KR101436299B1 - Antifouling paints composition - Google Patents

Abstract

The antifouling coating composition comprising the antifouling enzyme-porous carrier composite of the present invention has an antifouling performance higher than that of the conventional antifouling enzyme-substrate composite, And economical problems can be solved by using a support having a low unit cost.
In addition, it can be effectively applied to various industrial fields (marine port industry, fluid transportation industry, water treatment industry, etc.) where the antifouling material is used if it is used after being developed as a coating material by mixing with various polymer materials widely used as paint materials It is possible to use it as a substitute for existing chemical fouling materials which are restricted in use due to environmental pollution.

Description

[0001] Antifouling paints composition [0002]

More particularly, the present invention relates to an antifouling coating composition containing a much larger amount of an antifouling enzyme than an antifouling composition containing a conventional antifouling enzyme

The antifouling paint composition is intended to prevent or control the attachment and growth of marine organisms causing surface contamination of the seawater-deposited coating film. When exposed to water for a long period of time, various kinds of aquatic organisms, such as seashells, oysters, mussels such as shellfishes and shellfishes, plants such as seaweeds, and aquatic bacteria, And the appearance becomes poor or its function is lost. Particularly, when these aquatic organisms adhere to the bottom of the ship and proliferate, surface roughness of the entire outer shell of the ship may increase, leading to deterioration of linear velocity or fuel consumption. Removing aquatic organisms from the bottom requires more than necessary effort and long working time. In addition, when bacteria adhere to a submerged structure attached to an underwater structure and mucus (slime material) or slime adheres to it, or when large-scale adherent creatures adhere to an underwater structure (such as a steel structure) In the case of damaging the corrosion-resistant coating film of an underwater structure, there is a problem that the strength or function of an underwater structure is lowered and the service life is remarkably shortened.

In order to prevent such a problem, it is general practice to coat an antifouling coating composition containing copper (tributyltin methacrylate, methyl methacrylate, etc.) and copper oxide (Cu ₂ O) as an antifouling paint excellent in antifouling property on the bottom part to be.

The copolymer constituting the antifouling paint composition is hydrolyzed in seawater and is converted into bistributyltin oxide (Bu ₃ Sn-OSnBu ₃ (Bu is butyl group)) or tributyltin halide (Bu ₃ SnX (X is halogen atom )), Thereby exhibiting an antifouling effect. Since the copolymer is a hydrolyzable self-polishing paint, the hydrolyzed copolymer itself is also converted into water-soluble and dissolved in seawater, so that the resin remains on the surface of the bottom coating film and remains active Keep the surface.

However, the abovementioned organic tin compounds are very toxic and highly likely to cause marine pollution, malformed fish or malformed clams, and destruction of aquatic ecosystems through the food chain. Due to these problems, it has been required to develop a tin-free antifouling paint which can replace the conventional organotin-based antifouling paints.

In recent years, various materials such as zinc, copper, silyl, silicon, and copper dioxide and abrasion-resistant materials have been used to replace tin. Conventional paints use a binder partially gelled by mixing a metal ester compound such as metal acetate with an acid group-containing polymer. Such a binder has poor film-forming ability and storage stability to cause cracking, poor abrasiveness, and difficulty in application as a high viscosity. In addition, conventional acrylic polymers such as zinc acrylate mixed with a metal ester compound have a problem in that they are not well controlled in abrasion and are insecure in long-term abrasion.

In addition, these substances have also been reported to adversely affect the ecosystem, including heavy metals.

Korean Patent Application No. 2001-7010883 discloses a composition for shipwash prevention comprising an antifouling enzyme or a microorganism producing the same in an epoxy or glass fiber. Korean Patent Application No. 2002-7012611 discloses an anti-staining composition comprising rosin and an antifouling enzyme, and the rosin has an effect of immobilizing the antifouling enzyme and preventing the antifouling enzyme from being discharged to the outside. However, all of these prior arts have a problem that the amount of antifouling enzyme fixed on the support is extremely small and the antifouling effect is low, and when the time passes, the antifouling enzyme easily flows out to the outside and the antifouling effect is drastically deteriorated.

As described above, the anticorrosive coating composition containing the antifouling enzyme has a problem that the antifouling performance is remarkably low when it is applied to an actual industry due to an extremely low activity, and the antifouling effect is drastically decreased when a long time passes .

