Organosilicon compound, hydrolytic condensate thereof, coating composition, and coated article

Abstract

The organosilicon compound represented by formula (1) can form a coating composition having excellent hydrophilicity, antifogging properties and water resistance. # imgabs0 # (In the formula, R1 each independently represents a hydrogen atom, an alkyl group having 1-10 carbon atoms, or an aryl group having 6-10 carbon atoms, R2 each independently represents an alkyl group having 1-10 carbon atoms or an aryl group having 6-10 carbon atoms, X represents a divalent saturated hydrocarbon group having 2-20 carbon atoms, into which a sulfur atom may be interposed, and n is an integer of 1-3. )

Description

Technical Field

[0001] The present invention relates to an organosilicon compound, a hydrolysis condensate thereof, a coating composition containing the organosilicon compound, and a coated article. Background Art

[0002] In recent years, there has been an increasing demand for improved fogging properties of substrates made of inorganic materials such as glass and organic materials such as plastics. This improvement in substrate fogging properties is typically achieved by coating the substrate surface with a hydrophilic coating. For example, coating compositions containing as a main component an organosilicon compound having a sulfobetaine structure in which the nitrogen atom in the nitrogen-containing heterocyclic structure has a positive charge are known as coating agents capable of imparting hydrophilicity to substrates (see Patent Documents 1 and 2).

[0003] However, the water resistance of coating films using the above-mentioned coating compositions is insufficient. When in contact with water, the surface properties such as the above-mentioned hydrophilicity and anti-fogging properties may be deteriorated. Further improvement is desired.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2019-48966

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 2022-82176 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide an organosilicon compound capable of forming a coating composition having excellent hydrophilicity and anti-fogging properties and water resistance.

[0010] Means for solving problems

[0011] The present inventors conducted intensive research to solve the above-mentioned problems and, as a result, discovered that a specific organosilicon compound having a glycerol derivative structure can provide a coating composition having excellent water resistance and capable of imparting sustained hydrophilicity and anti-fogging properties to substrates made of inorganic materials such as glass and organic materials such as plastics. This led to the completion of the present invention.

[0012] That is, the present invention provides:

[0013] 1. An organosilicon compound represented by the following formula (1):

[0014] [Chemistry 1]

[0015]

[0016] (Where R 1Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R 2 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 divalent saturated hydrocarbon group having 2 to 20 carbon atoms which may be interposed with a sulfur atom, and n is an integer of 1 to 3.

[0017] 2. The organosilicon compound according to 1, which is represented by the following formula (2) or the following formula (3):

[0018] [Chemistry 2]

[0019]

[0020] (Where R 1 、R 2 and n have the same meanings as above, m is an integer of 1 to 10, and k is an integer of 2 to 10.)

[0021] 3. A composition comprising the hydrolysis condensate of the organosilicon compound according to 1 or 2.

[0022] 4. A coating composition comprising the organosilicon compound according to 1 or 2, a hydrolysis condensate of the organosilicon compound, or both.

[0023] 5. A coated article comprising a substrate and a coating film composed of the coating composition according to 4, formed directly or through one or more other layers on at least one surface of the substrate.

[0024] Effects of the Invention

[0025] The organosilicon compound of the present invention can form a coating composition having excellent water resistance and capable of imparting sustained hydrophilicity and antifogging properties to substrates such as glass. DETAILED DESCRIPTION

[0026] The present invention will be described in detail below.

[0027] The organosilicon compound of the present invention is represented by the following formula (1).

[0028] [Chemistry 3]

[0029]

[0030] In formula (1), R 1 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.

[0031] R 1The alkyl group may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and cyclohexyl.

[0032] As R 1 Specific examples of the aryl group include phenyl and tolyl.

[0033] Among these, R 1 An alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group or an ethyl group is more preferred.

[0034] 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 and aryl groups include the following: 1 The same groups as those exemplified in , among which methyl group is preferred.

[0035] X represents a divalent saturated hydrocarbon group having 2 to 20 carbon atoms which may have a sulfur atom interposed therein, and is preferably a group represented by the following formula.

[0036] [Chemistry 4]

[0037]

[0038] (In the formula, m is an integer from 1 to 10, and k is an integer from 2 to 10.)

[0039] That is, the organosilicon compound of the present invention is preferably a compound represented by the following formula (2) or the following formula (3).

[0040] [Chemistry 5]

[0041]

[0042] (Where R 1 、R 2 , n, m and k have the same meanings as above.)

