KR20210036022A - Coating layer of environmental-friendly silicone based antifouling paint for preventing the attachment of marine organisms - Google Patents

Abstract

Proposed is an environmental-friendly silicone-based antifouling paint layer for preventing attachment of marine organisms, in which silicone oil floats slowly to maintain a function of preventing the adhesion of marine organisms for a long time, and increase the interlayer adhesion. The coating layer includes a lower layer, an intermediate layer and an upper layer, the intermediate layer and the upper layer contain 65 to 85% by weight of a silicone compound based on the total antifouling paint layer, the undercoat layer, the intermediate layer, and the upper layer have thicknesses of 280 to 320 μm, 90 to 110 μm, and 130 to 170 μm, respectively, the intermediate layer is applied for 12 to 48 hours after the application of the lower layer, the upper layer is applied for 4 to 12 hours after the intermediate layer is applied, the upper layer contains antibacterial substances, and the upper layer contains 5 to 15% by weight of reactive silicone oil of the following formula (1) having a molecular weight of 2,000 or less, with respect to the entire antifouling paint layer.

Description

{Coating layer of environmental-friendly silicone based antifouling paint for preventing the attachment of marine organisms}

The present invention relates to an antifouling paint layer, and more particularly, to a silicone-based eco-friendly antifouling paint layer containing silicone oil to prevent the adhesion of marine organisms such as barnacles, mussels, and greens.

In general, after forming a biofilm in the ocean, aquatic microorganisms grow while acquiring nutrients, maintaining cellular enzyme activity, and sharing metabolism with other microorganisms. These marine organisms secrete substances such as polysaccharides, nucleic acids, fatty acids, and proteins, and many biofilms are formed in the process of interaction between these substances and microorganisms. The larvae of marine organisms such as barnacles and mussels attach to the biofilm of these microorganisms and grow. Recently, antifouling paints using silicone oil to prevent marine organisms from adhering to the surface have been proposed by breaking away from the conventional method of killing marine organisms due to global environmental regulations. When silicone oil floats on the surface of the antifouling paint, it makes the surface of the antifouling paint slippery to prevent the formation of the biofilm, thereby preventing the adhesion of marine organisms.

Japanese Laid-Open Patent No. 2016-23306 proposes an adhesive tape or sheet that uses silicone oil to prevent adhesion of aquatic organisms. However, since the above patent uses an adhesive tape or sheet, the process of attaching to the adherend is very complicated. In addition, it is difficult to apply if the adherend is a complex shape. Accordingly, it is desirable to apply an antifouling paint to allow the silicone oil to slowly float and maintain the function for a long time. However, the conventional antifouling paint lacks a specific method for gradually causing the silicone oil to rise. In addition, since the antifouling paint is usually applied as a base layer/intermediate layer/top layer, it is necessary to increase the interlayer adhesion.

The problem to be solved by the present invention is to provide a silicone-based eco-friendly antifouling paint layer for preventing the adhesion of marine organisms, which keeps the function of preventing the adhesion of marine organisms for a long time by allowing the silicone oil to slowly rise, and increasing the adhesion between layers.

The silicone-based eco-friendly antifouling paint layer for preventing the adhesion of marine organisms to solve the problem of the present invention is composed of a bottom layer, a middle layer, and a top layer, and the middle layer and the top layer contain a silicone compound by 65 to 85 weight of the entire antifouling paint layer. Include %. At this time, the thicknesses of the undercoat layer, middle coat layer and top coat layer are 280 to 320 μm, 90 to 110 μm, and 130 to 170 μm, respectively, and the middle coat layer is applied 12 to 48 hours after the base coat layer is applied, and the top coat The layer is formed by applying 4 to 12 hours after the middle layer is applied, and the top coat layer contains an antibacterial material, and the top coat layer is a total antifouling paint using a reactive silicone oil of the following formula (1) having a molecular weight of 2,000 or less. It contains 5 to 15% by weight based on the layer.

