KR102180837B1 - Copolymeric binder for antifouling paint, method for manufacturing the same and antifouling paint composition containing the same - Google Patents

Abstract

The present invention relates to a copolymer binder for antifouling paint, a method of manufacturing the same, and an antifouling paint composition including the same, and more particularly, it is used as a top coat for a coating system that paints on a submerged part of an underwater structure including a ship. It relates to a copolymer binder for antifouling paint capable of inhibiting the adhesion and growth of organisms, a method of manufacturing the same, and an antifouling paint composition including the same.
The antifouling coating composition according to the present invention is capable of self-abrasion by hydrolysis, has excellent abrasion resistance, and at the same time has excellent crack resistance such as no cracking or peeling of the coating film. In addition, it is possible to form an antifouling coating film that has low frictional resistance due to the hydrophilic coating surface, and exhibits excellent antifouling performance, particularly in a stagnant environment or a high pollution environment.

Description

Copolymer binder for antifouling paint, its manufacturing method, and antifouling paint composition including the same {COPOLYMERIC BINDER FOR ANTIFOULING PAINT, METHOD FOR MANUFACTURING THE SAME AND ANTIFOULING PAINT COMPOSITION CONTAINING THE SAME}

The present invention relates to a copolymer binder for antifouling paint, a method of manufacturing the same, and an antifouling paint composition including the same, and more particularly, it is used as a top coat for a coating system that paints on a submerged part of an underwater structure including a ship. It relates to a copolymer binder for antifouling paint capable of inhibiting the adhesion and growth of organisms, a method of manufacturing the same, and an antifouling paint composition including the same.

The antifouling coating composition is aimed at inhibiting the adhesion and growth of various marine organisms that cause contamination of the submerged portion of the ship shell plate exposed to sea water for a long time. When various marine organisms adhere to the surface of the coating film, the fuel cost, which is closely related to the weight and operating speed of the ship, can be greatly increased. After launching the ship, as the time to be exposed to seawater increases, the weight of the hull increases significantly as various marine organisms attach to the flooded area of the ship, and this results in a significant increase in fuel cost compared to the initial launch. . In addition, the adhesion of marine organisms increases the roughness of the shell of the ship flooded area. This greatly increases the resistance between the hull and seawater when the ship is running, thereby exhibiting the effect of lowering the speed, and thus, the burden of using more fuel in order to operate at the same speed is removed. Among the antifouling paints being applied to solve this problem, the most successful product in recent years is an antifouling paint in the form of applying a self-abrasive polymer (SPC, Self-Polishing Copolymer) as a binder.

U.S. Patent No. 3,167,473 and British Patent No. 1,475,590 disclose an antifouling agent and a pigment component in a copolymer binder composed of a monomer in which tributyl tin is bonded in a salt form to an unsaturated carboxylic acid and a known acrylic unsaturated monomer. The antifouling coating composition in which the mixture is mixed is described. While the above copolymer exhibits excellent antifouling performance and uniform wear performance, it has been subject to regulation due to the biological problem of organotin compounds that are eluted during hydrolysis. Finally, in 2003, the International Maritime Organization's Treaty of Banning the Use of Tin-Based Antifouling Paints As a result, its use was completely prohibited. Accordingly, various antifouling paint products (Tin Free) that do not contain tributyl tin and other tin-based ingredients have been released.

Japanese Patent Application No. 78-21889 discloses an antifouling coating composition in which a partially gelled binder is applied by bonding 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 problem in that it is difficult to apply due to a poor coating film formation ability and coating storage property, and thus a crack or peel phenomenon occurs during abrasion and high viscosity.

Japanese Patent Application Nos. 81-165992 and 83-196900 disclose a resin binder for an antifouling coating composition having a single metal ester structure in a polyester main chain. However, the metal ester bond of the binder has a problem in that it is difficult to maintain a coating film for a long time because the abrasion rate in an alkaline aqueous solution such as seawater is remarkably fast, and the resin has a small molecular weight, so that the coating film formation ability is poor.

Non-tin-based binders as described above have a disadvantage that their viscosity is too high and long-term storage is poor.This has a d-orbital in which the metal forming ionic bonds is empty, so it is coordination with the carbonyl group having polarity in the binder. (coordination complex) is formed. In addition, in the case of a binder having an ionic bond, the glass transition temperature increases, resulting in brittle the coating film, easily cracking due to external impact, and poor bendability. In addition, the binder has a disadvantage that repainting is impossible due to relatively poor adhesion compared to the existing organic tin-based antifouling coating composition. It is known that this problem of repaintability is due to an increase in lipophilicity due to the organic acid constituting the binder. Compared to an organic tin-based binder having an ionic bond, the binder exhibits excessive hydrolysis, and particularly, in many cases, excessive elution occurs unnecessarily at the initial stage of seawater deposition. For this reason, when abrasion occurs, a phenomenon in which the coating film is partially flaking from the surface often occurs, which causes poor surface roughness. In addition, since the acid value of the copolymer having a carboxyl group is limited to 40 or less in the binder, when the acid value is low, it is difficult to sufficiently solubilize the copolymer after the metal ester is eluted, so that surface contamination by marine organisms cannot be prevented and the initial wear rate Compared to this, it is difficult to expect long-term antifouling performance because the wear rate decreases rapidly.

