KR101760060B1 - Titanium dioxide photocatalyst composition for glass coating and preparation method thereof - Google Patents

Abstract

The present invention relates to a titanium dioxide photocatalyst glass coating composition and a method of preparing the same, and more particularly, to a titanium dioxide photocatalyst glass coating composition which is excellent in photocatalytic efficiency in ultraviolet and visible light regions A titanium dioxide photocatalyst glass coating composition having excellent antifouling and anti-fogging effect, transparent by transmitting visible light, and selectively blocking infrared rays and ultraviolet rays to prevent heat insulation, human body protection and deterioration.

Description

TECHNICAL FIELD The present invention relates to a titanium dioxide photocatalyst glass composition and a preparation method thereof,

The present invention relates to a titanium dioxide photocatalytic glass coating composition and a process for its preparation.

Titanium dioxide is a strong photocatalyst material. It has a function of decomposing organic matter decomposing organic mixture by irradiation of ultraviolet rays and a photo-excitation hydrophilization function of superfluidizing the surface. It is used for preventing dust, bacteria, organic pollutants and the like And is widely used as a coating material. In addition, it is abundant in resources and is inexpensive, and is stable as acid, alkali and biologically, and has excellent durability and abrasion resistance and is used as a typical photocatalyst material.

Coated glass with titanium dioxide photocatalyst differs from ordinary glass in that water drops when water is dropped, resulting in thinly spreading of water without adhering to the glass after ultraviolet light is applied. This is due to strong attraction between the adsorbed water layer and water molecules , The adsorbed water layer is formed by adsorbing water like a thin film by interacting with light-absorbed water molecules in the air, in which the delocalized electrons in a shallow trap state trapped by oxygen defects on the surface of titanium dioxide. In this way, supersonic water generated during the absorption of TiO 2 is resistant to staining and antifogging by preventing the adhesion of contaminants and self-cleaning which makes attached pollutants easily washed by rainfall or water. Films and the like.

However, conventional titanium dioxide has a disadvantage in that it can not be activated because it does not receive light energy in a space where light does not reach, and can be activated only in an ultraviolet region because of a relatively large band gap. As a result, the coated glass, which receives ultraviolet rays and generates hydroxyl groups (-OH) and interacts with water molecules, is hydrophilized, and when the ultraviolet ray irradiation is stopped, the water evaporates and loses its hydrophilicity. Therefore, in order to prevent this, development of a photocatalyst having an activity in visible light region of about 43% of the sunlight in addition to the ultraviolet region which is only 4% of the entire wavelength band of sunlight is under development. For example, a composite material of a semiconductor material such as CdS or CdSe and titanium dioxide has been developed as a photocatalyst material having an activity in the visible light region. However, this structure generates electrons by receiving light energy and transmits electrons to the conduction band of titanium dioxide The photocatalytic activity through the reduction reaction shows that the photocatalyst through the reduction reaction can not completely decompose the pollutant unlike the photocatalyst through the oxidation reaction.

On the other hand, the coated glass is required to transmit light in the visible light region to secure transparency, which is a characteristic of the glass, and to selectively block light in the infrared and ultraviolet ray regions. Generally, a tanning film and a metal coating are mainly used for ultraviolet ray shielding. However, it is difficult to secure visibility by blocking not only ultraviolet ray but also visible ray, and there is a problem that mining is bad. In order to effectively block the ultraviolet rays and keep the visible light transmittance at a high level, organic materials such as benzotriazole-based or benzophenone-based materials and inorganic materials such as zinc oxide have been widely used. However, the durability and ultraviolet shielding effect of the organic material is low, and the zinc oxide has a yellowish color, so that the visible light transmittance is lowered and the transparency is decreased.

On the other hand, as research and development on coating technology for ultraviolet ray and infrared ray have been actively developed, a glass coating technique having durability and abrasion resistance is required, and the use of appropriate binder is required for this. Binders can be classified into organic binders and inorganic binders. In the case of organic binders, there are disadvantages of low heat resistance and low protection, and the use of inorganic binders is increasing.

