JPH07278467A - Antifouling coating composition and antifouling treatment using the same - Google Patents

Abstract

PURPOSE:To obtain an antifouling coating compsn. not requiring addn. thereto of any chemical, having the capability of forming a coating film exhibiting excellent antifouling properties for a long period of time through contact thereof with water and resultant swell, and not carrying exudation of the coating itself and the release of any harmful substance into water. CONSTITUTION:This antifouling coating compsn. comprises a graft copolymer obtd. by copolymerizing monomer mixture of a hydrophilic vinyl monomer of the general formula (wherein R<1> is hydrogen atom or methyl group; R<2> is an alkyl group, phenyl group, or a substd. phenyl group; and (q) is an integer of at least 1), a vinyl monomer having hydroxyl group and a vinyl monomer having carboxyl group as the indispensable components in the presence of a polymer having reactive double bonds on the silicone side chains via ether bonds therebetween.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling coating composition which can be used in a chemical-free type and is particularly suitable for coating supply and drainage channels, and an antifouling treatment method using the same.

[0002]

2. Description of the Related Art Preventing adhesion of barnacles, cell plastics, mussels, algae, etc. to an underwater structure is extremely important for maintaining its function. As a method therefor, a method of applying an antifouling paint on the surface of an underwater structure has been widely used. As such an antifouling paint, a paint using an organotin copolymer that has an antifouling effect on living organisms and is slightly soluble in water, a paint using an antifouling agent such as cuprous oxide, etc. can give. However, when using antifouling paints such as these, harmful substances are eluted in water,
It contributes to marine pollution, and its impact on seafood cannot be ignored. Therefore, there has been a demand for a pollution-free antifouling paint that does not release such harmful substances into water. As such a pollution-free antifouling paint, there is a silicone-based paint using a silicone-modified resin, silicone rubber, silicone oil, etc. (Japanese Patent Publication No. 53-35974).
JP-A-51-96830, JP-A-53-7998
No. 0 publication).

[0003]

These conventionally known antifouling paints all prevent adhesion of aquatic organisms by the lubricity of silicone. However, these paints have problems such as repaintability of the paint film, storage stability of the paint, and maintenance of lubricity. The present inventors, as a result of repeated intensive research on the above problems, by applying a resin that swells to the object to be coated, paying attention to that larvae of aquatic organisms cannot recognize the object to be coated as a base, A composition containing a specific graft copolymer as an antifouling coating resin is very effective, and it has been found that excellent antifouling property can be obtained by applying the composition to an object to be coated, thereby completing the present invention. Came to do.

[0004]

That is, the present invention provides a compound of the general formula (I) in the presence of a polymer (A) having a reactive double bond in the side chain of silicone through an ether bond.

[Chemical 5] (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is an alkyl group, a phenyl group or a substituted phenyl group, and q is an integer of 1 or more), and a hydroxyl group. And an antifouling coating composition containing a graft copolymer obtained by copolymerizing a monomer mixture (B) containing a vinyl monomer having a vinyl group and a vinyl monomer having a carboxyl group as an essential component, and an antifouling coating composition using the same. Regarding the waste treatment method. In the present invention, as the polymer (A) having a reactive double bond in the side chain of silicone via an ether bond, a polymer having a reactive double bond in the side chain via an aliphatic polyether is used. More preferred, especially the general formula (II)

[Chemical 6] (However, R ³ is mainly

[Chemical 7] An organic group consisting of R ⁴ is

[Chemical 8] , A, b, c, l, m and n are the numbers of the respective repeating units, a is an integer of 1 or more, b is an integer of 0 to 25, c is an integer of 0 to 26, and 1 and n are Positive integer, m is 0 or a positive integer, b + c is selected to be 1 or more, and the repeating units in the main chain and side chains are randomly arranged) Those obtained by reacting the copolymer with a compound having a group capable of reacting with the hydroxyl group of the polyalkylene silicone copolymer and a reactive double bond are preferable.