[0043] In particular, regarding m and k, m is preferably an integer of 1 to 8, more preferably 3, and k is preferably an integer of 2 to 6, more preferably 5, from the viewpoint of the hydroxyl content per unit mass of the organosilicon compound of the present invention and the antifogging property.

[0044] Specific examples of the organosilicon compound of the present invention are shown below, but the present invention is not limited to these.

[0045] [Chemistry 6]

[0046]

[0047] (In the formula, Me means methyl. Same below.)

[0048] The organosilicon compound represented by the above formula (1) can be produced, for example, by a method of subjecting a mercapto group-containing silane compound represented by the following formula (I) to a glycerol derivative represented by the following formula (II) to a thiol-ene reaction, or by a method of subjecting a hydrosilane represented by the following formula (III) to a hydrosilylation reaction with a glycerol derivative represented by the following formula (II).

[0049] [Chemistry 7]

[0050]

[0051] (Where R 1 、R 2 , k, m and n have the same meanings as above.)

[0052] Specific examples of the mercapto group-containing silane compound represented by the above formula (I) are shown below, but the present invention is not limited thereto. Among these, 3-mercaptopropyltrimethoxysilane represented by the following structural formula (4) is preferred.

[0053] [Chemistry 8]

[0054]

[0055] As the glycerol derivative represented by the above formula (II), 7-octene-1,2,3-triol is preferred.

[0056] Specific examples of the hydrosilane represented by the above formula (III) are shown below, but the present invention is not limited thereto. Among these, trimethoxysilane represented by the following structural formula (5) is preferred.

[0057] [Chemistry 9]

[0058]

[0059] The thiol-ene reaction of the mercapto group-containing silane compound represented by the above formula (I) and the glycerol derivative represented by the above formula (II) can be carried out according to a known thiol-ene reaction.

[0060] In the thiol-ene reaction, a catalyst such as an organic peroxide or an azo compound may be used as needed.

[0061] Specific examples of the organic peroxide include benzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, and dicumyl peroxide.

[0062] Specific examples of the azo compounds include 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo(methylethyl)diacetate, 2,2'-azobisisobutane, 2,2'-azobisisobutylamide, 2,2'-azobisisobutyronitrile (AIBN), methyl 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, 3,5-dihydroxymethylphenylazo-2-methylmalononitrile, 2,2'-azobis-2-methylvaleronitrile, dimethyl 4,4'-azobis-4-cyanovalerate, and 2,2'-azobis-2,4-dimethylvaleronitrile.

[0063] The amount of the catalyst used is preferably 0.00001 to 10 parts by mass based on 100 parts by mass of the total amount of the mercapto group-containing silane compound represented by the above formula (I) and the glycerol derivative represented by the above formula (II).

[0064] In the thiol-ene reaction, a solvent may be used as needed.

[0065] Examples of usable solvents include alcohols such as methanol, ethanol, isopropanol, and tert-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.

[0066] The reaction temperature of the thiol-ene reaction is preferably 0 to 150° C., more preferably 50 to 150° C. When a solvent is used, the reaction temperature can be set according to the boiling point of the solvent. The reaction time is preferably 1 to 150 hours, more preferably 5 to 100 hours.

[0067] The ratio of the mercapto group-containing silane compound represented by the above formula (I) to the glycerol derivative represented by the above formula (II) in the thiol-ene reaction is preferably 0.75 to 1.25 mol, more preferably 0.9 to 1.1 mol, of the glycerol derivative (II) per 1 mol of the mercapto group-containing silane compound (I).

[0068] The hydrosilylation reaction of the hydrosilane represented by the above formula (III) and the glycerol derivative represented by the above formula (II) can be carried out according to a known hydrosilylation reaction.

[0069] Examples of hydrosilylation catalysts include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, and complexes of chloroplatinic acid with olefins, vinylsiloxanes, acetylene alcohols, and the like. The amount added can be appropriately selected depending on the desired curing rate, but is generally preferably 0.1 to 500 ppm, more preferably 1 to 200 ppm, calculated as the mass of the platinum group metal relative to the total mass of the hydrosilane represented by formula (III) and the glycerol derivative represented by formula (II) used in the reaction.

[0070] The conditions for the hydrosilylation reaction are not particularly limited, but preferably the reaction temperature is 20 to 120° C. and the reaction time is 1 to 8 hours, more preferably the reaction temperature is 20 to 100° C. and the reaction time is 1 to 6 hours.

