KR101810774B1 - Antifouling coating composition, antifouling coating film, antifouling substrate, and method for producing antifouling substrate - Google Patents

Abstract

An object of the present invention is to provide an antifouling coating composition for forming an antifouling coating film excellent in long-term antifouling property, long-term water-resistance and crack resistance when exposed to long-term daylight.
In order to solve the above problems, the antifouling paint composition of the present invention has a structure derived from a structural unit (1) derived from triisopropylsilyl methacrylate (i), 2-methoxyethyl (meth) acrylate (ii) (3) derived from the monomer (2) and other monomers having polymerizable double bonds (excluding triisopropylsilyl methacrylate and 2-methoxyethyl (meth) acrylate) (A) and trimethylisobutenylcyclohexene carboxylic acid (B), wherein the silylmethacrylate copolymer (A) is a silyl methacrylate copolymer.

Description

TECHNICAL FIELD The present invention relates to an antifouling coating composition, an antifouling coating, an antifouling coating, and a method for producing antifouling substrate,

More particularly, the present invention relates to an antifouling coating composition which is effective for antifouling of a surface of a substrate exposed to water and an antifouling coating film using the antifouling coating composition, an antifouling base, and a process for producing an antifouling base will be.

The surface of the substrate, which is exposed for a long time in water such as a ship, an underwater structure, a fishing net, etc., is easily attached to various kinds of aquatic organisms such as oysters, mussels, barnacles, When these aquatic organisms grow on the substrate surface, various problems arise. For example, when the base material is a ship, the surface roughness increases from the waterline to the bottom of the ship, resulting in a decrease in the speed of the ship and an increase in the fuel consumption. In addition, when the substrate is a fishing net such as a fish net or a net, the mesh may be obstructed by aquatic organisms, resulting in serious problems such as lethality due to oxygen deficiency of aquatic organisms or fish. Also, in the case where the substrate is a water supply pipe of a seawater such as a thermal power plant or a nuclear power plant, the water supply pipe of the seawater (cooling water) may be blocked or the flow rate may be lowered, which may hinder the circulation system.

To solve such problems, research and development of an antifouling paint (antifouling paint composition) applied to a substrate has been proceeding in order to prevent adhesion of aquatic organisms to various substrates.

As a conventional antifouling paint composition, a coating composition comprising a hydrolyzable resin as a resin component (binder component) is known. As a representative example thereof, a coating composition containing a hydrolyzable resin containing a triorganosilyl group has been developed, and this coating composition is applied to prevent adhesion of aquatic organisms to the bottom of a ship.

As the hydrolyzable resin containing a triorganosilyl group, it is generally known that a monomer component comprising triisopropylsilyl acrylate and / or triisopropylsilyl methacrylate is (co) polymerized. In the antifouling paint composition containing the hydrolyzable resin, a monocarboxylic acid such as a rosin compound is generally used in combination to improve flame retardancy (Patent Documents 1 to 8).

Patent Document 7 also discloses an antifouling coating film formed of an antifouling paint composition containing a triisopropylsilyl acrylate copolymer and trimethylisobutenylcyclohexenecarboxylic acid, and is excellent in stainproofness, consumption and condition (presence or absence of cracks) (Examples 5 to 8, 11 to 13, 16 to 18, 20, and 22 to 24). Patent Document 8 also discloses an antifouling coating film formed of an antifouling coating composition containing a triisopropylsilyl (meth) acrylate copolymer and trimethylisobutenylcyclohexenecarboxylic acid, and has excellent long-term durability.

Japanese Patent Application Laid-Open No. 2001-226440 Japanese Patent Application Laid-Open No. 2005-82725 International Publication No. 2010/071180 Japanese Patent Application Laid-Open No. 10-30071 International Publication No. 2009/001619 International Publication No. 2009/066632 Japanese Patent Application Laid-Open No. 2005-179345 International Publication No. 2013/073580

However, as a result of investigation by the present inventors, it has been found that there is a problem in that an antifouling coating film formed from an antifouling coating composition containing a (co) polymer of triisopropylsilyl (meth) acrylate and a rosin compound cracks when exposed to long- I could. For example, when a block painted with an antifouling paint is exposed to sunlight for a long period of time at the time of newbuilding, cracks are generated, or when the antifouling coating on the surface of the ship is exposed to sunlight for a long time in relation to a drop quantity or ship ballast water during operation, Occurs. In the case of the former, it is necessary to repair the antifouling coating film, thereby increasing the shipbuilding process. In the latter case, the antifouling property during the operation of the antifouling coating film may be lowered or cracks may be generated, thereby causing irregularities on the bottom coating film surface, thereby increasing the resistance to water flow friction. Since the hardness of the rosin or its metal salt is high, when the coating film containing the rosin or the metal salt thereof is exposed to sunlight, drying of the coating film is progressed with time, and the hardness of the coating film is increased. In addition, rosin is a natural product, which is unstable in terms of quality stability and stable supply against the future.

It was also found that the coating film formed from the antifouling paint composition comprising the triisopropylsilyl acrylate copolymer and trimethylisobutenylcyclohexene carboxylic acid described in Patent Document 7 had room for improvement in terms of long-term water resistance.

The antifouling coating film formed of the antifouling coating composition containing the tri-i-propylsilyl (meth) acrylate copolymer disclosed in Patent Document 8 and trimethylisobutenylcyclohexenecarboxylic acid also suppresses the occurrence of cracks when exposed to long daylight There was room for improvement.

Accordingly, the present invention relates to a process for producing a polyurethane resin which is excellent in long-term antifouling property (particularly stainproofing property) and long-term water resistance (specifically, adhesion to a substrate of a coating film in a case where it is immersed in water for a long period, An antifouling coating composition for forming an antifouling coating film excellent in crack resistance (hereinafter also referred to as " long-term weatherability ") when the antifouling coating film is formed, and an antifouling coating film containing the antifouling coating film and a method for producing the same Purpose.

The inventors of the present invention have studied extensively in view of the above-mentioned problems, and found that a silyl ester copolymer in which triisopropylsilyl methacrylate and 2-methoxyethyl (meth) acrylate are copolymerized and trimethylisobutenylcyclohexenecarboxylic acid The antifouling coating film formed from the antifouling paint composition of the present invention can solve the above-mentioned problem, and the present invention has been accomplished.

The antifouling paint composition of the present invention relates to the following [1] to [12], for example.

