KR101321832B1 - Additive for antifouling agent, method of manufacturing thereof and antifouling agent comprising the same - Google Patents

Abstract

The present invention relates to an antifouling agent, a method for preparing the same, and an antifouling agent including the same, and more particularly, a carrier having metal nanoparticles having a particle diameter of 100 nm or less attached to a surface thereof, wherein the carrier is an antimicrobial or bactericidal compound. It relates to an additive for phosphorus antifouling agent, a method for producing the same and an antifouling agent comprising the same.

Description

Additives for antifouling agents, preparation method thereof, and antifouling agents including the same {{ITITIVE FOR ANTIFOULING AGENT, METHOD OF MANUFACTURING THEREOF AND ANTIFOULING AGENT COMPRISING THE SAME}

The present invention relates to an antifouling agent, a method for producing the same, and an antifouling agent including the same.

In general, many nanoparticles have been reported to have an antimicrobial or bactericidal effect against microorganisms. For example, in a paper on antimicrobial activity against silver nanoparticles, silver nanoparticles have antimicrobial and bactericidal activity against prokaryotes, but are not antimicrobial and bactericidal against other eukaryotes.

In addition, in the evaluation of the antimicrobial activity of copper (Cu) nanoparticles, it is known that copper nanoparticles have antimicrobial antibacterial activity against Escherichia coli, Staphylococcus aureus, Lyseria monocytogenes and molds. That is, the copper nanoparticles are included in a solvent containing tetra butyl ammonium perchloride and acetonitrile, and the copper nanoparticles-solvent thus prepared are mixed with various polymers, or copper nanoparticles And polyvinyl methyl ketone (PVMK, polyvinylmethylketone), polyvinyl chloride (PVC, polyvinylchloride) or polyvinylidene fluoride (PVDF, polyvinylidene fluoride) and the compound was made to antibacterial or sterilization test. 4 hours after incubation of E. coli, Staphylococcus aureus, and fungi in the compound containing the copper nanoparticles, the concentration of copper in the culture medium was measured. As a result, copper element was detected. Is eluted, and it is reported that copper nanoparticles have the outstanding antibacterial and bactericidal effect.

In addition, composite materials containing acryl and copper nanoparticles having various carbon atoms were synthesized and antimicrobial sterilization experiments were performed on marine fauna and flora using various green algae, eukaryotic, and prokaryotic cells. As a result, various microorganisms were sterilized, and when the amount of copper eluted was measured over time, it was continuously eluted for about 180 hours and copper nanoparticles were reported to play an antibacterial sterilization role.

Copper, which is currently used for antifouling agents, is used as a copper oxide (CuO) powder. Generally, about 40 to 60 wt% of copper oxide is added to the antifouling agent based on the total weight. On the other hand, if a small amount of nano copper is used, sufficient antifouling effect can be obtained.

There are chemical methods and physical methods for making metal nanoparticles that show the properties of hindering the adhesion of various microorganisms and organic materials in antifouling agents. In the case of chemical methods, copper nanoparticles are made and various methods are used for uniform mixing with existing antifouling agents. It was necessary to bond the organics with the copper nanoparticles.

In addition, in the conventional physical method, when metal nanoparticles are formed by condensation in vacuum or air using pulverization or plasma to form metal nanoparticles, the metal nanoparticles are non-uniform in size or the added metal nanoparticles agglomerate with each other to increase in size. There was a problem that the effect as particles is lowered.

In order to solve the problems of the prior art as described above, the present invention provides an antifouling additive, which is excellent in antimicrobial and bactericidal properties, uniform in size of the metal nanoparticles and uniformly attached to the surface of the carrier, a manufacturing method thereof, and an antifouling agent comprising the same. It aims to do it.

In order to achieve the above object, the present invention includes a carrier having a metal nanoparticles having a particle diameter of 100nm or less attached to the surface, the carrier is an antimicrobial or bactericidal compound provides an additive for antifouling.

In addition, the present invention is a) vacuum chamber, comprising the step of inert gas such that the vacuum degree is 1 to 10 ^-4 torr, b) forming a metal vapor, c) the metal vapor is scattered in the opposite direction of the carrier After moving to the carrier direction, d) the carrier is stirred at 1 to 200rpm and e) providing a method for producing an additive for antifouling agent comprising the step of forming metal nanoparticles on the surface of the carrier.

The present invention also provides an antifouling agent containing the additive for the antifouling agent.