Therefore, development of a glass-coated photocatalyst having a wide active region and having excellent transparency, hardness and water resistance is required. Accordingly, in the present invention, a composite metal oxide is used to exhibit excellent photocatalytic efficiency in the visible light region by lowering the band gap to a level absorbing light in the visible light region, and to have an ultraviolet and infrared light shielding effect. Durability, stain resistance, and glass adhesion.

An object of the present invention is to provide a titanium dioxide photocatalyst glass coating composition having improved transparency, durability, stain resistance and optical properties by forming a composite structure of titanium dioxide nanoparticles and a composite metal oxide using an inorganic binder, and a method for producing the same.

In order to achieve the above object,

(a) mixing 27 to 33% by weight of titanium tetra-isopropoxide (TTIP), 0.1 to 3% by weight of nitric acid, and 60 to 70% by weight of distilled water to prepare titanium dioxide sol; (b) preparing an inorganic binder by mixing 1 to 10% by weight of an alkoxysilane compound, 1 to 3% by weight of methanol, 1 to 3% by weight of ethanol, 10 to 20% by weight of propanol and 60 to 80% by weight of isopropanol. (c) 40 wt% of an alkyl silicate oligomer solution and 27 wt% of a composite metal oxide were placed in a high-speed shear mixer and stirred for 1 to 2 minutes. Then, 2,2 ', 4,4'-tetrahydroxybenzophenone: (20:80) were added to a high-speed shear mixer and stirred for 1 to 2 minutes. 7% by weight of denatured ethanol was added and stirred for 1 to 2 minutes. Then, 20% by weight of butylcellosolve Followed by stirring for 1 to 2 minutes to prepare a composite metal oxide sol; (d) stirring the organic solvent and butyl cellosolve in a high-speed shear mixer for 1 to 2 minutes; (e) adding the titanium dioxide sol (a) to the stirring solution of (d) and stirring for 1 to 2 minutes; (f) The composite metal oxide sol of (c) is added to the stirring solution of (e), and the mixture is stirred for 1 to 2 minutes. After the inorganic binder of (b) is added, stirring is performed for 1 to 2 minutes to obtain a titanium dioxide photocatalyst And (c) preparing a titanium dioxide photocatalyst glass coating composition.

The alkyl silicate oligomer solution in step (c) of the present invention may be prepared by mixing 1 to 10% by weight of an alkyl silicate oligomer, 40 to 50% by weight of ethanol, 40 to 50% by weight of isopropanol and 0 to 5% by weight of acetic acid desirable.

In the step (d) of the present invention, the organic solvent is preferably mixed in a ratio of 95 to 99% by weight of propanol, 0 to 5% by weight of isopropanol, 0 to 1% by weight of methanol and 0 to 1% by weight of ethanol .

The titanium dioxide sol of the present invention preferably has a pH of 2 to 3.

In addition, the titanium dioxide photocatalytic glass coating composition of the present invention is characterized in that it comprises 3 to 7.5% by weight of titanium dioxide sol, 3 to 7.5% by weight of inorganic binder, 3 to 7.5% by weight of composite metal oxide sol, 82 to 87% And 3% by weight of rosorb.

The alkoxysilane compound of the present invention may be at least one selected from the group consisting of methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, allyltriethoxy Silane, dimethyl diethoxy silane, and diphenyl diethoxy silane.

In addition, the composite metal oxide of the present invention preferably includes a mixture of antimony tin oxide (ATO) and zinc oxide or a mixture of antimony oxide and tin oxide.

The particle size of the ATO of the present invention is preferably 60 to 80 nm.

The particle size of the zinc oxide, antimony oxide and tin oxide of the present invention is preferably 10 to 30 nm.

In addition, the present invention provides a titanium dioxide photocatalyst glass coating composition prepared according to the above production method.

The present invention also provides a glass substrate comprising a coating film made of the titanium dioxide photocatalyst glass coating composition on the glass substrate surface.

