KR20020017707A - Coating components for preventing steam and the coating goods obtained from them - Google Patents

Abstract

PURPOSE: Provided are a coating composition for anti-fogging, which has a ultraviolet screening effect, an improved hardness of a coated surface, and excellent antistatic property, and coated products obtained from the composition. CONSTITUTION: The coating composition comprises 0.01-80wt% of a silane compound(formula 1:£((R1O)3Si-R2-NHCOOR3-)2NR6(R4-Q-R5)|+ X-), 0-30wt% of a metal oxide(formula 2:RcdM(ORb)a), 0-10wt% of a titanium compound, 0-20wt% of an organic stabilizer, and 20-99.9wt% of distilled water in the presence of an acid or base catalyst such as acetic acid, formic acid, triethylamine, pyridine, and etc. And the coated product is produced by coating a support with the composition, wherein the support is selected from the group consisting of fabrics, an aluminium foil, a polyolefin film, polyurethane film, and etc. In the formula, R1 is methyl, ethyl, propyl, isopropyl, or hydrogen, R2, R4, and R6 are less than C20 straight or branched alkyl or phenyl, R3 is less than C50 with ethylene oxide, propylene oxide, or isopropylene oxide, Q is -OCOR5, CH2, R5 is C8-C18 straight or branched alkyl, X is an anion selected from halogen or CH3SO4, M is Si, Ti, Al, Zr, etc., a is an integer of less than 4, b is C0-C4 straight or branched alkyl or hydrogen, Rc is less than C20 straight or branched alkyl, and d is an integer of 0-3.

Description

Coating composition for preventing anti-fog and coating product obtained therefrom {Coating components for preventing steam and the coating goods obtained from them}

The present invention relates to an antifogging coating composition, and more particularly, 0.01 to 80% by weight of a silane compound, 0 to 30% by weight of silicon oxide, and 0 to 10% by weight of titanium oxide, which are new organic-inorganic hybrid materials under an acid or basic catalyst. %, An organic stabilizer 0 to 20% by weight and distilled water 20 to 99.9% by weight, and a coating product coated on the support.

Although coating materials using organic polymers have been widely applied in real life, these compositions have poor adsorbability with glass or metal surfaces, and therefore, additives are used for the purpose of improving the adhesiveness through an additional process (multi-coating) in the coating process. many. However, the silane compound chemically bonded to the intramolecular cationic surfactant developed by the present inventors not only has the advantage of solving the phase separation problem and liquid turbidity of organic-inorganic composite materials by introducing an inorganic precursor into the molecule. The present invention provides an advantage of improving the low adsorption property of organic polymers.

Transparent polymer materials, such as automotive glass, spectacle lenses, ski glasses, agricultural films, or transparent glass such as bathroom mirrors or greenhouse glass, the surface temperature of the substrate changes from the low temperature environment to the high temperature and high humidity environment. If lower, the condensation of water on the surface of the substrate is frosted and opaque, the user experiences inconvenience, and in the case of greenhouses or plastic houses, the amount of sunshine is less due to the water droplets condensed on the surface of the substrate And water droplets can cause the crops to become cold and to have a major impact on yield reduction. Therefore, if the hydrophilicity is given to the surface portion of the base material, the water droplets flow down to the surface of the coating film in the process of condensation, thereby solving all the problems caused by the condensed water droplets.

In addition to the hydrophilic coating on the surface, as a method of imparting anti-fog effect, a method of water-repellent treatment by coating the surface of the substrate with a silicone-based or fluorocarbon-based material having a lower surface tension than water is proposed, but the anti-fogging effect is very unsatisfactory. In addition, a method of obtaining hydrophilic radicals on the surface by plasma treatment to obtain a simmering effect is known, but the large-area treatment is not easy and the processing cost is expensive, and thus it is not commercialized.

Therefore, many studies are currently underway to form a coating film that imparts both hydrophilicity and abrasion resistance to obtain antifogging effect. Japanese Patent Laid-Open Nos. 55-69678, 55-86848, 56-53070, 61-239, 63-172778 and the like exemplify compositions using hydrophilic acrylic resins, but when they give excellent anti-fog effect, wear resistance is poor. In the case of providing excellent wear resistance, the anti-fog effect is inferior, which makes it difficult to commercialize a coating film having two properties at the same time.

