KR101115200B1 - A copolymer binder for the anti-fouling and anti-fouling paint composition containing it - Google Patents

Abstract

The present invention relates to a copolymer binder for an antifouling paint and an antifouling paint composition comprising the same, and more particularly, comprising a copolymer binder, an elution promoting component, and other additives, the storage stability and initial antifouling property. It relates to this excellent antifouling coating composition;

(a) 10 to 60% by weight of the metal ester monomer,

(b) 1 to 50% by weight of the silyl (meth) acrylate monomer,

(c) 5 to 70% by weight of an acrylic or vinyl unsaturated monomer, and

(d) 1-20% by weight of vinyl polysiloxane

Antifouling coating composition, metal ester, silyl (meth) acrylate, vinyl polysiloxane, hull.

Description

Copolymer binder for antifouling paints and antifouling paint composition comprising same {A COPOLYMER BINDER FOR THE ANTI-FOULING AND ANTI-FOULING PAINT COMPOSITION CONTAINING IT}

The present invention is a top coat of a coating film coated on a ship hull (hull outside) and the underwater structure (underwater structure), a copolymer binder for antifouling paint applied to prevent the adhesion and growth of marine life, and comprising the same The present invention relates to an antifouling coating composition, and more particularly, comprising a copolymer binder composed of a metal ester monomer, a silyl (meth) acrylate monomer, an acrylic or vinyl unsaturated monomer, and a vinyl polysiloxane, an elution promoting component, and other additives. The present invention relates to an antifouling paint composition having excellent storage stability and initial antifouling property.

 The antifouling coating composition aims to prevent or control the attachment and growth of marine organisms that cause surface contamination of seawater deposition coatings. When various marine organisms are attached to the surface of the coating, the frictional force between the surface of the coating and the seawater may increase during the operation of the vessel, which may significantly increase the fuel cost, which accounts for a large portion of the operating expenses. Recently, the most successful antifouling paints applied to ships are antifouling paints using SPC (Self-Polishing Copolymer) as a binder.

U.S. Patent No. 3,167,473 and U.S. Patent No. 1,475,590 disclose antifouling agents and pigment components in copolymers comprising monomers in which tributyl tin is bonded to salts of unsaturated carboxylic acids in salt form and known acrylic unsaturated monomers. There is described an antifouling coating composition prepared by mixing.

While the copolymer shows good antifouling performance and uniform abrasion performance, it has been regulated due to the biological problem of the tin-based compound eluted during hydrolysis. A variety of tin free antifouling paints have been released.

Japanese Patent Application No. 78-21889 describes the application of a partially gelled binder to an antifouling coating composition by mixing a metal ester compound such as zinc acetate in a copolymer having a carboxyl group in the side chain. The antifouling coating composition containing the binder is poor in coating film forming ability and paint storage ability, so that a crack phenomenon occurs during cracking or abrasion, and the viscosity thereof is difficult to apply.

Japanese Patent Application Nos. 81-165992 and 83-196900 disclose resin binders for antifouling paint compositions having one metal ester structure in a polyester main chain. However, the metal ester bond of the binder has a remarkably fast abrasion rate in an aqueous alkaline solution such as seawater, making it difficult to maintain the coating film in the long term, and the resin has a low molecular weight and poor coating film forming ability.

European Patent No. 204456 describes a metal ester-containing polyester resin with improved film forming capability with a hydrolyzable binder. The binder contains at least one functional group represented by the formula -X- [OMR] _X in the side chain of the resin (where X is -CO-, -SO _2- , PO (OH)-or -PO- And M is a metal element such as zinc, copper, tellurium, x is 1 or 2, R is a functional group having an organic acid group such as -OR ¹ or -SR ¹ (wherein R ¹ is an organic residue to be)).

However, such binders have the disadvantage of being too high in viscosity and poor long-term storage. This is because the metal forming the ionic bond has an empty d-orbital to form a coordination complex with a polar carbonyl group in the binder.

In addition, the binder having an ionic bond has a high glass transition temperature, so that the coating film is not easily broken, cracks are easily generated due to external impact, and bendability is poor. In addition, the binder has a disadvantage in that it is impossible to repaint due to the relatively poor adhesion compared to the conventional tin-based antifouling coating composition. This recoating problem is known to be due to the increased lipophilic property due to the organic acid constituting the binder.

