KR100533905B1 - Anti-fogging coating composition comprising ultra-violet light curable hydrophilic organic-inorganic hybrid materials - Google Patents

Abstract

The present invention relates to an ultraviolet curable hydrophilic organic-inorganic hybrid material and an anti-fog coating composition comprising the same, which reacts an organic compound having a hydrophilic group with an alkoxysilane compound, reacts the resulting hydrophilic polymer with a nano-sized silica sol, The anti-fog coating composition comprising the organic-inorganic hybrid composite of the present invention prepared by hydrating and condensing a nano-sized organic-inorganic hybrid having a hydrophilic group and an alkoxysilane having an ultraviolet photocurable unsaturated hydrocarbon group at the end thereof, It has excellent transparency and improved anti-fog property and at the same time improves the surface hardness, and has the effect of increasing the material adhesion during coating.

Description

Anti-fog coating composition comprising UV-curable hydrophilic organic-inorganic hybrid material {ANTI-FOGGING COATING COMPOSITION COMPRISING ULTRA-VIOLET LIGHT CURABLE HYDROPHILIC ORGANIC-INORGANIC HYBRID MATERIALS}

The present invention relates to an anti-fogging coating including a UV-curable hydrophilic organic-inorganic hybrid material, and more specifically, to a nano-sized metal oxide capable of ultraviolet curing and increasing hydrophilic groups, photoreactors and surface hardness within a molecule. It relates to an antifogging coating using an organic-inorganic hybrid composite.

When the temperature difference between indoor and outdoor in winter is large, or the relative humidity in the air is high due to the rapid change of temperature, it is difficult to check external objects due to small water vapor droplets on the windows of the building, the windows of the car, and the glasses. Will suffer. The phenomenon is that water vapor in the air condenses on the glass due to a sharp temperature difference, forming droplets of tens to hundreds of microns in size due to the difference in surface tension between the condensation surface and the water, which causes light to scatter and blur the image.

As an effort to solve the 'fogging' phenomenon, a technique for giving antifogging characteristics through surface treatment using a surfactant has been developed, but many methods using a coating agent have been developed and used due to the problem that its characteristics cannot be maintained for a long time. come.

EP 0 716 051 proposes a method of preparing a metal oxide using an inorganic alkoxide, introducing the same into an organic polymer having anti-fogging properties, and thermally curing to improve the surface hardness. US Patent No. 5,739,181 discloses: Disclosed is a method of preparing a photocurable coating agent that adds silica and silane compounds to an organic material having a photocurable unsaturated hydrocarbon group to impart antifogging properties. However, these methods have a problem that the initial anti-fogging property of the coating surface is significantly lower than the prior art in which the surfactant is introduced, causing light interference, scattering, blurring or distortion of the surface, and introduced to improve surface hardness and other physical properties. One inorganic metal oxide, silica, and the like are not chemically bonded and are physically dispersed, and thus have a limitation of deterioration in stability due to self-aggregation by sedimentation or phase separation during long-term storage. In addition, since the added inorganic material does not contain a hydrophilic group in the molecule and does not have an anti-fog property, when used to increase the surface hardness, the anti-fog property of the coating agent is inhibited, so its use content is limited.

US Patent Publication No. 2002 / 0061950A1, Korean Patent Application Publication No. 2000-8569 and Korean Patent No. 302,326 disclose a method of preparing a coating liquid exhibiting antifogging properties by introducing polyvinyl alcohol, which is a water-soluble organic polymer. Since polyvinyl alcohol is easily soluble in water, the durability and surface hardness of the coating film are drastically reduced when the humidity is high, and the prepared coating solution contains more water than necessary due to process limitations and has a low solid content. There is a limit to achieving an improvement and an improvement in the coating working speed.

As a method for solving this problem, Korean Patent No. 297,952 proposes a method for preparing an antifogging coating that can be heat or UV curable using an alkoxysilane having a photocurable hydrophilic organic monomer and an unsaturated hydrocarbon group. However, according to this method, due to compatibility problems between raw materials, the storage period of the coating liquid is short, and since the organic monomer having an unsaturated hydrocarbon group is used, shrinkage occurs inside the coating film during thermal curing or ultraviolet curing coating. This results in poor long-term weather resistance of the coating film and alkoxysilanes and metal oxides having unsaturated hydrocarbon groups, which do not contribute to the antifogging property of the coating film, and thus the coating surface hardness and the antifogging property are improved beyond a certain limit as the addition amount is limited. It does not have the disadvantage.

Accordingly, the present inventors have found that the improvement of the surface hardness and the anti-fogging property have an inverse relationship with each other, and as a result of the efforts to solve the above problems, the present inventors have developed a coating agent having excellent anti-fogging property without reducing the surface hardness. .

Accordingly, an object of the present invention is to provide an organic-inorganic hybrid composite and a method for manufacturing the same, which includes both nano-sized metal oxides capable of ultraviolet photocuring and capable of increasing hydrophilic groups, photoreactors and surface hardness on a molecular basis.

Another object of the present invention to provide an anti-fog coating composition comprising the organic-inorganic hybrid composite.

In order to achieve the above object, in the present invention (1) (a) has a hydrophilic ionic group at the terminal of the molecule and at least one selected from ether group (-O-) and carbonyl group (-CO) inside the molecule, Reacting an organic compound having an unsaturated hydrocarbon group at the terminal with an alkoxysilane compound having an unsaturated hydrocarbon group at the end to prepare a hydrophilic acrylic polymer, or (b) having a hydrophilic ionic group at the terminal of the molecule and an amine group (-NH ₂ ) in the molecule, Reacting an organic compound having at least one selected from an ether group (—O—) and a hydroxyl group (—OH) with an alkoxysilane compound having an isocyanate group (—NCO) to prepare a hydrophilic urethane polymer; (2) reacting the polymer produced in step (1) with a nano-sized silica sol to produce a nano-sized organic-inorganic hybrid having hydrophilicity; And (3) hydrating and condensing the organic-inorganic hybrid produced in step (2) with an alkoxysilane having an ultraviolet photocurable unsaturated hydrocarbon group at its end, wherein the organic-inorganic hybrid composite is produced. It provides an organic-inorganic hybrid composite prepared by, and an anti-fog coating composition comprising the organic-inorganic hybrid composite.

Hereinafter, the present invention will be described in detail.