In addition, Japanese Patent Laid-Open Nos. 57-156553, 59-78302, 60-80832, 60-44971, 61-14853, 61-153147, 62-153134, Japanese Patent Laid-Open No. 3-42238, US Pat. No. 4098840, 4522966, and the like. A method of forming a coating film cured by heat or ultraviolet rays after coating a monomer and an oligomer by mixing with a hydrophilic resin is disclosed. However, the coating film prepared in this manner has excellent wear resistance compared to a composition made of hydrophilic acrylic resin. Although there is, there is a disadvantage that the anti-fog effect is significantly lower than acrylic. In addition, there is a tendency that the adhesion to the coating substrate is very poor so that the coating film is separated from the substrate and the antifogging effect is lost.

According to US Pat. Nos. 3,773,776, 4,016,129, 4,478,909, 5,134,021, antifogging films using polyvinyl alcohol and silica have been introduced.

These organic-inorganic composites use simple hydrogen bonds and use aluminum precursors together with reaction catalysts to solve the phase separation problem, leading to better inorganic network formation. In addition, the Florin compound is used as a surface active agent to enhance the antifogging effect.

These organic-inorganic composites can improve the above-mentioned phase separation problem and transparency to some extent when contacted with water for a long time. However, due to the high water reactivity of the aluminum precursor, the manufacturing process is difficult and the economic cost is high. There is this.

U.S. Pat. No. 4,446,033 introduces silane compounds with amino groups, which can be applied to detergents as single molecules or provide enhanced cleaning functions associated with enamel-coated surfaces.

In addition, these compounds are often used as additives in barrier coating materials. However, the present invention does not exhibit hydrophilicity and thus cannot be applied to a hydrophilic coating, and a solution prepared in an aqueous solution through a sol-gel process is basic due to free amine, so that gelation occurs easily. Have

In order to solve the above problems, the present inventors have proposed a new type of silane in Korean Patent Application Nos. 1999-2073 (1999. 1. 3), 1999-16788 and 1999-21425 (1999. 6. 9). Coupling agents and organic copolymers have been disclosed. These compounds have a simple manufacturing process and are excellent in transparency, moisture resistance, etc. in physical properties, but have low hydrophilicity, which limits their application to antifog films. As a result, they have been researched to improve hydrophilicity. In order to complete the present invention, the coating solution obtained by reacting an organic copolymer with an alkoxysilane and an inorganic material such as silicon oxide or titanium oxide is excellent in anti-fogging and antistatic, adsorptive and transparent. Reached.

In order to solve this conventional problem, extensive research has found an organic-inorganic hybrid material obtained by crosslinking an organic polymer in which inorganic particles and silane groups are present by chemical bonding, and completed the present invention based thereon.

An object of the present invention is to provide a coating composition having an excellent anti-fog effect, improving the UV blocking effect and hardness of the coating surface, and further having excellent antistatic properties.

It is another object of the present invention to provide a coating product obtained by using the composition.

The composition of the present invention for achieving the above object is 0.01 to 80% by weight of the silane compound represented by the formula (1) as a new organic-inorganic hybrid material under an acid or basic catalyst, 0 to 30 silicon oxide represented by the formula (2) It consists of 0 weight% and 0-10 weight% titanium oxide, 0-20 weight% of organic stabilizers represented by General formula (3), and 20-99.9 weight% of distilled water.

In order to achieve another object of the present invention, the coating product of the present invention is a coating product obtained by coating the coating composition on a polyolefin film with a thickness of 0.01-50 μm.

1 is an ultraviolet absorption spectrum measured after coating the coating composition of the present invention on a polyethylene film,

2 is an ultraviolet absorption spectrum measured after coating the coating composition of the present invention on a polyethylene terephthalate film,

3 is an ultraviolet absorption spectrum measured by the antifogging film coated with the coating composition of the present invention,

Figure 4 is a photograph of measuring the transparency of the thin film of the present invention anti-fog coating composition.

As described above, the present invention maintains the excellent hydrophilicity of the silane compound, which is an organic component represented by the following general formula (1), and has heat resistance, durability, UV protection, and strong surface of the inorganic component represented by the following general formula (2). It relates to a composition for hydrophilic coating having a hardness.