[One]

(2) derived from a structural unit (1) derived from triisopropylsilyl methacrylate (i), a structural unit derived from 2-methoxyethyl (meth) acrylate (ii), and another monomer having a polymerizable double bond (Excluding triisopropylsilyl methacrylate and 2-methoxyethyl (meth) acrylate). The silyl methacrylate-based copolymer (A) containing the structural unit (3) derived from (iii) Wow,

Trimethylisobutenylcyclohexenecarboxylic acid (B)

And an antifouling paint composition.

[2]

The antifouling paint composition according to the above [1], wherein the other monomer (iii) is an ester or a carboxylic acid.

[3]

The antifouling paint composition according to the above [1] or [2], wherein the proportion of the structural unit (1) in the silyl methacrylate-based copolymer (A) is 30 to 70% by weight.

[4]

The antifouling paint composition according to any one of [1] to [3], wherein the proportion of the structural unit (2) in the silyl methacrylate-based copolymer (A) is 5 to 40% by weight.

[5]

The silyl methacrylate ratio (W _A / W _B) of 99, based on weight of the content (W _A) and the content (W _B) of the trimethyl isobutoxy ethenyl cyclohexene carboxylic acid (B) of the copolymer (A) / 1 to 40/60. [5] The antifouling paint composition according to any one of [1] to [4] above,

[6]

The antifouling paint composition according to any one of [1] to [5], further comprising a rosin and / or a monocarboxylic acid compound (excluding trimethylisobutylcyclohexenecarboxylic acid) (C) .

[7]

(D), an organic antifouling agent (E), a coloring pigment (F), an extender pigment (G), a pigment dispersant (H), a plasticizer (I), a sagging agent (J) The antifouling paint composition according to any one of [1] to [6], wherein the antifouling paint composition according to any one of [1] to [6], which contains at least one component selected from the group consisting of water, a dehydrating agent (L) and a solvent (M)

[8]

An antifouling coating film formed from the antifouling paint composition according to any one of [1] to [7].

[9]

An antifouling substrate having a substrate and the antifouling coating film according to the above [8], which is provided on the surface of the substrate.

[10]

An antifouling substrate according to the above [9], which is in contact with seawater or fresh water.

[11]

The antifouling substrate according to the above [9] or [10], wherein the substrate is an underwater structure, a ship exterior plate, or a fish.

[12]

A step of applying or impregnating the antifouling paint composition according to any one of the above [1] to [7] to the surface of the substrate, and a step of curing the antifouling paint applied or impregnated to the substrate by the step Or

A step of forming a coating film from the antifouling paint composition and curing the coating film to form an antifouling coating film, and a step of sticking the antifouling coating film to a substrate

A method for producing an antifouling substrate.

The antifouling coating film of the present invention is excellent in long-term antifouling property (particularly stiffness antifouling property) and long-term water resistance (specifically, adhesion of the coating film in water, particularly in the case of immersion in seawater for a long period of time, crack resistance and abrasion resistance) Is excellent. The antifouling coating composition of the present invention can form an antifouling coating film exhibiting such effects. Further, according to the method for producing an antifouling substrate of the present invention, an antifouling substrate exhibiting such effects can be produced.

The antifouling paint composition, antifouling coating film, antifouling substrate and method for producing the antifouling substrate of the present invention will be described in detail below.

[ Antifouling paint composition]

The antifouling paint composition of the present invention (also simply referred to as "antifouling paint") contains a specific silyl methacrylate-based copolymer (A) and trimethylisobutenylcyclohexene carboxylic acid (B) And may contain an arbitrary component.

1. Silyl methacrylate copolymer (A)

The silyl methacrylate-based copolymer (A) may contain structural units (also referred to as "structural units", "repeating units", etc.) derived from triisopropylsilyl methacrylate (i) A structural unit (2) derived from a monomer (ii) (hereinafter also referred to as "monomer (ii)"), 2-methoxyethyl (meth) acrylate (Iii) (hereinafter, also referred to as " monomer (iii) ")), which is derived from the monomer (iii), except for triisopropylsilyl methacrylate (i) and 2-methoxyethyl Is a silyl methacrylate-based copolymer (A) having a structural unit (3). The term "structural unit derived from X" means that, when X is represented by A ¹ A ² C = CA ³ A ⁴ (C═C is a polymerizable carbon-carbon double bond), for example, a structure represented by the following formula Unit.

Also, (meth) acrylate is a generic name of acrylate and methacrylate, and (meth) acrylic acid is a generic name of acrylic acid and methacrylic acid.

From the viewpoint of producing an antifouling coating film having more stable consumption over a long period of time, the monomer (ii) preferably contains 2-methoxyethyl methacrylate containing 2-methoxyethyl methacrylate in an amount of 50% Methoxyethyl acrylate, more preferably 2-methoxyethyl methacrylate.

Other monomer having a polymerizable double bond (except for triisopropylsilyl methacrylate (i) and 2-methoxyethyl (meth) acrylate (ii)), (iii) is a triisopropylsilyl methacrylate (I) and 2-methoxyethyl (meth) acrylate (ii). Examples of the group having a polymerizable double bond include a vinyl group and a (meth) acryloyl group.

The monomer (iii) is preferably an ester having a polymerizable double bond and a carboxylic acid having a polymerizable double bond. If the monomer (iii) is a compound of these, the monomer (iii) has good compatibility with the triisopropylsilyl methacrylate (i) and the 2-methoxyethyl (meth) acrylate (ii) (I), (ii) and (iii) are homogeneously dispersed because of the same degree of reactivity to the silyl methacrylate (i) and the 2-methoxyethyl (meth) acrylate (In other words, randomly) to introduce the silyl methacrylate-based copolymer (A).

That is, when the polymerization reactivities between the respective monomers are extremely different and the monomers are difficult to copolymerize with each other, there arises a problem that the resulting polymer is a homopolymer or a copolymer having a nonuniform distribution of the structural units. When the monomer (iii) It is possible to prepare the methacrylate-based copolymer (A) which is stably silylated by reducing this problem.

Examples of the esters and carboxylic acids to be used as the monomer (iii) include (meth) acrylates other than the triisopropylsilyl methacrylate (i) and 2-methoxyethyl (meth) acrylate (ii) (Meth) acrylate containing a metal ester group, (meth) acrylate, and (meth) acrylate containing an organosiloxane group can be obtained by reacting a monocarboxylic acid, a dicarboxylic acid, a dicarboxylic acid and a half ester thereof . Examples of the monomers (iii) other than esters and carboxylic acids include styrenes.