International Patent No. 91-1554 and U.S. Patent No. 5,199,977 describe techniques for introducing nonvolatile amines, alcohols, compounds such as urea and phenol as ligands to stabilize metals in the metal ester-containing binder structure and reduce viscosity. Are listed. Examples of the amines applied here may include rosin amines composed of 12 to 20 carbon atoms. When an amine is applied as a ligand, the initial wear rate can be controlled, and by coordination with the metal, it is possible to stabilize the metal and reduce the viscosity. However, these amines have too low solubility in water compared to the binder, resulting in a rapid decrease in the wear rate of the binder over time. In addition, when exposed for a long period of time, cracks may develop in the seawater line. The ligands such as phenol, urea, and alcohol described together are relatively poor in water resistance and cause swelling, flaking, and discoloration of the coating film.

Japanese Patent No. 2-196869 discloses a hydrolyzable copolymer composed of trimethylsilyl (meth)acrylate and a known unsaturated monomer. However, trimethylsilyl (meth)acrylate is reported to have a degree of hydrolysis of about 70% compared to the existing tin-based binder. This is because silicon has a relatively strong covalent bond compared to tin in the metal ester structure, so the degree of hydrolysis in seawater This is believed to be due to falling. Therefore, the content of trimethylsilyl (meth)acrylate to be hydrolyzed must be higher than that of other antifouling coating compositions. Trimethylsilyl (meth)acrylate monomer is relatively expensive in terms of price, and when the content is higher than necessary, there is a problem in that the crack resistance of the binder becomes poor. In addition, if a material having a small number of carbon atoms of an alkyl group bonded to silicon is applied to increase the hydrolysis property, long-term storage is poor.

Korean Patent No. 97-700680 describes a method of mixing a plastic (meth)acrylate copolymer to solve the problem of the copolymer composed of the trimethylsilyl (meth)acrylate monomer, but in this case, long-term wear in seawater There is a problem in that the wear rate gradually decreases as a large amount of non-hydrolyzable binder remains after it has been used.

Japanese Patent Application No. 81-165992 Japanese Patent Application No. 83-196900

In order to solve the above problems, the present invention is a hydrophilic binder obtained by stirring a hydrolyzable copolymer containing at least one different metal, a polyether-modified silicone oil, and fumed silica under specific conditions using a planetary mixer, It provides a method of manufacturing the same and a magnetic wear type non-tin antifouling coating composition comprising the same.

The copolymer binder for antifouling paint according to an embodiment of the present invention,

Based on the total weight of the copolymer binder for antifouling paint,

(a) 60 to 80% by weight of a metal-containing hydrolyzable copolymer;

(b) 10-30% by weight of polyether-modified silicone oil; And

(c) containing 10 to 30% by weight of fumed silica,

The (a) metal-containing hydrolyzable copolymer, based on the total weight of the copolymer,

(a1) 10 to 60% by weight of a metal ester represented by the following formula (1);

(a2) 1 to 50% by weight of silyl (meth)acrylate represented by the following formula (3); And

(a3) 5 to 70% by weight of an acrylic or vinyl-based component different from the above (a1) and (a2) is included.

[Formula 1]

In Formula 1, R ¹ is H or CH ₃ , R ² is a functional group containing a metal and hydrolyzed in seawater, represented by the following Formula 2, and x is an arbitrary integer of 1 or more,

[Formula 2]

In Formula 2, M is a metal having an oxidation number of 2 or more, and K is an organic substituent having 1 or more carbon atoms and may contain nitrogen, oxygen, sulfur or other metals including M,

[Formula 3]

In Chemical Formula 3, R ¹ is H or CH ₃ , R ³ is a functional group containing silicon and hydrolyzed in seawater, and is represented by the following Chemical Formula 4, and y is an arbitrary integer of 1 or more,

[Formula 4]

In Formula 4, L ₁ , L ₂ , L ₃ are organic substituents having 1 or more carbon atoms and may be the same or different from each other.

The total of the components (a), (b), and (c) may be 100% by weight, and the total of the (a1), (a2), and (a3) components may be 100% by weight.

The copolymer binder for the antifouling paint may be prepared by stirring the above (a), (b), and (c) with a planetary mixer at 120 to 150°C for 6 hours or more.

(a) metal-containing hydrolyzable copolymer

The copolymer may be a single metal in a random form or a hydrolyzable copolymer containing a plurality of different metals. The number average molecular weight (Mn) of the hydrolyzable copolymer containing different metals measured by gel permeation chromatography (GPC, Gel Permeation Chromatography) is preferably 2,000 to 150,000. In general, when the number average molecular weight of the solid content of the copolymer is less than 2,000, the viscosity of the binder is too low, making it difficult to prepare a coating composition, and there is a tendency that the abrasion rate of the formed antifouling coating film is not kept constant. In addition, the low molecular weight of the binder weakens the stress between the particles inside the coating film, which may lead to cracking of the coating film and discoloration due to moisture when exposed to sea water for a long time. When the number average molecular weight exceeds 150,000, the viscosity of the binder is too high to be applied to the coating composition. In the case of the antifouling coating film, the hydrolysis reaction of the surface proceeds, but there is a tendency that abrasion does not occur. Therefore, the molecular weight of the copolymer is one of the important factors affecting the viscosity and abrasion performance of the binder constituting the antifouling coating composition.

