KR20140126497A - functional coating material using oyster shell - Google Patents

Abstract

The present invention relates to a functional coating material using oyster shells, and more specifically, to a functional coating material using oyster shells which are prepared by adding one or more nano-metal additives selected from nano-copper (Cu), nano-silver (Ag), nano-zinc (Zn), nano-platinum (Pt), nano-gold (Au) to oyster shells additive which is extracted by mixing an acid solvent with oyster shells. Therefore, the functional coating material can improve antimicrobial and antiviral functions by forming a coating material by mixing an antimicrobial extract including calcium (Ca) and the like as active ingredients of oyster shells with nano-metal additives.

Description

{Functional coating material using oyster shell}

The present invention relates to a functional coating agent using an oyster shell, and more particularly, to a functional coating agent using an oyster shell, and more particularly, to an antimicrobial, antiviral, antimicrobial and antimicrobial agent by fusing an antimicrobial extract containing calcium (Ca) And to a functional coating agent using an oyster shell showing a high efficiency for sexual activity.

Oyster shell industry, which is centered on clean waters in Korea, is highly appreciated in economic terms, but oyster shells incidentally generated in oyster production have caused many problems in terms of waste generation.

Oyster shells, a by-product of domestic oyster production, are reported to produce about 280,000 tons per year, of which about 130,000 tons are recycled and the remaining 150,000 tons are buried and left unattended. Therefore, annual oyster shells of about 150,000 tons are accumulating.

Oyster shells are mainly composed of calcium carbonate (CaCO ₃ ) produced in nature, and are composed of various other effective ingredients, and are widely used in both oriental and oriental. Also, it has been known that the adsorption efficiency of contaminants is very high due to the large specific surface area by having a porous structure surrounded by multiple layers with a thin film.

The main component of the oyster shell is calcium carbonate (CaCO ₃ , about 90%) and contains a small amount of other protein components and small amounts of metal oxides.

This oyster shell has been used in various fields and has been disclosed in Korean Patent Application Publication No. 10-2004-0089807 (published on Oct. 22, 2004) as "pollution-free fertilizer using shell" Is made up of 30% to 45% of shell powder, 25% to 35% of sulfur powder, and 15% to 40% of herbicidal and herbicidal medicinal herbs to neutralize the acidified soil and increase the yield by activating plant growth It is used as a fertilizer.

Another prior art is disclosed in Korean Patent Application Publication No. 10-2004-0085856 (published on Oct. 8, 2004) entitled " Wastewater treatment agent using shell and its production method " A small amount of sodium material such as sodium hydroxide (NaOH) is mixed with a shell of shellfish, seaweed, oyster and the like, heated to a predetermined temperature and then pulverized and powdered, and a part or all of powdered natural shell polymer And is used as a wastewater treatment agent.

Another prior art is disclosed in Korean Patent Registration No. 10-0968108 (published on July 7, 2010) entitled " Coating composition utilizing oyster shell and method for producing the same, Has a polymer functional and ceramic surface effect by mixing the oyster shell powder, white cement, meta kaolin, Al ₂ O ₃ , silica sand, polyacrylic ester system, and water obtained from washing, firing and pulverization steps, , The water is 10-15 wt%, the white cement is 5-15 wt%, the meta kaolin is 5-10 wt%, the polyacrylic ester system is 20-40 wt%, the water is 10-15 wt%, the water cement is 5-15 wt%, the Al ₂ O ₃ is used as a water-soluble coating agent using ₅ to 10 wt% of silica and 10 to 20 wt% of silica as raw materials.

However, despite the fact that shells are being buried and left, there is no information on the use of shells for antibacterial and antiviral coatings.

