KR101467836B1 - Paint composition containing porous composite compound - Google Patents

Abstract

The present invention relates to a paint composition containing a porous composite compound and a process for producing the same.
Further, a method for producing a porous composite compound contained in the paint composition is a method of forming a porous silica-coated body having a three-dimensional net structure by covering a metal oxide with a silica airgel. This makes it possible to provide a heat insulating paint excellent in heat insulating performance while maintaining a high photocatalytic activity.

Description

[0001] The present invention relates to a paint composition containing a porous composite compound,

The present invention relates to a paint composition containing a porous composite compound, and more particularly, to a paint composition having a composite function such as a decontamination function, an adiabatic function and the like by containing a porous silica-coated body as a three- .

Photocatalyst is a substance that receives light and promotes a chemical reaction. For example, titanium dioxide (TiO ₂₎ A method in which a photocatalyst powder is directly used or a binder is added to a powder to form a coating on a support or a carrier and a method in which a titanium compound such as titanium tetrachloride or titanium alkoxide is coated on a support, A method of forming an anatase-type titanium dioxide thin film on the surface of a support using a gel method, and the like. In order to use titanium dioxide powder itself as a photocatalyst, powdered titanium dioxide mixed with anatase or anatase and rutile crystal structure should be synthesized through a sulfuric acid method and a chlorine method as a primary material. The titanium dioxide powder thus prepared is used in the form of a slurry or surface-coated on a support.

However, metal oxides such as titanium dioxide, when blended with other materials, become stiff and whitish and flocculate, and because of the activity of photocatalysts that decompose most organic materials and decompose into carbon dioxide and water, There is a problem that the crystal structure is deformed at a high temperature, and thus the application is limited in the industrial field.

This problem also occurs in functional paints containing photocatalysts. Recently, it has been known that cement, wallpaper, flooring material, paint, etc. used in residential environment release various toxic volatile organic compounds to act as a main cause of respiratory diseases and atopic diseases, There is an increasing demand for functional paints having resolution, purification, antibacterial, deodorization, and antifouling functions. In order to impart functionality to paints according to this tendency, materials having photocatalytic activity such as titanium dioxide are used. However, since the photocatalyst tends to cause aggregation and oxidize and destroy the binder contained in the paint, It is difficult to contain a photocatalyst. When such a low-level photocatalyst is contained, there is a problem in that the photocatalytic activity under the condition of substantially no light is insufficient.

In addition, conventional functional paints have only focused on functions such as decomposition and purification of the above-mentioned harmful substances. Paint having an adiabatic function has not yet been developed, and in the case of conventional functional paints having a heat insulating function, , Acrylic emulsion, calcium carbonate, emulsion resin, etc., so that even if the heat insulating effect is exhibited, the problem of releasing harmful substances can not be solved.

Therefore, in order to provide functions such as decomposition and purification of harmful substances excellent in paint and functions such as heat insulation, it is necessary to develop materials having excellent dispersibility and stability while maintaining high photocatalytic activity and heat insulation.

Disclosure of Invention Technical Problem [8] The present invention is to solve the problems of the conventional paint as described above, and it is an object of the present invention to provide a photocatalytic coating composition which is excellent in dispersibility and stability, It is an object of the present invention to provide a functional paint excellent in degradation of harmful substances and antibacterial function even in a small environment. Particularly, it is an object of the present invention to provide a paint composition containing a porous composite compound that maintains a high harmful substance decomposition function and at the same time has excellent heat insulating function.

(a) In order to achieve the above object, the present invention provides a process for producing a mixture of metal oxides on a sol by mixing any one of water glass (Na ₂ SiO ₃ ), potassium silicate, calcium silicate and silica sol with metal oxide ;

(b) gelling the mixture of metal oxides to form a metal oxide gel;

(c) surface modifying the metal oxide gel;

(d) drying the metal oxide gel to form a porous composite compound coated with a silica airgel around the metal oxide; And

and (e) calcining the porous composite compound. The present invention also provides a paint composition containing the porous composite compound.

 According to the above production method, the porous composite compound can be formed into a three-dimensional network structure porous silica clad body in which a metal oxide is mixed with water glass to be gelled and a silica airgel is coated around the metal oxide.

