Antifouling coating composition

Abstract

The present invention relates to an antifouling coating composition comprising a first polysiloxane resin containing a silanol group, a second polysiloxane resin containing a polyalkylene oxide group at a single terminal and represented by Chemical Formula 1, a third polysiloxane resin modified with a polyalkylene oxide at both terminals, and an antifouling agent.

Description

Technical Field

[0001] This application claims priority based on Korean Patent Application No. 10-2023-0154551, filed on November 9, 2023, the entire contents of which are incorporated herein by reference.

[0002] This invention relates to an antifouling coating composition, the manufactured coating film of which maintains excellent antifouling performance even after long-term exposure to seawater, and maintains good slip properties due to its excellent surface characteristics. Background Technology

[0003] Man-made structures such as boats and hulls submerged in water are susceptible to fouling due to the adhesion of aquatic organisms such as green algae, brown algae, barnacles, and mussels. This fouling increases friction during navigation through seawater, reducing the speed of the man-made structure and consequently increasing fuel costs. Therefore, boats and hulls are typically equipped with antifouling coatings to protect their surfaces. These antifouling coatings include a primer with rust-preventing properties, a topcoat to protect the surface from prolonged seawater exposure, and an intermediate coat to improve adhesion between the primer and topcoat.

[0004] Based on their working principle, antifouling coatings are classified into self-polishing coatings (SPC) and fouling-release coatings (FRC). Specifically, FRC is a silicone-based coating containing silicone resin and / or silicone oil that minimizes the adhesion of barnacles and other organisms to the surface by utilizing the properties of a smooth surface. This type of FRC coating comprises: silicone resin with surface properties that prevent aquatic organism adhesion, such as hydrophobicity and a rubber-like elastic modulus; and / or silicone oil with a slippery texture that allows even if aquatic organisms adhere, they can be easily removed by seawater rinsing, thus forming a coating with excellent antifouling performance. However, traditional FRC coatings have the following drawback: over time, under conditions of no or very weak seawater flow during ship anchorage and low-speed navigation, the removal performance of aquatic organisms adhering to the coating surface decreases, resulting in a rapid decline in antifouling performance.

[0005] As a method to overcome the above problems, a solution has been proposed to add antifouling agents to fouling-removing coatings to ensure antifouling performance under long-term berthing and low-speed navigation conditions. For example, Korean Patent No. 1798604 (Patent Document 1) discloses a coating composition, which is a fouling-modifying coating composition, comprising a polysiloxane-based binder system, at least one hydrophilic modified polysiloxane at 0.01 to 20% dry weight, and at least one biocide, wherein the at least one hydrophilic modified polysiloxane does not contain groups capable of reacting with binders or crosslinking agents. However, the composition of Patent Document 1 uses a non-reactive hydrophilic modified polysiloxane. Initially, this material can seep to the coating surface, which helps prevent marine organisms from attaching. However, over time, there is a drawback: the non-reactive hydrophilic modified polysiloxane contained in the coating is consumed, and the content of hydrophilic additives remaining on the coating surface decreases. Therefore, under long-term immersion conditions, the antifouling performance decreases compared to the initial stage.

[0006] Therefore, there is an urgent need to develop an antifouling coating composition that can maintain excellent antifouling performance for a long time under conditions of long-term exposure to seawater or long-term berthing and low speed, and that the manufactured coating can maintain a smooth surface with minimal adhesion of barnacles and other organisms even when exposed to seawater for a long time, thus achieving excellent antifouling performance. Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] In view of this, the present invention aims to provide an antifouling coating composition, the coating of which can maintain excellent antifouling performance for a long time under conditions of long-term exposure to seawater or long-term mooring and low speed, and the manufactured coating can maintain a smooth surface with minimal adhesion of barnacles and other organisms even when exposed to seawater for a long time, thus having excellent slip properties and thus excellent antifouling performance.

