JPH09208860A - Antifouling coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifouling coating material which exhibits a good antifouling effect for a long period of time and is excellent also in safety and sanitation by blending a specific graft copolymer derived from a polyalkylene- silicone copolymer, an antifouling agent, and a solubility modifier. SOLUTION: This coating material comprises a graft copolymer (A) obtained by polymerizing 5-20wt.% unsaturated polymer (a), obtained by reacting a polyalkylene-silicone copolymer represented by formula 1 (wherein R is formula II; X/Y=75/25-25/75; and m/n=85/15-70/30) with a compound having a group capable of reacting with the hydroxyl group of the copolymer and a reactive double bond, with 95-80wt.% ethylenically unsaturated monomer (b) copolymerizable with the copolymer (a); at least one antifouling agent (B) selected among copper-base antifouling agents, nitrogenous sulfur-base antifouling agents, chlorinated antifouling agents, pyridine compounds, and other antifouling agents; and a solubility modifier (C).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling paint used for ship bottoms, fishing nets and the like, especially a graft copolymer of a polyalkylene silicone-copolymer which is hydrolyzed in seawater, a predetermined antifouling agent and a dissolution control agent. Antifouling paint consisting of.

[0002]

2. Description of the Related Art On the surface of an object that is left under the surface of water, such as a structure or a ship bottom, which is left in the so-called seawater for a long time, various kinds of bacteria such as algae, barnacles, slimes, fungi and diatoms are called. As aquatic organisms such as adhere to, grow and multiply, efficient operation of the ship is hindered. Also,
The attachment of aquatic organisms to aquaculture nets and wire nets causes poor growth and death of fish. As a countermeasure, various antifouling paints are applied. As such an antifouling paint, a vehicle composed of a hydrophilic resin such as rosin and a hydrophobic resin such as a vinyl resin or a chlorinated rubber resin is mixed with an antifouling agent, and gradually added to seawater. Antifouling paint using a polymer or copolymer of an organic tin-containing unsaturated monomer that hydrolyzes into water (JP-B-40-21426, JP-B-51-12)
No. 049), or an antifouling paint comprising a graft copolymer of polyalkylene silicone-copolymer which gradually hydrolyzes in seawater, an antifouling agent and an antifouling aid (Japanese Patent Publication No. 7-57787). Are known.

However, although the hydrophilic resin such as rosin and the antifouling agent exhibit the antifouling effect, the antifouling effect is not sufficient, and the rosin and the antifouling agent are eluted. After that, since a resin insoluble in seawater remains on the coating film to form a skeleton layer, there are problems such as adhesion of marine organisms to it and a decrease in the speed of a ship. on the other hand,
Has a good antifouling effect and does not produce a skeleton layer, but it has a safety and hygiene problem that toxic organic tin compounds are eluted into seawater due to hydrolysis and adversely affect seafood. Is an antifouling paint that solves the above problem to some extent, but has the drawback that it cannot exhibit an excellent antifouling effect over a long period of a year.

[0004]

Therefore, the present invention overcomes the problems of conventional antifouling paints, exhibits a good antifouling effect for a long period of time, and is excellent in terms of safety and hygiene. The purpose is to provide dirty paint.

[0005]

[Means for Solving the Problems] In order to achieve such an object, as a result of extensive studies, an antifouling paint using a graft copolymer of polyalkylene silicone-copolymer, which is suggested in the prior art, as a vehicle, In a certain range not specifically shown in the graft copolymer of polyalkylene silicone-copolymer, by using an antifouling agent not specifically shown in, a remarkable antifouling effect is found. Completed the invention. That is, the invention according to claim 1 of the present invention is (b) the general formula (1);

