KR101347724B1 - Method For Preparing Multi-Functional Filler Useful For Wall Finishing Materials - Google Patents

Abstract

The present invention relates to a method for producing a multifunctional filler for use in wall finishing materials, such as paint and wall coverings, and more specifically, to the human body by drying and heat-treated with a photocatalyst sol and nano silver colloid aqueous solution in zeolite A method for producing a multifunctional filler for wall finishing which adsorbs and decomposes harmful volatile organic compounds (VOC), formaldehyde, NOx, SOx and radon gas and prevents bacteria and fungi from inhabiting paints and finishes. will be.

Description

Method for Preparing Multi-Functional Filler Useful For Wall Finishing Materials}

The present invention is a method for producing a multifunctional filler for use in wall finishing materials, such as paint and wall coating material, more specifically, after the wet surface treatment of zeolite with a photocatalyst sol and a solution of nanosilver colloid, dried and heat treated, and then wall finishing material Multifunctional filler for wall finishing which absorbs and decomposes volatile organic compounds (VOC), formaldehyde, NOx, SOx and radon gas, which are harmful to the human body, and prevents bacteria and molds from growing in paints and finishes. It relates to a manufacturing method of.

Recently, there is an increasing demand for environmentally friendly paints with reduced volatile organic compounds and functional wall finishes to improve indoor air quality. Wall finishing materials for improving indoor air quality can be classified into far-infrared and anion-emitting paints, photocatalytic functional paints, and harmful gas adsorption functional paints.

In the case of far-infrared and anion-emitting paint, there is a problem in which radon gas causing lung cancer is generated from the added far-infrared and anion-releasing natural minerals.

In the case of the photocatalytic functional paint, there is a function of decomposing harmful gas, but as the indoor air circulates, only the harmful gas at a close distance to the wall is decomposed, so that the decomposition ability is deteriorated.

In the case of the adsorption functional paint, porous fillers such as activated carbon, charcoal, and zeolite are used as the adsorbent. In the case of activated carbon or charcoal, the color of the paint is black, which is not suitable for finishing. On the other hand, when using the zeolite as the adsorbent can satisfy a variety of colors, there is a problem in long-term use because the adsorption amount of the zeolite is limited when the harmful gas is continuously adsorbed to the zeolite. In addition, TiO ₂ exhibiting zeolite and photocatalytic functionality Although the harmful gas adsorbed on the zeolite by the addition of the powder is decomposed by the photocatalytic reaction, it is not economical because a large amount of expensive TiO ₂ powder is used.

On the other hand, mold and bacteria grow on the surface of the paint in a humid environment. In the case of the fungus generated in this way, it moves into the air and enters through the respiratory system of the human body, and bacteria enters the human body through skin contact to generate various diseases. There is a problem.

It is added to wall finishing materials, such as paints and wall coverings, to reduce harmful gases such as volatile organic compounds, formaldehyde, radon gas, NOx and SOx, which are harmful to the human body, both indoors and outdoors. There is a need to develop a multifunctional filler for wall finishing that can improve the quality of indoor air by preventing the generation and habitat of bacteria and to produce wall finishing for economical efficiency.

The inventors of the present invention have repeatedly studied to solve these problems, and when the surface of the zeolite is wet-treated with a TiO ₂ photocatalyst sol and a nano silver colloid aqueous solution, and then dried and heat treated to add a multifunctional filler to the paint, Improve indoor air quality by continually reducing harmful gases such as volatile organic compounds, formaldehyde, radon gas, NOx and SOx, which are harmful to the human body in the outdoors, and preventing the formation and habitat of mold and bacteria under humid conditions. The present invention has been accomplished by finding out that it is possible to provide a multifunctional filler for finishing materials which is economical.

Accordingly, it is an object of the present invention to provide a multifunctional filler for finishing materials that has adsorption and decomposition of harmful gases, antibacterial and economical.