_{[((R 1 O) 3} Si-R 2 -NHCOOR 3 -) 2 NR 6 (R 4 -QR 5)] + X - .......... formula (1)

[Wherein R ₁ is selected from methyl, ethyl, propyl, isopropyl or hydrogen, R ₂ , R ₄ , R ₆ represents a straight or branched alkyl group or a phenyl group having 20 or less carbon atoms, R ₃ is ethylene oxide, propylene oxide Or less than 50 carbon atoms imposed with isopropylene oxide, Q represents -OCOR ₅ and -CH ₂ as a linking group, and R ₅ represents a straight or branched chain alkyl group having 8 to 18 carbon atoms. X is a halogen compound; F, Cl, Br, I or an anion selected from CH ₃ SO ₄ .

R ^c _d M (OR ^b ) _a .......... Equation (2)

[Wherein M is a metal element, Si, Ti, Al, Zr, W, Ge and the like; a is an integer of 4 or less; R ^b represents a straight or branched chain alkyl group having 0 to 4 carbon atoms, or represents hydrogen; R ^c represents a saturated, unsaturated straight or branched chain alkyl group having up to 20 carbon atoms, with or without nitrogen, sulfur, oxygen; d represents an integer of 0 to 3.]

In the above formula according to the present invention, examples of the substituted or unsubstituted linear or branched alkyl group include hydrocarbon groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group , t-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropofylpropyl group , 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2- Ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropyl group, 1-t-butyl-2-methylpropyl group, isocyanopropyl group, stilyl group, vinyl group, aryl Hydrocarbon groups such as groups, chloroaryl groups, cyclohexenyl groups, and n-nonyl groups; Such as methoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, methoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, dimethoxymethyl group, diethoxymethyl group, dimethoxyethoxy and diethoxyethyl group Alkoxyalkyl Groups:

Chloromethyl group, 2,2,2-trichloromethyl group. Halogenated alkyl groups such as trifluoromethyl groups, 1,1,1,3,3,3-hexafluoro-2-propyl groups:

Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy group or an alkoxy group.

As the above-mentioned acid catalyst, an organic acid or an inorganic acid may be used, but as the organic acid, acetic acid, formic acid, bromoacetic acid, chloroacetic acid, fluoroacetic acid, α-fluoropropionic acid, ο-fluorobenzoic acid, and hydroxyacetic acid , Lactic acid, salicylic acid, tartaric acid, paratoluic acid, polyphosphoric acid or pyrophosphoric acid may be used, and inorganic acid may be phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, iodic acid, tartaric acid or perchloric acid. have. Caustic soda, ammonia, potassium hydroxide, sodium hydroxide, n-butylamine, di-n-butylamine, tri-n-butylamine, triethylamine, imidazole, pyridine or ammonium perchlorate can be used as the base catalyst.

As the inorganic precursor of the formula (2), the central metal uses a metal oxide of silane, titanium, zirconium, aluminum, or tungsten, and these metal oxides may be used alone or in combination. Examples of such inorganic precursors include titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, zirconium tetraethoxide, zirconium tetrapropoxide, zirconium tetrabutoxide, aluminum triethoxide and aluminum tripropoxide. Side, aluminum tributoxide, tungsten nucleoethoxide, tungsten hexamethoxide, tungsten hexapropoxide, germanium tetramethoxide, germanium tetraethoxide, germanium tetrapropoxide, tetramethoxy silane, tetraethoxysilane , Tetrapropoxysilane, tetrabutoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltripropoxysilane, vinyltriacetoxysilane, vinyldimethoxyethoxysilane, aminopropyltriethoxysilane, amino Propyltrimethoxysilane, Aminopropyltripropoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltrimethoxysilane, 3-acrylic Oxypropyldimethoxysilane, 3-acryloxypropyldiethoxysilane, 3-acryloxypropyldipropoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane , 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltripropoxysilane, N- (2-aminoethyl-3-aminopropyl) -trimethoxysilane (DIAMO), N -(2-aminoethyl-3-aminopropyl) -triethoxysilane, N-(-2-aminoethyl-3-aminopropyl) -tripropoxysilane, N- (2-aminoethyl-3-aminopropyl ) -Tributoxysilane, trimethoxysilylpropyldiethylenetriamine (TRIAMO), triethoxysilylpropyldiethylenetriamine, tripropoxysilylpropyldiethylenetri Amine, tributoxysilylpropyldiethylenetriamine, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-glycidoxy Propyltrimethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethylmethyldiethoxysilane, 2-glycidoxyethylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-glycidoxyethylethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 2-glycidoxy Propylethyldiethoxysilane, 2-glycidoxyethylpropyldimethoxysilane, 2- (3,4-ethoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-ethoxycyclohexyl) ethyltrie Methoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-cle Ropropyltripropoxysilane, 2-chloropropyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, dimethylgimethoxysilane or 3- Chloropropylmethyldimethoxysilane. Meanwhile, metal oxide particles of silica, boehmite, alumina, zirconia, or titania may be used instead of these inorganic precursors.

