Hydrophilic composition, coating agent, and coated article

Abstract

A hydrophilic composition that includes at least one of an organic silicon compound represented by formula (1), a condensate of an organic silicon compound represented by formula (1), and the product of reacting an organic silicon compound represented by formula (1) and metal oxide particles makes it possible to obtain a hydrophilic coating film that has excellent durability. (In the formula, the R1s each independently represent a hydrogen atom, a C1–10 alkyl group, or a C6–10 aryl group, the R2s each independently represent a C1–10 alkyl group or a C6–10 aryl group, X represents a hydrogen atom, a k-valent metal cation, or an ammonium cation, k is 1 or 2, provided that k is 1 when X is a hydrogen atom or an ammonium cation, m is an integer from 1 to 10, inclusive, and n is an integer from 1 to 3, inclusive.)

Description

Hydrophilic compositions, coatings, and coated articles

[0001] The present invention relates to hydrophilic compositions, coating agents, and coated articles.

[0002] In recent years, there has been a growing demand for improvements in the cloudiness of substrates made from inorganic materials such as glass and organic materials such as plastics. Generally, improvement of substrate cloudiness is achieved by coating the surface of the substrate with a hydrophilic film. For example, a composition mainly composed of an organosilicon compound having a sulfobetaine structure in which the nitrogen atom in the nitrogen-containing heterocyclic structure has a positive charge is known as a coating agent that can impart hydrophilicity to a substrate (see Patent Documents 1 and 2).

[0003] However, the coating film to which the above coating agent is applied does not have sufficient water resistance, and when it comes into contact with water, the surface properties such as hydrophilicity and antifogging described above may deteriorate, and further improvement is desired.

[0004] Japanese Patent Publication No. 2019-48966 Japanese Patent Publication No. 2022-82176

[0005] The present invention has been made in view of the above circumstances, and aims to provide a hydrophilic composition, coating agent, and coated article that provide a film with excellent hydrophilicity, anti-fogging properties, and water resistance.

[0006] As a result of diligent research to solve the above problems, the present inventors have discovered that a hydrophilic composition using a specific organosilicon compound having a sulfonic acid derivative structure can provide a coating to substrates formed from inorganic materials such as glass or organic materials such as plastics, which can impart excellent water resistance, durable hydrophilicity, and anti-fogging properties, thus completing the present invention.

[0007] In other words, the present invention provides: 1. A hydrophilic composition comprising one or more selected from the group consisting of an organosilicon compound represented by the following formula (1), a condensate of the organosilicon compound, and a reaction product of the organosilicon compound and metal oxide particles. (In the formula, R 1 Each of these independently represents a hydrogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group, R 2) 1. Each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, X represents a hydrogen atom, a k-valent metal cation, or an ammonium cation, k is 1 or 2, except when X is a hydrogen atom or an ammonium cation, k is 1, m is an integer from 1 to 10, and n is an integer from 1 to 3. 2. A hydrophilic composition 1 containing water, 3. A coating agent comprising the hydrophilic composition 1 or 2, 4. A hydrophilic film obtained by curing the hydrophilic composition 1 or 2, 5. A coated article having a substrate and the hydrophilic film 4 formed directly or via one or more other layers on at least a portion of the surface of the substrate, 6. Metal oxide particles whose surface is surface-treated with an organosilicon compound represented by the following formula (1), (In the formula, R 1 Each of these independently represents a hydrogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group, R 2 Each of the following independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms; X represents a hydrogen atom, a k-valent metal cation, or an ammonium cation; k is 1 or 2, except when X is a hydrogen atom or an ammonium cation, k is 1; m is an integer from 1 to 10; and n is an integer from 1 to 3.

[0008] The hydrophilic composition of the present invention provides a coating film on organic substrates such as plastics and inorganic substrates such as glass that offers excellent water resistance and moisture resistance, as well as durable hydrophilicity and anti-fogging properties.

[0009] The present invention will now be described in detail. The composition of the present invention contains an organosilicon compound represented by the following formula (1).

[0010]

[0011] In equation (1), R 1 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. 1The alkyl group may be linear, branched or cyclic. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl group and the like. R 1 Specific examples of the aryl group of R include phenyl group, tolyl group and the like. Among these, R 1 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group.

