KR20110029023A - Antifouling paint composition - Google Patents

Abstract

PURPOSE: An antifouling paint composition is provided to ensure no cuprous oxide, to control low wear rate of an antifouling coating film, and to secure long-term anti-fouling property in a low coating film thickness. CONSTITUTION: An antifouling paint composition includes, based on 100 parts by weight of the total paint composition, (A) 10 ~ 50 parts by weight of a copolymer consisting of (a) 10 ~ 60 weight% of metal-containing ester monomer, (b) 1 ~ 50 weight% of silyl(meth)acrylate, abd (c) 5 ~ 70 weight% of acryl or vinyl-based unsaturated monomer capable of radical polymerization, as a binder; (B) 0.5 ~ 20 parts by weight of silane, silane coating additive or their mixture; (C) 0.1 ~ 30 parts by weight of 4,5-dichloro-2-octyl-4-isothiazoline-3-one encapsulated with an organic antifouling agent, 2-p-chlorophenyl-3 cyano-4-bromo-5-trifluoromethylpyrrol or their mixture.

Description

Antifouling paint composition {ANTIFOULING PAINT COMPOSITION}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling coating composition which is applied as a top coat to a ship's hull outside and an underwater structure, to prevent the attachment and growth of marine organisms. (A) 10 to 60% by weight of ester monomer containing (a) metal, (b) 1 to 50% by weight of silyl (meth) acrylate monomer and (c) radical polymerization based on 100 parts by weight of the total coating composition. 10 to 50 parts by weight of a copolymer comprising 5 to 70% by weight of the acrylic or vinyl unsaturated monomers possible; (B) 0.5 to 20 parts by weight of silane, silane coating additive or mixture thereof; And (C) 4,5-dichloro-2-octyl-4-isothiazolin-3-one, 2-p-chlorophenyl-3-cyano-4-bromo-5-trifluoro encapsulated with an organic antifouling agent It contains 0.1 to 30 parts by weight of romyl pyrrole or mixtures thereof, and exhibits long-term antifouling properties even at a relatively low coating thickness without substantially including organic tin compounds and cuprous oxide, and thus exhibits low environmental hazards and excellent antifouling properties. It relates to a coating composition and an antifouling coating film thereby.

Hulls, underwater structures, and the like are exposed to water for a long time, such as animals such as oysters, mussels, and shellfish; Plants such as green algae, red algae and brown algae; In addition, the appearance and damage of the aquatic organisms (bacteria), such as aquatic organisms (attach, breeding) may increase the friction between the ship surface and the sea water, which may lower the ship speed, fuel consumption. In addition, when bacteria adhere to and propagate to underwater structures, and cause decay, or when large adherents adhere to and propagate on surfaces of underwater structures, such as steel structures, to damage the corrosion preventing coating of the underwater structures, the underwater structures There is a possibility that damage such as a decrease in the strength and the function of the membrane and the lifespan significantly decreases.

In order to prevent such damage, various antifouling paints are applied to the hull and underwater structures of ships, and new types of antifouling paints have been continuously proposed.

US Pat. No. 3,167,473 and UK Pat. No. 1,475,590 disclose antifouling agents and pigment components in copolymers comprising monomers in which tributyl tin is bonded in salt form to unsaturated carboxylic acids and known acrylic unsaturated monomers. An antifouling coating composition prepared by mixing the above is disclosed. While the copolymer shows good antifouling performance and uniform abrasion performance, it has been regulated due to the biological problem of the hydrolyzed eluting tin-based compound, and according to the 2003 Prohibition on the Use of Tin-based Antifouling Paint, A variety of (tin free) antifouling paint products are available.

Japanese Patent Application Nos. 81-165992 and 83-196900 describe resin binders for antifouling paint compositions having a single metal ester structure in polyester cast iron.

EP 204456 describes a metal ester-containing polyester resin which improves film forming ability 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. Here, X is -CO-, -SO _2- , PO (OH)-or -PO-, M is a metal element such as zinc, copper, tellurium, x is 1 or 2, R is -OR Or a functional group having an organic acid group such as -SR.