[0071] During the hydrosilylation reaction, the ratio of the hydrosilane represented by the above formula (III) to the glycerol derivative represented by the above formula (II) is preferably 0.75 to 1.25 mol, more preferably 0.9 to 1.1 mol, of the glycerol derivative (II) per 1 mol of the hydrosilane (III).

[0072] The coating composition of the present invention contains one or more of the organosilicon compound represented by the above formula (1) and its hydrolysis-condensation product.

[0073] In particular, by hydrolyzing and condensing the organosilicon compound of the present invention represented by the above formula (1), the durability of the resulting film can be further improved. During the hydrolysis and condensation, other organosilicon compounds may be added to carry out co-hydrolysis and condensation within the scope that does not impair the purpose of the present invention.

[0074] Specific examples of other organosilicon compounds include methyltrimethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripentoxysilane, methyltripentoxysilane, methyltriphenoxysilane, methyltripenzyloxysilane, methyltriphenethoxysilane, glycidyloxymethyltrimethoxysilane, glycidyloxymethyltriethoxysilane, α-glycidyloxyethyltrimethoxysilane, α-glycidyloxyethyltriethoxysilane, β-glycidyloxy β-Glycidoxypropyltrimethoxysilane, β-Glycidoxyethyltriethoxysilane, α-Glycidoxypropyltrimethoxysilane, α-Glycidoxypropyltriethoxysilane, β-Glycidoxypropyltrimethoxysilane, β-Glycidoxypropyltriethoxysilane, γ-Glycidoxypropyltrimethoxysilane, γ-Glycidoxypropyltriethoxysilane, γ-Glycidoxypropyltripropoxysilane, γ-Glycidoxypropyltributoxysilane, γ-Glycidoxypropyltributoxysilane, γ-Glycidoxypropyl Triphenoxysilane, α-glycidyloxybutyltrimethoxysilane, α-glycidyloxybutyltriethoxysilane, β-glycidyloxybutyltriethoxysilane, γ-glycidyloxybutyltrimethoxysilane, γ-glycidyloxybutyltriethoxysilane, δ-glycidyloxybutyltrimethoxysilane, δ-glycidyloxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4- β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, 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)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxy 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 Alkane, 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-chloropropylmethyldiethoxysilane, dimethoxysilane Methyldiacetoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R)-N-1-phenylethyl-N'-triethoxysilylpropylurea, (R)-N-1-phenylethyl-N'-trimethoxysilylpropylurea, 3-isocyanatepropyltriethoxysilane, trifluoropropyltrimethoxysilane, bromopropyltriethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, etc. These can be used alone or in combination of two or more.

[0075] In the hydrolysis condensation, catalysts such as acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, and maleic acid; bases such as ammonia, methylamine, and ethylamine; and metal salts of hydrochloric acid, sulfuric acid, and nitric acid can be used.

[0076] Examples of the solvent used in the hydrolysis condensation reaction include alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, tert-butanol, pentanol, ethylene glycol, propylene glycol, and 1,4-butanediol; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ketone solvents such as acetone and methyl ethyl ketone; aprotic solvents such as dimethyl sulfoxide and N,N-dimethylformamide; water; and mixed solvents thereof. One or more of these solvents can be used.

[0077] Among these, alcoholic solvents and water are preferred.

[0078] The reaction temperature of the hydrolysis condensation is preferably 0°C to the boiling point of the solvent, more preferably 0 to 120°C, and further preferably 5 to 80°C.

[0079] The reaction time is preferably 10 minutes to 80 hours, more preferably 30 minutes to 50 hours, and even more preferably 30 minutes to 2 hours.

[0080] The coating composition of the present invention may further contain water, organosilicon compounds other than those mentioned above, alcohols such as methanol and ethanol, and other additives, within a range not impairing the purpose of the present invention.

[0081] Examples of other additives include acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, and maleic acid; bases such as ammonia, methylamine, and ethylamine; inorganic oxides; leveling agents; and surfactants.

[0082] In particular, from the perspective of obtaining a highly durable hydrophilic film, the coating composition of the present invention preferably contains an inorganic oxide.

[0083] As the inorganic oxide, silica fine particles, alumina fine particles, titania fine particles, magnesium fluoride fine particles and the like are preferred, and it is more preferred to use them in the form of a colloidal solution.

[0084] The leveling agent and surfactant are contained in order to improve the uniformity of the coating film. They can be appropriately selected from known leveling agents and surfactants, and it is preferable to use readily available commercial products.