According to the present invention, it is possible to provide an antifouling additive which exhibits excellent antibacterial and bactericidal power even with a low content of the metal nanoparticles, and has a uniform size of the metal nanoparticles and is uniformly attached to a carrier, and a method of manufacturing the same. The antifouling agent is easily dispersed in the metal nanoparticles exhibits excellent sterilization or antibacterial effect.

1 is a photograph of the appearance of zinc pyrithione before metal nanoparticles are attached.
Figure 2 is a photograph of the appearance of the copper-zinc pyrithione prepared in Example 1.
Figure 3 is a photograph of the copper-zinc pyridion prepared in Example 1 observed with an electron microscope.
FIG. 4 is a graph showing component test results by an energy spectroscopic detector of copper-zinc pyrithione prepared in Example 1. FIG.
5 is a photograph taken by electron microscopy after dissolving the copper-zinc pyrithione prepared in Example 1 in dichloromethane.
FIG. 6 is a graph showing component test results by an energy spectrophotometer after dissolving the copper-zinc pyrithione prepared in Example 1 in dichloromethane.
7 is a photograph of the appearance of copper pyrithione before metal nanoparticles are attached.
Figure 8 is a photograph of the appearance of the copper-copper pyrithione prepared in Example 2.
Figure 9 is a photograph of the copper-copper pyrithione prepared in Example 2 observed with an electron microscope.
FIG. 10 is a graph showing component test results by an energy spectroscopic detector of copper-copper pyrithione prepared in Example 2. FIG.
11 is a photograph taken by electron microscopy after dissolving the copper-copper pyrithione prepared in Example 2 in dichloromethane.
12 is a graph showing the component test results by the energy spectroscopic detector after dissolving the copper-copper pyrithione prepared in Example 2 in dichloromethane.
Figure 13 is a photograph showing the halozone test results of the copper-zinc pyrithione prepared in Example 1.
Figure 14 is a photograph showing the halozone test results of the copper-copper pyrithione prepared in Example 2.
15 is a schematic diagram of a direction in which metal vapor is scattered.

Hereinafter, the present invention will be described in detail.

The present invention includes a carrier having a metal nanoparticle having a particle diameter of 100 nm or less attached to a surface thereof, and wherein the carrier is an antimicrobial or bactericidal compound.

The additive for antifouling agents, unlike general chemical copper powder manufacturing, for antifouling agents consisting of additives in which metal nanoparticles are directly attached to the carrier by using antimicrobial or bactericidal compounds included in existing antifouling agents, ie, metal nanoparticle-carriers Additive. The antifouling agent additive is easily added to the existing antifouling agent, and easily disperses the metal nanoparticles, thereby improving the performance of the antifouling agent.

It is preferable that the diameter of the metal nanoparticles is 100 nm or less. In this case, when the diameter exceeds 100 nm, the volume of the antifouling agent is increased, and there is a problem in that an excessive amount of the metal nanoparticles is used to achieve the purpose of the antifouling agent. .

Existing antifouling additives are made of the metal nanoparticle-carrier of the present invention, whereas the additives for antifouling agents are formed through a complicated process of combining various organic substances with the metal nanoparticles and mixing them with the antifouling agent when the metal nanoparticles are added. In the case of the antifouling additive, the neutral metal nanoparticles are charged and attached to the carrier and are easily mixed with the components contained in the antifouling agent.

Furthermore, when the metal nanoparticle-carrier is used, even if the metal nanoparticle-carrier is included in an amount of 1 to 5% by weight based on the total weight of the antifouling agent, the metal nanoparticle-carrier exhibits a sufficient role as an antifouling agent. By increasing the effectiveness and duration of the antifouling agent.

The carrier may be zinc pyrithione, copper pyrithione, tolyfluanid, dichlofluanid, copper thiocyanate, geneb ( Zineb), Irgarol and seanine is preferably at least one selected from the group consisting of. More preferably, zinc pyrithione or copper pyrithione is preferred, and the zinc pyrithione or copper pyrithione is included in the antifouling agent and serves as a bactericidal aid, and at the same time binds to the metal nanoparticles as a carrier. It serves to mix the metal nanoparticles with the antifouling agent.