Japanese Patent No. 63-128084 discloses a metal-containing resin composition obtained by heating and reacting a gas resin having an acid group, a metal salt of a low boiling point organic base acid and a high boiling point monobasic acid while removing the low boiling point organic base out of the system. An antifouling paint containing as is disclosed.

However, the antifouling coating composition described above also contains a metal antifouling agent such as copper nitrite which is relatively environmentally harmful, and the resulting coating film needs room for improvement in terms of environment friendliness.

However, in the case of the antifouling coating film containing no cuprous oxide, a relatively soft coating film is obtained compared with the metallic antifouling agent, and thus, the wear rate in the alkaline aqueous solution such as seawater is remarkably high, making it difficult to maintain the coating film in the long term. There are disadvantages. Therefore, in order to exhibit long-term antifouling performance, a higher coating thickness is required, and in the field, the coating is required to be divided at several times, which may cause a problem of increased labor and increased costs.

For this reason, it has excellent antifouling performance even at a lower coating film, and the coating film may be worn at a constant speed for a long time to form an excellent antifouling coating film, and there is a strong demand for development of an antifouling coating composition which is less harmful to the environment.

The present invention has been made to solve the above problems, does not contain an organic tin compound and nitrous oxide, has a low risk to the environment and excellent antifouling properties, antifouling coating composition that can exhibit long-term antifouling even at a relatively low film thickness To provide a technical problem.

In order to achieve the above object, the present invention is based on 100 parts by weight of the total weight of the coating composition,

(A) 10 to 60 wt% of (a) a metal ester monomer containing a binder, (b) 1 to 50 wt% of a silyl (meth) acrylate monomer, and (c) an acrylic or vinyl unsaturated monomer capable of radical polymerization. 10 to 50 parts by weight of a copolymer including from 70% by weight;

(B) 0.5 to 20 parts by weight of silane, silane coating additive or mixture thereof; And

(C) 4,5-dichloro-2-octyl-4-isothiazolin-3-one, 2-p-chlorophenyl-3-cyano-4-bromo-5-trifluoro encapsulated with an organic antifouling agent It provides an antifouling coating composition comprising 0.1 to 30 parts by weight of methyl pyrrole or mixtures thereof.

Hereinafter, the present invention will be described in detail.

<Self-wearing copolymer (A)>

The antifouling coating composition of the present invention comprises (a) 10 to 60% by weight of an ester monomer containing a metal, (b) 1 to 50% by weight of a silyl (meth) acrylate monomer, and (c) 5 to 5 acrylic or vinyl monomers. Copolymers comprising 70% by weight.

The binder used in the present invention has a structure containing at least one metal as a random hydrolyzable copolymer composed of the above components. In addition, the binder is a pale yellow copolymer having a solid content of 30 to 70% by weight.

The binder used in the present invention preferably has a number average molecular weight (Mn) of 2,000 to 150,000 measured by gel permeation chromatography (GPC). In general, when the number average molecular weight is less than 2,000, the wear rate of the formed antifouling coating film tends not to be kept constant, and when the number average molecular weight is more than 150,000, the viscosity of the binder is too high, making it difficult to apply to the antifouling coating composition. In the case of the antifouling coating film, the surface hydrolysis reaction proceeds, but wear does not tend to occur. Therefore, the number average molecular weight is one of important factors affecting the viscosity and wear performance of the binder constituting the antifouling coating composition.

Component (a) constituting the binder used in the present invention is represented by the following general formula (1), it can be prepared by reacting the metal acid of 2 or more metal and the organic acid having a carboxyl group to the carboxyl group of (meth) acrylic acid.

In Formula 1, R ¹ is H or CH ₃ , R ² is a hydrolyzable metal-containing functional group represented by the following formula (2), x is any integer of 1 or more, preferably 1 to 300.