[0012] R 2 each independently represents an alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. Specific examples of these alkyl groups and aryl groups are the same as those exemplified for R 1 above, but among them, a methyl group is preferred.

[0013] X represents a hydrogen atom, a k-valent metal cation or an ammonium cation. Here, k is 1 or 2, provided that k is 1 when X is a hydrogen atom or an ammonium cation. Specific examples of the monovalent metal cation include Na + , K + and the like. Specific examples of the divalent metal cation include Mg 2+ , Ca 2+ , Ba 2+ and the like. Specific examples of the ammonium cation include ammonium ion, methylammonium ion, dimethylammonium ion, trimethylammonium ion, triethylammonium ion and the like. Among these, a hydrogen atom, Na 1 6>, ammonium ion are preferred.

[0014] That is, the organosilicon compound represented by the above formula (1) is preferably a compound represented by the following formulas (2) to (4).

[0015] (In the formula, R 1 , R 2 , n and m represent the same meanings as above.)

[0016] m is an integer from 1 to 10, and is preferably an integer from 3 to 8 in terms of the content of sulfonic acid derivative moieties per unit mass and anti-fogging properties, and more preferably 8 in terms of water resistance. n is an integer from 1 to 3, is preferably 2 or 3, and more preferably 3.

[0017] Specific examples of organosilicon compounds represented by the above formula (1) are given below, but are not limited to these.

[0018] (In the formula, Me represents a methyl group. The same applies below.)

[0019] The organosilicon compound represented by formula (1) above can be produced, for example, by reacting a mercapto group-containing silane compound represented by formula (I) below with hydrogen peroxide, or by reacting the organosilicon compound represented by formula (2) above with any monovalent metal cation or ammonium cation M. 1 , or divalent metal cation M 2 It can be manufactured by reacting the two substances.

[0020] (In the formula, M 1 is a monovalent metal cation or ammonium cation, M 2 (It is a divalent metal cation.)

[0021] Specific examples of mercapto group-containing silane compounds represented by the above formula (I) are shown below, but are not limited to these. Among these, 3-mercaptopropyltrimethoxysilane represented by the following formula (5) is preferred.

[0022]

[0023] The reaction between the mercapto group-containing silane compound represented by formula (I) above and hydrogen peroxide can be carried out according to known oxidation reactions. In this oxidation reaction, a solvent may be used as needed. Suitable solvents include alcohols such as methanol, ethanol, isopropanol, and t-butanol; ketones such as acetone and methyl isobutyl ketone; ethers such as dibutyl ether; esters such as ethyl acetate; aromatic hydrocarbons such as toluene; and aliphatic hydrocarbons such as hexane and decane. The reaction temperature for the oxidation reaction is preferably 0 to 90°C, more preferably 25 to 75°C, and should be set according to the boiling point of the solvent if one is used. The reaction time is preferably 1 to 150 hours, more preferably 5 to 100 hours.

[0024] The preferred ratio of the mercapto group-containing silane compound represented by formula (I) to hydrogen peroxide during the oxidation reaction is 0.75 to 10.25 moles of hydrogen peroxide per mole of mercapto group-containing silane compound (I), and more preferably 4 to 6 moles.

[0025] The organosilicon compound represented by formula (1) above can be subjected to hydrolysis condensation to further improve the durability of the resulting film. When performing hydrolysis condensation, other organosilicon compounds may be added and co-hydrolysis condensation may be performed, as long as the objectives of the present invention are not impaired.

