Antifouling coating composition, antifouling film, composite film, and in-water structure

1. An antifouling coating composition, comprising:

a hydrolyzable resin having at least one kind of silicon-containing group selected from the group consisting of the groups represented by the following general formulas (I), (II), (III) and (IV) and a metal-atom-containing group containing a divalent metal atom M; and

a thermoplastic resin and/or a plasticizer,

wherein said thermoplastic resin is at least one kind selected from the group consisting of chlorinated paraffin, polyvinyl ether, rosin, and a vinyl chloride-isobutyl vinyl ether copolymer,

wherein said plasticizer is at least one kind selected from the group consisting of a phthalate ester plasticizer and a phosphate ester plasticizer,

wherein the total content of said thermoplastic resin and/or plasticizer is 3 to 100 parts by mass per 100 parts by mass of said hydrolyzable resin:

wherein a and b each independently represents an integer of 2 to 5, m represents an integer of 0 to 50, and n represents an integer of 3 to 80; and R 1 to R 5 each independently represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group or a substituted phenoxy group;

wherein c and d each independently represents an integer of 2 to 5, and p represents an integer of 0 to 50; R 6 , R 7 and R 8 each independently represents an alkyl group, R a or R b ;

wherein R a represents

wherein x represents an integer of 0 to 20; and R 23 to R 27 are the same or different and each represent an alkyl group, and

R b represents

wherein y represents an integer of 1 to 20; and R 28 and R 29 are the same or different and each represent an alkyl group;

wherein e, f, g and h each independently represents an integer of 2 to 5, q and s each independently represents an integer of 0 to 50, and r represents an integer of 3 to 80; and R 9 to R 12 each independently represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group or a substituted phenoxy group;

wherein i, j, k and l each independently represents an integer of 2 to 5, t and u each independently represents an integer of 0 to 50, and v and w each independently represents an integer of 0 to 20; and R 13 to R 22 are the same or different and each represents an alkyl group;

wherein said metal-atom-containing group is at least one kind of group selected from the group consisting of the groups represented by the following general formulas (V) and (VI):

wherein M represents a divalent metal atom, and R 30 represents an organic acid residue; and

wherein M represents a divalent metal atom;

wherein said hydrolyzable resin is a resin comprising:

a constituent unit derived from at least one kind of silicon-containing polymerizable monomer (a) selected from the group consisting of: a monomer (a1) represented by the following general formula (I′), a monomer (a2) represented by the following general formula (II′), a monomer (a3) represented by the following general formula (III′) and a monomer (a4) represented by the following general formula (IV′); and

a constituent unit derived from a metal-atom-containing polymerizable monomer (b) containing a divalent metal atom M:

wherein R 31 represents a hydrogen atom or a methyl group, and a, b, m, n and R 1 to R 5 represent the same meaning as previously mentioned;

wherein R 32 represents a hydrogen atom or a methyl group, and c, d, p and R 6 to R 8 represent the same meaning as previously mentioned;

wherein R 33 and R 34 represent a hydrogen atom or a methyl group, and e, f, g, h, q, r, s and R 9 to R 12 represent the same meaning as previously mentioned; and

wherein R 35 and R 36 represent a hydrogen atom or a methyl group, and i, j, k, l, t, u, v, w and R 13 to R 22 represent the same meaning as previously mentioned;

wherein said metal-atom-containing polymerizable monomer (b) includes at least one kind selected from the group consisting of a monomer (b1) represented by the following general formula (V′) and a monomer (b2) represented by (VI′):

wherein R 37 represents a hydrogen atom or a methyl group, and M and R 30 represent the same meaning as previously mentioned; and

wherein R 38 and R 39 represent a hydrogen atom or a methyl group, and M represents the same meaning as previously mentioned;

wherein the ratio between the content of said constituent unit derived from the silicon-containing polymerizable monomer (a) and the content of said constituent unit derived from the metal-atom-containing polymerizable monomer (b) containing a divalent metal atom M is in the range of 45/55 to 85/15 by mass ratio.

2. An antifouling film formed from the antifouling coating composition according to claim 1 .

3. A ship having the antifouling film according to claim 2 .

4. A composite film having a primer film formed from an antirust paint, and an antifouling film formed from the antifouling coating composition according to claim 1 , overlaid on said primer film.

5. An in-water structure having the antifouling film according to claim 4 .

6. The composite film according to claim 4 , further having an intermediate film formed on an entire or part of a surface of said primer film between said primer film and said antifouling film.

7. The composite film according to claim 6 , wherein said intermediate film is a coating film formed from an antifouling coating composition containing an antifouling agent.