Surface treatment agent
A surface treatment agent containing: (A) a water repellent oil repellent polymer having a repeating unit derived from at least one water repellent oil repellent monomer selected from (A1) fluorine-containing monomers and (A2) non-fluorine monomers having a hydrocarbon group with 7-40 carbon atoms; (B) a silicone polymer represented by formula R 53 3 Si—O—[—Si(R 51 ) 2 —O—] a —[—Si(R 51 )(R 52 )—O—] b —SiR 53 3 (wherein each R 51 group independently represents hydrogen, alkyl having 1-20 carbon atoms, aryl having 6-20 carbon atoms or alkoxy having 1-4 carbon atoms; each R 52 independently represents a saturated hydrocarbon group having 23-40 carbon atoms; each R 53 independently represents a hydrogen atom, an alkyl group having 1-20 carbon atoms, an aryl group having 6-20 carbon atoms, an alkoxy group having 1-4 carbon atoms or a saturated hydrocarbon group having 23-40 carbon atoms; a represents an integer of 0 or more; b represents an integer of 1 or more; and (a+b) is 10-200); and (C) a liquid medium.
1. A surface treatment agent comprising:
(A) a water- and oil-repellent polymer having a repeating unit derived from at least one water- and oil-repellent monomer selected from
(A1) a fluorine-containing monomer and
(A2) a fluorine-free monomer having a hydrocarbon group having 7 to 40 carbon atoms,
where the amount of the water- and oil-repellent monomer is 30 to 100 wt % based on the amount of the water- and oil-repellent polymer;
(B) a silicone polymer of the formula:
(R 53 ) 3 Si—O—[—Si(R 51 ) 2 —O—] a —[—Si(R 51 )(R 52 )—O—] b —Si(R 53 ) 3
wherein each R 51 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms,
each R 52 independently represents a saturated hydrocarbon group having 23 to 40 carbon atoms,
each R 53 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a saturated hydrocarbon group having 23 to 40 carbon atoms,
a represents an integer of 0 or more, b represents an integer of 1 or more, and (a+b) is 10 to 200; and
(C) a liquid medium.
2. The surface treatment agent according to claim 1 , wherein
the water- and oil-repellent monomer is the fluorine-containing monomer (A1), and
the fluorine-containing monomer (A1) is a compound of the formula:
CH 2 ═C(—X 11 )—C(═O)—Y 11 —Z 11 —Rf
wherein X 11 is a hydrogen atom, a monovalent organic group or a halogen atom,
Y 11 is —O— or —NH—,
Z 11 is a direct bond or a divalent organic group, and
Rf is a fluoroalkyl group having 1 to 20 carbon atoms.
3. The surface treatment agent according to claim 2 , wherein in the fluorine-containing monomer (A1), X 11 is a hydrogen atom, a methyl group or a chlorine atom, Y 11 is —O—, Z 11 is a direct bond, or an alkylene group having 1 to 20 carbon atoms, and Rf is a perfluoroalkyl group.
4. The surface treatment agent according to claim 2 , wherein in the fluorine-containing monomer (A1), the number of carbon atoms in Rf is 1 to 6.
5. The surface treatment agent according to claim 1 , wherein the water- and oil-repellent monomer is the fluorine-free monomer (A2).
6. The surface treatment agent according to claim 5 , wherein the fluorine-free monomer (A2) is a monomer of the formula:
CH 2 ═C(—X)—C(═O)—Y—R n
wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is a divalent to tetravalent linking group having at least one group selected from —O— and —NH—,
R is a hydrocarbon group having 7 to 40 carbon atoms, and
n is an integer of 1 to 3.
7. The surface treatment agent according to claim 6 , wherein in the fluorine-free monomer (A2), Y is —Y′—, —Y′—C(═O)—, —C(═O)—Y′—, —Y′—C(═O)—Y′—, —Y′—R′—, —Y′—R′—Y′—, —Y′—R′—Y′—C(═O)—, —Y′—R′—C(═O)—Y′—, —Y′—R′—Y′—C(═O)—Y′— or —Y′—R′—Y′—R′—
wherein Y′ is a direct bond, —O— or —NH—, and
R′ is —(CH 2 ) m —, wherein m is an integer of 1 to 5, or —C 6 H 6 -(phenylene group).