Since the metal oxide precursors provided with the silane compound have good reactivity, they are used together with a chelate ligand represented by the following formula (3).

R ₈ -CO-CHR ₉ -R ₁₀ .......... Equation (3)

[Wherein R ₈ is a substituted or unsubstituted linear or branched alkyl group, an alkoxy group, a monovalent hydrocarbon and R ₉ is a substituted cyclo group having 8 or less carbon atoms or 12 or less carbon atoms together with R ₈ , selected from a minority, alkyl, haloalkyl and acyl group It represents an alkyl group and these compounds may include one or more groups substituted with chloro group nitro group, acyl group, cyano group or carboxy ester. R ₁₀ is a substituted or unsubstituted linear or branched alkyl group, a hydrocarbon having 8 or less carbon atoms substituted with a halogen group, cyano group, amino group, and ketone group, or may be represented by Chemical Formula CH ₂ R ₁₁ . R ₁₁ represents a substituted or unsubstituted linear or branched alkyl group having 8 or less carbon atoms or a monovalent hydrocarbon including polyethylene oxide, polypropylene oxide, polyether or ether group.]

Examples of specific chelating ligands include acetylacetonate, methylacetoacetate, propylacetoacetate, I-butylacetoacetate, pentylacetoacetate, heptylacetoacetate, heptylacetoacetate, octylacetoacetate, ethylacetoacetate, bisacetylacetate Ethyl acetoacetate, di-n-butoxide monoethyl acetoacetate, di-i-propoxide monomethyl acetoacetate, acetylacetone or benzoyl acetone is used.

The organic solvent used for this invention can be used in order to improve the applicability | paintability of a coating solution, and to improve adhesiveness with a coating base material. The amount of the organic solvent can be used in the range of 0 to 100 parts by weight of the total amount of the coating solution, preferably 30 to 50 parts by weight. When the amount of the organic solvent increases, the thickness of the coating film becomes thin, or the density of the coating film decreases, thereby affecting wear resistance, weather resistance, and durability. Specific examples of the organic solvent include alcohols having 1 to 8 carbon atoms, such as methanol, ethanol, isopropanol, butanol, and the like, and hydrocarbons having 1 to 8 carbon atoms, methoxy ethanol, ethoxy ethanol, isopropoxy ethanol, and the like. Ether alcohols, such as butoxy ethanol, can be used, and these organic solvents can be used individually or in mixture.

In addition, depending on the type of coating substrate, the coating solution coating method may be a flow coating method, spin coating method, dip coating method, or bar coating method. , The thickness of each coating method will exist, so if the thickness is thin, the coating should be carried out several times to have a thickness of about 1 ~ 20㎛. If the thickness is too thin, the wear resistance is reduced and the persistence of the fog is lost. If the thickness is too thick, there is a risk of cracking during drying of the coating film. In addition, in order to increase the adhesion between the coating material, inorganic materials such as glass are first washed with alcohol, and in the case of general polymer substrates, pretreatment processes such as corona discharge may be used.

In addition, surfactants, ultraviolet absorbers, lubricants, defoamers, wetting agents, antioxidants, thickeners or leveling agents and the like may be added to increase the usefulness of the organic copolymer.

In general, cationic surfactants are insoluble in water due to the lipophilic alkyl group, whereas the compound has a relatively high distribution of ethylene oxide and propylene oxide groups in the molecule, and has a silane group at the end group, thereby making it an acid or basic catalyst. It was synthesized to be easily dissolved in water by hydrolysis under, having a hydroxyl group.

The present invention will be described in more detail below.

The silane compound of formula (1) according to the present invention can be prepared by the method described in Patent Application No. 2000-3733 (January 26, 2000) filed by the present inventor.