SUMMARY OF THE INVENTION Accordingly, the present invention has been made to overcome the above-mentioned problems, and an object of the present invention is to provide a composition containing an antifouling enzyme, which contains a considerably large amount of antifouling enzyme as compared with a conventional composition containing an antifouling enzyme, And an anti-fouling composition in which the antifouling enzyme hardly flows out to the outside.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide an antifouling enzyme-porous carrier composite comprising a porous carrier and an antifouling enzyme carried inside the pores of the carrier.

As one embodiment of the present invention, the present invention provides a coating composition comprising an antifouling enzyme-porous carrier mixed with a coating material.

Here, the antifouling enzyme may be carried on the inside of the porous carrier to form a complex by cross-linking.

The porous carrier may be selected from the group consisting of silica, alumina, niobium, tantalum, zirconium, carbon, magnesium, and titanium.

Wherein the antifouling enzyme is selected from the group consisting of acylase, lactonase, protease, peroxidase, aminopeptidase, phosphatase, transaminase, serine-endopeptidase, cysteine-endopeptidase and metalloendopeptidase It can be more than one.

According to another embodiment of the present invention, the porous carrier may include magnetic nanoparticles.

According to a preferred embodiment of the present invention, the pore size of the inside of the porous carrier may be 1 to 1000 nm.

According to another preferred embodiment of the present invention, the porous carrier may or may not contain a functional group capable of covalently bonding with the enzyme in the porous carrier.

According to another preferred embodiment of the present invention, the antioxidant-porous carrier complex may be contained in an amount of 0.01 to 50% by weight based on the total coating composition.

A method of making a coating composition according to one embodiment of the present invention comprises the steps of:

(1) adsorbing an antifouling enzyme in pores of a porous carrier;

(2) adding a cross-linking agent to the porous support on which the antifouling enzyme is adsorbed to form cross-linking between the antifouling enzymes to form a porous support-antifouling enzyme complex; And

(3) mixing the porous carrier-antifouling enzyme complex with a coating material

The antifouling enzyme complex may have a diameter larger than the inlet size of the porous carrier pores. Therefore, it can be stably immobilized in the carrier without easily escaping from the pores of the porous carrier.

Alternatively, as another embodiment of the present invention, an antifouling enzyme complex may be prepared by simultaneously adding an enzyme and a crosslinking agent to the porous carrier in the step (1).

The crosslinking agent is selected from the group consisting of diisocyanate, dianhydride, diepoxide, dialdehyde, diimide, 1-ethyl-3-dimethylaminopropylcarbodiimide, glutaraldehyde, bis (imidoesters) Esters) and diacid chlorides. ≪ / RTI >

The antifouling coating composition comprising the antifouling enzyme-porous carrier composite of the present invention has an antifouling performance higher than that of the conventional antifouling enzyme-substrate composite, And economical problems can be solved by using a support having a low unit cost.

In addition, it can be effectively applied to various industrial fields (marine port industry, fluid transportation industry, water treatment industry, etc.) where the antifouling material is used if it is used after being developed as a coating material by mixing with various polymer materials widely used as paint materials It is possible to use it as a substitute for existing chemical fouling materials which are restricted in use due to environmental pollution.

1 is a schematic view showing a step of immobilizing an antifouling enzyme after making spherical porous silica into magnetic-porous silica.
2 shows an image of a commercially available spherical porous silica material (left) and a magnetic-porous silica (right) chemically attached with magnetic nanoparticles.
Fig. 3 is a photograph showing a state in which the antifouling enzyme-magnetic-porous silica antifouling material is separated from the solution by using a magnetic field formed by a magnet.
FIG. 4 is a graph showing the results of measurement of antifouling enzyme (Free AC) using a fluorescence-spectrophotometer, magnetic-porous silica complex adsorbed with antifouling enzyme (ADS-AC / Mag-S-MPS) (NER-AC / Mag-S-MPS).
FIG. 5 is an experiment conducted to confirm the antifouling effect of a magnetic-porous silica composite (NER-AC / Mag-S-MPS) crosslinked after adsorption of an antifouling enzyme under the condition that a biofilm is formed. (B, wastewater + S. aeruginosa + Mag-S-MPS) containing the magnetic-porous silica material under the conditions of the progress of the contamination, (C, wastewater + S. aeruginosa + NER-AC / Mag-S-MPS) containing the magnetic-porous silica material. The graph shows the relative permeability over time for the initial permeability value by checking the permeability of the membrane filter induced contamination under each condition.
6 is a schematic diagram of the equipment installed for measuring the permeability.
FIG. 7 shows an image obtained by observing the surface of the separation membrane from which pollution was induced through a confocal scanning microscope through the respective conditions shown in FIG.
FIG. 8 is a schematic view showing an apparatus for measuring a trans-membrane pressure (TMP) which is changed by biofilm formation when a flow passing through a membrane filter is induced at a constant flow rate.
9 is a graph showing the results of experiments in which the permeation pressure (trens membrane pressure) (TMP) of biofilm formation was measured under the condition that only the coating material was applied to the separation membrane filter and the mixture of the antifouling enzyme-magnetic-porous silica and the coating material was applied to the separation membrane filter to be.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