[0009] The measures taken to solve the problem

[0010] This invention provides an antifouling coating composition comprising: a first polysiloxane resin containing silanol groups, a second polysiloxane resin containing polyalkylene oxides at one end, a third polysiloxane resin modified with polyalkylene oxides at both ends, and an antifouling agent.

[0011] The second polysiloxane resin is represented by the following chemical formula 1:

[0012] [Chemical Formula 1]

[0013]

[0014] In chemical formula 1,

[0015] R 1 and R 4 Each is independently an alkylene group having 1 to 18 carbon atoms.

[0016] R 2 and R 3 Each of them is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.

[0017] R 5 To R 7 Each is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R 5 To R 7 At least one of them is an alkoxy group having 1 to 10 carbon atoms.

[0018] n is a real number from 1 to 100.

[0019] m is a real number from 1 to 500.

[0020] The effects of the invention

[0021] The antifouling coating composition according to the present invention enables its coating film to maintain excellent antifouling performance for extended periods under conditions of prolonged exposure to seawater or prolonged mooring and low speed. Furthermore, the coating film made from the aforementioned antifouling coating composition maintains a smooth surface with minimal adhesion of barnacles and other organisms, even after prolonged exposure to seawater, exhibiting excellent slip properties. Therefore, its antifouling performance is significantly superior, making it ideal for use as an antifouling coating for man-made structures immersed in water. Detailed Implementation

[0022] The present invention will now be described in detail.

[0023] The "viscosity" of the present invention is measured by conventional methods known in the art, for example, at room temperature (20°C or 25°C) using a Brookfield viscometer (rotary spindle viscometer) or a KU (Krebsunit) viscometer.

[0024] Furthermore, the "weight-average molecular weight" of the present invention can be measured by methods known in the art, for example, it can be expressed as a value measured by gel permeation chromatography (GPC).

[0025] The antifouling coating composition according to the present invention comprises a first polysiloxane resin containing silanol groups, a second polysiloxane resin containing polyalkylene oxides at one end, a third polysiloxane resin modified with polyalkylene oxides at both ends, and an antifouling agent.

[0026] The first polysiloxane resin containing silanol groups, due to its high Si-O bonding strength, can reduce the surface energy of the manufactured coating and impart elasticity to it, thereby weakening the adhesion of marine organisms and improving the antifouling performance of the coating. However, coatings containing only this resin have the following drawbacks: the manufactured coating is too hydrophobic, resulting in reduced dissolution of antifouling agents containing polar groups. Therefore, when the coating is immersed in seawater for a long time, marine organisms adhere more easily. In addition, it has insufficient compatibility with other organic components constituting the coating.

[0027] Furthermore, the second polysiloxane resin contains a polyalkylene oxide group as a hydrophilic group at one end and an alkoxy group directly bonded to silicon at the other end. Therefore, due to its structural hydrophilicity, the second polysiloxane resin exhibits excellent compatibility with the organic components constituting the coating. Additionally, by containing curing functional groups, it acts as a curing agent to cure the composition. However, coatings containing only this resin have the following drawbacks: the resulting coating film has excessively high hydrophilicity, making it easier for marine organisms to adhere to it. Consequently, the antifouling performance of ships using this coating decreases during navigation, and the coating film strength and water resistance also decrease accordingly.

[0028] Furthermore, the third polysiloxane resin contains polyalkylene oxides at both ends, giving it a hydrophilic structure and thus excellent compatibility with the organic components constituting the coating. Additionally, its hydrophobic properties impart a smooth feel to the manufactured coating, preventing aquatic organisms from attaching and allowing them to slide off during ship navigation. However, coatings containing this resin alone have the following drawbacks: the excessively high hydrophilicity of the resulting coating makes it easier for marine organisms to attach, leading to decreased antifouling performance of the ship during navigation, as well as reduced coating strength and water resistance.

[0029] In view of this, the antifouling coating composition according to the present invention comprises the first polysiloxane resin, the second polysiloxane resin and the third polysiloxane resin, thereby allowing the hydrophobicity and hydrophilicity of the manufactured coating film to be appropriately adjusted, resulting in low surface energy, excellent elasticity and smoothness, and smooth dissolution of the antifouling agent, thus providing excellent antifouling performance.