The metal-containing hydrolyzable copolymer is preferably 60 to 80% by weight based on the total weight of the binder for antifouling paint. If the component is less than 60% by weight, a collapse phenomenon may occur due to a decrease in the strength of the coating film, and if it is more than 80% by weight, a partial variation in surface tension may occur due to an imbalance in the hydrophilicity and hydrophobicity ratio of the coating film surface.

(a1) metal ester

The component (a1) can be prepared by reacting a metal M having an oxidation number of 2 or more and an organic acid having a carboxyl group at the end of the carboxyl group of (meth)acrylic acid, and the metal participating in the reaction is generally in the form of an oxide in the formula of M _n O _a (M is a metal, O is an oxygen atom, and n and a are integers of 1 to 3, which may be the same or different, and are determined by the number of oxidations of the metal). In particular, the organic acid having a carboxyl group may include a monovalent organic acid, a polyhydric organic acid having a divalent or higher value, and a monovalent organic acid obtained by a condensation reaction of an acid anhydride with an alcohol or amine compound. Examples of metal oxides include zinc oxide (ZnO), copper oxide (CuO), calcium oxide (CaO), boric anhydride (B ₂ O ₃ ), and the like, and the organic acids include acetic acid, nicotinic acid, abietic acid, and abietic acid. Derivatives and naphthenic acid are monovalent organic acids, malonic acid, adipic acid, terephthalic acid, succinic anhydride, maleic anhydride, phthalic anhydride, tetraphthalic anhydride, citraconic anhydride, itaconic anhydride, hexahydrophthalic anhydride, 4-methyltetra Phthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride and the like may be examples of polyhydric organic acids or acid anhydrides, and methoxy methanol, ethoxy methanol, butoxy methanol, methoxy ethanol, methoxy Ethanol, butoxy ethanol, ethoxymethoxy methanol, butoxymethoxy methanol, methoxyethoxy methanol, ethoxyethoxy methanol, butoxyethoxy methanol, methoxymethoxy ethanol, ethoxymethoxy ethanol, hexanamine , Aniline, 2-methoxy ethylamine, 3-ethoxy propylamine, aminoacetaldehyde dimetalacetal, 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 may be examples of alcohol or amine compounds. However, the examples described above do not limit the scope of the present invention.

The content of the component (a1) metal ester is preferably 10 to 60% by weight based on the total weight of the component (a) metal-containing hydrolyzable copolymer. Component (a1) Metal ester is a major component that imparts hydrolytic properties to a binder, and the abrasion performance (abrasion rate) of the antifouling coating composition is mainly determined by the content of component (a1). If component (a1) is used in an amount of less than 10% by weight, even if the hydrolysis reaction of the binder proceeds, it does not dissolve in seawater, so the antifouling paint composition to which it is applied does not wear out, and if it exceeds 60% by weight, the antifouling paint composition applied with it does not wear rapidly. As it progresses, there may be a problem that the wear rate cannot be regulated uniformly.

The component (a1) metal ester may contain an organic acid.

In addition, the component (a1) metal ester may include abietic acid or a derivative thereof, which is an organic acid having a carboxyl group, and a half ester.

In order to increase the strength and hardness of the antifouling coating film, it is most preferable to use abietic acid or a derivative thereof among the organic acids having a carboxyl group contained in the component (a1). This is referred to as component (a1-1). In preparing the component (a1-1), the abietic acid or abietic acid derivative may be used alone, or may be used in combination with other organic acids having a carboxyl group as illustrated.

The strength and hardness of the antifouling coating is to prevent deformation of the coating when a wooden block is placed in the ship building, damage to the coating due to a fender when mooring the quay wall, and the movement of the coating due to the flow of seawater during ship operation. It is a physical property that is absolutely required for an antifouling coating. However, since the abietic acid and its derivatives are monovalent basic acids having a polycyclic structure and tend to increase steric hindrance with adjacent functional groups, the hydrolysis rate is low, it is difficult to obtain a uniform coating film abrasion rate, and the flexibility of the coating film is reduced. Long-term exposure to seawater may cause cracks in the coating.

Therefore, in the present invention, in order to solve the above problems and at the same time improve antifouling performance in a stagnant state, a half ester was introduced. This is called component (a1-2).

The (a1-2) half-ester is prepared by reacting an acid anhydride and an alcohol containing at least one ether group, and the reaction formula at this time is as follows.

[Scheme 1]

In Scheme 1, X and Y are CH ₂ , CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , or CH ₂ CH ₂ CH ₂ CH ₂ and may be the same as or different from each other. Z is O, N or NH, and n is an integer of 1,2 or 3.

(a1-2) Examples of the acid anhydride used when preparing the half-ester include succinic anhydride, maleic anhydride, phthalic anhydride, tetraphthalic anhydride, citraconic anhydride, Itaconic anhydride, 3-methyltetrahydrophthalic anhydride, and the like, and such examples are not intended to limit the present invention.

Examples of the alcohols include methoxymethanol, ethoxymethanol, butoxymethanol, methoxyethanol, ethoxyethanol, butoxyethanol, methoxymethoxyethanol, ethoxymethoxymethanol, butoxymethoxymethanol, and methoxyethanol. Oxymethanol, ethoxyethoxymethanol, butoxyethoxymethanol, methoxymethoxyethanol, ethoxymethoxyethanol, and the like, and such examples are not intended to limit the present invention.