The polyalkylene silicone copolymer represented by the above general formula (II) can be obtained by reacting a reactive polyorganosiloxane with a polyether and optionally polystyrene, and the side chain of the reactive silicone oil. In addition, it has a structure in which an aliphatic polyether and optionally polystyrene are bound. The general formula (II) does not limit the order of arrangement of the repeating units enclosed in parentheses, and naturally includes the case where the repeating units are randomly arranged (see the general formula (II
I) and general formula (IV) as well). The silicone content of the polyalkylene silicone copolymer is preferably 25 to 45% by weight. If the silicone content is outside this range, the surface tension tends to be poor. In addition, since the hardness of the coating film obtained only with the aliphatic polyether tends to be insufficient when bonded to the side chain, polystyrene is further bonded (that is, n is 1 or more) to the coating film obtained. It is preferable to improve hardness. In this case, the value of a in the general formula (II) of polystyrene bonded to the side chain is preferably 1 or more, more preferably 26 or less,
It is particularly preferable that the molecular weight is about 100 to 1000. The terminal of R ^{3 in} the general formula (II) is hydrogen or a polymerization initiator residue introduced at the terminal when a polystyrene oligomer is produced, and does not particularly affect the characteristics of the present compound. Further, the values of b and c in the general formula (II) of the aliphatic polyether bonded to the side chain are such that b is 0 to
It is preferably selected such that an integer of 25, c is an integer of 0 to 26, and b + c is 1 or more, and its molecular weight is 50 to
It is more preferably about 1500. If the molecular weight is out of this range, it is difficult to obtain a proper antifouling property. By reacting the polyalkylene silicone copolymer represented by the general formula (II) with a compound having a group capable of reacting with a hydroxyl group of the polyalkylene silicone copolymer and a reactive double bond, the side chain of the silicone is reactive. The polymer (A) having the double bond of can be produced.

Examples of the compound include maleic anhydride, acrylic acid, methacrylic acid, acrylic acid anhydride, methacrylic acid anhydride, α, β-unsaturated carboxylic acids (anhydrides) such as acid chlorides thereof, or their hydroxyl groups. Preferred examples are those having a sex property. Further, as the compound, a compound having an isocyanato group and a reactive double bond can also be used. In this case, when using a reaction product obtained by reacting a polyvalent isocyanate having two or more isocyanato groups and a hydroxyl group-containing ethylenically unsaturated monomer (the former) and using an isocyanato group-containing ethylenically unsaturated monomer There is a case (the latter). In the case of the former, as the polyvalent isocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, diphenylmethane diisocyanate, 2,
2,4-trimethylhexamethylene diisocyanate,
Cyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, isopropylidene bis (4
-Cyclohexyl isocyanate), a burette of hexamethylene diisocyanate, a trimer of isophorazine diisocyanate containing an isocyanurate ring, and the like, and a compound having two or more isocyanato groups, preferably 2,2,4-trimethylhexa It is a diisocyanate compound having an isocyanato group having different reactivity such as methylene diisocyanate and tolylene diisocyanate.

As the hydroxyl group-containing ethylenically unsaturated monomer, those having one hydroxyl group are preferable, and hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and 2-hydroxybutyl acrylate, and 2 There are hydroxyalkyl methacrylates such as -hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and 2-hydroxybutyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like. The polyvalent isocyanate compound and the hydroxyl group-containing ethylenically unsaturated monomer are blended so that the former isocyanato group / the latter hydroxyl group are in an equivalent ratio of 1.0 / 0.5 to 1.0 / 0.7. It is preferable to react. There may be unreacted hydroxyl group-containing unsaturated monomer. The reaction temperature is usually 0 to 15
0 ° C., preferably 40 to 100 ° C., during the reaction,
A urethane reaction catalyst such as dibutyltin dilaurate may be used. In addition, a polymerization inhibitor such as bis (2-hydroxy-3-tertiarybutyl 5-ethylphenyl) methane or hydroquinone may be present in the reaction. The reaction is preferably carried out in a suitable organic solvent. Examples of the organic solvent include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and cellosolve acetate.

In the latter case, as the isocyanato group-containing polymerizable monomer, isocyanatoalkyl acrylates such as isocyanatomethyl acrylate, isocyanatoethyl acrylate and isocyanatobutyl acrylate, isocyanatomethyl methacrylate, isocyanatoethyl methacrylate, Isocyanatoalkyl methacrylate such as isocyanatobutyl methacrylate can be used. These compounds are 100 g of the resulting polymer (A).
Therefore, it is preferable to react so that the reactive double bond has 0.01 to 0.55 mol, particularly 0.1 to 0.4 mol. If it is less than 0.01 mol, graft polymerization tends to be difficult during subsequent copolymerization with the monomer mixture (B), while if it exceeds 0.55 mol, gelation tends to occur during polymerization. .

