KR20060078276A - Copolymer binder and anti-fouling paint composition containing the same - Google Patents

Abstract

The present invention relates to a copolymer binder for an antifouling coating composition and an antifouling coating composition comprising the same, and more particularly, 20 to 60 wt% of the following component (a), 5 to 20 wt% of the component (b) and component (c A silyl (meth) acrylate copolymer binder for an antifouling coating composition comprising 5 to 70% by weight) and an antifouling coating composition comprising the same:

(a) silyl (meth) acrylate monomer components;

(b) an acrylic unsaturated monomer component having a silicone oil structure; And

(c) acrylic or vinyl unsaturated monomer components.

Antifouling coating composition, silyl (meth) acrylate, silicone oil, hull.

Description

Copolymer Binder and Antifouling Coating Composition Comprising the Same {COPOLYMER BINDER AND ANTI-FOULING PAINT COMPOSITION CONTAINING THE SAME}

The present invention is a silyl (meth) acrylate for an antifouling coating composition which is applied as a top coat of a coating film coated on a ship hull outside and an underwater structure to prevent adhesion and growth of marine life. The present invention relates to a copolymer binder and a silyl self-wear antifouling coating composition comprising the same.

The antifouling coating composition aims to prevent or control the attachment and growth of marine organisms that cause surface contamination of seawater deposition coatings. The hull bottom (aquatic bottom), aquatic structures, etc. may be attached to the surface of animals such as shellfish, oysters, shellfish mussels and shellfish, plants such as shellfish (seaweed) and various aquatic organisms such as aquatic bacteria when exposed to water, Multiplication results in poor appearance or loss of function. In particular, when these aquatic organisms adhere to and propagate at the bottom, the surface roughness of the entire ship's outer shell may increase, which may lower ship speed or increase fuel consumption. Removing aquatic creatures from the bottom requires more effort and longer working time. In addition, mucus (mud matter) or slime (slime) adheres to and propagates on bacteria that attach to and propagate to underwater structures, or large organisms with stickiness adhere to and propagate to underwater structures (for example, steel structures). In the case of damaging the anti-corrosion coating of the underwater structure, there is a problem in reducing the strength or function of the underwater structure to significantly shorten the life.

In order to prevent such a problem, it is common to coat an antifouling coating composition containing a copolymer of tributyltin methacrylate, methyl methacrylate and copper nitrous oxide (Cu ₂ O) as an antifouling paint having excellent antifouling properties on the bottom. to be. The copolymer constituting the antifouling coating composition is hydrolyzed in seawater to form bistributyltin oxide (Bu ₃ Sn-O-SnBu ₃ (Bu is a butyl group)) or tributyltin halide (Bu ₃ SnX (X is Organic tin compounds such as halogen atoms)) are released to exhibit antifouling effects. In addition, since the copolymer is a hydrolyzable self-polishing paint, the hydrolyzed copolymer itself is also changed to water solubility and dissolved in seawater, so that no residue of resin remains on the surface of the bottom coating film and thus remains active. Keep the surface.

However, the above-mentioned organotin compounds are highly toxic and are likely to cause marine pollution, the occurrence of malformed fish or shellfish, the destruction of aquatic ecosystems through the food chain, and the like. Due to these problems, the development of a tin free antifouling paint that can replace the conventional organic tin antifouling paint has been required.

The silyl ester antifouling paints introduced through Japanese Patent Laid-Open Nos. 1992-264168, 1992-264169 and 1992-264170 can be an example of such a non-tin antifouling coating composition. However, for these antifouling coating compositions, Japanese Patent Laid-Open Publication Nos. 1994-157940 and 1994-157941 have described problems of poor antifouling properties and cracking or peeling of the coating film.