[Formula 2] In Formula 2, M is a metal of 2 or more oxides, Y is nitrogen, oxygen, sulfur or one or more carbon atoms containing M, preferably an organic substituent of 3 to 30 carbon atoms]

The metal (M) of 2 or more oxidation numbers participating in the reaction is generally in the form of a metal oxide (MO _a : where M is a metal, O is an oxygen atom, and a represents the oxidation number of the metal / 2), for example Zinc oxide (ZnO), copper oxide (CuO), calcium oxide (CaO), boric anhydride (B ₂ O ₃ ) and the like are added to the reactor.

In the present invention, the organic acid having a carboxyl group may be a monovalent organic acid, a divalent or higher polyvalent organic acid, and the monovalent organic acid includes a monovalent organic acid obtained by a condensation reaction of an acid anhydride and an alcohol compound (or an amine compound). Monovalent organic acids include, for example, acetic acid, nicotinic acid, abietic acid, naphthenic acid, and the like; As the polyvalent organic acid, for example, malonic acid, adipic acid, terephthalic acid, or the like may be used, but is not limited thereto. Acid anhydrides are, for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetraphthalic anhydride, citraconic anhydride, itaconic anhydride, hexahydrophthalic anhydride, 4-methyltetraphthalic anhydride, 4-methylhexahydrophthalic anhydride, 3- Methyltetrahydrophthalic anhydride and the like; The alcohol compound is, for example, methoxymethanol, ethoxymethanol, butoxymethanol, methoxyethanol, butoxyethanol, ethoxymethoxymethanol, butoxymethoxymethanol, methoxyethoxymethanol, eheethoxymethanol, Butoxyethoxymethanol, methoxy methoxy ethanol, ethoxy methoxy ethanol, etc .; Amine compounds are, for example, hexaneamine, aniline, 2-methoxyethylamine, 3-ethoxypropylamine, aminoacetaldehyde dimetalacetal, aminoacetaldehyde diethylacetal, 4-aminobutyraldehyde diethylacetal, 4 -Pentyloxyaniline, 4-hexyloxyaniline, 4- {2- (2-methoxyethoxy) ethoxy} aniline, 1-methoxy-2-phenoxyethylamine, and the like may be used, but is not limited thereto. .

Component (a) in the present invention comprises 10 to 60% by weight of the binder copolymer. When the component (a) is contained in less than 60% 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 may not be worn. Abrasion behavior of the composition may be rapidly progressed may cause a problem that can not constantly control the wear rate.

Component (b) constituting the binder used in the present invention is represented by the following formula (3).

In Formula 3, R ¹ is H or CH ₃ , R ³ is a hydrolyzable silicon-containing functional group represented by the following formula (4), z is any integer of 1 or more, preferably 1 to 300.

In Formula 4, L ₁ , L _2, and L ₃ are organic substituents having 1 or more carbon atoms, preferably 1 to 10, and may be the same or different from each other.

In the present invention, component (b) may be, for example, tributylsilyl acrylate, tributylsilyl methacrylate, triisopropylsilyl acrylate, triisopropylsilyl methacrylate, and the like, but is not limited thereto.

In the present invention, the component (b) serves to help the binder to dissolve in seawater as the hydrolysis proceeds, and to improve the water resistance of the formed coating film, thereby maintaining the wear rate of the paint in the seawater stably. Component (b) in the present invention comprises 1 to 50% by weight of the binder copolymer. In the present invention, when the component (b) is included in less than 1% by weight may not play a role of maintaining a constant wear rate, when contained in more than 50% by weight the wear behavior is rapidly progressed to maintain a constant wear rate There may be a problem that you can't control it.

In the present invention, the acrylic or vinyl unsaturated monomer (c) capable of radical polymerization may be one widely used in the art, and there is no particular limitation thereto. For example, vinyl acetate, styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acryl Ethylene, ethylhexyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, and the like It is not limited. Component (c) in the present invention comprises 5 to 70% by weight of the binder copolymer. In the present invention, when the component (c) is included in less than 5% by weight may have a problem that the strength of the coating film may be lowered, and when included in more than 70% by weight, antifouling performance may be reduced.

The binder used in the present invention can be prepared by random copolymerization in the presence of a radical polymerization initiator according to various known polymerization methods such as solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization.