Compared with the general tin-based binder having an ionic bond, the binder exhibits excessive hydrolysis properties, and in particular, excessive elution often occurs in the initial stage of seawater deposition. For this reason, the phenomenon of partial flaking of the coating film from the surface during wear often occurs, which provides a cause of poor surface roughness.

In addition, the binder is limited to the acid value of the copolymer having a carboxy group to 40 or less, such that when the acid value is low, it is difficult to sufficiently accept the copolymer after elution of the metal ester, it is difficult to prevent surface contamination by marine organisms, The wear rate decreases sharply compared to the wear rate, making long-term antifouling performance difficult.

Japanese Patent Application No. 90-196869 describes a hydrolyzable copolymer composed of trimethylsilyl (meth) acrylate and a known unsaturated monomer. However, trimethylsilyl (meth) acrylate has been reported to have a degree of hydrolysis of about 70% compared to the conventional tin-based binder, which shows that the hydrolysis degree of seawater is more covalent than silicon in the metal ester structure. It is considered unfavorable because it falls.

Therefore, the content of hydrolyzed trimethylsilyl (meth) acrylate should be higher than other antifouling paint compositions, but trimethylsilyl (meth) acrylate monomer is relatively very expensive in terms of cost, and if the content is higher than necessary, the binder There is a problem that the crack resistance of the poor. In addition, when a material having a small carbon number of an alkyl group bonded to silicon is applied in order to increase hydrolyzability, there is a problem in that long-term storage is poor.

An object of the present invention is to solve the problems of the conventional antifouling coating composition as described above, in order to minimize the surface energy of the coating film to prevent the adhesion of marine life, a specific hydrolyzable copolymer containing one or more metals It is to provide a new self-wearing non-tin antifouling coating composition excellent in storage stability and initial antifouling by adding a binder.

The antifouling coating composition of the present invention is characterized by comprising a copolymer binder composed of the following components:

(a) 10 to 60% by weight of the metal ester monomer,

(b) 1 to 50% by weight of the silyl (meth) acrylate monomer,

(c) 5 to 70% by weight of an acrylic or vinyl unsaturated monomer, and

(d) 1-20% by weight of vinyl polysiloxane

The sum of the contents of the components is 100% by weight.

The copolymer binder used in the present invention is a random hydrolyzable copolymer, a light yellow copolymer having a solid content of 30 to 70% by weight, and has a structure containing one or more metals. In addition, the binder has a number average molecular weight (Mn) of 2,000 to 1, which is one of important factors affecting the viscosity and abrasion performance of the binder constituting the antifouling coating composition, measured by gel permeation chromatography (GPC). Although it is preferable that it is 150,000, when it is less than 2,000, the viscosity of a binder is too low and it is difficult to manufacture an antifouling coating composition, and the abrasion rate of the formed antifouling coating film tends not to be kept constant. In addition, when the number average molecular weight exceeds 150,000, the viscosity of the binder is too high, making it difficult to apply to the antifouling coating composition, and in the case of the antifouling coating film, surface hydrolysis reaction proceeds, but wear does not occur.

 Component (a) constituting the copolymer binder used in the present invention has a structure represented by the following formula (1), and is prepared by reacting an organic acid having a carboxyl group with a metal having at least 2 oxides and a carboxyl group of (meth) acrylic acid. Can be.

[Wherein R ₁ is H or CH ₃ , R ₂ is a hydrolyzable metal-containing functional group represented by the following general formula (3), and x is any integer of 1 or more]

[Wherein M is a metal having two or more oxides and K is an organic substituent having one or more carbon atoms containing nitrogen, oxygen, sulfur or M]

Metals having two or more oxides that participate in the reaction for preparing the component (a) are generally metal oxides (MO _a : Here, M is a metal, O is an oxygen atom, a represents the oxidation number of the metal), for example zinc oxide (ZnO), copper oxide (CuO), calcium oxide (CaO), boric anhydride (B ₂ O ₃ ) and the like.