Japanese Patent Application Laid-Open No. 1990-196869 discloses an acid functional copolymer (A) (this component can be prepared by copolymerization of trimethylsilyl methacrylate, ethyl methacrylate and methoxyethyl acrylate monomer in the presence of an azo initiator. And an antifouling coating composition comprising a polyvalent cationic compound (B) (a salt of a polyvalent metal soluble in an organic solvent) and an antifouling agent, which has a carboxy group blocked with a trimethylsilyl group. However, this antifouling coating composition has a problem of poor storage stability due to gelation and thickening and unsatisfactory crack resistance of the coating film formed therefrom.

Japanese Patent Application Laid-Open No. 1988-215780 describes an antifouling paint resin having a number average molecular weight of 3,000 to 40,000 produced by copolymerizing a vinyl monomer having an organic silyl group such as trialkylsilyl ester with another common vinyl monomer. . The antifouling paint resin can be blended with an organic water coupler such as trimethyl orthoformate, an antifouling agent such as copper nitrous oxide, and a pigment such as iron oxide red. However, as described in Japanese Patent Application Laid-Open No. 1994-157940, this antifouling paint resin causes gelation or thickening during storage, and the coating film formed from the antifouling paint composition has a weak resistance to cracking and peeling. Have

Japanese Patent Laid-Open No. 1993-32433 corresponding to Japanese Patent Laid-Open No. 1988-215780 includes an antifouling agent (A), a polymer binder (B) [-(CH ₂ -CXCOOR)-(B)-(here, X is H or CH ₃ , R is SiR ' ₃ or Si (OR') ₃ (R 'is an alkyl group), B is a residue of an ethylenically unsaturated monomer) and consists of repeating units represented by a specific hydrolysis Indicating the rate] is disclosed. A solvent, a water-sensitive pigment, an inert pigment, a filler, a retardant, etc. can be mix | blended with this antifouling paint composition. However, the coating film formed from this antifouling coating composition has a problem of poor crack resistance.

Japanese Patent Application Laid-Open No. 1995--18216 has an organosilicon triester group represented by the general formula (a) -COO-SiR ¹ R ² R ³ (R ¹ to R ³ each represent an alkyl group having 1 to 18 carbon atoms). An antifouling coating composition composed of a polymer (A), a copper or a copper compound (B) of an organosilicon-containing monomer, and a silicon compound (C) having an alkoxy group as in the following general formula is described.

(Wherein R ⁴ to R ⁶ represent a hydrogen atom or a (cyclo) alkoxy group having 1 to 18 carbon atoms, R ⁷ represents an alkyl group having 1 to 18 carbon atoms, n is an integer of 1 to 3)

However, the coating film formed of the antifouling paint composition has a problem of poor crack resistance and antifouling property, in particular, in a high pollution environment, where a high pollution environment frequently stands for long-term stationary operation and stops in a sea where the ship is eutrophic like the inland sea. It is a state of repeating or operating at low speed of about 10 knots or less.

Japanese Patent Application Laid-Open No. 1996-199095 discloses monomer (A) represented by General Formula X-SiR ¹ R ² R ³ and general formula Y- (CH (R ⁴ )) described in Japanese Patent Application Laid-Open No. 1995--102193. (B ⁵ ) (R ⁴ is an alkyl group, R ⁵ is an alkyl group or a cycloalkyl group, Y is acryloyloxy group, methacryloyloxy group, maleoyloxy group or fumaroyloxy group) (B An antifouling coating composition comprising, as a main component, a copolymer composed of a vinyl monomer (C) optionally copolymerizable with monomers (A) and (B) and an antifouling agent is described.

Japanese Patent Application Laid-Open No. 1996-269388 discloses general formula X-SiR ¹ R ² R ³ (R ¹ to R ³ are each hydrocarbon groups having 1 to 20 carbon atoms, which may be the same or different from each other, and X is an acryloyloxy group. , Monomer (A) represented by methacryloyloxy group, maleoyloxy group, fumaroyloxy group or itaconoyloxy group) and general formula Y- (CH ² CH ² O) nR ⁴ (R ⁴ is an alkyl group or Aryl group, Y is acryloyloxy group, methacryloyloxy group, maleoyloxy group, fumaroyloxy group or itaconoyloxy group, n is an integer of 1-25), and is comprised from monomer (B) represented by Disclosed is an antifouling coating composition containing a copolymer and a copper salt (copper pyrithione) of bis (2-pyridinethiol-1-oxide) as an essential component. However, the antifouling coating composition described in this publication is an unsatisfactory level of antifouling in a stagnant environment, and there is much room for further improvement in terms of storage stability.