In the manufacturing method of the binder used by this invention, the azo type compound, peroxide, etc. which are generally used conventionally can be used as said radical polymerization initiator. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), and 2,2'-azobis (2,4-dimethylvalle. Ronitrile), and the like, and benzoyl peroxide, tertiary butyl peroxy acetate, tertiary butyl peroxy acetate, cumene hydroperoxide, tertiary butyl peroxide, tertiary butyl peroxy benzoate, Tertiary butyl peroxy isopropyl carbonate may be used, but is not limited thereto.

In the antifouling coating composition of the present invention, the binder contains 10 to 50 parts by weight, preferably 20 to 45 parts by weight, more preferably 30 to 40 parts by weight, based on 100 parts by weight of the total coating composition. In the present invention, when the binder is included in less than 10 parts by weight, the antifouling agent may be relatively more eluted than the hydrolysis of the binder, and thus may not exhibit long-term antifouling performance. There may be problems such as speed, storage stability and cracks in the dry coating.

<Silane or silane coating additive (B)>

In the non-organic tin-based anti-wear antifouling paints, metal antifouling agents, in particular copper oxide, are widely used to express antifouling performance. However, copper nitrous oxide also exhibits relatively high environmental hazards, and antifouling paints without metal antifouling agents are required. However, when the metal type antifouling agent, especially cuprous oxide, is not included in the antifouling coating composition, the coating film is softened. As a result, the seawater penetrates into the coating film to promote hydrolysis, and the organic antifouling agent has a relatively high solubility with seawater. They are more likely to be eluted with seawater earlier, making it difficult to express long-term antifouling performance.

In order to solve the above problem, silane was introduced in the antifouling coating composition of the present invention. In general, silanes are widely used in paints as adhesion / adhesion enhancers, coupling agents, crosslinking agents, surface modifiers, and hydrophobic materials. In the antifouling coating composition, silane or additives surface modified with silane were applied.

This imparts a water repellent effect to the coating film, prevents seawater infiltration into the coating film and controls the wear behavior of the coating film more uniformly, thereby prolonging antifouling performance.

In the present invention, the silane may be preferably an alkoxy silane, for example tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltrie Methoxysilane, methyltributoxysilane, ethyltributoxysilane, butyltrimethoxysilane, octyltrioctyloxysilane, phenyltrimethoxysilane, methyltrichloroethoxysilane, methyltrifluoroethoxysilane, fluoro Ropropyltrimethoxysilane, benzyltriethoxysilane, cyclohexyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, dimethyldifluoroethoxysilane , Dimethyldichloroethoxysilane, dimethyldibutoxysilane, diphenyldiethoxysilane, difluoropropyldimethoxysilane, dicyclohexyldicyclohexyloxysilane, trimethylmethoxysilane, Methyl silane, can be used, such as the the a-fluoro-a-trimethyl silane, trimethyl chloro silane to, trimethyl-butoxy silane, triethyl silane in may be used by mixing one or more, or both.

In addition, in the present invention, an additive surface-treated with silane may be used to give a more uniform wear performance of the anti-corrosion coating film. Examples of the material to be coated include zinc oxide (ZnO), copper oxide (CuO), and oxidation. Titanium (TiO ₂ ), aluminum oxide (Al ₂ O ₃ ), silicon oxide (SiO _2), magnesium oxide (MgO), and the like, and zinc oxide (ZnO) is most preferably used. In addition, the zinc oxide is more preferable to use a nano-particle (nano-particle) that is more uniformly distributed on the surface of the coating film to give a long-term uniform wear performance to allow the long-term expression of antifouling performance.

The silane and silane coating additives may be used alone or in combination, but more preferably used in combination.

In the antifouling coating composition of the present invention, the silane, the silane coating additive, or a mixture thereof may include 0.5 to 20 parts by weight, more preferably 2 to 15 parts by weight, based on 100 parts by weight of the total coating composition. In the present invention, when the silane, the silane coating additive, or a mixture thereof is included in an amount of less than 0.5 parts by weight, there is little water repellent effect, so that the effect of controlling the wear rate of the coating film may be weak, and may be included in an amount of more than 20 parts by weight. If the coating film becomes too hydrophobic and inhibits hydrolysis of the coating film, the coating film may be rapidly inhibited.