Next, the monomer mixture (B) will be described. In the hydrophilic vinyl monomer represented by the general formula (I) used in the present invention, R ² is an alkyl group having 1 to 15 carbon atoms such as a methyl group, an ethyl group, a propyl group, a phenyl group or a methylphenyl group. Group, alkyl-substituted phenyl group such as ethylphenyl group (total carbon number is 7 to 1)
5) and the like, but an alkyl group having 1 to 3 carbon atoms is particularly preferable. Q is 1 or more, which is appropriately determined by R ² .
It is preferably an integer of 2 to 30, and particularly preferably 2 to 9 from the viewpoint of coating film strength. The content of the hydrophilic vinyl monomer represented by the above general formula (I) is preferably 20 to 60% by weight, more preferably 20 to 40% by weight, based on the total monomer mixture (B) used for copolymerization. If the blending amount is small, the coating film does not swell sufficiently, so that the antifouling property tends to be poor, and if the blending amount is large, the strength of the coating film tends to be poor.

As the vinyl monomer having a hydroxyl group,
For example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate,
Preferred examples thereof include hydroxyalkyl esters of acrylic acid or methacrylic acid such as hydroxypropyl methacrylate, and particularly preferred is hydroxyethyl acrylate or hydroxyethyl methacrylate. The blending amount of these is preferably 5 to 40% by weight, more preferably 20 to 30% by weight, based on the total monomer mixture (B) used for the copolymerization, from the viewpoint of coating film characteristics.

As the vinyl monomer having a carboxyl group, unsaturated carboxylic acids such as acrylic acid and methacrylic acid are preferred, and methacrylic acid is particularly preferred from the viewpoint of coating strength. The blending amount of these is preferably 5 to 30% by weight, particularly 10 to 20% by weight, based on the total monomer mixture used for the copolymerization, from the viewpoint of coating film characteristics.

Further, as the component of the monomer mixture (B), as the copolymerizable ethylenically unsaturated monomer other than the above monomers, for example, the following ones can be used. (A) Ester of acrylic acid or methacrylic acid, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, hydrogenated dicyclopentadiene acrylate Derivatives, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, hydrogenated dicyclopentadiene methacrylate derivatives, etc., acrylonitrile, methacrylonitrile, etc. (B) Vinyl aromatic compounds; for example, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene and the like.

These ethylenically unsaturated monomers may be used alone or in combination of two or more. The blending amount of these is preferably 10 to 50% by weight with respect to the total monomer mixture (B) used for the copolymerization, and particularly 1
5 to 30% by weight is preferable. If it is less than 10% by weight, the water solubility of the coating film becomes high, and the coating film tends to be eluted without swelling. If it exceeds 50% by weight, the swelling of the coating film becomes insufficient.

In order to obtain a graft copolymer, the monomer mixture (B) is blended and copolymerized in the presence of the polymer (A). The blending ratio of the polymer (A) and the monomer mixture (B) is (A) 5 to 40% by weight, particularly 10 to 20% by weight in the presence of (B) 95 to 60% by weight, particularly 90 to 8%.
It is preferably 0% by weight. If the amount of the component (A) is less than 5% by weight, the coating film does not swell sufficiently and the antifouling property tends to be poor.

The component (B) is polymerized in the presence of the polymer (A), if necessary, by using an aromatic hydrocarbon such as xylene or toluene, a ketone such as methyl ethyl ketone or methyl isobutyl ketone, methanol, ethanol or isopropanol. , N-butanol and other alcohols, methyl cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve such as cellosolve acetate, carbitol such as butyl carbitol, ethers such as diethylene glycol dimethyl ether, and esters such as ethyl acetate and butyl acetate. A solvent can be used as a reaction solvent or a diluent solvent. As the polymerization catalyst, peroxide radical initiators such as benzoyl peroxide and ditertiary butyl peroxide, and azo radical initiators such as azobisisobutyronitrile and azobisvaleronitrile are used. As the polymerization method, solution polymerization is convenient and preferable, but suspension polymerization, bulk polymerization, ionic polymerization, photopolymerization, radiation polymerization and the like can also be used.

