Fluoropolymers and treatment agent

Patent metadata

Field	Value
Publication number	US-9677220-B2
Application number	US-201013510787-A
Country	US
Kind code	B2
Filing date	Nov 18, 2010
Priority date	Nov 20, 2009
Publication date	Jun 13, 2017
Grant date	Jun 13, 2017

Abstract

Disclosed is a fluorine-containing polymer prepared by polymerizing (I) a polyfluoroalkyl group-containing (meth)acrylate which is substituted at alpha-position, in the presence of (II) a blocked isocyanate compound. A water- and oil-repellent composition containing the fluorine-containing polymer can impart the excellent water- and oil-repellency, and excellent durability thereof to substrates.

First claim

The invention claimed is:

1. A fluorine-containing polymer prepared by polymerizing a monomer comprising:
(I) a polyfluoroalkyl group-containing acrylate which is substituted at the alpha-position with a monovalent organic group other than a methyl, or with a halogen atom, wherein the polyfluoroalkyl group has 1 to 6 carbon atoms,
wherein the polyfluoroalkyl group-containing acrylate (I) comprises a compound of the formula:
CH 2 ═C(—X)—C(═O)—Y—Z—Rf  (I)

wherein X is a monovalent organic group other than a methyl group, or a halogen atom;
Y is —O— or —NH—;
Z is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic or cycloaliphatic group having 6 to 18 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), a —CH 2 CH(OZ 1 )CH 2 — group (wherein Z 1 is a hydrogen atom or an acetyl group), a —(CH 2 ) m —SO 2 —(CH 2 ) n — group, or a —(CH 2 ) m —S—(CH 2 ) n — group (wherein m is from 1 to 10 and n is from 0 to 10); and
Rf is a linear or branched polyfluoroalkyl group having 1 to 6 carbon atoms;

in the presence of:
(II) a blocked isocyanate compound, wherein a blocking agent in the isocyanate compound (II) is a pyrazole or an active methylene-containing compound, and
(III) a functional organopolysiloxane, wherein the functional organopolysiloxane (III) is a functional organopolysiloxane comprising siloxy units having the average formula:
(R 2 SiO) a (RR N SiO) b (RR F SiO) c
wherein a is 0-4000, b is 0-1000, c is 1-1000,
R is independently a monovalent organic group,
R N is a monovalent amino-functional organic group, and
R F is a monovalent mercapto-, vinyl-, (meth)acrylamide- or (meth)acrylate-functional organic group; and

wherein the functional organopolysiloxane bonds to the fluorine-containing polymer through a functional organic group, and wherein the blocked isocyanate compound is a compound having a blocked isocyanate group and no polymerizible unsaturated group.

2. The polymer according to claim 1 , wherein the Rf group in the polyfluoroalkyl group-containing acrylate (I) is a perfluoroalkyl group.

3. The polymer according to claim 1 , wherein the blocking agent in the isocyanate compound (II) is a pyrazole compound of the formula:

wherein each of R 11 is, the same or different, an alkyl group, an alkenyl group, an aralkyl group, N-substituted carbamyl group, a phenyl group, NO 2 , a halogen atom or a —C(═O)OR 12 group
wherein R 12 is an alkyl group having 1 to 4 carbon atoms, and
n is 0, 1, 2 or 3.

4. The polymer according to claim 1 , wherein the isocyanate compound (II) is a compound of the formula:
A-Y m
wherein A is a m-valent aliphatic group, alicyclic group, heterocyclic group or aromatic group, Y is, the same or different,

in which each of R 11 is, the same or different, an alkyl group, an alkenyl group, an aralkyl group, N-substituted carbamyl group, a phenyl group, NO 2 , a halogen atom or a —C(═O)OR 12 group
wherein R 12 is an alkyl group having 1 to 4 carbon atoms, and
n is 0, 1, 2 or 3; or
—NH—C(═O)—CH—(C(═O)—OR 21 ) 2

R 21 is a hydrocarbon group having 1 to 30 carbon atoms, or
a monovalent moiety containing a hydrophilic group, and
m is 1 to 10; or
—NHCOO—(R 31 —O) k —R 32

R 31 is an alkylene group having 2 to 5 carbon atoms,
R 32 is a C1-C10 aliphatic (or alkyl) group, and
k is 2 to 50.