[0026] Other specific examples of organosilicon compounds include methyltrimethoxysilane, methyltrippropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripentoxysilane, methyltriamiloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, and β-glycid Xyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-Glycidoxybutyltrimethoxysilane, α-Glycidoxybutyltriethoxysilane, β-Glycidoxybutyltriethoxysilane, γ-Glycidoxybutyltrimethoxysilane, γ-Glycidoxybutyltriethoxysilane, δ-Glycidoxybutyltrimethoxysilane, δ-Glycidoxybutyltriethoxysilane, (3,4-Epoxycyclohexyl)methyltrimethoxysilane, (3,4-Epoxycyclohexyl)methyltriethoxysilane, β-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane Lan, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrippropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-Epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-Trifluoropropyltrimethoxysilane, γ-Mercaptopropyltrimethoxysilane, γ-Mercaptopropyltriethoxysilane, β-Cyanoethyltriethoxysilane, Chloromethyltrimethoxysilane, Chloromethyltriethoxysilane, N-(β-Aminoethyl)γ-Aminopropyltrimethoxysilane, N-(β-Aminoethyl)γ-Aminopropylmethyldimethoxysilane, γ-Aminopropylmethyldimethoxysilane, N-(β-Aminoethyl)γ-Aminopropyltriethoxysilane, N-(β-Aminoethyl)γ-Aminopropylmethyldiethoxysilane, Dimethyldimethoxysilane, Phenylmethyldimethoxysilane, Dimethyldiethoxysilane, Phenylmethyldiethoxysilane, γ-Chloropropylmethyldimethoxysilane, γ-Chloropropyl Examples include tyldiethoxysilane, dimethyldiacetoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R)-N-1-phenylethyl-N'-triethoxysilylpropylurea, (R)-N-1-phenylethyl-N'-trimethoxysilylpropylurea, 3-isocyanatetopropyltriethoxysilane, trifluoropropyltrimethoxysilane, bromopropyltriethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, etc., which can be used alone or in combination of two or more.

[0027] For hydrolysis and condensation, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, etc.; alkalis such as ammonia, methylamine, ethylamine, etc.; metal salts such as hydrochloric acid, sulfuric acid, nitric acid, etc. may be used as catalysts. As the solvent used in the hydrolysis and condensation reaction, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol, 1,4-butanediol, etc.; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, etc.; ketone solvents such as acetone, methyl ethyl ketone, etc.; aprotic solvents such as dimethyl sulfoxide, N,N-dimethylformamide, etc.; water; mixed solvents thereof, etc. may be mentioned, and these solvents can be used alone or in two or more kinds. Among these, alcohol solvents and water are preferred. [[ID=I]] [[ID=II]]

[0028] [[ID=III]]The reaction temperature for hydrolysis and condensation is preferably from 0°C to the boiling point of the solvent, more preferably from 0 to 120°C, and even more preferably from 5 to 80°C. The reaction time is preferably from 10 minutes to 80 hours, more preferably from 30 minutes to <50 hours, and even more preferably from 30 minutes to 2 hours. [[ID=IV]] [[ID=V]]

[0029] [[ID=VI]]The composition of the present invention may further contain water, the above-mentioned other organosilicon compounds, alcohols such as methanol and ethanol, and other additives, etc., as long as the object of the present invention is not impaired. Examples of other additives include acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, etc.; alkalis such as ammonia, methylamine, ethylamine, etc.; inorganic oxides; leveling agents; surfactants, etc. [[ID=VII]] [[ID=VIII]]

[0030] [[ID=IX]]In particular, since a highly durable hydrophilic film can be obtained, the composition of the present invention preferably contains inorganic oxide particles. As the inorganic oxide particles, particles such as silica, alumina, titania, magnesium fluoride, etc., are preferred, and it is more preferable to use them as a colloidal solution. [[ID=X]] [[ID=XI]]

[0031] [[ID=XII]]The above leveling agent and surfactant are contained to improve the coating film uniformity, and can be appropriately selected from known ones and used, but it is preferable to use commercially available products that are easily available [[ID=XIII]] [[ID=XIV]]

[0032] The organosilicon compound represented by the above formula (1) contained in the composition of the present invention may be reacted with silanol groups on inorganic oxide particles, preferably silica particles (for example, aqueous silica sol: acidic sol ST-O manufactured by Nissan Chemical Industries, Ltd., organosilica sol: organosilica sol IPA-ST manufactured by Nissan Chemical Industries, Ltd., etc., preferably ST-O). By reacting inorganic oxide particles with the organosilicon compound represented by the above formula (1) and using the surface-treated inorganic oxide particles, a highly durable hydrophilic film can be obtained. In addition, the inorganic oxide particles surface-treated with the organosilicon compound represented by the above formula (1) are excellent in water dispersibility, and thus can be suitably used as abrasive grains in processes such as silicon wafer polishing and chemical mechanical polishing (CMP: Chemical Mechanical Polishing) of semiconductor devices.

