An Anti-fouling composition and application thereof

Abstract

An anti-fouling paint and a manufacture method thereof are developed. The anti-fouling paint comprises a modified epoxy using a stable colloidal solution as a biocide agent. The stable colloidal solution comprises a three-component nanocomposite of titanium dioxide, silver metal and silver chloride. The stable colloidal solution can be used in different forms of spry, film, coat, paint, and filter. The anti-fouling paint is used in shipping, municipal, construction, oil and gas, medical, cosmetics and marine equipment industries which cause a better and more stable performance compared to the conventional anti-fouling paints.

Description

An anti-fouling composition and application thereof

[0001] The present disclosure is related to an anti-fouling composition and a manufacture method thereof, especially an anti-fouling paint containing a modified epoxy using a stable colloidal solution as a biocide agent.

[0002] Barnacles, saltwater organisms, can attach to boat hulls and flat surfaces and make them slimy due to growth of algae in a short period of time. Algae pave the way for the adhesion of other organisms. Barnacles and moss are deposited on the hulls of ships and boats, causing them to move slowly, use more fuel, and make maneuvering more difficult. Invasive organisms are spread by sediment under boats and ships. Barnacles slow a boat by 50%.

[0003] A special coating which is applied to the hull and propellers of a marine craft and equipment to prevent corrosion and the growth of marine organisms such as barnacles, slime, algae and mossy weed is known as anti-fouling, anti-algae, or bottom paint. Corrosion and fouling are interrelated in that poor corrosion resistance leads to the disruption of the paint, hence the loss of anti-fouling properties. Poor fouling resistance also leads to corrosion due to barnacles cutting their way to the substrate and disrupting the paint. Typical anti-fouling paint contains a biocide or a toxin in the paint, which is released into the area surrounding the hull to poison any attached organisms and prevent others from adhering to the paint.

[0004] There are some problems and challenges in using anti-fouling paint. Environmental and water pollution caused by the release of toxic substances contained in biocide agents is one of the problems. So, this limits the use of conventional biocide agents. The other problems include the poor performance, instability, and short life of conventional anti-fouling paints which caused poor corrosion protection.

[0005] Some articles and patents provided solutions to deal with viruses, for example patent CN113652166A is about an eco-friendly interior finishing wall coating with antiviral and antibacterial properties and the method of preparing it, which comprise preparation of nano inorganic antiviral and antibacterial powder, preparation of pure water polyurethane acrylate nano narrow-band emulsion, and preparation of pure water nano antibacterial and antiviral coating.

[0006] Also, CN113025103A is about antibacterial film and its preparation method. In this patent, the antiviral and antibacterial films compromise a main film forming substance (tetra butyl titanate and 3-(2, 3-epoxypropoxy) propyl trimethoxy silane)), ethanol and water as a solvent, ethyl acetoacetate and acetylacetone as a hydrolysis catalyst, glacial acetic acid as a pH regulator and a bactericidal antiviral agent.

[0007] These patents are similar to this work in term of technical problem, but it is very different in solution to deal with viruses.

[0008] Therefore, developing an environmentally friendly, stable, and effective anti-fouling paint is necessary to overcome the aforementioned challenges and reduce the significant economic losses resulting from biofouling on man-made marine facilities.

[0009] This summary is intended to provide an overview of the subject matter of this disclosure, and is not intended to identify essential elements or key elements of the subject matter, nor is it intended to be used to determine the scope of the claimed implementations. The proper scope of this disclosure may be ascertained from the claims set forth below in view of the detailed description below and the drawings.

[0010] In a general aspect, the present disclosure is directed to an exemplary stable colloidal solution as a biocide agent. The exemplary stable colloidal solution may comprise at least one antibacterial agent that may comprise titanium dioxide, silver metal, or a combination thereof, at least one oxidizing agent, at least one stabilizer.