[0030] First polysiloxane resin

[0031] The first polysiloxane resin is the main resin of the composition, and its function is to impart low surface energy and elasticity to the coating film made from the composition containing the resin, and to undergo a crosslinking reaction with the curing agent to form the coating film.

[0032] Typical vinyl resins or chlorinated rubber resins contain carbon-hydrogen bonds or carbon-chlorine bonds. The bonding strength of these bonds is lower than that of silicon-oxygen (Si-O) bonds, thus they can also form bonds with aquatic organisms, allowing them to attach. However, the first polysiloxane resin has silicon-oxygen (Si-O) bonds with high bonding strength, making it difficult for it to form bonds with aquatic organisms, thereby making it difficult for aquatic organisms to attach.

[0033] For example, the first polysiloxane resin may comprise a polysiloxane resin having silanol groups at both ends. Specifically, the first polysiloxane resin may be represented by the following chemical formula 4.

[0034] [Chemical Formula 4]

[0035]

[0036] In chemical formula 4, R 30 and R 31 Each independently is C 1-18 alkyl, C 2-18 alkenyl or C 6-18 The aryl group, where i is an integer from 1 to 10,000.

[0037] Specifically, R 30 and R 31 Each can be independently of C 1-12 C 1-10 C 1-8 C 1-6 C 1-4 Or C 1-2 The alkyl group, in this case, can be linear or branched.

[0038] In addition, i can be an integer from 100 to 5,000, or an integer from 200 to 1,000, an integer from 400 to 700, or an integer from 450 to 550.

[0039] When i is within the above range, the drying properties, curing properties, and long-term antifouling properties of the composition are improved. When R 30 and R 31 When the number of carbon atoms is within the above range, the smoothness of the manufactured coating is improved.

[0040] Furthermore, the viscosity of the first polysiloxane resin at 25°C can be 2,500 cps to 6,500 cps, 3,000 cps to 6,000 cps, 3,500 cps to 5,500 cps, or 4,500 cps to 5,000 cps. When the viscosity of the first polysiloxane resin at 25°C is within the above range, the drying properties, curing properties, and long-term antifouling properties of the coating composition are improved. When the viscosity of the first polysiloxane resin at 25°C is lower than the above range, the resulting coating film has low elasticity and insufficient antifouling performance; when it exceeds the above range, the compatibility with other components of the coating is insufficient, resulting in problems such as insufficient workability or decreased storage stability of the coating.

[0041] The first polysiloxane resin can be included in the coating composition in an amount of 30 to 50 parts by weight, 32 to 48 parts by weight, or 35 to 45 parts by weight, relative to 3 to 15 parts by weight of the second polysiloxane resin. When the content of the first polysiloxane resin is within the above range, hydrophilic groups are introduced into the manufactured coating film, resulting in excellent long-term antifouling properties. However, when the content of the first polysiloxane resin is below the above range, the content of hydrophobic substances in the manufactured coating film decreases, making it easier for marine organisms to adhere, thus causing a decrease in antifouling properties; when it exceeds the above range, the increased content of hydrophobic substances in the coating leads to a decrease in the compatibility between the components in the coating.

[0042] Second polysiloxane resin

[0043] The role of the second polysiloxane resin is to impart hydrophilicity to the manufactured coating film and to react with the first polysiloxane resin as a curing agent to cure the coating composition.

[0044] Specifically, the second polysiloxane resin contains a polyalkylene oxide group bonded to silicon at one end and at least one alkoxy group bonded to silicon at the other end. That is, the second polysiloxane resin contains a polyalkylene oxide group as a hydrophilic group, imparting hydrophilicity to the coating film and exhibiting excellent compatibility with other components of the coating. Furthermore, the second polysiloxane resin contains at least one alkoxy group bonded to silicon, which, through reaction with the first polysiloxane resin, acts as a curing agent to cure the coating composition.