<Organic Antifouling Agent (C)>

The antifouling coating composition of the present invention is substantially free of metal type antifouling agents, in particular copper nitrous oxide. In the present invention, 4,5-dichloro-2-octyl-4-isothiazolin-3-one (hereinafter referred to as "DCOIT") as an organic antifouling agent in order to impart better antifouling performance compared to an antifouling coating film containing copper oxide. ), 2-p-chlorophenyl-3-cyano-4-bromo-5-trifluoromethyl pyrrole (hereinafter referred to as "Tralopyril") or mixtures thereof are used.

DCOIT is represented by the following Chemical Formula 5.

DCOIT is used as an effective antifouling agent for bacteria slime, algae, barnacle and tubeworms, but it is relatively dissolved in solvent when applied in antifouling paint composition. Due to the high environmental load and high solubility with seawater, it may not be effective for long-term antifouling performance, and the application of a large amount of DCOIT may show a characteristic that the dryness of the coating film is remarkably inferior, in particular of the antifouling coating composition of the present invention. In this case, since the cuprous oxide, which is a metal antifouling agent, is not included, the coating film may be softened, and thus it may be easily eluted into the seawater.

Therefore, in the antifouling coating composition of the present invention, a product in which DCOIT is encapsulated in micro units is used. This protects the DCOIT in a capsule form to control its solubility with seawater, allowing the antifouling coating to exhibit even longer-term uniform antifouling performance. And since it is added to the composition in the solid phase does not affect the environmental load, even when the excess application may not affect the drying at all. Encapsulated DCOIT may be commercially available, such as, but not limited to, Sea Nine CR XB3-R39x from Rohm and Haas.

In the antifouling coating composition of the present invention, Tralopyril may be used together with DCOIT encapsulated with an organic antifouling agent.

Tralopyril is less harmful to the environment than metal type antifouling agents such as cuprous oxide, and the antifouling coating composition obtained by using in combination with the DCOIT is excellent in impregnation of the coating substrate, and the coating film has a long term antifouling performance, It is excellent in uniform abrasion performance of coatings over long periods of time, and can be suitably applied to offshore structures used continuously in long-term seawater.

In the antifouling coating composition of the present invention, DCOIT, Tralopyril, or a mixture thereof encapsulated with an organic antifouling agent may include 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total coating composition. In the present invention, when the organic antifouling agent is included in the antifouling coating composition within the above range, the antifouling property of the coating film obtained is excellent and exhibits uniform antifouling performance in the long term.

The components that may be further included in the antifouling coating composition of the present invention are as follows.

<Colored pigment>

As the pigment pigment in the antifouling coating composition of the present invention, various pigments of organic or inorganic type known in the art may be used.

For example, carbon black, phthalocyanine blue, or the like may be used as the organic pigment, and as the inorganic pigment, for example, neutral pigments such as titanium bag, bengal (iron oxide red), iron oxide powder, chalk and zinc (ZnO, Basic oxides such as zinc oxide, white lead, red lead, and the like, and may be used, but are not limited thereto. In the antifouling coating composition of the present invention, the colored pigment may preferably include 1 to 20 parts by weight based on 100 parts by weight of the total weight of the coating composition.

Constitutional Pigments

The extender pigments that can be used in the antifouling coating composition of the present invention include, for example, talc, silica, mica, clay, calcium carbonate, kaolin, magnesium carbonate, barium carbonate, barium sulfate, bentonite used as a sedimentation inhibitor, and the like. The species may be used in combination of two or more kinds, but is not limited thereto. In the antifouling paint composition of the present invention, the extender pigment may preferably include 1 to 40 parts by weight based on 100 parts by weight of the total coating composition.

<Other organic auxiliary antifouling agents>

The antifouling coating composition of the present invention may further include other organic auxiliary antifouling agent as necessary.