Specific examples of the monomer (iii) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, 2-ethylhexyl (meth) acrylate, lauryl (Meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, stearyl (meth) acrylate, stearyl (Meth) acrylic acid esters such as methacrylic acid methoxy ester, (meth) acrylic acid ethoxy ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid hydroxyethyl ester, , (Meth) acrylic acid hydroxybutyl ester, and other (meth) acrylic acid esters;

Monocarboxylic acids such as (meth) acrylic acid;

Dicarboxylic acids such as itaconic acid, maleic acid, and succinic acid, and half esters (monoesters) and diesters thereof;

Styrenes such as styrene and? -Methylstyrene;

Vinyl esters such as vinyl acetate and vinyl propionate;

These may be used alone or in combination of two or more.

The silyl methacrylate copolymer (A) is preferably contained in the antifouling paint composition of the present invention in an amount of 5 to 40% by weight, more preferably 8 to 30% by weight, from the viewpoints of improving paint workability and long- .

In addition, the silyl methacrylate copolymer (A) is excellent in coating workability, long-term storage stability, film water resistance (in other words, mechanical properties of the film), film hydrolysis resistance (in other words, consumption of the film) , It is contained in an amount of preferably 10 to 60% by weight, more preferably 12 to 50% by weight, based on 100% by weight of the solid content of the antifouling paint composition of the present invention. Here, the solid content of the antifouling paint composition is the residue obtained by removing volatile components by maintaining 1.5 g of the antifouling paint composition in a thermostatic chamber under conditions of 1 atm and 108 캜 for 3 hours.

The weight average molecular weight of the silyl methacrylate-based copolymer (A) is preferably 5,000 to 100,000, and more preferably 10,000 to 60,000. The coating film formed from the antifouling coating composition containing the silyl methacrylate copolymer (A) having a weight average molecular weight in this range is excellent in hydrolysis property, stiffness is further improved, and excellent long-term mechanical properties (Such as the adhesion of the antifouling coating film of the present invention to the base material, the undercoat coating film and the like in the case of being dipped in water for a long period of time, and appearance characteristics such as cracks, etc.).

The weight average molecular weight is a value measured by a gel permeation chromatography (GPC) method and is a value obtained using a standard polystyrene calibration curve. GPC conditions for molecular weight measurement are as follows.

≪ GPC condition >

Device: " HLC-8120GPC " (manufactured by Tosoh Corporation)

Column: " SuperH2000 + H4000 " (manufactured by Tosoh Corporation, 6 mm (inside diameter), 15 cm (length)

Eluent: tetrahydrofuran (THF)

Other conditions

Flow rate: 0.500 ml / min

Detector: RI

Column thermostatic bath temperature: 40 ° C

Standard material: polystyrene

Preparation of sample: A small amount of calcium chloride is added to a solution containing the copolymer (A), followed by dehydration, followed by filtration with a membrane filter to obtain a GPC measurement sample.

(W _{(2) + (3)} ) of the structural unit ( ₁₎ , the structural unit (2) and the structural unit (3) in the silyl methacrylate copolymer (A) (hereinafter also referred to as "weight ratio of (I)") ratio (i. e., W _(1), / W _{(2) + (3))} is preferably 30/70 ~ 70/30, and more preferably 40 / 60 to 65/35, and more preferably 45/55 to 65/35.

When the weight ratio (I) is in the above range, an antifouling paint composition having good film hydrolysis (consumptiveness), static antifouling property and coating film water resistance (mechanical property) can be obtained.

Ratio (i. E., W ₂ / W of the structural unit (2) weight (W ₂₎ and the structural unit (1) and the total weight of the structural unit (3) (W _{(1) + (3))} of _{( 1) + 3)} (hereinafter also referred to as "weight ratio of (II)") is preferably 5 / 95-40 / 60, more preferably 5 / 95-30 / 70, 7/93 and more preferably To 29/71, particularly preferably from 10/90 to 28/72.

When the weight ratio (II) is in the above range, the antifouling coating film formed of the antifouling paint composition exhibits long-term antifouling properties such as good stainproofing ability because it can exhibit sufficient film film consumption (renewability) when immersed in water, The occurrence of cracks can be reduced over a long period of time.

The silyl methacrylate copolymer (A) is obtained by copolymerizing (iii) triisopropylsilyl methacrylate (i), 2-methoxyethyl (meth) acrylate And then copolymerized by a polymerization method. Examples of the polymerization method include solution polymerization, bulk polymerization, semi-batch polymerization, suspension polymerization, coordination polymerization, radical polymerization or emulsion polymerization in radical polymerization or ionic polymerization. Among them, considering the possibility of preparing the copolymer (A) having a low viscosity by improving the productivity and the workability of the silyl methacrylate copolymer (A), toluene, xylene, methyl isobutyl ketone, It is preferable to perform the solution polymerization of the above monomers (i) to (iii) using an organic solvent which is generally used such as butyl.

When the viscosity of the copolymer (A) is low, the amount of the solvent added to lower the viscosity of the antifouling paint composition can be reduced, thereby reducing the amount of VOC (Volatile Organic Compounds) of the antifouling paint composition . In addition, since the viscosity of the antifouling paint composition can be reduced, the paint workability of the paint composition and the appearance (leveling property) of the antifouling coating film can be improved.

As the catalyst used for the radical polymerization, known catalysts can be widely used. For example, 2,2'-azobis (2-methyl Azo compounds such as 2,2'-azobis (isobutyronitrile) (AMBN), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobisisobutyronitrile, Butyl peroxy-2-ethyl hexanoate, t-butyl peroxybenzoate, t-butyl peroxy octoate and the like.

The ratio of the respective contents (weights) of the structural units (1) to (3) contained in the copolymer (A) corresponds to the ratio of the addition amount (weight) of the monomers (i) to (iii) There is a tendency. Therefore, the above-mentioned " weight ratio (I) " and " the above-mentioned weight ratio (II) " can be adjusted to desired values based on the added weight ratio of the monomers provided for the polymerization reaction.

2. Trimethylisobutenylcyclohexenecarboxylic acid (B)

The antifouling paint composition of the present invention promotes the dissolution of the antifouling agent from the antifouling coating film formed with the antifouling agent in the case where the antifouling paint composition does not cause cracking when exposed to sunlight for a long period of time, And trimethylisobutenylcyclohexenecarboxylic acid as an essential component from the viewpoint of improving the static antifouling property of the coating film.

Examples of the trimethylisobutylcyclohexenecarboxylic acid (B) include the reaction products of 2,6-dimethylocta-2,4,6-triene and methacrylic acid, and 1,2,3- Cyclohex-3-ene-1-carboxylic acid and 1,4,5-trimethyl-2- (2-methylprop-1-enyl) -En-1-yl) cyclohex-3-ene-1-carboxylic acid as a main component (85% or more).

