Antifouling composition, method for its production and article treated therewith
View Patent ↗To provide an antifouling composition which is a fluorine-type antifouling composition using a short chain perfluoroalkyl group and which is excellent in antifouling properties and water/oil repellency and presents good durability against washing. An antifouling composition comprising a fluorocopolymer which comprises from 30 to 65 mass % of polymerized units (a) having a C1-6 perfluoroalkyl group, from 1 to 67 mass % of polymerized units (b1) having —(C 2 H 4 O)— and from 3 to 34 mass % of polymerized units (b2) having —(C 4 H 8 O)—, wherein the content of —(C 2 H 4 O)— is from 20 to 65 mass %, and the content of —(C 4 H 8 O)— is from 2 to 13 mass %.
1. An antifouling composition comprising a fluorocopolymer which comprises from 30 to 65 mass % of polymerized units (a) based on the following monomer (a), from 1 to 67 mass % of polymerized units (b1) based on the following monomer (b1) and from 3 to 34 mass % of polymerized units (b2) based on the following monomer (b2), wherein the content of —(C 2 H 4 O)— is from 20 to 65 mass %, and the content of —(C 4 H 8 O)— is from 2 to 13 mass %:
monomer (a): a compound represented by (Z—Y) n X, wherein Z is a C 1-6 perfluoroalkyl group or a monovalent group represented by C m F 2m+1 O(CFWCF 2 O) d CFK— wherein m is an integer of from 1 to 6, d is an integer of from 0 to 4, and each of W and K which are independent of each other, is a fluorine atom or a trifluoromethyl group, Y is a bivalent organic group or a single bond, n is 1 or 2, when n is 1, X is —CR═CH 2 , —COOCR═CH 2 , —OCOCR═CH 2 , —OCH 2 -φ-CR═CH 2 or —OCH═CH 2 , and when n is 2, X is —CH[—(CH 2 ) p CR═CH 2 ]—, —CH[—CH 2 ) p COOCR═CH 2 ]—, —CH[—(CH 2 ) p OCOCR═CH 2 ]—or —OCOCH═CHCOO—, R is a hydrogen atom, a methyl group or a halogen atom, φ is a phenylene group, and p is an integer of from 0 to 4,
monomer (b1): a compound represented by CH 2 ═CR 1 -G 1 -(C 2 H 4 O) q1 —R 2 ,
monomer (b2): a compound represented by CH 2 ═CR 3 -G 2 -(C 2 H 4 O) q2 —(C 4 H 8 O) q3 —R 4 , wherein each of R 1 , R 2 , R 3 and R 4 which are independent of one another, is a hydrogen atom or a methyl group, each of q1 and q3 which are independent of each other, is an integer of from 1 to 50, q2 is an integer of from 1 to 50, each of G 1 and G 2 which are independent of each other, is
—COO(CH 2 ) r — or —COO(CH 2 ) t —NHCOO— wherein r is an integer of from 0 to 4, and t is an integer of from 1 to 4.
2. The antifouling composition according to claim 1 , wherein the fluorocopolymer contains from 2 to 10 mass % of polymerized units (c) based on the following monomer (c):
monomer (c): a compound represented by CH 2 ═CR 5 -M-Q-NR 6 R 7 or CH 2 ═CR 5 -M-Q-N(O)R 6 R 7 , wherein R 5 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 6 and R 7 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 of hydrogen atoms substituted by hydroxy groups, or R 6 , R 7 and the nitrogen atom may form a piperidino group or a pyrrolidinyl group, or R 6 , R 7 , the oxygen atom and the nitrogen atom may form a morpholino group.
3. The antifouling composition according to claim 1 , wherein the fluorocopolymer contains from 1 to 5 mass % of polymerized units (d) based on the following monomer (d):
monomer (d): a monomer which is copolymerizable with the above monomers (a), (b1) and (b2) 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.
4. The antifouling composition according to claim 2 , which contains the fluorocopolymer containing the polymerized units (c) and an aqueous medium, wherein the content of a volatile organic solvent is at most 1 mass %.
5. The antifouling composition according to claim 3 , wherein the monomer (d) is a compound having a blocked isocyanate group.
6. The antifouling composition according to claim 1 , wherein in (Z—Y) n X representing the monomer (a), Z is a C 1-6 perfluoroalkyl group, Y is a bivalent organic group, and n is 1 and X is —OCOCR═CH 2 , or n is 2 and X is —OCOCH═CHCOO— wherein R is a hydrogen atom, a methyl group or a halogen atom.
7. The antifouling composition according to claim 6 , wherein the monomer (a) is F(CF 2 ) s Y 1 —OCOCR═CH 2 wherein s is an integer of from 1 to 6, R is a hydrogen atom, a methyl group or a halogen atom, and Y 1 is a C 1-10 alkylene group.