The silica airgel coated around the metal oxide has a structure in which spherical silica particles having a size of 2 to 5 nm are combined to form a three-dimensional network-like cluster to form a porous structure having nano unit pores. Accordingly, the present invention can be manufactured by coating an airgel with silica having a low thermal conductivity around the metal oxide, thereby improving the porosity and providing excellent thermal stability.

In addition, at the same time, since it has a three-dimensional net structure, it solves the problem that light is blocked by silica and reaches the inner photocatalyst, so that the photocatalytic activity can be maintained without lowering the activity, the specific surface area is widened, And the aggregation between the photocatalyst particles is prevented, and the dispersibility is improved. In this way, the 3-dimensional porous silica gel is coated on the periphery of the photocatalyst to prevent the photocatalyst from contacting with the organic support and the binder. Thus, the decomposition of the organic support and the binder, which were problems in the conventional photocatalyst, is prevented. A schematic view of the porous composite compound prepared by the production method of the present invention is shown in Fig. As shown in FIG. 1, silica airgel (SiO ₂ ) covers the periphery of a metal oxide such as titanium dioxide (TiO ₂ ).

Further, the porous composite compound produced by the production method of the present invention can be coated with a silica airgel to further contain Si so that a component such as expensive Ti can be contained in a significantly smaller amount than a compound having a conventional commercial photocatalytic activity . Therefore, the manufacturing cost can be reduced compared to the conventional compound having photocatalytic activity.

The porous composite compound produced by the above production method may have a three-dimensional net structure. The metal oxide used in the step (a) is preferably an oxide having photocatalytic activity, and examples thereof include TiO ₂ , ZnO ₂ , ZnO, SrTiO ₃ , CdS, GaP, InP, GaAs, BaTiO ₃ , KNbO ₃ , Fe ₂ O ₃ , Ta ₂ O ₅ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , NiO, Cu ₂ O, SiO ₂ , SiO ₂ , MoS ₂ , InPb, RuO ₂ and CeO ₂ . When titanium dioxide (TiO ₂ ) is used, titanium dioxide itself may be used, or a visible light photocatalyst produced by doping titanium dioxide with an anion such as nitrogen, sulfur, fluorine, or carbon may be used. Titanium dioxide is harmless to the human body, has excellent photocatalytic activity, has superior light corrosion resistance and is inexpensive.

In addition, a metal such as Pt, Rh, Ag, Cu, Sn, Ni and Fe may be added to the metal oxide, and another metal oxide may be added to the metal oxide to be used as a composite metal oxide. Titanium intermediates such as Ti (OH) ₄ , TiO (OH) ₂ can also be used.

In the step (a), any one of the metal oxide, the water glass, the potassium silicate, the calcium silicate, and the silica sol may be at least one selected from the group consisting of the silica contained in the metal oxide and the water glass, potassium silicate, calcium silicate, Is preferably mixed so as to have a weight ratio of 0.01 to 10: 1, and the metal oxide may further include a step of treating the metal oxide with a modifier to increase the -OH bonding force between the silica and the metal oxide. As the metal oxide modifier, a solution obtained by diluting an acid such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid, polycarboxylic acid, etc. or a base such as sodium hydroxide or ammonia water with water or hydrogen peroxide water may be used. It is preferable to treat them. Then, the mixed solution of the metal oxide and the water glass is strongly stirred to prepare a mixed sol.

The metal oxide gel of step (b) may be formed by adding an acidic solution having an acidity of pH 1 to 10 to a mixture of metal oxides to gel. At this time, hydrochloric acid, sulfuric acid, nitric acid or the like may be diluted in a solvent, and methanol, ethanol, butanol, isopropanol or the like may be mixed with water as a solvent. In addition, the temperature or stirring speed of the process can be adjusted to control the gelation rate and uniformity.

The surface modification of step (c) may be performed by adding a metal oxide gel into an organic solvent and adding an organic silane. As the organic solvent, ethanol, butanol, hexane and the like can be used. The organosilane may be selected from the group consisting of trimethylchlorosilane (TMCS), hexamethyldisilazane (HNDS), methyltrimethoxysilane, and trimethylethoxysilane. It is preferable that the wetting gel of the metal oxide obtained through the steps (a) and (b) is put into an organic solvent and the surface is modified by adding a certain amount of organosilane. Also, the rate of modification and the hydrophobicity of the surface can be controlled by adjusting the amount of the organic solvent or organosilane added.