[0085] The organic silicon compound represented by the above formula (1) contained in the coating composition of the present invention can be mixed with silica sol (for example, aqueous silica sol: Na + Stabilized alkaline sol ST-30L, organic silica sol: organic silica sol IPA-ST manufactured by Nissan Chemical Co., Ltd., preferably ST-30L) to react with silanol groups.

[0086] In this case, specific examples and preferred examples of the solvent used in the reaction include the same solvents as exemplified in the above-mentioned hydrolysis condensation reaction.

[0087] The reaction temperature is preferably 0°C to the boiling point of the solvent, more preferably 0 to 120°C, and further preferably 5 to 80°C.

[0088] The reaction time is preferably 10 minutes to 80 hours, more preferably 30 minutes to 50 hours, and even more preferably 30 minutes to 2 hours.

[0089] In the present invention, the solution obtained by the above method can be used as a coating composition directly. If necessary, the solution can be concentrated, diluted by adding a solvent, or replaced with another solvent.

[0090] The content of the organosilicon compound represented by the above formula (1) and its hydrolysis-condensation product contained in the coating composition of the present invention is not particularly limited, but is preferably 0.0001 to 50% by mass, more preferably 0.001 to 30% by mass, based on the total composition from the viewpoint of hydrophilicity.

[0091] The coating composition of the present invention can impart hydrophilicity to at least one surface of various substrates by being applied directly or through one or more other layers.

[0092] Specific examples of the material constituting the substrate 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, polyurethane resin, nylon resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, fluororesins (polytetrafluoroethylene resin, polychlorotrifluoroethylene resin, polyvinylidene fluoride resin, perfluoroalkoxy fluororesin, tetrafluoroethylene-hexafluoropropylene copolymer resin, ethylene-tetrafluoroethylene ... The present invention also includes but is not limited to ethylene-chlorotrifluoroethylene copolymer resin, polybutadiene, polyisocyanurate, SBR, nitrile rubber, EPM, EPDM, epichlorohydrin rubber, chloroprene rubber, polysulfide, butyl rubber, etc.; metals (iron, aluminum, stainless steel, titanium, copper, brass, alloys thereof, etc.); natural fibers such as cellulose, cellulose derivatives, cellulose analogs (chitin, chitosan, laver polysaccharide, etc.), cotton, silk, wool, etc.; regenerated fibers such as rayon; semi-synthetic fibers such as acetate; synthetic fibers such as vinylon, polyester, nylon, polyethylene, polypropylene, polyurethane, and aramid fiber; composite fibers of these fibers (polyester / cotton, etc.), etc., and examples of their forms include substrates, sheets, films, and fibers.

[0093] In addition, decorative plywood may be used, for example, where the surface of these substrates has been treated with chemical conversion treatment, corona discharge treatment, plasma treatment, acid or alkali solution treatment, or where the substrate body and the surface layer are coated with different types of coatings. Other layers include those obtained by coating with polyester resins, polyurethane resins, aminoalkyd resins, lacquers, spray coatings, or water-based varnishes.

[0094] A hydrophilic coating film can be obtained by coating the coating composition of the present invention on a substrate and, if necessary, drying it by heating to form a coating film.

[0095] As the coating method, a known method can be used, for example, rod coating, dip coating, spin coating, spray coating, flow coating, brush coating, gravure coating, roller transfer, blade coating, air knife coating, slit coating, screen coating, inkjet coating, flexographic printing, etc.

[0096] Example

[0097] The following examples and comparative examples are given to illustrate the present invention in detail, but the present invention is not limited to the following examples. 1 H-NMR) spectra were measured in heavy methanol (CD3OD) using AVANCE III 400 manufactured by BURKER.

[0098] [1]Manufacturing of organosilicon compounds

[0099] [Example 1-1]

[0100] [Chemistry 10]

[0101]

[0102] In a nitrogen-purged 100 mL reaction vessel, 3.92 g of 3-mercaptopropyltrimethoxysilane, 3.48 g of 7-octene-1,2,3-triol (manufactured by Kuraray Co., Ltd., the same below), 64.2 g of methanol, and 0.18 g of azobisisobutyronitrile (AIBN) were placed and reacted at 60°C for 1 hour. After the reaction, filtration was performed to obtain 60 g of a 10% by mass methanol solution of organosilicon compound A-1.