SUMMARY OF THE INVENTION The gist of the present invention is to provide a method for producing a multifunctional filler for wall finishing comprising the following steps:

Zeolite is mixed with a nano silver colloidal solution in a weight ratio of 1: 1, stirred at room temperature and 200 rpm for 2 hours, and then dried at 110 ℃ for 4 hours, and

The zeolite treated in the above step was mixed with the TiO ₂ sol as a photocatalyst in a weight ratio of 1: 1, stirred at room temperature and 200 rpm for 2 hours, then dried at 110 ° C. for 4 hours, and again at 300 to 600 ° C. Heating for hours.

According to the present invention, the nano-silver colloidal aqueous solution is obtained by completely dissolving 2.5 to 10 parts by weight of NaBH ₄ , 5 to 15 parts by weight of AgNO ₃ and 75 to 92.5 parts by weight of distilled water at 100 rpm at room temperature, based on a total of 100 parts by weight. Lose.

In addition, according to the present invention, TiO ₂ sol as a photocatalyst is added dropwise to 10 to 30 parts by weight of titanium isopropoxide based on a total of 100 parts by weight with stirring of 70 to 90 parts by weight of distilled water at room temperature at 200 rpm. Prepared by hydrolysis of titanium isopropoxide by stirring for another 2 hours.

In addition, according to the present invention, distilled water is adjusted to pH 2-4 by nitric acid.

As described above, the multifunctional filler for wall finishing material according to the present invention is a harmful gas such as volatile organic compounds, formaldehyde, radon gas, NOx, SOx, etc., harmful to the human body existing indoors and outdoors when a certain amount is added to the paint and the wall coating material. It is continuously reduced for a long time, improves the quality of indoor air by preventing the occurrence and habitat of mold and bacteria under humid conditions, and has high economical characteristics. Therefore, it can be used as a filler for wall finishing materials such as paints and wall coverings.

Hereinafter, the present invention will be described in more detail.

The manufacturing method according to the present invention includes two steps as follows.

The first step is to treat the zeolite with an aqueous nanosilver colloid solution.

The nano-silver colloidal aqueous solution is prepared by completely dissolving NaBH ₄ 2.5-10 parts by weight, AgNO ₃ 5-15 parts by weight and distilled water 75-92.5 parts by stirring at room temperature at 100 rpm.

The nano silver colloidal solution prepared as described above was mixed with a zeolite of 4A type in a weight ratio of 1: 1, stirred at 200 rpm at room temperature for 2 hours, and then dried at 110 ° C. for 4 hours.

The second step is to treat the zeolite treated with an aqueous solution of colloidal nanosilver with TiO ₂ sol, a photocatalyst.

10 to 30 parts by weight of titanium isopropoxide Ti (OCH (CH ₃ ) ₂ ) ₄ was adjusted to pH 2 to 4 by nitric acid based on 100 parts by weight of the total TiO ₂ sol as a photocatalyst. After dropping with stirring at room temperature at 200 rpm,

After the dropwise addition, stirring was continued for 2 hours to prepare TiO ₂ sol by hydrolyzing titanium isopropoxide as shown in the following Reaction Formula (1).

Ti (OCH (CH ₃ ) ₂ ) ₄ + 4H ₂ O-> Ti (OH) ₄ + 4CH (CH ₃ ) ₂ OH

Scheme (1)

Zeolites treated with nano-silver colloidal aqueous solution were used as photocatalyst TiO ₂ The sol was mixed in a 1: 1 weight ratio and stirred at 200 rpm for 2 hours at room temperature, dried at 110 ° C. for 4 hours, and then heat-treated at 300 ° C. to 600 ° C. for 2 hours to prepare a multifunctional filler for wall finishing.

In the first step according to the present invention, it is preferable to use 75 to 92.5 parts by weight of distilled water based on 100 parts by weight of the total composition of the nano-silver colloidal aqueous solution.

NaBH ₄ acts to stabilize the nano-silver colloidal aqueous solution, the amount used is 2.5 to 10 parts by weight, preferably 3 to 5 parts by weight based on 100 parts by weight of the total composition of the nano-silver colloidal aqueous solution. If the amount of NaBH ₄ is less than 2.5 parts by weight, the nanosilver colloidal solution is unstable, and even if it is 10 parts by weight or more, the stability no longer increases.