The titanium dioxide photocatalyst glass coating composition according to the present invention is a composite structure of titanium dioxide nanoparticles and a composite metal oxide using an inorganic binder and has an excellent anti-fouling and anti-fogging effect by increasing the range from the ultraviolet ray region to the visible ray region, It is possible to secure a clear clock of the glass, and the maintenance cost is remarkably reduced by simple maintenance. It also has transparency by transmitting light in the visible light region, and selectively blocks infrared and ultraviolet rays to provide insulation, protection of the human body and prevention of deterioration.

Hereinafter, the titanium dioxide photocatalytic glass coating composition according to the present invention and a method for producing the same will be described in detail.

A method for preparing a titanium dioxide photocatalytic glass coating composition according to the present invention comprises the steps of (a) mixing 27 to 33% by weight of titanium tetraisopropoxide (TTIP), 0.1 to 3% by weight of nitric acid and 60 to 70% Producing; (b) preparing an inorganic binder by mixing 1 to 10% by weight of an alkoxysilane compound, 1 to 3% by weight of methanol, 1 to 3% by weight of ethanol, 10 to 20% by weight of propanol and 60 to 80% by weight of isopropanol. (c) 40 wt% of an alkyl silicate oligomer solution and 27 wt% of a composite metal oxide were placed in a high-speed shear mixer and stirred for 1 to 2 minutes. Then, 2,2 ', 4,4'-tetrahydroxybenzophenone: (20:80) were added to a high-speed shear mixer and stirred for 1 to 2 minutes. 7% by weight of denatured ethanol was added and stirred for 1 to 2 minutes. Then, 20% by weight of butylcellosolve Followed by stirring for 1 to 2 minutes to prepare a composite metal oxide sol; (d) stirring the organic solvent and butyl cellosolve in a high-speed shear mixer for 1 to 2 minutes; (e) adding the titanium dioxide sol (a) to the stirring solution of (d) and stirring for 1 to 2 minutes; (f) The composite metal oxide sol of (c) is added to the stirring solution of (e), and the mixture is stirred for 1 to 2 minutes. After the inorganic binder of (b) is added, stirring is performed for 1 to 2 minutes to obtain a titanium dioxide photocatalyst And preparing a glass coating composition.

The titanium dioxide sol is prepared by mixing 27 to 33% by weight of titanium tetra-isopropoxide (TTIP) and 60 to 70% by weight of distilled water at a stirring speed of 200 to 400 rpm at 40 to 80 캜 for 2 to 8 hours, By weight, and stirring at 40 to 80 DEG C for 15 to 48 hours. In this case, distilled water acts as a catalyst to disperse TTIP and substitute alkoxy group (-OR) of TTIP with hydroxyl group (-OH), acts as a catalyst to control the reaction rate of silver nitrate synthesis, and acts as a peptizing agent in synthesis. In general, it is known that the rate of hydrolysis is high under an acidic catalyst and that the rate of polymerization is high under a basic catalyst. Since TTIP is a highly reactive transition metal, hydrolysis and polymerization rate . In addition, when the amount of nitric acid is small, the mutual repulsive force that disperses the colloidal particles is larger than the attractive force between the particles, which results in a relatively low viscosity value. When the amount of nitric acid is large, the aggregation of particles occurs, And the surface area is decreased. Therefore, it is preferable to add 0.1 to 3% by weight of nitric acid. If the reaction time is too short after the addition of the nitric acid, the peptization does not occur and the viscosity becomes high. If the reaction time is long, the gelation proceeds and the reaction time is preferably from 15 to 48 hours since it can not be used as a sol.

It is preferable that the particles of the titanium dioxide sol are of the Atanase type of 10 nm or less. Titanium dioxide has three structures, anatase, rutile and brookite. The anatase structure has superior photocatalytic activity to photodissociate contaminants present in water or air compared to rutile and brookite structures. In addition, when the particle size of the titanium dioxide sol is more than 10 nm, the particle size of the final titanium dioxide photocatalyst glass coating composition may increase, which is a problem in that the efficiency of the photocatalyst is inferior.