[0103] 1 H-NMR (CD3OD): δ3.69~3.59ppm (s, 9H, -Si(OCH3)3), 3.83~3.28ppm (m, 4H, OCH-, OCH2-), 2. 62~2.45ppm (m, 4H, -SCH2-), 1.79~1.21ppm (m, 10H, -CH2-), 0.83~0.72ppm (m, 2H, -SiCH2-)

[0104] [Examples 1-2]

[0105] [Chemistry 11]

[0106]

[0107] In a nitrogen-purged 100 mL reaction vessel, 5.32 g of 8-mercaptooctyltrimethoxysilane, 3.48 g of 7-octene-1,2,3-triol, 76.8 g of methanol, and 0.18 g of AIBN were placed and reacted at 60° C. for 1 hour. After the reaction, filtration was performed to obtain 70 g of a 10% by mass methanol solution of organosilicon compound B-1.

[0108] 1 H-NMR (CD3OD): δ3.70~3.59ppm (s, 9H, -Si(OCH3)3), 3.80~3.25ppm (m, 4H, OCH-, OCH2-), 2. 68~2.47ppm (m, 4H, -SCH2-), 1.81~1.20ppm (m, 20H, -CH2-), 0.82~0.71ppm (m, 2H, -SiCH2-)

[0109] [Examples 1-3]

[0110] [Chemistry 12]

[0111]

[0112] In a nitrogen-purged 100 mL reaction vessel, 32.0 g of 7-octene-1,2,3-triol and 0.03 g of a platinum catalyst, CAT-PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.), were placed. After heating to 80°C, 36.7 g of trimethoxysilane was added dropwise, and the mixture was reacted at 80°C for 2 hours. After the reaction, the remaining trimethoxysilane was distilled off and filtered to obtain 50 g of organosilicon compound C-1.

[0113] 1 H-NMR (CD3OD): δ3.68~3.61ppm (s, 9H, -Si(OCH3)3), 3.83~3.26ppm (m, 4H, OCH-, OCH2-), 1.75~1.30ppm (m, 8H, -CH2-), 0.82~0.73ppm (m, 2H, -SiCH2-)

[0114] [Comparative Example 1-1]

[0115] [Chemistry 13]

[0116]

[0117] In a nitrogen-purged 100 mL reaction vessel, 4.9 g of 3-mercaptopropyltrimethoxysilane, 3.3 g of 3-allyloxy-1,2-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.), 74.0 g of methanol, and 0.24 g of AIBN were placed and reacted at 60°C for 1 hour. After the reaction, the mixture was filtered to obtain 68 g of a 10% by mass methanol solution of organosilicon compound D-1.

[0118] [Comparative Example 1-2]

[0119] [Chemistry 14]

[0120]

[0121] 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-propane sultone (manufactured by Tokyo Chemical Industry Co., Ltd.), and 35.9 g of methanol were placed and reacted at 25°C for 24 hours. After the reaction, the mixture was filtered to obtain 40 g of a 20% by mass methanol solution of organosilicon compound E-1.

[0122] [Comparative Examples 1-3]

[0123] [Chemistry 15]

[0124]

[0125] 5.07 g of trimethoxy-4-(N,N-dimethylamino)phenylsilane, 1.92 g of 1,3-propane sultone (manufactured by Tokyo Chemical Industry Co., Ltd.), and 5.31 g of methanol were placed in a reactor and reacted at 25° C. for 24 hours. After the reaction, the mixture was filtered to obtain 12 g of a 59% by mass methanol solution of organosilicon compound F-1.

[0126] [2] Production of coating composition

[0127] [Example 2-1]

[0128] In a nitrogen-purged 200 mL mixing container, 50 g of a 10% by mass methanol solution of the organosilicon compound A-1 obtained in Example 1-1, 49.95 g of ion-exchanged water, and 0.05 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless transparent liquid coating composition A-2.

[0129] [Example 2-2]

[0130] In a nitrogen-purged 200 mL mixing container, 50 g of a 10% by mass methanol solution of the organosilicon compound B-1 obtained in Example 1-2, 49.95 g of ion-exchanged water, and 0.05 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless transparent liquid coating composition B-2.

[0131] [Examples 2-3]

[0132] In a nitrogen-purged 200 mL mixing container, 5 g of the organosilicon compound C-1 obtained in Example 1-3, 94.95 g of ion-exchanged water, and 0.05 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless, transparent liquid coating composition C-2.

[0133] [Comparative Example 2-1]

[0134] In a nitrogen-purged 200 mL mixing container, 50 g of a 10% by mass methanol solution of the organosilicon compound D-1 obtained in Comparative Example 1-1, 49.95 g of ion-exchanged water, and 0.05 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless transparent liquid coating composition D-2.