In the above (a1-2) half-ester production, the reaction molar ratio of alcohols containing ether groups and acid anhydrides is preferably 1:1.1 to 2.0, and the reaction temperature is 100 to 150°C in the absence of a solvent. It is better to proceed within the range.

When the reaction molar ratio is less than 1.1, the reaction does not proceed well, and when the reaction molar ratio exceeds 2.0, the reaction time is lengthened and the active ingredient is reduced. In addition, when the reaction temperature is less than 100°C, the reaction rate is slow, and when the reaction temperature exceeds 150°C, there is a disadvantage in that a divalent ester is produced as a side reaction at high temperature.

The (a1-2) half-ester in the present invention reduces the internal stress of the antifouling coating film to suppress cracking of the coating film, and is generated by using the abietic acid or a derivative thereof by making the wear rate of the antifouling coating film uniform. It can compensate for the problem that becomes. Therefore, in the present invention, component (a1) can be prepared to have two different structures at the same time, such as component (a1-1) and component (a1-2), and materials that can be used in the manufacture are as follows: Can be organized together.

Component (a1-1): abietic acid or a derivative thereof

Component (a1-2): Half-ester

Therefore, in the present invention, in order to prepare the component (a1), a metal having an oxidation number of 2 or more and (a1-1) and (a1-2) may be used together.

According to an embodiment of the present invention, the (a1) metal ester is 50 to 85% by weight of abietic acid or a derivative thereof based on 100% by weight of the total weight of the organic acid contained in the metal ester; And 15 to 50% by weight of half ester.

That is, when the total amount of the organic acid contained in the (a1) metal ester represented by Chemical Formula 1 is 100% by weight, the component (a1-1) + the component (a1-2) may be 100% by weight.

(a1) In preparing the metal ester, the abietic acid or a derivative thereof may be used in an amount of 30 to 90% by weight based on the total weight% of the organic acid contained in the metal ester, and it is more preferable to use 50 to 85% by weight. can do. If it is less than 30% by weight, the wet layer of the antifouling coating film becomes thick, which may impair long-term antifouling performance, and the strength and hardness of the coating film are weakened, and thus various properties of the coating film cannot be satisfied. When it exceeds 90% by weight, the wear rate of the antifouling coating film is significantly decreased, and the internal stress of the coating film is rapidly increased, which may cause a phenomenon in which the degree of cracking of the coating film due to aging of the coating film becomes severe.

In preparing the component (a1) metal ester, the half-ester may be 10 to 70% by weight based on the total weight% of the organic acid, more preferably 15 to 50% by weight.

When the amount of the half-ester in the organic acid of the metal ester is less than 10% by weight, it is difficult to obtain a uniform wear rate of the antifouling coating film, and it is difficult to prevent cracking of the coating film. In addition, when the amount exceeds 70% by weight, the reaction time is prolonged during the preparation of the binder, and the strength of the antifouling coating film is reduced, and the properties of the various coating films shown above are weakened, and the conventional problems cannot be solved. In addition, due to the non-uniform wear rate of the antifouling coating film, it may result in thickening of the wet layer of the coating film, which may hinder long-term antifouling performance.

(a2) silyl (meth)acrylate

The component (a2) is an acrylic component containing silicon bonded to an organic substituent, and the organic substituent group bonded to the silicon may be the same or different. Tributylsilyl acrylate, tributylsilyl methacrylate, triisopropylsilyl acrylate, triisopropylsilyl methacrylate, and the like may be examples of the above components, and such examples do not limit the scope of the present invention.

The silyl (meth)acrylate content is preferably 1 to 50% by weight based on the total weight of the component (a) metal-containing hydrolyzable copolymer. Since the component (a1) metal ester is a monomer component that hydrolyzes rapidly in seawater, water resistance is often poor as time passes. Component (a2) silyl (meth)acrylate can control or prevent such problems. have. Component (a2) silyl (meth)acrylate plays a role in helping the binder to dissolve in seawater as hydrolysis proceeds, while at the same time improving the water resistance of the formed coating film to stably maintain the wear rate of the paint in seawater. . When component (a2) silyl (meth)acrylate is used in an amount of less than 1% by weight, it cannot play a role in maintaining a constant abrasion rate, and when it exceeds 50% by weight, it wears as in the case of excessive application of component (a1) metal ester. The behavior progresses rapidly and the wear rate cannot be regulated constantly.

(a3) acrylic or vinyl component

(A3) copolymerizable with the components (a1) and (a2) is an acrylic or vinyl component, which is 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 Rate, butoxyethyl acrylate, butoxyethyl methacrylate, and the like can be exemplified, and such examples do not limit the scope of the present invention.

The content of the component (a3) acrylic or vinyl component is preferably 5 to 70% by weight based on the total weight of the component (a) metal-containing hydrolyzable copolymer. Component (a3) The acrylic or vinyl-based component serves to form the main chain of the binder, and its content can generally be determined according to the content of the components (a1) and (a2).

(b) 10 to 30% by weight of polyether modified silicone oil

In the present invention, the polyether-modified silicone oil is used for controlling the surface tension of the coating film. The content of the polyether-modified silicone oil may be 10 to 30% by weight based on the total weight of the copolymer binder for the antifouling paint. When used in an amount of less than 10% by weight, the surface tension may be partially deviated from the coating film due to the non-uniform ratio of hydrophilic and hydrophobicity on the surface of the coating film, and when used in excess of 30% by weight, workability decreases due to lower compatibility.