Embedded image An unsaturated group-containing polymer obtained by reacting a compound having a group capable of reacting with the hydroxyl group of the polyalkylene silicone-copolymer and a reactive double bond with the polyalkylene silicone-polymer represented by a) 5 to
A graft copolymer (A) obtained by polymerizing 20% by weight and 95-80% by weight of an ethylenically unsaturated monomer (b) copolymerizable with the polymer (a); Copper oxide;
Copper thiocyanate: Copper-based antifouling agent such as copper powder, zinc dimethyldithiocarbamate; Tetramethylturam disulfide; Nitrogen-containing sulfur antifouling agent such as bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, tetra Chloroisophthalonitrile; N, N-dimethyldichlorophenylurea; chlorine-containing antifouling agents such as dichlorooctylisothiazolone and its inclusion compounds, tetrachloropyridine; zinc pyrithione; pyridine compounds such as pyridinetriphenylborane; other fluorodichloromethylthiophthalimide; dimethyl Phenylfluorodichloromethylthiosulfamide; nonylphenol; one or more antifouling agents (B) selected from the group consisting of antifouling agents such as zinc oxide, and (c) a dissolution controller (C), Antifouling paint consisting of containing Characterized in that there. (1) The polyalkylene silicone copolymer represented by the general formula (1) needs to have an m / n ratio of 85/15 to 70/30. If it exceeds 85/15, blisters and the like will occur in the coating film when it is made into a paint, and the water resistance will be poor, and if it is less than 70/30, the antifouling property will be poor. In addition, the x / y ratio needs to be 75/25 to 25/75. This is because if the x / y ratio exceeds 75/25, the water resistance is poor, and if it is less than 25/75, the erosion (coating film elution property) is poor and the long-term antifouling retention property is poor. The molecular weight of the aliphatic polyether bonded to the side chain of the polyalkylene silicone copolymer is preferably about 1000 to 2500.

(2) Polyalkylene silicone copolymer
Examples of the compound having a group capable of reacting with a hydroxyl group and a reactive double bond include maleic anhydride, acrylic acid, methacrylic acid, acrylic anhydride, methacrylic anhydride, and α, β-unsaturated acid chlorides thereof. Carboxylic acids or their carboxylic acid derivatives can be used. Also,
As the compound, a compound having an isocyanate group and a reactive double bond can be used. In this case, a reaction product obtained by reacting a polyvalent isocyanate having two or more isocyanate groups with a hydroxyl group-containing ethylenically unsaturated monomer is used, and a case where an isocyanate group-containing ethylenically unsaturated monomer is used. Sometimes a quantity is used. In the former case, the polyvalent isocyanate may be hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, diphenylmethane dihydrate. Isocyanate
2,2,4-trimethylhexamethylene diisocyanate
, Cyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, isopropylidene bis (4-cyclohexyl isocyanate), hexamethylene diisocyanate biuret, and isocyanurate ring A compound having two or more isocyanate groups, such as an isophorone diisocyanate trimer, preferably 2,2,4-trimethylhexamethylene diisocyanate.
It is a diisocyanate compound having an isocyanate group having a different reactivity, such as tritium and tolylene diisocyanate. As the hydroxyl group-containing ethylenically unsaturated monomer, those having one hydroxyl group are preferable, and 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate are preferred.
Hydroxyalkyl acrylate such as 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate and the like. Examples thereof include hydroxyalkyl methacrylate, N-methyl acrylamide, N-methyl methacrylamide and the like.

In the latter case, as the isocyanate group-containing polymerizable monomer, an isocyanoalkyl acrylate such as isocyanomethyl acrylate, isocyanoethyl acrylate or isocyanobutyl acrylate is used. G, isocyanomethyl methacrylate, isocyanoethyl methacrylate
And isocyanoalkyl methacrylic acid such as isocyanobutyl methacrylic acid can be used.

(3) As the ethylenically unsaturated monomer (b) to be polymerized with the unsaturated group-containing polymer (a), for example, the following ones can be used.

(B1) 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, methacrylic acid Methyl, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, etc.

(B2) Vinyl aromatic compound; for example, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene and the like.

(B3) Hydroxyl group-containing monomer; eg hydroxyethyl acrylate, hydroxyethyl methacrylate
, Hydroxypropyl acrylate, hydroxypropyl methacrylate, and other acrylic acid or methacrylic acid hydroxyacrylic esters.

(B4) Others: acrylonitrile, methacrylonitrile, vinyl acetate, etc.