In addition, the air ratio (that is W _A / W _B) of the copolymer (A) content (W _A) and trimethyl isobutoxy ethenyl cyclohexene carboxylic content of the acid (W _B) in the antifouling paint composition of the present invention is preferably a weight basis Is preferably from 99/1 to 40/60, more preferably from 95/5 to 50/50, and still more preferably from 90/10 to 55/45. When the weight ratio is within this range, the antifouling coating film formed from the antifouling paint composition has an effect of enhancing the flammability (in other words, the film abatement property) of the antifouling coating film and the antifouling property (especially the antifouling property) and the cracking resistance when the coating film is exposed to long- Can be improved.

3. Rosin and / or monocarboxylic acid compound (C)

The antifouling paint composition of the present invention may further contain a rosin and / or a monocarboxylic acid compound (excluding trimethylisobutenylcyclohexenecarboxylic acid) (C) to further improve the antifouling property of the antifouling coating film formed from the antifouling paint composition ) May be contained. Examples of the rosin include rosin derivatives such as rosin, hydrogenated rosin, and disproportionated rosin such as rosin, wood rosin and tall oil rosin. Examples of the monocarboxylic acid compound include aliphatic or alicyclic monocarboxylic acids and their metal salts And the like. Specific examples of the monocarboxylic acid compound include naphthenic acid, versatate acid, stearic acid, salicylic acid, and salts thereof.

The content of the rosin and / or the monocarboxylic acid compound (C) in the antifouling paint composition of the present invention is preferably in the range of 100 parts by weight or more based on 100 parts by weight of the trimethylisobutenylcyclohexenecarboxylic acid (B) from the viewpoints of coating film consumption, antifouling property, Preferably 1 to 200 parts by weight, more preferably 3 to 150 parts by weight, and still more preferably 5 to 100 parts by weight.

4. Inorganic Copper Compound (D)

The antifouling paint composition of the present invention may further contain an inorganic copper compound (D) in order to further improve the antifouling property of the antifouling coating film formed from the antifouling paint composition. Examples of the copper compound include copper oxide, copper thiocyanate, and cupronitrile.

The content of the inorganic copper compound (D) in the antifouling paint composition of the present invention is preferably 10 to 800 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the copolymer (A) Is 100 to 750 parts by weight. The content of the inorganic copper compound (D) is usually about 0.1 to 70% by weight, preferably about 0.1 to 60% by weight, based on 100% by weight of the antifouling coating composition. The inorganic copper compound (D) is preferably a copper compound which does not contain 2% or more of metallic copper as an impurity based on the total weight thereof.

5. Organic antifouling agent (E)

The antifouling paint composition of the present invention may further contain an organic antifouling agent (E) in order to further improve the antifouling effect of the antifouling coating film formed from the antifouling paint composition, especially the vegetable marine life. The organic antifouling agent (E) is not particularly limited as long as it is an organic compound that imparts antifouling properties to the antifouling coating film.

Examples of the organic antifouling agent (E) include metal pyrithiones such as copper pyrithione and zinc pyrithione, metal pyrithiones such as 4,5-dichloro-2-n-octyl-4-isothiazolin- (Trifluoromethyl) -1H-pyrrole-3-carbonitrile, a borane-nitrogen base addition product (pyridine triphenylborane, 4-isopropylpyridine diphenylmethyl N-dimethyl-N '- (3,4-dichlorophenyl) urea, N- (2,4,6-trichlorophenyl) maleimide, 2-methylthio- 6-cyclopropylamino-1,3,5-triazine, 2,4,5,6-tetrachloroisophthalonitrile, bisdimethyldithiocarbamoylzinc ethylenebis dithiocarbamate, chloromethyl-n- Octyl disulfide, N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, tetraalkyl thiuram disulfide, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, 2,3-dichloro-N- (2 ', 6'-diethylphenyl) male Imide, 2,3-dichloro-N- (2'-ethyl-6'-methylphenyl) maleimide and the like.

The content of the organic antifouling agent (E) in the antifouling paint composition of the present invention is preferably in the range of from 0.1 to 10 parts by weight, more preferably from 10 to 30 parts by weight, based on 100 parts by weight of the copolymer (A ) Is preferably 0.1 to 500 parts by weight, more preferably 0.5 to 300 parts by weight, based on 100 parts by weight. The content of the organic antifouling agent (E) is usually about 0.1 to 30% by weight, preferably about 0.1 to 20% by weight, based on 100% by weight of the antifouling coating composition.

The antifouling paint composition of the present invention may further contain a coloring pigment (F), an extender pigment (G), a pigment dispersant (H), a plasticizer (I), a sagging inhibitor (J), a sedimentation inhibitor (K), a dehydrating agent (M) may be contained. These (F) to (M) will be described in detail below.

6. Coloring Pigment (F)

The antifouling paint composition of the present invention may contain a coloring pigment (F) for controlling the color tone of the antifouling coating film formed from the antifouling paint composition or for imparting any color tone.

Examples of the coloring pigment (F) include various known organic or inorganic coloring pigments. Examples of organic colored pigments include carbon black, naphthol red, and phthalocyanine blue. Examples of the inorganic coloring pigments include Bengala, barite powder, titanium bag, and yellow iron oxide.

The antifouling paint composition of the present invention may contain a colorant other than the coloring pigment (F) such as a dye in place of or in addition to the coloring pigment (F).

The content of the coloring pigment (F) in the antifouling paint composition of the present invention is not particularly limited so long as the antifouling coating film formed from the antifouling paint composition has improved colorability, hiding ability, weathering discoloration resistance, antifouling property and film water resistance (mechanical property) A) is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 10 parts by weight based on 100 parts by weight of the composition.

The content of the colored pigment (F) is usually about 0.1 to 30% by weight, preferably about 0.1 to 20% by weight, based on 100% by weight of the antifouling paint composition.

7. Extension Pigment (G)

The extender pigment (G) can improve physical properties such as crack resistance of an antifouling coating film formed of an antifouling paint composition.

Examples of the extender pigment G include talc, silica (diatomaceous earth, acidic clay, etc.), mica, clay, feldspar, zinc oxide, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, , Barium sulfate, and zinc sulfide. Among these, talc, silica, mica, clay, calcium carbonate, kaolin, barium sulfate, feldspar potassium and zinc oxide are preferable.