(Patent Document 1) Korean Patent Application Publication No. 10-2004-0089807 (published on October 22, 2004) (Document 2) Korean Patent Application Publication No. 10-2004-0085856 (Published Date October 8, 2004) (Document 3) Korea Patent Office Registration No. 10-0968108 (Published on July 8, 2010)

DISCLOSURE Technical Problem Accordingly, the present invention has been made in order to solve the problems of the prior art described above. Accordingly, it is an object of the present invention to provide a method for producing antibacterial, anti- It is an object of the present invention to provide a functional coating agent using oyster shell which shows high efficiency against viral.

In order to accomplish the above object, the present invention provides an oyster shell antimicrobial extract obtained by mixing an oyster shell with an acid solvent containing an acid, wherein the extract is selected from the group consisting of nanoparticles (Cu), nano silver (Ag), nano zinc (Zn) (Pt), and nano gold (Au) is added to a functional coating agent using an oyster shell.

The functional coating agent using the oyster shell may be formed by adding 1 to 3 parts by weight of an oyster shell antibacterial extract, 0.3 to 1 part by weight of a nanocatalyst additive, and 0.5 to 1.5 parts by weight of a binder to 90 to 100 parts by weight of a solvent.

The oyster shell antimicrobial extract may include a primary agitation step of mixing and stirring oyster shell powder with water; A second agitation step of mixing and stirring the acid after the primary agitation; And an antimicrobial extract-forming step of separating the oyster shell antimicrobial extract from the solution after aging the second agitation.

The acid may be selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, oxalic acid, tartaric acid, . ≪ / RTI >

The functional coating agent using the oyster shell preferably contains a stabilizer.

Accordingly, an antimicrobial extract containing calcium (Ca) and the like among the effective components of the extract of oyster shells is fused with a nano-metal additive to form a coating agent, thereby exhibiting high efficiency for antibacterial and antiviral properties.

The present invention according to the above-mentioned constitution has an effect of exhibiting high efficiency for antibacterial and antiviral properties by forming a coating agent by fusing an antimicrobial extract containing calcium (Ca) and the like among the active ingredients of the oyster shell extract with a nano metal additive have.

1 is a schematic diagram of an apparatus for an antiviral experiment according to the present invention,
2 is a diagram showing a control of Staphylococcus aureus,
FIG. 3 is a graph showing the result of an antibacterial experiment on Staphylococcus aureus using a zebra filter specimen as a filter specimen coated with a functional coating liquid,
FIG. 4 is a graph showing the result of an antibacterial test on Staphylococcus aureus using a nonwoven filter specimen with a filter coating sample coated with a functional coating solution.
FIG. 5 is a graph showing the result of an antibacterial experiment on Staphylococcus aureus using a prefilter specimen as a filter specimen coated with a functional coating solution,
6 is a view showing a control of E. coli,
FIG. 7 is a graph showing the result of an antibacterial test on E. coli using a zebra filter specimen as a filter specimen coated with a functional coating solution,
8 is a graph showing the result of an antibacterial test on E. coli using a nonwoven filter specimen with a filter coating sample coated with a functional coating solution,
9 is a graph showing the results of an antibacterial test on E. coli using a prefilter specimen as a filter specimen coated with a functional coating liquid,
10 is a graph showing antiviral performance against coating liquid exposure time.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Fig. 1 is a schematic view of an apparatus for antiviral experiment according to the present invention, Fig. 2 is a control diagram of Staphylococcus aureus, Fig. 3 is a filter specimen coated with a functional coating solution, FIG. 4 is a graph showing the result of an antibacterial test on Staphylococcus aureus using a non-woven filter specimen as a filter specimen coated with a functional coating liquid, and FIG. FIG. 5 is a graph showing the result of an antibacterial test on Staphylococcus aureus using a prefilter specimen as a filter specimen coated with a functional coating solution, FIG. 6 is a view showing a control of E. coli, 7 is a graph showing the result of an antibacterial test on E. coli using a zebra filter specimen as a filter specimen coated with a functional coating solution, FIG. 9 is a graph showing the result of an antibacterial test for E. coli using a nonwoven filter specimen with a liquid-coated filter specimen. FIG. 9 is a graph showing the results of an antibacterial test for E. coli using a prefilter specimen, FIG. 10 is a graph showing the antiviral performance against the exposure time of the coating solution. FIG.