The term " antifouling enzyme " refers to an enzyme contained in an antifouling composition to prevent adhesion and growth of contaminants on the surface of a substance through biological antifouling. For example, surface attachment and growth of biological contaminants is driven by a unique quorum sensing system, while quorum sensing materials are compounds of the N-acyl homoserine lactone (AHL) family, This compound acts to hydrolyze and quorum quenching the signal. Meanwhile, the antifouling enzyme disclosed in Korean Patent Application No. 2001-7010883 and Korean Patent Application No. 2002-7012611 can be included in the present invention.

The term 'porous carrier' refers to a carrier having a plurality of pores having a size of 1 to 1000 nm in the interior, and may include microporous (pore <2 nm), mesoporous (2 nm <pore < 50 nm), and macroporous (pore> 50 nm) materials.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a step of supporting an enzyme in pores of a porous carrier. FIG.

First, the nano magnetic particles are supported in the pores of the porous carrier, and then the enzyme is filled into the porous carrier. Then, the enzymes are adsorbed in the pores of the porous carrier as shown in the lower right of FIG. However, except for some enzymes adsorbed inside the porous carrier, the remaining enzymes are contained in the pores without any bonding. Therefore, when the liquid is introduced from the outside or external pressure is applied, the remaining enzymes, except for some adsorbed enzymes, As shown in FIG. In addition, some of the adsorbed enzymes also decrease in adsorption power over time and eventually leak out. As a result, the stability of the enzyme of the porous carrier is deteriorated.

On the other hand, when a cross-linking agent is added to the enzymes contained in the pores, cross-linking is formed between the enzymes adsorbed in the pores and the non-adsorbed enzymes to form an enzyme complex. As a result, the crosslinked enzyme complex becomes larger than the size of the pore openings of the porous carrier. As a result, not only a remarkably large amount of enzyme can be carried on the inside of the porous carrier, Since the enzyme aggregate is located, the inside of the porous carrier is not modified to form a functional group capable of covalently bonding with the enzyme, so that even if a direct binding relationship such as a covalent bond between the porous carrier and the antifouling enzyme is not formed, For a long period of time.

First, the porous carrier used in the present invention will be described. Usually, any porous carrier used to support the enzyme can be used without limitation. Preferably, the porous carrier may be at least one selected from the group consisting of silica, alumina, niobium, tantalum, zirconium, carbon, magnesium and titanium, and may be selected from the group consisting of mesoporous silica (MPS), mobile composition of matter It can be used in the form of SBA (Santa Barbara materials), CNS (MPS with cyano-funtional groups), ordered mesoporous carbon (OMC), mesocellular carbon foam (MCF-C) or supplementary cementitious materials (SCMS) or mesocellular foam.

On the other hand, the antifouling enzyme which can be used in the present invention can be used without limitation as long as the antifouling enzyme can be carried on the inside of the porous carrier to cause an antifouling effect in the coating. Preferably, the antifouling enzyme is selected from acylase, lactonase, But are not limited to, any one selected from the group consisting of aminopeptidase, phosphatase, transaminase, serine-endopeptidase, cysteine-endopeptidase, and metalloendopeptidase.