The organic acid having a carboxyl group participating in the reaction for producing the component (a) includes a monovalent organic acid, a divalent or higher polyvalent organic acid, and the monovalent organic acid is a condensation reaction of an acid anhydride and an alcohol compound (or an amine compound). The monovalent organic acid obtained is included. Examples of the monovalent organic acid include acetic acid, nicotinic acid, abidic acid, naphthenic acid, and the like. Examples of the polyvalent organic acid include malonic acid, adipic acid, terephthalic acid, and the like. Examples of the acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, tetraphthalic anhydride, citraconic anhydride, itaconic anhydride, hexahydrophthalic anhydride, 4-methyltetraphthalic anhydride, 4-methylhexahydrophthalic anhydride, 3- And methyltetrahydrophthalic anhydride. Examples of the alcohol compounds include methoxymethanol, ethoxymethanol, butoxymethanol, methoxyethanol, butoxyethanol, ethoxymethoxymethanol, butoxymethoxymethanol and methoxye. Methoxymethanol, ethoxyethoxymethanol, butoxyethoxymethanol, methoxymethoxyethanol, ethoxymethoxyethanol and the like. Examples of the amine compound include hexaneamine, aniline, 2-methoxyethylamine, 3- Ethoxypropylamine, aminoacetaldehyde dimetalacetal, aminoacetaldehyde diethyl acetal, 4-aminobutyraldehyde diethyl acetal, 4 -Pentyloxyaniline, 4-hexyloxyaniline, 4- {2- (2-methoxyethoxy) ethoxy} aniline, 1-methoxy-2-phenoxyethylamine, and the like. However, these examples do not limit the scope of the present invention.

In the copolymer binder used in the present invention, the component (a) is the main component to impart hydrolysis properties, the wear performance (wear rate) of the antifouling paint composition is mainly determined by the content of the component (a) , The content of component (a) is preferably 10 to 60% by weight. If the component (a) is used in less than 10% by weight, even if the hydrolysis reaction of the binder proceeds, it does not dissolve in seawater, so that the antifouling coating composition to which it is applied does not wear, and when the component (a) is used in excess of 60% by weight, The wear behavior of the antifouling paint composition to which this is applied rapidly progresses, which causes a problem that the wear rate cannot be constantly adjusted.

The component (b) which comprises the said copolymer binder used for this invention has a structure of following General formula (2).

[Wherein, R ₁ is H or CH ₃ , R ₃ is a hydrolyzable silicon-containing functional group represented by the following general formula (4), and y is any integer of 1 or more]

[Wherein, L ₁ , L ₂ and L ₃ are one or more organic substituents having 1 or more carbon atoms and may be the same or different from each other]

Examples of the component (b) include tributylsilyl acrylate, tributylsilyl methacrylate, triisopropylsilyl acrylate, triisopropylsilyl methacrylate, and the like, but these examples do not limit the scope of the present invention. .

Since the component (b) hydrolyzes quickly in the seawater, the component (b) often has poor water resistance as time passes, and serves to control or prevent this problem. That is, component (b) serves to help the binder to dissolve in seawater by hydrolysis, and to improve the water resistance of the formed coating film, thereby maintaining a stable wear rate of the paint in seawater.

In the copolymer binder used in the present invention, the content of the component (b) is preferably 1 to 50% by weight, the role of maintaining a constant wear rate when using the component (b) less than 1% by weight If it is used in excess of 50% by weight, the wear behavior rapidly progresses as in the case of excessive application of component (a), and thus the wear rate cannot be constantly adjusted.

Component (c) constituting the copolymer binder used in the present invention is a known acrylic or vinyl unsaturated compound capable of radical polymerization, such as vinyl acetate, styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, It may be one or more selected from oxyethyl acrylate, ethoxy ethyl methacrylate, butoxy ethyl acrylate, butoxy ethyl methacrylate, etc., but these examples do not limit the scope of the present invention.

In the copolymer binder used in the present invention, the content of component (c) may be determined by the remaining amount according to the content of components (a), (b) and (d), preferably 5 to 70 weight. %, Component (c) plays a role in forming the main chain of the binder.

Component (d) constituting the copolymer binder used in the present invention has a structure represented by the following formula (5), and is equipped with a one-component curing system by curing only by addition of a catalyst.

[Wherein, R ₁ is an organic substituent having 1 to 4 carbon atoms, R ₂ is a vinyl group, m and n are any integer of 1 to 20 (if less than 1, it is easily removed in the coating film and there is no antifouling effect, If it exceeds 20, it is not copolymerized due to the decrease in reactivity).]