… 식(1)

… Equation (1)

In the coating layer of the present invention, the silicone compound may be polydimethylsiloxane. The antimicrobial material may be a non-ejectable carbon nanotube or copper sulfide that is not ionized in water, or a mixture thereof. The carbon nanotubes may be supported on or mixed with the ceramic powder. The ceramic powder may be at least one selected from silicates such as MCM mesoporous materials (MCM-41, MCM-48), zeolite, clay, titanium oxide, silica, talc, calcium carbonate, and mica. The copper sulfide may be coated on the surface of the ceramic powder.

In a preferred coating layer of the present invention, the undercoating layer is made by mixing a main component (a) and a curing component (b), the main component (a) contains an electrical insulating resin, and the electrical insulating resin is epoxy It can be resin. The insulating resin may include plate-shaped glass flakes with respect to the insulating resin. The electrical insulating resin may lower the polar group in the molecule and increase the molar volume of one of bisphenol diglycidyl ether polymer, ethylene glycol monoethyl ether, glycioxypropyltrimesysilane, and dicyclopentadiene polymer.

In the coating layer of the present invention, the top coating layer may include self-healing powder. The self-healing powder may include a filler having irregularities or pores on the surface, a self-healing agent filled in the filler, and a film surrounding the filler and the self-healing body.

According to the silicone-based eco-friendly antifouling coating layer for preventing the adhesion of marine organisms of the present invention, by adjusting the content, layer thickness, and coating time of the composition including reactive silicone oil having a molecular weight of 2,000 or less, the silicone oil gradually rises to prevent the adhesion of marine organisms. It keeps the preventing function for a long time and increases the interlayer adhesion.

1 is a photograph taken after allowing the samples coated with the antifouling paint of Examples and Comparative Examples of the present invention to stand still in seawater for 3 months.
2 is a view for explaining the self-healing of the top layer of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The embodiments described below may be modified in various forms, and the scope of the present invention is not limited to the embodiments described below. Embodiments of the present invention are provided to more completely describe the present invention to those of ordinary skill in the art. Meanwhile, in the drawings, the thicknesses of films (layers, patterns) and regions may be exaggerated for clarity. Also, when it is mentioned that a film (layer, pattern) is on, top, bottom, or one side of another film (layer, pattern), it can be formed directly on the other film (layer, pattern) or between them A film (layer, pattern) may be interposed.

An embodiment of the present invention is to maintain the function of preventing the adhesion of marine organisms for a long time by adjusting the content, layer thickness, and coating time of the composition including the reactive silicone oil having a molecular weight of 2,000 or less, so that the silicone oil slowly rises, We present an antifouling paint layer that enhances the adhesion between layers. To this end, the composition and coating time of the antifouling coating layer will be specifically examined, and the eco-friendly effect of the composition including the silicone oil and the effect of preventing the adhesion of marine organisms will be described in detail.

The antifouling coating layer of the present invention is composed of an undercoat layer/intermediate layer/upper layer. The resin of the undercoating layer is a curable adhesive, which facilitates adhesion to an adherend, for example, a bisphenol-A type, and contains 15 to 35% by weight of the total antifouling paint layer. The curable adhesive of the undercoat layer is polyamide and polyamide adduct type, and contains 10 to 30% by weight based on the total antifouling paint layer. The intermediate layer is applied with a silicone compound, and the top coat layer includes a silicone compound and contains 5 to 15% by weight of silicone oil based on the total antifouling coating layer.

In some cases, the undercoating layer may include an insulating resin for insulation from an adherend. This is because the adherend may be a device that utilizes electricity or may be a corrosive material, so insulation is required. The undercoat layer is prepared by mixing the main component (a) and the curing component (b). At this time, the main component (a) and the cured component (b) may be mixed in a ratio of 58:42. The main component (a) includes 60 to 80 parts by weight of plate-shaped glass flakes, 20 to 40 parts by weight of ceramic powder, other additives, and a diluent based on 100 parts by weight of the insulating resin. The insulating resin is preferably an epoxy resin having a molecular weight of 30,000 g/mol, for example. The epoxy resin is preferably a bisphenol A type epoxy, and if necessary, any one selected from a novolac type epoxy, a cycloaliphatic epoxy, and a flame retardant epoxy may be used by mixing. The bisphenol A type epoxy may impart mechanical/electrical properties, dimensional stability, and excellent chemical resistance properties, and the novolak type epoxy may increase mechanical strength, and the cycloaliphatic epoxy may be used in electrical insulation products. For outdoor use and durability can be increased, and flame-retardant epoxy can impart excellent flame retardancy and heat resistance.