[0045] In particular, when the second polysiloxane resin is used as a curing agent, the main adhesive resin structure is endowed with polyalkylene oxides, which are hydrophilic groups of the second polysiloxane resin, thereby limiting the consumption of hydrophilic groups. As a result, the antifouling effect of the hydrophilic groups is maintained for a long time, so that the manufactured coating film can maintain a similar antifouling effect during immersion. By adjusting the content of polyalkylene oxides in the second polysiloxane resin, the curing properties and slip properties of the hydrophobic silicone coating film can also be easily adjusted.

[0046] The second polysiloxane resin is represented by the following chemical formula 1.

[0047] [Chemical Formula 1]

[0048]

[0049] In chemical formula 1, R 1 and R 4 Each is independently an alkylene group having 1 to 18 carbon atoms, R 2 and R 3 Each is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, R 5 To R 7 Each is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R 5 To R 7 At least one of them is an alkoxy group having 1 to 10 carbon atoms, n is a real number from 1 to 100 or from 1 to 50, and m is a real number from 1 to 500 or from 1 to 100. In this case, the alkyl, alkenyl, and alkoxy groups can be straight-chain or branched.

[0050] Specifically, R 1 and R 4 Each can be independently of C 1-12 C 1-10 C 1-8 C 1-6 C 2-6 Or C 2-4Alkylene. Here, alkylene refers to a branched, straight, or cyclic saturated hydrocarbon group derived from the removal of one hydrogen atom from the carbon atom of an alkyl group. Examples of alkylene include methylene (-CH2-), 1,1-ethylene (-CH(CH3)-), 1,2-ethylene (-CH2CH2-), 1,1-propylene (-CH(CH2CH3)-), 1,2-propylene (-CH2CH(CH3)-), 1,3-propylene (-CH2CH2CH2-), 1,4-butylene (-CH2CH2CH2CH2-), 2,4-butylene (-CH2(CH3)CH2CH2-), etc., but are not limited thereto.

[0051] In addition, R 2 and R 3 Each can be independently of C 1-8 C 1-6 C 1-4 Or C 1-2 Alkyl groups.

[0052] For example, R 5 To R 7 Each can be independently of C 1-8 C 1-6 C 1-4 Or C 1-2 Alkyl groups, or C 1-8 C 1-6 C 1-4 Or C 1-2 alkoxy groups, and R 4 To R 6 At least one or all of them can be alkoxy groups. That is, R 5 To R 7 All can be alkoxy groups with the number of carbon atoms as described above, or methoxy groups (-O-CH3).

[0053] n is a real number from 1 to 100, in another example it can be a real number from 1 to 50, in yet another example it can be a real number from 5 to 20, and in yet another example it can be a real number from 7 to 15; m can be a real number from 1 to 500, in another example it can be a real number from 1 to 100, in yet another example it can be a real number from 10 to 30, and in yet another example it can be a real number from 15 to 25.

[0054] The viscosity of the second polysiloxane resin at 25°C can be 200 cps to 1,500 cps, 300 cps to 1,200 cps, 600 cps to 900 cps, or 700 cps to 800 cps. When the viscosity of the second polysiloxane resin at 25°C is within the above range, it exhibits good flowability and workability, as well as suitable reactivity. However, when the viscosity of the second polysiloxane resin at 25°C is lower than the above range, a decrease in flowability occurs; when it exceeds the above range, a decrease in reactivity and workability occurs.

[0055] Furthermore, relative to 30 to 50 parts by weight of the first polysiloxane resin, the second polysiloxane resin can be included in the coating composition at an amount of 3 to 15 parts by weight, 4 to 11.5 parts by weight, or 5 to 10 parts by weight. When the content of the second polysiloxane resin is within the above range, it has the effect of introducing hydrophilic groups into the manufactured coating film and providing excellent antifouling properties. However, when the content of the second polysiloxane resin is below the above range, the compatibility with other organic components constituting the coating is insufficient, and the antifouling agent dissolves rapidly from the manufactured coating film, resulting in insufficient long-term antifouling properties of the coating film; when it exceeds the above range, aquatic organisms easily adhere to it, resulting in insufficient antifouling properties of the coating film, and the strength and water resistance of the manufactured coating film are also insufficient.