The content of the extender pigment (G) in the antifouling paint composition of the present invention is not particularly limited so long as the antifouling coating film formed from the antifouling paint composition is a copolymer (A), an antifouling paint composition, an antifouling paint composition, Is preferably 0.1 to 500 parts by weight, more preferably 50 to 300 parts by weight, based on 100 parts by weight of the resin composition. The content of the extender pigment (G) is usually about 0.1 to 50% by weight, preferably about 0.1 to 40% by weight, based on 100% by weight of the antifouling paint composition.

8. Pigment Dispersant (H)

Examples of the pigment dispersant (H) include various known organic or inorganic pigment dispersants. Examples of the pigment dispersant include aliphatic amines or organic acids (for example, "Duomin TDO" (manufactured by LION Corporation) and "Disperbyk101" (manufactured by BYK Corporation)).

The content of the pigment dispersant (H) in the antifouling paint composition of the present invention is preferably in a range of from 0.1 to 10 parts by weight, more preferably from 1 to 100 parts by weight, based on 100 parts by weight of the copolymer (A) from the viewpoint of reducing the coating film viscosity of the antifouling paint composition, Preferably 0.01 to 100 parts by weight, more preferably 0.01 to 50 parts by weight. The content of the pigment dispersant (H) is usually about 0.1 to 10% by weight, preferably about 0.1 to 5% by weight based on 100% by weight of the antifouling paint composition.

9. Plasticizer (I)

The antifouling paint composition of the present invention preferably contains the plasticizer (I) in order to improve the anti-cracking property of the resulting antifouling coating film. Examples of the plasticizer (I) include chlorinated paraffin (also referred to as chlorinated paraffin), petroleum resin, ketone resin, TCP (tricresyl phosphate), polyvinyl ethyl ether, dialkyl phthalate and the like. Among them, chlorinated paraffin (chlorinated paraffin), petroleum resin and ketone resin are preferable as the plasticizer (I) from the viewpoint of improvement of coating film water resistance (mechanical property) and coating film hydrolytic capacity (consumability) of the antifouling coating film formed from the antifouling paint composition . The plasticizer (I) may be used singly or in combination of two or more.

Specific examples of the chlorinated paraffin include "Toyoparaque 150" and "Toyoparax A-70" (all manufactured by Tosoh Corporation).

Examples of the petroleum resin include C5, C9, styrene, dichloropentadiene and hydrogenated products thereof. Specific examples of the petroleum resin stream include "Quinton 1500" and "Quinton 1700" (both manufactured by Nippon Zeon Co., Ltd.).

The content of the plasticizer (I) in the antifouling paint composition of the present invention is preferably from 100 to 100 parts by weight based on 100 parts by weight of the copolymer (A) 100 from the viewpoint of improving the coating film hydrolysis (consumption), antifouling property and coating film water resistance (mechanical properties) of the antifouling coating film formed from the antifouling paint composition Is preferably 0.1 to 300 parts by weight, more preferably 0.1 to 200 parts by weight, and still more preferably 0.1 to 150 parts by weight, based on 100 parts by weight of the resin.

The content of the plasticizer (I) is usually about 0.1 to 30% by weight, preferably about 0.1 to 20% by weight, based on 100% by weight of the antifouling paint composition.

10. Anti-sagging agent (J)

The antifouling paint composition of the present invention may contain an anti-sagging agent (J) (also referred to as a flow inhibitor) from the viewpoint of reducing the occurrence of sagging by the paint composition when the base material is coated with the antifouling paint composition .

Examples of the antigging agent (J) include amide wax, hydrogenated castor oil wax, mixtures thereof, synthetic fine silica (Aerosil (registered trademark), etc.), and among them, amide wax or synthetic fine silica is preferable. When the amide wax or synthetic fine silica is used as the anti-sagging agent (J), the storage stability of the antifouling paint composition is improved, and on the antifouling coating film after forming the antifouling coating film, a coating film composed of the same kind of antifouling paint composition or the different coating composition (Also referred to as interlayer adhesion or overlapping property) between the antifouling coating film and the top coating film can be prevented.

As a commercially available product of the anti-sagging agent (J), "DIPARON A630-20X" (manufactured by Goosumoto Chemicals Co., Ltd.) or "ASAT-250F" (manufactured by Ito Oil Chemical Co., Ltd.) can be mentioned.

The content of the anti-sagging agent (J) in the antifouling paint composition of the present invention is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the copolymer (A). The content of the anti-sagging agent (J) is usually about 0.1 to 20% by weight, preferably about 0.1 to 10% by weight based on 100% by weight of the antifouling paint composition. When the content of the anti-sagging agent (J) is set in this range, it is possible to improve the storage stability of the antifouling paint composition and to improve the storage stability of the antifouling coating film on the antifouling coating film It is possible to prevent the adhesion between the antifouling coating film and the top coat film (interlayer adhesion, overlapping property) from deteriorating.

11. Anti-settling agent (K)

The antifouling paint composition of the present invention may contain a sedimentation inhibitor (K) in view of the ability to prevent the formation of precipitates in the coating composition during storage and to improve the agitability.

Examples of the sedimentation inhibitor (K) include stearates of Al, Ca or Zn, polyethylene waxes, and oxidized polyethylene waxes, and among them, oxidized polyethylene waxes are preferred. As a commercially available product of the oxidized polyethylene wax, "DIPARON 4200-20X" (manufactured by Gusumoto Chemicals Co., Ltd.) can be mentioned.

The content of the anti-settling agent (K) in the antifouling paint composition of the present invention is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the copolymer (A). The content of the anti-settling agent (K) is usually about 0.1 to 20% by weight, preferably about 0.1 to 10% by weight, based on 100% by weight of the antifouling coating composition. When the content of the sedimentation inhibitor (K) is set in this range, it is possible to improve the storage stability of the antifouling paint composition and to improve the storage stability of the antifouling coating film on the antifouling coating film by using the same kind of antifouling paint composition or different coating composition It is possible to prevent the adhesion between the antifouling coating film and the top coat film (interlayer adhesion, overlapping property) from deteriorating.

12. Dehydrating agent (L)

The antifouling paint composition of the present invention has excellent storage stability because it contains the copolymer (A) having a good storage stability, but it is possible to obtain better long-term storage stability by adding a dehydrating agent (L) if necessary. Examples of the dehydrating agent (L) include an inorganic dehydrating agent and an organic dehydrating agent.

As the inorganic dehydrating agent, synthetic zeolite, anhydrous gypsum and semi-gypsum gypsum are preferable. Examples of the organic dehydrating agent include alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltriethoxysilane, dimethyldiethoxysilane and trimethylethoxysilane, condensates thereof, polyalkoxysilane And orthoformic acid alkyl esters such as methyl orthoformate and ethyl orthoformate are preferable.