Japanese Patent Application Laid-Open No. 1996-269390 discloses general formula X-SiR ¹ R ² R ³ (R ¹ to R ³ are each selected from alkyl and aryl groups, which may be the same or different from each other, and X is acryloyloxy group, meta A polymer of the monomer (A) represented by a chryloyloxy group, maleoyloxy group, fumaroyloxy group or itaconoyloxy group, general formula Y- (CH ₂ CH ₂ O) _n -R ⁴ (R ⁴ is Alkyl group or aryl group, Y is acryloyloxy group, methacryloyloxy group, maleoyloxy group, fumaroyloxy group or itaconoyloxy group, n is an integer of 1-25, and is represented by the monomer (B) An antifouling coating composition composed of a polymer and an antifouling agent is described. However, the coating film formed from the antifouling coating composition described in this publication has the possibility of further improving the antifouling property in the stagnant environment and the storage stability of the coating composition.

Japanese Patent Laid-Open No. 1996-277372 discloses a monomer (A) represented by General Formula X-SiR ¹ R ² R ³ and general formula Y- (CH ₂ CH ₂ O described in Japanese Patent Laid-Open No. 1996-269388. An antifouling coating composition containing a copolymer of a monomer mixture composed of a monomer (B) represented by _n -R ⁴ and a triphenylboronepyridine complex is described. (The resin component and the aquatic organism adhesion inhibitor each contain no metal. Polymer and organic inhibitor). However, the coating film formed from the coating composition described in this publication is not satisfactory antifouling property in a stagnant environment, and there is a possibility that the storage stability of the coating composition is improved.

Japanese Patent Application Laid-Open No. 1998-30071 discloses one or more rosin compounds (A) consisting of rosin, rosin derivatives or rosin metal salts, wherein the general formulas X-SiR ¹ R ² R ³ (R ¹ to R ³ are each derived from an alkyl group and an aryl group) May be the same or different from each other as a selected group, X is one or more monomers represented by acryloyloxy group, methacryloyloxy group, maleoyloxy group, fumaroyloxy group, itaconoyloxy group or citraconoyloxy group) An antifouling coating comprising the polymer of (M) and / or one or more monomers (M) and an organosilyl ester group (B) containing polymer of at least one polymerizable monomer other than this monomer (M) and an antifouling agent (C) The composition is described.

However, the antifouling coating compositions described in the above publications have various characteristics such as crack resistance, peeling resistance (adhesion), antifouling performance (especially antifouling under stagnant or high contaminated environments), long-term antifouling and self-polishing properties of the formed coating film. The balance between is unsatisfactory.

Japanese Patent Publication No. 1993-82865 describes 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate as optional copolymerizable components. Japanese Patent Application Laid-Open Nos. 1997-48947, 1997-48948, 1997-48949, 1997-48950, 1997-48951, 1993-32433, US Patent No. 4,593,055, and Japanese Patent Publication 1990-1968669 and International Patent Application Nos. 1991-14743 describe silyl (meth) acrylate copolymers. However, these publications do not mention copolymers of monomers having hydroxy groups or copolymers prepared by combining silyl (meth) acrylates having at least linear alkyl groups and silyl (meth) acrylates having branched alkyl groups. In addition, the antifouling coating composition to which the copolymers described in these publications are applied has various kinds of properties such as crack resistance, peeling resistance (adhesiveness), antifouling performance (especially antifouling and long term antifouling under high contaminated environment) and self-polishing properties of the formed coating film. There is room for improvement in the balance between the properties.