[0056] Third polysiloxane resin

[0057] The role of the third polysiloxane resin is to impart surface properties (hydrophilic or hydrophobic) and smoothness to the manufactured coating, thereby improving its antifouling performance.

[0058] The third polysiloxane resin is obtained by modifying both ends with polyalkylene oxides. That is, the third polysiloxane resin contains polyalkylene oxides as hydrophilic groups and hydrophobic silicon, exhibiting excellent compatibility with other components of the coating and imparting a smooth texture to the manufactured coating, thereby preventing the adhesion of aquatic organisms.

[0059] Specifically, the third polysiloxane resin can be represented by the following chemical formula 2.

[0060] [Chemical Formula 2]

[0061]

[0062] In chemical formula 2,

[0063] R 10 and R 15 Each is independently an alkylene group having 1 to 18 carbon atoms.

[0064] R 11 To R 14Each of them is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

[0065] a and c are each independent real numbers from 1 to 20.

[0066] b is an integer from 1 to 50.

[0067] Specifically, R 10 and R 15 Each can be independently of C 1-10 C 1-8 C 1-6 Or C 1-3 Alkylene. Here, alkylene refers to a branched, straight, or cyclic saturated hydrocarbon group derived from the removal of one hydrogen atom from the carbon atom of an alkyl group. Examples of alkylene include methylene (-CH2-), 1,1-ethylene (-CH(CH3)-), 1,2-ethylene (-CH2CH2-), 1,1-propylene (-CH(CH2CH3)-), 1,2-propylene (-CH2CH(CH3)-), 1,3-propylene (-CH2CH2CH2-), 1,4-butylene (-CH2CH2CH2CH2-), 2,4-butylene (-CH2(CH3)CH2CH2-), etc., but are not limited thereto.

[0068] R 11 To R 14 Specifically, each can be independently represented as C 1-8 C 1-6 C 1-4 Or C 1-2 The alkyl group. In this case, the alkyl and alkenyl groups can be linear or branched.

[0069] For example, a and c can each independently be a real number from 1 to 20, a real number from 1 to 15, a real number from 5 to 15, or a real number from 7 to 13.

[0070] b can be an integer from 1 to 50, an integer from 5 to 40, an integer from 10 to 35, an integer from 10 to 30, an integer from 15 to 25, or an integer from 17 to 23.

[0071] The viscosity of the third polysiloxane resin at 25°C can be 100 cps to 1,300 cps, 200 cps to 1,000 cps, 300 cps to 650 cps, or 400 cps to 500 cps. When the viscosity of the third polysiloxane resin is within the above range, a coating film with excellent drying, curing, and storage properties and suitable surface leveling can be produced. However, when the viscosity of the third polysiloxane resin at 25°C is lower than the above range, there is a problem of decreased drying properties of the coating composition; when it exceeds the above range, there is a problem of decreased storage properties of the coating composition.

[0072] Furthermore, relative to 30 to 50 parts by weight of the first polysiloxane resin, the third polysiloxane resin can be included in the coating composition at an amount of 5 to 15 parts by weight, 7 to 13 parts by weight, or 8 to 12 parts by weight. When the content of the third polysiloxane resin is within the above range, it has the effect of introducing hydrophilic groups into the manufactured coating film and providing excellent antifouling properties. However, when the content of the third polysiloxane resin is below the above range, the compatibility with other organic components constituting the coating is insufficient, the antifouling agent dissolves rapidly, and the long-term antifouling properties of the coating film are insufficient; when it exceeds the above range, aquatic organisms easily adhere to it, the antifouling properties of the coating film are insufficient, and the strength and water resistance of the manufactured coating film are insufficient.