<Production of Hydrophilic Polymer>

In the present invention, (a) an organic compound having a hydrophilic ionic group at the terminal and at least one selected from ether group (-O-) and carbonyl group (-CO) in the molecule and having an unsaturated hydrocarbon group in the molecule or at the terminal Reacting an alkoxysilane compound having an unsaturated hydrocarbon group on (b) a hydrophilic ionic group at the terminal of the molecule and selected from an amine group (-NH ₂ ), an ether group (-O-) and a hydroxyl group (-OH) inside the molecule A hydrophilic polymer can be obtained by making the organic compound which has 1 or more types, and the alkoxysilane compound which has an isocyanate group (-NCO) react.

① Preparation of Acrylic Polymer

An organic compound having a hydrophilic ion group at the terminal of the molecule, an ether group (-O-) and / or a carbonyl group (-CO) in the molecule, having an unsaturated hydrocarbon group in the molecule or at the terminal, and an alkoxysilane having an unsaturated hydrocarbon group at the terminal The compound can be reacted under a thermal onset catalyst to produce a hydrophilic acrylic polymer.

The organic compound having an unsaturated hydrocarbon group (-CH = CH ₂ ) in or at the end of the molecule exhibits hydrophilic and acrylic polymerization characteristics, and has at least one functional hydrocarbon group (-CH = CH ₂ ) in or at the end of the molecule; At least one hydrophilic ionic group selected from amine group (-NH ₂ ), hydroxyl group (-OH) and thiol group (-SH) at the terminal of the molecule, and ether group (-O-) and / or carbonyl group (-CO) inside the molecule ).

Representative examples of the polymer form of the hydrophilic organic compound include poly (ethyleneglycol) phenylether methacrylate, poly (ethylene glycol) diacrylate (PEGDA), Poly (propylene glycol) dimethacrylate, poly (propylene glycol) diacrylate (PPGDA), poly (ethylene glycol) dimethacrylate (poly (ethylene glycol) dimethacrylate), poly (ethylene glycol) acrylate, poly (ethylene glycol) methyl ether acrylate, poly (propylene glycol) acrylate (propylene glycol) acrylate), poly (ethylene glycol) phenyl ether methacrylate, poly (ethylene glycol) 2,4,6-tris (1-phenylethyl) phenyl And the like Terre methacrylate (poly (ethyleneglycol) 2,4,6-tris (1-phenylethyl) phenyl ether methacrylate).

Further examples of organic monomers having one unsaturated hydrocarbon group (-CH = CH ₂ ) and a hydroxyl group (-OH) at the terminal of the molecule include 2-hydroxyethylmethacrylate (2-HEMA), 2- Hydroxypropylacrylate (2-HPA) and the like, having at least two functional unsaturated hydrocarbon groups (-CH = CH ₂ ) at the end of the molecule and ether group (-O-) or carbonyl group (- Examples of organic monomers having CO) include dipentaerythritol caprolacton hexa acrylate, ethoxylate (9) ethoxylated (9) trimethylol propane tri acrylate, Ethoxylated (4) pentaerythritol tetra acrylate, ethoxylated (6) trimethylol propane tri acrylate, and the like. 4-tert-butyl cyclohexyl acrylate (glycidyl vinyl benzyl ether), N, N-diglycidyl aniline (N, N-diglycidyl anilline), Bis (4-glycidyloxyphenyl) methane, 2- (sulfooxy) ethyl methacrylate ammonium salt, and the like may be used.

The alkoxysilane compound is an unsaturated hydrocarbon at the R position in the compound represented by the formula RxSi (OR ') _4-x , wherein R and R' are alkyl groups of C _1-10 and x is an integer of 1 to 3 Group (-CH = CH ₂ ).

Representative examples of the alkoxysilane compound include (3-acryloxypropyl) methyl-dimethoxysilane, methacryloxypropyltrimethoxy silane (MAPTMOS), Acryloxy propyl trimethoxy silane (APTMOS), (methacryloxymethyl) phenyldimethyl silane, methacryloxypropyl-tris (trimethylsiloxy) silane (methacryloxy proppyl- trimethylsiloxy silane), and vinyl triethethoxysilane.

An unsaturated hydrocarbon group (-CH = CH ₂ ) linked to the alkoxysilane compound may be acrylic polymerized with an unsaturated hydrocarbon group (-CH = CH ₂ ) present at the end of the hydrophilic organic compound under thermal initiation catalyst to form a chemical bond. Can be.

It is preferable that the reaction equivalent ratio of the unsaturated hydrocarbon group of the said hydrophilic organic compound to the unsaturated hydrocarbon group of the alkoxysilane is 1: 1-1: 1.5. When the equivalent ratio is less than 1: 1, there is a problem of reducing the gelation and stability of the reactant as the unsaturated hydrocarbon group (-CH = CH ₂ ) of the alkoxysilane remains during acrylic polymerization.

The acrylic polymerization reaction between the hydrophilic organic compound having an unsaturated hydrocarbon group in the molecule or the terminal and the alkoxysilane is carried out by putting the alkoxysilane and the solvent having an unsaturated hydrocarbon group in a reactor and stirring at a temperature of 40 to 80 ° C, and in the molecule or The solution obtained by dissolving a hydrophilic organic compound having an unsaturated hydrocarbon group (-CH = CH ₂ ) and a thermal start catalyst in a solvent in a terminal is slowly added dropwise for 10 to 120 minutes and then reacted for 4 to 10 hours. In the acrylic reaction, when the stirring temperature is lower than 40 ° C, the reaction rate is significantly lowered and the progress of the reaction is difficult. When the stirring temperature is higher than 80 ° C, the reaction is difficult to control, so that the reaction product gels.

As the solvent for dissolving the alkoxysilane, all known in the field of acrylic polymerization reaction can be used, specifically, isopropyl alcohol, diacetone alcohol, n-butanol ), Toluene, xylene, xylene, ethyl cellusolve, butyl cellusolve, methyl isobutyl ketone, methyl ethyl ketone, ethyl acetate ethyl acetate), normal butyl acetate, and the like, among which, isopropyl alcohol, n-butanol, toluene, ethylcellulose solution, methyl isobutyl ketone, methyl ethyl ketone, ethyl acetate, and the like are preferably used. Can be.

The solvent is preferably used in an amount of 40 to 90% by weight based on solids relative to the total reactants. When the amount of the solvent used is less than 40% by weight, the reactants are easily gelled, and when it is more than 90% by weight, the purity of the reactants due to side reactions occurs.

