KR20120079866A - Hydrolyzable metal-containing copolymer and method for preparing the same, and anti-fouling paint composition comprising the same - Google Patents

Abstract

PURPOSE: A hydrolytic metal-containing copolymer is provided to have excellent strength, hardness, hydrolytic property, crack resistance, anti-fouling property, and storage safety at the same time. CONSTITUTION: A hydrolytic metal-containing copolymer comprises, as polymerization units, a silyl (meth)acrylate monomer, an acryl based or vinyl based unsaturated monomer, an unsaturated carboxylic acid ester monomer ester-linked by abietic acid or a carboxy group of derivatives thereof, and divalent metal as mediums, and an unsaturated carboxylic ester monomer ester-linked by a carboxy group of a monoester of dicarboxylic acid, and divalent metal as mediums. An anti-fouling paint composition comprises the hydrolytic metal-containing copolymer as a binder.

Description

HYDROLYZABLE METAL-CONTAINING COPOLYMER AND METHOD FOR PREPARING THE SAME, AND ANTI-FOULING PAINT COMPOSITION COMPRISING THE SAME}

The present invention relates to a hydrolyzable metal-containing copolymer, a method for producing the same, and an antifouling coating composition comprising the same, and more particularly, an unsaturated carboxylic ester monomer containing a carboxyl group of abietic acid or a derivative thereof as a polymerized unit; And an unsaturated carboxylic ester monomer containing a carboxyl group of the monoester of dicarboxylic acid together, so that excellent strength, hardness, hydrolyzability (self-wear resistance), crack resistance and stagnation antifouling property can be simultaneously ensured. The present invention relates to a metal-containing copolymer, a method for producing the same, and an antifouling coating composition comprising the same as a binder.

As a top coat of coatings on the hull outside and underwater structures, the antifouling coating composition prevents and controls the attachment and growth of marine organisms that cause surface contamination of seawater deposition coatings. The purpose. When various marine organisms are attached to the surface of the coating film, the frictional force between the surface of the coating film and the seawater may increase during the operation of the ship, thereby greatly increasing fuel costs, which occupy a significant portion of the operating cost. Among the anti-fouling paints currently being applied to ships, the most successful products are anti-fouling paints using SPC (Self-Polishing Copolymer) as a binder.

U.S. Patent Nos. 3,167,473 and 1,475,590 disclose antifouling agents in copolymers comprising monomers in which tributyl tin is bonded to salts of unsaturated carboxylic acids in salt form and known acrylic unsaturated monomers; An antifouling coating composition prepared by mixing a pigment component is disclosed. The copolymer has an advantage of excellent antifouling performance and uniform wear performance. However, tin-based antifouling paints have been regulated due to the biological problems of tin-based compounds that are eluted during hydrolysis, and are tin-free to replace tin-based antifouling paints under the 2003 Prohibition on the Use of Tin-based Antifouling Paints. Various antifouling paint products have been released.

For example, Japanese Patent No. 78-21889 discloses a method of applying a partially gelled binder to an antifouling coating composition by mixing a metal ester compound such as zinc acetate to a copolymer having a carboxyl group in the side chain. However, the antifouling coating composition containing the copolymer has a poor film forming ability and paint storage property, so that a peel phenomenon occurs during cracking or abrasion, and the viscosity thereof is difficult to apply. In addition, Japanese Patent 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 problem that it is difficult to maintain the coating film in the long term because the wear rate in an aqueous alkali solution such as seawater is too high and the molecular weight of the resin is small, so that the coating film formation ability is poor.

That is, the non-tin-based binder as described above has the disadvantage that the viscosity is too high and the long-term storage property is poor, which is a carbonyl group that is polar in the binder because the metal forming the ionic bond has an empty d- orbital (orbital) This is because they form a coordination complex with. In addition, the binder having an ionic bond is brittle due to the increase in the glass transition temperature, easily cracked by the external impact and poor bendability. In addition, there is a disadvantage that the re-coating is impossible 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 due to the organic acid constituting the binder. In addition, it exhibits excessive hydrolysis characteristics compared to general tin-based binders having ionic bonds, and in particular, excessive elution occurs unnecessarily at the initial stage of seawater deposition, which causes partial flaking of the coating film from the surface during wear. This often occurs, providing a cause for poor surface roughness. In addition, the binder as described above limits the acid value of the copolymer having a carboxyl group to a low acid value of 40 mg KOH / g or less, and it is difficult to sufficiently accept the copolymer after the metal ester is eluted, thereby preventing surface contamination by marine organisms. It is difficult to expect long-term antifouling performance because the wear rate decreases rapidly compared to the initial wear rate.

