Fluorine-containing polymer and surface treatment agent
A fluorine-containing polymer including a repeat unit derived from a fluorine-containing monomer (A1) and a repeat unit derived from a hydrocarbon group-bearing fluorine-free monomer (A2). The fluorine-free monomer (A2) is preferably at least one monomer selected from (A2-1) R 22 —C(═O)—NH—R 23 —O—R 21 , (A2-2) CH 2 ═C(—R 32 )—C(═O)—Y 31 —Z 31 (—Y 32 —R 31 ) n , and (A2-3) X 41 N(H) r —R 41 . Also disclosed is a surface treatment agent containing (A) the fluorine-containing polymer and (B) a liquid medium, as well as a method for producing the surface treatment agent and a method for producing a treated substrate.
1. A surface treatment agent comprising:
(A) a fluorine-containing polymer,
(B) a liquid medium, and
(C) a surfactant comprising a nonionic surfactant;
wherein the surface treatment agent is an aqueous dispersion in which the fluorine-containing polymer (A) is dispersed in water or a mixture of water and an organic solvent, and
wherein the fluorine-containing polymer (A) comprises:
a first side chain having a fluoroalkyl group having 1 to 20 carbon atoms, and
a second side chain having a monovalent hydrocarbon group having 7 to 40 carbon atoms, wherein
the second side chain has a divalent —NH— group or a trivalent —N═ group between the monovalent hydrocarbon group and a backbone chain, and
the backbone chain is a backbone chain derived from an ethylenically unsaturated polymerizable group.
2. A surface treatment agent comprising:
(A) a fluorine-containing polymer,
(B) a liquid medium, and
(C) a surfactant comprising a nonionic surfactant;
wherein the surface treatment agent is an aqueous dispersion in which the fluorine-containing polymer (A) is dispersed in water or a mixture of water and an organic solvent,
wherein the fluorine-containing polymer (A) comprises:
(A1) a repeating unit derived from a fluorine-containing monomer which is an ethylenically unsaturated monomer having a fluoroalkyl group having 1 to 20 carbon atoms, and
(A2) a repeating unit derived from a fluorine-free monomer which is an ethylenically unsaturated monomer having a monovalent hydrocarbon group having 7 to 40 carbon atoms and a divalent —NH— group or a trivalent —N=group.
3. A surface treatment agent comprising:
(A) a fluorine-containing polymer,
(B) a liquid medium, and
(C) a surfactant comprising a nonionic surfactant;
wherein the surface treatment agent is an aqueous dispersion in which the fluorine-containing polymer (A) is dispersed in water or a mixture of water and an organic solvent, and
wherein the fluorine-containing polymer (A) comprises (A1) a repeating unit derived from a fluorine-containing monomer, and (A2) a repeating unit derived from a fluorine-free monomer having a hydrocarbon group, wherein
the fluorine-containing monomer (A1) is a compound represented by 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, and
the fluorine-free monomer having a hydrocarbon group (A2) is at least one monomer selected from the group consisting of
(A2-1) an amide group-containing monomer represented by 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,
(A2-2) a nitrogen-containing monomer represented by formula:
CH 2 =C (—R 32 )—C(═O)—Y 31 —Z 31 (—Y 32 —R 31 ) n
wherein R 31 is a hydrocarbon group having 7 to 40 carbon atoms,
R 32 is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom,
Y 31 is —O— or —NH—,
Y 32 is —O—C(═O)—NH— or —NH—C(═O)—O— or —NH—C(═O)—NH—,
Z 31 is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and
n is 1 or 2, and
(A2-3) an acrylamide monomer represented by formula:
X 41 N (H) r —R 41
wherein R 41 is a hydrocarbon group having 7 to 40 carbon atoms,
X 41 is a monovalent group which is CH 2 —C(—R 42 )—C(—O)— wherein R 42 is a hydrogen atom or a methyl group, or a divalent group which is —C(═O)—CH═CH—C(═O)—, and
r is 0 when X 41 is divalent, or is 1 when X 41 is monovalent.
4. The surface treatment agent according to claim 3 , 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 having 1 to 8 carbon atoms.
5. The surface treatment agent according to claim 2 , 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 ,
the fluorine-free monomer (A2-1) is at least one compound selected from the group consisting of palmitic acid amidoethyl (meth)acrylate and stearic acid amidoethyl (meth)acrylate,
the fluorine-free monomer (A2-2) is at least one compound selected from the group consisting of
the fluorine-free monomer (A2-3) is at least one compound selected from the group consisting of lauryl (meth)acrylamide, cetyl (meth)acrylamide, stearyl (meth)acrylamide, behenyl (meth)acrylamide, N-lauryl maleimide, N-cetyl maleimide, N-stearyl maleimide, and N-behenyl maleimide.
6. The surface treatment agent according to claim 2 , wherein the fluorine-containing polymer (A) further has a repeating unit derived from a further monomer (A3) other than the monomers (A1) and (A2), and
the further monomer (A3) is at least one selected from the group consisting of
(A3-1) a repeating unit derived from a fluorine-free non-crosslinkable monomer, and
(A3-2) a repeating unit derived from a fluorine-free crosslinkable monomer.
7. The surface treatment agent according to claim 6 , wherein the fluorine-free non-crosslinkable monomer (A3-1) is a compound represented by formula:
CH 2 =CA-T
wherein A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom,
T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 40 carbon atoms, or a chain or cyclic organic group having 1 to 41 carbon atoms and having an ester bond.
8. The surface treatment agent according to claim 6 , wherein
the fluorine-free non-crosslinkable monomer (A3-1) is at least one compound selected from the group consisting of stearyl (meth)acrylate and behenyl (meth)acrylate, and/or 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 (A3-2) is at least one compound selected from the group consisting of diacetone acrylamide, (meth)acrylamide, N-methylol acrylamide, 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.
9. The surface treatment agent according to claim 6 , wherein an amount of the fluorine-containing monomer (A1) is 0.1 to 95% by weight, an amount of the fluorine-free monomer (A2) is 0.1 to 95% by weight, and an amount of the further monomer (A3) is 0 to 80% by weight, based on the fluorine-containing polymer (A).
10. The surface treatment agent according to claim 1 , wherein the liquid medium (B) is a mixture of water and an organic solvent.
11. The surface treatment agent according to claim 1 , wherein the surface treatment agent is a water repellent agent, an oil repellent agent, a soil resistant agent, a soil release agent, a peel agent, or a mold release agent.
12. A method for producing the surface treatment agent according to claim 2 , comprising:
polymerizing a monomer mixture comprising the fluorine-containing monomer (A1) and the fluorine-free monomer having a hydrocarbon group (A2) in the presence of the liquid medium to obtain a dispersion or a solution of the fluorine-containing polymer (A).
13. A method for producing a treated substrate, comprising applying the surface treatment agent according to claim 1 to a substrate.
14. The surface treatment agent according to claim 6 , wherein A is a halogen atom selected from a chlorine atom, a bromine atom, or an iodine atom.