The polyether-modified silicone oil used in the present invention may use various types of silicone oils regardless of viscosity, ignition point, no flash point, glycol type of polyether part, terminal terminator of polyether part, etc. Preferably, it may be a polyether-modified silicone oil having an HLB value in the range of 2 to 12. These silicone oils may be used alone or in combination of two or more. When a silicone oil having an HLB value of less than 2 or greater than 12 is used, a poor coating film appearance may be formed due to a problem of long-term antifouling degradation due to excessive elution or poor compatibility.

(c) 10 to 30% by weight of fumed silica

In the present invention, fumed silica is used to control the elution rate of polyether-modified silicone oil.

The fumed silica content may be 10 to 30% by weight based on the total weight of the copolymer binder for the antifouling paint. When used in less than 10% by weight, the binder reinforcing role of silica may decrease, resulting in variations in coating strength. When used in excess of 30% by weight, silica is easily separated and agglomerated from the binder, so that there is no significant effect on physical properties of the coating film. In addition, it shows the result of poor workability.

Various types of fumed silica used in the present invention can be used regardless of the surface area per unit weight and the carbon content, but it is preferable to use fumed silica having a hydrophobicity of less than or equal to 5.5 hydrogen ion concentration (pH). When the hydrogen ion concentration exceeds 5.5, it may be combined with unreacted organic acids during the preparation of the copolymer, thereby generating a low viscosity in the subsequent mixing process. Also, in the case of hydrophilic fumed silica, it may cause the collapse of the coating film during long-term deposition after application of the paint.

In order to prepare a final binder by mixing (a), (b), and (c), it is preferable to use a planetary mixer. Fumed silica has a very fine particle size of nano size and high porosity, and its compatibility with liquid raw materials is very poor due to its low specific gravity. For this reason, when a general stirrer is used, there is a concern that problems such as generation of dust due to poor compatibility and reduction of stirring efficiency, generation of a large amount of air bubbles due to high porosity, and reduction of physical properties due to uneven mixing may occur. Therefore, it can be said that it is desirable to use a planetary mixer, which can effectively remove air bubbles and is advantageous for high viscosity dispersion.

In addition, the temperature and time conditions for this process are preferably stirred for 6 hours or more under the conditions of about 120 ~ 150 ℃. If the stirring is performed at a temperature of less than 120°C or the stirring time is less than 6 hours, there is a concern that a partial gel may be generated during the manufacture of the paint due to the non-uniform mixing state due to air bubbles that have not been removed. In addition, when stirring is performed at a temperature above 150°C, due to excessive heat, the components (a) and (b) are denatured and the cohesive force between the binder and the silicon raw material decreases. When the finished binder is applied to the paint, such as poor flowability. There is a concern that a problem occurs in physical properties or the viscoelasticity of the coating film is lowered, thereby simultaneously reducing strength and flexibility.

A method for producing a copolymer binder for an antifouling paint according to an embodiment of the present invention,

60 to 80% by weight of a metal-containing hydrolyzable copolymer; 10-30% by weight of polyether modified silicone oil; 10 to 30% by weight of fumed silica; and stirring at 120 to 150°C for 6 hours or more with a planetary mixer.

The metal-containing hydrolyzable copolymer,

Based on the total weight of the copolymer,

(a1) 10 to 60% by weight of metal ester,

(a2) 1 to 50% by weight of silyl (meth)acrylate (a2); And

(a3) 5 to 70% by weight of an acrylic or vinyl-based component different from (a1) and (a2) may be included.

The components (a1), (a2), (a3) and the steps of stirring with a planetary mixer are as described above.

The antifouling coating composition according to an embodiment of the present invention includes the above-described copolymer binder for antifouling paint.

The content of the copolymer binder for the antifouling paint may be 10 to 50% by weight based on the total weight of the antifouling paint composition. If it is less than 10% by weight, a sufficient abrasion rate cannot be exhibited to exhibit an appropriate antifouling performance, and if it is more than 50% by weight, hydrolysis of the coating film may occur excessively, causing collapse of the coating film or deterioration of properties.

The antifouling coating composition may further include additives and auxiliary agents such as auxiliary binders, antifouling agents, pigments, solvents, anti-settling agents, and stabilizers.

Antifouling agent

In the antifouling coating composition of the present invention, copper oxide can be used as an antifouling agent. In addition, one or more types of organic antifouling agents can be used to supplement antifouling performance. Examples of organic antifouling agents include copper salt pyrithione, zinc salt pyrithione, 4,5-dichloro-2-octyl-4-isothiazolin-3-one, N-3,4-dichlorophenyl-N,N-dimethylurea, Zinc ethylene-1,2-bis dithiocarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-triazine, triphenylborone pyridine, and the like.

In the antifouling coating composition of the present invention, the antifouling agent is preferably contained in an amount of 30 to 50% by weight based on 100% by weight of the total weight of the antifouling coating composition. In the present invention, when the content of the organic antifouling agent is less than 30% by weight, it is difficult to expect effective antifouling performance, and when it exceeds 50% by weight, durability and water resistance of the antifouling coating film are lowered, which is not preferable.