8. An article treated with the antifouling composition as defined in claim 1 .
9. The antifouling composition according to claim 1 , wherein in monomer (b2) R 3 is a methyl group.
10. The antifouling composition according to claim 1 , wherein in monomer (b2) R 4 is a hydrogen atom.
11. The antifouling composition according to claim 1 , wherein in monomer (b2) q2 and/or q3 is an integer from 2 to 20.
12. The antifouling composition according to claim 1 , wherein monomer (b2) is at least one monomer selected from the group consisting of poly(ethylene oxide-tetramethylene oxide) monoacrylate (CH 2 ═CHCOO-[(EO) q2 -(TO) q3 ]—H), poly(ethylene oxide-tetramethylene oxide) monomethacrylate (CH 2 ═C(CH 3 )COO-[(EO) q2 -(TO) q3 ]—H), methoxypoly(ethylene oxide-tetramethylene oxide) monoacrylate (CH 2 ═CHCOO-[(EO) q2 -(TO) q3 ]—CH 3 ), methoxypoly(ethylene oxide-tetramethylene oxide) monomethacrylate (CH 2 ═C(CH 3 )COO-[(EO) q2 -(TO) q3 ]—CH 3 ).
13. A method for producing an antifouling composition, which comprises polymerizing a monomer mixture comprising from 30 to 65 mass % of the following monomer (a), from 1 to 67 mass % of the following monomer (b1) and from 3 to 34 mass % of the following monomer (b2), wherein the content of —(C 2 H 4 O)— is from 20 to 65 mass %, and the content of —(C 4 H 8 O)— is from 2 to 13 mass %, in the presence of a polymerization initiator in a medium:
monomer (a): a compound represented by (Z—Y) n X, wherein Z is a C 1-6 perfluoroalkyl group or a monovalent group represented by C m F 2m+1 O(CFWCF 2 O) d CFK— wherein m is an integer of from 1 to 6, d is an integer of from 0 to 4, and each of W and K which are independent of each other, is a fluorine atom or a trifluoromethyl group, Y is a bivalent organic group or a single bond, n is 1 or 2, when n is 1, X is —CR═CH 2 , —COOCR═CH 2 ,—OCOCR═CH 2 , —OCH 2 -φ-CR═CH 2 or —OCH═CH 2 , and when n is 2, X is —CH[—(CH 2 ) p CR═CH 2 ]—, —CH[—(CH 2 ) p COOCR═CH 2 ]—, —CH[—CH 2 ) p OCOCR═CH 2 ]— or —OCOCH═CHCOO—, R is a hydrogen atom, a methyl group or a halogen atom, φ is a phenylene group, and p is an integer of from 0 to 4,
monomer (b1): a compound represented by CH 2 ═CR 1 -G 1 -(C 2 H4O) q1 —R 2 ,
monomer (b2): a compound represented by CH 2 ═CR 3 -G 2 -(C 2 H 4 O) q2 —(C 4 H 8 O) q3 —R 4 ,
wherein each of R 1 , R 2 , R 3 and R 4 which are independent of one another, is a hydrogen atom or a methyl group, each of q1 and q3 which are independent of each other, is an integer of from 1 to 50, q2 is an integer of from 1 to 50, each of G 1 and G 2 which are independent of each other, is
—COO(CH 2 ) r — or —COO(CH 2 ) t —NHCOO— wherein r is an integer of from 0 to 4, and t is an integer of from 1 to 4.
14. The method for producing an antifouling composition according to claim 13 , wherein the monomer mixture contains from 2 to 10 mass % of the following monomer (c):
monomer (c): a compound represented by CH 2 ═CR 5 -M-Q-NR 6 R 7 or CH 2 ═CR 5 -M-Q-N(O)R 6 R 7 , wherein R 5 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 6 and R 7 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 of hydrogen atoms substituted by hydroxy groups, or R 6 , R 7 and the nitrogen atom may form a piperidino group or a pyrrolidinyl group, or R 6 , R 7 , the oxygen atom and the nitrogen atom may form a morpholino group.
15. The method for producing an antifouling composition according to claim 13 , wherein the monomer mixture contains from 1 to 5 mass % of the following monomer (d):
monomer (d): a monomer which is copolymerizable with the above monomers (a), (b1) and (b2) 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.
16. The method for producing an antifouling composition according to claim 13 , wherein in monomer (b2) R 3 is a methyl group.
17. The method for producing an antifouling composition according to claim 13 , wherein in monomer (b2) R 4 is a hydrogen atom.
18. The method for producing an antifouling composition according to claim 13 , wherein in monomer (b2) q2 and/or q3 is an integer from 2 to 20.
19. The method for producing an antifouling composition according to claim 13 , wherein monomer (b2) is at least one monomer selected from the group consisting of poly(ethylene oxide-tetramethylene oxide) monoacrylate (CH 2 ═CHCOO-[(EO) q2 -(TO) q3 ]—H), poly(ethylene oxide-tetramethylene oxide) monomethacrylate (CH 2 ═C(CH 3 )COO-[(EO) q2 -(TO) q3 ]—H), methoxypoly(ethylene oxide-tetramethylene oxide) monomethacrylate (CH 2 ═C(CH 3 )COO-[(EO) q2 -(TO) q3 ]—CH 3 ).