It is preferable that the metal nanoparticle is at least one selected from the group consisting of cobalt, copper, silver, nickel, manganese, palladium, indium and iron. More preferably, copper nanoparticles are used. The metal nanoparticles may be cobalt, copper, silver, nickel, manganese and iron, as well as cobalt-nickel-manganese, cobalt-iron, cobalt-indium, copper-silver, manganese-iron and nickel-iron as their alloys. Can be. The relative sterilizing power of the metal nanoparticles is shown in the order of cobalt> copper> silver> nickel> manganese> palladium> iron, and in the case of alloys, cobalt-nickel-manganese> cobalt-iron> cobalt-indium> manganese-iron> nickel-iron It shows the bactericidal power of.

The mechanism representing the bactericidal activity of the metal nanoparticles comprises 1) disruption of the cell wall due to the transition potential of the bacterial cell wall of the metal nanoparticles, and 2) induction of ATP (Adenosine triphosphate) deficiency of the cell by the metal nanoparticles. And bactericidal effect.

The present invention provides a carrier in a vacuum chamber, in which an inert gas is included such that the vacuum degree is 1 to 10 ^-4 torr, b) a metal vapor is formed, and c) the metal vapor is scattered in the opposite direction of the carrier. Moving in the direction, d) the carrier is stirred at 1 to 200rpm, and e) forming a metal nanoparticle on the surface of the carrier.

In the method for preparing the antifouling agent additive, the direction in which the metal vapor is scattered in the process of forming and scattering the metal vapor so as to scatter toward the opposite direction, that is, the upward direction, is not the downward direction in which the carrier is located.

When metal vapors are produced at low deposition rates, the vaporization of a small amount of liquid in a solid metal vaporizes instantaneously, producing metal vapors. On the other hand, in order to produce metal vapor at high deposition rates, the metal must be produced in large quantities from solid to liquid and the liquid back into gas to produce metal vapor. In this case, when the scattering direction of the metal vapor is in the direction in which the carrier is positioned, that is, in the downward direction, the metal vapor cannot be prevented from flowing down in the direction in which the carrier is located in the process of forming the liquid, and thus the metal vapor cannot be formed at a high deposition rate. However, by adjusting the degree of vacuum, the scattering direction of the metal vapor is scattered in the opposite direction in which the carrier is located, that is, the upward direction as shown in FIG. It is possible to move, thus increasing the deposition rate.

At this time, it is preferable to maintain the vacuum degree of the vacuum chamber 1 to 10 ^-4 torr. When the vacuum degree exceeds 1 torr, the metal increase maintains the straightness, so that the metal vapor cannot move in the downward direction in which the carrier is stirred. In addition, when the vacuum degree is less than 10 ^-4 torr, the carrier close to the deposition source from which the metal vapor is generated is deposited with thick metal nanoparticles, but the further away from the deposition source, the metal nanoparticles are not deposited on the carrier. . That is, when the vacuum degree is 1 to 10 ^-4 torr, the metal vapor flies upward and the distance of the mean free path of the atoms is short due to the collision between the metal vapor and the inert gas under the influence of the inert gas filled therein. As a result, the atoms of the metal vapor are moved downward by gravity, and as a result, the metal vapor generated from the deposition source is moved from the initial scattering direction toward the carrier position.

The vacuum degree of the vacuum chamber is controlled by including an inert gas in the vacuum chamber, and the inert gas is preferably argon gas (Ar) or neon (Ne).

The carrier is preferably stirred at a speed of 1 to 200 rpm by the screw of the stirring tank. If the stirring speed is less than 1 rpm, the stirring is not sufficiently performed, so that the metal nanoparticles are not uniformly attached to the carrier surface. If the stirring speed exceeds 200rpm, there is a problem in that the carrier is stirred.

That is, the metal vapor is bonded to the surface of the carrier and a nucleus for forming the metal nanoparticles is formed, and then the carrier is stirred, rotated and mixed before the nucleus grows further from the metal vapor and increases in size, and then the metal nanoparticles Metal vapor is attached to the surface of the new carrier to which no is attached. Therefore, the metal nanoparticles attached to the carrier may be uniformly attached to control the size of the metal nanoparticles and the amount of the metal nanoparticles attached to the carrier.

The step of forming the metal vapor is preferably formed by any one method selected from the group consisting of resistance heating, electron beam heating, plasma heating, induction heating and laser heating. The resistive heating method, the electron beam heating method, the plasma heating method, the induction heating method and the laser heating method are methods for forming metal vapor from the metal by physical methods.

