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

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 R1 to R5 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;
• R6, R7 and R8 each independently represents an alkyl group, Ra or Rb;
• wherein Ra represents
• wherein x represents an integer of 0 to 20;
• and R23 to R27 are the same or different and each represent an alkyl group, and
• Rb represents
• wherein y represents an integer of 1 to 20;
• and R28 and R29 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 R9 to R12 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 R13 to R22 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 R30 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 R31 represents a hydrogen atom or a methyl group, and a, b, m, n and R1 to R5 represent the same meaning as previously mentioned;
• wherein R32 represents a hydrogen atom or a methyl group, and c, d, p and R6 to R8 represent the same meaning as previously mentioned;
• wherein R33 and R34 represent a hydrogen atom or a methyl group, and e, f, g, h, q, r, s and R9 to R12 represent the same meaning as previously mentioned;
• and
• wherein R35 and R36 represent a hydrogen atom or a methyl group, and i, j, k, l, t, u, v, w and R13 to R22 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 R37 represents a hydrogen atom or a methyl group, and M and R30 represent the same meaning as previously mentioned;
• and
• wherein R38 and R39 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.