The thermal initiation catalyst may be any one known in the art, and specific examples thereof include commercially available TRIAM-605 (diallyl chlorendate), TRIAM-606 (diallyl hexahydrophthalate), TRIAM-705 (triallyl trimellitate or triallyl 1,2). , 4-benzenetricarboxylate)), V-30 (2-cyano-2-propylazoformamide), V-40 (1,1'-azobis (cyclohexane-1-carbonitrile)), V-50 (2,2'-azobis ( 2-amidino -propane) dihydrochloride), V-59 (2,2'-azobis (2-methylbutyronitrile)), V-60 (2,2'-azo bisisobutyronitrile), V-65 (2,2'-azobis ( 2,4-dimethylvaleronitrile)), V-70 (2,2'-4-methoxy-2,4-dimethylvaleronitrile) and AIBN (2,2'-azobis (2-methylpropanenitrile)) may be used. Among them, V-40, V-50, V-59, V-60, V-65, V-70, AIBN and the like are preferable.

The thermal starting catalyst amount is preferably used in an amount of 0.01 to 1% by weight based on solids relative to the total reactants. When the amount of catalyst used is less than 0.01% by weight, the reaction rate is significantly lowered, so that the reaction is difficult to proceed. If it is more than%, it is difficult to control the reaction and gelation of the reactant occurs.

② Preparation of Urethane Polymer

Hydrophilic ionic groups at the molecular terminal ends, for example, hydroxyl groups (-OH), has an amine group (-NH ₂₎ or a thiol group (-SH), amine group within the molecule (-NH _2), ether group (-O- ) And / or an organic compound having a hydroxyl group (—OH) and an alkoxysilane compound having an isocyanate group (—NCO) may be reacted under a urethane reaction catalyst to prepare a hydrophilic urethane polymer.

The organic compound having at least one hydrophilic group in the hydroxyl group (-OH), the amine group (-NH ₂ ) and the thiol group (-SH) used in the present invention is a monomer exhibiting hydrophilicity and urethane polymerization reaction characteristics, In oligomeric or polymeric form, at least one of hydroxyl (-OH), amine (-NH ₂ ) and thiol (-SH) molecules at the terminal, and amine (-NH ₂ ), ether ( -O-) and hydroxyl group (-OH).

Examples of the hydrophilic organic compound include glycol compounds having a bifunctional or higher hydroxyl group (-OH), ethers, polyester polyols, polyether caprolactone polyols, polycarbonate polyols, polyamines, and the like. Among them, representative examples thereof include polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylenetriol, polyoxytetramethyleneglycol, and polyethyleneadiphate. Polypropylene adipate, polybutylene adipate, polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMG), Ethylene diamine (EDA), diethylenetriamine (diethylene t riamine; DETA).

The alkoxysilane compound is an isocyanate group at the R position in the compound represented by the formula RxSi (OR ') _4-x , wherein R and R' are an alkyl group of C _1-10 and x is an integer of 1 to 3. (-NCO). Representative examples of the isocyanate group-containing alkoxysilane include γ-isocyanatopropyltrimethoxysilane.

Isocyanate group (-NCO) linked to the alkoxysilane compound is at least one hydrophilic group and urethane selected from hydroxyl group (-OH), amine group (-NH ₂ ) and thiol group (-SH) present at the terminal of the hydrophilic organic compound Urethane polymerization may be carried out under the reaction catalyst to form a chemical bond.

The equivalent ratio of the functional group of the hydrophilic ionic group, such as hydroxyl group (-OH), amine group (-NH ₂ ) or thiol group (-SH) to isocyanate (-NCO) functional group, present at the terminal of the organic compound is 1: 1. It is preferably in the range from 1 to 1.5, in order to prevent precipitation separation and degradation of wear resistance of the coating solution to be produced due to the remaining of the reactor in the organic compound having hydrophilic properties.

The urethane reaction catalyst is preferably used in an amount of 0.001 to 1% by weight based on solids relative to the total reactants. When the amount of the catalyst used is less than 0.001% by weight, the urethane reaction rate is significantly lowered, making it difficult to obtain a hybrid composite. When the amount of the catalyst used is more than 1% by weight, it is difficult to control the reaction rate, which causes gelation of the reactants due to heat generated during the reaction. Phenomenon occurs. Representative examples of the urethane reaction catalyst, dibutyltindiraurate (dibutyltindiraurate), dibutyltindibromide (dibutyltindibromide), dibutyltindichloride, 1,4- diazabicyclo (2,2,2) octane Of these, dibutyltin dichloride or 1,4-diazabicyclo (2,2,2) octane is preferred.

The solvent used in the urethane reaction serves to adjust the reaction rate of the reactants and the viscosity after the reaction, which is preferably used in an amount of 5 to 95% by weight relative to the total amount of the reactants. Typical examples include methyl ethyl ketone (MEK), toluene, toluene, N, N-dimethyl formamide (DMF), ethyl acetate, and isopropyl alcohol. IPA), acetone, tetrahydrofuran (THF), cyclohexanone and the like.

<Preparation of Nano-Scale Organic-Inorganic Hybrid with Hydrophilic Group>

Hydrophilic and condensation reaction of the hydrophilic acrylic or urethane polymer and the nano-sized silica sol obtained through the polymerization of acrylic or urethane under hydrolysis catalyst can be obtained to obtain an organic-inorganic hybrid for hydrophilic functional group-containing antifogging coating. .

The nano-sized silica sol used in the present invention forms partial condensates by a sol-gel reaction that causes hydration and partial condensation reactions, or forms colloidal particles of several tens to hundreds of nanoscales to form the oil- Participate in reactions for the production of inorganic hybrids.

The silica sol is preferably used in an amount of 15 to 95% by weight based on solids relative to the total reactants. When the amount of silica sol used is less than 15% by weight, the hardness of the coating film formed by curing the coating solution prepared using the hybrid is greatly reduced. When the amount of the silica sol is greater than 95% by weight, shrinkage occurs during curing of the coating film, and thus the film is easily damaged.