As other organic auxiliary antifouling agents, for example, N-3,4-dichlorophenyl-N, N-dimethylurea, zinc ethylene-1,2-bis dithiocarbamate, metal salt pyrithione type (zinc salt pyrithione, copper salt) Pyrithione), 2-methylthio-4-t-butylamino-6-cyclopropylamino-triazine, triphenyl boron pyridine, etc. are mentioned.

The antifouling coating composition of the present invention preferably contains a metal salt pyrithione system, and more preferably contains a zinc salt pyrithione. Such other organic antifouling agents may be used in an amount of 1 to 50 parts by weight, preferably 5 to 40 parts by weight based on 100 parts by weight of the total weight of the coating composition in the antifouling coating composition including DCOIT and Tralopyril.

<Plasticizer>

The antifouling coating composition of the present invention may include a plasticizer so that the antifouling coating film formed may contribute to resistance to cracking caused by prolonged exposure. A plasticizer can mention paraffin chloride, polyvinyl ethyl ether, a tricresyl phosphate, etc., for example, It can be used 1 type or in combination of 2 or more types in the antifouling coating composition of this invention. In the antifouling coating composition of the present invention, the plasticizer may preferably include 1 to 20 parts by weight based on 100 parts by weight of the total weight of the coating composition.

<Flow and sedimentation inhibitor>

Examples of the anti-settling agent which may be included in the antifouling coating composition of the present invention include salts such as organoclay-based aluminum, calcium and zinc stearate salts, lecithin salts and alkylsulfonate salts, polyethylene wax, amide wax and castor. Free waxes, polyamide waxes, synthetic finely divided silicas, polyethylene oxide waxes, and the like, and may be used alone or in combination of two or more thereof.

In addition, rosin or rosin derivatives may be applied to the antifouling paint composition of the present invention, for example, rosin and rosin disproportionated rosin, such as rosin rosin, wood rosin, tall oil rosin, etc. And rosin derivatives such as hydrogenated rosin, polymerized rosin and rosin amine.

In the antifouling coating composition of the present invention, the rosin or the rosin derivative may be used in one kind or in combination of two or more kinds, and may include 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the coating composition. have. If the content of the rosin or rosin derivative component is less than 0.5 parts by weight, it is difficult to expect the effect of supplementing the initial antifouling performance, if it exceeds 20 parts by weight can significantly reduce the hardness of the coating film, weaken the water resistance can cause the coating film collapse.

In addition to the above components, the antifouling coating composition of the present invention includes aliphatic and aromatic solvents, which are generally used in antifouling coating compositions such as solvents such as xylene, toluene and sorbeth, ketones, esters, ethers and alcohol solvents. Depending on the paint properties may be included in 1 to 50 parts by weight based on 100 parts by weight of the coating composition.

As a coating method of the antifouling coating composition of the present invention, conventionally well-known methods such as air spray, airless spray, roller, and brush can be employed without limitation.

According to the present invention, it is possible to provide an antifouling coating composition that is substantially free of cuprous oxide and can control the wear rate of the antifouling coating film to form a coating film having excellent antifouling performance at a low coating thickness, particularly long-term antifouling performance in a stagnant environment. have.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the embodiments are only illustrated to help the understanding of the present invention, but the scope of the present invention is not limited thereto.

Example

1. Preparation of self-wearing copolymer

Xylene and n-butyl alcohol are added to the reaction vessel (round flask) with a stirrer, a condenser, a thermometer, a thermocouple, a dropping funnel and a heating mantle. It was charged, heated to 80-90 ° C. and stirred to reflux. While maintaining the reflux temperature for 2 to 5 hours, 120 g of a metal ester monomer prepared by reacting acrylic acid, zinc oxide and acetic acid, 90 g of triisopropylsilyl acrylate, 60 g of methyl methacrylate and 30 g of butyl acrylate as an acrylic unsaturated monomer 15 g of benzoyl peroxide as a radical polymerization initiator was added to the reaction vessel using a dropping apparatus. 3 g of benzoyl peroxide mixed solution was further added and stirred at the same temperature for 2 hours.