In the step (d), the metal oxide gel is preferably dried at 60 to 200 ° C in a drying oven at a normal pressure for 1 to 24 hours, and dried at a temperature and for a time within the range to obtain a desired pore size of the metal oxide. If the temperature is raised rapidly to a temperature higher than the above temperature range or if it is dried at a higher temperature than the above range for a long time, porosity may be lost.

Also, supernatant drying can be used for drying. When dried by supercritical drying, there is almost no surface tension and the product is not damaged.

The method for preparing the porous composite compound may further include the step (e) of calcining the porous composite compound after the step (d). The hydrophilic and hydrophobic properties of the compound can be controlled by firing the porous composite compound. The calcination of the porous composite compound in step (e) is preferably performed at a calcination temperature of 400 to 800 ° C for 1 to 24 hours. This is because by removing the organic matter that makes hydrophobic on the silica gel surface, the hydrophilic property can be maintained while maintaining the pores and the skeleton. If the temperature is lower than the above range, the organic material is not removed and thus has hydrophobicity. If the temperature is higher than the above range, the skeleton may be shrunk and the product may be damaged.

On the other hand, the porous composite compound produced by the above production method can be a porous silica-coated body having a three-dimensional net structure by covering the metal oxide with a silica airgel. The porous composite compound preferably has a porosity of 80 to 99% from the viewpoint of having sufficient heat insulation against air. In addition, the crystal phase is anatase, and the particle size may be 10 to 30 nm.

The porous composite compound of the present invention preferably has a specific surface area of 300 to 1000 m ² / g, more preferably 400 to 800 m ² / g.

In addition, the porous composite compound of the present invention can control hydrophilicity and hydrophobicity by firing, and it is possible to chemically adjust the amount of the solvent, the kind of the surface modifier, the mixing ratio of titanium oxide and water glass, Pore size and density can be controlled.

Further, the paint composition containing the porous composite compound may further contain a binder. As the binder, an organic binder, an inorganic binder, or a combination thereof may be used.

For example, organic adhesives such as acrylics, epoxy resins, polysiloxanes, fluorinated polymers, silicone-based polymers and the like and silicon compounds such as silicates, colloidal silicas, polyorganosiloxanes and the like, phosphates such as zinc phosphate, aluminum phosphate, Inorganic adhesives such as lime, gypsum, enamel frits, glass lining glazes, plasters may be used. Plasters used are, for example, gypsum plaster, plaster, dolomite and the like. The fluorinated polymers used are, for example, fluorinated polyvinyls, fluorinated polyvinylidene, trifluorofluorinated chlorinated polyethylene, tetrafluorinated polyethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluorinated ethylene-polyethylene A perfluorocyclopolymer, a vinyl ether-fluoroolefin copolymer, a vinyl ether-fluoroolefin copolymer, a fluoroethylene-perfluoroalkyl vinyl ether copolymer, a fluoroethylene-perfluoroalkyl vinyl ether copolymer, Vinyl ester-fluoroolefin copolymers, various fluorinated elastomers, and the like. Silicone based polymers used include linear silicone resins, acrylic modified silicone resins, and various silicone elastomers.

The porous composite compound is preferably contained in an amount of 0.001 to 50% by weight based on the total weight of the binder.

In addition, the paint composition containing the porous composite compound of the present invention further comprises at least one pigment. Color pigments are classified into inorganic pigments and organic pigments. The inorganic pigment is an inorganic substance with a coloring component, and many colors are bright and clear, but the hiding power is great and the heat resistance / light fastness is excellent. Organic pigments are classified as natural pigments and synthetic pigments. They are relatively low in physical properties such as heat resistance and light resistance, but have a wide range of color, clear color, There are advantages. Since the pigments differ in color tone, sharpness, hiding power, tinting strength or fastness, the pigments in the present invention are not limited to any one, and two or more pigments may optionally be used in combination . The pigment forms an opaque colored film on the surface of the object in powder state, whereas the dye dissolves in water and oil, is dispersed as monomolecules, and binds to molecules and is colored. This dye (dye) is used as a coloring agent.