When chemically forming metal nanoparticles, it is necessary to combine various organic materials to facilitate mixing with antifouling agents, but by using a physical method to form a non-charged neutral metal nanoparticles and bind them to a carrier By mixing with the antifouling agent, it is possible to produce an additive for the antifouling agent. In addition, in the case of a chemical method, impurities may be contained during the manufacturing process, so an additional step is required. However, when the physical method is used, an additional step for removing the impurities is unnecessary. In addition, in the chemical method, the metal nanoparticles have different redox potentials between metals, so that it is difficult to form a uniform alloy, and the particles may be manufactured in a spherical shape, and the manufacturing cost is high.

Therefore, the problem of forming the metal nanoparticles by the chemical method can be solved by introducing a physical method such as resistance heating method, electron beam heating method, plasma heating method, induction heating method and laser heating method. Furthermore, the problem of controlling the size of metal nanoparticles when using physical methods can be overcome by attaching the metal nanoparticles to a stirred carrier.

The present invention includes a carrier having a metal nanoparticle having a diameter of 100 nm or less attached to a surface thereof, and the carrier includes an antifouling agent which is an antimicrobial or bactericidal compound.

The present invention will be described in more detail with reference to the following examples. However, these embodiments are merely exemplary and do not limit the technical scope of the present invention.

<Examples>

Example 1 Additive for Copper-Zinc Pyrithione Antifouling Agent

After argon (Ar) gas was injected into the vacuum chamber to adjust the vacuum degree to 10 ^-3 torr, copper vapor was generated by a DC sputter using copper as a deposition source. In this case, the copper vapor is scattered in a direction opposite to the direction in which the carrier contains zinc pyrithione (Zn Pyrithione), that is, an upward direction.

The zinc pyrithione is stirred by a rotating screw installed in the stirring tank, wherein the stirring speed of the zinc pyrithione by the screw is maintained at 100 rpm.

After the metal vapor was maintained to react with zinc pyrithione for a predetermined time, copper-zinc pyrithione containing 10,000 ppm copper nanoparticles was prepared.

<Example 2> Additive for copper-copper pyrithione antifouling agent

In Example 1, it was carried out in the same manner as in Example 1 except for using copper pyrithione as a carrier.

<Experimental Example>

1. Surface observation

The change in appearance of the copper-zinc pyrithione and copper-copper pyrithione prepared in Examples 1 and 2 was observed by visual and electron microscopy.

2. EDS  Component analysis

Copper-zinc pyrithione and copper-copper pyrithione prepared in Examples 1 and 2 were subjected to quantitative and qualitative analysis of components using an energy dispersive spectroscopy (EDS).

3. Recrystallization after Solvent Treatment

After dissolving the copper-zinc pyrithione and copper-copper pyrithione prepared in Examples 1 and 2 in dimethyl chloromethane (Dichloromethane) and observed the recrystallized form of the copper nanoparticles through an electron microscope.

4. Antimicrobial Evaluation

The halo zone test (KS-0692-1991) was performed to evaluate the antimicrobial activity against the copper-zinc pyridion and copper-copper pyrithione prepared in Examples 1 and 2. The strains used were Staphylococcus aureus and E. coli (Escherichia), and tryptic soy broth (TSB) was used as a medium, and the change was observed visually.

5. Evaluation

As a result of the surface observation, it can be seen that the color becomes dark after the copper nanoparticles are formed. That is, after forming 10,000 ppm of copper nanoparticles on a carrier of zinc pyrithione powder which was initially white as shown in FIG. 1, the color was changed to pale green as shown in FIG. 2.

3, which was observed with an electron microscope, shows that zinc pyrithione has a needle-like structure, and it can be confirmed that the zinc pyrithione has a rough shape on its surface. In this enlarged picture, it can be seen that large islands are formed, and very small particles form islands in another shape. That is, it can be seen that the copper nanoparticles are uniformly attached to the surface using zinc pyrithione as a carrier.

4 is an investigation of the components of the copper-zinc pyrithione prepared in Example 1 using an energy dispersive spectroscopy (EDS), the high peak zinc is zinc present in the zinc pyrithione It can be confirmed that, the copper peak can be confirmed that the copper component of the copper nanoparticles introduced through the process.

FIG. 5 is a photograph of a crystal obtained by dissolving the copper-zincpyridion prepared in Example 1 in dichloromethane as a solvent and recrystallizing it. The island form on the carrier, which was shown before dissolving in dichloromethane, was not observed, and the surface of the carrier was confirmed to be very smooth.