[0011] The above general aspect may have one or more of the following features. In an exemplary implementation, the exemplary stable colloidal solution may further comprise at least one solvent. In an exemplary implementation, the at least one solvent may comprise at least one Diol solvent, at least one polar solvent, or the combination thereof. In an exemplary implementation, the at least one oxidizing agent comprises silver chloride, silver bromide, silver iodide, silver nitrate, or a combination thereof. In an exemplary implementation, the at least one stabilizer may be at least one polymeric stabilizer.

[0012] In another general aspect, the present disclosure is directed to an exemplary manufacturing method of an exemplary stable colloidal solution. The exemplary manufacturing method may comprise synthesizing a single step composite by adding at least one antibacterial agent and at least one oxidizing agent in a reactor, and adding the single step composite to a mixture of at least one solvent and at least one stabilizer.

[0013] The above general aspect may have one or more of the following features. In an exemplary implementation, the synthesizing a single step composite may further comprise preparing a sodium solution by mixing sodium chloride into Diol solvent and adding the sodium solution into the reactor. In an exemplary implementation, a concentration of the single step composite may be in a range of 30.0%-70.0% by weight. In an exemplary implementation, the single step composite may be a single step nanocomposite. In an exemplary implementation, the reactor is an ultrasonic reactor.

[0014] In another general aspect, the present disclosure is directed to an exemplary modified resin for producing of a coating. The exemplary modified resin may comprise at least one polymer as a resin and an exemplary stable colloidal solution as a biocide agent.

[0015] The above general aspect may have one or more of the following features. In an exemplary implementation, a concentration of the exemplary stable colloidal solution is in a range of 0.01%-10.0% by weight. In an exemplary implementation, the at least one polymer may comprise epoxy, acrylic, polyester, polyurethane, or the combination thereof.

[0016] In another general aspect, the present disclosure is directed to an exemplary anti-fouling paint. The exemplary anti-fouling paint may comprise a modified resin with a biocide agent that may comprise titanium dioxide, silver metal, and silver chloride, that a molar ratio of silver metal to titanium dioxide may be in a range of 0.01:1 to 0.4:1 by mole, that a molar ratio of silver metal to silver chloride may be in a range of 0.5:1 to 2:1 by mole.

[0017] The above general aspect may have one or more of the following features. In an exemplary implementation, the exemplary anti-fouling paint may further comprise at least one solvent, at least one pigment, at least one additive, or a combination thereof.

[0018] In an exemplary implementation, the modified resin may be a modified epoxy resin.

[0019] In an exemplary implementation, a concentration of the modified epoxy resin is in a range of 20.0%-60.0% by weight.

[0020] In another general aspect, the present disclosure is directed to an exemplary manufacturing method of an exemplary anti-fouling paint. The exemplary manufacturing method may comprise synthesizing a single step composite, preparing an exemplary stable colloidal solution by adding the single step composite to a mixture of at least one solvent and at least one stabilizer, preparing an exemplary modified resin, preparing the exemplary anti-fouling paint by adding at least one solvent, at least one pigment, at least one additive into the exemplary modified resin.

[0021] The above general aspect may have one or more of the following features. In an exemplary implementation, the synthesizing a single step composite may comprise mixing titanium dioxide, silver nitrate and Diol solvent in a reactor and adding sodium chloride and Diol solvent solution into the reactor.

[0022] In an exemplary implementation, the preparing the exemplary modified resin comprises preparing a preheated resin by heating a resin, and the stable colloidal solution and the preheated resin in a speed range of 100-120 rpm.