Pigment

As the pigment in the antifouling coating composition according to the present invention, various kinds of pigments of organic and inorganic types known in the art may be used. Among the colored pigments that can be used in the antifouling coating composition according to the present invention, carbon black, phthalocyanine blue, etc. may be used as organic pigments, and titanium white, bengala (iron oxide red), iron oxide powder, chalk (chalk) as inorganic pigments Neutral pigments such as zinc, white lead, red lead, and the like, which are basic and reactive with acidic substances in the paint may be used, but are not limited thereto. Extending pigments that can be used in the antifouling paint composition according to the present invention include talc, silica, mica, clay, calcium carbonate, kaolin, magnesium carbonate, barium carbonate, barium sulfate, bentonite used as an anti-settling agent, and one of them. Or it may be used in combination of two or more, but is not limited thereto.

In the antifouling coating composition according to the present invention, the pigment is preferably contained in an amount of 10 to 20% by weight based on 100% by weight of the total weight of the coating composition.

solvent

Solvents that can be used in the antifouling coating composition according to the present invention include aromatic hydrocarbons (xylene, toluene, etc.), aliphatic hydrocarbons (hexane, heptane, etc.), esters (ethyl acetate, butyl acetate, etc.), and ketones (methyl ethyl ketone. , Methyl isobutyl ketone), and the like, and these solvents may be used in combination of one or more.

In the antifouling coating composition of the present invention, the solvent is preferably contained in an amount of 1 to 15% by weight based on 100% by weight of the total weight of the coating composition.

additive

The antifouling coating composition of the present invention may include one or more additives in addition to the above-mentioned components, for example, a thickener for preventing sedimentation and flow (organic clay-based aluminum, calcium, stearate salt of zinc, lecithin salt, alkyl Salts such as sulfonates, polyethylene wax, amide wax, castor oil wax, polyamide wax and synthetic finely divided silica, polyethylene oxide wax, etc.) and plasticizers such as chlorinated paraffin, rosin to control the abrasion behavior of antifouling coatings Alternatively, rosin derivatives and the like may be mentioned, and one type or two or more types may be used in combination.

In the antifouling coating composition of the present invention, the solvent is preferably contained in an amount of 1 to 10% by weight based on 100% by weight of the total weight of the coating composition.

The antifouling coating composition according to an embodiment of the present invention is capable of self-abrasion by hydrolysis, has excellent abrasion resistance, and has excellent crack resistance such as no cracking or peeling of the coating film. In addition, it is possible to form an antifouling coating film that has low frictional resistance due to the hydrophilic coating surface, and exhibits excellent antifouling performance, particularly in a stagnant environment or a high pollution environment.

Hereinafter, the present invention will be described in more detail through examples. Objects, features, and advantages of the present invention will be easily understood through the following examples. The present invention is not limited to the embodiments described herein and may be embodied in other forms. The embodiments introduced herein are provided so that the disclosed content may be thorough and complete, and the spirit of the present invention may be sufficiently transmitted to those of ordinary skill in the art to which the present invention pertains. Therefore, the present invention should not be limited by the following examples.

Examples 1 to 8 and Comparative Examples 1 to 4 Preparation of antifouling coating composition

Preparation of metal-containing hydrolyzable copolymer

Xylene and n-butyl alcohol in a reaction vessel (round flask) equipped with a mechanical stirrer, condenser, thermocouple, dropping funnel and heating mantle in a content of 130 g. Then, the mixture was heated to 110°C and stirred to reflux. While maintaining the reflux temperature for 4 hours, (a1) 30% by weight of methacrylate as an acrylic acid having a carboxyl group as a side chain, (a2) 40% by weight of triisopropylsilyl acrylate, (a3) methyl methacrylic as an acrylic component 20% by weight of rate and 10% by weight of butyl acrylate, 5 parts by weight of benzoyl peroxide, a radical polymerization initiator based on 100 parts by weight of the total content of the components (a1), (a2), (a3), using a dropping device Was put in. An additional 1 part by weight or less of the benzoyl peroxide mixed solution was added, and stirred at the same temperature for 2 hours. A light yellow transparent metal-containing copolymer solution was prepared by adding a metal oxide, various organic acids, and organic solvents to the copolymer prepared through the polymerization process and stirring for 3 hours. After that, the mixture was dried in an oven at 150° C. for 15 minutes to obtain a metal-containing copolymer.

Preparation of copolymer binder for antifouling paint

(A) metal-containing hydrolyzable copolymer and (b) polyether-modified silicone oil, (c) fumed prepared by the above method in a planetary mixer equipped with a thermometer and a heating mantle. After adding silica, the mixture was stirred. After stirring for 1 hour at room temperature of 20 to 25 ℃, the temperature was gradually raised and stirred at 30 to 35 ℃ for another hour. Thereafter, the planetary mixer or high speed dissolve was gradually heated up to a certain temperature and the temperature was maintained. The final binder was prepared by stirring for a predetermined time under the above temperature conditions. The content of ingredients, stirring equipment, and process conditions are shown in Table 1.

Antifouling paint composition manufacturing

An antifouling coating composition was prepared by mixing the prepared binder, an antifouling agent, a pigment, a solvent, and an additive. Components and contents are listed in Table 1.