[Preparation example]

Manufacture of Magnetic-Porous Silica Material

Magnetic-porous silica for immobilization of antioxidant enzyme was prepared by immobilizing magnetic nanoparticles on a porous silica material using chemical adsorption. 1 g of spherical mesoporous silica and 0.5 g of Fe (NO ₃ ) ₃ 9H ₂ O were dissolved in 20 ml of ethanol and prepared. The mixture was stirred until the ethanol solution was completely evaporated at room temperature, and the remaining sample was completely dried at 100 ° C to 400 ° C at a rate of 3 ° C per minute to prepare magnetic-porous silica.

[Comparative Example]

Antifouling enzyme  Using adsorption method Antifouling enzyme  Fixation method ( Enzyme adsorption , ADS )Depending on the Antifouling enzyme - Magnetic-Porous Composite Manufacturing

Porous silica was prepared by mixing the magnetic porous silica prepared in Example 1 with an antifouling enzyme (acylase, AC) to obtain enzyme adsorbed enzyme-adsorbed enzyme. Specifically, 10 mg of the magnetic-porous silica prepared in Example 1 and 1.5 ml of antifouling enzyme were mixed in a 2 ml centrifuge tube. The antifouling enzyme was prepared at a concentration of 2 mg / ml in 100 mM phosphate buffer Respectively. The prepared antifouling enzyme-magnetic-porous silica mixture was stirred at 50 rpm using a stirrer at room temperature for 30 minutes. Through this process, the antifouling enzyme is adsorbed on the surface of the magnetic-porous silica pores. The supernatant was removed by centrifugation, and the supernatant was removed by using a 100 mM Tris buffer solution for 30 minutes using a stirrer to remove the unbound antioxidant enzyme and to cap the remaining unreacted antifouling enzyme-adhering functional groups on the polymer nanofibers. rpm. After completion of the capping reaction, the remaining Tris buffer solution was washed with 100 mM phosphate buffer solution.

Antifouling enzyme  After adsorption The cross-linking method  Used Antifouling enzyme - Preparation of magnetic-porous silica composite

The nanoscale enzyme reactor (NER) was used to mix the magnetic-porous silica prepared in Example 1 with an antifouling enzyme (acylase, acylase, AC) Were synthesized. Specifically, magnetic-porous silica having enzyme adsorption was synthesized by mixing the magnetic-porous silica prepared in the preparation example with an antifouling enzyme (acylase, AC). Specifically, 10 mg of the magnetic-porous silica and 1.5 ml of the antifouling enzyme prepared in the above Preparation Example were mixed in a 2 ml centrifuge tube. The antifouling enzyme was prepared at a concentration of 2 mg / ml in 100 mM phosphate buffer Respectively. The prepared antifouling enzyme-magnetic-porous silica mixture was stirred at 50 rpm using a stirrer at room temperature for 30 minutes. Through this process, the antifouling enzyme is adsorbed on the surface of the magnetic-porous silica pores. Then, glutaraldehyde, which is a crosslinking agent, was added in an amount of 0.1% of the total volume in order to induce cross-linking through covalent bonds between adsorbed antifouling enzymes. For sufficient crosslinking, the mixture was stirred at room temperature for 2 hours using a rocker at 50 rpm. The supernatant was removed by centrifugation and the supernatant was removed by using a 100 mM Tris buffer solution for 30 minutes using a stirrer to remove unbound antifouling enzyme and capping the unreacted antifouling enzyme- The mixture was stirred at 200 rpm. After completion of the capping reaction, the remaining Tris buffer solution was washed with 100 mM phosphate buffer solution. The antifouling enzyme-magnetic-porous silica composite (NER-AC / Mag-S-MPS) using the nano-enzyme reaction method after the adsorption of the antifouling enzyme prepared by this process is stored at 4 ° C until use, Storage is possible.

Antifouling enzyme -Magnetic-porous silica composite Antifouling enzyme  Activity and stability measurement

(ADS-AC / Mag-S-MPS) adsorbed with an antifouling enzyme prepared by the above Example 1 and Comparative Example, a nanoscale enzyme reactor (NER) method The antifouling enzyme activity of the antifouling enzyme-magnetic-porous silica composite (NER-AC / Mag-S-MPS) was measured using a fluorescence spectrophotometer (Shimadzu RF-5301).