In the present invention, the weight ratio of the pigment and the dye may be optionally varied. In addition, various other compounds may be added to the paint composition of the present invention if necessary, but these additives are preferably added to such an extent that they do not impair the shelf life, photoactivity, durability or non-coloring property of the paint. Examples of such additive compounds include filler (s) such as quartz, calcite, clay, talc, barite and / or Na-Al-silicate; Pigments such as non-photocatalytic TiO ₂ , lithopone and other inorganic pigments; Dispersing agents such as polyphosphates, polyacrylates, phosphonates, naphthenes and ligninsulfonates; Wetting agents including cationic, anionic, amphoteric and / or nonionic surfactants; Defoamers such as silicone emulsions, hydrocarbons and long chain alcohols; Stabilizers comprising most of the cationic compounds; Coagulants including alkali-stable esters, glycols and hydrocarbons; Such as cellulose derivatives (e.g., carboxymethylcellulose or hydroxylethylcellulose), xanthan gum, polyurethanes, polyacrylates, modified starches, bentones and other lamellar silicates. Additive; Water repellents such as alkyl silicates, siloxanes, wax emulsions, fatty acid Li salts; Conventional bactericides or insecticides may be included.

The porous composite compound of the present invention is characterized in that the metal oxide is coated with the three-dimensional porous silica airgel around the metal oxide while maintaining the activity of the high photocatalyst of the metal oxide, so that the metal oxide does not contact the organic support and the binder directly. It is possible to prevent the decomposition of the organic support and the binder, which are problems, as well as to improve the adhesion of the silica itself to prolong the life of the composition. Therefore, when such a porous composite compound is contained in a paint composition, there is no deformation of the composition itself, and agglomeration is prevented. The coating film is not peeled off even after drying, and is harmless to the human body.

In addition, the porous composite compound contained in the paint composition of the present invention is coated with the silica airgel having a three-dimensional network structure around the metal oxide, thereby enlarging the specific surface area, thereby effectively removing harmful substances from the conventional photocatalyst powder. Particularly, it can effectively decompose environmental pollutants such as nitrogen oxides (NO _x ) and sulfur oxides (SO _x ) and substances such as TVOC, formaldehyde and ammonia. Therefore, when such a porous composite compound is contained in a paint composition, it is possible to make an environmentally-friendly functional building and facility which is harmless to human body and has a function of decomposing pollutants, air purification and deodorizing function when used in medical institutions, houses, water and sewage treatment facilities.

Furthermore, since the porous composite compound contained in the paint composition of the present invention is coated with a silica airgel around the metal oxide in a three-dimensional network structure, heat reflection and heat resistance effects are generated therefrom, and a high melting point and high durability are obtained It exhibits excellent insulation effect. Therefore, when it is used in a building, the cooling and heating cost reduction effect can be obtained by preventing the indoor heat loss and preventing condensation. In addition, the ultraviolet ray shielding effect can suppress the increase in the sensation temperature and can also suppress the aging of the paint.

The heat insulating paint using the paint composition containing the porous composite compound of the present invention can be produced by a conventional method for producing a paint. For example, the porous composite compound according to the present invention may be mixed with 0.001 to 50% by weight of binder, other additives including pigments and dyes, and water in relation to the total weight of the binder to prepare a paint composition, And the mixture is shaken for 3 hours in the vessel, and sufficient mixing is carried out and dispersed to prepare an insulating paint.

Meanwhile, the porous composite compound according to the present invention can easily control hydrophilicity and hydrophobicity due to firing, and therefore, it is possible to provide a paint having a hydrophobic surface by containing it in a paint composition. As a result, hydrophilicity and hydrophobicity can be controlled depending on the purpose and function of the paint. Accordingly, it is possible to provide a hydrophobic paint composition having water-repellent properties that do not allow water to be impregnated even when water is added by controlling the firing temperature.

According to the present invention, there is provided a paint composition containing a porous composite compound having a high specific surface area and excellent photocatalytic activity and having a high dispersibility by forming a porous silica covering body having a three-dimensional network structure by covering a silica airgel around the metal oxide, A method for producing a porous composite compound is provided. In addition, the composite compound of the porous silica covering material produced by the production method according to the present invention can have a high porosity, and thus can provide very excellent heat insulating performance to the paint composition.