Representative examples of the silica sol include commercially obtainable SNOWTEX 40 (40% SiO ₂ , diameter: 10-20 nm, Nissan Chemical), SNOWTEX C (20% SiO ₂ , diameter: 10-20 nm, Nissan Chemistry), SNOWTEX O (20% SiO ₂ , Diameter: 10-20nm, Nissan Chemical), MA-ST (30% SiO ₂ , Diameter: 10-20nm, Nissan Chemical), IPA-ST (30% SiO ₂ , Diameter : 10-20nm, Nissan Chemical), LUDOX HS-40 (40% SiO ₂ , Diameter: 12nm, Dupont), LUDOX HS-30 (30% SiO ₂ , Diameter: 12nm, Dupont), LUDOX SM (50% SiO ₂ , Diameter: 7 nm, Dupont), LUDOX AM (30% SiO ₂ , Diameter: 12 nm, Dupont), NYACOL DP5820 (30% SiO ₂ , Diameter: 20nm, NYACOL), NYACOL DP5480 (30% SiO ₂ , Diameter: 50nm, Niacol), NYACOL DP5540 (30% SiO ₂ , Diameter: 100nm, Niacol), LEVASIL 50CK / 20% (20% SiO ₂ , Diameter: 75nm, BAYER), LEVASIL 50CK / 30% (30% SiO ₂ , Diameter: 75nm, Bayer), LEVASIL 100/30% (30% SiO ₂ , Diameter: 30nm, Bayer), LEVASIL 200/30% (30% SiO ₂ , Diameter: 15nm, Bayer), LEVASIL 200 A / 30% (30% SiO ₂ , Diameter: 15 nm, Bayer), LEVASIL 300F / 30% (30% SiO ₂ , Diameter: 9 nm, Bayer) and the like, preferably SNOWTEX 40, MA-ST, IPA-ST, LUDOX HS-40, LUDOX HS- 30, LUDOX SM, LUDOX AM, NYACOL DP5820, LEVASIL 200/30% and the like can be used.

The hydrolysis catalyst used in the hydrolysis and condensation reaction process is preferably using an aqueous hydrochloric acid or acetic acid solution of 0.001 to 1.2N concentration, the hydrolysis and condensation reaction is carried out for 2 to 30 hours at 5 to 80 ℃ It is preferable.

Preparation of Hydrophilic Organic-Inorganic Hybrid Composites

In the present invention, a method for producing an organic-inorganic hybrid composite comprising hydrating and condensing a nano-size organic-inorganic hybrid having a hydrophilic group obtained above and an alkoxysilane having an ultraviolet photocurable unsaturated hydrocarbon group, and from therefrom It provides an organic-inorganic hybrid composite prepared.

The organic-inorganic hybrid composite is obtained as the photocurable alkoxysilane chemically bonds to the surface of the silica sol in the organic-inorganic hybrid through a sol-gel reaction.

Used in the preparation of the organic-inorganic hybrid composite, an alkoxysilane having an unsaturated hydrocarbon group at the terminal is represented by the following general formula (1):

R _X Si (OR ') _4-X

Where

R is one selected from C _1-10 alkyl group, phenyl group, vinyl group, (meth) acrylic group, epoxy group, amino group, mercapto group and hydroxy group, R 'is C _1-5 alkyl group, x is 1 to 3 Integer of.

In general, in the alkoxysilane represented by the formula (1), in the case of x = 2, that is, R ₂ Si (OR ') ₂ , or x = 3, that is, having a structure of RSi (OR') ₃ is mainly used In particular, x = 2 alkoxysilane can increase the flexibility by reducing the crosslinking density of the coating film prepared from the organic-inorganic hybrid composite.

In the present invention, as the alkoxysilane compound, it is preferable to use a trialkoxysilane having a functional group (R) capable of imparting photocuring properties to the coating film, for example, an acryl group, a vinyl group, or a methacryl group. Representative examples of the alkoxysilanes include vinyltrimethoxysilane, acryloxypropyltrimethoxysilane, methacryloxytrimethoxysilane, and the like, among which acryloxy propyltrimethoxysilane or methacryloxytrimethoxysilane desirable.

Nano-scale organic-inorganic hybrid having the hydrophilic group is preferably used in the range of 25 to 75% by weight based on the total weight of the reactants. When the amount of the hybrid is less than 25% by weight, the hardness and the anti-fogging property of the coating film is easily lowered after curing, and when the amount of the hybrid is greater than 75% by weight, the functional group of the alkoxysilane reacting with the silica sol present on the surface of the hybrid Lacking, the photocuring rate is significantly lowered.

The hydrolysis catalyst and water used in the hydrolysis and polycondensation may be used in an aqueous solution of 0.001 to 1.2 N hydrochloric acid or acetic acid in an amount of 5 to 15 wt% based on the total weight of the reactants. The process is preferably carried out at 5 to 80 ℃ for 2 to 30 hours.

The present invention also provides an antifogging coating composition comprising the organic-inorganic hybrid composite, an organic compound having at least one hydrophilic group and an unsaturated hydrocarbon group, an organic solvent, and a photocuring initiator.

In the anti-fogging coating composition of the present invention, the amount of the hydrophilic organic-inorganic hybrid composite can be used arbitrarily adjusted according to the anti-fogging effect range and the control range of the surface hardness, preferably 2 to 20% by weight relative to the total weight of the coating agent It is used in the range of, more preferably in the range of 5 to 15% by weight is appropriate. When added in an amount less than 2% by weight, the surface hardness of the coating film and the persistence of anti-fogging properties are inferior, and when added in an amount of more than 20% by weight, the photocuring speed of the coating film is slowed and the viscosity of the coating liquid is increased to make the coating film thick. The film becomes uneven in appearance.

The organic compound has an ether group (-O-) and / or a hydroxyl group (-OH) and an unsaturated hydrocarbon group at the end, and increases the compatibility of the hydrophilic organic-inorganic hybrid composite and enhances the antifogging effect of the coating surface. Do it. The organic compound is preferably used in the range of 10 to 70% by weight, preferably 20 to 40% by weight based on the total weight of the coating agent. When the amount of the organic compound used is less than 10% by weight, the viscosity of the coating liquid increases when the coating film is cured, resulting in a thick coating film, resulting in a slow photocuring rate of the coating film, uneven film appearance, and an excess of 70% by weight. When added, the surface hardness of the coating film is lowered, the durability of the anti-fogging property is lowered, and the phase separation phenomenon due to the heat stability decrease and the transparency of the coating film are deteriorated by the heat generated from the ultraviolet light source during photocuring.

The organic compound may be in the form of monomers, oligomers or polymers, and typical examples thereof include hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate (HPMA), and hydroxyethyl. Acrylate (hydroxyethyl acrylate; HEA), hydroxypropyl acrylate (HPA), polypropyleneglycol 5 methacrylate, polyethyleneglycol 6 methacylate, polypropylene glycol 6 Acrylate (polypropyleneglycol 6 acrylate), polyethyleneglycol 6 acrylate, polyalkyleneglycol methacylate, ammonium sulphatoethyl methacrylate, 2- (2- Ethoxyethoxy) ethyl acrylate (2- (2-ethoxyethoxy) ethyl acrylat e), polyethyleneglycol 200 diacylate, triethyleneglycol diacrylate, tripropyleneglycol diacrylate, polyethyleneglycol 400 diacylate, penta Erythritol tetraacrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, 3 mole addition ethoxylate trimethylolpropane triacrylate (3 mole added ethoxylated trimethylolpropane triacrylate), 3 mole added propoxylated trimethylolpropane triacrylate, 6 mole added ethoxylated trimethylolpropane triacryl ate), 6 mole added propoxylated trimethylolpropane triacrylate, 9 mole added ethoxylated trimethylolpropane triacrylate, 15 mole added ethoxyl Latex trimethylol propane triacrylate (15 mole added ethoxylated trimethylolpropane triacrylate), ethoxylated pentaerythritol tetraacrylate, and the like.