In addition, the insulating resin is selected from bisphenol diglycidyl ether polymer, ethylene glycol monoethyl ether, glycitoxypropyltrimesysilane, dicyclopentadiene polymer to lower the polar group in the molecule and It is good to increase the volume). In this way, when the polar group in the molecule is lowered and the mole volume is increased, insulation resistance and rigidity of the insulating resin can be increased.

The silicone compound is preferably polydimethylsiloxane, and the silicone compound of the intermediate layer and the top layer contains 65 to 85% by weight of the total antifouling coating layer. Compared to the total antifouling coating layer, the content of the silicone compound contains 65 to 85% by weight and 5 to 15% by weight of silicone oil. That is, the silicone compound is included in the intermediate layer and the top coat layer, and the silicone oil is included in the top coat layer.

On the other hand, the intermediate layer includes a polyurethane containing a polydimethylsiloxane component. For example, using a mixed polyol in which methylenediphenyl diisocyanate and 1,4-butanediol are used as hard segment components, and polydimethylsiloxane diol and poly(tetramethylene ether glycol) are mixed as soft segment components, and a polydimethylsiloxane component is included. The polyurethane was synthesized. When a polyurethane containing a polydimethylsiloxane component is included in the intermediate layer, the external force disappears and the polyurethane is restored to its original state. When the intermediate layer is restored to its original state, the stability of the top layer is improved.

In addition, since the polydimethylsiloxane of the intermediate layer is the same material as the polydimethylsiloxane of the top coating layer, the bonding strength between the intermediate layer and the top coating layer is increased through the polydimethylsiloxane. That is, when polyurethane containing polydimethylsiloxane is included in the intermediate layer, the intermediate layer is easily restored to its original state and the bonding strength with the top layer is increased. The content of polyurethane including polydimethylsiloxane varies depending on the thickness of the intermediate layer and the environment to which it is applied.

The antifouling coating layer of the present invention includes a composition comprising an antibacterial substance, which is an antibacterial and bactericidal substance, a silicone compound for controlling surface properties, and a silicone oil as essential components. That is, the top coat layer of the antifouling coating layer according to the present invention includes a silicone compound, a silicone oil, an antibacterial substance, and other additives. The silicone compound is, for example, a hydrocarbon compound containing a silicon (Si) atom, and the bonding group of the silicon (Si) atom of the silicone compound is a polar group selected from a hydroxy group, an alkoxy having 1 to 10 carbon atoms, an amide group, an ester group, and a siloxy group. Substituted or unsubstituted ones may be used. As a specific example of such a silicone compound, one selected from 2-(trimethylsilyloxy)ethyl methacrylate, tris(3-methacryloxypropyl)silane, 3-tris(trimethylsiloxy)silyl propyl methacrylate, and polydimethylsiloxane It can be used above.

The silicone compound according to the present invention is 65 to 85% by weight based on the total antifouling coating layer including the intermediate layer. If the content of the silicone compound is too small, the effect of increasing the contact angle of the coated surface cannot be expected, and too much If included in the content, hydrophilicity is rapidly deteriorated, as well as the hardness becomes too large, so that the surface may be hard and brittle. The silicone compound is environmentally friendly, is stable in seawater, and prevents adhesion of marine organisms by increasing the contact angle of the surface.

The reactive silicone oil according to an embodiment of the present invention is as shown in Equation (1) below.