Specifically, the antifouling enzyme-polymer nanofiber composite, which was stored at 4 ° C, was prepared by diluting to 0.5 mg / ml based on the weight of magnetic-porous silica using 100 mM phosphate buffer. Then, 10 mM N-acetyl-L-methionine is prepared as a reaction solution, and 1.9125 mg of N-acetyl-L-methionine is dissolved in 100 mM phosphate buffer. The activity of the antifouling enzyme was measured using the two solutions thus prepared. To measure the activity of the antifouling enzyme, 1 ml of an antifouling enzyme-magnetic-porous silica complex and 1 ml of a 10 mM N-acetyl-L-methionine solution were mixed and stirred for a fixed period of time under N-acetyl-L-methionine Decomposition reaction. N-acetyl-L-methionine is decomposed into acetic acid and L-methionine by an antifouling enzyme, and the decomposed L-methionine is reacted with OPA solution in which 0.1 mg of o-phthalaldehyde (OPA) is dissolved in 50 mM sodium borate buffer Fluorescence. The amount of L-methionine that can bind to the OPA material increases with time, and thus the fluorescence value displayed on the fluorescence-spectrophotometer also increases.

Figure 4 shows the results of measuring the activity of Free AC, ADS-AC / Mag-S-MPS and NER-AC / Mag-S-MPS samples. As shown in the graph.

As shown in FIG. 4, it was confirmed that the antifouling enzyme-magnetic-porous silica composite (NER-AC / Mag-S-MPS) using the cross-linking method after the adsorption of the antifouling enzyme had the highest antifouling enzyme activity stability. The antioxidant-polymer nanofiber composites were continuously agitated in a 100 mM phosphate buffer solution at 200 rpm using a stirrer. The activity half-lives of free AC and ADS-AC were found to be less than 1 day and less than 5 days, respectively . However, NER-AC showed activity stabilized more than 80% after 33 days.

Through the confirmation of the permeability of the membrane filter Antifouling enzyme - Confirmation of inhibition of biofilm formation of magnetic - porous silica composites.

The antifouling enzyme activity of the antifouling enzyme-magnetic-porous silica composite (NER-AC / Mag-S-MPS) prepared in Example 1 was conditioned to induce contamination in the membrane filter, The change in permeability was determined by.

(39.5 ml) + S. aeruginosa (0.5 ml)), and the conditions of progressive contamination (b, wastewater (38.7 ml) + S (C), wastewater (38.7 ml) + S (0.5 ml) was added to the conditions under which the contamination proceeded, followed by addition of the antifouling enzyme-magnetic-porous silica material (0.5 ml) and NER-AC / Mag-S-MPS (0.8 ml of 0.5 mg / ml) were prepared and the membrane filters were collected at intervals of one day. Using the apparatus shown in FIG. 6, the recovered membrane was measured by passing 10 ml of distilled water through the membrane by a pressure of 10 kPa. The graph shown in FIG. 5 shows the permeability of the membrane filter in which contamination was induced under each condition, and the relative permeability value with time with respect to the initial permeability value. The permeability was measured under the condition that the contamination proceeded as it is (a, wastewater (39.5 ml) + S. aeruginosa (0.5 ml)), condition in which the magnetic- 38.7 ml) + S. aeruginosa (0.5 ml) + Mag-S-MPS (0.8 ml of 0.5 mg / ml)) showed a relative permeability of less than 50% of the initial value after 3 days, (C), wastewater (38.7 ml) + S. aeruginosa (0.5 ml) + NER-AC / Mag-S-MPS (0.8 ml of 0.5 mg / ml) Greater than or equal to 50% relative permeability was maintained, and a sharp decrease in flow as seen in the other samples of FIG. 5 was not observed. These results show excellent antifouling effect of NER-AC / Mag-S-MPS sample.

Through biofilm identification of contaminated membrane filters Antifouling enzyme - Confirmation of inhibition of biofilm formation of magnetic - porous silica composites.

The antifouling enzyme activity of the antifouling enzyme-magnetic-porous silica composite (NER-AC / Mag-S-MPS) prepared in Example 1 was conditioned to induce contamination in the membrane filter, The confocal laser scanning microscope (CLSM) image was confirmed on the surface of the sample.

(39.5 ml) + S. aeruginosa (0.5 ml)), and the conditions of progressive contamination (b, wastewater (38.7 ml) + S (C), wastewater (38.7 ml) + S (0.5 ml) was added to the conditions under which the contamination proceeded, followed by addition of the antifouling enzyme-magnetic-porous silica material (0.8 ml of 0.5 mg / ml) was prepared and the filter was collected at 1-day intervals to obtain confocal laser scanning microscope (CLSM) images. And the results are shown in FIG.