In addition, according to the present invention, there can be provided a paint composition containing a porous composite compound excellent in the harmful component removing effect and a method for producing the same. The porous composite compound according to the present invention can be effectively mixed with other substances contained in the paint composition because it can prevent agglomeration without decomposing the composition of other organic compounds by coating silica airgel. Therefore, they are uniformly mixed and have excellent stability, Harmless and environmentally friendly paint can be provided.

1 is a schematic view of a porous composite compound according to an embodiment of the present invention.
FIG. 2 is a photograph of a porous composite compound according to an embodiment of the present invention taken by SEM (scanning electron microscope, Hitachi S-4700) and TEM (transmission electron microscope, JEM 2000 FXII, JEOL).
FIG. 3 is a graph showing an X-ray diffraction pattern of a porous composite compound according to an embodiment of the present invention and a crystalline phase of a comparative example.
FIG. 4 is a graph showing the results of measurement of the amount of adsorbed nitrogen according to the atmospheric pressure of the porous composite compound according to Comparative Example and one embodiment of the present invention.
FIG. 5 is a graph showing the results of measurement of the photocatalytic activity of the porous composite compound according to one embodiment of the present invention and the acetaldehyde photocatalytic activity of the comparative example.
6 is a view schematically showing a nitrogen oxides (NOx) removal test evaluation device.
7 is a graph showing a result of removal of NOx by a porous composite compound according to an embodiment of the present invention.
FIG. 8 is a graph showing the results of acetaldehyde removal of a paint containing a porous composite compound according to an embodiment of the present invention. FIG.
FIG. 9 is a view showing a color shift result of a paint containing a porous composite compound according to an embodiment of the present invention.
10 is a graph showing an adiabatic evaluation of a paint containing a porous composite compound according to an embodiment of the present invention.

Hereinafter, the present invention will be described with reference to the following examples. The examples are intended to further illustrate the present invention and are not intended to limit the scope of the present invention.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope of the invention.

Example  One

Hereinafter, a process for preparing a porous composite compound according to an embodiment of the present invention will be described.

12 g of titanium dioxide (TiO ₂ ) powder treated with aqueous hydrogen peroxide was added to 200 g of commercial water glass (containing 30 wt% of SiO ₂ ) and stirred to prepare a titanium dioxide mixed sol. The acidity was adjusted to pH 7 by adding a small amount of an aqueous sulfuric acid solution. The resulting wet gel is then washed several times with hot water to remove any sodium that remains on the wet gel, and then dehydrated and separated. To the obtained wet gel, trimethylchlorosilane (TMCS) was added so that the weight ratio of n-hexane to the wet gel was 4, the weight ratio of the wet gel was 2 so that the weight ratio of ethanol was 1, and the surface was modified at room temperature for 5 hours . Thereafter, the product is separated and recovered, and the product is placed in a drying oven under atmospheric pressure, and dried at 60 ° C for 12 hours and at 200 ° C for 12 hours to prepare a porous composite compound having a titanium dioxide and silica weight ratio of 0.2.

Example  2

The following describes the preparation of the porous composite compound according to another embodiment of the present invention. Description of the same contents as the first embodiment described above will be omitted.

Except that 24 g of titanium dioxide (TiO ₂ ) treated with aqueous hydrogen peroxide was added to 200 g of commercial water glass (containing 30 wt% of SiO ₂ ) to obtain a porous composite compound having a weight ratio of titanium dioxide and silica of 0.4 .

Example  3

The following describes the preparation of the porous composite compound according to another embodiment of the present invention. Description of the same contents as the first embodiment described above will be omitted.

A porous composite compound having a weight ratio of titanium dioxide and silica of 0.8 was prepared in the same manner as in Example 1, except that 48 g of titanium dioxide (TiO ₂ ) treated with hydrogen peroxide was added to 200 g of commercial water glass (SiO ₂ 30 wt%). .

Example  4

The following describes the preparation of the porous composite compound according to another embodiment of the present invention. Description of the same contents as the first embodiment described above will be omitted.