Accordingly, World Patent Nos. 91-1554 and US Pat. No. 5,199,977 disclose compounds such as amines, alcohols, ureas and phenols which are nonvolatile as ligands for stabilization and low viscosity of metals in the metal ester-containing binder structure as described above. Disclosed is a technique to be introduced. Examples of the amines applied here include rosin amines having 12 to 20 carbon atoms, and when the amine is applied as a ligand, the initial wear rate can be controlled and the metal can be stabilized and low viscosity can be coordinated. However, these amines have a solubility in water that is too low compared to the conventional binder structure, resulting in a rapid decrease in the wear rate of the binder over time. In addition, cracks may occur at seawater lines when exposed for long periods of time. On the other hand, ligands such as alcohol, urea, and phenol disclosed together are relatively poor in water resistance, causing swelling, flaking and discoloration of the coating film.

On the other hand, Japanese Patent No. 2-196869 discloses 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 is more covalently bonded to silicon than tin in the metal ester structure. It is because it falls. Therefore, the content of hydrolyzed trimethylsilyl (meth) acrylate should be higher than that of other antifouling coating compositions. The trimethylsilyl (meth) acrylate monomer is relatively very expensive and the crack resistance of the binder is higher than necessary. There is a problem that becomes poor. In addition, when a material having a small carbon number of an alkyl group bonded to silicon in order to increase hydrolyzability has a problem of poor long-term storage.

Accordingly, Korean Patent No. 97-700680 describes a method of mixing a plastic (meth) acrylate copolymer in order to solve the problem of the copolymer composed of the trimethylsilyl (meth) acrylate monomer. In this case, however, the wear rate decreases gradually as many non-hydrolyzable binders remain after long-term wear in seawater.

U.S. Patent No. 3,167,473 U.S. Patent 5,199,977 British Patent No. 1,475,590 Japanese Patent No. 78-21889 Japanese Patent No. 81-165992 Japanese Patent No. 83-196900 Japanese Patent No. 2-196869 World Patent No. 91-1554 Korean Patent No. 97-700680

The present invention is to solve the problems of the prior art as described above, containing a non-tin-based hydrolyzable metal that can simultaneously secure excellent strength, hardness, hydrolysis resistance (magnetic wear resistance), crack resistance, stagnation stain resistance and storage stability It is a technical problem to provide a copolymer and an antifouling coating composition comprising the same as a binder.

In order to achieve the above technical problem, the present invention is (a) silyl (meth) acrylate monomer as a polymer unit; (B) acrylic or vinyl unsaturated monomers; (C) unsaturated carboxylic ester monomers ester-linked with a carboxyl group of abietic acid or a derivative thereof via a divalent metal; And (d) unsaturated carboxylic ester monomers ester-linked via the carboxyl group of the monoester of the dicarboxylic acid and a divalent metal; It provides a hydrolyzable metal-containing copolymer comprising a.

In addition, in another aspect of the invention (1) copolymerizing a silyl (meth) acrylate monomer, an acrylic or vinyl unsaturated monomer and an unsaturated carboxylic monomer to prepare a carboxyl group-containing copolymer; And (2) reacting the copolymer prepared in step (1) in the presence of abietic acid or a derivative thereof and a monoester of dicarboxylic acid with a divalent metal. It provides a manufacturing method.

In another aspect, the present invention provides an antifouling coating composition comprising the hydrolyzable metal-containing copolymer as a binder.

When the antifouling coating composition comprising the hydrolyzable metal-containing copolymer of the present invention is used as a binder, self-wearing by hydrolysis is possible while the thickness of the wet layer is low, and coating film cracking and peeling do not occur even though the hardness is high. It is excellent in crack resistance and can form an antifouling coating film excellent in antifouling performance, especially in a stagnant environment or a high pollution environment.

Hereinafter, the present invention will be described in detail.

[ Hydrolyzable  Polymerization Unit of Metal-Containing Copolymer]

(A) Silyl ( Mat ) Acrylate  Monomer

The hydrolyzable metal-containing copolymer of the present invention includes a silyl (meth) acrylate monomer (hereinafter also referred to as "(valent) component"). Unsaturated carboxylic acid esters described below are monomer components that quickly undergo hydrolysis in seawater, and thus often have poor water resistance as time passes. However, by including the component (A), these problems can be controlled and prevented. That is, the component (A) plays a role of helping the binder to dissolve in seawater as the hydrolysis proceeds, and at the same time, improves the water resistance of the formed coating film and plays a role of stably maintaining the wear rate of the coating film in seawater.

Specifically, the (A) component may be one having a structure of Formula 3 below.

(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), y is an arbitrary integer of 1 or more as a repeating unit.

[Formula 4]

In Chemical Formula 4, L ₁ , L _2, and L ₃ are each independently an organic substituent having 1 or more carbon atoms.