As shown. In order to form the functional coating agent using the oyster shell according to the present invention, the antimicrobial extract containing calcium is first extracted using oyster shell powder.

Calcium carbonate (CaCO ₃ ), which is the main component of oyster shell powder used as a material for improving antibacterial activity according to the present invention, is generally insoluble in water. In order to obtain high efficiency antimicrobial activity, the concentration of calcium ion (Ca ion) was analyzed and an experiment was conducted to improve solubility.

The concentration of calcium ion at various pHs through the change of stirring method and acid addition was confirmed by inductively coupled plasma (ICP) analysis.

The oyster shell antimicrobial extract is extracted by the following method.

 1. 60 to 80 parts by weight of water (pure water) is added to 20 parts by weight of the oyster shell powder, and the mixture is subjected to high-speed agitation (1,000 to 2,000 rpm, optimum 1,500 rpm) for 30 to 60 minutes.

 2. Add 20 parts by weight of inorganic acid (phosphoric acid, 85%) in 5 parts by weight, four times, slowly and stir at high speed (1,000 ~ 2,000 rpm, optimum 1,500 rpm) for 2 hours. In this case, hydrochloric acid (hydrochloric acid), nitric acid (phosphoric acid), sulfuric acid (sulfuric acid) can be used as various inorganic acids, but phosphoric acid is the best. Acetic acid, butyric acid, oxalic acid, and tartaric acid can be used as organic acids, but acetic acid is the best.

3. Agitate for 24 hours after completion of stirring.

4. After aging, centrifuge the solution using a vacuum filter and use the solution.

The oyster shell antimicrobial extracts formed according to the above procedure were mixed with Ca ²⁺ The concentrations are shown in Table 1 below.

In the case of high-speed stirring, the mixture was stirred at about 20 ° C for 60 minutes, transferred to a sample bottle, and allowed to stand for 24 hours to separate the precipitate and the supernatant.

In case of ultrasonic dispersing machine, the pulse strength was set to 40% and stirred for 60 minutes. After transferring to the sample bottle, the mixture was allowed to stand for 24 hours to separate the precipitate and supernatant.

In Table 1, Experimental Example 1 shows the case where no acid was used, and depending on the kind of acid treated, Ca ²⁺ It can be seen that the concentration is different.

And example purposes of Ca ^{2 +} levels high experiment of the present invention preferred, the Experimental Example 3 and Experimental Example 4, Ca ^{2 +,} or the concentration and determined that high, the characteristic odor of acetic acid when the Example 4 I-bar, in Experimental Example 3 < / RTI >

The functional coating agent using the oyster shell antibacterial extract comprises 1 to 3 parts by weight of an oyster shell antibacterial extract, 0.3 to 1 part by weight of a nanocatalyst additive, and 0.5 to 1.5 parts by weight of a binder, relative to 90 to 100 parts by weight of a solvent.

Here, the solvent is usually water (pure water).

The nanocatalyst additive is formed by adding at least one nano-metal additive selected from the group consisting of nano-copper (Cu), nano-silver (Ag), nano-zinc (Zn), nano-platinum (Pt) Use nano copper.

The binder is an inorganic binder having TEOS (tetraethylorthosilicate) and GPTMS (? -Glycidoxypropyltrimethoxysilane) as precursors. However, for the purpose of flexibility and adhesion, PVA (polyvinylalcohol), PAA (polyacrylic acid), PU Polyurethane or the like may be formed and used in combination with the organic binder. That is, the binder may be variously selected depending on the type of the substrate to be coated with the coating agent.