Examples of the component (d) include vinylmethylsiloxane, polydimethylsiloxane, vinyldimethylsilicone, methylhydrodimethylsiloxane, trimethoxyvinylmethylsilicone, trimethoxydimethylsilicone, and the like, but these examples limit the scope of the present invention. It is not.

The component (d) contains a vinyl group at the end of the polysiloxane, and thus has excellent compatibility and reactivity with the resin of the component (c), which is acrylic or vinyl, and the release property in which the silicone component of the component (d) lowers the surface tension of the coating film surface. It has a (Release Effect), so it has excellent antifouling property to prevent deposits. In addition, the coating film, which is a characteristic of the vinyl resin, is not easily broken and has a characteristic of making elasticity. The coating film is not discolored due to weather resistance against UV and the like.

Therefore, component (d) helps to reduce the surface tension of the coating film when the hydrolysis proceeds and the binder dissolves in the seawater, while improving the crack resistance, weather resistance and heat resistance of the formed coating film, thereby preventing the antifouling property in the seawater. It keeps the stable.

In the copolymer binder used in the present invention, the content of the component (d) is preferably 1 to 20% by weight, when used in less than 1% by weight can not properly exhibit the effect of improving the antifouling properties and other coating properties When used in excess of 20% by weight, compatibility problems occur during copolymerization of the binder, and drying of the coating film may be delayed.

The antifouling coating composition of the present invention preferably contains 10 to 30% by weight of the above-described copolymer binder as a binder. When the content of the copolymer binder is less than 10% by weight, a sufficient wear rate may be exhibited to exhibit appropriate antifouling performance. If it is more than 30% by weight, the hydrolysis of the coating film becomes so severe that it may cause the coating film to collapse or deteriorate in properties.

In addition, the antifouling coating composition of the present invention may further include an elution promoting component.

In the antifouling coating composition of the present invention, the dissolution promoting component serves to control the initial antifouling performance, that is, to promote the wear behavior of the coating film in seawater to increase the antifouling agent dissolution rate.

The dissolution promoting component may be used by selecting one or more from the group consisting of rosin, rosin derivatives, monocarboxylic acids and salts thereof. Examples of the rosin include rosin rosin, wood rosin, and tall oil rosin. Examples of derivatives include (low melting point) disproportionated rosin, hydrogenated rosin, polymerized rosin and rosin amine, and examples of monocarboxylic acids include fatty acids having 5 to 30 carbon atoms, synthetic fatty acids and naphthenic acid, and the like. Examples of salts include metal salts of rosin and rosin derivatives (copper salts, zinc salts or magnesium salts).

It is preferable that the dissolution promoting component is contained in the antifouling coating composition of the present invention 2 to 20% by weight, when used less than 2% by weight, it is difficult to exhibit the effect of supplementing the initial antifouling performance, used in excess of 20% by weight In this case, there is a problem that the hardness of the coating film is significantly lowered, the water resistance is weakened, and the coating film collapses.

The antifouling coating composition of the present invention may include one or more conventional known antifouling paint additives, for example, known antifouling agents in the form of pigments, organic compounds or inorganic compounds, improvement of coating film strength, control of wear rate, and Examples include zinc oxide, anti-settling agent, anti-settling agent, plasticizer such as paraffin chloride, and antifoaming agent that contribute to improvement of crack resistance of antifouling coating film.

Known antifouling agents in the form of organic compounds are preferably used in an amount of 0.1 to 20% by weight, and when used below 0.1% by weight, the antifouling performance against marine plants and bacteria is lowered. There is a problem of weakening the coating film defects.

Known antifouling agents in the form of inorganic compounds are preferably used in an amount of 5 to 50% by weight, and when used in an amount of less than 5% by weight, the antifouling performance cannot be exhibited. Cause.

Plasticizers such as zinc oxide, antisagging agents, sedimentation inhibitors, anti-fouling coatings, and plasticizers such as paraffin chloride and antifoaming agents can be selectively used as needed. The total amount exceeds 10% by weight. It is used in a range that does not.

 In addition, various known organic and inorganic pigments (for example, titanium white, iron oxide, organic red pigment and talc, etc.) may be used in the antifouling coating composition of the present invention. In addition, various solvents generally used in antifouling coating compositions such as aliphatic and aromatic (for example, xylene, toluene, etc.) solvents, ketones, esters, and ether solvents may be added.

The present invention can be understood in more detail by the following examples, but the following examples are only for illustrating the present invention and are not intended to limit the scope of protection of the present invention.