To 250 g of the carboxyl group-containing copolymer prepared through the polymerization process, 35 g of zinc oxide as a metal oxide, 135 g of acetic acid as an organic acid, and 42 g of xylene as an organic solvent were added and stirred for 2 to 6 hours to obtain a pale yellow transparent copolymer binder solution.

2. Preparation of antifouling coating composition

The antifouling coating composition was prepared according to the following methods with the ingredients and contents shown in Tables 1 to 3.

As a first step, all the components except the flow / settling inhibitor and the finishing solvent in Tables 1 to 3 were added to the vessel and mixed with a stirrer.

The second step is a dispersion step, in which a mixture mixed with a stirrer was dispersed using a disperser to prepare a coating composition having an average particle size of 60 μm or less.

Into the coating composition dispersed in the third step, the flow and sedimentation inhibitor and the finishing solvent were added and mixed with a stirrer to prepare an antifouling coating composition. The antifouling performance and the abrasion performance of each antifouling coating composition thus prepared were evaluated. The results are shown in Tables 4 and 5, respectively.

Experimental Example

The antifouling performance and wear performance in the static state of the antifouling coating composition were evaluated by the following method.

Antifouling performance test

Anti-fouling coating composition prepared by sandblasting-treated 300 × 150 × 1.6 (mm) steel plate 200㎛, anticorrosive coat 200㎛, sealer paint 100㎛ and the formulation shown in Tables 1-3 (Dry coating standard) was applied continuously at daily intervals, and cured and dried at room temperature for one week. The test specimens thus manufactured were deposited at a position below 0.5m by sea level using a raft-type pontoon installed in the Ulsan harbor (East coast) and Jangheung offshore (South coast). The degree of contamination of the coating due to the attachment of marine organisms was observed for 18 months at 2 month intervals after deposition. The antifouling properties were evaluated based on the criteria described below.

5 points. Without marine organisms attached (non-contaminated)

4 points… Thin slime layer is observed

3 points… A thick slime layer is observed or the area of vegetable contamination is less than 20% of the effective area of the specimen

2 points… Vegetable contamination area is more than 20% and less than 50% of the effective area of the specimen

1 point… Vegetable contamination area is more than 50% and less than 100% of the effective area of the specimen

Wear performance test

Antifouling coating composition 100 prepared by sandblasting 150 × 70 × 1 (mm) sized stainless steel sheet, 100μm epoxy-based anticorrosive coat, 50μm sealer paint and the formulations shown in Tables 1 to 3 The micrometer was continuously coated at daily intervals, and cured and dried at room temperature for one week. The specimen thus prepared was installed outside a rotor tester with a diameter of 600 mm and a height of 300 mm, and then rotated at 25 knot speed to measure the change in film thickness for 6 months at intervals of 1 month to evaluate the uniformity and speed of wear. .

Each of the components used in the combination compositions shown in Tables 1 to 3 were used as the following products.

Rosin: Gum Rosin [Jianxi sino native products]

Plasticizer: Paraffin plastoil 152 [Handy chemical corporation]

Bengala: Iron Oxide Red 308 [Woo shin pigment co., Ltd.]

Titanium bag: TIPAQUE CR-9 [Ishihara Sangyo Kaisha, Ltd.]

ㆍ Talk: NA-400 [Young woo chemical co., Ltd.]

Trimethoxysilane: KBM-13 [Shin-Etsu Chemical]

ㆍ Dimethyldimethoxysilane: KBM-22 [Shin-Etsu Chemical]

Nanoparticle Zinc Oxide: ADNANO Z805 [Degussa AG]

4,5-dichloro-2-octyl-4-isothiazolin-3-one (a) ^* : Sea Nine 211 [Rohm & Haas]

ㆍ 4,5-Dichloro-2-octyl-4-isothiazolin-3-one (a) ^** : Sea Nine CR XB3-R39x [Rohm & Haas]

2-p-chlorophenyl-3-cyano-4-bromo-5-trifluoromethyl pyrrole: Tralopyril

ㆍ Zinc salt pyrithione: Zinc Omadine Powder [Arch UK biocide Ltd]

Copper salt pyrithione: Copper Omadine Powder [Arch UK biocide Ltd]

N-3,4-dichlorophenyl-N, N-dimethylurea: Preventol A6 [Bayer]

Zinc ethylene-1,2-bis dithiocarbamate: Zineb NAUTEC [Atofina chem.]