[0023] The drawing figure only demonstrates one or more embodiments in accord with the present teaching, by way of example only, not by way of limitation. Therefore, the drawing figure does not limit the extent of the present disclosure. Also, reference numerals with similar numbers in the figures demonstrate similar or the same elements.Fig.1

[0024] illustrates a flowchart of an implementation of a general representation of a manufacturing method of an exemplary stable colloidal solution, consistent with one or more exemplary embodiments of the present disclosure.Fig.2

[0025] illustrates a flowchart of an implementation of a general representation of a manufacturing method of an exemplary anti-fouling paint, consistent with one or more exemplary embodiments of the present disclosure.Fig.3

[0026] illustrates a HR-TEM test result of three-component nanocomposite, consistent with one or more exemplary embodiments of the present disclosure.Fig.4

[0027] illustrates a high-angle annular dark-field detector result of three-component nanocomposite, consistent with one or more exemplary embodiments of the present disclosure.Fig.5

[0028] illustrates results of algae absorption of prepared samples at a wavelength of 650 nm via a spectrophotometer, consistent with one or more exemplary embodiments of the present disclosure.

[0029] In the following detailed description, numerous specific details are set forth by way of examples in order to provide a thorough understanding of the relevant teachings. However, it should be apparent that the present teachings may be practiced without such details. In other instances, well-known processes, procedures, components, and / or circuitry have been described at a relatively high-level, without detail, in order to avoid unnecessarily obscuring aspects of the present teachings. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present disclosure is defined only by the appended claims.

[0030] The following detailed description is presented to enable a person skilled in the art to make and use the processes and devices disclosed in exemplary embodiments of the present disclosure. For purposes of explanation, specific nomenclature is set forth provide a thorough understanding of the present disclosure. However, it will be apparent to one skilled in the art that these specific details are not required to practice the disclosed exemplary embodiments. Descriptions of specific exemplary embodiments are provided only as representative examples. Various modifications to the exemplary implementations will be readily apparent to one skilled in the art, and the general principles defined herein may be applied to other implementations and applications without departing from the scope of the present disclosure. The present disclosure is not intended to be limited to the implementations shown, but is to be accorded the widest possible scope consistent with the principles and features disclosed herein.

[0031] The present disclosure describes an exemplary modified resin using an exemplary stable colloidal solution as a biocide agent that may be used in an exemplary anti-fouling paint. Some benefits of using the exemplary modified resin with the exemplary stable colloidal solution as a biocide agent, as described in the present disclosure, compared to conventional anti-fouling paints may include, but are not limited to, greater effectiveness, improved stability, better fouling and corrosion resistance in marine and industrial environments or in climates characterized by strong seasonal temperature changes. In other words, directly adding antimicrobial agents to traditional anti-fouling paint formulations can result in various issues, such as agglomeration.

[0032] Additionally, in one or more exemplary embodiments, the present disclosure describes an exemplary anti-fouling paint method. In an exemplary embodiment, the exemplary anti-fouling paint manufacturing method may comprise at least three main steps. A first step may comprise preparation of an exemplary stable colloidal solution as a biocide agent and a second step may comprise preparation of an exemplary modified resin by modifying a suitable resin using the exemplary stable colloidal solution. A third step may comprise preparation of an exemplary anti-fouling paint by adding a suitable set of additives into the exemplary modified resin. The term “suitable resin” may refer to a polymer which is desire to an exemplary anti-fouling paint. The term “set of additives” may refer to a set of required ingredients including solvent and pigment which is desire to an exemplary anti-fouling paint.

[0033] In an exemplary embodiment, aspects and features of an exemplary stable colloidal solution as a biocide agent, an exemplary manufacturing method of the exemplary stable colloidal solution, an exemplary modified resin for producing of an anti-fouling paint, and an exemplary anti-fouling paint will be described in greater detail, below.