Hereinafter, the preparation method thereof will be described by reacting a cationic surfactant of formula (4) with an alkoxysilane having an isocyanate group of formula (5) under a nitrogen or argon stream.

_{[(H- (OR 7) n} ) 2 -NR 6 (R 4 -QR 5)] + X - .......... formula (4)

[Wherein R ₄ , R ₅ are as defined in formula (1). R ₇ is ethylene oxide, propylene oxide or isopropylene oxide, and represents n = 1 to 25.}

(R ₁ O) ₃ Si-R ₂ -N = C = O ............... Equation (5)

[Wherein R ₁ , R ₂ are as defined in formula (1).]

Cationic surfactants of formula (4) are commercially available from Sherex Chemical Company, Inc. under the tradename methyl bis (2-hydroxyethyl) cocoammonium chloride (trade name; VARIQUAT638), methylbis (polyethoxyethanol) alkylammonium chloride (Brand name; VARIQUAT K-1215), Ethyl bis (polyethoxy ethanol) alkylammonium ethyl sulfate (Brand name; VARIQUAT 66) can be used or it can be manufactured and used by a well-known method. See, for example, Eric Jungermann, Surfactant Science Series, vol. 4, "Cationic Surfactants", Marcel Dekker, Inc., New York, 1970. or James M. Richmond, Surfactant Science Series, vol. 34, "Cationic Surfactants Organic Chemistry", Marcel Dekker, Inc., New York, 1990. or International Patent WO 94/20597, US Patent Nos. 4,863,620, 4,789,491, 5,066,414, 4,767,547, 4,370,272, It may be prepared according to No. 4,401,577 or E. Prat, J. Kahre, and N. Totan, J. Jpn. Oil Chem. Soc., 44 (4), 341, 1995, R. Puchta, P. Krings and P. Sandkuhler, Dusseldrorf, Tenside Surf. Det., 30 (3), 186, 1993, or "Cationic Surface Active Agents as Fabric Softners", R. R. Egan, Journal of the American Oil Chemicals' Society, January 1978, pages 118-121.

As an example, the production method will be described in more detail below. After dissolving 10 g of triethanol amine in 150 ml of anhydrous methylene chloride, 5 ml of triethylamine is added thereto, and a solution of 36.8 g of palmitoyl chloride in 50 ml of methyl chloride is dropped. Drop. After adding all of the palmitoyl chloride solution dropwise, the mixture was further reacted under atmospheric pressure for 3 hours, and then washed three times with water to remove excess triethylamine. The reaction is dehydrated with magnesium sulphate (MgSO ₄ ) and the solvent is removed under reduced pressure. Separation was carried out by column chromatography (developing solvent: ethyl acetate 1: hexane 4) to obtain 14.03 g (yield: 54%) of di (2-hydroxyethyl) palmitoyloxyethylamine (di (2-hydroxyethyl) palmitoyloxyethylamine). It was.

10 g of the synthesized di (2-hydroxyethyl) palmitoyloxyethylamine was dissolved in acetonitrile, and 5 g of iodomethane (CH ₃ I) was added thereto, and the mixture was refluxed at room temperature and atmospheric pressure overnight. After the reaction was stopped and allowed to stand at room temperature, 13.53 g (yield: 99%) of methyl di (2-hydroxyethyl) palmitoyloxyethylammonium iodide was synthesized by filtration of a white solid.

Alkoxysilanes having an isocyanate group of formula (5) can be prepared using the commercially available Witco SILQUEST® using 3- (triethoxysilyl) propyl isocyanate (product number; 41,336-4) from Aldrich ^. Isocyanato A-1310 can be used.

Specifically describing a method for preparing a silane compound, which is a new type of organic precursor, according to the present invention, a compound corresponding to Formula 4, for example, methyl di (2-hydroxyethyl) palmitoyloxyethylammonium iodide After dissolving 1.18 g in 20 ml of anhydrous tetrahydrofuran (THF), 2 g of 3- (triethoxysilyl) propyl isocyanate corresponding to Formula 5 was added thereto, and 0.05 ml of dibutyltin dilaurate, a metal catalyst. Add. After the reaction mixture was reacted for 24 hours, the solvent and the unreacted 3- (triethoxysilyl) propyl isocyanate were removed under reduced pressure to prepare 2.2 g of a silane compound as an organic precursor.

