to the high solubility of the raw material compounds. Because the coating of the present invention exhibits the above-described properties, it can impart water- and oil-repellency (including oil resistance and stain resistance) to a variety of products, such as smartphones, devices such as solar cells, clothing, shoes, car bodies, and windshields. [Example]

[0096] The present invention will be described in more detail with reference to examples, but these examples are for the purpose of illustrating the present invention and are not intended to limit the present invention in any way. Unless otherwise specified, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0097] The evaluations in the examples were carried out by the following methods.

[0098] (contact angle) Using a contact angle measuring instrument (NIC Co., Ltd., CAME1), 50 μL of each solvent was dropped onto the surface, and the contact angle was measured after 30 seconds.

[0099] [Test Example 1] The following raw materials were mixed and stirred at room temperature to prepare approximately 5 ml of a film-forming composition for each example.

[0100] (Example 1-1) TTMS-C3: 2% by mass, methanol: 97.7% by mass, acetic acid: 0.3% by mass [ka]

[0101] (Example 1-2) TTMS-BDMS: 2% by mass, methanol: 97.7% by mass, acetic acid: 0.3% by mass [ka]

[0102] (Examples 1-3) TTMSMS-C3: 2% by mass, methanol: 97.7% by mass, acetic acid: 0.3% by mass [ka]

[0103] (Examples 1-4) TTMSMS-BDMS: 2% by mass, methanol: 97.7% by mass, acetic acid: 0.3% by mass [ka]

[0104] The following substrates, each measuring 1.8 cm × 1.8 cm, were prepared. A glass substrate and a silicon substrate were each immersed in the film-forming composition prepared as described above at room temperature overnight, then removed, washed with methanol, and dried at 120°C for 2 hours to form a film on the substrate.

[0105] The contact angles of the surfaces of the substrates on which the films were formed were measured using water, decane, hexadecane, and oleic acid (initial contact angles).

[0106] The substrate on which the film was formed was immersed in water at room temperature for 2 days and 6 days, and the contact angle of the film surface was measured using water, decane, hexadecane, and oleic acid (contact angle after water immersion).

[0107] The initial contact angle and the contact angle after 2 days of water immersion are shown in Table 1. The initial contact angle and the contact angles after 2 days and 6 days of water immersion, measured using water and hexadecane, are shown in Figure 1.

[0108] [Table 1]

[0109] [Test Example 2] Monomers indicated by 2A to 2D below were mixed in the molar ratios shown in Table 2 below and dissolved in 0.5 mL of toluene to prepare a monomer mixture. Next, 0.3 to 0.8 equivalents of AIBN were added, and the mixture was stirred overnight at 70°C to polymerize the mixture. 100 μL of a chloroform solution (10.5 mL) containing 50 mg of polymer was dropped onto a glass substrate, which was then rotated at 1000 rpm for 60 seconds to form a film on the glass substrate.

[0110] Monomer 2A: [ka]

[0111] Monomer 2B: [ka]

[0112] Monomer 2C: [ka]

[0113] Monomer 2D: [ka]

[0114] The contact angles of the surfaces of the films formed on the substrates were measured using water, decane, hexadecane, oleic acid, and castor oil.

[0115] The results are shown in Table 2.

[0116] [Table 2]

[0117] [Test Example 3] The following polymers, TMS-EP-P and TTMSMAS-EP-P, were formed into films on a glass substrate by dropping 100 μL of a chloroform solution (10.5 mL) containing the polymer (50 mg) onto the glass substrate and rotating it at 1000 rpm for 60 seconds.

[0118] Example 3-1 TMS-EP-P: [ka]

[0119] In the above formula, I represents an integer.

[0120] (Example 3-2) TTMSMAS-EP-P: [ka]

[0121] In the above formula, I represents an integer.

[0122] The contact angles of the surfaces of the films formed on the substrates were measured using water, decane, hexadecane, oleic acid, and castor oil.

[0123] The results are shown in Table 3.