The inorganic binder is prepared by mixing 1 to 10 wt% of an alkoxysilane compound, 1 to 3 wt% of methanol, 1 to 3 wt% of ethanol, 10 to 20 wt% of propanol and 60 to 80 wt% of isopropanol, And stirring at a stirring speed of 1200 rpm for 20 to 120 minutes.

If the content of the alkoxysilane compound is less than 1% by weight based on the total weight of the inorganic binder, the hardness may be lowered and the durability may be decreased and the adhesion may be deteriorated. If it exceeds 10% by weight, . Therefore, it is preferable to add 1 to 10% by weight of the alkoxysilane.

Wherein the composite metal oxide is a component for blocking infrared rays and ultraviolet rays, and comprises 5 to 10% by weight of antimony tin oxide (ATO), 3 to 5% by weight of zinc oxide, 7 to 11% by weight of an alkoxysilane compound, 3 wt.% Of methanol, 1 to 3 wt.% Of methanol, 60 to 80 wt.% Of propanol, 1 to 3 wt.% Of isopropanol and 3 to 10 wt.% Of butyl cellosolve, 6 wt.% Of antimony oxide, By weight and 70% by weight of ethanol.

The alkyl silicate oligomer solution in step (c) is preferably mixed in an amount of 1 to 10% by weight of an alkyl silicate oligomer, 40 to 50% by weight of ethanol, 40 to 50% by weight of isopropanol and 0 to 5% by weight of acetic acid. The alkyl silicate oligomer may be selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, cyclohexyltri Examples of the silane coupling agent include methoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane allyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di Phenyl dimethoxy silane, and diphenyl diethoxy silane.

In the step (d), the organic solvent may be mixed in a proportion of 95 to 99% by weight of propanol, 0 to 5% by weight of isopropanol, 0 to 1% by weight of methanol and 0 to 1% by weight of ethanol.

The electrostatic repulsive force is induced on the surface of the silver nitrate particles to prevent agglomeration between the particles and to stabilize the titanium dioxide sol. In this case, the titanium dioxide sol preferably has a pH of 2 to 3.

The amount of the titanium dioxide sol is preferably in the range of 3 to 7.5% by weight, and if it is less than 3% by weight, adhesion of the titanium dioxide sol is reduced depending on the kind of the used substrate. If it exceeds 7.5% The components can damage the substrate.

In addition, the inorganic binder serves to decompose the organic material together with the photocatalyst and to increase durability and adhesion, and is preferably used in the range of 3 to 7.5% by weight. If the amount of the inorganic binder is less than 3% by weight, durability, stain resistance and adhesiveness to glass deteriorate. If the inorganic binder is more than 7.5% by weight, the amount of titanium dioxide and the composite metal oxide used for solar heat shielding decreases, There is a problem that the solar heat blocking effect is lowered.

In addition, the composite metal oxide sol is preferably used in an amount of 3 to 7.5% by weight. If it is less than 3% by weight, the solar heat shielding effect is reduced. If the amount exceeds 7.5% by weight, Is difficult to form.

The alkoxysilane compound plays a role of enhancing the adhesion, and is preferably a silane compound such as methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane , Allyltriethoxysilane, dimethyldiethoxysilane, and diphenyldiethoxysilane, and it is preferably an ethyl silicate polymer.

If the particle size of the ATO is less than 60 nm, the ATO particles aggregate due to self-cohesion after dispersing, and it is difficult to redisperse. When the particle size exceeds 80 nm, Which is irregular and interferes with the flow of the small particle size solution.

The particle size of the zinc oxide, antimony oxide and tin oxide is preferably 10 to 30 nm. If the particle size is less than 10 nm, it is not easy to handle during the formation of the sol. When the particle size exceeds 30 nm, There is a problem that the efficiency of the photocatalyst is lowered because the surface area per volume of the composite metal oxide is widened.

The present invention also relates to a titanium dioxide photocatalyst glass coating composition prepared according to the above process.