Among these, HEMA, polyethylene glycol 6 methacrylate, polyethylene glycol 6 acrylate, polyethylene glycol 200 diacrylate, triethylene glycol diacrylate, polyethylene glycol 400 diacrylate, pentaerythritol tetraacrylate, dipentaerythritol penta Acrylate, pentaerythritol triacrylate, 3 molar addition type propoxylatetrimethylolpropane triacrylate, 6 molar addition type ethoxylate trimethylolpropane triacrylate, 6 molar addition type propoxylate trimethylolpropane triacrylate, 9 Mole addition type ethoxylate trimethylol propane triacrylate, 15 mole addition type ethoxylate trimethylol propane triacrylate, etc. are preferable.

The photocuring initiator forms a radical by light and crosslinks the unsaturated hydrocarbon group present in the coating liquid, and is preferably used in an amount of 1 to 10% by weight based on the total weight of the coating agent. Representative examples of the photocuring initiator, commercially available as Irgacure 184 (1-hydroxy cyclohexyl phenyl ketone), Irgacure 819 (bis (2,4,6-trimethyl benzoyl) -phenyl-phosphine-oxide), BP (benzophenone ), TPO (2,4,6-trimethylbenzoyl-diphenyl phosphine), Irganox 1010 (pentaerythritol bis (3- (3,5-di-tert-butyl 1) propionate), Irganox 1035 (triodiethylene bis (3- (3, 5-di-tert-butyl 1) propionate) and Irganox 1076 (octadecyl (3- (3,5-di-tert-butyl 1) propionate)), among which Irgacure 184, Irgacure 819, Irganox 1076 or TPO desirable.

When preparing the anti-fog coating of the present invention can be used by adding an organic solvent for the purpose of increasing the productivity by adjusting the viscosity of the coating solution and adjusting the workability, the amount is 0 to 90% by weight, preferably with respect to the total weight of the coating Preference is given to adding in an amount of 30 to 70% by weight. When the amount of the organic solvent is used in excess of 90% by weight, the thickness of the coating film is reduced to a thickness less than a predetermined thickness, the surface hardness is lowered, and the anti-fog property and the transparency of the coating film are affected by the working conditions during the coating operation. Representative examples of the organic solvent, isopropyl alcohol, diacetone alcohol, n-butanol, toluene, xylene, ethyl cellusolve, butyl cellusolve, methyl isobutyl Ketone (methylisobutyl ketone), methyl ethyl ketone, ethyl acetate, normal butyl acetate, and the like, among which isopropyl alcohol, n-butanol, toluene, ethylcellulose solution, methyl Isobutyl ketone, methyl ethyl ketone, ethyl acetate and the like are preferable.

The anti-fog coating agent of the present invention is a hydrophilic organic-inorganic hybrid composite in which all of the organic functional groups having a hydrophilic property in the molecular unit, an unsaturated hydrocarbon group capable of ultraviolet photocuring, and a nano-sized metal oxide which increases the surface hardness are chemically bonded. Since it solves the inverse relationship between the surface hardness characteristic and the anti-fog characteristic, which is a problem of the conventional anti-fog coating agent, it is possible to improve both the surface hardness and the anti-fog characteristic, and also after the surface is saturated with water or coated Unlike conventional coatings, in which antifogging properties are significantly reduced after a certain period of time, they exhibit excellent antifogging properties regardless of the passage of time or surface moisture, and excellent photocuring properties because they contain a photocurable unsaturated hydrocarbon group inside the molecule. Coating working time It is possible to improve the speed and yield.

In addition, the coating film formed by using the coating agent, has a high hydrophilicity compared to the conventional coating film and exhibits excellent long-term anti-fogging properties, polycarbonate (PC), polyacrylate (PA), polyethylene terephthalate (PET), polymethyl It has excellent adhesion to transparent plastic sheet or film such as methacrylate (PMMA) and imparts high surface hardness.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Preparation of Organic-Inorganic Hybrid Composites

Preparation Example 1

248 g of methacryloxypropyltrimethoxy silane was added to 200 g of isopropyl alcohol and stirred uniformly at 50 ° C. Then, 156 g of 2-hydroxyethyl methacrylate and 2 g of V-60 were added to 150 g of isopropyl alcohol at room temperature. The mixed solution dissolved uniformly was dripped for 90 minutes. The reaction was carried out for 8 hours from when the dropping was completed to obtain an acrylic polymer. 60 g of 0.01 N hydrochloric acid solution was added thereto, and the mixture was stirred uniformly at 30 ° C. for 30 minutes. Then, 700 g of IPA-ST (30% SiO ₂ , diameter: 10-20 nm, Nissan Chemical) was added dropwise for 10 minutes, and then stirred for 3 hours. Stirring gave a hydrophilic organic-silicon oxide hybrid. 40 g of 0.01 N hydrochloric acid solution was added dropwise to 184 g of methacryloxypropyl trimethoxy silane at 30 ° C. for 10 minutes, followed by dropwise addition of a hydrophilic organic water-silicon oxide hybrid synthesized to the reacted material for 30 minutes. An organic-inorganic hybrid composite containing all of the hydrophilic groups, photoreactors, and nano-sized metal oxides in a molecule of% was obtained.

Preparation Example 2

An organic-inorganic hybrid composite was prepared in the same manner as in Example 1, except that MA-ST (30% SiO ₂ , diameter: 10-20 nm, Nissan Chemical Co., Ltd.) was used instead of IPA-ST as a nano-sized silica sol. Obtained.