… 식(1)

… Equation (1)

The reactive silicone oil of formula (1) has a molecular weight of 2,000 or less, and _{improves the slip property by attaching a CH 2} OH group end group, and is preferably 5 to 15% by weight, more preferably 8, with respect to the entire antifouling coating layer. ~12% by weight is good. If it is less than 5% by weight, it is completely buried in the top coat layer so that the silicone oil does not float. If it is more than 15% by weight, the film strength of the top coat layer is weakened and drying of the coat film is delayed. The reactive silicone oil according to an embodiment of the present invention has improved slip properties by attaching a _{CH 2 OH group end group.}

On the other hand, if the molecular weight of the reactive silicone oil is greater than 2,000, even if the content of the antifouling paint is adjusted, the silicone oil of formula (1) does not float. Accordingly, a molecular weight of 2,000 or less of the reactive silicone oil of Formula (1) is a critical value at which floating occurs. Accordingly, in order for the silicone oil of formula (1) of the present invention to float, the condition that the molecular weight of the reactive silicone oil of formula (1) is 2,000 or less is essential. This is based on the technical idea that the rise of the reactive silicone oil of the present invention is related to the type, content, and molecular weight of the silicone oil. Accordingly, the rise of the silicone oil cannot be obtained through repeated experiments of the silicone oil without considering the above technical idea. The lower limit of the molecular weight of the reactive silicone oil of Formula (1) can be easily set by a person skilled in the art within the scope of the present invention.

The antibacterial material is to prevent the adhesion of marine organisms by sterilization and antibacterial, and there are an elution type and a non-dissolution type. The non-release type is to prevent adhesion by using the characteristics of a silicone compound with a smooth surface, and the elution type is to use an organic type, an organic metal type, an inorganic type, etc., which have antifouling properties, alone or as a mixture, and use various organic and polymeric binders. The antifouling performance is continuously given by abrasion and elution. In the case of the elution type, copper, zinc, or their oxides are gradually ionized in seawater to obtain an antibacterial effect, but copper is a pollutant designated as a soil pollutant in the Soil Environment Conservation Act (1995), and the toxicity of zinc is relatively low. According to the Ministry of Health and Social Affairs Environmental Conservation Act test, it causes headache and diarrhea at 5-6 ppm, and causes life risk at 1,000 ppm. The allowable limit in water is set at 1 mg/ℓ or less in the water quality standard of the Waterworks Act, and 5 mg/ℓ or less in the emission limit. In addition, silver ions (Ag+) presented in conventional eluted antibacterial substances are classified as environmental nanotoxic ions.

As such, the material applied to the elution type has a fatal adverse effect on the underwater environment. In the antifouling coating layer according to the embodiment of the present invention, in order to solve the problem of the elution type, a non-dissolving type antibacterial material that is dissolved in water and is not ionized is applied to the antifouling coating layer. Accordingly, an antibacterial material, a silicone compound that controls surface properties, and a silicone oil are essential components. The antibacterial substance is composed of, for example, carbon nanotubes and ceramic powder, and is mixed with a silicon compound. That is, adhesion is prevented by using the properties of the silicone compound with a smooth surface, and the propagation of aquatic microorganisms in contact with the carbon nanotubes, which is an antibacterial material mixed with the silicone compound, is prevented.

In the carbon nanotube according to the embodiment of the present invention, hexagonal shapes made of six carbons are connected to each other to form a tubular shape. The diameter of the tube is only a few to tens of nanometers, and the nanometer is one billionth of a meter, which is one hundred thousandths the thickness of a normal hair. The electrical conductivity of carbon nanotubes is similar to that of copper, its thermal conductivity is the same as that of diamond, which is the best in nature, and its strength is 100 times better than that of steel. The carbon nanotubes of the present invention may be multi-walled carbon nanotubes (MWNT) or single-walled carbon nanotubes (SWNTs). As such carbon nanotubes have antibacterial properties, as is well known, aquatic microorganisms and marine organisms are prevented from adhering to power generation facilities.

The carbon nanotubes are biocompatible materials capable of minimizing water pollution, for example, and are MCM mesoporous materials (MCM-41, MCM-48), zeolite, clay, titanium oxide, silica, talc, calcium carbonate, and Maikawa. It may be supported on at least one ceramic powder selected from the same silicate or may be mixed with the ceramic powder. The ceramic powder supporting carbon nanotubes is a porous body. In this way, the carbon nanotubes supported or mixed in the porous ceramic powder are mixed with a silicon compound and coated on an adherend to form a coating film.