[0135] [Comparative Example 2-2]

[0136] In a nitrogen-purged 200 mL mixing container, 25 g of a 20% by mass methanol solution of the organosilicon compound E-1 obtained in Comparative Example 1-2, 25 g of methanol, 49.95 g of ion-exchanged water, and 0.05 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless transparent liquid coating composition E-2.

[0137] [Comparative Examples 2-3]

[0138] In a nitrogen-purged 200 mL mixing container, 8.5 g of a 59% by mass methanol solution of the organosilicon compound F-1 obtained in Comparative Example 1-3, 41.5 g of methanol, 49.95 g of ion-exchanged water, and 0.05 g of acetic acid were placed and stirred at 25° C. for 1 hour to obtain a colorless, transparent liquid coating composition F-2.

[0139] [3] Production and evaluation of coated articles

[0140] [Examples 3-1 to 3-3, Comparative Examples 3-1 to 3-3]

[0141] 0.1 g of each of the coating compositions A-2 to F-2 obtained in Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3 was dropped onto the surface of a glass plate having a length of 5.0 cm, a width of 15 cm, and a thickness of 1.5 mm. The resulting mixture was evenly applied to the entire surface using a non-woven fabric and then dried at 105° C. for 10 minutes to produce a glass plate having a coating composed of each coating composition.

[0142] The following tests were performed on each of the obtained films. The results are shown in Table 1.

[0143] (1) Anti-fog properties

[0144] Each of the above films was sprayed with exhaled breath, and the case where the film surface fogged was scored as "×", and the case where no fogging was scored as "○". Furthermore, the film was placed above a 40°C warm water bath at a height of 3 cm from the water surface for 60 seconds, and the case where the film surface did not fog was scored as "◎" to evaluate the anti-fogging property.

[0145] (2) Water dripping marks

[0146] The coating film, which had been placed in a 40°C warm water bath for 60 seconds in the anti-fog evaluation described above, was then air-dried at 25°C for 10 minutes. The surface was then illuminated with a 1000 lm light and visually inspected for any water dripping. Observed water dripping was rated "+" and no water dripping was rated "-."

[0147] (3) Water resistance

[0148] Each of the films was immersed in water at 25° C. for 24 hours and 240 hours, and the surface water was absorbed with a paper towel. The film was then naturally dried at 25° C. for 10 minutes, and the anti-fogging property was evaluated.

[0149] (4)Moisture resistance

[0150] Each of the films was allowed to stand for 240 hours in a thermo-hygrostat (KCL-2000W, Tokyo Rikaki Co., Ltd.) set at 80°C and 95% RH, and then naturally dried at 25°C for 10 minutes, and the anti-fogging properties were evaluated.

[0151] (5) Heat resistance

[0152] Each of the films was allowed to stand for 240 hours in a thermostat (SPHH-201, Espec) set at 120° C. Then, the film was allowed to stand at 25° C. for 10 minutes, and the anti-fogging property was evaluated.

[0153] [Table 1]

[0154]

[0155] As shown in Table 1, it was found that the glass plates treated with the coating compositions of Examples 3-1 to 3-3 exhibited excellent and persistent anti-fogging properties.

[0156] On the other hand, Comparative Example 3-1 showed insufficient initial anti-fog properties, and Comparative Example 3-2 showed signs of water dripping, but the anti-fog properties disappeared after the water resistance test and the humidity resistance test, indicating poor durability. Furthermore, Comparative Example 3-3 showed insufficient anti-fog properties after the 240-hour water resistance test and the humidity resistance test.

Claims

1. An organosilicon compound represented by the following formula (1): [Chemistry 1] Where R 1 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R 2 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 divalent saturated hydrocarbon group having 2 to 20 carbon atoms which may have a sulfur atom interposed therein, and n is an integer of 1 to 3.

2. The organosilicon compound according to claim 1, which is represented by the following formula (2) or the following formula (3): [Chemistry 2] Where R 1 、R 2 and n have the same meanings as above, m is an integer of 1-10, and k is an integer of 2-10.

3. A composition comprising the hydrolysis-condensation product of the organosilicon compound according to claim 1 or 2.

4. A coating composition comprising the organosilicon compound according to claim 1 or 2, a hydrolysis-condensate of the organosilicon compound, or both.

5. A coated article comprising a substrate; and a coating film comprising the coating composition according to claim 4 formed on at least one surface of the substrate directly or through one or more other layers.

Images