The present invention also relates to a glass substrate comprising a coating film made of the titanium dioxide photocatalyst glass coating composition on the glass substrate surface.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example

Manufacturing example  1: Production of titanium dioxide sol

355 ml of titanium tetra-isopropoxide (TTIP) and 800 ml of distilled water were mixed for 6 hours at a stirring rate of 200 rpm at 40 ° C., 2 to 3 ml of nitric acid was added, and the mixture was stirred at 40 ° C. for 48 hours to prepare titanium dioxide sol Respectively.

Manufacturing example  2: Manufacture of inorganic binders

8 wt% of alkoxysilane compound, 2 wt% of methanol, 2 wt% of ethanol, 13 wt% of propanol and 75 wt% of isopropanol were mixed and stirred at 60 ° C and 1000 rpm for 20 to 60 minutes to prepare an inorganic binder.

Manufacturing example  3: Preparation of composite metal oxide sol

1) Composite metal oxide sol A

40 wt% of an alkyl silicate oligomer solution mixed with 7 wt% of alkyl silicate oligomer, 45 wt% of ethanol, 45 wt% of isopropanol and 3 wt% of acetic acid, 8 wt% of antimony tin oxide (ATO) 27 weight% of composite metal oxide mixed with 4 weight% of zinc oxide, 8 weight% of alkoxysilane, 2 weight% of ethanol, 2 weight% of methanol, 67 weight% of propanol, 2 weight% of isopropanol and 7 weight% of butyl cellosolve The mixture was stirred for 2 minutes and then 6 wt% of a mixed solution of 2,2 ', 4,4'-tetrahydroxybenzophenone: denatured ethanol (20:80) was added to a high-speed shear mixer and stirred for 2 minutes. %, And the mixture was stirred for 2 minutes. Then, 20% by weight of butylcellosolve was added and stirred for 2 minutes to prepare a composite metal oxide sol A.

2) Compound metal oxide sol B

40 wt% of an alkyl silicate oligomer solution mixed with 7 wt% of an alkyl silicate oligomer, 45 wt% of ethanol, 45 wt% of isopropanol and 3 wt% of acetic acid, 6 wt% of antimony oxide, 24 wt% 27% by weight of a composite metal oxide mixed in an amount of 70% by weight was placed in a high-speed shear mixer and stirred for 2 minutes. 6% by weight of a mixed solution of 2,2 ', 4,4'-tetrahydroxybenzophenone: denatured ethanol (20:80) The mixture was stirred for 2 minutes, 7% by weight of denatured ethanol was added, and the mixture was stirred for 2 minutes. Then, 20% by weight of butylcellosolve was added and stirred for 2 minutes to prepare a composite metal oxide sol B.

Example

Example  One

84 wt% of an organic solvent and 3 wt% of butyl cellosolve mixed in a ratio of 97 wt% of propanol, 1 wt% of isopropanol, 1 wt% of methanol and 1 wt% of ethanol were put into a high-speed shear mixer and stirred for 2 minutes, 5% by weight of the titanium dioxide sol of Production Example 1 was added and stirred for 2 minutes. When the reaction was completed, 5% by weight of the composite metal oxide sol A of Preparation Example 3 was added and stirred for 2 minutes. Then, 3% by weight of the inorganic binder of Preparation Example 2 was added and stirred for 2 minutes to prepare a titanium dioxide photocatalyst glass coating composition .

Example  2

The procedure of Example 1 was repeated except that the titanium dioxide sol of Production Example 1, the inorganic binder of Production Example 2 and the composite metal oxide sol A of Production Example 3 were used at a weight ratio of 5: 5: 3 Respectively.

Example  3

The procedure of Example 1 was repeated except that the titanium dioxide sol of Preparation Example 1, the inorganic binder of Preparation Example 2 and the composite metal oxide sol A of Preparation Example 3 were used in a weight ratio of 3: 5: 5 Respectively.

Example  4

The procedure of Example 1 was repeated except that a composite metal oxide sol B was used in place of the composite metal oxide sol A of Production Example 3.