Component (A) is an acrylic monomer containing silicon bonded to an organic substituent, and the organic substituents bonded to silicon may be the same or different. Specifically, as the (a) component, tributylsilyl acrylate, tributylsilyl methacrylate, triisopropylsilyl acrylate, triisopropylsilyl methacrylate, and the like may be used alone or in combination of two or more thereof. It is not necessarily limited thereto.

The component (A) is preferably used in an amount of 1 to 50% by weight of the entire copolymer. If the content is less than 1% by weight of the total copolymer it may be difficult to maintain a constant wear rate, if the content exceeds 50% by weight of the total copolymer wear behavior is rapidly progressed to control the wear rate is constant It can be difficult.

(B) acrylic or Vinyl  Unsaturated monomer

The acrylic or vinyl unsaturated monomer (hereinafter, also referred to as "(b) component") included in the hydrolyzable metal-containing copolymer of the present invention serves as a main chain of the copolymer.

As the component (B), one or more of the known acrylic or vinyl unsaturated monomers copolymerizable with the component (A) and (C) and (D) described later can be used. In one embodiment, as the component (b), one or more selected from the group consisting of (meth) acrylic acid ester, styrene and vinyl ester may be used. For example, 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, ethoxyethyl acrylate, ethoxyethyl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, etc. It may be used by mixing more than one type, but is not necessarily limited thereto.

The content of component (B) can generally be determined relatively according to the content of component (A) and the components (C) and (D) described below. For example, when (a) component is contained in the range of 1 to 50% by weight, and the sum of the component (d) and (d) is 10 to 60% by weight, the component (b) is contained in an amount of 5 to 70% by weight. May be included.

(All) Aviete  Or unsaturated ester-linked via the carboxyl group of the derivative and a divalent metal Carboxylic acid  Ester monomer

Unsaturated carboxylic acid ester monomers (or metal esters) generally included in hydrolyzable metal-containing copolymers used as binders for antifouling paints are the main components for imparting hydrolytic properties to the binder. That is, the wear performance (wear rate) of the antifouling paint composition tends to be determined mainly by the content of the unsaturated carboxylic ester monomer.

In general, unsaturated carboxylic ester monomers have the structure of Formula 1 below.

[Formula 1]

In General Formula 1, R ₁ is H or CH ₃ , R ₂ is a hydrolyzable metal-containing functional group represented by the following General Formula 2, and x is an arbitrary integer of 1 or more as a repeating unit.

[Formula 2]

In the general formula 2, M is a metal of 2 or more oxides, K is an organic substituent of one or more carbon atoms containing nitrogen, oxygen, sulfur or M.

The unsaturated carboxylic ester monomer may be divided into components having different structures according to the kind of K included in the R ₂ functional group of the general formula (1).

The unsaturated carboxylic acid ester monomer having the structure of Formula 1 may generally be prepared by reacting a metal having at least two oxidation numbers with an organic acid having a carboxyl group at the terminal of the carboxyl group of (meth) acrylic acid.

Metals participating in the reaction are generally represented by the formula of M _n O _a in the form of oxides (M is a metal, O is an oxygen atom, n and a are each independently integers of 1 to 3 to the oxidation number of the metal). Determined accordingly). As the metal oxide, zinc oxide (ZnO), copper oxide (CuO), calcium oxide (CaO), boric anhydride (B ₂ O ₃ ), or the like may be used, but is not limited thereto. Organic acids having a carboxyl group include monovalent organic acids, divalent or higher polyvalent organic acids, and monovalent organic acids obtained from condensation reactions of acid anhydrides with alcohols or amine compounds. Specifically, monovalent organic acids such as acetic acid, nicotinic acid, abidic acid, naphthenic acid, and polyvalent organic acids such as malonic acid, adipic acid, and terephthalic acid may be used, but are not limited thereto. Acid anhydrides include succinic anhydride, maleic anhydride, phthalic anhydride, tetraphthalic anhydride, citraconic anhydride, itaconic anhydride, hexahydrophthalic anhydride, 4-methyltetraphthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-methyltetra anhydride Hydrophthalic anhydride and the like can be used, and examples of the alcohol or amine compound include methoxy methanol, ethoxy methanol, butoxy methanol, methoxy ethanol, ethoxy ethanol, butoxy ethanol, ethoxy methoxy methanol, butoxy methoxy methanol. , Methoxyethoxy methanol, ethoxyethoxy methanol, butoxyethoxy methanol, methoxymethoxy ethanol, ethoxymethoxy ethanol, hexaneamine, aniline, 2-methoxy ethylamine, 3-ethoxy propylamine, Aminoacetaldehyde dimethylacetal, aminoacetaldehyde diethylacetal, 4-aminobutyraldehyde diethylacetal, 4-pentyloxy aniline, 4-hex Siloxy aniline, 4- {2- (2-methoxyethoxy) ethoxy} aniline, 1-methoxy-2-phenoxyethylamine and the like can be used, but is not necessarily limited thereto.