5. A water- and oil-repellent composition comprising a fluorine-containing polymer having repeating units derived from a monomer comprising:
(I) a polyfluoroalkyl group-containing acrylate which is substituted at the alpha-position with a monovalent organic group other than a methyl, or with a halogen atom, wherein the polyfluoroalkyl group has 1 to 6 carbon atoms,
wherein the polyfluoroalkyl group-containing acrylate (I) comprises a compound of the formula:
CH 2 ═C(—X)—C(═O)—Y—Z—Rf  (I)

wherein X is a monovalent organic group other than a methyl group, or a halogen atom;
Y is —O— or —NH—;
Z is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic or cycloaliphatic group having 6 to 18 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), a —CH 2 CH(OZ 1 )CH 2 — group (wherein Z 1 is a hydrogen atom or an acetyl group), a —(CH 2 ) m —SO 2 —(CH 2 ) n - group, or a —(CH 2 )m—S—(CH 2 ) n - group (wherein m is from 1 to 10 and n is from 0 to 10); and
Rf is a linear or branched polyfluoroalkyl group having 1 to 6 carbon atoms;

wherein the water- and oil-repellent composition comprises:
(II) a blocked isocyanate compound,
wherein a functional organopolysiloxane (III) bonds to the fluorine-containing polymer through a functional organic group, wherein the functional organopolysiloxane (III) is a functional organopolysiloxane comprising siloxy units having the average formula:
(R 2 SiO) a (RR N SiO) b (RR F SiO) c
wherein a is 0-4000, b is 0-1000, c is 1-1000,
R is independently a monovalent organic group,
R N is a monovalent amino-functional organic group, and
R F is a monovalent mercapto-, vinyl-, (meth)acrylamide- or (meth)acrylate-functional organic group; and

wherein the blocked isocyanate compound is a compound having a blocked isocyanate group and no polymerizible unsaturated group, wherein a blocking agent in the blocked isocyanate compound is a pyrazole or an active methylene-containing compound.

6. A water- and oil-repellent composition comprising the fluorine-containing polymer according to claim 1 .

7. The water- and oil-repellent composition according to claim 6 , which comprises a cluster formed by the fluorine-containing polymer and the blocked isocyanate compound.

8. A water- and oil-repellent composition comprising a fluorine-containing polymer and a blocked isocyanate compound,
wherein the fluorine-containing polymer has repeating units derived from a monomer comprising a polyfluoroalkyl group-containing (meth)acrylate substituted at the alpha-position with a monovalent organic group other than a methyl, or with a halogen atom, wherein the polyfluoroalkyl group has 1 to 6 carbon atoms,
wherein the polyfluoroalkyl group-containing (meth)acrylate (I) comprises a compound of the formula:
CH 2 ═C(—X)—C(═O)—Y—Z—Rf  (I)

wherein X is a monovalent organic group other than a methyl group, or a halogen atom;
Y is —O— or —NH—;
Z is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic or cycloaliphatic group having 6 to 18 carbon atoms, a —CH 2 CH 2 N(R 1 )SO— group (wherein R 1 is an alkyl group having 1 to 4 carbon atoms), a —CH 2 CH(OZ 1 ) CH 2 — group (wherein Z 1 is a hydrogen atom or an acetyl group), a —(CH 2 ) m —SO 2 —(CH 2 ) n — group, or a —(CH 2 ) m -S—(CH 2 ) n - group (wherein m is from 1 to 10 and n is from 0 to 10); and
Rf is a linear or branched polyfluoroalkyl group having 1 to 6 carbon atoms;

wherein the fluorine-containing polymer does not contain the blocked isocyanate compound, wherein a functional organopolysiloxane bonds to the fluorine-containing polymer through a functional organic group, wherein the functional organopolysiloxane is a functional organopolysiloxane comprising siloxy units having the average formula:
(R 2 SiO) a (RR N SiO) b (RR F SiO) c
wherein a is 0-4000, b is 0-1000, c is 1-1000,
R is independently a monovalent organic group,
R N is a monovalent amino-functional organic group, and
R F is a monovalent mercapto-, vinyl-, (meth)acrylamide- or (meth)acrylate-fu

Assignees

• Uesugi Norimasa
• Kubota Kouji
• Yamamoto Ikuo
• Hupfield Peter Cheshire
• Daikin Ind Ltd

Inventors

• Uesugi Norimasa
• Kubota Kouji
• Yamamoto Ikuo
• Hupfield Peter Cheshire

Classifications

• D06M15/277

  containing fluorine · CPC title

• C09K3/18

  for application to surfaces to minimize adherence of ice, mist or water thereto (rendering particulate materials free flowing, in general, e.g. making them hydrophobic B01J2/30); Thawing or antifreeze materials for application to surfaces (used in liquids for heat-transfer, heat-exchange or heat-storage or for the production of heat or cold other than by combustion, e.g. radiator liquids, C09K5/00) · CPC title

• C09K2003/1081

  Water-proofed materials · CPC title

• C08F220/24

  containing perhaloalkyl radicals · CPC title

• D06M15/576

  containing fluorine · CPC title