The dehydrating agent (L) is preferably contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the copolymer (A).

13. Solvent (M)

The antifouling paint composition of the present invention may contain a solvent (M) such as water or an organic solvent as necessary in order to improve the dispersibility of the copolymer (A) or the like or adjust the viscosity of the composition. The solvent (M) may be a solvent used for preparing the copolymer (A), or may be a solvent separately added when the copolymer (A) and other components are mixed as required.

Examples of the organic solvent include aromatic organic solvents such as xylene, toluene and ethylbenzene; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aliphatic (alcohols having 1 to 10 carbon atoms such as ethanol, isopropyl alcohol, To about 10, preferably about 2 to about 5) monohydric alcohols; and ester solvents such as ethyl acetate and butyl acetate.

The content of the solvent (M) in the antifouling paint composition of the present invention is usually 20 to 80% by weight, preferably 30 to 70% by weight, based on 100% by weight of the antifouling coating composition.

(Method for producing antifouling paint composition)

The antifouling paint composition of the present invention can be produced by suitably using a known method. For example, by adding the copolymer (A), trimethylisobutenylcyclohexene carboxylic acid (B) and, if necessary, other components at once or in any order to a stirring vessel and mixing by known stirring and mixing means .

After mixing the respective components, an anti-sagging agent (J) (amide wax (e.g., Diparron A630-20X)) is added at the end and dispersed (for example, by stirring the mixture for about 10 to 20 minutes It is preferable to prepare an antifouling paint composition. This is because the occurrence of sagging can be reduced when the obtained antifouling paint composition is applied to a substrate.

Examples of the stirring and mixing means include a high speed dispenser, a sand grind mill, a basket mill, a ball mill, a three roll mill, a Ross mixer, a planetary mixer, a universal Shinagawa stirrer and the like.

[ Antifouling coating and antifouling equipment]

The antifouling coating film of the present invention is composed of the solid content of the antifouling paint composition of the present invention. When the antifouling coating film of the present invention is formed of the antifouling paint composition of the present invention and the antifouling paint composition contains the solvent (M), for example, the antifouling paint composition of the present invention applied on the substrate may be, And drying or curing using a drying means such as a heater (i.e., removing the solvent M).

Further, the antifouling substrate of the present invention comprises a substrate and an antifouling coating film of the present invention formed on the surface of the substrate, and the antifouling coating composition of the present invention is applied to a substrate (the substrate is also an object of antifouling or an object to be coated) The coating composition applied or impregnated onto the substrate by applying or impregnating the coating composition using a coating means such as an air spray, an airless spray, a brush, a roller, or the like, for example, Followed by drying and curing using a drying means to form an antifouling coating film on the substrate.

Alternatively, the antifouling substrate of the present invention can be produced by forming an antifouling coating film on the surface of the temporary substrate from the antifouling coating composition of the present invention, peeling the antifouling coating film from the temporary substrate, and attaching the antifouling coating film to the substrate. At this time, the antifouling coating film may be pasted on the substrate through the adhesive layer.

The substrate is not particularly limited, but is preferably a substrate which is in contact with seawater or fresh water. Specifically, it is used as a substrate for various power plants (thermal power, atomic power) such as water supply and drainage, manzan road, seabed tunnel, (Such as the sea floor from the ship's draft), fishery materials (fishing ropes, fish nets, floats, buoys, etc.), and the like.

As a material of these substrates, steel, aluminum, wood, FRP and the like can be mentioned particularly in the case of a marine outer plate. Natural or synthetic fibers can be mentioned in the case of fishing nets, and in the case of floats and buoys, And the material thereof is not particularly limited as long as it is a substrate which is required to have antifouling property in water.

When the surface of these substrates is, for example, in the bottom of the base, the surface of the primer-treated substrate after the primer such as the anticorrosive paint is usually applied on the surface of the base made of steel is coated with the antifouling paint composition (Antifouling paint) is applied, and the antifouling paint composition is applied or impregnated (the impregnation is carried out especially when the base material is a fishing nets, etc.). When the antifouling coating composition is formed to form an antifouling coating film, (D), the organic antifouling agent (E), and the like) to the antifouling coating film is excellent, and the antifouling coating film has excellent antifouling properties (for example, ), The antifouling component can be released for a long period of time.

Usually, the surface of the base material may have a layer formed by primer treatment or a layer formed by various binder coatings. In the case where the base material is a marine outer plate (particularly, its bottom), an underwater structure, etc., the antifouling paint composition is applied to the surface of the base material a plurality of times (hereinafter also referred to as thick coating), and the dried film thickness of the formed coating film is about 100 to 600 μm .), The obtained antifouling base exhibits excellent antifouling property, appropriate flexibility and excellent crack resistance.

When the substrate is a deteriorated antifouling coating film-coated steel sheet, a fishing net or the like in the production of the antifouling substrate, the antifouling coating composition of the present invention may be applied directly to the surface of the substrate. Alternatively, The base material may be impregnated with an antifouling paint composition. If the base material is a steel sheet raw material, a base material such as a rust preventive agent or a primer is previously applied to the surface of the base material to form a base layer, The antifouling paint composition of the present invention may be applied. Further, the antifouling coating film of the present invention may be additionally formed on the surface of the antifouling coating film or the base material on which the conventional antifouling coating film is formed for the purpose of pluralities.

The thickness of the antifouling coating film of the present invention formed by one coating operation is not particularly limited, but is about 30 to 250 占 퐉, for example, when the substrate is a ship or an underwater structure.

The underwater structure having an antifouling coating film of the present invention can keep the function of an underwater structure for a long period of time due to its ability to prevent adhesion of aquatic organisms over a long period of time. Further, the fishing net having the antifouling coating film of the present invention can prevent clogging of the mesh due to the possibility of environmental pollution as well as prevention of adhesion of aquatic organisms.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[Assessment Methods]

Evaluation of the copolymer, coating composition, coating film and the like to be described later was carried out as follows.

(1) Content of solid content in polymer solution

1.5 g (X ₁ (g)) of the polymer solution was kept in a constant-temperature bath under the conditions of 1 atm and 108 캜 for 3 hours to remove volatile components to obtain solid components (non-volatile components). Subsequently, the amount (X ₂ (g)) of the remaining solid (non-volatile component) was measured, and the content (%) of the solid content contained in the polymer solution was calculated based on the following formula.