The unsaturated carboxylic ester monomer (hereinafter referred to as "(poly) component") ester-linked via a divalent metal via the carboxyl group of abiate acid or a derivative thereof contained in the hydrolyzable metal-containing copolymer of the present invention is a carboxyl group. It is an unsaturated carboxylic ester monomer prepared using abiate acid or a derivative thereof among the organic acids, which can increase the strength and hardness of the antifouling coating film. The strength and hardness of the antifouling coating film is to prevent the coating film deformation caused by wood block settling during the shipbuilding process, the coating damage caused by the fender during the mooring of the quay, and the seam of the seawater during the ship operation. In order to be required physical properties.

In the preparation of the component (c), abiete acid and its derivatives may be used alone or in combination of two or more thereof, and may be used in combination with other organic acids having a carboxyl group as exemplified above.

Specifically, the component (C) may be a polymer unit having a structure represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, R ₁ is H or CH ₃ , M is a divalent metal, A is a carboxyl group exclusion of abietic acid or derivatives thereof.

(D) of dicarboxylic acids Monoester  Unsaturated esters linked by carboxyl groups and divalent metals Carboxylic acid  Ester monomer

The hydrolyzable metal-containing copolymer of the present invention is an unsaturated carboxylic ester monomer, which contains a carboxyl group of the monoester (or half ester) of the (C) component and the dicarboxylic acid (hereinafter, "Also called (d)").

Since both abietic acid and its derivatives are monovalent basic acids having a cyclic structure, steric hindrance with adjacent functional groups tends to increase, so that when applied to antifouling coating films, the hydrolysis rate is low and it is difficult to obtain a uniform coating film wear rate. Lack of flexibility in coatings can cause cracks in coatings over prolonged exposure to seawater.

Accordingly, the present invention is an unsaturated carboxylic ester monomer prepared using a monoester of dicarboxylic acid as an organic acid having a carboxyl group together with the component (C) to solve the above problems and to secure excellent antifouling property. (D) The components were introduced together. That is, the monoester of dicarboxylic acid reduces the internal stress of the antifouling coating film, suppresses the occurrence of cracking of the coating film, and maintains the wear rate of the antifouling coating film, thereby compensating the above problems caused when using abiate or its derivatives. Ingredient.

Specifically, the component (d) may be a polymerized unit having a structure of Formula 2 below.

[Formula 2]

In Formula 2, R ₁ is H or CH ₃ , M is a divalent metal, E is the carboxyl group exclusion of the monoester of the dicarboxylic acid.

The monoester of dicarboxylic acid used in the preparation of (D) component may be prepared by reacting dicarboxylic acid or its anhydride with an alcohol having at least one ether group. .

Wherein X and Y are each independently CH ₂ , CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ or CH ₂ CH ₂ CH ₂ CH ₂ , Z is O, N or NH, n is an integer of 1 to 3 to be.

Dicarboxylic acids used in the preparation of monoesters of dicarboxylic acids include all known various kinds of dicarboxylic acids, and acid anhydrides include succinic anhydride, maleic anhydride, and phthalic anhydride. Ride, tetraphthalic anhydride, citraconic anhydride, itaconic anhydride, 3-methyltetrahydrophthalic anhydride, and the like, but are not necessarily limited thereto. Alcohols having at least one ether group used in the preparation of monoesters of dicarboxylic acids include methoxymethanol, ethoxymethanol, butoxymethanol, methoxyethanol, ethoxyethanol, butoxyethanol, methoxymethoxyethanol , Ethoxymethoxymethanol, butoxymethoxymethanol, methoxyethoxymethanol, ethoxyethoxymethanol, butoxyethoxymethanol, methoxymethoxyethanol, ethoxymethoxyethanol, and the like. It is not limited.

It is preferable that the reaction mole ratio of dicarboxylic acid or its anhydride: alcohol having an ether group in the monoester preparation of dicarboxylic acid is 1: 1.1 to 1: 2.0. If the molar ratio of the alcohol to dicarboxylic acid or anhydride thereof is less than 1.1, the reaction may not proceed well. If the molar ratio exceeds 2.0, the reaction time may be longer and the active ingredient may be reduced.

In addition, the reaction temperature is preferably in the range of 100 ° C to 150 ° C in the absence of a solvent. If the reaction temperature is less than 100 ℃ reaction rate is too slow to ensure economic feasibility, if it exceeds 150 ℃ there may be a problem that the divalent ester is produced due to the side reaction at high temperature.