2-Methylthio-4-t-butylamino-6-cyclopropylamino-triazine: Irgarol 1051 [Ciba geigy]

Triphenylboron pyridine: Borocide PK [Invista]

Copper Nitrite: LOLO TINT 97 [American Chemet]

Aliphatic amide wax (20% xylene paste): Monoral 4000X [HS Chem.]

ㆍ Xylene: Xylene [SK corporation]

Claims (9)

To 100 parts by weight of the total coating composition, (A) 10 to 60 wt% of (a) a metal ester monomer containing a binder, (b) 1 to 50 wt% of a silyl (meth) acrylate monomer, and (c) an acrylic or vinyl unsaturated monomer capable of radical polymerization. 10 to 50 parts by weight of a copolymer including from 70% by weight; (B) 0.5 to 20 parts by weight of silane, silane coating additive or mixture thereof; And (C) 4,5-dichloro-2-octyl-4-isothiazolin-3-one, 2-p-chlorophenyl-3-cyano-4-bromo-5-trifluoro encapsulated with an organic antifouling agent An antifouling coating composition comprising methyl pyrrole or a mixture thereof in an amount of 0.1 to 30 parts by weight. The antifouling coating composition according to claim 1, wherein the copolymer (A) has a number average molecular weight (Mn) of 2,000 to 150,000. The antifouling coating composition according to claim 1, wherein the metal ester monomer (a) has a structure represented by the following Chemical Formula 1:

In Chemical Formula 1, R ¹ is H or CH ₃ , R ² is a hydrolyzable metal-containing functional group of formula (2), and x is any integer of 1 or more;

In Chemical Formula 2, M is a metal having two or more oxides, and Y is an organic substituent having one or more carbon atoms including nitrogen, oxygen, sulfur, or M. The antifouling coating composition according to claim 3, wherein M is zinc oxide, copper oxide, calcium oxide or boric anhydride. The antifouling coating composition according to claim 1, wherein the silyl (meth) acrylate monomer (b) has a structure represented by the following Chemical Formula 3:

In Formula 3, R ¹ is H or CH ₃ , R ³ is a hydrolyzable silicon-containing functional group of formula 4, z is any integer of 1 or more,

In Formula 4, L ₁ , L _2, and L ₃ are organic substituents having 1 or more carbon atoms, which may be the same as or different from each other. The method of claim 1, wherein the silane is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltribu Methoxysilane, butyltrimethoxysilane, octyltrioctyloxysilane, phenyltrimethoxysilane, methyltrichloroethoxysilane, methyltrifluoroethoxysilane, fluoropropyltrimethoxysilane, benzyltriethoxysilane , Cyclohexyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, dimethyldifluoroethoxysilane, dimethyldichloroethoxysilane, dimethyldibutoxysilane, Diphenyldiethoxysilane, difluoropropyldimethoxysilane, dicyclohexyldicyclohexyl silane, trimethylmethoxysilane, trimethylethoxysilane, trimethylfluoroethoxysilane, tri Til chloroethoxy silane, trimethyl-butoxy silane, triethyl silane, and the antifouling paint composition, characterized in that is selected from the group consisting of a mixture thereof. The antifouling coating composition according to claim 1, wherein the material to be coated with silane in the silane coating additive is zinc oxide, copper oxide, titanium oxide, aluminum oxide, silicon oxide, or magnesium oxide. The antifouling coating composition according to claim 7, wherein the material to be coated with silane is zinc oxide. The antifouling coating composition according to claim 1, further comprising at least one selected from pigmented pigments, extender pigments, organic auxiliary antifouling agents, plasticizers and anti-settling agents.