The graft copolymer thus obtained is the main component of the antifouling coating composition of the present invention. The antifouling coating composition of the present invention may be mixed with other known resins (acrylic resin, polysiloxane resin, etc.) to the extent that the good swelling properties of the graft copolymer are not impaired, or a curing agent is used in combination. You can also do it. Examples of the curing agent that can be used in the present invention include melamine resins, resins used as curing agents for phenolic resins, metal chelate compounds,
Examples thereof include epoxy silane, amino silane, polyfunctional amine, isocyanate and the like.

The metal chelate compounds usable in the present invention include aluminum-isopropylate, aluminum-sec-butyrate, mono-sec-butoxyaluminum diisopropylate, aluminum acetylacetonate, aluminum diisopropoxide monoethyl acetate, aluminum. Di-n-butoxide monomethyl acetoacetate, aluminum di-n-butoxide monoethyl acetoacetate, aluminum diisobutoxide monomethyl acetoacetate, aluminum diisobutoxide monoethyl acetoacetate, aluminum di-sec-butoxide monoethyl acetoacetate, aluminum tris (Acetylacetonate), Aluminum tris (ethylacetoacetate), Aluminum monoacetylacetonate Aluminum chelates such as bis (ethylacetoacetate) and alkylacetoacetate aluminum diisopropylate, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, tetrastearyloxytitanium, diisopropoxybis ( Acetylacetonato) titanium, di-n-butoxybis (triethanolaminate) titanium, titanium isopropoxyoctylene glycolate, titanium stearate, and other titanium chelates, zirconium-n-propylate, zirconium-n-butyrate, tetra-n -Zirconium chelates such as butoxyzirconium are preferred.

Preferred examples of the epoxysilane include γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. As aminosilane,
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl)
Preferred examples include γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ- (diethylenetriamino) propyltrimethoxysilane, and γ-ureidopropyltriethoxysisilane. . Preferable examples of the polyfunctional amine include ethylenediamine, diethylenediamine, triethylenediamine, phenylenediamine, and 4,4′-dipyridyl.

Examples of the isocyanate include hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, diphenylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, cyclohexylmethane diisocyanate, methylcyclohexane diisocyanate and isopropylidene bis ( Compounds having two or more isocyanate groups such as 4-cyclohexyl isocyanate, burette of hexamethylene diisocyanate, and trimer of isophorone diisocyanate containing an isocyanurate ring, and these non-blocked isocyanate compounds as an isocyanate blocking agent. Blocked isocyanate compounds are preferred. Examples of the isocyanate blocking agent include phenols such as phenol, m-cresol, xylenol, and thiophenol, alcohols such as methanol, ethanol, butanol, 2-ethylhexanol, cyclohexanol, and ethylene glycol monomethyl ether. , Active hydrogen-containing compounds such as caprolactam, ethyl acetoacetate, diethyl malonate, etc. Among these curing agents, metal chelate compounds and aminosilanes are preferable from the viewpoint of curability, and metal from the viewpoint of long pot life. A chelate compound is particularly preferable, and these curing agents may be used alone or in combination of two or more, as a one-pack type coating composition, or a resin composition containing the above graft copolymer as a main component and cured. Agent and pair Can be used as a combined two-part coating composition. May be used in combination of various antifouling agents, if necessary.

The antifouling coating composition of the present invention thus obtained can be applied to an object to be coated by a known method such as brush coating, roll coating, spray coating or airless spray coating. Further, it can be dried and cured by natural drying, heat drying or the like. INDUSTRIAL APPLICABILITY The antifouling coating composition of the present invention is particularly useful as an antifouling paint having an absorption and drainage channel as an object to be coated, which does not require elution of a coating film.