Optionally, copper sulfide may be further added as an antimicrobial substance. The chemical structure of copper sulfide is _{a hexagonal crystal of Cu x} S _y , and the ratio of x/y satisfies 0.8 to 1.5. The ratio of x/y, which is 0.8 to 1.5, is a condition for forming a hexagonal crystal structure of copper sulfide, and when the binding ratio of x/y is 0.8 or less, the concentration of sulfur (S) is too high and the antibacterial property is good. Chemical stability does not form a crystal structure. When the concentration is 1.5 or more, the sulfur (S) concentration decreases and the antimicrobial property decreases. Such copper sulfide may be coated on itself or the ceramic powder by various methods such as wet coating, plating, and evaporation, and mixed with the silicon compound. Such copper sulfide acts as a non-release type according to an embodiment of the present invention.

Copper sulfide uses Escherichia Coli (ATCC 25922) as a strain, and then the test bacterial solution is brought into contact with the specimen, left to stand at 25° C. for 24 hours, cultured, and counted to evaluate the antibacterial properties of the specimen. It is sterilized or sterilized at a level of ^{10 4} ~ 10 ⁶ depending on the content of copper sulfide. If there is no copper sulfide, it is 10 to ¹⁰ levels. In particular, when copper sulfide is coated on the ceramic powder, the antibacterial property is increased compared to the case where it is dispersed in the ceramic powder.

The antimicrobial material according to the embodiment of the present invention is 1 to 5% by weight based on the total antifouling coating layer, and if it is less than 1% by weight, the antifouling effect is lowered, and if it exceeds 5% by weight, the antifouling performance compared to the amount used is improved, but the silicone compound The effect of is relatively low. On the other hand, since carbon nanotubes are relatively expensive, it is not preferable to use more than 5% by weight. At this time, the copper sulfide is preferably 5 to 80% by weight based on the carbon nanotubes. If it is less than 5% by weight, the antimicrobial effect by the copper sulfide is insignificant, and if it is more than 80% by weight, the content of carbon nanotubes is excessively reduced, thereby reducing the antibacterial effect by the carbon nanotubes. In addition, the ceramic powder is 3 to 15% by weight with respect to the total antifouling paint layer, and outside the above range, the fluidity of the antifouling paint layer is high or low, so that the coating operation is not easy.

Other additives mixed in the antifouling paint of the present invention constitute the remaining content, and there are plasticizers, surface control agents, dispersants, antifoaming agents, leveling agents, coupling agents, etc., and these are already known, so a detailed description thereof will be omitted here. do. In some cases, dissolution-type antimicrobial substances may be added within the range permitted by environmental standards. In an example of the present invention, zinc pyrithione was added.

The antifouling paint layer according to the present invention is coated on a ship, power generation equipment, etc. as an adherend to form a thin curable coating layer. The coating layer has a lipophilic and hydrophilic reactor derived from a silicone compound, and chemically adsorbs moisture by a hydrophilic reactor to change a contact angle. In addition, since the coating layer of the present invention does not affect the physical properties of the power generation facility, it is a non-emissive type, so it continuously maintains antifouling properties.

In the embodiment of the present invention, the higher the interlayer adhesion, the better the antifouling coating layer. In order to increase the interlayer adhesion, the thickness of the undercoat layer is 280 to 320 μm, the intermediate layer is 90 to 110 μm, and the upper coat layer is preferably 130 to 170 μm. That is, it is preferable that the lower coat layer is thicker than the middle coat layer and the upper coat layer, and the middle coat layer is the thinnest. In addition, the middle coat layer is applied 12 to 48 hours after the application of the undercoat layer, and in the case of the middle coat layer, the top coat layer is applied 4 to 12 hours after the application. In practice, the application of the intermediate layer can be specified after 12 hours, and the top coating layer can be specified after 4 hours.

The layer thickness and application time of the present invention are based on the technical idea of increasing the interlayer adhesion. Accordingly, the interlayer adhesion cannot be obtained through repeated experiments without considering the technical idea. In the case of a top coat layer including silicone oil, if there is no silicone material in the middle layer, peeling occurs between layers due to the movement of the silicone oil. That is, if there is no silicon-based material in the intermediate layer, interlayer adhesion is inferior.