15 parts by weight of a tetraethylorthosilicate (TEOS) compound, 5 parts by weight of gamma -butyrolactone (hereinafter referred to as " yttrium oxide ") was added dropwise to a mixture of 35 parts by weight of ethanol and 18 parts by weight of distilled water, 25 parts by weight of glycidoxypropyltrimethoxysilane (GPTMS) were hydrolyzed and condensation-polymerized at 40 ° C to 70 ° C for 3 hours with rapid stirring and added to 2 parts by weight of an aluminum metal catalyst to obtain a surface-treated polysilicate To prepare a composition. 40 parts by weight of the prepared composition, 25 parts by weight of distilled water, 20 parts by weight of isopropyl alcohol, 5 parts by weight of an amine curing agent, 1 part by weight of a pH adjusting agent and 10 parts by weight of an aqueous acrylic polymer as an organic polymer resin were mixed for about 3 hours, .

If necessary, a stabilizer is added.

The physical properties of the functional coating agent formed through the above process are shown in Table 2 below.

In Table 2, the material added in each experimental example represents the weight ratio.

≪ Antibacterial activity test &

In Table 2, the antimicrobial activity of the filter coated with the functional coating agent prepared in Experimental Example 6 to Experimental Example 11 of Table 2 formed in the present invention was examined by shaking flask method.

The antimicrobial activity is carried out in the following order.

1. Test specimens coated with a functional coating solution for 4 in. ² (25.8 cm ² ) in size.

2. Dilute the strain to be used for the test with decanter using dilution water, and inoculate the sterilized neutral solution with 1.6 × 10 ⁵ CFU / ml. In the present invention, Staphylococcus aureus and E. coli were used as strains.

3. 250 ml triangular flask with 4 in. Put the filter cut into ² (25.8 cm ² ) size.

4. Inject 50 ± 0.5 ml of prepared inoculum (1.6 × 10 ⁵ CFU / ml) into the triangular flask.

5. Allow the triangular flask to react at a constant rate of 150 RPM (15 minutes in this case) in a shaking incubator at 35 ° C.

6. After the reaction time has elapsed, dilute the reaction solution by decimal method and determine the viable cell count by comparing with the control (control) by pour plate method.

<Antiviral Test>

In addition, the anti-viral test in Table 2 can be performed by applying the functional coating agent prepared in Experimental Example 6 to Experimental Example 11 of Table 2 formed in the present invention to the filter and then knowing the antiviral property of the filter through the Kitasato Research Center saw.

The antiviral experiments are carried out in the following order.

1. Prepare two specimens of the filter specimen coated with the functional coating solution for the test.

2. Place the prepared filter specimen in a Petri dish and inoculate 0.2 ml of virus suspension (1.4 × 10 ⁸ TCID ₅₀ / ml) into the specimen as shown in Figure 1. In the present invention, influenza A virus (H1N1) was used as the virus.

3. The specimens inoculated with the virus suspension are incubated at room temperature for 3, 6 and 9 hours.

4. After incubation, the virus is recovered with phosphate buffer (PBS).

5. Determine the 50% Tissue Culture Infections Dose (TCID ₅₀ ) as measured on CrFKcell by comparing the amount of virus remaining with the control.

Experimental Example 6 in which the weight ratio of oyster shell extract to the ointment extract was 0.5 and the amount of the nano-metal catalyst added was 0.1 in Table 2, was not excellent in antimicrobial activity.

Experimental Example 8 in which the weight ratio of the oyster shell extract and the amount of the nano-metal catalyst added was 0.1 in terms of the weight ratio, and the antiviral test was not performed because the antimicrobial activity was not excellent.

Experimental Example 7, in which the weight ratio of the oyster shell extract was 0.5 and the addition amount of the nano-metal catalyst was 0.5 in terms of weight ratio, showed excellent antimicrobial activity, but the antiviral performance was not excellent.

Experimental Examples 9 to 11, in which the addition amount of the nano-metal catalyst was 0.5 and the amount of the oyster shell extract was 1 or more, are excellent in antibacterial and antiviral performance.