Except that 72 g of titanium dioxide (TiO ₂ ) treated with aqueous hydrogen peroxide was added to 200 g of commercial water glass (SiO ₂ 30 wt%) to obtain a porous composite compound having a weight ratio of titanium dioxide and silica of 1.2, .

Comparative Example

Hereinafter, in order to more clearly illustrate the characteristics of the embodiments of the present invention, the photocatalyst materials used in the prior art will be described as comparative examples and compared with the embodiments of the present invention.

As a comparative example, P-25 powder of EVONIK Industries was used as a titanium dioxide (TiO ₂ ) powder not coated with a silica airgel.

Table 1 below shows the compositions of Example 1 according to the present invention and Comparative Examples. The content of each compound was analyzed by EDX (Energy dispersive X-ray spectroscope; Horiba, EX-250).

ingredient Comparative Example Example 1 weight% atom% weight% atom% C K 16.0 25.5 17.7 25.7 O K 52.0 61.8 47.7 52.5 Na K - - 0.2 0.1 Si K - - 34.2 21.6 S K - - - - Ti K 32.0 12.7 0.2 0.1 total 100.0 100.0 100.0 100.0

2A and 2B show photographs of Example 1 of the present invention taken by SEM (scanning electron microscope, Hitachi S-4700) and TEM (transmission electron microscope, JEM 2000 FXII, JEOL). As shown in FIG. 2A, the porous photocatalyst powder particles are 10 to 30 nm in size, and the particles are intertwined with each other to form a hole having a diameter of about 10 to 50 nm. In addition, we can see that they are making big tangles (B).

Crystalline phase and thermal stability analysis

The crystal phases of Example 4 and Comparative Example were analyzed by X-ray diffraction pattern (XRD) in order to compare the crystal phase of the composite compound, and it is shown in Fig. In order to confirm the thermal stability, the results of annealing at 200 to 1000 ° C in an oxygen atmosphere are also shown.

In the case of the comparative example, the anatase diffraction peak appears to be large and pointed, whereas in Example 4, the diffraction peak of Example 4 is smaller and wider than that of the comparative example. Therefore, it can be seen that the particles of the titanium dioxide of the present invention are smaller. It is well known that conventional titanium dioxide is converted to an rutile crystal structure from an anatase by calcination at 800 ° C. However, in the case of the present invention, only the peak of anatase was observed even after the heat treatment was performed up to 800 ° C. As a result, it is confirmed that the present invention has a high porosity by coating titanium dioxide with a silica airgel.

Photocatalyst  Active 1

Prior to the measurement of the photocatalytic activity, the specific surface area (m ² / g) of Examples 1 to 4 and Comparative Example of the present invention and the average pore size are shown in Table 2 below.

Surface area m ² / g Average pore size (nm) Comparative Example 55 8 Example 1 408 4 Example 2 406 4 Example 3 350 4 Example 4 141 4

As shown in Table 2, the specific surface area of the comparative example is as small as 55 m ² / g. However, in the case of Examples 1 to 4 of the present invention, it is 3 to 8 times as wide as that of Comparative Example. Further, as the amount of titanium dioxide added increases from Example 1 to Example 4, the specific surface area decreases. The average pore size is widely known to be comparable to the absence of pores in the particles.

Meanwhile, in order to compare the effect according to the specific surface area and the pore size, the amount of adsorbed nitrogen according to the comparative example and the pressure of Example 1 of the present invention was measured and shown in FIG. As shown in the graph of FIG. 4, in the comparative example, the amount of nitrogen adsorbed by the increase of the atmospheric pressure sharply increases from P / P ₀ of about 0.8 or more, and the maximum amount of adsorbed nitrogen is only about 300 cm ³ / g. However, in the first embodiment of the present invention, the amount of nitrogen adsorbed increases with the increase of atmospheric pressure, and the amount of nitrogen adsorbed at the maximum is also about 600 cm ³ / g. In the case of the present invention, since titanium dioxide is coated with a silica airgel to form a porous silica covering body, the specific surface area is about 6 times larger and the average pore diameter is smaller by 1/2 than that of the comparative example, I can do it.

Photocatalyst  Active 2

As an activity of the photocatalyst, an experiment for measuring the acetaldehyde decomposing activity of the complex compound is carried out.