These ethylenically unsaturated monomers may be used alone or in combination of two or more. As the monomer, it is preferable to mainly use acrylic ester of acrylic acid or methacrylic acid, styrene, etc. because of excellent coating strength and coating film performance such as salt water resistance.

(4) The graft copolymer of the present invention can be obtained by polymerizing the unsaturated group-containing polymer (a) and the ethylenically unsaturated monomer (b). Here, (a) is 5 to 20% by weight, and (b) is 95 to 80, respectively.
% By weight. When the weight ratio of (a) and (b) is less than 5/95, the erosion property (coating film elution property) of the coating film becomes poor and the long-term antifouling retention property becomes poor. On the other hand, 20/8
If it exceeds 0, the coatability and water resistance of the coating film are poor.

The antifouling agent (B) is a graft copolymer (A).
Elutes as water is hydrolyzed and prevents aquatic organisms from adhering to objects below the surface of the water, but cuprous oxide; thiocyan is the one that exhibits a remarkable antifouling effect in relation to (A). Sun copper; copper-based antifouling agents such as copper powder; zinc dimethyldithiocarbamate; tetramethylturam disulfide; bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate and other nitrogen-containing sulfur antifouling agents, tetrachloro Isophthalonitrile; N, N-dimethyldichlorophenylurea; chlorine-containing antifouling agents such as dichlorooctylisothiazolone and its inclusion compounds, tetrachloropyridine; zinc pyrithione; pyridine compounds such as pyridine-triphenylborane; other fluorodichloromethylthiophthalimide; dimethyl Phenylfluorodichloromethylthiosulfami ; -; a zinc oxide nonylphenol Le. The blending ratio of (B) to (A) is 85.
It is preferably / 15 to 15/85. 15/85
If it is less than 90%, the antifouling retention property is insufficient, and if it is 85/15 or more, it is difficult to form a coating film.

The dissolution regulator (C) has a function of finely adjusting the elution rate of (B) from (A), and includes rosin and rosin compounds such as maleic acid modified rosin, DOP; DBP. TCP; plasticizer such as chlorinated paraffin; polyvinyl alcohol; polyvinyl ether; polyacrylic acid soda; polyamide resin; polylactic acid resin and other water-soluble and slightly water-soluble polymers.

By adopting such a constitution, a coating film using (A) as a vehicle in seawater is affected for a long period of time while undergoing interaction based on its affinity with (B) and the like and the dissolution adjusting function of (C). Along with continuously forming a fresh coating film by gradually hydrolyzing over, the antifouling agent excellent in antifouling effect is gradually eluted. It has an excellent antifouling effect. Therefore, the paint is useful as an antifouling paint for ship bottoms, fishnets and the like.

The invention according to claim 2 is the antifouling paint according to claim 1, wherein the glass transition temperature of the graft copolymer (A) is 20 ° C to 60 ° C.

The glass transition temperature of the graft copolymer (A) is preferably 20 ° C to 60 ° C. When the glass transition temperature is 20 ° C or lower, the water resistance of the coating film is poor and phenomena such as blistering are likely to occur, and when it is 60 ° C or higher, the viscosity of the graft copolymer becomes too high and the coating film has abnormalities such as foaming. There is a tendency for people to easily overcome such phenomena. For aquaculture nets that require flexibility, low glass transition temperature graft copolymers are advantageous, and in locations with large water resistance such as ships,
Graft copolymers with high glass transition temperatures are preferred.

In the invention according to claim 3, the weight average molecular weight of the graft copolymer (A) is 35,000 to 70,
The antifouling paint according to claim 1 or 2, which is 000.

The weight average molecular weight of the graft copolymer (A) is preferably 35,000 to 70,000. If the weight average molecular weight is less than 35,000, the water resistance of the coating film is poor and phenomena such as whitening are likely to occur.
If it exceeds 0, the solubility in water tends to be poor.

In the invention according to claim 4, the dissolution control agent (C) is rosin: a rosin and a rosin compound such as a maleic acid-modified rosin, DOP; DBP; TCP, a plasticizer such as chlorinated paraffin, and polyvinyl alcohol. 4. An antifouling coating composition according to claim 1, which is a water-soluble or slightly water-soluble polymer such as polyvinyl ether, polyacrylic acid soda, polyamide resin, and polylactic acid. To do.

