Method of preparing water- and oil-repellent soil-resistant composition
The present invention provides a water- and oil-repellent soil-resistant composition comprising (A) a fluorine-containing polymer having repeating units derived from a monomer comprising a fluorine-containing monomer and (B) a silane compound. The water- and oil-repellent soil-resistant composition comprising the fluorine-containing acrylate polymer can impart the excellent water- and oil-repellency and soil resistance to the porous substrate and is free from an organic solvent.
1. A method of preparing a fluorine-containing polymer, comprising:
polymerizing (A) a monomer comprising a fluorine-containing monomer in the presence of (B) a silane compound to give a mixture of a fluorine-containing polymer and the silane compound; wherein said fluorine-containing monomer is of the formula:
CH 2 ═C(—X)—C(═O)—O—Y—Rf (I)
wherein X is a hydrogen atom, an linear or branched alkyl group having 1 to 21 carbon atoms, a halogen atom, a CFX 1 X 2 group (wherein X 1 and X 2 is a hydrogen atom or a halogen atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group,
Y is a direct bond,
an aliphatic group having 1 to 10 carbon atoms,
an aromatic or cycloaliphatic group having 6 to 10 carbon atoms,
a —CH 2 CH 2 N(R 1 )SO 2 — group,
wherein R 1 is an alkyl group having 1 to 4 carbon atoms, or
—CH 2 CH(OY 1 )CH 2 — group,
wherein Y 1 is a hydrogen atom or an acetyl group, and
Rf is a linear or branched fluoroalkyl or fluoroalkenyl group having 1 to 21 carbon atoms, or a fluoroether group having totally 1 to 200 repeating units selected from the group consisting of the repeating units: —C 3 F 6 O—, —C 2 F 4 O— and —CF 2 O—.
2. The method according to claim 1 , wherein the monomer (A) further comprises:
(b) a fluorine-free monomer, and
(c) optionally present, a crosslinkable monomer,
in addition to (a) the fluorine-containing monomer.
3. The method according to claim 1 , wherein the Rf is a fluoroalkyl group having 1 to 6 carbon atoms.
4. The method according to claim 1 , wherein the Rf group is a perfluoroalkyl group.
5. The method according to claim 2 , wherein the fluorine-free monomer (b) is an acrylate of the general formula:
CH 2 ═CA 1 COOA 2
wherein A 1 is a hydrogen atom, a methyl group or a halogen atom other than a fluorine atom, and A 2 is a hydrocarbon group having 1 to 30 carbon atoms, particularly an alkyl group represented by C n H 2n+1 wherein n is 1 to 30.
6. The method according to claim 2 , wherein the fluorine-free monomer (b) is a (meth)acrylate monomer having a cyclic hydrocarbon group.
7. The method according to claim 2 , wherein the crosslinkable monomer (c) is a monomer having at least two reactive groups, a monomer having least two carbon-carbon double bonds, or a monomer having at least one carbon-carbon double bond and at least one reactive group.
8. The method according to claim 1 , wherein the silane compound is of the formula:
R 4 Si
wherein each R is a monovalent organic group, which can be the same or different, denotes a hydrocarbon, substituted hydrocarbon, hydroxyl, hydrocarbonoxy or substituted hydrocarbonoxy group.
9. The method according to claim 1 , wherein the silane compound is a trialkoxysilane, triacetoxysilane, dialkoxysilane, monoalkoxysilane, tetraalkoxysilane or partially condensed silicate.
10. The method according to claim 1 which is conducted in the absence of an organic solvent.
11. A masonry substrate having a water- and oil-repellent soil resistant composition applied thereto comprising:
(A) a fluorine-containing polymer comprising repeating units derived from a fluorine-containing monomer of the formula:
CH 2 ═C(—X)—C(═O)—O—Y—Rf (I)
wherein X is a hydrogen atom, an linear or branched alkyl group having 1 to 21 carbon atoms, a halogen atom, a CFX 1 X 2 group (wherein X 1 and X 2 is a hydrogen atom or a halogen atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group,
Y is a direct bond,
an aliphatic group having 1 to 10 carbon atoms,
an aromatic or cycloaliphatic group having 6 to 10 carbon atoms,
a —CH 2 CH 2 N(R 1 )SO 2 — group,
wherein R 1 is an alkyl group having 1 to 4 carbon atoms, or
—CH 2 CH(OY 1 )CH 2 — group,
wherein Y 1 is a hydrogen atom or an acetyl group, and
Rf is a linear or branched fluoroalkyl or fluoroalkenyl group having 1 to 21 carbon atoms, or a fluoroether group having totally 1 to 200 repeating units selected from the group consisting of the repeating units: —C 3 F 6 O—, —C 2 F 4 O— and —CF 2 O—; and
(B) a silane compound; wherein said composition does not contain an organic solvent.
12. The masonry substrate of claim 11 , wherein said composition further contains at least one dilution medium comprising a silane compound which is different than silane compound (B).