First, 0.5 g of each of Examples 1 to 4 and Comparative Example of the present invention was charged as a catalyst in a 2 L reactor, and then 2000 ppm of acetaldehyde was introduced and equilibrium adsorption was carried out. Then, UV (10W x 3ea) (Sankyodenki) lamps were irradiated for 2 hours and analyzed by gas chromatograph (HP 6890) and FID detector. The results are shown in Fig.

As shown in FIG. 5, the initial activity of the comparative example is low, but the activity increases with time, and after about 2 hours, the degradation performance is about 98%. And in the case of the present invention, the initial activity is extremely high, about 70%, except for Example 4. The activity of 96, 92, 88 and 85% in the order of Example 1> Example 2> Example 3> Example 4 according to elapse of time.

In the comparative example, as shown in the composition table of Table 1, Ti is contained in an amount significantly higher than that of Examples 1 to 4 of the present invention by 32.0% by weight based on the total weight of the composition. Therefore, when comparing the content of titanium dioxide contained per unit g, the results of FIG. 5 indicate that the first photocatalytic activity of Example 1 is higher than that of the comparative example, and the photocatalytic activity of the photocatalyst is about 5 times higher.

Measurement of Removal Effect of Harmful Substances in Porous Composites (Nitrogen Oxides)

In order to measure the removal effect of nitrogen oxides (NO _x ) among harmful substances of the porous composite compound according to an embodiment of the present invention, a KS L ISO 22197-1 nitrogen oxide removal test evaluation device is used (FIG. 6).

In the experiment of the porous composite compound (Example 1) and the comparative example according to the embodiment of the present invention, the concentration of nitrogen oxide was changed by a method of 0.5 hours (light interception) -3 hours (UV irradiation) -0.5 hours .

The results of measuring the degree of nitrogen oxide removal of the powders of Example 1 and Comparative Example are shown in FIG. Only by from general compound of Comparative Example powders time examining the UV NO concentrations fall gradually increased to 0.45 ppm not stay in the 0.6 ppm Murray having a photocatalytic activity, it is relatively NO ₂ a significant amount generated NO _x concentration of NO to 0.85 ppm The concentration of _x is only a 15% reduction.

However, in Example 1 powder, almost no NO ₂ is produced, and after the UV irradiation, both of NO and NO _x stay near 0.5 ppm and increase very slowly, and after 3 hours, the NO _x concentration decreases to 40 ppm by 0.6 ppm. This is because the porous composite compound according to an embodiment of the present invention is coated with silica airgel to form a three-dimensional network structure, thereby having a larger specific surface area and thus having a better photocatalytic activity.

Therefore, the porous composite compound according to the present invention has excellent nitrogen oxide removal effect.

Measurement of Removal Effect of Hazardous Substances in Paints Containing Porous Composite Compound (Acetaldehyde)

In order to observe the acetaldehyde removal performance of the heat insulating paint using the paint composition according to an embodiment of the present invention, 10 g of the paint containing 20% by weight of the porous composite compound of Example 1 was dried, The effect of removing harmful substances is measured in the same manner as the evaluation method described.

As shown in FIG. 8, after the UV irradiation, the acetaldehyde removal reaction proceeded, and the acetaldehyde removal rate after two hours was measured as high as 33%.

This means that since the paint composition according to the present invention has the geometrical structure of the porous composite compound, the active point is not poisoned by the paint resin but has excellent optical activity.

Paint Color variation  Whether the comparison experiment

In order to confirm whether or not the oxidation of the binder and the pigment deformation of the conventional photocatalytic paint of the paint composition according to an embodiment of the present invention are solved, a color shift test is performed.

A paint containing a conventional photocatalyst-containing paint and a porous composite compound (Example 1) according to an embodiment of the present invention is applied to a steel plate, and then the paint is subjected to a color change experiment by sunlight. At this time, Rhodamin B, which is a red color, is added together as a substance capable of confirming the color change by the photocatalyst. Then, the color variation of the two paints was photographed by time zone, and the results are shown in Fig.

From the observation results shown in Fig. 9, it was found that the paint containing ordinary photocatalyst almost completely disappeared red after 1 hour and changed to white after 6 hours, whereas in the case of paint containing porous composite compound, The red color is maintained.