The preferred relative content ratios of component (C) and component (D) are in weight ratio (C) component: (D) component = 30 to 90: 10 to 70, more preferably (C) component: (D) component = 50 85: 15-50. In one embodiment, when only the component (C) and component (D) are used as the unsaturated carboxylic acid ester monomer, the component (C) is 50 to 85 to 100% by weight of the sum of the component (C) and the component (D). 15% by weight and (D) component may be used. If the relative content ratio (weight ratio) of the component (C) is less than 30, the wet layer of the antifouling coating film becomes thick, which hinders long-term antifouling performance, and the strength and hardness of the coating film may be weakened to satisfy various coating film properties. If exceeded, the wear rate of the antifouling coating film is remarkably decreased, the internal stress of the coating film is sharply increased, and the cracking of the coating film may become severe with age. In addition, if the relative content ratio (weight ratio) of the component (d) is less than 10, it is difficult to obtain a uniform wear rate of the antifouling coating film, and it may be difficult to prevent cracking of the coating film. The strength of the antifouling coating film is weakened and various coating film properties are not solved, and thus, the conventional problem cannot be solved, and the wet layer of the coating film can be thickened due to the nonuniform wear rate of the antifouling coating film, thereby preventing long-term antifouling performance.

The component (C) and the component (D) are preferably used in an amount of 10 to 60 wt% in total in the total copolymer. When the content is less than 10% by weight of the total copolymer, even if the hydrolysis reaction of the binder proceeds, it is not dissolved in seawater so that the antifouling coating composition to which it is applied may not be worn, and if the content exceeds 60% by weight of the total copolymer ( A) As in the case of excessive application of the component, the wear behavior of the antifouling paint composition to which it is applied is rapidly progressed, which may cause a problem in that the wear rate cannot be constantly controlled.

The hydrolyzable metal-containing copolymer of the present invention is a random type copolymer prepared by including the components (A) to (D), and has a structure including one or more metals. The number average molecular weight (Mn) of the copolymer according to the present invention is preferably 2,000 to 150,000 (as measured by gel permeation chromatography (GPC)). If the number-average molecular weight of the copolymer solid content is less than 2,000, the viscosity of the binder is too low, making it difficult to prepare a coating composition, the wear rate of the formed antifouling coating film tends not to be kept constant, and the coating film due to the low molecular weight of the binder The interparticle stress is weakened, which can lead to cracking of the coating and discoloration due to moisture when exposed to seawater for a long time. On the other hand, when the number average molecular weight is more than 150,000, the viscosity of the binder is too high, it is difficult to apply to the coating composition, in the case of the antifouling coating film may exhibit a tendency that the hydrolysis reaction proceeds but wear does not occur. Therefore, the number average molecular weight of the copolymer is one of important factors affecting the viscosity and wear performance of the binder constituting the antifouling paint composition.

[ Hydrolyzable  Preparation of Metal-Containing Copolymer]

The hydrolyzable metal-containing copolymer of the present invention can be prepared through a conventional polymerization process using the above-mentioned (A) to (D) components and necessary additives in an appropriate amount. Here, the preferred content of the polymerized unit (A) to (D) component is 1 to 50 parts by weight of (A) component as described above; (B) 5-70 parts by weight of the component; And 10 to 60 parts by weight of the component (c) and the component (d).

Specifically, the hydrolyzable metal-containing copolymer of the present invention is a divalent metal, abies acid or a derivative thereof, and a dicarboxylic acid in the main chain formed by copolymerizing the (A) component, the (B) component and the unsaturated carboxylic acid monomer. It can be prepared sequentially by reacting the monoesters of together to form the final (poly) component and (d) component. In addition, the component (C) and the component (D) may be prepared first, and then mixed with the component (A) and the component (B), followed by copolymerization.

Preferably, (1) preparing a carboxyl group-containing copolymer by copolymerizing a silyl (meth) acrylate monomer, an acrylic or vinyl unsaturated monomer and an unsaturated carboxylic acid monomer; And (2) reacting the copolymer prepared in step (1) in the presence of abietic acid or a derivative thereof and a monoester of dicarboxylic acid with a divalent metal. The hydrolyzable metal-containing copolymer of the present invention To prepare.

[ Antifouling paint  Composition]

According to another aspect of the present invention, there is provided an antifouling coating composition comprising a hydrolyzable metal-containing copolymer as described above as a binder.

The antifouling coating composition of the present invention preferably comprises 10 to 30% by weight of the copolymer in the total composition. If the content is less than 10% by weight may not exhibit sufficient antifouling performance and wear performance, if the content is more than 30% by weight can be severe hydrolysis of the coating film may cause collapse of the coating film or degradation of properties.

The antifouling coating composition of the present invention can be prepared by a conventional process by adding components commonly used in antifouling coating compositions in addition to the copolymer of the present invention comprising the above (A) to (D) components. In one embodiment, the antifouling coating composition of the present invention is at least one selected from the group consisting of co-binders, antifouling agents, pigments, solvents, precipitation inhibitors, antisagging agents, plasticizers, antifoaming agents and stabilizers It may further include an additive.