The amount of AgNO ₃ used is 5 to 15 parts by weight, preferably 6 to 10 parts by weight based on 100 parts by weight of the total composition of the nanosilver colloid aqueous solution. If the amount of AgNO ₃ is 5 parts by weight or less, the antimicrobial activity against mold and bacteria after treatment with zeolite is not complete, and even if 15 parts by weight or more is used, the antibacterial property is no longer improved.

The distilled water used in the second step of the present invention is 70 to 90 parts by weight based on 100 parts by weight of the total composition of the TiO ₂ sol as a photocatalyst, and the pH is preferably 2 to 4. If the pH is less than ₂ , hydrolysis of the TiO ₂ sol may proceed rapidly and gelation may occur. If the pH exceeds 4, the hydrolysis of the TiO ₂ sol becomes too late, making it difficult to prepare the TiO ₂ sol.

In addition, the amount of titanium isopropoxide, the photocatalyst used in the second step of the present invention, is 10 to 30 parts by weight, preferably 12 to 20 parts by weight, based on 100 parts by weight of the total composition of the photocatalyst TiO ₂ sol. . If the amount of the titanium isopropoxide is less than 10 parts by weight, the photocatalytic effect is hardly exhibited sufficiently, and if it exceeds 30 parts by weight, the photocatalytic effect does not increase any more.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the Examples do not limit the present invention.

<Examples>

Example  One

In a 500 mL beaker equipped with a stirrer, 2.5 g of NaBH ₄ was added to 47.5 g of distilled water with stirring at 100 rpm at room temperature to completely dissolve it. Separately, 5 g of AgNO ₃ was added to 45 g of distilled water with stirring at 100 rpm at room temperature to completely dissolve it. An aqueous solution of AgNO ₃ dissolved in NaBH ₄ was added dropwise while stirring at 100 rpm at room temperature to prepare 100 g of a nano silver colloidal solution. 100 g of 4A-type synthetic zeolite (Jimtech, JST-MS40) was added thereto, and 200 rpm at room temperature. After stirring with water and dried at 110 ° C.

On the other hand, 10 g of titanium isopropoxide was added dropwise while stirring at 200 rpm at room temperature to 90 g of distilled water adjusted to pH 2 using nitric acid in a 500 mL beaker equipped with a stirrer. After the dropwise addition, the mixture was continuously stirred for 2 hours, and then 100 g of the nano-silver colloidal solution-treated zeolite was added thereto, stirred at 200 rpm for 2 hours, dried at 110 ° C. for 4 hours, and then heat-treated at 300 ° C. for 2 hours. A multifunctional filler for the finish was prepared.

Example  2

In a 500 mL beaker equipped with a stirrer, 7.5 g of NaBH ₄ was added to 42.5 g of distilled water with stirring at 100 rpm at room temperature to completely dissolve it. Separately, 10 g of AgNO ₃ was added to 40 g of distilled water with stirring at 100 rpm at room temperature to completely dissolve it. An aqueous solution of AgNO ₃ dissolved in NaBH ₄ was added dropwise while stirring at 100 rpm at room temperature to prepare 100 g of nanosilver colloidal aqueous solution, and 100 g of 4A type synthetic zeolite (Jsim-Tech, JST-MS40) was added thereto and 200 rpm at room temperature. After stirring with water and dried at 110 ° C.

Meanwhile, 20 g of titanium isopropoxide was added dropwise to 80 g of distilled water adjusted to pH 4 using nitric acid in a 500 mL beaker equipped with a stirrer while stirring at room temperature at 200 rpm. After the dropwise addition, the mixture was continuously stirred for 2 hours, and then 100 g of the nano-silver colloidal solution-treated zeolite was added thereto, stirred at 200 rpm for 2 hours, dried at 110 ° C. for 4 hours, and then heat-treated at 600 ° C. for 2 hours. A multifunctional filler for the finish was prepared.