Example  5

The procedure of Example 4 was repeated except that the titanium dioxide sol of Preparation Example 1, the inorganic binder of Preparation Example 2 and the composite metal oxide sol B of Preparation Example 3 were used in a weight ratio of 5: 5: 3 Respectively.

Example  6

The procedure of Example 4 was repeated except that the titanium dioxide sol of Preparation Example 1, the inorganic binder of Preparation Example 2 and the composite metal oxide sol B of Preparation Example 3 were used in a weight ratio of 3: 5: 5 Respectively.

Comparative Example  One

82 wt% of an organic solvent and 3 wt% of butyl cellosolve mixed in a ratio of 97 wt% of propanol, 1 wt% of isopropanol, 1 wt% of methanol and 1 wt% of ethanol were put into a high-speed shear mixer and stirred for 2 minutes, 7.5% by weight of titanium dioxide sol of Production Example 1 was added and stirred for 2 minutes. When the reaction was completed, 7.5 weight% of the composite metal oxide sol A of Preparation Example 3 was added and stirred for 2 minutes.

Comparative Example  2

The same procedure as in Comparative Example 1 was carried out except that the inorganic binder of Production Example 2 was used instead of the composite metal oxide sol A of Production Example 3.

The component component ratios of Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 1 below.

Titanium dioxide sol (% by weight) Inorganic binder (% by weight) Composite metal oxide sol (wt%) Organic solvent (% by weight) Butyl cellosolve (% by weight) Example 1 5 3 5 84 3 Example 2 5 5 3 84 3 Example 3 3 5 5 84 3 Example 4 5 3 5 84 3 Example 5 5 5 3 84 3 Example 6 3 5 5 84 3 Comparative Example 1 7.5 - 7.5 82 3 Comparative Example 2 7.5 7.5 - 82 3

Experimental Example  1: Evaluation of optical characteristics

In order to evaluate the optical properties of the titanium dioxide photocatalyst glass coating composition according to the present invention, the transmittance for visible light and near-infrared light was measured using a UV-vis spectrometer. The titanium dioxide photocatalytic glass coating composition prepared in Examples 1 to 6 and Comparative Examples 1 and 2 was applied to the glass surface twice repeatedly so as to sufficiently wet the glass surface, followed by drying in the air for 10 minutes. The transmittance of visible light (530 nm) and near-infrared light (980 nm) were measured on a glass coated and uncoated glass coated with a titanium dioxide photocatalyst glass coating composition using a UV-vis spectrometer and the results are shown in Table 2 below .

Visible light (530 nm) Transmittance (%) Near infrared (980 nm) transmittance (%) Example 1 82.7 43.1 Example 2 84.6 52.2 Example 3 87.3 49.5 Example 4 81.5 43.8 Example 5 84.8 53.6 Example 6 86.9 48.8 Comparative Example 1 81.7 50.3 Comparative Example 2 82.2 72.1

In Table 2, it can be seen that Examples 1 to 6 and Comparative Example 1 have a far lower infrared transmittance than Comparative Example 2 because of the addition of the composite metal oxide. Also, in Examples 1 to 6 and Comparative Examples 1 and 2, visible light transmittance was excellent, and it was found that even when a composite metal oxide and an inorganic binder were added, excellent visible light transmittance of titanium dioxide was maintained and transparency was obtained .

Experimental Example  2: Super hydrophilic  Character rating

The contact angle was measured using a contact angle meter (Phoenix 300, SEO) to evaluate the superhydrophilicity of the titanium dioxide photocatalyst glass coating composition according to the present invention. The contact angle was measured by dropping water droplets on the glass surface coated with the titanium dioxide photocatalyst glass coating composition prepared in the same manner as in Experimental Example 1. The measured values are shown in Table 3 below.