Specifically, conventional cobinders, known antifouling agents in the form of organic or inorganic compounds, pigments (such as zinc oxide, etc.), which serve to improve coating strength, control the wear rate and color, etc., various known organic and inorganic pigments Various solvents commonly used in antifouling coating compositions such as titanium white, red iron oxide, organic red pigments and talc, aliphatic, aromatics (such as xylene, toluene, etc.), ketones, esters, and ethers; An antifouling agent, a conventional flow preventing agent, a plasticizer (for example, paraffin chloride, etc.) which contributes to the improvement of crack resistance of the antifouling coating film, a conventional antifoaming agent, and a conventional stabilizer may be added to the antifouling coating composition of the present invention. In addition, various resins such as acrylic resins, polyalkylvinyl ethers (vinyl ether (co) polymers), fillers, viscoelastic modifiers, storage stabilizers, and the like may additionally be included.

Preferably, the antifouling coating composition of the present invention further comprises at least one dissolution control component selected from the group consisting of rosin, rosin derivatives, monocarboxylic acids and salts thereof. Therefore, it is possible to effectively control the long-term antifouling performance by controlling the dissolution rate of the antifouling agent together with the controlled wear behavior of the coating film in seawater. As rosin, rosin rosin, wood rosin, and tall oil rosin can be used as a representative, and as rosin derivatives (low melting point) disproportionated rosin, hydrogenated rosin, polymerized rosin, metal salts of rosin and rosin derivatives (copper Salts, zinc salts or magnesium salts), rosin amines, and the like, but are not necessarily limited thereto. Rosin and rosin derivatives can be used individually or in mixture of 2 or more types. As the monocarboxylic acid, fatty acids having 5 to 30 carbon atoms and synthetic fatty acids or naphthenic acid may be used, but are not necessarily limited thereto.

The content of the dissolution adjusting component may be relatively determined in view of the antifouling performance and the water resistance of the coating film. Specifically, the dissolution control component is preferably added in an amount of 0.1 to 25% by weight (solid content conversion) in the total antifouling paint composition. If the content is less than 0.1% by weight may not exhibit the initial antifouling performance complementary effect, if the content exceeds 25% by weight may weaken the hardness and water resistance of the coating film may cause the coating film collapse.

The antifouling coating composition of the present invention may be applied to any underwater transportation means, underwater structures, etc., which need to be prevented from pollution, and in particular, it can be applied to a ship hull to effectively prevent and control the attachment and growth of marine life.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are only for the understanding of the present invention, and the scope of the present invention in any sense is not limited to these examples.

Example  1 to 8 and Comparative example  1-4

[Preparation of Hydrolyzable Metal-containing Copolymer]

A hydrolyzable metal-containing copolymer was prepared by the following procedure with the ingredients and contents shown in Table 1 below.

The organic solvents xylene and n-butyl alcohol are placed in a reaction vessel (round flask) equipped with a mechanical stirrer, a condenser, a thermometer, a dropping funnel and a heating mantle. It was charged, heated and stirred to reflux. (A) TIPSA as a component, maintaining reflux temperature for 2 to 5 hours; (B) MMA, EA and BA as components; Methacrylic acid as an acrylic acid monomer which has a carboxyl group as a side chain; was put into the reaction container using tertiary mill peroxide as a radical polymerization initiator using the dropping apparatus. In addition, tertiary peroxide mixed solution was further added in small amounts, and stirred at the same temperature for 2 hours. Copper oxide (5-6 parts by weight) as a metal oxide, a monoester of abiate and dicarboxylic acid as an organic acid, and xylene (30 parts by weight) as an organic solvent, in the carboxyl group-containing copolymer prepared through the polymerization process. Was added and stirred for 2 to 6 hours to prepare a pale yellow transparent metal-containing copolymer solution. Here, the monoester of the dicarboxylic acid is prepared by reacting methyltetrahydroanhydride and methoxypropanol at a molar ratio of 1: 1.5 at 130 ° C to 140 ° C.

The nonvolatile content (calculated as the weight of the residue after drying in an oven at 150 ° C. for 15 minutes) in the prepared copolymer solution was 30 to 70 wt%, and the physical properties thereof are shown in Table 2 below.

Table 1 Components and Contents of Hydrolyzable Metal-Containing Copolymers

(C) Component: A component prepared by reacting and combining methacrylic acid, abietic acid and copper oxide

(D) Component: A component prepared by reaction and bonding of methacrylic acid, monoester of dicarboxylic acid and copper oxide

TIPSA: triisopropylsilyl acrylate

MMA: Methyl Methacrylate

EA: ethyl acrylate

BA: Butyl Acrylate

TAPO: turmeric mill peroxide

[Table 2] Physical property results of the prepared copolymer

Example  9 to 16 and Comparative example  5 to 8

[Production of antifouling coating composition]

Using the copolymer prepared according to the above as a binder to prepare an antifouling coating composition in the formulation shown in Table 3. The coating film properties, antifouling performance and abrasion performance (wear rate) of the prepared compositions are shown in Tables 4 to 6, respectively.