[0033] In this case, specific examples and preferred examples of the solvent used in the reaction include the same solvents as those exemplified in the above hydrolysis and condensation reaction. The reaction temperature is preferably from 0 °C to the boiling point of the solvent, more preferably from 0 to 120 °C, and even more preferably from 5 to 80 °C. The reaction time is preferably from 10 minutes to 80 hours, more preferably from 30 minutes to 50 hours, and even more preferably from 30 minutes to 2 hours.

[0034] In the present invention, the solution obtained by the above method may be used as a coating agent as it is, or, if necessary, the solution may be concentrated, diluted by adding a solvent to the solution, or the solvent in the solution may be replaced with another solvent before use.By reacting inorganic oxide particles with the organosilicon compound represented by the above formula (1) and using the surface-treated inorganic oxide particles, a highly durable hydrophilic film can be obtained. In addition, the inorganic oxide particles surface-treated with the organosilicon compound represented by the above formula (1) are excellent in water dispersibility, and thus can be suitably used as abrasive grains in processes such as silicon wafer polishing and chemical mechanical polishing (CMP: Chemical Mechanical Polishing) of semiconductor devices. The content of the organosilicon compound represented by the above formula (1), the condensate of the organosilicon compound, and the reaction product of the organosilicon compound and metal oxide particles contained in the composition of the present invention is not particularly limited, but from the viewpoint of hydrophilicity, it is preferably 0.0001 to 50% by mass, more preferably 0.001 to 30% by mass, based on the total composition.

[0035] The compositions of the present invention can impart hydrophilicity to various substrates by being applied directly to at least one surface of these substrates or via one or more other layers. Specific examples of materials constituting the substrates include glass; synthetic resins {polymethyl methacrylate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, ABS resin, polycarbonate resin, polystyrene resin, epoxy resin, unsaturated polyester resin, melamine resin, diallyl phthalate resin, polyimide resin, urethane resin, nylon resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, fluororesins (polytetrafluoroethylene resin, polychlorotrifluoroethylene resin, polyvinylidene fluoride resin, perfluoroalkoxy fluororesins, tetrafluoroethylene / hexafluoropropylene copolymer resin, ethylene / tetrafluoroethylene copolymer resin, ethylene / chlorotrifluoroethylene Examples of materials include: oroethylene copolymer resins, polybutadiene, polyisopropylene, SBR, nitrile rubber, EPM, EPDM, epichlorohydrin rubber, neoprene rubber, porsulfide, butyl rubber, etc.; metals (iron, aluminum, stainless steel, titanium, copper, brass, alloys thereof, etc.); metal oxides; cellulose, cellulose derivatives, cellulose analogs (chitin, chitosan, porphyran, etc.), natural fibers such as cotton, silk, and wool; regenerated fibers such as rayon; semi-synthetic fibers such as acetate; synthetic fibers such as vinylon, polyester, nylon, polyethylene, polypropylene, polyurethane, and polyaramid fibers; and composite fibers of these fibers (polyester / cotton, etc.). Their forms include substrates, sheets, films, and fibers. Furthermore, substrates whose surfaces have been treated with chemical conversion treatment, corona discharge treatment, plasma treatment, or acid or alkaline solutions, as well as decorative plywood coated with different types of paint on the substrate body and surface, can also be used. Other layers include those obtained by polyester resin coating, polyurethane resin coating, amino alkyd resin coating, lacquer coating, spray coating, and water-based wax coating.

[0036] The composition of the present invention can be applied to a substrate and, if necessary, heated and dried to obtain a hydrophilic coating. Known methods can be used for application, such as bar coating, dip coating, spin coating, spray coating, float coating, brush coating, gravure coating, roll transfer, blade coating, air knife coating, slit coating, screen coating, inkjet, flexographic printing, etc.