Contact angle (°) Glass surface 51.80 Example 1 3.92 Example 2 3.61 Example 3 3.84 Example 4 3.89 Example 5 3.74 Example 6 3.85 Comparative Example 1 23.43 Comparative Example 2 3.69

 Superhydrophilic property is a property of making a thin film without making water droplets even when the surface is wet, and generally refers to when the contact angle is 5 ° or less. On the other hand, depending on the contact angle, hydrophilicity can be divided into 30 ° or less, hydrophobicity 60 to 90 °, water repellency 90 ° or more, and super water repellency 150 ° or more. As shown in Table 3, in Examples 1 to 6 and Comparative Example 2, the hydrophilic property was increased due to the addition of the inorganic binder, the contact angle was all less than 5 °, the coated glass surface exhibited superhydrophilic property, and the inorganic binder was not added In Comparative Example 1, in which the hydrophilic titanium dioxide was coated on the surface of the glass, it was confirmed that the contact angle was 30 ° or less, indicating hydrophilicity.

Experimental Example  3: Evaluation of stain resistance effect

In order to evaluate the stain resistance effect of the titanium dioxide photocatalytic glass coating composition according to the present invention, a carbon black stain evaluation test showing a test result similar to outdoor exposure contamination was conducted. A 5% carbon black solution in which carbon black was added to ethanol and dispersed by ultrasonic treatment was applied to a glass surface coated with a titanium dioxide photocatalyst glass coating composition prepared in the same manner as in Experimental Example 1 by air spraying and then dried at 80 ° C for 2 hours After washing with water, the color change was confirmed. The color change was measured with a minimum score of 0 and a maximum score of 5 according to the degree of color change, and the results are shown in Table 4 below.

Degree of color change Example 1 1.5 Example 2 0.8 Example 3 1.0 Example 4 1.6 Example 5 1.1 Example 6 0.9 Comparative Example 1 2.9 Comparative Example 2 1.2

As shown in Table 4, Examples 1 to 6 and Comparative Example 2 showed excellent stain resistance due to the use of an inorganic binder and showed almost no change in hue. In Comparative Example 1, inorganic binders were not added It was confirmed that the stain resistance effect was somewhat low. From the above results, it can be seen that the inorganic binder increases the stain resistance effect and has an excellent antifouling effect on the coated glass.

Experimental Example  4: Photocatalyst  Activity evaluation

In order to evaluate the photocatalytic activity of the titanium dioxide photocatalytic glass coating composition according to the present invention, organic decomposition experiments were conducted under visible light. Formaldehyde, one of representative indoor contaminants, was selected as the organic material. A 100 ppm formaldehyde solution was applied to the glass surface coated with the titanium dioxide photocatalyst glass coating composition prepared in the same manner as in Experimental Example 1 by air spray and irradiated with light using a 300 W xenon lamp (Oriel instruments). At this time, the light activation in the visible light region was confirmed by using a UV filter which cuts off ultraviolet rays of 420 nm or less. The concentration of carbon dioxide produced by the decomposition of formaldehyde by the visible light photocatalytic reaction was measured for 2 hours at intervals of 20 minutes using gas chromatography (Agilent 6890N, Agilent Technologies). The results are shown in Table 5 below.

Concentration of produced carbon dioxide (ppm) Example 1 10.82 Example 2 9.23 Example 3 10.37 Example 4 9.98 Example 5 8.54 Example 6 10.15 Comparative Example 1 9.51 Comparative Example 2 2.41

As shown in Table 5, Examples 1 to 6 and Comparative Example 1 exhibited high photocatalytic efficiency under visible light due to the activity in the visible light region due to the addition of the composite metal oxide. On the other hand, in Comparative Example 2, the composite metal oxide was not added and the photocatalytic activity was low in the visible light region.

Experimental Example  5: Attachment  evaluation

In order to evaluate the adhesion of the titanium dioxide photocatalyst glass coating composition according to the present invention, the glass surface coated with the titanium dioxide photocatalyst glass coating composition prepared in the same manner as in Experimental Example 1 was cut at intervals of 1 mm, A peeling test was conducted by repeating the operation of attaching a cellophane tape to the glass surface and abruptly peeling it off five times. The results are shown in Table 6 below. ≪ tb > < TABLE > Id = Table 6 Columns = 6 < tb >

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Attachment ○ ○ ○ ○ ○ ○ △ ○

As shown in Table 6, in Examples 1 to 6 and Comparative Example 2, it was confirmed that the degree of adhesion with glass was improved due to the addition of an inorganic binder and that it had excellent adhesion. In Comparative Example 1, It can be seen that the adhesiveness is somewhat deteriorated.