Manufacturing example  1 to 10

[Manufacture of Binder]

Xylene and n-butyl alcohol, organic solvent components, are placed in a reaction vessel (round flask) with a mechanical stirrer, a condenser, a thermometer, a dropping funnel, and a heating mantle. It was added at a content of and heated to reflux to stir. While maintaining the reflux temperature for 2 to 5 hours, the metal ester monomer (component (a1) or component (a2)) and the silyl (meth) acrylate monomer (component (b)) in the amounts shown in Table 1 below Isopropylsilyl acrylate, methyl methacrylate and butyl acrylate as the acrylic unsaturated monomer (component (c)) or vinyl dimethyl silicone as the styrene, vinyl polysiloxane monomer (component (d)), under benzoyl peroxide as a radical polymerization initiator In the presence, it was put in a reaction vessel using a dropping apparatus. In addition, a small amount of the mixed solution of benzoyl peroxide was further added and stirred at the same temperature for 2 hours.

Light yellow transparent air was prepared by adding zinc oxide (35 g) as a metal oxide, acetic acid (135 g) as an organic acid, and xylene (42 g) as an organic solvent to 250 g of the carboxyl group-containing copolymer prepared through the polymerization process. The combined binder solution was obtained.

The nonvolatile content in the copolymer binder solution prepared as described above was 30 to 70% by weight as a result of calculating the weight of the residue after drying in an oven at 150 ° C. for 15 minutes.

[Table 1]

Components of Binder and Its Content

Note: Component (a1) is a metal ester monomer component prepared by reacting acrylic acid, zinc oxide and acetic acid, and component (a2) is a metal ester monomer component prepared by reacting methacrylic acid, copper oxide and acetic acid.

Example  1 to 12 and Comparative example  1 to 3

[Production of antifouling coating composition]

The antifouling coating compositions of the present invention were prepared by adding the binders prepared in Preparation Examples 1 to 10, respectively, to the contents shown in Table 2 below, and the antifouling performance and wear performance (wear rate) of the antifouling coating compositions prepared as described above. And the appearance of the coating film were compared and evaluated, and the results are shown in Tables 3, 4, and 5, respectively. The initial viscosity in 25 degreeC of the antifouling paint composition was 90-110 (ku).

The antifouling performance and wear performance (wear rate) in the static state for the antifouling coating composition were evaluated by the following method.

Antifouling Performance test

An antifouling coating composition prepared by sandblasting-treated 300 × 150 × 2 (mm) steel plate 200 μm, anticorrosive coat 200 μm, binder coat 100 μm and the formulation shown in Table 2 Dry coating film thickness) was continuously coated at daily intervals, and cured and dried at room temperature for one week. Thus prepared specimens were immersed at a position below 1m by sea level using a raft-type pontoon installed in Ulsan Defense Port (East Coast) and Geoje Island offshore (South Coast). The degree of contamination of the coating due to the adhesion of marine organisms was periodically observed every month after deposition, and the antifouling performance was evaluated according to the criteria described below.

Class 5: Without marine organisms attached (non-polluted),

Level 4: thin slime layer observed

Grade 3: A thick slime layer is observed or the area of vegetable contamination is less than 20% of the effective area of the specimen,

Grade 2: Plant contaminated area greater than 20% and less than 50% of the effective area of the specimen,

Grade 1: Plant contamination is greater than 50% and less than 100% of the effective area of the specimen (X: Animal contamination).

Wear performance (speed) test

Anti-fouling coating composition prepared by sandblasting 150 × 70 × 1 (mm) stainless steel sheet 50㎛ epoxy coating anticorrosive coat 50㎛, seam coat 50㎛ and the formulation shown in Table 2 Was continuously coated at daily intervals, and cured and dried at room temperature for one week. The specimen thus prepared was installed outside a rotating drum having a diameter of 600 (mm) and a height of 300 (mm), and then rapidly rotated at a speed of 25 (knot) at a constant temperature of 25 ° C for 6 months at a thickness of 1 month. The wear rate was evaluated by measuring the change.

Coating Crack resistance  exam

Anti-fouling coating composition prepared by sandblasting 150 × 70 × 1 (mm) stainless steel sheet 50㎛ epoxy coating anticorrosive coat 50㎛, seam coat 50㎛ and the formulation shown in Table 2 Was continuously coated at daily intervals, and cured and dried at room temperature for one week. The specimens thus prepared were deposited in seawater deposition tanks at intervals of three months, six months, one year, and two years to evaluate the occurrence of cracks and poor appearance of the coating film.