[0037] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0038] [1] Production of organosilicon compounds [Synthesis example 1]

[0039] In a 1 L reaction vessel purged with nitrogen, 49.1 g of 3-mercaptopropyltrimethoxysilane, 585 g of methanol, and 28.3 g of 30% by mass hydrogen peroxide solution were added and the mixture was reacted at 75°C for 1 hour. After the reaction, 640 g of a solution of organosilicon compound A-1 (solid content concentration 7% by mass) was obtained by filtration.

[0040] [Synthesis Example 2]

[0041] In a 1 L reaction vessel purged with nitrogen, 66.6 g of 3-mercaptooctyltrimethoxysilane, 585 g of methanol, and 28.3 g of 30% by mass hydrogen peroxide solution were added and the mixture was reacted at 75°C for 1 hour. After the reaction, 650 g of a solution of organosilicon compound B-1 (solid content concentration 9% by mass) was obtained by filtration.

[0042] [Synthesis Example 3]

[0043] In a nitrogen-purged 200 mL reaction vessel, 100 g of the solution of organosilicon compound A-1 obtained in Synthesis Example 1 and 6 g of a 40% by mass sodium hydroxide aqueous solution were added, and the mixture was reacted at 25°C for 10 minutes. After the reaction, the mixture was filtered to obtain 104 g of the solution of organosilicon compound C-1 (solid content concentration 6% by mass).

[0044] [Synthesis Example 4]

[0045] In a 200 mL reaction vessel purged with nitrogen, 100 g of the solution of organosilicon compound A-1 obtained in Synthesis Example 1 and 2 g of 28% by mass aqueous ammonia were added and the mixture was reacted at 25°C for 10 minutes. After the reaction, 100 g of the solution of organosilicon compound D-1 (solid content concentration 7% by mass) was obtained by filtration.

[0046] [Synthesis Example 5]

[0047] In a 200 mL reaction vessel purged with nitrogen, 100 g of a solution of organosilicon compound A-1 obtained in Synthesis Example 1 and 1.9 g of a 74% by mass aqueous calcium hydroxide solution were added, and the reaction was carried out at 25°C for 10 minutes. After the reaction, 100 g of a solution of organosilicon compound E-1 (solid content concentration 7% by mass) was obtained by filtration.

[0048] [Synthesis Example 6] 100 g of the solution of organosilicon compound A-1 obtained in Synthesis Example 1 and 10 g of a 20% by mass acidic silica sol aqueous dispersion (manufactured by Nissan Chemical Corporation, ST-O) were placed in a nitrogen-purged 200 mL reaction vessel and reacted at 75°C for 5 hours. After the reaction, 100 g of a dispersion of organosilicon compound-treated silica F-1 (solid content concentration 9% by mass) was obtained by filtration.

[0049] [Synthesis Example 7] 100 g of the solution of organosilicon compound B-1 obtained in Synthesis Example 2 and 10 g of a 20% by mass acidic silica sol aqueous dispersion (manufactured by Nissan Chemical Corporation, ST-O) were placed in a nitrogen-purged 200 mL reaction vessel and reacted at 75°C for 5 hours. After the reaction, 100 g of a dispersion of organosilicon compound-treated silica G-1 (solid content concentration 10% by mass) was obtained by filtration.

[0050] [Comparative Synthesis Example 1]

[0051] In a 100 mL reaction vessel purged with nitrogen, 6.22 g of trimethoxy-3-(N,N-dimethylamino)propylsilane, 2.76 g of 1,3-propanesultone (manufactured by Tokyo Chemical Industry Co., Ltd.), and 35.9 g of methanol were added and the mixture was reacted at 25°C for 24 hours. After the reaction, 40 g of a 20% by mass methanol solution of organosilicon compound H-1 was obtained by filtration.

[0052] [Comparative Synthesis Example 2]

[0053] 5.07 g of trimethoxy-4-(N,N-dimethylamino)phenylsilane, 1.92 g of 1,3-propanesultone (manufactured by Tokyo Chemical Industry Co., Ltd.), and 5.31 g of methanol were added to a reactor and reacted at 25°C for 24 hours. After the reaction, 12 g of a 59% by mass methanol solution of organosilicon compound I-1 was obtained by filtration.