Table 3 Components and Contents of Antifouling Coating Compositions

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.]

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

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

Aliphatic amide wax paste: Monoral 5500M [HS Chem.]

Copper Oxide: Red Copp 97N Premium [American Chemet]

Xylene: Xylene [SK corporation]

Coating film properties, antifouling performance and wear performance (wear rate) for each prepared antifouling coating composition were evaluated by the following method.

Coating strength evaluation (banner settle pressure test)

An epoxy-based anti-corrosive coat was coated on a sandblasted 100 × 300 × 3 (mm) steel sheet to 150 μm, and dried at room temperature (20 ° C.) for 1 day to form a coating film. On the surface of the coating film, an epoxy binder coat (sealer coat) was additionally coated to 100 mu m, and dried at room temperature (20 DEG C) for 1 day to form a coating film. Next, 300 µm (dry coating film thickness) of the antifouling coating composition prepared by the formulation shown in Table 3 was continuously coated at a daily interval, and then cured and dried at room temperature for one week to prepare test specimens.

After the test specimens were dried for an additional 1, 3, 5 and 7 days at room temperature, a 20 × 20 × 20 (mm) wooden block was placed on top of the test specimen and 50 kgf / cm 2 in the vertical direction from above the wooden specimen. Was applied for 40 minutes, and the strain of the coating film thickness was measured. The coating film thickness strain was measured at a reduced rate by measuring the initial coating film thickness of the dry coating film and the coating film thickness after pressure was applied to the neck piece.

The evaluation of the anti-banner settling test is indicated according to the following criteria as a result of the seventh-day strain.

* Coating strength grade

5: less than 3% strain

4: more than 3% of strain less than 5%

3: 5% or more strain less than 7%

2: strain 7% or more to less than 10%

1: more than 10% strain

Crack resistance  exam

An epoxy-based anticorrosive coating was applied to a sandblasted 100 × 300 × 1.5 (mm) steel sheet to 150 μm, dried at room temperature (20 ° C.) for 1 day to form a coating film, and then added to the surface of the coating film. The epoxy binder coating material was coated so as to be 100 µm, and dried at room temperature (20 ° C) for 1 day to form a coating film. Next, 600 μm (dry coating film thickness) of the antifouling coating composition prepared by the formulation shown in Table 3 was applied for 3 days at intervals of one day, and cured and dried at room temperature for one week to prepare test specimens.

The test specimens were immersed in 23 ° C. natural seawater for 24 hours and again removed from the seawater and dried for 24 hours outdoors. This cycle was repeated 30 times. Visual confirmation after wet-dry cycling was performed to evaluate crack resistance according to the following criteria.

* Crack resistance grade

5: no cracks or cosmetic defects

4: Cracks occur in less than 5% of the total area of the test specimen

3: Cracks occur at more than 5% and less than 20% of the total area of the test specimen

2: Cracks occur from more than 20% to less than 50% of the total area of the test specimen

1: Cracks occur at more than 50% and less than 70% of the total area of the test specimen

0: Cracks occur in more than 70% of the total area of the test specimen

[Table 4] Mechanical property evaluation of the antifouling coating composition coating film

As shown in Table 4, in the case of Example, both the coating film strength and the crack resistance were excellent. Specifically, as the content of the (C) component increased, the hardness and toughness of the coating film increased, resulting in low strain, and the content of the (D) component increased the crack resistance. On the other hand, in the comparative example which did not contain (C) component and (D) component, either the coating film strength or the crack resistance characteristic was remarkably poor.

Stagnant Antifouling performance  exam

Sand-blasted 550 × 150 × 2 (mm) steel sheets were coated with 200 µm epoxy-based anticorrosive paint, 100 µm binder paint, and 300 µm (dry coating thickness) of the antifouling coating composition prepared by the formulations shown in Table 3. It was continuously coated, 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 raft installed in Ulsan Defense Port (East Coast) and Geojedo offshore (South Coast). Every three months after the deposition, the degree of contamination of the coating due to the adhesion of marine organisms was observed for 18 months periodically.