Hereinafter, in order to describe in detail the physical properties of the antifouling coating layer for preventing the adhesion of marine organisms of the present invention, the following examples are presented. However, the present invention is not particularly limited to the following examples. At this time, the contact angle (°), surface energy (dyne/cm), surface tension (dyne/cm), static friction coefficient, dynamic friction coefficient, and interlayer adhesion are the model names MSA-Single (manufacturer, KRUSS), Surface Tension Analyzer (manufacturer , SEO) and Cross Hatch Cutter (YCC-230 (2mm/6 blade) (manufacturer, YOSHIMITSU) measuring interlayer adhesion. In this case, if the interlayer adhesion is 0 as adhesion, the cut surface is smooth, and the peeled square grid is No. If the interlayer adhesive strength is 1, small pieces of the coating film are peeled off at the intersection of the cutting line, and the peeled crosscut area is within 5% If the interlayer adhesive strength is 2, the coating film is small pieces along the cutting plane and/or at the intersection of the cutting lines. The peeled crosscut area is 5% to 15%.

<Example 1>

In Example 1 of the present invention, polydimethylsiloxane (Shin-Etsu silicone) of the middle layer and the top layer is 70% by weight based on the total antifouling coating layer on the undercoat layer, and 10% by weight of silicone oil (Dow Corning) on the top coat layer. , 5% by weight of ceramic powder, and 3.5% by weight of carbon nanotubes (Wonil Corporation). After the antifouling coating layer was prepared, it was coated on a PVC panel. At this time, the thicknesses of the undercoat layer, middle coat layer and top coat layer were 300 μm, 100 μm, and 150 μm, and the middle coat layer was applied 12 hours after the undercoat layer was applied and the top coat layer was applied 4 hours after the middle coat layer was applied. The ceramic powder was suitably mixed with at least one of titanium oxide, silica, talc, calcium carbonate, mica and layered silicate. Then, the contact angle, surface energy, surface tension, static friction coefficient, dynamic friction coefficient, and interlayer adhesion of the sample were checked.

<Comparative Examples 1 and 2>

Comparative Example 1 is a product of Japan C company and Comparative Example 2 is a product of Denmark H company, in the same manner as in Example 1, the contact angle, surface energy, surface tension, static friction coefficient, dynamic friction coefficient, and interlayer adhesion of the coating layer were confirmed. For the intermediate layers of Comparative Examples 1 and 2, a silicone-based resin or an epoxy-based or urethane-based resin was applied.

Table 1 shows the physical properties of the coating layers of Example 1 and Comparative Examples 1 and 2 of the present invention. 1 is a photograph of Example 1 and Comparative Examples 1 and 2 after 3 months in seawater. The contact angle is an average value obtained by multiple measurements rather than one measurement.

division Example 1 Comparative Example 1 Comparative Example 2 Oil injury O X X Contact angle (°) 104 97 99 Surface energy (dyne/cm) 13.1 29 27 Surface tension (dyne/cm) 23 28 26 Static friction coefficient 0.78 1.2 1.1 Dynamic friction coefficient 0.46 1.1 1.0 Interlayer adhesion (adhesion) 0 2 One

According to Table 1, in the embodiment of the present invention, silicone oil is floated onto the surface of the antifouling paint layer. In contrast, in Comparative Examples 1 and 2, the silicone oil does not float on the surface of the antifouling coating layer. The contact angle of Example 1 was 104°, and the contact angles of Comparative Examples 1 and 2 were 97° and 99°, respectively. The contact angle of Example 1 was increased compared to Comparative Examples 1 and 2, and as the contact angle increased, the adhesion was inferior. The surface energy and surface tension of Example 1 were 13.1 and 23, respectively, but Comparative Example 1 was 29 and 28, respectively, and Comparative Example 2 was 27 and 26, respectively. The surface energy and surface tension of Example 1 were considerably smaller than those of Comparative Examples 1 and 2, and when the surface energy and the surface tension were decreased, the adhesion was lowered.