This means that the paint composition containing the porous composite compound according to the present invention has a structure surrounded by silica to prevent direct organic decomposition phenomenon while having photoactivity, thereby solving the problems of conventional photocatalytic paint.

Measurement of heat insulation performance of paint containing porous composite compound

In order to measure the heat insulation performance of the paint composition according to an embodiment of the present invention, the heat insulation paint using the paint composition according to the present invention and the general paint are heated with an infrared lamp, respectively, and the temperature change on the opposite side is observed. DA-1364 manufactured by Daewon Polymer Co., Ltd. was used as a general paint, and the paint of the present invention contains 20 wt% of the porous composite compound of Example 1 in the DA-1364.

As a result, as shown in Fig. 10, the paint using the porous composite compound photocatalyst powder of the present invention was maintained at 74 占 폚 even after 3 hours of surface temperature. On the other hand, in the case of ordinary paints, the surface temperature rapidly increases immediately after the application of heat and increases to 105 ° C. after 20 minutes. From this, it can be confirmed that the paint according to the present invention exhibits excellent heat insulation properties as compared with conventional general paints.

This is because, in the case of the porous composite compound contained in the paint of the present invention, titanium dioxide is coated with a silica airgel to form a porous silica coating body, and thus has excellent thermal stability.

Claims (17)

(a) mixing a metal oxide with water glass (Na ₂ SiO ₃ ), potassium silicate, calcium silicate and silica sol to prepare a mixture of metal oxides on a sol;
(b) forming a metal oxide gel by adding a solution of the metal oxide having a pH of 1 to 10 to the mixture;
(c) subjecting the metal oxide gel to an organic solvent and adding an organosilane to the surface of the metal oxide gel;
(d) drying the metal oxide gel to form a porous composite compound; And
and (e) calcining the porous composite compound. The porous composite compound according to claim 1, The paint composition according to claim 1, wherein the porous composite compound formed in step (d) has a three-dimensional net structure. The paint composition according to claim 1, wherein the metal oxide is an oxide having photocatalytic activity. The paint composition according to claim 3, wherein the metal oxide is titanium dioxide (TiO ₂ ). 5. The paint composition according to claim 4, wherein the titanium dioxide is doped with nitrogen or carbon. The method of claim 1, wherein in step (a), the metal oxide and any one of the water glass, potassium silicate, calcium silicate, and silica sol is at least one selected from the group consisting of a silica contained in any one of water glass, potassium silicate, calcium silicate, Wherein the weight ratio of the metal oxide to the silica is 0.01 to 10: 1. delete The paint composition according to claim 1, wherein the step (e) further comprises controlling the hydrophilicity and hydrophobicity of the porous composite compound by controlling a firing temperature. The paint composition of claim 1, wherein the paint composition further comprises a binder. The paint composition according to claim 9, wherein the binder is an organic binder, an inorganic binder, or a combination thereof. The paint composition according to claim 9, wherein the porous composite compound is contained in an amount of 0.001 to 50% by weight based on the total weight of the binder. An insulating paint prepared using a paint composition containing a porous composite compound,
Wherein the porous composite compound is the porous composite compound according to claim 1. (a) mixing a metal oxide with water glass (Na ₂ SiO ₃ ), potassium silicate, calcium silicate and silica sol to prepare a mixture of metal oxides on a sol;
(b) forming a metal oxide gel by adding a solution of the metal oxide having a pH of 1 to 10 to the mixture;
(c) subjecting the metal oxide gel to an organic solvent and adding an organosilane to the surface of the metal oxide gel;
(d) drying the metal oxide gel to form a porous composite compound; And
(e) calcining the porous composite compound, (A) preparing a porous composite compound, and
(B) mixing the prepared porous composite compound and a binder together to form a porous composite compound. 14. The method of claim 13, wherein in step (a), the metal oxide and any one of the water glass, potassium silicate, calcium silicate, and silica sol is at least one selected from the group consisting of silica, potassium silicate, calcium silicate, Wherein the weight ratio of the metal oxide to the silica is 0.01 to 10: 1. delete delete [14] The method of claim 13, wherein the step (e) further comprises controlling the hydrophilicity and hydrophobicity of the porous composite compound by controlling a firing temperature.

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