The features and other advantages of the present invention as described above will be described more clearly with reference to the examples described below and the physical property measurement shown here is taken in the same way.

Anti-fog test: The organic-inorganic copolymer is coated on a substrate to form a coating film, and the time taken for the steam to fully frost on a 10 × 10 cm coating film while contacting with 50 ^° C. saturated steam is measured.

Abrasion resistance (Teva wear resistance): Quantitative value of the cloudyness of the coating film according to ASTM D-1004 and ASTM D-1003 (cloudiness Δ% at 100 cycles)

Example 1 Preparation of Silane Precursor with Polyethylene Oxide Group

2 g of methyl bis (polyethoxyethanol) alkyl ammonium chloride (trade name: VARIQUAT K-1215, Sherex) was dissolved in 20 ml of anhydrous tetrahydrofuran (THF), followed by 3- (trie) corresponding to formula (3) 1 g of oxycyryl) propyl isocyanate is added and 0.05 ml of dibutyltin dilaurate, a metal catalyst, is added. The reaction mixture was allowed to react for 24 hours under reflux, and then, under reduced pressure, the solvent and unreacted 3- (triethoxysilyl) propyl isocyanate were removed to obtain an organic precursor, methyl bis [poly (ethoxyethanol) 3- (tri 2.4 g of ethoxysilyl) propylcarbamate] alkyl ammonium chloride were prepared.

Example 2 Preparation of Organic Copolymer Using Silane Precursor

Polyethylene oxide silane precursor prepared in Example 1, tetraethylolsosil

Kate (tetraethylorthosilicate, Aldrich), titanium (IV) isopropoxide.

(Titanium (IV) isopropoxide (Aldrich) and ethyl acetoacetate (Aldrich) were dissolved in 50 ml of ethanol at the composition ratio of Table 1 below, and 0.2 ml of 0.01 N hydrochloric acid was slowly added dropwise thereto under stirring, followed by 1 ml of distilled water. After reacting for 3 hours at room temperature, 50 ml of distilled water was added to prepare a transparent organic-free copolymer.

Table 1

Component ratio (silane precursor / converted SiO ₂ amount / converted TiO ₂ amount / ethyl acetoacetate) Reaction weight ratio (g) (silane precursor / Si (OEt) ₄ amount / Ti (OiPr) ₄ amount / ethyl acetoacetate)) 10/0/0/0 1/0/0/0 9/1/0/0 0.9 / 0.347 / 0/0 8/2/0/0 0.8 / 0.694 / 0/0 9 / 0.5 / 0.5 / 0 0.9 / 0.173 / 0.178 / 0 8 / 1.5 / 0.5 / 0 0.8 / 0.52 / 0.178 / 0 8/1/1/0 0.8 / 0.347 / 0.356 / 0 7/2/1/0 0.7 / 0.694 / 0.356 / 0 7/0/1/2 0.7 / 0 / 0.356 / 0.2

Example 3 Preparation of Organic Copolymers Using a Silane Precursor:

Methyl-palmitoyloxyethyl-di- [3- (triethoxysilyl) propylamidooxyethyl] ammonium iodide 0.9 g, tetraethylolsosilicate 0.173 g, titanium (IV) isopro instead of polyethylene oxide silane precursor It was prepared in the same manner as in Example 2 except for using 0.178 g of oxide.

Comparative Example 1

Ω-methoxy poly (ethylene glycol) 3- (triethoxysilyl) propyl carbamate in place of the polyethylene oxide silane precursor: Lee, M. -H .; Ko, S. T .; Lee, K. S .; Rhee, S.B. Mol. Cryst. Liq. Cryst. 1997, 229-232] was prepared in the same manner as in Example 2 with the composition of Table 2.

TABLE 2

Component ratio (silane precursor / converted SiO ₂ amount / converted TiO ₂ amount / ethyl acetoacetate) Reaction weight ratio (g) (silane precursor / Si (OEt) ₄ amount / Ti (OiPr) ₄ amount / ethyl acetoacetate)) 8/1/1/0 0.8 / 0.347 / 0.356 / 0 9/1/0/0 0.9 / 0.347 / 0/0

<Example 4>

In order to measure the hydrophilicity and abrasion according to the component change of the organic copolymer, the organic copolymer and the composite material solution prepared by the composition of Table 3 using the method of Example 2 and Comparative Example 1 were prepared in the polyolefin film. After spray coating on (Eternal Chemical Co., Ltd., 60 micrometers in thickness), it was made to dry at 80 ^degreeC and 12 hours in an electric oven so that it might become 1-10 micrometers in thickness. In order to measure the degree of hydrophilicity, the coated film in a 50 ^° C. thermostat was kept in contact with water vapor, and then the frost free time was measured.