TABLE 2

Components and Contents of Antifouling Coating Compositions

[Table 3]

Antifouling performance test result of antifouling paint composition

As shown in Table 3, the antifouling coating composition prepared by using the binder according to the present invention exhibited excellent long-term antifouling properties as the antifouling performance in the stagnant state is generally 4-5 grades.

In addition, as the contents of the metal ester monomer component and the silyl (meth) acrylate monomer component of the present invention increased, the antifouling performance was good, and Example 1 to which an antifouling enhancement component (vinyl polysiloxane monomer) applied by surface energy as a component of the binder was applied. In the case of -12, compared with the comparative examples 1-3 which were not applied, it turned out that it shows the same level or a more favorable result from the viewpoint of antifouling performance.

[Table 4]

Evaluation of Wear Performance of Antifouling Coating Composition

As shown in Table 4, the antifouling paint compositions of Examples 1 to 12 to which the binder of the present invention and the elution promoting component were added have an initial wear rate of 11 to 16 (µm / month), and the antifouling paints of Comparative Examples 1 to 3 It can be seen that the initial wear rate is higher than the composition, while the long term wear rate is low.

Therefore, it can be seen that the antifouling coating composition of the present invention is excellent in long-term antifouling properties and is suitable for ships having a low flight rate.

TABLE 5

Coating film crack resistance test result

○: Good appearance of coating film, X: Crack generation and poor appearance on coating film

As shown in Table 5, in Comparative Examples 1 to 3 using the binder without the vinyl polysiloxane monomer component as an antifouling agent, the appearance of the coating film was poor and cracks occurred in the coating film, making it difficult to apply as a marine coating material. It can be seen that Examples 1 to 12 using the present invention can be sufficiently applied to ships by improving the appearance and hardness of the coating film.

According to the present invention, the rate of hydrolysis can be preferably controlled by the dissolution promoting component, which is excellent in storage stability, and can have properties of low friction antifouling paint due to the antifouling effect through the reduction of the surface energy of the vinyl polysiloxane component. It is possible to provide an antifouling coating composition which is unlikely to cause cracking and peeling of the coating film due to the crack resistance characteristic of the coating film, and forms an antifouling coating film having excellent initial antifouling properties under a stagnant environment or a high pollution environment.

Claims (5)

Copolymer binder for antifouling paint consisting of the following components: (a) 10 to 60% by weight of the metal ester monomer, (b) 1 to 50% by weight of the silyl (meth) acrylate monomer, (c) 5 to 70% by weight of an acrylic or vinyl unsaturated monomer, and (d) 1-20% by weight of vinyl polysiloxane The sum of the contents of the components is 100% by weight. The copolymer binder according to claim 1, wherein the metal ester monomer (a) has a structure represented by the following general formula (1).

[Wherein R ₁ is H or CH ₃ , R ₂ is a hydrolyzable metal-containing functional group represented by the following general formula (3), and x is any integer of 1 or more]

[Wherein M is a metal having two or more oxides and K is an organic substituent having one or more carbon atoms containing nitrogen, oxygen, sulfur or M] The copolymer binder according to claim 1, wherein the silyl (meth) acrylate monomer (b) has a structure represented by the following formula (2).

[Wherein, R ₁ is H or CH ₃ , R ₃ is a hydrolyzable silicon-containing functional group represented by the following general formula (4), and y is any integer of 1 or more]

[Wherein, L ₁ , L ₂ and L ₃ are one or more organic substituents having 1 or more carbon atoms and may be the same or different from each other] The copolymer binder according to claim 1, wherein the vinyl polysiloxane monomer (d) has a structure represented by the following formula (5).

[Wherein, R ₁ is an organic substituent having 1 to 4 carbon atoms, R ₂ is a vinyl group, and m and n are any integer of 1 to 20.] 10 to 30% by weight of the copolymer binder of claim 1 based on the total weight of the antifouling coating composition; 2 to 20% by weight of the dissolution promoting component selected from the group consisting of rosin, rosin derivatives, monocarboxylic acids and salts thereof based on the total weight of the antifouling coating composition; Antifouling coating composition comprising a.