Example  3

In a 500 mL beaker equipped with a stirrer, 10 g of NaBH ₄ was added to 40 g of distilled water with stirring at 100 rpm at room temperature to completely dissolve it. Separately, 13 g of AgNO ₃ was added to 37 g of distilled water with stirring at 100 rpm at room temperature to completely dissolve it. An aqueous solution of AgNO ₃ dissolved in NaBH ₄ was added dropwise while stirring at 100 rpm at room temperature to prepare 100 g of nanosilver colloidal aqueous solution, and 100 g of 4A type synthetic zeolite (Jsim-Tech, JST-MS40) was added thereto and 200 rpm at room temperature. After stirring with water and dried at 110 ° C.

Meanwhile, 30 g of titanium isopropoxide was added dropwise with stirring at 200 rpm at room temperature to 70 g of distilled water adjusted to pH 3 using a nitric acid in a 500 mL beaker equipped with a stirrer. After the dropwise addition, the mixture was continuously stirred for 2 hours, and then 100 g of the nano-silver colloidal solution-treated zeolite was added thereto, stirred at 200 rpm for 2 hours, dried at 110 ° C. for 4 hours, and heat-treated at 500 ° C. for 2 hours. A multifunctional filler for the finish was prepared.

Comparative Example  One

As a comparative example, pure 4A-type synthetic zeolite (Jsim-Tech, JST-MS40) was used.

<Experimental Example>

The multifunctional fillers of the present invention prepared in Examples 1 to 3 were subjected to methylene blue degradability, deodorization test and antimicrobial test.

Experimental Example  1 (methylene blue  By decomposition Photocatalyst  Property evaluation)

Methylene blue degradability evaluation was carried out to evaluate the photocatalytic properties of the multifunctional filler for the wall finish produced by the present invention. After immersing the filler of the present invention obtained in Examples 1 to 3 and the powder of Comparative Example 1 in a methylene blue (MB) 0.001 M solution for 20 minutes, and then drying away from direct sunlight, photocatalytic properties were measured. Photocatalytic properties were measured by a potency measuring instrument (manufactured by Sinku-Riko, Japan, PCC-1), and after 20 minutes with a photodetector by emitting ultraviolet light having a wavelength of 340 nm, the amount of MB degradation on the zeolite surface was measured by ΔABS. In the initial light transmittance, the MB is decomposed by the irradiation of ultraviolet rays, and the light transmittance increases, and the better the photocatalyst characteristic, the greater the absolute value toward (-). The experimental results are shown in Table 1.

division Example 1 Example 2 Example 3 Comparative Example 1 Methylene blue degradable
(△ ABS) -1825 -1860 -1885 -475

In Table 1, Examples 1-3 have markedly improved the methylene blue decomposition property compared with the comparative example 1, and show that there exists a photocatalytic effect. On the other hand, in comparison with Examples 1 to 3, the concentration of TiO ₂ sol, which is a photocatalyst treated with zeolite increases, and the methylene blue degradability also increases.

Experimental Example  2 (deodorization test)

Deodorization test for Examples 1 to 3 and Comparative Example 1 was measured by the method of KICM-FIR-1004 to measure the concentration change of the ammonia test gas and the hydrogen sulfide test gas with the elapsed time by the gas detection tube method, Deodorization rate results of the ammonia test gas and the hydrogen sulfide test gas are shown in Tables 2 and 3, respectively.