The antifouling agent (B) can be obtained by using the dissolution adjusting agent.
Fine adjustment of the elution rate from the coating film can be effectively performed.

The invention according to claim 5 is such that the ratio of the graft copolymer (A) to the dissolution modifier (C) is 1 in terms of solid content.
It is 00 / 0-60 / 40, It is the antifouling paint according to claim 1, 2, 3 or 4.

The ratio of the graft copolymer (A) to the solubility control agent (C) is 100/0 to 60 / in terms of solid content.
40 is preferable, and particularly preferably 95/5 to 70/30
It is. When the ratio of (A) and (C) is less than 60/40, the solubility of the coating film in water becomes too large, and the dissolution rate of the antifouling agent becomes too high, resulting in a long-term antifouling effect. I can't expect.

[0026]

Embodiments of the present invention will be described below.

The polyalkylene silicone-copolymer graft copolymer (A) is a compound having a group capable of reacting with the hydroxyl group of the polyalkylene silicone copolymer represented by the general formula (1) and a reactive double bond. 5 to 20% by weight of an unsaturated group-containing polymer (a) obtained by reacting
And an ethylenically unsaturated monomer (b) which is copolymerizable with the polymer (a) (95 to 80% by weight).

Here, (1) The polyalkylene silicone copolymer represented by the general formula (1) can be obtained by reacting a reactive polyorganosiloxane with a polyether.

(2) The unsaturated group-containing polymer (a) is a polyalkylene silicone copolymer, and a compound having a group capable of reacting with the hydroxyl group of the polyalkylene silicone copolymer and a reactive double bond. Is obtained by a known method. In the reaction, 0.01 to 0.55 mol, particularly 0.1 to 0.5 mol of the reactive double bond is added to 100 g of the resulting unsaturated group-containing polymer (a). It is preferable to adjust the charged amounts of both so as to have about 0.4 mol and to react. If it is less than 0.01 mol, subsequent graft copolymerization with an ethylenically unsaturated monomer becomes difficult, while 0.55
This is because if it exceeds the molar amount, gelation tends to occur during polymerization.

One of the compounds having a group capable of reacting with the hydroxyl group of the polyalkylene silicone copolymer and a reactive double bond is a polyvalent isocyanate and the ethylenically unsaturated monomer having a hydroxyl group. It is obtained by reacting with the above. In this case, the former isocyanate group and the latter hydroxyl group are mixed in an equivalent ratio of 1.0 / 0.5 to 1.0 / 0.7. It is preferable to react. At that time, there may be an unreacted hydroxyl group-containing unsaturated monomer. The reaction temperature is usually 0 to 150 ° C, preferably 40 to 100 ° C, and a urethane reaction catalyst such as dibutyltin dilaurate may be used in the reaction. In addition, a polymerization inhibitor such as bis (2-hydroxy-3-t-butyl-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.

(3) Graft polymerization of the ethylenically unsaturated monomer (b) onto the unsaturated group-containing polymer (a) may be carried out, if necessary, with xylene, toluene, methyl isobutyl ketone, butyl acetate, cellosolve acetate, etc. The organic solvent containing no hydroxyl group can be used as a reaction solvent or a diluent solvent. Also,
As the polymerization catalyst, a peroxide radical initiator such as benzoyl peroxide or di-t-butylperoxide, an azo radical initiator such as azobisisobutyronitrile or azobisvaleronitrile, or the like is used. As a method,
Solution polymerization is preferable because it is simple and preferable, but suspension polymerization, bulk polymerization, ionic polymerization, photopolymerization, radiation polymerization and the like can also be used.

(4) The antifouling paint according to the present invention can be produced by kneading and dispersing the thus obtained graft copolymer (A), the antifouling agent and the dissolution regulator.

[0033]

Next, embodiments of the present invention will be described. Less than,
“Parts” means “parts by weight” and “%” means “% by weight”.