Antifouling paint composition manufacturing (unit: weight %) Example Comparative example One 2 3 4 5 6 7 8 One 2 3 4 bar
sign
more Contains metal
Copolymer 19 19 19 19 19 19 19 19 19 19 19 19 Fumed silica c1 3 4 3 3 3 3 3 3 3 Fumed silica c2 3 Fumed silica c3 3 Silicone oil b1 6 5 6 6 6 6 6 6 6 6 Silicone oil b2 6 Stirring equipment PL PL PL PL PL PL PL PL - H.S.D PL PL Stirring temperature 130℃ 130℃ 130℃ 130℃ 145℃ 130℃ 130℃ 130℃ - 130℃ 80℃ 160℃ Stirring time
(time) 6 6 8 12 6 6 6 6 - 6 3 6 Plasticizer 2 2 2 2 2 2 2 2 2 2 2 2 Bengala 4 4 4 4 4 4 4 4 4 4 4 4 Zincation 8 8 8 8 8 8 8 8 8 8 8 8 Talc 6 6 6 6 6 6 6 6 6 6 6 6 Copper salt pyrithione 7 7 7 7 7 7 7 7 7 7 7 7 Aliphatic amide wax 3 3 3 3 3 3 3 3 3 3 3 3 Nitrous oxide 30 30 30 30 30 30 30 30 30 30 30 30 Xylene 12 12 12 12 12 12 12 12 12 12 12 12 Sum 100 100 100 100 100 100 100 100 100 100 100 100

PL: Planetary mixer

H.S.D: High Speed Dissolver

-Fumed silica c1: Aerosil R972, Fumed Silica [Evonik Degussa]

pH 3.6 ~ 5.5, Hydrophobic Type

-Fumed silica c2: Aerosil R812, Fumed Silica [Evonik Degussa]

pH 5.5 ~ 7.5 Hydrophobic Type

-Fumed silica c3: Aerosil 130, Fumed Silica [Evonik Degussa]

pH 3.7 ~ 4.7 Hydrophilic Type

-Silicone oil b1: DC-5211 [Dow Corning Corporation]

HLB 10.5

-Silicone oil b2: DC-193 [Dow Corning Corporation]

HLB 12.2

-Plasticizer: Paraffin plastoil 152 [Handy chemical corporation]

-Bengala (pigment): Iron Oxide Red 308 [Woo shin pigment]

-Zincization (pigment): special patent for zinc oxide [Hanil Chemical]

-Talc (pigment): NA-400 [Young woo chemtec.]

-Copper salt pyrithione (antifouling agent): Copper Omadine Powder [Lonza]

-Copper oxide (antifouling agent): LOLO Tint 97 LM [American Chemet]

-Aliphatic amide wax paste (thickener): Monoral 5500M [HS Chem.]

-Xylene (organic solvent): Xylene [SK corporation]

Experimental Example 1 Antifouling performance evaluation

An antifouling paint composition prepared by the blending shown in Table 1 and an epoxy-based anticorrosive coat 200㎛, a binder paint 100㎛ and a sandblasted steel plate of 550×150×2(mm) size ( Dry coating thickness) was continuously applied at daily intervals, cured and dried at room temperature for one week. The specimens thus prepared were immersed to be located 1m below sea level using a immersion test device (Raft) installed in the Byeonjin Port of Ulsan (East Coast) and the offshore Mokpo (West Coast). After immersion, the degree of contamination of the coating film due to the adhesion of marine organisms was observed for 24 months at 3 months intervals (a total of 8 times), and the antifouling performance was evaluated according to the criteria described below, and the results are shown in Table 2.

The evaluation criteria are as follows;

5: The condition of no attachment of marine organisms (non-polluting condition),

4: a state in which a thin slime layer is 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 condition that the area of vegetable contamination is 20-50% of the effective area of the specimen,

1: The area of vegetable contamination is 50-100% of the effective area of the specimen (X: animal contamination has occurred).

As shown in Table 2, a binder prepared by stirring the components (a) to (c) prepared in the present invention with a planetary mixer at 120 to 150° C. for 6 hours or longer, and an antifouling coating composition prepared using the same It showed better long-term antifouling properties. In particular, when fumed silica with a hydrogen ion concentration of 5.5 or less and polyester-modified silicone oil with an HLB value in the range of 2 to 12 were used, it exhibited very excellent long-term antifouling properties.

In addition, even if components (a) to (c) are used, in case of using a binder prepared without complying with the process conditions for stirring with a planetary mixer at 120 to 150°C for 6 hours or more, poor antifouling performance over time. Shown.

Antifouling performance evaluation
term Example Comparative example One 2 3 4 5 6 7 8 One 2 3 4 3 months 5 5 5 5 5 5 5 5 5 5 5 5 6 months 5 5 5 5 5 5 5 4 4 5 5 4 9 months 5 5 5 5 5 4 4 3 4 4 4 4 12 months 4 4 4 4 5 4 4 3 3 3 4 4 15 months 4 4 4 4 4 3 3 2 3 3 3 3 18 months 4 3 4 4 4 3 3 2 2 3 3 3 21 months 3 3 4 3 3 3 3 One One 2 3 2 24 months 3 3 3 3 3 2 2 One One 2 2 2

Experimental Example 2 Evaluation of frictional resistance

An antifouling coating composition prepared according to the formulation shown in Table 1 was coated on a stainless steel cylindrical drum having a diameter of 100 mm and a height of 100 mm with 100 μm (based on the thickness of the dry coating film) and dried at room temperature for one week. The drum thus produced was installed in a seawater tank to a depth of 500 mm, and then rotated at a speed of about 15 knots, and initial frictional resistance was measured using a torque meter. At this time, the frictional resistance of the stainless steel drum to which nothing was painted was measured, set as the standard frictional resistance, and compared with the frictional resistance of the drum coated with each antifouling coating composition, the increase/decrease width was evaluated. In addition, after measuring the initial frictional resistance, the drum coated with the antifouling coating composition was immersed in seawater for one month, and then the frictional resistance was measured again, and the change according to the immersion period was measured together, and the results are shown in Table 3.