From these results, it was confirmed that oyster shell extract and nano-metal catalyst were the main factors affecting antibacterial activity. Stable antibacterial activity was observed in 0.5 part of nano metal, and stable antimicrobial and antiviral activity was observed in more than 1 part of oyster shell extract I could confirm that it appeared.

In particular, Experimental Example 11 shows excellent antimicrobial and antiviral properties, and the content of the coating agent of Experimental Example 11 is shown in Table 3 below.

The antibacterial test results for Staphylococcus aureus using the coating agent of Table 3 are shown in Figs. 2 to 5. The antibacterial test was carried out in the same manner as described above.

Fig. 2 shows the control of Staphylococcus aureus. Fig. 3 shows the results of an antibacterial experiment on Staphylococcus aureus using zebra filter specimens as filter specimens coated with a functional coating solution. Fig. 5 shows the results of antibacterial tests on Staphylococcus aureus using a nonwoven filter specimen with a filter coated with a coating solution. Fig. 5 shows the results of an antibacterial test on a Staphylococcus aureus strain using a prefilter specimen, This is the result of an antibacterial experiment. As shown in FIGS. 2 to 5, when the functional coating solution according to the present invention was used, it was confirmed that Staphylococcus aureus was killed.

The results of the antibacterial test on E. coli using the coating agent of Table 3 are shown in Figs. 6 to 9. Fig. The antibacterial test was carried out in the same manner as described above.

FIG. 6 shows the control of E. coli. FIG. 7 shows the result of an antibacterial test on E. coli using a zebra filter specimen as a filter specimen coated with a functional coating solution. FIG. FIG. 9 is a result of an antibacterial test on Escherichia coli using a prefilter specimen as a filter specimen coated with a functional coating solution. FIG. 9 is a result of an antibacterial test on Escherichia coli using a nonwoven filter specimen as a filter specimen. 6 to 9, it was confirmed that E. coli was killed when the functional coating solution according to the present invention was used.

The results of the antiviral tests on influenza A virus (H1N1) using the coating agent of Table 3 are shown in Table 4 below. Antiviral experiments were carried out in the same manner as described above.

In Table 4, the unit is TCID ₅₀ / mL, the measurement limit is 6.3 × 10 ¹ TCID ₅₀ / mL, and NT is not tested.

In Table 4, it can be seen that almost no virus is killed even when the control is exposed for 15 minutes.

On the other hand, when exposed to the coating of the present invention, it is found that the measurement limit is less than 6.3 × 10 ¹ TCID ₅₀ / mL over 2 minutes. This is shown in Fig.

This means that when the coating agent of the present invention is used, the virus is killed after about 2 minutes.

Claims (5)

(Cu), nano silver (Ag), nano zinc (Zn), nano platinum (Pt), and nano gold (Au) were added to the oyster shell antimicrobial extract extracted by mixing the oyster shell with an acid solvent containing an acid. Wherein the nano metal additive is added to the functional coating agent. The functional coating agent according to claim 1,
1 to 3 parts by weight of an oyster shell antibacterial extract, 0.3 to 1 part by weight of a nanocatalyst additive, and 0.5 to 1.5 parts by weight of a binder are added to 90 to 100 parts by weight of a solvent. 2. The antimicrobial ointment extract according to claim 1,
A first stirring step of mixing and stirring the oyster shell powder with water;
A second agitation step of mixing and stirring the acid after the primary agitation;
And a step of forming an antibacterial extract to separate the oyster shell antimicrobial extract from the solution after aging after the second agitation. 4. The method according to any one of claims 1 to 3,
The acid may be selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, oxalic acid, tartaric acid, Wherein the functional coating agent is selected from the group consisting of polyvinylpyrrolidone, 5. The functional coating agent according to claim 4, wherein the functional coating agent using the oyster shell is a stabilizer.

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