Synthesis Example 1 (Polymer (a) containing unsaturated group)
Synthesis of) A polyalkylene silicone copolymer having the composition shown in Table 1 represented by the following general formula was placed in a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer and a nitrogen gas inlet in an amount of 300 parts, and xylene was added. 400 parts and 0.75 part of maleic anhydride were further charged and reacted at 130 ° C. for 2 hours to synthesize an unsaturated vessel-containing polymer (a) having about 0.11 mol of reactive double bond per 100 g of resin. A resin solution (solid content: 45%) containing it was obtained.

[0035]

Embedded image

[Table 1] Synthesis Example 2 (Synthesis of Graft Copolymers 1 to 11) Azobisiso was added to 100 parts of the compounding parts (unsaturated group-containing polymer (a) and ethylenically unsaturated monomer (b)) shown in Table 2. Using 0.5 part of butyronitrile and 0.2 part of di-t-butylperoxide, a graft copolymer (A) was synthesized as follows.

That is, the unsaturated group-containing polymer (a) is shown in Table 2.
Charge the flask so that the compounding part shown in, and then
n-butanol was added to the solid content of the polymer (a) in an amount of 30
Charge the flask so that it becomes%. Then, the temperature was raised to 110 ° C., a mixed solution of the monomer (b) shown in Table 2, azobisisobutyronitrile and di-t-butylperoxide was added dropwise over 2 hours, and then at the same temperature. The temperature was kept for 1 hour, then the temperature was raised to 130 ° C. and the reaction was carried out for 3 hours to obtain a graft copolymer (A). Table 2 shows the weight average molecular weight of the copolymer (A). Further, with respect to the copolymer (A),
Add solvent (xylene) so that the solid content is about 50%,
Table 2 shows the heating residue and the glass transition temperature of the obtained solution (A).

[0037]

[Table 2] Examples 1 to 12 and Comparative Examples 1 to 9 Various antifouling paints were prepared by kneading and dispersing based on the compounding compositions shown in Tables 3 and 4. Then, performance comparisons were conducted according to the performance test items. The test results are summarized in Tables 5 and 6.

[0038]

[Table 3] Here, Comparative Examples 1 to 5 use the antifouling agent described in the above prior art.

Comparative Example 6 is an unsaturated group-containing polymer (a).
And 30% by weight of ethylenically unsaturated monomer (b)
This is an example of a case where the graft copolymer (A) is obtained by blending the composition with the weight%.

In Comparative Example 7, the ratio of Y to X of the polyalkylene silicone copolymer represented by the above general formula (X
In this example, / Y) is 10/90.

Comparative Example 8 is an example in which the glass transition point is 15 ° C.

Comparative Example 9 is an example in which the weight average molecular weight of the graft copolymer (A) is 30,000.

[0043]

[Table 4]

[Table 5]

[Table 6] Performance test items (1) Erosion test Sandpaper-coated 7.5 mm x 20.0 mm x
A 2.0 mm thick steel plate with a tar-epoxy-based paint to a film thickness of 10
The paint was applied once to a thickness of 0 μm, and then a vinyl tar-based ship bottom anticorrosive paint was applied to a thickness of 50 μm. Example 1
18 and the antifouling paints obtained in Comparative Examples 1 to 9 had a film thickness of 10
Coating was performed so as to be 0 μm. The test plate thus obtained was mounted on a rotary tester and the seawater velocity was 1
The drum was rotated so as to have 5 knots, and a rotary test was performed for 3 months, and the difference in initial film thickness and film thickness after aging was measured to evaluate self-polishing property. The conditions of the rotary test are as follows.

Seawater temperature: 26 ° C. Seawater pH: 8.2 (2) Seawater resistance Sandblasted 100 mm × 300 mm × 1.6 m
m to a steel plate, a tar epoxy paint was applied once to a film thickness of 100 μm, and a vinyl tar based ship bottom anticorrosive paint was applied to a thickness of 50 μm. Examples 1-18,
The antifouling paints obtained in Comparative Examples 1 to 9 were applied to a film thickness of 100 μm. The test plate thus obtained was immersed in seawater for 6 months, and then the state of the coating film was evaluated.