Preparation Example 3

248 g of methacryloxypropyltrimethoxy silane was added to 200 g of isopropyl alcohol and stirred uniformly at 50 ° C., and then 211 g of 2- (sulfoxy) ethyl methacrylate ammonium salt and 2 g of V-65 were 200 g of isopropyl alcohol. The mixed solution dissolved uniformly at room temperature was added dropwise to the mixture for 90 minutes. The reaction was carried out for 8 hours from when the dropping was completed to obtain an acrylic polymer. 60 g of 0.01 N hydrochloric acid solution was added thereto, and the mixture was stirred uniformly at 30 ° C. for 30 minutes. Then, 700 g of IPA-ST (30% SiO ₂ , diameter: 10-20 nm, Nissan Chemical) was added dropwise for 10 minutes, and then stirred for 3 hours. Stirring gave a hydrophilic organic-silicon oxide hybrid. 40 g of 0.01 N hydrochloric acid solution was added dropwise to 184 g of methacryloxypropyl trimethoxy silane at 30 ° C. for 10 minutes, followed by dropwise addition of the hydrophilic organic water-silicon oxide hybrid synthesized to the reacted material for 30 minutes. An organic-inorganic hybrid composite containing all of the hydrophilic groups, photoreactors, and nano-sized metal oxides in a molecule of% was obtained.

Preparation Example 4

An organic-inorganic hybrid composite was prepared in the same manner as in Example 3, except that MA-ST (30% SiO ₂ , diameter: 10-20 nm, Nissan Chemical Co., Ltd.) was used instead of IPA-ST as a nano-sized silica sol. Obtained.

Preparation Example 5

An organic-inorganic hybrid composite was prepared by the same procedure as in Preparation Example 3, except that AIBN was used instead of V-65 as a thermal initiator catalyst.

Preparation Example 6

234 g of acryloxypropyltrimethoxy silane was added to 200 g of isopropyl alcohol and stirred uniformly at 50 ° C. Then, 375 g of poly (ethylene glycol) acrylate and 3 g of V-65 were uniformly added to 300 g of isopropyl alcohol at room temperature. The dissolved mixed solution was added dropwise for 90 minutes. The reaction was carried out for 8 hours from when the dropping was completed to obtain an acrylic polymer. 60 g of 0.01 N hydrochloric acid solution was added thereto, and the mixture was stirred uniformly at 30 ° C. for 30 minutes. Then, 1000 g of IPA-ST (30% SiO ₂ , diameter: 10-20 nm, Nissan Chemical) was added dropwise for 10 minutes, and then stirred for 3 hours. Stirring gave a hydrophilic organic-silicon oxide hybrid. 40 g of 0.01 N hydrochloric acid solution was added dropwise to 174 g of acryloxypropyl trimethoxy silane at 30 ° C. for 10 minutes, and the hydrophilic organic water-silicon oxide hybrid synthesized on the reacted material was added dropwise for 30 minutes. An organic-inorganic hybrid composite was obtained, which contained all of hydrophilic group, photoreactor, and nano-sized metal oxide in the molecule of.

Preparation Example 7

An organic-inorganic hybrid composite was prepared by the same procedure as in Preparation Example 6, except that MA-ST (30% SiO ₂ , diameter: 10-20 nm, Nissan Chemical Co., Ltd.) was used instead of IPA-ST as a nano-sized silica sol. Obtained.

Preparation Example 8

An organic-inorganic hybrid composite was prepared by the same procedure as in Preparation Example 6, except that AIBN was used instead of V-65 as a thermal initiator catalyst.

Preparation Example 9

200 g of polyethylene glycol (average molecular weight = 400) was added to the reactor, and 0.001 g of dibutyl tin dilaurate was added thereto, followed by dropwise addition of 121 g of ??-isocyanatopropyltrimethoxysilane over 30 minutes while stirring. It was. After dripping was completed, the reaction was carried out at 60 ° C. for 90 minutes and cooled to obtain a urethane polymer. 50 g of the reaction product was taken into a reactor maintained at 30 ° C, 100 g of acryloxypropyltrimethoxysilane was added thereto, followed by dropwise addition of 25 g of 0.001N aqueous hydrochloric acid solution over 20 minutes while stirring, followed by MA-ST ( 100 g of 30% SiO ₂ , diameter: 10-20 nm, Nissan Chemical) was added dropwise over 30 minutes. After the reaction for 4 hours at 40 ℃ cooled to obtain a reaction product organic-inorganic hybrid complex.

Preparation of Antifog Coating Composition

Example 1

20 g of the organic-inorganic hybrid composite obtained in Preparation Example 1 was taken to maintain the temperature of the reactor at 20 ° C., 20 g of HEMA (hydroxyethyl methacrylate) and 0.001 g of 4-methoxy phenol were added thereto, and the mixed solution was stirred. . Irgacure 184 0.5g and TPO 0.3g as a photoinitiator were added thereto, 10g of 9-easy diacrylate oligomer and 40g of isopropyl alcohol were added thereto, and stirred for 1 hour to prepare a final anti-fog coating.

Examples 2-9

Instead of the organic-inorganic hybrid composite obtained in Preparation Example 1, except that each obtained in Preparation Examples 2 to 9 were used, the anti-fog coating was prepared in the same manner as in Example 1.

Example 10

Antifogging by the same procedure as in Example 9, except that 50 g of poly (ethylene glycol) 2,4,6-tris (1-phenylethyl) phenylether methacrylate was used instead of the 9-easy diacrylate oligomer. A coating was obtained.

Example 11

An antifog coating was obtained by the same procedure as in Example 9, except that 100 g of methacryloxypropyltrimethoxy silane was used instead of acryloxypropyltrimethoxy silane.

Comparative Example 1

By the method disclosed in the embodiment of the Republic of Korea Patent No. 297,952, a coating composition in which a silica sol and a photocurable silane is mixed with a hydrophilic organic material was prepared.

248 g of methacryloxypropyltrimethoxy silane was added to 200 g of isopropyl alcohol and stirred uniformly at 50 ° C. Then, 156 g of 2-hydroxyethyl methacrylate and 2 g of V-60 were added to 150 g of isopropyl alcohol at room temperature. The mixed solution dissolved uniformly was dripped for 90 minutes. The reaction was carried out for 8 hours from when the dropping was completed to obtain an acrylic polymer. 700 g of IPA-ST (30% SiO ₂ , diameter: 10-20 nm, Nissan Chemical) was added dropwise thereto for 10 minutes and stirred for 3 hours to obtain a composite. 184 g of methacryloxypropyltrimethoxy silane was added dropwise to the obtained compound for 30 minutes to finally obtain a complex. 20 g of the obtained complex was taken to maintain the temperature of the reactor at 20 ° C., 20 g of HEMA (hydroxyethyl methacrylate) and 0.001 g of 4-methoxyphenol were added thereto, followed by stirring the mixed solution. Irgacure 184 0.5g and TPO 0.3g as a photoinitiator were added thereto, 10g of 9-easy diacrylate oligomer and 40g of isopropyl alcohol were added thereto, and stirred for 1 hour to prepare a final anti-fog coating.