[0034] ASTABLE COLLOIDAL SOLUTION AS A BIOCIDE AGENT

[0035] The antibacterial properties of titanium dioxide nanoparticles and silver nanoparticles enable the inhibition of biofouling in both light and dark conditions. In fact, in the presence of light, the inhibition of biofouling is achieved by reducing the band gap of titanium dioxide, allowing absorption of visible light, and preventing the recombination of electrons and holes. In the absence of light, the presence of silver contributes to cell destruction of microorganisms. Indeed, the antimicrobial activities of titanium dioxide and silver nanoparticles play a crucial role in addressing biofouling issues. By preventing biofouling, these technologies help reduce fuel consumption, decrease wear and tear on marine equipment, maintain optimal speeds for ships and boats, and save valuable time spent on cleaning and maintenance tasks. Meanwhile, the use of oxidizers like silver chloride may be necessary to address the release of these nanoparticles that could potentially pollute the waters, it is important to consider the environmental implications. Additionally, the anti-biological fouling properties and stability of the titanium dioxide, nano silver and silver chloride nanocomposite have a significant increase due to the synergistic effect.

[0036] In an exemplary embodiment, a stable colloidal solution as a biocide agent developed to overcome above-mentioned problems.

[0037] In an exemplary embodiment, an exemplary stable colloidal solution as a biocide agent may comprise at least one antibacterial agent that may comprise titanium dioxide, silver metal, or a combination thereof, at least one oxidizing agent, at least one stabilizer. In an exemplary embodiment, a size scale of titanium dioxide and silver metal may be a nanoscale.

[0038] In some exemplary embodiment, the exemplary stable colloidal solution may further comprise at least one solvent. In an exemplary embodiment, the at least one solvent may comprise at least one Diol solvent, at least one polar solvent, or the combination thereof.

[0039] In an exemplary embodiment, the at least one oxidizing agent comprises silver chloride, silver bromide, silver iodide, silver nitrate, or a combination thereof.

[0040] In an exemplary embodiment, the at least one stabilizer may be at least one polymeric stabilizer.

[0041] In an exemplary embodiment, the exemplary stable colloidal solution may be used as an antivirus and antimicrobial agent. In an exemplary embodiment, the exemplary stable colloidal solution may be added into a matrix. In an exemplary embodiment, the matrix may comprise a polymer, a ceramic, a solvent, or a combination thereof. In an exemplary embodiment, the solvent may comprise water, polar solvent, and nonpolar solvent.

[0042] In an exemplary embodiment, the exemplary stable colloidal solution may be used in a different forms, for example, but not limited to, spry, film, coat, paint, and filter. In an exemplary embodiment, the exemplary stable colloidal solution may be frizzed as a porous composition.

[0043] the exemplary stable colloidal solution application may be, for example, but not limited to, shipping, municipal, construction, oil and gas, medical, cosmetics and marine equipment industries.

[0044] AMANUFACTURING METHOD OF AN EXEMPLARY STABLE COLLOIDAL SOLUTION

[0045] illustrates a flowchart of an implementation of a general representation of a manufacturing method of an exemplary stable colloidal solution100, consistent with one or more exemplary embodiments of the present disclosure. In an exemplary embodiment, as illustrated in, the manufacturing method of an exemplary stable colloidal solution method100may comprise synthesizing a single step composite by adding at least one antibacterial agent and at least one oxidizing agent in a reactor102, adding the single step composite to a mixture of at least one solvent and at least one stabilizer104. Adding sodium chloride causes the formation of nitrate on the surface of at least one antibacterial agent.

[0046] In an exemplary implementation, the synthesizing a single step composite may further comprise preparing a sodium solution by mixing sodium chloride into Diol solvent and adding the sodium solution into the reactor.

[0047] In an exemplary embodiment, a concentration of the single step composite may be in a range of 30.0%-70.0% by weight.

[0048] In an exemplary implementation, the single step composite may be a single step nanocomposite.

[0049] In an exemplary implementation, the reactor is an ultrasonic reactor. The ultrasonic reactor reduces silver nitrate to silver metal and causes doping at least one antibacterial agent with at least one oxidizing agent.

[0050] The range of concentration has an effect on stability as well as a uniformity of the exemplary stable colloidal solution.