8. The surface treatment agent according to claim 1 , wherein the fluorine-free monomer (A2) is at least one monomer selected from the group consisting of a compound of the formula:
CH 2 ═C(—X 1 )—C(═O)—Y 1 —R 1
wherein X 1 is a hydrogen atom, a monovalent organic group or a halogen atom,
Y 1 is —O— or —NH—, and
R 1 is a hydrocarbon group having 7 to 40 carbon atoms;
a compound of the formula:
CH 2 ═C(—X 2 )—C(═O)—Y 2 —Z 1 (—Z 2 —R 2 ) p
wherein X 2 is a hydrogen atom, a monovalent organic group or a halogen atom,
Y 2 is —O— or —NH—,
Z 1 is a direct bond, or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms,
Z 2 each is independently a direct bond, or a divalent to tetravalent linking group having at least one group selected from —O— and —NH—,
R 2 each is independently a hydrocarbon group having 7 to 40 carbon atoms, and
p is 1 or 2; and
a compound of the formula:
R 22 —C(═O)—NH—R 23 —O—R 21
wherein R 21 is an organic residue having an ethylenically unsaturated polymerizable group,
R 22 is a hydrocarbon group having 7 to 40 carbon atoms, and
R 23 is a hydrocarbon group having 1 to 5 carbon atoms.
9. The surface treatment agent according to claim 1 , wherein the fluorine-containing monomer (A1) is at least one compound selected from the group consisting of
CH 2 —C(—H)—C(═O)—O—(CH 2 ) 2 —C 6 F 13 ;
CH 2 ═C(—CH 3 )—C(═O)—O—(CH 2 ) 2 —C 6 F 13 ; and
CH 2 —C(—Cl)—C(═O)—O—(CH 2 ) 2 —C 6 F 13 ; and
the fluorine-free monomer (A2) is at least one compound selected from the group consisting of
stearyl (meth)acrylate and behenyl (meth)acrylate;
palmitic acid amidoethyl acrylate and stearic acid amidoethyl acrylate;
wherein m is an integer of 1 to 5, and n is an integer of 7 to 40, and
a methacrylate having a methyl group at the α-position and an acrylate having a chlorine atom at the α-position in any of the above chemical formulae; and
lauryl (meth)acrylamide, cetyl (meth)acrylamide, stearyl (meth)acrylamide and behenyl (meth)acrylamide.
10. The surface treatment agent according to claim 1 , wherein the amount of the water- and oil-repellent polymer (A) is 0.1 to 60 wt % based on the amount of the surface treatment agent, and
the amount of the silicone polymer (B) is 1 to 100 parts by weight based on 100 parts by weight of the water- and oil-repellent polymer (A).
11. The surface treatment agent according to claim 1 , wherein the water- and oil-repellent polymer further has at least one selected from the group consisting of a repeating unit derived from a fluorine-free non-crosslinkable monomer (A3), and a repeating unit derived from a fluorine-free crosslinkable monomer (A4).
12. The surface treatment agent according to claim 11 , wherein the fluorine-free non-crosslinkable monomer (A3) is at least one compound selected from the group consisting of vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, vinylidene bromide and vinylidene iodide, and
the fluorine-free crosslinkable monomer (A4) is at least one compound selected from the group consisting of diacetone acrylamide, (meth)acrylamide, N-methylolacrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, butadiene, isoprene, chloroprene and glycidyl (meth)acrylate.
13. The surface treatment agent according to claim 1 , wherein in the silicone polymer, none of R 51 and R 53 is an alkyl group having 3 to 22 carbon atoms.
14. The surface treatment agent according to claim 1 , wherein in the silicone polymer, R 51 and R 53 each is independently a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms.
15. The surface treatment agent according to claim 11 , wherein the amount of the water- and oil-repellent monomer is 32 to 98 wt % based on the amount of the water- and oil-repellent polymer (A),
the amount of the fluorine-free non-crosslinkable monomer (A3) is 2 to 68 wt % based on the amount of the water- and oil-repellent polymer, and
the amount of the fluorine-free crosslinkable monomer (A4) is 50 parts by weight or less based on 100 parts by weight of the water- and oil-repellent monomer.
16. The surface treatment agent according to claim 1 , wherein the surface treatment agent is a water- and oil-repellent agent, a soil resistant agent or a soil release agent.
17. The surface treatment agent according to claim 1 , wherein the fluorine-free monomer (A2) does not include behenyl (meth)acrylate.
18. The surface treatment agent according to claim 1 , wherein none of R 51 and R 53 has an alkyl group having 3 to 22 carbon atoms or an unsaturated hydrocarbon group having 8 to 40 carbon atoms.
19. A method for producing the surface treatment agent according to claim 1 , the method comprising:
(i) preparing an aqueous dispersion of a water- and oil-repellent polymer (A) by polymerizing in the presence of a liquid medium a monomer containing at least one water- and oil-repellent monomer selected from
(A1) a fluorine-containing monomer and
(A2) a fluorine-free monomer having a hydrocarbon group having 7 to 40 carbon atoms, the water- and oil-repellent polymer (A) having a repeating unit derived from the water- and oil-repellent monomer in an amount of 30 to 100 wt % based on the amount of the water- and oil-repellent polymer; and
(ii) adding a silicone polymer (B) to the aqueous dispersion of the water- and oil-repellent polymer.
20. A method for producing a treated substrate, the method comprising applying to the substrate the surface treatment agent according to claim 1 .