Japanese Patent Application Laid-Open No. 1988-215780 discloses an antifouling coating composition composed of a copolymer prepared by using methyl methacrylate, n-butyl methacrylate, acrylamide and the like and a cuprous oxide. It has a similar problem to the antifouling paint described in the above.

Japanese Patent Laid-Open No. 1999-335619 discloses a copolymer of another ethylenically unsaturated monomer copolymerizable with a monomer having a triorganic silyl group represented by the following general formula (k), a monobasic acid having a carboxyl group, and an antifouling agent containing a metal. An antifouling coating composition is described.

Formula (k)

(In Formula (k), R ¹ is H or CH ₃ , R ² to R ⁴ each independently represent a group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, and an aryl group.)

Japanese Patent Laid-Open No. 1999-343451 includes a copolymer of another ethylenically unsaturated monomer copolymerizable with a monomer having a triorganic silyl group represented by the following general formula (l), a monobasic acid having a carboxyl group, and an antifouling agent containing a metal. An antifouling coating composition is described.

General formula (l)

(In Formula (l), R ¹ to R ³ each independently represent a group selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, and an aryl group.)

Japanese Patent Application Laid-Open No. 2000-63737 discloses a copolymer of another ethylenically unsaturated monomer copolymerizable with a monomer having a triorganic silyl group represented by the general formula (k), a monobasic acid metal soap having a carboxyl group, and an antifouling containing a metal. An antifouling coating composition comprising an agent is described.

However, the antifouling coating compositions described in these publications are not satisfactory in terms of storage stability, and it is inevitable to use a large amount of solvent to lower the viscosity of the antifouling coating. In relation to the environmental pollution problem, which has recently become an issue, there is a demand for lowering the amount of the solvent contained in the antifouling coating composition to below the standard value, but it is difficult to prepare an antifouling paint having a low solvent content from the above-described composition. .

An object of the present invention is to solve the problems of the conventional antifouling coating composition as described above, silyl-based wear-resistant antifouling with a silyl (meth) acrylate copolymer and an acrylic unsaturated monomer component having a silicone oil structure as a binder It is to provide a coating composition.

The binder for an antifouling coating composition according to the present invention is a silyl (meth) acrylate comprising 20 to 60% by weight of component (a), 5 to 20% by weight of component (b) and 5 to 70% by weight of component (c). It is characterized in that the copolymer:

(a) a silyl (meth) acrylate monomer component represented by the following general formula (1);

(b) an acrylic unsaturated monomer component having a silicone oil structure represented by the following general formula (2); And

(c) acrylic or vinyl unsaturated monomer components.

The binder of the present invention is a hydrolyzable silyl (meth) acrylate copolymer of random form, which consists of the above components (but the sum of the contents of the above components is 100% by weight).

The binder of the present invention preferably has a number average molecular weight (Mn) of 2,000 to 150,000, particularly preferably 3,000 to 100,000, as measured by gel permeation chromatography (GPC). In general, when the number average molecular weight is less than 2,000, the viscosity of the binder is too low, making it difficult to prepare an antifouling coating composition, and the wear rate of the antifouling coating film formed tends not to be kept constant. In addition, 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 antifouling paint composition, in the case of the antifouling coating film, the surface hydrolysis reaction proceeds, but wear does not occur. Therefore, the number average molecular weight is one of the important factors affecting the viscosity and wear performance of the binder constituting the antifouling coating composition.

The component (a) which comprises the binder of this invention is an unsaturated carboxylic acid silyl ester like copolymerizable (meth) acrylic acid, and is represented by following General formula (1).