[0073] Antifouling agent

[0074] The purpose of antifouling agents is to enhance the antifouling properties of the manufactured coating.

[0075] The antifouling agent may be any substance that can be commonly added to an antifouling coating composition without particular restriction. For example, it may include one or more substances selected from the group consisting of copper pyrithione, cuprous oxide (Cu2O), 4,5-dichloro-2-propylisothiazo-3(2H)-one, zinc ethylene-1,2-bis-dithiocarbamate, zinc pyrithione, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, and medetomidine. Specifically, the antifouling agent may contain one or more selected from the group consisting of copper pyrithione and zinc pyrithione.

[0076] Furthermore, relative to 30 to 50 parts by weight of the first polysiloxane resin, the antifouling agent may be included in the coating composition at an amount of 0.1 to 10 parts by weight, 0.5 to 1.5 parts by weight, or 0.8 to 1.3 parts by weight. When the content of the antifouling agent is within the above range, the antifouling performance of the manufactured coating film will be excellent. When the content of the antifouling agent exceeds the above range, the antifouling performance of the coating film will be insufficient.

[0077] The antifouling coating composition may further include silicate oligomers.

[0078] silicate oligomers

[0079] The silicate oligomer acts as a curing agent, forming a coating film by reacting with the hydroxyl groups (-OH) of the first and / or third polysiloxane resins.

[0080] Furthermore, the silicate oligomer can be represented by the following chemical formula 3.

[0081] [Chemical Formula 3]

[0082]

[0083] In chemical formula 3,

[0084] R 20 and R 23 Each is independently an alkyl group having 1 to 18 carbon atoms.

[0085] R 21 and R 22 Each is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0086] h is an integer from 1 to 20.

[0087] For example, R 20 and R 23 Each can be independently of C 1-12 C 1-10 C 1-8 C 1-6 C 2-6 Or C 2-4 Alkyl groups.

[0088] R 21 and R 22 Each can be independently of C 1-8 C 1-6 C 1-4 Or C 1-2 Alkyl groups, or C 1-8 C 1-6 C1-4 Or C 1-2 The alkoxy group. Specifically, R 21 and R 22 At least one or all of them can be alkoxy groups. That is, R 21 and R 22 All of them can be alkoxy groups with the number of carbon atoms as described above, or methoxy groups (-O-CH3) or ethoxy groups (-O-CH2-CH3).

[0089] For example, h can be 1 to 15, 1 to 10, or 2 to 7.

[0090] The weight-average molecular weight (Mw) of the silicate oligomer can be from 100 g / mol to 1,200 g / mol, 200 g / mol to 1,000 g / mol, or 400 g / mol to 800 g / mol. When the weight-average molecular weight of the silicate oligomer is within the above range, the following effects are observed: the curability of the coating containing it is improved, the shelf life of the coating is enhanced, the film shrinkage caused by the condensation reaction is reduced, and the workability is excellent. However, when the weight-average molecular weight of the silicate oligomer is below the above range, it is prone to volatilization from the coating containing it under high temperature conditions, thereby reducing the curability and shelf life of the coating; when it exceeds the above range, the reactivity and curability of the coating containing it decrease, and the viscosity of the coating increases or the workability deteriorates due to increased viscosity.

[0091] Furthermore, relative to 30 to 50 parts by weight of the first polysiloxane resin, the silicate oligomer can be included in the coating composition at an amount of 0.1 to 20 parts by weight, 1 to 15 parts by weight, or 3 to 10 parts by weight. When the content of the silicate oligomer is within the above range, it has the following advantages: the curing performance of the coating is improved, the shelf life is easy to adjust, and no shrinkage occurs during the manufacture of the coating film due to the excessive condensation curing reaction. However, when the content of the silicate oligomer is below the above range, there is a problem of slowed condensation reaction rate and decreased curability during the manufacture of the coating film, resulting in insufficient coating workability; when it exceeds the above range, the shelf life of the coating containing it decreases, and excessive shrinkage occurs when the coating film is manufactured through the excessive condensation reaction.