[0054] [Comparative Synthesis Example 3] In a nitrogen-purged 200 mL reaction vessel, 12 g of the solution of organosilicon compound I-1 obtained in Comparative Synthesis Example 2, 88 g of methanol, and 10 g of a 20% by mass acidic silica sol aqueous dispersion (manufactured by Nissan Chemical Corporation, ST-O) were added, and the mixture was reacted at 75°C for 5 hours. After the reaction, 100 g of a dispersion of organosilicon compound-treated silica J-1 (solid content concentration 9% by mass) was obtained by filtration.

[0055] [2] Preparation of coating agent (hydrophilic composition) [Example 1-1] 71 g of a 7% by mass solution of organosilicon compound A-1 obtained in Synthesis Example 1, 28.95 g of deionized water, and 0.05 g of acetic acid were added to a 200 mL nitrogen-purged mixing container and stirred at 25°C for 1 hour to obtain a colorless, transparent liquid coating agent A-2.

[0056] [Example 1-2] 56 g of a 9% by mass solution of organosilicon compound B-1 obtained in Synthesis Example 2, 43.95 g of deionized water, and 0.05 g of acetic acid were added to a 200 mL nitrogen-purged mixing container and stirred at 25°C for 1 hour to obtain a colorless, transparent liquid coating agent B-2.

[0057] [Examples 1-3] In a 200 mL nitrogen-purged mixing container, 83 g of a 6% by mass solution of organosilicon compound C-1 obtained in Synthesis Example 3, 16.95 g of deionized water, and 0.05 g of acetic acid were added and stirred at 25°C for 1 hour to obtain a colorless, transparent liquid coating agent C-2.

[0058] [Examples 1-4] 71 g of a 7% by mass solution of organosilicon compound D-1 obtained in Synthesis Example 4, 28.95 g of deionized water, and 0.05 g of acetic acid were added to a 200 mL nitrogen-purged mixing container and stirred at 25°C for 1 hour to obtain a colorless, transparent liquid coating agent D-2.

[0059] [Examples 1-5] 71 g of a 7% by mass solution of organosilicon compound E-1 obtained in Synthesis Example 5, 28.95 g of deionized water, and 0.05 g of acetic acid were added to a 200 mL nitrogen-purged mixing container and stirred at 25°C for 1 hour to obtain a colorless, transparent liquid coating agent E-2.

[0060] [Examples 1-6] 56 g of a 9% by mass dispersion of organosilicon compound-treated silica F-1 obtained in Synthesis Example 6 and 43.95 g of ion-exchanged water were placed in a 200 mL nitrogen-purged mixing container and stirred at 25°C for 1 hour to obtain a colorless, semi-transparent liquid coating agent F-2.

[0061] [Example 1-7] 50.4 g of a 10% by mass dispersion of organosilicon compound-treated silica G-1 obtained in Synthesis Example 7 and 49.55 g of ion-exchanged water were placed in a nitrogen-purged 200 mL mixing container and stirred at 25°C for 1 hour to obtain a colorless, semi-transparent liquid coating agent G-2.

[0062] [Comparative Example 1-1] In a 200 mL nitrogen-purged mixing container, 25 g of a 20% by mass solution of organosilicon compound H-1 obtained in Comparative Synthesis Example 1, 25 g of methanol, 49.95 g of deionized water, and 0.05 g of acetic acid were added and stirred at 25°C for 1 hour to obtain a colorless, transparent liquid coating agent H-2.

[0063] [Comparative Example 1-2] In a 200 mL nitrogen-purged mixing container, 8.5 g of a 59% by mass solution of organosilicon compound I-1 obtained in Comparative Synthesis Example 2, 41.5 g of methanol, 49.95 g of deionized water, and 0.05 g of acetic acid were added and stirred at 25°C for 1 hour to obtain a colorless, transparent liquid coating agent I-2.

[0064] [Comparative Example 1-3] 56 g of a 9% by mass dispersion of organosilicon compound-treated silica J-1 obtained in Comparative Synthesis Example 3 and 43.95 g of ion-exchanged water were placed in a 200 mL nitrogen-purged mixing container and stirred at 25°C for 1 hour to obtain a colorless, semi-transparent liquid coating agent J-2.