Table 3-1 Degree of Hydrophilicity According to Component Changes of Organic Copolymers

Component ratio (silane precursor / converted amount of SiO ₂ / converted amount of TiO ₂ / ethylacetoacetate amount) Hydrophilicity (period without frost) Taber Wear Resistance 10/0/0/0 120 days 6.3 9/1/0/0 210 days or more 6.7 8/2/0/0 90 days 7.6 9 / 0.5 / 0.5 / 0 210 days or more 7.5 8 / 1.5 / 0.5 / 0 120 days 7.2 8/1/1/0 15th 8.0 7/2/1/0 1 hours 9.1 7/0/1/2 80 days 7.8

Table 3-2 Comparative degree of hydrophilicity according to the component change of the organic copolymer

Component ratio (silane compound / converted amount of SiO ₂ / converted amount of TiO ₂ / amount of ethyl acetoacetate) Hydrophilicity (period without frost) Taber Wear Resistance 8/1/1/0 4 hours 8.1 9/1/0/0 10 minutes 6.6

<Example 4>

In order to measure the UV blocking property according to the component change of the organic copolymer, the organic copolymer solution prepared in the composition of Table 4 using the method of Example 2 was prepared in a polyolefin film (Eternal Chemical, 60 μm in thickness). And polyethylene terephthalate (Green Cross Medical Co., Ltd., thickness 1.3mm) was coated to 1 to 2㎛. In addition, to prepare a bulk film thickness of 40 ~ 50㎛, put the solution prepared by using the method of Example 2 in a petri dish (Green Cross Medical Co., Ltd., PET material) having a diameter of 8.5cm and atmospheric pressure, 60 ^o Dry at C for 24 hours. The measured ultraviolet absorption spectrum is shown in FIGS.

Table 4-1 Organic copolymer composition ratio coated on polyethylene film (FIG. 1)

Display number in Figure 1 Component ratio (silane precursor / converted SiO ₂ / converted TiO ₂ / ethyl acetoacetate) One 9/1/0/0 2 9 / 0.5 / 0.5 / 0 3 7/0/1/2 4 7/1/2/0

Table 4-2 Organic copolymer composition ratio coated on polyethylene terephthalate film (Fig. 3)

Display number in Figure 2 Component ratio (silane precursor / converted SiO ₂ / converted TiO ₂ / ethyl acetoacetate) One 0/0/0/0 2 8/2/0/0 3 9 / 0.5 / 0.5 / 0 4 7/0/1/2

Table 4-3 Organic Copolymer Composition of Bulk Film (FIG. 4)

In Fig. 3 Component ratio (silane precursor (or polyvinyl alcohol) / converted SiO ₂ / converted TiO ₂ ) One 8 (polyvinyl alcohol) / 2/0 2 7/3/0 3 8 / 1.5 / 0.5 4 7/2/1

Example 5

The organic copolymer solution prepared by using the method of Example 2 (composition ratio: precursor 8 / SiO ₂ 1.5 / TiO ₂ 0.5) to measure the thin film transparency of the organic copolymer was polyethylene terephthalate (Green Cross Medical Industry). (Note), the thickness of 1.3mm) was coated to 30 to 40㎛, and then dried at atmospheric pressure, 60 ^° C. for 12 hours. The photograph taken using the prepared thin film is shown in FIG. 4.

The organic-free copolymer prepared by the present invention can be utilized in antistatic agents, UV protection and anti-fog coatings by showing excellent anti-fog property, transparency and UV-blocking property.