(3) Exposure resistance Sandblasted 100 mm x 300 mm x 1.6 m
m to a steel plate, a tar epoxy paint was applied once to a film thickness of 100 μm, and a vinyl tar based ship bottom anticorrosive paint was applied to a thickness of 50 μm. Examples 1-18,
The antifouling paints obtained in Comparative Examples 1 to 9 were applied to a film thickness of 100 μm. After the test plate thus obtained was exposed outdoors for 6 months, the state of the coating film was evaluated.

(4) Recoatability Sandblasted 100 mm x 300 mm x 1.6 m
m to a steel plate, a tar epoxy paint was applied once to a film thickness of 100 μm, and a vinyl tar based ship bottom anticorrosive paint was applied to a thickness of 50 μm. Examples 1-18,
The antifouling paints obtained in Comparative Examples 1 to 9 were applied to a film thickness of 100 μm. The test plate thus obtained was immersed in seawater for 3 months, and then the same type of antifouling paint obtained in Examples 1 to 18 and Comparative Examples 1 to 9 was applied again to a film thickness of 100 μm.
It was painted to be m. Furthermore, after being immersed in seawater for 3 months, the interlayer adhesion was evaluated.

(5) Antifouling property Sandblasted 100 mm x 300 mm x 1.6 m
m to a steel plate, a tar epoxy paint was applied once to a film thickness of 100 μm, and a vinyl tar based ship bottom anticorrosive paint was applied to a thickness of 50 μm. Examples 1-18,
The antifouling paints obtained in Comparative Examples 1 to 9 were applied to a film thickness of 100 μm. The test plate thus obtained was attached to a raft and immersed for 3, 6 and 12 months to evaluate the antifouling property.

[0048]

As described above, the antifouling coating composition of the present invention has a gradual hydrolysis of the graft copolymer (A) forming the vehicle and an affinity between the (A) and the antifouling agent (B). The interaction based on sex, the dissolution control function of the dissolution control agent (C), and the excellent antifouling function of (B) are well meshed, and an excellent antifouling effect on aquatic organisms for a long period of a year is obtained. Demonstrate. Therefore, it is extremely useful for surface coating of ship bottoms, undersea structures, fishing nets, etc.

Claims (5)

[Claims] 1. (a) General formula (1); An unsaturated group-containing polymer obtained by reacting a compound having a group capable of reacting with the hydroxyl group of the polyalkylene silicone-copolymer and a reactive double bond with the polyalkylene silicone-polymer represented by a) 5 to
A graft copolymer (A) obtained by polymerizing 20% by weight and 95-80% by weight of an ethylenically unsaturated monomer (b) copolymerizable with the polymer (a); Copper oxide;
Copper thiocyanate: Copper-based antifouling agent such as copper powder, zinc dimethyldithiocarbamate; Tetramethylturam disulfide; Nitrogen-containing sulfur antifouling agent such as bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, tetra Chloroisophthalonitrile; N, N-dimethyldichlorophenylurea; chlorine-containing antifouling agents such as dichlorooctylisothiazolone and its inclusion compounds, tetrachloropyridine; zinc pyrithione; pyridine compounds such as pyridinetriphenylborane; other fluorodichloromethylthiophthalimide; dimethyl Phenylfluorodichloromethylthiosulfamide; nonylphenol; one or more antifouling agents (B) selected from the group consisting of antifouling agents such as zinc oxide, and (c) a dissolution controller (C), Antifouling paint consisting of containing 2. The antifouling paint according to claim 1, wherein the glass transition temperature of the graft copolymer (A) is 20 ° C. to 60 ° C. 3. The weight average molecular weight of the graft copolymer (A) is 35,000 to 70,000.
Antifouling paint as described. 4. The dissolution regulator (C) is rosin: rosin such as maleic acid-modified rosin and rosin compounds, DOP; DB.
P; TCP; plasticizer such as chlorinated paraffin, polyvinyl alcohol; polyvinyl ether; polyacrylic acid
The antifouling coating composition according to claim 1, which is a water-soluble or slightly water-soluble polymer such as a polyamide resin and a polylactic acid. 5. The antifouling coating composition according to claim 1, wherein the ratio of the graft copolymer (A) to the dissolution regulator (C) is 100/0 to 60/40 in terms of solid content. .