 Deodorization Rate of Ammonia Test Gas Elapsed time Example 1 Example 2 Example 3 Comparative Example 1  30 minutes 78.9% 79.7% 80.4% 54.3%  60 minutes 84.3% 87.6% 88.5% 58.7% 120 minutes 94.6% 95.1% 96.4% 67.5%

Deodorization Rate of Hydrogen Sulfide Test Gas Elapsed time Example 1 Example 2 Example 3 Comparative Example 1  30 minutes 74.8% 76.7% 78.4% 52.3%  60 minutes 82.3% 84.7% 85.5% 55.7% 120 minutes 90.6% 91.6% 92.7% 62.5%

In Tables 2 and 3, in Examples 1 to 3, the deodorization rate was 90% or more after 120 minutes, and in Comparative Example 1, the deodorizing effect of the multifunctional filler for wall finishing material prepared by the present invention was 70% or less. High. On the other hand, in comparison with Examples 1 to 3, the deodorizing effect increases as the concentration of TiO ₂ sol, which is a photocatalyst treated with zeolite increases.

Experimental Example  3 (antibacterial test)

The antimicrobial test for the fillers of Examples 1 to 3 and Comparative Example 1 was carried out by the antimicrobial test and E. coli and P. aeruginosa test by the KICM-FIR-1001 and KICM-FAB-261 method of the Korea Institute of Construction and Living Testing, The results of the antifungal test (KICM-FIR-1001) and the E. coli and P. aeruginosa test (KICM-FAB-261) are shown in Tables 4 and 5, respectively.

Antifungal test Example 1 Example 2 Example 3 Comparative Example 1 Growth inhibition rate 100% 100% 100% 10%

Escherichia coli and P. aeruginosa test E. coli reduction rate Elapsed time Example 1 Example 2 Example 3 Comparative Example 1 6 hours later 68.5% 72.7% 78.4% 0% After 24 hours 95.4% 97.2% 98.8% 0% Pseudomonas aeruginosa reduction rate Elapsed time Example 1 Example 2 Example 3 Comparative Example 1 6 hours later 69.4% 74.7% 80.4% 0% After 24 hours 95.7% 97.8% 98.8% 0%

As a result of the antimicrobial test of Tables 4 and 5, the growth inhibition rate of the mold was excellent as 100%, and showed a reduction rate of more than 95% after 24 hours for E. coli and P. aeruginosa. On the other hand, Comparative Example 1 without the antibacterial test showed a growth inhibition rate of only 10% in the antifungal test, and showed no antimicrobial activity against Escherichia coli and no. On the other hand, in comparison with Examples 1 to 3, the antimicrobial activity increased as the concentration of the colloidal nanosilver colloid increased.

The above description is merely illustrative of the technical spirit of the present patent, and those skilled in the art to which the present patent belongs may make various modifications and changes without departing from the essential characteristics of the present patent.

In addition, the embodiments disclosed in the present patent are not intended to limit the technical spirit of the present patent but to describe the technical spirit of the present patent.

Therefore, the protection scope of the present patent should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present patent.

Claims (4)

Zeolite is mixed with a nano silver colloidal solution in a weight ratio of 1: 1, stirred at room temperature and 200 rpm for 2 hours, and then dried at 110 ℃ for 4 hours, and
The zeolite treated in the above step was mixed with the TiO ₂ sol as a photocatalyst in a weight ratio of 1: 1, stirred at room temperature and 200 rpm for 2 hours, then dried at 110 ° C. for 4 hours, and again at 300 to 600 ° C. A method of making a multifunctional filler for wall finishing, comprising heating for a time.
The method of claim 1, wherein the nano-silver colloidal aqueous solution is completely dissolved by stirring at 2.5 rpm of NaBH ₄ 2.5 to 10 parts by weight, AgNO ₃ 5 to 15 parts by weight and distilled water at 75 rpm to 100 rpm based on a total of 100 parts by weight. A method for producing a multifunctional filler for wall finishing material, which is obtained.
The TiO ₂ sol as a photocatalyst is added dropwise to 10 to 30 parts by weight of titanium isopropoxide based on a total of 100 parts by weight with stirring of 200 to 90 parts by weight of distilled water at 200 rpm at room temperature. A method for producing a multifunctional filler for wall finishing, characterized in that it is prepared by hydrolyzing titanium isopropoxide by stirring for a time.
The method for producing a multifunctional filler for wall finishing according to claim 3, wherein distilled water is adjusted to pH 2 to 4 by nitric acid.