Claims (7)

0.01 to 80% by weight of a silane compound represented by the following formula (1), 0 to 30% by weight of a metal oxide represented by the following formula (2) and 0 to 10% by weight of a titanium oxide as a new organic-free hybrid material under an acid or basic catalyst %, Organic stabilizer 0 to 20% by weight and distilled water 20 to 99.9% by weight of antifog coating composition. _{[((R 1 O) 3} Si-R 2 -NHCOOR 3 -) 2 NR 6 (R 4 -QR 5)] + X - .......... formula (1) [Wherein R ₁ is selected from methyl, ethyl, propyl, isopropyl or hydrogen, R ₂ , R ₄ , R ₆ represents a straight or branched alkyl group or a phenyl group having 20 or less carbon atoms, R ₃ is ethylene oxide, propylene oxide Or less than 50 carbon atoms imposed with isopropylene oxide, Q represents -OCOR ₅ and -CH ₂ as a linking group, and R ₅ represents a straight or branched chain alkyl group having 8 to 18 carbon atoms. X is a halogen compound; F, Cl, Br, I or an anion selected from CH ₃ SO ₄ . R ^c _d M (OR ^b ) _a .......... Equation (2) [Wherein M is a metal element, Si, Ti, Al, Zr, W, Ge and the like; a is an integer of 4 or less; R ^b represents a straight or branched chain alkyl group having 0 to 4 carbon atoms, or represents hydrogen; R ^c represents a saturated, unsaturated straight or branched chain alkyl group having up to 20 carbon atoms, with or without nitrogen, sulfur, oxygen; d represents an integer of 0 to 3.] The method of claim 1, wherein the metal oxide is titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, zirconium tetraethoxide, zirconium tetrapropoxide, zirconium tetrabutoxide, aluminum triethoxide, aluminum tri An antifog coating composition comprising propoxide, aluminum tributoxide, tungsten hexaethoxide, or metal oxide particles of silica, boehmite, alumina, zirconia, and titania, alone or in combination. The metal oxide of claim 1, wherein the metal oxide is tetraethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyldimethoxyethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N- (3 -Acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, N- ( 2-aminoethyl-3-aminopropyl) -trimethoxysilane (DIAMO), N- (2-aminoethyl-3-aminopropyl) -triethoxysilane, trimethoxysilylpropyldiethylenetriamine (TRIAMO) , Triethoxysilylpropyldiethylenetriamine, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane, 2-glycidoxyethyl Methyldiethoxysilane, 2-glycidoxyethylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxy Column, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-ethoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-ethoxycyclohexyl) ethyltriethoxysilane, ethyl Trimethoxysilane, methyltriethoxysilane, 3-chloropropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, dimethyldimethoxy Antifogging coating composition characterized by using silane or 3-chloropropylmethyldimethoxysilane alone or in combination. The method of claim 1, wherein the acid or basic catalyst is acetic acid, formic acid, bromoacetic acid, chloroacetic acid, fluoroacetic acid, α-fluoropropionic acid, ο- fluorobenzoic acid, hydroxyacetic acid, lactic acid, salicylic acid , Tartaric acid, paratoluic acid, polyphosphoric acid, pyrophosphoric acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, iodic acid, tartaric acid, perchloric acid, sodium hydroxide, ammonia, potassium hydroxide, sodium hydroxide, n-butylamine, Di-n-butylamine, tri-n-butylamine, triethylamine, imidazole, pyridine, ammonium perchlorate, and the like. Coating solution. The method of claim 1, wherein the organic stabilizer is an acetylacetonate, methyl acetoacetate, propyl acetoacetate, I-butyl acetoacetate, pentyl acetoacetate, hectyl aceto containing polyethylene oxide, polypropylene oxide, polyether or ether group Acetate, heptylacetoacetate, octylacetoacetate, ethylacetoacetate, bisacetylacetonate, bisethylacetoacetate, di-n-butoxide monoethylacetoacetate, di-i-propoxide monomethylacetoacetate, acetylacetone or Antifogging coating composition, characterized in that to use benzoyl acetone. New organic-inorganic hybrid material under an acid or basic catalyst, 0.01-80% by weight of the silane compound represented by the formula (1), 0-30% by weight of the metal oxide represented by the formula (2), 0-10% by weight titanium oxide %, Organic stabilizer 0-20% by weight and distilled water 20-99.9% by weight of the coating composition for antifogging coating, characterized in that the coating on the support to a thickness of 0.01-50 ㎛. The antifogging agent according to claim 6, wherein the support body is selected from the group consisting of textile paper, aluminum foil, aluminum plate, mylar film, polyolefin film, polyurethane film, polyvinylchloride film, polycarbonate film, and glass. Coating products.