[0124] [Table 3]

[0125] [Test Example 4] Monomers 4A to 4C below were mixed in the molar ratios shown in Table 4 below and dissolved in 0.5 ml of toluene to prepare a monomer mixture. Next, 0.3 to 0.8 equivalents of AIBN were added, and the mixture was polymerized by stirring at 70°C overnight to prepare a polymer. Nylon fabric (warp and weft: nylon 40 denier / 48 filaments, warp density: 194 ends / inch, weft density: 115 ends / inch, high-density taffeta) was immersed in the polymer chloroform solution overnight and heated at 120°C for 2 hours to cure the polymer and form a film on the surface of the fabric.

[0126] Monomer 4A: [ka]

[0127] Monomer 4B: [ka]

[0128] Monomer 4C: [ka]

[0129] The contact angles of the surfaces of the films formed on the surfaces of the fabrics were measured using water, decane, hexadecane, oleic acid, and castor oil.

[0130] The results are shown in Table 4.

[0131] [Table 4]

[0132] In Test Example 4, the contact angles of decane, hexadecane (HD), and oleic acid (OA) were 0°. Furthermore, the contact angles were generally low. This is thought to be because Examples 4-1 to 4-5 had flexible molecular structures and the cloth surface was highly uneven, so some Si(CH3)3 groups did not appear on the surface, resulting in a low contact angle.

[0133] [Test Example 5] (pre-coating) A sol-gel solution was prepared as a pre-coating agent by mixing 10.42 g of tetraethyl orthosilicate (TEOS), 8.74 g of ethanol, 0.45 mL of hydrochloric acid, and 5.76 mL of water. A nylon fabric (nylon 40d high-density taffeta) was immersed in the sol-gel solution, removed, and dried at 110°C for 10 minutes to perform pre-coating.

[0134] (PDMS coating) The precoated fabric and glass substrates that had been plasma-treated for 15 minutes were coated with PDMS (polydimethylsiloxane) as follows: A Petri dish (64 mm diameter, 20 mm height) containing 60 μL of 1,3-dichloro-1,1,3,3-teramethyldisiloxane (DCTMDSO) and the substrates were placed in a sealed container and exposed to DCTMDSO vapor at 20°C for 120 minutes. After that, the substrates were removed and dried at 110°C for 60 minutes to complete the PDMS coating.

[0135] (film formation) The following alcohol and solvent were mixed and stirred at room temperature for 1 minute to prepare 5 ml of a film-forming composition for each example. The pre-coated and PDMS-coated substrate was immersed in the film-forming composition at room temperature overnight, then removed, washed with toluene, and dried for 60 minutes to form a film. Note that no film was formed in Comparative Example 5-1.

[0136] (Example 5-1) Alcohol 5A: 1% by mass, toluene: 99% by mass 5A: [ka]

[0137] (Example 5-2) Alcohol 5B: 1% by mass, toluene: 99% by mass 5B: [ka]

[0138] (Example 5-3) Alcohol 5C: 1% by mass, toluene: 99% by mass 5C: [ka]

[0139] The contact angles of the coating surfaces were measured using water, decane, hexadecane, oleic acid, and castor oil.

[0140] The results are shown in Table 5.

[0141] [Table 5]

[0142] [Test Example 6] (pre-coating) A sol-gel solution was prepared as a pre-coating agent by mixing 10.42 g of tetraethyl orthosilicate (TEOS), 8.74 g of ethanol, 0.45 mL of hydrochloric acid, and 5.76 mL of water. A nylon fabric (nylon 40d high-density taffeta) was prepared as a substrate, immersed in the sol-gel solution, removed, and dried at 110°C for 10 minutes to perform pre-coating.

[0143] (PDMS coating) The precoated fabric and glass substrates that had been plasma-treated for 15 minutes were coated with PDMS (polydimethylsiloxane) as follows: A Petri dish (64 mm diameter, 20 mm height) containing 60 μL of 1,3-Dichloro-1,1,3,3-teramethyldisiloxane (DCTMDSO), a Petri dish containing the amount of water shown in Table 6, and the various substrates were placed in a sealed container. After exposing the substrates to the vaporized DCTMDSO and water vapor for the time shown in Table 6, the various substrates were removed and dried at 110 °C for 60 minutes to complete the PDMS coating.

[0144] (film formation) 5 ml of a film-forming composition for each example was prepared by mixing the alcohol and solvent listed below and stirring at room temperature for 1 minute. The pre-coated and PDMS-coated substrate was immersed in the film-forming composition at room temperature overnight, then removed and dried at 110°C for 60 minutes to form a film.