Content (%) of solids content = X ₂ / X ₁ 100

(2) Average molecular weight of copolymer

The weight average molecular weight (Mw) of the copolymer was measured using GPC (gel permeation chromatography) under the following conditions.

GPC conditions

Device: " HLC-8120GPC " (manufactured by Tosoh Corporation)

Column: " SuperH2000 + H4000 " (manufactured by Tosoh Corporation, 6 mm (inside diameter), 15 cm (length)

Eluent: tetrahydrofuran (THF)

Flow rate: 0.500 ml / min

Detector: RI

Column thermostatic bath temperature: 40 ° C

Standard material: polystyrene

Preparation of samples: A small amount of calcium chloride was added to the polymer solution prepared in each Production Example, followed by dehydration, and then filtered with a membrane filter to obtain a GPC measurement sample.

(3) Viscosity of polymer solution

The viscosity (unit: mPa 占 퐏) of the polymer solution at a liquid temperature of 25 占 폚 was measured using an E-type viscometer (Toki Sangyo Co., Ltd.).

(4) Coating accelerated deterioration test (evaluation of coating appearance and adhesion)

An epoxy paint (epoxy AC paint, trade name "Banano 500", available from Kikuchi Kogyo Co., Ltd.) was applied onto a sandblasted plate (150 mm x 70 mm x 1.6 mm) with an applicator to a dry film thickness of 150 m (Trade name " SILVAC SQ-K ", manufactured by Chugoku Kogyo Co., Ltd.) was applied on the cured coating film to a dry film thickness of 40 탆 by using an applicator. To prepare a test plate.

Each of the coating compositions of the above Examples and Comparative Examples was applied on a test plate (that is, on a dry film surface formed of a vinyl binder coating) to a dry film thickness of 150 mu m using an applicator and dried at 23 DEG C for 1 day, And the coating composition was applied on the surface of the antifouling coating film to a dry film thickness of 150 mu m and dried at 23 DEG C for 7 days to form an antifouling coating film to prepare a test plate with an antifouling coating film.

The test plate with the antifouling coating film was immersed in artificial seawater at 50 DEG C, and the appearance and adhesion of the antifouling coating film were examined at intervals of one month from the initiation of immersion, based on the following evaluation criteria.

Appearance evaluation

The degree of cracking was visually observed on the antifouling coating film side of the antifouling film-attached test plate and the degree of cracking was rated according to JIS K5600-8-4 as shown in the following table.

Adhesion evaluation

Using an NT cutter, four pieces of cutting lines were placed on the surface of the antifouling coating film on the antifouling coating film surface at intervals of 4 mm on each side of the antifouling coating film. Nine squares were formed on the surface of the antifouling coating film and Cellotape (registered trademark) After squeezing, the tape was rapidly peeled from the cell and the squares were observed. Subsequently, the area (hereinafter also referred to as " remaining area of coating film ") of the coating film remaining in the quadrangle after the peeling operation in the case where the area of the nine squares is 100% is calculated, The adhesion was evaluated on the basis.

[Evaluation Criteria of Adhesion]

0: Remaining area of the coating film is 95% or more.

1: Remaining area of the coating film is less than 75 to 95%.

2: the residual area of the coating film is less than 50 to 75%.

3: Remaining area of the coating film is less than 50%.

(5) Internal exposure test (evaluation of external appearance of coating film)

An epoxy paint (epoxy AC paint, trade name "Banano 500", available from Kikuchi Kogyo Co., Ltd.) was applied onto a sandblasted plate (150 mm x 70 mm x 1.6 mm) with an applicator to a dry film thickness of 150 m (Trade name " SILVAC SQ-K ", manufactured by Chugoku Kogyo Co., Ltd.) was applied on the cured coating film to a dry film thickness of 40 탆 by using an applicator. And dried at room temperature for 1 day to prepare a test plate.

Subsequently, the coating compositions of the above Examples and Comparative Examples were applied on the test plate (that is, on the cured coating film surface formed of the vinyl binder coating) the following day to have a dry film thickness of 150 mu m using an applicator and dried at 23 DEG C for 1 day The antifouling coating film was formed on the surface of the antifouling coating film so as to have a dry film thickness of 150 mu m, followed by drying at 23 DEG C for 7 days to form an antifouling coating film.

This antifouling coating film-attached test plate was installed on an outdoor exposure bench installed in the site of Chiku Kogyo Co., Ltd., Otake-shi, Hiroshima City, with the antifouling coating film side facing upward and inclined at an angle of 45 ° with respect to the ground, The state of the coating film was observed after 1, 3, and 6 months from the start of exposure.

(6) Static Fouling Test

An epoxy paint (epoxy AC paint, trade name " BANNO 500 ", manufactured by Chukogyo Kogyo Co., Ltd.) was applied on a sandblasted plate (300 mm x 100 mm x 3.2 mm) with an applicator to a dry film thickness of 150 m (Trade name " Silax SQ-K ", manufactured by Chugoku Kogyo K.K.) was coated on the cured coating film so as to have a dry film thickness of 40 mu m, And dried for 1 day to prepare a test plate.

Subsequently, the coating compositions of the above Examples and Comparative Examples were applied on a test plate (that is, on a dry film surface formed of a vinyl binder coating) the following day to have a dry film thickness of 150 mu m using an applicator and dried at 23 DEG C for 1 day, The antifouling coating film was formed on the surface of the antifouling coating film so as to have a dry film thickness of 150 mu m and dried at 23 DEG C for 7 days to prepare a antifouling coating film adhesion test board.

The area of the area where the aquatic organisms on the antifouling coating film are adhered (hereinafter referred to as " area of the antifouling coating film " when the total area of the antifouling coating film of the test plate is 100% (Also referred to as " adhesion area ") (%) was measured, and the stainproofing property was evaluated based on the following evaluation criteria.

[Evaluation standard]

0: The attachment area is 0%.

0.5: The adhesion area is less than 0 to 10%.

1: The adhesion area is less than 10 to 20%.

2: The attachment area is less than 20 ~ 30%.

3: The attachment area is less than 30 ~ 40%.

4: The attachment area is less than 40 to 50%.

5: The mounting area is 50 to 100%.

(7) Coating film consumption test

Each of the coating compositions obtained in Examples and Comparative Examples was applied to a hard vinyl chloride plate (50 mm x 50 mm x 1.5 mm) with an applicator so as to have a dry film thickness of 150 mu m and dried to prepare a test plate. The obtained test plate was mounted on a rotary drum, and the rotary drum was immersed in seawater and rotated at a peripheral speed of 15 knots under a condition of a seawater temperature of 25 DEG C to measure the consumable film thickness for 12 months at an interval of one month from the start of immersion, Respectively.