[0065] [3] Preparation and Evaluation of Coated Articles [Examples 2-1 to 2-7, Comparative Examples 2-1 to 2-3] 0.1 g of each coating agent A-2 to J-2 obtained in Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-3 was dropped onto the surface of a glass plate measuring 5.0 cm in length, 15 cm in width, and 1.5 mm in thickness. After uniformly coating the entire surface using a nonwoven fabric, the plate was dried at 105°C for 10 minutes to produce glass plates with coatings made from each coating agent. The following tests were performed on each of the obtained coatings. The results are shown in Table 1.

[0066] (1) Anti-fogging properties: Exhaled breath was blown onto each of the above coatings. If the surface of the coating fogged up, it was marked as "×" and if it did not fog up, it was marked as "○". Furthermore, the coating was placed above a 40°C hot water bath at a height of 3 cm above the water surface for 60 seconds. If the surface of the coating did not fog up, it was marked as "◎" to evaluate its anti-fogging properties. (2) Water drip marks: After evaluating the anti-fogging properties by placing the coating above a 40°C hot water bath for 60 seconds, the coating was air-dried at 25°C for 10 minutes. The surface was then illuminated with a 1,000 lm lamp, and it was visually checked whether water drip marks were visible on the coating surface. If water drip marks were observed, it was marked as "+" and if no water drip marks were observed, it was marked as "-". (3) Water resistance Each of the above coatings was immersed in water at 25°C for 24 hours and 240 hours, the surface water was absorbed with a paper wiper, and then it was air-dried at 25°C for 10 minutes to evaluate its anti-fogging properties. (4) Humidity resistance Each of the above coatings was left standing in a constant temperature and humidity chamber (KCL-2000W, Tokyo Rikakikai Co., Ltd.) set to 80°C and 95% RH for 240 hours. After that, it was air-dried at 25°C for 10 minutes to evaluate its anti-fogging properties. (5) Heat resistance Each of the above coatings was left standing in a constant temperature chamber (SPHH-201, ESPEC Corporation) set to 120°C for 240 hours. After that, it was left standing at 25°C for 10 minutes to evaluate its anti-fogging properties.

[0067]

[0068] As shown in Table 1, the glass plates of Examples 2-1 to 2-7, which are coated with the coating agent (hydrophilic composition) of the present invention, exhibit excellent and long-lasting anti-fogging properties. In particular, Examples 2-2 and 2-7, which use organosilicon compounds with long alkylene chain lengths or silica treated with organosilicon compounds with long alkylene chain lengths, show excellent water resistance over long periods of time. On the other hand, Comparative Example 2-1 showed water stains, and its anti-fogging properties disappeared after the water resistance test and humidity resistance test, indicating poor durability. Furthermore, Comparative Example 2-2 showed insufficient anti-fogging properties after the 240-hour water resistance test and humidity resistance test, and Comparative Example 2-3 showed insufficient anti-fogging properties after the humidity resistance test.

Claims

1. A hydrophilic composition comprising one or more selected from the group consisting of an organosilicon compound represented by the following formula (1), a condensate of the organosilicon compound, and a reaction product of the organosilicon compound and metal oxide particles. (In the formula, R 1 Each of these independently represents a hydrogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group, R 2 Each of these independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, X represents a hydrogen atom, a k-valent metal cation, or an ammonium cation, k is 1 or 2, except when X is a hydrogen atom or an ammonium cation, k is 1, m is an integer from 1 to 10, and n is an integer from 1 to 3.

2. The hydrophilic composition according to claim 1, comprising water.

3. A coating agent comprising the hydrophilic composition according to claim 1 or 2.

4. A hydrophilic coating obtained by curing the hydrophilic composition according to claim 1 or 2.

5. A coated article having a base material and a hydrophilic coating according to claim 4, formed directly or via one or more other layers on at least a portion of the surface of the base material.

6. Metal oxide particles whose surface is surface-treated with an organosilicon compound represented by the following formula (1). (In the formula, R 1 Each of these independently represents a hydrogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group, R 2 Each of these independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, X represents a hydrogen atom, a k-valent metal cation, or an ammonium cation, k is 1 or 2, except when X is a hydrogen atom or an ammonium cation, k is 1, m is an integer from 1 to 10, and n is an integer from 1 to 3.

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