.......(1)

.......(One)

[Wherein, R ¹ is H or CH ₃ , and R ² to R ⁴ are each a phenyl group which may have a substituent containing one or more carbon atoms or a straight chain or cycloalkyl group, and an alkyl group, an aryl group or a halogen element, can be different]

Examples of the component (a) include trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tripropylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, tributylsilyl (meth) acrylic Silyl (meth) acrylates having the same R ² to R ⁴ , or di-tert-butyl-methyl, such as acrylate, tri-tert-butylsilyl (meth) acrylate and triisobutylsilyl (meth) acrylate, etc. Silyl (meth) acrylate, secondary-butyl-dimethylsilyl (meth) acrylate, dimethylpropylsilyl (meth) acrylate, monomethyldipropylsilyl (meth) acrylate and methylethylpropylsilyl (meth) acrylate and the like. Likewise, there are silyl (meth) acrylates in which R ² to R ⁴ are partially or wholly different, and one or more of them may be selected and used. In particular, triisopropylsilyl (meth) acrylate and triisobutyl silyl (meth) acrylate are most suitable for copolymer formation stability, ease of manufacture, or control of coating film formation, storage stability and wear rate when applied to antifouling coating compositions. desirable.

However, such examples do not limit the scope of the present invention.

In the binder of the present invention, the content of the component (a) is preferably 20 to 60% by weight. If the component (a) is used in less than 20% by weight does not have a sufficient wear rate for exhibiting antifouling performance, when using more than 60% by weight there is a problem that the hardness of the coating film is lowered.

Component (b) constituting the binder of the present invention has a single-ended reactive silicone oil structure and is represented by the following general formula (2).                     

......(2)

......(2)

[Wherein R ⁵ is H or CH ₃ , R ⁶ is a phenyl group which may have a linear or cycloalkyl group having 1 or more carbon atoms and a substituent including an alkyl group, an aryl group or a halogen element, and n is any integer of 1 or more to be]

In the binder of the present invention, the component (b) serves to delay the attachment of marine microorganisms through surface energy control.

Component (b) constituting the binder of the present invention is 3- [tris (trimethylsilyloxy) silyl] propyl methacrylate, 3- [tris (triethylsilyloxy) silyl] propyl methacrylate, 3- [tris ( Tripropylsilyloxy) silyl] propyl methacrylate may be selected from the group consisting of at least one, and it is most preferable to use 3- [tris (trimethylsilyloxy) silyl] propyl methacrylate.

In the binder of the present invention, the content of the component (b) is preferably 5 to 20% by weight. This is because when the component (b) is used at less than 5% by weight, the effect of preventing marine organism adhesion is reduced, and when the component (b) is used at more than 20% by weight, the compatibility with the component (a) is reduced.

Component (c) constituting the binder of the present invention may be derived from known acrylic or vinyl unsaturated compounds capable of radical polymerization. For the appropriate strength of the antifouling coating film, it is preferable to use (meth) acrylates, styrenes and vinyl esters among the above compounds. Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, octyl (meth) acrylate, and methoxyethyl acrylate. Examples of styrenes include styrene, vinyltoluene, and methyl. Styrene and the like, and examples of vinyl esters include vinyl acetate, vinyl benzoate, vinyl propionate, vinyl butyrate, and one or more of these compounds. However, when a combination of methoxyethyl acrylate, which is a hydrophilic monomer, and styrene, which is hydrophobic, may be used, the wear performance of the antifouling coating composition may be affected.

In the binder of the present invention, the content of component (c) may be determined by the remaining amount according to the content of components (a) and (b) and is preferably 5 to 70% by weight. If the component (c) is used in less than 5% by weight, the strength of the coating film is lowered. If the component (c) is used in excess of 70% by weight, the antifouling performance is deteriorated. Component (c) serves to make up the main chain of the binder.

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

In the binder manufacturing method of this invention, the azo type compound, peroxide, etc. which are generally used conventionally can be used as said radical polymerization initiator. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), and 2,2'-azobis (2,4-dimethylvaleronitrile). Examples of the peroxide include benzyl peroxide, tertiary butyl peroxy acetate, tertiary butyl peroxy acetate, cumene hydroperoxide, tertiary butyl peroxide, tertiary butyl peroxy benzoate, 3 And higher butyl peroxy isopropyl carbonate. In particular, 2,2'-azobisisobutyronitrile and benzoyl peroxide among the compounds are most preferred in terms of copolymer production stability or ease.