[0021]

EXAMPLES Examples of the present invention will be described below. Hereinafter, "part" means "part by weight" and "%" means "% by weight". Synthesis Example 1 (Production of Polymer (A)-) The following general formula (III)

[Chemical 9] Polyalkylene silicone copolymer (trade name: FZ2181 manufactured by Nippon Unicar Co., Ltd., hydroxyl value 2)
0, number average molecular weight of about 11,000) was placed in a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen gas inlet, 300 parts, and 400 parts of xylene and 0.75 part of maleic anhydride were further added. The mixture was reacted at 130 ° C. for 2 hours to synthesize a polymer (A)-having a reactive double bond in an amount of about 0.11 mol per 100 g of the resin, and a resin solution (solid content 70%) containing the polymer was obtained.

Synthesis Example 2 (Synthesis of Reaction Product (Grafting Agent) of Tolylene Diisocyanate and 2-Hydroxyethyl Acrylate) In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen gas inlet. Tolylene diisocyanate (TD
I) 63.3 parts, methyl ethyl ketone 29.3 parts, polymerization inhibitor AW-500 (Kawaguchi Chemical Co., Ltd. product name, methylenebis (2-ethyl-4-t-butylphenol) 0.1)
60 parts of dibutyltin dilaurate 60 parts
2-Hydroxyethyl acrylate 3 while keeping warm at ℃
After 6.7 parts was dropped over 1 hour, the mixture was reacted at the same temperature for 1 hour to obtain a grafting agent. A solvent (methyl ethyl ketone) was added to the obtained grafting agent so that the solid content was about 70%. The resulting grafting agent had a heating residue of 70.
The viscosity was 6%, the viscosity (Gardner / 25 ° C.) A ⁻ , and the number of colors (Gardner) was 1 or less.

Synthetic Example 3 (Production of Polymer (A)-) The polyalkylene silicone copolymer FZ2181 (manufactured by Nippon Unicar Co., Ltd.) used in Synthetic Example 1 was thermometer, reflux condenser, stirrer and nitrogen gas inlet. Charge 300 parts and 400 parts of xylene into a four-necked flask equipped with
The temperature was raised to 0 ° C. Then, 50 parts of the grafting agent obtained in Synthesis Example 2 was added and reacted for 2 hours to synthesize a polymer (A)-having a reactive double bond in an amount of about 0.35 mol per 100 g of the resin. Resin solution containing (solid content 50
%) Was obtained.

Synthesis Example 4 (Production of Polymer (A)-) The following general formula (IV)

[Chemical 10] A polyalkylene silicone copolymer (trade name: F-264-36, manufactured by Nippon Unica Co., Ltd., number average molecular weight: about 7,000) represented by is equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen gas inlet. 300 parts of xylene and 400 parts of xylene were charged into a one-necked flask and the temperature was raised to 130 ° C. Then, 70 parts of the grafting agent obtained in Synthesis Example 2 was added and reacted for 2 hours to synthesize a polymer (A)-having a reactive double bond in an amount of about 0.5 mol per 100 g of the resin. A resin solution containing 50% solids was obtained.

Examples 1 to 4 and Comparative Examples 1 and 2 (Production of Graft Copolymer) 2,2 'based on 100 parts of the compound (polymer (A), monomer mixture (B)) shown in Table 1 -A graft copolymer was prepared as follows using 0.5 part of azobisisobutyronitrile. That is, Synthesis Example 1, 3 or 4
The resin solution obtained in 1. was charged into a flask so that the solid content shown in Table 1 was obtained (however, Comparative Example 2 was not charged), and then n-butanol was added to the solid content of the resin solution to 300 times.
% (However, in Comparative Example 2, 55 parts of n-butanol was charged). After that, the temperature was raised to 110 ° C., and a mixture of the monomer mixture (B) and 0.5 parts of 2,2′-azobisisobutyronitrile having the composition shown in Table 1 was added dropwise over 2 hours, and then the same temperature was applied. Keep it warm for 1 hour, then 1
The temperature was raised to 30 ° C. and the reaction was carried out for 3 hours to obtain a graft copolymer. A solvent (1-butanol) was added to the obtained graft copolymer so that the solid content was about 40%. The viscosity and acid value are shown together in Table 1.

[0026]

[Table 1]

Evaluation of Antifouling Property The graft copolymer shown in Table 1 was treated with SM of 7 cm × 20 cm.
It was applied to a C (sheet molding compound) plate so as to have a dry film thickness of 40 μm, dried at 100 ° C. for 3 hours, and then immersed in seawater for 12 months. Table 2 shows the results of the immersion test.