As shown in Table 3, a binder prepared by stirring the components (a) to (c) prepared in the present invention with a planetary mixer at 120 to 150°C for 6 hours or longer, and an antifouling paint composition prepared using the same Compared to that, the frictional resistance reduction effect was very excellent, and in particular, when immersed in seawater for one month than the initial immersion in seawater, the frictional resistance reduction effect was more excellent. Particularly, when fumed silica with a hydrogen ion concentration of 5.5 or less and polyester-modified silicone oil with an HLB value in the range of 2 to 12 were used, the frictional resistance reduction effect was very good.

Even when the components (a) to (c) were used, when a binder prepared without complying with the process conditions of stirring with a planetary mixer at 120 to 150° C. for 6 hours or more was used, the frictional resistance increased rapidly.

Friction resistance evaluation Friction resistance increase or decrease Early deposition 1 month immersion Example 1 -2.50% -4.00% Example 2 -2.00% -3.50% Example 3 -2.50% -3.90% Example 4 -2.60% -4.10% Example 5 -2.70% -4.10% Example 6 -2.10% 0.20% Example 7 -2.00% -1.10% Example 8 -1.00% 0.40% Comparative Example 1 -1.20% 0.20% Comparative Example 2 -1.50% -1.70% Comparative Example 3 -1.40% -1.70% Comparative Example 4 -2.20% -2.10%

Claims (11)

Based on the total weight of the copolymer binder for antifouling paint,
(a) 60 to 80% by weight of a metal-containing hydrolyzable copolymer;
(b) 10-30% by weight of polyether-modified silicone oil; And
(c) containing 10 to 30% by weight of fumed silica,
The (a) metal-containing hydrolyzable copolymer, based on the total weight of the copolymer,
(a1) 10 to 60% by weight of a metal ester represented by the following formula (1);
(a2) 1 to 50% by weight of silyl (meth)acrylate represented by the following formula (3);
(a3) containing 5 to 70% by weight of an acrylic or vinyl-based component different from the above (a1) and (a2),
The (b) polyether-modified silicone oil has an HLB value of 2 to 12,
The (c) fumed silica is a copolymer binder for an antifouling paint having a pH of 5.5 or less.

[Formula 1]

In Formula 1, R ¹ is H or CH ₃ , R ² is a functional group containing a metal and hydrolyzed in seawater, represented by the following Formula 2, and x is an arbitrary integer of 1 or more,
[Formula 2]

In Formula 2, M is a metal having an oxidation number of 2 or more, and K is an organic substituent having 1 or more carbon atoms and may contain nitrogen, oxygen, sulfur or other metals including M,
[Formula 3]

In Chemical Formula 3, R ¹ is H or CH ₃ , and R ³ is a functional group containing silicon and hydrolyzed in seawater, and is represented by the following Chemical Formula 4, and y is an arbitrary integer of 1 or more.

[Formula 4]

In Formula 4, L ₁ , L ₂ , L ₃ are organic substituents having 1 or more carbon atoms, and may be the same as or different from each other. The method according to claim 1,
The (a), (b), (c), a copolymer binder for antifouling paint, characterized in that prepared by stirring with a planetary mixer at 120 ~ 150 ℃ 6 hours or more.
The method according to claim 1,
The component (a1) metal ester is characterized in that it contains an organic acid,
Copolymer binder for antifouling paint.
The method of claim 3,
The organic acid is,
Abietic acid or a derivative thereof; And a copolymer binder for antifouling paint, characterized in that consisting of half ester.
The method of claim 4,
The organic acid is based on 100% by weight of the total weight of the organic acid,
50 to 85% by weight of abietic acid or a derivative thereof; And
Copolymer binder for antifouling paint, characterized in that consisting of 15 to 50% by weight of half ester.
delete delete (a) 60 to 80% by weight of a metal-containing hydrolyzable copolymer;
(b) 10-30% by weight of polyether-modified silicone oil;
(c) 10 to 30% by weight of fumed silica;
Including the step of stirring with a planetary mixer for at least 6 hours at 120 ~ 150 ℃,
The (b) polyether-modified silicone oil has an HLB value of 2 to 12,
The fumed silica is a method for producing a copolymer binder for an antifouling paint having a hydrophobic pH of 5.5 or less.
The method of claim 8,
The (a) metal-containing hydrolyzable copolymer,
Based on the total weight of the copolymer,
(a1) 10 to 60% by weight of metal ester,
(a2) 1 to 50% by weight of silyl (meth)acrylate (a2); And
(a3) A method for producing a copolymer binder for antifouling paint, comprising 5 to 70% by weight of an acrylic or vinyl-based component different from (a1) and (a2).
An antifouling paint composition comprising a copolymer binder for antifouling paint according to any one of claims 1 to 5.
The method of claim 10,
The antifouling coating composition is an antifouling coating composition comprising 10 to 50% by weight of a copolymer binder for an antifouling paint based on the total weight of the antifouling paint composition.