[0092] The antifouling coating composition may further contain a solvent.

[0093] solvent

[0094] The solvent is used to adjust the viscosity of the coating composition, as well as the appearance characteristics and drying speed of the manufactured coating film.

[0095] The solvent may be, for example, aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetylacetone, methyl ethyl ketone, methyl acetone, methyl butyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, and ethyl acetone; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, propylene glycol methyl ether acetate, methoxypropanol, and ethyl ethoxypropionate; and alcohol solvents such as 2-ethylhexanol, isobutanol, n-butanol, propanol, and 1-methoxy-2-propanol, which may be appropriately selected according to the characteristics or evaporation rate of the resin contained in the composition.

[0096] Commercially available aromatic hydrocarbon solvents include, for example, Kocosol #100 and Kocosol #150.

[0097] Furthermore, relative to 30 to 50 parts by weight of the first polysiloxane resin, the solvent may be included in the coating composition in amounts of 5 to 60 parts by weight, 10 to 40 parts by weight, or 14 to 30 parts by weight. When the solvent content is below the above range, the coating viscosity is high, the workability is reduced, or the appearance characteristics of the resulting coating film are insufficient; when it exceeds the above range, the drying properties of the coating decrease, and the application interval with the primer and the soaking interval after the final coating are excessively prolonged.

[0098] additive

[0099] The antifouling coating composition may further include one or more additives selected from the group consisting of strength enhancers, pigments, and curing catalysts. In this case, the strength enhancers, pigments, and curing catalysts may be used without particular restriction, provided that each of them is a substance generally applicable to antifouling coatings.

[0100] The additive may be included in the coating composition in amounts of 1 to 40 parts by weight, 5 to 30 parts by weight, or 10 to 20 parts by weight relative to 30 to 50 parts by weight of the first polysiloxane resin.

[0101] In the antifouling coating composition, the first polysiloxane resin and the third polysiloxane resin can be the main agents, and the second polysiloxane resin and the silicate oligomer can be the curing agents.

[0102] The viscosity of the antifouling coating composition at 25°C can be 60 KU to 140 KU, 70 KU to 130 KU, or 80 KU to 110 KU. When the viscosity of the antifouling coating composition at 25°C is within the above range, the workability of the coating composition and the anti-sagging properties of the manufactured coating film are excellent.

[0103] Furthermore, based on the total weight of the composition, the solid content of the antifouling coating composition can be from 40% to 95% by weight, 60% to 90% by weight, or 70% to 85% by weight. When the solid content of the antifouling coating composition is within the above range, the coating composition has excellent workability, and the resulting coating film has excellent anti-sagging and surface leveling properties.

[0104] As described above, the antifouling coating composition according to the present invention produces a coating film that maintains excellent antifouling performance for extended periods even under prolonged exposure to seawater or long-term mooring and low-speed conditions. Furthermore, the coating film manufactured from the said antifouling coating composition maintains a smooth surface with minimal adhesion of barnacles and other organisms, even after prolonged exposure to seawater, exhibiting excellent slip properties. This results in significantly superior antifouling performance, making it highly suitable for use as an antifouling coating for man-made structures immersed in water.

[0105] The invention will be described in more detail below by way of examples. However, these examples are only for the purpose of helping to understand the invention, and the scope of the invention is not limited to these examples in any sense. Detailed Implementation

[0107]

Example

[0108] Examples 1 to 16 and Comparative Examples 1 to 5. Preparation of antifouling coating compositions.

[0109] The antifouling coating composition was prepared by mixing the components according to the compositions listed in Tables 1 to 3.

[0110]

[0111]

[0112]

[0113] The physical properties, manufacturers, and product names of the components used in the comparative examples and embodiments are shown in Table 4.