[0051] AMODIFIDED RESIN FOR PRODUSING OF A COATING

[0052] Conventional anti-fouling paints contain biocide agents directly into resin. If these agents comprise nanomaterials such as titanium dioxide and silver metal, they cause agglomeration and as a result reduce the properties of the resin. Meanwhile, if the resin is modified by these biocide agents, the mentioned problem will be overcome.

[0053] Furthermore, the present disclosure describes an exemplary modified resin for producing of a coating. In an exemplary embodiment, the exemplary modified resin may comprise at least one polymer as a resin and an exemplary stable colloidal solution as a biocide agent.

[0054] In an exemplary implementation, a concentration of the exemplary stable colloidal solution is in a range of 0.01%-10.0% by weight.

[0055] In an exemplary implementation, a manufacturing method of exemplary modified resin may comprise heating and mixing.

[0056] The range of concentration has an effect on stability as well as a uniformity of the exemplary modified resin.

[0057] AN ANTI-FOULING PAINT

[0058] Additionally, the present disclosure describes an exemplary anti-fouling paint. In an exemplary embodiment, the exemplary anti-fouling paint may comprise a modified resin with a biocide agent that may comprise titanium dioxide, silver metal, and silver chloride, that a molar ratio of silver metal to titanium dioxide may be in a range of 0.01:1 to 0.4:1 by mole, that a molar ratio of silver metal to silver chloride may be in a range of 0.5:1 to 2:1 by mole.

[0059] In an exemplary implementation, the exemplary anti-fouling paint may further comprise at least one solvent, at least one pigment, at least one additive, or a combination thereof.

[0060] In an exemplary implementation, the modified resin may be a modified epoxy resin.

[0061] In an exemplary implementation, a concentration of the modified epoxy resin is in a range of 20.0%-60.0% by weight.

[0062] The optimized molar ratio has an effect on stability as well as longevity of the exemplary anti-fouling paint.

[0063] A MANUFACTURING METHOD OF AN EXEMPLARYANTI-FOULING PAINT

[0064] illustrates a flowchart of an implementation of a general representation of a manufacturing method of an exemplary anti-fouling paint200, consistent with one or more exemplary embodiments of the present disclosure. In an exemplary embodiment, as illustrated in, the manufacturing method of an exemplary anti-fouling paint200may comprise synthesizing a single step composite202, preparing an exemplary stable colloidal solution by adding the single step composite to a mixture of at least one solvent and at least one stabilizer204, preparing an exemplary modified resin206, preparing the exemplary anti-fouling paint by adding at least one solvent, at least one pigment, at least one additive into the exemplary modified resin208.

[0065] In an exemplary embodiment, the synthesizing a single step composite may comprise mixing titanium dioxide, silver nitrate and Diol solvent in a reactor and adding sodium chloride and Diol solvent solution into the reactor.

[0066] In an exemplary implementation, the preparing the exemplary modified resin comprises preparing a preheated resin by heating a resin, and the stable colloidal solution and the preheated resin in a speed range of 100-120 rpm.

[0067] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to make and use the present invention, and are not intended to limit the scope of what the inventors regard as their invention nor are they intended to represent that the experiments below are all or the only experiments performed. Furthermore, the efficiency as well as stability properties were assessed using different test methods as described in examples below.Examples

[0068] EXAMPLE 1:Preparation of ATHREE-COMPONENT NANOCOMPOSITE

[0069] InExample 1, preparation of a three-component nanocomposite was carried out, consistent with one or more exemplary embodiments of the present disclosure. In this example, in a first step, 20 gr of titanium dioxide nanoparticles, 250 ml of 0.1 M silver nitrate, and 250 ml of Diol solvent are mixed in a ultrasonic reactor for 40 minutes. The ultrasonic reactor causes the reduction of silver nitrate to metallic silver and the doping of silver particles with titanium dioxide. At the same time, 1 gr of sodium chloride dissolved in Diol solvent is added to the ultrasonic reactor during the reaction which finally three-component nanocomposite of silver metal, titanium dioxide, silver chloride was obtained.