[0145] (Example 6-1, Example 6-2) Alcohol 6A: 1% by mass, toluene: 99% by mass 6A: [ka]

[0146] (Examples 6-3 and 6-4) Alcohol 6B: 1% by mass, toluene: 99% by mass 6B: [ka]

[0147] The contact angles of the coating surfaces were measured using water, decane, hexadecane, oleic acid, and castor oil.

[0148] The results are shown in Table 6.

[0149] [Table 6]

[0150] [Test Example 7] A film made of chitosan-modified nanofibers (hereinafter also referred to as "chitosan-modified nanofiber film") represented by the following formula was prepared as a substrate: In the following formula, x and y represent natural numbers. [ka]

[0151] (PDMS coating) Chitosan-modified nanofiber films were coated with PDMS (polydimethylsiloxane) as follows: A petri dish (64 mm diameter, 20 mm height) containing 40 μL of 1,3-dichloro-1,1,3,3-teramethyldisiloxane (DCTMDSO), a petri dish containing the amount of water shown in Table 7, and the chitosan-modified nanofiber film were placed in a sealed container. The substrates were exposed to the vaporized DCTMDSO and water vapor for the time shown in Table 6, and then the substrates were removed and dried at 110°C for 60 minutes to perform the PDMS coating.

[0152] (film formation) The following alcohol and solvent were mixed and stirred at room temperature for 1 minute to prepare 5 ml of a film-forming composition for each example. A PDMS-coated substrate was immersed in the film-forming composition at room temperature overnight, then removed and dried at 110°C for 60 minutes to form a film.

[0153] (Examples 7-1 to 7-4) Alcohol 7A: 1% by mass, toluene: 99% by mass 7A: [ka]

[0154] (Examples 7-5 to 7-8) Alcohol 7B: 1% by mass, toluene: 99% by mass 7B: [ka]

[0155] The contact angles of the coating surfaces were measured using water, decane, hexadecane, oleic acid, and castor oil.

[0156] The results are shown in Table 7.

[0157] [Table 7]

Claims

1. On the surface, the following general formula (1) 【Chemistry 1】 (In general formula (1), * represents a bond, and R １ , R ２ , and R ３ are the same or different and represent substituents having a terminal alkyl group. １ , R ２ , and R ３ At least one of the groups is an alkyl group having 1 to 5 carbon atoms. A coating characterized by having a silyl group represented by the formula:

2. The R １ , R ２ , and R ３ The coating of claim 1 , wherein at least one of the groups is a methyl group.

3. The coating of claim 1 , wherein the silyl group is a trimethylsilyl group.

4. The coating of claim 1 , wherein the silyl group is a tris(trimethylsilyl)methylsilyl group.

5. A film-forming composition for forming the film according to any one of claims 1 to 4, comprising a compound represented by the following general formula (1): 【Chemistry 2】 (In general formula (1), * represents a bond, and R １ , R ２ , and R ３ are the same or different and represent a substituent having a terminal alkyl group, provided that R １ , R ２ , and R ３ At least one of the groups is an alkyl group having 1 to 5 carbon atoms. A film-forming composition containing a compound having a silyl group represented by the formula:

6. The R １ , R ２ , and R ３ The film-forming composition according to claim 5 , wherein at least one of the groups is a methyl group.

7. The film-forming composition according to claim 5 , wherein the silyl group is a trimethylsilyl group.

8. The film-forming composition according to claim 5 , wherein the silyl group is a tris(trimethylsilyl)methylsilyl group.

9. 6. The film-forming composition according to claim 5, wherein the compound is at least one compound selected from the group consisting of a silane coupling agent, an alcohol, and methyl methacrylate.

10. The silane coupling agent is represented by the following formula (7): 【Transformation 3】 (In formula (7), R １０ and R １１ are the same or different and represent a linear or branched alkylene group having 0 to 10 carbon atoms, and n represents an integer. is a silane coupling agent represented by The alcohol is represented by the following formula (10): 【Chemistry 4】 (In formula (10), R １０ and R １１ are the same or different and represent a linear or branched alkylene group having 0 to 10 carbon atoms, and n represents an integer. is an alcohol represented by The film-forming composition according to claim 9.

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