The static and dynamic coefficients of Example 1 were 0.78 and 0.46, respectively, but Comparative Example 1 was 1.2 and 1.1, respectively, and Comparative Example 2 was 1.1 and 1.0, respectively. The static friction coefficient and the dynamic friction coefficient of Example 1 were very small compared to those of 1 and 2 for comparison, and when the static friction coefficient and the dynamic friction coefficient were decreased, the adhesion was deteriorated. That is, in Example 1 of the present invention, compared to Comparative Examples 1 and 2, the contact angle increases, the surface energy and the surface tension decrease, and the static friction coefficient and the dynamic friction coefficient decrease. All of these tendencies effectively block the adhesion and propagation of marine organisms on the surface of the antifouling paint layer. The interlayer adhesive strength of Example 1 was 0, but Comparative Examples 1 and 2 were 2 and 1, respectively. Accordingly, the interlayer adhesive strength of Example 1 of the present invention including polydimethylsiloxane in the middle layer and the top layer was high.

The antifouling paint layer according to the embodiment of the present invention has been conducted in a number of experiments, with respect to the total antifouling paint layer, the undercoat layer is 15 to 35% by weight, the middle coat layer and the upper coat layer silicon compound is 65 to 85% by weight, the top coat layer. When the reactive silicone oil of Formula (1) contains 5 to 15% by weight and the antimicrobial material of the top coat layer is 3 to 5% by weight, it was confirmed that the technical idea of the present invention was implemented. Example 1 presented above is merely a preferred example.

The antifouling coating layer according to the embodiment of the present invention has a contact angle of 100° or more in water and has a slippery surface, making it difficult to attach and reproduce marine organisms including aquatic microorganisms. Even if marine organisms are attached, the antibacterial effect of sterilization or sterilization is exerted by the carbon nanotubes, copper sulfide, or a mixture thereof included in the antifouling coating layer of the present invention, so that the propagation of marine organisms including aquatic microorganisms can be blocked. . In addition, since the antifouling coating layer of the present invention does not dissolve copper ions, zinc ions, silver ions, etc., which are conventionally toxic, in water, it can be said to be eco-friendly. Further, by including the polyurethane containing polydimethylsiloxane in the intermediate layer, it is possible to increase the original state recovery ability and the bonding strength with the top layer.

<Comparative Examples 3 and 4>

Comparative Example 3 is the same as Example 1, except that the thicknesses of the lower coat layer, the middle coat layer, and the upper coat layer are all 150 μm. Comparative Example 4 is the same as in Example 1, except that the coating time of the intermediate layer is 10 hours and the coating time of the top layer is 2 hours.

Table 2 shows the physical properties of the coating layers of Example 1 and Comparative Examples 3 and 3 of the present invention.

division Example 1 Comparative Example 3 Comparative Example 4 Interlayer adhesion (adhesion) 0 One 2

According to Table 2, the interlayer adhesive strength of Example 1 was 0, but Comparative Examples 3 and 4 were 1 and 2, respectively. Accordingly, it was confirmed that the thickness of the undercoat layer, the middle coat layer, and the upper coat layer, and the coating time of the middle coat layer and the top coat layer affect the interlayer adhesion. The thickness of the undercoat layer is greater than that of the intermediate layer and the upper coat layer, and the size of the intermediate layer is the smallest. In addition, when the coating time of the intermediate layer and the top layer is less than 12 hours and 4 hours, respectively, the interlayer adhesion is inferior.

Meanwhile, in the antifouling coating layer of the present invention, cracks may occur in the top coating layer due to external impact or change over time. An embodiment of the present invention proposes a method for self-healing the crack.

2 is a view for explaining the self-healing of the top layer according to an embodiment of the present invention.

According to FIG. 2, the top coat layer 10 includes self-healing powder 20. The self-healing powder 20 is composed of a filler 21 having irregularities or pores on the surface, a self-healing agent 22 filled in the filler 21, and a film 23. If a crack occurs in the top coat layer 10 outside the self-healing powder 20, the crack propagates to the film 23 to cause a crack in the film 23. When a fine crack occurs in the self-healing film 25, the self-healing agent 22 in the self-healing powder 20 flows out to heal the top coat layer 10 to remove the crack.