* Antifouling performance grade

5: No attachment of marine organisms (non-contaminated)

4: thin slime layer observed

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

2: The plant contamination area is more than 20% and less than 50% of the effective area of the specimen

1: Plant contamination is greater than 50% and less than 100% of the effective area of the specimen

[Table 5] Antifouling performance evaluation of antifouling paint composition

As shown in Table 5, in the case of including the components (A) to (D), both the initial antifouling performance and the long-term antifouling performance was excellent. On the other hand, in the case of Examples 15 and 16 where the amount of the (D) component was relatively high, the excellent initial antifouling performance showed a tendency to decrease with time, but still showed an acceptable range of antifouling performance. On the other hand, in Comparative Examples 5 to 7 of the antifouling paints without using the (D) component or the (D) and (D) components, the initial and long-term antifouling performance was poor, and the Comparative Example using only the (D) component. In case of 8, the initial antifouling performance was good, but the long term antifouling performance was poor.

Wear performance evaluation

Sand-blasted 150 × 70 × 1 (mm) sized stainless steel sheet was continuously coated with antimicrobial anticorrosive paint 50㎛, binder paint 50㎛ and antifouling paint composition 100㎛ prepared in the formulation shown in Table 3 at daily intervals. Cured and dried at room temperature for one week. The specimen thus prepared was installed outside a rotating drum with a diameter of 600 mm and a height of 300 mm, and then rapidly rotated at a speed of 25 knots at a constant temperature of 25 ° C. to measure the change in film thickness for six months at an interval of one month to evaluate the wear rate. It was.

[Table 6] Evaluation of wear performance of antifouling paint composition

As shown in Table 6, the embodiment showed a high wear rate and a uniform wear rate. Specifically, the higher the relative content of component (D) to the component (C), the higher the wear rate, and when the component (D) and component (D) were included in an appropriate ratio, the wear rate was more uniform throughout the test period. Indicated. On the other hand, when the component (D) or (A) was not used as in the comparative example, the wear rate was generally low (Comparative Examples 5 to 7), and the wear behavior was also very uneven (Comparative Examples 6 and 7). The wear rate was high, but the wear behavior was very nonuniform.

Claims (12)

As a polymerization unit
(A) silyl (meth) acrylate monomers;
(B) acrylic or vinyl unsaturated monomers;
(C) unsaturated carboxylic ester monomers ester-linked with a carboxyl group of abietic acid or a derivative thereof via a divalent metal; And
(D) unsaturated carboxylic ester monomers ester-linked via a carboxyl group of a monoester of dicarboxylic acid and a divalent metal;
Hydrolyzable metal-containing copolymer comprising a. The method according to claim 1, wherein the component (A) is at least one selected from the group consisting of tributylsilyl acrylate, tributylsilyl methacrylate, triisopropylsilyl acrylate and triisopropylsilyl methacrylate. Hydrolyzable metal-containing copolymer. The hydrolyzable metal-containing copolymer according to claim 1, wherein the component (b) is at least one selected from the group consisting of (meth) acrylic acid esters, styrene and vinyl esters. The hydrolyzable metal-containing copolymer according to claim 1, wherein the component (C) is a polymerized unit having a structure represented by the following general formula (1):
[Formula 1]

In Formula 1, R ₁ is H or CH ₃ , M is a divalent metal, A is a carboxyl group exclusion of abietic acid or derivatives thereof. The hydrolyzable metal-containing copolymer according to claim 1, wherein the component (d) is a polymerized unit having a structure represented by the following Chemical Formula 2:
(2)

In Formula 2, R ₁ is H or CH ₃ , M is a divalent metal, E is the carboxyl group exclusion of the monoester of the dicarboxylic acid. According to claim 1, (A) 1 to 50 parts by weight of the component; (B) 5-70 parts by weight of the component; And 10 to 60 parts by weight of the sum of the component (C) and the component (D). 7. The hydrolyzable metal-containing copolymer according to claim 6, wherein the relative content ratio of component (C) and component (D) is (C) component: (D) component = 50 to 85: 15 to 50 by weight. . The hydrolyzable metal-containing copolymer according to claim 1, wherein the monoester of dicarboxylic acid is a monoester prepared from dicarboxylic acid or anhydride thereof and an alcohol having at least one ether group. The hydrolyzable metal-containing copolymer according to claim 8, wherein the reaction molar ratio of dicarboxylic acid or anhydride thereof to an alcohol having an ether group is 1: 1.1 to 1: 2.0. (1) preparing a carboxyl group-containing copolymer by copolymerizing a silyl (meth) acrylate monomer, an acrylic or vinyl unsaturated monomer and an unsaturated carboxylic acid monomer; And
(2) reacting the copolymer prepared in step (1) in the presence of abietic acid or a derivative thereof and a monoester of dicarboxylic acid with a divalent metal,
A method for producing a hydrolyzable metal-containing copolymer according to any one of claims 1 to 9. An antifouling coating composition comprising the hydrolyzable metal-containing copolymer according to any one of claims 1 to 9 as a binder. The antifouling coating composition according to claim 11, further comprising one or more elution control ingredients selected from the group consisting of rosin, rosin derivatives, monocarboxylic acids and salts thereof.