[0070] EXAMPLE2:PreparationofAStable Colloidal Solution

[0071] InExample2, preparation of an exemplary stable colloidal solution was carried out, consistent with one or more exemplary embodiments of the present disclosure. In this example, a mixture of solvent and stabilizer is added to the three-component nanocomposite (obtained inExample 1).

[0072] EXAMPLE3: Preparation of AModified Epoxy Resin

[0073] InExample3, preparation of a modified epoxy resin was carried out, consistent with one or more exemplary embodiments of the present disclosure. In this example, in a first step, epoxy resin is heated. In a final step, the stable colloidal solution (obtained inExample2) and the preheated epoxy resin are mixed in a speed of 110 rpm.

[0074] EXAMPLE4: Preparation of An Anti-Fouling Paint

[0075] InExample4preparation of an exemplary anti-fouling paint was carried out, consistent with one or more exemplary embodiments of the present disclosure. In this example, the exemplary anti-fouling paint was obtained by adding pigment and solvent into the modified epoxy resin (obtained inExample2).

[0076] In order to investigate the properties of the synthesized three-component nanocomposite, the HR-TEM test was conducted to investigate the formation of silver and silver chloride nanoparticles on the surface of titanium dioxide and the distance between the crystal lattices of three nanoparticles. Based on the results of this test (), the lattice distance is 0.23 nm corresponding to the (111) face of cubic silver nanoparticles, 0.32 nm related to the silver chloride nanoparticles (111) face and 0.35 nm related to the (101) face of titanium dioxide (anatase). As a result, the lattice distance measured from different regions indicates the formation of a three-component nanocomposite structure.

[0077] Furthermore, the High-angle annular dark-field detector () clearly shows the presence of the silver element in nanoparticles (silver metal and silver chloride) on titanium dioxide because the presence of the heavy element silver compared to the light element titanium creates a brighter image contrast in the final result of analysis.

[0078] Additionally, in order to analyzing the efficiency of the exemplary anti-fouling paint in algae-rich environments, two samples were prepared, one as a control sample and the other as a sample coated with the exemplary anti-fouling paint. Next, these two samples were placed in a spirulina algae culture medium (algae cells were grown in a Zarrouk culture medium and sterilized water with 3.5% salinity) at a temperature of 25 2 . The amount of algae absorbed on the surface of the samples is shown inby measuring the amount of absorption at a wavelength of 650 nm using a spectrophotometer.

[0079] EXAMPLE5: Preparation of An Anti-Fouling spry

[0080] InExample5, preparation of an anti-fouling spry was carried out, consistent with one or more exemplary embodiments of the present disclosure. In this example, the anti-fouling spry was obtained by adding the exemplary stable colloidal solution (obtained in first step of previous example) into 500 gr of water and use it as anti-fouling and antivirus spry for disinfecting surfaces.

[0081] While particular aspects of the present subject matter described herein have been shown and described, it will be apparent to those skilled in the art that, based upon the teachings herein, changes and modifications may be made without departing from this subject matter described herein and its broader aspects and, therefore, the appended claims are to encompass within their scope all such changes and modifications as are within the true spirit and scope of this subject matter described herein. Furthermore, it is to be understood that the invention is solely defined by the appended claims. It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases “at least one” to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim recitation to inventions containing only one such recitation, even when the same claim includes the introductory phrases “at least one” and indefinite articles such as “a” or “an” (e.g., “a” and / or “an” should typically be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should typically be interpreted to mean at least the recited number (e.g., the bare recitation of “two recitations,” without other modifiers, typically means at least two recitations or two

[0082] It will be understood that the terms and expressions used herein have the ordinary meaning as is accorded to such terms and expressions with respect to their corresponding respective areas of inquiry and study except where specific meanings have otherwise been set forth herein. Relational terms such as first, second, and third and the like may be used solely to distinguish one entity or action from another without necessarily requiring or implying any actual such relationship or order between such entities or actions. The terms “comprises,” “comprising,” “include,” “including,” or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, apparatus, or device that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, apparatus, or device. An element proceeded by “a” or “an” does not, without further constraints, preclude the existence of additional identical elements in the process, method, article, or device that comprises the element. Moreover, “may” and other permissive terms are used herein for describing optional features of various embodiments. These terms likewise describe selectable or configurable features generally, unless the context dictates otherwise.