The composition for self-healing according to an embodiment of the present invention varies depending on the type of the top coat layer 10. For example, it contains solid particles of Grubbs catalyst and liquid dicyclopentadiene (DCPD), which is a self-healing agent embedded in the self-healing powder 20. When a crack due to deterioration of the top coat layer 10 is transmitted to the film 23, the crack ruptures the film 23 and releases the DCPD to the crack plane. The DCPD is mixed with the Grubbs catalyst and undergoes ring opening substitution polymerization (ROMP), and is cured to provide structural continuity of the cracked portion. Another example of such a self-healing agent is isophorone diisocyanate (IPDI). Another example of self-healing agents can be classified into non-covalently bonded molecules capable of hydrogen bonding, π-π interactions, electrostatic forces, and metal coordination bonds.

In the above, the present invention has been described in detail with reference to a preferred embodiment, but the present invention is not limited to the above embodiment, and various modifications are made by those of ordinary skill in the art within the scope of the technical idea of the present invention. It is possible.

10; Top layer 20; Self-healing powder
21; Filler 22; Self-healing agent
23; film

Claims (11)

It consists of a lower layer, a middle layer and an upper layer,
The intermediate layer and the top layer contain 65 to 85% by weight of a silicone compound based on the total antifouling coating layer,
The thicknesses of the undercoat layer, middle coat layer and top coat layer are 280 to 320 μm, 90 to 110 μm, and 130 to 170 μm, respectively, and the middle coat layer is applied 12 to 48 hours after the coat layer is applied, and the top coat layer is It is applied and formed in 4 to 12 hours after the middle coat layer is applied, and the top coat layer contains an antibacterial material,
The top coat layer is a silicone-based eco-friendly antifouling paint layer for preventing marine organisms from adhering to 5 to 15% by weight of the reactive silicone oil of Formula (1) below having a molecular weight of 2,000 or less with respect to the total antifouling paint layer.

… Equation (1) The silicone-based eco-friendly antifouling coating layer according to claim 1, wherein the silicone compound is polydimethylsiloxane. The silicone-based eco-friendly antifouling coating layer for preventing the adhesion of marine organisms according to claim 1, wherein the antimicrobial material is a non-release type carbon nanotube or copper sulfide or a mixture thereof that is not ionized in water. The silicon-based eco-friendly antifouling coating layer for preventing marine organisms from attaching according to claim 3, wherein the carbon nanotubes are supported on or mixed with the ceramic powder. The method of claim 4, wherein the ceramic powder is at least one selected from silicates such as MCM mesoporous materials (MCM-41, MCM-48), zeolite, clay, titanium oxide, silica, talc, calcium carbonate, and mica. A silicone-based eco-friendly antifouling paint layer for preventing the adhesion of marine organisms. [4] The silicone-based eco-friendly antifouling paint layer for preventing marine organisms from adhesion according to claim 3, wherein the copper sulfide is coated on the surface of the ceramic powder. The method of claim 1, wherein the undercoat layer is made by mixing a main component (a) and a curing component (b), and the main component (a) contains an electrical insulating resin, and the electrical insulating resin is an epoxy resin. A silicone-based eco-friendly antifouling paint layer for preventing the adhesion of marine organisms. [8] The silicone-based eco-friendly antifouling coating layer for preventing marine organisms from attaching according to claim 7, wherein the insulating resin contains 50 to 100% by weight of plate-shaped glass flakes based on the insulating resin. The method of claim 7, wherein the electrically insulating resin is one of bisphenol diglycidyl ether polymer, ethylene glycol monoethyl ether, glycioxypropyltrimesysilane, and dicyclopentadiene polymer to lower the polar group in the molecule and molar volume. A silicone-based eco-friendly antifouling paint layer for preventing adhesion of marine organisms, characterized in that to increase. The silicone-based eco-friendly antifouling coating layer according to claim 1, wherein the top coat layer contains self-healing powder. The silicone-based for preventing adhesion of marine organisms according to claim 10, wherein the self-healing powder comprises a filler having irregularities or pores on the surface, a self-healing agent filled in the filler, and a film surrounding the filler and the self-healing body. Eco-friendly antifouling paint layer.

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