[0028]

[Table 2]

Example 5 A coating composition was prepared by adding 40 g of a 10 wt% xylene solution of titanium chelate (T-50, manufactured by Nippon Soda Co., Ltd.) to 100 g of the graft copolymer of Example 3. . Example 6 An aluminum chelate (trade name ALCH-TR, manufactured by Kawaken Fine Chemicals Co., Ltd.) was added to 100 g of the graft copolymer of Example 3.
40 g of a 10% by weight xylene solution of the above) was added to produce a coating composition. Example 7 15 g of a 3 wt% xylene solution of aminosilane (trade name A-1122, manufactured by Nippon Unicar Co., Ltd.) was added to 100 g of the graft copolymer of Example 3 to prepare a coating composition.

Example 8 15 g of a 3 wt% xylene solution of epoxysilane (trade name A-187, manufactured by Nippon Unicar Co., Ltd.) was added to 100 g of the graft copolymer of Example 3 to prepare a coating composition. Example 9 20 g of a 1 wt% xylene solution of ethylenediamine was added to 100 g of the graft copolymer of Example 3 to prepare a coating composition.

Evaluation of Antifouling Property 2 The coating compositions shown in Examples 5 to 9 were applied to a 7 cm × 20 cm SMC (sheet molding compound) plate so as to have a dry film thickness of 40 μm, and then at 20 ° C. for 24 hours. After drying, it was immersed in seawater for 12 months. Table 3 shows the results of the immersion test.

[0032]

[Table 3]

[0033]

The antifouling coating composition of the present invention exhibits excellent antifouling property for a long period of time by swelling when contacted with water. Further, since it is not necessary to elute the coating film itself or to add chemicals, it does not release harmful substances into water, so that it is extremely useful especially as a pollution-free antifouling coating composition for water supply and drainage channels.

Claims (10)

[Claims] 1. In the presence of a polymer (A) having a reactive double bond in the side chain of silicone via an ether bond,
General formula (I) (Wherein, R ¹ is a hydrogen atom or a methyl group, R ² is an alkyl group, a phenyl group or a substituted phenyl group, and q is an integer of 1 or more), and a hydroxyl group. An antifouling coating composition comprising a graft copolymer obtained by copolymerizing a monomer mixture (B) containing, as an essential component, a vinyl monomer having a carboxyl group and a vinyl monomer having a carboxyl group. 2. The polymer (A) has the general formula (II): (However, R ³ is mainly An organic group consisting of R ⁴ is a, b, c, l, m and n are the numbers of the respective repeating units, a is an integer of 1 or more, b is an integer of 0 to 25, c is an integer of 0 to 26, and 1 and n are positive. , M is 0 or a positive integer, b + c is selected to be 1 or more, and the repeating units in the main chain and side chains are randomly arranged). The antifouling coating composition according to claim 1, which is obtained by reacting a compound having a group capable of reacting with a hydroxyl group of the polyalkylene silicone copolymer and a reactive double bond. 3. The graft copolymer is a polymer (A) 5-5.
Monomer mixture (B) 95-6 in the presence of 40% by weight
The antifouling coating composition according to claim 1 or 2, which is obtained by copolymerizing 0% by weight. 4. The monomer mixture (B) has the general formula (I):
The antifouling coating according to claim 1, 2 or 3, which comprises 20 to 60% by weight of the hydrophilic vinyl monomer represented by the formula, 5 to 40% by weight of a vinyl monomer having a hydroxyl group, and 5 to 30% by weight of a vinyl monomer having a carboxyl group. Composition. 5. The method according to claim 1, further comprising a curing agent.
The antifouling coating composition as described in 3 or 4. 6. A two-pack type antifouling coating composition comprising a combination of a main agent containing the graft copolymer according to claim 1, 2, 3 or 4 and a hardening agent. 7. The antifouling coating composition according to claim 5, wherein the curing agent is a metal chelate compound. 8. The antifouling coating composition according to claim 5, wherein the curing agent is aminosilane or epoxysilane. 9. The curing agent is a polyfunctional amine.
Or the antifouling coating composition as described in 6 above. 10. A method for antifouling treatment, which comprises applying the composition according to any one of claims 1 to 9 to an object to be coated.