Claims

A stable colloidal solution as a biocide agent comprising:at least one antibacterial agent comprising titanium dioxide, silver metal, or a combination thereof;at least one oxidizing agent; andat least one stabilizer.The stable colloidal solution of claim 1, further comprising at least one solvent.The stable colloidal solution of claim 2, wherein the at least one solvent comprises at least one Diol solvent, at least one polar solvent, or the combination thereof.The stable colloidal solution of claim 1, wherein the at least one oxidizing agent comprises silver chloride, silver bromide, silver iodide, silver nitrate, or a combination thereof.The stable colloidal solution of claim 1, wherein the at least one stabilizer is at least one polymeric stabilizer.A manufacturing method of a stable colloidal solution of any one of claims 1 to 5 comprising:synthesizing a single step composite by adding at least one antibacterial agent, at least one oxidizing agent and Diol solvent in a reactor;adding the single step composite to a mixture of at least one solvent and at least one stabilizer.The manufacturing method of claim 6, wherein the synthesizing a single step composite further comprises preparing a sodium solution by mixing sodium chloride into Diol solvent and adding the sodium solution into the reactor.The manufacturing method of claim 6, wherein a concentration of the single step composite is in a range of 30.0%-70.0% by weight.The manufacturing method of claim 6 or 7, wherein the single step composite is a single step nanocomposite.The manufacturing method of claim 6 and 7, wherein the reactor is an ultrasonic reactor.A modified resin for producing of a coating comprising:at least one polymer as a resin; anda stable colloidal solution as a biocide agent of any one of claims 1 to 5.The modified resin of claim 10, wherein a concentration of the stable colloidal solution is in a range of 0.01%-10.0% by weight.The modified resin of claim 10, wherein the at least one polymer comprises epoxy, acrylic, polyester, polyurethane, or the combination thereof.An anti-fouling paint comprising:a modified resin with a biocide agent comprising titanium dioxide, silver metal, and silver chloride, wherein a molar ratio of silver metal to titanium dioxide is in a range of 0.01:1 to 0.4:1 by mole, wherein a molar ratio of silver metal to silver chloride is in a range of 0.5:1 to 2:1 by mole.The anti-fouling paint of the claim 13, further comprising at least one solvent, at least one pigment, at least one additive, or a combination thereof.The anti-fouling paint of the claim 13, wherein the modified resin is a modified epoxy resin.The anti-fouling paint of the claim 13 or 16, wherein a concentration of the modified resin is in a range of 20.0%-60.0% by weight.A manufacturing method of an anti-fouling paint of any one of claims 14 to 17 comprising:synthesizing a single step composite;preparing a stable colloidal solution of any one of claims 1 to 5 by adding the single step composite to a mixture of at least one solvent and at least one stabilizer;preparing a modified resin of any one of claims 11 to 13;preparing the anti-fouling paint by adding at least one solvent, at least one pigment, at least one additive into the modified resin.The manufacturing method of claim 18, wherein the synthesizing a single step composite comprises mixing titanium dioxide, silver nitrate and Diol solvent in a reactor and adding sodium chloride and Diol solvent solution into the reactor.The manufacturing method of claim 18, wherein the preparing the modified resin comprises preparing a preheated resin by heating a resin, and the stable colloidal solution and the preheated resin in a speed range of 100-120 rpm.

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