Antifouling composition, method for its production and article treated therewith
View Patent ↗Antifouling composition containing a fluorocopolymer which contains from 30 to 70 mass % of polymerized units (a′) having a C1-6 perfluoroalkyl group, from 20 to 69 mass % of polymerized units (b′) having an alkylene oxide chain and from 1 to 10 mass % of polymerized units (c′) having an amino group, and which has anionic groups at its main chain terminals. Method of making.
1. An antifouling composition comprising a fluorocopolymer which comprises from 30 to 70 mass % of polymerized units (a′) based on the following monomer (a), from 20 to 69 mass % of polymerized units (b′) based on the following monomer (b) and from 1 to 10 mass % of polymerized units (c′) based on the following monomer (c), and which has anionic groups at its main chain terminals:
monomer (a): a compound represented by F(CF 2 ) s Y—OCOCR═CH 2 , wherein s is an integer of from 1 to 6, R is a hydrogen atom, a C 1-3 alkyl group or a halogen atom, and Y is a C 1-10 alkylene group,
monomer (b): a compound represented by CH 2 ═CR 1 —COO—(R 2 O) q —R 3 , wherein R 1 is a hydrogen atom or a methyl group, R 2 is a C 2-4 alkylene group, R 3 is a hydrogen atom, a C 1-8 alkyl group, a (meth)acryloyl group or a glycidyl group, q is an integer of from 1 to 140, and when q is from 2 to 140, the plurality of —(R 2 O)— present in one molecule may be the same or different from one another,
monomer (c): a compound represented by CH 2 ═CR 4 -M-Q-NR 5 R 6 or CH 2 ═CR 4 -M-Q-N(O)R 5 R 6 , wherein R 4 is a hydrogen atom or a methyl group, M is —COO— or —CONH—, Q is a C 2-4 alkylene group or a C 2-3 alkylene group having some or all of hydrogen atoms substituted by hydroxy groups, each of R 5 and R 6 which are independent of each other, is a benzyl group, a C 1-8 alkyl group or a C 2-3 alkyl group having some or all of hydrogen atoms substituted by hydroxy groups, or R 5 , R 6 and the nitrogen atom may form a piperidino group or a pyrrolidinyl group, or R 5 , R 6 , the oxygen atom and the nitrogen atom may form a morpholino group.
2. The antifouling composition according to claim 1 , wherein the fluorocopolymer further comprises from 1 to 5 mass % of polymerized units (d′) based on the following monomer (d):
monomer (d): a monomer which is copolymerizable with monomers (a), (b) and (c) and which has at least one crosslinkable functional group selected from the group consisting of an isocyanate group, a blocked isocyanate group, an urethane bond, an alkoxysilyl group, an epoxy group, an N-methylol group and an N-alkoxymethyl group, and has no polyfluoroalkyl group.
3. The antifouling composition according to claim 2 , wherein the monomer (d) is a compound having a blocked isocyanate group.
4. The antifouling composition according to claim 1 , wherein as the monomer (b), at least two types of the monomer (b) different in R 2 are used.
5. The antifouling composition according to claim 1 , wherein the anionic groups are carboxy groups.
6. The antifouling composition according to claim 1 , wherein the anionic groups are present in an amount of from 0.1 to 3.0 mass % per 100 mass % of the fluorocopolymer.
7. The antifouling composition according to claim 1 , which comprises the fluorocopolymer and an aqueous medium, wherein the content of a volatile organic solvent is at most 1 mass %.
8. An article treated with the antifouling composition as defined in claim 1 .
9. A method for producing an antifouling composition, which comprises polymerizing a monomer mixture comprising from 30 to 70 mass % of the following monomer (a), from 20 to 69 mass % of the following monomer (b) and from 1 to 10 mass % of the following monomer (c), in the presence of a polymerization initiator having an anionic group and/or a chain transfer agent having an anionic group:
monomer (a): a compound represented by F(CF 2 ) s Y—OCOCR═CH 2 , wherein s is an integer of from 1 to 6, R is a hydrogen atom, a C 1-3 alkyl group or a halogen atom, and Y is a C 1-10 alkylene group,
monomer (b): a compound represented by CH 2 ═CR 1 —COO—(R 2 O) q —R 3 , wherein R 1 is a hydrogen atom or a methyl group, R 2 is a C 2-4 alkylene group, R 3 is a hydrogen atom, a C 1-8 alkyl group, a (meth)acryloyl group or a glycidyl group, q is an integer of from 1 to 140, and when q is from 2 to 140, the plurality of —(R 2 O)— present in one molecule may be the same or different from one another,
monomer (c): a compound represented by CH 2 ═CR 4 -M-Q-NR 5 R 6 or CH 2 ═CR 4 -M-Q-N(O)R 5 R 6 , wherein R 4 is a hydrogen atom or a methyl group, M is —COO— or —CONH—, Q is a C 2-4 alkylene group or a C 2-3 alkylene group having some or all of hydrogen atoms substituted by hydroxy groups, each of R 5 and R 6 which are independent of each other, is a benzyl group, a C 1-8 alkyl group or a C 2-3 alkyl group having some or all of hydrogen atoms substituted by hydroxy groups, or R 5 , R 6 ; and the nitrogen atom may form a piperidino group or a pyrrolidinyl group, or R 5 , R 6 , the oxygen atom and the nitrogen atom may form a morpholino group.
10. The method for producing an antifouling composition according to claim 9 , wherein the monomer mixture further comprises from 1 to 5 mass % of the following monomer (d):
monomer (d): a monomer which is copolymerizable with monomers (a), (b) and (c) and which has at least one crosslinkable functional group selected from the group consisting of an isocyanate group, a blocked isocyanate group, an urethane bond, an alkoxysilyl group, an epoxy group, an N-methylol group and an N-alkoxymethyl group, and has no polyfluoroalkyl group.
11. The method for producing an antifouling composition according to claim 9 , wherein the polymerization initiator having an anionic group is an azo compound having a carboxy group.
12. The antifouling composition according to claim 1 , wherein the amount of anionic groups present in the fluorocopolymer at its main chain terminals is at least 0.1 mass % per 100 mass % of the fluorocopolymer.
13. The antifouling composition according to claim 12 , wherein the amount of anionic groups present in the fluorocopolymer at its main chain terminals is at most 3.0 mass %.
14. The antifouling composition according to claim 12 , wherein the amount of anionic groups present in the fluorocopolymer at its main chain terminals is at most 2.0 mass %.
15. The antifouling composition according to claim 1 , wherein the amount of anionic groups present in the fluorocopolymer at its main chain terminals is at least 0.3 mass % per 100 mass % of the fluorocopolymer.
16. The antifouling composition according to claim 15 , wherein the amount of anionic groups present in the fluorocopolymer at its main chain terminals is at most 3.0 mass %.
17. The antifouling composition according to claim 15 , wherein the amount of anionic groups present in the fluorocopolymer at its main chain terminals is at most 2.0 mass %.