Comparative Example 2

As disclosed in the examples of U.S. Patent Publication No. 2002 / 0061950A1, polymethylmethacrylate having a molecular weight of 150000 and 20% by weight of the total weight was hydrolyzed was dissolved in a solution of methanol: water = 1: 1 by 2.3% by weight. 52 g of the mixture was stirred for 10 minutes at 47.1 g of 10% polyvinyl alcohol (Dp = 2000) solution at 25 ° C., and then 0.9 g of acetylacetone was added for 15 minutes to prepare an antifogging coating.

Comparative Example 3

Antifog coating agent by the same procedure as in Example 1, except that 20 g of polyethylene glycol (molecular weight = 400) was used instead of the organic-inorganic hybrid composite containing all of the hydrophilic group, the photoreactor and the nano-sized metal oxide in the molecule. Was prepared.

Comparative Example 4

An anti-fog coating was prepared by the same procedure as in Example 1 except that no organic-inorganic hybrid composite was added.

Physical property evaluation

Test Example 1

The anti-fog coatings prepared in Examples 1 to 11 and Comparative Examples 1, 3 and 4, respectively, were coated by a flow method on a transparent polycarbonate plate, followed by primary at 65 ° C. for 5 minutes to remove the solvent. It was dried, and once cured at 10mpm speed in a UV lamp curing machine (Fusion 'D' type bulb) to form a coating film.

Test Example 2

The anti-fog coating agent prepared in Comparative Example 2 was coated on a transparent polycarbonate plate by a flow method, and then cured at 100 ° C. for 10 minutes to form a coating film.

The physical properties of the coating film formed on the polycarbonate (PC) substrates of the coating agents obtained in Examples 1 to 11 and Comparative Examples 1 to 4, respectively, were measured, and the measuring methods and evaluation criteria of the physical properties were as follows:

(1) Adhesiveness: Evaluated by ASTM D3359-87.

Curing the clearcoat draw knife with a 11-line horizontal and vertical, respectively to reach up to the 1mm gap material to the coating film made 100 that field of 1mm X 1mm that the above given the cellophane tape is excellent in adhesive strength suddenly 180 ^o angle Peel close to This is repeated three times at the same position. The criteria for determining adhesion are as follows:

5B: no coating film fall off of the cut edges, no coating film peeling in the lattice;

4B: Deterioration of the edge is weakly observed and peeling occurs within 5% of the total;

3B: peeling and chipping of corners is observed and peels within 15%;

2B: peeling and chipping are seen even within the lattice and peels within 35%;

1B: large ribbon delamination appeared and peeled at 35% -65%;

0B: Peeled at an area of 65% or more and poor adhesion.

(2) Hot water resistance: evaluated by ASTM D3359-87 (evaluation method is the same as the adhesion test). After dipping the specimen in which the coating film was formed in distilled water at 100 ° C., immersing for 15 minutes, taking it out and drying it, it was confirmed that the coating was separated or cracked.

(3) Anti-fog effect: When the surface of the specimen is blown by a person's hot breath for 3 seconds, the steam does not become frost, 5, and the steam takes more than 10 seconds to disappear, 1, Is as follows:

 Test method and grade standard Warmbreath test If the surface of the anti-fog coated specimen is blown for 3 seconds with a human's hot breath, it is called Rating 5 if the steam is not frost, and if it takes more than 10 seconds for the steam to fade, it is called Rating 1. Freezer test When the anti-fog coated specimen is put in a freezing machine at minus 20 degrees for 10 minutes and taken out, it is called Rating 5 when there is no fog produced within 30 seconds, and it is called Rating 1 when it takes more than 6 minutes to lose steam. Steam test When the anti-fog coated specimen is exposed to water vapor for 2 seconds, the steaming produced within 60 seconds disappears, and it is called Rating 5; if the steaming takes more than 6 minutes, it is called Rating 1. Cold water test When the anti-fog coated specimen is immersed in cold water at 5 degrees for 10 seconds and taken out, it is called Rating 5 if the steam is not cold.

(4) Pencil hardness: evaluated by ASTM D3363-74. If the pencil is placed on the plane of the coated specimen at an angle of 45 ° and is pushed with a constant force, the hardness of the pencil shall be the surface hardness if the scratched pattern or the coating film is not broken more than two times.

(5) Anti-fog weather resistance: When the coated specimen is placed at a distance of 15 cm from the shower, 50 ° C water is sprayed at 80 psi for 30 minutes to evaluate the adhesion of the coating film and the anti-fog property by the warm breath test. The evaluation method of the experiment is the same as the adhesion test, and the antifogging characteristic evaluation is the same as the evaluation criteria of the warm breath test.

Physical properties of the coating film according to the above-described physical property evaluation criteria are shown in Table 1 below:

Adhesion Hot water resistance Anti-fog Pencil hardness Weather resistance PC materials (no coating) - - 1/1/1/1 2B - Example One 5B clear 5/4/5/4 2H 5 2 5B clear 5/4/5/5 2-3H 5 3 5B Broken coating 5/5/5/5 F 4 4 5B Broken coating 5/5/5/5 H 5 5 5B Broken coating 5/5/5/5 2H 5 6 5B clear 5/5/5/4 2H 5 7 5B clear 5/5/5/5 2-3H 5 8 5B clear 5/5/5/5 2H 5 9 5B Paint fade 5/5/4/5 H 4 10 5B clear 5/4/5/4 1 ~ 2H 5 11 5B clear 5/3/5/4 2H 5 Comparative example One 5B Broken coating 5/3/5/2 HB 3 2 0B Paint detached 5/5/3/2 2B One 3 2B Broken coating 5/4/4/3 B 2 4 3B Paint fade 3/1/2/1 B to HB One

From the results of Table 1 above, the UV-curable and organic-inorganic hybrid composite containing all of the nano-sized metal oxide that can increase the hydrophilic group, photoreactor and surface hardness in the molecule and the anti-fogging coating agent comprising the same Has an excellent material adhesion and surface hardness of 5B or more, and shows a very good antifogging effect compared to the compositions and coatings according to the prior art (Comparative Examples 1 and 2) from various antifogging experiments, and also has a hydrophilic group, a photoreactor and Compared to the case where no organic-inorganic hybrid composite containing nano-sized metal oxides is added (Comparative Example 4), or when non-reactive hydrophilic organic materials are added (Comparative Example 3), a very high sustained effect and excellent durability in hot water and weather resistance are achieved. It shows the persistence of coating film properties.