Claims (11)

(a) mixing 29.9 to 33% by weight of titanium tetra-isopropoxide (TTIP), 0.1 to 3% by weight of nitric acid and 65 to 70% by weight of distilled water to prepare a titanium dioxide sol;
(b) preparing an inorganic binder by mixing 6 to 10% by weight of an alkoxysilane compound, 1 to 3% by weight of methanol, 1 to 3% by weight of ethanol, 12 to 20% by weight of propanol and 65 to 80% by weight of isopropanol.
(c) 40 wt% of an alkyl silicate oligomer solution and 27 wt% of a composite metal oxide were placed in a high-speed shear mixer and stirred for 1 to 2 minutes. Then, 2,2 ', 4,4'-tetrahydroxybenzophenone: (20:80) were added to a high-speed shear mixer and stirred for 1 to 2 minutes. 7% by weight of denatured ethanol was added and stirred for 1 to 2 minutes. Then, 20% by weight of butylcellosolve Followed by stirring for 1 to 2 minutes to prepare a composite metal oxide sol;
(d) stirring the organic solvent and butyl cellosolve in a high-speed shear mixer for 1 to 2 minutes;
(e) adding the titanium dioxide sol (a) to the stirring solution of (d) and stirring for 1 to 2 minutes;
(f) The composite metal oxide sol of (c) is added to the stirring solution of (e), and the mixture is stirred for 1 to 2 minutes. After the inorganic binder of (b) is added, stirring is performed for 1 to 2 minutes to obtain a titanium dioxide photocatalyst Preparing a glass coating composition,
Wherein the composite metal oxide comprises a mixture of antimony tin oxide (ATO) and zinc oxide or a mixture of antimony oxide and tin oxide.
The method according to claim 1,
Wherein the alkyl silicate oligomer solution in step (c) is mixed in an amount of 5 to 10 wt% of an alkyl silicate oligomer, 44 to 50 wt% of ethanol, 40 to 50 wt% of isopropanol, and 1 to 5 wt% of acetic acid Method for producing titanium dioxide photocatalyst glass coating composition
The method according to claim 1,
Wherein the organic solvent in the step (d) is mixed in a ratio of 95 to 99% by weight of propanol, 1 to 5% by weight of isopropanol, 0 to 1% by weight of methanol and 0 to 1% by weight of ethanol, Method for producing coating composition
The method according to claim 1,
Wherein the titanium dioxide sol has a pH of from 2 to 3, and a method of producing the titanium dioxide photocatalyst glass coating composition
The method according to claim 1,
The titanium dioxide photocatalyst glass coating composition comprises 4 to 7.5% by weight of titanium dioxide sol, 3 to 7.5% by weight of inorganic binder, 3 to 7.5% by weight of composite metal oxide sol, 82 to 87% by weight of organic solvent and 3% By weight based on the total weight of the titanium dioxide photocatalyst glass composition.
The method according to claim 1,
The alkoxysilane compound may be at least one selected from the group consisting of methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, dimethyldiethoxy Silane, and diphenyldiethoxysilane. ≪ RTI ID = 0.0 > 8. < / RTI >
delete The method according to claim 1,
Wherein the ATO has a particle size of 60 to 80 nm.
The method according to claim 1,
Wherein the particle size of the zinc oxide, antimony oxide and tin oxide is 10 to 30 nm.
A titanium dioxide photocatalytic glass coating composition prepared according to the manufacturing method according to any one of claims 1 to 6, 8 and 9
A glass substrate comprising a coating film made of a titanium dioxide photocatalyst glass coating composition according to claim 10 on a glass substrate surface