In the manufacturing method of the binder of this invention, when the binder of this invention is applied as a component of an antifouling paint composition, the solution polymerization and bulk polymerization by which superposition | polymerization advances in the organic solvent are more preferable. Organic solvents usable in the solution polymerization include aromatic hydrocarbons (xylene, toluene, etc.), aliphatic hydrocarbons (hexane, heptane, etc.), esters (ethyl acetate, butyl acetate, etc.), alcohols (isopropyl alcohol, butyl) Alcohols, etc.), ethers (dioxane, diethyl ether, etc.), ketones (methyl ethyl ketone, methyl isobutyl ketone), and the like, and these solvents may be used in combination of one or more.

The antifouling coating composition of the present invention is characterized by including the above-described binder of the present invention as a binder, the content of which is preferably 10 to 30% by weight. In addition, the antifouling coating composition of the present invention may further include an inorganic or organic antifouling agent.

Copper powder or a copper compound may be used as the inorganic antifouling agent, and isothiazolones, thiocarbamates, pyrithiones, ureas, pyridines, and the like may be used as the organic antifouling agent.

In addition to the antifouling agent, the antifouling coating composition of the present invention may include one or more kinds of additives. For example, zinc oxide, an antigging agent, and the like, which serve to improve coating strength, adjust wear rate, and color, etc. Thickeners (clays, benton pastes, amide waxes) that act as anti-settling agents, plasticizers such as paraffin chloride, which contribute to improved crack resistance of antifouling paint coatings, such as acrylic resins and polyalkylvinyl ethers [vinylether (co) polymers] Various resins and antifoaming agents. In addition, various known organic and inorganic pigments (eg, titanium white, iron oxide, organic red pigments and talc, etc.) may be used in the antifouling coating composition of the present invention.

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

Examples 1-3 and Comparative Examples 1-3

[Manufacture of Binder]

Xylene, an organic solvent component, is added to the reaction vessel (round flask) with a mechanical stirrer, a condenser, a thermometer, a thermocouple, a dropping funnel, and a heating mantle. It is charged, heated and stirred to reflux. While maintaining the reflux temperature for 2 to 5 hours, as the silyl (meth) acrylate monomer (component (a)) in the content shown in Table 1 below, acrylic having a triisopropylsilyl acrylate, single-ended reactive silicone oil structure 3- [tris (trimethylsilyloxy) silyl] propyl methacrylate as the unsaturated monomer (component (b)), methyl methacrylate as the acrylic unsaturated monomer (component (c)) and benzoyl peroxide as a radical polymerization initiator Into the reaction vessel using a dropping device under. In addition, a small amount of the mixed solution of benzoyl peroxide was further added and stirred at the same temperature for 2 hours.

The non-volatile content in the copolymer binder solution prepared as described above was 40 to 60% by weight as a result of calculating the weight of the residue after drying in an oven at 150 ° C. for 15 minutes.

Table 1.Components of Binder and Their Contents (Unit: wt%)

           bookbinder Ingredient (a) Component (b) Component (c) Polymerization initiator (parts by weight) Triisopropyl Acrylate  3- [tris (trimethylsilyloxy) silyl] propylmethacrylate Methyl methacrylate Butyl Acrylate Styrene Benzoil peroxide Example 1 35 10 55 One Example 2 35 15 50 One Example 3 35 20 45 One Comparative Example 1 35 65 One Comparative Example 2 40 60 One Comparative Example 3 45 55 One Comparative Example 4 50 50 One Comparative Example 5 55 45 One Comparative Example 6 60 40 One Comparative Example 7 40 55 5 One Comparative Example 8 40 50 10 One Comparative Example 9 40 45 15 One Comparative Example 10 60 35 5 One Comparative Example 11 60 30 10 One Comparative Example 12 35 65 3 Comparative Example 13 35 65 5

Examples 4-6 and Comparative Examples 14-26

[Production of antifouling coating composition]

The antifouling coating compositions were prepared by adding the binders prepared in Examples 1 to 3 and Comparative Examples 1 to 13 to the contents shown in Table 2, respectively. (Wear rate) was compared and evaluated, and the result was shown to Tables 3 and 4, respectively. The initial viscosity in 25 degreeC of the antifouling paint composition was 90-110 (ku).