As described above, the organic-inorganic hybrid composite of the present invention and the anti-fog coating agent prepared therefrom can be used for transparent plastic optical materials, bathroom mirrors, automobile glass, greenhouse transparent window, etc. And it is excellent in the photocuring properties, the production yield and workability is good, especially after coating hardening of the substrate and the excellent bending property and adhesion is possible to apply to all transparent materials and applications.

Claims (15)

(1) (a) 1 having a hydroxyl group (-OH), an amine group (-NH ₂ ) or a thiol group (-SH) at the terminal of the molecule and selected from an ether group (-O-) and a carbonyl group (-CO) inside the molecule A hydrophilic acrylic polymer is prepared by reacting an alkoxysilane compound having at least one species and having an ethylenically unsaturated hydrocarbon group in the molecule or terminal with an alkoxysilane compound having an ethylenically unsaturated hydrocarbon group at the terminal, or (b) a hydroxyl group (- OH), an amine group (-NH ₂ ) or a thiol group (-SH) and at least one member selected from among an amine group (-NH ₂ ), an ether group (-O-) and a hydroxyl group (-OH) Reacting an organic compound with an alkoxysilane compound having an isocyanate group (—NCO) to prepare a hydrophilic urethane polymer; (2) reacting the polymer produced in step (1) with a nano-sized silica sol to produce a nano-sized organic-inorganic hybrid having hydrophilicity; And (3) A method for producing an organic-inorganic hybrid composite, comprising hydrating and condensing an organic-inorganic hybrid produced in step (2) with an alkoxysilane having an acryl, vinyl or methacryl group at its end. The method of claim 1, The reaction equivalence ratio of the unsaturated hydrocarbon group of the organic compound which has an ethylenically unsaturated hydrocarbon group at the terminal to the ethylenically unsaturated hydrocarbon group of the alkoxysilane in the range (1) of (1) is 1: 1: 1: 1.5. The method of claim 1, Method (a) of step (1), characterized in that the polymerization process of the organic compound having an ethylenically unsaturated hydrocarbon group at the end and the alkoxysilane is carried out at 40 to 80 ℃. The method of claim 1, In (a) of step (1), the organic compound having an ethylenically unsaturated hydrocarbon group at its end may be poly (ethylene glycol) phenyl ether methacrylate, poly (ethylene glycol) diacrylate, poly (propylene glycol) dimethacrylate, Poly (propylene glycol) diacrylate, poly (ethylene glycol) dimethacrylate, poly (ethylene glycol) acrylate, poly (ethylene glycol) methyl ether acrylate, poly (propylene glycol) acrylate, poly (ethylene glycol) Phenyl ether methacrylate, poly (ethylene glycol) 2,4,6-tris (1-phenylethyl) phenyl ether methacrylate, 2-hydroxyethyl methacrylate (2-HEMA), 2-hydroxypropyl acryl Rate (2-HPA), dipentaerythritol caprolactone hexaacrylate, ethoxylate (9) trimethylolpropane triacrylate, ethoxylate (4) pentaerythritol tetraacrylate , Ethoxylate (6) trimethylol propane triacrylate, 4-tert-butylcyclohexyl acrylate, glycidyl vinylbenzyl ether, N, N- diglycidyl aniline, bis (4-glycidyloxyphenyl A monomer selected from methane and 2- (sulfoxy) ethyl methacrylate ammonium salt. The method of claim 1, The alkoxysilane having an ethylenically unsaturated hydrocarbon group at the end in (a) of step (1) is (3-acryloxypropyl) methyl-dimethoxysilane, methacryloxypropyltrimethoxysilane (MAPTMOS), acryloxypropyltrimeth And methoxysilane (APTMOS), (methacryloxymethyl) phenyldimethylsilane, methacryloxypropyl-tris (trimethylsiloxy) silane, and vinyltriethoxysilane. The method of claim 1, Characterized by using from 0.01 to 1% by weight of a thermal initiation catalyst on a solids basis to the total reactants in the acrylic polymer preparation process of step (1). The method of claim 1, The reaction equivalent ratio of the hydroxyl, amine or thiol group of the organic compound to the isocyanate group (-NCO) of the alkoxysilane in (b) of step (1) is in the range of from 1: 1 to 1: 1.5. The method of claim 1, In (b) of step (1), the organic compound is polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene triol, polyoxytetramethylene glycol, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyethylene And glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMG), ethylenediamine (EDA) and diethylenetriamine (DETA). The method of claim 1, The alkoxysilane compound having an isocyanate group (-NCO) in (b) of step (1) is characterized in that γ-isocyanatopropyltrimethoxysilane. The method of claim 1, Characterized in that 0.001 to 1% by weight of the urethane reaction catalyst is used on a solids basis with respect to the total reactants in the urethane polymer preparation process of step (1). The method of claim 1, Characterized in that the nano-sized silica sol reacted with the polymer in step (2) is used in the range of 15 to 95% by weight relative to the total weight of the reactants. The method of claim 1, The organic-inorganic hybrid reacted with the alkoxysilane in step (3) is used in the range of 25 to 75% by weight relative to the total weight of the reactants. An organic-inorganic hybrid composite prepared according to the method of any one of claims 1 to 12. 2 to 20% by weight of the organic-inorganic hybrid composite of claim 13, 10 to 70% by weight of an organic compound having an ethylenically unsaturated hydrocarbon group and at least one selected from an ether group (-O-) and a hydroxyl group (-OH), organic solvent 0 Anti-fog coating composition comprising from 90% by weight to 1 to 10% by weight photocuring initiator. The method of claim 14, Organic compounds include hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate (HPMA), hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), polypropylene glycol 5 methacrylate, polyethylene Glycol 6 methacrylate, polypropylene glycol 6 acrylate, polyethylene glycol 6 acrylate, polyalkylene glycol methacrylate, ammoniumsulfatoethyl methacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, Polyethylene glycol 200 diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol 400 diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, 3 molar addition ethoxylate trimethylolpropane triacrylate, 3 molar parts Soluble propoxylate trimethylolpropane triacrylate, 6 molar addition ethoxylate trimethylolpropane triacrylate, 6 molar addition propoxylate trimethylolpropane triacrylate, 9 molar addition ethoxylate trimethylolpropane triacrylate, Anti-fog coating composition, characterized in that selected from 15 molar addition type ethoxylate trimethylolpropane triacrylate and ethoxylate pentaerythritol tetraacrylate.