FIG. 6 is a result of analyzing a component in which copper re-crystallized in Example 1 is dissolved in dichloromethane and dried and then recrystallized in the inside of zinc pyrithione; zinc in zinc pyrithione It can confirm that the copper component of a component and a copper nanoparticle is detected. This is because the initial copper nanoparticles adhere on the zinc pyrithione powder, but after dissolving it in a solvent of dichloromethane, the copper nanoparticles cannot be identified in appearance by uniformly mixing with zinc pyrithione during copper recrystallization of the copper nanoparticles. It can only be confirmed through analysis.

7 is an external appearance of the initial copper pyrithione, and FIG. 8 illustrates a state in which copper nanoparticles are attached using copper pyrithione as a carrier.

FIG. 9 is an electron microscope photograph of the copper pyrithione to which the copper nanoparticles are attached, and it may be confirmed that the copper nanoparticles are roughly attached to the needle-shaped carrier surface.

Figure 10 shows the energy spectroscopic detector analysis results, it can be seen that the peak of the peak (peak) of the analysis results. It can be seen that the peak of copper is a copper component for copper constituting copper pyrithione and copper nanoparticles attached to the copper pyrithione.

FIG. 11 shows the copper nanoparticles recrystallized after dissolving the copper pyrithione in which the copper nanoparticles are formed in dichloromethane, and it can be seen that the needle-shaped carrier was reformed. This indicates that, unlike FIG. 9, the copper nanoparticles attached to the surface of the copper pyrithione are recrystallized and mixed uniformly with the copper pyrithione, thereby confirming that the surface of the carrier is smooth.

12 shows the copper-copper pyrithione after the solvent treatment with an energy spectrophotometer, and did not show a difference from the results confirmed by the energy spectroscopic detector before the solvent treatment. Indicates that it is mixed uniformly.

13 and 14 show the results of the evaluation of the antimicrobial activity for the copper-zinc pyrithione and copper-copper pyrithione prepared in Examples 1 and 2. As a result of the halo zone test, the strains were not grown in the center of the plate in which the copper-zinc pyrithione and copper-copper pyrithione prepared in Examples 1 and 2 were located. And the copper-zinc pyrithione and copper-copper pyrithione prepared in 2 are grown only on the outside of the plate not located, and the copper-zinc pyrithione and copper-copper pyrithione prepared through It can be confirmed that there is antibacterial activity against cocci and Escherichia coli.

Claims (7)

As an additive for antifouling agents, which includes a carrier having metal nanoparticles having a particle diameter of 100 nm or less attached to the surface, and the carrier is an antimicrobial or bactericidal compound,
The metal nanoparticle is copper,
The carrier is at least one selected from the group consisting of zinc pyrithione, copper pyrithione, tolylufluoride, diclofloanide, copper thiocyanate, geneb, irgarol and cinnain Additives for antifouling agents. delete delete a) vacuum chamber, in which the inert gas is included such that the vacuum degree is from 1 to 10 ^-4 torr,
b) metal vapor is formed,
c) the metal vapor is scattered in the opposite direction of the carrier and then moved in the carrier direction,
d) the carrier is stirred at 1 to 200 rpm and
e) a method of preparing an additive for antifouling agent, comprising the step of forming metal nanoparticles on the surface of the carrier. The antifouling method according to claim 4, wherein the forming of the metal vapor is performed by any one method selected from the group consisting of resistance heating, electron beam heating, plasma heating, induction heating and laser heating. Process for preparing additives for preparation. Antifouling agent containing an additive for antifouling agent prepared according to the manufacturing method of claim 4. As an additive for antifouling agents, which includes a carrier having metal nanoparticles having a particle diameter of 100 nm or less attached to the surface, and the carrier is an antimicrobial or bactericidal compound,
The metal nanoparticle is at least one selected from the group consisting of cobalt, copper, silver, nickel, manganese, palladium, indium and iron,
The carrier is at least one selected from the group consisting of zinc pyrithione, copper pyrithione, tolylufluoride, diclofloanide, copper thiocyanate, geneb, irgarol and cinnain,
a) vacuum chamber, in which the inert gas is included such that the vacuum degree is from 1 to 10 ^-4 torr,
b) metal vapor is formed,
c) the metal vapor is scattered in the opposite direction of the carrier and then moved in the carrier direction,
d) the carrier is stirred at 1 to 200 rpm and
e) an additive for antifouling agent prepared according to a manufacturing method comprising the step of forming metal nanoparticles on the surface of the carrier.

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