[0114]

[0115]

[0116] Test Example: Evaluation of the antifouling properties of antifouling coating compositions

[0117] The antifouling properties of the antifouling coating compositions used in the examples and comparative examples were evaluated.

[0118] Specifically, the intermediate coating composition (manufacturer: KCC, product name: Lo-Frick T200) was applied to the sample at a thickness of 35 μm using a rotary cup spray (Bell coating), followed by a first curing at 150°C for 25 minutes. Then, the antifouling coating compositions of the examples and comparative examples were applied at a thickness of 150 μm using a rotary cup spray, and the residual moisture in the coating was evaporated in a drying oven at 80°C for 3 minutes (drying). A second curing at 150°C for 25 minutes was then performed to form the final coating film. The static antifouling properties of the final coating film were then measured, and the results are shown in Table 5.

[0119] Static antifouling performance was assessed based on an antifouling coating thickness of 150 μm. The coated samples were immersed in the ocean for 6, 12, or 18 months, and the area of ​​contamination on the sample surface was measured using image analysis.

[0120]

[0121] As shown in Table 5, the coatings made from the antifouling coating compositions of Examples 1 to 16 exhibit excellent static antifouling properties, small fouling area, and excellent antifouling properties even after prolonged immersion in seawater for more than 12 months.

[0122] However, the coatings manufactured in Comparative Example 1 (which does not contain the second polysiloxane resin), Comparative Example 2 (which does not contain the third polysiloxane resin), and Comparative Example 3 (which does not contain the antifouling agent) have significantly insufficient antifouling properties.

[0123] Unlike the second polysiloxane resin of the present invention, the coating of Comparative Example 4, which contains a non-reactive second polysiloxane resin-4 with polyalkylene oxides at one end and no alkoxy groups at one end, showed a significant decrease in antifouling properties after being immersed in seawater for more than 12 months.

Claims

1. An antifouling coating composition comprising: The first polysiloxane resin contains silanol groups. The second polysiloxane resin contains polyalkylene oxides at a single end. The third polysiloxane resin, whose two ends are modified with polyalkylene oxide, and Antifouling agent, in, The second polysiloxane resin is represented by the following chemical formula 1: [Chemical Formula 1] ; In chemical formula 1, R 1 and R 4 Each is independently an alkylene group having 1 to 18 carbon atoms. R 2 and R 3 Each of them is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R 5 To R 7 Each is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R 4 To R 6 At least one of them is an alkoxy group having 1 to 10 carbon atoms. n is a real number from 1 to 100. m is a real number from 1 to 500.

2. The antifouling coating composition according to claim 1, wherein, The viscosity of the first polysiloxane resin at 25°C is 2,500 cps to 6,500 cps.

3. The antifouling coating composition according to claim 1, wherein, The first polysiloxane resin comprises a polysiloxane resin having silanol groups at both ends.

4. The antifouling coating composition according to claim 1, wherein, The viscosity of the second polysiloxane resin at 25°C is 200 cps to 1,500 cps.

5. The antifouling coating composition according to claim 1, wherein, The third polysiloxane resin comprises a polysiloxane resin represented by the following chemical formula 2: [Chemical Formula 2] ; In chemical formula 2, R 10 and R 15 Each is independently an alkylene group having 1 to 18 carbon atoms. R 11 To R 14 Each of them is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms. a and c are each independent real numbers from 1 to 20. b is an integer from 1 to 50.

6. The antifouling coating composition according to claim 1 further comprises a silicate oligomer represented by the following chemical formula 3: [Chemical Formula 3] ; In chemical formula 3, R 20 and R 23 Each is independently an alkyl group having 1 to 18 carbon atoms. R 21 and R 22 Each is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. h is an integer from 1 to 20.

7. The antifouling coating composition according to claim 1, comprising 30 to 50 parts by weight of a first polysiloxane resin, 3 to 15 parts by weight of a second polysiloxane resin, 5 to 15 parts by weight of a third polysiloxane resin, and 0.1 to 10 parts by weight of an antifouling agent.

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