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

Antifouling performance test

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

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

Level 4: thin slime layer observed

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

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

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

Wear performance (speed) test

A sandblasted 150 × 70 × 1 (mm) size stainless steel sheet with an anticorrosive coat 50 μm, a binder coat 50 μm and an antifouling coating composition 100 μm prepared by the formulation shown in Table 2 The paint was continuously applied at daily intervals, and cured and dried at room temperature for one week. The specimen thus prepared was installed outside a rotating drum having a diameter of 600 (mm) and a height of 300 (mm), and then rapidly rotated at a speed of 25 (knot) at a constant temperature of 25 ° C for 6 months at a thickness of 1 month. The wear rate was evaluated by measuring the change.

Table 2. Components and Contents of Antifouling Coating Composition (Unit: wt%)

ingredient Antifouling paint composition Example 4 Example 5 Example 6 Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparative Example 18 Comparative Example 19 Comparative Example 20 Comparative Example 21 Comparative Example 22 Comparative Example 23 Comparative Example 24 Comparative Example 25 Comparative Example 26        bookbinder Example 1 25 Example 2 25 Example 3 25 Comparative Example 1 25 Comparative Example 2 25 Comparative Example 3 25 Comparative Example 4 25 Comparative Example 5 25 Comparative Example 6 25 Comparative Example 7 25 Comparative Example 8 25 Comparative Example 9 25 Comparative Example 10 25 Comparative Example 11 25 Comparative Example 12 25 Comparative Example 13 25 Antifouling agent 1 (copper oxide) 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Antifouling agent 2 (pyrithione) 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 zinc oxide 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Pigment (Iron Oxide) 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Thickener (Clay) 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Organic Solvent (Zylene) 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15

Table 3. Antifouling performance test of antifouling paint composition

   time Antifouling performance Example 4 Example 5 Example 6 Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparative Example 18 Comparative Example 19 Comparative Example 20 Comparative Example 21 Comparative Example 22 Comparative Example 23 Comparative Example 24 Comparative Example 25 Comparative Example 26 3 months 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 6 months 5 5 5 4 4 4 4 4 5 5 5 5 4 4 4 4 9 months 5 5 5 4 4 4 4 4 4 4 5 5 4 4 4 4 12 months 5 5 5 3 4 4 4 4 4 4 4 4 4 3 3 4 15 months 4 5 5 3 3 3 3 4 4 4 4 4 3 3 3 3 18 months 4 4 5 2 2 3 3 4 4 3 4 3 3 2 2 2

As shown in Table 3, the antifouling coating compositions of Examples 4 to 6 prepared using the binder according to the present invention had excellent antifouling performance in the stagnant state, generally 4 to 5 grades, especially for a long time of 9 months or more. The antifouling performance was maintained at a grade 4-5, showing excellent long-term antifouling properties. This is because component (b) of the present invention delays the attachment of marine microorganisms through surface energy control.

In addition, since the antifouling coating composition using the binder of Example 3 compared to Example 2 and Example 2 has excellent long-term antifouling performance, the longer term antifouling performance is increased as the content of component (b) of the present invention is increased. It can be seen that good.