[Production Example A1]

53 parts by weight of xylene was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen introduction tube and a dropping funnel, and while stirring the xylene under a nitrogen atmosphere, the mixture was heated under atmospheric pressure until the temperature of the xylene in the reaction vessel reached 85 캜 Respectively. 60 parts by weight of TIPSMA (triisopropylsilyl methacrylate), 10 parts by weight of MEMA (2-methoxyethyl methacrylate) and 20 parts by weight of MMA (methyl methacrylate) while maintaining the temperature of the xylene in the reaction vessel at 85 占 폚. , 10 parts by weight of BA (butyl acrylate) and 1 part by weight of AMBN (2,2'-azobis (2-methylbutyronitrile)) was added to the reaction vessel over 2 hours using a dropping funnel Respectively.

Subsequently, 0.5 part by weight of t-butyl peroxyoctoate was further added to the reaction vessel, and stirring of the liquid in the reaction vessel with a stirrer was continued for 2 hours while maintaining the liquid temperature in the reaction vessel at 85 캜 under atmospheric pressure. Further, the liquid temperature in the reaction vessel was elevated from 85 DEG C to 110 DEG C, stirring was performed for 1 hour, and then 14 parts by weight of xylene was added to the reaction vessel. Then, the liquid temperature in the reaction vessel was lowered and stirring was stopped when the liquid temperature reached 40 DEG C, To obtain a polymer solution A1 containing a methacrylate copolymer.

Various physical properties of the polymer solution A1 were measured. The results are shown in Table 2.

[Production Examples A2 to A9 and Production Examples B1 to B2]

A polymer solution containing a silyl (meth) acrylate copolymer was prepared in the same manner as in Production Example A1, except that a monomer mixture having the composition shown in Table 2 or 3 was used in place of the monomer mixture used in Production Example A1 And various physical properties were measured. The results are shown in Tables 2 and 3. In Tables 2 and 3, the polymer solutions A2 to A9 and the polymer solutions B1 to B2 represent the solutions containing the copolymers obtained in Production Examples A2 to A9 and Production Examples B1 to B2, respectively. Further, MEA and EA represent 2-methoxyethyl acrylate and ethyl acrylate, respectively.

[Example 1]

≪ Preparation of antifouling paint composition >

17.8 parts by weight of xylene as a solvent and 0.5 part by weight of trimethylisobutenylcyclohexenecarboxylic acid (1,2,3-trimethyl-5- (2-methylprop-1-en-1-yl) Cyclohex-3-ene-1-carboxylic acid and 1,4,5-trimethyl-2- (2-methylprop- 6.4 parts by weight of a reaction product of 2,6-dimethylocta-2,4,6-triene and methacrylic acid (50% xylene solution) having a main component (not less than 85%) and 16 parts by weight of polymer solution A1 And mixed using a paint shaker until each component was uniformly dispersed or dissolved. 3 parts of talc FC-1, 4 parts of zinc oxide (zinc oxide No. 3), 45 parts of copper oxide NCI301, 0.3 parts of novopharm Red F5RK, 0.3 parts of titanium backing R 2 parts by weight of -5N, 1 part by weight of Coppermadine (copper pyrithione) and 2 parts by weight of Diparron 4200-20X) were added and stirred for 1 hour using a paint shaker to disperse these components.

After dispersing, 2.5 parts by weight of Diparron A630-20X was further added and stirred for 20 minutes using a paint shaker. The mixture was filtered with a filter net (mesh diameter: 80 mesh) to remove the residue, and the filtrate (coating composition A1) ≪ / RTI > Table 4 shows the manufacturing cost of the various additives.

Various properties of the obtained coating composition A1 were evaluated. The results are shown in Table 7.

[Examples 2 to 19 and Comparative Examples 1 to 4]

A coating composition was prepared in the same manner as in Example 1 except that the kinds and amounts of the blending components were changed as shown in Tables 5 to 6, and various physical properties were measured. The results are shown in Tables 7 to 8.

In addition, the coating compositions A2 to A19 and the coating compositions B1 to B4 shown in Tables 5 to 8 show the coating compositions obtained in Examples 2 to 19 and Comparative Examples 1 to 4, respectively.

Claims (12)

(2) derived from a structural unit (1) derived from triisopropylsilyl methacrylate (i), a structural unit derived from 2-methoxyethyl (meth) acrylate (ii), and another monomer having a polymerizable double bond (Excluding triisopropylsilyl methacrylate and 2-methoxyethyl (meth) acrylate). The silyl methacrylate-based copolymer (A) containing the structural unit (3) derived from (iii) Wow,
Trimethylisobutenylcyclohexenecarboxylic acid (B)
And an antifouling paint composition. The method according to claim 1,
Wherein the other monomer (iii) is an ester or a carboxylic acid. The method according to claim 1,
Wherein the proportion of the structural unit (1) in the silyl methacrylate-based copolymer (A) is 30 to 70% by weight. The method according to claim 1,
Wherein the proportion of the structural unit (2) in the silyl methacrylate-based copolymer (A) is 5 to 40% by weight. The method according to claim 1,
The silyl methacrylate ratio (W _A / W _B) of 99, based on weight of the content (W _A) and the content (W _B) of the trimethyl isobutoxy ethenyl cyclohexene carboxylic acid (B) of the copolymer (A) / 1 to 40/60. The method according to claim 1,
An antifouling paint composition further comprising a rosin and / or a monocarboxylic acid compound (excluding trimethylisobutenylcyclohexenecarboxylic acid) (C). The method according to claim 1,
(D), an organic antifouling agent (E), a coloring pigment (F), an extender pigment (G), a pigment dispersant (H), a plasticizer (I), a sagging agent (J) , A dehydrating agent (L), and a solvent (M). An antifouling coating film formed from the antifouling paint composition according to any one of claims 1 to 7. An antifouling substrate having the substrate and the antifouling coating film according to claim 8 provided on the surface of the substrate. 10. The method of claim 9,
An antifouling substrate in contact with seawater or fresh water. 10. The method of claim 9,
Wherein said substrate is an underwater structure, shipboard plate, or fishing vessel. A step of applying or impregnating the antifouling paint composition according to any one of claims 1 to 7 to the surface of the substrate and a step of curing the antifouling paint applied or impregnated to the substrate by the step Or
A step of forming a coating film from the antifouling paint composition and curing the coating film to form an antifouling coating film, and a step of sticking the antifouling coating film to a substrate
A method for producing an antifouling substrate.