As shown in FIG. 7, in the sample containing the antifouling enzyme-magnetic-porous silica composite (NER-AC / Mag-S-MPS) using the nanoscale enzyme reactor (NER) It was observed that the biofilm formation was inhibited by comparing the color distribution and the color distribution of the biofilm expressed in green in the test.

On the surface of the membrane filter Antifouling enzyme - Magnetic - Porous silica composite was applied to confirm biofilm formation inhibition performance.

The antifouling enzyme-magnetic-porous silica composite (NER-AC / Mag-S-MPS) prepared in Example 1 was mixed with the paint and applied to the surface of the membrane filter, The pressure was varied depending on the presence or absence of the biofilm formation under the condition that the membrane filter was permeated at a constant flow rate.

Specifically, if a flow is formed in the membrane filter at a constant flow rate using the apparatus of FIG. 8, a pressure to maintain the flow rate of the membrane, which is generated by the biofilm on the surface of the membrane filter, pressure, and TMP). 9, it was observed that the TMP was increased by the biofilm formed over time in the case of the membrane filter coated with only the paint, whereas the membrane coated with the coating material containing the antifouling enzyme-magnetic-porous silica was observed In the case of the filter, the formation of biofilm was inhibited and the trend of TMP increase was slowed down.

INDUSTRIAL APPLICABILITY The paint composition for preventing abrasion of the present invention can be useful for preventing or controlling the attachment and growth of living things.

Claims (14)

An antifouling enzyme-porous carrier complex comprising a porous carrier and an antifouling enzyme carried on the inside of pores of the carrier, wherein the antifouling enzyme is selected from the group consisting of acylase, lactonase, protease, peroxidase, aminopeptidase, phosphatase, Wherein the antifouling enzyme-porous carrier composite is any one selected from the group consisting of acase, serine-endopeptidase, cysteine-endopeptidase, and metalloendopeptidase, or a mixture thereof. The antifouling enzyme-porous carrier composite according to claim 1, wherein the porous carrier comprises magnetic nanoparticles. The antifouling enzyme-porous carrier composite according to claim 1, wherein the porous carrier is any one selected from the group consisting of silica, alumina, niobium, tantalum, zirconium, carbon, magnesium, and titanium. delete An antifouling paint composition comprising an antifouling enzyme-porous carrier composite according to any one of claims 1 to 3. [6] The anticorrosive coating composition according to claim 5, wherein the antifouling enzyme-porous carrier composite is contained in an amount of 0.01 to 50% by weight. The coating composition according to claim 5, wherein the coating material is any one selected from the group consisting of acrylic, epoxy, urethane, silicate, and polyester or a mixture thereof. A method for producing an anti-stain coating composition comprising an antifouling enzyme-porous carrier composite,
(1) adsorbing an antifouling enzyme in pores of a porous carrier;
(2) adding a cross-linking agent to the porous support on which the antifouling enzyme is adsorbed to form cross-linking between the antifouling enzymes to form an antifouling enzyme-porous support complex ; And
(3) mixing the antifouling enzyme-porous carrier composite with a coating material
Wherein the coating composition is a coating composition. The method according to claim 8, further comprising pretreating the magnetic nanoparticles on the porous carrier. 9. The composition of claim 8, wherein the crosslinking agent is selected from the group consisting of diisocyanate, dianhydride, diepoxide, dialdehyde, diimide, 1-ethyl- , Bis (succinimidyl ester), and diacid chloride. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method of claim 8, wherein the porous carrier is selected from the group consisting of silica, alumina, niobium, tantalum, zirconium, carbon, magnesium, and titanium. The antifouling agent according to claim 8, wherein the antifouling enzyme is composed of acylase, lactonase, protease, peroxidase, aminopeptidase, phosphatase, transaminase, serine-endopeptidase, cysteine-endopeptidase and metalloendopeptidase Or a mixture thereof. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method according to claim 8, wherein the antifouling enzyme-porous carrier composite is contained in an amount of 0.01 to 50 wt%. 9. The method according to claim 8, wherein the coating material is any one selected from the group consisting of acrylic, epoxy, urethane, silicate, and polyester, or a mixture thereof.

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