Table 4. Abrasion performance test of antifouling paint composition (unit: um / month)

Hourly wear rate 1 month 2 months 3 months 4 months 5 months 6 months Average wear rate Example 4 6.3 4.5 4.2 4.1 3.8 5.1 4.7 Example 5 6.6 4.5 4.7 4.6 4.2 5.5 5.0 Example 6 6.7 4.8 4.8 4.5 4.8 5.9 5.3 Comparative Example 14 5.9 4.1 3.9 4.1 3.5 4.8 4.4 Comparative Example 15 7.1 5.2 4.8 5.1 4.8 5.9 5.5 Comparative Example 16 7.5 6.2 4.5 5.7 5.5 6.6 6.0 Comparative Example 17 8.3 7.1 5.5 7.0 5.5 7.4 6.8 Comparative Example 18 8.2 7.9 5.1 7.2 6.0 7.5 7.0 Comparative Example 19 8.5 7.9 5.8 7.8 6.9 7.5 7.4 Comparative Example 20 7.9 5.9 5.6 6.8 5.6 6.2 6.3 Comparative Example 21 8.9 7.8 6.8 7.7 7.2 7.9 7.7 Comparative Example 22 10.1 9.5 8.9 9.2 9.0 10.2 9.5 Comparative Example 23 8.0 7.5 5.5 7.0 6.2 7.0 6.9 Comparative Example 24 7.1 6.5 5.1 5.9 5.8 6.1 6.1 Comparative Example 25 5.8 3.8 3.7 4.1 3.4 4.9 4.3 Comparative Example 26 5.5 3.9 3.8 4.0 3.0 4.1 4.1

As shown in Table 4, it was found that the antifouling coating compositions of Examples 4 to 6 using the binder of the present invention had a lower average wear rate than the antifouling coating compositions of Comparative Examples 14 to 26 without using the binder of the present invention. Can be.

Therefore, the antifouling coating composition of the present invention is excellent in long-term antifouling properties as the average wear rate is low, and is suitable for ships that are stationary for long periods of time in the sea, frequently repeating operation and stopping, or operating at a low speed of about 10 knots or less. Able to know.

According to the present invention, it is possible to provide an antifouling coating composition which is excellent in storage stability, hardly occurs coating film cracking and peeling, and forms an antifouling coating film excellent in antifouling performance, particularly in a stagnant environment or a high pollution environment.

Claims (5)

20 to 60% by weight of the silyl (meth) acrylate monomer component represented by the following General Formula (1), 5 to 20% by weight of the acrylic unsaturated monomer component having the silicone oil structure represented by the following General Formula (2), and acrylic or A silyl (meth) acrylate copolymer binder for antifouling paint composition comprising 5 to 70% by weight of a vinyl unsaturated monomer component:

.......(One) [Wherein, R ¹ is H or CH 3, and R ² to R ⁴ are each a phenyl group which may have a linear or cycloalkyl group having 1 or more carbon atoms and a substituent including an alkyl group, an aryl group or a halogen element, and are the same as or different from each other. Can be]

......(2) [Wherein R ⁵ is H or CH ₃ , R ⁶ is a phenyl group which may have a linear or cycloalkyl group having 1 or more carbon atoms and a substituent including an alkyl group, an aryl group or a halogen element, and n is any integer of 1 or more to be] The method of claim 1, wherein the acrylic unsaturated monomer component having a silicone oil structure is 3- [tris (trimethylsilyloxy) silyl] propyl methacrylate, 3- [tris (triethylsilyloxy) silyl] propyl methacrylate and A silyl (meth) acrylate copolymer binder for antifouling paint composition, characterized in that at least one member is selected from the group consisting of 3- [tris (tripropylsilyloxy) silyl] propyl methacrylate. The silyl (meth) acrylate copolymer binder for antifouling coating composition according to claim 1, wherein the binder has a number average molecular weight in the range of 2,000 to 150,000. An antifouling coating composition comprising the binder according to any one of claims 1 to 3 as a binder. The antifouling coating composition according to claim 4, further comprising at least one of an inorganic or organic antifouling agent, a pigment, a flow inhibitor, a sedimentation inhibitor, and a plasticizer.